BENEFICIENT AGENT DISPOSAL, HAIR OR SKIN TREATMENT COMPOSITION, HAIR OR SKIN TREATMENT COMPOSITION A

专利摘要:
benefit agent delivery particle, laundry, hair or skin treatment composition, laundry treatment composition, hair or skin treatment composition and benefit agent delivery particle production process of the present invention refers to a composition comprising a beneficial agent delivery particle comprising at least one of hydroxylpropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxylpropyl guar, hydroxyethyl ethyl cellulose or methyl cellulose. the beneficial agent delivery particle may additionally comprise a non-polysaccharide polymer, preferably an aminoplast polymer. the benefit agent delivery particle may comprise a perfume. The invention also provides a particle manufacturing process in which the perfume oil is encapsulated using an emulsion polymerization to form core-wrap particles (in the alternative that the perfume may be adsorbed later) and an additional layer. polymer is formed on the outer surface of the core-wrap particles in the presence of a release aid.
公开号:BR112014004133B1
申请号:R112014004133-4
申请日:2012-07-30
公开日:2019-02-19
发明作者:Honggang Chen；Christopher Clarkson Jones；Xiaoyun Pan；Jinfang Wang
申请人:Unilever N.V.；
IPC主号:

专利说明:

Invention Patent descriptive report
Benefit Agent Availability Particle,
Treatment Composition for Washing of Clothes, Hair or Skin, Composition of Treatment for Washing of Clothes, Composition of Treatment of Hair or Skin and Production Process of Beneficial Agent Disposal Particles
Field of the Invention [0001] The present invention relates to surface treatment compositions and, more specifically, to compositions comprising particles comprising a beneficial agent (preferably perfume) and the deposition aid. The invention also relates to the provision of the beneficial agent (preferably perfume), for example, for fabric when washing clothes, or for substrate surfaces of the human body, such as skin or more preferably hair.
Background of the Invention [0002] The present invention will be described with particular reference to perfume as a beneficial agent, although the technology is considered to be applicable to other beneficial agents used in surface treatment processes.
[0003] In laundry washing applications, the deposition of a perfume is used, for example, during fabric treatment processes, such as washing and conditioning the fabric. The deposition methods are diverse and include deposition during the washing or rinsing stages of the washing process, or direct deposition before or after washing, such as by spraying or rubbing or by using impregnated sheet materials during drying in clothes dryer or water additives during steam ironing. Perfume is often incorporated into a carrier or delivery system. Carrier systems for
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2/67 perfumes are typically based on encapsulation or closure of the perfume within a matrix.
[0004] After deposition on a surface, there is the problem in which the perfume's longevity of adherence to that surface, in an environment containing surfactant, is inherently weak. A perfume that has been deposited on a fabric can be removed again during the scheduled wash, or the perfume can be removed from its holder into the washing liquor. Therefore, protection of the perfume is required before and after it has been deposited on the surface. Many of these same problems are faced with other beneficial agents, which, like perfume, are typically relatively expensive and are present in laundry compositions at relatively low levels.
[0005] Similar problems occur in the fields of skin and hair treatment, where perfumes and / or other beneficial agents must be deposited on the skin or on the hair.
[0006] WO 07/62833 refers to compositions comprising particles of encapsulated core-wrap perfume, decorated with a polysaccharide that is substantive for cellulose. The preferred polysaccharides described in that document are locust bean gum, tamarind xyloglucan, guar gum or mixtures thereof. Thus, it is known to have particles comprising a beneficial agent (perfume), which use a substantive polysaccharide for cellulose as an availability aid to assist the particles to bind to a specific substrate. The compositions can also comprise one or more enzymes. Appropriate enzymes, disclosed in the reference, include, among others, those known as cellulase.
[0007] The term cellulase refers to a class of enzymes that show a range of possible reactions on a variety of substrates. A problem with substantive cellulose polysaccharides is that they have a structure that is generally similar to cellulose, and as such, are subject to
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3/67 attack by “cellulase”.
[0008] Aids for providing similar benefit agents have been suggested for polyester based on polymers containing phthalates, similar to so-called dirt release polymers. These phthalate polymers are subject to hydrolysis problems and are non-substantive for cotton. [0009] Numerous documents describe the fact that cellulosic materials can also function as dirt release polymers and anti-redeposition agents. The use of methyl and ethyl cellulose ethers in detergent compositions is described in US patent 2,373,863, Vitalis (1945). A large number of cellulosic materials for use in detergents are described in US patent 2,994,665, Reich, et al. (1961); see also US patent 3,523,088, Dean, et al. (1970). DE 1,054,638, Van der Werth, November 2, 1956, describes C12 alkyl benzene sulfonates in combination with carboxylated cellulose derivatives. GB 1,084,061 describes low amounts of cellulosic materials as stabilizers for liquid detergents. GB 927,542, GB 765,811 and GB 340,232 5 also teach cellulosic materials in detergents.
[0010] US patent 4174305 describes detergent compositions of alkyl benzene sulfonate containing cellulose ether dirt releasing agents. US patent 4732639 describes the fact that some alkyl or alkyl / hydroxy-alkyl cellulose derivatives (with a degree of molar substitution of up to 3.0) are effective as dirt-releasing polymers and / or anti-reposition polymers. UK 1314897 describes the fact that hydroxy-propyl methyl cellulose for use as an anti-redeposition agent and dirt release aid, but from that document (as noted in US patent 6191093), it can be seen that performance is unsatisfactory in pure cotton articles. US patent 6200351 describes non-ionic hydroxyalkyl cellulose ethers suitable for use as soil release polymers in combination with polyester soil release polymers, which in particular include hydroxy-ethyl, hydroxy-propyl and / or hydroxy
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4/67 butyl celluloses which may additionally carry alkyl ether groups, more particularly, methyl, ethyl and / or propyl groups.
[0011] There is a need for a deposition system that is effective for both cotton and polyester, and that is stable against hydrolysis and attack by enzymes. There is also a need to find effective deposition aids for other substrates.
Summary of the Invention [0012] We now determine that particles comprising a beneficial agent that use certain nonionic derivatives, substituted cellulosic derivatives as an availability aid are effective for both cotton and polyester, as well as for hair.
Accordingly, a first aspect of the present invention relates to a composition comprising a beneficial agent delivery particle having on the external surface of the particle one or more delivery auxiliaries that include polysaccharides selected from the group consisting of: hydroxy-propyl methyl cellulose , hydroxy-ethyl methyl cellulose, hydroxy-propyl guar, hydroxy-ethyl ethyl cellulose or methyl cellulose.
[0014] Without wishing to be bound by a theory, it is believed that the subgroup identified in the larger class of modified cellulosic materials has properties that make them well suited as deposition aids on both cotton and polyester. The spacing ring of these (3-1-4 5 polymers is such that each alternative ring of the polymer is well positioned to allow an interaction of pseudo hydrogen bonding with the π (pi) electron clouds of the polyester phthalate rings. , these particular polymers have a balance of hydrophobicity and hydrophilicity which means that they are able to interact with tissue without becoming so hydrophobic as to be insoluble. Other nonionic modified polysaccharides, for example, hydroxyl ethyl cellulose, do not have the properties correct and have poor performance as deposition aids on polyester.
[0015] Preferably, the benefit agent availability particle
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5/67 comprises a non-polysaccharide polymer, more preferably an amino-acid polymer. Typically, the non-polysaccharide polymer is cross-linked in the form of relatively large water-insoluble macromolecules.
[0016] Preferably, the beneficial agent delivery particle comprises a perfume. Highly preferred particles comprise a core comprising the beneficial agent and at least one wrapper comprising the water-insoluble non-polysaccharide polymer, the nonionic polysaccharide being attached to the outer surface of the peripheral wrap.
[0017] Such particles have an internal region, typically forming a "core" that contains the beneficial agent and a water-insoluble "wrap" that protects the beneficial agent and regulates the flow of the beneficial agent in and out of the core. The core may comprise a droplet of the beneficial agent or may comprise a polymeric matrix in which the beneficial agent is adsorbed.
[0018] The particle can be a carrier (charger) that controls the thermodynamic (rather than kinetic) partition of the beneficial agent between the interior region and elsewhere. This is particularly advantageous when the addition of perfume or other beneficial agent is required at a late stage, as the particles and the beneficial agent can thus be dosed into a product separately. Alternatively, the wrap is largely impervious to the benefit agent and the benefit agent is released upon the rupture of the wrap.
[0019] Preferably, the beneficial agent delivery particle comprises a core and at least one wrap. In particularly preferred embodiments, the perfume is present in the core and the delivery aid is attached to the outside of the peripheral wrap. Although it is preferable that the delivery assistant is attached directly to the wrap, it can be attached via a kind of connection.
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6/67 [0020] The term “connection” is intended to mean the fact that the delivery aid is not removed with water, so the delivery aid is a permanent part of the encapsulated and not a water-soluble coating.
[0021] It is anticipated that another benefit of the particles of availability of the benefit agent of the present invention is that they will also provide some benefit of releasing dirt in laundry washing applications due to the improved affinity for cotton, a benefit that the aid of availability it gains through its attachment to a particle.
[0022] A further aspect of the present invention relates to a composition for treating hair, skin or washing clothes, comprising:
(a) a particle according to the first aspect of the present invention, and, (b) at least one surfactant.
[0023] In a particularly preferred embodiment, the present invention relates to a liquid treatment composition comprising at least one anionic or non-ionic surfactant.
[0024] Preferably, for hair and / or skin treatment compositions, the surfactant comprises at least 3% by weight of an alkyl sulfate ether based on the total composition.
[0025] Advantageously, the delivery aid is not susceptible to hydrolysis and is not attacked by enzymes that are typically used in laundry washing compositions.
[0026] In a preferred embodiment, the laundry washing treatment compositions of the invention comprise at least one enzyme for a polysaccharide substrate. Preferably it is selected from hemicellulase, cellulase (which is particularly preferred), polygalacturonase, xylanase, pectinase, mannanase (which is also particularly preferred), lyase pectate, ligninase, pululanase, pentosanase, arabinosidase, hyaluronidase,
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7/67 chondroitinase, laccase, glycosyl hydrolase, and amylases, or mixtures thereof. In another preferred embodiment, the compositions of the present invention contain polyesterase. Both can be present, polyesterase and polysaccharide-substrate enzymes.
[0027] The stability of the availability aid in the presence of these common enzymes, particularly cellulase, provides a significant advantage over the previously known deposition systems based on Locust Bean Gum.
[0028] In another preferred embodiment, the compositions of the present invention contain polyesterase. Both can be present, polyesterase and polysaccharide-substrate enzymes.
[0029] Preferably, the beneficial agent delivery particle comprises a core and at least one wrap. In particularly preferred embodiments, the perfume is present in the core and the delivery aid is attached to the outside of the peripheral wrap. Although it is preferred that the delivery aid is connected directly to the wrap, it can be connected via a kind of connection.
[0030] Yet an additional aspect of the present invention consists of a process for the production of particles of availability of beneficial agent, in which:
(a) a core is encapsulated using emulsion polymerization to form core-shell particles, and, (b) an additional polymeric layer is formed on the outer surface of the core-shell particles in the presence of at least one polysaccharide selected from the group consisting of hydroxyl-propyl methyl cellulose, hydroxyl-ethyl methyl cellulose, hydroxyl-propyl guar, hydroxyl-ethyl ethyl cellulose or methyl cellulose, the beneficial agent being present in the nucleus or present as a nucleus during step (a) of process or adsorbed within the nucleus in a subsequent step.
Detailed Description of the Invention
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In order that the present invention can be further understood, it is described in further detail below with particular reference to preferred aspects. Where percentages are given, unless otherwise stated, they are percentages by weight. Similarly, all reasons are reasons by weight, unless otherwise specified. Where chemical structures of polymers are given, they refer to the general form, showing the substituent groups that are present, but that do not represent the actual availability of the substituent groups, or the degree of substitution.
[0032] Except in the operation and in comparative examples, or where otherwise explicitly indicated, all numbers in this description indicate quantities or ratios of material or reaction conditions, physical properties and / or use should be understood as modified by the word "about".
Auxiliary of Availability [0033] In those cellulose ethers in which some of the hydroxyl groups in the repetitive units of glucose have been hydroxy-alkylated, the average number of hydroxyl groups replaced per unit of glucose is referred to as the degree of substitution (DS). The complete substitution must provide a DS of 3. However, if the substituting group itself contains a hydroxyl group, it can also be etherified. When this occurs, the number of moles of substituting groups per glucose ring, moles of substitution (MS), can be greater than 3.
[0034] In certain embodiments of the present invention, some of the OH groups (when present) in the hydroxyl-alkyl side group are replaced with alkyl ethers. Typically, these are C ₁ -C ₂₀ alkyl ethers, and can, in specific cases, be replaced by C16-C22 ethers. The most preferred alkyl chain is stearyl.
Specific Availability Aids [0035] Hydroxy-propyl methyl cellulose (HPMC) has the repeated structure illustrated
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9/67 below in general terms:
ÇHj ch ^oh
ch ₉ [0036] Insofar as the hydroxypropoxy substituents can be attached to each other on the side chains, the degree of substitution for HPMC can be greater than 3.
[0037] In usable HPMC derivatives "Sangellose", some of the OH-groups in the hydroxyl-propyl side group are replaced with alkyl ethers. Typically, these are C1-C20 alkyl ethers, θ can, in specific cases, be replaced by C16-C22 ethers. The most preferred alkyl chain is stearyl.
[0038] Hydroxy-ethyl methyl cellulose (HEMC), has the repeated structure shown below in general terms:
[0039] Insofar as the ethoxy substituents can be attached to each other on the side chains, the degree of substitution can be greater than 3.
[0040] Hydroxy-propyl guar (HPG) has the repeated structure shown below in general terms:
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[0041] As the hydroxypropoxy substituents can be linked to each other in the side chains, the degree of substitution in HPG can be greater than 3.
[0042] In usable HPG derivatives, at least some of the methyl groups in the side groups are quaternized. Suitable quaternary groups include -N (CH ₃ ) ₃ .
[0043] Hydroxy-ethyl ethyl cellulose (HEEC) has the repeated structure illustrated below in general terms:
[0044] HEEC is the least preferred of the availability aids claimed here.
[0045] Methyl cellulose (ME) has the repeated structure shown below in general terms:
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[0046] The maximum theoretical degree of substitution (DS) is 3.0, however the most typical values are 1.3-2.6.
[0047] Especially good results were obtained when the deposition aid was one that had a viscosity, in a 2% by weight aqueous solution, above 1000 mPa.s. Viscosity measurements were made using a Brookfield viscometer, Axis # 3 , @ 30 rpm. Lower viscosity materials are measured using Axis # 2, @ 60 rpm.
[0048] Preferably the nonionic polysaccharide deposition aid has a molecular weight above 50kD and more preferably above 140kD, more preferably still above 500kD.
[0049] The DS is typically in the range of 1.0 to 3, more preferably above 1.5 to 3, most preferably, when possible, from 2.0 to 3.0.
[0050] A typical MS for the deposition aid is 1.5-6.5. Preferably the MS is in the range of 2.8 to 4.0, more preferably above 3.0, more preferably still 3.2 to 3.8.
[0051] As will be seen in the examples in this description, as the molecular weight is reduced the performance of the deposition aid generally decreases.
Benefit Agents [0052] Benefit agents provide a range of benefits to, where appropriate, skin, tissues or hair.
[0053] Various beneficial agents can be incorporated into the particles. When the end use of the particles is in connection with the preferred formulations containing surfactant, any compatible benefit agent can be used, which can provide a benefit to the substrate being treated
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12/67 with a composition preferably containing a surfactant. The advantages of the particles of the invention in the presence of surfactant are good retention of the beneficial agent in the storage of a formulation and controllable release of the beneficial agent during and after using the product.
[0054] Benefit agents provide a range of benefits for clothing. These include softening, conditioning, lubricating, fat-reducing benefits, ease of ironing, humidification, color preservation and / or anti-piling, quick drying, UV protection, shape retention, dirt release, texturing, repeatability. insects, fungicide, dyeing and / or fluorescent benefit to the fabric.
[0055] A highly preferred benefit is the availability of fragrance (be it free and / or encapsulated) or pro-fragrance.
[0056] Beneficial agents are perfumes (whether free and / or encapsulated), pro-fragrance, clays, enzymes, defoamers, fluorescents, bleaching agents and precursors thereof (including photo-bleaches), tint dyes and / or pigments, fabric conditioning agents (for example, cationic surfactants including water-insoluble ammonium quaternary materials and / or silicones), lubricants (for example, sugar polyesters), photo-protective agents (including sunscreens), antioxidants, agents reducing agents, scavengers, color care additives (including dye fixing agents), unsaturated oil, emollients, insect repellents and / or pheromones, trim modifiers (for example, polymer latex particles, such as, PVAc) and antimicrobial and microbial control agents. Mixtures of two or more of these agents can be used. Private benefit agents are described in further detail below.
[0057] Other preferred benefit agents are flavorings and fragrances, pro-fragrances, clays, enzymes, defoamers, fluorescents, bleaching agents and precursors thereof (including photo-bleaches), dyes and / or pigments, conditioning agents ( for example,
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13/67 cationic surfactants including water-insoluble quaternary ammonium materials, fatty alcohols and / or silicones), lubricants (eg sugar polyesters), color agents and photoprotectors (including sunscreens), antioxidants, ceramides, agents reducers, scavengers, color care additives (including dye fixing agents), unsaturated oil, emollients, moisturizers, insect repellents and / or pheromones, trim modifiers (for example, polymer latex particles such as, PVAc) and antimicrobial and microbial control agents. Mixtures of two or more of these agents can be used. Private benefit agents are described in further detail below.
[0058] For dermal compositions, preferred beneficial agents include one or more fragrances, moisturizers, sunscreens, skin lightening agents, antimicrobials, oils and insect repellents. For hair compositions, the list of beneficial agents is the same with the addition of color protection agents and dyes.
[0059] Antimicrobial agents include Triclosan ™, climbazol, octapirox, ketoconizole, zinc pyrithione, and quaternary ammonium compounds.
[0060] Anti-dandruff agents are beneficial agents suitable for use in hair treatment compositions and are active against dandruff and are typically antimicrobial agents and preferably antifungal agents. Antifungal agents typically exhibit a minimum inhibitory concentration of about 50 mg / mL or less against Malassezia spp.
[0061] Suitable anti-dandruff benefit agents include selected compounds of ketoconazole, climbazole, octopirox, pyrithione metal salts, and mixtures thereof. The preferred azole-based antifungal agents are ketoconazole and climbazole.
[0062] Preferred pyrithione metal salts are zinc, copper, silver and zirconium pyrithione. Most preferred is zinc pyrithione.
[0063] Preferably, the anti-dandruff active substance is present in a concentration of 0.01 to 5% by weight of the composition, more preferably of
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0.1 to 2.5% by weight of the composition.
[0064] Preferred sunscreens and skin lightening agents are composed of vitamin B3. Suitable vitamin B3 compounds are selected from niacin, niacinamide, nicotinyl alcohol or derivatives or salts thereof. Other vitamins that act as skin lightening agents can be advantageously included in the skin lightening composition to provide additional skin lightening effects. These vitamins include vitamin B6, vitamin C, vitamin A or its precursors. Vitamin mixtures can also be used in the composition of the present invention. An especially preferred additional vitamin is vitamin B6. Other non-limiting examples of skin lightening agents usable here include adapalene, aloe extract, ammonium lactate, arbutin, azelaic acid, butyl hydroxy anisol, butyl hydroxy toluene, citrate esters, deoxyarbutin, derivatives of 1,3 diphenyl propane, 2,5-dihydroxyl benzoic acid and its derivatives, 2- (4-acetoxyphenyl) -1,3 ditane, 2- (4-Hydroxylphenyl) -1,3 ditane, ellagic acid, glycan pyranosyl-1-aseorbate, gluconic acid, glycolic acid, green tea extract, 4-Hydroxy-5-methyl-3 [2H] -furanone, hydroquinone, 4-hydroxyanisole and its derivatives, derivatives of 4-hydroxy benzoic acid, hydroxycaprylic acid, inositol ascorbate, kolic acid, lactic acid , lemon extract, linoleic acid, magnesium ascorbyl phosphate, 5-octanoyl salicylic acid, 2,4-resorcinol derivatives, 3,5-resorcinol derivatives, salicylic acid, 3,4,5 trihydroxybenzyl derivatives, and mixtures of themselves. Sunscreens usable in the present invention are 2-ethylhexyl-p-methoxycinnamate, butyl methoxy dibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyl dimethylpaminobenzoic acid and mixtures thereof. Particularly preferred sunscreen is chosen from 2-ethyl hexyl-p-methoxycinnamate, 4, -t-butyl-4'methoxydibenzoyl methane or mixtures thereof. Other conventional sunscreen agents that are suitable for use in the skin whitening composition of the invention include 2-hydroxy-4-methoxybenzophenone, octyldimethyl-p-aminobenzoic acid, digaloyltrioleate, 2,2-dihydroxy-4
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15/67 methoxybenzophenone, ethyl-4- (bis (hydroxypropyl)) aminobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexylsalicylate, glyceryl-p-aminobenzoate, 3,3,5trimethylcyclohexylyl -salicylate, methylanthranilate, p-dimethyl-aminobenzoic acid or aminobenzoate, 2-ethylhexyl-p-dimethyl-amino-benzoate, 2-phenyl benzimidazol-5-sulfonic acid, 2- (p-dimethylaminophenyl) -5-sulfonic acid benzoxazole and mixtures of these compounds.
Preferred antioxidants include vitamin E, retinol, hydroxytoluene-based antioxidants such as Irganox ™ or commercially available antioxidants such as those in the Trollox ™ series.
Association of Benefit Agents and Holders [0066] The availability helper is linked to a particle that comprises the benefit agent itself, or is itself a carrier for the benefit agent. An example of such a delivery aid may be a perfume anti-dandruff, insect repellent or other particle bearing a beneficial agent with the aid attached to the particle surface.
[0067] Although it is preferred to use polymeric particles, preferably encapsulated core-wrap, many other types of particles can be envisaged as carriers of beneficial agent.
[0068] Perfumes have been adsorbed onto clay or zeolite material which are then mixed into particulate detergent compositions: US patent 4,539,135 describes particulate laundry washing compounds comprising a clay or zeolite material carrying perfume. Perfume combinations, in general, with larger pore zeolites, such as zeolites X and Y, are also taught in the prior art. East German Patent Application No. 248,508 refers to perfume dispensers containing a zeolite faujasita type (for example, zeolite X and Y) loaded with perfume. Also, East German Patent Application No. 137,599, published on September 12, 1979, teaches compositions for use in washing powder agents to provide thermally regulated perfume release.
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16/67 [0069] The zeolites A, X and Y are taught for use in these compositions. Other perfume delivery systems are taught in WO 97/34982 and WO 98/41607, published in the name of The Procter & Gamble. WO 97/34982 describes particles comprising perfume-laden zeolite and a release barrier, which is an agent derived from a wax and having a size (i.e., a cross-sectional area) larger than the size of the pore openings of the zeolite carrier. WO 98/41607 describes glass particles comprising agents useful in laundry or cleaning compositions and a glass derived from one or more hydroxy compounds at least partially soluble in water.
[0070] Silicas, amorphous silicates, crystalline monolayer silicates, layered silicates, calcium carbonates, double salts of calcium carbonate / sodium sodium carbonates, sodalites, alkali metal phosphates, pectin, chitin microcounts, carboxyalkylcellulose, gums, resins, gelatin, gum arabic, porous starches, modified starches, carboxyalkyl starches, cyclodextrins, maltodextrins, synthetic polymers such as polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), cellulose ethers, polystyrene, polyacrylates, polymethacrylates, polymers aminoplast, crosslinkers and mixtures thereof, can all provide a basis for perfume particles.
[0071] However, perfume particles are preferred, especially polymeric particles that comprise an amino acid polymer.
[0072] Particles bearing the beneficial agent are typically between 100 nanometers and 50 microns in size. Particles larger than these already enter the visible range.
[0073] The preferred particle size range is in the sub-micron range or in the micron range.
[0074] Suitable particles in the sub-micron range include nanoparticles, latex, and mini-emulsion products with a typical size in the range of 100-600 nanometers.
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17/67 [0075] Suitable particles in the micron range include the known types of encapsulated melamine / urea-formaldehyde, silica, clays, starch and zeolite particles and coacervates with a typical size range of 1-50 microns, preferably 5 -30 microns.
[0076] In one aspect of the present invention, the non-ionic polysaccharide, as a deposition aid, is bound to the preformed particles at least partially.
[0077] The delivery aid is connected to the particle by means of a covalent bond, by entrainment or strong adsorption, preferably by a covalent bond or entrainment, and more preferably by means of a covalent bond. The term "through entrainment" as used here is intended to mean the fact that the delivery aid is adsorbed onto the particle as the polymerization proceeds and the particle grows in size. It is believed that under such circumstances, part of the adsorbed delivery aid is embedded within the particle. In this way, at the end of the polymerization, part of the availability aid is attached and connected to the polymeric matrix of the particle, while the rest is free to extend into the aqueous phase. [0078] The availability aid is preferably and mainly linked to the particle surface and is not, in any significant amount, distributed through the internal volume of the particle. Thus, the particle that is produced using the delivery aid according to the preferred process of the invention can be considered to be a "capillary particle". As noted above, it is important that the non-ionic polysaccharide delivery aid is not removed by water, as it can no longer function effectively as an availability aid. Thus, for example, a spray dryer coating of the non-ionic polysaccharide on the particles would not result in a non-ionic polysaccharide that would be an effective availability aid, since it would be removed from the particles by exposure to water.
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18/67 [0079] The polymeric particles carrying the present invention can comprise a wide selection of monomer units. The term "monomeric units" is intended to mean the monomeric units of the polymer chain; thus, references to "a polymeric particle comprising insoluble monomer units", as used herein, mean that the polymeric particles are derived from insoluble monomers, and so on.
[0080] As noted above, monomer units are preferably derived from monomers that are suitable for step growth polymerization or free radical / addition polymerization. As noted above, particularly preferred are particles of nucleus / aminoplast wrap (e.g., melamine / formaldehyde or urea / formaldehyde) with the beneficial agent present in the core and the non-ionic polysaccharide delivery aid attached to the outer surface of the wrap.
[0081] When the particle itself is not the beneficial agent, the beneficial agent is typically present in an amount of 10-85% by total weight of the carrier particle, preferably from 20 to 75% by the total weight of the particle.
[0082] Although it is essential for the present invention that the delivery aid comprises at least one of the specified nonionic polysaccharides, additional delivery aid may be present on the particle surface. These polysaccharides can be advantageously selected from other cellulose and polyester polysaccharide derivatives, in order to give better substantivity to a plurality of substrates. Additional particularly preferred polysaccharide deposition aids include chitosan, locust bean gum, xyloglucan, guar gum and dextran. Particularly preferred additional polyester deposition aids include polymers having one or more non-ionic hydrophilic components comprising oxyethylene, polyoxyethylene,
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19/67 oxypropylene or polyoxypropylene, and one or more hydrophobic components comprising terephthalate segments.
Volatile Benefit Agents including Perfume as the Benefit Agent [0083] Perfume is an example of a volatile benefit agent. Typical volatile beneficial agents have a molecular weight of 50 to 500. The perfume appropriately has a molecular weight of 50 to 500.
[0084] When pro-fragrances are used, the molecular weight, in general, will be higher.
[0085] Usable perfume components include materials of natural and synthetic origin. They include simple compounds and mixtures. Specific examples of such components can be found in the current literature, for example in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA). These substances are well known to those skilled in the art of perfumery, flavoring and / or flavoring consumer products, that is, substances that impart an odor and / or flavor or flavor to a traditionally perfumed or flavored consumer product, or to modify the odor and / or taste of said consumer product.
[0086] The term perfume, in this context, not only means a fully formulated product fragrance, but also selected components of that fragrance, particularly those that have a tendency to loss, such as so-called 'top notes'. The perfume component can also be in the form of a pro-fragrance. WO 2002/038120 (P&G), for example, refers to photo-labile pro-fragrance conjugates that upon exposure to electromagnetic radiation are capable of releasing a kind of fragrance.
[0087] Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6 (2): 80 [1955]). Examples of well-known top notes include citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. Top notes typically comprise 15-25% in
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20/67 weight of a perfume composition and, in some embodiments of the invention that contain an increased level of top-notes, it is predicted that at least 20% by weight must be present within the encapsulated.
[0088] Typical perfume components that are advantageous to encapsulate include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 degrees Celsius.
[0089] It is also advantageous to encapsulate perfume components that have a low LogP (that is, those that will be distributed in water), preferably with a LogP of less than 3.0. These relatively low boiling point and relatively low LogP materials have been called “late blooming” perfume ingredients and include the following materials: Alyl Caproate, Amyl Acetate, Amyl Propionate, Anisic Aldehyde, Anisol, Benzaldehyde, Benzyl Acetate, Benzyl Acetone, Benzyl Alcohol, Benzyl Formiato, Benzyl Iso Valerate, Benzyl Propionate, Beta Range Hexenol, Camphor Gum, Levo-Carvone, d-Carvone, Cinnamic Alcohol, Cinamyl Formiate, Cis-Jasmone, cis-3-Hexenyl Acetate, Alcohol Cumínico, Ciclal C, Dimethyl Benzyl Carbinol, Dimethyl Benzyl Carbinol Acetate, Ethyl Acetate, Ethyl Acetate Acetate, Ethyl Amyl Ketone, Ethyl Benzoate, Ethyl Butyrate, Ethyl Hexyl Ketone, Ethyl Phenyl Acetate, Eucalyptol, Eugenol, Fenchyl Acetate (Floret Acetate) Decenyl Acetate), Frutene (Decenyl Propionate tricycle), Geraniol, Hexenol, Hexenyl Acetate, Hexyl Acetate, Hexyl Formiate, Hydrotropic Alcohol, Hydroxycitonelal, Indone, Isoamil Alcohol, Iso Mentona, I sopulegil Acetate, Isoquinolone, Ligustral, Linalool, Linalool Oxide, Linalyl Formiate, Menthol, Menthol Acetophenone, Methyl Amyl Ketone, Methyl Anthranylate, Methyl Benzoate, Methyl Benyl Acetate, Methyl Eugenol, Methyl Heptenone, Methyl Heptone, Methyl Heptone, Methyl Heptone Ketone, Methyl Phenyl Carbinyl Acetate, Methyl Salicylate, Methyl-NMethyl Anthranilate, Nerol, Octalactone, Octyl Alcohol, p-Cresol, p-Cresol Methyl Ether, p-Methoxy Acetophenone, p-Methyl Acetophenone, Fenoxy Ethanol, Phenyl Acetaldehyde Acetate, Phenyl Ethyl Alcohol, Phenyl Ethyl Dimethyl Carbinol, Prenyl Acetate,
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21/67
Propyl Bornate, Pulegone, Rose Oxide, Safrole, 4-Terpinenol, Alpha-Terpinenol, and / or Viridine.
[0090] It is common for a plurality of perfume components to be present in a formulation. In the encapsulates of the present invention, it is anticipated that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components from the list given for late blooming perfumes, given above, present in the encapsulated perfume.
[0091] Part or all of the perfume may be in the form of a pro-fragrance. For the purposes of the present invention, a pro-fragrance is any material that comprises a fragrance precursor that can be converted into a fragrance. The pro-fragrance can, for example, be a lipid in a food. Food lipids typically contain structural units with pronounced hydrophobicity. Most lipids are derived from fatty acids. In these 'acyl' lipids, fatty acids are predominantly present as esters and include mono-, di-, triacyl glycerols, phospholipids, glycolipids, diol lipids, waxes, sterol esters and tocopherols. In their natural state, plant lipids comprise antioxidants to prevent oxidation. Although these lipids can be removed at least in part during the isolation of oils from plants, some antioxidants can remain. These antioxidants can be pro-fragrances. In particular, carotenoids and related compounds, including vitamin A, retinol, retinal, retinoic acid and pro-vitamin A are capable of being converted into fragrance species, including ionones, damascones and damascenones. Preferred fragrance food lipids include olive oil, palm oil, canola oil, squalene, sunflower seed oil, wheat germ oil, almond oil, coconut oil, grape seed oil, rapeseed, castor oil, corn oil, cottonseed oil, safflower oil, peanut oil, poppy seed oil, palm kernel oil, rice bran oil, oil
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22/67 canola, soy oil, pumpkin seed oil, jojoba oil and mustard seed oil.
[0092] Appropriate pro-fragrances are those that generate perfume components that are aldehydes. Aldehydes usable in perfumery include, but are not limited to, phenylacetaldehyde, p-methyl phenylacetaldehyde, p-isopropyl phenylacetaldehyde, methinonyl acetaldehyde, phenylpropanal, 3- (4-t-butylphenyl) -2methylpropanal, 3- (4-t-butylphenyl) -propanal, 3- (4-methoxyphenyl) -2-methylpropanal, 3- (4isopropylphenyl) -2-methylpropanal, 3- (3,4-methylenedioxyphenyl) -2-methyl propanal, 3- (4ethylphenyl) -2,2- dimethylpropanal, phenylbutanal, 3-methyl-5-phenylpentanal, hexanal, trans-2-hexenal, cis-hex-3-enal, heptanal, cis-4-heptenal, 2-ethyl-2-heptenal, 2,6-dimethyl-5- heptenal, 2,4-heptadienal, octanal, 2-octenal, 3,7-dimethyloctanal, 3,7dimethyl-2,6-octadien-1 -al, 3,7-dimethyl-1,6-octadien-3-al, 3,7-dimethyl-6-octenal, 3,7-dimethyl-7-hydroxyoctan-1-al, nonanal, 6-nonenal, 2,4-nonadienal, 2,6nonadienal, decanal, 2-methyl decanal, 4-decennial , 9-decennial, 2,4-decadienal, undecanal, 2-methylldecanal, 2-methylundecanal, 2,6,10-trimethyl-9-undecenal, undec-10-enyl aldehyde, undec-8-enanal, dodecanal, tridecanal, tetradecanal, the nisaldehyde, bourgenonal, cinnamic aldehyde, a-amylcininamaldehyde, a-hexyl cinnamaldehyde, methoxy-cinnamaldehyde, citronelal, hydroxy-citronelal, isocyclocitral, citronyl oxiacetaldehyde, cortexaldehyde, cuminic aldehyde, hydroxy aldehyde, heliotropic, hydrochloride, heliotropic, heliotropic vanillin, ethyl vanillin, benzaldehyde, p-methyl benzaldehyde, 3,4-dimethoxybenzaldehyde, 3- and 4- {4-hydroxy-4methyl-pentyl) -3-cyclohexene-1-carboxaldehyde, 2,4-dimethyl-3-cyclohexene -1 carboxaldehyde, 1-methyl-3- (4-methylpentyl) -3-cyclohexen-carboxaldehyde, pmethylphenoxyacetaldehyde, and mixtures thereof.
[0093] Another group of perfumes with which the present invention can be applied are the so-called 'aromatherapy' materials. These materials include many components also used in perfumery, including essential oil components, such as Salvia Esclaréia, Eucalyptus, Geranium, Lavender, Macis Extract, Nerol, Nutmeg, Mint, Sweet Violet and Valerian Leaf.
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23/67 [0094] By means of the present invention, these materials can be transferred to textile articles that will be used or otherwise come into contact with the human body (such as scarves and bed linen) or are deposited directly on the skin or human hair.
[0095] Volatile beneficial agents also include insect repellent materials (the insect should be read widely to include other pests that are arthropods, but not strictly hexopods - for example, ticks). Many of these materials overlap with the perfume component class and some are odorless to humans or have a non-perfume odor. Commonly used repellents include: DEET (N, N-diethyl-mtoluamide), lemon eucalyptus essential oil (Corymbia citriodora) and its active compound p-menthane-3,8-diol (PMD), Icaridine, also known as Picaridine, D -Limonene, Bayrepel, and KBR 3023, Nepetalactone, also known as catnip oil, Citronella oil, Permethrin, Neem oil and Swamp Myrtle. Known insect repellents derived from natural sources include: Achillea alpina, alpha-terpinene, Basil oil (Ocimum basilicum), American Callicarpa (Beauty Berry), Camphor, Carvacrol, Castor oil (Ricinus communis), Cat Weed oil (Nepeta sp.), Cedar oil (Cedrus atlantica), Celery extract (Apium graveolens), Cinnamon (Cinnamomum Zeylanicum, leaf oil), Citronella oil (Cymbopogon fleusus), Clover oil (Eugenic caryophyllata), Eucalyptus (70% + eucalyptol, also known as cineol), fennel oil (Foeniculum vulgare), Garlic oil (Allium sativum), Geranium oil (also known as Pelargonium graveolens), Lavender oil (Lavandula officinalis), essential oil Lemon Eucalyptus (Corymbia citriodora) and its active ingredient p-menthane-3,8-diol (PMD), Lemongrass oil (Cymbopogon flexuosus), Marigolds (Tagetes sp.), Marjoram (Tetranychus urticae and Eutetranycbus orientalis), oil of Neem (Azadirachta indica), Oleic acid, mint (Menta piperita x), Rosemary (Mentha pulegium), Pyrethrum (from Chrysanthemum sp., in particular C. and C. cinerariifolium
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24/67 coccineum), Rosemary oil (Rosmarinus officinalis), Spanish Flag Lantana camara (Helopeltis theivora), Solanum villosum berry juice, Tea Tree oil (Melaleuca alternifolia) and Thyme (Thymus sp.) And mixtures thereof .
[0096] The perfume or other volatile benefit agent, can be encapsulated alone or co-encapsulated with carrier materials, additional deposition aids and / or fixatives. Preferred materials to be co-encapsulated in the present invention into carrier particles include waxes, paraffins, stabilizers and fixatives.
[0097] An optional yet preferred component of carrier particles is a formaldehyde scavenger. This component is particularly advantageous in carrier particles which may comprise formaldehyde as a consequence of its manufacturing process or components.
[0098] The formaldehyde scavenger is chosen from sodium bisulfite, urea, cysteine, cysteamine, lysine, glycine, serine, carnosine, histidine, glutathione, acid
3,4-diaminobenzoic acid, allantoin, glycouryl, anthranilic acid, methylanthranilate, methyl 4-aminobenzoate, ethyl acetoacetate, acetoacetamide, malonamide, ascorbic acid, 1,3-dihydroxyacetone dimer, biuret, oxamide, benzoguanamine, pyroglutamic acid, pyroglutamic acid gaiato, ethyl gaiato, propyl gaiato, triethanol amine, succinamide, thiabendazole, benzotriazole, triazole, indoline, sulfanilic acid, oxamide, sorbitol, glucose, cellulose, poly (vinyl alcohol), poly (vinyl amine), hexane diol, ethylenediamine-N , N'-bisacetoacetamide, N- (2-ethylhexyl) acetoacetamide, N- (3-phenylpropyl) acetoacetamide, lilial, helional, melonal, triple, 5,5-dimethyl-1,3-cyclohexanedione, 2,4- dimethyl-3-cyclohexenecarboxaldehyde, 2,2-dimethyl-1,3-dioxan-4,6-dione, 2-pentanone, dibutyl amine, triethylenetetramine, benzylamine, hydroxycitronelol, cyclohexanone, 2-butanone, pentane dione, dehydroacetic acid, chitosan, or a mixture thereof. Preferred formaldehyde sequestrants are sodium bisulfite, ethyl acetoacetate, acetoacetamide, N-ethylenediamine, N'-bisacetoaeetamide, ascorbic acid, 2,2-dimethyl-1,3-dioxan-4,6-dione, helional, triple, lilial and mixtures of
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25/67 same.
Enzymes [0099] It is preferred that the laundry washing compositions according to the present invention comprise one or more enzymes. When present in a cleaning composition, the aforementioned enzymes can be present at levels from about 0.00001% by weight to about 2% by weight, from about 0.0001% by weight to about 1% by weight. weight, or even from about 0.001% by weight to about 0.5% by weight of the enzyme protein by weight of the composition.
Process Details [0100] In highly preferred embodiments, in which the particles have a distinct core and envelope, a typical process for producing the particles will involve at least one emulsion polymerization step.
[0101] For such embodiments where the core essentially comprises a hydrophobic benefit agent, emulsion polymerization can take the form of dispersing the benefit agent in an aqueous system with materials suitable for forming the required polymeric wrap present in the benefit agent or in the aqueous system. Polymerization then proceeds on the droplet surface of the dispersed benefit agent (or benefit agent plus fixative or carrier) to form a wrap around a core comprising the benefit agent. Such methods are well known, for example, for producing encapsulates of perfume aminoplast.
[0102] In those embodiments of the present invention that have a polymer-containing core, polymerization can take place in at least two phases, in which the wrap and core are formed sequentially. The wrap can be polymerized after the core or the order of polymerization can be reversed:
[0103] Nucleus first: in this approach, the nucleus is formed first and the envelope is deposited on the nucleus.
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26/67 [0104] Core in second place: in this approach, polymerization occurs in at least two phases. At the beginning of these phases, a wrap is formed through a growth polymerization in stages. This wrapper contains and contains the reagents for the chain growth reaction that occurs at a later stage. The temporal separation of these phases is accomplished by controlling the reagents present and the reaction conditions.
[0105] Typically, at least one of the components of the envelope formation reaction is retained from the initial reaction mixture and added gradually to control the progress of the reaction in the envelope formation phase. Advantageously, the first phase of the reaction is carried out under conditions in which the chain growth reaction is inhibited. These conditions include a sufficiently low temperature (for a thermally activated reaction) or sufficiently low light conditions (for a photo activated reaction). Once the envelope formation reaction has proceeded sufficiently, conditions are modified (for example, by increasing the temperature or exposing the reaction mixture to light) to cause the reaction to start to form the inner region. A preferred method is one in which the emulsion is formed comprising the polymeric growth components of the chain in a non-aqueous dispersed phase and the polymeric growth components in stages are at the interface between the dispersed phase and the continuous aqueous phase.
[0106] Typically the aqueous phase comprises an emulsifying agent and one of the co-monomers for the stepped growth polymer. Depending on the chemistry of the polymer chosen, it may also contain any diol, alcohol or amine crosslinking agent. The dispersed phase comprises the chain growth monomer, the initiator, any isocyanate or vinyl crosslinking agents, the other co-monomer for the stepped growth polymer and any optional benefit agent.
[0107] The beneficial agent can be present in the reaction mixture, at a level to give the levels of beneficial agent in the resulting particles
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27/67 at the levels described above, although it is also possible to form “empty” particles and subsequently expose them to a beneficial agent which can be adsorbed into the particle's nucleus.
[0108] Surface modification materials are generally added to the aqueous phase to carry to the end of the process, where, for example, additional monomer (s) can be added to form wrap material and connect the additional materials to the outside of the particle.
[0109] For simple core-wrap particles, the core excluding the beneficial agent is preferably less than or equal to 80% by weight of the mass, and the wrap is generally 20% by weight or more of the particle mass.
[0110] In a preferred embodiment, the emulsion polymerization step is a polymerization called a "mini-emulsion, carried out with a phase droplet size dispersed below one micron. Sufficiently fine emulsions can be obtained through a range of methods, including sonication and / or via dynamic mixers or high shear static mixers. Mini-emulsion products have excellent emulsion properties.
Emulsifying Agents [0111] Many emulsifying agents are known for use in emulsion polymerization. Emulsifying agents suitable for use in the polymerization process may comprise, but are not limited to, nonionic surfactants, such as polyvinylpyrrolidone (PVP), polyethylene glycol sorbitan monolaurate (Tween 20), polyethylene glycol sorbitan monopalmitate (tween 40), polyethylene glycol sorbitan monooleate (Tween 80), polyvinyl alcohol (PVA), and poly (ethoxy) nonyl phenol, ethylene maleic anhydride (EMA) copolymer, Easy-Sperse ™ (from ISP Technologies Inc.), ionic surfactants, such as partially neutralized salts of polyacrylic acids, such as sodium or potassium polyacrylate or sodium or potassium polymethacrylate, Brij ™ -35, Hypermer ™ A 60, or sodium lignosulfate and mixtures thereof.
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28/67 [0112] Emulsifiers may also include, but are not limited to, acrylic acid-alkyl acrylate copolymer, poly (acrylic acid), polyoxyalkylene sorbitan fatty esters, co-carboxy polyalkylene anhydrides, polyalkylene anhydrides -maléic, poly (methyl vinyl ether-maleic anhydride), poly (propylene-co-maleic anhydride), poly (co-maleic butadiene), and poly (acetate-co-maleic vinyl anhydride), polyvinyl alcohols, polyalkylene glycols, polyoxyalkylene glycols, and mixtures thereof.
[0113] Preferred emulsifying agents are fatty alcohol ethoxylates (particularly of the Brij ™ class), ether sulfate salts (including SLES), alkyl and alkaryl sulfonates and sulfates (including LAS and SDS) and quaternary cationic salts (including CTAC and CTAB) .
[0114] The nature of the emulsifying agent can be selected to ensure that the finished particle is compatible with the environment in which it is to be used.
[0115] In particular, cores that are formed in the presence of anionic surfactant systems (eg SLES 1-4 EO, preferably 1-3 EO and the others mentioned above) are compatible with products in which the environment comprises a surfactant anionic, such as, for example, body wash and shampoos.
[0116] The nuclei that are formed in the presence of a cationic surfactant (for example, a quaternary cationic salt as mentioned above, and in particular one of the trimethyl ammonium alkyl halides) are compatible with products in which the environment comprises a cationic surfactant, for example example, a hair conditioner.
[0117] It is particularly preferred that the emulsifying agent still comprises a non-ionic surfactant. This is believed to produce a particle that deposits better on the skin or hair than that produced only with a charged surfactant emulsifier. It is also preferred that the non-ionic surfactant is hydrophilic, in order to promote the formation of a mini-emulsion state. Ethoxylated alcohols with more than ten moles of
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29/67 ethoxylation, for example, Synperonic A20 (C1320EO), produce good results.
[0118] The DLS data of the samples show that, as the level of surfactant grows, the particle size becomes smaller, this is also advantageous.
[0119] Preferably, the ratio of non-ionic to anionic emulsifier should be greater than 1: 1 (ie, non-ionic is present in excess) and the total surfactant level should be> 3% by weight of the polymerization mixture. Co-surfactant [0120] Typically, a co-surfactant will be present in the dispersed phase during polymerization and some part of this co-surfactant will remain in the resulting particle. Co-surfactants suitable for use in the present invention include hexadecane, cetyl alcohol, lauroyl peroxide, n-dodecyl mercaptan, dodecyl methacrylate, stearyl methacrylate, polystyrene, polydecene, mineral oils, C13-C15 alkyl benzoate isopropyl myristate and polymethyl methacrylate and polymethyl methacryl.
[0121] Preferred co-surfactants comprise hexadecane, polydecene and isopropyl myristate.
[0122] Taking a weight% of the oily phase as a total, the co-surfactant is typically 0-20%, preferably 1-15%, more preferably 2-12.5%.
Catalyst [0123] Depending on the reagents present, an optional catalyst may be present in the dispersed phase of the emulsion. For example, in isocyanate / diol reactions, a catalyst can advantageously minimize isocyanate hydrolysis to the primary amine, which can react with additional isocyanate to form polyurea. This undesirable reaction can result in an excess of diol being left at the end of the process, which can potentially lead to the formation of an unpleasant odor and interfere with crosslinking reactions.
[0124] Suitable catalysts can comprise amino compounds or
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Organo-metallic 30/67, such as, N, N'-dimethylaminoethanol, N, N'-dimethylcyclohexylamine, bis- (2-dimethylaminoethyl) ether, N, N'-dimethylacetiiamine, diaminobicyclooctane, stannous octoate and dibutyl dilaurate 1,3bis (dimethylamino) butane, pentamethyldiethylenetriamine and mixtures thereof.
[0125] When required, the level of catalyst is typically 0.1-2% with respect to chain growth monomer.
Connecting the Deposition Aid [0126] As noted above, polymerization can occur in at least two phases. In one method, during the initial phase, the envelope is formed by a reaction that, in preferred embodiments, occurs at less than about 60 degrees Celsius, typically 15-55 degrees Celsius. In the later phase, the core is polymerized at a preferred temperature of more than about 70 degrees Celsius, typically 70-95 degrees Celsius. Both reactions are allowed to proceed long enough for the polymerization to be essentially completed, 1-3 hours being a typical time for each stage.
[0127] The deposition aid is typically added at or near the end of the wrap formation when, for example, the additional wrap forming material (eg, additional isocyanate and the co-monomer) is also added to turn on the aid of deposition to the external surface of the particle by forming additional wrap material that encloses a portion of the deposition aid and leads to a “capillary particle in which the“ hair ”comprises the deposition aid. In the alternative embodiment, the particles can essentially be formed completely and the deposition aid connected by means of a chemical bond.
Preferred Formulations [0128] In one embodiment of the present invention, the particle core comprises a rubberized polymeric material, that is, one that has a Tg, such that it is rubberized under storage conditions. Suitable materials for the formation of nuclei with this property are
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31/67 C2-C30 acrylates or methacrylates, preferably C3-C18, more preferably C3-C12, butyl and methyl derivatives are particularly preferred. It is intended that the core is a good solvent for the beneficial agent.
[0129] Preferably the particle wrap is a glassy material, that is, one that has a Tg, such that, it is glassy in storage conditions. Suitable materials for forming wraps with this property include methyl methacrylates. The wrap is intended to be a kinetic barrier for the beneficial agent, as well as for maintaining the integrity of the capsule. Typically the wrap has a thickness of 10-100 nm, preferably 20-40 nm.
[0130] The particles are typically included in the compositions at levels from 0.001% to 10%, preferably from 0.005% to 5%, more preferably still from 0.01% to 3% by weight of the total composition.
Washing Treatment Compositions [0131] The particles of the present invention with attached delivery aid can be incorporated into laundry washing compositions. This can be done by mixing a paste / dispersion product with some or all of the other components of the composition, for powders, preferably by spraying on the components. Advantageously, the paste / dispersion needs to be dried intensively (if not at all) and this reduces the losses of the beneficial agent.
[0132] The active ingredient in laundry washing compositions is preferably a surface active agent or a fabric conditioning agent. More than one active ingredient can be included. For some applications, a mixture of active ingredients can be used.
[0133] The compositions of the present invention can be in any physical form, for example, a solid, such as a powder or granules, a tablet, a solid bar, a paste, a gel or a liquid, especially a base liquid watery. In particular, the compositions can be used in
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32/67 laundry compositions, especially in liquid, powder or tablet composition for washing. Liquids are particularly preferred, as the problems of hydrolysis and attack by enzymes on the deposition aid are more marked in liquid compositions.
[0134] Clothes washing compositions are specially programmed washing (fabric washing) compositions or softening compositions added to the rinse. The programmed wash compositions may include a fabric softening agent and the softener compositions added to the rinse may include surface active compounds, particularly nonionic surfactant compounds.
[0135] It is preferred that the compositions according to the present invention comprise one or more enzymes. When present in a composition, the aforementioned enzymes can be present at levels from about 0.00001% by weight to about 2% by weight, from about 0.0001% by weight to about 1% by weight or up to even from about 0.001% by weight to about 0.5% by weight of the enzyme protein by weight of the composition.
[0136] A particularly preferred embodiment of the present invention relates to a laundry washing treatment composition comprising:
a) a delivery agent particle of a benefit agent having on the external surface of the particle one or more delivery aids, which include non-ionic polysaccharides selected from the group consisting of: hydroxy-propyl methyl cellulose, hydroxy-ethyl methyl cellulose, hydroxy- propyl guar, hydroxyethyl ethyl cellulose or methyl cellulose, the optionally further comprising a non-polysaccharide polymer (preferably an amino-acid polymer), and the beneficial agent optionally comprising a perfume,
b) at least one anionic or non-ionic surfactant, and,
c) an enzyme selected from cellulase, mannanase and mixtures thereof.
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Hair Treatment Compositions [0137] It is especially preferred that the compositions of the present invention are hair treatment compositions, and in particular are compositions for hair shampoo and / or hair conditioning compositions. As noted above, the preferred benefit agents for delivery are one or more fragrances, moisturizers, sunscreens, skin lightening agents, antimicrobials (especially anti-dandruff agents), oils, insect repellents, color protection agents and dyes. [0138] Although surfactants suitable for use in hair treatment compositions are described in greater detail below, a particularly preferred hair treatment composition (shampoo) comprises a solution of 3-18% by weight of alkyl ether sulfate, 1-4 % of a zwitterionic or amphoteric surfactant and 0.1-5% inorganic salt.
[0139] A particularly preferred embodiment of the present invention relates to a hair treatment composition comprising:
a) a beneficial agent delivery particle having on the external surface of the particle one or more delivery aids, which include non-ionic polysaccharides selected from the group consisting of: hydroxy-propyl methyl cellulose, hydroxy-ethyl methyl cellulose, hydroxy-propyl guar, hydroxy-ethyl ethyl cellulose or methyl cellulose, the optionally additionally comprising a non-polysaccharide polymer (preferably an amino-acid polymer), and, optionally, the benefiting agent comprises a perfume,
b) at least one anionic or non-ionic surfactant.
[0140] Hair conditioning compositions are especially preferred as the compositions of the present invention that give especially good deposition of particles containing the beneficial agent in the distal region of the hair, while compositions without the deposition aid give poor deposition in that region. .
Use in Products
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34/67 [0141] The compositions of the final product of the present invention can be in any physical form, for example, a solid bar, a paste, a gel or a liquid, or especially an aqueous based liquid.
[0142] The particles are typically included in said compositions at levels from 0.001% to 10%, preferably from 0.005% to 7.55%, more preferably still from 0.01% to 5% by weight of the total composition.
[0143] Depending on the end use, compositions according to the present invention will typically contain one or more surfactants (which can be anionic, cationic, non-ionic, zwitterionic and amphoteric), surfactant and / or non-surfactant conditioning agents , fatty alcohols, suspending and thickening agents, polymers, silicones and tinting agents.
Surfactants [0144] The particles of the present invention can advantageously be incorporated into the surfactant-containing compositions, especially for use in hair treatment or washing.
[0145] Compositions formulated comprising may contain an active surface compound (surfactant) which may be surface active compounds chosen from soap and non-anionic, cationic, non-ionic, amphoteric and zwiterionic soap and mixtures thereof. Many suitable surface active compounds are available and are fully described in the literature, for example, in Surface-Active Agents and Detergents, Volumes I and II, by Schwartz, Perry and Berch. The preferred surface active compounds that can be used are composed of anionic and nonionic synthetic soaps and non-soaps.
Surfactants: anionic [0146] Anionic surfactants suitable for laundry washing compositions are well known to those skilled in the art. Examples include primary and secondary alkyl sulfates, particularly C ₈ to C ₁₈ primary alkyl sulfates; alkyl ether sulfates; olefin sulfonates; alkyl xylene sulfonates; dialkyl sulfosuccinates; and fatty acid sulfonate ester. The salts
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35/67 sodium is generally preferred. Sodium alkyl sulfates in general form the volume of anionic surfactant present in laundry washing compositions due to its low cost.
[0147] For hair treatment compositions, examples of suitable anionic cleansing surfactants are alkyl sulfates, alkyl ether sulfates, alkaryl sulfonates, alkanoyl isethionates, alkyl succinates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, N-alkyl sarcosinates, alkyl phosphates , alkyl ether phosphates, and alkyl ether carboxylic acids and salts thereof, especially their sodium, magnesium, ammonium and mono-, di- and triethanolamine salts. Mixtures of surfactants used in skin and hair compositions are generally milder than those used in laundry compositions.
[0148] The alkyl and acyl groups in general contain 8 to 18, preferably 10 to 16 carbon atoms and can be unsaturated. The alkyl ether sulfates, alkyl ether sulfosuccinates, alkyl ether phosphates and alkyl ether carboxylic acids and salts thereof can contain from 1 to 20 units of ethylene oxide or propylene oxide per molecule.
[0149] Typical anionic cleansing surfactants for use in hair shampoo compositions of the present invention include one or more of sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium lauryl sulfate, sodium lauryl ether sulfate, sodium lauryl ether sulfosuccinate , ammonium lauryl sulfate, ammonium lauryl ether, sodium dodecylbenzene sulfonate, triethanolamine dodecylbenzene sulfonate, sodium cocoyl isethionate, sodium lauryl isethionate, carboxylic acid lauryl ether and sodium N-lauryl sarcosinate.
[0150] Preferred anionic surfactants for use in hair care compositions of the present invention are alkyl sulfates and alkyl ether sulfates.
[0151] These materials have the respective formulas R ² SO3M and R ¹ O (C2H4O) _x SO ₃ M, where R ² is alkyl or alkenyl of 8 to 18 carbon atoms, x is an integer having a value of about from 1 to about 10, and M is a
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36/67 cation, such as ammonium, alkanolamines, such as triethanolamine, monovalent metals, such as sodium and potassium, and polyvalent metal cations, such as magnesium and calcium. More preferably, in hair compositions R ² has 12 to 14 carbon atoms, in a straight chain rather than a branched chain in the present invention.
[0152] Preferred anionic surfactants for use in hair treatment compositions are selected from sodium lauryl sulfate and sodium lauryl ether (n) EO (where n ranges from 1 to 3); more preferably sodium lauryl ether (n) EO sodium (where n is 1 to 3); more preferably still sodium lauryl ether (n) EO sodium, where n = 1.
[0153] Preferably, the level of alkyl ether sulfate in a hair treatment composition according to the invention is from 0.5% by weight to 25% by weight of the total composition, more preferably from 3% by weight to 18% by weight, more preferably from 6% by weight to 15% by weight of the total composition.
[0154] The total amount of anionic cleansing surfactant in hair treatment compositions (shampoo) of the present invention, in general, ranges from 0.5% by weight to 45% by weight, more preferably 1.5% by weight up to 20% by weight.
Surfactants: non-ionic [0155] The compositions according to the present invention may contain non-ionic surfactants. Nonionic surfactants that can be used include primary and secondary alcohol ethoxylates, especially C8 to C20 aliphatic ethoxylates with an average of 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially of C10 ethoxylated aliphatic alcohols to C15 primary and secondary with an average of 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxyamides (glucamide).
[0156] It is preferable that the level of nonionic surfactant is from 0% by weight to 30% by weight, preferably from 1% by weight to 25% by weight, more
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37/67 preferably from 2 wt% to 15 wt%, by weight of a fully formulated laundry washing composition comprising the particles of the present invention.
[0157] Hair treatment compositions may contain non-ionic surfactant. More preferably, non-ionic surfactants are present in hair treatment compositions in the range of 0 to 5% by weight.
[0158] Non-ionic surfactants that can be included in the hair treatment compositions of the present invention include primary or secondary straight or branched chain (C8 - C18) aliphatic condensation products or phenols with alkylene oxides, usually ethylene and in general having from 6 to 30 ethylene oxide groups. Alkyl ethoxylates are particularly preferred. Most preferred are alkyl ethoxylates having the formula R- (OCH2CH2) nOH, where R is a C12 to C15 alkyl chain, and does not range from 5 to 9.
[0159] Other non-ionic surfactants suitable for use in hair care compositions include mono- or di-alkyl alkanolamides. Examples include coconut mono- or di-ethanolamide and coconut mono-isopropanolamide.
[0160] Additional non-ionic surfactants, which can be included in compositions of the invention are alkyl polyglycosides (APGs). Typically, APG is one that comprises an alkyl group connected (optionally via a bridge group) to a block of one or more glycosyl groups. Preferred APGs are defined by the following formula:
RO- (G) n where R is a branched or straight chain or a straight chain alkyl group that can be saturated or unsaturated and G is a saccharide group.
[0161] R can represent an average alkyl chain length of about C5 to about C20. Preferably R represents an average alkyl chain length of about C8 to about C12.
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Most preferably, the value is between about 9.5 to about 10.5. G can be selected from C5 or C6 monosaccharide residues, and is preferably a glycoside. G can be selected from the group comprising glucose, xylose, lactose, fructose, mannose and derivatives thereof. Preferably G is glucose.
[0162] The degree of polymerization of the APG, n, can have a value of about 1 to about 10 or more. Preferably, the value of n is in the range of about 1.1 to about 2. Most preferably, the value of n is in the range of about 1.3 to about 1.5.
[0163] Alkyl polyglycosides suitable for use in the present invention are commercially available and include, for example, those materials identified as: Oramix NS10 ex Seppic; Plantaren 1200 and Plantaren 2000 ex Henkel.
[0164] Other non-ionic sugar-derived surfactants which can be included in compositions of the present invention include the C10-C18 N-alkyl polyhydroxy (C1-C6) fatty acid amides 30, such as N-methyl C12-C18 glucamides, as described, for example, in WO 92 06154 and US 5,194,639, and the N-alkoxy polyhydroxy fatty acid amides, such as N- (3-methoxypropyl) glucamide C10-C18.
Surfactants: amphoteric and zwitterionic [0165] The amphoteric or zwitterionic surfactant can be included in an amount ranging from 0.5% by weight to about 8% by weight, preferably from 1% by weight to 4% by weight of a composition according to the present invention, particularly a hair treatment composition.
[0166] Examples of amphoteric or zwitterionic surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkylamino acyls, amyl acyls and amylos; glutamates, with the alkyl and acyl groups ranging from 8 to 19
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39/67 carbon atoms. Typical amphoteric and zwitterionic surfactants for use in the head treatment compositions of the present invention include lauryl amine oxide, cocodimethyl sulfopropyl betaine, lauryl betaine, cocamidopropyl betaine and sodium cocoanfoacetate.
[0167] A particularly preferred amphoteric or zwitterionic surfactant is cocamidopropyl betaine.
[0168] Mixtures of any of the preceding amphoteric or zwitterionic surfactants may also be appropriate. Preferred mixtures are those of cocamidopropyl betaine with additional amphoteric or zwitterionic surfactants as described above. An additional preferred amphoteric or zwitterionic surfactant is sodium cocoanfoacetate.
Surfactants: cationic [0169] The compositions of the present invention for hair treatment and laundry use can be called conditioners, and typically contain a conditioning surfactant. Hair conditioning compositions will typically comprise one or more conditioning surfactants, which are cosmetically acceptable and suitable for topical application to hair.
[0170] Suitable conditioning surfactants include those selected from cationic surfactants, used simply or in admixture. Preferably, the cationic surfactants have the formula N ₊ R ₁ R ₂ R ₃ R ₄ where R ¹ , R ² , R ³ and R ⁴ are independently alkyl (C1 to C30) or benzyl. Preferably, one, two or three of R ¹ , R ² , R ³ and R ⁴ are independently alkyl (C4 to C30) and the other group or other groups R ¹ , R ² , R ³ and R ⁴ are alkyl (C1- C ₆ ) or benzyl. More preferably, one or two of R ¹ , R ² , R ³ and R ⁴ are independently alkyl (C ₆ to C ₃₀ ) and the other groups R ¹ , R ² , R ³ and R ⁴ are alkyl groups (C 1 -C 6 ) or benzyl. Optionally, the alkyl groups can comprise one or more ester (-OCO- or -COO-) and / or ether (-O-) bonds within the alkyl chain. The alkyl groups can optionally be substituted with one or more hydroxyl groups. Alkyl groups can be of
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40/67 straight or branched chain and, for alkyl groups having 3 or more carbon atoms, can be cyclic. The alkyl groups may be saturated or may contain one or more double carbon-carbon bonds (for example, oleyl). The alkyl groups are optionally ethoxylated on the alkyl chain with one or more ethyleneoxy groups.
[0171] Cationic surfactants suitable for use in conditioner compositions according to the present invention include cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetylpyridinium chloride, tetramethylammonium chloride, tetraethylammonium chloride, octyltrimethylammonium chloride, hexylmethylamine chloride , octyldimethylbenzylammonium chloride, decildimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, didodecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, sebotrimethylammonium chloride, diethyl chloride, hydrochloride, hydrochloride, hydrochloride PEG-2-ofeamonium chloride and the corresponding hydroxides thereof. Suitable additional cationic surfactants include those materials bearing the CTFA designations of Quaternium-5, Quaternium31 and Quaternium-18. Mixtures of any of the preceding materials may also be appropriate. A cationic surfactant particularly usable for use in conditioners according to the invention is cetyltrimethylammonium chloride, commercially available, for example, as GENAMIN CTAC, ex Hoechst Celanese. Another cationic surfactant particularly usable for use in conditioners according to the invention is behenyltrimethylammonium chloride, commercially available, for example, as GENAMIN KDMP, ex Clariant.
[0172] Another example of a class of cationic surfactants suitable for use in the present invention, especially in hair care compositions, alone or together with one or more other cationic surfactants, is a combination of (i) and (ii) below:
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41/67 (i) an amine starch corresponding to the general formula (I):
R ¹ CONH (CH2) mN (R ² ) R ³ (I) in which R ¹ is a hydrocarbyl chain having 10 or more carbon atoms, R ² and R ³ are independently selected from hydrocarbyl chains of 1 to 10 atoms carbon, in is an integer from 1 to about 10; and (ii) an acid.
[0173] As used herein, the term hydrocarbyl chain means an alkyl or alkenyl chain.
[0174] Preferred amidoamine compounds are those corresponding to formula (I) in which R ¹ is a hydrocarbyl residue having from about 11 to about 24 carbon atoms, R ² and R ³ are each independently hydrocarbyl residues, preferably alkyl groups, having from 1 to about 4 carbon atoms, in m is an integer from 1 to about 4.
[0175] Preferably, R ² and R ³ are methyl or ethyl groups.
[0176] Preferably, m is 2 or 3, that is, an ethylene or propylene group.
[0177] Preferred amidoamines usable here include stearamidopropyl dimethylamine, stearamidopropyl diethylamine, stearamidoethyl diethylamine, stearamidoethyl-dimethylamine, palmitamidopropyl-dimethylamine, palmitamidopropyl-diethylamine, palmitamidoethyl-diethylamine, dimethylamine-amylethylamine, dimethylamine-amylamine dimethylamine, araquidamidopropyl-dimethylamine, araquidamidopropyl-diethylamine, araquidamidoethyl-diethylamine, araquidamidoethyldimethylamine, and mixtures thereof.
[0178] Particularly preferred amidoamines usable here are stearamidopropyl-dimethylamine, stearamidoethyl-diethylamine, and mixtures thereof.
[0179] Commercially available amidoamines usable here include: stearamidopropyl-dimethylamine with brand names LEXAMINE S-13
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42/67 available from Inolex (Philadelphia Pennsylvania, USA) and AMIDOAMINE MSP available from Nikko (Tokyo, Japan), stearamidoethyl-diethylamine with a brand name AMIDOAMINE S available from Nikko, behenamidopropyl-dimethylamine with the name brand name INCROMINE BB available from Croda (North Humberside, England), and several amidoamines with the brand names of the SCHERCODINE series available from Scher (Clifton New Jersey, USA).
[0180] A protonating acid may be present. The acid can be any organic or mineral acid that is capable of protonating amidoamine in the conditioner composition. Suitable acids usable here include hydrochloric acid, acetic acid, tartaric acid, fumaric acid, lactic acid, malic acid, succinic acid, and mixtures thereof. Preferably, the acid is selected from the group consisting of acetic acid, tartaric acid, hydrochloric acid, fumaric acid, lactic acid and mixtures thereof.
[0181] The main role of the acid is to protonate amidoamine in the hair treatment composition, thus forming a tertiary amine salt (TAS) in situ in the hair treatment composition. TAS is effectively a non-permanent quaternary ammonium cationic surfactant or a quaternary pseudo-ammonium.
[0182] Appropriately, the acid is included in an amount sufficient to protonate more than 95 mol% (293 K) of the amidoamine present.
[0183] In hair conditioners of the present invention, the level of cationic surfactant will generally vary from 0.01% to 10%, more preferably from 0.05% to 7.5%, more preferably from 0.1% to 5% by weight of the composition.
[0184] For laundry conditioners, diluted products typically contain up to about 8%, preferably from 2 to 8% by weight 30 of the active softener, while concentrated products can contain from about 8 to about 50 %, preferably from 8 to 25% by weight of the active substance. Compositions of more than about 25%
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43/67 by weight of the active substance are defined as super concentrated, depending on the active substance system, and should also be considered to be covered by the present invention. The fabric conditioning agent can, for example, be used in amounts of preferably 2% to 30%, more preferably 5% to 25%, and most preferably 8% to 20% by weight of the composition. The fabric softener active substance, for use in fabric conditioner compositions of the present invention typically comprises an ester-bound quaternary ammonium triethanolamine (QAC) compound.
[0185] Preferably, QAC is derived from raw materials of palm or tallow. These raw materials can be pure or based predominantly on palm or tallow. Mixtures of different raw materials can be used. The QAC fatty acid chains preferably comprise from 20 to 35% by weight of saturated C18 chains and from 20 to 35% by weight of monounsaturated C18 chains by weight of the total fatty acid chains. In a preferred embodiment as a laundry washing conditioner, the QAC fatty acid chains comprise from 25 to 30% by weight, preferably from 26 to 28% by weight of saturated C18 chains and from 25 to 30% by weight, preferably from 26 to 28% by weight of monounsaturated C18 chains, by weight of total fatty acid chains. In a preferred embodiment, the QAC fatty acid chains comprise from 30 to 35% by weight, preferably from 33 to 35% by weight of saturated C18 chains and from 24 to 35% by weight, preferably from 27 to 32% by weight of monounsaturated C18 chains, by weight of the total fatty acid chains. The preferred quaternary ammonium materials for use in the present invention can be derived from raw materials having a total iodine index of 30 to 45, preferably 30 to 42, and more preferably 36.
[0186] Commercial examples of laundry conditioning agents include Stepantex ™ UL85, ex Stepan, Prapagen ™ TQL, ex Clariant and
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44/67
Tetranyf ™ AHT-1, ex Kao, (both di- [hydrogenated tallow ester] triethanolammonium methyl sulfate), AT-1 (di- [tallow ester] triethanolammonium sulfate), and L5 / 90 (di- [ palm ester] triethanolammonium methyl sulfate), both ex Kao, and Rewoquat ™ WE15 (a triethanol-ammonium methyl sulfate diester having acyl fatty residues derived from C10-C20 and C16-C18 unsaturated fatty acids), ex Witco Corporation . The active substances of quaternary ammonium are also suitable, such as Stepantex VK90, Stepantex VT90, SP88 (ex-Stepan), Ceca NoraminePrapagen TQ (ex-Clariant), Dehyquart AU-57 (ex-Cognis), Rewoquat WE18 (ex-Degussa) and Tetranyl L190 P, Tetranyl L190 SP and Tetranyl L190 S (all ex-Kao).
[0187] In laundry washing conditioners, the presence of non-ionic, as a flocculation prevention agent, enables the formation of a “diluted thick fabric conditioner composition that does not flocculate in use. Lutensol ™ AT25 (BASF) based on coconut chain and 25 EO groups is an example of an appropriate nonionic surfactant. Other suitable surfactants include Renex 36 (Trideceth-6), ex Uniqema; Tergitol 15-S3, ex Dow Chemical Co .; Dihydrol LT7, ex Thai Ethoxylate Itd; Cremophor CO40, ex BASF and Neodol 91-8, ex Shell.
Oily Conditioning Agents [0188] The compositions according to the present invention, especially the hair treatment compositions can also comprise a dispersed, water insoluble and non-volatile oil conditioning agent. Preferably, such non-silicone oily conditioning agents are present in hair conditioner compositions. [0189] The term "insoluble" is intended to mean that the conditioning agent is not soluble in water (distilled or equivalent) at a concentration of 0.1% (w / w) at 25 ° C.
[0190] Oily or fatty conditioning agents are selected from hydrocarbon oils, fatty esters and mixtures of
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45/67 same. Straight chain hydrocarbon oils will preferably contain from about 12 to about 30 carbon atoms. Also suitable are the polymeric hydrocarbons of alkenyl monomers, such as C2-C6 alkenyl monomers.
[0191] Specific examples of suitable hydrocarbon oils include paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecan, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane, and mixtures thereof. Branched-chain isomers of these compounds can also be used, as well as longer chain hydrocarbons.
[0192] Suitable fatty esters are characterized by having at least 10 carbon atoms, and include esters with hydrocarbyl chains derived from fatty acids or alcohols. Monocarboxylic acid esters include esters of alcohols and / or acids of the formula R'COOR in which R 'and R independently mean alkyl or alkenyl radicals and the sum of carbon atoms in R' and R is at least 10, preferably at least any less
20. Di- and trialkyl and alkenyl esters of carboxylic acids can also be used.
[0193] Particularly preferred fatty esters are mono-, di- and triglycerides, more specifically the mono-, di-, and tri-esters of glycerol and long-chain carboxylic acids, such as C1-C22 carboxylic acids. Preferred materials include cocoa butter, palm stearin, sunflower oil, soy oil and coconut oil.
[0194] The oily or fatty material is suitably present at a level of 0.05% by weight to 10% by weight, preferably from 0.2% by weight to 5% by weight, more preferably from about 0.5% by weight up to 3% by weight. The term “oils”, as used in this description, are distinguished from perfume materials by the fact that perfume materials are listed as odorous materials in Arctander's “Perfume and Flavor Materials of Natural Origin (ISBN-10: 0-931710-36 -7), or listed as odorous materials in
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46/67 several databases, including Flavourbase 2010, ESO 2000 (updated in 2006) and PMP 2001. Perfume materials are generally present as part of a complex mixture of components where each odorous component is present at a level below 0.5% by weight of the composition as a whole. The oils present for other purposes are generally present at levels above 0.5% by weight of the composition as a whole.
[0195] The laundry washing compositions of the present invention may contain a non-ionic softener material, which is preferably an oil and more preferably an oily sugar derivative.
Fatty Alcohol [0196] The hair conditioners of the present invention will typically also incorporate a fatty alcohol. The combined use of fatty alcohols and cationic surfactants in compositions is considered to be especially advantageous because it leads to the formation of a lamellar phase, in which the cationic surfactant is dispersed.
[0197] Representative fatty alcohols comprise 8 to 22 carbon atoms, more preferably 16 to 22. Fatty alcohols are typically compounds containing straight chain alkyl groups. Examples of suitable fatty alcohols include cetyl alcohol, stearyl alcohol and mixtures thereof. The use of these materials in conditioner compositions is also advantageous in that they contribute to the overall conditioning properties of the compositions of the present invention.
[0198] The level of fatty alcohol in hair conditioners of the present invention will generally vary from 0.01 to 10%, preferably from 0.1% to 8%, more preferably from 0.2% to 7%, most preferably from 0.3% to 6% by weight of the composition. The weight ratio of the cationic surfactant to fatty alcohol is suitably 1: 1 to 1:10, preferably 1: 1.5 to 1: 8, optimally from 1: 2 to 1: 5. If the weight ratio of the cationic surfactant to fatty alcohol in hair care compositions is too high, this can lead to eye irritation as a result of the composition. If the reason
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47/67 is very low, it can make the hair feel creaking for some consumers.
[0199] Fatty alcohol may be present in laundry washing conditioners as a complexing fatty agent and is preferably present in an amount greater than 0.3 to 5% by weight based on the total weight of the composition. More preferably, the fatty component is present in an amount of 0.4 to 4%. The weight ratio of the monoester component of the ammonium-quaternary fabric softening material to the fatty complexing agent is preferably from 5: 1 to 1: 5, more preferably from 4: 1 to 1: 4, more preferably from 3: 1 to 1: 3, for example, 2: 1 to 1: 2.
Suspension Agent:
[0200] Preferably, an aqueous composition of the present invention additionally comprises a suspending and / or viscosity enhancing agent.
[0201] Examples of suitable materials include: natural gums, such as carrageenan gum, xanthan gum, arabic gum, tragacanth and guar gum, and derivatives thereof, such as, hydroxypropyl guar and hydroxypropyl guar triamoniochloride; inorganic thickeners such as colloidal aluminum magnesium silicate (Veegum), finely divided silica, natural clays such as bentonite and synthetic clays, such as the synthetic hectorite available as Laponite (ex Laporte Industries Ltd), [0202] Preferred are the selected materials of polyacrylic acids, cross-linked polymers of acrylic acid, acrylic acid copolymers with a hydrophobic monomer, monomer copolymers containing carboxylic acid and acrylic esters, cross-linked copolymers of acrylic acid and acrylate esters, heteropolysaccharide gums and derivatives of heteropolysaccharide crystalline long chain. The long-chain acyl derivative is desirably selected from ethylene glycol stearate, fatty acid alkanolamides having from 16 to 22 carbon atoms and mixtures thereof.
[0203] Distestate as long chain acyl derivatives are preferred
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48/67 ethylene glycol and 3 polyethylene glycol distearate, as they give a pearly appearance to the composition.
[0204] Polyacrylic acid is commercially available as Carbopol 420, Carbopol 488 or Carbopol 493.
[0205] Acrylic acid polymers cross-linked with a polyfunctional agent can also be used; they are commercially available as Carbopol 910, Carbopol 934, Carbopol 941 and Carbopol 980. An example of a suitable copolymer of a monomer containing carboxylic acid and acrylic acid esters is Carbopol 1342. All Carbopol materials (brand name) are available at from Goodrich.
[0206] Suitable crosslinked polymers of acrylic acid and acrylate esters are Pemulen TR1 or Pemulen TR2. A heteropolysaccharide gum is xanthan gum, for example, one available as Kelzan mu.
[0207] Mixtures of any of the aforementioned suspending agents can be used in the present invention. A mixture of cross-linked acrylic acid polymer and long-chain crystalline acyl derivative is preferred.
[0208] The suspending agent will generally be present in a hair treatment composition at levels of 0.1% to 10%, preferably from 0.5% to 6%, more preferably from 0.9% to 4% per total weight of the suspending agent based on the total weight of the composition in the present invention.
Silicone [0209] The compositions of the present invention may contain emulsified droplets of a silicone. In hair treatment composition, they provide improved conditioning performance.
[0210] Suitable silicones include polydiorganosiloxanes, in particular polydimethylsiloxanes, which bear the designation CTFA of dimethicone. Also suitable for use in the composition of the present invention (particularly shampoos and conditioners) are polydimethyl siloxanes having hydroxyl end groups, which bear the designation CTFA of dimethicone. also
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49/67 suitable for use in compositions of the present invention are silicone gums having a slight degree of cross-linking, as described, for example, in WO 96/31188.
[0211] The viscosity of the emulsified silicone itself (not the emulsion or the final composition) is typically at least 10,000 cst at 25 ° C, viscosity of the emulsified silicone itself is preferably at least 60,000 cst, more preferably at least minus 500,000 cst, ideally at least 1,000,000 cst. Preferably, the viscosity does not exceed 10 ⁹ cst for ease of formulation.
[0212] Emulsified silicones for use in the compositions of the present invention will typically have an average silicone droplet size in the composition of less than 30, preferably less than 20, more preferably less than 10 microns, ideally 0.01 to 1 micron. Silicone emulsions having an average silicone droplet size of 0.15 microns are generally referred to as microemulsions.
[0213] Emulsified silicones for use in the compositions of the present invention will typically have a size in the composition of less than 30, preferably less than 20, more preferably less than 15. Preferably average silicon droplet is greater than 0.5 micron, more preferably greater than 1 micron, ideally 2 to 8 microns.
[0214] Silicone particle size can be measured using a laser light scattering technique, for example, using a 2600D Particle Size Meter from Malvern Instruments.
[0215] Suitable examples of preformed emulsions include Xiameter MEM 1785 and microemulsion DC2-1865 available from Dow Corning. These are dimethiconol emulsions / microemulsions. These crosslinked silicone gums are also available in a pre-emulsified form, which is advantageous for ease of formulation.
[0216] An additional preferred class of silicones for inclusion in compositions of the present invention, especially treatment compositions
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50/67 hair are the functional amino silicones. The term functional amino silicone should be understood as a silicone containing at least one primary, secondary or tertiary amine group, or a quaternary ammonium group. Examples of suitable amino functional silicones include: polysiloxanes bearing the designation CTFA of amodimethicone.
[0217] Specific examples of amino functional silicones suitable for use in the present invention are the aminosilicone oils DC2-8220, DC28166 and DC2-8566 (all ex Dow Corning), [0218] Suitable quaternary silicone polymers are described in EP-A0 530 974. A preferred quaternary silicone polymer is K3474, ex Goldschmidt.
[0219] Also suitable are emulsions of amino functional silicone oils with non-ionic and / or cationic surfactants.
[0220] Preformed amino functional silicone emulsions are available from silicone oil suppliers such as Dow Corning and General Electric. Specific examples include Cationic Emulsion DC939 and non-ionic emulsions DC2-7224, DC2-8467, DC2-8177 and DC2- 8154 (all ex Dow Corning).
[0221] The total amount of silicone is preferably from 0.01% by weight to 10% by weight of the total composition, more preferably from 0.1% by weight to 5% by weight, more preferably still 0.5% by weight up to 3% by weight is an appropriate level.
Cationic Polymers [0222] Cationic polymers are preferred ingredients in inventive hair treatment compositions to improve performance.
[0223] Suitable cationic polymers can be homopolymers, which are cationically substituted or can be formed from two or more types of monomers. The average molecular weight (Mw) of polymers in general will be between 100,000 and 2 million Daltons. The polymers will have groups containing cationic nitrogen, such as quaternary ammonium or
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51/67 protonated amino groups, or mixtures thereof. If the molecular weight of the polymer is very low, then the conditioning effect will be weak. If it is too high, there may be problems with extensive high viscosity leading to the strictness of the composition when it is poured.
[0224] The group containing cationic nitrogen will generally be present as a substituent in a fraction of the total monomeric units of the cationic polymer. Thus, when the polymer is not a homopolymer, it may contain non-cationic spacer monomer units. Such polymers are described in the CTFA Cosmetic Ingredient Directory, 3rd edition. The ratio of cationic to non-cationic monomer units is selected to provide polymers having a cationic charge density in the required range, which is generally 0.2 to 3.0 meq / gm. The cationic charge density of the polymer is appropriately determined via the Kjeldahl method as described in the US Pharmacopoeia in chemical tests for nitrogen determination.
[0225] Suitable cationic polymers include, for example, copolymers of vinyl monomers having cationic amine or quaternary ammonium functionality with water-soluble spacer monomers, such as, (meth) acrylamide, alkyl and dialkyl (methyl) acrylamides, alkyl ( met) acrylate, vinyl caprolactone and vinyl pyrrolidine. The substituted alkyl and dialkyl monomers preferably have C1-C7 alkyl groups, more preferably C1-3 alkyl groups. Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol.
[0226] Cationic amines can be primary, secondary or tertiary amines, depending on the particular species and the pH of the composition. In general, secondary and tertiary amines, especially tertiary ones, are preferred.
[0227] Vinyl monomers substituted with amine and amines can be polymerized in the form of amine and then converted to ammonium by quaternization.
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52/67 [0228] Cationic polymers may comprise mixtures of monomer units derived from monomer substituted with amine- and / or quaternary ammonium and / or compatible spacer monomers.
[0229] Suitable cationic polymers include, for example:
- cationic polymers containing quaternary ammonium diallyl, including, for example, dimethyldiallylammonium chloride homopolymer and acrylamide and dimethyldiallylammonium chloride copolymers, referred to in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively;
- mineral acid salts of amino-alkyl esters of the homo- and copolymers of unsaturated carboxylic acids having 3 to 5 carbon atoms, (as described in US patent 4,009,256);
- cationic polyacrylamides (as described in WO95 / 22311).
[0230] Cationic polysaccharide polymers suitable for use in compositions of the present invention include monomers of the formula:
AO- [RN ⁺ (R ¹⁾ (R ²⁾ (R ³⁾ X ^-], wherein: A is an anhydroglucose residual group, such as a residual starch anhydroglucose or cellulose. R is an alkylene, oxyalkylene, polyoxyalkylene or hydroxyalkylene group or combinations thereof. R ¹ , R ² and R ³ independently represent alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl or alkoxyaryl groups, each group containing up to about 18 carbon atoms. The total number of carbon atoms for each cationic component (that is, the sum of carbon atoms in R ¹ , R ² and R ³ ) is preferably about 20 or less, and X is an anionic counterion.
[0231] Another type of cationic cellulose includes the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with epoxide substituted with lauryl dimethyl ammonium, referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from Amerchol Corporation, for example, under the brand name of Polymer LM-200.
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53/67 [0232] Other suitable cationic polysaccharide polymers include cellulose ethers containing quaternary nitrogen (for example, as described in US patent 3,962,418), and copolymers of etherified cellulose and starch (for example, as described in US patent 3,958) .581).
[0233] A particularly suitable type of cationic polysaccharide polymer that can be used is a derivative of cationic guar gum, such as hydroxypropyltrimethylammonium guar chloride (commercially available from Rhodia in its JAGUAR trademark series). Examples of such materials are JAGUAR C13S, JAGUAR C14, JAGUAR C15, JAGUAR C17, JAGUAR C16, Jaguar CHT and JAGUAR C162.
[0234] Mixtures of any of the aforementioned cationic polymers can be used.
[0235] The cationic polymer in general will be present in a hair shampoo composition of the present invention at levels of 0.01 to 5%, preferably from 0.05 to 1%, more preferably from 0.08 to 0.5% by weight total of the cationic polymer based on the total weight of the composition.
[0236] The amount of polymer used in the laundry washing compositions of the present invention is suitably from 0.001 to 0.5% by weight, preferably from 0.005 to 0.4% by weight, more preferably from 0.05 to 0.35 % by weight, and most preferably from 0.1 to 0.25% by weight, by weight of the total composition. An example of a preferred polymer is Flosoft 270LS ex SNF.
Minority [0237] As additional optional components for inclusion in compositions according to the present invention, the following conventional adjuvant materials, known for use in cosmetic compositions, can be mentioned: emulsifiers, humectants, suspending agents, rheology modifiers, pearling agents, opacifiers, salts, perfumes, buffering agents, coloring agents, emollients, moisturizers, foam stabilizers, sun protection materials, agents
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54/67 antimicrobials, preservatives, antioxidants, and natural oils and extracts. Some or all of these materials may be present in the volume of the composition, as well as some may be present in the beneficial agent delivery particles.
Tint Dye [0238] Optional tint dyes can be used in the laundry and hair care compositions of the present invention. Violet and blue appear as preferred dyes. Tint dyes can perform a variety of functions with respect to the yellowing of the substrate. For example, in laundry compositions, any unsaturated quaternary ammonium compounds are subjected to the same degree of UV light and / or radical-catalyzed transition metal ion auto-oxidation, with an associated risk of yellowing of the fabric and, thus, the shade dye reduces the risk of yellowing from this source.
[0239] Different shade dyes give different levels of color. The level of shade dye present in compositions of the present invention therefore depends on the type of shade dye. Preferred global ranges, suitable for the present invention, are those from 0.00001 to 0.1% by weight, more preferably from 0.0001 to 0.01% by weight, more preferably still from 0.0005 to 0.005% by weight by weight of the total composition.
[0240] So that the present invention can be further understood and implemented in practice, it will be further described with reference to the following examples. In the examples, as in the rest of the description, all percentages are by weight, unless otherwise specified.
EXAMPLES [0241] In the examples, the following abbreviations are used for deposition aids according to the present invention.
- hydroxypropyl methyl cellulose (HPMC),
- hydroxyethyl methyl cellulose (HEMC),
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- hydroxypropyl guar (HPG),
- hydroxyethyl ethyl cellulose (HEEC),
- methyl cellulose (MC)
Example 1: Particle deposition performance in tissues [0242] Hydrogen chloride 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDAC) was obtained from Alfa Aesor and all other chemicals were obtained from Sinopharm Chemical Reagent Co., Ltd.
a) Synthesis of functional polystyrene carboxyl particle (3.6 um) [0243] Polystyrene particles functionalized with carboxyl were synthesized via dispersion copolymerization. A 500 ml three-mouthed flask was fed with 140 ml of ethanol and 12.0 ml of Dl water containing 38.0 g of styrene, 1.4 g of acrylic acid and 3.0 g of poly (N-vinylpyrrolidiene) . A nitrogen blank was maintained and stirred at a rate of 500 rpm. This solution was deoxygenated by bubbling nitrogen for 1.0 hour. After vigorous deoxygenation, the temperature was raised to 70 ° C and 6.0 g of AIBN was added to this solution. The reaction was maintained at 70 ° C for 20 hours. After being cooled to room temperature, the latex was centrifuged at 10,000 rpm for 15 minutes and the supernatant was decanted and removed. The latex particles were re-dispersed in 100 mL of ethanol, centrifuged at 10,000 rpm for 15 minutes and the supernatant decanted and removed. The latex was then re-dispersed in ethanol and centrifuged again, the supernatant was decanted and removed and the functional carboxyl polyester particles were collected.
b) Purification of latex particles [0244] The functional carboxyl polyester particles (3.6 pm) were purified via the following procedure:
[0245] Step 1: 1.0 mL of latex was diluted with 0.5 mL of pH 7.01 buffer, and centrifuged at 10,000 rpm for 15 minutes. Washing in pH 7 buffer was repeated once.
[0246] Step 2: The supernatant was decanted and removed and the latex was removed
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56/67 dispersed in water Dl. The solution was centrifuged again at 10,000 rpm for 15 minutes and the supernatant was decanted and removed. The wash in deionized water was also repeated once.
c) Graft of polysaccharides on latex particles (3.6 um) via EDAC coupling [0247] Direct chemical coupling with EDAC coupling was used to graft the polysaccharide onto the PS (Polystyrene) particles.
[0248] The above purified latex was re-dispersed in 500 ml of Dl water with a solids content of 5.5% (w / w). 25 ml of deionized water and 0.28 g of EDAC were added to 4.57 ml of the purified latex above (5.5% solids content) and the resulting mixture was stirred at 25 ° C for 3 hours. Then the latex was centrifuged at 1000 rpm for 10 minutes and purified with pH 7 buffer and deionized water according to Step 1 and Step 2 shown in Example 1 b. Then the latex was re-dispersed in 20 ml of deionized water.
[0249] The polysaccharide solution (0.9 g / L) was prepared separately and stirred at 25 ° C for 3 hours to ensure complete dissolution of any dispersed gel materials. 10 ml of EDAC-modified PS particles were mixed with 5.6 or 66.7 ml of polysaccharide solution, as the polysaccharide feed ratio for the OS particles of 0.05: 1 or 0.6: 1 , respectively. The mixture was then stirred at 45 ° C for 24 hours, after which the latex was centrifuged at 10,000 rpm for 15 minutes and purified in pH 7 buffer and deionized water again according to Steps 1 and 2 shown in Example 10b. Finally, the latex was re-dispersed in 10 ml of deionized water to give a final latex dispersion of 1.0% (w / w) polysaccharide grafted particles.
d) Preparation of comparative example (polystyrene latex without surface-bound polysaccharide) [0250] A comparative sample (control) without any addition of polysaccharide was prepared according to the identical procedure shown in Example 1a. The final solids content of latex was adjusted to 1.0% (w / w).
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57/67 [0251] Polystyrene latex distributions (3.6 pm, with or without polysaccharides) were evaluated with sodium dodecylbenzenesulfonate (LAS) and Synperonic A7 as a surfactant stock solution using the constant temperature stirring apparatus (model THZ platform, provided by Shanghai Jing Hong laboratory instrument Co., Ltd.).
e) Preparation of stock solutions [0252] The stock solution of surfactant was prepared by dissolving LAS (5.0 g) and Synperonic A7 (5.0 g) in deionized water to a total of 1.0 liter. The surfactant concentration of the final solution is 10 g / L (50% LAS, 50% Synperonic A7). The base buffer stock solution was prepared by dissolving sodium carbonate (7.546 g) and sodium bicarbonate (2.419 g) in deionized water to a total of 1.0 liter. The concentration of the base buffer is 0.1 M.
f) Bottle washing procedure [0253] The stirring apparatus at constant temperature was used to simulate the washing procedure to assess deposition performance. The typical procedure was as described below.
[0254] 55 mL of model washing liquor (1.0 g / L surfactant and 0.01 M base buffer) containing 600 ppm polystyrene latex (3.6 pm) with or without grafted polysaccharide was prepared in a bottle 120 mL and a 5.0 mL aliquot was taken to read absorbance at 400 nm. This absorbance value represents 100% of particles in the washing solution before the bottle washing process.
[0255] One piece (20x20cm) of non-fluorescent polyester mesh (around 5.0 g) or three pieces (10x10cm) of non-fluorescent cotton fabric (totally around 4.5 g) were then placed inside the bottle and the bottle was sealed. The shaker bath was heated to 40 ° C and the bottle was fixed inside and shaken at 125 rpm for 30 minutes to simulate the programmed wash. The tissues were then removed and twisted by hand and an aliquot of 10.0 mL was removed from the programmed washing solution for reading
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58/67 absorbance at 400 nm. The amount of polystyrene latex adsorbed by the fabric can be determined by the difference in turbidity before / after the programmed washing stage.
[0256] The bottle was then vigorously washed. The twisted tissues were placed back in the bottles and 50 ml of Dl water was added. The bottle was shaken at 40 ° C for 10 minutes at 125 rpm to simulate a rinse procedure. The tissues were then removed and twisted by hand again. A 10.0 mL aliquot was removed from the rinse solution to read absorbance at 400 nm. The amount of polystyrene latex loss absorbed from the fabric in rinse stage 1 can be determined according to the turbidity. The rinse procedure was repeated once and the amount of polystyrene latex loss from the tissue in rinse stage 2 can be determined.
[0257] The results of deposition of latex particle model systems on polyester are illustrated in the following table. Multiple results are given for some materials:
Material & Supplier Viscosity Molecular weight Graft [a] Washing Dep. Rinse Dep. HPMC (ShinEtsu) -4000 3550 (1%,25 ° C) - 20% 86% 68% HPMC (ShinEtsu) -15000 17,200(1%, 25 ° C) - 25% 78% 62% HPMC (ShinEtsu) ™100000 89,800 (1%,25 ° C) - 29% 83% 67% HPMC (Ashland) -K200M 218,300 (2%,25 ° C) - 30% 96% 92% HPMC (DAI DO)Sangellosis - - - 94% 87% HEMC (TCI) M0322 20-40(2%, 20 ° C) 80k [c] 53% 84% 66%
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HPG gum(Ashland) HP40s 5650(1%, 25 ° C) 5335k [c] - 97% 90% HEEC (TCI) E0131 - - - 53% 32% MC (TCI) M0290 13-18(2%, 20 ° C) 38k [c] - 71% 56% MC (TCI) M0291 20-30(2%, 20 ° C) 50k [c] - 62% 41% MC (TCI) M0292 80-120(2%, 20 ° C) 92k [c] - 79% 54% MC (TCI) M0293 350-550(2%, 20 ° C) 160k [c] - 79% 57% MC (TCI) M0294 1000-1800(2%, 20 ° C) 295k [c] 29% 64% 44% MC (TCI) M0185 3500-5600(2%, 20 ° C) 351k [c] 17% 86% 71% MC (TCI) M0295 7000-10000(2%, 20 ° C) 318k [c] 61% 80% 67% Hydroxyethyl Cellulose (TCI) H0242 (Comparative) 200-300(2%, 20 ° C) 380k [c]39% 19% Hydroxyethyl Cellulose (TCI) H0418 (Comparative) 4500-6500(2%, 20C) 557k [c]57% 37% Hydroxyethyl Cellulose (TCI) H0392 (Comparative) 800-1500(2%, 20 ° C) 1384k [c]44% 23% Hydroxyethyl Cellulose (Ashland) 250HR (Comparative) 1900(2%, 20 ° C) 1559k [c]44% 33% Hydroxymethyl hydroxyethyl cellulose (Ashland) Polysurf 67 (Comparative) 8000 (1%,25 ° C) - - 48% 27%
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Hydroxymethyl hydroxyethyl cellulose (Ashland) Pluss330 (Comparative) 490(1%, 25 ° C)27.8 35% 21% Ethyl cellulose (Ashland)N7(Comparative) 7(5%, 25 ° C) [b] 26.0% 7.7% Ethyl cellulose (Ashland)N50(Comparative) 50(5%, 25 ° C) [b] 32.1% 10.5% Ethyl cellulose (Ashland)N14(Comparative) 14(5%, 25 ° C) [b] 32.7% 12.4% Butyrate AcetateCellulose (Aldrich)(Comparative)30k23% -3% Carboxymethyl cellulose (TCI) C0045 (Comparative)«130kDP = 50052% 30% Carboxymethyl cellulose (TCI) C0603 (Comparative)~ 273kDP = 1050 27% 39% 11% Starch (Alfa Aesar)(comparative) - - 22% 46% 31% Carragena (TCI)C1804 (comparative) - - - 33% 16% Carragena (TCI)C1805 (comparative) - - - 26% 11% Pectin (TCI) P0024(comparative) - - - 37% 19%
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Tamarind gum (TCI) T0909 (comparative)- - 55% 36% Xanthan gum (TCI)X0048(comparative)- - 32% 14% Gum arabic (Sínopharm ChemicalReagent Co., Ltd)(comparative) 60-170(1%, 25 ° C) - - 35% 14% Hydroxypropyl (cationic) modified guar gum (Ashland) HPCG1000 (comparative) 520 (1%,25 ° C) - - 98% 60%
[a] The polysaccharide feed rate to the PS particle is 0.6: 1.
[b] The solvent is 80% toluene and 20% ethanol. For all other viscosity data, the solvent is water.
[c] Results of laboratory analysis
Example 2: Deposition of particles on cotton [0258] The following results were obtained when the latex particles of the
Example 2 were deposited on cotton:
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Material & Supplier Viscosity Molecular weight Graft [a] Washing Dep. Rinse Dep. Original Particle (without availability aid) - - - 52.4% 43.9% HPMC (DAIDO)(Sangellosis) - - - 82.8% 66.9% HPMC (Ashland) - K200M 218,300(2%, 25 ° C) - - 86.0% 64.6% MC (TCI) M0185 3500-5600(2%, 20 ° C) 351k [b]82.4% 61.1% Hydroxyethyl Cellulose(Ashland) 250HR 1900(2%, 20 ° C) 1559k [b]72.5% 65.7% HEMC (TCI) M0322 20-40 (2%,20 ° C) 80k [b] 60% 78.4% 65.5% HPG gum (Ashland)HP40s 5650(1%, 25 ° C) 5335k [b] 68% 70.2% 59.6%
[a] the polysaccharide feed ratio for the PS particle is 0.05;
[b] results of laboratory analysis [0259] The Table below shows some consolidated results for Examples 2 and 3, in which the deposition percentage is recorded after rinsing for both polyester and cotton. It can be seen that the particles according to the present invention (those using HPMC, MC and HMC) show excellent deposition on both polyester and cotton, however, in the comparative example (using HEC), good deposition on cotton occurs, but there is failure to give good deposition in polyester.
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Material & Supplier Dep. Polyester Dep. Cotton Original Particle (without auxiliary control) - 43.9% HPMC (DAIDO) (Sangellosis) 87% 66.9% HPMC (Ashland) -K200M 92% 64.6% HEMC (TCI) M0322 66% 65.5% HPG Gum (Ashland) HP40s 90% 59.6% MC (TCI) M0185 71% 61.1% Hydroxyethyl Cellulose (Ashland) 250HR (comparative) 33% 65.7%
Example 3: Surface bonding of HEMC over perfume encapsulants via melamine formaldehyde wrap formation [0260] The preformed melamine formaldehyde perfume encapsulates were 15 microns in size and were obtained from Givaudan Limited. Particle solids were 41.6% by weight and perfume solids were 28.0% by weight, respectively. The grade of hydroxyethyl methyl cellulose (HEMC) used was Walocel MW 40000 PFV supplied by Dow Wolf Cellulosics.
[0261] The following procedure outlines the synthetic modification to bond HEMC to the surface via the formation of additional melamine formaldehyde (MF) wrap:
a) Preparation of the prepolymer [0262] To a 100 ml conical flask were added 19.5 g of formalin (37% by weight of aqueous formaldehyde) and 44.0 g of water. The pH of the solution was adjusted to 8.9 using 0.3 g of 5% by weight aqueous sodium carbonate. 10 g of melamine and 0.64 g of sodium chloride were added and the mixture was stirred for 10 minutes at room temperature. The mixture was heated to
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65 ° C and stirred until it becomes clear. This mixture is referred to herein as "prepolymer (1)".
b) Binding of HEMC to perfume encapsulants in melamine formaldehyde [0263] A solution of HEMC at 1% by weight was prepared by dissolving 1.0 g of HEMC in 99.0 g of deionized water by stirring overnight. in an orbital shaker (VWR Standard 5000 Shaker in setting number 4). 50 g of this HEMC solution was transferred to a 250 ml round-bottom flask, equipped with a stirrer and condenser at the top. 23.6 g of melamine formaldehyde encapsulated paste (41.6% by weight of particulate solids) was added and the mixture was heated to 75 ° C with stirring. 0.9 g of a freshly prepared prepolymer solution (1) was added and the pH was adjusted to 4.1, using approximately 2 g of 10% by weight aqueous formic acid solution. The mixture was left under stirring at 75 ° C for 2 hours. The solution was then cooled and the pH was adjusted to 7 using approximately 7 g of aqueous 5% by weight aqueous calcium carbonate solution.
[0264] A final dispersion (approximately 100 g) was obtained consisting of 10% by weight of encapsulated solids containing an additional wrapper of 2% by weight of melamine formaldehyde and 5% by weight (based on the final particle weight) of HEMC .
[0265] Similarly, a range of alternative hydrophobically modified polysaccharides was prepared. For some, the reaction temperature has been reduced and the reaction time has been increased. This was done to ensure that they were below the cloud point for the polysaccharides to achieve solubility and maximize grafting. Details for all of them can be found in the following table:
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Polysaccharide Degree Provider Cloud point(° C) Reaction temperature Reaction time (hours) Hydroxypropyl MethylCellulose (HPMC) Metolose90SH-15000SR ShinEtsu 66 60 20 Hydrophobically Modified Guar Gum (HMGG) N-HanceHP40S Ashland > 80 75 2 Hydrophobically Modified Guar Gum (C22)(HM22GG) EsacolHM22 Lamberti Spa > 80 75 2 Hydroxybutyl MethylCellulose (HBMC) 20,026-3 Aldrich 38 35 48 Methyl Cellulose(MC) M7140 Aldrich 38 35 48
Example 4: Hair deposition from shampoo and conditioners [0266] Hair deposition from shampoo and conditioners of hydrophobically modified polysaccharides linked to perfume encapsulants (in Example 3) was evaluated as follows:
a) Preparation of hair care formulations [0267] Model shampoo formulations were prepared by adding 12% of the active substance SLES, 1.6% of the active substance CAPB and 1% of the active substance sodium chloride to deionized water. From this, formulations were prepared containing 1% of the active substance encapsulated MF with or without grafted polysaccharide.
[0268] Model hair conditioner formulations have been prepared
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66/67 by adding 0.38% lactic acid, Lexamine S-13 1.25%, Genamin BTLF 0.87%, Lanette S3 5%, Nipagin M 0.2%. From these formulations containing 1% of the active substance MF, encapsulated with or without grafted polysaccharide were prepared.
b) Hair washing, extraction and analysis procedure [0269] Braids of dark brown European hair (DBE) with 2 ”in length, weighing 0.3 g, were initially washed based on a 14% SLES solution. Then a standard washing protocol was used for shampoo and conditioner formulations. Both the root and distal part of the hair braids were tested.
[0270] Treatment with Shampoo: using tap water draining at 35-40 degrees Centigrade, flow rate of 3-4 liters per minute, the braids were vigorously wetted and the excess water was removed.
[0271] 0.1 g of shampoo per g of hair was applied along the length of each braid and these were shaken by rubbing between the hands for 30 seconds. The braids were then rinsed with warm running water for 30 seconds. The excess water was removed and the braid was allowed to dry.
[0272] Conditioner Treatment: using tap water draining at 35-40 degrees Centigrade, flow rate of 3-4 liters per minute, the braid was vigorously wetted and the excess water was removed.
[0273] 0.2g of conditioner per g of hair was applied along the length of each braid and it was shaken by rubbing between the hands for 1 minute. The braids were then rinsed in warm running water for 1 minute. The excess water was removed and the braid was allowed to dry.
[0274] Five repetitions of braids were washed per treatment for reproducibility purposes.
[0275] When dried, each braid was placed in a glass bottle and 2ml of Ethanol was added to extract any deposits. The bottles were rolled in a bottle for 2 hours. From each vial, 100 μL aliquots were removed and placed in a 96-well plate. The plate was then measured with
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67/67 regarding fluorescence in a high performance Thermo Varioskan Flash Spectrometer. The deposition efficiency of MF encapsulates can be determined by comparing the calibration of fluorescence versus concentration and the expected fluorescence for complete deposition.
[0276] The results of deposition of MF encapsulates on the hair are illustrated in the following table:
Material Shampoo Deposition Efficiency (%) Conditioner Deposition Efficiency (%) Root Distal Root Distal Unmodified encapsulated (comparative) 3 3 3 0.5 Modified with HEMC 18 10 16 7 Modified with HPMC 13 10 8 8 Modified with HMGG 15 7 12 7 Modified with HM22GG 8 4 Modified with HBMC 4 1 Modified with MC 7 6
[0277] The results show that the binding of modified polysaccharides to the surface of the perfume encapsulators improves the availability to the hair in both shampoo and conditioner formulations.

权利要求:
Claims (17)
[1]
Claims
1. BENEFIT AGENT AVAILABILITY PARTICLE, characterized by presenting, on the external surface of the particle, one or more availability aids that are non-ionic polysaccharides selected from the group comprising: hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl guar, hydroxyethyl ethyl cellulose or methyl cellulose, the particle comprising a core, which comprises the beneficial agent and at least one wrap, which comprises a water-insoluble non-polysaccharide polymer, the non-ionic polysaccharide being attached to the outermost surface of the wrap, and the core comprising a droplet of the beneficial agent, and the particle providing the beneficial agent having a size between 100 nm and 50 microns.
[2]
2. PARTICLE, according to claim 1, characterized by the fact that the delivery aid comprises hydroxypropyl guar.
[3]
3. PARTICLE, according to claim 1, characterized by the fact that the delivery aid comprises hydroxy-propyl methyl cellulose.
[4]
4. PARTICLE, according to claim 1, characterized by the fact that the delivery aid comprises hydroxy-ethyl methyl cellulose.
[5]
5. PARTICLE, according to claim 1, characterized by the fact that the delivery aid comprises hydroxyl ethyl ethyl cellulose.
[6]
6. PARTICLE, according to claim 1, characterized by the fact that the delivery aid comprises methyl cellulose.
[7]
7. PARTICLE according to any one of claims 1 to 6, characterized in that the, or each of the non-ionic polysaccharide delivery aids has a molecular weight above 20 kD, preferably above 100 kD, more preferably above 500 kD.
[8]
8. PARTICLE according to any one of claims 1 to 6, characterized by the fact that the molar replacement of the
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2/3 availability is in the range of 2.8 to 4.0, more preferably above 3.0, more preferably from 3.2 to 3.8.
[9]
PARTICLE according to any one of claims 1 to 8, characterized in that it additionally comprises a non-polysaccharide polymer, preferably an amino acid polymer.
[10]
10. PARTICLE according to any one of claims 1 to 9, characterized by the fact that it comprises a perfume.
[11]
11. PARTICLE, according to claim 10, characterized in that the perfume has a molecular weight of 50 to 500.
[12]
12. COMPOSITION OF TREATMENT FOR WASHING CLOTHES, HAIR OR SKIN, characterized by comprising:
The. a particle as defined in any of claims 1-11,
B. at least one surfactant.
[13]
13. COMPOSITION, characterized by comprising:
(a) a particle as defined in any of claims 1-11, and, (b) an enzyme selected from the group comprising hemicellulase, cellulase, polygalacturonase, xylanase, pectinase, mannanase, pectate lyase, ligninase, pululanase, pentosanase, arabinosidase, hyaluronidase, chondroitinase, laccase, glycosyl hydrolase and amylase or mixtures thereof.
[14]
14. COMPOSITION OF TREATMENT FOR WASHING CLOTHES, characterized by comprising:
(a) a particle as defined in any of claims 1-11, (b) at least one anionic or nonionic surfactant, and, (c) an enzyme selected from cellulase, mannanase and mixtures thereof.
[15]
15. COMPOSITION OF TREATMENT FOR WASHING CLOTHES, according to any one of claims 12 to 14, characterized by
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3/3 fact that the composition is a liquid or gel.
[16]
16. HAIR OR SKIN TREATMENT COMPOSITION, characterized by comprising:
(a) a particle as defined in any one of claims 1 to 11, (b) at least one anionic or non-ionic surfactant, preferably
3-18% by weight of alkyl ether sulfate.
[17]
17. PROCESS FOR THE PRODUCTION OF PARTICLES OF BENEFICIAL AGENT AVAILABILITY, as defined in any one of claims 1 to 11, characterized by the fact that:
(a) a beneficial agent, preferably a perfume oil, is encapsulated using emulsion polymerization to form core-wrap particles, and, (b) an additional layer of polymer is formed on the outer surface of the core-wrap particles in the presence of at least one of: hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl guar, hydroxyethyl ethyl cellulose or methyl cellulose.

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法律状态:
2017-09-05| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2018-07-03| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2019-01-29| B09A| Decision: intention to grant|

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2019-02-19| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/07/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/07/2012, OBSERVADAS AS CONDICOES LEGAIS |

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2021-02-23| B25A| Requested transfer of rights approved|Owner name: UNILEVER IP HOLDINGS B.V. (PB) |

优先权:

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申请号 | 申请日 | 专利标题

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CNPCT/CN2011/001413|2011-08-24|

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CN2011001413|2011-08-24|

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PCT/EP2012/064898|WO2013026657A1|2011-08-24|2012-07-30|Benefit agent delivery particles comprising non-ionic polysaccharides|

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