acrylic-based staged shell-core polymer, personal care surfactant and cleaning compositions, and met

专利摘要:
acrylic-based staged shell-core polymer, personal care surfactant and cleaning compositions, and, methods for making an acrylic-based staged shell-core polymer and to thicken an aqueous composition. multi-stage acrylic-based core-shell polymer are disclosed which comprise a linear core polymer and at least one subsequently polymerized shell polymer is cross-linked. core-shell polymers surprisingly provide desirable rheological, clarity and aesthetic properties in compositions containing aqueous surfactant, particularly at low ph.
公开号:BR112013000383B1
申请号:R112013000383
申请日:2011-07-07
公开日:2020-04-14
发明作者:L Dashiell David；S Filla Deborah；Gray Gary；J Mullay John；Tamareselvy Krishnan；J Smith Steven；Yang Yi
申请人:Lubrizol Advanced Mat Inc；
IPC主号:

专利说明:

“CASE-NUCLEUS POLYMER IN ACRYLIC-BASED STAGES, SURFACE COMPOSITIONS AND PERSONAL CARE CLEANING, AND METHODS FOR MAKING A CASE-NUCLEUS POLYMER IN STAGES BASED ON ACRYLIC AND THICKEN A COMPOSITION”
TECHNICAL FIELD
In one aspect, the present invention relates to shell-core polymers based on staged acrylic comprising a linear core and at least one cross-linked outer shell. In another aspect, the invention relates to an acrylic based shell-core thickener suitable for use in aqueous systems. A further aspect of the invention concerns the formation of stable aqueous compositions containing a staged acrylic shell-core polymer rheology modifier, a surfactant and optionally several components that are substantially insoluble materials that require suspension or stabilization. In addition, a further aspect of the invention concerns the formation of stable and rheologically clear phase surfactant compositions formulated in low pH ranges.
BACKGROUND OF THE INVENTION
Rheology modifiers are also referred to as thickeners or viscosifiers, they are ubiquitous in personal care cleaning formulations containing surfactant. The rheological properties (for example, viscosity and flow characteristics, foaming, dispersibility and others), aesthetic properties (for example, clarity, sensory effects and others), smoothness (dermal and mitigation of eye irritation) and the ability to suspend and stabilize soluble and insoluble components within a surfactant-based formulation are often modified by the addition of a thickener.
Often thickeners are introduced into surfactant formulations in solid form and mixed under conditions effective to dissolve the thickener in the liquid surfactant composition in order to effect an increase in viscosity. Often, the mixture must be carried out at elevated temperatures (hot processing) in order to promote the dissolution of the solid thickener and obtain the desired viscosity improvement. In addition, solid thickeners (eg, carbomer powders) are known to resist wet-out on contact with the surface of an aqueous-based system. Consequently, the carbomers are supplied as finely divided powders and / or must be changed to reduce the particle size, which helps in dissolving by increasing the relative surface area of the particle. During processing, carbomer powders can become electrostatically charged when they are transferred into or out of containers and tend to adhere to oppositely charged surfaces including airborne powder, which requires specialized extraction and powder equipment. This means that the preparation of aqueous dispersions is cluttered and time consuming unless special precautions are taken and expensive equipment is used. Formulators of compositions containing thickened surfactant constituents want the ability to formulate their products at ambient temperatures (cold processing), consequently, formulators want thickeners, which can be introduced into liquid surfactant compositions in liquid rather than solid form . It provides the formulator with a higher degree of precision in introducing the thickener into the liquid surfactant composition, allows the ability to formulate products at room temperatures (cold processing) and better facilitates automated processing without the need for special security and safety equipment. handling.
An important class of rheology modifier commonly used to thicken formulations containing an aqueous based surfactant are the alkali-soluble or alkali-soluble (ASE) emulsion polymers. ASE polymers are linear or cross-linked copolymers that are synthesized from (meth) acrylic acid and alkyl acrylates. The cross-linked polymers immediately thicken on neutralization with an inorganic or organic base. As liquid emulsions, ASE polymers are easily processed and formulated in formulations containing liquid surfactant by the product formulator. Examples of formulation based on surfactant thickened by ASE polymer are given in U.S. Patent No. 6,635,702; International Published Application No. WO 01/19946 and European Patent No. 1 690 878 Bl, which discloses the use of a polymeric thickener for aqueous compositions containing, although these thickeners offer good viscosity, suspension properties and clarity in formulations containing surfactant at almost neutral pH values (pH> 6.0), they become cloudy in acidic pH ranges, resulting in poor clarity.
The microbial combination of bacteria, yeasts and / or fungi in cosmetics, toiletries and personal care products is very common and has been of great interest to the industry for many years. The present products containing surfactants are typically formulated with a preservative to protect the product from deterioration, discoloration or waste and to ensure that the product is safe for topical application to skin, scalp and hair in humans and animals. Three classes of preservative compounds that are commonly used in products containing surfactant are formaldehyde donors such as diazolinyl urea, imidazolinyl urea and DMDM Hydantoin; halogenated compounds including 2,4-dichlorobenzyl alcohol, Chloroxylenol (4-chloro-3,5-dimethyl-phenol), Bronopol (2-bromo-2-nitropropane-1,3-diol) and iodopropynyl butyl carbamate and paraben compounds including methyl -paraben, ethyl-paraben, propyl-paraben, butylparaben, isopropyl-paraben and benzyl-paraben.
While these preservatives have been used successfully in personal care products for many years, they are of recent interest to the scientific community and the public that some of these compounds may pose health risks. Consequently, there is an interest in replacing the compounds mentioned above in products containing surfactant that are topically applied or come into contact with the skin, scalp or human hair while maintaining good antimicrobial effectiveness, smoothness and do not form safety considerations.
Organic acids (eg, sorbic, citric and benzoic), such as those used as preservatives in the food industry, have been increasingly sought after as the ideal replacement for previous preservative systems in formulations containing surfactant. The microbial activity of organic acids is connected to the associated or protonated species of the acid molecule. When the pH of a formulation containing organic acid increases, dissociation of the proton occurs to form acid salts. The dissociated form of organic acids (acid salts) has no antimicrobial activity when used alone, effectively limiting the use of organic-based acids to pH values below 6 (Weber, K. 2005. New alternatives to paraben-based preservative blends. Cosmetics & Toiletries 120 (1): 57-62).
The literature also suggested that the formulation of products in the natural pH range pH (between about 3 and 5) 1) reduces the amount of preservative required in a product by intensifying the effectiveness of the preservative, 2) stabilizes and increases the effectiveness of many active cosmetic ingredients, 3) it is beneficial to repair and maintain the skin barrier tissue and 4) to support the natural skin flora to the exclusion of over-colonization by harmful microorganisms (Wiechers, JW 2008. Formulating at pH 4-5: How lower pH benefits the skin and formulations. Cosmetics & Toiletries 123 (12): 61-70).
When the industry wants new products based on thickened surfactants that are formulated in the acidic pH range, there is an increasing need for a rheology modifier that, when used in combination with a surfactant, provides the high clarity formulation under pH conditions acid while maintaining a good viscosity / rheology profile, suspension (yield value) and enhanced aesthetics.
SUMMARY OF THE INVENTION
In one aspect, the embodiments of the present invention relate to polymeric compositions based on acrylic which comprise polymeric morphologies in stages, structured or core-shell.
In one aspect, an embodiment of the invention relates to a staged shell-core polymer comprising a linear acrylic (non-crosslinked) polymer stage and an acrylic based cross-shell stage polymer.
In one aspect, an embodiment of the invention relates to a multi-stage polymer comprising the core polymer stage comprising a linear acrylic based polymer and at least one other stage comprising an acrylic based polymeric stage .
In one aspect, an embodiment of the invention relates to a thickened aqueous composition comprising a shell-core polymer in stages of the invention.
In one aspect, one embodiment of the invention relates to a thickened aqueous composition comprising an acrylic based shell-core polymer and a surfactant selected from anionic, cationic, amphoteric and non-ionic surfactants and mixtures thereof.
In one aspect of the invention, the embodiments relate to aqueous compositions with a low pH having good rheological and clarity properties comprising an acrylic based shell-core polymer, an anionic surfactant, an amphoteric surfactant, an pH adjustment and an optional surfactant selected from a cationic surfactant, a non-ionic surfactant and mixtures thereof.
In one aspect of the invention, the embodiments relate to aqueous compositions with a low pH having good rheological and clarity properties comprising an acrylic based shell-core polymer, an anionic surfactant, an amphoteric surfactant, an pH adjustment, an acid based preservative and an optional surfactant selected from a cationic surfactant, a non-ionic surfactant and mixtures thereof.
In one aspect, the embodiments of the invention relate to stable, low pEI compositions of aqueous personal care, home care, health care and institutional and industrial care having good rheological and clarity properties comprising a shell-core polymer in acrylic based stages, an anionic surfactant, an amphoteric surfactant, a pH adjusting agent, an optional acid-based preservative and an optional surfactant selected from a cationic surfactant, a non-ionic surfactant and mixtures of these.
In one aspect, the embodiments of the invention relate to stable compositions of personal care, home care, health care and institutional and industrial care having good rheological and clarity properties that comprise a shell-core polymer in stages based on acrylic, an anionic surfactant, an amphoteric surfactant, a pH adjusting agent, an insoluble component and / or a particulate material that is stabilized or suspended in the composition, an optional acid-based preservative and an optional surfactant selected from a cationic surfactant, a nonionic surfactant and mixtures of these.
In one aspect, the embodiments of the invention relate to a composition containing aqueous surfactant formulated at a low pH comprising a staged shell-core polymer, an anionic surfactant, an amphoteric surfactant, a pH adjusting agent and a surfactant option selected from a cationic surfactant, a non-ionic surfactant and mixtures thereof whose composition has a combination of superior clarity properties and yield value.
In yet another aspect, the invention relates to a composition of personal care, domestic care, health care and institutional and industrial that comprises the shell-core polymer in stages of the invention in combination with a beneficial agent, adjuvant and / or additive, with or without a surfactant.
These stable compositions can maintain can maintain a uniform acceptable rheology, without significant increases or decreases in viscosity, without any separation, sedimentation or skimming or loss of clarity over extended periods of time, such as for at least one month at 45 ° C.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 represents a two-stage core-shell polymer comprising a linear core polymer surrounded by or partially surrounded by a cross-linked shell polymer.
Figure 2 depicts a multi-stage shell-core polymer comprising an innermost linear polymer core and a cross-linked polymer shell. The contiguous polymeric stages are configured in alternating orders of linear or reticulated polymeric types.
Figure 3 represents a polymerized core-shell polymer and multiple stage in the order of random stages. The polymer is configured to contain contiguous linear and cross-linked polymeric stages.
Figure 4 shows a transmission electron micrograph (TEM) image of a shell-core polymer in stages of the invention.
DESCRIPTION OF EXEMPLARY CARE
Exemplary embodiments according to the present invention will be described. Various modifications, adaptations or variations of the exemplary embodiments described here may become evident to those skilled in the art as they are disclosed. It will be understood that all such modifications, adaptations or variations that rely on the explanations of the present invention and through which these explanations have advanced in the art, are considered to be within the scope and spirit of the present invention.
The polymers and compositions of the present invention may suitably comprise, consist of or consist essentially of the components, elements and process designs described herein. The invention disclosed illustratively here can be practiced properly in the absence of any element that is not specifically disclosed here.
Unless otherwise stated, all percentages, parts and ratios expressed herein are based on the weight of the total compositions of the present invention.
As used here and throughout the specification, the terms core-shell morphology, core-shell structure, core-shell polymer, structured polymer, shell-core polymer in stages and “polymer in stages” are used interchangeably and mean a particle polymeric prepared by a sequential or staged polymerization process in which each sequence or stage of repeating monomer units is polymerized until completion before the subsequent sequence or stage of repeating units are polymerized. These polymers have a structure in which the polymers that form the core portion, sequence or stage and the polymers that form the shell portion, sequence or stage, are physically and / or chemically linked and / or attracted to each other. The structure and / or chemical composition (e.g., monomeric composition and / or quantity) of the copolymer particles of this invention changes from the inside to the outside of the particle and, as a result,
These gradient zones can also have different physical and chemical properties. Sometimes these changes can be gradual, producing a morphology having a gradient of polymeric structure or composition along any radius of these. Alternatively, changes in polymeric structure or composition can be relatively defined by moving extremely along a radius of the central particle, producing a morphology having a relatively distinct core portion comprising a polymeric composition and a relatively distinct shell portion comprising a different polymeric composition. The staged core-shell morphology can comprise layers or multiple zones of different polymeric composition along the core polymer defined here is a linear polymer and at least one shell layer comprises a cross-linked polymer. The rate of change in the particle's polymeric morphology is not particularly critical as long as the polymer has the necessary properties described here. Consequently, as used here, the terms core and shell refer to the internal or external polymer content of the particle, respectively, and the use of said terms should not be construed as meaning that the polymer particles of the particle will necessarily present a distinct interface between the internal polymers and external of the particle.
It is understood that the shell-core polymer particle in stages may not only be a form in which the core portion is completely coated or encapsulated within the shell portion, but also a form in which the core portion is only partially coated or encapsulated. It should also be understood that in the description of the core polymers and the “shell polymers of the shell-core polymers in stages of the invention there may be a significant amount of polymer interpenetration that resides in the core and shell of the polymer particles. In this way, the core polymers can sometimes extend into the particle shell which forms a domain in the shell particle and vice versa.
The terms core polymers and shell polymers and similar terminology are used here to describe the polymeric material in the named portion of the polymeric particle in general without attempting to identify any particular polymers as strictly shelled or strictly core polymers.
As used herein, the term (meth) acrylic acid is understood to include both acrylic acid and methacrylic acid. Similarly, the term alkyl (meth) acrylate as used herein is understood to include alkyl acrylate and alkyl methacrylate.
The term low pH refers to a pH value of 6 or below in one aspect, from about 0.5 to about 5.9 in another aspect, from about 2 to about 5.5 in another aspect, and from about 3.5 to about 5 still in an additional aspect.
The term high clarity means a turbidity value of <40 NTU in one aspect, <30 NTU in another aspect and <20 NTU in another aspect as measured in a thickened / surfactant aqueous polymer composition comprising 2.4% in polymer weight (active polymer solids) and 12.7% by weight of a combination of anionic and amphoteric surfactant and the remaining water, in which the anionic to amphoteric surfactant is present in a ratio of about 4.5: 1 (calculated on a weight to weight basis of an active surfactant) and where the pH of the specified composition ranges from about 4.5 to about 5.
The term personal care products as used herein includes, but is not limited to, cosmetics, toilet products, cosmeceuticals, beauty aids, insect repellents, personal hygiene and cleaning products applied to the body, including skin, hair, scalp and nails of humans and animals.
The term household care products as used herein includes, but is not limited to, products used in a domestic environment for cleaning surfaces or maintaining sanitary conditions, such as in the kitchen and bathroom (for example, hard surface cleaners, care with manual or automatic crockery, toilet cleaners and disinfectants) and laundry products for fabric care and cleaning (eg detergents, fabric conditioners, pretreatment stain removers) and others.
The term health care products as used herein includes, but is not limited to, pharmaceutical products (controlled pharmaceutical products), pharmaceuticals, oral care products (mouth and teeth), such as oral suspensions, mouthwashes, toothpaste , toothpastes and others and products and applications sold directly (topical and transdermal), such as plasters and others, applied extremly to the body, including the skin, scalp, nails and mucous membranes of humans and animals, for the improvement of a related condition with health or medical to, in general, maintain hygiene or well-being and others.
The term institutional and industrial care (I&I) as used here includes, but is not limited to, products used to clean surfaces or maintain sanitary conditions in institutional and industrial environments, textile treatments (for example, textile conditioners, carpet cleaners and articles upholstery), automotive care (for example, manual and automatic automotive washing detergents, tire shine, leather conditioners, liquid automotive polishers, plastic polishers and conditioners), paints and coatings and others.
As used herein, the term rheological properties and grammatical variations include, without limitation, such properties as Brookfield viscosity, increase or decrease in viscosity in response to shear stress, flow characteristics, gel properties, such as hardness, resilience , fluidity and others, foam properties, such as foam stability, foam density, ability to hold a peak and others, suspension properties such as yield value and aerosol properties, such as ability to form aerosol droplets when dispensed from the pump based on propellant or mechanics type aerosol dispensers.
The term aesthetic property and its grammatical variations when applied to compositions refers to the visual and tactile psychosensory product properties, such as color, clarity, softness, stickiness, lubricity, texture, conditioning and sensation and others.
Here, as well as anywhere in the specification and claims, individual numerical values (including numerical carbon atom values) or limits, can be combined to form additional undisclosed and / or non-established ranges.
The headings provided here serve to illustrate, but not to limit the invention in any way.
Core-shell polymer
Shell-core polymers at stages within the scope of the invention include, but are not limited to, those embodiments illustrated in the drawings. The stage-core shell polymers of the present invention are acrylic based copolymers comprising a linear core polymer and at least one cross-linked shell polymer. As shown in Fig. 1, the core-shell polymer 1 comprises at least two stages produced sequentially in the emulsion, an inner core first stage 2 comprising a copolymer based on non-cross-linked or linear acrylic and an outer shell or last stage 3 which comprises a cross-linked acrylic base copolymer. As shown in Fig. 2, a core-shell polymer 1 having intermediate stages of a linear polymer 4 'and a crosslinked polymer 5' can be sequentially polymerized and located between the innermost linear core stage polymer 4 and a stage polymer outermost crosslinked shell 5. Each linear and crosslinked polymer stage can be the same or different in terms of repeating unit composition and the relative increase in monomeric repeating units in the polymer backbone. In a multi-stage shell-core polymer (a core-shell polymer comprising more than two stages), the configuration of sequentially polymerized stages can be orderly, for example, alternating contiguous stages between a linear polymer and a crosslinked polymer as in Fig. 2 or as illustrated in Fig. 3 the stage configuration of the core-shell polymer 1 can be random, for example, two or more contiguous stages can be linear 6, 6 'or cross-linked 7, 7', 7, subject to provided that the innermost core stage 6 is a linear (non-crosslinked) polymer and at least one of the outer shells, for example, stage 7 is a crosslinked polymer.
In one aspect, the staged shell-core polymer comprises from about 5% to about 95% by weight of the linear core polymer based on acrylic and from about 95% to about 5% by weight of the shell polymer crosslinked based on acrylic, based on the total weight of the shell-core polymer in stages. In another aspect, the staged kernel core polymer comprises from about 20% to about 80% by weight of the linear core polymer based on acrylic and from about 80% to about 20% by weight of the crosslinked shell polymer based on acrylic, based on the total weight of the shell-core polymer in stages. In yet another aspect, the staged shell-core polymer comprises from about 60% to about 40% by weight of the linear core polymer based on acrylic and from about 40% to about 60% by weight of the polymer cross-linked shell based on acrylic, based on the total weight of the shell-core polymer in stages.
Core polymer component
The linear core polymer is a linear polymer based on acrylic that is polymerized in the absence of a crosslinking monomer. In one embodiment, the core polymer is polymerized from a monomeric mixture comprising a) a first monomeric component selected from one or more ethylenically unsaturated monomers containing at least one group of carboxylic acid; b) a monomeric component second ethylenically unsaturated selected from at least one linear alkyl ester or branched Ci to C ₅ (meth) acrylic acid, at least one hydroxyalkyl ester Ci to C ₅ (meth) acrylic acid and mixtures thereof and c) optionally , at least one monomeric component selected from a monomer represented by the formulas:
i) CH ₂ = C (R) C (O) OR ¹ , where R is selected from hydrogen or methyl and R ¹ is selected from C ₆ -C ₀ alkyl, C ₆ to C ₁₀ hydroxyalkyl, - (CH ₂ ) ₂ OCH ₂ CH3 and (CH ₂ ) ₂ C (O) OH and salts thereof;
ii) CH ₂ = C (R) X, where R is hydrogen or methyl and X is selected from -C ₆ H ₅ , CN, -C (O) NH ₂ , -NC ^ O, -C (O) NHC (CH ₃ ) ₃ , -C (O) N (CH ₃ ) ₂ ,
C (O) NHC (CH ₃ ) ₂ (CH ₂ ) ₄ CH ₃ and -C (O) NHC (CH ₃ ) ₂ CH ₂ S (O) (O) OH and salts thereof;
iii) CH ₂ = CHOC (O) R ¹ , where R ¹ is straight or branched C ¹ -C 6 alkyl and iv) CH ₂ = C (R) C (O) OAOR ² , where A is a bivalent radical selected from CH ₂ CH (OH) CH ₂ e-CH ₂ CH (CE ₂ OH) -, R is selected from hydrogen or methyl and R ² is an acyl residue of a saturated or unsaturated C10 to C ₂₂ fatty acid.
Exemplary ethylenically unsaturated monomers containing at least one carboxylic acid group that are presented under a monomeric component a) include (meth) acrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, crotonic acid, acotinic acid, and salts thereof and mixtures of these.
In one aspect of the invention, the amount of at least one monomer-containing carboxylic acid group presented under the first monomeric component a) ranges from about 10% to 80% by weight, from about 20% to about 70% by weight in another aspect, and from about 35% to about 65% by weight in another aspect based on the total weight of the monomers.
Exemplary alkyl (meth) acrylate and hydroxy (meth) acrylate exemplars presented under monomeric component b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, iso-amyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate (butane diol mono (meth) acrylate) and mixtures thereof.
In one aspect of the invention, the alkyl and hydroxy (meth) acrylate alkyl monomers presented under the second monomer component b) are used in an amount ranging from about 90% to about 20% by weight, from about 80 % to about 25% by weight in another aspect, and from about 65% to about 35% by weight in yet another aspect, based on the total weight of the monomers.
Exemplary ethylenically unsaturated monomers presented in formulas i) to iv) of optional monomeric component c) include ethyl diglycol (meth) acrylate, 2-carboxyethyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , octyl (meth) acrylate, decyl (meth) acrylate, 6-hydroxyiexyl (meth) acrylate, 10-hydroxydocyl (meth) acrylate, styrene, a-methyl styrene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N, N'dimethylaminoacrylamide t-butylacrylamide, t-octylacrylamide, N-vinyl pyrrolidone, 2-acrylamido-2-methylpropane sulfonic acid, vinyl acetate, vinyl propionate, vinyl butanoate, vinyl valerate, vinyl hexanoate, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl laurate, ACE ™ monomer and (M) ACE ™ available from Hexion Specialty Chemicals, Inc., Columbus, OH and mixtures thereof.
The preceding monomers are commercially available and / or can be synthesized by procedures well known in the art.
The ACE monomer (CAS No. 94624-09-06) is the reaction product of glycidyl t-decanoate (CAS No. 71206-09-2) and acrylic acid. The (M) ACE monomer is synthesized by the reaction of glycidyl t-decanoate and methacrylic acid.
The monomers shown in the formula iv) the optional monomer component C) can be synthesized by the esterification reaction of glycidol with a Cio to C22 fatty acid T ^o obtain the glycidyl ester of the respective fatty acids. The glycidyl ester formed in this way, in turn, can be reacted through its epoxy functionality with the carboxyl portion of (meth) acrylic acid to obtain a preformed monomer. Alternatively, the fatty acid glycidyl ester can be added to the polymerization mixture comprising the monomers previously described and reacted in situ with a portion of the one or more ethylenically unsaturated monomers containing at least one carboxylic acid group described under the monomeric component a) , subject to the condition that the reagent stoichiometry is designed such that only a portion of the carboxyl groups is reacted. In other words, sufficient acid functionality must be retained to serve the purpose of the present invention.
In one aspect of the invention, glycidyl esters suitable for forming the preformed and formed in situ monomeric components described under formula iv) are disclosed in U.S. Patent No. 5,179,157 (column 13). The relevant disclosure of which is hereby incorporated by reference. A glycidyl ester of neodecanoic acid and isomers thereof is commercially available under the brand name Cardura ™ El OP from Hexion Specialty
Chemicals, Inc.
In one aspect of the invention, the monomers presented in formulas i) to iv) of the optional monomeric component c) are used in an amount ranging from about 0% to about 35% by weight, from about 1% to about from 30% by weight in another aspect, from about 2% to about 15% by weight in yet another aspect, and from about 5% to about 10% by weight in another aspect, based on weight total monomers.
In another aspect of the invention, the non-crosslinked core polymer is polymerized from a monomeric composition comprising:
a) from about 10% to about 80% by weight of at least one carboxylic acid monomer comprising acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, acotinic acid, maleic acid or combinations thereof;
b) from about 90% to about 20% by weight of at least one C 1 to C ₅ alkyl ester and / or at least one C 1 to C ₅ hydroxyalkyl ester of acrylic acid or methacrylic acid and
c) from about 0 to about 35 by weight of at least one a, b-ethylenically unsaturated monomer selected from a monomer represented by the formulas:
i) CH ₂ = C (R) C (O) OR ¹ , where R is selected from hydrogen or methyl and R ¹ is selected from C0-C10 alkyl, Cg to Cio hydroxyalkyl, - (CH ₂ ) ₂ OCH ₂ CH3 and (CH ₂ ) ₂ C (O) OH;
ii) CH ₂ = C (R) X, where R is hydrogen or methyl and X is selected from -CgHs, CN, -C (O) NH ₂ , -NC4H ₆ O, -C (O) NHC (CH ₃ ) ₃ , -C (O) N (CH ₃ ) ₂ , C (O) NHC (CH ₃ ) ₂ (CH ₂ ) ₄ CH ₃ and -C (O) NHC (CH ₃ ) ₂ CH ₂ S (O) (O) OH;
iii) CH HOCCOjR ^1, wherein R ¹ is alkyl and _R linear CI8 or branched and IV) CH ₂ = C (R) C (O) OAOR ^2, wherein A is a bivalent radical selected from -CH ₂ CH (OH ) CH ₂ and -CH ₂ CH (CH ₂ OH) -, R is selected from hydrogen or methyl and R ² is an acyl residue of a fatty acid Cio to C ₂₂ linear or branched saturated or unsaturated.
In one aspect, the linear non-crosslinked polymer component has a viscosity value greater than 500 mPas (Brookfield RVT, 20 rpm, axis No. 1) measured as a polymer solids concentration of 5 weight percent in deionized water and neutralized to pH 7 with an 18 weight percent NaOH solution.
In another aspect, linear non-crosslinked polymers of the core stage have a numerical average molecular weight (M _n ) greater than 100,000 daltons as measured by gel permeation chromatography (GPC) calibrated with a poly (methyl methacrylate) (PMMA ) standard. In another aspect, the M _n of the core polymer ranges from about 100,000 daltons to about 500,000 daltons, from about 105,000 daltons to about 250,000 daltons in another aspect from 110,000 daltons to about 200,000 daltons still in one another aspect and from 115,000 daltons to about 150,000 daltons in another aspect.
Shell polymer component
The crosslinked shell polymer is an acrylic based crosslinked polymer that is polymerized from a monomeric composition comprising the crosslinking monomer. In one embodiment, the shell polymer is polymerized from a monomeric mixture comprising al) a first monomeric component selected from one or more ethylenically unsaturated monomers containing at least one group of carboxylic acid; bl) a second ethylenically unsaturated monomer component selected from at least one alkyl ester linear or branched Ci to C ₅ (meth) acrylic acid, at least one hydroxyalkyl ester of Ci to C ₅ (meth) acrylic acid and mixtures thereof; CJ a third monomeric component selected from at least one compound having reactive groups capable of crosslinking the shell polymer and optionally dl), at least one monomeric component selected from a monomer represented by the formulas:
i) CH ₂ = C (R) C (O) OR ', where R is selected from hydrogen or methyl and R ¹ is selected from C ₆ -C ₀ alkyl, C ₆ to C ₀ hydroxyalkyl, (CH ₂ ) 2OCH ₂ CH ₃ and (CH ₂ ) ₂ C (O) OH and salts thereof;
ii) CH ₂ = C (R) X, where R is hydrogen or methyl and X is selected from -C ₆ H ₅ , CN, -C (O) NH ₂ , -NCqHôO, -C (O) NHC (CH ₃ ) ₃ , -C (O) N (CH ₃ ) ₂ ,
C (O) NHC (CH ₃ ) ₂ (CH ₂ ) ₄ CH ₃ and -C (O) NHC (CH ₃ ) ₂ CH ₂ S (O) (O) OH and salts thereof;
iii) CH ₂ = CHOC (O) R ¹ wherein R ¹ is alkyl and _R linear CI8 or branched and IV) CH ₂ = C (R) C (O) OAOR ^2, wherein A is a bivalent radical selected from CH ₂ CH (OH) CH ₂ and -CH ₂ CH (CH ₂ OH) -, R is selected from hydrogen or methyl and R ² is a residue of the acyl of a fatty acid Cio to C ₂₂ linear or branched saturated or unsaturated.
Exemplary ethylenically unsaturated monomers containing at least one carboxylic acid group which are presented under a monomeric component (a) include (meth) acrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, crotonic acid, acotinic acid, and salts thereof and mixtures of these.
In one aspect of the invention, the amount of at least one monomer-containing carboxylic acid group presented under the first monomeric component a) ranges from about 10% to 80% by weight, from about 20% to about 70% by weight in another aspect, and from about 35% to about 65% by weight in another aspect based on the total weight of the monomers.
Exemplary alkyl (meth) acrylate and hydroxy (meth) acrylate exemplars presented under monomeric component b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, iso-amyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate (butane diol mono (meth) acrylate) and mixtures thereof.
In one aspect of the invention, the alkyl and hydroxy (meth) acrylate alkyl monomers presented under the second monomeric component bl) are used in an amount ranging from about 90% to about 15% by weight, from about 80 % to about 25% by weight in another aspect, and from about 65% to about 35% by weight in yet another aspect, based on the total weight of the monomers.
In one aspect of the invention, the third monomeric component (Ci) is selected from at least one crosslinking monomer. A crosslinking monomer is used to generate a polymer having a partially or substantially crosslinked three-dimensional network. In one aspect, the crosslinking monomer is a polyunsaturated compound. Exemplary polyunsaturated compounds include di (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-butylene glycol di (met) acrylate, 1,6-hexanediol di (met) acrylate, neopentyl glycol di (met) acrylate, 1,9-nonanediol di (met) acrylate, 2,2'-bis (4 - (acryloxypropyloxyphenyl) propane, 2,2'-bis (4- (acryloxydiethoxy-phenyl) propane and zinc acrylate (ie 2 (C ₃ H ₃ O2) Zn ⁺⁺ ); tri (meth) acrylate compounds such such as, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate and tetramethylolmethane tri (meth) acrylate; tetra (meth) acrylate compounds such as ditrimethylolpropane tetra (meth) acrylate, tetramethylolmethane tetra (meth) acrylate and pentaerythritol) acrylate; hexa (meth) acrylate compounds such as dipentaerythritol hexa (meth) acrylate; allyl compounds such as allyl (meth) acrylate, diallyphthalate, dialyl itaconate, dially fumarate and dially maleate polyalkyl sucrose res having 2 to 8 allyl groups per molecule, polyalkyl esters of pentaerythritol such as pentaerythritol diallyl ether, pentaerythritol trialyl ether and pentaerythritol tetraally ether; polyethyl esters of trimethylolpropane such as trimethylolpropane diallyl ether and trimethylolpropane trialyl ether. Other suitable polyunsaturated compounds include divinyl glycol, divinyl benzene and methylenebisacrylamide.
In another aspect, suitable polyunsaturated monomers can be synthesized by means of an esterification reaction of a polyol made of ethylene oxide or propylene oxide or combinations of these with unsaturated anhydride such as maleic anhydride, citraconic anhydride, itaconic anhydride or an addition reaction with unsaturated isocyanate such as 3-isopropenyl-aa-dimethylbenzene isocyanate.
In addition, the following unsaturated compounds can be used as crosslinkers that are reactive with carboxyl groups pending on the polymer backbone: polyalalkanols such as 1,3dichlorisopropanol and 1,3-dibromoisopropanol; sulfonium zwitterions, such as the tetrahydrothiophene adduct of novolac resins; haloepoxialkanes such as epichlorohydrin, epibromohydrin, 2-methyl epichlorohydrin and epi-iodohydrin; polyglycidyl esters such as 1,4-butanediol diglicidyl ether, glycerine-1,3diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycolic diglycidyl ether, polypropylene glycol diglycine glyceryl ether glycol ether ether, resins epoxy and mixtures of the foregoing. Mixtures of two or more of the preceding polyunsaturated compounds can also be used to crosslink the shell polymer component of the present invention.
The crosslinking monomer component can be used in an amount ranging from about 0.01 to about 5% by weight in one aspect, from about 0.03 to about 3% by weight in another aspect, and from about 0.05 to about 1% by weight in another aspect, based on the total weight of all monomers that make up the acrylate based shell polymer component.
Exemplary ethylenically unsaturated monomers presented in formulas i) to iv) of optional monomeric component dl) include ethyl diglycol (met) acrylate, 2-carboxyethyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , octyl (meth) acrylate, decyl (meth) acrylate, 6-hydroxyiexyl (meth) acrylate, 10-hydroxydocyl (meth) acrylate, styrene, a-methyl styrene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N, N'dimethylaminoacrylamide t-butylacrylamide, t-octylacrylamide, N-vinyl pyrrolidone, 2-acrylamido-2-methylpropane sulfonic acid, vinyl acetate, vinyl propionate, vinyl butanoate, vinyl valerate, vinyl hexanoate, vinyl octanoate, vinyl nonanoate, vinyl decanoate, vinyl neodecanoate, vinyl laurate, ACE ™ monomer and (M) ACE ™ available from Hexion Specialty Chemicals, Inc., Columbus, OH and mixtures thereof.
The preceding monomers are commercially available and / or can be synthesized by procedures well known in the art or as described herein.
As previously reported for the monomers of the formula C) (iv) monomers according to formula IV) dl optional monomer component) may be synthesized by glycidol reaction with a fatty acid Cio to C ₂ 2 T ^o obtain an intermediate glycidyl ester which, in turn, can be reacted through its epoxy functionality with the (meth) acrylic acid carboxyl portion to obtain a preformed monomer.
Alternatively, the intermediate glycidyl ester can be added to the polymerization mixture comprising the monomers previously described and reacted in situ with a portion of the one or more ethylenically unsaturated monomers containing at least one group of carboxylic acid described under the monomeric component a), subject with the condition that the reagent stoichiometry is designed such that only a portion of the carboxyl groups is reacted.
In one aspect of the invention, the monomers presented under formulas i) to iv) of the optional monomeric component dl) are used in an amount ranging from about 0% to about 35% by weight, from about 1% to about from 30% by weight in another aspect, from about 2% to about 15% by weight in yet another aspect, and from about 5% to about 10% by weight in another aspect, based on weight total monomers.
None of the monomers used to polymerize the core and shell polymers of the present invention are associative monomers. Associative monomers are ethylenically polymerizable monomers containing a hydrophilic polyalkoxide segment terminated by a hydrophobic group. The polyalkoxide segment usually consists of ethylene polyoxide units or propylene oxide units or combinations of these located between ethylenic unsaturation at one end of the molecule and a hydrophobic end located at the other end. The hydrophobe can be selected from a group of long-chain hydrocarbons containing 8 to 30 carbon atoms. Polymers incorporating associative monomers are referred to in the art as hydrophobically modified linear emulsion polymers (HASE).
Core-shell polymer preparation
The shell-core polymer in stages of the invention comprises a linear core and a crosslinked shell attached and / or associated with said core. In neutralizing the core polymer with a base, the core polymer remains attached or associated with the shell polymer. The shell-core polymer in stages of the invention comprises at least two polymeric stages synthesized sequentially by free radical emulsion polymerization techniques in stages known in the art.
The core or stage polymer is synthesized in a first stage of emulsion polymerization from a monomeric mixture emulsified in an aqueous phase comprising core monomers a), b) and optionally c) as disclosed above. The mixture of monomers for the formation of the nucleus is devoid of crosslinking monomers. The emulsified core monomers are polymerized in the presence of a suitable free radical that forms an initiator to provide an emulsion of a linear non-crosslinked core stage polymer. Correspondingly, a shell-stage polymer is formed in a second emulsion polymerization stage. In this second stage, an emulsified monomeric mixture comprising shell monomers a1, bl), crosslinking monomer CJ and optional monomer dl) (as previously disclosed) is polymerized in the presence of the first stage latex previously prepared from the core polymer stage and additional free radical forming initiator. The final product is a double stage polymer comprising a linear non-crosslinked core encircled or partially encircled with a crosslinked shell. Alternatively, a preformed coating seed emulsion polymer can be used as the core polymer followed by the formation of the shell polymer in a second stage as described above.
In another aspect of the invention, the core polymer can be synthesized by means of successive free radical emulsion polymerization stages to obtain a multilayer or multiple stage core polymer. The mixture of core monomer used to polymerize each layer or successive stages can be the same or different from those used in the polymerization layer or stage that immediately precede it. Similarly, the shell polymer can be synthesized through successive free radical emulsion polymerization stages to obtain a multilayer or multiple stage shell polymer. Like a core monomer mixture, the shell monomer mixture used to polymerize successive shell layers or stages may be the same or different from those used in the immediately preceding polymerization layer or stage.
Alternatively, successive free radical emulsion polymerization stages can be performed to obtain multi-stage polymer morphologies such that successive polymer stages differ by the type of polymer (i.e., linear or cross-linked), subject to the condition that the core polymer or first stage must be linear and at least one of the shell polymer stages must be cross-linked. At a stage where it is desired to have a linear polymer, the emulsion polymerizable monomeric mixture will be devoid of crosslinking monomer and at a stage where it is desired to have a crosslinked polymer the emulsion polymerizable monomeric mixture will comprise a crosslinking monomer.
Each stage of the core-shell polymer of the invention can be prepared from a monomeric mixture comprising one or more chain transfer agents. The chain transfer agent can be any chain transfer agent that reduces the molecular weight of the polymers in stages of the invention. Suitable chain transfer agents include but are not limited to, compounds containing thio and sulfide, such as alkyl mercaptans Ci-C] _8, mercaptocarboxílicos acids mercaptocarboxílicos esters, thioesters, alkyl disulfide Ci-Cie arilbissulfetos, thiols polyfunctional , such as trimethylolpropane-tris- (3-mercaptopropionate), pentaerythritol-tetra- (3-mercaptopropionate), pentaerythritol-tetra- (thioglycolate) and pentaerythritol-tetra- (thiolactate), dipentaerythritol-hexa- (other thioglycol); phosphites and hypophosphites; haloalkyl compounds, such as carbon tetrachloride, bromotrichloromethane and others and catalytic chain transfer agents such as, for example, cobalt complexes (for example, cobalt (II) chelates).
In one aspect of the invention, the chain transfer agent is selected from octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan (ODM), isooctyl 3mercaptopropionate (IMP), butyl 3-mercaptopropionate, 3mercaptopropionic acid , butyl thioglycolate, isooctyl thioglycolate and dodecyl thioglycolate.
When used, the chain transfer agent can be present in an amount ranging from about 0.1% to 10% by weight, based on the weight of the total monomeric mixture.
Emulsion polymerization can be carried out in a batch process in stages, in a monomer addition process measured in stages, or polymerization can be started as a batch process and then the monomer loading can be continuously in stages in the reactor ( seed process). Typically, the polymerization process is carried out at a reaction temperature in the range of about 20 to about 99 ° C, however, higher or lower temperatures can be used. To facilitate the emulsification of the monomeric mixture, the emulsion polymerization is carried out in the presence of at least one surfactant. In one embodiment, the emulsion polymerization is carried out in the presence of a surfactant ranging from about 1% to about 10% by weight in one aspect, from about 3% to about 8% in another aspect , and from about 3.5% to about 7% by weight in another aspect, based on the weight base of the total emulsion. The emulsion polymerization reaction mixture also includes one or more free radical initiators that are present in an amount ranging from about 0.01% to about 3% by weight based on the total monomeric weight. The polymerization can be carried out in an aqueous medium or aqueous alcohol.
Surfactants to facilitate emulsion polymerizations include anionic, non-ionic, amphoteric and cationic surfactants, as well as mixtures of these. Most commonly, anionic and nonionic surfactants can be used as well as mixtures of these.
Suitable anionic surfactants to facilitate emulsion polymerizations are well known in the art and include, but are not limited to, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, sodium phenoxy benzene sulfonate (C ₆ -C ₆ ), dialkyl phenoxy benzene sulfonate (C ₆ -Ci6), sodium benzene sulfonate dialkyl phenoxy (C ₆ -C ₆₎ disodium laureth sulfosuccinate disodium 3, dioctyl sodium sulfosuccinate, sodium di-sec-butyl naphthalene sulfonate, disodium dodecyl diphenyl ether sulfonate, disodium n-octadecyl sulfosuccinate, phosphate branched alcohol ethoxylated esters and others.
Nonionic surfactants suitable for facilitating emulsion polymerizations are well known in the polymer art and include, without limitation, linear or branched C8-C30 fatty alcohol ethoxides, such as ethoxylated capryl alcohol, ethoxylated lauryl alcohol, ethoxylated myristyl, cetyl ethoxylated alcohol, stearyl ethoxylated alcohol, cetearyl ethoxylated alcohol, ethoxylated sterol, oleyl ethoxylated alcohol and beenyl ethoxylated alcohol; alkoxylated alkylphenol, such as ethoxylated octylphenol and polyoxyethylene polyoxypropylene block copolymers and the like. Additional fatty alcohol ethoxylates suitable as non-ionic surfactants are described below. Other useful non-ionic surfactants include C ₈ -C ₂ 2 fatty acid esters of polyoxyethylene glycol, ethoxylated mono and diglycerides, sorbitan esters and ethoxylated sorbitan esters, C ₈ -C ₂₂ fatty acid glycol esters, oxide block copolymers ethylene and propylene oxide and combinations of these. The number of ethylene oxide units in each of the preceding ethoxylates can vary from 2 and above in one aspect and from 2 to about 150 in another aspect.
Exemplary free radical initiators include, but are not limited to, water-soluble inorganic persulfate compounds, such as ammonium persulfate, potassium persulfate and sodium persulfate; peroxides, such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide and lauryl peroxide; organic hydroperoxides, such as cumene hydroperoxide and t-butyl hydroperoxide; organic peracids, such as peracetic acids and soluble oil, free radical-producing agents, such as 2,2'azobisisobutyronitrile and others and mixtures thereof. Peroxides and peracids can optionally be activated with reducing agents, such as sodium bisulfite, sodium formaldehyde, or ascorbic acid, transition metals, hydrazine and others. Particularly suitable free radical polymerization initiators include water-soluble azo polymerization initiators, such as 2,2'-azobis compounds (tert-alkyl) having a water solubilizing substituent on the alkyl group. Preferred azo polymerization catalysts include Vazo® free radical polymerization initiators, available from DuPont, such as Vazo® 44 (2,2'-azobis (2- (4,5-dihydroimidazolyl) propane), Vazo® 56 ( 2,2'-azobis (2-methylpropionamidine) dihydrochloride) and Vazo® 68 (4,4'-azobis (4-cyanovaleric acid)).
Optionally, other emulsion polymerization additives and processing aids that are well known in the emulsion polymerization art, such as auxiliary emulsifiers, solvents, buffering agents, chelating agents, inorganic electrolytes, polymeric stabilizers and pH adjusting agents may be included in the polymerization system.
In one aspect, an auxiliary emulsification aid selected from an ethoxylated C ₂ to C ₂ 2 fatty alcohol (or mixtures thereof) can be added to the polymerization medium. In one aspect, fatty alcohol contains about 5 to about 250 moles of ethoxylation, about 8 to 100 moles in another aspect, and about 10 to 50 moles in another aspect. Exemplary ethoxylated fatty alcohols include ethoxylated lauryl alcohol, ethoxylated myristyl alcohol, ethoxylated cetyl alcohol, ethoxylated stearyl alcohol, ethoxylated cetearyl alcohol, ethoxylated sterol, ethoxylated oleyl alcohol and ethoxylated alcohol. In another aspect, suitable fatty alcohols include Ceteth-20, Ceteareth-20 and esteareth-20, Behenth-25 and mixtures thereof.
If used, the amount of ethoxylated fatty alcohol can vary from about 0.1% to 10% by weight in one aspect, from about 0.5% to about 8% by weight in another aspect, and from about 1% to about 5% by weight in another aspect, based on the percentage by weight of the total monomers present in the polymerization medium.
In a typical two-stage polymerization, a mixture of core stage monomers is added to the first reactor under an inert atmosphere to a solution of emulsifier surfactant (eg anionic surfactant) in water. Additional processing aids can be added when desired (for example, auxiliary emulsifiers). The reactor contents are agitated to prepare a monomeric emulsion. To a second reactor equipped with an agitator, an inert gas inlet and feed pumps are added under an inert atmosphere a desired amount of additional anionic surfactant water and additional processing aids. The contents of the second reactor are heated with stirring by mixing. After the contents of the second reactor reach a temperature in the range of about 55 to 98 ° C, a free radical initiator is injected into the aqueous surfactant solution formed in this way in the second reactor and a portion of the monomeric emulsion of the first reactor is gradually measured in the second reactor in a period that typically ranges from about half an hour to about four hours. The reaction temperature is controlled in the range of about 45 to about 95 ° C. After completing the addition of monomer in the core, an additional amount of free radical initiator can optionally be added to the second reactor, if desired and the mixture The resulting reaction mixture is typically maintained at a temperature of about 45 to 95 ° C for a period of time sufficient to complete the polymerization reaction and obtain a first stage core polymer particle emulsion.
To the first reactor containing the remaining monomer emulsion in the core stage, a cross-linked polyunsaturated monomer is added and emulsified with it to form a monomeric emulsion of shell and second stage. Additional shell stage monomers can be emulsified in the mixture if desired. Alternatively, a shelled monomer emulsion containing a desired complement of shelled state monomers, including a cross-linked polyunsaturated monomer, can be formed in a separate reactor according to the same procedures as summarized to formulate the monomer core. Monomers in shell or second stage with crosslinker are measured in the second reactor at a constant rate and mixed with the core polymer emulsion. Simultaneously with the monomer feed in the shell stage, a free radical initiator in an amount sufficient to initiate the polymerization is measured in the reaction mixture where the monomers in the shell stage or second stage are polymerized in the presence of the core stage. or first-stage polymer. The temperature is maintained at around 85 ° C for about 2.5 hours or until polymerization is complete. The unreacted monomer can be eliminated by adding more initiator, as is well known in the emulsion polymerization technique. Typically, the staged shell-core polymer or staged polymer emulsion product has a total polymeric solids content in the range of about 10 to about 45 weight percent. While the polymer is synthesized in an emulsion, it must be recognized that the shell-core polymer in stages can be supplied in the form of dry powder if required.
While a typical two-stage polymer process is, in general, immediately described above, multi-stage or multi-layer polymers can be formed by sequential emulsion polymerization of monomeric fillers in the presence of polymer particles from a previously formed emulsion polymer. .
Surfactants
In one aspect, an embodiment of the present invention relates to stable aqueous compositions comprising a rheology modifier based on staged core-shell acrylic and a surfactant. Suitable surfactants include anionic, cationic, amphoteric and non-ionic surfactants, as well as mixtures of these. Such compositions are useful in personal care cleaning compositions containing various components, such as substantially insoluble materials that require suspension or stabilization (for example, a silicone, an oily material, a teen material, aesthetic and cosmetic pearls and particles, gas bubbles, exfoliating and others). The invention also relates to the incorporation of an acidic material before or after the addition of an alkaline material to reduce the pH of the composition without negatively impacting the viscosity, rheological and clarity properties of the composition.
The anionic surfactant can be any of the anionic surfactants known or previously used in the technique of aqueous surfactant compositions. Suitable anionic surfactants include, but are not limited to, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkaryl sulfonates, α-olefm sulfonates, alkyl amide sulfonates, alkaryl polyether ether sulfates, alkyl amido ether sulfates, alkyl monoglyceryl ether sulfates, alkyl monoglycerides monoglyceride sulfonates, alkyl succinates, alkyl sulfosuccinates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl amidosulfosuccinates; alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alkyl amido ether carboxylates, N-alkyl amino acids, N-acyl amino acids, alkyl peptides, N-acyl taurates, alkyl isethionates, carboxylate salts in which the acyl group is derived from grax acids and the alkali metal, alkaline earth metal, ammonium, amine and triethanolamine salts thereof.
In one aspect, the cation portion of the preceding salts is selected from sodium, potassium, magnesium, ammonium, mono-, di- and triethanolamine salts and mono-, di- and tri-isopropylamine salts. The alkyl and acyl groups of the foregoing surfactants contain from about 6 to about 24 carbon atoms in one aspect from 8 to 22 carbon atoms in another aspect and from about 12 to 18 carbon atoms in another aspect and can be unsaturated. The aryl groups in the surfactants are selected from phenyl or benzyl. The ether containing the surfactants presented above can contain from 1 to 10 units of ethylene oxide and / or propylene oxide per molecule of surfactant in one aspect and from 1 to 3 units of ethylene oxide per molecule of surfactant in another aspect.
Examples of suitable anionic surfactants include sodium, potassium, lithium, magnesium and ammonium salts of laureth sulfate, trideceth sulfate, mireth sulfate, C12-C13 pareth sulfate, C12-C14 pareth sulfate and C12-C15 pareth sulfate, ethoxylated with 1, 2 and 3 moles of ethylene oxide; sodium, potassium, lithium, magnesium, ammonium and triethanolamine lauryl sulfate, coconut sulfate, tridecyl sulfate, mirstyl sulfate, cetyl sulfate, cetearyl sulfate, stearyl sulfate, oleyl sulfate and tallow sulfate, disodium lauryl sulfosuccinate, sodium laureth sulfosuccinate, sodium coco sodium , sodium C12-C14 olefin sulfonate, sodium laureth-6 carboxylate, sodium methyl cocoyl taurate, sodium cocoyl glycinate, sodium myristyl sarcocinate, sodium dodecylbenzene sulfonate, sodium cocoyl sarcosinate, sodium cocoyl glutamate, potassium myristoyl glutamate, triethanolamine acid and monolaurate. fatty acid, including the sodium, potassium, ammonium and triethanolamine salts of saturated or unsaturated fatty acids containing from about 8 to about 22 carbon atoms.
Cationic surfactants can be any of the cationic surfactants known or previously used in the technique of aqueous surfactant compositions. Suitable classes of cationic surfactants include, but are not limited to, alkyl amines, alkyl imidazolines, ethoxylated amines, quaternary compounds and quaternized esters. In addition, alkyl amine oxides can function as a cationic surfactant at a low pH.
Alkylamine surfactants can be salts of C12-C22 alkylamines primary, secondary and tertiary greases, substituted and unsubstituted substances sometimes referred to as amidoamines. Non-limiting examples of alkylamines and salts thereof include dimethyl cocamine, dimethyl palmitamine, dioctylamine, dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, ethyl stearylamine, N-sebopropane diamine, ethoxylated stearylamine, stearylamine, styreneamine and styreneylamine. , dimethyl lauramine, stearylamine hydrochloride, soyamine chloride, stearylamine formate, N-sebopropane dichloride diamine and amodimethicone (INCI name for a silicone polymer and blocked with amino functional groups, such as aminoethylamino propylsiloxane).
Non-limiting examples of amidoamines and salts thereof include stearamido propyl dimethyl amine, stearamidopropyl dimethylamine citrate, palmitamidopropyl diethylamine and cocamidopropyl dimethylamine lactate.
Non-limiting examples of alkyl imidazoline surfactants include alkyl hydroxyethyl imidazoline, such as stearyl hydroxyethyl imidazoline, coconut hydroxyethyl imidazoline, ethyl hydroxymethyl oleyl oxazoline and others.
Non-limiting examples of ethoxylated amines include PEG-cocopolyamine, PEG-15 tallow amine, quaternium-52 and others.
Among the useful quaternary ammonium compounds the cationic surfactants, some correspond to the general formulas: (R ⁵ R ⁶ R ⁷ R ⁸ N) E ', where R ⁵ , R ⁶ , R ⁷ , and R ⁸ are independently selected from one aliphatic group having from 1 to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkyl starch, hydroxyalkyl, aryl or alkylaryl group having from 1 to about 22 carbon atoms in the alkyl chain and E is a salt-forming anion such as those selected from halogen, (e.g., chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfate and alkyl sulfate. Aliphatic groups may contain, in addition to carbon and hydrogen atoms, ether bonds, ether bonds and other groups, such as amino groups. Longer-chained aliphatic groups, for example, those of about 12 carbons or higher, can be saturated or unsaturated. In one respect, the aryl groups are selected from phenyl and benzyl.
Exemplary quaternary ammonium surfactants include, but are not limited to, cetyl trimethylammonium, cetylpyridinium chloride, dicetyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, dioctadyl dimethyl ammonium chloride, dimethyl dimethyl ammonium chloride ammonium, didocosyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium acetate, behenyl trimethyl ammonium, benzalconium chloride, benzetonium chloride and di (coconutalkyl) dimethyl ammonium, diebodimethyl chloride (ammonium chloride) hydrogenated tallow) dimethyl ammonium, di (hydrogenated tallow) dimethyl ammonium acetate, disebodimethyl ammonium methyl sulfate, disebo dipropyl ammonium phosphate and disebo dimethyl ammonium nitrate.
At low pH, amine oxides can protonate and behave similarly to N-alkyl amines. Examples include, but are not limited to, dimethyl dodecylamine oxide, oleyldi (2hydroxyethyl) amine oxide, dimethyltetradecylamine oxide, di (2hydroxyethyl) oxide-tetradecylamine oxide, dimethylhexadecamine oxide, beoxide oxide, beoxide oxide, beoxide oxide deciltetradecilamina oxide, oxide diidroxietil alcoxipropilamina C ₂ -15, diidroxietil cocamine oxide, lauramine oxide diidroxietil, diidroxietil stearamine oxide, tallowamine oxide diidroxietil, seed plama hydrogenated amine oxide, amine oxide, hydrogenated tallow oxide hydroxyethyl hydroxypropyl Ci ₂ Ci5 alkoxypropylamine, lauramine oxide, myristamine oxide, ketylamine oxide, oleamidopropylamine oxide, oleamine oxide, palmitamine oxide, PEG-3 lauramine oxide, potassium oxide oxide, oxide oxide, oxide oxide soyamidopropylamine, cocamidopropylamine oxide, stearamine oxide, seboamine oxide oxide and mixtures of these.
Amphoteric or zwitterionic surfactants are molecules containing acidic and basic portions and having the ability to behave like an acid or a base. Suitable surfactants can be any of the known or previously used amphoteric surfactants in the art of aqueous surfactant compositions. Exemplary classes of amphoteric surfactants include, but are not limited to, amino acids (for example, N-alkyl amino acids and N-acyl amino acids), betaines, sultaines and alkyl amphocarboxylates.
Surfactants based on an appropriate amino acid in the practice of the present invention include surfactants represented by the formula:
R-N C (O) O M
Y where R ¹⁰ represents a saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms or an acyl group containing a saturated or unsaturated hydrocarbon group having 9 to 22 carbon atoms, Y is hydrogen or methyl Z is selected hydrogen, CH3, -CH (CH3) 2, -CH2CH (CH3) 2, -CH (CH3) CH2CH3, -CH2C6H5, CH2C6H4OH, -CH2OH, -CH (OH) CH3, - (CH2) 4NH2, - (CH2 ) 3NHC (NH) NH2, CH2C (O) O'M ⁺ , - (CH2) ₂ C (O) O'M ⁺ . M is a salt-forming cation. In one aspect, R ¹⁰ represents one selected from an alkyl Cio ^to C ₂₂ linear or branched radical, an alkenyl group Cio to C ₂₂ linear or branched, an acyl group represented by R ⁿ C (O) -, wherein R ¹¹ it is selected from a straight or branched C9 to C ₂₂ alkyl group, a straight or branched C ₉ to C ₂₂ alkenyl group. In one aspect, M ⁺ is selected from sodium, potassium, ammonium and triethanolamine (TEA).
Amino acid surfactants can be derived from the alkylation and acylation of α-amino acids such as, for example, alanine, arginine, aspartic acid, glutamic acid, glycine, isoleucine, leucine, lysine, phenylalanine, serine, tyrosine and valine. Representative N-acyl amino acid surfactants are, but are not limited to the mono and di-carboxylate salts (eg sodium, potassium, ammonium and TEA) of Nacetylated glutamic acid, eg sodium cocoyl glutamate, sodium lauroyl glutamate , sodium myristoyl glutamate, sodium palmitoyl glutamate, sodium stearoyl glutamate, disodium cocoil glutamate, disodium stearoyl glutamate, potassium cocoyl glutamate, potassium lauroyl glutamate and potassium miristoil glutamate; the carboxylate salts (for example, sodium, potassium, ammonium and TEA) of Nacetylated Alanine, for example, sodium cocoyl alaninate and TEA lauroyl alaninate; the carboxylate salts (for example, sodium, potassium, ammonium and TEA) of Nacetylated glycine, for example, sodium cocoyl glycinate and potassium cocoyl glycinate; the carboxylate salts (for example, sodium, potassium, ammonium and TEA) of N-acetylated sarcosine, for example, sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium myristoyl sarcosinate, oleoyl sarcosinate and ammonium lauroyl sarcosinate and mixtures of the preceding surfactants.
The betaines and sultaines useful in the present invention are selected from alkyl betaines, alkylamino betaines and alkylamido betaines, as well as the corresponding sulfobetaines (sultaines) represented by the formulas:
R ¹³
R — N — R — A M
I + - +
R — NH-j-CH ^ j ^ -N-R-A M
R ¹³ o ^r13
R-C-NH-fCH ^ N-R-A M
R ¹³ where R ¹² is a C7-C22 alkyl or alkenyl group, each R ¹³ is independently a C-C4 alkyl group, R ¹⁴ is a C1-C5 alkylene group or a hydroxy substituted C1-C5 alkylene group, n is an integer from 2 to 6, A is a carboxylate or sulfonate group and M is a salt-forming cation. In one aspect, R ¹² is a Cn-C18 alkyl group or a C11-C18 alkenyl group. In one respect, R ¹³ is methyl. In one aspect, R ¹⁴ is methylene, ethylene or hydroxy propylene. In one aspect, n is 3. In another aspect, M is selected from sodium, potassium, magnesium, ammonium and mono-, di- and triethanolamine cations.
examples of suitable betaines include, but are not limited to, lauryl betaine, coconut betaine, oleyl betaine, cocohexadecyl dimethylbetaine, lauryl amidopropyl betaine, cocoamidopropyl betaine and cocamidopropyl hydroxysultaine.
Alkylamphocarboxylates such as alkylaminoacetates and alkylamphopropionates (mono- and disubstituted carboxylates) can be represented by the formula:
₁₂ íl _{z X} R ¹⁵
RC-NH-f-CHãhK 16 ^{k 2 1 n} CH ₂ CH ₂ OR where R ¹² is a C7-C22 alkyl or alkenyl group, R ¹⁵ is CH2C (O) O- Nf, -CH2CH2C (O) O'M ⁺ or -CH2CH (OH) CH ₂ SO ₃ - R ¹⁶ is a hydrogen or -CH ₂ C (O) O 'M ⁺ and M is a cation selected from sodium, potassium, magnesium, ammonium and mono-, di- and triethanolamine .
Exemplary alkylamphocarboxylates include, but are not limited to, sodium cocoanfoacetate, sodium lauroanfoacetate, sodium capriloanfoacetate, disodium cocoanphodiacetate, disodium lauroamphodiacetate, disodium caprilanphodiacetate, disodium capriloanododiacetate, disodium cocoamphodiodionpropionate, disodium.
The nonionic surfactant can be any of the nonionic surfactants known or previously used in the technique of aqueous surfactant compositions. Suitable non-ionic surfactants include, but are not limited to, aliphatic, primary or secondary (C ₆ -C ₈ ) straight or branched chain acids, alcohols or phenols; alkyl ethoxylates; alkoxylated alkyl phenol (especially ethoxylated and mixed ethoxy / propoxy moieties); alkylene oxide condensates on an alkyl phenol block; alkylene oxide condensates of alkanols and ethylene oxide / propylene oxide block copolymers. Other suitable non-ionic surfactants include mono- or dialkyl alkanolamides; alkyl polyglycosides (APGs); sorbitan fatty acid esters; polyoxyethylene sorbitan fatty acid esters; polyoxyethylene sorbitol esters; polyoxyethylene acids and polyoxyethylene alcohols. Other examples of suitable nonionic surfactants include coconut mono or diethanolamide, coconut glycoside, decyl diglycoside, lauryl diglycoside, coconut diglycoside, polysorbate 20, 40, 60 and 80, linear ethoxylated alcohols, cetearyl alcohol, lanolin alcohol, stearic acid, glyceryl stearate, PEG -100 stearate, laureth 7 and oleth 20.
In another embodiment, non-ionic surfactants include, but are not limited to, alkoxylated methyl glycosides such as, for example, methyl gluceth-10, methyl gluceth-20, PPG-10 methyl glucose ether and PPG-20 methyl glucose ether, available from Lubrizol Advanced Materials, Inc., under the trade names, Glucam® E10, Glucam® E20, Glucam® PIO and Glucam® P20, respectively and hydrophobically modified alkoxylated methyl glycosides, such as PEG 120 methyl glucose dioleate, PEG- 120 methyl glucose trioleate and PEG-20 methyl glucose sesquistearate, available from Lubrizol Advanced Materials, Inc., under the trade names, Glucamate® DOE-120, Glucamate ™ LT and Glucamate ™ SSE-20, respectively, are also suitable. Other exemplary hydrophobically modified alkoxylated methyl glycosides are disclosed in United States Patent No. 6,573,375 and 6,727,357, the disclosures of which are hereby incorporated by reference in their entirety.
Other surfactants that can be used in the present invention are presented in more detail in WO 99/21530, U. S. Patent No. 3,929,678, U. S. Patent No. 4,565,647, U. S. Patent No. 5,720,964 and U. S. Patent No. 5,858,948. In addition, suitable surfactants are also described in McCutcheon’s Emulsifiers and Detergents (North American and International Editions, by Schwartz, Perry and Berch), which is thus fully incorporated by reference.
While the amounts of surfactant used in the composition comprising the shell-core polymer in stages of the invention can vary widely depending on the desired application, the amounts that are frequently used, in general, vary from about 1% to about 80% by weight in one aspect, from about 3% to about 65% by weight in another aspect, from about 5% to about 30% by weight in yet another aspect, from about 6% to about 20% by weight in another aspect, and from about 8% to about 16% by weight, based on the total weight of personal care, home care, health care and institutional and industrial composition in which they are included.
In one aspect of the invention, the personal care, home care, health care and I&I care compositions of the invention comprise a staged shell-core polymer in combination with at least one anionic surfactant. In another aspect of the invention, the compositions comprise a staged shell-core polymer with at least one anionic surfactant and at least one amphoteric surfactant. In one aspect, the anionic surfactant is selected from alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkaryl sulfonates, alkaryl polyether etherates and mixtures thereof in which the alkyl group contains 10 to 18 carbon atoms, the aryl group is a phenyl and the group ether contains 1 to 10 moles of ethylene oxide. Representative anionic surfactants include, but are not limited to, sodium and ammonium lauryl ether sulfate (ethoxylated with 1, 2 and 3 moles of ethylene oxide), sodium, ammonium and triethanolamine lauryl sulfate.
In one aspect, the amphoteric surfactant is selected from an alkyl betaine, an alkylamino betaine, an alkylamido betaine and mixtures thereof. Representative betaines include, but are not limited to, lauryl betaine, coconut betaine, cocohexadecyl dimethylbetaine, cocoamidopropyl betaine, cocoamidopropylirdoxy sultaine and mixtures thereof.
The personal care, home care, health care and I&I care compositions comprising the shell-core polymer in stages of the invention can be formulated at pH ranges from about 0.5 to about 12. The desired pH for the compositions of the present invention is obviously dependent on specific end product applications. In general, personal care applications have a desired pH range of about 3 to about 7.5 in one aspect, and about 3.5 to about 6 in another aspect. Surprisingly, the core-shell / surfactant compositions in stages of the invention when formulated at low pH values give a clear formulation while maintaining desired rheological properties (e.g., viscosity and yield values). In another aspect, the shell-core polymer in stages / surfactant compositions of the invention when formulated at pH values of about 6 and below give a clear formulation while maintaining the desired rheological properties of the composition in which they are included. In yet another aspect, the core-shell / surfactant compositions in stages of the invention when formulated at pH values of about 5.0 and below give a clear formulation while maintaining the desired rheological properties of the composition in which they are included. In another aspect, the nucleoscak / surfactant compositions in stages of the invention when formulated at pH values of about 3.5 to about 4.5 give a clear formulation while maintaining the desired rheological properties of the composition in which they Are included.
In general, home care applications have a desired pH range of about 1 to about 12 in one aspect, and about 3 to about 10 in another aspect, depending on the desired end-use application.
The pH of the composition of the present invention can be adjusted with any acidic and / or basic pH-adjusting composition and agents known in the art. The shell-core polymer in stages of rheology modifiers of the present invention are, in general, supplied in their acid form. These polymers modify the rheology of the formulation by neutralizing the carboxyl groups in the polymer with an alkaline material. Without wishing to be bound in theory, this causes ionic repulsion between similar charged portions along the polymer's main chain and a three-dimensional expansion of the polymeric network, resulting in an increase in viscosity and other rheological properties. This phenomenon is referred to in the literature as a “space filling” mechanism compared to an associative thickness mechanism for HASE polymers.
In one embodiment, compositions comprising the shell-core polymers in stages of the invention can be acidified (pH reduction) without neutralizing the polymer. In another embodiment, compositions comprising the shell-core polymer in stages can be neutralized with an alkaline material. In a further embodiment, compositions comprising the core-shell polymer can be neutralized subsequent to being acidified. In yet another embodiment, compositions comprising shell-core polymers in stages can be acidified subsequent to neutralization.
An alkaline material is incorporated to neutralize the polymer and can be referred to as a neutralizing agent or pH adjusting agent. Many types of neutralizing agents can be used in the present invention, including inorganic and organic bases and combinations thereof. Examples of organic bases include, but are not limited to, alkali metal hydroxides (especially sodium, potassium and ammonium) and salts of such alkaline inorganic acids, such as sodium borate (borax), sodium phosphate, pyrophosphate sodium and others and mixtures of these. Examples of organic bases include, but are not limited to, triethanolamine (TEA), diisopropanolamine, triisopropanolamine, aminomethyl propanol, dodecylamine, cocamine, oleamine, morpholine, triamylamine, triethylamine, tetrakis (hydroxypropyl) ethylenediamine, L-arginine, aminomethyl, aminomethyl, aminomethyl tromethamine (2-amino 2-hydroxymethyl-1,3-propanediol) and PEG-15 cocamine. Alternatively, other alkaline materials can be used alone or in combination with the inorganic and organic bases mentioned above. Such materials include surfactants, surfactant mixtures, surfactants or pre-neutralized materials that when combined in a composition containing the shell-core polymer in stages of the invention are able to partially neutralize or neutralize the carboxyl groups in the shell-core polymer chain in stages. Any material capable of increasing the pH of the composition is suitable.
Various acidic materials can be used as a pH adjusting agent in the present invention. Such acidic materials include organic acids and inorganic acids, for example, acetic acid, citric acid, tartaric acid, alpha-hydroxy acids, beta-hydroxy acids, salicylic acid, lactic acid, glycolic acid and natural fruit acids or inorganic acids, for example example, hydrochloric acid, nitric acid, sulfuric acid, sulfamic acid, phosphoric acid and combinations thereof. As discussed above, the addition of the acid pH adjusting agent can be incorporated before or after the addition of the basic pH adjusting agent into a desired composition. The addition of the acidic material after the addition of the alkaline neutralizing agents significantly improved the rheological properties. This is discussed in more detail under the retro acid formulation technique below.
When alkaline pH adjusting agents, other acidic materials can be used alone or in combination with the inorganic and organic acids mentioned above. Such materials include materials that when combined into a composition containing the cascanucle polymer in stages of the invention are able to reduce the pH of the composition. It will be recognized by the skilled person that acid pH adjusting agents can serve more than one function. For example, acid preservative compounds and acid-based cosmeceutical compounds (eg alpha and beta-hydroxy acids) not only serve their primary preservative and cosmeceutical functions, respectively, they can also be used to reduce and maintain the pH of a desired formulation.
Buffering agents can be used in the compositions of the invention. Suitable buffering agents include, but are not limited to, alkali or alkaline earth metal carbonates, phosphates, bicarbonates, citrates, borates, acetates, acid anhydrides, succinates and others, such as sodium phosphate, sodium citrate, sodium acetate, sodium bicarbonate and sodium carbonate.
The pH adjusting agent and / or buffering agent is used in any amount necessary to obtain and / or maintain a desired pH value in the composition.
Retro Acid Formulation
The polymeric rheology modifiers of the present invention do not begin to form substantial viscosity until a pH of about 5 or 6 is reached. There are some household and personal care applications, however, that require a pH less than 6 for optimal and desired performance. This limited the use of such polymers in such compositions. In addition, it is still difficult to formulate stable applications in this low pH range.
It has been observed that if these compositions are increased to an almost neutral or still alkaline pH and then subsequently reduced in pH, the viscosity value and yield in general remain unchanged or, frequently, do increase. This formulation technique will be referred to here as “Retro Acid” thickening or Retro Acid Addition. This formulation technique expands the scope of application of the present polymers and now allows formulation in the acid pH regime. Additionally, the “Retro Acid” thickening process can also still be used to increase the viscosity and stability of the compositions formulated in the slightly acidic and alkaline pH regime.
The one or more shell-core polymers in stages of the invention can be formulated into a desired composition in any order during the formulation procedure. An alkaline material is added or mixed to increase the pH of the composition to at least about 5 in one aspect, to at least about 6 in another aspect and more to at least about 6.5 in another aspect. The alkaline material can be any compound that can neutralize the shell-core polymer in stages at a specified pH. In one aspect, the alkaline material can be selected from any of the alkaline pH adjusting agents described above, such as, for example, sodium hydroxide, potassium hydroxide, triethanolamine or another fatty acid amine neutralizing agent commonly used in said applications. Alternatively, other alkaline materials can be used, such as surfactants. In one aspect, the pH can be adjusted to at least about 0.5, 1, 1.5 or 2 pH units above the final target pH of the composition. In another aspect, the pH can be adjusted to at least 3, 4 or 5 pH units above the final target pH of the composition. Subsequent to pH adjustment with the alkaline material, an acidic material is added to reduce the pH of the composition to the desired target pH for the composition. In one aspect of the invention, the target pH ranges from about 3.5 to about 6, from about 4 to about 5.5 in another aspect, and from about 4.5 to 5 in another aspect.
The material used to increase the pH of the composition can be any acidic material. In one aspect, the acidic material is selected from any of the acidic pH adjusting agents described above, such as, for example, an organic acid, such as citric acid, acetic acid, alpha-hydroxy acid, beta-hydroxy acid, acid salicylic acid, lactic acid, glycolic acid, natural fruit acids or combinations thereof. In addition, inorganic acids, for example, hydrochloric acid, nitric acid, sulfuric acid, sulfamic acid, phosphoric acid and combinations thereof can be used. Mixtures of organic acids and inorganic acids are also considered.
The shell-core polymer in stages of the present invention can be formulated with or without at least one surfactant. Such compositions can comprise any combination of optional additives, adjuvants and beneficial agent suitable for desired personal care, home care, health care and institutional and industrial care product known in the art. The choice and quantity of each optional component used will vary with the purpose and character of the final product and can be easily determined by a person skilled in the formulation technique and in the literature. It is recognized that various additives, adjuvants and beneficial agents and components presented here may serve more than one function in a composition, such as, for example, surfactants, emulsifiers, solubilizers, conditioners, emollients, humectants, lubricants, pH adjusting agents and acid based preservatives.
While overlapping the weight ranges for the various components and ingredients that may be contained in the compositions of the invention have been expressed for the selected embodiments and aspects of the invention, it should be readily apparent that the specific amount of each component in the care compositions personnel, home care, health care and I&I care compositions will be selected from their disclosed range such that the quantity of each component is adjusted such that the sum of all components in the composition will total 100 percent by weight. The quantities used will vary with the purpose and character of the desired product and can be easily determined by a person skilled in the formulation technique and in the literature.
Optional additives and adjuvants include, but are not limited to, insoluble materials, pharmaceutical and cosmeceutical actives, chelators, conditioners, diluents, solvents, fragrances, humectants, lubricants, solubilizers, emollients, © pacifiers, dyes, anti-dandruff agents, preservatives, dispersion aids , emulsifiers, sunscreens, fixing, botanical polymers, viscosity modifiers and others, as well as the numerous other optional components to enhance and maintain the properties of a desired personal care, home care, health care and I&I care composition .
Insoluble Material
Materials or compounds that require stabilization and / or suspension can be soluble or insoluble in water. Such compounds include insoluble silicones, silicone gums and resins, volatile and non-volatile silicone oils, natural and synthetic waxes and oils and fatty acids, perolescent materials, particulates or other types of compounds and / or components presented below.
Silicones
In one aspect, silicones are used as conditioning agents that are commonly used in rinsing hair conditioning products and shampoo products, such as so-called two-in-one cleaning shampoos / conditioners. In one aspect, the conditioning agent is an insoluble silicone conditioning agent. Typically, the conditioning agent will be mixed into the shampoo composition to form a separate batch phase of dispersed insoluble particles (also referred to as droplets). The silicone capillary conditioning agent can be a silicone fluid and can also comprise other ingredients, such as a silicone resin, to improve the decomposition efficiency of the silicone fluid or enhance hair shine especially when the silicone conditioning agent is used. high refractive index (for example, above about 1.6) is used. The optional silicone capillary conditioning agent phase may comprise volatile silicone, volatile silicone or combinations thereof. The silicone particle conditioning agent may comprise volatile silicone, non-volatile silicone or combinations thereof. In one aspect, non-volatile silicone conditioning agents are used. If volatile silicones are present, they will be incidental to their use as a solvent or carrier for commercially available forms of non-volatile silicone material ingredients, such as silicone gums. Capillary silicone conditioning agents for use in the present invention have a viscosity of about 0.5 to about 50,000,000 centistokes (1 centistokes equals 1 x 10 ' ⁶ m ² / s) in one aspect, of about 10 to about 30,000,000 centistokes in another aspect, from about 100 to about 2,000,000 in another aspect, and from about 1,000 to about 1,500,000 centistokes in an additional aspect, as measured at 25 ° C .
In one embodiment, the silicone particle conditioning agent can have a volume-average particle diameter ranging from about 0.01 pm to about 500 pm. For the application of small particle to hair, the average particle diameter in volumes ranges from about 0.01 pm to about 4 pm in one aspect, from about 0.01 pm to about 2 pm in another aspect, and from about 0.01 pm to about 0.5 pm in yet another aspect. For the application of a larger particle to the hair, the average particle diameter in volumes typically ranges from about 5 pm to about 125 pm in one aspect, from about 10 pm to about 90 pm in another aspect, from about 15 pm to about 70 pm in yet another aspect, and from about 20 pm to about 50 pm in another aspect.
The fundamental material in the sections including silicones that discuss fluids, gums and silicone resins, as well as the manufacture of silicones, are found in Encyclopedia of Polimer Science and Engineering, vol. 15, 2d ed., Pp 204-308, John Wiley & Sons, Inc. (1989), incorporated herein by reference. Silicone fluids are generally described as alkylsiloxane polymers. Non-limiting examples of suitable silicone conditioning agents and optional suspending agents for silicone are described in U.S. Patent No. 34,584, U.S. Patent No. 5,104,646 and U.S. Patent No. 5,106,609, the descriptions of which are incorporated herein by reference.
Silicone oils include polyalkyl, polyaryl siloxanes or polyalkylaryl siloxanes which according to the following formula:
R ²⁰ R ²⁰ R
R-Si-O — Psi-ol-SiR
I * I JW |
R ²⁰ R ²⁰ R where R ²⁰ is an aliphatic group, independently selected from alkyl, alkenyl and aryl, R ²⁰ can be substituted or unsubstituted and w is an integer from 1 to about 8,000. Unsubstituted R groups suitable for use in the present invention include, but are not limited to, alkoxy, aryloxy, alkaryl, arylalkyl, arylalkenyl, alkaline and ether-substituted aryl groups, substituted by hydroxyl and substituted by aliphatic halogen. Suitable R ²⁰ groups also include amines, cationic amines and quaternary ammonium groups.
In one aspect of the invention, exemplary alkyl and alkenyl R ²⁰ substituents include C1-C5 alkyl and C1-C5 alkenyl groups. In another aspect, R ²⁰ is methyl. The aliphatic moieties of other groups containing alkyl and alkenyl (such as alkoxy, alkaryl and alkaline) can be straight or branched chains and contain C _r C ₅ in one aspect of C1-C4 in another aspect and Ci-C ₂ in another aspect. As discussed above, the R substituents can also contain amino functionalities (for example, alkaline groups), which can be primary, secondary or tertiary amines or quaternary ammonium. These include mono-, di- and trialkylamino and alkoxyamino groups, where the chain length of the aliphatic portion is as described above. Exemplary aryl groups in the preceding embodiments include phenyl and benzyl.
Exemplary siloxanes are polydimethyl siloxane, polydiethylsiloxane and polymethylphenylsiloxane. These siloxanes are available, for example, from Momentive Performance Materials and their Viscasil R and SF 96 series and from Dow Coming marketed under the Dow Coming 200 series. Exemplary polyalkylarylsiloxane fluids that can be used include, for example, polymethylphenylsiloxanes. These siloxanes are available, for example, from Momentive Performance Materials such as methyl phenyl fluid SF 1075 or from Dow Coming as 556 Cosmetic Grade Fluid or from Wacker Chemical Corporation, Adrian, MI, under the trade name Wacker-Belsil® PDM series of phenyl modified silicones (for example, PDM 20, PDM 350 and PDM 1000).
Cationic silicone fluids are also suitable for use with the compositions of the invention. Cationic silicone fluids can be represented, but not limited to the general formula):
(R ²¹ ) _and G3-f — Si— (OSiG2) _g (OSiGf (Ri) (2-f) h θ SiG3_ _and (R) f where G is hydrogen, phenyl, hydroxy or C _r C ₈ alkyl (for example, methyl or phenyl) and is 0 or an integer having 1 to 3; f is 0 or 1; g is a number from 0 to 1,999; h is an integer from 1 to 2,000 in one aspect and from 1 to 10 in another aspect; the sum of _{g and} h is a number from 1 to 2,000 in one aspect and from 50 to 500 in another aspect of the invention; R ²¹ is a monovalent radical according to the general formula C _q H _2q L, where q is an integer having a value from 2 to 8 and L is selected from the following groups:
a) -N (R ²² ) CH2CH2N (R ²² ) 2
b) -N (R ²² ) ₂
c) -bTCR ^ CA-
d) -N (R ²² ) CH ₂ CH ₂ N ⁺ H2R ²² CA 'where R ²² is independently selected from hydrogen, C1-C20 alkyl, phenyl, benzyl and CA ”is a halide counter ion selected from chloride, bromide , fluoride and iodide.
In another aspect, a cationic silicone useful in core-shell compositions in stages of the invention can be represented by the formula:
OH
I23
CH — CH-CH _r N- (R) ₃ CA
R ²³ R “R ^R - ⁱ - ° + | ⁱ - ° AF ⁱ - ⁰ 4i ^s r ^R2 '
R ²³ R ²³ R ²³ R where R ²³ represents a radical selected from a group of CrC8 alkyl or CrC8 alkenyl; R ²⁴ independently represents a radical selected from a C 1 -C ₈ alkylene radical or a C _r C ₈ alkyleneoxy radical; CA is a halide ion; r represents an integer ranging from 2 to 20 in one aspect and 2 to 8 in another aspect; s represents an integer ranging from 20 to 200 in one aspect and from 20 to 50 in another aspect. In one respect, R ²³ is methyl. In another aspect, Q is a chloride ion. An example of a quaternary silicone polymer useful in the present invention is Abil® T Quat 60, available from Evonik Goldschmidt Corporation, Hopewell, VA.
Another class of suitable silicone fluids is insoluble silicone gum. These gums are polysiloxane materials having a viscosity at 25 ° C greater than or equal to 1,000,000 centistokes. Silicone gums are described in U.S. Patent No. 4,152,416; Noll and Walter, Chemistry and Technology of Silicones, New York: Academic Press 1968 and in general Electric Silicona Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76, all of which are incorporated herein by reference. Silicone gums typically have a mass weight of the molecule in excess of about 200,000 daltons, generally between about 200,000 to about 1,000,000 daltons, specific examples of which include polydimethylsiloxane, polydimethylsiloxane / methylvinylsiloxane copolymer, polydimethylsiloxane copolymer / diphenyl siloxane / methylvinylsiloxane and mixtures thereof.
Another category of insoluble, non-volatile silicone fluid conditioning agents are high refractive index polysiloxanes, having a refractive index of at least about 1.46 in one aspect, at least about 1.48 in another aspect, at least about 1.52 in another aspect and at least about 1.55 in an additional aspect. The refractive index of the polysiloxane fluid will generally be less than about 1.70, typically less than about 1.60. In this context, polysiloxane “fluid” includes oils, resins and gums.
The high refractive index polysiloxane fluid includes that represented by the general formula presented by the polyalkyl, polyaryl and polyalkylaryl siloxanes described above, as well as cyclic polysiloxanes (cyclomethicone) represented by the formula:
wherein the substituent R ²⁰ is as defined above and the number of repeat units, k, varies from about 3 to about 7 in one aspect and from 3 to 5 in another aspect. The high refractive index polysiloxane fluid may contain an amount of aryl containing sufficient R20 substituents to increase the refractive index to a desired level, which is described above. In addition, R ²⁰ and k must be selected as long as the material is not volatile. Aryl-containing substituents include those containing alicyclic and heterocyclic five- and six-membered aryl rings and those containing fused five- or six-membered rings. Aryl rings can be replaced or not replaced. The substituents include aliphatic substituents and may also include alkoxy substituents, acyl substituents, ketones, halogens (e.g., Cl and Br), amines, etc. Exemplary aryl-containing groups include substituted and unsubstituted arenes, such as phenyl and phenyl derivatives such as phenyls with alkenyl substituents or C _r C ₅ alkyl, for example, allyphenyl, methyl phenyl and ethyl phenyl, vinyl phenyls such as styrene and phenylalkines (e.g., C2-C4 phenylalkines). heterocyclic aryl groups include substituents derived from furan, imidazole, pyrrole, pyridine, etc. Substituents of the fused aryl ring include, for example, naphthalene, coumarin and purine.
The high refractive index polysiloxane fluid may have an aryl grade containing substitutes of at least about 15% by weight in one aspect, at least about 20% by weight in another aspect, at least about 25% by weight in another aspect, at least about 35% by weight still in one aspect and at least about 50% by weight in an additional aspect, based on the weight of the polysiloxane fluid. Typically, the degree of aryl substitution will be less than about 90% by weight, more typically less than about 85% by weight and can generally range from about 55% to about 80% by weight of the polysiloxane fluid .
In another aspect, the high refractive index polysiloxane fluid has a combination of phenyl or substituted phenyl derivatives. The substituents can be selected from C1-C4 alkyl (for example, methyl), hydroxy and C1-C4 alkylamino.
When high refractive index silicones (silicone resins, silicone waxes and phenyl-modified silicones) are used in the compositions of the present invention, they can optionally be used in the solution with a blowing agent, such as a silicone resin or a surfactant. suitable, to reduce the surface tension by an amount sufficient to intensify the expansion and therefore increase the shine (subsequent to drying) of hair treated with such compositions. Silicone fluids suitable for use in the compositions of the present invention are disclosed in U.S. Patent No. 2,826,551; 3,964,500; 4,364,837 and British Patent No. 849,433, all of which are incorporated into this by reference. High refractive index polysiloxanes and polyaryl siloxanes (trimethyl pentaphenyl trisiloxane, available under the trade name DC PH1555 HRI) are offered from Dow Coming Corporation (Midland, MI), Huis America (Piscataway, NJ) and Momentive Performance Materials Inc (Albany, NY). Examples of silicone waxes include SF 1632 (INCI Name: Ceteryl Methicone) and SF1642 (INCI Name: Alkyl Dimethicone C30-C45), also available from Momentive Performance Materials, Inc.
Silicone resins and resin gels can be included as a silicone conditioning agent suitable for use in the compositions of the present invention. These resins are cross-linked polysiloxanes. Cross-linking is introduced through the incorporation of trifunctional and tetrafunctional silanes with monofunctional and / or bifunctional silanes during the manufacture of the silicone resin.
As is also understood in the art, the degree of crosslinking that is required in order to result in a silicone resin will vary according to the specific silane units incorporated in the silicone resin. In general, silicone materials that have a sufficient level of the trifunctional or tetra-functional siloxane monomer units (and since, a sufficient level of crosslinking) such that it forms a rigid or hard film are considered to be silicone resins. The ratio of oxygen atoms to silicon atoms is indicative of the level of crosslinking in a particular silicone material. The silicone materials that have at least about 1.1 oxygen atoms per silicon atom will generally be the silicone resins in this. In one respect, the oxygen: silicon atoms ratio is at least about 1.2: 1.0. Silanes used in the manufacture of silicone resins include monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-, methylphenyl-, monovinyl- and methylvinyl-chlorosilanes and terachlorosilane, with substituted methyl silanes being most commonly used. In one aspect, suitable silicone resins are SS4230 (INCI name: Cyclopetasiloxane (e) Trimethylsiloxysilicate) and SS4267 (INCI name: Dimethicone (e) Trimethylsiloxysilicate) available from Momentive Performance Materials, Inc. Suitable silicone resin gels include RG100 (Name INCI: cyclopetasiloxane cross-polymer (e) Dimethicone / vinyltrimethylsiloxysilicate) from Wacker Chemical Corporation.
Silicone materials and silicone resins can be identified according to the shorthand nomenclature system known to that person with common skill in the technique as “MDTQ” nomenclature. under this designation system, the silicone is described according to the presence of several units of siloxane monomer that manufacture the silicone. Briefly, the symbol M says indicates the monofunctional unit (CH ₃ ) ₃ SiOo, 5; D indicates the bifimensional unit (CH ₃ ) 2SiO; T indicates a tri-functional (CH ₃ ) SiOi unit _{; 5} and Q indicates the quad- or tetra-functional SiO _{2 unit} . The first of the unit symbols (for example, M ', D', T and Q ') indicates substituents other than methyl and must be specifically defined for each occurrence. Typical alternative substituents include groups such as vinyl, phenyls, amines, hydroxyls, etc. The molar ratios of various units, in terms of subscripts to the symbol indicating the total number of each type of unit in the silicone (or an average thereof) or as specifically indicative ratios in combination with the complete molecular weight of the silicone material description under the system MDTQ. High relative molar amounts of T, Q, Τ 'and / or Q' to D, D ', M and / or M' in a silicone resin is indicative of the higher levels of crosslinking. As discussed earlier, however, the total level of crosslinking can also be indicated by oxygen to the silicon ratio.
Exemplary silicone resins for use in the compositions of the present invention include, but are not limited to, MQ, MT, MTQ, MDT and MDTQ resins. In one respect, methyl is the substitute for silicone resin. In another aspect, the silicone resin is selected from the MQ resins, where the M: Q ratio is from about 0.5: 1.0 to about 1.5: 1.0 and the average molecular weight of the resin of silicon is about 1000 to about 10,000 daltons.
When used as non-volatile silicone fluids having a refractive index below 1.46, the weight ratio of the non-volatile silicone fluid to a silicone resin component ranges from about 4: 1 to about 400: 1 in one aspect, from about 9: 1 to about 200: 1 in another aspect, from about 19: 1 to about 100: 1 in another aspect, particularly when the silicone fluid component is a polydimethylsiloxane fluid or a mixture of polydimethylsiloxane fluid and polydimethylsiloxane gum as described above. To the extent that a silicone resin forms a part of the same phase in its compositions as the silicone fluid, that is, the active conditioning, the sum of the fluid and resin should be included in determining the level of the silicone conditioning agent in the composition.
The volatile silicones described above include cyclic and linear polydimethylsiloxanes and others. As previously described in the formula for cyclic polysiloxanes (cyclomethicone), these typically contain about 3 to about 7 silicon atoms, alternating with oxygen atoms, in a cyclic ring structure. However, each R20 Substituent and repeating unit, k, in the formula is selected so that the compound is not volatile. Typically, the substituent R20 is substituted with two alkyl groups (for example, methyl groups). Linear volatile silicones are silicone fluids, as described above, having viscosities of no more than about 25 mPaü-s. Volatile means that the silicone has a measured vapor pressure, or a vapor pressure of at least 2 mm Hg at 20 ° C. Non-volatile silicones have a vapor pressure of less than 2 mm Hg at 20 ° C. A description of volatile cyclic and linear silicones is found in Todd and Byers, Silicona volatile Fluids for Cosmetics, Cosmetics and Toiletries, Vol. 91 (1), pp. 27-32 (1976) and in Kasprzak, Silicona volatile, Soap / Cosmetics / Chemical Specialties, pp. 40-43 (December 1986), each incorporated by reference.
Exemplary volatile cyclomethicones are cyclomethicone D4 (octamethylcyclotetrasiloxane), cyclomethicone D5 (decamethylcyclopentasiloxane), cyclomethicone D6 (dodecamethylcyclohexyloxane) and mixtures of these (for example, D4 / D5 and D5 / D6). Volatile cyclomethicone and cyclomethicone mixtures are commercially available from Momentive Performance Materials Inc as SF1202, SF 1214, SF1256 and SF1258, Dow Coming, Midland, MI under the indications of the Xiameter® cyclomethicone fluid product PMX-0244, PMX-245, PMX-246, PMX-345 and Dow Coming® 1401 fluid. Mixtures of volatile cyclomethicone and volatile linear dimethicone are also considered within the scope of the invention.
Exemplary volatile linear dimethicones include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and mixtures thereof. Volatile linear dimethicones and dimethicone mixtures are commercially available from Dow Coming as Xiameter® PMX-200 silicone fluids (eg 0.65 CS, 1 CS, 1.5 CS and 2 CS product indications) and silicone fluid Xiameter® PMX 21184.
Emulsified silicones are also suitable for use in the compositions of the invention. In one aspect, suitable emulsified silicones are dimethicone emulsions with at least one emulsifier selected from non-ionic, anionic, amphoteric, cationic surfactant, and / or cationic polymer and mixtures thereof. In one aspect, useful silicone emulsions have an average silicone particle size in the composition of less than 30 pm, less than 20 pm in another aspect and less than 10 pm in another aspect. In another aspect of the invention, the average silicon particle size of the emulsified silicone in the composition is less than 2 pm and in another it ranges from 0.01 to 1 pm. Silicone emulsions having an average silicone particle size of <0.15 pm are generally referred to as microemulsions. The particle size can be measured by means of a laser light scattering technique, using a 2600D Sizer particle from Malvern Instruments. Silicone emulsions suitable for use in the invention are also commercially available in a pre-emulsified form. Examples of suitable commercially available preformed emulsions include Dow Coming® MEM-1664, 2-1352, MEM-1764, MEM-1784, HMW 2220, 2-1865, MEM-1310, MEM-1491 and 57137 emulsions. These are emulsions / microemulsions of dimethicone. Preformed amino functional silicone emulsions are also available from suppliers of silicone oils such as Dow Coming (CE-8170, 5-7113, 2-8194, 949 and CE 8401) and Momentive Performance Materials.
Particularly suitable are the functional silicone emulsions of amino oils with non-ionic and / or cationic surfactant. Examples include Dow Coming® 939 cationic emulsion, 949 cationic emulsion, cationic microemulsion 2-8194 and cationic emulsion 2-8299 and nonionic emulsion 2-8177; as well as SM2115 and SME253, non-ionic microemulsions provided by Momentive Performance Materials. Mixtures of any of the above types of silicone can also be used. Other examples of functional amino silicone are aminosilicone oils. Suitable commercially available aminosilicone oils include Dow Coming® Q2-8166, Q2-8220 and 2-8566 and SF 1708, (Momentive Performance Materials).
Other suitable silicone oils include dimethicone copolyols, which are branched or linear copolymers of dimethylsiloxane (Dimethicone) modified with alkylene oxide units. The alkylene oxide units can be arranged as random or block copolymers. A generally useful class of dimethicone polyols are block copolymers having pendant blocks and / or terminals of polydimethylsiloxane and blocks of polyalkylene oxide, such as blocks of ethylene polyoxide, polypropylene oxide, or both. Dimethicone copolyols can be soluble or insoluble in water depending on the amount of polyalkylene oxide present in the dimethicone polymer and can be anionic, cationic, or non-ionic in character.
Water-dispersible or water-soluble silicones can also be used in the compositions of the invention. Such water-soluble silicones contain adequate anionic functionality, cationic functionality, and / or non-ionic functionality to render the water-soluble or water-dispersible silicone. In one aspect, water-soluble silicones contain a polysiloxane backbone on which at least one anionic portion is grafted. The anionic portion can be grafted to a terminal end of the polysiloxane structure, or it will be grafted as a pending secondary group, or both. For the anionic group is meant any portion of hydrocarbon that contains at least one anionic group or at least one group that can be ionized into an anionic group following neutralization by a base. As previously discussed, the number of anionic hydrocarbon groups that are grafted onto the silicone chain are chosen in such a way that the corresponding silicone derivative is water-soluble or water-dispersible after neutralization of the ionizable groups with the base. Anionic silicone derivatives can be selected from existing commercial products or can be synthesized by any means known in the art. Nonionic silicones contain alkylene oxide terminal and / or secondary chain pendant units (for example, the dimethicone copolyols discussed above). Another example of non-ionic silicones is Wacker's silicon polyglycosides (for example, WackerBelsil® SPG 128 VP, SPG 130 VP and VSR 100 VP).
Silicones with anionic groups can be synthesized by the reaction between (i) a polysiloxane containing a silinic hydrogen and (ii) an olefinic unsaturated content compound that also contains an anionic functional group. An example of such a reaction is the hydrosilylation reaction between poly (dimethylsiloxanes) containing the Si-H groups and an olefin, CH ₂ = CHR ²⁷ , where R ²⁷ represents a portion containing an anionic group. The olefin can be monomeric, oligomeric or polymeric. Polysiloxane compounds that contain pendent reactive thio (-SH) groups are also suitable for grafting an unsaturated anionic group containing compound to the poly (siloxane) structure.
According to one aspect of the present invention, anionic monomers containing ethylenic unsaturation are used alone or in combination and are selected from unsaturated, linear or branched carboxylic acids. Exemplary unsaturated carboxylic acids are acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid and crotonic acid. The monomers can optionally be partially or completely neutralized by the base to form an ammonium salt, alkaline earth metal, alkaline. Suitable bases include, but are not limited to, alkaline earth, alkaline (e.g., sodium, potassium, lithium, magnesium, calcium) and ammonium hydroxides. It will be noted that, similarly, the polymeric and oligomeric graft segments formed from the preceding monomers can be post-neutralized with the base (sodium hydroxide, aqueous ammonia, etc.) to form a salt. Examples of such silicone derivatives that are suitable for use in the present invention are described in European Patent Application No. EP 0 582 152 and International Patent Application Publication No. WO 93/23009. An exemplary class of silicone polymers are polysiloxanes containing repeating units represented by the following structure:
G ¹ CH ₃ ¹ * ^CH 3
GS— (G) where G ¹ represents hydrogen, C 1 -C 10 alkyl and phenyl radical; L ² is alkylene Ci-Ci _0; G ³ represents an anionic polymeric residue obtained from the polymerization of at least one anionic monomer containing ethylenic unsaturation; j is 0 or 1; t is an integer ranging from 1 to 50 and i is an integer from 10 to 350. In an embodiment of the invention, G ¹ is methyl; j is 1 and G2 is a propylene radical; G ³ represents a polymeric radical obtained from the polymerization of at least one unsaturated monomer containing a group of carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, maleic acid, and acotinic acid and others ).
In one aspect, the content of the carboxylate group in the final polymer ranges from 1 mol of carboxylate per 200 g of polymer to 1 mol of carboxylate per 5000 g of polymer. In one aspect, the average molecular weight number of the silicone polymer ranges from about 10,000 to about 1,000,000 daltons and from 10,000 to 100,000 daltons in another aspect. Exemplary unsaturated monomers containing a group of carboxylic acids are acrylic acid and methacrylic acid. In addition, to the carboxylic acid group containing monomers, C ₁ -C ₂ alkyl acrylic acid esters and methacrylic acid can be copolymerized in the polymeric structure. Exemplary esters include, but are not limited to, ethyl and butyl esters of acrylic and methacrylic acid. A commercially available silicone acrylate polymer is branded by 3M Company under the trade name Silicones Plus Polimer 9857C (VS80 Dry). These polymers contain a polydimethylsiloxane (PDMS) structure in which random repeating units of polyacrylic (meth) acrylic and the poly (meth) acrylate butyl ester are grafted (via a thiopropylene group). These products can be obtained conventionally by radical copolymerization between polydimethylsiloxane functionalized by thiopropyl and a mixture of monomers comprising (meth) acrylic acid and butyl (meth) acrylate.
In another aspect, the water-soluble silicone copolyol useful in the practice of the present invention are silicon copolyol carboxylates represented by the formula:
CH ₃ CH, CH, CH ₃ CH ₃
I Γ I 1 Γ ¹ 1 F ¹ 1 I 28
R-Si- ^ O-Si ^ O-Si-yO-Si- ^ O-Si-R ch ₃ r ²⁹ r ³⁰ ch ₃
CH ₂ CH ₂ CH ₂ O (EO) (PO) (EO) —R ³¹ abc where R ²⁸ and R ²⁹ are independently selected from C 1 -C ₃₀ alkyl, C ₆ -C ₄ aryl, C _7- C ₁₅ aralkyl, alcaryl C _r Ci ₅ , or a group of
Alkenyl of 1 to 40 carbons, hydroxyl, -R -G 'or - (CH ₂ ) 3O (EO) a (PO) b (EO) _c -G', with the prescription that both R28 and R ²⁹ are not methyl ; R ³⁰ is selected from C1-C5 alkyl or phenyl; in this formula a, b and c are independently integers ranging from 0 to 100; EO is ethylene oxide,
- (CH ₂ CH ₂ O) -; PO is propylene oxide, - (CH ₂ CH (CH ₃ ) O) -; in this formula o is an integer that ranges from 1 to 200, p is an integer that ranges from 0 to 200 and q is an integer that ranges from 0 to 1000; ^R31 is hydrogen, Ci-C ₃₀ alkyl, aryl, C7 -C15 aralkyl, C7 -C15 alkaryl, or alkenyl group from 1 to 40 carbons , or -C (O) -X wherein X 5 is C _r C ₃₀ alkyl, C ₆ -Ci ₄ aryl, C7-C15 aralkyl, C _r C 5 alkaryl, or an alkenyl group of 1 to 40 carbons, or a mixture thereof; R is a divalent group selected from an alkylene radical of 1 to 40 carbon atoms that can be interrupted with a 6 to 18 carbon arylene group or an alkylene group containing 2 to 8 carbon unsaturation and G 'is independently selected from a represented portion by the formula:
—C-OH —C-0 M —S-OH
O 0 0 11 - + II II - + -SOUND —O-S-OH —0-S-0 M li; li; li; 0 0 0
OO OO.
II 33 II II 33 II —C-R-C-OH. —C-R-C-0 M>
wherein R ³³ is a bivalent group selected from alkylene of 1 to 40 carbons, an unsaturated group containing 2 to 5 carbon atoms, or an arylene group of 6 to 12 carbon atoms; where M is a cation selected from Na, K, Li, NH4, or an amine containing at least one C1-C10 alkyl, 15 C ₆ -Ci ₄ aryl (eg, phenyl, naphthyl), C ₂ -Ci ₀ alkenyl, hydroalkyl C _r C10, arylalkyl C ₇ -C ₂ 4 or groups of C ₇ -C ₂₄ alkaryl. Representative R33 radicals are: -CH ₂ CH ₂ -, -CH = CH-, -CH = CHCH ₂ - and phenylene.
In another embodiment, the water-soluble silicones useful in the practice of the present invention can be represented by an anionic silicone copolyol represented by the formula:
CH- CH, CK
R — Si - [- 0 — Si— ch ₃ r ^3S r ”
CK CH
I 1 I 34
Ο-Si — kO-Si-R
I 37 ^Jc I
R CH ₃ where R ³⁴ is methyl or hydroxyl; R ³⁵ is selected from C 1 -C 8 alkyl or phenyl; R ³⁶ represents the radical - (CH2) ₃ O (EO) _x (PO) _y (EO) _z SO3'M ⁺ ; where M is a cation selected from Na, K, Li, or NH ₄ ; in this formula x, y and z are independently integers ranging from 0 to 100; R ³⁷ represents the radical - (CH ₂ ) ₃ O (EO) _x (PO) _y (EO) _z -H; in this formula a and c independently represent integers ranging from 0 to 50b and it is an integer ranging from 1 to 50; EO is ethylene oxide, for example, - (CH ₂ CH ₂ O) -; PO is propylene oxide, for example, - (CH ₂ CH (CH ₃ ) O) -.
In yet another embodiment, the water-soluble silicones useful in the practice of the present invention can be represented by an anionic silicone copolyol represented by the formula:
CH, CH, CH, CH,
3B I Γ I 1 Γ 11I 38
R — Si — HD-Si — H-O-Si — kO-Si-R
I ^L I 39 ^J ° ^L I 40 ^Jq I ch ₃ r rch
OOOQ where R and R independently are -CH ₃ or a radical represented by: - (CH ₂ ) ₃ O (EO) _a (PO) b (EO) _c -C (O) -R ^4l -C (O) OH , subject to the condition that both R38 and R39 are not -CH3 at the same time; R ⁴¹ is selected from the divalent radical -CH2CH ₂ , -CH = CH- and phenylene; R ⁴⁰ is selected from C _r C ₅ alkyl or phenyl; in this formula a, b and c are independently integers ranging from 0 to 20; EO is an ethylene oxide residue, for example, - (CH ₂ CH ₂ O) -; PO is a propylene oxide residue, for example, - (CH ₂ CH (CH ₃ ) O) -; in this formula o is an integer that ranges from 1 to 200 and q is an integer that ranges from 0 to 500.
Other water-soluble silicones useful in the invention are quartzized silicon copolymer polymers. These polymers have a pending quartenary nitrogen functional group present and are represented by the formula:
R ⁴² CH ₂ C (O) O- (EO) _z (PO) _y (EO) _x - (CH _{2) 3} CH ₃ CH3 _CH3 CH3 _CH3 r ⁴³ r ⁴⁴ CH3 _CH3 ⁴² wherein R represents a four-year substituent N ⁺ R ⁴⁵ R ⁴⁶ R ⁴⁷ CA, where R ⁴⁵ and R ⁴⁶ , and R ⁴⁷ , independently, are selected from hydrogen and linear and branched C1-C24 alkyl and CA 'represents a suitable counter anion to swing the cationic charge on the nitrogen atom; R ⁴³ is selected from CrCio alkyl and phenyl; R ⁴⁴ is (CH2) 3O (EO) _x (PO) _y (EO) _z -H, where EO is an ethylene oxide residue, for example, - (CH ₂ CH ₂ O) -; PO is a propylene oxide residue, for example, - (CH2CH (CH ₃ ) O) -; in this formula a is an integer from 0 to 200, b is an integer from 0 to 200 and c is an integer from 1 to 200; in this formula x, y and z are integers and are independently selected from 0 to 20. In one aspect, the anion CA 'represents an anion selected from chlorine, bromine, iodide, sulfate, methylsulfate, sulfonate, nitrate, phosphate and acetate.
Other suitable water-soluble silicones are substituted silicone copolyols represented by the formula:
(CH ₂ ) ₃ O (EO) _x (PO) _y (EO) _z -H
CH3 _CH3 CH3 _CH3
CH _r Si- / o-SiAF ° -Si- | ^ ⁰ “^ A ⁰ - ^“ ^CH 3 ch ₃ ch ₃ r ⁴⁸ ch ₃ ch ₃ where R ⁴⁸ is selected from -ΝΗ (ΟΗ ₂ ) _η ΝΗ _{2 or} - (CH ₂ ) _n NH 2; in this formula n is an integer from 2 to 6 eg, it is an integer from 0 to 20; where EO is an ethylene oxide residue, for example, - (CH ₂ CH ₂ O) -; PO is a propylene oxide residue, for example, - (CH ₂ CH (CH ₃ ) O) -; in this formula a is an integer from 0 to 200, b is an integer from 0 to 200 and c is an integer from 1 to 200; in this formula x, y and z are integers and are independently selected from 0 to 20.
Still other water-soluble silicones can be selected from non-ionic silicone copolyols (dimethicone copolyols) represented by the formula:
R50 (R ⁴⁹ ) 3Si (OSiR ⁴⁶ R ⁴⁷ ) x (OSi) _y OSi (R ⁴⁹ ) ₃
I çh ₂ çh ₂ çh ₂ O - (EO) _a (PO) _b (EO) _c -H where R ⁴⁹ , independently, represents a radical selected from CrC30 alkyl, C6-C14 aryl and C2-C20 alkenyl; R ⁵⁰ represents a radical selected from C ₁ -C ₃ alkyl, C ₂ -C ₂ aryl and C ₂ -C ₂ o alkenyl; EO is an ethylene oxide residue, for example, - (CH ₂ CH ₂ O) -; PO is a propylene oxide residue, for example, - (CH ₂ CH (CH ₃ ) O) -; in this formula a, b and c are, independently, 0 to 100; in this formula x is 0 to 200 and y is 1 to 200.
In another embodiment, water-soluble silicones can be selected from non-ionic silicone copolyols represented by the formula:
R ⁵¹ R ⁵¹
HO- (EO) _c (PO) _b (EO) _c (CH ₂ ) ₃ Si (OSiR ⁵¹ R ⁵² ) _n OSi (CH ₂ ) ₃ O (EO) _a (PO) _b (EO) _c -H
R ⁵² R 'wherein R ⁵¹ and R ⁵² independently represents a radical selected from C _r C ₃₀ alkyl, C ₆ -C ₄ aryl and C ₂ -C ₂₀ alkenyl; EO is an ethylene oxide residue, for example,
- (CH ₂ CH ₂ O) -; PO is a propylene oxide residue, for example, - (CH ₂ CH (CH ₃ ) O) -; in this formula a, b and c are independently 0 to 100 and in this formula n is 0 to 200.
In the formulas presented above, the EO and PO residues can be arranged in block sequences, random or non-random.
Water-soluble silicones are disclosed in U.S. Patent No. 5,136,063 and 5,180,843, the findings of which are incorporated herein by reference. Such silicones are commercially available under the Silsoft® and Silwet® trade names of Momentive Performance Materials. Specific product indications include, but are not limited to, Silsoft product indications 430, 440, 475, 805, 810, 840, 870, 875, 880, 895, 900 and 910; product indication Silwet L-7604. Other commercially available products include Dow Coming® 5103 and 5329; Abil® product indications B 88183, B 8843, Evonik Goldschmidt and Silsense ™ dimethicone copolyols, such as Silsense Copoliol-1 and Silsense Copoliol-7, available from Lubrizol Advanced Materials, Inc, Cleveland, OH.
The concentration of the silicone agents described above can vary from about 0.01% to about 10%, by weight of the composition that is included. In another aspect, the amount of the silicone agent ranges from about 0.1% to about 8%, from about 0.1% to about 5% in yet another aspect, and from about 0.2 % to about 3% by weight in another aspect, all based on the total weight of the composition.
Natural and synthetic waxes, oils, fatty acids and alcohols
In one aspect, natural and synthetic waxes, oils, fatty acids, fatty alcohols, as well as their derivatives are useful in the compositions of the present invention as a beneficial agent and can be useful, for example, as conditioners, emollients and wetting agents for hair. and skin.
Natural and synthetic wax agents that can be used appropriately in the compositions of the invention include, but are not limited to, carnauba wax, hydrolyzed carnauba wax, carnauba acid wax, ethoxylated carnauba wax (e.g. carnauba wax PEG12), candelilla wax, hydrolyzed candelilla wax, hydrogenated castor wax, bay laurel wax, alpha wax, paraffin wax, ozokerite wax, olive wax, ouricuri wax, palm seed wax, rice wax, hydrogenated jojoba wax, beeswax, modified beeswax, for example, oxidized beeswax, ethoxylated beeswax (for example, PEG-6 beeswax, PEG-8 beeswax, bees PEG-12, beeswax PEG-20), beeswax esters of dimethicone copolyol and dimethicone beeswax ester (eg hydroxyethoxypropyl dimethicone beeswax, PEG- dimethicone beeswax 8 and Dimeticonol beeswax disp name of the Lubrizol Advanced Materials, Inc. under Ultrabee®), cerabeline wax, marine waxes, lanolin and derivatives thereof and polyolefin waxes, for example, polyethylene wax and mixtures thereof.
Lanolin and lanolin derivatives are selected from lanolin, lanolin wax, lanolin oil, lanolin alcohols, lanolin fatty acid esters such as lanolin fatty acid isopropyl esters (for example, lanolin fatty acids) isopropyl), alkoxylated lanolin, acetylated lanolin alcohols and combinations thereof. Lanolin and lanolin derivatives are commercially available from Lubrizol Advanced Materials, Inc. under the trade names Lanolin LP 108 USP, Lanolin USP AAA, Acetulan ™, Ceralan ™, Lanocerin ™, Lanogel ™ (product indications 21 and 41), Lanogene ™, Modulan ™, Ohlan ™, Solulan ™ (product indications 16, 75, L-575, 98 and C-24) and Vilvanolin ™ (product indications C, CAB, L-101 and P).
Oily agents suitable for use in the compositions of the present invention include, but are not limited to, hydrocarbon oils having at least about 10 carbon atoms, such as cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturated or unsaturated) and hydrocarbons branched chain aliphatics (saturated or unsaturated), including polymers and mixtures thereof. Straight-chain hydrocarbon oils typically contain about 12 to 19 carbon atoms. Branched-chain hydrocarbon oils, including hydrocarbon polymers, will typically contain more than 19 carbon atoms. Specific non-limiting examples of these hydrocarbon oils include paraffin oil, mineral oil, petrolatum, saturated or unsaturated dodecane, saturated or unsaturated tridecane, saturated or unsaturated tetradecan, saturated or unsaturated pentadecan, saturated or unsaturated hexadecane, polybutene, polydecene and mixtures thereof. Branched-chain isomers of these compounds, as well as longer chain length hydrocarbons, may also be used, examples of which include highly branched saturated or unsaturated alkanes such as permethyl-substituted isomers, for example, hexadecane-substituted isomers and eicosane, such as 2,2,4,4,6,6,8,8-octamethyl-10-methylundecane and 2,2,4,4,6,6-hexamethyl-8methylnonane, available from Permetil Corporation. Hydrocarbon polymers such as polybutene and polydecene are also useful.
Mineral oils and petrolates include cosmetic grades, USP and NF and are commercially available from Penreco under the trade names Drakeol® and Penreco®. Mineral oils include hexadecane and paraffin oil.
Liquid polyolefin oils can be used in the compositions of the present invention. Liquid polyolefin agents are typically poly-a-olefins that have been hydrogenated. Polyolefins for use in this can be prepared by polymerizing C4 to about C14 olefinic monomers. Non-limiting examples of olefinic monomers for use in the preparation of polyolefin liquids therein include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1tetradecene and 1-hexadecene , branched isomers such as isobutylene, 4-methyl-1-pentene and mixtures thereof. In one aspect, a suitable hydrogenated polyolefin is the copolymer of isobutylene and butene. A commercially available material of this type is Panalane® L-14E (INCI name: hydrogenated polyisobutene) marked by Lipo Chemicals Inc, Patterson, N.J.
Fluorinated and perfluorinated oils are also considered within the scope of the present invention. Fluorinated oils include perfluoropolyethers described in European Patent No. EP 0 486 135 and the fluorohydrocarbon compounds described in International Patent Application Publication No. WO 93/11103. Fluoridated oils can also be fluorocarbons such as fluoramines, for example, perfluorotributylamine, fluoridated hydrocarbons, such as perfluorodecahydronaphthalene, fluoroesters and fluoroethers.
Natural oils that are useful in the practice of this invention include, but are not limited to, peanuts, sesame, avocado, coconut, cocoa butter, canola, babassu, almond, corn, grape seed, cotton seed, sesame seed , nut, castor, olive, jojoba, palm, palm seed, soy, wheat germ, linseed, safflower, shea seed, sunflower seed, eucalyptus, lavender, vetiver, litsea, cubeba, lemon, sandalwood, rosemary, chamomile , savory, nutmeg, cinnamon, hyssop, caraway, orange, geranium, bergamot and Cade oils, fish oils, as well as glycerides (mono- and triglycerides) derived from plant oils, vegetable oils and animal fats (eg tallow and bacon) and mixtures thereof.
Oils as beneficial agents can be in the form of organogel particles (oil and wax) as described in U.S. Patent No. 6,737,394.
Suitable glycerides (mono-, di- and triglycerides) can be derived by esterifying glycerol, a monoglyceride, or a diglyceride with some fatty acids by techniques well known in the art, or by glycerolysis of animal fats and vegetable oils in the presence of a based on elevated temperature and under an inert atmosphere (See RSC Green Chemistry Book Series, The Royal Society of Chemistry, The Future of Glicerol: New Uses Of A Versatile Material, Chapter 7, Mario Pagliaro and Michele Rossi, © 2008). Fatty acids suitable for use in the esterification reaction include saturated and unsaturated C8-C ₃₀ fatty acids.
Also useful in the compositions of the present invention are free fatty acids and their derivatives. Suitable fatty acids include saturated and unsaturated C8-C ₃₀ fatty acids. Exemplary fatty acids include, but are not limited to, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, ricinoleic acid, vaccenic acid, linoleic acid, α-linolenic acid, γlinolenic acid , arachidic acid, gadoleic acid, arachidonic acid, EPA (5,8,11,14,17-eicosapentaenoic acid), behenic acid, erucic acid, DHA (4,7,10,13,16,19-docosahexaenoic acid), lignoceric acid and mixtures thereof.
Alkoxylated fatty acids are also useful in this and can be formed by esterifying a fatty acid with an ethylene oxide and / or propylene oxide or with a preformed polymeric ether (for example, polyethylene glycol or polypropylene glycol). The product is a polyethylene oxide ester, polypropylene polyester, or a respective fatty acid polyethylene / polypropylene polyester. In one aspect, an ethoxylated fatty acid can be represented by the formula:
R'-C (O) O (CH2CH2O) _n '-H, where R' represents the aliphatic residue of a fatty acid and n 'represents the number of ethylene oxide units. In another aspect, n 'is an integer that ranges from about 2 to about 50, from about 3 to about 25 in another aspect, and from about 3 to about 10 in an additional aspect. In yet another aspect of the invention, R 'is derived from a saturated or unsaturated fatty acid containing 8 to 30 carbon atoms. In another aspect, diesters can be formed by reacting two moles of fatty acid with one mole of polyethylene or polypropylene glycol. Diesters can be represented by the formula:
R'-C (O) O (CH2CH ₂ O) _n - (O) CR 'where R' en 'are as defined immediately above.
Exemplary alkoxylated fatty acids include, but are not limited to, capric acid ethoxylate, lauric acid ethoxylate, myristic acid ethoxylate, stearic acid ethoxylate, oleic acid ethoxylate, coconut fatty acid ethoxylate and others, where the number of ethylene oxide units in each of the foreign ethoxylates can range from 2 and above in one aspect and from 2 to about 50 in another aspect. More specific examples of ethoxylated fatty acids are PEG-8 stearate (8 means the number of repeat ethylene oxide units), PEG8 distearate, PEG-8 oleate, PEG-8 beenate, PEG-8 caprate , PEG8 caprylate, PEG cocoates (PEG without a number indication means the number of units in the ethylene oxide bands 2 to 50), PEG-15 dicocoate, PEG-2 diisononanoate, PEG-8 diiso-stearate, PEG dilaurate, PEG dioleates, PEG- distearates, PEG ditalates, PEG isostearates, PEG jojoba acids, PEG laurates, PEG linolenates, PEG myristates, PEG oleatates, PEG palmitates, PEG ricinoleates , PEG stearates, PEG talate and others.
Another fatty acid derivative that can be used appropriately in the compositions of the invention is a fatty acid ester. Fatty acids can be esterified by alcohols in the presence of a suitable acid catalyst to give a desired fatty acid ester. In one aspect, any of the saturated and unsaturated C ₈ -C ₃ fatty acids disclosed above can be esterified by a saturated or unsaturated C1-C22 alcohol to give the respective fatty acid ester. In another aspect, esters of the longer chain fatty acid can be derived from the esterification of the fatty acids mentioned above by a saturated Cg-C ₃₀ fatty acid or unsaturated tt H and can be represented by the formula: RC (O) OR in that R independently represents a straight or branched, saturated and unsaturated alkyl group containing 1 to 24 carbon atoms. Suitable fatty alcohols include the fatty alcohols that are disclosed below.
Exemplary fatty acid esters include, but are not limited to, methyl laurate, hexyl laurate, hexyl isolaurate, decyl oleate, methyl cocoate, isopropyl stearate, isopropyl isostearate, butyl stearate, decyl stearate, stearate octyl, cetyl stearate, stearyl stearate, oleyl stearate, myristyl myristate, stearoyl octyldodecyl stearate, octylhydroxy stearate, isopropyl myristate, oleyl myristate, isopropyl palmitate, ethyl ethyl palmitate, hexyl palmitate, hexyl palmitate decila, decila isooleate, oleyl oleate, isodecyl neopentanoate, diisopropyl sebacate, isostearyl lactate, lauryl lactate, cetearyl octanoate and mixtures thereof.
Still other fatty esters suitable for use in the compositions of the present invention are mono-, di and tri-alkyl and alkenyl esters of carboxylic acids, such as esters of C ₂ -C ₈ monocarboxylic acids, C4-C10 dicarboxylic acids, C tricarboxylic acids _6- Cio (eg esters of C _r C ₂₂ acetic acid, lactic acid, succinic acid, glutaric acid, adipic acid, citric acid, trimellic acid, trimethic acid and 1,3,5-penticarboxylic acid). Specific non-limiting examples of mono-, di- and tri-alkyl and alkenyl esters of carboxylic acids include lauryl acetate, cetyl propionate, lauryl lactate, myristyl lactate, cetyl lactate, diisopropyl adipate, diexildecyl adipate, adipate dioleyl and tristearyl citrate.
Other fatty esters suitable for use in the compositions of the present invention are those known as polyhydric alcohol esters. Such polyhydric alcohol esters include alkylene glycol esters, such as ethylene glycol fatty acid mono and diesters, diethylene glycol fatty acid mono and diesters, polyethylene glycol, mono and di fatty acid esters -propylene glycol fatty acid esters, polypropylene glycol fatty acid mono and diesters and sorbitol mono and fatty esters, in which the acyl portion of the fatty acid ester is derived from a C ₈ - fatty acid C ₂₂ saturated or unsaturated. These esters can be optionally ethoxylated. Representative polyhydric alcohol fatty acid esters include, but are not limited to, polypropylene glycol monooleate, polypropylene glycol monostearate, glycerol fatty acid mono and diesters, polyglycerol fatty acid polyesters, ethoxylated glyceryl monostearate, 1,3-butylene glycol monostearate, 1,3-butylene glycol distearate, polyoxyethylene polyol fatty acid ester, sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters.
Other esters of polyhydric alcohol include esters of partial polyglycerols. These esters contain 2 to 10 glycerol units and are esterified with 1 to 4 C ₈ -C ₃₀ fatty acid residues, optionally hydroxylated, linear or branched, saturated or unsaturated. Representative partial polyglycerol esters include, but are not limited to, diglycerol monocaprilate, diglycerol monocaprate, diglycerol monolaurate, triglycerol monocaprilate, triglycerol monocaprate, triglycerol monolaurate, tetraglycerol monocaprilate, tetraglycerol monocaprilate, tetraglycerol monolayer, of pentaglycerol, pentaglycerol monocaprate, pentaglycerol monolaurate, hexaglycerol monocaprilate, hexaglycerol monocaprate, hexaglycerol monolaurate, hexaglycerol monomyristate, hexaglycerol monohydrate, decaglyceride monoglycerate, decaglycerol monolayer , decaglycerol monostearate, decaglycerol monooleate, decaglycerol monohydroxystearate, decaglycerol tipprilate, decaglycerol hint, decaglycerol dilaurate, decaglycerol dimiristate, decaglycerol diisostearate, diestearate glycerol, decaglycerol dioleate, decaglycerol dihydroxystearate, decaglycerol tricaprilate, decaglycerol tricaprate, decaglycerol trilaurate, decaglycerol tri-esterate, decaglycerol tri-stearate, decaglycerol tri-stearate, and decaglycerol tri-glycerol tristate, decaglycerol trihydrate
Fatty alcohols suitable for use in the compositions of the invention include, but are not limited to, saturated and unsaturated C ₈ -C ₃₀ fatty alcohols. Exemplary fatty alcohols include caprylic alcohol, pelargonic alcohol, capric alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, isocetyl alcohol, stearyl alcohol, isostearyl alcohol, cetearyl alcohol, palmitoleyl alcohol, elaidyl alcohol, sterol, alcohol oleyl, linoleyl alcohol, elaidolinoleyl alcohol, linolenyl alcohol, ricinoleyl alcohol, arachidyl alcohol, icocenyl alcohol, beenyl alcohol, erucyl alcohol, lignoceryl alcohol, ceryl alcohol, montanyl alcohol, myricyl alcohol and mixtures thereof. Fatty alcohols are widely available and can be obtained by hydrogenating oils and fats from esterified animals and vegetables.
The compounds of the alkoxylated fatty alcohol are ethers formed from the reaction of a fatty alcohol with the alkylene oxide, usually ethylene oxide or propylene oxide. Suitable ethoxylated fatty alcohols are fatty alcohol adducts and ethylene polyoxide. In one aspect of the invention, ethoxylated fatty alcohols can be represented by the formula R '- (OCH ₂ CH2) n-OH, where R' represents the aliphatic residue of the precursor fatty alcohol and n represents the number of ethylene oxide units. In another aspect of the invention, R 'is derived from a fatty alcohol containing 8 to 30 carbon atoms. In one aspect, n is an integer that ranges from 2 to 50, 3 to 25 in another aspect and 3 to 10 in an additional aspect. In an additional aspect, R 'is derived from a fatty alcohol immediately presented in the paragraph above. Exemplary ethoxylated fatty alcohols, but are not limited to caprylic alcohol ethoxylate, lauryl alcohol ethoxylate, myristyl alcohol ethoxylate, cetyl alcohol ethoxylate, stearyl alcohol ethoxylate, cetearyl alcohol ethoxylate, ethanol ethoxylate and oleyl alcohol ethoxylate , beenyl alcohol ethoxylate, in which the number of ethylene oxide units in each of the foreign ethoxylates can vary from 2 and above in one aspect and from 2 to about 150 in another aspect. It is recognized that propoxylated adducts from previous fatty alcohols and propoxylated adducts from previous fatty alcohols / mixed ethoxylates are also considered within the scope of the invention. The ethylene oxide and propylene oxide units of the ethoxylated / propoxylated fatty alcohols can be arranged in random order or in blocks.
Exemplary ethoxylated sterols include ethoxylated plant sterols such as, for example, soy sterols. The degree of ethoxylation is greater than about 5 in one aspect and at least about 10 in another aspect. Suitable ethoxylated sterols are PEG-10 soy sterol, PEG-16 soy sterol and PEG-25 soy sterol.
Additional examples of ethoxylated alcohols, but are not limited to Beheneth 5-30 (the 5-30 meaning the repeat range of ethylene oxide units), Ceteareth 2-100, Ceteth 1-45, Cetoleth 24-25, Choleth 10-24, Coceth 3-10, C ₉ -11 Pareth 3-8, Cn-15 Pareth 5-40, Cn-21 Pareth 3-10, Cj ₂ -13 Pareth 3-15, Deceth 4-6, Dodoxinol 5 -12, Glycereth 7-26, Isoceteth 10-30, Isodeceth 4-6, Isolaureth 3-6, isosteareth 3-50, Laneth 5-75, Laureth 1-40, Nonoxynol 1-120, Nonilnonoxynol 5-150, Octoxynol 3 -70, Oleth 2-50, PEG 4-350, Steareth 2-100 and Trideceth 2-10.
Specific examples of propoxylated alcohols, but are not limited to cetyl ether PPG-10, cetyl ether PPG-20, cetyl ether PPG-28, cetyl ether PPG-30, cetyl ether PPG-50, lanolin alcohol ether PPG-2 , lanolin alcohol ether PPG-5, lanolin alcohol ether PPG-10, lanolin alcohol ether PPG-20, lanolin alcohol ether PPG-30, lauryl ether PPG-4, lauryl ether PPG-7, ether oleyl PPG-10, oleyl ether PPG-20, oleyl ether PPG-23, oleyl ether PPG-30, oleyl ether PPG-37, oleyl ether PPG-50, stearyl ether PPG-11, stearyl ether PPG-15, lanolin ether PPG-2, lanolin ether PPG-5, lanolin ether PPG-10, lanolin ether PPG-20, lanolin ether PPG-30 and myristyl ether PPG-1.
j
Specific examples of ethoxylated / propoxylated alcohols but are not limited to PPG-1 Beheneth-15, PPG-12 Capryleth-18, PPG-2Ceteareth-9, PPG-4-Ceteareth-12, PPG-10-Ceteareth-20, PPG -1 -Ceteth-1, PPG-1 -Ceteth-5, PPG-1-Ceteth-10, PPG-1-Ceteth-20, PPG-2-Ceteth-1, PPG5 2-Ceteth-5, PPG-2- Ceteth-10, PPG-2-Ceteth-20, PPG-4-Ceteth-1, PPG-4Ceteth-5, PPG-4-Ceteth-10, PPG-4-Ceteth-20, PPG-5-Ceteth-20, PPG-8Ceteth-1, PPG-8-Ceteth-2, PPG-8-Ceteth-5, PPG-8-Ceteth-10, PPG-8-Ceteth20, PPG-2 C12-13 Pareth-8, PPG-2 Ci ₂ -15 Pareth-6, PPG-4 C13-15 Pareth-15, PPG-5 C ₉ -15 Pareth-6, PPG-6 C ₉ -11 Pareth-5, PPG-6 C ₁₂ -15 Pareth-12, PPG10 6 Ci ₂ -18 Pareth-11, PPG-3 Ci ₂ -14 Sec-Pareth-7, PPG-4 Ci ₂ -14 Sec-Pareth-5,
PPG-5 Ci ₂ -14 Sec-Pareth-7, PPG-5 Ci ₂ -14 Sec-Pareth-9, PPG-1-Deceth-6, PPG-2-Deceth-3, PPG-2-Deceth-5, PPG-2-Deceth-7, PPG-2-Deceth-10, PPG2-Deceth-12, PPG-2-Deceth-15, PPG-2-Deceth-20, PPG-2-Deceth-30, PPG2-Deceth- 40, PPG-2-Deceth-50, PPG-2-Deceth-60, PPG-4-Deceth-4, PPG-415 Deceth-6, PPG-6-Deceth-4, PPG-6-Deceth-9, PPG -8-Deceth-6, PPG-14Deceth-6, PPG-6-Deciltetradeceth-12, PPG-6-Deciltetradeceth-20, PPG-6Deciltetradeceth-3 0, PPG-13 -Deciltetradeceth-24, PPG-20-Deciltetradeceth10, PPG-2-Isodeceth-4, PPG-2-Isodeceth-6, PPG-2-Isodeceth-8, PPG-2Isodeceth-9, PPG-2-Isodeceth-10, PPG-2-Isodeceth-12, PPG-2- Isodeceth-18, 20 PPG-2-Isodeceth-25, PPG-4-Isodeceth-10, PPG-12-Laneth-50, PPG-2Laureth-5, PPG-2-Laureth-8, PPG-2-Laureth-12 , PPG-3-Laureth-8, PPG-3Laureth-9, PPG-3-Laureth-10, PPG-3-Laureth-12, PPG-4 Laureth-2, PPG-4 Laureth-5, PPG-4 Laureth- 7, PPG-4-Laureth-15, PPG-5-Laureth-5, PPG-6Laureth-3, PPG-25-Laureth-25, lauryl ether PPG-7, PPG-3-Myreth-3, PPG25 3-Myreth -ll, Lanolina hidr ogenate PPG-20-PEG-20, hydrogenated lauryl acid ether PPG-2-PEG-11, lanolin PPG-12-PEG-50, lanolin oil PPG-12-PEG-65, lanolin oil PPG-40-PEG -60, PPG-1-PEG-9 lauryl glycol ether, PPG-3-PEG-6 oleyl ether, PPG-23-Steareth-34, PPG-30 Steareth-4, PPG-34-Steareth-3, PPG-3 8 Steareth-6, PPG-1 Trideceth-6, PPG77
Trideceth-6 and PPG-6 Trideceth-8.
Guerbet esters are also suitable in the compositions of the invention. Guerbet esters can be formed from the esterification of a mono- or polyfunctional carboxylic acid with a Guerbet alcohol. Alternatively, the ester can be formed by reacting a Guerbet acid with a mono- or polyfunctional alcohol. For a review of Guerbet chemistry, see O'Lenick, A. J., Jr. 2001. Guerbet chemistry. Journal of Surfactants and Detergents 4: 311-315. Guerbet esters are commercially available from Lubrizol Advanced Materials, Inc. under product indications G-20, G-36, G-38 and G-66.
In addition to the preceding benefit agents, other benefit agents for hair and skin include, allantoin, urea, pyrrolidone carboxylic acid and its salts, hyaluronic acid and its salts, sorbic acid and its salts, amino acids (for example, lysine, arginine, cystine, guanidine), C ₃ -C ₆ polyhydroxy alcohols such as glycerin, propylene glycol, hexylene glycol, hexanotriol, ethoxydiglycol and sorbitol and the esters thereof, polyethylene glycols (for example, Polyox WSR-25, Polyox WSR-N- 60K and Polyox WSR-N-750, available from Dow Chemical), sugars and starches, sugar and starch derivatives (e.g., alkoxylated glucose), panthenols such as dl-panthenol, lactamide monoethanolamine, acetamide monoethanolamine and others and mixtures thereof.
Natural and synthetic waxes, oils, fatty acids and alcohols, as well as the other beneficial agents described above can be used in an amount ranging from about 0.1% to about 30% by weight in one aspect, from about from 0.5% to 25% by weight in another aspect, from about 3% to 20% by weight in an additional aspect and from 5% to about 10% by weight in an additional aspect, based on the total weight of the composition in which it is included.
Pharmaceutical and cosmeceutical assets
The compositions of the present invention can be formulated with a pharmaceutical and / or cosmeceutical active to release a desired effect. Examples of such active ingredients include, but are not limited to, caffeine, vitamin C, vitamin D, vitamin E, anti-stretch brand compounds, astringents (for example, alum, oatmeal, yarrow, witch hazel, laurel berry and isopropyl alcohol) , drainage compounds, depilatories (eg calcium and sodium hydroxide, calcium and sodium thioglycolate, or mixtures thereof), hair growth promoting compounds (eg, monoxidyl), nourishing compounds for the skin and hair, protective compounds skin and hair, self-tanning compounds (for example, mono- or polycarbonyl compounds such as, for example, isatin, alloxane, ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, tyrosine, tyrosine esters and dihydroxyacetone), UV absorbers (by example, methylexyl methoxy cinnamate, octinoxate, octisalate, oxybenzone), skin illuminators (eg kojic acid, hydroquinone, arbutin, fruital, vegetable extracts or plant, such as lemon peel extract, chamomile, green tea, blackberry paper extract and others, derivatives of ascorbyl acid, such as ascorbyl palmitate, ascorbyl stearate, ascorbyl magnesium phosphate and others), compounds lip augmentation, anti-aging, anti-cellulite and anti-acne compounds (eg acidic agents such as alpha-hydroxy acids (AHAs), beta-hydroxy acids (BHAs), alpha amino acids, alpha-keto acids (AKAs), acetic acid, azelaic acid and mixtures thereof, anti-inflammatory compounds (eg aspirin, ibuprofen and naproxen), analgesics (eg acetaminophen), antioxidant compounds, antiperspirants (eg aluminum halides, aluminum hydroxides) , aluminum sulfate, zirconium oxide (zirconyl), zirconium hydroxide (zirconyl) and mixtures or complexes thereof), deodorant compounds (for example, 2-amino-2-methyl-1-propanol (AMP), ammonium phenolsulfonate; benzalkonium chloride; benzethonium chloride, bromochlorophene, cetyltrimethylammonium bromide, cetyl pyridinium chloride, chlorophyllin-copper complex, chlorothymol, chloroxylenol, cloflucarban, dequalinium chloride, dichlorophene, dichloro-m-xylenol, dichlorohydrochloride, dihydrochloride , lauryl pyridinium chloride, methylbenzetone chloride, phenol, sodium bicarbonate, sodium phenolsulfonate, triclocarbon, triclosan, zinc phenolsulfonate, zinc ricinoleate and mixtures thereof) and suitable mixtures of any of the above.
Peaceful / Teenage Materials
Some formulations are often opacified by the perolescent materials deliberately incorporated in this to achieve an appearance similar to the cosmetically attractive pearl, known as perolescente. An opacifier is often included in a composition to mask an unwanted aesthetic property, such as to improve the color of a composition that is darkened due to the presence of a particular ingredient, or to mask the presence of the particular substance in the composition. Opacifiers can also be included in aqueous compositions to improve aesthetics and consumer acceptance of an otherwise aesthetically unpleasant composition. For example, an opacifier can give a teen-like appearance in a clear composition, thus communicating a creamy, smooth and consistent appearance to the consumer. People skilled in the art are aware of the problems faced by formulators consistently in preparing a stable adolescent formulation. A detailed debate is observed in the “Opacities and pearling agents in shampoo” by Hunting, Cosmetic and Toiletries, Vol. 96, pages 65-78 (July 1981), incorporated in this by reference.
The opacifying or perolescent material includes ethylene glycol monostearate, ethylene glycol distearate, ethylene glycol polystearate, stearic alcohol, mism coated with bismuth oxychloride, metal oxides coated with mica (eg titanium dioxide, chromium oxide, oxides iron), myristyl myristate, guanine, gloss (polyester or metallic) and mixtures of these. Other adolescent materials can be seen in U.S. Patent No. 4,654,207, U.S. Patent No. 5,019,376 and U.S. Patent No. 5,384,114, which are incorporated herein by reference.
In one aspect, the amount of the perolescent material can be used in amounts ranging from about 0.05% to about 10% by weight, and from about 0.1% to about 3% by weight in another aspect, based on the total weight of the stabilized composition.
Opacifiers
An opacifier is an ingredient included in a composition to reduce or eliminate the clear or transparent appearance of the composition. In addition, an opacifier can also provide other advantageous properties in a composition, such as emulsification, suspension and thickness properties.
An opacifier can be selected from a number of different chemical classes including inorganic compounds, for example, various aluminum and magnesium salts and organic compounds, similar to fatty alcohols, fatty esters and various polymers and copolymers. A representative listing of opacifiers is noted in CTFA Cosmetic Ingredient Handbook, J. Nikitakis, ed., The Cosmetic, Toiletry and Fragrance Association, Inc., Washington, D.C., 1988, on page 75.
Particulars
Other numerous substantially insoluble compounds and components that require stabilization and / or suspension can be used in the compositions of the invention. Examples of such other insoluble compounds include pigments, scrubs and anti-dandruff agents.
Exemplary pigments are metallic compounds or semi-metallic compounds and can be used in ionic, non-ionic or oxidized form. The pigments can be in this form individually or in the mixture or as the individual mixed oxides or mixtures thereof, including mixtures of mixed oxides and pure oxides. Examples are titanium oxides (eg TiO ₂ ), zinc oxides (eg ZnO), aluminum oxides (eg A1 ₂ O ₃ ), iron oxides (eg Fe ₂ O ₃ ), manganese oxides (eg MnO), silicon oxides (eg SiO ₂ ), silicates, cerium oxide, zirconium oxides (eg ZrO ₂ ), barium sulfate (BaSO ₄ ) and mixtures thereof.
Other examples of pigments include D&C Red N °. 30, D&C Red N °. 36, D&C Orange No. 17, Green 3 Lake, Ext. Yellow 7 Lake, Orange 4 Lake, Red 28 Lake, the calcium lakes of D&C Red Nos. 7, 11,31 and 34, the barium lake of D&C Red N °. 12, the strontium lake D&C Red N °. 13, the aluminum lakes of FD&C Yellow No. 5 and No. 6, the aluminum lakes of FD&C No. 40, the aluminum lakes of D&C Red N °. 21, 22, 27 and 28, the aluminum lakes of FD&C Blue No. 1, the aluminum lakes of D&C Orange No. 5, the aluminum lakes of D&C Yellow No. 10; the zirconium lake of D&C Red N °. 33, iron oxides, color changing thermochromic pigments with temperature, calcium carbonate, aluminum hydroxide, calcium sulfate, kaolin, ferric ammonium ferrocyanide, magnesium carbonate, carmine, barium sulfate, mica, bismuth oxychloride, zinc stearate, manganese violet, chromium oxide, titanium dioxide nanoparticles, barium oxide, ultramarine blue, bismuth citrate, hydroxyapatite, zirconium silicate, carbon black particles and others. Other suitable particulates include various optical modifiers as described in U.S. 7,202,199.
Numerous cosmetically useful particle exfoliating agents are known in the art and the selection and amount is determined by the desired exfoliating effect from the use of the composition, as recognized by that person skilled in cosmetic techniques. Useful sphaalizing agents include, but are not limited to, natural abrasives, inorganic abrasives, synthetic polymers and the like and mixtures thereof. Representative exfoliants include, but are not limited to, crushed or powdered pumice, stone, zeolites, nut shells (eg almond, pecan, walnut, coconut and others), nut flours (eg almond and others), fruit kernels (eg apricot, avocado, olive, peach and others), husks, seed and grain (eg, oat bran, corn bran, rice bran, grape seed, kaki seed , wheat, jojoba seed, luffa seed, rose seed and others), vegetable substance (eg tea tree leaves, corn cob, fruit fibers, kelp, luffa sponge, microcrystalline cellulose and others) , bivalve mollusk shells (oyster shells and others), calcium carbonate, dicalcium pyrophosphate, chalk, silica, kaolin clay, silicic acid, aluminum oxide, stanic oxide, sea salt (for example, Dead Sea Salt) , talc, sugars (for example, table, brown and others), polyethylene, polystyrene ene, microcrystalline polyamides (nylon), microcrystalline polyesters, polycarbonates and stainless steel fibers. The preceding scrubs can be used in the form of granules, powders, flours and fibers.
Other generally insoluble components suitable for use in the present compositions include clay, expandable clay, laponite, gas bubbles, liposomes, micro-spheres, cosmetic beads and flakes. Cosmetic pearls, flakes and capsules can be included in a composition for their aesthetic appearance or they can function as micro and macroencapsulants for the release of agents beneficial to the skin and hair. Exemplary pearl components include, but are not limited to, agar pearls, alginate pearls, jojoba pearls, gelatin pearls, Styrofoam ™ pearls, polyacrylate, polymethyl methacrylate (PMMA), polyethylene pearls, Unispheres ™ cosmetic pearls and Unipearls ™ (Induchem USA, Inc., New York, NY), Lipocapsule ™, Liposphere ™ and Lipopearl ™ microscapsules (Lipo Technologies Inc., Vandalia, OH) and Confetti II ™ dermal release flakes (United-Guardian, Inc., Hauppauge, NY).
Any suitable anti-dandruff agent can be used in the compositions of the present invention. Exemplary anti-dandruff agents include, but are not limited to, sulfur, zinc pyrithione, zinc omadine, miconazole nitrate, selenium sulfide, pyroctone olamine, N, N-bis (2hydroxyethyl) undeconamide, Cade oil, pine tar, Allium strain extract, Picea abies and Undecileneth-6 extract and others and mixtures of these.
In one aspect of the invention, the amount of the particulate component can vary from about 0.1% to about 10% by weight based on the total weight of the composition.
Botanicals
Optionally, the compositions of the invention may contain botanical material extracts. The extracted botanical materials can include any water-soluble or oil-soluble material extracted from the particular plant, fruit, nut or seed. In one aspect of the invention, the botanical active antiperspirant compositions are present in an amount ranging from about 0.1% to about 10% by weight, from about 0.5% to about 8% in weight in another aspect, and from about 1% to about 5% by weight in an additional aspect, based on the total weight of the composition.
Suitable botanical agents may include, for example, Echinacea extracts (for example, sp. Angustifolia, purpurea, pallida), yucca glauca, willow herb, basil leaves, Turkish oregano, carrot root, grapefruit, fennel seed, rosemary, turmeric, thyme, blueberry, peppers, blackberry, spirulina, black currant fruit, tea leaves, such as, for example, Chinese tea, black tea (eg var. Flowery Orange Pekoe, Golden Flowery Orange Pekoe, Fine Tippy Golden Flowery Orange Pekoe), green tea (eg var. Japanese, Green Darjeeling), oolong tea, coffee seed, dandelion root, date fruit, gingko leaf, green tea , hawthorn berry, licorice, sage, strawberry, sweet pea, tomato, vanilla fruit, comfrey, amica, centella asiatica, lily, chestnut, ivy, magnolia, oats, pansy, skull flower, sea buckthorn, nettle white and witch hazel. Botanical extracts include, for example, chlorogenic acid, glutathione, glycyrrhizin, neoesperidin, quercetin, rutin, morine, myricetin, absinthe and chamomile.
Cationic polymers and compounds
Cationic polymers and compounds are useful in the compositions of the invention. That person skilled in the art will recognize that many of these cationic agents serve multiple functions. Typically, these agents are useful as conditioners (e.g., hair and skin), antistatic agents, fabric softeners and as antimicrobial agents. Cationic polymers can be synthetically derived or obtained by modifying natural polymers such as cationically modified and polygalactomannan polysaccharides.
Representative cationic polymers include, but are not limited to, homopolymers and copolymers derived from radically free polymerizable methacrylic ester or acrylic or amide monomers. Copolymers may contain one or more units of derivatives of acrylamides, methacrylamides, diacetone acrylamides, methacrylic or acrylic acids or their esters, vinillactam such as vinyl pyrrolidone or vinyl caprolactam and vinyl esters. Exemplary polymers include copolymers of acrylamide and ethyl dimethyl starch methacrylate quaternized with dimethyl sulfate or with an alkyl halide; copolymers of acrylamide and methacryloyl oxymethyl of trimethyl ammonium; the copolymer of acrylamide and methacryloyl oxyethyl trimethyl ammonium methosulfate; vinyl pyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers, optionally quaternized, such as products sold under the name GAFQUAT ™ by International Specialty Products Inc., Wayne,
NJ; dimethyl amino ethyl methacrylate / vinyl caprolactam / vinyl pyrrolidone terpolymers, such as the product sold under the trade name GAFFIX ™ VC 713 by International Specialty Products Inc .; the vinyl pyrrolidone / methacrylamidopropyl dimethylamine copolymer, branded under the trade name STYLEZE ™ CC 10 available from International Specialty Products Inc. and the vinyl pyrrolidone / dimethyl amino propyl methacrylamide copolymers quartzized as the product sold under the trade name GAFQUAT ™ HS 100 by International Specialty Products, Inc.
The cationic agents can also be selected from the four-year polymers of vinyl pyrrolidone and vinyl imidazole such as products sold under the trade name Luviquat® (product name FC 370 and FC 550) by BASF. Other cationic polymer agents that can be used in the compositions of the invention include polyalkyleneimines such as polyethyleneimines, polymers containing vinyl pyridine or vinyl pyridinium units, condensates of polyamines and epichlorohydrins, quartenary polysaccharides, quartenary polyurethanes, quartenary silicones and chenine derivatives.
Other non-limiting examples of quartenary ammonium compounds (monomeric or polymeric) useful as cationic agents in the present invention include acetamidopropyl trimonium chloride, beenamidopropyl dimethylamine, beenamidopropyl ethylldimonium sulphate, beentrimonium chloride, cetethyl morpholium chloride, cetrethyl chloride cocoamidopropyl ethyldimonium, dichethyldimonychloride, dimethicone hydroxypropyl trimonium chloride, hydroxyethyl chloride beenamidopropyl dimonium, Quatémio-22, Quatémio-26, Quatémio-27, Quatémio-52, Quatémio-63, Quatémio-63, Quatémio-70, Quatémio-70 , Quatémium-76, hydrolyzed collagen, PEG-2-chloride chloride, PPG-9 diethylmonium chloride, PPG-25 diethylmonium chloride, PPG-40 diethylmonium chloride, stearalkonium chloride, ethyl dimonium stearamidopropyl ethosulfate, hydrolyzed wheat protein by hydroxypropyl steardinium, collagen hydrolyzed by hydroxypropyl steardinium, clo wheat germamidopropalconium straight, wheat germamidopropyl ethyldimony ethosulfate, Polyquatemium-1, Polyquatemium-4, Polyquatemium-6, Polyquatemium-7,
Polyquaternium-10,
Polyquaternium-22,
Polyquaternium-32,
Polyquaternium-3 9,
Polyquaternium-52,
Polyquaternium-61,
Polyquaternium-69,
Polyquaternium-73,
Polyquaternium-78,
Polyquaternium-82,
Polyquaternium-11,
Polyquaternium-24,
Polyquaternium-33,
Polyquémio-44, Polyquémio-53, Polyquémio-64, Polyquémio-70, Polyquémio-74, Polyquémio-79, Polyquémio-84,
Polyquaternium-15,
Polyquaternium-28,
Polyquaternium-3 5,
Polyquaternium-46,
Polyquaternium-55,
Polyquaternium-65,
Polyquaternium-71,
Polyquaternium-76,
Polyquaternium-80,
Polyquaternium-85,
Polyquaternium-16,
Polyquaternium-29,
Polyquaternium-3 7,
Polyquaternium-47,
Polyquaternium-59,
Polyquaternium-67,
Polyquaternium-72,
Polyquaternium-77,
Polyquaternium-81,
Polyquaternium-87, PEG-2-cocomonium chloride and mixtures of these.
Other useful cationic polymers include cationic polygalactomannans (for example, quartzized derivatives of guar and cassia, such as hydroxypropyl trimonium chloride, hydroxypropyl trimonium chloride and hydroxypropyl trimonium chloride).
Cationic agents useful in the invention also include, but are not limited to, proteins and protein derivatives, amines, protonated amine oxides, betaines and the like. Protein derivatives include casein hydrolyzed by hydroxypropyl cocodimony, collagen hydrolyzed by hydroxypropyl cocodimony, hair keratin hydrolyzed by hydroxypropyl cocodimony, rice protein hydrolyzed by hydroxypropyl cocodimony, silk hydrolyzed by hydroxypropyl cocodimonium, soy protein hydrolyzed by hydroxypropyl cocodimony wheat protein hydrolyzed by hydroxypropyl cocodimony, silk amino acids hydrolyzed by hydroxypropyl cocodimony, collagen hydrolyzed by hydroxypropyl trimonium, keratin hydrolyzed by hydroxypropyl trimonium, silk hydrolyzed by hydroxypropyl trimonium, rice bran hydrolyzed by hydroxypropyl trimonium, hydrolyzed soy protein hydrolyzed by hydroxypropyl vegetable by hydroxypropyl trimonium, hydrolyzed wheat protein by hydroxypropyl trimonium, hydrolyzed wheat protein, hydrolyzed sweet almond protein, hydrolyzed rice protein, prot hydrolyzed soy protein, hydrolyzed milk protein, hydrolyzed vegetable protein, hydrolyzed keratin, hydrolyzed collagen, hydrolyzed wheat gluten, hydrolyzed potassium cocoyl collagen, hydroxypropyl trimonium hydrolyzed collagen, hydrolyzed hydroxypropyl milk protein, hydrolyzed wheat protein hydroxypropyl lauryldimony, hydrolyzed hydroxypropyl lauryldimone collagen, keratin amino acids, collagen amino acids, soyethyldimony ethosulfate, morpholium soyethyl ethosulfate and others.
Monomeric quartenary ammonium compounds include, for example, alkylbenzyldimethyl ammonium salts, betaines, heterocyclic ammonium salts and tetraalkylammonium salts. Long-chain alkylbenzyldimethyl ammonium salts (fats) are used as conditioners, as antistatic agents and as fabric softeners, discussed in more detail below.
Non-limiting examples of alkylbenzyldimethylammonium salts include, but are not limited to, stearalkonium chloride, benzalkonium chloride, Quatémium-63, olealconium chloride, didecyldimony chloride and others. Betaine compounds include alkylamidopropyl betaines and alkylamidopropyl hydroxysultaines, as described in the formulas previously presented above. Non-limiting examples of alkyl betaine compounds include oleyl betaine, coco-betaine, cocoamidopropyl betaine, coco-hydroxy sultaine, coco / oleamidopropyl betaine, coco-sultaine, cocoamidopropylhydroxy sultaine and sodium lauramidopropyl hydroxifostain.
Heterocyclic ammonium salts include alkylethyl morpholium ethosulfates, isostearyl ethylimidonium ethosulfate and alkylpyridinium chlorides. Non-limiting examples of heterocyclic ammonium salts include, but are not limited to, cetylpyridinium chloride, isostearylethylimidonium ethosulfate and others.
Non-limiting examples of tetraalkylammonium salts include cocamidopropyl ethyldimonium ethosulfate, hydroxyethyl cetyldimonium chloride, Quatémio-18 and hydrolyzed hydroxypropyl cocodimonium protein, such as hair keratin and others.
A number of quarterly ammonium compounds are used as antistatic agents for conditioning and tissue care. These include alkylated long chain alkylated ammonium compounds such as dialkyldimethyl quarterly ammonium compounds, quarterly imidazoline compounds, quarterly amidoamine compounds, dialkyl ester quat derivatives of dihydroxypropyl ammonium compounds; dialkyl ester quat derivatives of ammonium methyltriethanol compounds, amide amine ester compounds and dimethyldiethanol ammonium chloride diester quat derivatives, as described in the article summary by Whalley, Fabric Conditioning Agents, HAPPI, pp. 55-58 (February 1995), incorporated herein by reference.
Non-limiting examples of dialkyldimethyl quartenary ammonium compounds, include N, N-dioleyl-N, Ndimethylammonium chloride, N, N-diseboyl-N, N-dimethylammonium ethosulfate, N, N-di (hydrogenated-seboyl chloride) ) -N, N-dimethylammonium and others. Non-limiting examples of quarterly imidazoline compounds include 1-Nmethyl-3-N-seboamidoethylimidazolium chloride, 3-methyl-lseboylamidoethyl-2-seboylimidazoline and others. Non-limiting examples of quartenary amidoamine compounds include salts of N-alkyl-N-methylN, N-bis (2-seboamidoethyl) ammonium where the alkyl group can be methyl ethyl hydroxyethyl and the like. Non-limiting examples of quat derivatives of the dialkyl ester of dihydroxypropyl ammonium compounds include chloride
1.2- diseboyloxy-3-N, N, N-trimethylammonium propane, chloride
1.2- dicanoloyloxy-3-N, N, N-trimethylammonium propane and others.
In addition, other types of long chain alkylated quartenary ammonium compounds (for example natural oil and derived fatty acid) are suitable fabric softening agents. In one aspect, long chain alkyl groups are derived from tallow, canola oil, or from palm oil, however, other alkyl groups derived from soybean oil and coconut oil, for example, are also suitable, as they are groups of lauryl, oleyl, ricinoleyl, stearyl and palmitile. Representative compounds include, but are not limited to, N, N-di (alkyloxyethyl) -N, Ndimethylammonium salts such as N, N-di (seboyloxyethyl) -N, N-dimethylammonium chloride, N, N-di chloride (canolyloxyethyl) -N, N-dimethylammonium and others; salts of N, N-di (alkyloxyethyl) -N-methyl-N- (2-hydroxyethyl) ammonium such as N, N-di (seboyloxyethyl) -N-methyl-N- (2-hydroxyethyl) ammonium chloride N, N-di (canolyloxyethyl) -N-methyl-N- (2-hydroxyethyl) ammonium and others; salts of N, Ndi (2-alkyloxy-2-oxoethyl) -N, N-dimethylammonium, such as N, N-di (2seboyloxy-2-oxoethyl) chloride -N, N-dimethylammonium, N, N- chloride di (2-canolyloxy-2oxoethyl) -N, N-dimethylammonium and others; salts of N, N-di (2alkyloxyethylcarbonyloxyethyl) -N, N-dimethylammonium, such as N, Ndi (2-seboyloxyethylcarbonyloxyethyl) -N, N-dimethylammonium, N, N-di (2canolyloxyethylcarbonyloxyethyl) -N, -dimethylammonium and others; N- (2-alkanoyloxy-2-ethyl) -N- (2-alkyloxy-2-oxoethyl) -N, N-dimethyl ammonium salts, such as N- (2-seboyloxy-2-ethyl) -N chloride - (2-seboyloxy-2-oxoethyl) -N, Ndimethyl ammonium, N- (2-canoloyloxy-2-ethyl) chloride -N- (2-canolyloxy-2oxoethyl) -N, N-dimethyl ammonium and others; N, N, N-tri (alkyloxyethyl) -N-methyl ammonium salts, such as N, N, N-tri (seboyloxyethyl) -N-methylammonium chloride, N, N, N-tri (canolyloxyethyl) chloride - N-methylammonium and others; salts of N- (2-alkyloxy-2oxoethyl) -N-alkyl-N, N-dimethyl ammonium, such as N- (2-seboyloxy-2 oxoethyl) -N-seboyl-N, N-dimethyl ammonium chloride of N- (2-canolyloxy-2-oxoethyl) N-canolyl-N, N-dimethyl ammonium and others.
In another aspect, compounds of quaternary ammonium fabric softeners include N-methyl-N, N-bis (seboamidoethyl) N- (2-hydroxyethyl) ammonium and N-methyl-N, N-bis (hydrogenatedbetoamidoethyl) methylsulfate -N- (2-hydroxyethyl) ammonium, dialkyl esterquat derivatives of methyltriethanol ammonium salts such as bis (acyloxyethyl) hydroxyethylmethylammonium and other methosulfate esters and N, Ndi (seboyloxyethyl) -N, N-dimethylammonium chloride, where the chains tallow are at least partially unsaturated.
In a further aspect, fabric softening agents include well-known dialkyldimethyl ammonium salts such as N, N-diseboyl-N, N-dimethyl ammonium sulfate, N, N-di (hydrogenatedeboyl) -N, N-dimethyl ammonium chloride , N, N-distearyl-N, N-dimethyl ammonium chloride, N, N-dibeenyl-N, N-dimethylammonium chloride, N, N-di (hydrogenated talow) -N, N-dimethyl ammonium chloride of N, N-dzseboyl-N, N-dimethyl ammonium, N, N-distearyl-N chloride, N-dimethyl ammonium, N, N-dibeenyl-N chloride, N-dimethyl ammonium and N, N- chloride dimethyl-N-stearyl-N-benzylammonium.
The compounds of the preceding nionomeric or polymeric quartenary ammonium salts can have any anionic group such as a counterion, for example, chloride, bromide, methosulfate (i.e., methylsulfate), acetate, format, sulfate, nitrate and others.
For fabric softener applications, any suitable quaternary ammonium agent can be used in combination with the shell-core polymer in stages of surfactant compositions of the present invention. For esters-containing fabric softening agents, the pH of the compositions can influence the stability of fabric softening agents, especially under prolonged storage conditions. The pH as defined in the present context, is measured in the clear compositions at about 20 ° C. In one aspect, the pH of the composition is less than about 6. In another aspect, the pH is in the range of about 2 to about 5, and about 2.5 to about 3.5 in an additional aspect.
In one aspect, cationic agents can be used in amounts ranging from about 0.05% to 15% by weight, from about 0.1% to about 10% by weight in another aspect, and from about 0 , 5% to about 3% by weight in an additional aspect, based on the weight of the final composition, but not limited to it.
Preservatives
In one aspect, any preservative suitable for use in personal care, home care, health care and institutional and industrial products can be used in the compositions of the present invention. Suitable preservatives include bicyclic oxazolidine, methyl paraben, propyl paraben, ethyl paraben, butyl paraben, benzyltriazole, DMDM hydantoin (also known as 1,3-dimethyl-5,5dimethyl hydantoin), imidazolidinyl urethane, phenoxyzone , benzoisothiazolinone, triclosan and suitable polyquaternium compounds disclosed above (for example, Polyquaternium-1).
In another aspect, acid-based preservatives are useful in the compositions of the present invention. The use of preservative with acid bases facilitates the formulation of products in the low pH range. The pH decrease of the formulation inherently provides an inhospitable environment for microbial development. In addition, formulation at low pH intensifies the effectiveness of the acid-based preservative and produces a personal care product that maintains an acid pH balance on the skin as discussed by Wiechers, 2008, supra. Surprisingly, it has been found that the shell-core polymers in stages of the invention can be used to thicken the surfactant conditions formulated at low pH while maintaining excellent clarity and rheological properties such as viscosity and yield value.
Any acid based preservative that is useful in personal care, home care, health care and institutional and industrial care products can be used in the compositions of the present invention. In one aspect the acid preservative is a compound of the carboxylic acid represented by the formula: R ⁵³ C (O) OH, where R ⁵³ represents hydrogen, a saturated and unsaturated hydrocarbonyl group containing 1 to 8 carbon atoms or Cô-Ciq aryl . In another aspect, R ⁵³ is selected from a hydrogen, a C _r C ₈ alkyl group, a C ₂ -C ₈ alkenyl group, or phenyl. Exemplary acids are, but are not limited to, formic acid, acetic acid, propionic acid, sorbic acid, caprylic acid and benzoic acid and mixtures thereof.
In another aspect, suitable acids include, but are not limited to, oxalic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, maleic acid, fumaric acid, lactic acid, glycolic acid, tartronic acid malic acid, tartaric acid, gluconic acid , citric acid, ascorbic acid, salicylic acid, phthalic acid, mandelic acid, benzyl acid and mixtures thereof.
The salts of the preceding acids are also useful as they retain effectiveness at low pH values. Suitable salts include the alkali metal (e.g., sodium, potassium, calcium) and ammonium acid salts listed above.
The acid-based preservative and / or its salts can be used alone or in combination with non-acidic preservatives typically used in personal care, home care, health care and institutional and industrial care products.
Preservatives typically comprise from about 0.01% to about 3.0% by weight in one aspect, from about 0.1% to about 1% by weight in another aspect, and from about 0.3% to about 1% by weight in an additional aspect, of the total weight of the personal care compositions of the present invention.
Auxiliary rheology modifier
In another aspect of the invention, the compositions of the invention can be formulated in combination with one or more auxiliary rheology modifiers and thickeners. Suitable rheology modifiers and thickeners include synthetic and semi-synthetic rheology modifiers. Exemplary synthetic rheology modifiers include acrylic based polymers and copolymers. A class of acrylic-based rheology modifiers are the alkaline soluble and dilatable alkaline functional carboxyl thickeners (ASTs) produced by the free radical polymerization of acrylic acid alone or in combination with other ethylenically unsaturated monomers. Polymers can be synthesized by precipitation / solvent as well as emulsion polymerization techniques. Exemplary synthetic rheology modifiers of this class include homopolymers of acrylic acid or methacrylic acid and polymerized copolymers of one or more acrylic acid monomers, substituted acrylic acid and C1-C30 alkyl salts and acrylic acid and substituted acrylic acid. As defined herein, the substituted acrylic acid contains a substituent positioned on the alpha and / or beta carbon atom of the molecule, wherein in one aspect the substituent is independently selected from C1-4 alkyl, -CN and -COOH. Optionally, other ethylenically unsaturated monomers such as, for example, styrene, vinyl acetate, ethylene, butadiene, acrylonitrile, as well as mixtures of these can be copolymerized in the structure. The preceding polymers are optionally cross-linked by a monomer that contains two or more moieties that contain ethylenic unsaturation. In one aspect, the crosslinker is selected from a polyalkenyl polyether of a polyhydric alcohol containing at least two alkenyl ether groups per molecule. Other exemplary crosslinkers are selected from sucrose allyl ethers and pentaerythritol allyl ethers and mixtures thereof. These polymers are not fully described in U.S. Patent No. 5,087,445; U.S. Patent No. 4,509,949 and U.S. Patent No. 2,798,053 incorporated into this by reference.
In one aspect, the AST rheology modifier or thickener is a crosslinked homopolymer polymerized from acrylic acid or methacrylic acid and is generally referred to under the INCI Name of Carbomer. Commercially available carbomers include Carbopol® polymers 934, 940, 941, 956, 980 and 996 available from Lubrizol Advanced Materials, Inc. In an additional aspect, the rheology modifier is selected from a crosslinked polymer copolymer of a first monomer selected from one or more acrylic acid monomers, substituted acrylic acid, acrylic acid salts and substituted acrylic acid salts and a second monomer selected from one or more C10-C30 alkyl acrylate esters of acrylic acid or methacrylic acid. In one aspect, monomers can be polymerized in the presence of a steric stabilizer as disclosed in U.S. Patent No. 5,288,814, which is incorporated herein by reference. Some of the preceding polymers are indicated under the INCI Nomenclature as C10-C30 acrylate / acrylate cross polymer and are commercially available under the trade names Carbopol® 1342 and 1382, Carbopol® Ultrez 20 and 21, Carbopol® ETD 2020 and Pemulen® TR -1 and TR-2 by Lubrizol Advanced Materials, Inc.
In another aspect, the auxiliary rheology modifier may be a linear, cross-linked poly (vinyl amide / acrylic acid) copolymer as disclosed in U.S. Patent No. 7,205,271, the disclosure of which is incorporated herein by reference.
Another class of optional synthetic rheology modifiers and thickeners suitable for use in the present invention include the hydrophobically modified ASTs, commonly referred to as alkaline soluble and alkaline swelling modified polymers (HASE). Typical HASE polymers are polymerized polymers with pH sensitive free radical addition or hydrophilic monomers (for example, acrylic 5 and / or methacrylic acid), hydrophobic monomers (for example, C 1 -C ₃₀ alkyl esters of acrylic acid and / or methacrylic acid, acrylonitrile, styrene), an “associated monomer” and an optional crosslinking monomer. The associative monomer comprises a final ethylenically unsaturated polymerizable group, the medium non-ionic hydrophilic session which is terminated by a final hydrophobic group. The non-ionic hydrophilic middle section comprises a polyoxyalkylene group, for example, polyethylene oxides, polypropylene oxide, or mixtures of polyethylene oxide / polypropylene oxide segments. The final hydrophobic end group is typically a C ₈ -C ₄ o aliphatic moiety. Exemplary aliphatic moieties are selected from branched and linear alkyl substituents, linear and branched alkenyl substituents, carbocyclic substituents, aryl substituents, aralkyl substituents, arylalkyl substituents and arylalkyl substituents. In one aspect, associated monomers can be prepared by condensing (for example, esterification or etherification) of a polyethoxylated and / or polypropoxylated aliphatic alcohol (typically containing a branched or unbranched C ₈ -C ₄₀ aliphatic moiety) with an ethylenically unsaturated monomer containing a carboxylic acid group (for example, acrylic acid, methacrylic acid), an unsaturated cyclic anhydride monomer (for example, maleic anhydride, itaconic anhydride, 25 citraconic anhydride), a monoethylenically unsaturated monoisocyanate (for example, α, α isocyanate -dimethyl-m-isopropenyl benzyl) or an ethylenically unsaturated monomer containing a hydroxyl group (for example, vinyl alcohol, allyl alcohol). Polyethoxylated and / or polypropoxylated aliphatic alcohols are adducts of ethylene oxide and / or propylene oxide of a monoalcohol containing the C ₈ -C ₄₀ aliphatic portion. Non-limiting examples of alcohols containing the C ₈ -C4o aliphatic portion are caprylic alcohol, isooctyl alcohol (2-ethyl hexanol), pelargonic alcohol (1-nonanol), decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cetyl alcohol, alcohol cetearyl (mixture of Ci6-Ci ₈ monoalcohols), stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, arylidyl alcohol, beenyl alcohol, lignoceryl alcohol, ceryl alcohol, montanyl alcohol, melissil, lacceryl alcohol, gedyl alcohol and alkyl substituted phenols C ₂ -C ₂ o (eg, nonyl phenol) and others.
Exemplary HASE polymers are disclosed in U.S. Patent No. 3,657,175; 4,384,096; 4,464,524; 4,801,671 and 5,292,843, which are incorporated herein by reference. In addition, an extensive summary of HASE polymers is noted in Gregory D. Shay, Chapter 25, AlkaliSwellable and Alkali-Soluble Thickener Technology A Review, Polymers in Aqueous Media - Performance Through Association, Advances in Chemistry Series 223, J. Edward Glass ( ed.), ACS, pp. 457-494, Division Polymeric Materials, Washington, DC (1989), the relevant findings of which are incorporated into this by reference. The commercially available HASE polymers are sold under the trade names, Aculyn® 22 (INCI name: Acrylate copolymer / Steareth-20 methacrylate), Aculyn® 44 (INCI name: PEG-150 / Decyl alcohol / SMDI copolymer), Aculyn 46 ® (INCI name: PEG-150 / Stearyl alcohol / SMDI copolymer) and Aculyn® 88 (INCI name: Acrylate cross-polymer / Steareth-20 methacrylate) by Rohm & Haas and Novethix ™ L-10 (INCI name: Copolymer of acrylates / Beheneth-25 methacrylate) from Lubrizol Advanced Materials, Inc.
In another embodiment, acid-swellable associative polymers can be used with the hydrophobically modified cationic polymers of the present invention. Such polymers generally have associative and cationic characteristics. These polymers are polymerized polymers with free radical addition of a monomer mixture that comprises a hydrophilic monomer substituted by an acid sensitive amino (e.g., alkyl dialkylamino (meth) acrylates or (meth) acrylamides), an associative monomer (defined above) ), a lower alkyl (meth) acrylate or other radically free polymerizable comonomers selected from hydroxyalkyl esters of (meth) acrylic acid, polyethylene glycol vinyl and / or allyl ethers, polyethylene glycol vinyl and / or allyl ethers, vinyl ethers and / or polyethylene glycol / polypropylene glycol allylics, (meth) acrylic acid polyethylene glycol esters, (meth) acrylic acid polypropylene glycol esters, polyethylene glycol / (meth) acrylic acid polypropylene glycol esters and combinations thereof. These polymers can be optionally cross-linked. For acid sensitive it is meant that the amino substituent becomes cationic at low pH values, typically ranging from about 0.5 to about 6.5. Exemplary acid-swellable associative polymers are commercially available under the trade name Structure® Plus (INCI name: Acrylates / Aminoacrylates / C10-C30 PEG-20 alkyl itaconate) from Akzo Nobel and Carbopol® Aqua CC (INCI name: Cross polymer of polyacrylates-1) from Lubrizol Advanced Materials, Inc. in one aspect acid 0 swellable polymer is a copolymer of one or more C1 -C5 alkyl esters of (meth) acrylic acid, alkyl methacrylate _Ci-C6 dialkylamino C1 C4, PEG / PPG-30/5 allyl ether, C10-C30 PEG 20-25 alkyl ether methacrylate, C ₂ -C ₆ alkyl hydroxy methacrylate cross-linked with diethylene glycol methacrylate. Other useful acid-swellable associative polymers are disclosed in US Patent No. 7,378,479, the disclosure of which is incorporated herein by reference.
Hydrophobically modified alkoxylated methyl glycoside, such as, for example, PEG-120 methyl glucose dioleate, PEG-120 methyl glucose trioleate and PEG-20 methyl glucose sesquiestearate, available from Lubrizol Advanced Materials, Inc., under trade names, Glucamate® DOE-120, Glucamate ™ LT and Glucamate ™ SSE-20, respectively, are also suitable as rheology aid modifiers.
Polysaccharides obtained from tree and shrub exudate, such as gum arabic, gum gahatti and gum tragacanth, as well as pectin; seaweed extracts, such as alginates and carrageenans (for example, lambda, cover, iota, and salts thereof); algae extracts, such as agar; microbial polysaccharides, such as xanthan, gelan and welana; cellulose ethers, such as ethylhexylethylcellulose, hydroxybutylmethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose and hydroxypropylcellulose; polygalactomannans, such as fenugreek gum, cassia gum, alfarobeira bean gum, tara gum and guar gum; starches, such as corn starch, tapioca starch, rice starch, wheat starch, potato starch and sorghum starch can also be used in the compositions therein as suitable auxiliary thickeners and rheology modifiers.
Rheology aid modifiers, when used, can be used alone or in combination and are typically used in an amount ranging from about 0.1% by weight to about 8% by weight in one aspect, from about 0.3 % by weight to about 3% by weight in another aspect, and from about 0.5% by weight to about 2% by weight in appearance, based on the total weight of the personal care compositions of the present invention.
Emulsifier
Emulsifiers when used in the compositions of the present invention include, but are not limited to, C1-C2 ₂ fatty alcohols, C12-C22 alkoxylated alcohols, C12-C22 fatty acids, C12-C22 alkoxylated fatty acids (the alkoxylated each having 10 to 80 units of ethylene oxide, propylene oxide and combinations of ethylene oxide / propylene oxide present in the molecule), APGs C ₈ -C ₂ 2, ethoxylated sterols (where the number of units in the ethylene oxide bands is 2 to about 150), partial polyglycerol esters, partial polyol esters and esters having 2 to 6 carbon atoms, partial polyglycerol esters and organosiloxanes and combinations thereof.
The emulsifiers APG ₂ -C ₈ alkyl C 2 are prepared by the reduction of glucose or an oligosaccharide with primary fatty alcohols having 8 to 22 carbon atoms and an alkyl group comprising C ₆ -C ₈ glicosidicalmente connected to a residue whose oligoglicosídeo average degree of oligomerization is 1 to 2. In addition to the APGs described as surfactants above, APGs are available under the trade name Plantacare® (Cognis Corporation, Cincinnati, OH). Exemplary alkyl glycosides and oligoglycosides are selected from octyl glycoside, decyl glycoside, lauryl glycoside, palmityl glycoside, isostearyl glycoside, stearyl glycoside, arachidyl glycoside and beenyl glycoside and mixtures thereof.
Emulsifiers based on partial polyol esters and esters having 2 to 6 carbon atoms are condensed with linear saturated and unsaturated fatty acids having 12 to 30 carbon atoms are, for example, glycerol or ethylene glycol monoesters and diesters or propylene glycol monoesters with saturated and unsaturated C12-C30 fatty acids.
Exemplary fatty alcohols and fatty acids, as well as their alkoxylates, partial polyglycerol esters, as well as organosiloxanes are described above.
Chelating Agents
Chelating agents can be used to stabilize the personal care, home care, health care and institutional care compositions of the invention against the harmful effects of metal ions. When used, suitable chelating agents include EDTA (tetraacid
100 ethyl acetate diamine) and salts thereof such as disodium EDTA, citric acid and salts thereof, cyclodextrins and the like and mixtures thereof. Such suitable chelators typically comprise from about 0.001 wt% to about 3 wt%, preferably about 0.01 wt% to about 2 wt% and more preferably about 0.01 wt% to about 1 wt. % by weight of the total weight of the personal care compositions of the present invention.
Auxiliary solvents and thinners
The personal care, home care, health care and institutional care compositions containing the thickener surfactant compositions of the present invention in combination with one or more of the preceding active ingredients and / or with one or more additives and / or adjuvants, conventionally or popularly included in the personal care, health care, home care and institutional care products discussed above can be prepared as water-based or water-free formulations and formulations containing auxiliary solvents and / or water-miscible diluents, but are not limited to this . The commonly used useful solvents are typically liquid, such as water (deionized, distilled or purified), alcohols, fatty alcohols, polyols and the like and mixtures thereof. Auxiliary hydrophobic or non-aqueous solvents are commonly used in products substantially free of water, such as nail polish, aerosol-propelling sprays, or for specific functions, such as removing oily stains, tallow, makeup, or to dissolve pigments, fragrances and others, or are incorporated into the oil phase of an emulsion. Non-limiting examples of auxiliary solvents, other than water, include straight and branched alcohols, such as ethanol, propanol, isopropanol, hexanol and others; aromatic alcohols, such as benzyl alcohol, cyclohexanol and others; fatty alcohol Ci ₂ -C ₃ o saturated, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, beenyl alcohol and others. Non-limiting examples of polyols include polyhydroxy alcohols, such as
101 glycerine, propylene glycol, butylene glycol, hexylene glycol, _C2-C4 alkoxylated alcohols and alkoxylated C ₂ -C ₄ polyols, such as ethoxylated ethers, propoxylated and butoxylated alcohols, diols and polyols having about 2 to about 30 carbon atoms it about 40 units of alkoxy, polypropylene glycol, polybutylene glycol and others. Non-limiting examples of auxiliary solvents or non-aqueous diluents include silicones and silicone derivatives, such as cyclomethicone and others, ketones such as acetone and methyl ethyl ketone; natural and synthetic oils and waxes, such as vegetable oils, plant oils, animal oils, essential oils, mineral oils, C ₇ -C ₄ o isoparaffins, alkyl carboxylic esters, such as ethyl acetate, amyl acetate, ethyl lactate and others, jojoba oil, shark liver oil and others. Some of the preceding auxiliary solvents or non-aqueous diluents can also be conditioners and emulsifiers.
Propellants
Where desired, any known aerosol propellant can be used to release the personal care, home care, health care and institutional care compositions containing stages of shell-core polymers of the present invention in combination with one or more of the preceding active ingredients and / or with one or more additives and / or adjuvants, conventionally or popularly included in such products. Exemplary propellants include, but are not limited to, lower melting hydrocarbons such as straight or branched C3-C6 hydrocarbons. Exemplary hydrocarbon propellants include propane, butane, isobutene and mixtures thereof. Other suitable propellants include ethers, such as, dimethyl ether, hydrofluorocarbons, such as, 1,1-difluoroethane and compressed gases, such as carbon dioxide and air.
In one aspect, these compositions may contain from about 0.1% to about 60% by weight of a propellant, and from about 0.5 to about 35% by weight in another aspect, based on the total weight of the propellant. composition.
102
The shell-core polymers in stages of the invention can be used in any composition of personal care, home care, health care and institutional and industrial care requiring modification of aesthetic and / or rheological properties. In a given composition or application, the shell-core polymers in stages of this invention may, but need not, serve more than one function, such as a thickener, stabilizer, emulsifier, film former, loader or deposition aid and others . The amount of shell-core polymer in stages that can be used depends on the purpose for which they are included in the formulation and can be determined by the person skilled in the formulation techniques. Thus, as long as the functional and psychochemical properties of a desired product are achieved, a total amount of shell-core polymer in stages on a weight basis of the total composition, typically can vary in the range of about 0.01% to about from 25% by weight in one aspect, from about 0.1% to about 15% by weight in another aspect, from about 0.5% to about 10% by weight in an additional aspect, and from about 1% to about 5% by weight still in an additional aspect, but not limited to this.
The composition of personal care, home care, health care and institutional and industrial care comprising shell-core polymers in stages of the invention can be packaged and dispensed from containers such as vases, tubes, sprayers, wipes, roll- ons, sticks and others, without limitation. There is no limitation as to the form of the product in which these polymers can be incorporated, as long as the purpose for which the product is used is achieved. For example, health care and personal care products containing the shell-core polymers in stages can be applied to the skin, hair, scalp and nails, without limitation in the form of gels, sprayers (liquid or foams), emulsions (creams, lotions) , pastes), liquids (rinses, shampoos), bars, ointments, suppositories and others.
103
In a personal care aspect, the cascanucleus polymers in stages of this invention are suitable for the preparation of personal care (cosmetics, toiletries, cosmeceuticals), including, without limitation, hair care products (shampoos, shampoo combination, such as two-in-one conditioning shampoos), post-rinsing shampoos, fixing and styling maintenance agents (including fixing aids, such as gels and sprays, treatment aids such as ointments, conditioners, permes, relaxers, hair straightening products and others), skin care products (facial, body, hands, scalp and feet), such as creams, lotions and cleaning products, anti-acne products, anti-aging products (exfoliating, keratolytic, anti-cellulite, anti-wrinkle and others) , skin protectors (sun care products, such as sunscreens, sun blockers, barrier creams, oils, silicones and others), skin color (brighteners, illuminators, tanning accelerators without sun and others), hair dyes (hair pigments, rinse hair dyes, illuminators, brighteners and others), pigmented skin dyes (body and face make-up, foundation creams, mask) , rouge, lip products and others) bath products and displays (body cleansers, body wash, display gel, liquid soap, soap bars, syndet bars, liquid conditioning bath oil, bubble bath, bath powders and others), nail care products (polishers, fortifying polish removers, lengtheners, strengtheners, cuticle removers, softness and others).
Toiletries and beauty aids containing the polymers of the invention may include, without limitation, hair removal products (shaving creams and lotions, epilators, aftershave skin conditioners and others), hair growth promoting products, deodorants and anti- perspirants, oral care products (mouth, teeth, gums), such as mouthwash, toothpaste, such as toothpaste, tooth powder, polishers
104 teeth, teeth whiteners, breath fresheners, denture adhesives and others; facial and body hair bleaches and others. Other beauty aids that can contain the shell-core polymers in stages of the invention and include, without limitation, sunless tanning applications containing artificial tanning accelerators, such as dihydroxyacetone (DHA), tyrosine, tyrosine esters and others: depigmentation of the skin, brighteners and illuminators, formulations containing such active ingredients as kojic acid, hydroquinone, arbutin, fruital, plant or vegetable extracts, (lemon peel extract, chamomile, green tea, blackberry paper extract and others), derivatives ascorbyl acid ascorbyl acid, ascorbyl stearate, ascorbyl magnesium phosphate and others).
The shell-core polymers in stages of the invention are useful as suspending agents for particulates making them suitable for dermal cleaning products containing particulates, insoluble, microabrasive and abrasive beneficial agents and combinations thereof. Dermal cleansing products include shampoos, body washes, gel displays, shower gels, masks and skin cleansers.
Body wash
In one aspect, a personal care composition in which the polymer of this invention is useful is a body wash. The typical components of body wash, in addition to thickened polymer cascanucleus in stage and water are: at least one surfactant; a sufficient pH adjusting agent (base and / or acid) to bind a pH of about 3.5 to about 7.5 in one aspect, from about 4.0 to about 6.5 in another aspect, and from about 5.0 to about 6.0 in an additional aspect and optional ingredients selected from the adjuvants, beneficial agents and additives discussed above and mixtures of these, including beneficial agents selected from silicones, teenagers, vitamins, oils, fragrances, pigments, preservatives including acids, botanicals, exfoliating agents, insoluble gas bubbles,
105 liposomes, micro-beads, cosmetic pearls and flakes. In one respect, ο surfactant is an anionic surfactant. In another aspect, the surfactant is a mixture of an anionic surfactant and an amphoteric surfactant, in the optional combination with a non-ionic surfactant. In another aspect, the surfactant is a mixture of an anionic surfactant and an amphoteric surfactant, in optional combination with a cationic and / or non-ionic surfactant. In one aspect, the anionic surfactant can be present in an amount ranging from about 5% to about 40% by weight, from about 6% to about 30% by weight in another aspect and from 8% to about 25% by weight in an additional aspect, based on the total weight of the body wash composition. When mixtures of amphoteric and anionic surfactants are used, the ratio of anionic surfactant: amphoteric surfactant can vary from about 1: 1 to about 15: 1 in one aspect, from about 1.5: 1 to about 10: 1 in another aspect, from about 2.25: 1 to about 9: 1 in an additional aspect, and from about 4.5: 1 to about 7: 1 yet in an additional aspect. The amount of acrylic polymer mixtures can vary from about 0.5% to about 5% by weight in one aspect, from about 1% to about 3% by weight in another aspect, and from about 1.5 % to about 2.5% by weight in an additional aspect, based on the total weight of the body wash composition.
The body wash embodiments of the invention can be formulated as moisturizing body wash, anti-bacterial body wash, shower gels, gel displays, liquid hand soaps, body scrubbers; bubble baths, facial scrubbers, foot scrubbers and others.
Shampoo compositions
In one aspect, a personal care composition in which the polymer of this invention is useful is a shampoo. The typical components of the shampoo, in addition to the stage-core polymer thickeners and water, are: at least one surfactant; a sufficient pH adjustment agent
106 (base and / or acid) to bind a pH of about 3.0 to about 7.5 in one aspect, from about 3.5 to about 6.0 in another aspect, and about 4, 0 to about 5.5 in an additional aspect and optional ingredients selected from the adjuvants, beneficial agents and additives discussed above and mixtures thereof, including beneficial agents selected from conditioning agents (for example, silicones and / or cationic conditioning agents; size silicones) particles and / or larger), perolescent agents, vitamins, oils, fragrances, pigments, preservatives including acids, botanicals and insoluble gas bubbles, liposomes and cosmetic pearls and flakes and anti-dandruff agents and mixtures thereof. In one aspect, the surfactant is an anionic surfactant. In another aspect, the surfactant is a mixture of an anionic surfactant and an amphoteric surfactant, in optional combination with a cationic and / or non-ionic surfactant. In one aspect, the anionic surfactant can be present in an amount ranging from about 5% to about 40% by weight, from about 6% to about 30% by weight in another aspect and from 8% to about 25% by weight in an additional aspect, based on the total weight of the shampoo composition. When mixtures of amphoteric and anionic surfactants are used, the ratio of anionic surfactant to amphoteric surfactant can vary from about 1: 1 to about 10: 1 in one aspect, from about 2.25: 1 to about 9: 1 in another aspect, and from about 4.5: 1 to about 7: 1 in an additional aspect. The amount of shell-core polymer in stages can vary from about 0.5% to about 5% by weight in one aspect, from about 1% to about 3% by weight in another aspect, and from about 1 , 5% to about 2.5% by weight in an additional aspect, based on the total weight of the shampoo composition.
Embodiments of the inventive shampoos can be formulated as 2 in 1 shampoos, baby shampoos, conditioner shampoos, body shampoos, humidified shampoos, temporary hair toning shampoos, 3 in 1 shampoos, dandruff shampoos, shampoos
107 hair toner, acid shampoo (neutralizing), medicated shampoos and salicylic acid shampoos and others.
Cleaners based on liquid fatty acid soap
In one aspect, a personal care composition in which the polymer of this invention is useful is a cleanser based on fatty acid soap. The typical components of a fatty acid based on soap cleaner, in addition to stage-core polymer thickeners are: at least one fatty acid salt; an optional surfactant or mixture of surfactants; a sufficient pH adjusting agent (base and / or acid) to bind a pH above 7 in one aspect, from about 7.5 to about 14 in another aspect, from about 8 to about 12 in yet another aspect, and from about 8.5 to about 10 in an additional aspect and optional ingredients selected from the adjuvants, beneficial agents and additives discussed above and mixtures of these, including beneficial agents selected from silicones, humectants, perolescent agents, vitamins, oils, fragrances, pigments, preservatives, botanicals, anti-dandruff agents, exfoliating agents, insoluble gas bubbles, liposomes, micro-spheres, cosmetic pearls and flakes.
In one aspect, fatty acid soaps are selected from at least one fatty acid salt (for example, sodium, potassium, ammonium) containing from about 8 to about 22 carbon atoms. In another aspect of the invention the liquid soap composition contains at least one fatty acid salt containing from about 12 to about 18 carbon atoms. The fatty acids used in soaps can be saturated and unsaturated and can be derived from synthetic sources, as well as from saponification and natural fats and oils by an appropriate base (for example, sodium, potassium and ammonium hydroxide). Exemplary saturated fatty acids include, but are not limited to, octanoic, decanoic, lauric, myristic, pentadecanoic, palmitic, marginal, steric, isosteric, nonadecanoic, arachidic, behenic and others and mixtures thereof. Unsaturated fatty acids
108 specimens include, but are not limited to, salts (eg sodium, potassium, ammonium) of myristoleic, palmitoleic, oleic, linoleic, linolenic and others and mixtures thereof. Fatty acids can be derived from animal fat such as tallow or from vegetable oil such as coconut oil, red oil, palm grain oil, palm oil, cottonseed oil, olive oil, soy oil , peanut oil, corn oil and mixtures of these. The amount of fatty acid soap that can be used in the liquid cleaning compositions of this embodiment ranges from about 1% to about 50% by weight in one aspect, from about 10% to about 35% by weight in another aspect, and from about 12% to 25% by weight in a further aspect of the invention, based on the weight of the total composition.
An optional anionic surfactant can be present in the soap composition in an amount ranging from about 1% to about 25% by weight in one aspect, from about 5% to about 20% by weight in another aspect and 8 % to about 15% by weight in an additional aspect, based on the weight of the total weight of the soap composition. Mixtures of amphoteric and anionic surfactants can be used. The ratio of anionic surfactant to amphoteric surfactant can vary from about 1: 1 to about 10: 1 in one aspect, from about 2.25: 1 to about 9: 1 in another aspect, and from about 4, 5: 1 to about 7: 1 in an additional aspect.
In the preceding soap embodiments of the invention, the amount of shell-core polymer in stages can vary from about 0.5% to about 5% by weight in one aspect, from about 1% to about 3% by weight. weight in another aspect, and from about 1.5% to about 2.5% by weight in an additional aspect, based on the total weight of the soap composition.
The liquid fatty acid soap based on the embodiments of the inventive cleaners can be formulated as body washes, shower gels, gel displays, liquid hand soaps, body scrubbers; bubble baths, facial scrubbers and scrubbers
109 feet, 2 in 1 shampoos, baby shampoos, conditioner shampoos, body shampoos, humidified shampoos, temporary hair toning shampoos, 3 in 1 shampoos, anti-dandruff shampoos, hair toning shampoos, (neutralizing) shampoo, anti-dandruff shampoos and salicylic acid shampoos and others.
Fasteners
The term "fixative" as applied to polymers encompasses the properties of film formation, adhesion, or coating deposited on the surface on which the polymer is applied. The terms “hair style, hair adjustment and hair fixer as commonly understood in hair care techniques and as used in it, refer to hair fixing agents which are hair fixers and which are topically applied to the hair to contribute actively to facilitate the styling and / or maintenance of fixed hair and to maintain the ability to restylate fixed hair. Since hair fixation compositions include hair styling, hair fixer and hair-dressing products that are conventionally applied to hair (wet or dry) in the form of gels, rinses, emulsions (water in oil, oil in water) or multiphase), such as lotions and creams, ointments, sprayers (pressurized or non-pressurized), spritzes, foams, such as mousses, shampoos, solids, such as sticks, semi-solids and others, or are applied from an auxiliary of hair fixing having the hair fixing composition impregnated in or coated in it, to conduct the hair fixing agent in contact with the hair for some period until it is removed, such as by washing.
In one embodiment, hair-fixing compositions encompass products that comprise at least one staged nucleus polymer of the present invention and a fixing polymer as a hair-fixing agent. The product can be applied to the hair (wet or dry) before, during or after setting the hair in the form (shorter or
110 straight) desired, without limitation as the shape of the product. The shell-core polymers in stages of the present invention are useful in combination with commercially available auxiliary hair fixing polymers, such as nonionic hair fixing polymers. cationic and amphoteric, cationic conditioning polymers and combinations of these.
Hair styling polymers and conventional hair fixers include natural gums and synthetic resins and polymers. The list of commercially available hair conditioner and hair fixing polymers can be readily seen in INCI Dictionary, supplier websites and commercial literature. See, for example, Encyclopedia Polymer published in Cosmetics & Toiletries®, 117 (12), December 2002 (Allured Publishing Corporation, Carol Stream, IL), the relevant findings that are incorporated into this by reference.
Suitable commercially available fixing polymers include, polyacrylates, polyvinyls, polyesters, polyurethanes, polyamides, polyquaterniums, modified cellulose, starches and mixtures thereof. These polymers can be nonionic, anionic, cationic and amphoteric in nature and include without limitation one or more copolymers of vinyl acetate / polyoxyethylene crotonic acid, copolymers of vinyl acetate of crotonic acid, copolymers of vinyl methacrylate, monoalkyl polyester esters (methyl vinyl ether (PVM) / maleic acid (MA)), such as, for example, PVM / MA copolymer ethyl butyl and isopropyl esters, acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers and poly (methacrylic acid / acrylamidomethyl propane sulfonic acid), acrylate copolymers, octylacrylamide / Acrylates / butylaminoethyl copolymer, Acrylates / octylacrylamide, vinyl acetate (VA) / polyvinyl acetate (N) / polyotonate copolymer / polycrylates / crotonates vinyl acetamide), poly (N-vinyl
111 formamide), modified corn starch, sodium polystyrene sulfonate, such as, for example, Polyquaternium-4, Polyquaternium-11,
Polyquaternium-28,
Polyquaternium-37,
Polyquaternium-47, polyether-1, of 1, Polyquaternium-29,, Polyquaternium-39,, Polyquaternium-55, polyurethanes, lauryl,
Polyquaternium-32,
Polyquaternium-44,
Polyquatemium-69, Polyquatemic acid copolymer copolymer such Polyquatemium-24,
Polyquémius-34, Polyquémius-46,
Polyquaternium-87,
VA / Acrylates / adipic methacrylate / dimethylaminohydroxypropyl diethylene AMP / Acrylates, methacrylol ethyl betaine copolymer / Acrylates, polyvinylpyrrolidone (PVP), vinyl pyrrolidone copolymer (VP) / dimethylaminoethyl vinyl acetate / dimethylmethyl Videol, Copolymer, copolymer VP / dimethylaminoethylmethacrylate, VP / de acrylates (DMAPA),
DMAPA, Copolymer of
Copolymer Copolymer VP / DMAPA acrylates, vinyl caprolactam copolymer / VP / dimethylaminoethyl methacrylate, VA copolymer / butyl maleate / sobomila copolymer, VA / crotonates copolymer, Acrylate / acrylate copolymer, acrylate / acrylate copolymer / vinyl propionate, PV polymers / vinyl acetate / vinyl propionate, VA / crotonates, VP copolymer / vinyl acetate, VP copolymer / acrylates, VA / crotonic acid / vinyl propionate, Acrylates / acrylamide, Acrylates / octylacrylamide, Acrylates / hydroxyacrylates copolymer, Acrylates / hydroxyester acrylates copolymer, Acrylates methacrylate / stereth-20 copolymer, tert-butyl acrylate copolymer / acrylic acid, diglycol / cyclohexanethyltate / isoalkylate / isoalkyl copolymer / isoaldehyde / isoalpha / isoalate / sulphate / isoalpha. of butyl and isobomyl acrylate copolymer, VA tertpolymers / alkylmaleate / N-substituted acrylamide ester, vinyl caprolactam terpolymer / VP / methacrylamidopropyl trimethylammonium chloride, methacrylate salt / acrylates / amine copolymer, polyvinylcaprolactam,
112 hydroxypropyl guar, poly sulfonic acid (methacrylic acid / acrylamidomethyl propane (AMPSA), ethylene carboxamide (EC) / AMPSA / methacrylic acid (MAA), polyurethane / acrylate copolymers / trimethyl hydroxypropyl guar, Acrylate copolymer, cross-polymer acrylates, AMP-Acrylates / allyl methacrylate copolymer, polyacrylate-14, polyacrylate cross-polymer-2, Acrylates oxide methacrylate / Lauryl acrylate / Stearyl acrylate / ethylamine, methyl methacrylate / methylacrylate betaines / polyurethane / acrylates copolymers, chitosan pyrrolidone salt carboxylic acid, chitosan glycolate, cationic polygalactomannans, such as, for example, quartzized guar derivatives, such as, for example, hydroxypropyl trimonium chloride and trimer hydroxypropyl guar chloride and quartzized derivatives of cassia, such as, for example, hydroxypropyl trimonium cassia chloride. Suitable fasteners are disclosed in U.S. Patent No. 7,205,271, the disclosure of which is incorporated herein by reference.
In one embodiment, an exemplary hair care composition comprises a stage-core polymer of the present invention in a fixative polymer in effective amounts to provide the hair care composition of a property, such as a hair fixative property. , a hair conditioning property, a viscous property (thickness, rheology modification), or a combination thereof. Optionally, the hair care composition can include one or more of an auxiliary hair conditioning agent, an auxiliary rheology modifying agent, solvents, propellants and a combination thereof.
The fixative polymer typically comprises about 0.01% to about 25% by weight in one aspect, from about 0.1% to about 10% by weight in another aspect and about 0.2% to about 5 % by weight in an additional aspect, of the total weight of the fixing composition.
Cosmeceuticals
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In a cosmeceutical aspect, the peel-core polymers in stages can be used as a thickener for active skin treatment lotions and creams containing, as active ingredients, acidic anti-aging, anti-cellulite and anti-acne agents, carboxylic acid hydroxy, such as alpha-hydroxy acid (AHA), beta-hydroxy acid (BHA), alpha-amino acid, alpha-keto acids (AKAs) and mixtures thereof. In one aspect, AHAs may include, but are not limited to, lactic acid, glycolic acid, acid fruits, such as malic acid, citric acid, tartaric acid, extracts of natural compounds containing AHA, such as apple extract, apricot extract and others, honey extract, 2-hydroxyoctanoic acid, glycolic acid (dihydroxypropionic acid), tartronic acid (hydroxypropanedioic acid), gluconic acid, mandelic acid, benzyl acid, azelaic acid, alpha lipoic acid, salicylic acid, AHA salts and derivatives, such such as arginine glycolate, ammonium glycolate, sodium glycolate, arginine lactate, ammonium lactate, sodium lactate, alpha-hydroxybutyric acid, alpha-hydroxyisobutyric acid, alpha-hydroxyisocaproic acid, alpha-hydroxyisovaleric acid, atrolactic acid and others. BHAs can include, but are not limited to, 3-hydroxy propanoic acid, beta-hydroxybutyric acid, beta-phenyl lactic acid, beta-phenylpyruvic acid and others. Alpha-amino acids include, but are not limited to, alpha-amino dicarboxylic acids, such as aspartic acid, glutamic acid and mixtures thereof, sometimes used in combination with fruit acid. AKAs includes pyruvic acid. In some anti-aging compositions, the acidic active agent can be retinoic acid, a halocarboxylic acid, such as trichloroacetic acid, an acidic antioxidant, such as ascorbic acid (vitamin C), a mineral acid, phytic acid, lysophosphatidic acid and others. Some acidic anti-acne actives, for example, may include salicylic acid, derivatives of salicylic acid, such as 5-octanoylsalicylic acid, retinoic acid and its derivatives and benzoic acid.
114
A debate on the use and formulation of active skin care compositions is in COSMETICS & TOILETRIES, C&T Ingredient Resource Series, “4HAs & Cellulite Products How They Work, published 1995 and Cosmeceutics”, published 1998, both available from Allured Publishing Corporation, incorporated in this by reference. Compositions containing the ascorbic acid acidified alpha-amino acid are described in U.S. No. 6,197,317 BI and a cosmeceutical preparation using these acids in a skin care, anti-aging regime is sold under the trade name, AFAs, by Excel Cosmeceutics (Bloomfield Hills, MI). The term AFA, as described in the supplier’s trade literature, was coined by the developer to describe the amino acid / vitamin C combination as Fruit of amino acids and as the acronym by Amino acid Filaggrin based Antioxidants.
Health care
The Health Care embodiments in which the present polymers can be included are medical products, such as topical and non-topical pharmaceuticals and devices. In the pharmaceutical formulation, a polymer embodiment of the invention can be used as a thickener and / or lubricant in such products as syrups, creams, ointments, gels, pastes, ointments, tablets, gel capsules, purgative fluids (enemas, emetic, colonic and others), suppositories, anti-fungal foams, eye products (ophthalmic products, such as eye drops, artificial tears, glaucoma medication release medications, contact lens cleaners and others), hearing products (softeners) wax, wax removers, ear drops of otitis medication and others), nasal products (drops, ointments, sprays and others) and wound care (liquid bandages, wound linings, antibiotic creams, ointments and others), without limitation to these.
Other forms of health care related to
115 foot care products, such as callous removers and keratolytic corn, foot humidification, medicated foot products such as anti-fungal athlete's foot ointments, gels, sprayers and others, as well as antifungal, anti-yeast and anti creams -bacterial, gels, spray and ointments.
In addition, the polymers present can be included in topical, transdermal and non-topical pharmaceutical applications and devices such as thickeners, expansion aids, suspending agents and film-forming agents in protective skin sprays, creams, lotions, gels and sticks for formulation insect repellents, itch-relieving agents, antiseptic agents, disinfectants, sunscreens, sunscreens, skin tighteners and toning agents and in wart removal compositions and others.
In another pharmaceutical aspect, the polymers of the invention can be used in the manufacture of pharmaceutical dosage forms (for example tablets, caplets, capsules and others) for the controlled and targeted release of pharmacologically active ingredients and drugs for the stomach and gout. These can be used as pharmaceutical excipients such as binders, enteric coatings, film-forming and controlled release agents. These can be used alone or in combination with another controlled release and / or enteric polymers known in pharmaceutical techniques.
This invention is illustrated by the following examples which are for the purpose of the illustration only and are not considered to limit the scope of the invention or the way in which it can be practiced. Unless otherwise specifically indicated, parts and percentages are given by weight.
Methods
Determination of molecular weight
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The numbers of the average molecular weights referenced in this are measured by GPC using a high temperature instrument PL-GPC 220 GPC manufactured by Polymer Laboratories (Varian, Inc.). Approximately 0.02 g of polymer sample is dissolved in 5 ml of dimethyl acetamide (DMAc), containing 250 ppm of butylated hydroxytoluene (BHT) and 0.05 molar NaNO ₃ . The test sample solution is gently stirred for about two hours and filtered by passing the sample solution through 0.45 pm of available PTFE Disc Filter. The chromatographic conditions are: Mobile phase: DMAc, with 250 ppm BHT and 0.05 m NaNO3, 70 ° C, 1.0 ml / min. Sample size: 100 μΐ of Column Series: PLgel (Guard + 2 x mixed-A), all 10 pm, in series. Waters Empower Pro LC / GPC software is used to analyze the results and to calculate M _n of the core and the polymer shell components of the invention.
Viscosity
The Brookfield rotary axis method (all viscosity measurements reported here are conducted by the Brookfield method whether or not mentioned): Viscosity measurements are calculated in mPa s, using a Brookfield rotary axis viscometer, Model RVT (Brookfield Engineering Laboratories, Inc.), at around 20 revolutions per minute (rpm), at an ambient temperature of about 20 to 25 ° C (hereinafter referred to as viscosity). Shaft sizes are selected according to the manufacturer's standard operating recommendations. In general, shaft sizes are selected as follows:
117
Shaft sizeNo. Viscosity range (mPas) 1 1-50 2 500- 1,000 3 1,000-5,000 4 5,000-10,000 5 10,000-20,000 6 20,000 - 50,000 7 > 50,000
Shaft size recommendations are for illustrative purposes only. The technician of ordinary skill in the art will select an appropriate shaft size for the system to be measured.
Yield value
Yield value, also referred to as yield voltage, is defined as the initial resistance to flow under tension. This is measured by the Yield Value Extrapolation Method (BYV) using a Brookfield viscometer (Model RVT) at an ambient temperature of about 20 to 25 ° C. The Brookfield viscometer is used to measure the torque required to rotate an axis through a liquid sample at speeds of 0.5 to 100 rpm. Multiplying the torque reading by the appropriate axis and speed constant gives the apparent viscosity. Yield value is the extrapolation of measured values at a cut-off rate of zero. BYV is calculated by the following equation:
BYV, dyn / cm ² = (η _α ι - ηα2) / 100 where η _α ι e = apparent viscosities obtained at two different axis speeds (0.5 rpm and 1.0 rpm, respectively). These techniques and the usefulness of yield value measurement are explained in Technical Data Sheet Number 244 (Revision: 5/98) by Noveon Consumer Specialties of Lubrizol Advanced Materials, Inc., incorporated herein by reference.
Clarity
The clarity (turbidity) of a composition is determined by
118
Nephelometric Turbidity Units (NTU) using a nephelometric turbidity meter (Mircro 100 Turbidimeter, HF Scientific, Inc.) at an ambient temperature of about 20 to 25 ° C. Distilled water (NTU = 0) is used as a standard. Six drachma screw cap vials (70 mm x 25 mm) are filled almost to the top with the test sample and centrifuged at 100 rpm until the bubbles are removed. During centrifugation, each sample vial is cleaned with tissue paper to remove any stains prior to placement in the turbidity meter. The sample is placed on the turbidity meter and a reading is taken. Once the reading stabilizes the NTU value is recorded. The flask is given a quarter turn and another reading is made and recorded. This is repeated until four readings have been taken. The lowest of the four readings is reported as a turbidity value. Compositions having an NTU value of about 50 or greater were judged to be cloudy or cloudy.
Suspension stability test
Suspension test procedure: The ability of a polymeric system to suspend active and / or aesthetically pleasing insoluble oily and particulate materials is important from the fixed point of product effectiveness and appeal. A six-drachma flask (approximately 70 mm high x 25 mm in diameter) is filled to the 50 mm spot with a shower gel test formulation. Each sample bottle is centrifuged to remove any trapped air bubbles contained in the formulation. Cosmetic beads (eg, Lipopearl ™ gelatin capsules; average diameter 500 to 3000 microns) were weighed in the centrifuged sample (1.0% by weight based on the weight of the total composition) and shaken lightly with a wooden stick until they were evenly dispersed throughout the shower gel sample. The position of approximately 10 of the beads within each sample bottle is observed by drawing a circle around the pearl with a black marker pen on the outer glass surface of the bottle and
119 photographed to establish the initial position of the beads inside the gel. The bottles are placed in a 45 ° C oven to age for a period of 12 weeks. The pearl suspension properties of each sample are monitored on a daily basis. The suspension results are visually classified using a 3 to 0 scale where: 3 indicates no visible sedimentation / increase with respect to the initial pearl position in the gel;
indicates sedimentation / slight increase or less than approximately% drop / increase in distance relative to the initial pearl position in the gel; 1 indicates more than Va fall / increase a Vi fall / increase in distance relative to the initial position in the shower gel and 0 indicates more than V2 fall / increase in distance relative to the initial position of the pearl in the shower gel. A rating of 0 or 1 indicates that a sample has failed and a rating of 2 or 3 indicates that the sample has passed.
Ingredient Abbreviation and Trade Name List
The following ingredients are used in the examples of the present invention:
Monomers AA Acrylic acid ACE ACE ™ Hydroxyl acrylator monomer is the reaction product of acrylic acid with Cardura ™. Cardura is the glycidyl ester of VERSATIC ™ 10 acid, a highly branched saturated carboxylic acid containing 10 carbon atoms nBA n-Butyl Acrylate tBAM t-butyl acrylamide AND THE Ethylacrylate 2-EHA 2-Ethylexyl Acrylate HEMA Hydroxyethyl Methacrylate BAD Methyl Acrylate MAA Methacrylic acid NVP N-vinyl pyrrolidone STY Styrene TEGDMA Triethylene glycol Dimethacrylate (crosslinker) TMPDAE Trimethylolpropane diallyl ether (crosslinker) TMPTA Trimethylolpropane Triacrylate (crosslinker) VND Neodecanoate vinyl Components Aculyn ™ 38 INCI name: Acrylate / Vinyl Neodecanoate cross polymer (an emulsion copolymer of vinyl neodecanoate and one or more monomers of acrylic acid, methacrylic acid or one of its
120
Monomerssimple cross-linked esters with a trimethylolpropane or pentaerythritol allyl ether), Rohm and Haas Company Carbopol® Aqua SF-1 INCI name: Acrylate copolymers (an emulsion copolymer of two or more monomers consisting of acrylic acid, methacrylic acid or one of its simple esters), Lubrizol Advanced Materials, Inc. Ceteath-20 Ethoxylated cetyl alcohol-20 - 20 moles of ethylation Chembetaína ™ CAD Cocamidopropyl Betaine (amphoteric surfactant), Lubrizol Advanced Materials, Inc. Chembetaína ™ CGF Cocamidopropyl Betaine (amphoteric surfactant - glycine free), Lubrizol Advanced Materials, Inc. Chembetaína ™ LEC INCI name: Lauramidopropyl Betaine (amphoteric surfactant), Lubrizol Advanced Materials, Inc. Chemonic ™ SI-7 PEG-7 Glyceryl soyate (non-ionic surfactant), Lubrizol Advanced Materials, Inc. Chemoryl ™ SFB10SK INCI name: Disodium Laureth Sulfosucinate (e) Sodium Cocoyl Isethionate (e) Cocamidopropyl Betaine (combination of sulfate and amide-free surfactant), Lubrizol Advanced Materials, Inc. Chemoxide ™ CAW INCI name: Cocamidopropylamine oxide (amine oxide surfactant), Lubrizol Advanced Materials, Inc. Dow Coming® 2-8194 Silicone INCI name: Amodimethicone and Trideceth-12 and Cetrimonium chloride (microemulsion of amine-functional silicone polymers), Dow Coming Ethal SA-20 INCI name: Steareth-20, Ethox Chemicals, LLC Florabeads ™ Gypsy Rose INCI name: Jojoba Esters (exfoliating agent pigmented with Red 30 (e) Talc), International Flora Technologies, Ltd. Florabeads ™ Sonora Sand INCI name: Jojoba Esters (exfoliating agent pigmented with iron oxides, Red 30 (e) Talc, TiO ₂ , Yellow 5 Lake), International Flora Technologies, Ltd. Florasun® 90 INCI name: Helianthus Annuus (sunflower oil), International Flora Technologies, Ltd. Foamaster® DF-160L Mineral oil based defoamer, Cognis Corporation Geogard® Ultra INCI name: Gluconolatone (e) Sodium benzoate, (preservative), Lonza Inc Glucam ™ E-10 INCI name: Methyl Gluceth-10 (non-ionic surfactant / humectant), Lubrizol Advanced Materials, Inc. Hycar7 2671 Acrylic latex binder, Lubrizol Advanced Materials, Inc. Jaguar Excel INCI Name: Guar Hydroxypropyltrimony Chloride (cjuatemized guar gum), Rhodia Inc. Lebermuth No. 508001-30 Fragrance oil (fresh green apple), The Lebermuth Company, Inc. Lebermuth No. 903000-62 Fragrance oil (tangerine grapefruit), The Lebermuth Company, Inc. Lipopearl ™ 0091 Beads Pigmented cosmetic pearls of gelatin and Gum cellulose gum containing decyl tristearate, tridecyl trimellitate, chromium hydroxide green, Mica, titanium dioxide, tocopheryl acetate and vitamin E, Lipo Technologies Inc. Lipopearl ™ 0293 Pigmented cosmetic pearls of gelatin and cellulose gum
121
Monomers Beads containing Decyl Tristearate, Tridecyl Trimellitate, Neopentyl Glycol, Mica, Titanium Dioxide, Tocopheryl Acetate and Vitamin E, Lipo Technologies Inc. Liposphere ™ 0031 Pigmented cosmetic pearls containing personal care benefit agents (Dimethicone, Neopentyl glycol), Lipo Technologies Inc. Merquat® Plus Polyquatemium-39 (cationic conditioning polymer; an acrylic acid terpolymer, diallyl dimethyl ammonium chloride and acrylamide), Nalco Company NeoIone® 950 Methylisothiazolinone (preservative), Rohm and Haas Company N-Hance® 3000 INCI name: Guar Hydroxypropyltrimony chloride (quatemized guar gum), Ashland Inc. (Ashland Aquaion Functional Ingredients) Phenonip Combination of phenoxyethanol, methyl paraben, ethyl paraben, propyl paraben, butyl paraben and isobutyl paraben,(antibacterial), Clariant Corpoaration-Nipa Laboratories Printrite® 595 Acrylic latex binder, Lubrizol Advanced Materials, Inc. Rheocare ™ TTA INCI name: Acrylate copolymers (an emulsion copolymer of two or more monomers consisting of acrylic acid, methacrylic acid or one of its simple esters), Cognis Corporation Stereath-20 ethoxylated stearyl alcohol containing 20 moles of ethoxylation Sulfochem ™ ALS Ammonium Lauryl Sulfate (anionic surfactant), Lubrizol Advanced Materials, Inc. Sulfochem ™ AOS Sodium C14-15 olefin sulfonate (anionic surfactant), Lubrizol Advanced Materials, Inc. Sulfochem ™ ALS-K Ammonium lauryl sulfate (anionic surfactant preserved with Kathon® CG preservative from Rohm and Haas Company), Lubrizol Advanced Materials, Inc. Sulfochem ™ EA-3 ammonium sulfate lauryl ether - 3 moles of ethoxylation (anionic surfactant), Lubrizol Advanced Materials, Inc. Sulfochem ™ ES-2 CWK Sodium Sulphate lauryl ether - 2 moles of ethoxylation (anionic surfactant preserved with Kathon® CG preservative from Rohm and Haas Company), Lubrizol Advanced Materials, Inc. Sulfochem ES-2K Sodium Sulphate lauryl ether - 2 moles of ethoxylation (anionic surfactant preserved with Kathon® preservative CG from Rohm and Haas Company), Lubrizol Advanced Materials, Inc. Sulfochem ™ ES-70 Sodium sulfate lauryl ether - 2 moles of ethoxylation (anionic surfactant), Lubrizol Advanced Materials, Inc. Sulfochem ™ SLS Sodium lauryl sulfate (anionic surfactant), Lubrizol Advanced Materials, Inc. Tween 20 Polysorbate 20 (solubilizer), Croda Inc NTL2312 Unispheres INCI name: Mannitol (e) Cellulose (e) Hydroxypropyl Methylcellulose (pigmented with green chromium hydroxide and loaded with vitamin E), Induchem AG Versene ™ 220 Tetrasodium Ethylene diaminetetraacetate tetrahydrate (chelating agent), Dow Chemical
122
Monomers ______________________________________________________
Zema ™ Propanediol | 1,3-propanediol bio-based, DuPont, Tate & Lyle
Example 1 (Two-stage polymers)
In a first reactor equipped with a stirrer (feed) containing 68.6 grams of deionized water (DI) and 6.67 grams of sodium lauryl sulfate (30% active in water weight / weight), 130.4 grams of ethyl acrylate and 69 grams of methacrylic acid are added under a nitrogen atmosphere and mixed at 500 rpm to form a monomeric emulsion. To a stirrer equipped with a second reactor, 1.340 grams of deionized water and 3.17 grams of sodium lauryl sulfate (30% active in water weight / weight) are added. The contents of the second reactor are heated with mixing agitation (200 rpm) under an atmosphere of nitrogen. When the contents of the second reactor reach a temperature of approximately 84 ° C, 27.0 grams of ammonium persulfate solution (2.0% w / w aqueous solution) is injected into the heated surfactant solution. The monomeric emulsion of the feed reactor is gradually measured (9.37 g / min.) In the second reactor over a period of about 30 minutes at a reaction temperature maintained at approximately 85 ° C and allowed to react in a polymerization reaction of first stage to form linear acrylic polymer particles of ethyl acrylate / methacrylic acid copolymer. Following the initial addition of the monomeric emulsion to the second reactor, the monomeric emulsion of the second stage is prepared in the feed reactor by adding 274.4 grams of deionized water (DI), 26.67 grams of sodium lauryl sulfate (30% active in water weight / weight), 521 grams of ethyl acrylate, 276 grams of methacrylic acid and 3.0 grams of trimethylolpropane triacrylate. The monomeric emulsion containing the added trimethylolpropane triacrylate is then measured in the second reactor over a period of 120 minutes at a controlled rate (7.5 g / min.) At a temperature maintained at approximately 85 ° C and polymerized in the presence of the core polymer particles linear in a second stage reaction
123 to form a crosslinked polymer shell (in the core polymer particles) which comprises polymerised ethyl acrylate / methacrylic acid / trimethylolpropane triacrylate. With the emulsion monomer feed, 60 grams of ammonium persulfate (0.37% w / w aqueous solution) is simultaneously measured in the reaction mixture in the second reactor and the reaction temperature is maintained at around 85 ° C for an additional two and a half hours to complete the polymerization. The resulting polymeric emulsion product is cooled to room temperature, discharged from the reactor and recovered. The core and shell monomer components are shown in Tables 1 and IA, respectively, and the compositional information of polymer stage is shown in Table 1C.
Example 2
In a first reactor equipped with a stirrer (feed) containing 68.6 grams of deionized water (DI) and 6.67 grams of sodium lauryl sulfate (30% active in water weight / weight), 5.0 grams of Ethal SA 20 , 130.4 grams of ethyl acrylate and 69 grams of methacrylic acid are added under a nitrogen atmosphere and mixed at 500 rpm to form a monomeric emulsion. To a stirrer equipped with a second reactor, 1340 grams of deionized water and 3.17 grams of sodium lauryl sulfate (30% active in water weight / weight) are added. The contents of the second reactor are heated with mixing agitation (200 rpm) under an atmosphere of nitrogen. When the contents of the second reactor reach a temperature of approximately 84 ° C, 27.0 grams of an ammonium persulfate solution (2.0% w / w aqueous solution) is injected into the heated surfactant solution. The monomeric emulsion of the feed reactor is gradually measured at a feed rate of 1.87 g / min. in the second reactor in a period of 30 minutes at a reaction temperature maintained at approximately 85 ° C. The monomeric emulsion is reacted in a first stage polymerization to form particles of
124 linear core polymer of ethyl acrylate / methacrylic acid copolymer.
Following the initial addition of the monomeric emulsion to the second reactor, the monomeric emulsion of the second stage is prepared in the feed reactor by adding 274.4 grams of deionized water (DL), 26.67 grams of sodium lauryl sulfate (30% active in water weight / weight), 20.0 grams of Ethal SA 20, 521.6 grams of ethyl acrylate and 276 grams of methacrylic acid and 3.0 grams of trimethylolpropane triacrylate. The monomeric emulsion containing the added trimethylolpropane triacrylate is then measured in the second reactor over a period of 120 minutes at a controlled rate at a temperature maintained at approximately 85 ° C. With the monomeric second-stage emulsion feed, 0.37% persulfate solution ammonium (aqueous weight / weight solution) is simultaneously measured at 0.67 ml / minute in the reaction mixture in the second reactor. The monomeric emulsion containing the crosslinking monomer is polymerized in the presence of the linear core polymer particles in the second stage reaction to form a crosslinked polymer shell (in the core polymer particles). The reaction temperature is maintained at around 85 ° C for an additional two and a half hours to complete the polymerization. The resulting polymeric emulsion product is cooled to room temperature, discharged from the reactor and recovered. The core and shell monomer components are shown in Tables 1 and IA, respectively, and the compositional information of polymer stage is shown in Table 1C.
Example C-l (Comparative)
An acrylic based emulsion polymer having a crosslinked core and linear shell identified as Cl polymer is polymerized from the components shown in Table 1. The emulsion polymerization procedure presented in Example 2 was followed except that a crosslinked core polymer is synthesized in the first stage reaction followed by the synthesis of a linear polymeric shell. In this
125 example, 10% of the monomeric emulsion prepared in the feed reactor as shown in Example 2 is measured in the second reactor over a period of 6 minutes at a temperature maintained at 85 ° C and at a feed rate of 24 ml / min . 3.0 grams of a crosslinking monomer (TMPTA) is then added to the second reactor and mixed for 10 minutes to obtain homogeneous monomeric emulsion. 27.0 grams of ammonium persulfate (2.0% w / w aqueous solution) is injected into the reactor with stirring and polymerized to form a cross-linked core particle. After holding for 10 minutes, the second stage comonomer emulsion (except the crosslinker) as shown in Example 2 is measured at 10.54 g / ml in the second reactor over a period of 2 hours 2 at a temperature maintained at 85 ° C The second stage monomeric emulsion containing in the crosslinker is polymerized in the presence of the crosslinked polymer core particles. The shell polymer is devoid of a crosslinking component monomer. The resulting polymeric emulsion product is cooled to room temperature, discharged from the reactor and recovered.
Example C-2 (Comparative)
A linear acrylic-based emulsion polymer identified as the C-2 polymer is polymerized from the components shown in Table 1. The polymer is synthesized as shown in Example 2, except that the polymerization is completed following the reaction and first stage and recovered.
Example C-3 (Comparative)
An acrylic based crosslinked emulsion polymer designated as C-3 polymer is polymerized from the components shown in Table 1. The crosslinking monomer is TMPTA. The polymer is synthesized as shown in Example 2 except that the polymerization is terminated following the reaction and first stage and recovered.
Examples 2, 3, 3a, 3b, 5, 7 to 14 and 16 to 19 (Polymers of two
126 stages)
The two-stage core-shell polymers are polymerized from the components shown in Tables 1 and IA according to the procedures presented in Example 2. Compositional polymer stage information is shown in Table 1C.
The polymer of Example 9a is evaluated to determine its particle morphology. Spherical particles of core-shell morphology are observed by transmission electron microscopy (TEM) using ruthenium dyeing with an affinity for styrene. The polymer of Example 9A comprises a styrene-rich core stage with respect to the shell stage which is devoid of styrene. To obtain the TEM image, a small capillary tube is used to fractionate the sample (approximately 5 μΐ) of the polymeric emulsion into approximately 5 ml of D.I. water. Approximately 10 μΐ of the diluted sample is placed in a carbon-coated Formvar TEM grid. The grid is placed on a screen suspended in a vaporization solution of ruthenium and sodium hypochlorite (0.05 g of ruthenium added to 10 ml of sodium hypochlorite (6% aqueous weight / weight). The grid is contacted with the steam for approximately 1.5 hours, allowed to dry and the dyed polymer sample is observed under a Phillips CM12 transmission electron microscope at an acceleration voltage of 120 kV in 100K resolution, the TEM image is shown in Fig. 4.
In Fig. 4 are seen numerous particles that are available as agglomerated spheres having a dark central core region (stained with ruthenium - rich in styrene) surrounded by a region of gray outer shell (not stained - devoid of styrene).
Example 4 (Multi-stage polymerization)
A three-stage polymer is as follows: In a first reactor equipped with a stirrer (feed) containing 34.3 grams of deionized water (D.I.) and 3.3 grams of sodium lauryl sulfate (30% active in water
127 weight / weight), 2.5 grams of Ethal SA-20, 65.1 grams of ethyl acrylate and 34.5 grams of methacrylic acid are added under a nitrogen atmosphere and mixed at 500 rpm to form a monomeric emulsion. To a stirrer equipped with a second reactor, 600 grams of deionized water and 1.27 grams of sodium lauryl sulfate (30% active in water weight / weight) are added. The contents of the second reactor are heated with mixing agitation (200 rpm) under an atmosphere of nitrogen. When the contents of the second reactor reach a temperature of approximately 84 ° C, 11.0 grams of a solution of ammonium persulfate (2.0% w / w aqueous solution) is injected into the heated surfactant solution. The monomeric emulsion of the feed reactor (maintained at approximately 85 ° C) is gradually measured at a feed rate of 0.94 g / min. in the second reactor in a period of 15 minutes. The monomeric emulsion is reacted in a first stage polymerization to form linear acrylic polymer particles of ethyl acrylate / methacrylic acid copolymer.
Following the initial addition of the monomeric emulsion to the second reactor, a second stage monomeric emulsion is prepared in the feed reactor by adding 171.5 grams of deionized water (DL), 16.67 grams of sodium lauryl sulfate (30% active in water weight / weight), 12.5 grams of Ethal SA-20, 325.5 grams of ethyl acrylate and 172.5 grams of methacrylic acid and 1.50 grams of trimethylolpropane triacrylate (TMPTA). The monomeric emulsion containing the added TMPTA (maintained at approximately 85 ° C) is measured in the second reactor over a period of 75 minutes at a controlled rate. With the second stage emulsion monomeric feed, 0.25% ammonium persulfate solution (aqueous weight / weight solution) is simultaneously measured at 0.67 ml / minute in the reaction mixture contained in the second reactor. The second stage monomeric emulsion is polymerized in the presence of the linear core polymer particles in the second stage reaction to form a crosslinked polymer shell (in the
128 particles of core polymer).
Following the second stage polymerization reaction, a third stage monomeric emulsion is prepared in the feed reactor by adding 137.2 grams of deionized water (DL), 13.33 grams of sodium lauryl sulfate (30% active in water weight / weight), 10.0 grams of Ethal SA-20, 325.5 grams of ethyl acrylate, 260.4 grams of methacrylic acid and 1.60 grams of TMPTA. In a third stage reaction, the monomeric emulsion containing the highest TMPTA level (maintained at approximately 85 ° C) is measured in the second reactor over a period of 60 minutes at a constant feed rate. Along with the emulsion monomer feed, 0.25% ammonium persulfate solution (aqueous weight / weight solution) is simultaneously measured at 0.67 ml / minute in the reaction mixture. The monomeric emulsion is polymerized in the presence of the two-stage linear core particles / cross-linked shell polymer obtained in the second stage to form a second cross-linked polymeric shell (in the two-stage core-shell polymer particles) with an increased cross-linked gradient zone . The reaction temperature is maintained at around 85 ° C for an additional two and a half hours to complete the polymerization. The resulting polymeric emulsion product is cooled to room temperature, discharged from the reactor and recovered. The multi-stage monomeric components and quantities are identified in Tables 1, ΙΑ, 1B, respectively, and compositional polymer stage information is shown in Table 1C.
Examples 6 and 15 (Multiple Stage Polymerization)
Shell-core multi-polymer in stages are polymerized from the components set forth in Tables 1.1 A and IB according to the procedures and conditions shown in Example 4. Table 1C presents compositional information of polymer stage.
129
Table 1 (Second stage monomeric components ¹ )
Ex. AND THE nB A 2EHA AC E VN D NV P ST Y tBA M HEMTHE MA A TMPT A C-l 65,2 - - - - - - - - 34.5 0.3 C-2 65,5 - - - - - - - - 34.5 - C-3 65,1 - - - - - - - - 34.5 0.4 1 65,4 - - - - - - - - 34.6 - 2 65,4 - - - - - - - - 34.6 - 3 65,4 - - - - - - - - 34.6 - 3rd 65,4 - - - - - - - - 34.63b 65,4 - - - - - - - - 34.64 65,4 - - - - - - - - 34.6 - 5 70,4 - - - - - - - - 29.6 - 6 65,5 - - - - - - - - 34.5 - 7 60,4 - - - 5.0 - - - - 34.6 - 8 60,4 - - - - 5.0 - - - 34.6 - 9 62,4 - - - - - 3.0 - - 34.6 - 9a 62,4 - - - - - 3.0 - - 34.6 - 10 62,4 - - - - - - 3.0 - 34.6 - 11 60,4 - - 5.0 - - - - - 34.6 - 12 55,5 5.2 - - - - - - - 39.3 - 13 52,5 - 5.3 - - - - - - 42.2 - 14 59,6 5.5 - - - - - - - 34.9 - 15 49,8 5.0 - - - - - - - 45.2 - 16 65,1 - - - - - - - - 34.9 - 17 65, - - - - - - - - 34.6 -
130
4 18 60,4 - - - - - - - 5.0 34.6 - 19 64,9 - - - - - - - 10.0 25.1 -
¹ All monomeric components are expressed in% by weight of total monomeric mixture for the stage.
Table IA (Second-stage monomeric components)
Ex. AND THE BAD nB A 2EH A AC E VN D NV P STY tBA M HE MA MAA AA TMP TA TM PD AE C-l 65.4- - - 34.6-C-2 - - --C-3 ---1 65.234.50.32 65.234.50.33 65.134.50.43rd 65.134.50.43b 65.134.50.44 65.134.60.35 70.1529.50.356 65.1734.530.37 60.2 5.0 34.50.38 60.25.0 34.50.39 62.2 3.0 34.50.39a 65.234.50.310 62.2 3.034.50.311 60.2 5.034.50.312 53.7 5.0 5.0 36.00.313 49.7 5.0 - 5.0 40.00.314 54.6 5.0 5.0 32.0 3.0 0.3 0.1 15 49.655.0 45.00.35 - 16 54.6 5.0 5.0 32.0 3.0 0.3 0.1 17 65.1 - - 34.50.3 0.1 18 60.2 - - 5.0 34.50.3 - 19 64.7 - - 10.0 25.00.3 -
'All monomeric components are expressed in% by weight of total monomeric mixture for the stage.
131
Table IB (Third stage monomeric components)
Ex. AND THE nB BAD TMPT TEGDM No. THE THE THE THE C-l - - - C-2 - C-3 - 1 - 2 - 3 - 4 65.134.5 0.45 - -6 65.1534.5 0.3 0.05 7 - 89101112131415 49.55 5.0 45.0 0.35 0.1 16 - - - - - 17 - - - - - 18 - - - - - 19 - - - - -
'All monomeric components are expressed in% by weight of total monomeric mixture for the stage.
Table 1C (Polymer stage components)
Ex.No. Polymeric type Core weight% % by weight of bark (second stage) % by weight of bark(third stage) C-l X 'connected core / linear shell 10 90 - C-2 linear 100 - - C-3 connected by X 100 - - 1 linear core / X-linked shell 20 80 - 2 linear core / X-linked shell 20 80 - 3 linear core / X-linked shell 20 80 - 3rd linear core / bonded shell 50 50 -
132
Ex. Polymeric type Core weight% % by weight of bark (second stage) % by weight of bark(third stage)by X 3b linear core / X-linked shell 60 40 - 4 linear core / connected by X 2 ^the stage / connected by X 3 ^the stage 10 50 40 5 linear core / X-linked shell 25 75 - 6 linear core / connected by X 2 ^the stage / connected by X 3 ^the stage 10 50 40 7 linear core / X-linked shell 20 ' 80 - 8 linear core / X-linked shell 20 80 - 9 linear core / X-linked shell 20 80 - 9a linear core / X-linked shell 20 80 - 10 linear core / X-linked shell 20 80 - 11 linear core / X-linked shell 20 80 - 12 linear core / X-linked shell 20 80 - 13 linear core / X-linked shell 20 80 - 14 linear core / X-linked shell 20 80 - 15 linear core / connected by X 2 ^the stage / connected by X 3 ^the stage 10 10 80 16 linear core / X-linked shell 20 80 - 17 linear core / X-linked shell 20 80 - 18 linear core / X-linked shell 20 80 - 19 linear core / P ^orX bonded shell 20 80 -
’Linked by X = cross-linked
Example 20
The shell-core polymers in stages of Examples 1, 2, 3a,
6, 9b, 12 and 18 are formulated separately in a cleaning composition
133 of light body wash comprising a combination of an anionic and amphoteric surfactant. The formulation components are shown in Table 2. Each component (except No. 12, 13 and 14 components) is added to a mixing vessel in the order listed in the table.
Components 12, 13 and 14 are formulated in the body wash samples during the test procedure described below. The solubilizer (component 8) and fragrance (component 9) are pre-mixed prior to addition to the reservoir. The components are combined under gentle agitation until a main homogeneous body wash formulation is obtained. Control polymers 10 C-1, C-2 and C-3 (30% active polymer solids) are identically formulated as above. The initial pH of each formulation is measured and recorded (Table 3).
Table 2 (Formulation of clear body wash)
Component Quantity and (% by weight) Occupation 1 D.L Water q.s. to 100 Diluent 2 Polymer (30% active polymer solids) 8.00 Rheology modifier 3 Sulfochem ™ ES-2 CWKSurfactant (26% active) 40.00 Detersive surfactant 4 Chembetaína ™ CADSurfactant (35% active) 6.70 Amphoteric surfactant 5 Merquat® Plus Polymer (10% active) 2.10 Conditioner polymer 6 EDTA Tetrasodium 0.05 Chelating agent 7 Phenonip® 0.50 Anti-bacterial 8 Tween 20 0.50 Fragrance solubilizer 9 Fragrance 0.50 Fragrance 10 FD&C Blue N °. 1 1.85 Pigment 11 FD&C Yellow N °. 6 0.85 Pigment 12 NaOH (18% aqueous weight / weight) q.s. at pH pH adjusting agent 13 Citric acid (50% aqueous weight / weight) q.s. at pH pH adjusting agent 14 Lipopearl ™ 0293 Pearls 1.0 Vitamin E release pearls
The pH of each of the main wash formulations
134 is then sequentially increased with NaOH (component 12) to a pH value of approximately 6.0 and 6.5, respectively, and then sequentially reduced (by adding retro-acid) with citric acid (component 13) a value pH of approximately 6.0, 5.5 and 5 4.5, respectively. At each pH value, 100 g and 20 g aliquots of each main body wash formulation are transferred to 4 oz jars. (118.29 ml) and bottles of 6 drachma (22.18 ml), respectively and centrifuged to remove any air bubbles included. The sample jars and vials containing the centrifuged formulations are capped and kept for 24 hours after which measurements of rheology and clarity properties are made. Viscosity and yield value measurements are performed on 100 gram samples and turbidity measurements are completed on 20 gram samples. The data are presented in Table 3.
Table 3 (Viscosity performance and clarity of body wash formulation)
Target PH Polymer C-l C-2 C-3 1 2 3rd 6 9a 12 18 Initial PH pH (real) 5.45 5.55 5.53 5.36 5.40 5.53 5.47 5.44 5.38 5.46 Viscosity (mPas) 2,060 2,330 3,870 4,100 3.950 4,000 3,940 3,430 3.750 3.720 Yield value (dyn / cm ² ) 36 14 104 236 142 98 170 148 94 146 Turbidity (NTU). 70.1 12.3 33 156 28.1 21.6 29.4 75 13.7 29.4 add base 6.0 pH (real) 6.04 6.06 6.04 6.02 6.03 6.07 6.11 5.98 6.08 6.01 Viscosity (mPas) 1,180 810 2.920 4,700 3,180 2.910 3,200 3,250 2,500 2.920 Yield value (dyn / cm ² ) 12 4 82 260 118 60 132 132 66 114 Turbidity (NTU) 42.5 5.75 22.1 29.0 16.3 11.7 16.6 46.1 10.1 19.1 add base 6.5 pH (real) 6.55 6.56 6.53 6.53 6.53 6.58 6.61 6.53 6.63 6.53 Viscosity (mPas) 1,700 1,080 2,880 3,900 3,170 3,600 3,050 3,230 3,220 2,620 Yield value (dyn / cm ² ) 10 6 48 128 74 40 74 62 42 56 Turbidity (NTU) 13.5 5.83 8.68 6.63 6.10 8.40 7.14 45.2 7.34 12.40 add acid 6.0 pH (real) 6.03 6.03 6.08 5.93 5.99 6.09 6.09 6.04 6.11 6.02 Viscosity (mPa-s) 1,700 1,080 2,890 5,700 3,610 3,430 3,680 3,580 2.930 3,340 Value ofYield 18 4 78 308 132 66 148 114 70 122
135
Target PH Polymer C-l C-2 C-3 1 2 3rd 6 9a 12 18(dyn / cm ² ) Turbidity (NTU) 43.6 5.83 23.0 36.3 17.6 12.2 18.3 25.6 11.5 19.4 add acid 5.5 pH (real) 5.55 5.53 5.60 5.50 5.48 5.45 5.49 5.52 5.61 5.51 Viscosity (mPas) 2.970 3,600 3,930 6,600 4,900 4,960 4,950 4,760 4,020 4,120 Yield value (dyn / cm ² ) 28 14 106 348 162 90 194 156 98 158 Turbidity (NTU) 52.7 6.46 31.3 37.7 16.8 13.4 18.7 24.6 15 24.3 add acid 4.5 pH (real) 4.59 4.55 4.60 4.52 4.51 4.62 4.45 4.55 4.60 4.55 Viscosity (mPas) 4,020 5,700 5.100 8.050 6,000 6.050 6.250 5,900 5,750 5,050 Yield value (dyn / cm ² ) 42 28 130 412 200 112 238 192 136 184 Turbidity (NTU) 53.1 3.54 27.3 30.0 12.1 7.42 15.1 24.9 9 20.2
From the combined rheology and turbidity data, it is evident that the body wash compositions formulated with the linear core / crosslinked shell polymer of the invention in stages have superior combined rheology and turbidity properties (at pH <6) when compared to 5 control polymer Cl having a cross-linked core and linear C-2 and C-3 linear or single-stage polymers that are linear or cross-linked, respectively. The polymers of the invention demonstrate better total yield values indicating improved suspension properties.
Example 21
The body wash samples of Example 20 containing polymer No. Cl, C-2, 1, 2 and 6 at pH 4.5 (in bottles of 6 drachma (22.18 ml)) are subsequently evaluated for their ability to suspend cosmetic beads at 45 ° C for a duration of 12 weeks. The 15 shower gel formulations containing control polymers C-1 and C-2 failed after 2 in the aging oven. Polymers 1, 2 and 6 were approved following 12 weeks in the aging oven.
136
Table 4 (Suspension stability at 12 weeks)
Polymer No. Okay Disapproved C-l No Yes C-2 No Yes 1 Yes No 2 Yes No 6 Yes No
Example 22
Physical combinations of C-3 single-stage cross-linked control polymer and C-2 linear control polymer and are prepared in the following combination ratios (C-3 / C-2 weight / weight): 80:20; 50:50; 40:60 and 20:80. The combinations are prepared from polymeric emulsions equivalent to the level of use of 2.4% by weight of active polymeric solids. Each combination is formulated into the main body wash groups according to the procedures, components and amounts shown in Example 20. Main body wash groups 100: 0 C-3 polymer and 0: 100 C-2 polymer are included for comparative purposes . The pH of each main combination is sequentially increased with NaOH to pH values of approximately 6.0 and 6.5, respectively, and then sequentially reduced with citric acid (through the addition of retro-acid) to a pH value of approximately 6 , 0, 5.5 and 4.5, respectively. At each pH value, 100 g and 20 g aliquots of each main body wash formulation are transferred to 4 oz jars. (118.29 ml) and bottles of 6 drachma (22.18 ml), respectively and centrifuged to remove any air bubbles included. Sample jars and vials containing the centrifuged formulations are capped and kept for 24 hours after which measurements of rheology and clarity properties are made. The viscosity, yield value and turbidity properties for base addition at pH 6.0 and acid addition at pH 6.0, 5.5 and 4.5 are measured and recorded in Table 5 (data for base addition at pH 6.5 is not recorded).
137
Table 5 (Performance of viscosity and clarity of polymeric combinations)
Polymeric combination ratios (C-3: C-2 weight / weight.) Target PH properties 100: 0 80:20 50:50 40: 60 20: 80 0: 100 Initial pH (initial) 5.53 5.52 5.48 5.48 5.53 5.55 Viscosity (mPas) 3,870 3,090 2,580 2.510 2.450 2,330 Yield value (dyn / cm ² ) 104 58 32 26 18 14 Turbidity (NTU) 32.5 32.3 28.6 26.3 19.9 12.3 add base 6.0 pH (real) 6.04 6.04 6.00 5.99 5.98 6.06 Viscosity (mPas) 2.920 2,200 1,470 1.24 0 1.01 0 810 Yield value (dyn / cm ² ) 82 36 14 8 6 4 Turbidity (NTU) 22.1 25.1 22.2 20.3 15.0 5.75 add base 6.5 Unmeasured properties add acid 6.0 pH (real) 6.08 6.01 5.96 6.02 5.98 6.03 Viscosity (mPas) 2,890 2,160 1,900 1.54 0 1.290 1,080 Yield value (dyn / cm ² ) 78 32 12 10 10 4 Turbidity (NTU) 23.0 29.3 26.0 20.9 16.4 5.83 add acid 5.5 pH (real) 5.60 5.52 5.51 5.51 5.48 5.53 Viscosity (mPas) 3,930 3,280 3,250 3.600 3.780 3,600 Yield value (dyn / cm ² ) 106 50 24 28 22 14 Turbidity (NTU) 31.3 35.1 27.3 24.8 17.9 6.46 add acid 4.5 pH (real) 4.60 4.51 4.42 4.44 4.46 4.55 Viscosity (mPas) 5.100 4,150 4,390 5.910 5.850 5,700 Yield value (dyn / cm ² ) 130 66 36 30 20 28 Turbidity (NTU) 27.3 36.9 31.6 28.4 20.3 3.54
When compared to the linear core / shell crosslinked polymer in stages in Table 3 above, the data show that the 5 physical combinations and the crosslinked polymers have lower combined rheology and turbidity properties through the pH values tested in the
138 body wash compositions.
Example 23
The shell-core polymers in stages of Examples 1, 2, 4, 7,
8, 9 and 10 are each formulated in a clear shower gel cleaning composition comprising a sodium-based surfactant and an amphoteric surfactant. A food-grade preservative, sodium benzoate, is added in place of alkyl parabens. The formulation components are shown in Table 6. Components 1 through 11 are added to a mixing vessel in the order listed in the table. Components 12, 13 and 14 are added to the shower gel formulations during the test procedure described below. The fragrance (component 7) and solubilizer (component 8) are premixed prior to addition to the reservoir. The components are combined under gentle agitation until a master mixture of homogeneous shower gel is obtained. The main groups of shower gel 15 containing commercially available control polymers, C-4 (Rheocare ™ TTA) and C-5 (Carbopol® Aqua SF-1) are identically formulated (2.4 wt% active polymer solids) as above.
Table 6 (Clear shower gel formulated with food-grade preservative)
Component Quantity (% by weight) Occupation 1 D.I. q.s. to 100 Diluent 2 Polymer (30% active polymer solids) 8.00 Modifierrheology 3 Sulfochem ™ ES-2 CWK Surfactant (28% active) 40.00 Detersive surfactant 4 Chembetaína ™ CADSurfactant (35% active) 6.70 Amphoteric surfactant 5 Merquat® Plus Polymer 2.10 Conditioner polymer 6 EDTA Tetrasodium 0.05 Chelating agent 7 Fragrance 0.50 Fragrance 8 Tween 20 0.50 Solubilizerfragrance 9 FD&C BlueN ⁰ .1 1.85 Pigment 10 FD&C Yellow N °. 6 0.85 Pigment 11 NaOH (18%) q.s. at pH 6.5 pH adjusting agent
139
12 Citric acid (50% aqueous weight / weight) q.s. at pH pH adjusting agent 13 Sodium benzoate 0.50 Preservative 14 Lipopearl ™ Pearls 1.0 Vitamin E release vehicle
The pH of each main formulation is adjusted to 6.5 with NaOH (component 11) and then sequentially reduced with citric acid (component 12) to a pH value of approximately 5.5, 5.0 and 4.0, respectively. Sodium benzoate (component 13) is added to each 5 sample set at pH 5.0 before additional citric acid is added to reach the final pH value of 4.0. At each pH value, 100 g and 20 g aliquots of each main gel formulation are transferred to 4 oz jars. (118.29 ml) and bottles of 6 drachma (22.18 ml), respectively and centrifuged to remove any air bubbles included. The jars and 10 sample vials containing the centrifuged aliquots are capped and kept for 24 hours at room temperature, after which measurements of rheology and clarity properties are made. The viscosity, yield value and turbidity properties for each adjusted pH sample are measured and recorded in Table 7.
Table 7 (Viscosity performance and clarity of shower gel formulation)
Polymer No. j Properties 1 2 4 7 8 9 T C-4 C-5 Turbidity (NTU) @ pH 6.5 3.0 4.9 5.3 2.88 5.36 2.03 | 11 22.9 12.0 Turbidity (NTU) @ pH 5.5 33.0 13 17 14.1 13.2 12.896.2 67 Turbidity (NTU) @ pH 5.0 30.0 12 16 14.7 13.1 12.5 11.1 96.0 74 Turbidity (NTU) @ pH 4.0 31.0 12.7 17 19.5 12.2 15 | 14.2 120 89 Viscoside of (mPas) 10,980 9,000 10,720 5.140 5.620 8,500 6.460 19,600 9,660
140
@ pH 4.0Yield value 0 (dyn / cm ² ) @ pH 4.0 476 220 368 86 168 236 142 620 508
In formulation samples that are treated with retro-acid at pH 4.0, Lipopearl ™ beads (1.0% by weight, based on the weight of the total composition) are added. The samples are tested corresponding to the suspension test procedure protocol described above.
The core-shell acrylate polymers in stages of this invention release excellent clarity at pH values below 6 in sodium surfactant formulations containing an acidic preservative. In contrast, commercial control polymers.
C-4 and C-5 are cloudy or opaque (higher NTU values) at pH values below 6 in the same formulation. All formulations (including commercial control polymers C-4 and C-5) have good pearl suspension properties at 45 ° C for 12 weeks.
Example 24
The peel-core polymers in stages of Examples 1, 2 and 4 are formulated separately in a clear conditioning shampoo composition comprising an anionic ammonium-based surfactant, an amphoteric surfactant and a subsequently added pearling agent. A food-grade preservative, sodium benzoate, is used as a preservative. Commercially available control polymers, C-4 (Rheocare ™ TTA) and C-5 (Carbopol® Aqua SF-1) are identically formulated (1.5% by weight of active polymer solids). The formulation is prepared from the components listed in Table 8.
141
Table 8 (Clear conditioner shampoo with added pearlescent agent)
Component Quantity (% by weight) Occupation 1 D.I. q.s. to 100 Diluent 2 Polymer (30% solidsactive polymeric) 5.00 Modifierrheology 3 Sulfochem ™ ALS-K Surfactant (30% active) 25.00 Detersive surfactant 4 Sulfochem ™ EA-3 Surfactant (27% active) 15.00 Detersive surfactant 5 Chemonic ™ SI-7 Surfactant 4.00 No surfactantionic 6 Dow Coming® 2-8194 Microemulsion of silicone 2.00 Conditioning agent 7 Fragrance 0.50 Fragrance 8 NaOH (18% aqueous weight / weight) q.s. at pH 6.5 pH adjusting agent 9 Citric acid (50% aqueousweight / weight) q.s. at pH 4.5 pH adjusting agent 10 Sodium benzoate 0.50 Preservative 11 D.I. 10.00 Diluent 12 Mica (dyed golden) 0.20 Teenage agent
Components 1 to 4 are added to a container in the order listed in the table and mixed under low agitation until homogenized. The pH of each formulation is adjusted to approximately 6.5 with NaOH (component 8) and then components 5 to 7 are added to each group and mixed homogeneously. The pH of each group is then sequentially reduced with citric acid (component 9) to a pH value of approximately 5.5, 5.0 and 4.0, respectively. Sodium benzoate 10 (component 10) is added to each sample at pH 5.0 before additional citric acid is added to reach a final pH value of 4.0. At each pH value, a 20 g sample of each group formulation is transferred to separate 6 drachma bottles (22.28 ml). The vials are capped, centrifuged to remove any trapped air bubbles contained in the formulation and kept at room temperature for 24 hours, after which measurements of turbidity properties are made. In addition, the viscosity and yield properties are measured for the final sample
142 (pH 4.0). The data are shown in Table 9.
Table 9 (Performance of viscosity and clarity of conditioner shampoo)
Polymer No. properties 1 2 4 C-4 C-5 Turbidity (NTU) @ pH 6.5 220 143 121 193 206 Turbidity (NTU) @ pH 5.5 36 30 15 117 38 Turbidity (NTU) @ pH 5.0 42 29 17 126 58 Turbidity (NTU) @ pH 4.0 40 18 14 100 61 Viscosity (mPas) @ pH 4.0 2,670 2.940 2.960 2,900 3,350 Yield value (dyn / cm ² ) ®pH4.0 72 52 66 56 100
To demonstrate that the polymers of the invention can stabilize a pearlized conditioning shampoo, a perolescent agent (component 12) is added to the D.I. (component 11) and evenly dispersed. The dispersion is then added to the conditioner shampoo samples previously adjusted with retro-acid adjusted to pH 4.0 and mixed until a homogeneous pearl formulation is achieved. Each of the conditioner shampoo samples are tested and evaluated corresponding to the suspension test procedure protocol described above.
The core-shell acrylate polymers release excellent clarity properties at pH values below 6 in ammonium-based surfactant formulations containing silicon microemulsion. In contrast, all commercial control polymers (C-4 and C-5) are cloudy or opaque (higher NTU values) at pH values below 6 in the same formulation. All formulations present a good suspension of perolescent agent at 45 ° C for 3 months.
Example 25
The shell-core polymers in the stages of Examples 2 and 4 are
143 formulated in a pearlized conditioning shampoo composition comprising a cationic polymer conditioning agent and a silicone conditioning agent. A food-grade preservative, sodium benzoate, is used as a preservative. The formulation is prepared from 5 of the components listed in Table 10.
Table 10 (Pearlescent shampoo)
Component Quantity (% by weight) Occupation 1 D.I. q.s. to 100 Diluent 2 Polymer (30% active polymer solids) 5.00 Modifierrheology 3 Sulfochem ™ ALSK Surfactant (30% active) 25.00 Detersive surfactant 4 Sulfochem ™ EA-3 Surfactant (27% active) 15.00 Detersive surfactant 5 Jaguar Excel (2.0% solution) 15.00 Cationic Agentconditioner 6 Chemonic ™ SI-7 Surfactant 4.00 No surfactantionic 7 Dow Coming® 2-8194 Microemulsion of silicone 2.00 Conditioning agent 8 Fragrance 0.50 Fragrance 9 - NaOH (18% aqueous weight / weight) q.s. apH 6.5 pH adjusting agent 10 Citric acid (50% aqueous weight / weight) q.s. at pH 4.0 pH adjusting agent 11 Sodium benzoate 0.50 Preservative 12 D.I. 10.00 Diluent 13 Mica (dyed golden) 0.20 Teenage agent
The components are formulated as shown in the
Example 24 above, except that a cationic conditioning polymer 10 (component 5) is used in addition to the silicone conditioning agent (component 7). Commercially available control polymer, C-5 (Carbopol® Aqua SF-1), is identically formulated (1.5% by weight of active polymer solids) as in Example 24. The pH of the polymeric formulations is immediately adjusted with NaOH (component 9) at 6.5 and 15 then sequentially decreasing with citric acid (component 10) at 5.5,
5.0 and 4.0 as in the previous example, except that 0.5% by weight of NaCl (with
144 based on the weight of the total formulation components) is added to a series of samples adjusted to pH 4.0. For comparison, a second series of samples is evaluated without adding NaCl. Viscosity and turbidity values are measured after adjusting the pH. The performance of viscosity and clarity data for each of the evaluated samples are shown in Table 11.
Table 11 (Viscosity and clarity performance)
properties 2 4 C-5 Turbidity (NTU) @ pH 6.5 194.0 200.0 353.0 Turbidity (NTU) @ pH 5.5 74.2 62.1 179.0 Turbidity (NTU) @ pH 5.0 69.1 57.7 181.0 Turbidity (NTU) @pH 4.0 (NaCl) 47.2 49.2 128.0 Viscosity (mPa-s) @ pH 6.5 4.870 4,350 3,500 Viscosity (mPa-s) @ pH 4.0 (w / o NaCl) 8,600 7,500 7.180 Viscosity (mPa-s) @ pH 4.0 (with NaCl) 12,000 11,450 12,060
To demonstrate that the polymers of the invention can stabilize a pearlized conditioning shampoo, a perolescent agent (component 13) is added to D.L water (component 12) and uniformly dispersed. The dispersion is then added to the conditioner shampoo samples previously adjusted with retro-acid to pH 4.0 and mixed until a homogeneous pearl formulation is achieved. Each of the pearlescent conditioner shampoo samples are tested and evaluated corresponding to the suspension test procedure protocol described above.
The core-shell acrylate polymers in stages of the invention release excellent clarity properties at pH values below 6 in ammonium-based surfactant formulations containing a
145 conditioner package comprising a cationic polymer and a silicone conditioning agent. The polymers of the invention maintain good clarity properties even after the addition of alkali metal salt such as NaCl. The commercial control polymer (C-5) while releasing good 5 rheological properties provides formulations that are cloudy and opaque (values
Higher NTU) at pH values below 6. All formulations present a good suspension of perolescent agent at 45 ° C for 3 months.
The cationic polymer can be replaced by and / or combined with other synthetic monomeric or polymeric cationic conditioners and / or the amount present in the formulation can be adjusted to maximize the synergy with the inventive polymers. Also, the silicone microemulsion conditioning agent can be replaced with larger sized particles in the emulsion if desired.
Example 26
A soap-based shower gel composition is formulated from the components shown in Table 12.
Table 12 (Soap-based shower gel)
Component Quantity (% by weight) Occupation Part A 1 Deionized water q.s. to 100 Diluent 2 Potassium hydroxide (87.5% aqueous weight / weight) 6.60 NeutralizerPart B 3 Deionized water q.s. to 100 Diluent 4 Glycerin 6.00 Humectant 5 Lauric acid 12.00 Fatty acid 6 Myristic acid (1499) 6.50 Fatty acid 7 Palmitic acid (1698) 1.50 Fatty acid 8 Polymer No. 2 (30% active polymeric solids) 7.0 Rheology modifierPartÇ 9 Mineral oil, type # 26 (24-28 mm2 / s) 10.00 Emollient 10 Propylene Glycol 2.00 Humectant 11 Neolone® 950 0.05 Preservative
Part A is prepared by dissolving potassium hydroxide
146 in D.I. and heating the composition to 80 ° C. Part B is separately prepared by adding glycerin and fatty acids (components 5, 6 and 7) to D.I. and mix until the fatty acids completely melt. Once the fatty acids fuse and are homogeneously mixed, polymer N °. 2 is added to the mixture. Part A is slightly added to part B while stirring while the temperature is maintained at 80 ° C. The composition of part AB is mixed for 30 to 60 minutes. When the homogeneous mixture is connected, the composition of Part AB is allowed to cool to room temperature (20-21 ° C). Mineral oil (component 9) is added to composition AB at a temperature of about 60-70 ° C. Still cooling to 40 ° C, components 10 and 11 are added and uniformly mixed in the formulation. The formulation is allowed to cool under gentle stirring until room temperature is reached. After 24 hours the following physical data is recorded: pH = 9.4; viscosity (axis No. 4 @ 20 rpm) = 6000 mPa s and yield value = 60 dyn / cm.
While this example exemplifies the in situ saponification of fatty acids with a base, a pre-neutralized fatty acid salt can also be used in the formulation of the cleaning formulation. In addition, high-clarity shower gel based on soap can also be made without the mineral oil component.
Example 27
A soap / surfactant mix shower gel composition is formulated from the components shown in Table 13.
147
Table 13 (Soap / surfactant mixture shower gel)
Component Amount of (% by weight) Occupation PartTHE 1 Deionized water q.s. to 100 Diluent 2 Potassium hydroxide (91.5% aqueous weight / weight) 4.35 NeutralizerPart B 3 Deionized water 25.42 Diluent 4 Glycerin 8.00 Humectant 5 Lauric acid 7.20 Fatty acid 6 Myristic acid 2.40 Fatty acid 7 Palmitic acid 2.40 Fatty acid 8 Polymer No. 2 (30% active polymeric solids) 7.0 Rheology modifierPart C 9 Sulfochem ES-2K (26.1% active) 15.00 Detersive surfactant 1 0 Chembetaína ™ CAD (35% active) 12.88 Amphoteric surfactant 11 Neolone® 950 0.05 Preservative 12 Liposphere ™ Pearls 0031 0.15 Cosmetic pearl containing humidifier 13 Lipopearl ™ 0091 Pearls 0.15 Cosmetic pearl containing humidifier 14 Citric acid (50% aqueous weight / weight) 0.5 depH adjusting agent
Part A is prepared by dissolving potassium hydroxide in D.I. and heating the composition to 80 ° C. Part B is separately prepared by adding glycerin and polymer No. 2 the water D.I. under mixing.
Fatty acids (components 5, 6 and 7) are added to Part B, which is heated to 80 ° C and mixed until the fatty acids are fully melted. Once the fatty acids fuse and are homogeneously mixed, Part A is slightly added to part B with stirring while maintaining the temperature at 80 ° C. The composition of part AB is mixed for 30 to 60 minutes. When the homogeneous mixture is connected, the composition of Part AB is allowed to cool to room temperature (20-21 ° C). The packaging of the
148 surfactant (components 9 and 10) is added in the order listed to composition AB under agitation and mixed until uniform. Still cooling to 40 ° C, components 11 to 14 are added in order and uniformly mixed in the formulation. The formulation is allowed to cool under gentle agitation until room temperature is reached. After 24 hours the following physical data is recorded: pH = 9.5; viscosity (axis No. 4 @ 20 rpm) = 2500 mPa · s and turbidity = 7.7 NTU.
Example 28
A humidifying body wash containing high oil 10 containing a food preservative is formulated from the components and procedures presented below. Commercially available control polymers, C-4 (Rheocare ™ TTA) and C-5 (Carbopol® Aqua SF-1) are identically formulated (2% by weight of active polymer solids). A formulation blank (no active rheology modification polymers) 15 is also prepared.
Table 14 (Humidifying body wash)
Component Quantity (% by weight) Occupation Part A 1 Deionized water q.s. to 100 Diluent 2 Versene ™ 220(EDTA Tetrasodium) 0.05 Chelating agent 3 Sulfochem ™ ALS Surfactant (30% active), 15.00 Detersive surfactant 4 Sulfochem ™ * EA-3 (27% active) 25.00 Detersive surfactantPart B 5 Florasun® 90 Sunflower oil 18.00 Conditioner / Emollient 6 Polymer No. 2 (30% active polymeric solids) 6.60 Rheology modifierPartÇ 7 N-Hance® 3000 0.30 Cationic Conditioner 8 Glycerin 99.7% USP 5.00 HumectantPartD 9 NaOH (18% aqueous weight / weight) 1.50 pH adjusting agent
149
10 Sodium benzoate 0.50 Preservative Part 11 Citric acid (100%) 0.25 pH adjusting agent AND 12 Chembetaína ™ CGF (35% active) 5.0 Amphoteric surfactant
Body wash is formulated according to the following procedure:
1) Combine the components of part A and mix until uniform. Adjust the mixing speed to keep defoaming to a minimum;
2) Add the components of part B in the order listed to Part A with mixing and mix until uniform;
3) In a separate container, pre-mix the components of part C and add Part AB and mix until uniform;
4) Add Part D (NaOH) to Part ABC and increase the mixing speed as needed to maintain a good swirl and
5) Add the components of part E one at a time in the order listed to Part ABCD with good mixing between the additions. Increase the speed of the mixture as necessary to keep the mixture whirling.
High oil content body wash formulations are assessed by Brookfield Viscosity (No. 6 @ 20 rpm axis) and visually assessed by texture and phase separation (after 1 week, 2 weeks and 8 weeks). The results are shown in the table below. Separation is defined here as the visible existence of 2 or more distinct layers or phases of any component in the formulation, including but not limited to insoluble substance, soluble substance, oily substances and others. For the phase stability classification: (0 = phase separation; 1 = no phase separation).
150
Table 15
Estabi phase age Polymer no. Active polymer solids Viscosity e (mPa-s) Texture 1week in 2 weeks in 8 week in Blank 0 19,590 - 0 0 0 C-4 2.0 11,440 Lisa 1 1 1 C-5 2.0 13,360 Lisa 1 1 1 2 2.0 14,910 Lisa 1 1 1
Example 29
A sulfate-free shower gel is formulated from the components listed in the table below. Polymers No. 2 and 4 are used 5 as a rheology modification component. The commercially available C-5 control is identical formulated for comparison purposes.
Table 16 (Sulfate-free shower gel)
Components Quantity (% by weight) Occupation 1 Deionized water q.s. to 100 Diluent 2 Polymer No. 2 (30% active polymeric solids) 8.0 Rheology modifier 3 NaOH (18% aqueousweight / weight) q.s. at pH pH adjusting agent 4 Chemoryl ™ SFB-10SKSurfactant mixture (32% active) 30.0 Mixture of mild detersive surfactant (sulfate free) 5 Cocamidopropyl Betaine (38% active) 8.0 Detersive amphoteric surfactant 6 Sodium benzoate 0.5 Preservative 7 Citric acid (50% aqueous weight / weight) q.s. at pH pH adjusting agent
The tested polymer (component 2) is added to D.L water (component 1) in a glass beaker and mixed gently. The pH of the formulation is adjusted with NaOH (component 3) to 6.5 and then the surfactants (component 4) and (component 5) are added to the contents of the beaker and mixed until homogenized. An aliquot of the shower gel formulation is transferred into a 6 drachma vial (22.18 ml) by pEl and turbidity measurements. The pH of the beaker shower gel contents is adjusted to 5.5
151 with citric acid (component 7). A pH aliquot adjusted to the shower gel composition is transferred into a 6 drachma flask (22.18 ml) by determining the turbidity. The pH of the shower gel in the beaker is again adjusted with citric acid (component 7) to 5.0 and another aliquot of the pH-adjusted bath is transferred in a 6 drachma flask (22.18 ml) by the turbidity test. The amount of the sodium benzoate recipe is added to the shower gel in the beaker (previously adjusted to pH 5.0) and a final pH adjustment is made with citric acid (component 7) to reach a pH of 4.0. After this final pH adjustment, 24 hours of the viscosity properties and yield value properties are measured. The data for rheology and turbidity measurements are listed in Table 17.
Table 17
Polymer h O properties 2 4 C-5 Turbidity (NTU) @ pH 6.5 5.65 8.59 52.1 Turbidity (NTU) @ pH 5.5 27.2 38.7 204 Turbidity (NTU) @ pH 5.0 31.6 42.7 221 Viscosity (mPas) @ pH 4.0 15,150 10,200 8,000 Yield value (dyn / cm ² ) @ pH 4.0 360 360 380
In low pH formulations, the polymers of the invention exhibit significantly better rheology and clarity in properties compared to a standard commercial acrylate copolymer.
Example 30
This example demonstrates the formulation of a facial scrub composition containing Polymer No. 2. The formulation components are listed in Table 18.
152 (Facial scrubbing)
Table 18
Component Quantity and (% by weight) Occupation 1 Deionized water q.s. to 100 Diluent 2 Disodium EDTA 0.05 Chelating agent 3 Polymer No. 2 (33.6% of active polymeric solids) 6.72 Rheology modifier 4 Sulfochem ™ AOS Surfactant (40% active), 7.575 Detersive surfactant 5 NaOH (18% aqueous weight / weight) q.s. at pH pH adjusting agent 6 Chemoryl ™ SFB-10SK Surfactant (32% active) 31.70 Amphoteric surfactant 7 Tween 20 1.0 Solubilizer 8 Lebermuth Fragrance Oil (N °, 903000-62) 0.45 Fragrance 9 Glucam ™ E-10 Methyl glycoside 0.50 No surfactantionic / humectant 10 Geogard® Ultra (sodium benzoate) 1.00 Preservative 11 Chembetaína LEC (35% active) 8.00 Amphoteric surfactant 12 Citric acid (50% aqueous weight / weight) q.s. at pH pH adjusting agent 13 Florabeads ™ Jojoba 28/60 Sonora Sand 0.10 Exfoliating agent 14 Florabeads ™ Jojoba 28/60 Gypsy Rose 0.10 Exfoliating agent
The facial scrub is formulated according to the following procedure:
1) With gentle mixing add disodium EDTA (component 2) to D.L water (component 1) heated to 30 to 40 ° C until the disodium EDTA is completely dissolved;
2) Add polymer No. 2 (component 3) until the mixture is completely dispersed and then add the detersive surfactant (component 4) and continue mixing until homogenized;
3) Under continuous agitation, neutralize the formulation with NaOH (component 5) Raise the pH of the formulation in the range of 6.6 to 6.8;
4) Add the amphoteric surfactant (component 6) and mix until homogenized;
5) In a pre-mixed polysorbate 20 from the separate container
153 (component 7) and fragrance oil (component 8) and add the formulation mixture and mix until homogenized;
6) Add the nonionic surfactant / humectant, the preservative and the amphoteric surfactant (components 9, 10 and 11, respectively) in the order listed and mix until homogenized;
7) Adjust the pH to 5.3 to 5.4 with citric acid (component 12) and add the exfoliating agents (components 13 and 14) and mix until homogenized.
Example 31
This example illustrates the formulation of a facial scrub containing the cosmeceutical agent, salicylic acid. The formulation components are listed in Table 19.
Table 19 (Facial scrubbing)
Component Amount of (% by weight) Occupation 1 Deionized water q.s. to 100 Diluent 2 Disodium EDTA 0.050 Chelating agent 3 Polymer No. 2 (33.6% of active polymeric solids) 6.72 Rheology modifier 4 Sulfochem ™ AOS Surfactant (40% active), 22.50 Detersive surfactant 5 NaOH (18% aqueous weight / weight) q- ^s - ^a P ^H pH adjusting agent 6 Chembetain ™ CAD Surfactant (35% active) 5.70 Amphoteric surfactant 7 Lebermuth Fragrance Oil (N °, 508001-30) 0.40 Fragrance 8 Deionized water 12.53 Diluent 9 Zema ™ propanediol 2.00 Diluent 10 Sulfochem ™ AOS Surfactant (40% active), 7.50 Detersive surfactant 11 Salicylic acid 2.00 Cosmeceutical 12 Chembetaína ™ CAD Surfactant (35% active) 5.70 Amphoteric surfactant 13 Glucam ™ E-10 Methyl Glycoside 0.50 No surfactantionic / U mectant 14 Geogard® Ultra (sodium benzoate) 1.00 Preservative 15 Citric acid (50% aqueous weight / weight) q.s. at pH pH adjusting agent 16 Unispheres ™ NLT-2312 Pearls 0.20 Cosmeceutical / Exfoliating
154
I I cosmetics I | I
The facial scrub is formulated as follows:
1) With gentle mixing add disodium EDTA (component 2) to D.I. (component 1) heated to 30 to 40 ° C until the disodium EDTA is fully dissolved;
2) Add polymer No. 2 (component 3) until the mixture is completely dispersed and then add the detersive surfactant (component 4) and continue mixing until homogenized;
3) Under continuous agitation, neutralize the formulation with NaOH (component 5) to raise the pH of the formulation in the range of 6.6 to 6.8;
4) In a separate container, pre-mix the amphoteric surfactant (component 6) and fragrance oil (component 7) and add the pre-mixture to the main batch formulation and mix until homogenized;
5) In a separate D.I. pre-mixed (component 8), propane diol (component 9), anionic surfactant (component 10), salicylic acid (component 11), amphoteric surfactant (component 12) and the nonionic surfactant / humectant component 13) and mix until uniform ;
6) Add the premix to the main batch formulation and mix until smooth;
7) Add sodium benzoate (component 14) and adjust the pH to 4.0 to 4.4 with citric acid (component 15);
8) Add the exfoliating agent (component 16) and mix until smooth.
Example 32
The following examples demonstrate a liquid dishwasher cleaner formulated with a polymer of the invention. The formulation components are shown in Table 20.
155
Table 20 (Liquid dishwasher cleaners)
Components Quantity (% by weight) Occupation 1 D.I. q.s. to 100 Diluent 2 Polymer No. 2 (2.0% by weight of active solids) 7.0 Rheology modifier 3 Sulfochem ™ SLS Surfactant (30% active) 37.39 Surfactant 4 Sulfochem ™ ES-70 Surfactant (70% active) 12.05 Surfactant 5 Chemoxide ™ CAW Surfactant (30% active) 3.11 Surfactant 6 Geogard® Ultra (sodium benzoate) 1.0 Preservative 7 NaOH (18% aqueous weight / weight) q.s. apH PH adjusting agent 8 Citric acid (50% aqueous weight / weight) q.s. at pH P-adjusting agent
Dishwasher liquid is formulated according to the following procedures:
1) In a beaker equipped with a magnetic stir bar, add the polymer (component 2) to D.I. (component 1) and mix under slow stirring (200 rpm);
2) Add surfactants (components 3, 4 and 5) in the order listed to the beaker and adjust the agitation rate to avoid excessive foam generation;
3) Add preservative (component 6) and mix until uniform and homogenized;
4) Adjust the pH of the composition with NaOH (component 7) and / or citric acid (component 8) to pH 5.5 and optionally
5) Add fragrance or color, as desired.
Example 33
This example demonstrates that the good rheological properties and clarity of the appropriate product are obtained by reducing the pH of the surfactant compositions comprising the shell-core polymers in stages of the invention and a food grade preservative without neutralizing the polymer
156 with an additional alkaline pH adjusting agent. The surfactant composition is formulated from the components listed in Table 21.
Table 21 (Composition of the thick acidified surfactant)
Component Quantity (% by weight) Occupation 1 D.I. q.s. to 100 Diluent 2 Polymer No. 3 (33.7% active polymer solids) 7.42 Modifierrheology 3 Sulfochem ™ ES-2 CWK Surfactant (28% active) 40.00 Detersive surfactant 4 Chembetaina ™ CADSurfactant (35% active) 6.70 Amphoteric surfactant 5 Sodium benzoate 0.25 Preservative 6 Citric acid (50% aqueous weight / weight) q.s. at pH pH adjusting agent
Components 1 through 5 are added to a container in the order listed in the table and mixed under slow stirring until a uniform main batch formulation is obtained. The initial pH of the formulation is measured and recorded. The pH of the formulation is sequentially reduced to approximately 5.0 and 4.5 with citric acid (component 6). At each 10 pH value, 100 g and 20 g aliquots of the main batch formulation are transferred to 4 oz jars. and 6 drachma bottles (22.18 ml), respectively and centrifuged to remove any included air bubbles. Sample jars and bottles containing the centrifuged formulations are capped and kept for 24 hours after which measurements of rheology and clarity properties are made. Viscosity and yield value measurements are made on 100 gram samples and turbidity measurements are completed on 20 gram samples. The data are shown in Table 22.
157
Table 22
pH (Initial) pH (5.0) pH (4.5) PH value 5.54 4.96 4.57 Viscosity (mPas) 3,340 3.810 3,930 Yield value (dyn / cm ² ) 132 142 146 Turbidity (NTU) 16.4 28.7 43
Example 34
This example illustrates the use of a shell-core polymer in stages as a thickener in a textile printing paste (Ex. 3 4A) and 5 in a textile coating formulation (Ex. 34B), at the weight of the active polymer% indicated in Table 23.
Table 23 (Textile treatment compositions)
Component Example 34A Example 34B 1 D.I. q.s. to 100% q.s. to 100% 2 Polymer No. 2 1.5 (% by weight of solidsactive) 0.76 (wt% of active solids) 3 Ammonium hydroxide (28% active) at pH pH9.7 pH8.5 4 Printrite® 595 connector 5.0 - 5 Hycar® 2671 connector - 41.86 6 Pigment 5.0 - 7 Foamaster® DF defoamer160L - 0.25 8 Ammonium Nitrate (25% aqueous weight / weight) - 0.45

权利要求:
Claims (26)
[1]
1. Staged shell-core polymer based on acrylic, characterized by the fact that it comprises from 5% to 60% by weight of a linear core polymer based on acrylic and from 95% to 40% by weight of at least one crosslinked shell polymer based on acrylic, where
I) said linear core polymer is polymerized from a monomer selected from:
a) from 10% to 80% by weight of at least one carboxylic acid monomer comprising acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, acotinic acid or maleic acid or combinations thereof;
b) from 90% to 20% by weight of at least one C1 to C5 alkyl ester and / or at least one C1 to C5 hydroxyalkyl ester of acrylic acid or methacrylic acid and optionally
c) from 1% to 35% by weight of at least one α, β-ethylenically unsaturated monomer selected from a monomer represented by the formulas:
i) CH2 = C (R) C (O) OR ¹ , where R is selected from hydrogen or methyl and R ¹ is selected from C6-C10 alkyl, C10 to C10 hydroxyalkyl, - (CH2ÉOCH2CH3 and (CH2) 2C (O ) OH ii) CH2 = C (R) X, where R is hydrogen or methyl and X is selected from -CóH5, CN, -C (O) NH2, -NC4H6O, -C (O) NHC (CH3) 3, -C (O) N (CH3) 2, C (O) NHC (CH3) 2 (CH2) 4CH3 and -C (O) NHC (CH3) 2CH2S (O) (O) OH;
iii) CH2 = CHOC (O) R ¹ , where R ¹ is straight or branched C1-C18 alkyl and iv) CH2 = C (R) C (O) OAOR ² , where A is a bivalent radical selected from
Petition 870200000421, of 02/01/2020, p. 10/20
CH2CH (OH) CH2- and -CH2CH (CH2OH) -, R is selected from hydrogen or methyl and R ² is an acyl residue of a saturated or unsaturated linear or branched C10 to C22 fatty acid and where
II) said at least one crosslinked shell polymer is polymerized from a monomer selected from;
a1) from 10% to 80% by weight of at least one carboxylic acid monomer comprising acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, acotinic acid or maleic acid or combinations thereof;
b1) from 90% to 15% by weight of at least one C1 to C5 alkyl ester and / or at least one C1 to C5 hydroxyalkyl ester of acrylic acid or methacrylic acid;
c1) from 0.01% to 5% by weight of at least one crosslinking monomer and optionally d1) from 1% to 35% by weight of at least one α, β-ethylenically unsaturated monomer selected from formulas i) to iv) above.
[2]
2. Staged shell-core polymer based on acrylic according to claim 1, characterized by the fact that monomeric component b) is selected from methyl (meth) acrylate, ethyl (meth) acrylate, npropyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, iso-amyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate (butane diol mono (meth) acrylate), and mixtures thereof.
[3]
3. Staged shell-core polymer based on acrylic according to claim 1, characterized by the fact that the monomeric component b1) is selected from methyl (meth) acrylate, ethyl (meth) acrylate, npropyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, iso-amyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate,
Petition 870200000421, of 02/01/2020, p. 11/20 hydroxybutyl (meth) acrylate (butane diol mono (meth) acrylate), and mixtures thereof.
[4]
4. Staged shell-core polymer based on acrylic according to claim 1, characterized by the fact that the monomeric component c1) is selected from ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, triethylene glycol di (met) acrylate, 1,3-butylene glycol di (met) acrylate, 1,6-butylene glycol di (met) acrylate, 1,6-hexanediol di (met) acrylate, neopentyl glycol di (met) acrylate, 1 , 9-nonanediol di (meth) acrylate, 2,2-bis (4- (acryloxy-propyloxyphenyl) propane, 2,2'-bis (4 (acryloxydiethoxy-phenyl) propane, trimethylolpropane tri (meth) acrylate, trimethyloletane tri ( met) acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol diallyl ether, pentaerythritol trialyl ether, pentaerythritol tetraallyl ether, trimethylolpropane diallyl ether and trimethylolpropane trialyl ether.
[5]
5. Surfactant composition, characterized by the fact that it comprises:
A) at least one surfactant selected from anionic, zwitterionic or amphoteric, cationic or non-ionic surfactant and combinations thereof;
B) at least one core-shell polymer based on acrylic, as defined in any one of claims 1 to 4; and
C) water.
[6]
6. Surfactant composition according to claim 5, characterized by the fact that the pH of said composition varies from 0.5 to 14, or from 2 to 7 or from 3 to 6.
[7]
7. Personal care cleaning composition, characterized by the fact that it comprises:
A) at least one surfactant selected from anionic surfactant and one zwitterionic or amphoteric and combinations thereof;
B) at least one acrylic-based staged shell-core polymer as defined in any one of claims 1 to 4;
Petition 870200000421, of 02/01/2020, p. 12/20
C) at least one acid based preservative; and
D) water.
[8]
Personal care cleaning composition according to claim 7, characterized in that it additionally comprises a pH adjusting agent selected from at least one alkalinity adjusting agent, at least one acidity adjusting agent and combinations thereof .
[9]
9. Cleaning composition according to claim 8, characterized in that the pH of said composition varies from 0.5 to 6, or from 2 to 5.5 or from 3 to 5.
[10]
10. Personal care composition, characterized by the fact that it comprises:
A) an acrylic based, shell-core polymer as defined in any one of claims 1 to 4;
B) at least one component selected from surfactants, hair and skin conditioning agents, emollients, emulsifiers, auxiliary rheology modifiers, thickening agents, vitamins and hair growth promoters, self-tanning agents, sunscreens, skin brighteners, anti-aging compounds, anti-wrinkle compounds, anti-cellulite compounds, anti-acne compounds, anti-dandruff agents, anti-inflammatory agents, analgesics, antiperspirant agents, deodorant agents, capillary fixatives, particulates, abrasives, humidifiers, antioxidants, keratolytic agents, antistatic agents, foam intensifiers, hydrotropes, solubilizing agents , chelating agents, antimicrobial agents, antifungal agents, pH adjusting agents, chelating agents, buffering agents, botanicals, hair dyes, oxidizing agents, reducing agents, propellants, insoluble components, thermochromic pigments, bleaching agents hair and skin, pigments, anti-caries, anti-tartar agents, anti-plaque agents, solvents, preservatives and combinations of these and
Petition 870200000421, of 02/01/2020, p. 13/20
C) water.
[11]
11. Staged shell-core polymer based on acrylic according to claim 1, characterized in that it comprises from 5% to 60% by weight of a linear first-stage polymer based on acrylic and from 95% to 40% % by weight of at least one acrylic-based external stage polymer, wherein at least one of said at least one acrylic-based external stage polymer must be cross-linked; said linear core polymer is polymerized in a first stage polymerization reaction from a monomeric composition comprising:
a) 10% to 80% by weight of at least one carboxylic acid monomer comprising acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, acotinic acid, maleic acid, and salts thereof, and combinations thereof;
b) from 90% to 20% by weight of at least one C1 to C5 alkyl ester and / or at least one C1 to C5 hydroxyalkyl ester of acrylic acid or methacrylic acid; and optionally
c) from 1% to 35% by weight of at least one α, β-ethylenically unsaturated monomer selected from a monomer represented by the formulas:
i) CH2 = C (R) C (O) OR ¹ , where R is selected from hydrogen or methyl; and R ¹ is selected from C6-C10 alkyl, C6 to C10 hydroxyalkyl, - (CH2ÊOCH2CH3 and (CH2) 2C (O) OH and salts thereof;
ii) CH2 = C (R) X, where R is hydrogen or methyl and X is selected from -CóH5, CN, -C (O) NH2, -NC4H6O, -C (O) NHC (CH3) 3, -C (O) N (CH3) 2, C (O) NHC (CH3) 2 (CH2) 4CH3 and -C (O) NHC (CH3) 2CH2S (O) (O) OH and salts thereof;
iii) CH2 = CHOC (O) R ¹ ,
Petition 870200000421, of 02/01/2020, p. 14/20 where R ¹ is straight or branched C1-C18 alkyl and iv) CH2 = C (R) C (O) OAOR ² , where A is a divalent radical selected from CH2CH (OH) CH2 e-CH2CH (CH2OH ) -, R is selected from hydrogen or methyl and R ² is an acyl residue from a saturated or unsaturated C10 to C22 fatty acid; wherein said first stage monomeric composition is free from any crosslinking monomers and wherein at least one of said at least one external stage polymer is polymerized from a monomeric composition comprising:
a1) from 10% to 80% by weight of at least one carboxylic acid monomer comprising acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, acotinic maleic acid, and salts thereof and combinations thereof;
b1) from 90% to 15% by weight of at least one C1 to C5 alkyl ester and / or at least one C1 to C5 hydroxyalkyl ester of acrylic acid or methacrylic acid;
c1) from 0.01% to 5% by weight of at least one crosslinking monomer and optionally d1) from 1% to 35% by weight of at least one α, β-ethylenically unsaturated monomer selected from formulas i) to iv) above.
[12]
12. Staged shell-core polymer based on acrylic according to claim 1 or 4, characterized by the fact that it comprises from 20% to 80% by weight of linear core polymer based on acrylic and from 80% to 20% % by weight of crosslinked shell polymer based on acrylic, based on the total weight of the shell-core polymer in stages.
[13]
13. Method for making a stucco-core polymer based on acrylic as defined in claim 1, characterized by the fact that said method comprises:
Petition 870200000421, of 02/01/2020, p. 15/20
I) polymerize a first monomeric first stage composition in the absence of a crosslinking monomer to obtain a linear first stage polymer, said monomeric first stage composition comprising:
a) from 10% to 80% by weight of at least one carboxylic acid monomer comprising acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, acotinic acid, maleic acid, and salts thereof and combinations thereof;
b) from 90% to 20% by weight of at least one C1 to C5 alkyl ester and / or at least one C1 to C5 hydroxyalkyl ester of acrylic acid or methacrylic acid and optionally
c) from 1% to 35% by weight of at least one α, β-ethylenically unsaturated monomer selected from a monomer represented by the formulas:
i) CH2 = C (R) C (O) OR ¹ , where R is selected from hydrogen or methyl and R ¹ is selected from C6-C10 alkyl, C10 to C10 hydroxyalkyl, - (CH2EOCH2CH3 and (CH2) 2C (O ) OH and salts thereof;
ii) CH2 = C (R) X, where R is hydrogen or methyl and X is selected from -CóH5, CN, -C (O) NH2, -NC4H6O, -C (O) NHC (CH3) 3, -C (O) N (CH3) 2, C (O) NHC (CH3) 2 (CH2) 4CH3 and -C (O) NHC (CH3) 2CH2S (O) (O) OH and salts thereof;
iii) CH2 = CHOC (O) R ¹ , where R ¹ is straight or branched C1-C18 alkyl and iv) CH2 = C (R) C (O) OAOR ² , where A is a bivalent radical selected from CH2CH ( OH) CH2 e-CH2CH (CH2OH) -, R is selected from hydrogen or methyl and R ² is an acyl residue of a linear C ₁₀ to C ₂₂ fatty acid or
Petition 870200000421, of 02/01/2020, p. 16/20 branched saturated or unsaturated followed by
II) polymerize a second stage monomeric composition in the presence of said first stage polymeric particle to obtain a crosslinked second stage polymer, said second stage monomeric composition comprising:
a1) from 10% to 80% by weight of at least one carboxylic acid monomer comprising acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, acotinic acid, maleic acid, and salts thereof and combinations thereof;
b1) from 90% to 15% by weight of at least one C1 to C5 alkyl ester and / or at least one C1 to C5 hydroxyalkyl ester of acrylic acid or methacrylic acid;
c1) from 0.01% to 5% by weight of at least one crosslinking monomer and optionally d1) from 1% to 35% by weight of at least one α, β-ethylenically unsaturated monomer selected from formulas i) to iv) above.
[14]
14. Method for making a staged shell-core polymer based on acrylic as defined in claim 11, characterized by the fact that said method comprises:
I) polymerize a first monomeric first stage composition in the absence of a crosslinking monomer to obtain a linear first stage polymer, said monomeric first stage composition comprising:
a) from 10% to 80% by weight of at least one carboxylic acid monomer comprising acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, acotinic acid, maleic acid, and salts thereof and combinations thereof;
(b) from 90% to 20% by weight of at least one C1 to C5 alkyl ester and / or at least one C1 to C5 hydroxyalkyl ester of acrylic acid, or
Petition 870200000421, of 02/01/2020, p. 17/20 methacrylic acid and optionally
c) from 1% to 35% by weight of at least one α, β-ethylenically unsaturated monomer selected from a monomer represented by the formulas:
i) CH2 = C (R) C (O) OR ¹ , where R is selected from hydrogen or methyl and R ¹ is selected from C6-C10 alkyl, C10 to C10 hydroxyalkyl, - (CH2) 2OCH2CH3 and (CH2) 2C (O) OH and salts thereof;
ii) CH2 = C (R) X, where R is hydrogen or methyl and X is selected from -CóH5, CN, -C (O) NH2, -NC4H6O, -C (O) NHC (CH3) 3, -C (O) N (CH3) 2, C (O) NHC (CH3) 2 (CH2) 4CH3 and -C (O) NHC (CH3) 2CH2S (O) (O) OH and salts thereof;
iii) CH2 = CHOC (O) R ¹ , where R ¹ is straight or branched C1-C18 alkyl and iv) CH2 = C (R) C (O) OAOR ² , where A is a bivalent radical selected from CH2CH ( OH) CH2 and -CH2CH (CH2OH) -, R is selected from hydrogen or methyl and R ² is an acyl residue from a saturated or unsaturated C10 to C22 fatty acid followed by
II) polymerize at least one external stage monomeric composition in the presence of a previously polymerized polymeric stage particle to obtain a multiple stage polymeric particle and in which at least one of said at least one external stage monomeric composition comprises:
a1) from 10% to 80% by weight of at least one carboxylic acid monomer comprising acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, acotinic acid, maleic acid, and salts thereof and combinations thereof;
Petition 870200000421, of 02/01/2020, p. 18/20 b1) from 90% to 15% by weight of at least one C1 to C5 alkyl ester and / or at least one C1 to C5 hydroxyalkyl ester of acrylic acid or methacrylic acid;
d) from 0.01% to 5% by weight of at least one crosslinking monomer; and optionally d1) from 1% to 35% by weight of at least one α, β-ethylenically unsaturated monomer selected from formulas i) to iv) above.
[15]
Method according to claim 12, characterized in that said monomer composition in said first stage monomer composition comprises an auxiliary emulsifier selected from an ethoxylated C10 to C22 fatty alcohol.
[16]
16. Method according to claim 15, characterized in that said second stage monomer composition comprises an auxiliary emulsifier selected from an ethoxylated C10 to C22 fatty alcohol.
[17]
17. Method according to claim 13, characterized in that said monomeric composition in said first stage monomeric composition comprises an auxiliary emulsifier selected from an ethoxylated C10 to C22 fatty alcohol.
[18]
Method according to claim 10, characterized in that said monomeric composition in at least one external stage monomeric composition comprises an auxiliary emulsifier selected from an ethoxylated C10 to C22 fatty alcohol.
[19]
19. Method for thickening an aqueous composition comprising the core-shell polymer in stages based on acrylic as defined in any one of claims 1 and 11, characterized in that said method comprises adding to said aqueous composition a pH adjusting agent selected from an acidic material, an alkaline material and mixtures thereof.
Petition 870200000421, of 02/01/2020, p. 19/20
[20]
20. Method according to claim 19, characterized in that said aqueous composition includes a surfactant.
[21]
21. Method according to claim 20, characterized by the fact that said surfactant is selected from an anionic surfactant, an amphoteric surfactant, an anionic, a cationic and mixtures thereof, or in which said surfactant is selected from at least one surfactant anionic, at least one amphoteric surfactant and mixtures of these.
[22]
22. The method of claim 20 or 21, characterized in that an alkaline pH adjusting agent is added to said composition or in which an acidic pH adjusting agent is added to said composition.
[23]
23. The method of claim 20 or 21, characterized in that an alkaline pH adjusting agent and an acid is added to said composition.
[24]
24. The method of claim 23, characterized in that said alkaline pH adjusting agent is added to said composition before said acidic pH adjusting agent is added.
[25]
25. The method of claim 24, characterized in that the pH of said composition is adjusted with said alkaline pH adjusting agent from 0.5 to 2 pH units above the initial pH of the composition and subsequently reduces the Alkaline adjusted pH of the composition by adding said acidic pH adjusting agent in an amount sufficient to obtain a final pH value ranging from 3.5 to 5.5.
[26]
26. Method according to claim 25, characterized by the fact that the initial pH of said composition is at least 5.0.

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KR20130091322A|2013-08-16|

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BR112013000383A2|2016-06-07|

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JP2017025342A|2017-02-02|

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-02-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-02-04| B15K| Others concerning applications: alteration of classification|Free format text: AS CLASSIFICACOES ANTERIORES ERAM: C08F 265/06 , C08F 285/00 , A61K 8/91 Ipc: A61K 8/02 (2006.01), A61K 8/81 (2006.01), A61K 8/9 |

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2020-04-14| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/07/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US36274210P| true| 2010-07-09|2010-07-09|

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PCT/US2011/043151|WO2012006402A1|2010-07-09|2011-07-07|Structured acrylate copolymer thickeners|

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