HIGH-EFFICIENT CAPSULES UNDERTAKING BENEFIT AGENT, PASTE FLUID, AGGLOMERATED, PROCESS FOR PRODUCING

专利摘要:
High efficiency capsule comprising benefit agent. The present invention relates to high efficiency particles and compositions as consumer products comprising such high efficiency particles as well as processes for the production and use of such high efficiency particles and compositions comprising such high particles. efficiency. Such high efficiency particles and compositions provide approximate release of benefit agent to a situs that is treated with such high efficiency particles and compositions. an encapsulated comprising a core and a wall, said wall having an outer surface and a coating encapsulating the core, said coating comprising defined amino polymers.
公开号:BR112012011580B1
申请号:R112012011580-4
申请日:2010-11-04
公开日:2019-10-08
发明作者:Johan Smets；Pascale Claire Annick Vansteenwinckel；Yonas Gizaw；Frank Hulskotter；Dieter Boeckh；Hans-Joachim Haehnle
申请人:The Procter & Gamble Company；
IPC主号:

专利说明:

Invention Patent Descriptive Report for HIGH EFFICIENCY CAPSULES THAT UNDERSTAND BENEFIT AGENT, FLUID PASTE, AGGLOMERATE, AGGLOMERATE PRODUCTION PROCESS, PRODUCT INTENDED FOR THE CONSUMER, CLEANING METHOD OR TREATMENT OF A SITUS AND PROCESSED PROCESS FOR A SITUS AND PROCESSED PROCESS FOR A SITUS PROCESS. .
FIELD OF THE INVENTION
The present invention relates to high efficiency packages and compositions, such as consumer products, which comprise these high efficiency packages, as well as processes for the production and use of such high efficiency packages and compositions comprising such packages. high efficiency.
BACKGROUND OF THE INVENTION
Beneficial agents, such as perfumes, silicone, waxes, flavorings, vitamins, fabric softening agents are expensive, and / or generally may be less effective when used at high levels in consumer products, for example, personal care compositions and compositions for treating fabrics. As a result, there is a desire to maximize the effectiveness of such beneficial agents. One method to achieve this goal is to improve the efficiency of the release of such beneficial agents. Unfortunately, it is difficult to improve the efficiency of release of beneficial agents, as these agents may be lost due to their physical and chemical characteristics, or such agents may be incompatible with other compositional components or with the situs being treated.
One method of improving the release efficiency of a benefit agent is to encapsulate that benefit agent. While such efforts can optimize the release efficiency of the benefit agent, further improvements in release efficiency are desired since encapsulated benefit agents may be lost before or after being applied to the site of interest due to factors such as mechanical interactions or chemicals, for example, the action of washing and / or rinsing liquids, follows on sheet 1a / 63
Petition 870190033938, of 09/09/2019, p. 5/16
1a / 63 and / or load interactions. In certain applications, the deposition of encapsulated benefit agents is enhanced by coating the encapsulated benefit agent with polymers. In general, such a polymeric coating optimizes the
Petition 870190033938, of 09/09/2019, p. 6/16
2/63 treated simultaneously, for example, a laundry load containing a variety of fabrics, each surface is typically treated to a different degree (more or less beneficial agent being released). In cases where the beneficial agent is a perfume, different levels of treatment of different fabrics in a laundry load can result in an excessively strong odor in some fabrics and an excessively weak odor in other fabrics. Applicants recognized that the source of the problem of unequal treatment is mainly due to the preferential deposition of encapsulates caused by the polymeric deposition aid device. Thus, what is needed are encapsulated benefit agents that have a high and uniform deposition profile on multiple different surfaces.
In the present application, applicants present encapsulated benefit agents and specific classes of amine containing polymers which, when combined, provide a high and uniform deposition profile on multiple different surfaces, for example hair / fur and skin, and on multiple fabrics such as cotton, high-surface cottons, poly-cotton and polyester.
SUMMARY OF THE INVENTION
The present application relates to high-efficiency packages and compositions, such as consumer products, which comprise these high-efficiency packages, as well as processes for the production and use of such high-efficiency packages and compositions which comprise such packages. high efficiency.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
For use in the present invention, consumer product means baby care products, beauty care, fabric and home care, family care, female care, health care, snack and / or drinks or devices generally intended to be used or consumed in the form in which they are sold. Such products include, but are not limited to, diapers, bibs, baby wipes
3/63 genics, products and / or methods related to hair / human hair treatment (humans, dogs, and / or cats), including bleaching, coloring, dyeing, conditioning, shampoo, hairstyles, deodorants and antiperspirants, personal hygiene, cosmetics, skin treatment including the application of creams, lotions and other products for topical application for consumer use including fine fragrances, and products for shaving or hair removal, products and / or methods related to the treatment of fabrics, hard surfaces and any other surfaces in the area of fabric care and home care, including: air care including air purifiers and aroma release systems, car care, dish washing, fabric conditioning (including fabric softeners and / or revitalizers), washing detergent of clothes, additive for washing and rinsing and / or care of clothes, cleaning and / or treatment of hard surfaces including cleaning products cleaning of floors and toilets, and other cleaning for consumer or institutional use, products and / or methods related to bathing, facial tissues, tissues, and / or paper towels, sanitary napkins, sanitary napkins, products and / or related methods oral care including toothpaste, dental gels, mouthwashes, denture adhesives, tooth whitening, over-the-counter health care products including cough and cold medicine, pain relievers, X-ray drugs, pet health and nutrition , processed food products intended primarily for consumption between customary meals or as an accompaniment to meals (some non-limiting examples include potato chips, tortilla chips, popcorn, pretzels, corn chips, cereal bars, vegetable chips, pestis, appetizers , multi-grain chip snacks, biscuits, cheese pestils, pork pururuca, pet corn baits, pellet snacks, extruded snacks and bagel chips), and coffee.
For use in the present invention, the term cleaning and / or treatment composition is a subset of products intended for the consumer that includes, except where otherwise indicated, beauty care, fabric care and home care products. Such products include, but are not limited to,
4/63 are limited to hair care products (humans, dogs, and / or cats), including bleaching, coloring, dyeing, conditioning, shampoo, hairstyles, deodorants and antiperspirants, personal hygiene, cosmetics, treatment of skin including the application of creams, lotions and other products for topical application for consumer use including fine fragrances, and products for shaving or hair removal, fabric care products, hard surfaces and any other surfaces in the area of tissue care and care of the home, including: air care including air purifiers and aroma release systems, car care, dish washing, fabric conditioning (including fabric softeners and / or revitalizers), laundry detergent, washing additive and rinse and / or care for clothes, cleaning and / or treating hard surfaces including floor and toilet cleaning products, cleaning agents granulated or powdered form, for multiple purposes or for heavy tasks, especially cleaning detergents, multi-purpose washing agents in the form of liquid, gel or paste, especially so-called heavy-duty liquids, liquid detergents for delicate fabrics , hand dishwashing agents or dishwashing agents for light tasks, especially high foaming types, machine dishwashing agents, including various tablet, granular, liquid and rinse aid types for home use and institutional, liquid cleaning and disinfecting agents, including bactericidal type for hand washing, cleaning bars, mouthwashes, denture cleaners, toothpaste, shampoos for cars or rugs, bathroom cleaners including toilet cleaner products, shampoos and conditioners with hair rinse, shower gels, fin fragrances foams and baths, and metal cleaners, as well as auxiliary cleaning compounds such as bleach additives and stain remover or pre-treatment types, substrate loaded products such as sheets for addition to machine drying, cleaning cloths and pads dry and moist, non-woven substrates and sponges, as well as sprays and nebulisations for consumer use and / or use
5/63 institutional, and / or methods related to oral treatment including toothpastes, dental gels, dental mouthwashes, denture adhesives, teeth whitening.
For use in the present invention, the term cleaning and / or treatment of fabric and / or hard surfaces is a subset of cleaning and treatment compositions that includes, except where indicated otherwise, washing agents in granular or powder form, for multiple purposes or for heavy tasks, especially cleaning detergents, multi-purpose washing agents in the form of liquid, gel or paste, especially so-called heavy-duty liquids, liquid detergents for delicate fabrics, agents for manual dish washing or dishwashing agents for light tasks, especially those of high foaming type, dishwashing agents for machines, including the various tablet types, granular, liquid and rinse aid for domestic and institutional use, liquid cleaning agents and disinfection, including bactericidal hand wash, cleaning bars, car shampoos or rugs, bathroom cleaners including toilet cleaners, and metal cleaners, fabric conditioning products including fabric softeners and / or revitalizers that can be in liquid, solid and / or machine-dried sheet form, as well as compounds cleaning aids such as bleach additives and stain remover or types for pretreatment, substrate products loaded as sheets for machine drying, dry and moistened cleaning cloths and pads, non-woven substrates and sponges, as well as sprays and nebulizations. All of these applicable products can be in standard, concentrated or even highly concentrated form, or even to the extent that such products can, in a certain sense, be non-aqueous.
For use in the present invention, articles such as one and one when used in a claim, are understood to mean one or more of what is claimed or described.
For use in the present invention, the terms include, include and
6/63 including are intended to be non-limiting.
For use in the present invention, the term solid includes granular, powder, bar and tablet product forms.
For use in the present invention, the term fluid includes products in the form of liquid, gel, paste and gas.
For use in the present invention, the term situs includes paper products, fabrics, clothing, hard surfaces, hair and skin.
Except where otherwise specified, all component or composition levels refer to the active portion of that component or composition and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
All percentages and ratios are calculated by weight, except where indicated otherwise. All percentages and ratios are calculated based on the total composition, except where indicated otherwise.
It should be understood that each maximum numerical limit mentioned in this specification includes each of the lower numerical limits, as if such lower numerical limits were expressly registered in this document. Each minimum numerical limit mentioned in this specification includes each of the upper numerical limits, as if such upper numerical limits were expressly registered in this document. Each numerical range mentioned in this specification includes each more restricted number range that is within that broader number range, as if such more restricted number ranges were expressly recorded in this document.
High-efficiency encapsulated and slurry / agglomerates comprising the same
An encapsulated which may comprise a core, a wall having an outer surface and a coating, said wall encapsulating said core, said coating coating the outer surface of said wall, said coating may comprise one or more poles 63 mere efficiency with the following formula:
al J b
NR ₂ R ^ ^ R ₃ where:
a) a and b can be whole numbers or averages (real numbers) of about 50 to 100,000;
b) each R1 can be independently selected from H, CH ₃ , (C = O) H, alkylene, alkylene with unsaturated CC bonds, CH ₂ -CROH, (C = O) -NH-R, (C = O) - (CH ₂ ) _n -OH, (C = O) -R, (CH ₂ ) _n -E, - (CH ₂ -CH (C = O)) _n -XR, - (CH ₂ ) _n -COOH, - (CH ₂ ) _n -NH ₂ , -CH ₂ ) _n - (C = O) NH ₂ , the index n can be an integer from about 0 to about 24, E can be an electrophilic group, R can be a saturated or unsaturated alkane, dialkyl-siloxy, dialkyloxy, aryl, alkylated aryl, which may also contain a selected portion of the group consisting of cyano, OH, COOH, NH ₂ , NHR, sulfonate, sulfate, -NH ₂ , amines quaternized, thiols, aldehyde, alkoxy, pyrrolidone, pyridine, imidazole, imidazolinium halide, guanidine, phosphate, monosaccharide, oligo or polysaccharide;
c) R2 or R3 may be absent or present:
(i) when R3 is present, each R2 can be independently selected from the group consisting of -NH ₂ , -COO-, - (C = O) -, -O-, -S-, -NH- (C = O) -, -NRi-, dialkyl-siloxy, dialkyloxy, phenylene, naphthalene, oxyalkylene, and each R3 can be independently selected from the same group as R1;
(ii) when R3 is absent, each R2 can be independently selected from the group consisting of -NH ₂ , -COO-, - (C = O) -, -O-, -S-, -NH- (C = O) -, -NR _r , dialkyl-siloxy, dialkyloxy, phenylene, naphthalene, oxyalkylene, and each R3 can be independently selected from the same group as R1, and (iii) when R2 is absent, each R3 can be independently selected from the same group as R1;
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d) said one or more efficiency polymers have an average molecular mass of about 1,000 Da to about 50,000,000 Da, of about 5,000 Da, to about 25,000,000 Da, of about 10,000 Da to about 10,000,000 Da, or even about 340,000 Da to about 1,500,000 Da, a degree of hydrolysis, for polyvinyl formamides, from about 5% to about 95%, from about 7% to about 60% , or even from about 10% to about 40%, and / or a charge density of about 1 meq / g of efficient polymer to about 23 meq / g of efficient polymer, about 1.2 meq / g polymer efficiency and 16 meq / g polymer efficiency, from about 2 meq / g polymer efficiency to about 10 meq / g polymer efficiency, or even about 1 meq / g polymer efficiency polymer at about 4 meq / g efficiency polymer.
In one aspect of said encapsulated, one or more polymers of efficiency are selected from the group consisting of polyvinyl amines, polyvinyl formamides, and polyalyl amines and copolymers thereof, with said one or more efficiency polymers having:
a) an average molecular mass of about 1,000 Da to about 50,000,000 Da, of about 5,000 Da, to about 25,000,000 Da, of about 10,000 Da to about 10,000,000 Da, or even about from 340,000 Da to around 1,500,000 Da;
b) a degree of hydrolysis, for said polyvinyl formamides, from about 5% to about 95%, from about 7% to about 60%, or even from about 10% to about 40%, and / or
c) a charge density of about 1 meq / g of efficient polymer to about 23 meq / g of efficient polymer, about 1.2 meq / g of efficient polymer and 16 meq / g of efficient polymer efficiency, from about 2 meq / g of efficient polymer to about 10 meq / g of efficient polymer, or even about 1 meq / g of efficient polymer to about 4 meq / g of efficient polymer.
In one aspect of said encapsulated, said coating may comprise one or more polyvinyl formamides, said polyvinyl formamides having:
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a) an average molecular mass of about 1,000 Da to about 50,000,000 Da, of about 5,000 Da, to about 25,000,000 Da, of about 10,000 Da to about 10,000,000 Da, or even about from 340,000 Da to around 1,500,000 Da;
b) a degree of hydrolysis, for said polyvinyl formamides, from about 5% to about 95%, from about 7% to about 60%, or even from about 10% to about 40%, and
c) a charge density of about 1 meq / g of efficient polymer to about 23 meq / g of efficient polymer, about 1.2 meq / g of efficient polymer and 16 meq / g of efficient polymer efficiency, from about 2 meq / g of efficient polymer to about 10 meq / g of efficient polymer, or even about 1 meq / g of efficient polymer to about 4 meq / g of efficient polymer. In the previously mentioned aspect, efficiency polymer is synonymous with polyvinyl formamide.
In one aspect of said encapsulated said encapsulated said can have a coating-to-wall ratio of about 1: 200 to about 1: 2, from about 1: 100 to about 1: 4, or even about from 1:80 to about 1:10.
In one aspect of the encapsulated said,
a) said core may comprise a material selected from the group consisting of perfumes, bleaches, dyes, insect repellents, silicones, waxes, flavorings, vitamins, fabric softening agents, skin care agents in one aspect, paraffins, enzymes, bactericidal agents, bleaches, sensory elements, and mixtures thereof;
b) said wall may comprise a material selected from the group consisting of polyethylene, polyamide, polystyrene, polyisoprene, polycarbonate, polyester, polyacrylate, aminoplastics, in one aspect said aminoplastic may comprise a polyurea, polyurethane, and / or urethane polyurea , in one aspect said polyurea may comprise polyoxy methylene urea and / or melamine formaldehyde, polyolefins, polysaccharides, in an alginate and / or chitosan aspect, gelatin, shellac, epoxy resins, vinyl polymers, water insoluble inorganic, silicone, and mixtures of
10/63 same.
In one aspect of said encapsulated, said core may comprise perfume and said wall may comprise melamine formaldehyde and / or crosslinked melamine formaldehyde.
In one aspect of said encapsulated, said core may comprise perfume and said wall may comprise melamine formaldehyde and / or crosslinked melamine formaldehyde, poly (acrylic acid) and poly (acrylic acid-butyl co-acrylate).
In one aspect of the encapsulated said, the encapsulated said may comprise a perfume that may comprise one or more perfume raw materials that provide enhanced perfume performance under high dirt conditions and in cold water. Suitable perfume materials can be found in published U.S. patent applications 2008 / 0031961A1 and 2008 / 0994454A1. A non-limiting list of such raw materials for perfume is presented in Table 1 below.
Table 1 - Useful perfume raw materials
Item Common name IUPAC Number 1 Methyl 2-butyrate Methyl 2-methyl butanoate 2 Methyl isopropyl 2-butyrate Propan-2-yl 2-methylbutanoate 3 Ethyl-2 methyl butyrate ethyl 2-methylbutanoate 4 Ethyl-2 methylpentanoate ethyl 2-methylpentanoate 5 Ethyl heptanoate ethyl heptanoate 6 Ethyl octanoate Ethyl octanoate 7 isobutyl hexanoate 2-methylpropyl hexanoate 8 Amyl Butyrate pentyl butanoate 9 Amyl heptanoate Pentyl heptanoate 10 Isoamyl isobutyrate 3-methyl butyl 2-methylpropanoate 11 Hexyl acetate hexyl acetate 12 hexyl butyrate hexyl butanoate 13 hexyl isobutyrate 2-methyl hexyl 14 hexyl isovalerate Hexyl 3-methyl butanoate 15 hexyl propionate hexyl propanoate 16 Ethyl 2-cyclohexylpropanoate ethyl 2-cyclohexylpropanoate 17 Ethyl 3,5,5-trimethyl hexanoate ethyl 3,5,5-trimethyl hexanoate 18 Glyceryl 5-hydroxydecanoate 2,3-dihydroxy propyl 5-hydroxydecanoate
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Item Common name IUPAC Number 19 Prenyl acetate Butenyl 3-methyl 2-acetate 20 Butenyl 3-methyl 2-acetate Butenyl 3-methyl 2-acetate 21 methyl 3-nonenoate methyl non-3-enoate 22 Ethyl (E) -dec-4-enoate Ethyl (E) -dec-4-enoate 23 Ethyl (E) -oct-2-enoate Ethyl (E) -oct-2-enoate 24 Ethyl 2,4-decadienoate ethyl (2E, 4Z) -deca-2,4-dienoate 25 Ethyl 3-octenoate ethyl (E) -oct-3-enoate 26 Citronellar acetate 3,7-dimethyloct-6-enyl acetate 27 Ethyl trans-2-decenoate ethyl (E) -dec-2-enoate 28 2-hexen-1-ile isovalerate [(E) -hex-2-enyl] acetate 29 2-hexen-1-yla proprionate [(E) -hex-2-enylJ propanoate 30 2-hexen-1-íla valerate [(E) -hex-2-enyl] pentanoate 31 3-hexen-1-yl (E) -2-hexenoate [(Z) -hex-3-enyl] (E) -hex-2-enoate 32 Methyl 3-hexen-1-yl 2-butyrate [(Z) -hex-3-enyl] 2-methylbutanoate 33 3-hexen-1-yl acetate [(Z) -hex-3-enyl] acetate 34 3-hexen-1-yl benzoate [(Z) -hex-3-enyl] benzoate 35 3-hexen-1-íla formate [(Z) -hex-3-enyl] formate 36 3-hexen-1-ila tiglate [(Z) -hex-3-enyl] (Z) -2-methylbut-2-enoate 37 2-methyl butyl methyl 2-butyrate 2-methyl butyl 2-methyl butanoate 38 Butyl isovalerate butyl 3-methyl butanoate 39 Geranyl acetate [(2E) -3,7-dimethylocta-2,6-dienyl] acetate 40 Geranyl Butyrate [(2E) -3,7-dimethylocta-2,6-dienyl] butanoate 41 Geranyl isovalerate [(3E) -3,7-dimethylocta-3,6-dienyl] 3-methyl butanoate 42 Geranyl proprionate [(2E) -3,7-dimethylocta-2,6-dienyl] propanoate 43 Allyl cyclohexane acetate prop-2-enyl 2-cyclohexyl acetate 44 Allyl cyclohexyl proprionate prop-2-enyl 3-cyclohexyl 45 ally cyclohexyl valerate prop-2-enyl 5-cyclohexylpentanoate 46 benzyl octanoate benzyl octanoate 47 cocolactone 6-pentyl-5,6-dihydropyran-2-one 48 coconut decanone 8-methyl-1-oxaspiro (4.5) decane-2-one 49 undecalactone range 5-heptioxolan-2-one 50 gamma-decalactone 5-hexyloxolane-2-one 51 gamma-dodecalactone 5-octyloxolane-2-one 52 jasmin lactone 6 - [(E) -pent-2-enyl] oxane-2-one 53 Jasmolactone 5 - [(Z) -hex-3-enyl] oxolane-2-one 54 Nonalactone 6-butyloxane-2-one
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Item Common name IUPAC Number 55 6-acetoxydihydroteaspirane [2a, 5a (S *)] - 2,6,10,10-tetramethyl-1-oxaspiro [4.5] decane-6-yl acetate 56 Phenoxy ethyl isobutyrate 2- (phenoxy) ethyl 2-metipropanoate 57 Pivacyclene58 Verdox (2-tert-butylcyclohexyl) acetate 59 cyclobutanate 3a, 4,5,6,7,7a-hexahydro-4,7-methane-1gindene-5 (or 6) -yl butyrate 60 Dimethyl anthranylate methyl 2-methylaminobenzoate 61 Methyl anthranylate methyl 2-amino benzoate 62 Octyl aldehyde Octanal 63 Nonanal Nonanal 64 Decyl aldehyde Decanal 65 Lauric aldehyde Dodecanal 66 Methyl nonyl acetaldehyde 2-methyl undecanal 67 Methyl octyl acetaldehyde 2-methyl dechannel 68 2,4 -hexadienal (2E, 4E) -hexa-2,4-dienal 69 Intreleven Aldehyde undec-10-enal 70 Decen-1-al (E) -dec-2-enal 71 Nonen-1-al (E) -2-nonen-1-al 72 Adoxal 2,6,10-trimethylundec-9-enal 73 Geraldehyde (4Z) -5,9-dimethyldeca-4,8-dienal 74 Iso citral cycle 2,4,6-trimethylcyclohex-3-ene-1-carbaldehyde 75 d-limonene, mainly 1-methyl-4-prop-1-ene-2-yla-cyclohexene 76 Ligustral 2,4-dimethylcyclohex-3-ene-1-carbaldehyde 77 Myrac aldehyde 4- (4-methylpent-3-enyl) cyclohex-3-ene-1carbaldehyde 78 Three-year tridec-2-enal 79 Triple 2,4-dimethyl-3-cyclohexene-1-carbonoxy aldehyde 80 Vertoliff 1,2-dimethylcyclohex-3-ene-1-carbaldehyde 81 Cycle C 2,4-dimethylcyclohex-3-ene-1-carbaldehyde 82 Anisic aldehydes 4-methoxy benzaldehyde 83 Helional 3- (1,3-benzodioxol-5-yl) -2-methylpropanal 84 Heliotropine 1,3-benzodioxol-5-carbaldehyde 85 Neocaspirene86 Beta naphthol ethyl ether 2-ethoxynaphthalene 87 Beta naphthol methyl ether 2-methoxynaphthalene 88 hyacinth ether 2-cyclohexyloxyethylbenzene 89 2-heptyl cyclopentanone (fleura- 2-heptylcyclopentane-1-one
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Item Common name IUPAC Numbermona)90 mentona-8-thioacetate O- [2 - [(1S) -4-methyl-2-oxocyclohexyl] propan-2-íla] ethanothioate 91 Nectaryl 2- [2- (4-methyl-1-cycloex-3enyl) propyl] cyclopentane-1-one 92 Phenyl naphthyl ketone naphthalene-2-yl-phenylmethanone 93 decen-1-yl cyclopentanone 2 - [(2E) -3,7-dimethylocta-2,6-dienyl] cyclopentane-1-one 94 fruitful cyclopentanone (Veloutone) 2,2,5-trimethyl-5-pentylcyclopentan-1-one 95 4-methoxy-2-methyl butane thiol (blackcurrant mercaptan) 4-methoxy-2-methylbutane-2-thiol 96 Grapefruit Mercaptano 2- (4-methyl-1-cyclohex-3-enyl) propane-2-thiol 97 Buccoxime N- (1,5-dimethyl-8-bicycle [3.2.1] octanylidene) hydroxylamine 98 labienox 2,4,4,7-tetramethyl-6,8-nonadiene-3-one oxime 99 Undecavertol (E) -4-methyldec-3-en-5-ol 100 Diethyl acetal decanal 1,1-diethoxydecane 101 Diethyl maleate diethyl but-2-enedioate 102 Ethyl acetoacetate ethyl 3-oxobutanoate 103 fructonil 2-methyldecanenitrile 104 Methyl dioxolan ethyl 2- (2-methyl-1,3-dioxolan-2-yl) acetate 105 Cetalox 3a, 6,6,9a-tetramethyl-2,4,5,5a, 7,8,9,9b-octahydro-1 H-benzo [e] [1] benzofuran 106 Cyclopentol107 Delta damascona (E) -1- (2,6,6-trimethyl-1-cyclohex-3-enyl) but-2-en-1-one 108 Eucalyptus 1,3,3-trimethyl-2-oxabicyclo [2,2,2] octane 109 Acetate flower110 methyl ionone gamma (E) -3-methyl-4- (2,6,6-trimethyl-1-cyclohex-2enyl) but-3-en-2-one 111 Levo trisandol112 Linalool 3,7-dimethylocta-1,6-dien-3-ol 113 Violiff [(4Z) -1-cyclooct-4-enyl] methyl carbonate 114 Cimal 3- (4-propane-2-yl phenyl) butanal 115 Bourgeonal 3- (4-tert-butylphenyl) propanal
Perfume microcapsules can be contained in a
14/63 fluid paste of perfume microcapsules.
In the context of the present invention, a perfume microcapsule slurry is defined as an aqueous dispersion containing 10% to 50% by weight of the perfume microcapsule slurry. The perfume microcapsule slurry may comprise at least 20%, more preferably at least 40%, by weight, of the perfume microcapsule slurry of encapsulated perfume ingredients.
The perfume microcapsule slurry of the present invention can comprise a water-soluble salt, which is present as a residual impurity of the perfume microcapsule slurry. This residual impurity could result from other ingredients in the perfume microcapsule slurry, which are purchased from several suppliers. In one aspect, the perfume microcapsule slurry is purchased from a supplier. The supplier can add additional water-soluble salt to the perfume microcapsule slurry to adjust the rheology profiles of the aqueous perfume microcapsule slurry, to optimize the stability of the slurry during transport and long-term storage.
In the context of the present invention, the water-soluble salts of the present invention mean water-soluble ionic compounds, compounds of positively charged cations and dissociated negatively charged anions. In the context of the present invention, water soluble can be defined as a solubility in demineralized water at room temperature and atmospheric pressure. The perfume microcapsule slurry may comprise from 1 mmol / kg to 750 mmol / kg of water-soluble salt. In another embodiment, the perfume microcapsule slurry may comprise from 10 mmol / kg to 750 mmol / kg of water-soluble salt. In yet another embodiment, the perfume microcapsule slurry may comprise from 1 to 265 mmol / kg of water-soluble salt.
In one aspect, the water-soluble salts present in the perfume microcapsule slurry are formed by polyvalent cations selected from the group comprising alkaline earth metals,
15/63 transition metals or metals, together with suitable monatomic or polyatomic anions. In another modality, the water-soluble salt comprises cations, the cations being selected from the group comprising beryllium, magnesium, calcium, strontium, barium, scandium, titanium, iron, copper, aluminum, zinc, germanium, tin. In another embodiment, the water-soluble salt comprises anions, the anions being selected from the group comprising fluorine, chlorine, bromine, iodine, acetate, carbonate, citrate, hydroxide, nitrate, phosphite, phosphate and sulfate. In one embodiment, anions are the monoatomic anions of halogens.
In addition to the encapsulants described here, a slurry is presented which may comprise an encapsulated encapsulated with efficiency polymer, said slurry having zeta potential of about -10 meV to about +50 meV, preferably about +2 meV to about +40 meV, more preferably about +5 meV to about +25 meV or about -40 meV to about +35 meV, preferably about -38 meV to about +25 meV, more preferably from about -35 meV to about +10 meV. In one aspect, said slurry can obtain the appropriate content of the efficiency polymer; as a result, the efficiency polymer that is part of the encapsulated and / or the encapsulated that comprises the efficiency polymer can be produced by combining a slurry comprising the encapsulated with one or more efficiency polymers.
In addition to the encapsulants described herein, a slurry which may comprise, based on the total weight of the slurry, a sufficient amount of encapsulates coated with polymer efficiency to provide said slurry from about 0.05% to about 10% , from about 0.1% to about 5%, from about 0.125% to about 2% of an efficiency polymer.
In one aspect, a slurry is presented which may comprise, based on the total weight of the slurry, from about 0.01% to about 5%, from about 0.05% to about 2% or even about 0.1% to about 1% of a polyvinyl formamide, from about 0% to about 5%
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MgCI ₂ , from about 0.1 to about 3% MgCl ₂ from about 0.2% to about 2.5% MgCl ₂ from about 0% to about 1% xanthan gum, about 0.05% to about 0.5%, about 0.1% to about 0.25% xanthan gum and one or more of the coated or uncoated encapsulates.
In one aspect of said slip, said polyvinyl formamide may have:
a) an average molecular mass of about 1,000 Da to about 50,000,000 Da, of about 5,000 Da, to about 25,000,000 Da, of about 10,000 Da to about 10,000,000 Da, or even about from 340,000 Da to around 1,500,000 Da;
b) a degree of hydrolysis, for said polyvinyl formamides, from about 5% to about 95%, from about 7% to about 60%, or even from about 10% to about 40%, and
c) a charge density of about 1 meq / g of polyvinyl formamide to about 23 meq / g of polyvinyl formamide, of about 1.2 meq / g of polyvinyl formamide and 16 meq / g of polyvinyl formamide, of about from 2 meq / g of polyvinyl formamide to about 10 meq / g of polyvinyl formamide, or even from about 1 meq / g of polyvinyl formamide to about 4 meq / g of polyvinyl formamide.
In one aspect, an improved slurry production process is presented which comprises combining, in any order, an encapsulated, an efficiency and optionally a stabilizer system and, optionally, a biocide. In one aspect, said efficiency polymer may comprise polyvinyl formamide, said stabilizing system may comprise MgCl ₂ and xanthan gum.
In one aspect of said improved slurry production process, said encapsulated and said efficiency are left in close contact for at least 15 minutes, for at least 1 hour, or even for 4 hours before said slurry is used in a product or used to produce a chipboard.
In one aspect, any of the aqueous encapsulates and / or pastes presented herein can be used to produce a agglomerate.
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In one aspect, a production process of the agglomerate is presented, and the said process comprises:
a) combining an encapsulated and / or slurry, a plasticizer, in one aspect, a plasticizer comprising water and, optionally, a binder and / or chelator to form a mixture;
b) combining said mixture with said dusting agent, in one aspect, a dusting agent comprising silica, to form a material, and
c) removing a sufficient amount of said plasticizer from said material to produce a product comprising, based on the total product weight of 1% to 50% plasticizer.
In one aspect, said plasticizer comprises water.
Suitable capsules that can be converted into the high-efficiency capsules presented herein can be produced in accordance with the applicants 'teachings including, but not limited to, the applicants' examples, the teachings of USPA 2008/0305982 A1 and / or USPA 2009 / 0247449 A1. Alternatively, suitable capsules can be purchased from Appleton Papers Inc. of Appleton, Wisconsin, USA.
In addition, the materials for the production of the aforementioned encapsulated products can be obtained from CP Kelco Corp. from San Diego, California, USA, BASF AG from Ludwigshafen, Germany, Rhodia Corp. from Cranbury, New Jersey, USA, Hercules Corp. from Wilmington, Delaware, USA, Agrium Inc. from Calgary, Alberta, Canada, ISP from New Jersey, USA, Akzo Nobel from Chicago, ILA, USA, Stroever Shellac Bremen from Bremen, Germany, Dow Chemical Company from Midland, Ml, USA , Bayer AG of Leverkusen, Germany, Sigma-Aldrich Corp., of St. Louis, Missouri, USA.
Suitable efficiency polymers, such as polyvinyl amide-polyvinyl amine copolymers, can be produced by the selective hydrolyzing of the starting polyvinyl formamide polymer.
Suitable efficiency polymers can also be formed by copolymerization of vinyl formamide with acrylamide, acrylic acid
18/63 co, acrylonitrile, ethylene, sodium acrylate, methyl acrylate, maleic anhydride, vinyl acetate, n-vinyl pyrrolidine.
Suitable efficiency polymers or oligomers can also be formed by cationic polymerization of vinyl formamide with protonic acids, such as methyl sulfonic acid, and / or Lewis acids, such as boron trifluoride.
Suitable efficiency polymers can be obtained from BASF AG in Ludwigshafen, Germany, and include Lupamin® 9010 and Lupamin® 9030.
Coated encapsulated production process
In one aspect, a process for producing a coated encapsulate is presented which comprises combining an encapsulated, and one or more efficient polymers.
In one aspect, a process for producing a coated encapsulate is presented, wherein said encapsulated, when combined with said one or more efficiency polymers, is contained in a slurry.
In one aspect, a process for producing a coated encapsulation is presented, with a sufficient amount of efficiency polymer being combined with said slurry to provide said slurry with, based on the total weight of the slurry, of about from 0.05% to about 10%, from about 0.1% to about 5%, or even from about 0.125% to about 2% of said efficiency polymer.
The high-efficiency polymers used in the production of the aforementioned coated encapsulants may be the efficiency polymers described in the High-efficiency encapsulated and slurry / agglomerates section that comprise the same in this specification. Consumer product
In one aspect, a consumer product comprising any of the encapsulates, and an agglomerate comprising such encapsulates and / or aqueous pastes described herein are presented.
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In one aspect of said consumer product, said consumer product may be a cleaning and / or treatment composition.
In one aspect of said consumer product, said consumer product may be a laundry detergent and / or fabric softener.
In one aspect of said consumer product, said consumer product may be a fluid laundry detergent. Said fluid laundry detergent may, in one aspect, comprise, based on the total weight of the fluid laundry detergent, from about 3% to about 80%, from about 3% to about 70%, from about 5% to about 60%, or even from about 8% to about 50% water.
In one aspect of said fluid detergent, said fluid detergent can be a liquid laundry detergent.
In one aspect of said consumer product, said consumer product may be a fluid fabric softener. Said fluid fabric softener may, in one aspect, comprise, based on the total weight of the fluid fabric softener, from about 30% to about 90%, from about 55% to about 90%, from about 65% to about 85%, or even about 70% to about 85% water.
In one aspect of said fluid fabric softener, said fluid fabric softener can be a liquid fabric softener.
In one aspect of said consumer product, said consumer product may be a solid detergent and an auxiliary ingredient.
In one aspect of said consumer product, said consumer product may be a fluid beauty care product, for example a shampoo. Said fluid beauty care product may, in one aspect, comprise, based on the total weight of the fluid beauty care product, from about 30% to about 95%, from about 55% to about 90%, or even about 65% to about 85% water.
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In one aspect of said consumer product, said consumer product may be a conditioner.
In one aspect, said consumer product may comprise a sufficient amount of slurry and / or encapsulated pulp to provide said consumer product with an efficient polymer content, based on the total weight of the consumer product, of about 0.0001% to about 0.1%, from about 0.001% to about 0.1%, or even from about 0.001% to about 0.05%.
In one aspect, said product intended for the consumer may comprise a material selected from the group consisting of an anionic surfactant, cationic surfactant, silicone and mixtures thereof, and said product intended for the consumer may also have:
a) a ratio between the anionic surfactant and the efficiency polymer of about 100,000: 1 to about 1: 1, about 25,000: 1 to about 10: 1, or even about 10,000: 1 to about 100: 1;
b) a ratio between the cationic surfactant and the efficiency polymer of about 100,000: 1 to about 1: 1, about 25,000: 1 to about 10: 1, or even about 10,000: 1 to about 100: 1, and / or
c) a ratio between the silicone and the polymer of efficiency of about 100,000: 1 to about 1: 1 of about 25,000.Ί to about 10: 1, or even about 10,000: 1 to about 100: 1.
In one aspect, the encapsulates presented here are suitable for use in consumer products, cleaning and treatment compositions, and compositions for cleaning and / or treating hard-packed fabrics or surfaces, detergents, and highly compacted consumer products, including compositions for cleaning and / or treating highly compacted fabrics or hard surfaces, for example highly compacted detergents that can be solid or fluid, in contents, based on the total weight of the product intended for the consumer, from about 0.001% to about 20 %, from about 0.01% to about 10%, from about 0.05% to about 5%, from about 0.1% to about 2%.
In one aspect, a product for the control is presented.
21/63 sumidor comprising an auxiliary ingredient selected from the group consisting of polymers, in one aspect, a cationic polymer, surfactants, builders, chelating agents, optical bleaches, dye transfer inhibiting agents, dispersants, enzymes, enzyme stabilizers, materials catalytic agents, bleach activators, polymer dispersing agents, clay and dirt / anti-redeposition agents, bleaching agents, polymer dye conjugates, clay dye conjugates, foam suppressants, dyes, bleach catalysts, additional perfume and / or systems for perfume release, structure elasticizing agents, fabric softeners, vehicles, hydrotropes, processing auxiliary elements, rheology modifiers, structuring agents, thickeners, pigments, water and mixtures thereof.
In one aspect, a consumer product is presented which comprises an auxiliary ingredient comprising a rheology modifier, thickener and / or structuring with a high shear viscosity, at a shear rate of 20 s-1 and at 21 ° C , from 1 to 7000 cps and a viscosity under low shear (at a shear rate of 0.5 s-1 at 21 ° C) greater than 1000 cps, or even from 1000 cps to 200,000 cps. In one aspect, for cleaning and treatment compositions, these rheology modifiers give the aqueous liquid composition a viscosity under high shear, at 20 s-1 and at 21 ° C, from 50 to 3000 cps and a viscosity under low shear (rate shear of 0.5 s-1 at 21 ° C) greater than 1000 cps, or even from 1000 cps to 200,000 cps. In one respect, rheology modifiers, thickeners and / or suitable structuring agents can be selected from the group consisting of polyacrylates, quaternized polyacrylates, polymethacrylates, polyamides, quaternized polymethacrylates, polycarboxylates, polymeric gums such as pectin, alginate, arabinogalactane, gum arabic, gum arabic, gum arabic. gellan gum, xanthan gum and guar gum, other non-gummy polysaccharides such as gellan gum, and combinations of these polymeric materials, fatty acids containing hydroxyl, fatty esters or fatty waxes, castor oil and its derivatives, derivatives of hydrogenated castor oil as oil hydrogenated castor and wax
22/63 hydrogenated castor, and mixtures thereof.
In one aspect, a product intended for the consumer is presented, the said product intended for the consumer being a fluid detergent and comprising, based on the total weight of the fluid detergent, less than about 80% water, less than about 60 % to about 2% water, from about 45% to about 7% water, from about 35% to about 9% water.
In addition to the encapsulated products described here, certain perfume delivery systems can be used in the aforementioned consumer products and / or products. Methods of preparing such perfume delivery systems are presented in USPA 2007/0275866 A1. Such perfume delivery systems include: polymer-assisted release (l_AP), molecule-assisted release (LAM), fiber-assisted release (LAF), amine-assisted release (l_AA), cyclodextrin (CD) release system, chord encapsulated in starch (AEA), inorganic vehicle release system (ZIC), pro-perfume (PP). These perfume delivery systems can be used in any combination in any type of consumer product, cleaning and / or treatment composition, cleaning composition and / or treatment of fabrics and hard surfaces, detergent, and highly compressed detergent.
Perfume microcapsule
It is advantageous to add perfume in the form of perfume ingredients encapsulated in a composition, since the encapsulation of the perfume ingredients allows a controlled and later directed release of the perfume ingredients. Perfume ingredients are the individual chemical compounds that are used to produce a perfume composition. A perfume composition comprises one or more perfume ingredients, the choice of the type and the number of ingredients depending on the desired final aroma. The present invention can comprise perfume microcapsules. It is well known to those skilled in the art that perfume microcapsules release perfume ingredients when handling fabrics and during use, providing freshness
23/63 improved longer lasting in fabrics, compared to the addition of pure perfume only. The release of the perfume ingredients is triggered by the mechanical effort that breaks the capsule wall and allows the diffusion of the encapsulated perfume ingredient.
A perfume microcapsule comprises a capsule surrounding a core comprising perfume ingredients. The capsule can be made of numerous materials, but the most preferred is a crosslinked melamine formaldehyde. The capsule wall material may comprise a suitable resin that includes the reaction product of an aldehyde and an amine, with suitable aldehydes including formaldehyde. Suitable amines can include those selected from the group comprising melamine, urea, benzoguanamine, glycoluryl, and mixtures thereof. Suitable melamines may include those selected from the group comprising methylol melamine, methylated methylol melamine, imino melamine and mixtures thereof. Suitable ureas may include those selected from the group comprising dimethylol urea, methylated dimethylol urea, urea-resorcinol, and mixtures thereof.
In the context of the present invention, any suitable perfume ingredient can be used. Those skilled in the art will recognize suitable perfume ingredients compatible for use in perfume microcapsules, and will know how to select combinations of ingredients to obtain the desired aromas.
In one aspect, at least 75%, 85% or even 90% of said perfume microcapsules can have a particle size of about 1 micron to about 80 microns, about 5 microns to 60 microns, from about 10 microns at about 50 microns, or even about 15 microns to about 40 microns.
At least 75%, 85% or even 90% of said perfume microcapsules can have a particle wall thickness of about 60 nm to about 250 nm, about 80 nm to about 180 nm, or even about from 100 nm to about 160 nm.
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The liquid fabric softener compositions of the present invention comprise from 0.05% to 0.8%, by weight, of the liquid fabric softener composition of encapsulated perfume ingredients, present in the form of a perfume microcapsule. This amount is necessary to ensure that a sufficient amount of perfume is deposited on the fabrics. Perfume and perfume microcapsules are removed during the washing process. Consequently, it is important that there is sufficient perfume in the liquid fabric softener composition to take into account the inevitable loss, and yet sufficient deposition on the fabrics occurs.
In one aspect, said perfume microcapsule can be spray dried.
Fluid paste of perfume and agglomerate microcapsules
Auxiliary materials
For the purposes of the present invention, a non-limiting list of auxiliary ingredients suitable for use in instant compositions which can be desirably incorporated into certain embodiments of the invention to, for example, assist or improve performance, is shown from this point onwards. treat the substrate to be cleaned, or even modify the aesthetics of the composition as is the case with perfumes, dyes, products for pretending or similar. It is understood that such auxiliary ingredients are additional elements to the components supplied through the applicants' aqueous encapsulated, agglomerates and / or pastes. The exact nature of these additional components, as well as their levels of incorporation, will depend on the physical form of the composition and the nature of the cleaning operation in which it will be used. Suitable auxiliary materials include, but are not limited to, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, polymer dispersing agents, dirt and clay removal agents / anti-redeposition agents, bleaches, foam suppressants, dyes, additional perfume and / or perfume release systems, agents
25/63 structure elastifying tests, fabric softeners, vehicles, hydrotropes, processing auxiliary elements and / or pigments. In addition to the description below, suitable examples of these other auxiliary compounds, as well as their levels of use, are found in US patents No. 5,576,282, No. 6,306,812 B1 and No. 6,326,348 B1, which are incorporated herein by reference .
Each auxiliary ingredient is not essential to the Applicants' compositions. Accordingly, certain modalities of the applicants' compositions do not contain one or more of the following auxiliary composite materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes , dispersing polymeric agents, clay and dirt / anti-redeposition agents, bleaching agents, foam suppressants, dyes, additional perfumes and perfume release systems, structural elastifying agents, fabric softeners, vehicles, hydrotropes, auxiliary elements to processing and / or pigments. However, when one or more auxiliary compounds are present, they can be present as detailed below:
Surfactants - The compositions according to the present invention can comprise a surfactant or a surfactant system in which the surfactant can be selected from nonionic surfactants, anionic surfactants, cationic surfactants, ampholytic surfactants, zwitterionic surfactants, semipolar nonionic surfactants. The surfactant is typically present in levels of about 0.1%, about 1%, or even about 5%, by weight, of the cleaning compositions, and up to about 99.9%, up to about 80%, or even up to about 35%, and up to about 30%, by weight, of the cleaning compositions.
Builders - The compositions of the present invention can comprise one or more detergent builders or builder systems. When present, the compositions will typically comprise at least about 1% builder, or from about 5% or 10% to about 80%, 50%, or even 30%, by weight, of said builder. Builders include, but are not limited to
26/63 salts of alkali metal polyphosphates, ammonium and ammonium alkanol, alkali metal silicates, alkaline earth metal carbonates and alkali metal, polycarboxylate compounds from aluminum silicate builders, polycarboxylate hydroxy ether, ethylene vinyl anhydride copolymers or ether is methyl, 1,3,5-trihydroxy benzene-2,4,6-trisulfonic acid and carboxy methyl-succinic oxide, the various alkali metal, ammonium and ammonium polyacetic acid salts substituted as ethylenediamine tetraacetic acid and nitrile triacetic acid, as well as polycarboxylates such as melitic acid, succinic acid, oxisuccinic acid, polymaleal acid, benzene 1,3,5-tricarboxylic acid, carboxy methyl oxide succinic acid and soluble salts thereof.
Chelating agents - The compositions of the present invention can also optionally contain one or more copper, iron and / or manganese chelating agents. If used, chelating agents will generally comprise from about 0.1% by weight of the composition of the present invention to about 15%, or even from about 3.0% to about 15% by weight of the compositions of the present invention.
Pigment transfer inhibiting agents - The compositions of the present invention may also contain one or more pigment transfer inhibiting agents. Suitable dye transfer inhibiting polymeric agents include, but are not limited to, polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinyl imidazole, polyvinyl oxazolidones and polyvinyl imidazoles, or mixtures thereof. . When present in the compositions of the present invention, dye transfer inhibiting agents are in the range of about 0.0001%, about 0.01%, about 0.05% by weight of the composition for cleaning at about 10%, about 2%, or even about 1% by weight of the cleaning composition.
Tinting agents - Fluorescent optical brighteners emit at least some visible light. In contrast, fabric tinting agents can change the tone of a surface, as they absorb at least a portion of the visible light spectrum. Tinting agents for suitable fabrics include dyes, dye-clay conjugates. The dyes suit
27/63 dos include small molecule dyes and polymeric dyes. Suitable small molecule dyes include those selected from the group consisting of:
(1) Direct blue dyes based on tris-azo, with the following 5 formula:
in which at least two of the naphthyl rings A, B and C are replaced by a sulfonate group, ring C can be replaced in position 5 with an NH ₂ or NHPh group, X is a benzyl or naphthyl ring substituted by up to 2 sulfonate groups and can be substituted in position 2 by an OH group which can also be replaced by an NH ₂ or NHPh group.
(2) Direct violet dyes based on bis-azo, with the following formula:
in which Z is H or phenyl, ring A is preferably replaced by a methyl and methoxy group at the positions indicated by arrows, ring A may also be a naphthyl ring, and group Y is a benzyl or naphthyl ring that is replaced by a sulfate group, which may be mono- or disubstituted by methyl groups.
(3) Blue or red acid dyes, with the following formula
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Ia:
nh ₂ o hn ^ ^y
N J J in which at least one of X and Y must be an aromatic group. In one aspect, both aromatic groups may be a substituted benzyl or naphthyl group, which may be substituted by water-solubilizing groups, such as alkyl, alkyloxy or aryloxy groups, and X and Y may not be substituted by water-solubilizing groups. , such as sulfonates or carboxylates. In another aspect, X is a nitro-substituted benzyl group, and Y is a benzyl group.
(4) Red acid dyes with the structure:
or
in which B is a naphthyl or benzyl group that can be substituted by non-water-solubilizing groups, such as alkyl, alkyloxy or aryloxy groups, and B may not be substituted by water-solubilizing groups, such as sulfonates or carboxylates.
(5) Dyes azo with the structure:
(HO ₃ S) _n
N = N
29/63 wherein X and Y are, independently of one another, hydrogen, alkyl CiC CiC ₄ -alkoxy or _4, Ra is hydrogen or aryl, Z is alkyl CiC ₄ alkoxy CiC ₄ -, halogen, hydroxyl or carboxyl, n is 1 or 2 and n is 0, 1 or 2, as well as corresponding salts and mixtures thereof.
(6) Triphenylmethane-based dyes with the following structures
N (CH ₂ CFy ₂
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and mixtures thereof. In another aspect, suitable small molecule dyes include the small molecule dyes mentioned below, some of which are selected from the group consisting of C.l. (Color Index) (Society of Dyers and Colorists,
Bradford, United Kingdom). 1,4-naphthalenedione, 1- [2- [2- [4 - [[4- (acetyloxy) butyl] ethylamino] -2-methyl phenyl] diazenyl] -5-nitro-3-thienyl] -ethanone, 1- hydroxy-2- (1-naphthalenylazo)-naphthalenedisulfonic acid, ion (2-), 1-hydroxy-2 - [[4- (phenylazo) phenyl] azo] naphthalenedisulfonic acid, ion (2-), 2 - [(1E ) - [4- [bis (3-methoxy-3-oxopropyl) amino] -2-methyl phenyl] azo] -5-nitro-3-thiophene carboxylic acid, ethyl ester, 2 - [[4 - [(210 cyanoethyl ) ethylamino] phenyl] azo] -5- (phenylazo) -3-thiophenocarbonitrile, 2- [2- [4 - [(2-cyanoethyl) ethylamino] phenyl] diazenyl] -5- [2- (4-nitrophenyl) diazenyl ] -3-thiophenecarbonitrile, 2-hydroxy-1- (1-naphthalenylazo)-naphthalenedisulfonic acid, ion (2-), 2-hydroxy-1 [[4- (phenylazo) phenyl] azo]-naphthalenedisulfonic acid, ion (2 -), 4,4 '- [[4- (dimethylamino) -2,5-cyclohexadiene-1-ylidene] methylene] bis [N, N-dimethyl-benzenamine, 15 6-hydroxy-5 - [(4- methoxy phenyl) azo] -2-naphthalene sulfonic acid, monosodium salt, 6-hydroxy-5 - [(4-methylphenyl) azo] -2-naphthalene sulfonic acid, monosodium salt 31/63 co, 7-hydroxy-8 - [[ 4 - (phenylazo) phenyl] azo] -1,3-naphthalenedisulfonic acid, ion (2-),
7- hydroxy-8- [2- (1-naphthalenyl) diazenyl] -1,3-naphthalenedisulfonic acid, ion (2-),
8- hydroxy-7- [2- (1-naphthalenyl) diazenyl] -1,3-naphthalenedisulfonic acid, ion (2-), 8-hydroxy-7- [2- [4- (2-phenyldiazenyl) phenyl] diazenyl ] -1,3-naphthalenedisulfonic acid, ion (2-), Acid Black 1, Acid Black 24, Acid Blue 113, Acid Blue 15, Acid Blue 17, Acid Blue 25, Acid Blue 29, Acid Blue 3, Acid Blue 40 , Acid Blue 45, Acid Blue 62, Acid Blue 7, Acid Blue 75, Acid Blue 80, Acid Blue 83, Acid Blue 9, Acid Blue 90, Acid Green 27, Acid Orange 12, Acid Orange 7, Acid Orange 14, Red Acid 150, Acid Red 151, Acid Red 17, Acid Red 18, Acid Red 266, Acid Red 27, Acid Red 4, Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 88, Acid Red 92 , Acid Red 94, Acid Red 97, Acid Violet 15, Acid Violet 17, Acid Violet 24, Acid Violet 43, Acid Violet 49, Basic Blue 159, Basic Blue 16, Basic Blue 22, Basic Blue 3, Blue B sodium 47, Basic Blue 66, Basic Blue 75, Basic Blue 9, Basic Violet 1, Basic Violet 2, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 35, C.L. Acid Black 1, C.L Acid Blue 10, C.L Acid Blue 113, C.l. Acid Blue 25, C.L Acid Blue 29, C.l. Acid Blue 290 C.l. Acid Red 103, C.l. Acid Red 150, C.l. Acid Red 52, C.l. Acid Red 73, C.l. Acid Red 88, C.l. Acid Red 91, C.l. Acid Violet 17, C.l. Acid Violet 43, C.l. Direct Blue 1, C.l. Direct Blue 120, C.l. Direct Blue 34, C.l. Direct Blue 70, C.l. Direct Blue 71, C.l. Direct Blue 72, C.l. Direct Blue 82, C.l. Direct Violet 51, C.l. Scattered Blue 10, C.l. Scattered Blue 100, C.l. Scattered Blue 101, C.l. Scattered Blue 102, C.l. Scattered Blue 106: 1, C.l. Scattered Blue 11, C.l. Scattered Blue 12, C.l. Scattered Blue 121, C.l. Scattered Blue 122, C.l. Scattered Blue 124, C.l. Scattered Blue 125, C.l. Scattered Blue 128, C.l. Scattered Blue 130, C.l. Scattered Blue 133, C.l. Scattered Blue 137, C.l. Scattered Blue 138, C.l. Scattered Blue 139, C.l. Scattered Blue 142, C.l. Scattered Blue 146, C.l. Scattered Blue 148, C.l. Scattered Blue 149, C.l. Dispersed Blue 165, C.l. Scattered Blue 165: 1, C.l. Scattered Blue 165: 2, C.l. Scattered Blue 165: 3, C.l. Scattered Blue 171, C.l. Scattered Blue 173, C.l. Scattered Blue 174, C.l. Blue Dis
32/63 perso 175, C.l. Scattered Blue 177, C.l. Scattered Blue 183, C.l. Scattered Blue 187, C.l. Scattered Blue 189, C.l. Scattered Blue 193, C.l. Scattered Blue 194, C.l. Scattered Blue 200, C.l. Scattered Blue 201, C.l. Scattered Blue 202, C.l. Scattered Blue 205, C.l. Scattered Blue 206, C.l. Scattered Blue 207, C.l. Scattered Blue 209, C.l. Scattered Blue 21, C.l. Scattered Blue 210, C.l. Scattered Blue 211, C.l. Scattered Blue 212, C.l. Scattered Blue 219, C.l. Scattered Blue 220, C.l. Scattered Blue 222, C.l. Scattered Blue 224, C.l. Scattered Blue 225, C.l. Scattered Blue 248, C.l. Scattered Blue 252, C.l. Scattered Blue 253, C.l. Scattered Blue 254, C.l. Scattered Blue 255, C.l. Scattered Blue 256, C.l. Scattered Blue 257, C.l. Scattered Blue 258, C.l. Scattered Blue 259, C.l. Scattered Blue 260, C.l. Scattered Blue 264, C.l. Scattered Blue 265, C.l. Scattered Blue 266, C.l. Scattered Blue 267, C.l. Scattered Blue 268, C.l. Scattered Blue 269, C.l. Scattered Blue 270, C.l. Scattered Blue 278, C.l. Scattered Blue 279, C.l. Scattered Blue 281, C.l. Scattered Blue 283, C.l. Scattered Blue 284, C.l. Scattered Blue 285, C.l. Scattered Blue 286, C.l. Scattered Blue 287, C.l. Scattered Blue 290, C.l. Scattered Blue 291, C.l. Scattered Blue 294, C.l. Scattered Blue 295, C.l. Scattered Blue 30, C.l. Scattered Blue 301, C.l. Scattered Blue 303, C.l. Scattered Blue 304, C.l. Scattered Blue 305, C.l. Scattered Blue 313, C.l. Scattered Blue 315, C.l. Scattered Blue 316, C.l. Scattered Blue 317, C.l. Scattered Blue 321, C.l. Scattered Blue 322, C.l. Scattered Blue 324, C.l. Scattered Blue 328, C.l. Scattered Blue 33, C.l. Dispersed Blue 330, C.l. Scattered Blue 333, C.l. Scattered Blue 335, C.l. Scattered Blue 336, C.l. Scattered Blue 337, C.l. Scattered Blue 338, C.l. Scattered Blue 339, C.l. Scattered Blue 340, C.l. Scattered Blue 341, C.l. Scattered Blue 342, C.l. Scattered Blue 343, C.l. Scattered Blue 344, C.l. Scattered Blue 345, C.l. Scattered Blue 346, C.l. Scattered Blue 351, C.l. Scattered Blue 352, C.l. Scattered Blue 353, C.l. Scattered Blue 355, C.l. Scattered Blue 356, C.l. Scattered Blue 357, C.l. Scattered Blue 358, C.l. Scattered Blue 36, C.l. Blue Dispersed 360, C.l. Scattered Blue 366, C.l. Scattered Blue 368, C.l. Scattered Blue 369, C.l. Scattered Blue 371, C.l. Scattered Blue 373, C.l. Scattered Blue 374, C.l. Scattered Blue 375, C.l. Scattered Blue 376, C.l. Scattered Blue 378, C.l. Scattered Blue 38, C.l. Scattered Blue 42, C.l. Scattered Blue 43, C.l. Scattered Blue 44, C.l. Scattered Blue 47, C.l.
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Scattered Blue 79, C.l. Scattered Blue 79: 1, C.l. Scattered Blue 79: 2, C.l. Scattered Blue 79: 3, C.l. Scattered Blue 82, C.l. Scattered Blue 85, C.l. Scattered Blue 88, C.l. Scattered Blue 90, C.l. Scattered Blue 94, C.l. Scattered Blue 96, C.l. Dispersed Violet 10, C.l. Dispersed Violet 100, C.l. Scattered Violet 102,
C.l. Dispersed Violet 103, C.l. Scattered Violet 104, C.l. Dispersed Violet 106, C.l. Scattered Violet 107, C.l. Dispersed Violet 12, C.l. Scattered Violet
13, C.l. Dispersed Violet 16, C.l. Dispersed Violet 2, C.l. Dispersed Violet 24, C.l. Dispersed Violet 25, C.l. Dispersed Violet 3, C.l. Dispersed Violet 33, C.l. Dispersed Violet 39, C.l. Dispersed Violet 42, C.l. Dispersed Violet 43, C.l.
Dispersed Violet 45, C.l. Dispersed Violet 48, C.l. Dispersed Violet 49, C.l.
Dispersed Violet 5, C.l. Dispersed Violet 50, C.l. Dispersed Violet 53, C.l.
Dispersed Violet 54, C.l. Dispersed Violet 55, C.l. Dispersed Violet 58, C.l.
Dispersed Violet 6, C.l. Dispersed Violet 60, C.l. Dispersed Violet 63, C.l.
Dispersed Violet 66, C.l. Scattered Violet 69, C.l. Dispersed Violet 7, C.l.
Dispersed Violet 75, C.l. Scattered Violet 76, C.l. Scattered Violet 77, C.l.
Dispersed Violet 82, C.l. Dispersed Violet 86, C.l. Dispersed Violet 88, C.l.
Dispersed Violet 9, C.l. Dispersed Violet 91, C.l. Dispersed Violet 92, C.l.
Dispersed Violet 93, C.l. Scattered Violet 93: 1, C.l. Scattered Violet 94, C.l.
Dispersed Violet 95, C.l. Dispersed Violet 96, C.l. Scattered Violet 97, C.l.
Scattered Violet 98, C.l. Dispersed Violet 99, C.l. Reactive Black 5, C.l. Reactive Blue 19, C.l. Reactive Blue 4, C.l. Reactive Red 2, C.l. Solvent Blue 43, C.l. Solvent Blue 43, C.l. Solvent Red 14, C.l. Acid Black 24, Acid Blue 113, Acid Blue 29, C.l. Direct Violet 7, C.l. Edible Red 14, CC Dianix Violet, Direct Blue 1, Direct Blue 71, Direct Blue
75, Direct Blue 78, Direct Blue 80, Direct Blue 279, Direct Violet 11, Violet
Straight 31, Straight Violet 35, Straight Violet 48, Straight Violet 5, Straight Violet
51, Direct Violet 66, Direct Violet 9, Blue Scattered 106, Blue Scattered 148, Blue Scattered 165, Blue Scattered 3, Blue Scattered 354, Blue Scattered 364, Blue Scattered 367, Blue Scattered 56, Blue Scattered 77, Blue Scattered 79,
Scattered Blue 79: 1, Scattered Red 1, Scattered Red 15, Scattered Violet 26, Scattered Violet 28, Scattered Violet 63, Scattered Violet 77, Eosin Y, Ethanol, 2.2 '- [[4 - [( 3,5-dinitro-2-thienyl) azo] phenyl]
34/63 imino] bis-, diacetate (ester), Lumogen Blue F 650, Violet Lumogen F 570, N- [2- [2- (3-acetyl-5-nitro-2-thienyl) diazenyl] -5- ( diethylamino) phenyl] -acetamide, N- [2 [2- (4-chloro-3-cyano-5-formyl-2-thienyl) diazenyl] -5- (diethylamino) phenyl] -acetamide, N- [5- [ bis (2-methoxy ethyl) amino] -2- [2- (5-nitro-2,1-benzisothiazol-3-yl) diazenyl] phenyl] -acetamide, N- [5- [bis [2- (acetyloxy) ethyl] amino] -2 - [(2-bromo-4,6-dinitrophenyl) azo] phenyl] -acetamide, naphthalimide, derivatives, Black Oil 860, Floxin B, pyrazole, cane rose, sodium 6-hydroxy-5- (4-isopropylphenylazo) -2-naphthalene sulfonate, Solvent Black 3, Solvent Blue 14, Solvent Blue 35, Solvent Blue 58, Solvent Blue 59, Solvent Red 24, Solvent Violet 13, Solvent Violet 8, Sudan Red 380, triphenyl methane, and triphenyl methane, derivatives and mixtures thereof.
Additional suitable tinting agents include, but are not limited to, thiophenes and thiazoles described below. Suitable thiophenes can be characterized by the following structure:
Ri and R2 can be independently selected from:
a) [(CH ₂ CR'HO) _x (CH ₂ CRHO) _y H] where R 'is selected from the group consisting of H, CH ₃ , CH ₂ O (CH ₂ CH ₂ O) _z H, and mixtures of same, R being selected from the group consisting of H, CH ₂ O (CH ₂ CH ₂ O) _Z H, and mixtures thereof, where x + y <5, where y £ 1, and where z = 0 to 5,
b) R1 = alkyl, aryl or aryl alkyl and R ₂ = [(CH ₂ CR'HO) _X (CH ₂
CRHO) _y H]
35/63 where R 'is selected from the group consisting of H, CH ₃ , CH ₂ O (CH ₂ CH ₂ O) zH, and mixtures thereof, with R being selected from the group consisting of H, CH ₂ O ( CH ₂ CH ₂ O) _Z H, and mixtures thereof, where x + y <10, where y> 1, and where z = 0 to 5,
c) R! = [CH ₂ CH ₂ (OR ₃ ) CH ₂ OR ₄ ] and R ₂ = [CH ₂ CH ₂ (OR ₃ ) CH ₂ OR ₄ ] where R ₃ is selected from the group consisting of H, (CH ₂ CH ₂ O) _Z H, and mixtures thereof, and where z = 0 to 10, where R ₄ is selected from the group consisting of (CrCi6) alkyl, aryl groups, and mixtures of the same, and
d) where R1 and R2 can be independently selected from the product of the amino addition of styrene oxide, glycidyl methyl ether, isobutyl glycidyl ether, isopropyl glycidyl ether, t-butyl glycidyl ether, 2-ethyl hexyl glycidyl ether and glycidyl ether hexadecyl, followed by the addition of 1 to 10 alkylene oxide units.
In one aspect, these thiophenes can be characterized by the following structure:
N [(CH ₂ CRTO) x (CH ₂ CRHO) yH] ₂ where R 'is selected from the group consisting of H, CH ₃ , CH ₂ O (CH ₂ CH ₂ O) _z H, and mixtures thereof, being that R is selected from the group consisting of H, CH ₂ O (CH ₂ CH ₂ O) _Z H, and mixtures thereof, where x + y <5, where y> 1, and where z = 0 to 5 .
Suitable thiazolium dyes include azo dyes that can have the formula (I) below:
36/63
Ν = Ν — X
Formula I where:
R3 and R4 can be identical or different and, independently of each other, are hydrogen, a saturated or unsaturated alkyl group (C1 to C22), an alkyl group (C (to C22) replaced by a halogen atom, a hydroxy alkyl group - (C ₂ to C ₂₂ ) optionally interrupted by oxygen, a polyether group derived from ethylene oxide, propylene oxide or butylene oxide, an amino- (Ci to C ₂₂ ) alkyl group, a substituted or unsubstituted phenyl group or a group benzyl, an alkyl group (C1 to C ₂₂ ) terminated in sulfonate, sulfate or carboxylate, or the radical groups R ₃ and R ₄ , together with the remaining molecule, can form a saturated or unsaturated, substituted, substituted heterocyclic or carbocyclic ring system or unsubstituted optionally substituted by halogen, sulfate, sulfonate, phosphate, nitrate and carboxylate;
X can be a radical group of the phenol series or a heterocyclic radical group or aniline series or m-toluidine series which can have formula II below;
on what:
R ₅ and R ₆ can be identical or different and, independently of one another, are a linear or branched alkyl group, saturated or unsaturated (CIC ₂₂₎ -, alkyl ether group (CIC ₂₂₎ - a hydroxy alkyl group - (C ₂ -C ₂₂ ) - optionally interrupted by oxygen, a polyether group derived from ethylene oxide, propylene oxide, butylene oxide, glycidyl
37/63 or combinations thereof, an amino- (C1-C22) alkyl group, a substituted or unsubstituted phenyl group or a benzyl group, a linear or branched (C1-C22) alkyl group - terminated in a linear or branched alkyl (C1-C22) -, hydroxyl group, acetate, sulfonate, sulfate, or carboxylate, or R ₅ and R ₆ or R ₅ and R ₇ or R ₆ and R7, together with 0 nitrogen atom, form a ring system having 5- to 6-membered, which may comprise an additional heteroatom, or R ₅ and R ₆ or R ₅ and R ₇ or R ₆ and R ₇ , optionally form a carbon atom of the benzene ring to a five or six membered heterocycle containing oxygen or containing nitrogen that can be substituted by one or more alkyl groups (C1-C22) -;
R ₇ can be identical or different and, independently of each other, are hydrogen, a halogen atom, a saturated or unsaturated alkyl group (C1 to C22), an alkyl ether group (Ci to C22), a hydroxyl group, a group hydroxy alkyl (C1 to C22), an alkoxy group (C1 to C22), a cyano group, a nitro group, an amino group, an alkylamino group (C-ι to C22)> a dialkyl amino group (C1 to C22) , a carboxylic acid group, a C (O) O- (Cia C22) alkyl group, a substituted or unsubstituted C (O) O phenyl group;
Q 'can be an anion that balances the charge as a whole of the compound of formula I, and the index q can be 0 or 1. Suitable anions include chlorine, bromine, methosulfate, tetrafluoroborate and acetate anions.
R1 can be an alkyl (C1 to C22), an aromatic alkyl or an alkyl sulfonate radical of formula (III) below;
Formula III where
R ₂ is hydrogen, methyl, ethyl, propyl, acetate or a hydroxyl group, mep are integers from 0 to (n-1), n is an integer from 1 to 6 and m + p = (n-1);
38/63 with the proviso that the heterocycle of formula (I) comprises at least two and at most three heteroatoms, the heterocycle having at most one sulfur atom;
In one aspect, a suitable thiazolium dye can have formula IV below:
Formula IV in which Rs and R ₉ can be identical or different and, independently of one another, can be a saturated or unsaturated (C1-C22) alkyl group -, a (C1-C22) alkyl group, a hydroxy alkyl group (C2-C ₂ 2) - optionally interrupted by oxygen, a polyether group derived from ethylene oxide, propylene oxide or butylene oxide, an amino- (Ci-C ₂₂ ) alkyl group, a substituted or unsubstituted phenyl group or a benzyl group, a (C1-C22) alkyl group - terminated in sulfonate, sulfate, or carboxylate, or R ₈ and R ₉ , together with the nitrogen atom, can form a ring system having 5 to 6 members, which may comprise an additional heteroatom, or R ₈ or R ₉ may form, with a carbon atom of the benzene ring, a five or six membered heterocycle optionally containing oxygen or containing nitrogen which can be replaced by one or more alkyl groups ( C1-C22) -, θ mixtures thereof, and R10 is hydrogen or methyl. For formula IV, Q 'is as described for formula I above.
In one aspect, suitable thiazolium dyes can have formula (V);
Ri Qq '
Formula V
39/63 where:
a.) Ri can be selected from a branched or unbranched alkyl (C1 to C22) moiety, an aromatic alkyl moiety, a polyalkylene oxide moiety or a moiety of formula (VI) below;
Formula VI where (i) R ₂ can be selected from hydrogen, methyl, ethyl, propyl, acetate or a hydroxyl moiety, mep can be, independently, integers from 0 to (n-1), with the proviso that n is an integer from 1 to 6 and m + p = (n-1) (ii) Y can be selected from a hydroxyl, sulfonate, sulfate, carboxylate or acetate moiety;
B. ) R ₃ and R ₄ :
i. ) can be independently selected from hydrogen, a saturated or unsaturated (C1-C22) alkyl portion -, a hydroxy- (C ₂ -C ₂ 2) alkyl portion -, a hydroxy- (C ₂ -C22) alkyl portion - comprising , in addition to hydroxyl oxygen, an oxygen atom, a polyether moiety, an amino- (C1-22) alkyl moiety, a substituted or unsubstituted phenyl moiety, a substituted or unsubstituted benzyl moiety, a (C1- alkyl moiety) C22) - terminated in sulfonate, sulfate, acetate, or carboxylate, or ii. ) when together they can form a saturated or unsaturated heterocyclic or carbocyclic moiety, or iii. ) when together they can form a saturated or unsaturated heterocyclic or carbocyclic moiety substituted by sulfate, sulfonate, phosphate, nitrate, and carboxylate;
ç. ) X can be the portion with formula VII below;
40/63
on what:
i. ) R5 and R ₆ :
(a) can be independently selected from hydrogen, a saturated or unsaturated (C1-C22) alkyl portion -, a hydroxy- (C2-C ₂ 2) alkyl portion -, a hydroxy- (C ₂ -C ₂ 2) alkyl portion - comprising, in addition to hydroxyl oxygen, an oxygen atom, a terminated or unfinished polyether moiety, an amino- (C1-22) alkyl moiety -, a substituted or unsubstituted phenyl moiety, a substituted or unsubstituted benzyl moiety , a (C-1-C22) alkyl moiety - comprising a C1-C4-ending alkyl ether moiety, sulfonate, sulfate, acetate or carboxylate, a thiazole moiety, or (b) when together they can form a saturated or unsaturated heterocyclic moiety , or (c) when together they form a saturated or unsaturated heterocyclic moiety substituted by one or more alkoxylate, sulfate, sulfonate, phosphate, nitrate and / or carboxylate moieties;
(d) when together with R ₇ , R ₈ , or R ₇ and R _{8 they} form one or more saturated or unsaturated heterocyclic moieties, optionally substituted by one or more alkoxylate, sulfate, sulfonate, phosphate, nitrate, and / or carboxylate moieties, or (e) when together they form a thiazole moiety;
ii. ) R ₇ and R ₈ can be independently selected from hydrogen or from a saturated or unsaturated alkyl moiety;
d.) Q can be an anion that balances the charge as a whole of the compound of formula I, and the index q is 0 or 1. Suitable anions include chlorine, bromine, methosulfate, tetrafluoroborate and acetate anions.
In one respect, for formula V:
41/63
The. ) Ri can be a methyl portion;
B. ) R ₃ and R ₄ can be hydrogen, and
ç. ) X can have formula VIII below:
Formula VIII where (i) Rs and Re can be as defined for formula VII above;
(ii) R ₇ can be hydrogen or a methyl moiety, and (iii) R ₈ can be hydrogen.
In one aspect, for formula VII R ₅ and R ₆ each independently comprise 1 to 20 alkylene oxide units and, independently, a selected portion of the group consisting of: styrene oxide, glycidyl methyl ether, ether isobutyl glycidyl, isopropyl glycidyl ether, t-butyl glycidyl ether, 2-ethyl hexyl glycidyl ether, or hexadecyl glycidyl ether.
Suitable polymeric dyes include those selected from the group consisting of polymers containing conjugated chromogens (dye-polymer conjugates) and polymers with copolymerized chromogens in the polymer main chain, as well as mixtures thereof.
In another aspect, suitable polymeric dyes include those selected from the group consisting of commercially available fabric-adherent dyes under the name of Liquitint® (Milliken, Spartanburg, South Carolina, USA), dye-polymer conjugates formed from at least one reactive dye and a polymer selected from the group consisting of polymers comprising a portion selected from the group consisting of a hydroxyl portion, a primary amine portion, a secondary amine portion, a thiol portion and mixtures thereof. In yet another aspect, suitable polymeric dyes include powdered dyes
42/63 thresholds selected from the group consisting of Liquitint® (Milliken, Spartanburg, South Carolina, USA) Violet CT, carboxy methyl cellulose (CMC) conjugated to a reactive blue, reactive violet or reactive red dye like CMC conjugated to C.l. Reactive Blue 19, sold by Megazyme, Wicklow, Ireland, under the product name AZO-CM-CELLULOSE, product code SACMC and mixtures thereof.
Suitable clay dye conjugates include those selected from the group consisting of at least one cationic / basic dye and smectite clay, as well as mixtures thereof. In another aspect, suitable clay dye conjugates include those selected from the group consisting of a cationic / basic dye selected from the group consisting of C.l. Basic Yellow 1 to 108, C.l. Basic Orange 1 to 69, C.l. Basic Red 1 to 118, C.l. Basic Violet 1 to 51, C.l. Basic Blue 1 to 164, C.l. Basic Green 1 to 14, C.l. Basic Brown 1 to 23, Basic Black Cl 1 to 11, and a clay selected from the group consisting of montmorillonite clay, hectorite clay, saponite clay, and mixtures thereof. In yet another aspect, suitable clay dye conjugates include those selected from the group consisting of.
Basic Blue Conjugate B7 C.l. 42595 montmorillonite, Basic Blue conjugate B9 C.l. 52015 montmorillonite, Basic Violet conjugate V3 C.l. 42555 montmorillonite, Basic Green conjugate G1 C.l. 42040 montmorillonite, Basic Red conjugate R1 C.l. 45160 montmorillonite, C.l. Basic Black 2, Basic Blue conjugate B7 C.l. 42595 hectorite, Basic Blue conjugate B9 C.l. 52015 hectorite, Basic Violet conjugate V3 C.l. 42555 hectorite, Basic Green conjugate G1 C.l. 42040 hectorite, Basic Red conjugate R1 C.l. 45160 hectorite, C.l. Basic Black 2 of hectorite, Basic Blue conjugate B7 C.l. 42595 saponite, Basic Blue conjugate B9 C.l. 52015 saponite, Basic Violet conjugate V3 C.l. 42555 saponite, Basic Green conjugate G1 C.l. 42040 saponite, Basic Red conjugate R1 C.l. 45160 saponite, C.l. Basic Black 2 of saponite and mixtures thereof.
43/63
Suitable pigments include those selected from the group consisting of flavantrona, indantrone, chlorinated indanthrone containing 1 to 4 chlorine atoms, pyrantrone, dichloropyrantrone, monobromodichloropyrantrone, dibromodichloropyrantrone, tetrabromopyrantrone, perylene-3,4,9,10-tetracarboxylic acid diide. that imide groups can be unsubstituted or substituted by C1-C3- alkyl or a phenyl or heterocyclic radical, and with phenyl and heterocyclic radicals can additionally carry substituents that do not confer solubility in water, amides of anthrapyrimidine carboxylic acid , violantrone, isoviolantrone, dioxazin-based pigments, copper phthalocyanine which can contain up to 2 chlorine atoms per molecule, polychloro-copper phthalocyanine or polybromochloro-copper phthalocyanine containing up to 14 bromine atoms per molecule, and mixtures thereof. In another aspect, suitable pigments include those selected from the group consisting of ultramarine blue (C.l. Pigment Blue 29), Ultramarine Violet (C.l. Pigment Violet 15), and mixtures thereof.
The aforementioned fabric tinting agents can be used in combination (any mixture of fabric tinting agents can be used). Suitable tinting agents for fabrics can be obtained from Aldrich of Milwaukee, Wisconsin, USA, Ciba Specialty Chemicals of Basel, Switzerland, BASF of Ludwigshafen, Germany, Dayglo Color Corporation of Mumbai, India, Organic Dyestuffs Corp. from East Providence, Rhode Island, USA, Dystar from Frankfurt, Germany, Lanxess from Leverkusen, Germany, Megazyme from Wicklow, Ireland, Clariant from Muttenz, Switzerland, and Avecia from Manchester, United Kingdom, and / or produced according to the examples contained herein.
Dispersants - The compositions of the present invention can also contain dispersants. Suitable water-soluble organic materials are homo or copolymeric acids, or their salts, in which the polycarboxylic acid contains at least two carboxyl radicals separated from each other by no more than two carbon atoms.
Enzymes - The compositions may comprise one or more
44/63 detergent enzymes that provide cleaning performance and / or fabric treatment benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pululanases, tannases, tannases , malanases, β-glycanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases or mixtures thereof. A typical combination is a cocktail of conventionally applicable enzymes, such as protease, lipase, cutinase and / or cellulase, together with amylase.
Enzyme Stabilizers - Enzymes for use in compositions, for example, detergents can be stabilized by various techniques. The enzymes used in this case can be stabilized by the presence of soluble water sources of calcium and / or magnesium ions in the final compositions that supply these ions to the enzymes.
Catalytic metal complexes - Applicants' compositions may include catalytic metal complexes. One type of bleach catalyst containing metal is a catalyst system that contains a transition metal cation with catalytic activity defined for bleach, such as copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations, an auxiliary metal cation with little or no catalytic activity for bleach, such as zinc or aluminum cations, and a hijacker that has defined stability constants for catalytic and auxiliary metal cations, particularly ethylenediamine tetraacetic acid, ethylene diamine tetra (methylene phosphonic acid), and soluble salts these substances in water. Such catalysts are disclosed in US Patent No. 4,430,243.
If desired, the compositions of the present invention can be catalyzed by means of a manganese compound. Such compounds and usage levels are well known in the art and include, for example, the manganese-based catalysts disclosed in US Patent No. 5,576,282.
Cobalt-based bleaching catalysts useful in the present invention are known and are described, for example, in patents
45/63
US No. 5,597,936 and 5,595,967. Such cobalt-based catalysts are readily prepared by known procedures, as described, for example, in US Patent Nos. 5,597,936 and 5,595,967.
The compositions of the present invention may also suitably include a transition metal complex of a rigid macropolicy linker - abbreviated as MRL. As a matter of practice, but without limiting it, the cleaning compositions and processes of the present invention can be adjusted to offer something in the order of at least one part per hundred million of the beneficial agent's MRL species in the medium of aqueous wash and can offer about 0.005 ppm to about 25 ppm, about 0.05 ppm to about 10 ppm and, or even about 0.1 ppm to about 5 ppm, the MRL in the wash liquid .
The transition metals suitable for use in the present transition metal based bleach catalyst include manganese, iron and chromium. MRLs suitable for use in the present invention are a special type of cross-linked ultra-rigid ligand, such as 5,12-diethyl-1,5,8,12tetraazabicyclo [6.6.2] hexadecane.
Suitable transition metal MRLs are readily prepared by known procedures, such as those described, for example, in WO 00/32601 and in US patent No. 6,225,464. Re-modifier
The liquid compositions of the present invention can comprise a rheology modifier. The rheology modifier can be selected from the group consisting of crystalline, non-polymeric, hydroxy-functional materials, polymeric rheology modifiers that impart shear-reducing viscosity characteristics to the aqueous liquid matrix of the composition. In one aspect, the rheology modifiers give the aqueous liquid composition a viscosity under high shear at the shear rate of 20 sec ' ¹ at 21 ° C, from 1 to 7000 cps and viscosity under low shear (shear rate 0.5 sec ' ¹ at 21 ° C) greater than 1000 cps or even 1000 cps at 200,000 cps. In one aspect, for com46 / 63 φ 10 cleaning and treatment positions, these rheology modifiers give the aqueous liquid composition a viscosity under high shear at 20 sec ¹ and at 21 ° C, from 50 to 3000 cps and a viscosity under shear (shear rate 0.5 sec ' ¹ at 21 ° C) greater than 1000 cps or even 1000 cps to 200,000 cps. The viscosity according to the present invention is measured using an AR 2000 rheometer of TA instruments using a steel plate spindle having a plate diameter of 40 mm and a span size of 500 pm. Viscosity under high shear at 20 sec ' ¹ and viscosity under low shear at 0.5 sec' ¹ can be obtained from a logarithmic shear rate gap of 0.1 sec ' ¹ to 25 sec ¹ in the period 3 minutes at 21 ° C. Crystalline hydroxy-functional materials are rheology modifiers that form filamentary structuring systems in the entire matrix of the composition in in situ crystallization in the matrix. Polymeric rheology modifiers are preferably selected from polyacrylates, polymer gums, other non-gummy polysaccharides and combinations of these polymeric materials.
Generally, the rheology modifier will comprise from 0.01% to 1%, preferably from 0.05% to 0.75% and, more preferably, from 0.1% to 0.5%, by weight of the composition of the present invention.
Structuring agents that are especially useful in the compositions of the present invention can comprise non-polymeric (except for conventional alkoxylation), crystalline hydroxy-functional materials that can form filamentary structuring systems throughout the liquid matrix when they are crystallized within the matrix locally. These materials can be characterized, generally, as fatty acids, fatty esters or crystalline fatty waxes, containing hydroxyl. In one aspect, rheology modifiers include crystalline rheology modifiers containing hydroxyl, include castor oil and its derivatives. In one aspect, rheology modifiers can be derived from hydrogenated castor oil such as hydrogenated castor oil and hydrogenated castor wax. Commercially available crystalline rheology modifiers containing castor oil-based hydroxyl include THIXCIN ™ available from Rheox, Inc.
47/63 (now Elementis).
Other types of rheology modifiers, in addition to the non-polymeric crystalline rheology modifiers containing hydroxyl described so far, can be used in the liquid detergent compositions of the present invention. Polymeric materials that provide shear thinning characteristics to the aqueous liquid matrix can also be employed.
Suitable polymeric rheology modifiers include those of the polyacrylate, polysaccharide or polysaccharide derivative type. Polysaccharide derivatives typically used as rheology modifiers comprise polymeric gum materials. Such gums include pectin, alginate, arabinogalactane (gum arabic), carrageenan, gellan gum, xanthan gum and guar gum.
If polymeric rheology modifiers are used in the present invention, such a preferred material is gelan gum. Gellan gum is a heteropolysaccharide prepared by fermentation of Pseudomonaselodea ATCC 31461. Gellan gum is commercially available from CP Kelco U.S., Inc., under the name KELCOGEL.
An additional suitable alternative and rheology modifier includes a combination of a solvent and a polycarboxylate polymer. More specifically, the solvent can be an alkylene glycol. In one aspect, the solvent may comprise dipropylene glycol. In one aspect, the polycarboxylate polymer can comprise a polyacrylate, polymethacrylate or mixtures thereof. In one aspect, the solvent may be present, based on the weight of the total composition, in a content of 0.5% to 15% or from 2% to 9% of the composition. In one aspect, polycarboxylate polymer can be present, based on the total weight of the composition, in a content of 0.1% to 10%, or from 2% to 5%. In one aspect, the solvent component may comprise a mixture of dipropylene glycol and 1,2-propanediol. In one aspect, the ratio between dipropylene glycol and 1,2-propanediol can be 3: 1 to 1: 3, or even 1: 1. In one aspect, the polyacrylate may comprise a copolymer of unsaturated mono- or dicarbonic acid and Ch-Cso alkyl ester of the (met) acid
48/63 acrylic. In another aspect, the rheology modifier may comprise a polyacrylate of unsaturated mono- or dicarbônico acid and Ci-C ₃₀ alkyl ester of (meth) acrylic acid. These copolymers are available from Noveon Inc under the trade name Carbopol Aqua 30®.
In the absence of the rheology modifier, and to provide the desired shedding viscosity characteristics under the liquid composition, the liquid composition can be internally structured through the chemical phase of the surfactant or gel phases.
Silicone emulsion
The compositions of the present invention can comprise a silicone emulsion. An emulsion is a mixture of a liquid (the dispersed phase) dispersed in another (the continuous phase). In the context of the present description, silicone emulsion also encompasses macroemulsion and microemulsion.
In one embodiment, the silicone emulsion of the present invention is added as an emulsion of silicone oil in water or a solvent containing aqueous solution in the range of 35-65 (%, by weight). In one embodiment, the silicone emulsion of the present invention can be any silicone emulsion.
In one embodiment, the average particle size of the silicone emulsion is 0.01 to 2 micrometers, more preferably 0.2 to 0.8 micrometer.
Preferably, the emulsified silicone oil is selected from the group comprising non-ionic nitrogen-free silicone oils, amino-functional silicone oils, and mixtures thereof.
In one embodiment of the present invention, the silicone emulsion is an amino-functional silicone, preferably amino dimethicone.
In a preferred embodiment of the present invention, the silicone emulsion is a non-ionic nitrogen-free silicone emulsion, preferably selected from the group comprising polydialkyl silicone, polydimethyl silicone, alkyloxylated silicone, ethoxylated silicone, propoxylated silicone, propoxylated silicone ethoxylated, quaternary silicone or derivatives
49/63 of these items and mixtures thereof. In a more preferred embodiment, the non-ionic nitrogen-free silicone emulsion is selected from the group comprising polydialkyl silicone, polydimethyl silicone, and mixtures thereof. In one embodiment, the silicone emulsion is polydimethyl silicone.
In this preferred embodiment, where the silicone emulsion is polydimethyl silicone, polydimethyl silicone has a viscosity between 0.0001 m ² .s ' ¹ and 0.1 m ² .s' ¹ , preferably between 0.0003 m ² . s ' ¹ and 0.06 m ² .s' ¹ , more preferably between 0.00035 m ² .s ' ¹ and 0.012 m ² .s' ¹ .
Solvents suitable for use in the solvent containing aqueous solution can be selected from the group comprising linear, branched, cyclic, saturated and / or unsaturated C1-C20 alcohols with one or more free hydroxy groups, amines, alkanolamines, and mixtures thereof. Preferred solvents are monoalcohols, diols, monoamine derivatives, glycerols, glycols and mixtures of these items, such as ethanol, propanol, propanediol, monoethanolamine, glycerol, sorbitol, alkylene glycols, polyalkylene glycols and mixtures of these items. The most preferred solvents are selected from the group comprising 1,2-propandiol, 1,3-propandiol, glycerol, ethylene glycol, diethylene glycol, and mixtures thereof.
The emulsion contains a water-soluble emulsifier, selected from the group of commercially available emulsifiers that include cationic, anionic, non-ionic or zwitterionic emulsifiers. In a preferred embodiment of this invention, the emulsifier is a non-ionic surfactant.
Alternatively, premixtures of silicone emulsions and solvents are used to overcome the problems of the process in terms of proper dispersion or dissolution of all ingredients throughout the composition.
In the context of the present invention, premixtures of the silicone emulsion include high internal phase (HIPE) emulsion. This is achieved by pre-mixing a silicone emulsion, such as polydimethyl silicone, and an emulsifier to create a HIPE and then mixing 50/63 if that HIPE in the composition, thus obtaining a good mixture resulting in a homogeneous mixture. These HIPEs comprise at least 65%, alternatively at least 70%, alternatively at least 74%, alternatively at least 80%, alternatively no more than 95%, in weight, of an internal phase (dispersed phase), the phase being inner layer may comprise a silicone emulsion. The internal phase can also be other beneficial agents for treating water-insoluble tissues that are not yet pre-emulsified. The internal phase is dispersed using an emulsifying agent. Examples of the emulsifying agent include a surfactant or surface tension reducing polymer. In one embodiment, the emulsifying agent range is at least 0.1% to 25%, alternatively from 1% to 10%, and alternatively from 2% to 6%, by weight, of the HIPE. In another embodiment, the emulsifying agent is soluble in water and reduces the surface tension of the water, in a concentration of less than 0.1%, 15 by weight, of deionized water, to less than 0.0007 N (70 dynes), alternatively less than 0.0006 N (60 dyne), alternatively less than 0.0005 N (50 dyne), alternatively equal to or greater than 0.0002 N (20 dyne). In another embodiment, the emulsifying agent is at least partially insoluble in water.
The external phase (continuous phase), in one mode, is water, alternatively it can comprise at least some amount of water, alternatively it can comprise little or no water. In another embodiment, the external water phase may comprise less than 35%, alternatively less than 30%, alternatively less than 25%, alternatively at least 1% by weight of HIPE. Non-aqueous HIPEs can also be prepared with a solvent such as the external phase with little or no water present. Typical solvents include glycerin and propylene glycol.
In another embodiment, the composition is a non-concentrated composition. In this modality, the silicone emulsion is not, at least initially, emulsified and can be emulsified in the fabric treatment composition itself.
51/63
The composition of the present invention may comprise a silicone emulsion which acts to maintain the physical stability of the liquid fabric softening composition after a freeze-thaw cycle and also after prolonged storage at low temperatures.
The silicone emulsion of the present invention is in a content of 0.5% to 10%. In another embodiment, the silicone emulsion of the present invention is in a content of 0.3% to 10%, preferably 0.3% to 5% and, most preferably, 0.5% to 3.0 % by weight of the liquid fabric softener composition.
I. Non-ionic nitrogen-free silicone emulsions:
In the context of the present invention, the silicone emulsion is preferably selected from the group comprising non-ionic nitrogen-free silicone emulsions with formulas (I), (II), (III), and mixtures thereof:
laughs
R ² - (R ¹ ) 2SiO - [(R ¹ ) 2SiO] _a - [(R ¹ ) (R ² ) SiO] b-Si (R ¹ ) 2-R ² (II);
R ¹ R ¹ R
I I
R ¹ --- Si --- O - (- Si --- O -j ^ -SiRi where each R ¹ is independently selected from the group consisting of linear, branched or cyclic alkyl groups, substituted or unsubstituted having from 1 to 20 carbon atoms, linear, branched or cyclic alkenyl groups, substituted or unsubstituted having from 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 20 carbon atoms, substituted or unsubstituted alkyl groups substituted, substituted or unsubstituted arylalkyl groups and substituted arylalkenyl groups
52/63 substituted or unsubstituted having from 7 to 20 carbon atoms, and mixtures thereof, each R ² is independently selected from the group consisting of linear, branched or cyclic alkyl groups, substituted or unsubstituted having from 1 to 20 carbon atoms, linear, branched or cyclic alkenyl groups, substituted or unsubstituted having from 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 20 carbon atoms, substituted or unsubstituted alkyl aryl groups, arylalkyl groups substituted or unsubstituted, substituted or unsubstituted arylalkenyl groups having from 7 to 20 carbon atoms and a poly copolymer group (ethylene oxide / propylene oxide) with the following general formula:
- (CH ₂ ) nO (C2H4O) _c (C ₃ H ₆ O) _d R ³ (IV) polydialkyl silicone, polydimethyl silicone, alkyloxylated silicone, quaternary silicone with at least one R ² being a poly (ethylenoxy / propyleneoxy) copolymer group (ethoxylated silicone emulsions, propoxylated silicone, ethoxylated propoxylated silicone), and each R ³ is independently selected from the group consisting of hydrogen, an alkyl with 1 to 4 carbon atoms, an acetyl group, and mixtures thereof, the w index has the value so that the viscosity of the nitrogen-free silicone polymer of formulas (I) and (III) is between 0.0001 m ² .s' ¹ (100 cSt) and 0.1 m ² .s ' ¹ (100,000 cSt), where a is 1 to 50, b is 1 to 50, n is 1 to 50, the total of c (for all polyalkylenoxy side groups) has a value of 1 to 100, the total of d is 0 to 14, the total of c + d has a value of 5 to 150
More preferably, the nonionic nitrogen-free silicone emulsion is selected from the group consisting of linear non-ionic nitrogen-free silicone emulsions with formulas (II) to (III) as described above, where R ¹ is selected from the group consisting of methyl, phenyl, phenylalkyl, and mixtures thereof, where R ² is selected from the group consisting of methyl, phenyl, phenylalkyl, and mixtures thereof, and from the group with the following general formula (IV), as defined above, and mixtures thereof, where R ³ is defined as above and the w index has a value such that the viscosity of the nitrogen-free silicone emulsion
53/63 of formula (III) is between 0.0001 m ² .s ' ¹ (100 cSt) and 0.1 m ² .s' ¹ (100,000 cSt), a is 1 to 30, b is 1 to 30, n is 3 to 5, total c is 6 to 100, total d is 0 to 3, and total c + d is 7 to 100.
With the highest preference, the nitrogen-free silicone emulsion is selected from the group comprising linear non-ionic nitrogen-free silicone emulsions with the following general formula (III) as described above, where R ¹ is methyl, that is, the silicone emulsion is polydimethyl silicone in this preferred modality, and the silicone emulsion is polydimethyl silicone, the w index has a value so that polydimethyl silicone has a viscosity between 0.0001 m ² .s' ¹ and 0.1 m ² .s' ¹ , preferably between 0.0003 m ² .s' ¹ and 0.06 m ² .s' ¹ , more preferably between 0.00035 m ² .s' ¹ and 0.012 m ² .s' ¹ .
II. Amino-functional silicone emulsions:
In one embodiment of the present invention, the silicone emulsion is an amino-functional silicone. Amino-functional silicone emulsions are materials with the following formula:
HO [Si (CH ₃ ) 2-O] _x {Si (OH) [(CH2) 3-NH- (CH2) 2-NH ₂ ] O} _y H where X and Y are integers that depend on the viscosity of the silicone emulsion. Preferably, the amino-functional silicone emulsion has a molecular weight such that it has a viscosity of 0.0005 m ² .s ' ¹ (500 cSt) to 0.5 m ² .s' ¹ (500,000 cSt). This material is also known as aminodimethicone.
Method of Use
Some of the products intended for the consumer presented here can be used to clean or treat a site, among others, a surface or fabric. Typically at least a portion of the situs is brought into contact with one embodiment of the Applicants' composition, in pure form or diluted in a liquid, for example, a washing liquid, and then the situs can be optionally washed and / or rinsed. In one aspect, a situs is optionally washed and / or rinsed, brought into contact with a particle according to the present invention or composition comprising said particle and then, optionally, washed and / or rinsed. In one aspect, a cleaning or treatment method54 / 63 for a situs is presented, which optionally comprises the washing and / or rinsing of said situs, the contact of said situs with the composition selected from the compositions and mixtures of the presented here and, optionally, the washing and / or rinsing of said situs. For the purposes of the present invention, washing includes, but is not limited to, rubbing and mechanical agitation. The fabric can comprise virtually any type of fiber capable of being washed or treated under normal conditions of consumer use. Liquids that can comprise the compositions shown can have a pH of about 3 to about 11.5. These compositions are typically used in concentrations of about 500 ppm to about 15,000 ppm, in solution. When the washing solvent is water, the water temperature is typically in the range of about 5 ° C to about 90 ° C and, when the situs comprises a fabric, the mass ratio between water and fabric is typically in the range of about 1: 1 to about 30: 1. Testing methods
1.) Average molecular weight: For the purposes of this specification and claims, the average molecular weight of a polymer is determined according to the ASTM D4001-93 (2006) method.
2.) Degree of hydrolysis: For the purposes of this specification and claims, the degree of hydrolysis is determined according to the method found in US patent no. 6,132,558, column 2, row 36 to column 5, row 25.
3.) Charge density: For the purposes of this specification and claims, the charge density of a polymer is determined with the aid of colloid titration, cf. D. Horn, Progress in Colloid & Polymer Sci. 65 (1978), 251 to 264.
4.) Zeta potential: For the purposes of this specification and claims, the zeta potential is determined as follows:
The. ) Equipment: Malvern Zetasizer 3000
B. ) Procedure for sample preparation:
(i) Add 5 drops of slurry containing the encapsulated product of interest to 20 mL of a 1 mM NaCI solution to dilute the slurry
55/63 fluid. It may be necessary to adjust the concentration to make the counting rate in the range of 50 to 300 Kcps.
(ii) the zeta potential is measured on the diluted sample without filtration (iii) inject the filtered slurry into the Zetasizer cell and insert the cell into the equipment. The test temperature is set to 25 ° C.
(iv) when the temperature is stable (usually 3 to 5 minutes), the measurement starts. For each sample, five measurements are made. Three samples are taken for each fluid paste of interest. The 15 readings are averaged.
c.) Equipment settings for measurements:
Parameter adjustments for the sample used:
Material: melamine RI 1.680, absorption 0.10 Dispersant: 1 mM NaCL Temperature: 25 ° C Viscosity: 0.8900 cP RI: 1,330 Dielectric constant: 100 Selection F (ka): Model: F (ka) Smoluchowski 1.5
Use the viscosity of the dispersant as the viscosity of the sample
Cell type: DTS1060C: clean disposable Zeta cells Measurements: 3 measurements
d.) Results: The zeta potential is recorded in mV as the average of the 15 readings taken for the fluid paste of interest.
Examples
Although particular embodiments of the present invention have been illustrated and described, it should be apparent to those skilled in the art that various other changes and modifications can be made without departing from the character and scope of the invention. Therefore, it is intended to cover in the appended claims all such changes and modifications that fall within the scope of the present invention.
56/63
Example 1: Melamine-formaldehyde (MF) capsule with 84% by weight of core and 16% by weight of wall
25 grams of deionized water are dissolved and mixed in 200 grams of acrylic acid copolymer emulsifier and butyl acrylate (Colloid C351, 25% solids, pka 4.5 to 4.7, (Kemira Chemicals, Inc. Kennesaw, Georgia , USA) The pH of the solution is adjusted to 4.0 using a sodium hydroxide solution, 8 grams of partially methylated methylol melamine resin (Cymel 385, 80% solid, (Cytec Industries West Paterson, New Jersey, USA)) to the emulsifying solution, 200 grams of perfume oil are added to the previous mixture under mechanical stirring and the temperature is raised to 50 ° C. After mixing at a higher speed until a stable emulsion is obtained, to the emulsion the second solution and 4 grams of sodium sulfate salt This second solution contains 10 grams of butyl acrylate-acrylic acid copolymer emulsifier (Colloid C351, 25% solids, pka 4.5 to 4.7, Kemira) , 120 grams of distilled water, sodium hydroxide solution to adjust the pH to 4.8, 25 grams of partially methylated methylol melanin resin (Cymel 385, 80% Cytec). This mixture is heated to 70 ° C and maintained overnight with continuous stirring to complete the encapsulation process. 23 grams of acetoacetamide (Sigma-Aldrich, Saint Louis, Missouri, USA) are added to the suspension. Using an Accusizer analyzer, model 780, an average capsule size of 30 pm is obtained.
Example 2
Procedure for the preparation of polymer coated perfume microcapsules.
Polymer-coated perfume microcapsules are prepared by weighing 99 g of perfume microcapsule slurry based on reference melamine formaldehyde (99.75%) and 1 g of Lupamin 9030, 16% active (ex BASF, Ludwigshafen , Germany) in a glass jar. The two ingredients are mixed briefly with a spoon. The ingredients are additionally mixed overnight in a stir shaker.
Example 3
Procedure for including perfume microcapsules coated in a liquid laundry detergent.
74.9 g of compact liquid detergent free of perfume microcapsules are weighed and 1.33 g of polymer coated microcapsules are added.
The resulting product is mixed with a mechanical mixer for 1 minute.
Example 4
A 9 kg aliquot of the perfume microcapsule slurry of example 2 is mixed using a Eurostar mixer (IKA) with an R1382 connection at a constant rotation of 200 RPM. 500 g of methyl cellulose carboxy (CP Kelco) are added to the aliquot under mixing using the Eurostar mixer with the same connection and speed described above. The slurry is mixed for a total of two hours or until a uniform slurry is formed.
Example 5
1.28 kg of precipitated silica Sipernat® 22S (Degussa) is added to an F-20 paddle mixer (Forberg). The mixer is initially activated for 5 seconds to distribute the silica evenly at the base of the mixer. The mixer is switched off and 8.25 kg of paste, produced according to example 4, are evenly distributed over the powder. The mixer is then operated at 120 rpm for a total of 30 seconds. After mixing, the wet particles are removed from the mixer and sieved using a 2000 micron sieve to remove the oversized. The product that passes through the screen is dried in batches of 500 g in a CDT 0.02 fluid bed dryer (Niro) to a final moisture content of 20%, by weight, measured by Karl Fischer. The dryer is operated at an inlet temperature of 140 ° C and an air speed of 0.68 m / s. Examples 6-13
Examples of granular detergent compositions for lava
58/63 of clothing comprising the perfume composition are included below.
Feedstock % by weight of laundry detergent compositions 6 7 8 9 10 11 12 13 Linear alkyl benzene sulfonate 7.1 6.7 11.0 10.6 6.9 4.5 10.1 8.9 Sodium C ₁₂ -is alkyl ethoxy sulfate, having an average molar degree of ethoxylation of 3 3.5 0.0 1.5 o.o 0.0 0.0 0.0 1.9 Acrylic acid / maleic acid copolymer 3.6 1.8 4.9 2.0 1.0 1.6 3.9 2.3 Sodium aluminosilicate (zeolites 4A) 4.0 0.5 0.8 1.4 16.3 0.0 17.9 2.4 Sodium tripolyphosphate 0.0 17.5 0.0 15.8 0.0 23.3 0.0 0.0 Sodium carbonate 23.2 16.8 30.2 17.3 18.4 9.0 20.8 30.0 Sodium sulphate 31.4 29.4 35.5 7.2 26.3 42.8 33.2 28.3 Sodium silicate 0.0 4.4 0.0 4.5 0.0 6.1 0.0 4.6 C ₁₄ alkyl ethoxylated alcohol. ₁₅ , having an average molar degree of ethoxylation of 7 0.4 2.6 0.8 2.5 3.1 0.3 3.8 0.4 Sodium Percarbonate 16.0 0.0 8.4 20.4 13.1 3.6 0.0 7.0 Sodium perborate o.o 9.9 0.0 0.0 0.0 0.0 0.0 0.0 Ethylacetylethylenediamine (TAED) 2.2 1.7 0.0 4.7 3.6 0.0 0.0 0.8 Calcium Bentonite 0.0 o.o 0.0 1.8 0.0 0.0 0.0 5.6 Citric acid 2.0 1.5 2.0 2.0 2.5 1.0 2.5 1.0 Protease (84 mg active / g) 0.14 0.12 0.0 0.12 0.09 0.08 0.10 0.08 Amylase (22 mg active / g) 0.10 0.11 0.0 0.10 0.10 0.0 0.14 0.08 Lipase (11 mg active / g) 0.70 0.50 0.0 0.70 0.50 0.0 0.0 0.0 Cellulase (2.3 mg active / g) 0.0 0.0 0.0 0.0 0.0 0.0 0.18 0.0 Benefit Agent Composition of Example 5 1.4 0.6 0.8 1.0 0.7 0.3 0.7 1.2 Water and miscellaneous qsp 100%
The equipment and materials described in examples 1 to 19
59/63 can be obtained from the following companies: IKA Werke GmbH & Co. KG, Staufen, Germany, CP Kelco, Atlanta, USA, Forberg International AS, Larvik, Norway, Degussa GmbH, Düsseldorf, Germany, Niro A / S, Soeberg, Denmark, Baker Perkins Ltd, Peterborough, United Kingdom, Nippon Shoku5 bai, Tokyo, Japan, BASF, Ludwigshafen, Germany, Braun, Kronberg, Germany, Industrial Chemicals Limited, Thurrock, United Kingdom, Primex ehf, Siglufjordur, Iceland, ISP World Headquarters, Polysciences, Inc. of Warrington, Pennsylvania, USA, Cytec Industries Inc., New Jersey, USA, International Specialty Products, Wayne, New Jersey, USA, P&G Chemicals Ameri10 cas, Cincinnati, Ohio, USA, Sigma-Aldrich Corp ., St. Louis, Missouri, USA,
Dow Chemical Company of Midland, Ml, USA
Examples 14-23: Tissue conditioner
Some non-limiting examples of tissue conditioners containing the polymer coated perfume microcapsules presented in this specification are summarized in the table below.
Examples (% by weight) 14 15 16 17 18 19 20 21 22 23 AAT ^a 14 16.47 14 12 12 16.47 - - 5 10 AAT ^b -3.00 - - - AAT ^C -- 6.5 - - Ethanol 2.18 2.57 2.18 1.95 1.95 2.57 - - 0.81Isopropyl Alcohol - - - - - - 0.33 1.22 - 1.0— Starch ^d 1.25 1.47 2.00 1.25 - 2.30 0.5 0.70 0.71 0.42 ^F -phase stabilizing polymer 0.21 0.25 0.21 0.21 0.14 0.18 0.15 0.14 0.2 0.1 Foam suppressor ⁹ - - - - - - - 0.1 - - Calcium chloride 0.15 0.176 0.15 0.15 0.30 0.176 - 0, ΙΟ, 15 - 0.025 DTPA ^h 0.017 0.017 0.017 0.017 0.007 0.007 0.20 - 0.002 0.002 Preservative (ppm) ^ij 5 5 5 5 5 5 - 250 * 5 5 Defoamer ^k 0.015 0.018 0.015 0.015 0.015 0.015 - - 0.015 0.015 Silicone ¹ 1- 3 -- - 1 - Dye 40 40 40 40 40 40 11 30- 30 30
60/63
Examples (% by weight) 14 15 16 17 18 19 20 21 22 23 (PPm) 300 Ammonium chloride 0.100 0.118 0.100 0.100 0.115 0.115 - - - - HCI 0.012 0.014 0.012 0.012 0.028 0.028 0.016 0.025 0.011 0.011 Polymer coated perfume microcapsules as described in example 2 0.2 0.02 0.1 0.15 0.12 0.13 0.3 0.4 0.24 0.1 Additional pure perfume 0.8 0.7 0.9 0.5 1.2 0.5 1.1 0.6 1.0 0.9 Deionized water t t t t t t t t t t
^to N, N-di (tallow oxyethyl) -N, N-dimethyl ammonium chloride.
^b Methyl bis bisulfate (tallow ethyl starch) 2-hydroxy ethylammonium.
^c Fatty acid reaction product with methyl diethanolamine at a 1.5: 1 molar ratio, quaternized with methyl chloride, resulting in a 1: 1 molar mixture of N, N-bis (stearoyl oxyethyl) chloride Ν , Ν-dimethyl ammonium and N- (stearoyl oxyethyl) N, -hydroxy ethyl N, N-dimethyl ammonium.
Cationic corn starch with high amylose content, available from National Starch under the trade name CATO®.
f Rheovis CDE ex BASF.
9 SE39, available from Wacker h Diethylene triamine pentacetic acid.
I KATHON® CG available from Rohm and Haas Co. PPM means parts per million.
j Gluteraldehyde k Silicone-based defoaming agent, available from Dow Corning Corp. under the trade name DC2310.
I Silicone emulsion, available under the trade name E3500 provided by Wacker
61/63 t Balance
Examples 24-29: Liquid laundry washing formulations (HDLs)
Ingredient 24 25 26 27 28 29 Alkyl ether sulfate 0.00 0.50 12.0 12.0 6.0 7.0 Dodecyl benzene sulfonic acid 8.0 8.0 1.0 1.0 2.0 3.0 Ethoxylated alcohol 8.0 6.0 5.0 7.0 5.0 3.0 Citric acid 5.0 3.0 3.0 5.0 2.0 3.0 Fatty acid 3.0 5.0 5.0 3.0 6.0 5.0 Sulfated ethoxy quaternized hexamethylene-diamine 1.9 1.2 1.5 2.0 1.0 1.0 Diethylene triamine pentamethylene phosphonic acid 0.3 0.2 0.2 0.3 0.1 0.2 Enzymes 1.20 0.80 0 1.2 0 0.8 Whitener (ABF based on disulfonated diamino stylbene) 0.14 0.09 0 0.14 0.01 0.09 Hydroxy ethyl cationic cellulose 0 0 0.10 0 0.200 0.30 Poly (acrylamide-codialyl dimethyl ammonium chloride) 0 0 0 0.50 0.10 0 Structuring based on hydrogenated castor oil 0.50 0.44 0.2 0.2 0.3 0.3 Boric acid 2.4 1.5 1.0 2.4 1.0 1.5 Ethanol 0.50 1.0 2.0 2.0 1.0 1.0 1.2 propanediol 2.0 3.0 1.0 1.0 0.01 0.01 Glutaraldehyde 0 0 19 ppm 0 13 ppm 0 Diethylene glycol (DEG) 1.6 0 0 0 0 0 2,3-methyl-1,3-propanediol (M pdiol) 1.0 1.0 0 0 0 0 Monoethanol amine 1.0 0.5 0 0 0 0 Sufficient NaOH to obtain a formulation with a pH of: pH 8 pH 8 pH 8 pH 8 pH 8 pH 8 Cumene sodium sulfonate (NaCS) 2.00 0 0 0 0 0 Silicone emulsion (PDMS) 0.003 0.003 0.003 0.003 0.003 0.003 Pure perfume 0.02 0.15 0.0 0.2 0.3 0.1 Polymer coated perfume microcapsules as described in example 2 0.2 0.02 0.1 0.15 0.12 0.13 Water balance balance balance balance balance balance
62/63
Example 30: Shampoo formulation
Ingredient Ammonium sulfate lauret (AE ₃ S) 6.00 Ammonium Lauryl Sulfate (ALS) 10.00 Lauret alcohol-4 0.90 Stearine trihydroxy ⁽⁷⁾ 0.10 Polymer coated perfume microcapsules as described in example 2 0.60 Sodium Chloride 0.40 Citric acid 0.04 Sodium citrate 0.40 Sodium benzoate 0.25 Ethylenediamine tetraacetic acid 0.10 Dimethicone ^{(9.10-11 )} 1.00 ⁽⁹⁾ Water and secondary components (100% q.s.) balance
The dimensions and values presented in the present invention should not be understood as being strictly limited to the exact numerical values mentioned. Instead, unless otherwise specified, each of these dimensions is intended to mean both the mentioned value and a range of functionally equivalent values around that value. For example, a dimension shown as 40 mm is intended to mean about 40 mm.
All documents cited in the Detailed Description of the Invention are, for the most part, incorporated herein by reference, and the citation of any document should not be construed as admitting that it represents prior art with respect to the present invention. If there is a conflict between any meaning or definition of a term mentioned in this document and the meaning or definition of the same term in a document incorporated by reference, the meaning or definition attributed to the term mentioned in this document will take precedence.
Although particular embodiments of the present invention have been illustrated and described, it should be apparent to those skilled in the art that
63/63 various other changes and modifications can be made without departing from the character and scope of the invention. Therefore, it is intended to cover in the appended claims all such changes and modifications that fall within the scope of the present invention.

权利要求:
Claims (15)
[1]
1. Encapsulated, characterized by the fact that it comprises a beneficial agent and a core and a wall, said wall having an external surface and a coating, said wall encapsulating said core, said coating covering the external surface of said wall, said coating comprising one or more efficiency polymers selected from the group consisting of one or more polyvinylformamides, said one or more efficiency polymers have an average molecular mass of 340,000 Da to 1,500,000 Da; degree of hydrolysis, for polyvinylformamides, from 10% to 40%; and an efficiency polymer charge density of 1 meq / g to an efficiency polymer of 16 meq / g.
[2]
2. Encapsulated according to claim 1, characterized by the fact that
a) said core comprises a material selected from the group consisting of perfumes; bleaches; dyes; insect repellents; silicones; waxes; flavors; vitamins; fabric softening agents; skin care agents; enzymes; antibacterial agents; bleaches; sensory elements;
b) said wall comprises a material selected from the group consisting of polyethylene; polyamides; polystyrenes; polyisoprene; polycarbonates; polyesters; polyacrylates; aminoplast.
[3]
3. Encapsulated according to claim 1 or 2, characterized in that said encapsulated has a ratio between the coating and the wall from 1: 200 to 1: 2, more preferably from 1: 100 to 1: 4, plus preferably from 1:80 to 1: 10
[4]
4. Slurry, characterized by the fact that it comprises an encapsulated as defined in any one of claims 1 to 3, said slurry having a zeta potential of -10 meV to +50 meV, preferably from +2 meV to +40 meV, more preferably from +5 meV to +25 meV or from 40 meV to +35 meV, preferably from -38 meV to +25 meV, more preferably from -35 meV to +10 meV, preferably said paste based on the total weight of the slurry, a sufficient amount of the
Petition 870190033938, of 09/09/2019, p. 7/16
2/4 said encapsulated to provide said slurry with 0.05% to 10%, preferably from 0.1% to 5%, more preferably from 0.125% to 2% of said efficiency polymer.
[5]
5. Agglomerate, characterized by the fact that it comprises the encapsulated and / or the slurry as defined in any one of claims 1 to 4.
[6]
6. Agglomerate production process as defined in claim 5, characterized by the fact that said process comprises:
a) combining an encapsulated and / or slurry as defined in any of claims 1 to 4, a plasticizer, preferably a plasticizer comprising water and, optionally, a binder and / or chelator to form a mixture;
b) combining said mixture with said dusting agent, preferably a dusting agent comprising silica, to form a material, and
c) removing a sufficient amount of said plasticizer from said material to produce a product comprising, based on the total product weight of 1% to 50% plasticizer.
[7]
7. Product intended for the consumer, characterized by the fact that it comprises:
a) an encapsulate selected from the encapsulated as defined in any of claims 1 to 3, the slurry as defined in claim 4, and / or the agglomerate as defined in claim 5, and
b) an auxiliary ingredient, preferably said auxiliary ingredient is selected from the group consisting of polymers, in one aspect, a cationic polymer, surfactants, builders, chelating agents, optical bleaches, dye transfer inhibiting agents, dispersants, enzymes, enzyme stabilizers, catalytic materials, bleach activators, polymer dispersing agents, clay and dirt / anti-redeposition agents, bleaches, polymer dye conjugates, clay dye conjugates, foam suppressants, dyes, catalysts
Petition 870190033938, of 09/09/2019, p. 8/16
3/4 bleaching, additional perfume and / or perfume delivery systems, structure elasticizing agents, fabric softeners, vehicles, hydrotropes, processing aids, rheology modifiers, structuring, thickeners, pigments, water and mixtures thereof .
[8]
8. Consumer product according to claim 7, characterized in that said consumer product comprising a sufficient amount of slurry and / or encapsulated paste to provide said consumer product with a polymer content of efficiency, based on the total weight of the product intended for the consumer, from 0.0001% to 0.1%, preferably from 0.001% to 0.1%, more preferably from 0.001% to 0.05%.
[9]
9. Product intended for the consumer, according to claim 7 or 8, characterized by the fact that said product intended for the consumer comprises a material selected from the group consisting of an anionic surfactant, cationic surfactant, silicone and mixtures thereof, said consumer product has:
a) a ratio between the anionic surfactant and the efficiency polymer of 100,000: 1 to 1: 1, preferably 25,000: 1 to 10: 1, more preferably 10,000: 1 to 100: 1;
b) a ratio between the cationic surfactant and the efficiency polymer of 100,000: 1 to 1: 1, preferably 25,000: 1 to 10: 1, more preferably 10,000: 1 to 100: 1, and / or
c) a ratio of silicone to polymer of 100,000: 1 to 1: 1 efficiency, preferably 25,000: 1 to 10: 1, more preferably 10,000: 1 to 100: 1.
[10]
10. Product intended for the consumer, according to any of claims 7 to 9, characterized by the fact that said product intended for the consumer comprises a rheology modifier, thickener and / or structuring with a viscosity under high shear, at a rate shear rate of 20 sec-1 and at 21 ° C, from 1 to 7000 cps and a viscosity under low shear (shear rate of 0.5 s-1 at 21 ° C) greater than 1000 cps, or even 1000 cps at 200,000 cps, preferably said
Petition 870190033938, of 09/09/2019, p. 9/16
4/4 rheology modifiers, thickeners and / or structuring agents are selected from the group consisting of polyacrylates, quaternized polyacrylates, polymethacrylates, polyamides, quaternized polymethacrylates, polycarboxylates, polymeric gums, alginate, arabinogalactan (gum arabic), carmine, gum, gum, gum, gum, gum, gum, gum, gum, gum, gum, gum, carmine of xanthan and guar gum, gelan gum, fatty acids containing hydroxyl, fatty esters or fatty waxes, castor oil, castor oil derivatives, hydrogenated castor oil derivatives and hydrogenated castor wax, and mixtures thereof.
[11]
Consumer product according to any of claims 7 to 10, characterized in that said consumer product is a fluid detergent and comprises, based on the total weight of the fluid detergent, less than 80% of water, less than 60% to 2% water, 45% to 7% water, 35% to 9% water.
[12]
12. Method of cleaning or treating a situs, characterized by the fact that it optionally comprises the washing and / or rinsing of said situs, the contact of said situs with the composition selected from the compositions as defined in any of the claims 1 to 3, and mixtures thereof and, optionally, washing and / or rinsing said situs.
[13]
13. Process for producing a coated encapsulation, characterized by the fact that it comprises combining an encapsulated, and one or more polymers of efficiency as defined in claim 1.
[14]
Process for producing a coated encapsulated according to claim 13, characterized in that said encapsulated, when combined with said one or more efficiency polymers, is contained in a flowable paste.
[15]
Process for producing a coated encapsulated according to claim 14, characterized in that a sufficient amount of efficiency polymer is combined with said slurry to provide said slurry with, based on the total weight of the slurry fluid, from 0.05% to 10%, preferably from 0.1% to 5%, more preferably from 0.125% to 2% of said efficiency polymer.

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

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2019-02-12| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-08-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2019-10-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/11/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/11/2010, OBSERVADAS AS CONDICOES LEGAIS |

优先权:

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申请号 | 申请日 | 专利标题

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US25890009P| true| 2009-11-06|2009-11-06|

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US25887409P| true| 2009-11-06|2009-11-06|

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US61/258,900|2009-11-06|

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US61/258,874|2009-11-06|

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US31192810P| true| 2010-03-09|2010-03-09|

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US61/311,928|2010-03-09|

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PCT/US2010/055393|WO2011056934A1|2009-11-06|2010-11-04|High efficiency capsules comprising benefit agent|

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