CA2153313A1 - Cleansing compositions - Google Patents
Cleansing compositionsInfo
- Publication number
- CA2153313A1 CA2153313A1 CA 2153313 CA2153313A CA2153313A1 CA 2153313 A1 CA2153313 A1 CA 2153313A1 CA 2153313 CA2153313 CA 2153313 CA 2153313 A CA2153313 A CA 2153313A CA 2153313 A1 CA2153313 A1 CA 2153313A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- composition according
- nonionic
- surfactant
- cationic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/361—Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
- A61K8/442—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof substituted by amido group(s)
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/731—Cellulose; Quaternized cellulose derivatives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/65—Mixtures of anionic with cationic compounds
- C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/32—Protein hydrolysates; Fatty acid condensates thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/34—Derivatives of acids of phosphorus
- C11D1/345—Phosphates or phosphites
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
Abstract
A personal cleansing product comprising: (a) from about 5 % to about 50 % by weight of one or more surfactants selected from anionic, nonionic, amphoteric, zwitterionic and cationic surfactants and mixtures thereof; (b) from about 3 % to about 40 % by weight of an insoluble nonionic oil or wax or mixture of insoluble nonionic oils or waxes; (c) from about 0.1 % to about 8 % by weight of fatty acid having a weight-average chain length of from 10 to 18 carbon atoms; (d) from about 1.5 % to about 10 % by weight of citric acid or water soluble citrate salt or mixture thereof, and (e) water. The cleansing products demonstrate excellent physical stability and viscosity characteristics across temperature in addition to good lathering, mildness, rinsibility and conditioning benefits.
Description
~1533~3 CLEANSING COMPOSITIONS
The present invention relates to cleansing compositions. In particular it relates to foam-producing personal cleansing compositions suitable for simlllt~neously cle~n~in~ 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.
BACK(~ROUND OF THE INVENTION
Foaming cosmetic compositions must satisfy a number of criteria including cle~n~in~ power, fo~min~ properties, mildness/low irritancy and physical stability. Oil-in-water emulsion systems typical of fo~minp cosmetic compositions represent a particular challenge with respect to stability and viscosity. While on one hand it is possible to llltilise agents specifically to inrlllce appropriate viscosity, care must be taken to ensure these agents work to m~int~in that viscosity over time. Certain fatty acids are known to be effective in the achievement of matrix viscosity.
However this is generally dependant upon the fatty acid forming stable complexes. It has been a particular problem that fatty acid added to achieve stability/viscosity in an oil-in-water emulsion can result in a reduction in viscosity over time. This is believed in part to be due to the secondary formation of insoluble cryst~lline moieties which break down the structure of the emulsion and lead to lower viscosity/thinnin~. The aforementioned problems can be exaggerated when products are exposed to extremes or variations of temperature.
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, r~ferred to as the stratum corneum, is known to be composed of 250 A protein bundles surrounded by 80 A thick layers. Hair simil~rly has a protective outer coating enclosing the hair fibre which is called the cuticle. Anionic surfactants 33 ~3 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 surl~c~nts are known to be mild. However, a major drawback of most mild synthetic surfactant systems when form~ te~l for shampooing or personal cle~n~in~ is poor lather performance compared to the highest shampoo and bar soap standards.
Thus, surf~ct~nt~ that are among the mildest, such as sodium lauryl glyceryl ether sulfonate, (AGS), are marginal in lather. The use of known high sll~lsin~ anionic sur~ct~nts with lather boosters, on the other hand, can yield acceptable lather volume and qualjty but, at the expense of clinical skin m~ ness. These two facts make the surfactant selection, the lather and mil-ln~ss benefit form~ tion process a ~ielic~te balancing act.
Despite the many years of research that have been expended by the toiletries in~lstry on personal cle~ncin~, the broad mass of consumers remain ~lies~tisfied by the mil~3ness of present day cle~ncin~ compositions, fin~lins~, for example, that they have to apply a separate cosmetic lotion or cream moislur~er to the skin after using a shower or bath preparation in order to m~in~in skin suppleness and hydration and to counteract the delipitli7in~ effect of the cleanser.
Thus a need exists for personal cle~n~in~ products which produce a foam which is ablln-l~nt, stable and of high quality, which are effective hair and skin cleansers, which will not dehydrate the skin or result in loss of skin suppleness, and which will provide a level of skin conditioning performance in a wash and rinse-off product which previously has only been provided by a separate post-cle~ncin~ cosmetic moisturizer, which ~ 3 ~ ~
has good rinsibility characteristics, and which at the same time has stable product and viscosity characteristics and remains fully stable under long term and stressed temperature storage conditions.
., SUMMARY OF THE INVENTION
The subject of the present invention is a stable, foaming cle~n~in~
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 personal cle~n~in composition comprising:
(a) from about 5 % to about 50% by weight of one or more surfactants selected from anionic, nonionic, amphoteric, zwitterionic and cationic surfactants and mixtures thereof;
(b) from about 3 % to about 40~ by weight of an insoluble, nonionic oil or wa~c or mixture of insoluble, nonionic oils OF
waxes;
(c~ from about ~.1% to about 8% by weight of fatty acid having a weight - average chain length of from about 10 to about 18 carbon atoms;
(d) from about 1.5% to about 10% by weight of citric acid or water soluble citrate salt or mixture thereof; and (e) water.
In preferred embo~imt~ts of the invention comprising mi~tures of anionic and amphoteric sur~ct~nts, the anionic surf~ct~nt and amphoteric surf~ct~nt together comprise from about 5% to about 30% by weight of the composition, and the weight ratio of anionic surf~ct~nt.amphoteric surf~ct~nt is in the range from about r:s to about 20:1. Prefeldbly the weight ratio of total surf~ct~nt: nonionic oil or wax is in the range from about 10:1 to about 1:3. r~eferably also the composition is in the form of an oil-in-water emulsion having a viscosity (Brookfield RVT, Helipath, Spindle TB, S rmp, 25C, lmin) in the range from 10,000 to 40,000 cps 3~3 and a yield point of at least 50 dynes/cm2 (Brookfield RVT, Spindle CP52, Plate Code A, 25C).
All concentrations and ratios herein are by weight of the cle~ncinp composition, unless otherwise specified. Surfactant chain lengths are also on a weight average chain length basis, unless otherwise specified.
The invention relates to a foam-producing cle~ncin~ composition with superior physical and viscosity st~bility characteristics (across temperature conditions) combined with excellent lathering, milclnçss to the skin and hair, together with good cleansing ability and conditioning performance. The invention also relates to a wash and rinse-off personal cle~ncin~ product having the above stability, lathering, milt~ness, rinsibility and conditioning benefits.
The cle~n~in~ compositions herein are based on a combination of mild surfactants which in general terms can be selected from anionic, amphoteric, nonionic and betaine surfactants and mixtures thereof. The compositions preferably comprise a mixture of anionic, nonionic and amphoteric surfactants and highly preferred` systems also incorporate a betaine surfactant. Other suit~ble compositions within the scope of the invention comprise mixtures of anionic with one or more nonionic or betaine surfactants or mixture thereof; and mixtures of amphoteric with one or more nonionic or betaine surf~ct~ntc or mi~cture thereof. The level of each of the anionic and amphoteric surf~ct~n~s is generally in the range from about 1% to about 20%, preferably from about 1% to about 15%, and especially from about 2% to about 13% by weight of the composition.
The weight ratio of anionic surfactant:amphoteric surf~ct~nt, on the other hand is generally from about 1:5 to about 20:1, preferably from about 1:2 to about 5:1, and especially from about 1:1 to about 2:1. The total level of anionic and amphoteric surf~ct~ntc is generally about 5% to about 30%, l,refeldbly from about 8% to about 25% and especially from about 10% to about 20% by weight of the cle~ncing composition. The nonionic or betaine surfactant, on the other hand, ~referably con.ctitl~teC 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 of the composition. The total level of anionic, nonionic and amphoteric surf~ct~ntc is generally 5215~31 3 from about 5% to about 45%, more preferably from about 7% to about 40% by weight of the cleansing composition. The total level of surfactant, inclusive of anionic, amphoteric, nonionic, betaine and other surfactant components, is preferably from about 5% to about 50%, more preferably from about 10% to about 35% by weight of composition.
Anionic surfactants suitable for inclusion in the compositions of the invention can generally be described as mild synthetic detergent surfactants and include ethoxylated alkyl sl-lfate~, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, N-acyl gllltamates, 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 C8-c22~ preferably C10-C18 Preferred for use herein from the viewpoint of optimllm milclness 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 m~Enesi~lm being the preferred counterions. Particularly prefe~led are the alkyl sl~lf~te~
cont~inin~ from about 2 to 6, preferably 2 to 4 moles of ethylene o~ide, such as sodium laureth-2 sulfate and sodium laureth-3 sulfate. In preferred embo~liment~, the anionic surfactant contains at least about 50%, especially at least about 75% by weight of ethoxylated alkyl slllf~te.
Pr~ferr~d compositions for use herein also contain an amphoteric surfact~nt. Amphoteric surf~ct~nts suitable for use in the compositions of the invention include:
(a) imi~7olinium surfactants of formula C H O R
1 ~ + ~
The present invention relates to cleansing compositions. In particular it relates to foam-producing personal cleansing compositions suitable for simlllt~neously cle~n~in~ 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.
BACK(~ROUND OF THE INVENTION
Foaming cosmetic compositions must satisfy a number of criteria including cle~n~in~ power, fo~min~ properties, mildness/low irritancy and physical stability. Oil-in-water emulsion systems typical of fo~minp cosmetic compositions represent a particular challenge with respect to stability and viscosity. While on one hand it is possible to llltilise agents specifically to inrlllce appropriate viscosity, care must be taken to ensure these agents work to m~int~in that viscosity over time. Certain fatty acids are known to be effective in the achievement of matrix viscosity.
However this is generally dependant upon the fatty acid forming stable complexes. It has been a particular problem that fatty acid added to achieve stability/viscosity in an oil-in-water emulsion can result in a reduction in viscosity over time. This is believed in part to be due to the secondary formation of insoluble cryst~lline moieties which break down the structure of the emulsion and lead to lower viscosity/thinnin~. The aforementioned problems can be exaggerated when products are exposed to extremes or variations of temperature.
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, r~ferred to as the stratum corneum, is known to be composed of 250 A protein bundles surrounded by 80 A thick layers. Hair simil~rly has a protective outer coating enclosing the hair fibre which is called the cuticle. Anionic surfactants 33 ~3 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 surl~c~nts are known to be mild. However, a major drawback of most mild synthetic surfactant systems when form~ te~l for shampooing or personal cle~n~in~ is poor lather performance compared to the highest shampoo and bar soap standards.
Thus, surf~ct~nt~ that are among the mildest, such as sodium lauryl glyceryl ether sulfonate, (AGS), are marginal in lather. The use of known high sll~lsin~ anionic sur~ct~nts with lather boosters, on the other hand, can yield acceptable lather volume and qualjty but, at the expense of clinical skin m~ ness. These two facts make the surfactant selection, the lather and mil-ln~ss benefit form~ tion process a ~ielic~te balancing act.
Despite the many years of research that have been expended by the toiletries in~lstry on personal cle~ncin~, the broad mass of consumers remain ~lies~tisfied by the mil~3ness of present day cle~ncin~ compositions, fin~lins~, for example, that they have to apply a separate cosmetic lotion or cream moislur~er to the skin after using a shower or bath preparation in order to m~in~in skin suppleness and hydration and to counteract the delipitli7in~ effect of the cleanser.
Thus a need exists for personal cle~n~in~ products which produce a foam which is ablln-l~nt, stable and of high quality, which are effective hair and skin cleansers, which will not dehydrate the skin or result in loss of skin suppleness, and which will provide a level of skin conditioning performance in a wash and rinse-off product which previously has only been provided by a separate post-cle~ncin~ cosmetic moisturizer, which ~ 3 ~ ~
has good rinsibility characteristics, and which at the same time has stable product and viscosity characteristics and remains fully stable under long term and stressed temperature storage conditions.
., SUMMARY OF THE INVENTION
The subject of the present invention is a stable, foaming cle~n~in~
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 personal cle~n~in composition comprising:
(a) from about 5 % to about 50% by weight of one or more surfactants selected from anionic, nonionic, amphoteric, zwitterionic and cationic surfactants and mixtures thereof;
(b) from about 3 % to about 40~ by weight of an insoluble, nonionic oil or wa~c or mixture of insoluble, nonionic oils OF
waxes;
(c~ from about ~.1% to about 8% by weight of fatty acid having a weight - average chain length of from about 10 to about 18 carbon atoms;
(d) from about 1.5% to about 10% by weight of citric acid or water soluble citrate salt or mixture thereof; and (e) water.
In preferred embo~imt~ts of the invention comprising mi~tures of anionic and amphoteric sur~ct~nts, the anionic surf~ct~nt and amphoteric surf~ct~nt together comprise from about 5% to about 30% by weight of the composition, and the weight ratio of anionic surf~ct~nt.amphoteric surf~ct~nt is in the range from about r:s to about 20:1. Prefeldbly the weight ratio of total surf~ct~nt: nonionic oil or wax is in the range from about 10:1 to about 1:3. r~eferably also the composition is in the form of an oil-in-water emulsion having a viscosity (Brookfield RVT, Helipath, Spindle TB, S rmp, 25C, lmin) in the range from 10,000 to 40,000 cps 3~3 and a yield point of at least 50 dynes/cm2 (Brookfield RVT, Spindle CP52, Plate Code A, 25C).
All concentrations and ratios herein are by weight of the cle~ncinp composition, unless otherwise specified. Surfactant chain lengths are also on a weight average chain length basis, unless otherwise specified.
The invention relates to a foam-producing cle~ncin~ composition with superior physical and viscosity st~bility characteristics (across temperature conditions) combined with excellent lathering, milclnçss to the skin and hair, together with good cleansing ability and conditioning performance. The invention also relates to a wash and rinse-off personal cle~ncin~ product having the above stability, lathering, milt~ness, rinsibility and conditioning benefits.
The cle~n~in~ compositions herein are based on a combination of mild surfactants which in general terms can be selected from anionic, amphoteric, nonionic and betaine surfactants and mixtures thereof. The compositions preferably comprise a mixture of anionic, nonionic and amphoteric surfactants and highly preferred` systems also incorporate a betaine surfactant. Other suit~ble compositions within the scope of the invention comprise mixtures of anionic with one or more nonionic or betaine surfactants or mixture thereof; and mixtures of amphoteric with one or more nonionic or betaine surf~ct~ntc or mi~cture thereof. The level of each of the anionic and amphoteric surf~ct~n~s is generally in the range from about 1% to about 20%, preferably from about 1% to about 15%, and especially from about 2% to about 13% by weight of the composition.
The weight ratio of anionic surfactant:amphoteric surf~ct~nt, on the other hand is generally from about 1:5 to about 20:1, preferably from about 1:2 to about 5:1, and especially from about 1:1 to about 2:1. The total level of anionic and amphoteric surf~ct~ntc is generally about 5% to about 30%, l,refeldbly from about 8% to about 25% and especially from about 10% to about 20% by weight of the cle~ncing composition. The nonionic or betaine surfactant, on the other hand, ~referably con.ctitl~teC 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 of the composition. The total level of anionic, nonionic and amphoteric surf~ct~ntc is generally 5215~31 3 from about 5% to about 45%, more preferably from about 7% to about 40% by weight of the cleansing composition. The total level of surfactant, inclusive of anionic, amphoteric, nonionic, betaine and other surfactant components, is preferably from about 5% to about 50%, more preferably from about 10% to about 35% by weight of composition.
Anionic surfactants suitable for inclusion in the compositions of the invention can generally be described as mild synthetic detergent surfactants and include ethoxylated alkyl sl-lfate~, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, N-acyl gllltamates, 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 C8-c22~ preferably C10-C18 Preferred for use herein from the viewpoint of optimllm milclness 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 m~Enesi~lm being the preferred counterions. Particularly prefe~led are the alkyl sl~lf~te~
cont~inin~ from about 2 to 6, preferably 2 to 4 moles of ethylene o~ide, such as sodium laureth-2 sulfate and sodium laureth-3 sulfate. In preferred embo~liment~, the anionic surfactant contains at least about 50%, especially at least about 75% by weight of ethoxylated alkyl slllf~te.
Pr~ferr~d compositions for use herein also contain an amphoteric surfact~nt. Amphoteric surf~ct~nts suitable for use in the compositions of the invention include:
(a) imi~7olinium surfactants of formula C H O R
1 ~ + ~
2 ~ 33~ PCT/US94/00354~
wherein R1 is C7-C22 alkyl or alkenyI, R2 is hydrogen or CH2Z, each Z is independently C02M or CH2C02M, and M is H, alkali metal, ~Ik~line earth metal, ammonium or alkanol~mmonium; and/or ammonium derivatives of formula (II) RlCONH ( CH2 ) 2N CH2 Z
wherein R1, R2 and Z are as defined above;
(b) aminoalkanoates of formula (III) RlNH(CH2)nC02M
and imino~ lk~noates of formula (IV) RlN[(CH2)mc02M]2 wherein n and m are numbers from 1 to 4, and Rl and M are indepenrlently 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, 4th Edition indicates the non-cyclic structure II. 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.
~WO 94/17166 215 ~ PCT/US94/00354 Examples of suitable amphoteric surfactants of type (a) include compounds of formula I and/or II in which R1 is CgH17 (especially iso-capryl), CgH1g and C11H23 alkyl. Especially preferred are the compounds in which R1 is CgH1g, Z is C02M and R2 is H; the compounds in which R1 is C11H23, Z is C02M and R2 is CH2C02M;
and the compounds in which R1 is C11H23, Z is C02M and R2 is H.
In CTFA nomenclature, materials preferred for use in the present invention include cocoamphocarboxypropionate, cocoamphocarbo~y propionic acid, and especially cocoampho~cet~te and cocoampho~ cet~te (other~vise referred to as cocoamphocarboxyglycinate). Specific commercial products include those sold under the trade names of 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 (Rhone-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 m~nllf~ctured and sold in the form of electroneutral complexes with, for example, hydroxide counterions or with anionic sulfate or sulfonate surf~c~nts, especially those of the slllf~te~ Cg-C1g alcohol, Cg-Clg ethoxylated alcohol or Cg-C1g acyl glyceride types. Preferred from the viewpoint of milclness and product stability, however, are compositions which are esse-nti~lly free of (non-etho~cylated) slllf~te~l alcohol surfactants. Note also that the concentrations and weight ratios of the amphoteric surfactants are based herein on the uncomplexed forms of the surf~ct~nt~, any anionic surf~c~nt counterions being considered as part of the overall anionic surf~ct~nt component content.
- Fx~mples of suitable amphoteric surf~ct~nts of type (b) include 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 WO 94tl7166 PCT/US94/00354 ~ 33~ 8 Mirataine by Rhone-Poulenc. Amphoterics preferred for use herein, however, are those of formula I and/or II.
The compositions of the invention also contain from about 3% to about 40%, preferably from about 4% to about 20%, and more preferably from about 5 % to about 15 ~ by weight of an insoluble nonionic oil or wax or mixture thereof, the oil or wax being insoluble in the sense that it is insoluble in the cle~n~in.f~ composition liquid matrix at a temperature of 25C. In addition, the oil or wax is present in composition in a level such that the weight ratio of total surfactant:oil or wax is in the range from about 10:1 to about 1:3" preferably from about 5:1 to about 1:2, and especially from about 2:1 to about 1:1, this being preferred from the viewpoint of providing personal cleansing compositions having optimum lathering, mil-3n~cs, emolliency and rinsibility.
Suitable oils and waxes for use herein can be selected from water-insoluble silicones inclusive of non-volatile polyallyl and polyaryl siloxane gums and fluids, volatile cyclic and linear polyalkylsilo~sanes, polyalkoxylated silicones, amino and quaternary ammonium modified silicones, rigid cross-linked and reinforced silicones and mixhlres thereof, C1-C24 esters of Cg-C30 fatty acids such as isopropyl myristate and cetyl ricinoleate, beeswax, saturated and l~nc~ rated fatty alcohols such as behenyl alcohol, hydrocarbons such as mineral oils, petrolatum and squalene, fatty sorbitan esters (see US-A-3988255, Seiden, issued October 26th 1976), lanolin and oil-like lanolin derivatives, ~nim~l and vegetable trigiycerides such as almond oil, peanut oil, wheat germ oil, lin.~ee~ oil, jojoba oil, oil of apricot pits, walnuts, palm nuts, pistachio nuts, ses~ms seeds, rapeseed, cade oil, corn oil, peach pit oil, poppyseed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, h~lemlt oil, olive oil, grapeseed oil, and sunflower seed oil, and C1-C24 esters of dimer and trimer acids such as diisopropyl dimerate, diisostearylm~ e, diisostearyldimerate and triisostearyltrimerate. Of the above, highly preferred from .he viewpoint of optimum lathering and mildness are the vegetable triglyceride oils.
rreferred from the viewpoint of conditioning effectiveness in a rinse-off application are compositions in the form of oil-in-water ~WO 94/17166 21 !~ ~ 3 I ~ PCT/US94/00354 emulsions wherein the average size of the emulsion droplets is in the range from about 1 to about 150 microns, preferably from about 2 to about 50 microns. (Droplet size being measured by, for example, laser diffraction using, e.g. a Malvern Series 2600.) The oil or wax is preferably used herein in combination with a mild surfactant system. Suitable mild surfactants include those having a Relative SkiII Barrier Penetration Value of less than about 75, preferably less than about 50 and more preferably less than about 40, Relative Skin Barrier Penetration Value being measured according to the test method set out in EP-A-0203750 (Incorporated herein by reference). Surf~ct~nts which have Relative Barrier Penetration Values of greater than 75 can be used along with the mild surfactant at low levels in the compositions of this invention, as long as their use does not significantly change the clinical skin mil~lness of the total cle~n.cin~ composition.
Thus according to another aspect of the invention, there is provided a personal cle~n.cin.~ composition comprising:
(a) from about 5% to about 50% by weight of a mixed surfactant system having a Relative Skin Barrier Penetration Value of less than about 75;
~b) from about 3 % to about 40% by weight of an insoluble, nonionic oil or wax or mixture of insoluble, nonionic oils or waxes;
(c) from about 0.1 % to about 8% by weight of fatty acid having a weight-average chain length of from 10 to 18 carbon atoms;
(d) from about 1.5% to about 10% by weight of citric acid or water soluble citrate salt or mi~cture thereof; and (e) water, wherein the weight ratio of total surf~ct~n~ nonionic oil or wa~c is in the range from about 10:1 to about 1:3, and wherein the composition is WO 94/17166 PCT/US94/00354 ~
2~33~3 lo in the form of an oil-in-water emulsion having a viscosity (Brookfield RVT, Helipath, Spindle TB, 5 rmp, 25C, lmin) in the range from 10,000 to 40,000 cps and a yield point of at least 50 dynes/cm2 (Brookfield RVT, Spindle CP52, Plate Code A, 25C).
The compositions herein preferably 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 nonionic surf~ct~nt Preferred herein from the viewpoint of optimum lathering and mil~lne~s are nonionic surfactants selected from C12-C14 fatty acid mono- and lieth~nol~mi-les;
polyhydroxy fatty acid amide surfactants having the general formula (V~) O Rg Il I
R8~C N Z2 where Rg is H, Cl-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R8 is Cs-C31 hydrocarbyl and Z2 is a polyhydroxyhydrocarbyl having a linear chain with at least 3 hydroxyls directly connecte~l to said chain, or an alkoxylated derivative thereof; and polyethyleneglycol glyceryl fatty ester surfactants having the formula (VII) RCOCH2 CH ( OH ) CH2 ( OCH2 CH2 ) nOH
wherein n is from about S ~o 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 from about 5 to 19 carbon atoms, preferably from about 9 to 17 carbon atoms, more ~re~l~bly from about 11 to 17 carbon atoms, most preferably from about 11 to 14 carbon atoms; and mixtures of said ethanol~mi~e, alkyl polyhydroxy fatty acid amide and/or glyceryl fatty ester surf~ct~nt~s. Also highly preferred herein are compositions which are essentially free of alkyl polysaccharide sur~ct~nts, this being preferred from the viewpoint of m~ ness and processability.
~WO 94/17166 11 PCT/US94/00354 The preferred polyhydroxy fatty acid amide surfactants are those in which Rg is C1 4 alkyl, preferably methyl, and R8 is C7-C1g alkyl or alkenyl, more preferably straight-chain Cg-C17 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 ~min~tion 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 ili~e~ 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 prefeldbly will be selected from the group consisting of-CH2(CHOH)n-CH20H,-CH(CH20H)-(CHOH)nl-CH20H,-CH2-(CHOH)2(CHOR')(CHOH)-CH20H, 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)4CH20H wherein R8 is a C11-C17 straight chain alkyl or alkenyl group.
Suitable glyceryl fatty ester surfactants include polyethyleneglycol derivatives of glyceryl cocoate, glyceryl caproate, glyceryl caprylate, glyceryl tallowate, glyceryl p~lm~te, 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 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 2 (PEG 28 glyceryl WO 94/17166 PCT/US94/00354~
~ 33~3 12 tallowate), Varonic LI 420 (PEG 200 glyceryl tallowate), and Varonic LI
63 and 67 (PEG 30 and PEG 80 glyceryl cocoates), and from Croda Inc.
(New York, USA) under their Crovol line of materials, such as Crovol A-40 (PEG 20 almond glyceride), Crovol A-70 (PEG 60 almond glyceride), Crovol M~0 (PEG 20 maize glyceride), Crovol M-70 (PEG 60 maize glyceride), Crovol PK~0 (PEG 12 palm kernel glyceride), and Crovol PK-70 (PEG 45 palm kernel glyceride). Especially preferred are monotallowate and cocoate fatty ester derivatives of polyethylene glycol, or mixtures thereof, particlllarly materials such as PEG 82 glyceryl monotallowate and PEG 30 glyceryl cocoate, and mixtures thereof. Also especially preferred herein is PEG (6) capric/caprylic glyceride (Softigen 767).
The compositions herein preferably 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 betaine surfactant. Betaine surfactants suitable for inclusion in the composition of the invention include alkyl betaines of the formula RsR6R7N+(CH2)nM (VIII) and amido betaines of the formula (IX) R5CO (CH2 ) m I (CH2 ) nM
wherein Rs is C12-C22 alkyl or alkenyl, R6 and R7 are independently Cl-C3 alkyl, M is H, alkali metal, ~Ik~line earth metal, ammonium or ~lk~nolammonium, and n, m are each numbers from 1 to 4. Preferred betaines include cocoamidopropyldimethylcarboxymethyl betaine and lauryl~mir~opropyldimethylcarboxymethyl betaine and Tego betaine.
The compositions of the invention 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 fatty acid is valuable both from the viewpoint of providing emolliency benefits and ,~WO 94/17166 . 2 1 ~ ~ 3 1 ~ PCT/US94/00354 also in combination with the citrate for controlling the viscosity of the final composition.
The compositions of the invention preferably also contain a cationic or nonionic polymeric skin or hair conditioning agent at a level from about 0.01% to about 5%, preferably from about 0.04% to about 2% and especially from about 0.05 % to about 1% . The polymer is found to be valuable for enhancing the cre~miness and quality of the foam as well as providing a hair or skin conditioning utility. In addition to the above the polymer is found to be valuable for enhancing the mil~lness of the product via mitigating the effects of harsher surfactant moieties.
Suitable polymers are high molecular weight materials (mass-average molecular weight determined, for instance, by light scattering, being generally from about 2,000 to about 3,000,000, preferably from about 5,000 to about 1,000,000).
Useful polymers are the cationic, nonionic, amphoteric, and anionic polymers useful in the cosmetic field. Preferred are cationic andl nonionic polymers used in the cosmetic fields as hair or skin conditioning agents.
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 ~limetllyldiallylammonium chloride and acrylic acid; cationic homopolymers of dimethyldiallylammonium chloride; cationic polyalkylene and ethoxypolyalkylene imine~; 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(RTM) 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 and Celquat. Other suitable cationic polymers are WO 94/17166 ~3, 14 PCT/US94/00354~
homopolymers of dimethyldiallyl~mmonium chloride available commercially under the trade name Merquat 100, copolymers of dimethyl aminoethylmethacrylate and acryl~mi(ie, copolymers of dimethyldiallylannmonium chloride and acryl~mitle, available commercially under the trade names Merquat 550 and Merquat S, quaternized vinyl pyrrolidone acrylate or methacrylate copolymers of amino alcohol available commercially under the trade name Gafquat, and polyalkylenetmines such as polyethylenimine and ethoxylated polyethylenimine.
The viscosity of the ~lnal composition (Brookfield RVT, Helipath, Spindle T-B, 5 rpm, 25C, 1 min) is preferably in the range of from about 10,000 to about 40,000 cps, more preferably from about 20,000 to about 30,000 cps and a yield point (shear skess at zero shear rate) of at least 50 dynes/cm2, preferably at least 100 dynes/cm2 (Brookfield RVT, Spindle CP52, Plate Code A, 25C). Preferred compositions have non-Newtonian viscosity characteristics. In highly preferred embo~im~nts, the composition of the invention also display a shear stress versus temperature profile such that (S4s-Ss)/Ss is less than about 0.4, preferably less than about 0.2, and more preferably less than about 0.1, where St is the shear stress in dynes/cm2 at temperature t(C) and at a shear rate of 500 sec~1 (13rookfield RVT, Spindle CP52, Plate Code A).
Another essenti~l component of the compositions of the invention is citric acid or water soluble citrate salt or mixtures thereof, especially Na, K, NH4 salts, at a level from about 1.5% to about 10% by weight preferably from about 2% to about 8% by weight, most preferably from about 2.5% to about 6% by weight. Citrate is important for providing improved physical and viscosity characteristics in combination with the oil and fatty acid components.
It is a feature of the compositions of the invention that the particular combination of ingredients employed therein give excellent stability even in the presence of fatty acids which can display cryst~llis~tion characteristics. Furthermore it is noted that this excellent stability is ~WO 94/17166 ~ 5~ 3 I 3 PCT/US94100354 observed even in the absence of known stabilising agents/viscosity modifiers.
The cleansing compositions can optionally include a hair or skin moisturizer which is soluble in the cleansing composition matrix. The preferred level of moisturizer 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 glycerine, polyethylene glycol, propylene glycol, sorbitol, polyethylene glycol and propylene glycol ethers of methyl glucose (e.g. methyl glucam-20), polyethylene glycol and propylene glycol ethers of lanolin alcohol (e.g. Solulan-75), sodium pyrrolidone carboxylic acid, lactic acid, urea, L-proline, gl~ni~line, pyrrolidone, hydrolyzed protein and other collagen-derived proteins, aloe vera gel and acet~mi~le MEA and mixtures thereof.
Of the above, glycerine is highly p,efelred.
An additional optional component of the composition of the invention is an adduct prepared from vegetable oils cont~inin~ non-conj~ qte~ polyllnc~hlrated fatty acid esters which are conjll~t~l and el~i-iini7e-1 and then modified via Diels-Alder addition with a member of the goup concicting of acrylic acid, fumaric acid and maleic anhydride.
The vegetable oil adduct preferably has the general formula (X).
fH2O (CO) R3 fHo ( co) (CH2 ) y ~ (CH2 ) XCH3 CH2O (CO) R4 Zl Zl wherein ~, y are integers of from 3 to 9, R3 and R4 are independantly selected from saturated and llnc~ rated C7-C22 hydrocarbyl, each Z
WO 94/17166 2~3~ 16 PCTIUS94/00354~
being CO2M and wherein M is H, or a salt forming cation, preferably ~lk~limetal, ammonium or alkanol ammonium. The adducts and their preparation are described in US-A-4740367, the adducts being marketed under the trade name` Ceraphyl GA (Van Dyke). The vegetable oil adduct is preferably added from about 0.5 % to about 5 %, preferably from about 1% to about 4% by weight of the composition.
A number of further additional optional materials can be added to the cle~n~in~ compositions. 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, Bronopol (2-bromo-2-nitropropane-1,3-diol), 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~,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 m~nesium sulfate and other electrolytes; colouring agents;
pearlescers and opacifiers such as ethylene glycol ~licte~-ate, TiO2 and TiO2-coated mica; perfumes and perfume solubilizers etc; zeolites such as Valfor BV400 and derivatives thereof; and Ca2+/Mg2+ sequestrants such as polycarboxylates, aminopolycarboxylate, polyphosphates, polyphosphonates, aminopolyphosphonates and gluconates etc. Water is also present at a level preferably of from about 45% to about 92%
prefe.~bly at least about 60% by weight of the compositions herein.
The pH of the compositions is preferably from about 4 to about 8, more preferably from about 4.5 to about 6.5.
~ WO 94/17166 PCT/US94/00354 17 21~3~13 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 1 Empigen CDL 60 - an aqueous mixture of 23.5 %
cocoampho~cet~te(the amphoteric of formula I and/or IV in which Rl is coconut alkyl, R2 is H, and Z is CO2Na) and 1.35% cocoamphodiacetate (the amphoteric of formula I and/or IV in which Rl is coconut alkyl, R2 is CH2CO2Na and Z is CO2Na).
Amphoteric 2 Sodium N-lauryl-beta-amino-propionate.
Anionic 1 Sodium laureth-2 sl-lf~te Anionic 2 Magnesium sodium laureth 3.6 sulfate GA Polyhydroxy fatty acid amide of formula VII in which R8 is Cll-C17 alkyl, Rg is methyl, and Z2 is CH2(CHOH)4CH20H
DEA Coconut diethanol~mi~e MEA Coconut monoethanol~mi~e Betaine Cocoamidopropylc1imethylcarboxymethyl betaine Polymer 1 Merquat 550 - Copolymer of acryl~mi~le and - dimethyldiallyl ammonium chloride, m.wt. 2.5 x 106 (8% solution) Polymer 2 Polymer JR-400 - hydroxyethylcellulose reacted with epichlorohydrin and quaternized with trimethyl~mine, m.wt. 4 x 106 WO 94/17166 PCT/US94/00354_ MA Myristic Acid Ceraphyl GA Maleated Soyabean Oil marketed by Van Dyke Preservative DMDM Hydantoin Pearlescer Ethyleneglycoldistearate/eml~lsifier mixture Oil Soyabean oil Softigen 767 PEG(6) caprylic/capryl glycerate Mg Magnesium sulfate heptahydrate WO 94/17166 21 5 3 3 1 ~ PCT/US94/00354 Examples I to VII
The following are personal cleansing compositions in the form of shower foam products and which are representative of the present invention:
II III IV V VI VII
.., Arnphoteric 1 7.5 3.0 S.0 S.0 2.5 5.0 5.0 Amphoteric 2 - S.0 3.0 - S.0 Anionic 1 2.5 - 6.0 4.0 7.5 10.0 10.0 Anionic 2 S.0 9.0 4.0 6.0 GA - 1.0 - 2.0 2.0 - 2.5 DEA 3.0 1.0 - 2.0 1.0 3.0 MEA - - - - - - 3.0 Betaine - 2.0 2.0 1.0 2.5 2.5 Polymer 1 - 0.1 0.2 - 0.1 0.2 Polymer 2 0.2 0.1 - 0.2 0.1 - 0.2 Softigen 767 - - - - - 2.0 1.0 M~ 4.0 2.0 l.S 1.0 2.0 2.0 2.0 Ceraphyl GA 2.0 1.0 - - - 2.0 1.0 Oil 8.0 12.0 9.0 12.0 8.0 10.0 1 1.0 Preservative 0.15 0. lS 0.15 0.15 0.15 0.2 0.2 Pearlescer O.S - - 1.0 1.0 2.0 1.0 33~3 20 II III IV V VI VII
Perfume 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Glycerine - - - - - - 3.0 Mg 1.0 - - - 2.0 Sodium Citrate2.0 3.0 2.0 5.0 2.0 4.0 3.0 Water to 100 ~ wo 94/17166 ~ ~ ~ 3 .~ 1 ~ PCT/US94tO0354 Compositions I to VII are prepared by forming a surfactant phase A
cont~inin~ a portion of the water, the anionic and amphoteric surfactants and the rem~inin~ water-soluble, oil-insoluble ingredients, forming an oil phase B cont~ining the MA, DEA, Softigen and oil, admixing B with A at about 40-70C, cooling to ambient temperature, then ~ in~ the rem~inin~ water, preservative and perfume. The average particle size of the emulsion droplets is about S micron. (Malvern Series 2600 laser diffraction). The compositions have a viscosity (Brookfield RVT, Helipath, Spindle TB, 5 rmp, 25C, lmin) in the range from 10,000 to 40,000 cps and a yield point of at least 50 dynes/cm2 (13rookfield RVT, Spindle CP52, Plate Code A, 25).
The cle~n~in~ products demonstrate excellent physical stability and viscosity characteristics across temperature in addition to good lathering, rinsibility and conditioning benefits.
wherein R1 is C7-C22 alkyl or alkenyI, R2 is hydrogen or CH2Z, each Z is independently C02M or CH2C02M, and M is H, alkali metal, ~Ik~line earth metal, ammonium or alkanol~mmonium; and/or ammonium derivatives of formula (II) RlCONH ( CH2 ) 2N CH2 Z
wherein R1, R2 and Z are as defined above;
(b) aminoalkanoates of formula (III) RlNH(CH2)nC02M
and imino~ lk~noates of formula (IV) RlN[(CH2)mc02M]2 wherein n and m are numbers from 1 to 4, and Rl and M are indepenrlently 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, 4th Edition indicates the non-cyclic structure II. 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.
~WO 94/17166 215 ~ PCT/US94/00354 Examples of suitable amphoteric surfactants of type (a) include compounds of formula I and/or II in which R1 is CgH17 (especially iso-capryl), CgH1g and C11H23 alkyl. Especially preferred are the compounds in which R1 is CgH1g, Z is C02M and R2 is H; the compounds in which R1 is C11H23, Z is C02M and R2 is CH2C02M;
and the compounds in which R1 is C11H23, Z is C02M and R2 is H.
In CTFA nomenclature, materials preferred for use in the present invention include cocoamphocarboxypropionate, cocoamphocarbo~y propionic acid, and especially cocoampho~cet~te and cocoampho~ cet~te (other~vise referred to as cocoamphocarboxyglycinate). Specific commercial products include those sold under the trade names of 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 (Rhone-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 m~nllf~ctured and sold in the form of electroneutral complexes with, for example, hydroxide counterions or with anionic sulfate or sulfonate surf~c~nts, especially those of the slllf~te~ Cg-C1g alcohol, Cg-Clg ethoxylated alcohol or Cg-C1g acyl glyceride types. Preferred from the viewpoint of milclness and product stability, however, are compositions which are esse-nti~lly free of (non-etho~cylated) slllf~te~l alcohol surfactants. Note also that the concentrations and weight ratios of the amphoteric surfactants are based herein on the uncomplexed forms of the surf~ct~nt~, any anionic surf~c~nt counterions being considered as part of the overall anionic surf~ct~nt component content.
- Fx~mples of suitable amphoteric surf~ct~nts of type (b) include 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 WO 94tl7166 PCT/US94/00354 ~ 33~ 8 Mirataine by Rhone-Poulenc. Amphoterics preferred for use herein, however, are those of formula I and/or II.
The compositions of the invention also contain from about 3% to about 40%, preferably from about 4% to about 20%, and more preferably from about 5 % to about 15 ~ by weight of an insoluble nonionic oil or wax or mixture thereof, the oil or wax being insoluble in the sense that it is insoluble in the cle~n~in.f~ composition liquid matrix at a temperature of 25C. In addition, the oil or wax is present in composition in a level such that the weight ratio of total surfactant:oil or wax is in the range from about 10:1 to about 1:3" preferably from about 5:1 to about 1:2, and especially from about 2:1 to about 1:1, this being preferred from the viewpoint of providing personal cleansing compositions having optimum lathering, mil-3n~cs, emolliency and rinsibility.
Suitable oils and waxes for use herein can be selected from water-insoluble silicones inclusive of non-volatile polyallyl and polyaryl siloxane gums and fluids, volatile cyclic and linear polyalkylsilo~sanes, polyalkoxylated silicones, amino and quaternary ammonium modified silicones, rigid cross-linked and reinforced silicones and mixhlres thereof, C1-C24 esters of Cg-C30 fatty acids such as isopropyl myristate and cetyl ricinoleate, beeswax, saturated and l~nc~ rated fatty alcohols such as behenyl alcohol, hydrocarbons such as mineral oils, petrolatum and squalene, fatty sorbitan esters (see US-A-3988255, Seiden, issued October 26th 1976), lanolin and oil-like lanolin derivatives, ~nim~l and vegetable trigiycerides such as almond oil, peanut oil, wheat germ oil, lin.~ee~ oil, jojoba oil, oil of apricot pits, walnuts, palm nuts, pistachio nuts, ses~ms seeds, rapeseed, cade oil, corn oil, peach pit oil, poppyseed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, h~lemlt oil, olive oil, grapeseed oil, and sunflower seed oil, and C1-C24 esters of dimer and trimer acids such as diisopropyl dimerate, diisostearylm~ e, diisostearyldimerate and triisostearyltrimerate. Of the above, highly preferred from .he viewpoint of optimum lathering and mildness are the vegetable triglyceride oils.
rreferred from the viewpoint of conditioning effectiveness in a rinse-off application are compositions in the form of oil-in-water ~WO 94/17166 21 !~ ~ 3 I ~ PCT/US94/00354 emulsions wherein the average size of the emulsion droplets is in the range from about 1 to about 150 microns, preferably from about 2 to about 50 microns. (Droplet size being measured by, for example, laser diffraction using, e.g. a Malvern Series 2600.) The oil or wax is preferably used herein in combination with a mild surfactant system. Suitable mild surfactants include those having a Relative SkiII Barrier Penetration Value of less than about 75, preferably less than about 50 and more preferably less than about 40, Relative Skin Barrier Penetration Value being measured according to the test method set out in EP-A-0203750 (Incorporated herein by reference). Surf~ct~nts which have Relative Barrier Penetration Values of greater than 75 can be used along with the mild surfactant at low levels in the compositions of this invention, as long as their use does not significantly change the clinical skin mil~lness of the total cle~n.cin~ composition.
Thus according to another aspect of the invention, there is provided a personal cle~n.cin.~ composition comprising:
(a) from about 5% to about 50% by weight of a mixed surfactant system having a Relative Skin Barrier Penetration Value of less than about 75;
~b) from about 3 % to about 40% by weight of an insoluble, nonionic oil or wax or mixture of insoluble, nonionic oils or waxes;
(c) from about 0.1 % to about 8% by weight of fatty acid having a weight-average chain length of from 10 to 18 carbon atoms;
(d) from about 1.5% to about 10% by weight of citric acid or water soluble citrate salt or mi~cture thereof; and (e) water, wherein the weight ratio of total surf~ct~n~ nonionic oil or wa~c is in the range from about 10:1 to about 1:3, and wherein the composition is WO 94/17166 PCT/US94/00354 ~
2~33~3 lo in the form of an oil-in-water emulsion having a viscosity (Brookfield RVT, Helipath, Spindle TB, 5 rmp, 25C, lmin) in the range from 10,000 to 40,000 cps and a yield point of at least 50 dynes/cm2 (Brookfield RVT, Spindle CP52, Plate Code A, 25C).
The compositions herein preferably 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 nonionic surf~ct~nt Preferred herein from the viewpoint of optimum lathering and mil~lne~s are nonionic surfactants selected from C12-C14 fatty acid mono- and lieth~nol~mi-les;
polyhydroxy fatty acid amide surfactants having the general formula (V~) O Rg Il I
R8~C N Z2 where Rg is H, Cl-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R8 is Cs-C31 hydrocarbyl and Z2 is a polyhydroxyhydrocarbyl having a linear chain with at least 3 hydroxyls directly connecte~l to said chain, or an alkoxylated derivative thereof; and polyethyleneglycol glyceryl fatty ester surfactants having the formula (VII) RCOCH2 CH ( OH ) CH2 ( OCH2 CH2 ) nOH
wherein n is from about S ~o 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 from about 5 to 19 carbon atoms, preferably from about 9 to 17 carbon atoms, more ~re~l~bly from about 11 to 17 carbon atoms, most preferably from about 11 to 14 carbon atoms; and mixtures of said ethanol~mi~e, alkyl polyhydroxy fatty acid amide and/or glyceryl fatty ester surf~ct~nt~s. Also highly preferred herein are compositions which are essentially free of alkyl polysaccharide sur~ct~nts, this being preferred from the viewpoint of m~ ness and processability.
~WO 94/17166 11 PCT/US94/00354 The preferred polyhydroxy fatty acid amide surfactants are those in which Rg is C1 4 alkyl, preferably methyl, and R8 is C7-C1g alkyl or alkenyl, more preferably straight-chain Cg-C17 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 ~min~tion 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 ili~e~ 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 prefeldbly will be selected from the group consisting of-CH2(CHOH)n-CH20H,-CH(CH20H)-(CHOH)nl-CH20H,-CH2-(CHOH)2(CHOR')(CHOH)-CH20H, 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)4CH20H wherein R8 is a C11-C17 straight chain alkyl or alkenyl group.
Suitable glyceryl fatty ester surfactants include polyethyleneglycol derivatives of glyceryl cocoate, glyceryl caproate, glyceryl caprylate, glyceryl tallowate, glyceryl p~lm~te, 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 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 2 (PEG 28 glyceryl WO 94/17166 PCT/US94/00354~
~ 33~3 12 tallowate), Varonic LI 420 (PEG 200 glyceryl tallowate), and Varonic LI
63 and 67 (PEG 30 and PEG 80 glyceryl cocoates), and from Croda Inc.
(New York, USA) under their Crovol line of materials, such as Crovol A-40 (PEG 20 almond glyceride), Crovol A-70 (PEG 60 almond glyceride), Crovol M~0 (PEG 20 maize glyceride), Crovol M-70 (PEG 60 maize glyceride), Crovol PK~0 (PEG 12 palm kernel glyceride), and Crovol PK-70 (PEG 45 palm kernel glyceride). Especially preferred are monotallowate and cocoate fatty ester derivatives of polyethylene glycol, or mixtures thereof, particlllarly materials such as PEG 82 glyceryl monotallowate and PEG 30 glyceryl cocoate, and mixtures thereof. Also especially preferred herein is PEG (6) capric/caprylic glyceride (Softigen 767).
The compositions herein preferably 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 betaine surfactant. Betaine surfactants suitable for inclusion in the composition of the invention include alkyl betaines of the formula RsR6R7N+(CH2)nM (VIII) and amido betaines of the formula (IX) R5CO (CH2 ) m I (CH2 ) nM
wherein Rs is C12-C22 alkyl or alkenyl, R6 and R7 are independently Cl-C3 alkyl, M is H, alkali metal, ~Ik~line earth metal, ammonium or ~lk~nolammonium, and n, m are each numbers from 1 to 4. Preferred betaines include cocoamidopropyldimethylcarboxymethyl betaine and lauryl~mir~opropyldimethylcarboxymethyl betaine and Tego betaine.
The compositions of the invention 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 fatty acid is valuable both from the viewpoint of providing emolliency benefits and ,~WO 94/17166 . 2 1 ~ ~ 3 1 ~ PCT/US94/00354 also in combination with the citrate for controlling the viscosity of the final composition.
The compositions of the invention preferably also contain a cationic or nonionic polymeric skin or hair conditioning agent at a level from about 0.01% to about 5%, preferably from about 0.04% to about 2% and especially from about 0.05 % to about 1% . The polymer is found to be valuable for enhancing the cre~miness and quality of the foam as well as providing a hair or skin conditioning utility. In addition to the above the polymer is found to be valuable for enhancing the mil~lness of the product via mitigating the effects of harsher surfactant moieties.
Suitable polymers are high molecular weight materials (mass-average molecular weight determined, for instance, by light scattering, being generally from about 2,000 to about 3,000,000, preferably from about 5,000 to about 1,000,000).
Useful polymers are the cationic, nonionic, amphoteric, and anionic polymers useful in the cosmetic field. Preferred are cationic andl nonionic polymers used in the cosmetic fields as hair or skin conditioning agents.
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 ~limetllyldiallylammonium chloride and acrylic acid; cationic homopolymers of dimethyldiallylammonium chloride; cationic polyalkylene and ethoxypolyalkylene imine~; 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(RTM) 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 and Celquat. Other suitable cationic polymers are WO 94/17166 ~3, 14 PCT/US94/00354~
homopolymers of dimethyldiallyl~mmonium chloride available commercially under the trade name Merquat 100, copolymers of dimethyl aminoethylmethacrylate and acryl~mi(ie, copolymers of dimethyldiallylannmonium chloride and acryl~mitle, available commercially under the trade names Merquat 550 and Merquat S, quaternized vinyl pyrrolidone acrylate or methacrylate copolymers of amino alcohol available commercially under the trade name Gafquat, and polyalkylenetmines such as polyethylenimine and ethoxylated polyethylenimine.
The viscosity of the ~lnal composition (Brookfield RVT, Helipath, Spindle T-B, 5 rpm, 25C, 1 min) is preferably in the range of from about 10,000 to about 40,000 cps, more preferably from about 20,000 to about 30,000 cps and a yield point (shear skess at zero shear rate) of at least 50 dynes/cm2, preferably at least 100 dynes/cm2 (Brookfield RVT, Spindle CP52, Plate Code A, 25C). Preferred compositions have non-Newtonian viscosity characteristics. In highly preferred embo~im~nts, the composition of the invention also display a shear stress versus temperature profile such that (S4s-Ss)/Ss is less than about 0.4, preferably less than about 0.2, and more preferably less than about 0.1, where St is the shear stress in dynes/cm2 at temperature t(C) and at a shear rate of 500 sec~1 (13rookfield RVT, Spindle CP52, Plate Code A).
Another essenti~l component of the compositions of the invention is citric acid or water soluble citrate salt or mixtures thereof, especially Na, K, NH4 salts, at a level from about 1.5% to about 10% by weight preferably from about 2% to about 8% by weight, most preferably from about 2.5% to about 6% by weight. Citrate is important for providing improved physical and viscosity characteristics in combination with the oil and fatty acid components.
It is a feature of the compositions of the invention that the particular combination of ingredients employed therein give excellent stability even in the presence of fatty acids which can display cryst~llis~tion characteristics. Furthermore it is noted that this excellent stability is ~WO 94/17166 ~ 5~ 3 I 3 PCT/US94100354 observed even in the absence of known stabilising agents/viscosity modifiers.
The cleansing compositions can optionally include a hair or skin moisturizer which is soluble in the cleansing composition matrix. The preferred level of moisturizer 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 glycerine, polyethylene glycol, propylene glycol, sorbitol, polyethylene glycol and propylene glycol ethers of methyl glucose (e.g. methyl glucam-20), polyethylene glycol and propylene glycol ethers of lanolin alcohol (e.g. Solulan-75), sodium pyrrolidone carboxylic acid, lactic acid, urea, L-proline, gl~ni~line, pyrrolidone, hydrolyzed protein and other collagen-derived proteins, aloe vera gel and acet~mi~le MEA and mixtures thereof.
Of the above, glycerine is highly p,efelred.
An additional optional component of the composition of the invention is an adduct prepared from vegetable oils cont~inin~ non-conj~ qte~ polyllnc~hlrated fatty acid esters which are conjll~t~l and el~i-iini7e-1 and then modified via Diels-Alder addition with a member of the goup concicting of acrylic acid, fumaric acid and maleic anhydride.
The vegetable oil adduct preferably has the general formula (X).
fH2O (CO) R3 fHo ( co) (CH2 ) y ~ (CH2 ) XCH3 CH2O (CO) R4 Zl Zl wherein ~, y are integers of from 3 to 9, R3 and R4 are independantly selected from saturated and llnc~ rated C7-C22 hydrocarbyl, each Z
WO 94/17166 2~3~ 16 PCTIUS94/00354~
being CO2M and wherein M is H, or a salt forming cation, preferably ~lk~limetal, ammonium or alkanol ammonium. The adducts and their preparation are described in US-A-4740367, the adducts being marketed under the trade name` Ceraphyl GA (Van Dyke). The vegetable oil adduct is preferably added from about 0.5 % to about 5 %, preferably from about 1% to about 4% by weight of the composition.
A number of further additional optional materials can be added to the cle~n~in~ compositions. 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, Bronopol (2-bromo-2-nitropropane-1,3-diol), 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~,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 m~nesium sulfate and other electrolytes; colouring agents;
pearlescers and opacifiers such as ethylene glycol ~licte~-ate, TiO2 and TiO2-coated mica; perfumes and perfume solubilizers etc; zeolites such as Valfor BV400 and derivatives thereof; and Ca2+/Mg2+ sequestrants such as polycarboxylates, aminopolycarboxylate, polyphosphates, polyphosphonates, aminopolyphosphonates and gluconates etc. Water is also present at a level preferably of from about 45% to about 92%
prefe.~bly at least about 60% by weight of the compositions herein.
The pH of the compositions is preferably from about 4 to about 8, more preferably from about 4.5 to about 6.5.
~ WO 94/17166 PCT/US94/00354 17 21~3~13 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 1 Empigen CDL 60 - an aqueous mixture of 23.5 %
cocoampho~cet~te(the amphoteric of formula I and/or IV in which Rl is coconut alkyl, R2 is H, and Z is CO2Na) and 1.35% cocoamphodiacetate (the amphoteric of formula I and/or IV in which Rl is coconut alkyl, R2 is CH2CO2Na and Z is CO2Na).
Amphoteric 2 Sodium N-lauryl-beta-amino-propionate.
Anionic 1 Sodium laureth-2 sl-lf~te Anionic 2 Magnesium sodium laureth 3.6 sulfate GA Polyhydroxy fatty acid amide of formula VII in which R8 is Cll-C17 alkyl, Rg is methyl, and Z2 is CH2(CHOH)4CH20H
DEA Coconut diethanol~mi~e MEA Coconut monoethanol~mi~e Betaine Cocoamidopropylc1imethylcarboxymethyl betaine Polymer 1 Merquat 550 - Copolymer of acryl~mi~le and - dimethyldiallyl ammonium chloride, m.wt. 2.5 x 106 (8% solution) Polymer 2 Polymer JR-400 - hydroxyethylcellulose reacted with epichlorohydrin and quaternized with trimethyl~mine, m.wt. 4 x 106 WO 94/17166 PCT/US94/00354_ MA Myristic Acid Ceraphyl GA Maleated Soyabean Oil marketed by Van Dyke Preservative DMDM Hydantoin Pearlescer Ethyleneglycoldistearate/eml~lsifier mixture Oil Soyabean oil Softigen 767 PEG(6) caprylic/capryl glycerate Mg Magnesium sulfate heptahydrate WO 94/17166 21 5 3 3 1 ~ PCT/US94/00354 Examples I to VII
The following are personal cleansing compositions in the form of shower foam products and which are representative of the present invention:
II III IV V VI VII
.., Arnphoteric 1 7.5 3.0 S.0 S.0 2.5 5.0 5.0 Amphoteric 2 - S.0 3.0 - S.0 Anionic 1 2.5 - 6.0 4.0 7.5 10.0 10.0 Anionic 2 S.0 9.0 4.0 6.0 GA - 1.0 - 2.0 2.0 - 2.5 DEA 3.0 1.0 - 2.0 1.0 3.0 MEA - - - - - - 3.0 Betaine - 2.0 2.0 1.0 2.5 2.5 Polymer 1 - 0.1 0.2 - 0.1 0.2 Polymer 2 0.2 0.1 - 0.2 0.1 - 0.2 Softigen 767 - - - - - 2.0 1.0 M~ 4.0 2.0 l.S 1.0 2.0 2.0 2.0 Ceraphyl GA 2.0 1.0 - - - 2.0 1.0 Oil 8.0 12.0 9.0 12.0 8.0 10.0 1 1.0 Preservative 0.15 0. lS 0.15 0.15 0.15 0.2 0.2 Pearlescer O.S - - 1.0 1.0 2.0 1.0 33~3 20 II III IV V VI VII
Perfume 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Glycerine - - - - - - 3.0 Mg 1.0 - - - 2.0 Sodium Citrate2.0 3.0 2.0 5.0 2.0 4.0 3.0 Water to 100 ~ wo 94/17166 ~ ~ ~ 3 .~ 1 ~ PCT/US94tO0354 Compositions I to VII are prepared by forming a surfactant phase A
cont~inin~ a portion of the water, the anionic and amphoteric surfactants and the rem~inin~ water-soluble, oil-insoluble ingredients, forming an oil phase B cont~ining the MA, DEA, Softigen and oil, admixing B with A at about 40-70C, cooling to ambient temperature, then ~ in~ the rem~inin~ water, preservative and perfume. The average particle size of the emulsion droplets is about S micron. (Malvern Series 2600 laser diffraction). The compositions have a viscosity (Brookfield RVT, Helipath, Spindle TB, 5 rmp, 25C, lmin) in the range from 10,000 to 40,000 cps and a yield point of at least 50 dynes/cm2 (13rookfield RVT, Spindle CP52, Plate Code A, 25).
The cle~n~in~ products demonstrate excellent physical stability and viscosity characteristics across temperature in addition to good lathering, rinsibility and conditioning benefits.
Claims (21)
1. A personal cleansing composition comprising:
(a) from about 5% to about 50% by weight of one or more surfactants selected from anionic, nonionic, amphoteric, zwitterionic, and cationic surfactants and mixtures thereof;
(b) from about 3% to about 40% by weight of an insoluble, nonionic oil or wax or mixture of insoluble nonionic oils or waxes;
(c) from about 0.1% to about 8% by weight of fatty acid having a weight - average chain length of from about 10 to about 18 carbon atoms;
(d) from about 1.5% to about 10% by weight of citric acid or water soluble citrate salt or mixtures thereof; and (e) water.
(a) from about 5% to about 50% by weight of one or more surfactants selected from anionic, nonionic, amphoteric, zwitterionic, and cationic surfactants and mixtures thereof;
(b) from about 3% to about 40% by weight of an insoluble, nonionic oil or wax or mixture of insoluble nonionic oils or waxes;
(c) from about 0.1% to about 8% by weight of fatty acid having a weight - average chain length of from about 10 to about 18 carbon atoms;
(d) from about 1.5% to about 10% by weight of citric acid or water soluble citrate salt or mixtures thereof; and (e) water.
2. A composition according to Claim 1 wherein the composition is in the form of an oil-in-water emulsion having a viscosity (Brookfield RVT, Helipath, Spindle TB, 5 rpm, 25°C, 1 min) in the range from 10,000 to 40,000 cps and a yield point of at least 50 dynes/cm2 (Brookfield RVT, Spindle CP52, Plate Code A, 25°C).
3. A composition according to Claim 1 or 2 wherein the citric acid or water soluble salt thereof is at a level from about 2% to about 8%
by weight, preferably from about 2.5% to about 6% by weight.
by weight, preferably from about 2.5% to about 6% by weight.
4. A composition according to any of Claims 1 to 3 wherein the anionic surfactant is selected from 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.
5. A composition according to any of Claims 1 to 4 comprising a mixture of anionic surfactant and amphoteric surfactant each in a level of from about 1% to about 15%, preferably from about 2% to about 13% by weight.
6. A composition according to any of Claims 1 to 5 wherein the anionic surfactant comprises an ethoxylated C 8-C22 alkyl sulfate.
7. A composition according to any of Claims 1 to 6 wherein the amphoteric surfactant is selected from:
(a) imidazolinium derivatives 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 (II) wherein R1, R2 and Z are as defined above:
(b) aminoalkanoates of formula (III) R1 NH(CH2)nCO2M
and iminodialkanoates of formula (IV) R1 N[(CH2)mCO2M]2 wherein n and m are numbers from 1 to 4, and R1 and M are independently selected from the groups specified in (a) above; and (c) mixtures thereof.
(a) imidazolinium derivatives 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 (II) wherein R1, R2 and Z are as defined above:
(b) aminoalkanoates of formula (III) R1 NH(CH2)nCO2M
and iminodialkanoates of formula (IV) R1 N[(CH2)mCO2M]2 wherein n and m are numbers from 1 to 4, and R1 and M are independently selected from the groups specified in (a) above; and (c) mixtures thereof.
8. A composition according to Claim 7 wherein the amphoteric is selected from the imidazolinium derivatives of formula I and/or ammonium derivatives of formula II.
9. A composition according to any of Claims 1 to 8 wherein the weight ratio of anionic surfactant:amphoteric surfactant is in the range from about 1:2 to about 5:1.
10. A composition according to Claim 9 wherever the weight ratio of anionic surfactant:amphoteric surfactant is in the range from about 1:1 to about 2:1.
11. A composition according to any of Claims 1 to 10 wherein the anionic surfactant and amphoteric surfactant together comprise from about 8% to about 25%, preferably from about 10% to about 20% by weight of the composition.
12. A composition according to any of Claims 1 to 11 additionally comprising from about 0.1% to about 20%, preferably from about 0.1% to about 10% by weight of nonionic surfactant.
13. A composition according to Claim 12 wherein the nonionic surfactant is selected from C12-C14 fatty acid mono-and diethanolamides; polyhydroxy fatty acid amide surfactants having the formula R8(CO)N(R9)Z2 wherein R9 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R8 is C5-C31 hydrocarbyl and Z2 is a polyhydroxyhydrocarbyl having a linear chain with at least 3 hydroxyls directly connected to said chain, or an alkoxylated derivative thereof; polyethyleneglycol glyceryl fatty ester surfactants having the formula (VII) 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 from about 5 to 19 carbon atoms, preferably from about 9 to 17 carbon atoms, more preferably from about 11 to 17 carbon atoms, most preferably from about 11 to 14 carbon atoms; and mixtures of said ethanolamide, polyhydroxy fatty acid amide and/or glyceryl fatty ester surfactants.
14. A composition according to any of Claims 1 to 13 comprising from about 4% to about 20%, preferably from about 5% to about 15%
by weight of the nonionic oil or wax or mixture thereof.
by weight of the nonionic oil or wax or mixture thereof.
15. A composition according to any of Claims 1 to 14 wherein the anionic, nonionic and amphoteric surfactant together comprise from about 5% to about 45%, preferably from about 7% to about 40%
by weight of the composition.
by weight of the composition.
16. A composition according to any of Claims 1 to 15 comprising from about 0.1% to about 20%, preferably from about 0.1% to about 10% by weight of betaine surfactant.
17. A composition according to any of Claims 1 to 16 additionally comprising from about 0.5% to about 6%, preferably from about 1.5 % to about 5 % by weight of a fatty acid having a weight-average chain length of from 10 to 18, preferably 12 to 16 carbon atoms.
18. A composition according to any of Claims 1 to 17 additionally comprising from 0.01% to 5%, preferably from about 0.04% to about 2 % and more preferably from 0.05 % to 1 % of a cationic or nonionic polymeric skin or hair conditioning agent, selected from 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 acrylic acid;
cationic homopolymers of dimethyldiallylammonium chloride;
cationic polyalkylene and ethoxypolyalkylene imines; quaternized silicones, and mixtures thereof.
cationic homopolymers of dimethyldiallylammonium chloride;
cationic polyalkylene and ethoxypolyalkylene imines; quaternized silicones, and mixtures thereof.
19. A composition according to any of Claims 1 to 18 additionally comprising moisturiser selected from glycerin, polyethylene glycol, propylene glycol, sorbitol, polyethylene glycol and polypropylene glycol ethers of methyl glucose, polyethylene glycol and polypropylene glycol ethers of lanolin alcohol, PEG(6) capric/caprylic glyceride, PEG (6) coconut glyceride, sodium pyrrolidone carboxylic acid, lactic acid, L-proline and mixtures thereof.
20. A composition according to any of Claims 1 to 19 wherein the anionic surfactant comprises at least 50%, preferably at least 75%
thereof of ethoxylated C8-C22 alkyl sulfate.
thereof of ethoxylated C8-C22 alkyl sulfate.
21. A composition according to any one of Claims 1 to 20 wherein the weight ratio of total surfactant nonionic oil or wax is in the range from about 5:1 to about 1:2, preferably from about 2:1 to about 1:1.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB939301295A GB9301295D0 (en) | 1993-01-23 | 1993-01-23 | Cleansing compositions |
GB9301295.3 | 1993-01-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2153313A1 true CA2153313A1 (en) | 1994-08-04 |
Family
ID=10729176
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2153313 Abandoned CA2153313A1 (en) | 1993-01-23 | 1994-01-11 | Cleansing compositions |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0689581A4 (en) |
JP (1) | JPH08505875A (en) |
CN (1) | CN1116858A (en) |
CA (1) | CA2153313A1 (en) |
GB (1) | GB9301295D0 (en) |
WO (1) | WO1994017166A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US6183732B1 (en) | 1997-03-06 | 2001-02-06 | Johnson & Johnson Consumer Companies | Chemical composition |
US6830755B2 (en) | 1999-10-01 | 2004-12-14 | Johnson & Johnson Consumer Companies, Inc. | Method for relaxing human beings using personal care compositions |
US6986747B2 (en) | 2002-01-29 | 2006-01-17 | Johnson & Johnson Consumer Companies | Method of measuring the stress or relaxation level of a mammal |
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US5914300A (en) * | 1994-06-01 | 1999-06-22 | Lever Brothers Company | Mild antimicrobial liquid cleansing formulations comprising hydroxy acid buffering compound or compounds as potentiator of antimicrobial effectiveness |
GB9414575D0 (en) * | 1994-07-19 | 1994-09-07 | Unilever Plc | Detergent composition |
GB9414574D0 (en) * | 1994-07-19 | 1994-09-07 | Unilever Plc | Detergent composition |
GB9424476D0 (en) * | 1994-12-03 | 1995-01-18 | Procter & Gamble | Cleansing compositions |
EP0818984B1 (en) | 1995-04-04 | 2002-01-30 | Imperial Chemical Industries Plc | Surfactant compositions |
DK0835096T3 (en) * | 1995-06-26 | 2001-11-19 | Procter & Gamble | Liquid cleaning compositions containing polyvalent metal cations for persons |
KR100439932B1 (en) * | 1995-08-07 | 2004-09-18 | 유니레버 엔.브이. | Liquid Cleansing Composition Comprising Soluble, Lamellar Phase Inducing Structurant |
US6077816A (en) * | 1995-08-07 | 2000-06-20 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Liquid cleansing composition comprising soluble, lamellar phase inducing structurant |
US5837274A (en) * | 1996-10-22 | 1998-11-17 | Kimberly Clark Corporation | Aqueous, antimicrobial liquid cleaning formulation |
US6174846B1 (en) | 1997-12-18 | 2001-01-16 | Lever Brothers Company, A Division Of Conopco, Inc. | Liquid composition with enhanced low temperature stability |
DE19814980A1 (en) * | 1998-04-03 | 1999-10-07 | Beiersdorf Ag | Cosmetic and dermatological compositions useful for rapid rejuvenation or maintenance of barrier function of skin |
US6534457B2 (en) | 2000-03-20 | 2003-03-18 | Unilever Home And Personal Care Usa, Division Of Conopco, Inc. | Extrudable multiphase composition comprising lamellar phase inducing structurant in each phase |
DE10318526A1 (en) * | 2003-04-24 | 2004-11-11 | Beiersdorf Ag | High fat cleaning emulsion |
US6906016B1 (en) | 2004-05-19 | 2005-06-14 | Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. | Personal product liquid cleansers comprising combined fatty acid and water soluble or water swellable starch structuring system |
JP5656276B2 (en) * | 2009-01-14 | 2015-01-21 | 株式会社ミルボン | Shampoo composition |
RU2543713C2 (en) | 2010-08-11 | 2015-03-10 | Колгейт-Палмолив Компани | Foaming detergent |
KR20130115315A (en) * | 2010-12-09 | 2013-10-21 | 콜게이트-파아므올리브캄파니 | Liquid cleansing composition containing long-chain fatty acid |
CA2819851C (en) | 2010-12-09 | 2015-11-24 | Colgate-Palmolive Company | Liquid cleaning compositions containing long-chain fatty alcohols |
JP6449466B2 (en) * | 2014-12-23 | 2019-01-09 | ロレアル | Composition for conditioning keratin fibers |
EP3724309B1 (en) * | 2017-12-12 | 2022-02-02 | Unilever Global IP Limited | Foamable cleaning composition |
EP3727279B1 (en) * | 2017-12-22 | 2022-01-26 | LVMH Recherche | Oil-in-water emulsified cosmetic |
CN110327799B (en) * | 2019-07-08 | 2021-08-31 | 广州正浩新材料科技有限公司 | Water-based erucamide emulsion and preparation method thereof |
WO2021232218A1 (en) | 2020-05-19 | 2021-11-25 | Carl Zeiss Vision International Gmbh | Spectacle lens with antifogging properties |
WO2021232216A1 (en) | 2020-05-19 | 2021-11-25 | Carl Zeiss Vision International Gmbh | Transparent article, in particular a spectacle lens, with antibacterial and/or antiviral properties and method for manufacturing thereof |
EP3928966A1 (en) | 2020-06-26 | 2021-12-29 | Carl Zeiss Vision International GmbH | Method for manufacturing a coated lens |
EP3944001A1 (en) | 2020-07-24 | 2022-01-26 | Carl Zeiss Vision International GmbH | Spectacle lens with edge sealing and method for manufacturing the same |
WO2022016482A1 (en) | 2020-07-24 | 2022-01-27 | Carl Zeiss Vision International Gmbh | Spectacle lens with antibacterial and/or antiviral properties and method for manufacturing the same |
WO2022099592A1 (en) | 2020-11-13 | 2022-05-19 | Carl Zeiss Vision International Gmbh | Spectacle lens with antibacterial and/or antiviral properties and method for manufacturing thereof |
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US4338211A (en) * | 1980-06-30 | 1982-07-06 | The Procter & Gamble Company | Liquid surfactant skin cleanser with lather boosters |
US4310433A (en) * | 1980-09-02 | 1982-01-12 | The Procter & Gamble Company | Superfatted liquid soap skin cleansing compositions |
US4341799A (en) * | 1980-12-29 | 1982-07-27 | Good Allen H | Lotion and method for cleansing and conditioning the skin therewith |
CA1201952A (en) * | 1982-09-23 | 1986-03-18 | Johnson & Johnson Inc. | Surfactant compositions |
EP0166232A3 (en) * | 1984-05-30 | 1987-07-15 | S.C. Johnson & Son, Inc. | Foaming hair cleanser and conditioner |
US4603005A (en) * | 1984-11-19 | 1986-07-29 | S. C. Johnson & Son, Inc. | Cleaning compositions containing alpha olefin/maleic anhydride terpolymers |
US4673525A (en) * | 1985-05-13 | 1987-06-16 | The Procter & Gamble Company | Ultra mild skin cleansing composition |
US5186857A (en) * | 1988-11-14 | 1993-02-16 | Imaginative Research Associates, Inc. | Self-foaming oil compositions and process for making and using same |
US5132037A (en) * | 1989-05-05 | 1992-07-21 | Lever Brothers Company, Division Of Conopco, Inc. | Aqueous based personal washing cleanser |
US5085857A (en) * | 1989-12-04 | 1992-02-04 | Chesebrough-Pond's Usa Co. | Conditioning shampoo comprising a surfactant, a non-volatile silicone oil and guar hydroxypropyltrimonium chloride as a cationic conditioning polymer |
GB9020594D0 (en) * | 1990-09-21 | 1990-10-31 | Procter & Gamble | Cleansing compositions |
IN184497B (en) * | 1990-10-12 | 2000-08-26 | Procter & Gamble |
-
1993
- 1993-01-23 GB GB939301295A patent/GB9301295D0/en active Pending
-
1994
- 1994-01-11 EP EP94908582A patent/EP0689581A4/en not_active Withdrawn
- 1994-01-11 CA CA 2153313 patent/CA2153313A1/en not_active Abandoned
- 1994-01-11 CN CN 94190975 patent/CN1116858A/en active Pending
- 1994-01-11 WO PCT/US1994/000354 patent/WO1994017166A1/en not_active Application Discontinuation
- 1994-01-11 JP JP6517066A patent/JPH08505875A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6183732B1 (en) | 1997-03-06 | 2001-02-06 | Johnson & Johnson Consumer Companies | Chemical composition |
US6830755B2 (en) | 1999-10-01 | 2004-12-14 | Johnson & Johnson Consumer Companies, Inc. | Method for relaxing human beings using personal care compositions |
US6986747B2 (en) | 2002-01-29 | 2006-01-17 | Johnson & Johnson Consumer Companies | Method of measuring the stress or relaxation level of a mammal |
Also Published As
Publication number | Publication date |
---|---|
CN1116858A (en) | 1996-02-14 |
WO1994017166A1 (en) | 1994-08-04 |
JPH08505875A (en) | 1996-06-25 |
EP0689581A1 (en) | 1996-01-03 |
EP0689581A4 (en) | 1996-08-21 |
GB9301295D0 (en) | 1993-03-17 |
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