DESCRIPTION

SILICONE-FREE COMPOSITION FOR KERATIN FIBERS IN THE FORM OF

ULTRA-FINE O/W EMULSION

TECHNICAL FIELD

The present invention relates to a silicone-free composition for keratin fibers in the form of an ultra-fine O/W emulsion, in particular a shampoo, which is transparent or translucent and can provide a better performance than a silicone-containing composition.

BACKGROUND ART

A transparent or translucent composition for keratin fibers, for example a transparent or translucent shampoo, has a beautiful appearance as a product, and thus it is an attractive product to consumers. Many transparent or translucent shampoos comprising silicones are widely known. Silicones are generally used in a hair-washing/conditioning composition to disentangle hair easily and provide flexibility and softness to the hair. For example, US 8425501 B2 discloses a shampoo composition with high optical transparency or translucency, comprising a silicone oil having an internal phase viscosity of less than about 50,000 est.

US 2004/0076596 Al discloses an optically transparent composition for a hair treatment, such as a shampoo, containing a hydrophobic silicone oil. EP 1330229 B2 discloses an optically transparent aqueous composition, for example a shampoo, containing a hydrophobic silicone oil.

Recently, consumers have become more sensitive to the safety of ingredients used in cosmetic products and have been interested in more environmentally friendly products. Regarding silicones, there are currently environmental concerns. Therefore, there has been a strong demand for silicone-free and transparent or translucent shampoos that can match the performance of silicone-containing shampoos.

However, if a natural oil, such as triglyceride oil, is used in a composition for keratin fibers instead of silicone oil, it is difficult to maintain the transparent or translucent appearance for a long time. Therefore, there have been no silicone-free compositions for keratin fibers with which consumers are thoroughly satisfied.

DISCLOSURE OF INVENTION

An objective of the present invention is to provide a silicone-free composition for keratin fibers, which not only has a transparent or translucent appearance but also imparts good sensory feelings to hair.

The above objective of the present invention can be achieved by a composition for keratin fibers, preferably hair, in the form of an O/W emulsion having oil droplets dispersed in an aqueous phase, the composition comprising at least one surfactant, wherein the oil droplets comprise at least one non-silicone oil, the number-average diameter of the oil droplets is less than 200 nm, and the composition does not comprise silicone or comprises less than 0.001% by weight of silicone relative to the total weight of the composition.

The non-silicone oil may be selected from the group consisting of oils of plant or animal origin, synthetic oils, hydrocarbon oils, and fatty alcohols, and mixtures thereof.

The non-silicone oil may preferably be a plant oil such as a triglyceride oil. The non-silicone oil may be present in an amount ranging from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, and more preferably 0.2 to 5% by weight, relative to the total weight of the composition.

The surfactant may be selected from the group consisting of anionic, cationic, nonionic, and amphoteric surfactants, and mixtures thereof.

Preferably, the surfactant is selected from the group consisting of monooxyalkylenated, polyoxyalkylenated, monoglycerolated, and polyglycerolated nonionic surfactants, such as polyoxyethylenated nonionic surfactants.

The surfactant may be present in an amount ranging from 10 to 70% by weight, preferably from 20 to 60% by weight, and more preferably 30 to 50% by weight, relative to the total weight of the composition. The number-average diameter of the oil droplets may be less than 180 nm, preferably less than 160 nm, and more preferably less than 140 nm.

The number-average diameter of the oil droplets may be more than 1 nm, preferably more than 5 nm, and more preferably more than 10 nm, and in particular more than 20 nm.

The composition may be a cleansing composition for hair such as a shampoo and a hair conditioner.

The composition may have a transparent appearance or a translucent appearance, preferably a transparent appearance.

Preferably, the composition does not comprise silicone.

The present invention also relates to a method for preparing a composition for keratin fibers, preferably hair, in the form of an O/W emulsion having oil droplets dispersed in an aqueous phase wherein the number-average diameter of the oil droplets is less than 200 nm, comprising:

- mixing at least one non-silicone oil and at least one surfactant;

- diluting the mixture with water so as to form the O/W emulsion; and

- optionally adding to the composition at least one additional agent selected from the group consisting of surfactants, condition agents, preservatives, pH adjusters, and other customary adjuvants used in the field of compositions for treating keratin fibers,

wherein the composition does not comprise silicone or comprises less than 0.001%) by weight of silicone relative to the total weight of the composition.

The present invention also relates to a cosmetic process for treating keratin fibers, preferably cleansing hair, comprising:

- applying the composition according to the present invention to the keratin fibers; and

- rinsing the treated keratin fibers with a sufficient amount of water. BEST MODE FOR CARRYING OUT THE INVENTION

After diligent research, the inventors have found that it is possible to provide a silicone-free composition for keratin fibers, preferably hair, in the form of an ultra-fine O/W emulsion, which not only has a transparent or translucent appearance but also can provide hair with superior sensory feelings.

Thus, one aspect of the present invention is a composition for keratin fibers, preferably hair, in the form of an O/W emulsion having oil droplets dispersed in an aqueous phase, the composition comprising at least one surfactant, wherein the oil droplets comprise at least one non-silicone oil, the number-average diameter of the oil droplets is less than 200 nm, and the composition does not comprise silicone or comprises less than 0.001% by weight of silicone relative to the total weight of the composition. The composition according to the present invention can provide hair with a good moisturizing feel, smoothness, combing property, and the like. Therefore, the composition according to the present invention can be a cosmetic composition, preferably a cleansing composition, and more preferably a shampoo. Hereinafter, the composition according to the present invention will be explained in a more detailed manner.

[Composition] The composition according to the present invention comprises less than 0.001% by weight of silicone, preferably less than 0.0005%% by weight of silicone, and more preferably less than 0.0001% by weight of silicone relative to the total weight of the composition. Most preferably, the composition does not comprise silicone. In other words, the composition according to the present invention is a "silicone-free" composition.

The silicone-free composition according to the present invention can provide hair with better sensory feelings such as a good moisturizing feel, smoothness, and combing property, while maintaining a transparent or translucent appearance due to the small size of oil droplets of an ultra-fine O/W emulsion. The transparency of the composition can be determined by measuring the turbidity with, for example, a turbidimeter (2100Q portable, Hach Company). Preferably, the composition has a turbidity of more than 0, preferably more than 10, and less than 200, preferably less than 150.

It is preferable that the composition according to the present invention be a cosmetic composition for keratin fibers, preferably a cleansing composition for keratin fibers, and more preferably a cleansing composition for hair and scalp. Thus, the composition according to the present invention may be a shampoo, a hair conditioner, a hair lotion, a disentangler, a hair cream or gel, a styling lacquer, a hairsetting lotion, a treating lotion, a dye composition (in particular for oxidation dyeing) optionally in the form of a colouring shampoo, a

hair-restructuring lotion, a permanent-waving composition, scalp shampoo or scalp conditioner, a lotion or gel for combating hair loss. Most preferably, the composition according to the present invention is a shampoo or a hair conditioner. Oil Droplets

The oil droplets (oil phase) of the O/W emulsion according to the present invention include at least one non-silicone oil. The amount of the oil phase can range from 0.1 to 80% by weight, preferably from 0.2 to 60% by weight, and more preferably from 0.5 to 30% by weight, relative to the total weight of the composition.

The oil phase is in the form of ultra-fine droplets, and thus the O/W emulsion according to the present invention is also referred to as "an ultra-fine O/W emulsion". The number-average diameter of the oil droplets in the ultra-fine O/W emulsion of the present invention is less than 200 nm, preferably less than 180 nm, and more preferably less than 160 nm, and in particular less than 140 nm. In general, the number-average diameter of the oil droplets is preferably more than 1 nm, more preferably more than 5 nm, and even more preferably more than 10 nm, and in particular more than 20 nm. The size of the oil droplets can be measured by, for example, a particle size analyzer (Vasco, Cordoun Technologies).

(Non-Silicone Oil)

The composition according to the present invention comprises at least one non-silicone oil. Two or more non-silicone oils may be used in combination. Thus, a single type of

non-silicone oil or a combination of different types of non-silicone oil may be used.

Here, "non-silicone oil" means a non-silicone compound or substance which is in the form of a liquid or a paste or a solid at room temperature (25°C) under atmospheric pressure (760 mmHg). As the non-silicone oils, those generally used in cosmetics may be used alone or in combination thereof.

The non-silicone oil may be selected from the group consisting of oils of plant or animal origin, synthetic oils, hydrocarbon oils, and fatty alcohols, and mixtures thereof.

It is preferable that the non-silicone oil be a natural oil selected from a plant oil or an animal oil.

As examples of plant oils, mention may be made of, for example, hydrocarbon-based oils of plant origin, such as phytostearyl esters such as phytostearyl oleate, phytostearyl isostearate and lauroyl/octyldodecyl/phytostearyl glutamate (Ajinomoto, Eldew PS203), triglycerides formed from fatty acid esters of glycerol, in particular in which the fatty acids may have chain lengths ranging from C ₄ to C ₃₆ and especially from C ₁₈ to C ₃₆ , these oils possibly being linear or branched, and saturated or unsaturated; these oils may especially be heptanoic or octanoic triglycerides, shea oil, alfalfa oil, poppy oil, winter squash oil, millet oil, barley oil, quinoa oil, rye oil, candlenut oil, passionflower oil, shea butter, aloe vera oil, sweet almond oil, peach stone oil, groundnut oil, argan oil, avocado oil, baobab oil, borage oil, broccoli oil, calendula oil, camelina oil, canola oil, carrot oil, safflower oil, flax oil, rapeseed oil, cotton oil, coconut oil (cocos nucifera oil), marrow seed oil, wheatgerm oil, jojoba oil, lily oil, macadamia oil, corn oil, meadowfoam oil, St John's Wort oil, monoi oil, hazelnut oil, apricot kernel oil, walnut oil, olive oil, evening primrose oil, palm oil, blackcurrant pip oil, kiwi seed oil, grapeseed oil, pistachio oil, winter squash oil, pumpkin oil, quinoa oil, musk rose oil, sesame oil, soybean oil, sunflower oil, castor oil and watermelon oil, and mixtures thereof, or alternatively caprylic/capric triglycerides, such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810 ^® , 812 ^® and 818 ^® by the company Dynamit Nobel. Mention may also be made of modified plant oils, for example, activated coconut oil, such as those sold under the names Scalpro or Acnaed by the company Biotropics.

As examples of animal oils, mention may be made of, for example, squalene and squalane.

As examples of synthetic oils, mention may be made of alkane oils such as isododecane and isohexadecane, ester oils, ether oils, and artificial triglycerides.

The ester oils are preferably liquid esters of saturated or unsaturated, linear or branched

C ₁ -C ₂₆ aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched C1-C26 aliphatic monoalcohols or polyalcohols, the total number of carbon atoms of the esters being preferably greater than or equal to 10, and preferably less than or equal to 30.

Preferably, for the esters of monoalcohols, at least one from among the alcohol and the acid from which the esters of the present invention are derived is branched.

Among the monoesters of monoacids and of monoalcohols, mention may be made of ethyl palmitate, ethyl hexyl palmitate, isopropyl palmitate, dicaprylyl carbonate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate and isostearyl neopentanoate.

Esters of C ₄ -C ₂₂ dicarboxylic or tricarboxylic acids and of C1-C22 alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of non-sugar C ₄ -C ₂₆ dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.

Mention may especially be made of: diethyl sebacate; isopropyl lauroyl sarcosinate;

diisopropyl sebacate; bis(2-ethylhexyl) sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; bis(2-ethylhexyl) adipate; diisostearyl adipate; bis(2-ethylhexyl) maleate; triisopropyl citrate; triisocetyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate.

As ester oils, one can use sugar esters and diesters of C ₆ -C ₃ o and preferably Ci ₂ -C ₂₂ fatty acids. It is recalled that the term "sugar" means oxygen-bearing hydrocarbon-based compounds containing several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides.

Examples of suitable sugars that may be mentioned include sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, especially alkyl derivatives, such as methyl derivatives, for instance methylglucose.

The sugar esters of fatty acids may be chosen especially from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C ₆ -C ₃₀ and preferably C ₁₂ -C ₂₂ fatty acids. If they are unsaturated, these compounds may have one to three conjugated or non-conjugated carbon-carbon double bonds.

The esters according to this variant may also be selected from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof. These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, especially, oleopalmitate, oleostearate and palmitostearate mixed esters, as well as pentaerythrityl tetraethyl hexanoate.

More particularly, use is made of monoesters and diesters and especially sucrose, glucose or methylglucose monooleates or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates.

An example that may be mentioned is the product sold under the name Glucate ^® DO by the company Amerchol, which is a methylglucose dioleate.

As examples of preferable ester oils, mention may be made of, for example, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate, ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecyl neopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprylate/caprate, methyl palmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate, isopropyl lauroyl sarcosinate, isononyl

isononanoate, ethylhexyl palmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropyl isostearate, isopropyl myristate, isodecyl oleate, glyceryl tri(2-ethylhexanoate),

pentaerythrityl tetra(2-ethylhexanoate), 2-ethylhexyl succinate, diethyl sebacate, and mixtures thereof.

As examples of artificial triglycerides, mention may be made of, for example, capryl caprylyl glycerides, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, glyceryl tri(caprate/caprylate) and glyceryl tri(caprate/caprylate/linolenate).

The hydrocarbon oils may be chosen from:

- linear or branched, optionally cyclic, C ₆ -C ₁₆ lower alkanes. Examples that may be mentioned include hexane, undecane, dodecane, tridecane, and isoparaffihs, for instance isohexadecane, isododecane and isodecane; and

- linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffins, liquid petroleum jelly, polydecenes and hydrogenated polyisobutenes such as Parleam ^® , and squalane.

As preferable examples of hydrocarbon oils, mention may be made of, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin, vaseline or petrolatum, naphthalenes, and the like; hydrogenated polyisobutene, isoeicosane, and decene/butene copolymer; and mixtures thereof.

The term "fatty" in the fatty alcohol means the inclusion of a relatively large number of carbon atoms. Thus, alcohols which have 4 or more, preferably 6 or more, and more preferably 12 or more carbon atoms are encompassed within the scope of fatty alcohols. The fatty alcohol may be saturated or unsaturated. The fatty alcohol may be linear or branched.

The fatty alcohol may have the structure R-OH wherein R is chosen from saturated and unsaturated, linear and branched radicals containing from 4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and more preferably from 12 to 20 carbon atoms. In at least one embodiment, R may be chosen from C ₁₂ -C ₂ o alkyl and C ₁₂ -C ₂ o alkenyl groups. R may or may not be substituted with at least one hydroxyl group.

As examples of the fatty alcohol, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol,

arachidonyl alcohol, erucyl alcohol, and mixtures thereof.

It is preferable that the fatty alcohol be a saturated fatty alcohol. Thus, the fatty alcohol may be selected from straight or branched, saturated or unsaturated C ₆ -C ₃₀ alcohols, preferably straight or branched, saturated C ₆ -C ₃₀ alcohols, and more preferably straight or branched, saturated Ci ₂ -C ₂₀ alcohols.

The term "saturated fatty alcohol" here means an alcohol having a long aliphatic saturated carbon chain. It is preferable that the saturated fatty alcohol be selected from any linear or branched, saturated C ₆ -C ₃₀ fatty alcohols. Among the linear or branched, saturated C ₆ -C ₃ o fatty alcohols, linear or branched, saturated C ₁₂ -C ₂₀ fatty alcohols may preferably be used. Any linear or branched, saturated C ₁₆ -C2o fatty alcohols may be more preferably used.

Branched C ₁ 6-C ₂₀ fatty alcohols may be even more preferably used.

As examples of saturated fatty alcohols, mention may be made of lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol, and mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol, octyldodecanol, hexyldecanol, or a mixture thereof (e.g., cetearyl alcohol) as well as behenyl alcohol, can be used as a saturated fatty alcohol.

The amount in the composition according to the present invention of the non-silicone oil ranges from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, and more preferably 0.2 to 5% by weight, relative to the total weight of the composition.

Surfactant

The composition according to the present invention comprises at least one surfactant. Two or more surfactants may be used in combination. Thus, a single type of surfactant or a combination of different types of surfactants may be used.

Any surfactant may be used for the present invention. The surfactant may be selected from the group consisting of anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants, and mixtures thereof.

(i) Anionic Surfactants

The composition may comprise at least one anionic surfactant. Two or more anionic surfactants may be used in combination.

It is preferable that the anionic surfactant be selected from the group consisting of

(C6-C ₃₀ )alkyl sulfates, (C ₆ -C ₃ o)alkyl ether sulfates, (C6-C ₃₀ )alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates; (C ₆ -C ₃ o)alkylsulfonates,

(C6-C ₃₀ )alkylamide sulfonates, (C ₆ -C ₃₀ )alkylaryl sulfonates, a-olefm sulfonates, paraffin sulfonates; (C ₆ -C ₃ o)alkyl phosphates; (C6-C ₃₀ )alkyl sulfosuccinates, (C ₆ -C ₃ o)alkyl ether sulfosuccinates, (C ₆ -C3o)alkylamide sulfosuccinates; (C ₆ -C3o)alkyl sulfoacetates; (C ₆ -C ₂₄ )acyl sarcosinates; (C ₆ -C ₂ 4)acyl glutamates; (C ₆ -C ₃ o)alkylpolyglycoside carboxylic ethers;

(C ₆ -C3 ₀ )alkylpolyglycoside sulfosuccinates; (C6-C3o)alkyl sulfosuccinamates; (C ₆ -C ₂ 4)acyl isethionates; N-(C6-C ₂₄ )acyl taurates; C ₆ -C3o fatty acid salts; coconut oil acid salts or hydrogenated coconut oil acid salts; (C ₈ -C ₂₀ )acyl lactylates; (C6-C3 ₀ )alkyl-D-galactoside uronic acid salts; polyoxyalkylenated (C ₆ -C ₃₀ )alkyl ether carboxylic acid salts;

polyoxyalkylenated (C ₆ -C3o)alkylaryl ether carboxylic acid salts; and polyoxyalkylenated (C ₆ -C3o)alkylamido ether carboxylic acid salts; and corresponding acid forms. In at least one embodiment, the anionic surfactants are in the form of salts such as salts of alkali metals, for instance sodium; salts of alkaline-earth metals, for instance magnesium; ammonium salts; amine salts; and amino alcohol salts. Depending on the conditions, they may also be in acid form. It is more preferable that the anionic surfactant be selected from salts of (C ₆ -C3 ₀ )alkyl sulfates, (C ₆ -C ₃₀ )alkyl ether sulfates or polyoxyalkylenated (C ₆ -C ₃₀ )alkyl ether carboxylic acids salified or not.

In particularly, the anionic surfactant may be (C ₆ -C ₃₀ )alkyl ether sulfates, such as lauryl sulfate, laureth sulfate, and salts and mixtures of these. More particularly, the lauryl sulfate may be sodium lauryl sulfate and the laureth sulfate may be sodium laureth sulfate. Most preferably, the anionic surfactant is sodium laureth sulfate.

(ii) Amphoteric Surfactants

The composition may comprise at least one amphoteric surfactant. Two or more amphoteric surfactants may be used in combination.

The amphoteric or zwitterionic surfactants can be, for example (non-limiting list), amine derivatives such as aliphatic secondary or tertiary amine, and optionally quaternized amine derivatives, in which the aliphatic radical is a linear or branched chain including 8 to 22 carbon atoms and containing at least one water-solubilizing anionic group (for example, carboxylate, sulphonate, sulphate, phosphate or phosphonate). The amphoteric surfactant may preferably be selected from the group consisting of betaines and amidoaminecarboxylated derivatives.

It is preferable that the amphoteric surfactant be selected from betaine-type surfactants. The betaine-type amphoteric surfactant is preferably selected from the group consisting of alkylbetaines, alkylamidoalkylbetaines, sulfobetaines, phosphobetaines, and

alkylamidoalkylsulfobetaines, in particular, (C8-C ₂ 4)alkylbetaines,

(C ₈ -C ₂₄ )alkylamido(C ₁ -C ₈ )alkylbetaines, sulphobetaines, and

(C ₈ -C ₂₄ )alkylamido(C ₁ -C ₈ )alkylsulphobetaines. In one embodiment, the amphoteric surfactants of betaine type are chosen from (C ₈ -C ₂₄ )alkylbetaines,

(C ₈ -C ₂₄ )alkylamido(C ₁ -C ₈ )alkylsulphobetaines, sulphobetaines, and phosphobetaines.

Non-limiting examples that may be mentioned include the compounds classified in the CTFA International Cosmetic Ingredient Dictionary & Handbook, 15th Edition, 2014, under the names cocobetaine, laurylbetaine, cetylbetaine, coco/oleamidopropylbetaine, cocamidopropylbetaine, palmitamidopropylbetaine, stearamidopropylbetaine, cocamidoethylbetaine, cocamidopropylhydroxysultaine, oleamidopropylhydroxysultaine, cocohydroxysultaine, laurylhydroxysultaine, and cocosultaine, alone or as mixtures. The betaine-type amphoteric surfactant is preferably an alkylbetaine and an

alkylamidoalkylbetaine, in particular cocobetaine and cocamidopropylbetaine.

Among the amidoaminecarboxylated derivatives, mention may be made of the products sold under the name Miranol, as described in U.S. Pat. Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982 (the disclosures of which are incorporated herein by reference), under the names Amphocarboxyglycinates and

Amphocarboxypropionates, with the respective structures:

R ₁ -CONHCH ₂ CH ₂ -N ⁺ (R ₂ )(R ₃ )(CH ₂ COO ^" ) M ⁺ X ^" (B 1 ) in which:

Ri denotes an alkyl radical of an acid Ri-COOH present in hydro lysed coconut oil, a heptyl, nonyl or undecyl radical,

R ₂ denotes a beta-hydroxyethyl group,

R ₃ denotes a carboxymethyl group,

M ⁺ denotes a cationic ion derived from alkaline metals such as sodium; ammonium ion; or an ion derived from an organic amine;

X ^" denotes an organic or inorganic anionic ion such as halides, acetates, phosphates, nitrates, alkyl(C ₁ -C ₄ )sulfates, alky^d-C-t)- or alky^d-C^aryl-sulfonates, particularly methylsulfate

R ₁ '-CONHCH ₂ CH ₂ -N(B)(C) (B2) in which:

Ri' denotes an alkyl radical of an acid Ri'-COOH present in coconut oil or in hydrolysed linseed oil, an alkyl radical, such as a C ₇ , C ₉ , Cn or Co alkyl radical, a Cn alkyl radical and its iso-form, or an unsaturated C ₁₇ radical,

B represents -CH ₂ CH ₂ OX',

C represents -(CH ₂ ) _Z -Y', with z=l or 2,

X' denotes a -CH ₂ -COOH group, -CH ₂ -COOZ\ -CH CH ₂ -COOH, -CH ₂ CH ₂ -COOZ' or a hydrogen atom, and

Y' denotes -COOH, -COOZ', -CH ₂ -CHOH-S0 ₃ Z', -CH ₂ -CHOH-S0 ₃ H radical or a

-CH ₂ -CH(OH)-S0 ₃ -Z' radical,

wherein Z' represents an ion of an alkaline or alkaline earth metal such as sodium, an ion derived from an organic amine or an ammonium ion;

and

Ra"-NH-CH(Y")-(CH ₂ )n-C(0)-NH-(CH ₂ )n-N(Rd)(Re) (B'2) in which:

Y" denotes -C(0)OH, -C(0)OZ", -CH ₂ -CH(OH)-S0 ₃ H or -CH ₂ -CH(OH)-S0 ₃ -Z", wherein Z" denotes a cationic ion derived from alkaline metal or alkaline-earth metals such as sodium, an ion derived from organic amine or an ammonium ion;

Rd and Re denote a d-C ₄ alkyl or d-C4 hydroxyalkyl radical;

R _a " denotes a C ₁₀ -C ₃₀ group alkyl or alkenyl group from an acid, and n and n' independently denote an integer from 1 to 3.

It is preferable that the amphoteric surfactant with formula B 1 and B2 be selected from

(C8-C24)-alkyl amphomonoacetates, (C ₈ -C ₂ 4)alkyl amphodiacetates, (C ₈ -C ₂₄ )alkyl

amphomonopropionates, and (C ₈ -C24)alkyl amphodipropionates

These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names Disodium Cocoamphodiacetate, Disodium Lauroamphodiacetate, Disodium

Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphopropionate, Disodium Caprylamphodipropionate, Disodium

Caprylamphodipropionate, Lauroamphodipropionic acid and Cocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate sold under the trade name Miranol ^® C2M concentrate by the company Rhodia Chimie.

Among compounds of formula (B'2) mention may be made of sodium diethylaminopropyl cocoaspartamide (CTFA) marketed by CHIMEX under the denomination CHIMEXANE HB.

(iii) Cationic Surfactants

The composition may comprise at least one cationic surfactant. Two or more cationic surfactants may be used in combination.

The cationic surfactant may be selected from the group consisting of optionally

polyoxyalkylenated, primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof.

Examples of quaternary ammonium salts that may be mentioned include, but are not limited to:

- those of general formula (B3) below:

wherein

Ri, R ₂ , R3, and R ₄ , which may be identical or different, are chosen from linear and branched aliphatic radicals including from 1 to 30 carbon atoms and optionally including heteroatoms such as oxygen, nitrogen, sulfur and halogens. The aliphatic radicals may be chosen, for example, from alkyl, alkoxy, C ₂ -C ₆ polyoxyalkylene, alkylamide,

(C ₁₂ -C22)alkylamido(C ₂ -C ₆ )alkyl, (C ₁₂ -C ₂₂ )alkylacetate and hydroxyalkyl radicals; and aromatic radicals such as aryl and alkylaryl; and X ^" is chosen from halides, phosphates, acetates, lactates, (C ₂ -C ₆ ) alkyl sulfates and alkyl- or alkylaryl-sulfonates;

- quaternary ammonium salts of imidazoline, for instance those of formula (B4) below:

(B4)

wherein:

R ₅ is chosen from alkenyl and alkyl radicals including from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow or of coconut;

R ₆ is chosen from hydrogen, Ci-C ₄ alkyl radicals, and alkenyl and alkyl radicals including from 8 to 30 carbon atoms;

R ₇ is chosen from Ci-C ₄ alkyl radicals;

R ₈ is chosen from hydrogen and C ₁ -C ₄ alkyl radicals; and

X ^" is chosen from halides, phosphates, acetates, lactates, alkyl sulfates, alkyl sulfonates, and alkylaryl sulfonates. In one embodiment, R ₅ and R ₆ are, for example, a mixture of radicals chosen from alkenyl and alkyl radicals including from 12 to 21 carbon atoms, such as fatty acid derivatives of tallow, R ₇ is methyl and R ₈ is hydrogen. Examples of such products include, but are not limited to, Quaternium-27 (CTFA 1997) and Quaternium-83 (CTFA 1997), which are sold under the names "Rewoquat®" W75, W90, W75PG and W75HPG by the company Witco;

- di or tri quaternary ammonium salts of formula (B5):

(B5)

wherein:

R ₉ is chosen from aliphatic radicals including from 16 to 30 carbon atoms;

Rio is chosen from hydrogen or alkyl radicals including from 1 to 4 carbon atoms or the group

-(CH ₂ ) ₃ (Rl6a)(Rl7a)(Rl8a)N ⁺ X-.;

Rn, Ri2, R ₁₃ , R ₁₄ , R _16a , Ri7a, and R _18a , which may be identical or different, are chosen from hydrogen and alkyl radicals including from 1 to 4 carbon atoms; and

X ^" is chosen from halides, acetates, phosphates, nitrates, ethyl sulfates, and methyl sulfates.

An example of one such diquaternary ammonium salt is FINQUAT CT-P of FINETEX

(Quaternium-89) or FINQUAT CT (Quaternium-75);

and

quaternary ammonium salts including at least one ester function, such as those of formula (B6) below:

(C _s H _2s O) _z - o

R 24 (0-CrHr2(OH)n)y -N— (CtH _t2 (OH)t1 23 X

R ' ₅ 22 (B6) wherein:

R ₂ 2 is chosen from d-C ₆ alkyl radicals and d-Ce hydroxyalkyl and dihydroxyalkyl radicals; R-23 is chosen from:

the radical below:

O

R '.26 c

linear and branched, saturated and unsaturated d-C22 hydrocarbon-based radicals R27, and hydrogen,

R25 is chosen from:

the radical below:

O

R '2. 8 c

linear and branched, saturated and unsaturated d-C ₆ hydrocarbon-based radicals R ₂₉ , and hydrogen,

R24, R2 ₆ , and R ₂₈ , which may be identical or different, are chosen from linear and branched, saturated and unsaturated, C7-C21, hydrocarbon-based radicals;

r, s, and t, which may be identical or different, are chosen from integers ranging from 2 to 6; each of rl and tl, which may be identical or different, is 0 or 1, and r2+rl=2r and tl+2t=2t; y is chosen from integers ranging from 1 to 10;

x and z, which may be identical or different, are chosen from integers ranging from 0 to 10; X ^" is chosen from simple and complex, organic and inorganic anions; with the proviso that the sum x+y+z ranges from 1 to 15, that when x is 0, R ₂₃ denotes R27, and that when z is 0, R2 ₅ denotes R29. R22 may be chosen from linear and branched alkyl radicals. In one embodiment, R22 is chosen from linear alkyl radicals. In another embodiment, R22 is chosen from methyl, ethyl, hydroxyethyl, and dihydroxypropyl radicals, for example methyl and ethyl radicals. In one embodiment, the sum x+y+z ranges from 1 to 10. When R ₂₃ is a hydrocarbon-based radical R27, it may be long and include from 12 to 22 carbon atoms, or short and include from 1 to 3 carbon atoms. When R2 ₅ is a hydrocarbon-based radical R29, it may include, for example, from 1 to 3 carbon atoms. By way of a non-limiting example, in one embodiment, R24, R2 ₆ , and R ₂₈ , which may be identical or different, are chosen from linear and branched, saturated and unsaturated, Cn-C2i hydrocarbon-based radicals, for example from linear and branched, saturated and unsaturated C ₁₁ -C2 ₁ alkyl and alkenyl radicals. In another embodiment, x and z, which may be identical or different, are 0 or 1. In one embodiment, y is equal to 1. In another embodiment, r, s and t, which may be identical or different, are equal to 2 or 3, for example equal to 2. The anion X ^" may be chosen from, for example, halides, such as chloride, bromide, and iodide; and Ci-C ₄ alkyl sulfates, such as methyl sulfate. However, methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate and lactate, and any other anion that is compatible with the ammonium including an ester function, are other non-limiting examples of anions that may be used according to the present invention. In one embodiment, the anion X ^" is chosen from chloride and methyl sulfate.

In another embodiment, the ammonium salts of formula (B6) may be used, wherein:

R22 is chosen from methyl and ethyl radicals,

x and y are equal to 1 ;

z is equal to 0 or 1 ;

r, s and t are equal to 2;

R23 is chosen from:

the radical below:

methyl, ethyl, and C ₁₄ -C ₂₂ hydrocarbon-based radicals, and hydi

R ₂₅ is chosen from:

the radical below:

O

and hydrogen;

R24, R26, and R28, which may be identical or different, are chosen from linear and branched, saturated and unsaturated, C ₁₃ -C ₁ hydrocarbon-based radicals, for example from linear and branched, saturated and unsaturated, C ₁₃ -C ₁₇ alkyl and alkenyl radicals.

In one embodiment, the hydrocarbon-based radicals are linear.

Non-limiting examples of compounds of formula (B6) that may be mentioned include salts, for example chloride and methyl sulfate, of diacyloxyethyl-dimethylammonium, of diacyloxyethyl-hydroxyethyl-methylammonium, of

monoacyloxyethyl-dihydroxyethyl-methylammonium, of triacyloxyethyl-methylammonium, of monoacyloxyethyl-hydroxyethyl-dimethyl-ammonium, and mixtures thereof. In one embodiment, the acyl radicals may include from 14 to 18 carbon atoms, and may be derived, for example, from a plant oil, for instance palm oil and sunflower oil. When the compound includes several acyl radicals, these radicals may be identical or different.

These products may be obtained, for example, by direct esterification of optionally oxyalkylenated triethanolamine, triisopropanolamine, alkyldiethanolamine or

alkyldiisopropanolamine onto fatty acids or onto mixtures of fatty acids of plant or animal origin, or by transesterification of the methyl esters thereof. This esterification may be followed by a quaternization using an alkylating agent chosen from alkyl halides, for example methyl and ethyl halides; dialkyl sulfates, for example dimethyl and diethyl sulfates; methyl methanesulfonate; methyl para-toluenesulfonate; glycol chlorohydrin; and 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, and "Rewoquat ^® WE 18" by the company Rewo-Goldschmidt. Other non-limiting examples of ammonium salts that may be used in the composition according to the present invention include the ammonium salts including at least one ester function described in U.S. Pat. Nos. 4,874,554 and 4,137,180.

The quaternary ammonium salts mentioned above that may be used in the composition according to the present invention include, but are not limited to, tetraalkylammonium chlorides, for instance dialkyldimethylammomum and alkyltrimethylammomum chlorides in which the alkyl radical includes from about 12 to 22 carbon atoms, such as

behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium and benzyldimethylstearylammonium chloride; palmitylamidopropyltrimethylammonium chloride; and stearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold under the name "Ceraphyl® 70" by the company Van Dyk.

According to one embodiment, the cationic surfactant that may be used in the composition according to the present invention is chosen from behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, Quaternium-83, Quaternium-87, Quaternium-22, beheny lamidopropy 1-2,3 -dihydroxypropyldimethylammonium chloride,

palmitylamidopropyltrimethylammonium chloride, and stearamidopropyldimethylamine.

(iv) Nonionic Surfactants

The composition may comprise at least one nonionic surfactant. Two or more nonionic surfactants may be used in combination.

The nonionic surfactants are compounds well known in and of themselves (see, e.g., in this regard, "Handbook of Surfactants" by M. R. Porter, Blackie & Son publishers (Glasgow and London), 1991, pp. 116-178).

The nonionic surfactants may be fatty acid amides, any amide comprising in its structure at least one hydrocarbon-based chain comprising at least 6 carbon atoms may be used. The fatty acid amides may be chosen from compounds derived from an amide of alkanolamine and of a saturated or unsaturated, linear or branched C ₈ -C3 ₀ fatty acid, the alkanolamine and/or the fatty acid being optionally oxyalkenylated and more particularly oxyethylenated with 1 to 50 mol of ethylene oxide. The fatty acid amides are preferably chosen from amides of a C ₂ -C ₁₀ alkanolamine and of a C ₁₄ -C ₃₀ fatty acid, and more preferably chosen from amides of a C ₂ -C ₁₀ alkanolamine and of a C ₁₄ -C ₂₂ fatty acid.

Advantageously, the fatty acid amide may be chosen from coconut acid

monoisopropanolamide, such as cocamide MIPA, oleic acid diethanolamide, myristic acid monoethanolamide, soybean fatty acid diethanolamide, stearic acid ethanolamide, oleic acid monoisopropanolamide, linoleic acid diethanolamide, stearic acid monoethanolamide, behenic acid monoethanolamide, isostearic acid monoisopropanolamide, eruic acid diethanolamide, ricinoleic acid monoethanolamide, and rapeseed fatty acid amide containing 4 mol of ethylene oxide. Most preferably, the fatty acid amide may be cocamide MIPA marketed by INNOSPEC ACTIVE CHEMICALS under the denomination EMPILAN CIS.

Also, the nonionic surfactants can, for example, be chosen from alcohols, alpha-diols, alkylphenols and esters of fatty acids, these compounds being ethoxylated, propoxylated or glycerolated and having at least one fatty chain comprising, for example, from 8 to 30 carbon atoms, it being possible for the number of ethylene oxide or propylene oxide groups to range from 2 to 50, and for the number of glycerol groups to range from 1 to 30. Maltose derivatives may also be mentioned. Non- limiting mention may also be made of copolymers of ethylene oxide and/or of propylene oxide; condensates of ethylene oxide and/or of propylene oxide with fatty alcohols; polyethoxylated fatty amides comprising, for example, from 2 to 30 mol of ethylene oxide; poly glycerolated fatty amides comprising, for example, from 1.5 to 5 glycerol groups, such as from 1.5 to 4; ethoxylated fatty acid esters of sorbitan comprising from 2 to 30 mol of ethylene oxide; ethoxylated oils of plant origin; fatty acid esters of sucrose; fatty acid esters of polyethylene glycol; polyethoxylated fatty acid mono or diesters of glycerol (C ₆ -C2 ₄ )alkylpolyglycosides; N-(C ₆ -C24)alkylglucamine derivatives; amine oxides such as (C ₁₀ -C ₁₄ )alkylamine oxides or N-(C ₁ o-C ₁₄ )acylaminopropylmorpholine oxides; and mixtures thereof.

The nonionic surfactants may preferably be chosen from monooxyalkylenated,

polyoxyalkylenated, monoglycerolated or polyglycerolated nonionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, and are preferably oxyethylene units.

Examples of monooxyalkylenated or polyoxyalkylenated nonionic surfactants that may be mentioned include:

- monooxyalkylenated or polyoxyalkylenated (C8-C ₂ 4)alkylphenols,

- saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C ₈ -C ₃₀ alcohols,

- saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C ₈ -C ₃₀ amides,

- esters of saturated or unsaturated, linear or branched, C ₈ -C ₃ o acids and of polyalkylene glycols,

- monooxyalkylenated or polyoxyalkylenated esters of saturated or unsaturated, linear or branched, C ₈ -C ₃₀ acids and of sorbitol,

- saturated or unsaturated, monooxyalkylenated or polyoxyalkylenated plant oils, and

- condensates of ethylene oxide and/or of propylene oxide, inter alia, alone or as mixtures.

The surfactants preferably contain a number of moles of ethylene oxide and/or of propylene oxide of between 1 and 100 and most preferably between 2 and 50. According to one of the embodiments of the present invention, the polyoxyalkylenated nonionic surfactants are chosen from polyoxyethylenated fatty acid glyceride (polyethylene glycol ether of fatty acid glyceride), polyoxyethylenated and polyoxypropylenated alkyl ether, polyoxyethylenated fatty alcohol (polyethylene glycol ether of fatty alcohol) and polyoxyethylenated fatty ester (polyethylene glycol ester of fatty acid).

Examples of polyoxyethyleated fatty acid glyceride or partial glyceride that may be mentioned include those with at least 30 polyalkylene units are with 30 to 1 000, preferably 30 to 500, more preferably 30 to 200 and most preferably 40 to 100 polyethyleneglycol units. Examples to those are PEG-30 hydrogenated castor oil, PEG-35 hydro genated castor oil, PEG-40 hydrogenated castor oil, PEG-45 hydrogenated castor oil, PEG-50 hydrogenated castor oil, PEG-55 hydrogenated castor oil, PEG-60 hydrogenated castor oil, PEG-65 hydrogenated castor oil, PEG-80 hydrogenated castor oil, PEG- 100 hydrogenated castor oil, PEG-200 hydrogenated castor oil, PEG-35 castor oil, PEG-50 castor oil, PEG-55 castor oil, PEG-60 castor oil, PEG-80 castor oil, PEG-100 castor oil, PEG-200 castor oil.

' Examples of polyoxyethylenated and polyoxypropylenated alkyl ether that may be mentioned include polyoxyethylenated (1-40 EO) and polyoxypropylenated (1-30 PO) alkyl (C ₁₆ -C3 ₀ ) ethers, especially polyoxyethylenated (15-40 EO) and polyoxypropylenated (5-30 PO) alkyl (Ci6-C ₂₄ ) ethers, which could be selected from the group consisting of PPG-6

Decyltetradeceth-30, PPG- 13 Decyltetradeceth-24, PPG-6 Decyltetradeceth-20, PPG-5 Ceteth-20, PPG-8 Ceteth-20, and PPG-23 Steareth-34.

Examples of polyoxyethylenated saturated fatty alcohols (or C8-C30 alcohols) that may be mentioned include the adducts of ethylene oxide with lauryl alcohol, especially those containing from 9 to 50 oxyethylene units and more particularly those containing from 10 to 12 oxyethylene units (Laureth-10 to Laurefh-12, as the CTFA names); the adducts of ethylene oxide with behenyl alcohol, especially those containing from 9 to 50 oxyethylene units (Beheneth-9 to Beheneth-50, as the CTFA names); the adducts of ethylene oxide with cetearyl alcohol (mixture of cetyl alcohol and stearyl alcohol), especially those containing from 10 to 30 oxyethylene units (Ceteareth-10 to Ceteareth-30, as the CTFA names); the adducts of ethylene oxide with cetyl alcohol, especially those containing from 10 to 30 oxyethylene units (Ceteth-10 to Ceteth-30, as the CTFA names); the adducts of ethylene oxide with stearyl alcohol, especially those containing from 10 to 30 oxyethylene units (Steareth-10 to

Steareth-30, as the CTFA names); the adducts of ethylene oxide with isostearyl alcohol, especially those containing from 10 to 50 oxyethylene units (Isosteareth-10 to Isosteareth-50, as the CTFA names); and mixtures thereof.

Examples of polyoxyethylenated unsaturated fatty alcohols (or C ₈ -C ₃ o alcohols) that may be mentioned include the adducts of ethylene oxide with oleyl alcohol, especially those containing from 2 to 50 oxyethylene units and more particularly those containing from 10 to 40 oxyethylene units (Oleth-10 to Oleth-40j as the CTFA names); and mixtures thereof.

As examples of monoglycerolated or polyglycerolated nonionic surfactants,

monoglycerolated or polyglycerolated C ₈ -C ₄ o alcohols are preferably used.

In particular, the monoglycerolated or polyglycerolated C ₈ -C ₄₀ alcohols may correspond to the following formula:

RO-[CH ₂ -CH(CH ₂ OH)-0]m-H or RO-[CH(CH ₂ OH)-CH20] _m -H in which R represents a linear or branched C ₈ -C ₄₀ and preferably C ₈ -C ₃ o alkyl or alkenyl radical, and m represents a number ranging from 1 to 30 and preferably from 1.5 to 10.

As examples of compounds that are suitable in the context of the present invention, mention may be made of lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4

Lauryl Ether), lauryl alcohol containing 1.5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleocetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.

The alcohol may represent a mixture of alcohols in the same way that the value of m represents a statistical value, which means that, in a commercial product, several species of polyglycerolated fatty alcohol may coexist in the form of a mixture.

Among the monoglycerolated or polyglycerolated alcohols, it is preferable to use the C ₈ /C ₁₀ alcohol containing 1 mol of glycerol, the C10 C12 alcohol containing 1 mol of glycerol and the C12 alcohol containing 1.5 mol of glycerol. The monoglycerolated or polyglycerolated C ₈ -C ₄₀ fatty esters may correspond to the following formula:

RO-[CH ₂ -CH(CH ₂ OR"')-0] _m -R" or R'0-[CH(CH20R'")-CH20] _m -R" in which each of R', R" and R'" independently represents a hydrogen atom, or a linear or branched C ₈ -C ₄₀ and preferably C ₈ -C ₃₀ alkyl-CO- or alkenyl-CO-radical, with the proviso that at least one of R', R" and R'" is not a hydrogen atom, and m represents a number ranging from 1 to 30 and preferably from 1.5 to 10. Examples of polyoxyethylenated fatty esters that may be mentioned include the adducts of ethylene oxide with esters of lauric acid, palmitic acid, stearic acid or behenic acid, and mixtures thereof, especially those containing from 9 to 100 oxyethylene units, such as PEG-9 to PEG-50 laurate (CTFA names: PEG-9 laurate to PEG-50 laurate); PEG-9 to PEG-50 palmitate (CTFA names: PEG-9 palmitate to PEG-50 palmitate); PEG-9 to PEG-50 stearate (CTFA names: PEG-9 stearate to PEG-50 stearate); PEG-9 to PEG-50 palmitostearate; PEG-9 to PEG-50 behenate (CTFA names: PEG-9 behenate to PEG-50 behenate); polyethylene glycol 100 EO monostearate (CTFA name: PEG- 100 stearate); and mixtures thereof.

According to one of the embodiments of the present invention, the nonionic surfactant may be selected from esters of polyols with fatty acids with a saturated or unsaturated chain containing for example from 8 to 24 carbon atoms, preferably 12 to 22 carbon atoms, and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units, such as glyceryl esters of a C ₈ -C ₂₄ , preferably C12-C22, fatty acid or acids and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units; sorbitol esters of a C ₈ -C ₂ 4, preferably Ci ₂ -C ₂ 2, fatty acid or acids and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units; sugar (sucrose, maltose, glucose, fructose, and/or alkylglycose) esters of a C ₈ -C ₂₄ , preferably Cn-Caa, fatty acid or acids and polyoxyalkylenated derivatives thereof, preferably containing from 10 to 200, and more preferably from 10 to 100 oxyalkylene units; ethers of fatty alcohols; ethers of sugar and a C ₈ -C ₂ 4, preferably C12-C22, fatty alcohol or alcohols; and mixtures thereof.

As glyceryl esters of fatty acids, glyceryl stearate (glyceryl mono-, di- and/or tristearate) (CTFA name: glyceryl stearate), glyceryl laurate or glyceryl ricinoleate and mixtures thereof can be cited, and as polyoxyalkylenated derivatives thereof, mono-, di- or triester of fatty acids with a polyoxyalkylenated glycerol (mono-, di- or triester of fatty acids with a polyalkylene glycol ether of glycerol), preferably polyoxyethylenated glyceryl stearate (mono-, di- and/or tristearate), such as PEG-20 glyceryl stearate (mono-, di- and/or tristearate) can be cited.

Mixtures of these surfactants, such as for example the product containing glyceryl stearate and PEG- 100 stearate, marketed under the name ARLACEL 165 by Uniqema, and the product containing glyceryl stearate (glyceryl mono- and distearate) and potassium stearate marketed under the name TEGIN by Goldschmidt (CTFA name: glyceryl stearate SE), can also be used.

The sorbitol esters of C ₈ -C24 fatty acids and polyoxyalkylenated derivatives thereof can be selected from sorbitan palmitate, sorbitan isostearate, sorbitan trioleate and esters of fatty acids and alkoxylated sorbitan containing for example from 20 to 100 EO. Preferably, the sorbitol esters of C ₈ -C ₂₄ fatty acids and polyoxyalkylenated derivatives thereof may be polyoxyethylene (20) sorbitan monostearate (CTFA name: polysorbate 60). Other examples of the sorbitol esters of C ₈ -C ₂₄ fatty acids and polyoxyalkylenated derivatives thereof that may be mentioned include sorbitan monostearate (CTFA name: sorbitan stearate), sold by the company ICI under the name Span 60, sorbitan monopalmitate (CTFA name: sorbitan palmitate), sold by the company ICI under the name Span 40, and sorbitan tristearate 20 EO (CTFA name: polysorbate 65), sold by the company ICI under the name Tween 65, polyethylene sorbitan trioleate (polysorbate 85) or the compounds marketed under the trade names Tween 20 or Tween 60 by Uniqema. As esters of fatty acids and glucose or alkylglucose, glucose palmitate, alkylglucose sesquistearates such as methylglucose sesquistearate, alkylglucose palmitates such as methylglucose or ethylglucose palmitate, methylglucoside fatty esters, the diester of methylglucoside and oleic acid (CTFA name: Methyl glucose dioleate), the mixed ester of methylglucoside and the mixture of oleic acid/hydroxystearic acid (CTFA name: Methyl glucose dioleate/hydroxystearate), the ester of methylglucoside and isostearic acid (CTFA name: Methyl glucose isostearate), the ester of methylglucoside and lauric acid (CTFA name: Methyl glucose laurate), the mixture of monoester and diester of methylglucoside and isostearic acid (CTFA name: Methyl glucose sesqui-isostearate), the mixture of monoester and diester of methylglucoside and stearic acid (CTFA name: Methyl glucose sesquistearate) and in particular the product marketed under the name Glucate SS by AMERCHOL, and mixtures thereof can be cited.

As ethoxylated ethers of fatty acids and glucose or alkylglucose, ethoxylated ethers of fatty acids and methylglucose, and in particular the polyethylene glycol ether of the diester of methylglucose and stearic acid with about 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose distearate) such as the product marketed under the name Glucam E-20 distearate by AMERCHOL, the polyethylene glycol ether of the mixture of monoester and diester of methyl-glucose and stearic acid with about 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose sesquistearate) and in particular the product marketed under the name Glucamate SSE-20 by AMERCHOL and that marketed under the name Grillocose PSE-20 by GOLDSCHMIDT, and mixtures thereof, can for example be cited.

As sucrose esters, saccharose palmito-stearate, saccharose stearate and saccharose

monolaurate can for example be cited.

As sugar ethers, alkylpolyglucosides can be used, and for example decylglucoside such as the product marketed under the name MYDOL 10 by Kao Chemicals, the product marketed under the name PLANTAREN 2000 by Henkel, and the product marketed under the name

ORAMIX NS 10 by Seppic, caprylyl/capryl glucoside such as the product marketed under the name ORAMIX CG 110 by Seppic or under the name LUTENSOL GD 70 by BASF, laurylglucoside such as the products marketed under the names PLANTAREN 1200 N and PLANTACARE 1200 by Henkel, coco-glucoside such as the product marketed under the name PLANTACARE 818 UP by Henkel, cetostearyl glucoside possibly mixed with cetostearyl alcohol, marketed for example under the name MONTANOV 68 by Seppic, under the name TEGO-CARE CG90 by Goldschmidt and under the name EMULGADE KE3302 by Henkel, arachidyl glucoside, for example in the form of the mixture of arachidyl and behenyl alcohols and arachidyl glucoside marketed under the name MONTANOV 202 by Seppic, cocoylethylglucoside, for example in the form of the mixture (35/65) with cetyl and stearyl alcohols, marketed under the name MONTANOV 82 by Seppic, and mixtures thereof can in particular be cited.

Mixtures of glycerides of alkoxylated plant oils such as mixtures of ethoxylated (200 EO) palm and copra (7 EO) glycerides can also be cited. The nonionic surfactant according to the present invention preferably contains alkenyl or a branched C ₁₂ -C22 acyl chain such as an oleyl or isostearyl group. More preferably, the nonionic surfactant according to the present invention is PEG-20 glyceryl triisostearate.

According to one of the embodiments of the present invention, the nonionic surfactant may be selected from copolymers of ethylene oxide and of propylene oxide, in particular copolymers of the following formula:

HO(C ₂ H ₄ 0)a(C ₃ H ₆ 0)b(C ₂ H ₄ 0) _c H in which a, b and c are integers such that a+c ranges from 2 to 100 and b ranges from 14 to 60, and mixtures thereof.

The amount in the composition according to the present invention of the surfactant ranges from 10 to 70% by weight, preferably from 20 to 60% by weight, and more preferably 30 to 50% by weight, relative to the total weight of the composition.

Aqueous Phase

The composition according to the present invention comprises an aqueous medium. The aqueous medium is made up of water or a mixture of water and at least one cosmetically acceptable solvent, for example C ₁ -C ₄ lower alcohols, such as ethanol, isopropanol, tert-butanol or n-butanol; polyols such as glycerin, propylene glycol and polyethylene glycols; and mixtures thereof. Preferably, the composition according to the present invention comprises water.

The amount of water is not limited, and may be from 40 to 99% by weight, preferably from 50 to 95% by weight, and more preferably 55 to 90% by weight, relative to the total weight of the composition. Conditioning Agent

The composition according to the present invention may comprise at least one conditioning agent. Two or more conditioning agents may be used in combination. Thus, a single type of conditioning agent or a combination of different types of conditioning agents may be used.

The conditioning agent can provide keratin fibers such as hair with conditioning effects.

Preferably, the conditioning agent may be cationic polymer(s) or amphoteric polymer(s). It is preferable that the conditioning polymer(s) be chosen from:

(1) Cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium salts, such as homopolymers or copolymers comprising, as main constituent of the chain, units

corresponding to the following formula:

wherein:

k and t are equal to 0 or 1 , the sum k+t being equal to 1 ;

R ₁₂ denotes a hydrogen atom or a methyl group;

R ₁₀ and Rn, independently of each other, denote an alkyl group having from 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group has preferably 1 to 5 carbon atoms, a lower (d-C ₄ ) amidoalkyl group, or RIO and Rl 1 may denote, jointly with the nitrogen atom to which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl. R ₁₀ and Rn, independently of each other, preferably denote an alkyl group containing from 1 to 4 carbon atoms.

Among the polymers defined above, mention may be made more particularly of the dimethyldiallylammonium chloride homopolymer sold under the name Merquat 100 by the company Nalco and its homologues of low weight-average molecular weights, and the copolymers of diallyldimethylammonium chloride and of acrylamide sold under the name Merquat 550.

(2) Quaternary diammonium polymers especially containing repeating units corresponding to the following formula:

wherein:

Ri3, Ri4, Ri ₅ and R ₁₆ , which may be identical or different, represent aliphatic, alicyclic or arylaliphatic groups containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or alternatively Ri ₃ , RH, R ₁₅ and R ₁₆ , together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally containing a second heteroatom other than nitrogen, or alternatively Rn, Ri4, Ris and Ri ₆ represent a linear or branched Ci-Ce alkyl group substituted with a nitrile, ester, acyl or amide group or a group CO-0-R ₁₇ -D or CO-NH-R ₁₇ -D where R ₁₇ is an alkylene and D is a quaternary ammonium group;

A and B ₁ represent polymethylene groups containing from 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups; and

X ^" denotes an anion derived from a mineral or organic acid.

A _{1 ?} R ₁₃ and R ₁₅ can form, with the two nitrogen atoms to which they are attached, a piperazine ring.

(3) Cationic polysaccharides, especially cationic celluloses and galactomannan gums. The cationic cellulose polymers may have at least one quaternary ammonium group. It may be preferable that the cationic cellulose polymers be quatemized hydroxyethyl celluloses modified with at least one quaternary ammonium group comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof. The alkyl radicals borne by the quaternary ammonium group may preferably contain from 8 to 30 carbon atoms, especially from 10 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.

More preferably, the cationic cellulose polymer may comprise at least one quaternary ammonium group including at least one C ₈ -C ₃₀ hydrocarbon group.

Examples of quatemized alkylhydroxyethylcelluloses containing C -C ₃₀ fatty chains that may be mentioned include the products Quatrisoft LM 200, Quatrisoft LM-X 529-18-A, Quatrisoft LM-X 529-18B (C ₁₂ alkyl) and Quatrisoft LM-X 529-8 (C ₁₈ alkyl) or Softcat Polymer SL100, Softcat SX-1300X, Softcat SX-1300H, Softcat SL-5, Softcat SL-30, Softcat SL-60 , Softcat SK-MH, Softcat SX-400X, Softcat SX-400H, SoftCat SK-L, Softcat SK-M, and Softcat SK-H, sold by the company Amerchol and the products Crodacel QM, Crodacel, QL (C ₁₂ alkyl) and Crodacel QS (Cj ₈ alkyl) sold by the company Croda.

Among these quatemized alkylhydroxyethylcelluloses the products corresponding to INCI name Polyquaternium-67 are preferred.

According to another embodiment of the present invention, the conditioning agent may be proteins, protein hydrolysates, and amino acids. Examples of proteins and protein hydrolysates that may be mentioned include casein, collagen, procollagen, gelatin, keratin, glycoproteins, hydrolyzed wheat protein, hydrolyzed soy protein, hydrolyzed oat protein, hydrolyzed rice protein, hydrolyzed vegetable protein, hydrolyzed yeast protein, and whey protein. Examples of amino acids that may be mentioned include arginine, asparagine, aspartic acid, carnitine, cocoyl sarcosine, glycine, glutamic acid, histidine, hydroxyproline, acetyl hydroxy proline, isoleucine, lysine, lauroyl lysine, lauroyl sarcosine, methionine, phenylalanine, polylysine, potassium cocoyl glutamate, proline, sarcosine, serine, rice amino acids, silk amino acids, wheat amino aids, sodium glutamate, sodium lauroyl glutamate, stearoyl sarcosine, threonine, tyrosine, tryptophan, and valine.

The conditioning agent(s) may be present in a content sufficient to provide keratin fibers with conditioning effects for example, ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, and more preferably from 0.5% to 5% by weight relative to the total weight of the composition.

Preservative

The composition according to the present invention may comprise at least one preservative. Non-limiting examples of preservatives include ethanol, polyvinyl alcohol, phenoxyethanol, benzyl alcohol, salicylic acid, sodium benzoate, caprylyl glycol, methyl paraben, propyl paraben, ethylhexylglycerin, 1,3 -propanediol and mixtures thereof. The preservative(s) may be present in a content sufficient to prevent decomposition by microbial growth, for example, 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 relative to the total weight of the composition. Thickener

The composition according to the present invention may comprise at least one thickener.

Non-limiting examples of thickener include polymeric and non-polymeric thickeners.

Exemplary polymeric thickeners include various native gums. Exemplary non-polymeric thickeners include oxyethylenated molecules and especially etoxylated alkyl or acyl derivatives of polyols such as PEG-55 propylene glycol oleate. Preferably, the thickener may be a blend of propylene glycol and PEG-55 propylene glycol oleate, for example that marketed by EVONIK under the denomination ANTIL® 141 LIQUID.

The thickener(s) may be present in a content sufficient to modify viscosity or rheology of the composition, for example, 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. pH Adjuster

The composition according to the present invention may preferably include at least one pH adjuster. The adjustment of the pH to the desired value may be carried out conventionally by addition of the pH adjuster, such as an organic or inorganic base or an organic or inorganic acid or salts thereof to the composition. The base includes, for example, ammonium hydroxide, sodium hydroxide, sodium carbonate or a primary, secondary or tertiary (poly) amine, such as monoethanolamine, diethanolamine, triethanolamine, isopropanolamine or 1, 3- propanediamine. The organic acid includes, for example, a carboxylic acid, a citric acid, a tartaric acid, and a lactic acid. The inorganic acid includes, for example, a hydrochloric acid, a nitric acid, orthophosphoric acid and a sulphonic acid. The salt includes, for example, sodium phosphate and trisodium phosphate.

The pH adjuster(s) may be present in a content sufficient to adjust the pH of the composition to the desired value, for example, ranging from 0.01% to 10% by weight, preferably from 0.1% to 5% by weight, and more preferably from 0.5% to 3% by weight relative to the total weight of the composition.

Additives

If necessary, as far as the desired properties of the composition according to the present invention can be maintained, the composition according to the present invention may further contain all the customary adjuvants encountered in the field of compositions for treating keratin fibers, for example, hydrophilic solvents, perfumes, fragrances, sequestrants such as EDTA (ethylenediaminetetraacetic acid) and its salts, foam modifiers, colorants, moisturizing agents, antidandruff agents, antiseborrhoeic agents, and the like.

The amount of the additives included in the composition according to the present invention is not limited, but may be from 0.01 to 30% by weight relative to the total weight of the composition.

[Preparation]

The composition according to the present invention can be manufactured through usual techniques in the art.

The composition according to the present invention may be prepared by mixing at least one non-silicone oil and at least one surfactant and then diluting the mixture with water with a conventional process so as to form an O/W emulsion wherein the number-average diameter of the oil droplets is less than 200 nm. Optionally, after the emulsion is formed, additional agents may be mixed with the composition.

For example, a shampoo according to the present invention may be obtained by mixing at least one non-silicone oil and at least one surfactant, diluting the mixture with water so as to form an O/W emulsion having oil droplets dispersed in an aqueous phase wherein the number-average diameter of the oil droplets is less than 200 nm, and then adding the emulsion to a shampoo base.

The conventional mixing process may be performed with a homogenizer, for example a turbine mixer.

[Process and Use]

It is preferable that the composition according to the present invention be a cosmetic composition for keratin fibers, preferably a cleansing composition for keratin fibers, and more preferably a cleansing composition for hair. Most preferably, the composition according to the present invention may be a shampoo and a hair conditioner.

The present invention may also relate to a cosmetic process for treating keratin fibers, preferably cleansing hair, comprising applying the composition according to the present invention to the keratin fibers, and rinsing the treated keratin fibers with a sufficient amount of water.

The present invention may also relate to the use of the composition according to the present invention as a cosmetic product for keratin fibers or in a cosmetic product for keratin fibers, preferably a conditioning product for hair, such as a shampoo and a hair conditioner.

Another aspect of the present invention may be the use of an O/W emulsion having oil droplets dispersed in an aqueous phase, wherein the oil droplets comprises at least one non-silicone oil and the number-average diameter of the oil droplets is less than 200 nm, in a silicone-free composition for keratin fibers, preferably hair, such as a shampoo or a hair conditioner,

in order to maintain the transparency or translucency of the composition and confer on the composition properties to provide hair with better sensory feelings such as a good

moisturizing feel, smoothness, and combing property. 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.

Example 1 and Comparative Example 1 Preparation method of inventive and comparative silicone-free shampoos

[Example 1]

The ingredients described in Table 1-B below were diluted with water under gentle mixing so as to form an ultra-fine emulsion for which the number-average diameter of a droplet thereof was about 40 nm, i.e., the ultra-fine O/W emulsion had a droplet size of less than 200 nm. A particle size analyzer (Vasco, Cordoun Technologies) was used to determine the droplet size of the ultra-fine emulsion. The refractive index and viscosity of the continuous aqueous phase were 1.33 and 0.89 cp at 25°C.

Separately, shampoo base ingredients described in Table 1 -A were mixed. The ultra-fine emulsion was then added to the shampoo base composition with gentle mixing so as to obtain an inventive silicone-free shampoo. The resultant inventive silicone-free shampoo maintained a transparent appearance.

[Comparative Example 1]

A comparative shampoo was prepared by adding all the ingredients described in Table 1 -B and water to the shampoo base ingredients described in Table 1-A so as to obtain a comparative silicone-free shampoo in the form of an O/W emulsion. The number-average diameter of a droplet thereof with respect to the resultant comparative silicone-free shampoo was more than 200 nm. The appearance of the comparative silicone-free shampoo was cloudy.

Table 1

In Table 1 , all ingredients are based on "% by weight" as active raw materials.

Evaluation

[Foam volume observation]

The inventive or comparative silicone-free shampoo was mixed with hardness-controlled deionized water (10 fH) in a blender (Oster Urban Blender 350 W) at maximum speed for 1 min. Foam volume was observed by measurement in standard volumetric cylinders.

[Sensory evaluation method] The same amount of the inventive or comparative silicone-free shampoo (0.4 g shampoo per 1 g of hair) was applied on a slightly-bleached Japanese hair tress (2.7 g) for 10 cycles and the hair was rubbed 10 times. After that, the hair tress was rinsed by stroking the hair tress with a finger 15 times for 30 seconds. The rinsing procedure was the same for the inventive and comparative silicone-free shampoo.

After the hair tress was dried, the amount of foam, the softness of hair, and the sensory properties of hair tress were observed by six panelists. A fine comb and panelists' fingers were used to evaluate the ease of finger combing. The sensory evaluation was done by touching and rubbing. The smoothness, moisturizing, and ease of finger combing were scored on a 1 to 5 scale (1 is bad, 5 is good).

[Wet combing force measurement] 3 g of natural Japanese hair tresses were treated with 1.2 g of the inventive or comparative silicone-free shampoo 12 times. Wet combing forces for both the hair samples were measured by using a DIA-STRON MTT 175 instrument. Each of the hair samples was measured 4 times and an average value was taken.

[Oil deposition analysis]

Three hair tresses (1 g each) were treated with the inventive or comparative silicone-free shampoo 10 times followed by natural air drying for 3 hours or longer. Each of the 1-gram hair tresses was subjected to extraction, and the extract was analyzed by HPLC-CAD to determine the remaining amount of cocos nucifera (coconut) oil on the hair tress. The extraction was done by cutting the hair tress into 0.5-cm pieces. An accurate amount of 100 mg of hair pieces was mixed with lmL of hexane. The test tube was stirred in MiniBlock for three hours at room temperature. The resultant extract was evaporated to dry and re-dissolved with 300 xL of dichloromethane, and then injected in the HPLC-CAD for analysis. The measurement was conducted twice for each of the three hair-tress samples.

The conditions for the HPLA-CAD are as follows:

HPLC type: Alliance 2695, WATERS + detector;

CAD: CORONA PLUS ESA, EUROSEP; and

Columns: Thermo hypersil and Symmetry Shield RP18 are tandemly connected.

Results

The results concerning the oil droplet sizes, the appearance, the foam volume, the sensory evaluations, the wet combing force, and the oil deposition are shown in Table 2.

Table 2

As shown in Table 2 above, while maintaining the transparent appearance, the inventive silicone-free shampoo can achieve not only more improved sensory feeling (good

moisturizing feel, smoothness, and combing) but also larger foam volume in comparison with the comparative silicone-free shampoo. The fact that the inventive silicone-free shampoo has the ease-of-combing property is also supported by the experimental data of the wet combing force measurement method. Furthermore, it is demonstrated that when the inventive silicone-free shampoo is used, oil is deposited on hair in a higher amount. This also supports that the inventive silicone-free shampoo can provide hair with a good moisturizing feel, smoothness, and combing property.

As a result, it is clear that a silicone-free composition for keratin fibers in the form of ultra-fine O/W emulsion can not only maintain the transparent appearance but also provide hair with better sensory feelings.