JP2024071575A - Silicone-free composition for keratin fiber in form of ultra-fine o/w emulsion - Google Patents

Abstract

To provide a silicone-free composition for a keratin fiber which not only has a transparent or translucent appearance but also imparts a good feeling to hair.SOLUTION: There is provided a composition for a keratin fiber, preferably for hair in a form of an O/W emulsion in which droplets are dispersed in an aqueous phase, where the composition contains at least one surfactant, the droplets have a number-average diameter of less than 200 nm and the composition contains no silicone or contains less than 0.001 mass% of silicone with respect to the total mass of the composition. The composition not only has a transparent or translucent appearance but also imparts an excellent feeling to the hair.SELECTED DRAWING: None

Description

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 give better performance than silicone-containing compositions.

Transparent or translucent compositions for keratin fibers, such as transparent or translucent shampoos, have a beautiful product appearance and are therefore attractive to consumers. Many transparent or translucent shampoos containing silicones are widely known. Silicones are generally used in hair washing/conditioning compositions to facilitate hair detangling and to provide flexibility and softness to the hair. For example, US8425501(B2) discloses a highly light-transmitting or semi-transmitting shampoo composition containing a silicone oil having an internal phase viscosity of less than about 50,000 cst. US2004/0076596(A1) discloses optically clear compositions for hair treatment, such as shampoos, containing hydrophobic silicone oils. EP1330229(B2) discloses optically clear aqueous compositions, such as shampoos, containing hydrophobic silicone oils.

In recent years, consumers have become more sensitive to the safety of ingredients used in cosmetics and have shown interest in more environmentally friendly products. There are currently environmental concerns regarding silicones. Therefore, there is a strong demand for silicone-free, clear or translucent shampoos that can match the performance of silicone-containing shampoos.

However, when natural oils such as triglyceride oils are used in place of silicone oils in compositions for keratin fibers, it becomes difficult to maintain a transparent or translucent appearance for a long period of time. Therefore, there is still no silicone-free composition for keratin fibers that completely satisfies consumers.

US8425501(B2) US2004/0076596(A1) EP1330229(B2) U.S. Patent No. 2,528,378 U.S. Patent No. 2,781,354 U.S. Patent No. 4,874,554 U.S. Patent No. 4,137,180

CTFA International Cosmetic Ingredient Dictionary & Handbook, 15th Edition, 2014 CTFA dictionary, 3rd edition, 1982 CTFA dictionary, 5th edition, 1993 CTFA, 1997 "Handbook of Surfactants", M. R. Porter, Blackie & Son, Glasgow and London, 1991, pp. 116-178

The object of the present invention is to provide a silicone-free composition for keratin fibers that not only has a transparent or translucent appearance but also imparts a good feel to the hair.

The above-mentioned object of the present invention can be achieved by a composition for keratin fibers, preferably hair, in the form of an O/W emulsion in which oil droplets are dispersed in an aqueous phase, the composition comprising at least one surfactant, the oil droplets comprising at least one non-silicone oil, the number-average diameter of the oil droplets being less than 200 nm, and the composition being free of silicone or comprising 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 vegetable or animal origin, synthetic oils, hydrocarbon oils, and fatty alcohols, and mixtures thereof.

The non-silicone oil may preferably be a vegetable 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, more preferably from 0.2% to 5% by weight, based on 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, more preferably from 30% to 50% by weight, based on the total weight of the composition.

The number average diameter of the oil droplets can 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 can be greater than 1 nm, preferably greater than 5 nm, more preferably greater than 10 nm, especially greater than 20 nm.

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

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

Preferably, the composition does not contain silicone.

The present invention also relates to a method for the preparation of a composition for keratin fibres, preferably hair, in the form of an O/W emulsion in which oil droplets are dispersed in an aqueous phase, the number average diameter of the oil droplets being less than 200 nm, comprising:
- mixing at least one non-silicone oil and at least one surfactant;
- diluting the mixture with water to form an O/W emulsion;
- optionally adding to the composition at least one additional agent selected from the group consisting of surfactants, conditioning agents, preservatives, pH adjusters and other customary adjuvants used in the field of compositions for treating keratinous fibers, wherein the composition is silicone-free 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 method for treating keratinous fibers, preferably for washing the hair, comprising the steps of:
- applying a composition according to the invention to keratin fibres,
- rinsing the treated keratinous fibers with a sufficient amount of water.

After extensive investigations, the inventors have discovered that it is possible to provide a silicone-free composition for keratin fibres, preferably hair, in the form of an ultra-fine O/W emulsion which not only has a transparent or translucent appearance but also provides an excellent feel to the hair.

Thus, one aspect of the invention is a composition for keratin fibres, preferably hair, in the form of an O/W emulsion in which oil droplets are dispersed in an aqueous phase, the composition comprising at least one surfactant, the oil droplets comprising at least one non-silicone oil, the number-average diameter of the oil droplets being less than 200 nm, and the composition being free of silicone or comprising 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, combability, etc. Therefore, the composition according to the present invention can be used as a cosmetic composition, preferably a cleansing composition, and more preferably a shampoo.

The composition according to the present invention will be described in more detail below in this specification.

[Composition]
The composition according to the invention comprises less than 0.001% by weight of silicone, preferably less than 0.0005% by weight of silicone, more preferably less than 0.0001% by weight of silicone, relative to the total weight of the composition. Most preferably, the composition is free of 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 sensations such as good moisturizing, smoothness, and combability, while maintaining a transparent or translucent appearance due to the small size of the oil droplets of the ultrafine O/W emulsion. The transparency of the composition can be determined by measuring the turbidity, for example, with a turbidimeter (2100Q portable, Hach Company). Preferably, the turbidity of the composition is greater than 0, preferably greater than 10, and less than 200, preferably less than 150.

The composition according to the invention is preferably a cosmetic composition for keratin fibres, preferably a cleaning composition for keratin fibres, more preferably a cleaning composition for hair and scalp. Thus, the composition according to the invention may be a shampoo, a hair conditioner, a hair lotion, a disentangler, a hair cream or gel, a styling lacquer, a hair setting lotion, a treatment lotion, a dyeing composition (especially for oxidative dyeing), optionally in the form of a colouring shampoo, a hair-restructuring lotion, a permanent wave composition, a scalp shampoo or conditioner, a hair loss inhibiting lotion or gel. Most preferably, the composition according to the invention is a shampoo or a hair conditioner.

Oil droplets The oil droplets (oil phase) of the O/W emulsion according to the invention comprise 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, 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 ultrafine droplets, therefore the O/W emulsion according to the invention is also called "ultrafine O/W emulsion". The number-average diameter of the oil droplets in the ultrafine O/W emulsion according to the invention is less than 200 nm, preferably less than 180 nm, more preferably less than 160 nm, 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, even more preferably more than 10 nm, in particular more than 20 nm. The particle size of the oil droplets can be measured, for example, by 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 oils may be used.

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

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

The non-silicone oil is preferably a natural oil selected from vegetable oils or animal oils.

Examples of vegetable oils include, for example, hydrocarbon-based oils of vegetable origin, such as phytostearyl esters, e.g. phytostearyl oleate, phytostearyl isostearate and lauroyl/octyldodecyl/phytostearyl glutamate (Ajinomoto Co., Eldew PS203), triglycerides formed from fatty acid esters of glycerol (in particular those in which the fatty acids may have a chain length ranging from C ₄ to C ₃₆ , in particular C ₁₈ to C ₃₆ ), which oils may optionally be linear or branched, saturated or unsaturated, in particular heptanoic or octanoic acid triglycerides, shea oil, alfalfa oil, poppy seed oil, winter squash oil, millet oil, and the like. oil), barley oil, quinoa oil, rye oil, kukui oil, passionflower oil, shea butter, aloe vera oil, sweet almond oil, peach kernel oil, peanut oil, argan oil, avocado oil, baobab oil, borage oil, broccoli oil, calendula oil, camellia oil, canola oil, carrot oil, safflower oil, flax oil, rapeseed oil, cottonseed oil, coconut oil, pumpkin seed oil, marrow seed oil, wheat germ oil, jojoba oil, lily oil, macadamia oil, corn oil, medfoam oil, St John's Wort oil, monoi oil Mention may also be made of modified vegetable oils, such as activated coconut oil, 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.

Examples of animal oils include squalene and squalane.

Examples of synthetic oils include 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 mono- or polyacids and liquid esters of saturated or unsaturated, linear or branched C ₁ -C ₂₆ aliphatic mono- or polyalcohols, the total number of carbon atoms of which is preferably 10 or more, preferably 30 or less.

Preferably, in the case of esters of monoalcohols, at least one of the alcohols and acids from which the esters of the invention are derived is branched.

Among the monoesters of monoacids and monoalcohols, mention may be made of ethyl palmitate, ethylhexyl 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 to C ₂₂ di- or tricarboxylic acids with C ₁ to C ₂₂ alcohols, and esters of mono-, di-, or tricarboxylic acids with non-sugar C ₄ to C ₂₆ dihydroxy, trihydroxy, tetrahydroxy, or pentahydroxy alcohols can also be used.

In particular, diethyl sebacate, isopropyl lauroyl sarcosine, 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, sugar esters and diesters of _C6 - _C30 , preferably _C12 - _C22, fatty acids can be used. The term "sugar" is recalled to mean oxygen-containing hydrocarbon-based compounds containing at least 4 carbon atoms, containing several alcohol functional groups, with or without aldehyde or ketone functional groups. These sugars can 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, as well as derivatives thereof, especially alkyl derivatives, such as methyl derivatives, e.g. methylglucose.

The sugar esters of fatty acids may in particular be selected from the group comprising esters or mixtures of esters of the sugars mentioned above with linear or branched, saturated or unsaturated _C6 - _C30 , preferably _C12 - _C22 fatty acids. When they are unsaturated, these compounds may have from 1 to 3 conjugated or non-conjugated carbon-carbon double bonds.

The esters according to this variant can also be selected from monoesters, diesters, triesters, tetraesters and polyesters, and mixtures thereof.

These esters may be, for example, oleate, laurate, palmitate, myristic acid, behenic acid, coconut acid, stearate, linoleate, linolenic acid, capric acid, and arachidonic acid esters, or mixtures thereof, such as, inter alia, mixed esters of oleopalmitic acid, oleostearic acid, and palmitostearic acid, and pentaerythrityl tetraethylhexanoate.

More particularly, mono- and diesters are used, in particular the mono- or dioleate, stearates, behenates, oleopalmitates, linoleates, linolenates, and oleostearates of sucrose, glucose, or methylglucose.

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

Examples of preferred ester oils include, 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, dicaprylate carbonate, ethyl oleate ... Examples of the glyceryl esters include glyceryl esters, isopropyl lauroyl sarcosine, 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.

Examples of artificial triglycerides include capryl caprylyl glyceride, glyceryl trimyristate, glyceryl tripalmitate, glyceryl trilinoleate, glyceryl trilaurate, glyceryl tricaprate, glyceryl tricaprylate, capric/caprylic triglyceride, and capric/caprylic/linolenic triglyceride.

The hydrocarbon oil may be selected from:
- linear or branched, optionally cyclic, C ₆ -C ₁₆ lower alkanes, examples which may be mentioned include hexane, undecane, dodecane, tridecane and isoparaffins, such as isohexadecane, isododecane and isodecane;
- linear or branched hydrocarbons containing more than 16 carbon atoms, such as liquid paraffin, liquid petrolatum, polydecenes and hydrogenated polyisobutenes, such as Parleam®, and squalane.

Preferred examples of hydrocarbon oils include, for example, linear or branched hydrocarbons such as isohexadecane, isododecane, squalane, mineral oils (e.g., liquid paraffin), paraffin, petrolatum or petrolatum, naphthalene, etc.; hydrogenated polyisobutene, isoeicosane, and decene/butene copolymers; and mixtures thereof.

The term "fatty" in fatty alcohol means containing a relatively large number of carbon atoms. Thus, alcohols having 4 or more, preferably 6 or more, more preferably 12 or more carbon atoms are included within the scope of fatty alcohols. Fatty alcohols may be saturated or unsaturated. Fatty alcohols may be linear or branched.

The fatty alcohol may have the structure R-OH, where R is selected from saturated and unsaturated, linear and branched groups 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 can be selected from _C12 - _C20 alkyl and _C12 -C20 alkenyl groups. R may or may not be substituted with at least one hydroxyl group.

Examples of fatty alcohols include 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.

The fatty alcohol is preferably a saturated fatty alcohol.

Thus, the fatty alcohol may be selected from linear or branched, saturated or unsaturated _C6 - _C30 alcohols, preferably linear or branched, saturated _C6 - _C30 alcohols, more preferably linear or branched, saturated _C12 - _C20 alcohols.

The term "saturated fatty alcohol" as used herein means an alcohol with a long aliphatic saturated carbon chain. The saturated fatty alcohol is preferably selected from any linear or branched, saturated _C6 -C30 fatty alcohol. Among the linear or branched, saturated _C6 - _C30 fatty alcohols, preferably, linear or branched, saturated _C12 - _C20 fatty alcohols can be used. More preferably, any linear or branched, saturated _{C16-C20 fatty alcohols can be used. Even more preferably, branched C16 - C20 fatty alcohols} can be used.

Examples of saturated fatty alcohols include 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 mixtures thereof (e.g., cetearyl alcohol) and behenyl alcohol can be used as the saturated fatty alcohol.

The amount of non-silicone oil in the composition according to the invention ranges from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, more preferably from 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 Surfactant The composition may contain at least one anionic surfactant. Two or more anionic surfactants may be used in combination.

Anionic surfactants include ( _C6 - _C30 ) alkyl sulfates, (C6-C30) alkyl ether sulfates, ( _C6 - _C30 ) alkyl amido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates; ( _C6 - _{C30 ) alkyl} sulfonates, ( _C6 - _C30 ) alkyl amido sulfonates, ( _C6 - _C30 ) alkylaryl sulfonates, alpha-olefin sulfonates, paraffin sulfonates; ( _C6 - _C30 ) alkyl phosphates _; (C6- _C30 ) alkyl sulfosuccinates, ( _C6 - _C30 ) alkyl ether sulfosuccinates, ( _C6 - _C30 ) alkyl amido sulfosuccinates; ( _C6 - _C30 ) alkyl sulfoacetates; ( _C6 - _C24 ) acylsarcosinates; ( _C6 (C 6 -C ₂₄ ) acyl glutamates;(C ₆ -C ₃₀ ) alkyl polyglycoside carboxylic acid ethers;(C ₆ -C ₃₀ ) alkyl polyglycoside sulfosuccinates;(C ₆ -C ₃₀ ) alkyl sulfosuccinamates;(C ₆ -C ₂₄ ) acyl isethionates;N-(C ₆ -C ₂₄ ) acyltaurates;C ₆ -C ₃₀ fatty acid salts;coconut salts or hydrogenated coconut salts;(C ₈ -C ₂₀ ) acyl lactylates;(C ₆ -C ₃₀ ) alkyl-D-galactosiduronates;polyoxyalkylenated (C ₆ -C ₃₀ ) alkyl ether carboxylates;polyoxyalkylenated (C ₆ -C ₃₀ ) alkyl aryl ether carboxylates;and polyoxyalkylenated (C ₆ -C ₃₀ ) alkyl aryl ether carboxylates. ) alkyl amide ether carboxylates; and the corresponding acid forms.

In at least one embodiment, the anionic surfactants are in the form of salts, such as alkali metal, e.g. sodium, alkaline earth metal, e.g. magnesium, ammonium salts, amine salts, and amino alcohol salts. Depending on the conditions, they may also be in the form of acids.

More preferably, the anionic surfactant is selected from (C ₆ -C ₃₀ ) alkyl sulfates, (C ₆ -C ₃₀ ) alkyl ether sulfates or chlorinated or non-chlorinated polyoxyalkylenated (C ₆ -C ₃₀ ) alkyl ether carboxylic acids.

In particular, the anionic surfactant may be a ( _C6 - _C30 ) alkyl ether sulfate, such as lauryl sulfate, laureth sulfate, and salts and mixtures thereof. 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 Surfactant The composition may contain 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 amines, and optionally quaternized amine derivatives, in which the aliphatic group is a straight or branched chain containing from 8 to 22 carbon atoms and at least one water-solubilizing anionic group (e.g., carboxylate, sulfonate, sulfate, phosphate, or phosphonate).

The amphoteric surfactant may preferably be selected from the group consisting of betaine and amidoamine carboxylated derivatives.

The amphoteric surfactant is preferably selected from betaine type surfactants.

The betaine type amphoteric surfactant is preferably selected from the group consisting of alkyl betaines, alkyl amido alkyl betaines, sulfo betaines, phospho betaines and alkyl amido alkyl sulfo betaines, in particular ( _C8 - _C24 ) alkyl betaines, ( _C8 - _C24 ) alkyl amido ( _C1 - _C8 ) alkyl betaines, sulfo betaines and ( _C8 - _C24 ) alkyl amido ( _C1 - _C8 ) alkyl sulfo betaines. In one embodiment, the betaine type amphoteric surfactant is selected from ( _C8 - _C24 ) alkyl betaines, ( _C8 - _C24 ) alkyl amido ( _C1 - _C8 ) alkyl sulfo betaines, sulfo betaines and phospho betaines.

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 coco betaine, lauryl betaine, cetyl betaine, coco/oleamidopropyl betaine, cocamidopropyl betaine, palmitamidopropyl betaine, stearamidopropyl betaine, cocamidoethyl betaine, cocamidopropyl hydroxysultaine, oleamidopropyl hydroxysultaine, coco hydroxysultaine, lauryl hydroxysultaine, and coco sultaine, either alone or in mixtures.

The betaine type amphoteric surfactants are preferably alkyl betaines and alkyl amido alkyl betaines, in particular coco betaine and cocamidopropyl betaine.

Among the amidoamine carboxylated derivatives, mention may be made of the products sold under the name Miranol, described in U.S. Pat. Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names amphocarboxyglycinates and amphocarboxypropionates, the disclosures of which are incorporated herein by reference, and which have the following respective structures:
R1 _{- CONHCH2CH2 -} N ⁺ _{( R2} )( _R3 )( ^CH2COO- )M ^{+ X-} (B1)
[Wherein,
R ₁ represents the alkyl group of the acid R ₁ -COOH present in the hydrolyzed coconut oil, a heptyl, nonyl or undecyl group,
_R2 represents a β-hydroxyethyl group;
_R3 represents a carboxymethyl group;
M ⁺ represents a cationic ion derived from an alkali metal such as sodium; an ammonium ion; or an ion derived from an organic amine;
X ^- denotes an organic or inorganic anionic ion, such as a halide, acetate, phosphate, nitrate, alkyl(C ₁ -C ₄ )sulfate, alkyl(C ₁ -C ₄ )- or alkyl(C ₁ -C ₄ )aryl-sulfonate, in particular methylsulfate and ethylsulfate, or M ⁺ and X ^- are absent;
_R1' - _{CONHCH2CH2- N} (B)(C) (B2)
[Wherein,
R ₁ ' denotes the alkyl group of the acid R ₁ '-COOH present in coconut oil or hydrolyzed linseed oil, an alkyl group such as a C ₇ , C ₉ , C ₁₁ or C ₁₃ alkyl group, a C ₁₇ alkyl group and its isoforms, or an unsaturated C ₁₇ group,
B represents _{-CH2CH2OX '} ;
C represents -( _CH2 ) _z -Y', where z=1 or 2;
X' represents a -CH2 _- COOH group, -CH2 _{-COOZ', -CH2CH2- COOH , -CH2CH2- COOZ} ' or a hydrogen atom;
Y' represents a -COOH, -COOZ', -CH2 _- CHOH _- SO3Z', -CH2 _- CHOH- _SO3H group or a _-CH2 -CH(OH) _-SO3 -Z'group;
Z' represents an ion of an alkali or alkaline earth metal such as sodium, an ion derived from an organic amine, or an ammonium ion];
as well as
_Ra''- NH-CH(Y'')-( _CH2 ) _n -C(O)-NH-( _CH2 ) _n' -N(Rd)(Re) (B'2)
[Wherein,
Y″ represents —C(O)OH, —C(O)OZ″, —CH ₂ —CH(OH)—SO ₃ H, or —CH ₂ —CH(OH)—SO ₃ —Z″, where Z″ represents a cationic ion derived from an alkali metal such as sodium or an alkaline earth metal, an ion derived from an organic amine, or an ammonium ion;
Rd and Re represent a C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl group;
R _a″ represents an acid-derived C ₁₀ -C ₃₀ alkyl or alkenyl group;
n and n' are independently an integer of 1 to 3.

The amphoteric surfactants having formula B1 and B2 are preferably selected from (C ₈ -C ₂₄ )-alkyl amphomonoacetates, (C ₈ -C ₂₄ )-alkyl amphodiacetates, (C ₈ -C ₂₄ )-alkyl amphomonopropionates, and (C ₈ -C ₂₄ )-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 capryloamphodipropionate, lauroamphodipropionic acid, and cocoamphodipropionic acid.

An example is cocoamphodiacetate, sold under the name Miranol® C2M concentrate by Rhodia Chimie.

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

(iii) Cationic Surfactant The composition may contain 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 primary, secondary or tertiary fatty amine salts, optionally polyoxyalkylenated, quaternary ammonium salts, and mixtures thereof.

Examples of quaternary ammonium salts that may be mentioned include, but are not limited to, the following:
- of general formula (B3)

[Wherein,
R ₁ , R ₂ , R ₃ and R ₄ are selected from linear and branched aliphatic groups, which may be the same or different, containing 1 to 30 carbon atoms and optionally containing heteroatoms such as oxygen, nitrogen, sulfur and halogens, and may be selected from, for example, alkyl, alkoxy, C ₂ -C ₆ polyoxyalkylene, alkylamido, (C ₁₂ -C ₂₂ ) alkylamido (C ₂ -C ₆ ) alkyl, (C ₁₂ -C ₂₂ ) alkylacetate and hydroxyalkyl groups; and aromatic groups, for example, aryl and alkylaryl, where X ⁻ is selected from halide, phosphate, acetate, lactate, (C ₂ -C ₆ ) alkylsulfate and alkyl- or alkylaryl-sulfonate;
- quaternary ammonium salts of imidazolines, such as those of formula (B4):

[Wherein,
_R5 is selected from alkenyl and alkyl groups containing from 8 to 30 carbon atoms, such as fatty acid derivatives of tallow or coconut;
R ₆ is selected from hydrogen, C ₁ -C ₄ alkyl groups, and alkenyl and alkyl groups containing from 8 to 30 carbon atoms;
R ₇ is selected from C ₁ -C ₄ alkyl groups;
R ₈ is selected from hydrogen and C ₁ -C ₄ alkyl groups;
^X- is selected from halide, phosphate, acetate, lactate, alkyl sulfate, alkyl sulfonate, and alkylaryl sulfonate. In one embodiment, _R5 and _R6 are, for example, a mixture of groups selected from alkenyl and alkyl groups containing 12 to 21 carbon atoms, for example fatty acid derivatives of beef tallow, _R7 is methyl, and _R8 is hydrogen. Examples of such products include, but are not limited to, Quaternium-27 (CTFA, 1997) and Quaternium-83 (CTFA, 1997), sold under the names "Rewoquat®" W75, W90, W75PG, and W75HPG by the company Witco;
- di- or tri-quaternary ammonium salts of formula (B5):

[Wherein,
_R9 is selected from an aliphatic group containing 16 to 30 carbon atoms;
R ₁₀ is selected from hydrogen, an alkyl group containing 1 to 4 carbon atoms, or a -(CH ₂ ) ₃ (R _16a ) (R _17a ) (R _18a ) N ⁺ X- _- group;
R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R _16a , R _17a and R _18a may be the same or different and are selected from hydrogen and alkyl groups containing 1 to 4 carbon atoms;
X ⁻ is selected from a halide ion, an acetate ion, a phosphate ion, a nitrate ion, an ethyl sulfate ion, and a methyl sulfate ion.
An example of such a diquaternary ammonium salt is FINQUAT CT-P (quaternium-89) or FINQUAT CT (quaternium-75) from FINETEX];
and quaternary ammonium salts containing at least one ester functional group, such as those of formula (B6) below:

[Wherein,
R ₂₂ is selected from C ₁ -C ₆ alkyl groups and C ₁ -C ₆ hydroxyalkyl and dihydroxyalkyl groups;
_R23 is,
The following groups:

, linear and branched, saturated and unsaturated C ₁ -C ₂₂ hydrocarbon-based radicals R ₂₇ , and hydrogen;
_R25 is
The following groups:

, linear and branched, saturated and unsaturated C ₁ -C ₆ hydrocarbon-based radicals R ₂₉ , and hydrogen;
R ₂₄ , R ₂₆ and R ₂₈ may be the same or different and are selected from linear and branched, saturated and unsaturated C ₇ -C ₂₁ hydrocarbon-based groups;
r, s, and t may be the same or different and are selected from integers ranging from 2 to 6;
Each of r1 and t1 may be the same or different and is 0 or 1, r2+r1=2r and t1+t2=2t;
y is selected from an integer ranging from 1 to 10;
x and z may be the same or different and are selected from integers ranging from 0 to 10;
^X- is selected from organic and inorganic anions, both simple and complex, with the proviso that the sum x+y+z ranges from 1 to 15, and when x is 0, _R23 represents _R27 , and when z is 0, _R25 represents _R29 . _R22 can be selected from linear and branched alkyl groups. In one embodiment, _R22 is selected from linear alkyl groups. In another embodiment, _R22 is selected from methyl, ethyl, hydroxyethyl, and dihydroxypropyl groups, such as methyl and ethyl groups. In one embodiment, the sum x+y+z ranges from 1 to 10. When _R23 is a hydrocarbon-based group _R27 , it may be long-chained and contain 12 to 22 carbon atoms, or short-chained and contain 1 to 3 carbon atoms. When _R25 is a hydrocarbon-based group _R29 , it may, for example, contain 1 to 3 carbon atoms. As a non-limiting example, in one embodiment, R ₂₄ , R ₂₆ , and R ₂₈ may be the same or different and are selected from linear and branched, saturated and unsaturated C ₁₁ -C ₂₁ hydrocarbon-based groups, such as linear and branched, saturated and unsaturated C ₁₁ -C ₂₁ alkyl and alkenyl groups. In another embodiment, x and z may be the same or different and are 0 or 1. In one embodiment, y is equal to 1. In another embodiment, r, s, and t may be the same or different and are equal to 2 or 3, such as 2. The anion X ⁻ may be selected, for example, from a halide ion, such as chloride, bromide, and iodide; and a C ₁ -C ₄ alkyl sulfate ion, such as methyl sulfate. However, methanesulfonate, phosphate, nitrate, tosylate, anions derived from organic acids, such as acetate and lactate, and all other anions compatible with ammonium containing an ester function are other non-limiting examples of anions that can be used according to the invention. In one embodiment, the anion X ⁻ is selected from chloride and methylsulfate.

In another embodiment, an ammonium salt of formula (B6)
R ₂₂ is selected from methyl and ethyl groups;
x and y are equal to 1,
z is equal to 0 or 1,
r, s, and t are equal to 2,
_R23 is,
The following groups:

, methyl, ethyl, and _C14 to _C22 hydrocarbon-based groups and hydrogen;
_R25 is
The following groups:

and hydrogen;
R ₂₄ , R ₂₆ , and R ₂₈ may be the same or different and may be selected from linear and branched, saturated and unsaturated C ₁₃ -C ₁₇ hydrocarbon-based groups, such as linear and branched, saturated and unsaturated C ₁₃ -C ₁₇ alkyl and alkenyl groups.

In one embodiment, the hydrocarbon group is linear.

Non-limiting examples of compounds of formula (B6) that may be mentioned include salts, such as the chlorides and methyl sulfates, of diacyloxyethyl-dimethylammonium, diacyloxyethyl-hydroxyethyl-methylammonium, monoacyloxyethyl-dihydroxyethyl-methylammonium, triacyloxyethyl-methylammonium, monoacyloxyethyl-hydroxyethyl-dimethylammonium, and mixtures thereof. In one embodiment, the acyl group may contain 14 to 18 carbon atoms and may be derived, for example, from vegetable oils, such as palm oil and sunflower oil. When the compound contains several acyl groups, these groups may be the same or different.

These products can be obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine, optionally oxyalkylenated, to fatty acids or to mixtures of fatty acids of vegetable or animal origin, or by transesterification of their methyl esters. This esterification may be followed by quaternization using alkylating agents selected from alkyl halides, such as methyl and ethyl halides; dialkyl sulfates, such as dimethyl and diethyl sulfate; methyl methanesulfonate; methyl para-toluenesulfonate; glycol chlorohydrins; and glycerol chlorohydrins.

Such compounds are sold, for example, by Cognis under the name Dehyquart®, by Stepan under the name Stepanquat®, by Ceca under the name Noxamium® and by Rewo-Goldschmidt under the name "Rewoquat® WE 18".

Other non-limiting examples of ammonium salts that can be used in the compositions according to the invention include ammonium salts containing at least one ester functional group as described in U.S. Pat. Nos. 4,874,554 and 4,137,180.

The above-mentioned quaternary ammonium salts that can be used in the compositions according to the invention include, but are not limited to, tetraalkylammonium chlorides, such as dialkyldimethylammonium chloride and alkyltrimethylammonium chloride (wherein the alkyl group contains from about 12 to 22 carbon atoms), such as behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride 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 surfactants that may be used in the composition according to the invention are selected from behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, quaternium-83, quaternium-87, quaternium-22, behenylamidopropyl-2,3-dihydroxypropyldimethylammonium chloride, palmitylamidopropyltrimethylammonium chloride, and stearamidopropyldimethylamine.

(iv) Nonionic Surfactant The composition may contain at least one nonionic surfactant. Two or more nonionic surfactants may be used in combination.

Nonionic surfactants are compounds well known in their own right (see, for example, in this regard, "Handbook of Surfactants", M. R. Porter, Blackie & Son, Glasgow and London, 1991, pp. 116-178).

The nonionic surfactant may be a fatty acid amide, any amide containing at least one hydrocarbon-based chain containing at least 6 carbon atoms in its structure may be used. The fatty acid amide may be selected from compounds derived from amides of alkanolamines and amides of saturated or unsaturated linear or branched _C8 to _C30 fatty acids, the alkanolamines and/or fatty acids being optionally oxyalkylenated, more particularly oxyethylenated with 1 to 50 moles of ethylene oxide.

The fatty acid amides are preferably selected from _C2 - _C10 alkanolamines and amides of _C14 - _C30 fatty acids, more preferably selected from _C2 - _C10 alkanolamines and amides of _C14 - _C22 fatty acids.

Advantageously, the fatty acid amides may be chosen from coconut fatty acid monoisopropanolamides, 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, erucic acid diethanolamide, ricinoleic acid monoethanolamide, and rapeseed fatty acid amides containing 4 mol of ethylene oxide. Most preferably, the fatty acid amides may be chosen from Cocamide MIPA, marketed under the name EMPILAN CIS by the company INNOSPEC ACTIVE CHEMICALS.

The non-ionic surfactants may also be chosen, for example, from esters of alcohols, α-diols, alkylphenols and fatty acids, which may be ethoxylated, propoxylated or glycerolized and have, for example, at least one fatty chain containing from 8 to 30 carbon atoms, the number of ethylene oxide or propylene oxide groups ranging from 2 to 50 and the number of glycerol groups ranging from 1 to 30. Mention may also be made of maltose derivatives. Copolymers of ethylene oxide and/or propylene oxide; condensates of ethylene oxide and/or propylene oxide with fatty alcohols; polyethoxylated fatty amides, for example, containing 2 to 30 moles of ethylene oxide; polyglycerolated fatty amides, for example, containing 1.5 to 5, for example 1.5 to 4, glycerol groups; ethoxylated fatty acid esters of sorbitan, containing 2 to 30 moles of ethylene oxide; ethoxylated oils of vegetable origin; fatty acid esters of sucrose; fatty acid esters of polyethylene glycol; polyethoxylated fatty acid mono- or diesters of glycerol (C ₆ -C ₂₄ ) alkyl polyglycosides; N-(C ₆ -C ₂₄ ) alkyl glucamine derivatives; amine oxides, for example (C ₁₀ -C ₁₄ ) alkyl amine oxides or N-(C ₁₀ -C ₁₄ ) acyl aminopropyl morpholine oxides; and mixtures thereof.

The nonionic surfactant may preferably be selected from monooxyalkylenated, polyoxyalkylenated, monoglycerolated, or polyglycerolated nonionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or combinations thereof, preferably oxyethylene units.

Examples of monooxyalkylenated or polyoxyalkylenated nonionic surfactants that may be mentioned, alone or in mixtures, include:
- monooxyalkylenated or polyoxyalkylenated ( _C8 - _C24 ) alkylphenols,
saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C ₈ to C ₃₀ alcohols,
saturated or unsaturated, linear or branched, monooxyalkylenated or polyoxyalkylenated C ₈ to C ₃₀ amides,
- esters of saturated or unsaturated, linear or branched C ₈ to C ₃₀ acids with polyalkylene glycols,
monooxyalkylenated or polyoxyalkylenated esters of saturated or unsaturated, linear or branched C ₈ to C ₃₀ acids with sorbitol,
saturated or unsaturated, monooxyalkylenated or polyoxyalkylenated vegetable oils, and
- especially condensation products of ethylene oxide and/or propylene oxide.

The surfactant preferably contains between 1 and 100, most preferably between 2 and 50, moles of ethylene oxide and/or propylene oxide. According to one embodiment of the invention, the polyoxyalkylenated nonionic surfactant is selected from polyoxyethylenated fatty acid glycerides (polyethylene glycol ethers of fatty acid glycerides), polyoxyethylenated and polyoxypropylenated alkyl ethers, polyoxyethylenated fatty alcohols (polyethylene glycol ethers of fatty alcohols) and polyoxyethylenated fatty esters (polyethylene glycol esters of fatty acids).

Examples of polyoxyethylenated fatty acid glycerides or partial glycerides that may be mentioned include those having at least 30 polyalkylene units, i.e. 30 to 1000, preferably 30 to 500, more preferably 30 to 200, most preferably 40 to 100 polyethylene glycol units. Examples include PEG-30 hydrogenated castor oil, PEG-35 hydrogenated 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, and PEG-200 castor oil.

Examples of polyoxyethylenated and polyoxypropylenated alkyl ethers that may be mentioned include polyoxyethylenated (1-40 EO) and polyoxypropylenated (1-30 PO) alkyl (C ₁₆ -C ₃₀ ) ethers, especially polyoxyethylenated (15-40 EO) and polyoxypropylenated (5-30 PO) alkyl (C 16 -C 24 ) ethers, which may 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 C ₈ -C ₃₀ alcohols) that may be mentioned are: ethylene oxide adducts of lauryl alcohol, especially those containing from 9 to 50 oxyethylene units, more particularly those containing from 10 to 12 oxyethylene units (CTFA names Laureth-10 to Laureth-12); ethylene oxide adducts of behenyl alcohol, especially those containing from 9 to 50 oxyethylene units (CTFA names Beheneth-9 to Beheneth-50); ethylene oxide adducts of cetearyl alcohol (mixtures of cetyl alcohol and stearyl alcohol), especially those containing from 10 to 30 oxyethylene units (CTFA names Beheneth-9 to Beheneth-50); ethylene oxide adducts of cetyl alcohol, especially those containing from 10 to 30 oxyethylene units (CTFA names: ceteth-10 to ceteth-30); ethylene oxide adducts of stearyl alcohol, especially those containing from 10 to 30 oxyethylene units (CTFA names: steareth-10 to steareth-30); ethylene oxide adducts of isostearyl alcohol, especially those containing from 10 to 50 oxyethylene units (CTFA names: isosteareth-10 to isosteareth-50); and mixtures thereof.

Examples of polyoxyethylenated unsaturated fatty alcohols (or _C8 - _C30 alcohols) that may be mentioned include the ethylene oxide adducts of oleyl alcohol, especially those containing from 2 to 50 oxyethylene units, more especially those containing from 10 to 40 oxyethylene units (CTFA names oleth-10 to oleth-40); and mixtures thereof.

As examples of mono- or polyglycerolated non-ionic surfactants, mono- or polyglycerolated C ₈ -C ₄₀ alcohols are preferably used.

In particular, the monoglycerolated or polyglycerolated C ₈ -C ₄₀ alcohol may correspond to the following formula:
RO-[ _CH2 -CH( _CH2OH )-O] _m -H or RO-[CH( _CH2OH ) _-CH2O ] _m -H
wherein R represents a linear or branched C ₈ -C ₄₀ , preferably C ₈ -C ₃₀ alkyl or alkenyl group, and m represents a number ranging from 1 to 30, preferably from 1.5 to 10.

Examples of compounds suitable in the context of the present invention include 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.

Alcohols may represent mixtures of alcohols, just as the value of m represents a statistical value, meaning that in a commercial product, several types of polyglycerolized fatty alcohols may coexist in the form of a mixture.

Among the mono- or polyglycerolated alcohols, preference is given to using _C8 / _C10 alcohols containing 1 mol of glycerol, _C10 / _C12 alcohols containing 1 mol of glycerol and _C12 alcohols containing 1.5 mol of glycerol.

The monoglycerolized or polyglycerolized C ₈ to C ₄₀ fatty esters have the formula:
R'O-[CH2 _- CH(CH2OR _' '') _- O] _m -R'' or R'O-[CH(CH2OR''')- _CH2O ] _m -R''
wherein each of R', R'', and R''' independently represents a hydrogen atom or a linear or branched _C8 to _C40 , preferably _C8 to _C30 alkyl-CO- or alkenyl-CO- group, 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, preferably 1.5 to 10.
It can be equivalent to.

Examples of polyoxyethylenated fatty esters that may be mentioned include ethylene oxide adducts of esters of lauric acid, palmitic acid, stearic acid or behenic acid, and mixtures thereof, especially those containing 9 to 100 oxyethylene units, such as PEG-9 to PEG-50 laurate (CTFA name: PEG-9 laurate to PEG-50 laurate); PEG-9 to PEG-50 palmitate (CTFA name: PEG-9 palmitate to PEG-50 palmitate); PEG-9 to PEG-50 stearate (CTFA name: PEG-9 stearate to PEG-50 stearate); PEG-9 to PEG-50 palmitostearate; PEG-9 to PEG-50 behenate (CTFA name: PEG-9 behenate to PEG-50 behenate); polyethylene glycol 100 EO monostearate (CTFA name: PEG-100 stearate); and mixtures thereof.

According to one embodiment of the invention, the nonionic surfactants are selected from the group consisting of esters of polyols with fatty acids having a saturated or unsaturated chain containing, for example, from 8 to 24 carbon atoms, preferably from 12 to 22 carbon atoms, and their polyoxyalkylenated derivatives, preferably containing from 10 to 200, more preferably from 10 to 100 oxyalkylene units, such as glyceryl esters of C ₈ -C ₂₄ , preferably C ₁₂ -C ₂₂ fatty acids, and their polyoxyalkylenated derivatives, preferably containing from 10 to 200, more preferably from 10 to 100 oxyalkylene units; sorbitol esters of C ₈ -C ₂₄ , preferably C ₁₂ -C ₂₂ fatty acids, and their polyoxyalkylenated derivatives, preferably containing from ₁₀ to ₂₀₀ , more preferably from ₁₀ to 100 oxyalkylene units; The polyoxyalkylenated derivatives thereof may be selected from sugar (sucrose, maltose, glucose, fructose, and/or alkylglycose) esters of C 8 -C 24 , preferably C 12 -C ₂₂ fatty acids and their polyoxyalkylenated derivatives, preferably containing from 10 to 200, more preferably from 10 to 100 oxyalkylene units; ethers of fatty alcohols; ethers of sugars and C ₈ -C ₂₄ , preferably C ₁₂ -C ₂₂ fatty alcohols; and mixtures thereof.

Among the glyceryl esters of fatty acids, mention may be made of glyceryl stearate (mono-, di- and/or tristearate) (CTFA name: glyceryl stearate), glyceryl laurate or glyceryl ricinoleate, as well as mixtures thereof, and among their polyoxyalkylenated derivatives, mention may be made of mono-, di- or triesters of fatty acids and polyoxyalkylenated glycerol (mono-, di- or triesters of fatty acids and polyalkylene glycol ethers of glycerol), preferably polyoxyethylenated glyceryl stearate (mono-, di- and/or tristearate), such as PEG-20 glyceryl stearate (mono-, di- and/or tristearate).

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

The sorbitol esters of _C8 - _C24 fatty acids and their polyoxyalkylenated derivatives may be selected from sorbitan palmitate, sorbitan isostearate, sorbitan trioleate and esters of fatty acids and alkoxylated sorbitans containing, for example, 20 to 100 EO. Preferably, the sorbitol esters of _C8 - _C24 fatty acids and their polyoxyalkylenated derivatives may be polyoxyethylene (20) sorbitan monostearate (CTFA name: Polysorbate 60). Other examples of sorbitol esters of _C8 to _C24 fatty acids and their polyoxyalkylenated derivatives that may be mentioned include sorbitan monostearate (CTFA name: sorbitan stearate) sold under the name Span 60 by the company ICI, sorbitan monopalmitate (CTFA name: sorbitan palmitate) sold under the name Span 40 by the company ICI, and sorbitan 20 EO tristearate (CTFA name: polysorbate 65) sold under the name Tween 65 by the company ICI, polyethylene sorbitan trioleate (polysorbate 85) or the compounds sold under the trade names Tween 20 or Tween 60 by the company Uniqema.

Esters of fatty acids and glucose or alkylglucose include, in particular, glucose palmitate, alkylglucose sesquistearate, for example methylglucose sesquistearate, alkylglucose palmitate, for example methylglucose palmitate or ethylglucose palmitate, methylglucoside fatty esters, diesters of methylglucoside and oleic acid (CTFA name: methylglucose dioleate), mixed esters of methylglucoside and oleic acid/hydroxystearic acid mixtures (CTFA name: methylglucose dioleate/hydroxystearic acid), esters of methylglucoside and isostearic acid (CTFA name: methylglucose isostearate), esters of methylglucoside and lauric acid (CTFA name: methylglucose laurate), mixtures of mono- and diesters of methylglucoside and isostearic acid (CTFA name: methylglucose sesqui-isostearate), mixtures of mono- and diesters of methylglucoside and stearic acid (CTFA name: methylglucose sesquistearate), in particular Glucate by AMERCHOL The following products are commercially available under the name SS, as well as mixtures thereof:

As ethoxylated ethers of fatty acids and glucose or alkyl glucose, there may be mentioned, for example, ethoxylated ethers of fatty acids and methyl glucose, in particular the polyethylene glycol ether of methyl glucose and a diester of stearic acid with about 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose distearate), for example the product sold under the name Glucam E-20 distearate by the company AMERCHOL, the polyethylene glycol ether of a mixture of mono- and diesters of methyl-glucose and stearic acid with about 20 moles of ethylene oxide (CTFA name: PEG-20 methyl glucose sesquistearate), in particular the product sold under the name Glucamate SSE-20 by the company AMERCHOL and under the name Grillocose PSE-20 by the company GOLDSCHMIDT, and mixtures thereof.

Examples of sucrose esters include sucrose palmitostearate, sucrose stearate, and sucrose monolaurate.

As sugar ethers, alkyl polyglucosides can be used, for example decyl glucoside, for example the product sold under the name MYDOL 10 by Kao Chemicals, the product sold under the name PLANTAREN 2000 by Henkel and the product sold under the name ORAMIX NS 10 by Seppic, caprylyl/capryl glucoside, for example the product sold under the name ORAMIX CG 110 by Seppic or under the name LUTENSOL GD 70 by BASF, lauryl glucoside, for example the product sold under the name PLANTAREN 1200 N and PLANTACARE 1200 by Henkel, coco-glucoside, for example the product sold under the name PLANTACARE 818/UP by Henkel, cetostearyl glucoside, optionally mixed with cetostearyl alcohol, for example the product sold under the name MONTANOV by Seppic. Mention may in particular be made of those sold under the names TEGO-CARE CG90 by the company Goldschmidt and EMULGADE KE3302 by the company Henkel, arachidyl glucoside, for example in the form of a mixture of arachidyl and behenyl alcohols and arachidyl glucoside sold under the name MONTANOV 202 by the company Seppic, cocoyl ethyl glucoside, for example in the form of a mixture with cetyl and stearyl alcohols (35/65) sold under the name MONTANOV 82 by the company Seppic, and mixtures thereof.

Mixtures of alkoxylated vegetable oil glycerides may also be mentioned, such as mixtures of ethoxylated (200 EO) palm and copra (7 EO) glycerides.

The non-ionic surfactant according to the present invention preferably contains an alkenyl or branched _C12 - _C22 acyl chain, such as an oleyl or isostearyl group. More preferably, the non-ionic surfactant according to the present invention is PEG-20 glyceryl triisostearate.

According to one embodiment of the invention, the nonionic surfactant is a copolymer of ethylene oxide and propylene oxide, in particular of the formula
HO( _{C2H4O ) a} ( _{C3H6O ) b ( C2H4O} ) _c H
wherein a, b, and c are integers such that a+c ranges from 2 to 100 and b ranges from 14 to 60.
and copolymers thereof, and mixtures thereof.

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

Aqueous Phase The composition according to the invention comprises an aqueous medium. The aqueous medium is composed of water or a mixture of water and at least one cosmetically acceptable solvent, for example a _C1 -C4 lower alcohol, such as ethanol, isopropanol, _tert -butanol or n-butanol; a polyol, such as glycerin, propylene glycol and polyethylene glycol; and mixtures thereof. Preferably, the composition according to the 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 from 55% to 90% by weight, based on the total weight of the composition.

(Conditioning agent)
The composition according to the 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.

Conditioning agents can provide conditioning effects to keratin fibers such as hair.

Preferably, the conditioning agent may be a cationic polymer or an amphoteric polymer.

The conditioning polymer is preferably selected from:
(1) Cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium salts, for example homopolymers or copolymers which contain, as main chain constituents, units corresponding to the following formula:

[Wherein,
k and t are equal to 0 or 1, and the sum k+t is equal to 1,
R ₁₂ represents a hydrogen atom or a methyl group;
R ₁₀ and R ₁₁ independently of each other represent an alkyl group containing from 1 to 6 carbon atoms, a hydroxyalkyl group, the alkyl group preferably containing from 1 to 5 carbon atoms, a lower (C ₁ -C ₄ ) amidoalkyl group, or R 10 and R 11 together with the nitrogen atom to which they are attached may represent a heterocyclic group such as piperidinyl or morpholinyl;
R ₁₀ and R ₁₁ independently of each other preferably represent an alkyl group containing from 1 to 4 carbon atoms.

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

(2) Quaternary diammonium polymers, particularly those having repeating units corresponding to the following formula:

[Wherein,
R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ may be the same or different and represent an aliphatic, cycloaliphatic or arylaliphatic group containing 1 to 20 carbon atoms, or a lower hydroxyalkylaliphatic group; or R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ together or separately, together with the nitrogen atom to which they are attached, form a heterocycle optionally containing a second heteroatom other than nitrogen; or R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ represent a linear or branched C 1 -C 6 alkyl group substituted with a nitrile, ester, acyl or amide group, or with a -CO-OR ₁₇ -D or -CO-NH-R ₁₇ -D group, where R ₁₇ is an alkylene group and D is _{a quaternary} ammonium group;
A ₁ and B ₁ represent a polymethylene group containing 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, which may contain one or more aromatic rings attached to or inserted in the main chain, or one or more oxygen or sulfur atoms, or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups;
^X- represents an anion derived from an inorganic acid or an organic acid;
A ₁ , R ₁₃ and R ₁₅ together with the two nitrogen atoms to which they are attached can form a piperazine ring.

(3) Cationic polysaccharides, especially cationic cellulose and galactomannan gum.

The cationic cellulose polymer may have at least one quaternary ammonium group. The cationic cellulose polymer may preferably be a quaternized hydroxyethyl cellulose modified with at least one quaternary ammonium group containing at least one fatty chain (e.g. an alkyl, arylalkyl or alkylaryl group containing at least 8 carbon atoms, or a mixture thereof). The alkyl group carried by the quaternary ammonium group may preferably contain from 8 to 30 carbon atoms, in particular from 10 to 30 carbon atoms. The aryl group preferably means a phenyl, benzyl, naphthyl or anthryl group.

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

Examples of quaternized alkyl hydroxyethylcelluloses containing _C8 to _C30 fatty chains that may be mentioned include the products Quatrisoft LM 200, Quatrisoft LM-X 529-18-A, Quatrisoft LM-X 529-18B ( _C12 alkyl) and Quatrisoft LM-X 529-8 ( _C18 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 Croda, and the products Crodacel QM, Crodacel QL ( _C12 alkyl) and Crodacel QS ( _C18 alkyl) sold by the company Croda.

Among these quaternized alkyl hydroxyethyl celluloses, the product with the INCI name Polyquaternium-67 is preferred.

According to another embodiment of the present invention, the conditioning agent may be a protein, a protein hydrolysate, and an amino acid.

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, acetylhydroxyproline, isoleucine, lysine, lauroyl lysine, lauroyl sarcosine, methionine, phenylalanine, polylysine, potassium cocoyl glutamate, proline, sarcosine, serine, rice amino acids, silk amino acids, wheat amino acids, sodium glutamate, sodium lauroyl glutamate, stearoyl sarcosine, threonine, tyrosine, tryptophan, and valine.

The conditioning agent may be present in an amount sufficient to provide a conditioning effect to the keratin fibers, for example, in an amount ranging from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, more preferably from 0.5% to 5% by weight, based on the total weight of the composition.

Preservatives The compositions 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, methylparaben, propylparaben, ethylhexylglycerin, 1,3-propanediol, and mixtures thereof.

The preservative may be present in an amount sufficient to prevent degradation due to microbial growth, for example, in an amount ranging from 0.01% to 5% by weight, preferably from 0.05% to 3% by weight, more preferably from 0.1% to 1% by weight, based on the total weight of the composition.

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

Non-limiting examples of thickeners include polymeric and non-polymeric thickeners. Exemplary polymeric thickeners include various natural gums. Exemplary non-polymeric thickeners include oxyethylated molecules, particularly ethoxylated 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, such as that marketed under the name ANTIL® 141 LIQUID by EVONIK.

The thickener may be present in an amount sufficient to modify the viscosity or rheology of the composition, for example in an amount ranging from 0.01% to 7% by weight, preferably from 0.05% to 5% by weight, more preferably from 0.1% to 3% by weight, based on the total weight of the composition.

pH Adjusting Agent The composition according to the invention can preferably contain at least one pH adjusting agent. The adjustment of the pH to the desired value can be conventionally carried out by adding a pH adjusting agent, such as an organic or inorganic base or an organic or inorganic acid or a salt thereof, to the composition. Bases include, for example, ammonium hydroxide, sodium hydroxide, sodium carbonate or primary, secondary or tertiary (poly)amines, such as monoethanolamine, diethanolamine, triethanolamine, isopropanolamine or 1,3-propanediamine. Organic acids include, for example, carboxylic acids, citric acid, tartaric acid and lactic acid. Inorganic acids include, for example, hydrochloric acid, nitric acid, orthophosphoric acid and sulfonic acid. Salts include, for example, sodium phosphate and trisodium phosphate.

The pH adjuster may be present in an amount sufficient to adjust the pH of the composition to the desired value, for example, in an amount 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, based on the total weight of the composition.

Additives If necessary, the compositions according to the invention can further contain all the customary adjuvants encountered in the field of compositions for treating keratinous fibers, such as hydrophilic solvents, perfumes, fragrances, sequestering agents such as EDTA (ethylenediaminetetraacetic acid) and its salts, foam regulators, colorants, moisturizers, antidandruff agents, antiseborrhoeic agents, etc., as long as the desired properties of the compositions according to the invention can be maintained.

The amount of additive contained in the composition according to the present invention is not limited, but may be from 0.01 to 30% by weight based on the total weight of the composition.

[Preparation]
The compositions according to the invention can be prepared by techniques conventional in the art.

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

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

Conventional mixing methods can be carried out using a homogenizer, such as a turbine mixer.

[Method and Use]
The composition according to the invention is preferably a cosmetic composition for keratin fibres, preferably a cleaning composition for keratin fibres, more preferably a cleaning composition for hair. More preferably, the composition according to the invention may be a shampoo or a hair conditioner.

The present invention also relates to a cosmetic method for treating keratinous fibers, preferably for washing hair, comprising the steps of applying a composition according to the present invention to the keratinous fibers and rinsing the treated keratinous fibers with a sufficient amount of water.

The present invention also relates to the use of the composition according to the invention as a cosmetic for keratin fibres or in cosmetic for keratin fibres, preferably in conditioning products for hair, such as shampoos and hair conditioners.

Another aspect of the present invention may be the use of an O/W emulsion having oil droplets dispersed in an aqueous phase, the oil droplets comprising at least one non-silicone oil and having a number average diameter of less than 200 nm, in a silicone-free composition for keratin fibers, preferably hair, such as a shampoo or hair conditioner,
It is intended to maintain the transparency or translucency of the composition and to impart to the composition properties that impart better sensory feel to the hair, such as good moisturizing feel, smoothness, and combability.

The present invention will now be described in more detail with reference to examples. However, these examples should not be construed as limiting the scope of the present invention.

Example 1 and Comparative Example 1
Methods for preparing silicone-free shampoos of the present invention and comparative examples
Example 1
The ingredients listed in Table 1-B below were diluted with water under gentle mixing to form an ultrafine emulsion in which the number average diameter of the droplets was about 40 nm, i.e., the ultrafine 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 ultrafine emulsion. At 25°C, the refractive index of the continuous aqueous phase was 1.33 and the viscosity was 0.89 cp.

Separately, the shampoo base ingredients listed in Table 1-A were mixed. The ultrafine emulsion was then added to the shampoo base composition with gentle mixing to obtain a silicone-free shampoo of the present invention. The resulting silicone-free shampoo of the present invention maintained a clear appearance.

Comparative Example 1
The comparative shampoo was prepared by adding all the components listed in Table 1-B and water to the shampoo base components listed in Table 1-A to obtain the comparative silicone-free shampoo in the form of an O/W emulsion. The number average diameter of the droplets for the resulting comparative silicone-free shampoo was greater than 200 nm. The comparative silicone-free shampoo had a cloudy appearance.

evaluation
[Observation of foam volume]
The silicone-free shampoo of the present invention or the comparative example was mixed with hardness-controlled deionized water (10 fH) in a blender (Oster Urban Blender 350W) at maximum speed for 1 minute. The foam volume was observed by measurement in a standard graduated cylinder.

[Sensory evaluation method]
The same amount of silicone-free shampoo of the present invention or the comparative example (0.4 g shampoo per 1 g hair) was applied to a slightly bleached Japanese hair tress (2.7 g) for 10 cycles, and the hair was rubbed 10 times. The tress was then stroked 15 times with fingers for 30 seconds, and the tress was rinsed. The rinsing procedure was the same for the silicone-free shampoo of the present invention and the comparative example.

After the tresses were dried, the amount of lather, hair softness, and sensory characteristics of the tresses were observed by six panelists. Finger combability was assessed using a fine-toothed comb and the panelists' fingers. Sensory assessment was performed by touch and rubbing. Smoothness, moisturizing properties, and finger combability were scored from 1 to 5 (1 being poor and 5 being excellent).

[Wet combing force measurement]
3 g of natural Japanese hair tresses were treated 12 times with 1.2 g of the silicone-free shampoo of the present invention or the comparative example. The wet comb force of both hair samples was measured using a DIA-STRON MTT 175 instrument. Each hair sample was measured 4 times and the average value was calculated.

[Analysis of oil adhesion]
Three hair tresses (1 g each) were treated 10 times with the silicone-free shampoo of the present invention or the comparative example, and then air-dried for at least 3 hours. One gram of each hair tress was extracted, and the extracts were analyzed by HPLC-CAD to determine the amount of coconut oil remaining on the hair tresses. The extraction was performed by cutting the hair tresses into 0.5 cm pieces. An accurate amount of 100 mg of hair fragments was mixed with 1 mL of hexane. The test tubes were stirred in a MiniBlock at room temperature for 3 hours. The resulting extracts were evaporated to dryness, redissolved in 300 μL of dichloromethane, and then inserted into the HPLC-CAD for analysis. Measurements were performed twice for each of the three hair tress samples.

The conditions for HPLA-CAD are as follows:
HPLC type: Alliance 2695, WATERS+ detector,
CAD: CORONA PLUS ESA, EUROSEP, and Column: Thermo hypersil and Symmetry Shield RP18 connected in series.

Results The results for oil droplet size, appearance, lather volume, sensory evaluation, wet comb force, and oil deposition are shown in Table 2.

As shown in Table 2 above, the silicone-free shampoo of the present invention can achieve a greater amount of foam as well as improved sensation (good moisturizing feel, smoothness, and combability) compared to the silicone-free shampoo of the comparative example while maintaining a transparent appearance. The fact that the silicone-free shampoo of the present invention has easy-to-comb properties is also supported by experimental data from the wet combing force measurement method. Furthermore, it is demonstrated that a greater amount of water is deposited on the hair when the silicone-free shampoo of the present invention is used. This also supports that the silicone-free shampoo of the present invention can provide good moisturizing feel, smoothness, and combability to the hair.

As a result, it is clear that silicone-free compositions for keratin fibers in the form of ultra-fine O/W emulsions are not only able to maintain a transparent appearance but also provide a better feel to the hair.

Claims (9)

(i) an O/W emulsion in which oil droplets are dispersed in an aqueous phase, the O/W emulsion comprising a polyoxyethylenated unsaturated fatty alcohol and a polyoxyethylenated nonionic surfactant which is a polyoxyalkylenated sorbitol ester of a _C8 - _C24 fatty acid, the oil droplets comprising at least one non-silicone oil and having a number average diameter of less than 200 nm; and (ii) at least one additional agent selected from the group consisting of a surfactant, a conditioning agent, a preservative, and a pH adjuster, the shampoo composition not comprising silicone, [provided that
1. A foamable composition in the form of a nanoemulsion or microemulsion, comprising:
(a) at least one oil;
(b) at least one polyglyceryl fatty acid ester;
(c) at least one _C6-30 alkyl (poly)glucoside type surfactant;
(d) at least one amphoteric surfactant;
(e) water; and a microemulsion comprising at least the following components:
(A) 0.5 to 70% by weight of an alkanol ammonium salt of an alkyl sulfate and/or an alkyl polyalkylene glycol ether sulfate having the following structure, or a mixture thereof;
here,
R ¹ =C ₈ - to C ₂₀ - carbohydrate radical;
p=an integer from 2 to 5, and p may be different from each m;
R ² =H, C ₁ - to C ₆ -alkyl or C ₂ - to C ₄ -hydroxyalkyl;
R ³ =H, C ₁ - to C ₆ -alkyl or C ₂ - to C ₄ -hydroxyalkyl;
^R4 = _C2- to _C4 -hydroxyalkyl;
m=an integer from 0 to 7;
(B) 20 to 95% by weight of water;
(C) 0.1 to 20 weight percent of one or more oil components;
(D) 0.1 to 20% by weight of one or more mono- or polyhydrogen C ₂ - to C ₂₄ -alcohols;
(E.1) 0.1 to 15% by weight of one or more UV filters; and/or
(E.2) 0.1 to 3% by weight of one or more anti-dandruff substances,
and
The above percentages are based on the total composition (except for microemulsions). The composition of claim 1, wherein the non-silicone oil is selected from the group consisting of oils of vegetable or animal origin, synthetic oils, hydrocarbon oils, and fatty alcohols, and mixtures thereof. The composition according to claim 1 or 2, wherein the non-silicone oil is a vegetable oil. The composition according to any one of claims 1 to 3, wherein the non-silicone oil is present in an amount ranging from 0.01% to 20% by weight relative to the total weight of the composition. The composition according to any one of claims 1 to 4, wherein the surfactant is present in an amount ranging from 10% to 70% by weight, based on the total weight of the composition. The composition according to any one of claims 1 to 5, wherein the number average diameter of the oil droplets is less than 180 nm. The composition according to any one of claims 1 to 6, wherein the number average diameter of the oil droplets is greater than 1 nm. The composition according to any one of claims 1 to 7, having a transparent or translucent appearance. A cosmetic method for treating keratinous fibers, comprising:
- applying a composition according to any one of claims 1 to 8 to keratin fibres;
- rinsing the treated keratinous fibers with a sufficient amount of water.