GB2297975A - A liquid personal cleaning composition - Google Patents

A liquid personal cleaning composition Download PDF

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GB2297975A
GB2297975A GB9500748A GB9500748A GB2297975A GB 2297975 A GB2297975 A GB 2297975A GB 9500748 A GB9500748 A GB 9500748A GB 9500748 A GB9500748 A GB 9500748A GB 2297975 A GB2297975 A GB 2297975A
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composition according
weight
nonionic
oil
cationic
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GB2297975B (en
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Sarah Louise Darke
Conor James O'prey
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Procter and Gamble Co
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Procter and Gamble Co
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742Nitrogen containing silicones
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36Carboxylic acids; Salts or anhydrides thereof
    • A61K8/361Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/10Washing or bathing preparations
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2079Monocarboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723Polyamines or polyalkyleneimines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59Mixtures
    • A61K2800/596Mixtures of surface active compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Emergency Medicine (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
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  • Dermatology (AREA)
  • Molecular Biology (AREA)
  • Cosmetics (AREA)

Abstract

a) from about 5% to about 60% by weight of surfactant selected from anionic, nonionic, zwitterionic and amphoteric surfactants and mixtures thereof; ```b) from about 0.1% to about 5% by weight of a water insoluble salt, such as zinc, calcium, magnesium, lithium, and aluminium salts, of a C 14-C22 fatty acid, preferably a C 16-18 fatty acid; ```c) optionally from about 0.01% to about 5% by weight of cationic or nonionic polymeric skin conditioning agent; ```d) from about 0.005% to about 5% by weight of a trihydroxystearin suspending agent; and ```e) water. The products may also include perfume or cosmetic wax oil up to 10% and/or humectants and provides soap-like skin feel, good cleansing efficacy and good product stability.

Description

CLEANSING COMPOSITIONS The present invention relates to cleansing compositions. In particular it relates to mild personal cleansing compositions with good skin feel attributes and foaming properties suitable for simultaneously cleansing and conditioning the skin and/or the hair and which may be used, for example, in the form of foam bath preparations, shower products, skin cleansers, hand, face and body cleansers, shampoos, etc. In addition, the cleansing compositions of the invention exhibit improved product stability.
Backgrourld Of The Invention Mild cosmetic compositions must satisfy a number of criteria including cleansing power, foaming properties and mildness/low irritancy/good feel with respect to the skin, hair and the ocular mucosae.
Skin is made up of several layers of cells which coat and protect the keratin and collagen fibrous proteins that form the skeleton of its structure. The outermost of these layers, referred to as the stratum corneum, is known to be composed of 250 A protein bundles surrounded by 80 A thick layers.
Hair similarly has a protective outer coating enclosing the hair fibre which is called the cuticle. Anionic surfactants can penetrate the stratum corneum membrane and the cuticle and, by delipidization destroy membrane integrity. This interference with skin and hair protective membranes can lead to a rough skin feel and eye irritation and may eventually permit the surfactant to interact with the keratin and hair proteins creating irritation and loss of barrier and water retention functions.
Ideal cosmetic cleansers should cleanse the skin or hair gently, without defatting and/or drying the hair and skin and without irritating the ocular mucosae or leaving skin taut after frequent use. Most lathering soaps, shower and bath products, shampoos and bars fail in this respect.
Certain synthetic surfactants are known to be mild. However, a major drawback of most mild synthetic surfactant systems when formulated for shampooing or personal cleansing is poor lather performance compared to the highest shampoo and bar soap standards. Thus, surfactants that are among the mildest, such as sodium lauryl glyceryl ether sulfonate, (AGS), are marginal in lather. The use of known high sudsing anionic surfactants with lather boosters, on the other hand, can yield acceptable lather volume and quality but at the expense of clinical skin mildness. These two facts make the surfactant selection, the lather and mildness benefit formulation process a delicate balancing act.
Despite the many years of research that have been expended by the toiletries industry on personal cleansing, the broad mass of consumers remain dissatisfied by the skin feel, mildness and rinsing characteristics of present day synthetic based cleansing compositions. Many consumers prefer the skin feel and rinsing characteristics of soap cleansing products.
However such soap based products cannot achieve the mildness attributes associated with mild synthetic surfactants. Moreover, a number of cationic and nonionic polymers which have been added to personal cleansing products for skin conditioning purposes are also found to be detrimental to skin feel, delivering a "slick" rather than soap-like feel on the skin.
Thus a need exists for personal cleansing products which deliver soap-like in-use skin feel characteristics but which will not dehydrate the skin or result in loss of skin suppleness, which will produce a foam which is stable and of high quality, which are effective hair and skin cleansers, which have good rinsibility characteristics, and which at the same time have stable product and viscosity characteristics and remain fully stable under long term and stressed temperature storage conditions.
It has now been found that personal cleansing compositions having improved (soap-like) skin feel, both in use and after use, together with improved product stability can be formed by the addition thereof of certain water-insoluble salts of fatty acids and trihydroxystearin suspending agent.
Summary Of The Invention The subject of the present invention is a mild, foam-producing cleansing product suitable for personal cleansing of the skin or hair and which may be used as foam bath and shower products, skin cleansers and shampoos etc. According to one aspect of the invention, there is provided a liquid personal cleansing composition comprising: (a) from about 5% to about 60% by weight of surfactant selected from anionic, nonionic, zwitterionic and amphoteric surfactants and mixtures thereof; (b) * from about 0.1% to 5% by weight of a water-insoluble salt of a C14 - C22 fatty acid; (c) from about 0.01% to about 5% by weight of cationic or nonionic polymeric skin conditioning agent; (d) from about 0.005% to about 5% by weight of trihydroxystearin suspending agent; and (e) water.
In a highly preferred embodiment, the invention takes the form of a foam producing liquid cleansing composition with superior skin feel and rinsing characteristics, improved perceived dryness and assessed tightness and expertly graded dryness, combined with excellent lathering, improved product stability and cleansing ability.
All concentrations and ratios herein are by weight of the cleansing composition, unless otherwise specified. Surfactant chain lengths are also on a weight average chain length basis, unless otherwise specified.
The liquid cleansing compositions herein are based on a combination of mild surfactants with certain water-insoluble fatty acid metal salts and trihydroxystearin suspending agent. Preferred embodiments also contain polymeric skin conditioning agents and/or perfume or cosmetic oils.
Water-insoluble fatty acid salt suitable for use hererin include zinc, magnesium, calcium, lithium, and aluminium salts of Cl4-C22, preferably C1 6-Cl8 fatty acids, and mixtures thereof. Highly preferred from the viewpoint of optimum skin feel and conditioning effectiveness are the zinc salts, especially zinc salts of C1 6-C18 fatty acids which are marketed under the designation zinc stearate. The water-insoluble fatty acid salts are especially valuable in combination with cationic or nonionic polymeric skin conditioning agents for providing improved skin conditioning as well as skin feel attributes typical of soap-based cleansing products.The total level of fatty acid metal salt is from about 0.1% to about 5%, preferably 0.2% to about 3%, more preferably from about 0.5% to about 2% by weight of composition, The compositions according to the present invention also include in preferred embodiments a skin conditioning cationic or nonionic polymer.
The polymeric skin conditioning agent is preferably present at a level from about 0.01% to about 5%, preferably from about 0.05% to about 3% and especially from about 0.1% to about 2% by weight.
Suitable polymers are high molecular weight materials (massaverage molecular weight determined, for instance, by light scattering, being generally from about 2,000 to about 5,000,000, preferably from about 5,000 to about 3,000,000 more preferably from 100,000 to about 1,000,000).
Representative classes of polymers include cationic and nonionic polysaccharides; cationic and nonionic homopolymers and copolymers derived from acrylic and/or methacrylic acid; cationic and nonionic cellulose resins; cationic copolymers of dimethyldiallylammonium chloride and acrylamide and or acrylic acid; cationic homopolymers of dimethyldiallylammonium chloride; cationic polyalkylene and ethoxypolyalkylene imines; quaternized silicones, and mixtures thereof.
By way of exemplification, cationic polymers suitable for use herein include cationic guar gums such as hydroxypropyl trimethyl ammonium guar gum (d.s. of from 0.11 to 0.22) available commercially under the trade names Jaguar C-14-S(RIM) and Jaguar C-17(RTM) and also Jaguar C 16(RTM), which contains hydroxypropyl substituents (d.s. of from 0.8-1.1) in addition to the above-specified cationic groups, and quaternized cellulose ethers available commercially under the trade names Ucare Polymer JR-30M, JR-400 and Celquat.Other suitable cationic polymers are homopolymers of dimethyldiallylammonium chloride available commercially under the trade name Merquat 100, copolymers of dimethyl aminoethylmethacrylate and acrylamide, copolymers of dimethyldiallylammonium chloride and acrylamide, available commercially under the trade names Merquat 550 and Merquat S, acrylic acid/dimethyldiallylammonium chloride/acrylamide copolymers available under the trade name Merquat 3300, quaternized vinyl pyrrolidone acrylate or methacrylate copolymers of amino alcohol available commercially under the trade name Gafquat, for example Polyquaternium 11, 23 and 28 (quaternized copolymers of vinyl pyrrolidone and dimethyl aminoethylmethacrylate - Gafquat 755N and HS-100), vinyl pyrrolidone/vinyl imidazolium methochloride copolymers available under the trade names Luviquat HM552, Polyquaternium 2, and polyalkyleneimines such as polyethylenimine and ethoxylated polyethylenimine. Highly preferred from the viewpoint of providing a "draggy" soap-like feel are the quaternized vinyl pyrrolidone acrylate and methacrylate copolymers In preferred embodiments the weight ratio of water-insoluble metal salt: polymeric skin conditioning agent is in the range from about 50:1 to about 1:10.
Mild surfactants suitable for inclusion in compositions according to the present invention can be selected from anionic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof. The total level of surfactant is preferably from about 5% to about 60%, more preferably from about 8% to about 40%, and especially from about 10% to about 35% by weight. The compositions preferably comprise a mixture of anionic with zwitterionic and/or amphoteric surfactants.The level of the individual anionic, zwitterionic and amphoteric surfactant components, where present, is in the range from about 1% to about 15%, and especially from about 2% to about 13% by weight of the composition, while the level of nonionic surfactant, where present, is in the range from about 0.1% to about 20% by weight, preferably from about 2% to about 16%, more preferably from about 3% to about 12% by weight. The total level of anionic, amphoteric, and zwitterionic surfactant components, is preferably from about 5% to about 50%, more preferably from about 8% to about 35% and especially from about 10% to about 30% by weight of composition. The weight ratio of anionic surfactant: zwitterionic and/or amphoteric surfactant is in the range from about 1:2 to about 6:1.Other suitable compositions within the scope of the invention comprise mixtures of anionic, zwitterionic and/or amphoteric surfactants with one or more nonionic surfactants. Preferred for use herein are soluble or dispersible nonionic surfactants selected from ethoxylated animal and vegetable oils and fats and mixtures thereof, sometimes referred to herein as "oil-derived" nonionic surfactants.
Anionic surfactants suitable for inclusion in the compositions of the invention can generally be described as mild synthetic detergent surfactants and include ethoxylated alkyl sulfates, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, N-acyl glutamates, acyl isethionates, alkyl sulfosuccinates, alpha-sulfonated fatty acids, their salts and/or their esters, alkyl ethoxy carboxylates, alkyl phosphate esters, ethoxylated alkyl phosphate esters, acyl sarcosinates and fatty acid/protein condensates, and mixtures thereof.Alkyl and/or acyl chain lengths for these surfactants are Cg-C22, preferably Cl 0-C 18 more preferably C12 C14- Preferred for use herein from the viewpoint of optimum mildness and lathering characteristics are the salts of sulfuric acid esters of the reaction product of 1 mole of a higher fatty alcohol and from about 1 to about 12 moles of ethylene oxide, with sodium and magnesium being the preferred counterions. Particularly preferred are the alkyl sulfates containing from about 2 to 6, preferably 2 to 4 moles of ethylene oxide, such as sodium laureth-2 sulfate, sodium laureth-3 sulfate and magnesium sodium laureth3.6 sulfate. In preferred embodiments, the anionic surfactant contains at least about 50%, especially at least about 75% by weight of ethoxylated alkyl sulfate.
The compositions for use herein suitably also contain an amphoteric surfactant. Amphoteric surfactants suitable for use in the compositions of the invention include: (a) imidazolinium surfactants of formula (I)
wherein R1 is C7-C22 alkyl or alkenyl, R2 is hydrogen or CH2Z, each Z is independently CO2M or CH2CO2M, and M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium; and/or ammonium derivatives of formula (Il)
wherein R1, R2 and Z are as defined above; (b) aminoalkanoates of formula (III) R1NH(CH2)nC02M iminodialkanoates of formula (IV) RlN[(CH2)mC02M]2 and iminopolyalkanoates of formula (V)
wherein n, m, p, and q are numbers from 1 to 4, and Rl and M are independently selected from the groups specified above; and (c) mixtures thereof.
Suitable amphoteric surfactants of type (a) are marketed under the trade name Miranol and Empigen and are understood to comprise a complex mixture of species. Traditionally, the Miranols have been described as having the general formula I, although the CTFA Cosmetic Ingredient Dictionary, 3rd Edition indicates the non-cyclic structure II while the 4th Edition indicates yet another structural isomer in which R2 is O-linked rather than N-linked. In practice, a complex mixture of cyclic and non-cyclic species is likely to exist and both definitions are given here for sake of completeness. Preferred for use herein, however, are the non-cyclic species.
Examples of suitable amphoteric surfactants of type (a) include compounds of formula I and/or II in which R1 is CSH17 (especially isocapryl), C9H1 9 and C11H23 alkyl. Especially preferred are the compounds in which R1 is C9H19, Z is CO2M and R2 is H; the compounds in which R1 is Ci 1H23, Z is CO2M and R2 is CH2CO2M; and the compounds in which R is C11H23, Z is C02M and R2 is H.
In CTFA nomenclature, materials suitable for use in the present invention include cocoamphocarboxypropionate, cocoamphocarboxy propionic acid, and especially cocoamphoacetate and cocoamphodiacetate (otherwise referred to as cocoamphocarboxygl ycinate). Specific commercial products include those sold under the trade names of Ampholak 7TX (sodium carboxy methyl tallow polypropyl amine), Empigen CDL60 and CDR 60 (Albright & Wilson), Miranol H2M Conc.
Miranol C2M Conc. N.P., Miranol C2M Conc. O.P., Miranol C2M SF, Miranol CM Special (Rh8ne-Poulenc); Alkateric 2CIB (Alkaril Chemicals); Amphoterge W-2 (Lonza, Inc.); Monateric CDX-38, Monateric CSH-32 (Mona Industries); Rewoteric AM-2C (Rewo Chemical Group); and Schercotic MS-2 (Scher Chemicals).
It will be understood that a number of commercially-available amphoteric surfactants of this type are manufactured and sold in the form of electroneutral complexes with, for example, hydroxide counterions or with anionic sulfate or sulfonate surfactants, especially those of the sulfated C8-C 18 alcohol, C8-C18 ethoxylated alcohol or C8-C 18 acyl glyceride types. Preferred from the viewpoint of mildness and product stability, however, are compositions which are essentially free of(non-ethoxylated) sulfated alcohol surfactants. Note also that the concentrations and weight ratios of the amphoteric surfactants are based herein on the uncomplexed forms of the surfactants, any anionic surfactant counterions being considered as part of the overall anionic surfactant component content.
Examples of preferred amphoteric surfactants of type (b) include Nalkyl polytrimethylene poly-, carboxymethylamines sold under the trade names Ampholak X07 and Ampholak 7CX by Berol Nobel and also salts, especially the triethanolammonium salts and salts of N-lauryl-beta-amino propionic acid and N-lauryl-imino-dipropionic acid. Such materials are sold under the trade name Deriphat by Henkel and Mirataine by Rh6ne- Poulenc.
The compositions herein can also contain from about 0.1% to about 20%, more preferably from about 0.1% to about 10%, and especially from about 1% to about 8% of a zwitterionic surfactant, especially an alkyl betaine or amidobetaine surfactant.
Betaine surfactants suitable for inclusion in the composition of the invention include alkyl betaines of the formula RsR6R7N+(CH2)nCO2M(VIII) and amido betaines of the formula (IX)
wherein R5 is C12-C22 alkyl or alkenyl, R6 and R7 are independently C1 C3 alkyl, M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium, and n, m are each numbers from 1 to 4. Preferred betaines include cocoamidopropyldimethylcarboxymethyl betaine, laurylamidopropyldimethylcarboxymethyl betaine and Tego betaine.
The compositions of the invention also comprise from about 0.005% to about 5%, preferably from about 0.01% to about 2%, especially from about 0.01% to about 1% by weight oftrihydroxystearin suspending agent.
The suspending agent suitable for use herein can be generally described as an organic gelling agent which is capable of forming a thixotropic gel network in the final composition matrix.
The trihydroxystearin suspending agent is particularly valuable herein in combination with the water-insoluble salts of fatty acids from the viewpoint of minimising settling of the water-insoluble salts of fatty acids and improving product stability. A further benefit of the trihydroxystearin suspending agent is that it is non-particulate and as such has reduced gritty skin feel negatives in comparison to more conventional suspending agents such as organo-clays and silica.
The preferred suspending agent for use in the compositions herein is trihydroxystearin available from Rheox, Inc, NJ. USA under the tradename Thixcin (RTM).
The compositions of the invention can also contain from about 0.1% to about 20%, preferably from about 1% to about 15%, and more preferably from about 2% to about 10% by weight of an oil derived nonionic surfactant or mixture of oil derived nonionic surfactants. Oil derived nonionic surfactants are valuable in compositions according to the invention for the provision of skin feel benefits both in use and after use.
Suitable oil derived nonionic surfactants for use herein include water soluble vegetable and animal-derived emollients such as triglycerides with a polyethyleneglycol chain inserted; ethoxylated mono and di-glycerides, polyethoxylated lanolins and ethoxylated butter derivatives. One preferred class of oil-derived nonionic surfactants for use herein have the general formula (VI)
wherein n is from about 5 to about 200, preferably from about 20 to about 100, more preferably from about 30 to about 85, and wherein R comprises an aliphatic radical having on average from about 5 to 20 carbon atoms, preferably from about 9 to 18 carbon atoms.
Suitable ethoxylated oils and fats of this class include polyethyleneglycol derivatives of glyceryl cocoate, glyceryl caproate, glyceryl caprylate, glyceryl tallowate, glyceryl palmate, glyceryl stearate, glyceryl laurate, glyceryl oleate, glyceryl ricinoleate, and glyceryl fatty esters derived from triglycerides, such as palm oil, almond oil, and corn oil, preferably glyceryl tallowate and glyceryl cocoate.
Suitable oil derived nonionic surfactants of this class are available from Croda Inc. (New York, USA) under their Crovol line of materials such as Crovol EP40 (PEG 20 evening primrose glyceride), Crovol EP 70 (PEG 60 evening primrose glyceride) Crovol A-40 (PEG 20 almond glyceride), Crovol A-70 (PEG 60 almond glyceride), Crovol M-40 (PEG 20 maize glyceride), Crovol M-70 (PEG 60 maize glyceride), Crovol PK-40 (PEG 12 palm kernel glyceride), and Crovol PK-70 (PEG 45 palm kernel glyceride) and under their Solan range of materials such as Solan E, E50 and X polyethoxylated lanolins and Aqualose L-20 (PEG 24 lanolin alcohol) available from Westbrook Lanolin. Further suitable surfactants of this class are commercially available from Sherex Chemical Co. (Dublin, Ohio, USA) under their Varonic LI line of surfactants. These include, for example, Varonic LI 48 (polyethylene glycol (n=80) glyceryl tallowate, alternatively referred to as PEG 80 glyceryl tallowate), Varonic LI 2 (PEG 28 glyceryl tallowate), Varonic LI 420 (PEG 200 glyceryl tallowate), and Varonic LI 63 and 67 (PEG 30 and PEG 80 glyceryl cocoates). Other oilderived emollients suitable for use are PEG derivatives of corn, avocado, and babassu oil, as well as Softigen 767 (PEG(6) caprylic/capric glycerides).
Also suitable for use herein are nonionic surfactants derived from composite vegetable fats extracted from the fruit of the Shea Tree (Butyrospermum Karkii Kotschy) and derivatives thereof. This vegetable fat, known as Shea Butter is widely used in Central Africa for a variety of means such as soap making and as a barrier cream, it is marketed by Sederma (78610 Le Perray En Yvelines, France). Particularly suitable are ethoxylated derivatives of Shea butter available from Karlshamn Chemical Co. (Columbos, Ohio, USA) under their Lipex range of chemicals, such as Lipex 102 E-75 (ethoxylated mono, di-glycerides of Shea butter).
Similarly, ethoxylated derivatives of Mango, Cocoa and Illipe butter may be used in compositions according to the invention. Although these are classified as ethoxylated nonionic surfactants it is understood that a certain proportion may remain as non-ethoxylated vegetable oil or fat.
Other suitable oil-derived nonionic surfactants include ethoxylated derivatives of almond oil, peanut oil, rice bran oil, wheat germ oil, linseed oil, jojoba oil, oil of apricot pits, walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cade oil, corn oil, peach pit oil, poppyseed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, hazlenut oil, olive oil, grapeseed oil, and sunflower seed oil.
Oil derived nonionic surfactants highly preferred for use herein from the viewpoint of optimum mildness and skin feel characteristics are PEG 60 evening primrose triglycerides; PEG 55 lanolin polyethoxylated derivatives and ethoxylated derivatives of Shea butter.
In addition to the above oil derived nonionic surfactants, the compositions of the invention can also comprise an auxiliary nonionic surfactant at levels from about 0.1% to about 20%, more preferably from about 0.1% to about 10%, and especially from about 1% to about 8% by weight. Surfactants ofthis class include C12-C14 fatty acid mono-and diethanolamides, sucrose polyester surfactants and polyhydroxy fatty acid amide surfactants having the general formula (VII).
The preferred polyhydroxy fatty acid amide surfactants are those in which Rg is C 1-4 alkyl, preferably methyl, and R3 is C7-C 19 alkyl or alkenyl, more preferably straight-chain C9-C 17 alkyl or alkenyl, or mixture thereof; and Z2 is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
Z2 preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z2 is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z2. It should be understood that it is by no means intended to exclude other suitable raw materials. Z2 preferably will be selected from the group consisting of-CH2(CHOH)n-CH20H,- CH(CH20H)-(CHOH)n1-CH20H,-CH2-(CHOH)2(CHOR')(CHOH)- CH2OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof.Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4 CH20H.
The most preferred polyhydroxy fatty acid amide has the formula Rg(CO)N(CH3)CH2(CHOH)4CH2OH wherein R8 is a Cl i-Cl7 straight chain alkyl or alkenyl group.
The compositions of the invention may also contain from about 0.1% to about 8%, preferably from about 0.5% to about 6%, and especially from about 1.5% to about 5% by weight of saturated acyl fatty acids having a weight average chain length of from 10 to 18, preferably from 12 to 16 carbon atoms. Highly preferred is myristic acid.
The compositions of the invention may also include an insoluble perfume or cosmetic oil or wax or a mixture thereof at a level up to about 10%, preferably up to about 3% by weight wherein the oil or wax is insoluble in the sense of being insoluble in the product matrix at a temperature of 25 C. Addition of such oils or waxes can provide emolliency, mildness and rinsibility characteristics to personal cleansing compositions according to the invention. It is a feature of the invention, however, that compositions having excellent emolliency and mildness together with desirable physical attributes (clarity etc.) can be delivered which are essentially oil-free, ie which contain less than about 1%, preferably less than 0.5% by weight of an added oil phase. Physically, preferred compositions of this type take the form of an optically-clear solution or microemulsion.In compositions including an additional perfume or cosmetic oil or wax, preferably the weight ratio of oil-derived nonionic surfactant to added oil is at least about 1:2, more especially at least about 3:1.
Suitable insoluble cosmetic oils and waxes for use herein can be selected from water-insoluble silicones inclusive of non-volatile polyalkyl and polyaryl siloxane gums and fluids, volatile cyclic and linear polyalkylsiloxanes, polyalkoxylated silicones, amino and quaternary ammonium modified silicones, rigid cross-linked and reinforced silicones and mixtures thereof, C 1 -C24 esters of CS-C30 fatty acids such as isopropyl myristate, myristyl myristate and cetyl ricinoleate, Cg-C30 esters of benzoic acid, beeswax, saturated and unsaturated fatty alcohols such as behenyl alcohol, hydrocarbons such as mineral oils, petrolatum squalane and squalene, polybutene, fatty sorbitan esters (see US-A-3988255, Seiden, issued October 26th 1976), lanolin and oil-like lanolin derivatives, animal and vegetable triglycerides such as almond oil, peanut oil, wheat germ oil, rice bran oil, linseed oil, jojoba oil, oil of apricot pits, walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cade oil, corn oil, peach pit oil, poppyseed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, hazlenut oil, olive oil, grapeseed oil, and sunflower seed oil, and C 1 -C24 esters of dimer and trimer acids such as diisopropyl dimerate, diisostearylmalate, diisostearyldimerate and triisostearyltrimerate.
The viscosity of the final composition (Brookfield RVT DCP, 1 rpm with Cone CP41 or CP52, 25 C, neat) is preferably at least about 500 cps, more preferably from about 1,000 to about 50,000 cps, especially from about 5,000 to about 30,000 cps, the viscosity being controlled using conventional hydrophilic gelling agents and thickeners.
The compositions of the invention thus can also contain a hydrophilic gelling agent at a level preferably from about 0.01% to about 10%, more preferably from about 0.02% to about 2%, and especially from about 0.02% to about 0.5%. The gelling agent preferably has a viscosity (1% aqueous solution, 20"C, Brookfield RVT) of at least about 4000 mPa.s, more preferably a least about 10,000 mPa.s and especially at least 50,000 mPa.s.
Suitably hydrophilic gelling agents can generally be described as water-soluble or colloidally water-soluble polymers, and include cellulose ethers (e.g. hydroxyethyl cellulose, methyl cellulose, hydroxypropylmethyl cellulose), polyvinylpyrrolidone, polyvinylalcohol, guar gum, hydroxpropyl guar gum and xanthan gum.
Preferred hydrophilic gelling agents herein, however, are acrylic acid/ethyl acrylate copolymers and the carboxyvinyl polymers sold by the B.F. Goodrich Company under the trade mark of Carbopol resins. These resins consist essentially of a colloidally water-soluble polyalkenyl polyether crosslinked polymer of acrylic acid crosslinked with from 0.75% to 2.00% of a crosslinked agent such as for example polyallyl sucrose or polyallyl pentaerythritol. Examples include Carbopol 934, Carbopol 940, Carbopol 950, Carbopol 980, Carbopol 951 and Carbopol 981. Carbopol 934 is a water-soluble polymer of acrylic acid crosslinked with about 1% of a polyallyl ether of sucrose having an average of about 5.8 allyl groups for each sucrose molecule. A most preferred polymer is Carbopol 951.Also suitably for use herein are hydrophobically-modified cross-linked polymers of acrylic acid having amphipathic properties available under the Trade Name Carbopol 1382, Carbopol 1342 and Pemulen TR-1 (CFTA Designation: Acrylates/10-30 Alkyl Acrylate Crosspolymer). A combination of the polyalkenyl polyether cross-linked acrylic acid polymer and hydrophobically modified cross-linked acrylic acid polymer is also suitable for use herein. The gelling agents herein are particularly valuable for providing excellent stability characteristics over both normal and elevated temperatures.
Neutralizing agents suitable for use in neutralizing acidic group contining hydrophilic gelling agents herein include sodium hydroxide, potasssium hydroxide, ammonium hydroxide, monoethanolamine, diethanolamine and triethanolamine.
The cleansing compositions can optionally include other hair or skin moisturizers which are soluble in the cleansing composition matrix. The preferred level of such moisturizers is from about 0.5% to about 20% by weight. In preferred embodiments, the moisturizer is selected from: 1. water-soluble liquid polyols; 2. essential amino acid compounds found naturally occurring in the stratum corneum of the skin; and 3. water-soluble nonpolyol nonocclusives and mixtures thereof.
Some examples of more preferred nonocclusive moisturizers are polybutene, squalane, glycerine, polyethylene glycol, propylene glycol, sorbitol, polyethylene glycol and propylene glycol ethers of methyl glucose (e.g. ethyl glucam E-20 and propylglucan P-10), polyethylene glycol and propylene glycol ethers of lanolin alcohol (e.g. Solulan-75), sodium pyrrolidone carboxylic acid, lactic acid, L-proline, guanidine, pyrrolidone, hydrolyzed protein and other collagen-derived proteins, aloe vera gel and acetamide MEA and mixtures thereof. Of the above, glycerine is highly preferred.
A number of additional optional materials can be added to the cleansing compositions each at a level of from about 0. 1% to about 2% by weight. Such materials include proteins and polypeptides and derivatives thereof; water-soluble or solubilizable preservatives such as DMDM Hydantoin, Germall 115, methyl, ethyl, propyl and butyl esters of hydroxybenzoic acid, EDTA, Euxyl (RTM) K400, natural preservatives such as benzyl alcohol, potassium sorbate and bisabalol; sodium benzoate and 2-phenoxyethanol; other moisturizing agents such as hyaluronic acid, chitin and starch-grafted sodium polyacrylates such as Sanwet (RTM) IM 1000, IM- 1500 and IM-2500 available from Celanese Superabsorbent Materials, Portsmith, VA, USA and described in US-A-4,076,663; solvents such as hexylene glycol and propylene glycol; anti-bacterial agents such as Oxeco (phenoxy isopropanol); low temperature phase modifiers such as ammonium ion sources (e.g. NH4 Cl); viscosity control agents such as magnesium sulfate and other electrolytes; colouring agents; pearlescers and opacifiers such as ethylene glycol distearate, TiO2 and TiO2-coated mica; perfumes and perfume solubilizers; cooling agents such as menthol at a level of 0.05% to about 1%; and zeolites such as Valfour BV400 and derivatives thereof and Ca2+/Mg2+ sequestrants such as polycarboxylates, amino polycarboxylates, polyphosphonates, amino polyphosphonates etc.
Water is also present at a level preferably of from about 45% to about 94% preferably at least about 60% by weight of the compositions herein.
The pH of the compositions is preferably from about 4 to about 10, more preferably from about 6 to about 9.
The invention is illustrated by the following non-limiting examples.
In the examples, all concentrations are on a 100% active basis and the abbreviations have the following designation: Amphoteric Cocoamphodiacetate Anionic 1 Sodium laureth-3 sulfate Anionic 2 Sodium lauroyl sarcosinate Anionic 3 Sodium laureth-2 sulfate Solan Solan (RTM) E (PEG 55 lanolin) Crovol Crovol (RTM) EP 70 (PEG 60 evening primrose triglycerides) GA Polyhydroxy fatty acid amide of formula VII in which R8 is C11-C17 alkyl, Rg is methyl, and Z2 is CH2(CHOH)4CH20H Betaine Cocoamidopropyl betaine Polymer 1 Polymer JR-400 - hydroxyethylcellulose reacted with epichlorohydrin and quaternized with trimethylamine, m.wt. 4 x 106 Polymer 2 Gafquat 755N Preservative Phenoxyethanol/sodium benzoate/EDTA (4:2: :1) Pearlescer Ethyleneglycoldistearate/emulsifier mixture Oil Soyabean Oil Softigen 767 PEG(6) caprylic/capric glycerides Examples I to VI The following are personal cleansing compositions in the form of shower gel or bath foam products and which are representative of the present invention:: I II III IV V VI Amphoteric 3.0 3.0 - - - - Anionic 1 6.0 6.0 13.0 - - Anionic 2 1.0 2.0 2.0 - - Anionic 3 - - - 12.5 12.0 10.0 GA 3.0 - - - - - Betaine - - 4.0 5.0 3.0 3.0 Oil - 4.0 4.0 - - - Softigen 767 - 3.0 Solan - 3.0 - - - - Crovol - - 1.0 - - Polymer 1 0.8 1.0 - - - - Polymer2 - - 0.5 0.5 0.1 0.2 Pearlescer 1.0 1.0 3.0 1.0 1.0 1.0 Preservative 1.0 1.0 1.0 1.0 1.0 1.0 Perfume 1.0 1.0 1.0 1.0 1.0 1.0 Glycerine 3.0 3.0 Carbomer 0.2 0.3 0.4 - - 1342 Zinc Stearate 0.8 0.5 0.8 2.5 0.5 1.0 Thixcin R 0.1 0.08 0.15 0.05 0.1 0.2 Menthol - - 0.2 0.2 0.1 0.5 Water -------------------------- to 100 -------------------------- Compositions I to VI are prepared by forming a surfactant phase A containing a portion of the water, the anionic, amphoteric and oil-derived nonionic surfactants and the remaining water-soluble, oil-insoluble ingredients. In compositions which comprise water-insoluble ingredients an oil phase B is formed from these oil-soluble ingredients which is then admixed with A at about 50 C and cooled to ambient temperature. Finally the remaining water, preservative and perfume are added.
The products provide excellent in-use and efficacy benefits including soap-like skin feel, skin conditioning, skin moisturising, product stability, cleansing, freshness, lathering and rinsibility.

Claims (20)

1. A liquid personal cleansing composition comprising: a) from about 5% to about 60% by weight of surfactant selected from anionic, nonionic, zwitterionic and amphoteric surfactants and mixtures therefor; b) from about 0. 1% to about 5% by weight of a water insoluble salt of a C 14-C22 fatty acid; c) optionally from about 0.01% to about 5% by weight of a cationic or nonionic polymeric skin conditioning agent; d) from about 0.005% to about 5% by weight of a trihydroxystearin suspending agent; and e) water.
2. A composition according to Claim 1 wherein the water-insoluble salt is selected from zinc, magnesium, calcium, lithium and aluminium salts of Ci 4-C22 fatty acids and mixtures thereof.
3. A composition according to Claim 2 wherein the water-insoluble salt is zinc stearate.
4. A composition according to any of Claims 1 to 3 comprising from about 0.5% to about 2% by weight of the water-insoluble salt of a C14-C22 fatty acid.
5. A composition according to any of Claims 1 to 4 comprising from about 0.01% to about 2%, preferably from about 0.01% to about 1% by weight of the trihydroxystearin suspending agent.
6. A composition according to any of Claims 1 to 5 wherein the composition has a viscosity (Brookfield RVT DCP, 1 rpm with Cone CP41 or CP52, 250C, neat) in the range from 1,000 to 50,000 cps.
7. A composition according to any of Claims 1 to 6 wherein the polymeric skin conditioning agent has a mass average molecular weight in the range from about 2000 to about 5,000,000 preferably between about 5000 to about 3,000,000.
8. A composition according to any of Claims 1 to 7 wherein the polymeric skin conditioning agent is selected from cationic and nonionic polysaccharides; cationic and nonionic homopolymers and copolymers derived form acrylic and/or methacrylic acid; cationic and nonionic cellulose resins; cationic copolymers of dimethyldiallylammonium chloride and acrylic acid; cationic homopolymers of dimethyldiallylammonium chloride; cationic polyalkylene and ethoxypolyalkylene imines; quaternized silicones, and mixtures thereof.
9. A composition according to any of Claims 1 to 8 wherein the weight ratio of water-insoluble fatty acid salt: polymeric skin conditioning agent is in the range from about 50:1 to about 1:10.
10. A composition according to any of Claims 1 to 9 comprising a mixture of anionic with zwitterionic and/or amphoteric surfactants and wherein the level of the individual anionic, zwitterionic and amphoteric surfactant components is in the range from about 1% to 15%, preferably from about 2% to about 13% by weight.
11. A composition according to any of Claims 1 to 10 comprising from about 0.1% to about 20% by weight of nonionic surfactant selected from ethoxylated oils or fats having the formula [V]
wherein n is from about 5 to 200, preferably from about 20 to about 100, more preferably from about 30 to about 85, and wherein R comprises an aliphatic radical having an average from about 5 to 20 carbon atoms, preferably from about 9 to 20 atoms, more preferably from about 11 to 18 carbon atoms, most preferably from about 12 to 16 carbon atoms.
12. A composition according to any of Claims 1 to 11 wherein the anionic surfactant is selected from ethoxylated alkyl sulfates, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, alkyl ethoxy carboxylates, N-acyl glutamates, acyl isethionates, alkyl sulfosuccinates, alpha-sulfonated fatty acids, their salts and/or their esters, alkyl phosphate esters, ethoxylated alkyl phosphate esters, acyl sarcosinates and fatty acid/protein condensates, and mixtures thereof.
13. A composition according to any of Claims 1 to 12 wherein the anionic surfactant comprises an ethoxylated C8-C22 alkyl sulfate.
14. A composition according to any of the Claims 1 to 13 wherein the amphoteric surfactant is selected from: (a) imidazolinium derivatives of formula [I]
wherein R1 is C7-C22 alkyl or alkenyl, R2 is hydrogen of CH2Z, each Z is independently CO2 or CH2 CO2M, and M is H, alkali metal, alkaline earth metal, ammonium or alkanolammonium; and/or ammonium derivatives of formula [II]
wherein R1, R2 and Z are as defined above: (b) aminoalkanoates of formula [III] Ri NH(CH2)nCO2M iminodialkanoates of formula [IV] Ri N[(CH2)mCO2M]2 and iminopolyalkanoates of formula (V)
wherein n, m, p, and q are numbers from 1 to 4, and R1 and M are independently selected from the groups specified above; and (c) mixtures thereof.
15. A composition according to Claim 14 wherein the amphoteric is selected from imidazolinium derivatives of formula I and/or ammonium derivatives of formula II.
16. A composition according to any of the Claims 1 to 15 wherein the weight ratio of anionic surfactant: zwitterionic and/or amphoteric surfactant is in the range of from about 1:2 to about 6: 1.
17. A composition according to any of the Claims 1 to 16 wherein the anionic, zwitterionic and amphoteric surfactants together comprise from about 8% to about 35%, preferably from about 10% to about 30% by weight of the composition.
18. A composition according to any of Claims 1 to 17 which additionally comprises from about 0. 1% to about 20% by weight of an auxiliary nonionic surfactant selected from C12-Cl4 fatty acid mono-and diethanolamides and polyhydroxy fatty acid amide surfactants.
19. A composition according to any of Claims 1 to 18 additionally comprising up to about 20% by weight of perfume or cosmetic oil.
20. A composition according to any of Claims 1 to 19 additionally comprising moisturiser selected from glycerin, polyethylene glycol, propylene glycol, sorbitol, polyethylene glycol and polypropylene glycol ethers of methyl glycose, sodium pyrrolidone carboxylic acid, L-proline and mixtures thereof.
GB9500748A 1995-01-14 1995-01-14 Cleansing compositions Expired - Fee Related GB2297975B (en)

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EP0887071A1 (en) * 1997-06-04 1998-12-30 Unilever Plc Cleansing composition containing an hydroxy functionalized wax as a stabilizer
WO1999020243A2 (en) * 1997-10-17 1999-04-29 The Procter & Gamble Company Cleansing compositions
US5916575A (en) * 1997-01-27 1999-06-29 The Procter & Gamble Company Cleaning products
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WO2003026607A2 (en) * 2001-09-25 2003-04-03 Crabtree & Evelyn, Ltd. Emollient skin conditioning cream and method
EP1601966A2 (en) * 2003-03-12 2005-12-07 Eppendorf 5 Prime, Inc. Methods and compositions for purification of nucleic acid from a host cell
WO2007103968A3 (en) * 2006-03-08 2007-10-25 Lubrizol Advanced Mat Inc Stable soap based cleansing system
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WO2011088089A1 (en) 2010-01-12 2011-07-21 The Procter & Gamble Company Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same
WO2012112828A1 (en) 2011-02-17 2012-08-23 The Procter & Gamble Company Bio-based linear alkylphenyl sulfonates
WO2012138423A1 (en) 2011-02-17 2012-10-11 The Procter & Gamble Company Compositions comprising mixtures of c10-c13 alkylphenyl sulfonates
WO2014138141A1 (en) 2013-03-05 2014-09-12 The Procter & Gamble Company Mixed sugar compositions
EP1328616B2 (en) 2000-10-27 2015-03-04 The Procter & Gamble Company Stabilized liquid compositions
US9622951B2 (en) 2012-10-29 2017-04-18 The Procter & Gamble Company Personal care compositions
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US6080707A (en) * 1995-02-15 2000-06-27 The Procter & Gamble Company Crystalline hydroxy waxes as oil in water stabilizers for skin cleansing liquid composition
US5968890A (en) * 1996-04-17 1999-10-19 Lever Brothers Company Cleansing composition containing polyethylene glycol
WO1997038672A1 (en) * 1996-04-17 1997-10-23 Unilever Plc Cleansing composition
US5916575A (en) * 1997-01-27 1999-06-29 The Procter & Gamble Company Cleaning products
EP0887071A1 (en) * 1997-06-04 1998-12-30 Unilever Plc Cleansing composition containing an hydroxy functionalized wax as a stabilizer
WO1999020243A3 (en) * 1997-10-17 1999-07-01 Procter & Gamble Cleansing compositions
WO1999020243A2 (en) * 1997-10-17 1999-04-29 The Procter & Gamble Company Cleansing compositions
WO1999038475A1 (en) * 1998-02-03 1999-08-05 The Procter & Gamble Company Styling shampoo compositions
EP1328616B2 (en) 2000-10-27 2015-03-04 The Procter & Gamble Company Stabilized liquid compositions
US7749523B2 (en) 2001-09-25 2010-07-06 Crabtree & Evelyn, Ltd. Emollient skin conditioning cream and method
WO2003026607A2 (en) * 2001-09-25 2003-04-03 Crabtree & Evelyn, Ltd. Emollient skin conditioning cream and method
WO2003026607A3 (en) * 2001-09-25 2003-07-03 Crabtree & Evelyn Ltd Emollient skin conditioning cream and method
GB2395662A (en) * 2001-09-25 2004-06-02 Crabtree & Evelyn Ltd Emollient skin conditioning cream and method
GB2395662B (en) * 2001-09-25 2005-04-06 Crabtree & Evelyn Ltd Emollient exfoliating composition and its use in cleansing and conditioning skin
EP1601966A2 (en) * 2003-03-12 2005-12-07 Eppendorf 5 Prime, Inc. Methods and compositions for purification of nucleic acid from a host cell
EP1601966A4 (en) * 2003-03-12 2007-05-02 Eppendorf 5 Prime Inc Methods and compositions for purification of nucleic acid from a host cell
AU2006232785B2 (en) * 2005-04-05 2010-07-01 Unilever Plc Fabric softening composition with cationic polymer, soap, and amphoteric surfactant
WO2007103968A3 (en) * 2006-03-08 2007-10-25 Lubrizol Advanced Mat Inc Stable soap based cleansing system
WO2009143516A1 (en) * 2008-05-23 2009-11-26 Colgate-Palmolive Company Detergent compositions containing zinc salts
WO2011088089A1 (en) 2010-01-12 2011-07-21 The Procter & Gamble Company Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same
US8933131B2 (en) 2010-01-12 2015-01-13 The Procter & Gamble Company Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same
WO2012112828A1 (en) 2011-02-17 2012-08-23 The Procter & Gamble Company Bio-based linear alkylphenyl sulfonates
WO2012138423A1 (en) 2011-02-17 2012-10-11 The Procter & Gamble Company Compositions comprising mixtures of c10-c13 alkylphenyl sulfonates
US9193937B2 (en) 2011-02-17 2015-11-24 The Procter & Gamble Company Mixtures of C10-C13 alkylphenyl sulfonates
US9622951B2 (en) 2012-10-29 2017-04-18 The Procter & Gamble Company Personal care compositions
WO2014138141A1 (en) 2013-03-05 2014-09-12 The Procter & Gamble Company Mixed sugar compositions
RU2725999C2 (en) * 2015-09-17 2020-07-08 Джонсон энд Джонсон Консьюмер Инк. Compositions containing zwitterionic alkyl alkanoylamides and/or alkyl alkanoates

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