WO2019008937A1

WO2019008937A1 - Foaming cleanser

Info

Publication number: WO2019008937A1
Application number: PCT/JP2018/020085
Authority: WO
Inventors: Nahoko Nakashima; Ryuji Hara
Original assignee: L'oreal
Priority date: 2017-07-04
Filing date: 2018-05-18
Publication date: 2019-01-10
Also published as: JP7063556B2; JP2019031445A

Abstract

The present invention relates to a composition for cleansing keratinous substances, preferably skin, comprising: (a) a surfactant system comprising: (a-1) at least one N-(C6-C30)acyl-amino acid based surfactant, (a-2) at least one amphoteric surfactant chosen from betaines, (C8-C20)alkyl betaines, (C8-C20)alkylamido(C1-C6)alkylbetaines, and mixtures thereof, (a-3) at least one salt of a C8-C20 fatty acid, and (a-4) at least one amphiphilic lipid material; (b) at least one non-associative crosslinked copolymer of (meth)acrylic acid, and of (C1-C4)alkyl ester of (meth)acrylic acid; (c) at least one associative copolymer of (meth)acrylic acid, and of (C1-C6)alkyl ester of (meth)acrylic acid; and (d) at least one triglyceride oil, wherein the amount of the surfactant system in the composition is less than 15% by weight relative to the total weight of the composition.

Description

DESCRIPTION

FOAMING CLEANSER TECHNICAL FIELD

The present invention relates to a cosmetic composition, in particular a foaming cleanser composition, comprising: (a) a surfactant system comprising a specific combination of several kinds of surfactants, (b) at least one non-associative crosslinked copolymer of (meth)acrylic acid, and of (Ci-C₄)alkyl ester of (meth)acrylic acid and vinyl ester, (c) at least one associative copolymer of (meth)acrylic acid, and of (d-C6)alkyl ester of (meth)acrylic acid, and (d) at least one triglyceride oil.

BACKGROUND ART

Foaming cleansing products have a cleansing action by virtue of the surfactants, which suspend the fatty residues and the pigments of, for example, make-up products. A good foaming property, rinsability, and skin-care property, for example, leaving a good feeling on the skin after rinsing off, such as skin mildness and a moisturizing sensation, are very important for cosmetic foaming cleanser products. In addition to these properties, stability is also important for foaming cleansing products for daily use by consumers.

To date, some prior art documents relating to foaming cleanser products have been published. For example, WO 2015/181789 discloses a foaming cleanser cosmetic composition containing, in a physiologically acceptable medium: a surfactant system comprising specific surfactants and at least one non associative crosslinked copolymer or acrylic acid and/or methacrylic acid. WO 2011/45191 discloses a liquid personal care composition comprising both low levels of specific fatty isethionate products and low overall fatty acid content.

WO 2001/19949 discloses a liquid cleansing composition comprising a surfactant selected from amphoteric, zwitterionic, or a mixture thereof; an anionic surfactant; a lamellar structurant selected from fatty acids, fatty esters, trihydroxystearin, fatty alcohols, or mixtures thereof; and a strong electrolyte.

JP-A-H7- 109498 discloses a detergent composition comprising (A) a secondary amide type-N-acylamino acid, (B) a cationic polymer, and (C) a triglyceride.

WO 2011/130460 discloses a surfactant-polymer blend comprising: (a) at least one amino acid surfactant; and (b) at least one hydrophobically-modified polymer polymerized from a monomer mixture comprising: (i) at least one α,β-ethylenically unsaturated carboxylic acid monomer; (ii) at least one nonionic, co-polymerizable α,β-ethylenically unsaturated monomer; and (iii) at least one ethylenically unsaturated hydrophobically-modified

associative monomer.

DISCLOSURE OF INVENTION However, there is still a demand for a foaming cleanser which has a good foaming quality, rinsability, skin-care quality, as well as good stability.

An objective of the present invention is to provide a stable foaming cleanser which has a good foaming quality, rinsability, and skin-care quality, for example, leaving a good feeling on the skin after rinsing off, such as skin mildness and a moisturizing sensation. Especially, an objective of the present invention is to provide a foaming cleanser having a good foaming quality, rinsability, and skin-care quality, while maintaining its viscosity substantially and not showing a significant viscosity reduction over time.

The above objective can be achieved by a composition for cleansing keratinous substances such as skin and lips, comprising:

(a) a surfactant system comprising:

(a-1) at least one N-(C₆-C₃₀)acyl-amino acid based surfactant,

(a-2) at least one amphoteric surfactant chosen from betaines, (C₈-C₂₀)alkyl

betaines, (C₈-C₂₀)alkylamido(C₁-C₆)alkylbetaines, and mixtures thereof, (a-3) at least one salt of a C₈-C₂₀ fatty acid, and

(a-4) at least one amphiphilic lipid material;

(b) at least one non-associative crosslinked copolymer of (meth)acrylic acid, and of

(Ci -C₄)alkyl ester of (meth)acrylic acid;

(c) at least one associative copolymer of (meth)acrylic acid, and of (C₁-C₆)alkyl ester of (meth)acrylic acid; and

(d) at least one triglyceride oil,

wherein the amount of the surfactant system in the composition is less than 15% by weight relative to the total weight of the composition.

The (b) non-associative crosslinked copolymer may comprise vinyl ester, preferably carboxylic acid vinyl ester, as a monomer.

The (c) associative copolymer may comprise ester of (meth)acrylic acid or itaconic acid, and of polyoxyalkylenated fatty alcohol, as a monomer.

The (a-1) N-(C₆-C₃₀)acyl-amino acid based surfactant may be an N-(C₈-Ci₈)acyl-amino acid based surfactant, preferably potassium N-cocoyl glycinate or sodium N-cocoyl glycinate, and more preferably potassium N-cocoyl glycinate.

The (a-1) N-(C₆-C₃₀)acyl-amino acid based surfactant may be present in the composition in an amount ranging from 0.1 to 7% by weight, preferably from 1 to 6% by weight, and more preferably from 2 to 5% by weight, with respect to the total weight of composition.

The (a-2) amphoteric surfactant may be chosen from among coco betaine, lauryl betaine, oxyethylenated (10 EO) lauryl betaine, oxy ethyl enated (10 EO) stearyl betaine,

cocamidopropyl betaine, lauramidopropyl betaine and mixtures thereof.

The (a-2) amphoteric surfactant may be present in an amount ranging from 0.1 to 6% by weight, preferably from 0.5 to 5% by weight, and more preferably from 1 to 4% by weight, with respect to the total weight of the composition.

The (a-3) salt of the Cs-C₂₀ fatty acid may be chosen from a salt of caproic acid, capric acid, caprylic acid, oleic acid, linoleic acid, lauric acid, myristic acid, stearic acid, palmitic acid, and mixtures thereof, and is preferably potassium cocoate. The (a-3) salt of the C₈-C₂₀ fatty acid may be present in an amount ranging from 0.1 to 6% by weight, in particular from 0.5 to 5% by weight, and more particularly from 1 to 4% by weight, with respect to the total weight of the composition.

The (a-4) amphiphilic lipid material may be lecithin.

The (a-4) amphiphilic lipid material may be present in an amount ranging from 0.01 to 5% by weight, preferably from 0.05 to 3% by weight, and more preferably from 0.1 to 1% by weight, with respect to the total weight of the composition.

The (d) triglyceride oil may be chosen from jojoba oil, babassu oil, sunflower oil, olive oil, canola oil, coconut oil, meadowfoam seed oil, Brazil nut oil, marula oil, maize oil, argan oil, soybean oil, marrow oil, grapeseed oil, linseed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, coriander oil, castor oil, avocado oil, shea butter oil, rapeseed oil, copra oil, shea butter, Nilotica shea butter, galam butter, Borneo butter or fat or tengkawang tallow, shorea butter, illipe butter, madhuca butter, Madhuca longifolia butter, mowrah butter, katiau butter, phulwara butter, mango butter, murumuru butter, kokum butter, ucuuba butter, tucuma butter, painya butter, coffee butter, apricot butter, macadamia butter, grapeseed butter, avocado butter, olive butter, sweet almond butter, cocoa butter, sunflower butter, and mixtures thereof and preferably, is selected from shea butter, olive oil, canola oil, meadowfoam seed oil and mixtures thereof.

The (a) surfactant system may comprise additional surfactants selected from anionic, amphoteric, nonionic and/or cationic foaming surfactants and non-foaming surfactants, which are different from the surfactants (a-1) to (a-4) in the (a) surfactant system.

The total amount of surfactants in the composition may be less than 15% by weight relative to the total weight of the composition.

The present invention also relates to a cosmetic process for cleansing keratinous substances, preferably skin, comprising the step of applying the composition according to present invention to the keratinous substances. BEST MODE FOR CARRYING OUT THE INVENTION

After diligent research, the inventors have discovered that a particular combination of the ingredients of the present invention can provide a stable foaming cleanser for keratinous substances such as skin and lips, which exhibits a good foaming quality, rinsability, as well as skin-care quality giving a moisturized sensation to the keratinous substances after rinsing off.

Thus, the composition according to the present invention is intended for cleansing keratinous substances such as skin and lips, and comprises:

(a) a surfactant system comprising:

(a-1) at least one N-(C₆-C₃₀)acyl-amino acid based surfactant,

(a-2) at least one amphoteric surfactant chosen from betaines, (C₈-C2o)alkyl betaines, (C₈-C2o)alkylamido(Ci-C₆)alkylbetaines, and mixtures thereof, (a-3) at least one salt of a C8-C20 fatty acid, and

(a-4) at least one amphiphilic lipid material;

(b) at least one non-associative crosslinked copolymer of (meth)acrylic acid, and of (Ci -C₄)alkyl ester of (meth)acrylic acid;

(c) at least one associative copolymer of (meth)acrylic acid, and of (d-C₆)alkyl ester of (meth)acrylic acid; and

(d) at least one triglyceride oil,

[Composition] The composition according to the present invention can be used for removing makeup and/or cleansing keratin substance such as skin, hair, including scalp and mucous membranes such as lips, preferably human skin, and in particular human facial skin and lips.

The viscosity of the composition according to the present invention is not particularly limited. The viscosity can be measured by using a rheometer, for example, a proRheo rheometer Rl 80 (proRheo GmbH), using a 25 mL cup together with mobile 4 at room temperature.

Preferably, the viscosity of the composition can range from 15 to 40 Pa s, preferably from 17 to 30 Pa s at room temperature and at 200 rpm., 10 min after mixing. The composition according to the present invention has improved stability while it maintains a good foaming property, rinsability, and skin-care quality giving a moisturized sensation to the skin after rinsing off. The "stability" here means that it practically keeps its viscosity just after being prepared at a given temperature, for example, from 4°C to 45°C, and a given period, for example for two months, and it does not show a significant viscosity reduction at said temperature and for said period. For example, the composition according to the present invention exhibits a viscosity reduction after being stored at 4°C and/or 45 °C for two months within 30%, preferably within 25%, and more preferably within 20% compared to initial viscosity. The form of the composition according to the present invention is not particularly limited, as long as it is water-based, and may take various forms such as an emulsion (O/W or W/O form), an aqueous gel, an aqueous solution, or the like. It is preferable that the composition according to the present invention be in the form of an O/W emulsion. The composition according to the present invention may preferably opaque. Also, the composition according to the present invention may preferably be gelled, and therefore, it can exhibit very good stability when, for example, being stored.

The composition according to the present invention is a composition for cleansing keratinous substances and mucosae, and is preferably a cosmetic composition for cleansing skin and lips. It is preferable that the composition according to the present invention be used for cleansing human skin. The skin here encompasses facial skin, neck skin, and the scalp.

Hereafter, the composition according to the present invention will be described in a detailed manner.

(Surfactant system)

The composition according to the present invention contains a (a) surfactant system that gives the composition its foaming nature. The said surfactant system comprises (a-1) at least one N-(C6-C3o)acyl-amino acid based surfactant, and (a-2) at least one amphoteric surfactant chosen from betaines, (C₈-C₂o)alkyl betaines, (C₈-C₂o)alkylamido(C₁-C₆)alkylbetaines, and mixtures thereof, (a-3) at least one salt of a C₈-C₂₀ fatty acid, and (a-4) at least one

amphiphilic lipid material.

The surfactant system is present in the composition in an amount of less than 15% by weight. Preferably, the surfactant system is present in the composition in an amount of 12% by weight or less, and more preferably 10.5% by weight or less, relative to the total weight of the composition. The surfactant system is preferably present in the composition in an amount of 0.1 % by weight or more, more preferably 1 % by weight or more, even more preferably 2% by weight or more, and in particular 4% by weight or more, relative to the total weight of the composition.

According to a more particular embodiment, the surfactant system is present in the

composition in an amount ranging from 0.1 to 12% by weight, in particular from 2 to 10.5% by weight, and more particularly from 4 to 10.5% by weight relative to the total weight of the composition.

(a-1) N-(C₆-C₃₀)acyl-amino acid based surfactant

The surfactant system in the composition according to the present invention comprises (a-1) at least one N-(C₆-C₃₀)acyl amino acid based surfactant. Two or more (a-1) N-(C₆-C₃₀)acyl amino acid based surfactants may be used in combination. Thus, a single type of

N-(C₆-C₃₀)acyl amino acid based surfactant or a combination of different types of

N-(C₆-C₃o)acyl amino acid based surfactants may be used.

The N-(C₆-C₃o)acyl amino acid based surfactant that may be present in the composition according to the present invention may be chosen in particular from among N-(C₆-C₃₀)acyl amino acid based surfactants such as glycine derivatives (glycinates) like N-(C₆- C₃₀)acyl glycinate based surfactants.

The amino acid moiety of the N-(C₆-C₃o)acyl amino acid based surfactant may be, for example, chosen from glycine, alanine, leucine, isoleucine, valine, arginine, glutamic acid, and aspartic acid, and is preferably glycine.

The N-acyl moiety of the N-(C₆-C₃₀)acyl amino acid based surfactant may comprise from 6 to 30 carbon atoms, preferably from 8 to 22 carbon atoms, even more preferably from 8 to 18 carbon atoms. Preferably, the N-(C6-C₃₀)acyl amino acid based surfactant is a salt of N-(C₆-C₃₀)-acyl amino acid, preferably an alkali metal salt, and even more preferably a potassium or sodium salt.

Examples of the N-(C₆-C₃₀)acyl amino acid based surfactant according to the present invention include:

· (C₆-C₃o)acyl glycinates, preferably (C₈-C₂₂)acyl glycinates, and even more preferably (C₈-C₁₈)acyl glycinates, such as alkali salts of N-cocoyl glycinate, like the one sold under the name Amilite GCK 12H® by the company Ajinomoto,

• (C₆-C₃o)acyl alaninates, and preferably (C₁₂-C₂₈)acyl alaninates, such as sodium N-lauroyl N-methyl amidopropionate sold under the name Sodium Nikkol Alaninate LN30® by the company Nikkol, or sold under the name Alanone ALE® by the company Kawaken, and triethanolamine N-lauroyl N-methyl alanine sold under the name Alanone Alta® by the company Kawaken,

• (C₆-C₃₀)acyl glutamates, especially (C₆-C₂₄)- or even (C₁₂-C2o)acyl glutamates, such as triethanolamine monococoyl glutamate sold under the name Acylglutamate CT-32® by the company Ajinomoto, or triethanolamine lauroyl glutamate sold under the name

Acylglutamate LT-12® by the company Ajinomoto, or stearoylglutamates like disodium stearoyl glutamate;

• (C₆-C₃o)acyl aspartates, especially of (C₆-C₂₄)acyl aspartates, such as the mixture of triethanolamine N-lauroyl aspartate and of triethanolamine N-myristoyl aspartate, sold under the name Asparack® by the company Mitsubishi.

In a particular embodiment, the N-(C₆-C₃o)acyl amino acid based surfactant is chosen from alkali salts of N-cocoyl glycinate, especially among potassium N-cocoyl glycinate, sodium N-cocoyl glycinate, or a mixture thereof, preferably potassium N-cocoyl glycinate.

Sodium N-cocoyl glycinate which may be contained in the product sold under the name Amilite GCS-12 ® and potassium N-cocoyl glycinate which may be contained in the product sold under the name Amilite GCK 12H® by the company Ajinomoto, may in particular be implemented in the foaming composition according to the present invention.

The N-(C₆-C₃₀)acyl-amino acid based surfactant is present in the surfactant system in a major weight amount. For the purposes of the present invention, the term "major amount" means that the N-(C₆-C3o)acyl-amino acid based surfactant is present in the surfactant system in a greater amount than each of the other surfactants taken alone, present within said surfactant system, with respect to the total weight of the surfactant system.

In particular, the N-(C₆-C₃₀)acyl-amino acid based surfactant may be present it in an amount over 30% by weight, in particular over 35% by weight, and more particularly over 40% by weight, with respect to the total weight of the surfactant system.

The N-(C₆-C₃₀)acyl-amino acid based surfactant may be present in a content of 0.1 % by weight or more, preferably 1% by weight or more, and more preferably 2% by weight or more, relative to the total weight of the composition. The N-(C₆-C3o)acyl-amino acid based surfactant may be present in a content of 7% by weight or less, preferably 6% by weight or less, and more preferably 5% by weight or less, relative to the total weight of the composition.

The N-(C₆-C₃₀)acyl amino acid based surfactant may be present in the composition according to the present invention in an amount ranging from 0.1 to 7% by weight, in particular from 1 to 6% by weight, and more particularly from 2 to 5% by weight, with respect to the total weight of composition.

(a-2) Amphoteric surfactant

The surfactant system in the composition according to the present invention comprises (a-2) at least one amphoteric surfactant chosen from betaines, (C₈-C₂₀)alkyl betaines,

(C₈-C₂₀)alkylamido(C₁-C₆)alkylbetaines, and mixtures thereof. Two or more (a-2) amphoteric surfactants may be used in combination. Thus, a single type of amphoteric surfactant or a combination of different types of amphoteric surfactants may be used.

Mention may in particular be made, as betaines, of (C₈-C₂₀)alkyl betaines, such as, for example, coco betaine, such as the product sold under the name Dehyton AB-30® by the company Cognis, lauryl betaine, such as the product sold under the name Genagen KB® by the company Clariant, oxyethylenated (10 EO) lauryl betaine, such as the product sold under the name Lauryl Ether (10 EO) Betaine® by the company Shin Nihon Rica, or oxyethylenated (10 EO) stearyl betaine, such as the product sold under the name Stearyl Ether (10 EO) Betaine® by the company Shin Nihon Rica.

Mention may be made, among (C8-C₂o)alkylamido(C₁-C₆)alkylbetaines and derivatives thereof, for example, of cocamidopropyl betaine, sold under the name Lebon 2000 HG® by the company Sanyo or sold under the name Empigen BB® by the company Albright &

Wilson, or lauramidopropyl betaine, sold under the name Rewoteric AMB12P® by the company Witco.

Preferably, the amphoteric surfactant is chosen from (C₈-C₂₀)alkyl betaines,

(C₈-C2o)alkylamido(C₁-C₆)alkylbetaines, and mixtures thereof, and preferably among coco betaine, lauryl betaine, oxyethylenated (10 EO) lauryl betaine, oxyethylenated (10 EO) stearyl betaine, cocamidopropyl betaine and mixtures thereof, and more preferably is selected from lauryl betaine, coco betaine and mixtures thereof and still more preferably is coco betaine. The amphoteric surfactant may be present in a content of 0.1% by weight or more, preferably 0.5% by weight or more, and more preferably 1% by weight or more, relative to the total weight of the composition. The amphoteric surfactant may be present in a content of 6% by weight or less, preferably 5% by weight or less, and more preferably 4% by weight or less, relative to the total weight of the composition.

The amphoteric surfactant may be present in the composition according to the present invention in an amount ranging from 0.1 to 6% by weight, in particular from 0.5 to 5% by weight, and more particularly from 1 to 4% by weight, with respect to the total weight of the composition.

According to a particular embodiment, the weight ratio between the amphoteric surfactant and N-(C₆-C₃o)acyl amino acid based surfactant ranges from 1 :1 to 1 :5 and preferably between 2:3 to 1 :3. (a-3) Salt of C₈-C₂₀ fatty acid

The surfactant system in the composition according to the present invention comprises (a-3) at least one salt of a C₈-C₂₀ fatty acid (soap). Two or more (a-2) salts of C₈-C₂₀ fatty acids may be used in combination. Thus, a single type of salt of a C₈-C₂o fatty acid or a

combination of different types of salts of C₈-C₂o fatty acids may be used.

Generally the salt of the Cs-C₂o fatty acid used is an alkali metal salt and/or a combination of metal and a salt of an organic base of a fatty acid with a carbon chain ranging from C₈ to C₂o, more preferably from C₁₂ to C₁₈, and most preferably from C₁₂ to C₁₄.

The fatty acid can in particular be selected from among caproic acid, capric acid, caprylic acid, oleic acid, linoleic acid, lauric acid, myristic acid, stearic acid, palmitic acid, and mixtures thereof. More particularly, the fatty acid which is suitable for the present invention is present in the form of a mixture of fatty acids and is contained in coconut oil, also known as coprah oil or copra oil.

The alkali metals that may be used for the soap include sodium, potassium, lithium and their mixtures. Preferably, the alkali metal is potassium.

In a preferred embodiment, the alkali metal salt of the C₈-C₂₀ fatty acid is potassium cocoate, also known as potassium coco soap that originates from the fatty acids present in coconut oil as mentioned above. For example, potassium cocoate may be present in an admixture with potassium N-cocoyl glycinate (N-(C₆-C₃₀)acyl amino acid based surfactant) like in the product sold under the name Amilite GCK-12H® by the company Ajinomoto as explained above and as shown in the examples of the present invention.

The metal salt of the C₈-C₂o fatty acid that may be used include a zinc laurate, magnesium stearate, magnesium myristate, zinc stearate and their mixtures.

The metal of the metal salt of the C₈-C₂o fatty acid can in particular be zinc or magnesium. The neutralization rate of the fatty acid may range from 70 to 90%, most preferably in the range from 80 to 85%.

Non-limiting examples of alkalis from metal/nonmetal/organic source which may be used for saponification of fatty acids are hydroxides, such as alkali metal hydroxides, for example sodium hydroxide or potassium hydroxide or such as alkaline-earth metal hydroxides, for example magnesium hydroxide, or even such as ammonium hydroxide, silicates of potassium, sodium, calcium, or organic bases such as ethanolamines, for example triethanolamine,

N-methylglucosamine, amino propanol and their derivatives, lysine, arginine and their salts such as guanadine salts.

The salt of the C₈-C₂₀ fatty acid may be present in a content of 0.1 % by weight or more, preferably 0.5% by weight or more, and more preferably 1% by weight or more, relative to the total weight of the composition. The salt of the C₈-C₂₀ fatty acid may be present in a content of 6% by weight or less, preferably 5% by weight or less, and more preferably 4% by weight or less, relative to the total weight of the composition. The salt of the C₈-C₂o fatty acid may be present in the composition according to the present invention in an amount ranging from 0.1 to 6% by weight, in particular from 0.5 to 5% by weight, and more particularly from 1 to 4% by weight, with respect to the total weight of the composition. According to a particular embodiment, the weight ratio between the salt of C₈-C₂o fatty acid and the N-(C₆-C3₀)acyl amino acid based surfactant ranges from 1 : 1 and 1 :5, in particular from 2:3 to 2:5.

(a-4) Amphiphilic lipid material

The surfactant system in the composition according to the present invention comprises (a-4) at least one amphiphilic lipid material. Two or more (a-4) amphiphilic lipid materials may be used in combination. Thus, a single type of amphiphilic lipid material or a combination of different types of amphiphilic lipid materials may be used. The amphiphilic lipid material used can be preferably selected from phospholipids. These phospholipids are preferably selected from phosphoacylglycerol, more preferably selected from lecithins. Lecithin according to the present invention may be from soya, sunflower, egg and mixtures thereof. In a particular embodiment, the lecithin is from soya, like the one sold under the name EMULMETIK 100 J by the company CARGILL.

The amphiphilic lipid material may be present in a content of 0.01% by weight or more, preferably 0.05% by weight or more, and more preferably 0.1% by weight or more, relative to the total weight of the composition. The amphiphilic lipid material may be present in a content of 5% by weight or less, preferably 3% by weight or less, and more preferably 1% by weight or less, relative to the total weight of the composition. The amphiphilic lipid material may be present in the composition according to the present invention in an amount ranging from 0.01 to 5% by weight, in particular from 0.05 to 3% by weight, and more particularly from 0.1 to 1% by weight, with respect to the total weight of the composition. According to a particular embodiment, the weight ratio between the amphiphilic lipid material and the N-(C6-C₃₀)acyl amino acid based surfactant ranges from 1 :2 and 1 : 15, in particular from 1 :4 to 1 : 10.

(Non-associative crosslinked copolymer of (meth)acrylic acid, and of (0-C₄)alkyl ester of (meth)acrylic acid)

The composition according to the present invention comprises (b) at least one non-associative crosslinked copolymer of (meth)acrylic acid and of (d-C₄)alkyl ester thereof. Two or more of the (b) non-associative crosslinked copolymer may be used in combination. Thus, a single type of non-associative crosslinked copolymer or a combination of different types of non-associative crosslinked copolymer may be used.

For the purpose of the present invention, the term "non-associative polymer" means that the polymer does not have the behavior of an associative polymer, i.e. a hydrophilic polymer, more particularly comprising at least one hydrophilic region and at least one hydrophobic region; that is capable, in an aqueous medium, of reversibly associating with each other or with other molecules.

According to a particular embodiment, said non-associative crosslinked copolymers are able to form a microgel.

According to the present invention, a microgel is a gel wherein at least 90%, preferably 95%, more preferably all of the gel is in the form of particles. According to one embodiment, the non-associative crosslinked copolymer disclosed herein may be in the form of a dispersion in water. The number-average size of the copolymer particles in the dispersion generally ranges from 10 to 500 nm, for example, from 20 to 200 nm and further, for example, from 50 to 150 nm. The non-associative crosslinked copolymers of (meth)acrylic acid and of (C!-C₄)alkyl esters thereof, act as a thickening polymer and also contribute to the ability of the composition to deposit the (d) triglyceride oil explained below and additional ingredients when present, as for example fillers, even after rinsing-off thereof. The non-associative crosslinked copolymers disclosed herein are partially or totally crosslinked with at least one standard crosslinking agent. The at least one crosslinking agent can be chosen, for example, from polyunsaturated compounds, such as polyehylenically unsaturated compounds. For example, these compounds can be chosen from polyalkenyl ethers of sucrose, polyalkenyl ethers of polyols, diallyl phthalates, divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, methylenebisacrylamide trimethylolpropane tri(meth)acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, zinc (meth)acrylate, castor oil derivatives and polyol derivatives manufactured from unsaturated carboxylic acids.

For the purpose of the present invention, the non-associative crosslinked copolymer of (meth)acrylic acid means that the copolymer comprises at least one acrylic acid unit or one methacrylic acid unit or a mixture thereof. The copolymer may comprise further units such as units formed by an alkyl ester of acrylic acid or methacrylic acid, preferably of acrylic acid, comprising less than 6 carbon atoms: i.e. a d-C₄ alkylacrylate for example, chosen from methyl acrylate, ethyl acrylate and butyl acrylate, called hereinafter "simple ester".

According to a particular embodiment, the non-associative crosslinked copolymer according to the present invention comprises at least one acrylic acid unit. According to a further embodiment, the non-associative crosslinked copolymer according to the present invention comprises at least one methacrylic acid unit. According to another embodiment, the non-associative crosslinked copolymer according to the present invention comprises at least an acrylic acid unit and a methacrylic acid unit.

In a particular embodiment, the non-associative crosslinked copolymer may comprise another monomer that is different from (meth)acrylic acid and from (d-C₄)alkyl ester thereof. For example, such monomer may be vinyl ester monomer. Preferably, the vinyl ester monomer can be carboxylic acid vinyl ester monomer. The carboxylic acid moiety of the carboxylic acid vinyl ester monomer may be linear or branched, preferably branched, saturated or unsaturated, preferably saturated, (C₄-C₃o)carboxylic acid, and in particular (C₆-C₁₄) carboxylic acid.

We can mention the non-associative crosslinked copolymer of vinyl neodecanoate and one or more monomers of acrylic acid, methacrylic acid, and one of their C₁-C₄ esters crosslinked with an allyl ether of trimethylolpropane or pentaerythritol such as the product sold under the commercial name ACULYN 38 ® (INCI name: ACRYLATES/VTNYL NEODECANOATE CROSSPOLYMER) sold by THE DOW CHEMICAL COMPANY.

As other examples of such non-associative crosslinked copolymers of acrylic acid and/or methacrylic acid, mention can be made of the non-associative crosslinked copolymers of acrylic acid and/or methacrylic acid and Ci-C₄ alkyl esters thereof.

As examples of such non-associative crosslinked copolymers of acrylic acid and/or methacrylic acid and (d-C₄) alkyl esters thereof, can be mentioned:

i) The crosslinked copolymers of acrylic acid and/or methacrylic acid and of an ester thereof comprising less than 6 carbon atoms, preferably a d-C₄ alkyl ester, and such as the copolymer sold under the commercial name ACULYN 33® by the company THE DOW CHEMICAL COMPANY and having the INCI name: ACRYLATES COPOLYMER.

ii) The crosslinked copolymers comprising at least one methacrylic acid unit and at least one C1-C4 alkyl acrylate unit. These copolymers are described, for example, in Patent Application No. WO 01/76552.

As used herein, the crosslinked copolymer comprising at least one methacrylic acid unit and at least one C1-C4 alkyl acrylate unit means a crosslinked copolymer comprising at least one methacrylic acid unit and at least one alkyl acrylate unit, wherein the alkyl acrylate unit is chosen from C1-C4 alkyl acrylates.

In the crosslinked copolymers disclosed herein, the methacrylic acid unit can be present, for example, in an amount ranging from 20% to 80% by weight, such as from 25% to 70% by weight, and further such as from 35% to 60% by weight, relative to the total weight of the copolymer.

In the crosslinked copolymer disclosed herein, the (Ci-C₄)alkyl acrylate unit can be present, for example, in an amount ranging from 15% to 80% by weight, such as from 25% to 75% by weight and further such as from 40% to 65% by weight, relative to the total weight of the copolymer. The (C₁-C₄)alkyl acrylate unit can be chosen, for example, from methyl acrylate, ethyl acrylate and butyl acrylate. In one embodiment, the (C₁-C₄)alkyl acrylate unit is ethyl acrylate.

Use can be made, for example, of the crosslinked copolymers comprising at least one methacrylic acid unit and at least one ethyl acrylate unit like the one sold under the name CARBOPOL AQUA SF- 1 ® by the company NOVEON (INCI name: acrylates copolymer).

Thus, in a preferred embodiment, the non-associative crosslinked copolymer of acrylic acid and/or methacrylic acid, and (C₁-C₄)alkyl esters thereof, is selected from:

- a crosslinked copolymer of acrylic acid and/or methacrylic acid and of an ester thereof comprising less than 6 carbon atoms, preferably a Ci-C₄ alkyl ester thereof,

- a crosslinked copolymer comprising at least one methacrylic unit and at least one d-C₄ alkyl acrylate unit, for example a ethyl acrylate unit,

- a crosslinked copolymer of vinyl neodecanoate and one or more monomers of acrylic acid, methacrylic acid or one of their (Ci-C₄) alkyl esters crosslinked with an allyl ether of trimethylolpropane or pentaerythritol, and

- mixtures thereof.

The (b) non-associative crosslinked copolymer is included in the composition according to the present invention in an active material content greater than or equal to 1% by weight, in particular greater than or equal to 1.5% by weight, more particularly greater than or equal to 2% by weight relative to the total weight of the composition. The (b) non-associative crosslinked copolymers is included in the composition according to the present invention in an active material content less than or equal to 10% by weight, in particular less than or equal to 8% by weight, more particularly less than or equal to 6% by weight, even more particularly less than or equal to 4% by weight, relative to the total weight of the composition.

For example, the (b) non-associative crosslinked copolymers may be present in the

composition according to the present invention in a content ranging from 1% to 10% by weight, from 1.5% to 10%) by weight, from 2% to 8% by weight, or from 2% to 4% by weight relative to the total weight of the composition. (Associative copolymers of (meth)acrylic acid, and of (d-C^alkyl ester of (meth)acrylic acid) The composition according to the present invention includes (c) at least one associative copolymer of (meth)acrylic acid, and of (C₁-C₆)alkyl ester thereof. Two or more the (c) associative copolymer may be used in combination. Thus, a single type of the (c)

associative copolymer or a combination of different types of the (c) associative copolymer may be used.

For the purpose of the present invention, the term "associative polymer" or "associative copolymer" refers to polymers or copolymers that are capable, in an aqueous medium, of reversibly combining with each other or with other molecules. The associative copolymer more particularly comprises at least one hydrophilic part and at least one hydrophobic part. For the purpose of the present invention, the term "hydrophobic group" means a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 16 to 30 carbon atoms.

The associative copolymers disclosed herein can be partially or totally crosslinked with at least one standard crosslinking agent. The at least one crosslinking agent can be chosen, for example, from polyunsaturated compounds, such as polyethylenically unsaturated compounds. For example, these compounds can be chosen from polyalkenyl ethers of sucrose, polyalkenyl ethers of polyols, diallyl phthalates, divinylbenzene, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, methylenebisacrylamide trimethylolpropane tri(meth)acrylate, diallyl itaconate, diallyl fumarate, diallyl maleate, zinc (meth)acrylate, castor oil derivatives and polyol derivatives manufactured from unsaturated carboxylic acids.

For the purpose of the present invention, the associative copolymer of (meth)acrylic acid means that the copolymer comprises at least one acrylic acid unit or one methacrylic acid unit or a mixture thereof. The associative copolymer may comprise further units such as units formed by an alkyl ester of acrylic acid or methacrylic acid, preferably of acrylic acid, comprising less than 6 carbon atoms: for example, a C₁-C₄ alkylacrylate, for example, chosen from methyl acrylate, ethyl acrylate and butyl acrylate, called hereinafter "simple ester".

According to a particular embodiment, the associative copolymer according to the present invention comprises at least one acrylic acid unit. According to a further embodiment, the associative copolymer according to the present invention comprises at least one methacrylic acid unit. According to another embodiment, the associative copolymer according to the present invention comprises at least an acrylic acid unit and a methacrylic acid unit.

In a particular embodiment, the associative copolymer may comprise another monomer that is different from (mefh)acrylic acid and from (d-C^alkyl ester thereof. For example, such monomer may be esters of ethylenically unsaturated hydrophilic monomers, such as

(meth)acrylic acid or itaconic acid, and of polyoxyalkylenated fatty alcohols. Preferably, the fatty alcohol moiety of the ester monomer can be linear or branched, preferably linear, saturated or unsaturated, preferably saturated, (Ci₂-C₃o)fatty alcohol, and in particular

(C₁₆-C₂₆) fatty alcohol. The polyoxyalkylene chain of the ester monomer preferentially consists of ethylene oxide units and/or propylene oxide units and even more particularly consists of ethylene oxide units. The number of oxyalkylene units generally ranges from 3 to 100, preferably from 7 to 50 and more preferably from 12 to 30. We can mention the associative copolymer of the product sold under the commercial name: NOVETHIX L-10 POLYMER® (INCI name: ACRYLATES/BEHENETH-25

METHACRYLATE COPOLYMER) sold by LUBRIZOL, the product sold under the commercial name: Aculyn® 22 (INCI name: ACRYLATES/STEARETH-20

METHACRYLATE COPOLYMER) sold by DOW CHEMICAL, the product sold under the commercial name: Aculyn® 88 (INCI name: ACRYLATES/STEARETH-20

METHACRYLATE CROSSPOLYMER) sold by DOW CHEMICAL, the product sold under the commercial name: STRUCTURE® 2001 (INCI name: ACRYLATES/STEARETH-20 ITACONATE COPOLYMER) sold by AKZO NOBEL, and the product sold under the commercial name: STRUCTURE® 3001 (INCI name: ACRYLATES/CETETH-20

ITACONATE COPOLYMER ) sold by AKZO NOBEL

The (c) associative copolymer that can be used according to the present invention may also be chosen from anionic associative copolymers containing acrylic and/or methacrylic units. The (meth)acrylic anionic associative copolymer that may be used according to the present invention may be chosen from those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and at least one hydrophobic unit of the type such as a

(Cio-C3o)alkyl ester of an unsaturated carboxylic acid.

More particularly, these (meth)acrylic associative copolymers are preferably chosen from those in which the hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the monomer of formula (I) below:

ΌΗ

R ' O in which R¹ denotes H or CH₃, i.e. acrylic acid or methacrylic acid units, and in which the hydrophobic unit of (C₁₀-C₃₀)alkyl ester of unsaturated carboxylic acid type corresponds to the monomer of formula (II) below:

in which R¹ denotes H or CH₃ (i.e. acrylate or methacrylate units), R² denoting a C₁₀-C3o and preferably C₁₂-C₂₂ alkyl radical. As (C₁₀-C₃₀)alkyl esters of unsaturated carboxylic acids according to formula (II), mention may be made more particularly of lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate. (Meth)acrylic associative copolymers of this type are described and prepared, for example, according to patents US 3 915 921 and US 4.509 949. The (meth)acrylic associative copolymer that may be used according to the present invention may more particularly denote polymers formed from a mixture of monomers comprising:

(i) acrylic acid and one or more esters of formula (III) below:

in which R³ denotes H or CH₃, R⁴ denoting an alkyl radical having from 12 to 22 carbon atoms, and optionally a crosslinking agent, for instance those consisting of from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit), and 0 to 6% by weight of crosslinking polymerizable monomer, or 98% to 96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0.1% to 0.6%> by weight of crosslinking polymerizable monomer; or

(ii) essentially acrylic acid and lauryl methacrylate, such as the product formed from

66% by weight of acrylic acid and 34% by weight of lauryl methacrylate.

For these embodiments of the present invention, the term "crosslinking agent" can mean a monomer containing the group

^{C H}2 = ^C\

and at least one other polymerizable group, the unsaturated bonds of the monomer being unconjugated relative to each other. As the crosslinking agent that may be used according to the present invention, mention may be made especially of polyallyl ethers especially such as polyallyl sucrose and polyallylpentaerythritol.

Among the said (meth)acrylic associative copolymers above, the ones particularly preferred according to the present invention are the products sold by the company Goodrich under the trade names Pemulen TR1, Pemulen TR2, Carbopol 1382, and more preferably still Pemulen TR1, and the product sold by the company S.E.P.C. under the name Coatex SX.

As the (meth)acrylic associative copolymer, mention may also be made of the copolymer of methacrylic acid/methyl acrylate/dimethyl-meta-isopropenylbenzyl isocyanate of ethoxylated alcohol sold under the name Viscophobe DB 1000 by the company Amerchol. Other (meth)acrylic associative copolymers that may be used according to the present invention may also be sulfonic polymers comprising at least one (meth)acrylic monomer bearing sulfonic group(s), in free form or partially or totally neutralized form and comprising at least one hydrophobic portion. The said hydrophobic portion present in the said sulfonic polymers that may be used according to the present invention preferably comprises from 8 to 22 carbon atoms, more preferably from 8 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms.

Preferentially, these sulfonic polymers that may be used according to the present invention are partially or totally neutralized with a mineral base (sodium hydroxide, potassium hydroxide or aqueous ammonia) or an organic base such as mono-, di- or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids, for instance arginine and lysine, and mixtures of these compounds.

These said sulfonic polymers generally have a number-average molecular weight ranging from 1000 to 20 000 000 g/mol, preferably ranging from 20 000 to 5 000 000 g/mol and even more preferably from 100 000 to 1 500 000 g/mol.

The sulfonic polymers that may be used according to the present invention may or may not be crosslinked. Crosslinked polymers are preferably chosen.

When they are crosslinked, the crosslinking agents may be selected from polyolefinically unsaturated compounds commonly used for the crosslinking of polymers obtained by free-radical polymerization. Mention may be made, for example, of divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol diacrylatedi(meth)acrylate or tetraethylene glycol diacrylatedi(meth)acrylate, trimethylolpropane triacrylate, methylenebisacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate,

tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl

(meth)acrylate, allyl ethers of alcohols of the sugar series, or other allyl or vinyl ethers of polyfunctional alcohols, and also allyl esters of phosphoric and/or vinylphosphonic acid derivatives, or mixtures of these compounds.

Methylenebisacrylamide, allyl methacrylate or trimethylolpropane triacrylate (TMPTA) will be used more particularly.

The degree of crosslinking will generally range from 0.01 mol% to 10 mol% and more particularly from 0.2 mol% to 2 mol% relative to the polymer.

The (meth)acrylic monomers bearing sulfonic group(s) of the sulfonic polymers that may be used according to the present invention are chosen especially from

(meth)acrylamidb(Ci-C₂₂)alkylsulfonic acids and

N-(Ci-C₂2)alkyl(meth)acrylamido(Ci-C22)alkylsulfonic acids, for instance

undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.

(Meth)acrylamido(C₁-C22)alkylsulfonic acids, for instance acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid,

2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, will more preferentially be used.

2-Acrylamido-2-methylpropanesulfonic acid (AMPS), and also partially or totally neutralized forms thereof, will even more particularly be used. The (meth)acrylic associative thickeners that may be used according to the present invention may be chosen especially from random amphiphilic AMPS polymers modified by reaction with a C₆-C22 n-monoalkylamine or C₆-C₂2 di-n-alkylamine, and such as those described in patent application WO 00/31154 (which forms an integral part of the content of the description). These polymers may also contain other ethylenically unsaturated hydrophilic monomers selected, for example, from (meth)acrylic acids, β-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols,

(meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.

The (meth)acrylic associative thickeners bearing sulfonic group(s) that may particularly preferably be used according to the present invention are preferably chosen from amphiphilic copolymers of AMPS and of at least one ethylenically unsaturated hydrophobic monomer comprising at least one hydrophobic portion containing from 8 to 50 carbon atoms, more preferably from 8 to 22 carbon atoms, more preferably still from 8 to 18 carbon atoms and more particularly 12 to 18 carbon atoms.

These same copolymers may also contain one or more ethylenically unsaturated monomers not comprising a fatty chain, such as (meth)acrylic acids, β-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds. These copolymers are described especially in patent application EP-A-750 899, patent US 5 089 578 and in the following Yotaro Morishima publications:

- Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese Journal of Polymer Science, Vol. 18, No. 40, (2000), 323-336;

- Micelle formation of random copolymers of sodium

2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering, Macromolecules, 2000, Vol. 33, No. 10 - 3694-3704;

- Solution properties of micelle networks formed by nonionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior - Langmuir, 2000, Vol. 16, No. 12, 5324-5332;

- Stimuli responsive amphiphilic copolymers of sodium

2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers, Polym. Preprint, Div. Polym. Chem. 1999, 40(2), 220-221. The ethylenically unsaturated hydrophobic monomers of these particular copolymers are preferably selected from the acrylates or acrylamides of formula (IV) below:

in which R and R , which may be identical or different, denote a hydrogen atom or a linear branched Ci-C₆ alkyl radical (preferably methyl); Y denotes O or NH; R⁶ denotes a hydrophobic hydrocarbon-based radical containing at least 8 to 50 carbon atoms, more preferentially from 8 to 22 carbon atoms, even more preferentially from 6 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms; x denotes the number of moles of alkylene oxide and ranges from 0 to 100. The radical R⁶ is preferably chosen from linear C₆-C₁₈ alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), or branched or cyclic C₆-C₁₈ alkyl radicals (for example cyclododecane (C12) or adamantane (C₁₀)); C₆-C₁₈ perfluoroalkyl radicals (for example the group of formula -(CH₂)2-(CF₂)9-CF₃); the cholesteryl radical (C27) or a cholesterol ester residue, for instance the cholesteryl oxyhexanoate group; aromatic polycyclic groups such as naphthalene or pyrene. Among these radicals, the ones that are more particularly preferred are linear alkyl radicals and more particularly the n-dodecyl radical.

According to a particularly preferred form of the present invention, the monomer of formula (IV) comprises at least one alkylene oxide unit (x > 1) and preferably a polyoxyalkylene chain. The polyoxyalkylene chain preferentially consists of ethylene oxide units and/or propylene oxide units and even more particularly consists of ethylene oxide units. The number of oxyalkylene units generally ranges from 3 to 100, more preferably from 3 to 50 and more preferably still from 7 to 25. Among these polymers, mention may be made of:

- copolymers, which may or may not be crosslinked and which may or may not be neutralized, comprising from 15% to 60% by weight of AMPS units and from 40% to 85% by weight of (C₈-Ci₆)alkyl(meth)acrylamide units or of (C₈-Ci₆)alkyl (meth)acrylate units, relative to the polymer, such as those described in patent application EP-A-750 899;

- terpolymers comprising from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of n-(C6-C₁₈)alkylacrylamide units, such as those described in patent US-5 089 578.

Mention may also be made of copolymers of totally neutralized AMPS and of dodecyl methacrylate, and also crosslinked and non-crosslinked copolymers of AMPS and of n-dodecylmethacrylamide, such as those described in the Morishima articles mentioned above.

Mention will be made of the copolymers constituted of

2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of formula (V) below:

in which X⁺ is a proton, an alkali metal cation, an alkaline-earth metal cation

ammonium ion;

and units of formula (VI) below: — CH₂ c

O= C

in which x denotes an integer ranging from 3 to 100, preferably from 5 to 80 and more preferentially from 7 to 25; R⁵ has the same meaning as that indicated above in formula (IV) and R⁸ denotes a linear or branched C₆-C₂₂ and more preferentially C₁₀-C₂₂ alkyl.

The polymers that are preferred are those for which x = 25, R⁵ denotes methyl and R⁸ represents n-dodecyl; they are described in the Morishima articles mentioned above. Furthermore, in formula (IV), the use of the monomers where x = 20 to 25, R⁵ denotes methyl and R⁸ represents Ci₂-C₂₄ alkyl group, preferably, for example, a lauryl group, myristyl group, palmityl group, stearyl group, or behenyl group is particularly preferred. Especially, the use of the monomers of the formula (IV), wherein x = 20 to 25, R⁵ denotes methyl and R⁸ represents Ci6-C₂₄ alkyl chain, such as stearyl group, or behenyl group is particularly preferred.

The polymers for which X⁺ denotes sodium or ammonium are more particularly preferred.

The (c) associative copolymers of (meth)acrylic acid and of alkyl ester thereof are included in the composition according to the present invention in an active material content greater than or equal to 0.01% by weight, in particular greater than or equal to 0.05% by weight, more particularly greater than or equal to 0.1 % by weight relative to the total weight of the composition. The (c) associative copolymers is included in the composition according to the present invention in an active material content less than or equal to 7% by weight, in particular less than or equal to 5% by weight, more particularly less than or equal to 3% by weight relative to the total weight of the composition.

For example, the (c) associative copolymers may be present in the composition according to the present invention in a content ranging from 0.01% to 7% by weight, preferably from 0.05%) to 5% by weight, and more preferably from 0.1%> to 3% by weight, relative to the total weight of the composition.

(Triglyceride Oil) The composition according to the present invention comprises (c) at least one triglyceride oil. Two or more the (c) triglyceride oils may be used in combination. Thus, a single type of triglyceride oil or a combination of different types of triglyceride oils may be used.

The presence of said triglyceride oil may be to provide a moisturizing effect or emollient effect after washing the keratinous substance, in particular skin.

The triglyceride oil which is suitable for the present invention is preferably of plant origin. The triglyceride oil is selected from an oil, a butter, and mixtures thereof.

Among the oil, the following may be cited: jojoba oil, babassu oil, sunflower oil, olive oil, canola oil, coconut oil, meadowfoam seed oil; Brazil nut oil, marula oil, maize oil, argan oil, soybean oil, marrow oil, grapeseed oil, linseed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, coriander oil, castor oil, avocado oil, shea butter oil, rapeseed oil and copra oil. Among the butters, the following may be cited: shea butter, Nilotica shea butter

(Butyrospermum parkii), galam butter (Butyrospermum parkii), Borneo butter or fat or tengkawang tallow (Shorea stenoptera), shorea butter, illipe butter, madhuca butter or (Bassia) Madhuca longifolia butter, mowrah butter (Madhuca latifolia), katiau butter (Madhuca mottleyana), phulwara butter (M. butyracea), mango butter (Mangifera indica), murumuru butter (Astrocaryum murumuru), kokum butter (Garcinia indica), ucuuba butter (Virola sebifera), tucuma butter, painya (kpangnan) butter (Pentadesma butyracea), coffee butter (Coffea arabica), apricot butter (Prunus armeniaca), macadamia butter (Macadamia ternifolia), grapeseed butter (Vitis vinifera), avocado butter (Persea gratissima), olive butter (Olea europaea), sweet almond butter (Prunus amygdalus dulcis), cocoa butter (Theobroma cacao) and sunflower butter.

More preferably, the triglyceride oil is selected from shea butter, olive oil, meadowfoam seed oil and canola oil, and still more preferably is shea butter. The triglyceride oil may be present in a content of 0.1% by weight or more, preferably 1% by weight or more, and more preferably 2% by weight or more, relative to the total weight of the composition. The triglyceride oil may be present in a content of 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less, relative to the total weight of the composition.

The triglyceride oil may be present in the composition according to the present invention in an amount ranging from 0.1 to 20% by weight, in particular from 1 to 15% by weight, and more particularly from 2 to 10% by weight, with respect to the total weight of the

composition.

(Other Ingredients) • Additional surfactant The composition according to the present invention may comprise additional surfactants, which may be selected from anionic, amphoteric (or zwitterionic), nonionic and/or cationic foaming surfactants, and non-foaming surfactants, and mixtures thereof, and that are different from the surfactants in the (a) surfactant system as described above. (i) Anionic foaming surfactants

The composition according to the present invention may also comprise one or more foaming anionic surfactants. Foaming surfactants are detergents and differ from surfactants used as emulsifiers in the value of their HLB (Hydrophilic-Lipophilic Balance), the HLB being the ratio of the hydrophilic part to the lipophilic part in the molecule. The term "HLB" is well known to those skilled in the art and is described, for example, in "The HLB system. A time-saving guide to Emulsifier Selection" (published by ICI Americas Inc., 1984). For emulsifiers, the HLB generally ranges from 3 to 8 for the preparation of W/O emulsions and from 8 to 18 for the preparation of O/W emulsions, whereas foaming surfactants generally have an HLB of greater than 20.

The term "anionic surfactant" means a surfactant comprising, as ionic or ionizable groups, only anionic groups.

In the present description, a species is termed as being "anionic" when it bears at least one permanent negative charge or when it can be ionized as a negatively charged species, under the conditions of use of the composition of the present invention (for example the medium or the pH) and not comprising any cationic charge.

The anionic surfactants may be sulfate, sulfonate and/or carboxylic (or carbox-ylate) surfactants. Needless to say, a mixture of these surfactants may be used.

It is understood in the present description that:

- carboxylate anionic surfactants comprise at least one carboxylic or carboxylate function (-COOH or -COO^") and may optionally also comprise one or more sulfate and/or sulfonate functions;

- the sulfonate anionic surfactants comprise at least one sulfonate function (-SO3H or -SO3^") and may optionally also comprise one or more sulfate functions, but do not comprise any carboxylate functions; and

- the sulfate anionic surfactants comprise at least one sulfate function but do not comprise any carboxylate or sulfonate functions.

The anionic surfactants that may be present in the composition according to the present invention may be chosen in particular from anionic derivatives of proteins of plant origin or of silk proteins, phosphates and (C₆-C₃o)alkyl phosphates, carboxylates, sulfosuccinates, (C₆-C₃o) acyl or alkyl acids, sulfates, sulfonates, isethionates, taurates, (C₆-C₃₀)alkyl sulfoacetates, polypeptides, anionic derivatives of (C₆-C₃₀)alkyl polyglucoside, and mixtures thereof. a) Anionic derivatives of proteins of plant origin are protein hydrolysates containing a hydrophobic group, it being possible for the said hydrophobic group to be naturally present in the protein or to be added by reaction of the protein and/or of the protein hydrolysate with a hydrophobic compound. The proteins are of plant origin or are derived from silk, and the hydrophobic group may in particular be a fatty chain, for example an alkyl chain comprising from 10 to 22 carbon atoms. As anionic derivatives of proteins of plant origin, mention may more particularly be made of apple, wheat, soybean or oat protein hydrolysates comprising an alkyl chain having from 10 to 22 carbon atoms, and salts thereof. The alkyl chain may especially be a lauryl chain and the salt may be a sodium, potassium and/or ammonium salt.

Thus, as protein hydrolysates comprising a hydrophobic group, mention may be made, for example, of salts of protein hydrolysates where the protein is a silk protein modified by lauric acid, such as the product sold under the name Kawa Silk by Kawaken; salts of protein hydrolysates where the protein is a wheat protein modified by lauric acid, such as the potassium salt sold under the name Aminofoam W OR by the company Croda (CTFA name: potassium lauroyl wheat amino acids) and the sodium salt sold under the name Proteol LW 30 by the company SEPPIC (CTFA name: sodium lauroyl wheat amino acids); salts of protein hydrolysates where the protein is an oat protein comprising an alkyl chain having from 10 to 22 carbon atoms and more especially salts of protein hydrolysates where the protein is an oat protein modified by lauric acid, such as the sodium salt sold under the name Proteol OAT (30% aqueous solution) by the company SEPPIC (CTFA name: sodium lauroyl oat amino acids); or salts of apple protein hydrolysates comprising an alkyl chain having from 10 to 22 carbon atoms, such as the sodium salt sold under the name Proteol APL (30% aqueous glycol solution) by the company SEPPIC (CTFA name: sodium cocoyl apple amino acids).

Mention may also be made of the mixture of lauroyl amino acids (aspartic acid, glutamic acid, glycine, alanine) neutralized with sodium N-methylglycinate sold under the name Proteol SAV 50 S by the company SEPPIC (CTFA name: sodium cocoyl amino acids). b) Examples of phosphates and (C₆-C₃o)alkyl phosphates that may be mentioned include mono(C₆-C₃₀)alkyl phosphates and di(C₆-C₃o)alkyl phosphates, such as the lauryl

monophosphate sold under the name MAP 20® by the company Kao Chemicals, the potassium salt of dodecylphosphoric acid, the mixture of monoester and diester

(predominantly diester) sold under the name Crafol AP-31 ® by the company Cognis, the mixture of octylphosphoric acid monoester and diester sold under the name Crafol AP-20® by the company Cognis, the mixture of ethoxylated (7 mol of EO) phosphoric acid monoester and diester of 2-butyloctanol, sold under the name Isofol 12 7 EO-Phosphate Ester® by the company Condea, the potassium or triethanolamine salt of mono(C₁₂-C₁₃)alkyl phosphate sold under the references Arlatone MAP 230K-40® and Arlatone MAP 230T-60® by the company Uniqema, the potassium lauryl phosphate sold under the name Dermalcare MAP XC-99/09® by the company Rhodia Chimie, and the potassium cetyl phosphate sold under the name Arlatone MAP 160 by the company Uniqema. c) As carboxylates, mention may be made of:

• (C₆-C₂₄)alkyl ether carboxylates, preferably (C₁2-C2o)alkyl ether carboxylates;

· (C₆-C₂4)alkyl(amido) ether carboxylates (AEC), in particular those comprising from

2 to 50 alkylene oxide and in particular ethylene oxide groups, such as the compounds sold by the company Kao under the name Akypo, such as sodium lauryl amido ether carboxylate (3 EO), sold under the name Akypo Foam 30® by the company Kao Chemicals;

• The polyoxyalkylenated alkyl(amido) ether carboxylic acids that may be used are preferably chosen from those of formula (1):

Ri-(OC₂H4)n-OCH2COOA (1)

in which:

- Pvi represents a linear or branched C₆-C₂₄ alkyl or alkenyl radical, an

alkyl(C₈-C9)phenyl radical, a radical R₂CONH-CH₂-CH₂- with R₂ denoting a linear or branched C9-C21 alkyl or alkenyl radical. Preferably, Ri is a C8-C₂₀ and preferably C₈-Ci₈ alkyl radical, and aryl preferably denotes phenyl,

- n is an integer or decimal number (average value) ranging from 2 to 24 and preferably from 2 to 10,

- A denotes H, ammonium, Na, K, Li, Mg or a monoethanolamine or triethanolamine residue.

It is also possible to use mixtures of compounds of formula (1), in particular mixtures of compounds containing different groups Ri . The polyoxyalkylenated alkyl(amido) ether carboxylic acids that are particularly preferred are those of formula (1) in which:

- i denotes a Ci₂-Ci₄ alkyl, cocoyl, oleyl, nonylphenyl or octylphenyl radical,

- A denotes a hydrogen or sodium atom, and

- n varies from 2 to 20 and preferably from 2 to 10.

Even more preferentially, use is made of compounds of formula (1) in which Ri denotes a C₁₂ alkyl radical, A denotes a hydrogen or sodium atom and n ranges from 2 to 10;

• polyoxyethylenated carboxylic acid salts, such as oxyethylenated (6 EO) sodium lauryl ether carboxylate (65/25/10 Cn-u-ie), sold under the name Akypo Soft 45 NV® by the company Kao Chemicals, polyoxyethylenated and carboxymethylated fatty acids originating from olive oil, sold under the name Olivem 400® by the company Biologia E Tecnologia, or oxyethylenated (6 EO) sodium tridecyl ether carboxylate, sold under the name Nikkol ECTD-6NEX® by the company Nikkol. d) (C₆-C₃₀) acyl or alkyl acids and alkali metal salts thereof, such as:

• (C₆-C₃o)acylsarcosinates, and preferably (Ci₂-C2s)acylsarcosinates, better still (Cn-C^acylsarcosinates or even better (C₁₆-C₂2)acylsarcosinates, such as the sodium lauroyl sarcosinate sold under the name Sarkosyl NL 97® by the company Ciba or sold under the name Oramix L30® by the company SEPPIC, sodium myristoyl sarcosinate sold under the name Nikkol Sarcosinate MN® by the company Nikkol, and sodium palmitoyl sarcosinate sold under the name Nikkol Sarcosinate PN® by the company Nikkol,

• (C6-C₃o)alkylcitrates, optionally oxyalkylenated, such as the oxyethylenated (9 mol) citric monoester of cocoyl alcohols sold under the name Witconol EC 1129 by the company Goldschmidt,

• (C₆-C₃o)alkylgalacturonates, such as the sodium dodecyl-D-galactoside uronate sold by the company Soliance. e) Succinates may be chosen from alkylsulfosuccinates, alkyl ether sulfosuccinates, alkylamidesulfosuccinates, with alkyl groups of these compounds comprising from 6 to 30 carbon atoms, especially from 12 to 28, better still from 14 to 24 or even from 16 to 22 carbon atoms. Examples of sulfosuccinates that may be mentioned include lauryl sulfosuccinate, the oxyethylenated (3 EO) lauryl alcohol monosulfosuccinate (70/30 C₁₂/C₁₄) sold under the names Setacin 103 Special® and Rewopol SB-FA 30 K 4® by the company Witco, the disodium salt of a hemisulfosuccinate of Ci₂-Ci₄ alcohols, sold under the name Setacin F Special Paste® by the company Zschimmer Schwarz, the oxyethylenated (2 EO) disodium oleamidosulfosuccinate sold under the name Standapol SH 135® by the company Cognis, the oxyethylenated (5 EO) laurylamide monosulfosuccinate sold under the name Lebon A-5000® by the company Sanyo, the oxyethylenated (10 EO) disodium salt of lauryl citrate

monosulfosuccinate sold under the name Rewopol SB CS 50® by the company Witco, and the ricinoleic monoethanolamide monosulfosuccinate sold under the name Rewoderm S 1333® by the company Witco. Poly dimethyl siloxane sulfosuccinates may also be used, such as disodium PEG- 12 dimethicone sulfosuccinate sold under the name Mackanate-DC30 by the company Maclntyre. f) Mention may be made, as sulfates, of alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, the alkyl groups comprising 6 to 30 carbon atoms, preferably from 12 to 28, better still from 14 to 24 or even from 16 to 22 carbon atoms, and the aryl group preferably denoting a phenyl or benzyl group. The sulphate surfactant may be in the form of alkali metal or alkaline earth metal, ammonium or amino alcohol salt. As examples of (C₆-C3o)alkyl sulfates, mention may be made of triethanolamine lauryl sulfate (CTFA name: TEA-lauryl sulfate), such as the product sold by the company Huntsman under the name Empicol TL40 FL or the product sold by the company Cognis under the name Texapon T42, which products are at 40% in aqueous solution. Mention may also be made of ammonium lauryl sulfate (CTFA name: ammonium lauryl sulfate), such as the product sold by the company Huntsman under the name Empicol AL 30FL, which is at 30% in aqueous solution. Mention may be made, as (C₆-C₃₀)alkyl ether sulfates, for example, of sodium lauryl ether sulfate (CTFA name: sodium laureth sulfate), such as that sold under the names Texapon N40 and Texapon AOS 225 UP by the company Cognis, or ammonium lauryl ether sulfate (CTFA name: ammonium laureth sulfate), such as that sold under the name Standapol EA-2 by the company Cognis. g) Mention may be made as sulfonates of alkylsulfonates, alkylamidosulfonates,

alkylarylsulfonates, a-olefinsulfonates, paraffin sulfonates, with alkyl groups comprising from 6 to 30 carbon atoms, especially from 12 to 28, better still from 14 to 24 or even from 16 to 22 carbon atoms; the aryl group preferably denoting a phenyl or benzyl group; these compounds possibly being polyoxyalkylenated, especially polyoxyethylenated, and then preferably comprising from 1 to 50 ethylene oxide units and better still from 2 to 10 ethylene oxide units, alkylsulfoacetates, and also the salts of these compounds. As examples of a-olefinsulfonates mention may be made of sodium a-olefinsulfonate (Ci₄-Ci₆), sold under the name Bio-Terge AS-40® by the company Stepan, sold under the names Witconate AOS Protege® and Sulframine AOS PH 12® by the company Witco or sold under the name Bio-Terge AS-40 CG® by the company Stepan, secondary sodium olefinsulfonate, sold under the name Hostapur SAS 30® by the company Clariant; or linear alkylarylsulfonates, such as sodium xylenesulfonate, sold under the names Manrosol SXS30®, Manrosol SXS40® and Manrosol SXS93® by the company Manro. h) Mention may be made, as isethionates, of acylisethionates comprising from 6 to 24, preferably from 12 to 18 carbon atoms, such as sodium cocoylisethionate, such as the product sold under the name Jordapon CI P® by the company Jordan. i) Mention may be made, as taurates, of the sodium salt of palm kernel oil methyltaurate, sold under the name Hostapon CT Pate® by the company Clariant; N-acyl-N-methyltaurates, such as sodium N-cocoyl-N-methyltaurate, sold under the name Hostapon LT-SF® by the company Clariant or sold under the name Nikkol CMT-30-T® by the company Nikkol, or sodium palmitoyl methyltaurate, sold under the name Nikkol PMT® by the company Nikkol. j) The anionic derivatives of (C₆-C₃o)alkyl polyglucosides can in particular be citrates, tartrates, sulfo succinates, carbonates and glycerol ethers obtained from alkyl polyglucosides. Mention may be made, for example, of the sodium salt of cocoylpolyglucoside (1,4) tartaric ester, sold under the name Eucarol AGE-ET^® by the company Cesaipinia, the disodium salt of cocoylpolyglucoside (1,4) sulfosuccinic ester, sold under the name Essai 512 MP^® by the company SEPPIC, or the sodium salt of cocoylpolyglucoside (1,4) citric ester, sold under the name Eucarol AGE-EC^® by the company Cesaipinia.

Preferably, the additional anionic surfactant is chosen from (C₆-C₃₀)alkyl sulfates,

(C₆-C₃o)alkyl ether sulfates such as sodium lauryl ether sulfate, (C₆-C3o)acylisethionates, (C₆-C₃₀) acyl or alkyl acids, in particular and mixtures thereof. (ii) Additional amphoteric and zwitterionic foaming surfactants

The composition according to the present invention may further comprise an amphoteric and zwitterionic surfactant that is different from the amphoteric surfactant chosen from betaines or (C₈-C₂₀)alkyl betaines, and (C₈-C₂₀)alkylamido(Ci-C₆)alkylbetaines mentioned above.

The additional amphoteric and zwitterionic surfactants can be chosen from, for example, sulfobetaines, (C8-C₂₀)alkylsulfobetaines, (C₈-C₂₀)alkylamido(C₁-C₆)alkylsulfobetaines (C₈-C₂₀)alkylamphoacetates and (C8-C₂₀)alkylamphodiacetates, and mixtures thereof.

Mention may be made, as sulfobetaines, of hydroxysultaines, cocamidopropyl

hydroxysultaines, such as the product sold under the name ewoteric AM CAS by the company Goldschmidt-Degussa or the product sold under the name Crosultaine C-50® by the company Croda.

The additional amphoteric surfactants that may be used in the present invention may be optionally quaternized secondary or tertiary aliphatic amine derivatives, in which the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phosphonate group.

Among the optionally quaternized secondary or tertiary aliphatic amine derivatives that may be used, mention may also be made of the products of respective structures (Al) and (A2) below:

(Al) Ra-CON(Z)CH₂-(CH₂)_m-N⁺(Rb)(Rc)(CH₂COO-) in which:

Ra represents a C₁₀-C₃o alkyl or alkenyl group derived from an acid Ra-COOH preferably present in hydrolysed coconut oil, a heptyl group, a nonyl group or an undecyl group,

Rb represents an α,β-hydroxyethyl group,

R_c represents a carboxymethyl group;

m is equal to 0, 1 or 2,

Z represents a hydrogen atom or a hydroxyethyl or carboxymethyl group; (A2) Ra'-CON(Z)CH₂-(CH₂)_m'-N(B)(B')

in which:

B represents -CH₂CH₂OX', with X' representing -CH₂-COOH, CH₂-COOZ^',

CH₂CH₂-COOH, -CH₂CH₂-COOZ'₅ or a hydrogen atom,

B' represents -(CH₂)_Z-Y', with z = 1 or 2, and Y' representing COOH, COOZ', CH₂-CHOH-S0₃H or -CH₂-CHOH-S0₃Z',

m' is equal to 0, 1 or 2,

Z represents a hydrogen atom or a hydroxy ethyl or carboxymethyl group,

Z' represents an ion resulting from an alkali or alkaline-earth metal, such as sodium, potassium or magnesium; an ammonium ion; or an ion resulting from an organic amine and in particular from an amino alcohol, such as monoethanolamine, diethanolamine and

triethanolamine, monoisopropanolamine, diisopropanolamine or triisopropanolamine,

2-amino-2-methyl-l-propanol, 2-amino-2 -methyl- 1,3 -propanediol and

tris(hydroxymethyl)aminomethane,

Ra- represents a C₁₀-C₃o alkyl or alkenyl group of an acid Ra-COOH preferably present in hydrolysed linseed oil or coconut oil, an alkyl group, in particular a C17 alkyl group, and its isoform, or an unsaturated C 17 group.

The compounds corresponding to formula (A2) are preferred. Among the compounds corresponding to formula (A2) in which X' represents a hydrogen atom, mention may be made of compounds classified in the CTFA dictionary, under the names sodium cocoamphoacetate, sodium lauroamphoacetate, sodium caproamphoacetate and sodium capryloamphoacetate. Other compounds corresponding to formula (A2) are disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caproamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium

caproamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid.

Examples that may be mentioned include the cocoamphodiacetate sold by the company Rhodia under the trade name Miranol® C2M Concentrate, the sodium cocoamphoacetate sold under the trade name Miranol Ultra C 32 and the product sold by the company Chimex under the trade name CHIMEXANE HA, and the sodium cocoamphohydroxypropylsulfonate, sold under the name Miranol CSE by the company Rhodia.

Use may also be made of the compounds of formula (A3):

(A3) Ra"-NH-CH(Y")-(CH₂)n-C(0)-NH-(CH₂)_n-N(Rd)(Re) in which:

- Ra" represents a Cio-C₃o alkyl or alkenyl group of an acid R_a"-C(0)OH preferably present in hydrolysed linseed oil or coconut oil;

- Y" represents the group -C(0)OH, -C(0)OZ", -CH₂-CH(0H)-S0₃H or the group CH2-CH(OH)-S0₃-Z", with Z" representing a cationic counterion resulting from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion resulting from an organic amine;

- R_d and Re represent, independently of each other, a C₁-C₄ alkyl or hydroxyalkyl radical; and

- n and n' denote, independently of each other, an integer ranging from 1 to 3. Among the compounds corresponding to formula (A3), mention may in particular be made of the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide, such as the one sold by the company Chimex under the name

CHIMEXANE HB. Preferably, the amphoteric or zwitterionic surfactant is chosen from

(C₈-C₂o)alkylamphoacetates such as sodium cocoamphoacetate, and mixtures thereof.

(iii) Nonionic foaming surfactant The nonionic foaming surfactants that may be present in the composition of the present invention may be chosen from alcohols, a-diols and (C₁-C2o)alkylphenols, these compounds being polyethoxylated and/or polypropoxylated and/or polyglycerolated, the number of ethylene oxide and/or propylene oxide groups possibly ranging from 1 to 100, and the number of glycerol groups possibly ranging from 2 to 30; or alternatively these compounds comprising at least one fatty chain comprising from 8 to 30 carbon atoms and especially from 16 to 30 carbon atoms.

Mention may also be made of condensates of ethylene oxide and of propylene oxide with fatty alcohols; polyethoxylated fatty amides preferably having from 2 to 30 ethylene oxide units, polyglycerolated fatty amides comprising on average from 1 to 5, and in particular from 1.5 to 4, glycerol groups; ethoxylated fatty acid esters of sorbitan preferably containing from 2 to 40 ethylene oxide units, fatty acid esters of sucrose, polyoxyalkylenated and preferably polyoxyethylenated fatty acid esters containing from 2 to 150 mol of ethylene oxide, including oxyethylenated plant oils, N-(C₆-C₂₄ alkyl)glucamine derivatives, amine oxides such as (C₁₀-C₁₄ alkyl)amine oxides or N-(Cio-Ci₄ acyl)aminopropylmorpholine oxides.

The nonionic surfactant may also be chosen from alkyl (poly)glycosides(APG), represented especially by the following general formula: RiO-(R20)t-(G)_v

in which:

- Ri represents a linear or branched alkyl or alkenyl radical comprising 6 to 24 carbon atoms and especially 8 to 18 carbon atoms, or an alkylphenyl radical whose linear or branched alkyl radical comprises 6 to 24 carbon atoms and especially 8 to 18 carbon atoms;

- R₂ represents an alkylene radical comprising 2 to 4 carbon atoms,

- G represents a sugar unit comprising 5 to 6 carbon atoms,

- 1 denotes a value ranging from 0 to 10 and preferably 0 to 4,

- v denotes a value ranging from 1 to 15 and preferably 1 to 4.

Preferably, the alkylpolyglycoside surfactants are compounds of the formula described above in which:

- Ri denotes a linear or branched, saturated or unsaturated alkyl radical comprising from 8 to 18 carbon atoms,

- R₂ represents an alkylene radical comprising 2 to 4 carbon atoms,

- 1 denotes a value ranging from 0 to 3 and preferably equal to 0,

- G denotes glucose, fructose or galactose, preferably glucose;

- the degree of polymerization, i.e. the value of v, possibly ranging from 1 to

15 and preferably from 1 to 4; the mean degree of polymerization more particularly being between 1 and 2.

The glycoside bonds between the sugar units are generally of 1-6 or 1-4 type and preferably of 1-4 type. Preferably, the alkyl(poly)glycoside surfactant is an alkyl(poly)glucoside surfactant. C₈/Ci₆ alkyl(poly)glycosides 1,4, and especially decyl glucosides and

caprylyl/capryl glucosides, are most particularly preferred.

Among the commercial products, mention may be made of the products sold by the company COGNIS under the names PLANT AREN® (600 CS U, 1200 and 2000) or PLANTACARE® (818, 1200 and 2000); the products sold by the company SEPPIC under the names ORAMIX CG 110 and ORAMIX NS 10; the products sold by the company BASF under the name LUTENSOL GD 70, or else the products sold by the company CHEM Y under the name AGIO LK.

Preferably, use is made of C₈/C₁₆-alkyl(poly)glycosides 1,4, especially as an aqueous 53% solution, such as those sold by Cognis under the reference Plantacare® 818.

Preferentially, the nonionic surfactants are chosen from (C₆-C₂4 alkyl)polyglycosides, and more particularly (C₈-C₁₈ alkyl)(poly)glycosides, ethoxylated C₈-C30 fatty acid esters of sorbitan, polyethoxylated C8-C30 fatty alcohols and polyoxyethylenated C₈-C₃₀ fatty acid esters, these compounds preferably containing from 2 to 150 mol of ethylene oxide, and mixtures thereof. The nonionic surfactant may also be chosen from oxyalkylenated glycerol esters. The oxyalkylenated glycerol esters are in particular the polyoxyethylenated derivatives of esters of glycerol and of a fatty acid and of their hydrogenated derivatives. These oxyalkylenated glycerol esters can be chosen, for example, from esters of glycerol and of fatty acids which are hydrogenated and oxyethylenated, such as PEG-200 hydrogenated glyceryl palmate, sold under the name Rewoderm LI-S 80 by the company Goldschmidt; oxyethylenated glycerol cocoates, such as PEG-7 glyceryl cocoate, sold under the name Tegosoft GC by the company Goldschmidt, and PEG- 30 glyceryl cocoate, sold under the name Rewoderm LI-63 by the company Goldschmidt; and mixtures thereof. The nonionic surfactant may also be chosen from oxyalkylenated sugar esters. The oxyalkylenated sugar esters are in particular polyethylene glycol ethers of fatty acid and sugar esters. These oxyalkylenated sugar esters can be chosen, for example, from oxyethylenated glucose esters, such as PEG- 120 methyl glucose dioleate, sold under the name Glucamate DOE 120 by the company Amerchol.

The nonionic surfactant may also be chosen from fatty acid alkanolamides. The fatty acid alkanolamides are preferably selected from C₈-C₂₂ fatty acid alkanolamides, and more preferably 0₂-C₁₈ fatty acid alkanolamides. In particular, the fatty acid alkanolamides can be Cocamide MEA as the product sold under the trade name COMPERLAN CMEA® by the company BASF.

According to a preferred embodiment of the present invention, the nonionic surfactant is an alkyl polyglucoside which may be chosen especially from decylglucoside, caprylyl/capryl glucoside, laurylglucoside, cocoylglucoside and caprylylglucoside, Cocamide MEA, and mixtures thereof.

(iv) Cationic foaming surfactant

According to one embodiment, the composition according to the present invention may comprise at least one cationic surfactant, in particular in the case where it comprises an amphoteric foaming surfactant. The cationic surfactants that may be used according to the present invention are especially optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, imidazoline derivatives, and amine oxides of cationic nature, and mixtures thereof.

Examples of quaternary ammonium salts include:

- those that have the general formula (2) below:

+

X ^"

R, R,

(2)

in which the radicals Ri to R4, which may be identical or different, represent a linear or branched aliphatic radical comprising from 1 to 30 carbon atoms or an aromatic radical, such as aryl or alkylaryl, at least one of the groups Ri to R containing from 8 to 30 carbon atoms and preferably from 12 to 24 carbon atoms. The aliphatic radicals may contain heteroatoms such as, in particular, oxygen, nitrogen, sulfur and halogen atoms. The aliphatic radicals are for example selected from (Ci-C₃₀)alkyl, (C₁-C₃₀)alkoxy, (C₂-C₆)polyoxyalkylene,

(d-Cs^alkylamide, (Ci₂-C₂₂)alkyl(C₂-C₆)alkylamido, (C₁₂-C₂₂)alkylacetate and

(Ci-C3o)hydroxyalkyl radicals: X^" is an anion chosen from the group consisting of halides, phosphates, acetates, lactates, (Ci-C₆)alkyl sulfates, and (C₁-C₄)alkylsulfonates or

(Ci-C₄)alkylarylsulfonates. Preferably Ri and R₂ denote a Ci-C₄ alkyl or a Ci-C₄ hydroxy alkyl.

- quatenary ammonium salts of imidazolinium, for instance the salt of formula (3) below

in which R₅ represents an alkenyl or alkyl radical containing from 8 to 30 carbon atoms, for example coconut or tallow fatty acid derivatives, R₆ represents a hydrogen atom, a Ci-C₄ alkyl radical or an alkenyl or alkyl radical containing from 8 to 30 carbon atoms, R7

represents a Ci-C₄ alkyl radical, R₈ represents a hydrogen atom or a Ci-C₄ alkyl radical or an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, X- is an anion chosen preferably from the group of halides, phosphates, acetates, lactates, (d-C₄)alkyl sulfates and (Ci-C₄)alkylsulfonates or (Ci-C₄)alkylaryl sulfonates. R₅ and R₆ preferably denote a mixture of alkenyl or alkyl radicals comprising from 12 to 21 carbon atoms, for example fatty acid derivatives of tallow, R₇ denotes methyl and R₈ denotes a hydrogen atom.

- the quaternary di- or triamrnonium salts of formula (4):

in which R9 denotes an alkyl radical containing approximately from 16 to 30 carbon atoms which is optionally hydroxylated and/or interrupted with one or more oxygen atoms, Rio represents a hydrogen atom or an alkyl group containing from 1 to 4 carbon atoms or the group -(CH2)₃-N⁺(R9a)(Rioa)(Riia); wherein R_9a, Rioa, and Rn_a, which may be identical or different, are chosen from hydrogen and an alkyl group comprising from 1 to 4 carbon atoms, Rn, Ri2, Rn and R_H, which are identical or different, are selected from hydrogen or an alkyl radical containing from 1 to 4 carbon atoms, and X^" is an anion selected from the group consisting of halides, acetates, phosphates, nitrates and (Ci-C₄)alkyl sulfates,

(Ci-C₄)alkylsulfonates and (Ci-C₄)alkylarylsulfonates, in particular methyl sulfate and ethyl sulfate.

Such compounds are, for example, FINQUAT CT-P (Quatemium 89) and FINQUAT CT (Quatemium 75) sold by the company F1NETEX. - quaternary ammonium salts comprising at least one ester function, for example those of formula (5) below:

in which:

- R₁₅ is chosen from C!-C₆ alkyl radicals and d-C₆ hydroxyalkyl or

(Ci-C₆)dihydroxyalkyl radicals;

- R₁₆ is chosen from:

O

ti

- the radical ¹⁹

- linear or branched, saturated or unsaturated C1-C22 hydrocarbon-based radicals R₂₀,

- a hydrogen atom,

- R₁₈ is chosen from:

O

II

R— C

- the radical ²¹

- linear or branched, saturated or unsaturated Ci-C₆ hydrocarbon radicals

R₂₂,

- a hydrogen atom.

- R₁₇, Ri9 and R₂i, which are identical or different, are chosen from linear or branched, saturated or unsaturated C₇-C₂₁ hydrocarbon radicals;

- r, s, and t, which may be identical or different, are integers ranging from 2 to 6; - rl and tl, which may be identical or different, are equal to 0 or 1 ;

- r2 + rl = 2 r and tl + 12 = 2 t;

- y is an integer ranging from 1 to 10;

- x and z, which may be identical or different, are integers ranging from 0 to 10;

- X^" is an anion;

with the proviso that the sum x + y + z is from 1 to 15, that when x is 0, then R₁₆ denotes R₂₀ and that when z is 0, then Ri₈ denotes R22.

The alkyl radicals R₁₅ may be linear or branched, and more particularly linear. Preferably Ri₅ denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl radical, and more particularly a methyl or ethyl radical.

Advantageously, the sum x + y + z is from 1 to 10. When Ri₆ is a hydrocarbon radical R20, it may be long and may have 12 to 22 carbon atoms, or may be short and may have from 1 to 3 carbon atoms.

When R₁₈ is a hydrocarbon radical R₂₂, it preferably has 1 to 3 carbon atoms. Advantageously, R₁₇, R19 and R₂₁, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C11-C21 hydrocarbon-based radicals, and more particularly from linear or branched, saturated or unsaturated Cn-C₂₁ alkyl and alkenyl radicals.

Preferably, x and z, which may be identical or different, are equal to 0 or 1.

Advantageously, y is equal to 1.

Preferably r, s, and t, which may be identical or different, are equal to 2 or 3, and more particularly are equal to 2.

The anion X^" is preferably a halide, preferably chloride, bromide or iodide, or a (Ci-C₄)alkyl sulfate, more particularly methyl sulfate, or (Ci-C₄)alkyl sulfonate like methanesulfonate, (Ci-C₄)alkylaryl sulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion that is compatible with the ammonium

containing an ester function.

The anion X^" is even more particularly chloride, methyl sulphate or ethyl sulfate.

The ammonium salts more particularly used are those of formula (5) in which:

- Ri₅ denotes a methyl or ethyl radical;

- x and y are equal to 1 ;

- z is equal to 0 or 1 ;

- r, s, and t are equal to 2;

- R₁₆ is chosen from:

- the radical R19-CO

- methyl, ethyl or Ci₄-C₂₂ hydrocarbon-based radicals,

- a hydrogen atom.

- R₁₈ is chosen from:

- the radical R₂₁-CO

- a hydrogen atom.

- R₁₇, R₁₉ and R₂i, which may he identical or different, are chosen from linear or branched, saturated or unsaturated C₁₃-C₁ hydrocarbon-based radicals, and preferably from linear or branched, saturated or unsaturated C₁₃-C₁₇ alkyl and alkenyl radicals. The hydrocarbon-based radicals are advantageously linear.

Among the quaternary ammonium salts of formula (2), preference is given, on the one hand, to tetraalkyl ammonium halides and preferably tetraalkylammonium chlorides, for instance dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl radical contains approximately 12 to 22 carbon atoms, in particular behenyltrimethylammomum chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride and benzyldimethylstearylammonium chloride, or else, on the other hand, to

palmitylamidopropyltrimethylammonium halides, and preferably chloride or the

stearamidopropyldimethyl(myristyl acetate)ammonium halides, and preferably chloride, such as the one sold under the name "Ceraphyl 70" by the company Van Dyk.

Examples of compounds of formula (5) that may be mentioned include the

diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium, monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium and monoacyloxyethylhydroxyemyldimemylammonium salts (chloride or methyl sulfate in particular), and mixtures thereof. The acyl radicals preferably contain 14 to 18 carbon atoms and are obtained more particularly from a plant oil such as palm oil or sunflower oil. When the compound contains several acyl radicals, these radicals may be identical or different. These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolarnine, an alkyldiethanolamine or an alkyldiisopropanolamine, which are optionally oxyalkylenated, with fatty acids or with fatty acid mixtures of plant or animal origin, or by transesterification of the methyl esters thereof. This esterification is followed by a quatemization using an alkylating agent such as an alkyl halide (preferably a methyl or ethyl halide), a dialkyl sulfate (preferably dimethyl or diethyl sulfate), methyl

methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol

chlorohydrin.

Such compounds are sold, for example, under the names Dehyquart by the company Cognis, Stepanquat by the company Stepan, Noxamium by the company CECA or Rewoquat WE 18 and Rewoquat W75 by the company Degussa.

The composition according to the present invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts. Use may also be made of the ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180. Use may also be made of behenoylhydroxypropyltrimethylammonium chloride, for example, sold by the company KAO under the name QUARTAMIN BTC 131. Preferably, the ammonium salts containing at least one ester function contain two ester functions.

Quaternary diammonium salts of formula (4) that are suitable for the present invention comprise, in particular, propanetallowdiammonium chloride.

Preferably, the cationic surfactants are chosen from the compounds of formula (4) and the compounds of formula (5), preferably from cetyltrimethylammonium,

behenyltrimethylammonium, and dipalmitoylethylhydroxyethylmethylammonium salts, and mixtures thereof, and more particularly from behenyltrimethylammonium chloride or methosulfate, cetyltrimethylammonium chloride or methosulfate, and

dipalmitoylethylhydroxyethylmethylammonium chloride or methosulfate, and mixtures thereof. Even more preferentially, the cationic surfactant is a behenyltrimethylammonium salt. The surfactant system may further comprise at least one foaming surfactant chosen from anionic, amphoteric, nonionic and/or cationic foaming surfactants, and mixtures thereof, the said anionic surfactant being in particular chosen from anionic derivatives of proteins of plant origin or of silk proteins, phosphates and (C₆-C₃o)alkyl phosphates, (C₆-C₂₄)alkyl ether carboxylates, (C₆-C₂₄)alkyl(amido) ether carboxylates, (C6-C₃₀)alkylsulfosuccinates, (C₆-C₃o) alkyl ether sulfosuccinates, (C₆-C₃₀)alkylamidesulfosuccinates, (C6-C30) acyl or alkyl acids, (C₆-C₃₀)alkyl sulfates, (C₆-C₃o)alkyl ether sulfates, (C₆-C₃o)alkylamido ether sulfates, (C₆-C₃₀)alkylaryl polyether sulfates, monoglyceride sulfates, (C₆-C₃₀)alkylsulfonates, (C₆-C₃o)alkylamidosulfonates, (C₆-C3o)alkylarylsulfonates, (C6-C₃o)a-olefinsulfonates, paraffin sulfonates, (C₆-C₂₄)acylisethionates, taurates, (C₆-C₃₀)alkyl sulfoacetates,

polypeptides, anionic derivatives of (C₆-C₃₀)alkyl polyglucoside, and mixtures thereof, more particularly from (C6-C₃₀)alkyl sulfates, (C₆-C₃o)alkyl ether sulfates, (C₆-C₂4)acyl isethionates, (C₆-C₃o) acyl or alkyl acids, and mixtures thereof, the said amphoteric or zwitterionic surfactant being in particular chosen from sulfobetaines, (C8-C₂₀)alkylsulfobetaines,

(C₈-C₂₀)alkylamido(C₁-C6)alkylsulfobetaines, (C₈-C₂₀)alkylamphoacetates and

(C₈-C₂₀)alkylamphodiacetates, more particularly from (C₈-C₂₀)alkylsulfobetaines,

(C8-C₂o)alkylamphoacetates and mixtures thereof, and the said nonionic surfactant being in particular chosen from alkyl polyglucosides (APGs), oxyalkylenated glycerol esters and oxyalkylenated sugar esters, and mixtures thereof, more particularly from APGs, and the said cationic surfactant being in particular chosen from optionally polyoxyalkylenated primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, quaternary ammonium salts of imidazolinium, and amine oxides of cationic nature, and mixtures thereof.

According to a particular embodiment, the composition according to the present invention is devoid of cationic surfactant.

(v) Non-foaming surfactant

The non-foaming surfactant may be chosen from among non-ionic foaming surfactants, and in particular mono-, di- or tri-esters of (C₆-C₃₀) fatty acids and of (poly)glycerol and mixtures thereof, and in particular mono-, di-, or tri-esters of (C₁₂-C₂₄) fatty acids and of (poly)glycerol and mixtures thereof.

The fatty acid moiety of the ester of fatty acid and (poly)glycerol may be in particular chosen from among lauric, myristic, palmitic, stearic, arachidic and behenic.

The mono-, di-, or tri-esters of (C₆-C₃o) fatty acids and of (poly) glycerol may from 1 to 10, preferably 1 to 6 glycerol units, and has preferably only one glycerol unit.

In particular, mention may be made of:

- glyceryl stearates, such as glyceryl monostearate, like the one sold under the name

DUB GMS 50/50 by STEARINERIE DUBOIS or under the name BFP 74 FLAKES by the company CARAVAN INGREDIENTS; mixtures of glyceryl mono- and distearate, such as the product sold under the name TEGIN PELLETS by EVONIK GOLDSCHMIDT or the product sold under the name CERASYNT SD by the company ISP; glyceryl isostearate such as the product PECEOL ISOSTEARIQUE sold by GATTEFOSSE; mixtures of glyceryl mono-, di- and tristearate like the one sold under the name LIPO GMS 450 V by the company LIPO CHEMICALS: polyglyceryl-2 diisostearate like the one sold under the name DERMOL DGDIS by the company ALZO; polyglyceryl-2 isostearate, like the one sold under the name SALACOS 41V by the company NISSHIN OILLIO; polyglyceryl-10 stearate, like the one sold under the name DECAGLYN 1-SV by the company NIKKO; polyglyceryl-2

triisostearate, like the one sold under the name COSMOL 43 N by the company NISSHIN OILLIO; polyglyceryl-4 isostearate like the one sold under the name ISOLAN GI 34

EVONIK GOLDSCHMIDT; polyglyceryl-3 isostearate, like the one sold under the name LAMEFORM TGI by the company COGNIS

- glyceryl laurates, such as polyglyceryl-10 laurate like the one sold under the name

DERMOFEEL G 10 L by the company DR STRAETMANS; polyglyceryl-6 laurate like the one sold under the name NIKKOL HEXAGLYN 1 L by the company NIHON

SURFACTANT; polyglyceryl-10 trilaurate like the one sold under the name SUNSOFT Q-123Y-C by the company TAIYO KAGAKU; polyglyceryl-2 laurate like the one sold under the name SUNSOFT Q- 12D-C by the company TAIYO KAGAKU; polyglyceryl-5 laurate, like the one sold under the name SUNSOFT A- 121E-C by the company TAIYO KAGAKU; a mixture of glyceryl mono and di-laurate, for example a 90/10 mixture of glyceryl mono- and di- laurate like the one sold under the name GRILLOMULS L-90 by the company

GRILLO-WERKE or like the one sold under the name TEGIN L 90 by the company

EVONIK; polyglyceryl-3 laurate like the one sold under the name

TRIGLYCERJN-MONOLAURAT by the company SAFIC-ALCAN; glyceryl monolaurate, like the one sold under the name GML by the company HENAN ZHENGTONG CHEMICAL or under the name SUNSOFT NO.750-C by TAIYO KAGAKU;

- glyceryl myristates, such as polyglyceryl-2 myristate, like the one sold under the name SUNSOFT Q- 14D-C by the company TAIYO KAGAKU; polyglyceryl-5 trimyristate, like the one sold under the name SUNSOFT A- 143E-C by the company TAIYO KAGAKU; polyglyceryl-5 myristate, like the one sold under the name SUNSOFT A-141E-C by the company TAIYO KAGAKU; polyglyceryl-10 myristate like the one sold under the name SUNSOFT Q- 14 Y-C by the company TAIYO KAGAKU; polyglyceryl-6 myristate, like the one sold under the name NIKKOL HEXAGLYN 1 -M sold by NIKKO;

- glyceryl palmitates, such as polyglyceryl-2 palmitate like the one sold by

SAKAMOTO YAKUHIN; polyglyceryl-3 palmitate like the one sold under the name

DERMOFEEL PP by the company DR STRAETMANS; polyglyceryl-10 dipalmitate, like the one sold under the name POLYALDO 10-2-P K FG by the company LONZA;

- glyceryl behenates, such as glyceryl dibehenate like the one sold under the name

COMPRITOL E ATO by the company GATTEFOSSE; polyglyceryl-6 behenate like the one sold under the name PELEMOL 6G22 by the company PHOENIX CHEMICAL; mixtures of glyceryl mono-, di- and tribehenate, like the one sold under the name BEHENATE DE GLYCEROL WL 251 by the company GATTEFOSSE

- and mixtures thereof.

In a particular embodiment, the non-foaming surfactant is chosen from among (C8-C₂₀) fatty acids, mono-, di-, or tri-esters of (C₆-C₃o) fatty acids and of (poly)glycerol, and mixtures thereof.

In a particular embodiment, non-foaming surfactants are chosen from among lauric acid, glyceryl monostearate, glyceryl distearate, and mixtures thereof.

The amount of the additional surfactant(s) in the composition according to the present invention may range from 0.1% to 10% by weight, preferably from 0.2% to 5% by weight, and more preferably from 0.5% to 3% by weight, relative to the total weight of the

composition.

In one specific embodiment of the present invention, when the composition according to the present invention comprises one or more additional surfactants above, it preferably comprises the sum of the (a) surfactant system and the additional surfactant(s) in an amount of less than 15% by weight, relative to the total weight of the composition. In other specific

embodiments of the present invention, the composition according to the present invention comprises the sum of the (a) surfactant system and additional surfactant(s) such as

exemplified above in an amount of 12% by weight or less, and preferably 10.5% by weight or less, relative to the total weight of the composition.

• Polyol According to a particular embodiment, the composition according to the present invention further comprises at least one polyol or a mixture of polyols.

For the purpose of the present invention, the term "polyol" should be understood to mean any organic molecule comprising at least two free hydroxyl groups.

A polyol suitable for the present invention may be a compound such as a saturated or unsaturated, linear, branched or cyclic alkyl bearing, on the alkyl chain, at least two -OH functions, in particular at least three -OH functions, and more particularly at least four -OH functions.

The polyols advantageously suitable for the formulation of the foaming cleanser composition according to the present invention are those having, in particular, from 2 to 20 preferably 2 to 16 carbon atoms, more preferably 2 to 10, and even more preferably 3 to 8 carbon atoms.

Among polyols, the following may be cited: glycerine, 1,3 -propanediol, isoprene glycol, pentylene glycol, hexylene glycol, glycols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol and dipropylene glycol, polyglycerols with 2 to 6 repeating units, for instance diglycerol, erythritol, arabitol, adonitol, sorbitol, dulcitol, glucose, fructose, xylose, trehalose, sucrose, maltose, saccharose and lactose, and mixtures thereof. According to a particular embodiment of the present invention, the polyol is not a polymer with repeating units.

According to a preferred embodiment, the polyol is glycerine. The amount of the polyol(s) in the composition according to the present invention may range from 0.1% to 30% by weight, preferably from 1% to 25% by weight, and more preferably from 5% to 20% by weight, relative to the total weight of the composition.

• Oxyalkylenated polymer

The composition according to the present invention may also comprise oxyalkylenated polymers. The oxyalkylenated polymers that may be used in the composition of the present invention are those with a molecular weight (MW) calculated by weight of greater than or equal to 300 000, the molecular weight preferably ranging from 400 000 to 4 x 10⁶ and better still from 500 000 to 2 x 10⁶.

According to one preferred embodiment of the present invention, the oxyethylenated polymer is a compound of formula (A): H-[0-R-]n-OH (A)

in which

- R represents a linear alkyl chain containing from 1 to 4 carbon atoms, and

- n is an integer ranging from 400 000 to 4 x 10⁶ and better still from 500 000 to 2 x 10⁶. Especially, the oxyalkylenated polymer of the present invention can be an oxyethylenated polymer as represented by formula (B) below:

H(OCH₂CH₂)_aOH (B) in which n is an integer ranging from 7000 to 90 000, preferably from 10 000 to 75 000, more preferably from 25 000 to 65 000, even more preferably from 35 000 to 55 000.

As the oxyalkylenated polymer preferably used in the composition of the present invention, mention may be made especially of PEG 14M (formula (A) in which n is 14 000) such as the product sold under the name Polyox WSR 205 by the company Amerchol, PEG-45M

(formula (A) in which n is 45 000) such as the product sold under the name Polyox WSR N-60 K by the company Amerchol, PEG-90M. (formula (A) in which n is 90000) such as the product sold under the name POLYOX WSR 301 by the company Dow Chemical, and PEG-180M such as the product sold under the trade name POLYOX WSR 308 by the company Dow Chemical, and mixtures thereof.

According to a particular embodiment of the present invention, the oxyalkylenated polymer is PEG-180M, in particular as sold under the name POLYOX WSR 308 by Dow Chemical. The oxyalkylenated polymer may be present in the composition of the present invention in an amount preferably ranging from 0.001% to 5% by weight and better still from 0.005% to 3% by weight, and even more preferably from 0.01% to 1% by weight, relative to the total weight of the composition. · Thickener

The composition according to the present invention may comprise at least one additional thickener this is different from the (b) non-associative crosslinked copolymer of (meth)acrylic acid, and of (C₁-C₄)alkyl ester of (meth)acrylic or the (c) at least one associative copolymer of (meth)acrylic acid, and of (Ci-C₆) alkyl ester of (meth)acrylic acid, as explained above.

As the additional thickeners, mention may in particular be made of water-soluble or water-dispersible thickening polymers. They may in particular be chosen from:

polyvinylpyrrolidone,

- polyvinyl alcohol,

modified or unmodified carboxyvinyl polymers, such as the products sold under the name Carbopol^® (CTFA name: carbomer) by the company Goodrich;

polyacrylamides;

polysaccharide biopolymers, for instance xanthan gum, guar gum, gum Arabic, locus bean gum, acacia gum, scleroglucans, chitin derivatives and chitosan derivatives,

carrageenans, gellans, alginates, or celluloses such as microcrystalline cellulose,

carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose,

hydroxypropylcellulose, and hydroxypropyl methylcellulose. Mention may be made of, for example, xanthan gum sold under the trade name Keltrol^® CG-T by the company CP Kelco and hydroxypropyl methylcellulose such as the product sold under the trade name BENECEL Kl 00M HYDROXYPROPYLMETHYL CELLULOSE® by the company ASHLAND.

hydrophilic fumed silicas obtained by high-temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. The hydrophilic silicas have a large number of silanol groups at their surface. Such hydrophilic silicas are, for example, sold under the names Aerosil 130^®, Aerosil 200^®, Aerosil 255^®, Aerosil 300^® and Aerosil 380^® by the company Degussa, or Cab-O-Sil HS-5^®, Cab-O-Sil EH-5^®, Cab-O-Sil LM-130^®, Cab-O-Sil MS-55^® and Cab-O-Sil M-5^® by the company Cabot. They preferably have a particle size that can be nanometric to micrometric, for example ranging from about 5 to 200 nm;

- hydrophilic clays; and mixtures thereof.

The additional thickener may be present in the composition of the present invention in an amount preferably ranging from 0.01% to 5% by weight and better still from 0.05% to 3% by weight, and even more preferably from 0.1% to 1% by weight, relative to the total weight of the composition.

• Polymeric quaternary ammonium salts The composition may also comprise at least one polymeric quaternary ammonium salt.

These compounds are conditioning agents, i.e. they produce a comfortable sensation of softness on the skin (moisturization maintenance).

The polymeric quaternary ammonium salts are cationic or amphoteric polymers containing at least one quaternized nitrogen atom. Polymeric quaternary ammonium salts that may especially be mentioned include the Polyquaternium products (CTFA name), which afford softness and creaminess to the foaming cream. These polymers may preferably be chosen from the following polymers: Polyquaternium 5, such as the product Merquat 5® sold by the company Nalco;

Polyquaternium 6, such as the product Salcare SC 30® sold by the company Ciba, and the product Merquat 100® sold by the company Nalco;

Polyquaternium 7, such as the products Merquat S®, Merquat 2200 and Merquat 550 sold by the company Nalco, and the product Salcare SC 10® sold by the company Ciba;

Polyquaternium 10, such as the product Polymer JR400® sold by the company Amerchol; Polyquaternium 11, such as the products Gafquat 755®, Gafquat 755N® and Gafquat 734® sold by the company ISP;

Polyquaternium 15, such as the product Rohagit KF 720 F® sold by the company Rohm; Polyquaternium 16, such as the products Luviquat FC905®, Luviquat FC370®, Luviquat HM552® and Luviquat FC550® sold by the company BASF;

Polyquaternium 22, such as the product Merquat 280® sold by the company Nalco;

Polyquaternium 28, such as the product Styleze CC10® sold by the company ISP;

Polyquaternium 39, such as the products Merquat Plus 3330® and Merquat 3330PR® sold by the company Nalco;

Polyquaternium 44, such as the product Luviquat Care® sold by the company BASF;

Polyquaternium 46, such as the product Luviquat Hold® sold by the company BASF; and Polyquaternium 47, such as the product Merquat 2001® sold by the company Nalco.

Preferably, the quaternary ammonium salts are chosen from Polyquaternium-7,

Polyquaternium- 10, Polyquaternium-39 and Polyquaternium-47, and mixtures thereof.

As an example of a particular conditioning agent, mention may be made of

Polyquaternium-39, sold especially by the company Nalco under the names Merquat Plus 3330® and Merquat 3330PR®.

The polymeric quaternary ammonium salts may be in an (active material) amount ranging, for example, from 0.01% to 5% by weight and better still from 0.05% to 1% by weight relative to the total weight of the composition. • Active agent

The composition may also comprise at least one active agent, in particular one cosmetic active agent.

The active agents can be chosen from benzenediol derivatives, mushroom extracts, peptides and/or acylated peptides thereof, salicylic acid and salicylic acid derivatives, C-glycoside derivatives, algal extracts, and mixtures thereof.

The benzenediol derivatives are in particular the compounds of formula (2) below:

in which:

Y is chosen from H, an alkyl or alkenyl group comprising from 1 to 8 carbon atoms, a phenyl, Na⁺, K⁺ or NH₄ ⁺,

Rl is chosen from H, a linear or branched, saturated or unsaturated alkyl group comprising from 1 to 18 carbon atoms, a -C(=0)-R2 group, in which R2 is a linear or branched, saturated or unsaturated alkyl group comprising from 1 to 17 carbon atoms or a -(CH₂)n-COOX group in which n is between 0 and 17, and X is chosen from H, an alkyl or alkenyl group comprising from 1 to 8 carbon atoms, a phenyl, Na⁺, ⁺ or NH₄ ⁺,

or one of its salts of organic or inorganic bases, or one of its enantiomers.

According to one preferred embodiment, the soothing agent of formula (2) is characterized in that Rl is a methyl and Y is H: it is 2-(4-hydroxyphenoxy)propionic acid.

The mushroom extracts are in particular Grifola frondosa^extracts, such as the product Eterniskin LS 9881 sold by the company Laboratoires Serobiologiques and/or Cognis and/or BASF. The algal extracts are in particular Chlorella extracts.

The peptides and/or acyl peptides are in particular chosen from acyl peptides, in particular di-, tri-, tetra-, penta- and hexapeptides* more particularly from:

the N-acetyl-L-Tyrosyl-L-Prolyl-L-Phenylalanyl-L-Phenylalaninamide peptide (INCI name: ACETYL TETRAPEPTIDE- 15).

Such a peptide is sold under the name Skinasensyl® PW LS 9852 by the company

Laboratoire Seriobiologique.

The acetylated peptide of the hexapeptide consisting of glutamic acid-glutamic acid-methionine-glutamine-arginine-arginylamide (INCI name: ACETYL

HEXAPEPTIDE-8).

Salicylic acid and salicylic acid derivatives, in particular of formula (3) below:

in which:

the radical Ra denotes:

a linear, branched or cyclic, saturated aliphatic chain containing from 2 to 22 carbon atoms;

an unsaturated chain containing from 2 to 22 carbon atoms, containing one or more double bonds which may be conjugated;

an aromatic nucleus bonded to the carbonyl radical directly or by means of saturated or unsaturated aliphatic chains containing from 2 to 7 carbon atoms;

it being possible for said groups to be substituted with one or more identical or different substituents chosen from:

(a) halogen atoms,

(b) the trifluoromethyl group,

(c) hydroxyl groups in free form or in a form esterified with an acid containing from 1 to 6 carbon atoms, or

(d) a carboxyl function in free form or in a form esterified with a lower alcohol containing from 1 to 6 carbon atoms;

Rb is a hydroxyl group;

and also salts thereof derived from an inorganic or organic base.

The compounds that are more particularly preferred are those in which the radical Ra is a C₃-Cn alkyl group. Among the compounds of formula (3) that are particularly preferred, mention may be made of: 5-n-octanoylsalicylic acid (or capryloylsalicylic acid);

5-n-decanoylsalicylic acid; 5-n-dodecanoylsalicylic acid; 5-n4ieptyloxysalicylic acid, and the corresponding salts thereof.

The C-glycoside derivatives are in particular of formula (4):

in which:

R denotes an unsubstituted linear C1-C4 alkyl radical, in particular

Ci-C₂ alkyl radical, in particular methyl;

S represents a monosaccharide chosen from D-glucose, D-xylose,

N-acetyl-D-glucosamine and L-fucose, and in particular D-xylose;

X represents a group chosen from -CO-, -CH(OH)- and -CH(NH₂)-, and

preferentially a -CH(OH)- group.

As non-limiting illustrations of C-glycoside derivatives that are more particularly suitable for use in the present invention, mention may be made in particular of the following derivatives:

C-beta-D-xylopyranoside-n-propan-2-one;

C-alpha-D-xylopyranoside-n-propan-2-one; C-beta-D-xylopyranoside-2-hydroxypropane;

C-alpha-D-xylopyranoside-2-hydroxypropane;

1 -(C-beta-D-glucopyranosyl)-2-hydroxypropane;

l-(C-alpha-D-glucopyranosyl)-2-hydroxypropane;

- l-(C-beta-D-glucopyranosyl)-2-aminopropane;

1 -(C-alpha-D-glucopyranosyl)-2-aminopropane;

3'-(acetamido-C-beta-D-glucopyranosyl)propan-2'-one;

3'-(acetamido-C-alpha-D-glucopyranosyl)propan-2'-one;

1 -(acetamido-C-beta-D-glucopyranosyl)-2-hydroxypropane;

- l-(acetamido-C-beta-D-glucopyranosyl)-2-aminopropane;

isomers thereof and mixtures thereof.

The active agent may be present in the composition of the present invention in an amount preferably ranging from 0.01% to 5% by weight and better still from 0.05% to 3% by weight, and even more preferably from 0.1% to 1% by weight, relative to the total weight of the composition.

• Adjuvants The compositions according to the present invention may also contain various adjuvants conventionally used in compositions for cleansing keratinous substances such as skin and lips, which may be selected from a physiologically acceptable medium, such as an aqueous medium, especially water, anionic, non-ionic, amphoteric or zwitterionic polymers, or mixtures thereof, oils different from (d) triglyceride oil, antioxidants, sequestering agents, fragrances, dispersing agents, film-forming agents, ceramides, preservatives, such as sodium dehydroacetate, phenoxyethanol, and chlorphenesin, co-preservatives, such as decylene glycol, ethylhexyl glycerin, and caprylyl glycol, and opacifying agents.

The aqueous medium of the compositions according to the present invention may contain, besides water, one or more water soluble solvents at room temperature (25°C), such as for example linear or branched monoalcohols comprising from 1 to 6 carbon atoms like ethanol, propanol, butanol, isopropanol, isobutanol, pentanol, and hexanol.

The composition according to the present invention comprises an aqueous medium, i.e. a medium comprising an amount of water of at least 50% by weight, preferably ranging from 50%) to 95% by weight and better still from 60% to 90% by weight relative to the total weight of the composition.

The pH of the composition according to the present invention may be adjusted to the desired value using acidifying or basifying agents commonly used in cleansing keratinous substances using conventional buffer systems.

The pH of the composition may be from 5 to 8, more preferably from 6 to 8.0. Among the basifying agents, mention may be made, by way of example, of ammonium hydroxide, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines and also their derivatives, sodium or potassium hydroxide and compounds of the formula below: R.

N-W - N

wherein

W denotes an alkylene such as propylene optionally substituted by a hydroxy 1 or a C!-C₄ alkyl radical, and R_a, Rb, Rc and Rd independently denote a hydrogen atom, an alkyl radical or a Ci-C₄ hydroxyalkyl radical, which may be exemplified by 1,3-propanediamine and

derivatives thereof. Sodium or potassium hydroxide may also be preferable.

[Preparation]

The composition according to the present invention can be prepared by mixing the ingredients (a) to (d), as essential ingredients, as well as optional ingredient(s), as explained above.

The method and means to mix the above essential and optional ingredients are not limited. Any conventional method and means can be used to mix the above essential and optional ingredients to prepare the composition according to the present invention.

In one specific embodiment of the present invention of the present invention, the composition according to the present invention can be prepared by mixing surfactants included in the (a) surfactant system at about 60 to 90°C to prepare a mixture, and then adding other components and mixing them after cooling down the mixture to about 20 to 50°C.

[Cosmetic Process] The composition according to the present invention may preferably be used as a cosmetic composition. The cosmetic composition may be a skin cosmetic composition, such as a skin cleansing composition. The skin here encompasses face skin,. neck skin, and the scalp.

The composition according to the present invention may also be used for mucosae such as the lips, and the like.

In particular, the composition according to the present invention may be intended for application onto a keratinous substance such as the skin or lips, preferably the skin. Thus, the composition according to the present invention can be used for a cosmetic process for the skin or lips, preferably a cleansing process for the skin or lips, and more preferably a cleansing process for the skin to remove make-up on the skin or lips.

The cosmetic process or cosmetic use for a keratinous substance such as the skin and the lips, according to the present invention comprises, at least, the step of applying onto the keratinous substance the composition according to the present invention.

EXAMPLES

The present invention will be described in a more detailed manner by way of examples.

However, these examples should not be construed as limiting the scope of the present invention.

[Compositions] Each of the cosmetic compositions for cleansing skin according to Examples 1-5 (Ex. 1 to Ex. 5) and Comparative Examples 1-6 (Comp. Ex. 1 to Comp. Ex. 6) was prepared in accordance with the following preparation protocol. The compositions are shown in the following Tables 1 and 2.

Among the ingredients, potassium cocoyl glycinate and potassium cocoate were from Amilite GCK 12H® by Ajinomoto, which contains 21% by weight of potassium cocoyl glycinate and 9% by weight of potassium cocoate as active raw materials. Coco-betaine was obtained from Cognis (product name: Dehyton AB-30®), which contains 30% by weight of

coco-betaine and 6.5 % by weight of sodium chloride as the active raw material.

Acrylates/vinyl neodecanoate crosspolymer was obtained from DOW CHEMICAL

COMPANY (product name: ACULYN 38®), which contains 19% by weight of this polymer as the active raw material. Acrylates/beheneth-25 methacrylate copolymer was obtained from LUBRIZOL (product name: NOVETHIX L-10 POLYMER®), which contains 30% by weight of this polymer as the active raw material. The numerical values for the amounts of the ingredients are all based on "% by weight" as active raw materials.

[Preparation Protocol]

1) Surfactants (potassium cocoyl glycinate, potassium cocoate, coco-betaine, and lecithin, and cocamide mea, glyceryl stearate se, and lauric acid, if present, were mixed at 70°C to prepare a mixture.

2) The mixture was cooled down to a temperature below 40°C.

3) Other ingredients were added to the mixture and mixed therein

4) Finally, the pH of the mixture was adjusted to 7.5.

[Evaluation] (Foaming Quality, Rinsability, and Moisturizing Effect)

The evaluation of foaming quality, rinsability, and moisturizing effect of each of the compositions according to Examples 1 to 5 and Comparative Examples 1 to 6 was conducted by an expert panel based on internal evaluation standard. Good moisturizing effect leads good feeling on the skin after rinse off, such as skin mildness and moisturizing sensation. These properties were evaluated in accordance with the evaluation criteria shown below.

Good: acceptable or good

Poor: rather bad or not acceptable

(Stability)

The viscosity of each of the compositions according to Examples 1-5 and Comparative Examples 1-6 was measured with a proRheo rheometer R180 (proRheo GmbH), using a 25 mL cup together with mobile 4 at 200 rpm and 25°C. The viscosity value after mixing the compositions for 10 minutes was read. The measurements were carried out just after the composition was prepared and after stored at 4°C or 45 °C for 2 months. The stability was evaluated in accordance with the evaluation criteria shown below. Good: viscosity reduction after stored for 2 months at 4°C and 45° was within 30% from the initial viscosity value

Poor: viscosity reduction after stored for 2 months at 4°C and 45° was more than 30% from the initial viscosity value

The evaluation results are summarized in Table 3 below.

Table 1

Table 2

Table 3

As can be seen from Table 3, the compositions according to each of Examples 1-5, which include the specific combination of the components (a) to (d) of the present invention exhibited good stability while maintaining good foaming quality, rinsability, and moisturizing effect.

On the other hand, the composition according to Comparative Example 1 , which lacks amphiphilic lipid material and associative copolymer of (meth)acrylic acid and of

(Ci-C₆)alkyl ester of (meth)acrylic acid, showed inferior stability. The composition according to Comparative Example 2, which lacks associative copolymer of (meth)acrylic acid and of (C₁-C₆)alkyl ester of (meth)acrylic acid, also showed inferior stability. Likely, the composition according to Comparative Example 3, which lacks amphiphilic lipid material, showed inferior stability. The composition according to Comparative Example 4, which includes lauric acid and glyceryl stearate as additional surfactants but lacks amphiphilic lipid material and associative copolymer of (meth)acrylic acid and of (Ci-C6)alkyl ester of

(meth)acrylic acid, showed poor foam quality. The composition according to Comparative Example 5, which also includes lauric acid and glyceryl stearate as additional surfactants but lacks associative copolymer of (meth)acrylic acid and of (C₁-C₆)alkyl ester of (meth)acrylic acid, showed poor foam quality. The composition according to Comparative Example 6, which includes PEG- 120 methyl glucose dioleate as additional thickener but lacks associative copolymer of (meth)acrylic acid and of (Ci-C₆)alkyl ester of (meth)acrylic acid, showed poor rinsability.

Therefore, it can be concluded that the composition according to the present invention can be very preferable as a composition for cleansing keratinous substances, since it exhibits good foaming quality, rinsability, and skin-care effect giving a moisturized sensation on the skin after rinsing off, as well as good stability.

Claims

A composition for cleansing keratinous substances, such as skin, comprising:

(a) a surfactant system comprising:

(a-1) at least one N-(C₆-C3o)acyl-amino acid based surfactant, (a-2) at least one amphoteric surfactant chosen from betaines,

(C₈-C₂₀)alkyl betaines, (C8-C2o)alkylamido(C₁-C₆)alkylbetaines, and mixtures thereof,

(a-3) at least one salt of a C₈-C₂o fatty acid, and

(a-4) at least one amphiphilic lipid material;

(b) at least one non-associative crosslinked copolymer of (meth)acrylic acid, and of (Ci-C₄)alkyl ester of (meth)acrylic acid;

(d) at least one triglyceride oil,

The composition according to Claim 1 , wherein the (b) non-associative crosslinked copolymer comprises vinyl ester, preferably carboxylic acid vinyl ester, as a monomer.

The composition according Claim 1 or 2, wherein the (c) associative copolymer comprises ester of (meth)acrylic acid or itaconic acid, and of polyoxyalkylenated fatty alcohol, as a monomer.

The composition according to any one of the preceding claims, wherein the (a-1) N-(C₆-C₃₀)acyl-amino acid based surfactant is N-(C₈-Ci₈)acyl-amino acid based surfactant, preferably potassium N-cocoyl glycinate or sodium N-cocoyl glycinate, and more preferably potassium N-cocoyl glycinate.

The composition according to any one of the preceding claims, wherein the (a-1) N-(C₆-C₃₀)acyl-amino acid based surfactant is present in the composition in an amount ranging from 0.1 to 7% by weight, preferably from 1 to 6% by weight, and more preferably from 2 to 5% by weight, with respect to the total weight of composition.

The composition according to any one of the preceding claims, wherein the (a-2) amphoteric surfactant is chosen from among coco betaine, lauryl betaine, oxyethylenated (10 EO) lauryl betaine, oxyethylenated (10 EO) stearyl betaine, cocamidopropyl betaine, lauramidopropyl betaine and mixtures thereof.

The composition according to any one of the preceding claims, wherein the (a-2) amphoteric surfactant is present in an amount ranging from 0.1 to 6% by weight, preferably from 0.5 to 5% by weight, and more preferably from 1 to 4% by weight, with respect to the total weight of the composition.

The composition according to any one of the preceding claims, wherein the (a-3) salt of the C₈-C₂o fatty acid is chosen from a salt of caproic acid, capric acid, caprylic acid, oleic acid, linoleic acid, lauric acid, myristic acid, stearic acid, palmitic acid, and mixtures thereof, and is preferably potassium cocoate.

9. The composition according to any one of the preceding claims, wherein the (a-3) salt of the C₈-C₂₀ fatty acid is present in an amount ranging from 0.1 to 6% by weight, in particular from 0.5 to 5% by weight, and more particularly from 1 to 4% by weight, with respect to the total weight of the composition.

10. The composition according any one of the preceding claims, wherein the (a-4)

amphiphilic lipid material is lecithin.

11. The composition according any one of the preceding claims, wherein the (a-4)

amphiphilic lipid material is present in an amount ranging from 0.01 to 5% by weight, preferably from 0.05 to 3% by weight, and more preferably from 0.1 to 1% by weight, with respect to the total weight of the composition.

12. The composition according to any one of preceding claims, wherein the (d)

triglyceride oil is chosen from jojoba oil, babassu oil, sunflower oil, olive oil, canola oil, coconut oil, meadowfoam seed oil, Brazil nut oil, marula oil, maize oil, argan oil, soybean oil, marrow oil, grapeseed oil, linseed oil, sesame oil, hazelnut oil, apricot oil, macadamia oil, arara oil, coriander oil, castor oil, avocado oil, shea butter oil, rapeseed oil, copra oil, shea butter, Nilotica shea butter, galam butter, Borneo butter or fat or tengkawang tallow, shorea butter, illipe butter, madhuca butter, Madhuca longifolia butter, mowrah butter, katiau butter, phulwara butter, mango butter, murumuru butter, kokum butter, ucuuba butter, tucuma butter, painya butter, coffee butter, apricot butter, macadamia butter, grapeseed butter, avocado butter, olive butter, sweet almond butter, cocoa butter, sunflower butter, and mixtures thereof and preferably, is selected from shea butter, olive oil, canola oil, meadowfoam seed oil and mixtures thereof.

13. The composition according to any one of the preceding claims, wherein the (a)

surfactant system comprises additional surfactants selected from anionic, amphoteric, nonionic and/or cationic foaming surfactants and non-foaming surfactants, which are different from the surfactants (a-1) to (a-4) in the (a) surfactant system.

14. The composition according to Claim 13, wherein the total amount of surfactants in the composition is less than 15% by weight relative to the total weight of the composition.

15. A cosmetic process for cleansing keratinous substances, preferably skin, comprising the step of applying the composition according to any one of the preceding claims to the keratinous substances.