JP2019014654A - Composition for dyeing keratin fibers - Google Patents

Abstract

The present invention uses acidic direct dyes, which can prevent or reduce skin contamination by direct dyes on the skin such as the scalp, while imparting excellent cosmetic effects such as good coloring strength to keratin fibers. To provide a stable and easy-to-use composition for dyeing keratin fibers. The invention relates to a composition for dyeing keratin fibers, preferably hair, preferably in the form of an O / W emulsion, comprising (a) at least one surfactant, and (b) It relates to a composition comprising at least one fatty substance, (c) at least one acrylic polymer, (d) at least one acid direct dye, and (e) water. The composition according to the present invention can prevent or reduce skin contamination by direct dyes to the skin such as the scalp, while imparting excellent cosmetic effects such as good coloring strength to keratin fibers. [Selection figure] None

Description

  The present invention relates to a composition for dyeing keratin fibers, in particular for dyeing keratin fibers with at least one acid direct dye, and a cosmetic method using the same.

  Dyeing keratin fibers, in particular human hair, with dyeing compositions containing oxidative coloring precursors commonly referred to as oxidizable bases, such as ortho- or para-phenylenediamine, ortho- or para-aminophenol and heterocyclic compounds It is known. These oxidation bases are generally combined with couplers. These bases and these couplers are colorless or lightly colored compounds that can be combined with oxidizing products to yield colored compounds via an oxidative condensation process.

  This type of coloring by oxidation has very high visibility and the ability to coat gray hair, making it possible to obtain colors in a variety of tones, but due to the use of oxidizing and alkaline agents ( In particular, by repeated application or in combination with other hair treatments, it causes damage to the keratin fibers.

  On the other hand, it is also known to dye keratin fibers, in particular human hair, with dyeing compositions containing direct dyes. Conventional direct dyes are in particular: benzene nitrate, anthraquinone, nitropyridine, azo, xanthine, acridine, azine, and triarylmethane types or natural colorants.

  For example, JP-A-2002-205923, JP-A-2009-269876, JP-A-7-316028, and JP-A-7-291842 disclose a composition for dyeing hair containing a direct dye. Disclosure.

  It is also known that thickeners can be incorporated into the staining composition to keep the staining composition from smearing on the face or outside the area being stained.

  For example, WO2016 / 016441 describes (a) at least one monomer of 2-acrylamido-2-methylpropanesulfonic acid, at least one monomer having a hydrophobic group and at least one ethylene that does not contain any hydrophobic group Disclosed is a colorant comprising at least one copolymer comprising a polymerizable unsaturated monomer and (b) at least one oxidative dye precursor and / or one direct dye. This publication mainly discloses colorants for oxidative hair coloring.

  Hair coloring using a direct dye has the advantage that it hardly causes allergy problems, causes no damage to the hair, and gives a clear color visibility compared to hair coloring using an oxidative dye.

JP 2002-205923 A JP 2009-269876 Japanese Unexamined Patent Publication No. 7-316028 Japanese Patent Laid-Open No. 7-291842 WO2016 / 016441 U.S. Pat.No. 2,528,378 U.S. Pat.No. 2,781,354 U.S. Pat.No. 4,874,554 U.S. Pat.No. 4,137,180 US-A-5364633 US-A-5411744 EP-A-0503853

CTFA International Cosmetic Ingredient Dictionary & Handbook, 15th edition, 2014 CTFA dictionary, 3rd edition, 1982 CTFA dictionary, 5th edition, 1993 CTFA, 1997 "Handbook of Surfactants", by M. R. Porter, Blackie & Son Publishers (Glasgow and London), 1991, 116-178 "Ullmann's Encyclopedia of Industrial Chemistry", Azo Dyes, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 14356007.a03 245, point 3.2 "Ullmann's Encyclopedia of Industrial Chemistry", Textile Auxiliaries, 2002, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 14356007.a26 227 "Ashford's Dictionary of Industrial Chemicals", 2nd edition, pages 14-39, 2001

  However, skin contamination has been an inevitable drawback of hair coloring methods that use direct dyes. In addition, there remains a need for dye compositions containing direct dyes that have good stability, usability and excellent cosmetic effects, such as good color strength.

  The object of the present invention is to use an acidic direct dye, which can prevent or reduce skin contamination by direct dye to the skin such as the scalp, while having an excellent cosmetic effect, for example, good coloring strength with keratin fibers It is to provide a stable and easy-to-use composition for dyeing keratin fibers.

Said object is a composition for dyeing keratin fibers, preferably hair,
(a) at least one surfactant;
(b) at least one fatty substance;
(c) at least one acrylic polymer;
(d) at least one acid direct dye;
(e) can be achieved by a composition comprising water.

  (a) The surfactant can be selected from a nonionic surfactant and an anionic surfactant.

  (b) The fatty substance may contain at least one fatty alcohol.

  (c) The acrylic polymer can be selected from acrylic copolymers containing at least one monomer having sulfonic acid groups, and acrylic acid polymers.

  The monomer having a sulfonic acid group of the acrylic copolymer has the following general formula (1):

[Wherein X ⁺ represents a cationic counter ion, particularly an alkali metal or alkaline earth metal, or ammonium, and R ₁ represents a hydrogen atom or a linear or branched C _{1 to} C ₆ alkyl group. Show]
Can be selected from the monomers corresponding to

  The acrylic copolymer is a monomer of acrylamide or formula (3):

[Wherein R ₁ represents a hydrogen atom or a linear or branched C _{1 to} C ₆ alkyl group, preferably methyl, Y represents O or NH, and R ₂ represents 6 to 50 Of carbon atoms, more preferably 6 to 22 carbon atoms, still more preferably 12 to 18 carbon atoms, and x represents a number in the range of 0 to 100]
The monomer represented by may further be included.

  The acrylic acid polymer may be a homopolymer of acrylic acid or methacrylic acid.

  The amount of (a) surfactant is in the range of 0.1% to 20% by weight, preferably 0.5% to 15% by weight, more preferably 1% to 10% by weight, based on the total weight of the composition. It's okay.

  (b) The amount of fatty substance is in the range of 1% to 50% by weight, preferably 5% to 40% by weight, more preferably 10% to 30% by weight, based on the total weight of the composition. Good.

  (c) The amount of the acrylic polymer is in the range of 0.01% to 20% by weight, preferably 0.05% to 5% by weight, more preferably 0.1% to 2% by weight, based on the total weight of the composition.

  The composition according to the invention may further comprise at least one organic solvent, preferably selected from (b) monoalcohols other than fatty substances.

  (b) The fatty substance is a liquid form of the fatty substance, less than 10% by weight, more preferably less than 5% by weight, preferentially less than 3% by weight, more preferably 1% by weight, based on the total amount of the composition. May be included in an amount of less than, in particular less than 0.5% by weight.

  The composition according to the invention may have a lamellar structure.

  (e) The amount of water may range from 40% to 90% by weight, preferably from 45% to 80% by weight, more preferably from 50% to 70% by weight, relative to the total weight of the composition. .

  The invention also relates to a method for dyeing keratin fibers, preferably hair, comprising the step of applying a composition according to the invention to keratin fibers.

  As a result of intensive studies, the present inventors have included a direct structured dye that is generated from a specific structure, but they prevent or reduce skin contamination by acidic direct dye on the skin such as the scalp. On the other hand, it has been found that it can provide a stable and easy-to-handle composition for dyeing keratin fibers, preferably hair, which gives the keratin fibers excellent cosmetic effects, for example good color strength. The present invention has been completed.

The composition according to the invention is therefore intended for dyeing keratin fibers, preferably hair,
(a) at least one surfactant;
(b) at least one fatty substance;
(c) at least one acrylic polymer;
(d) at least one acid direct dye;
(e) including water.

  The composition according to the invention can be used for dyeing keratin fibers, preferably hair.

  The composition according to the present invention can prevent or reduce skin contamination by acidic direct dyes on the skin such as the scalp, while imparting excellent cosmetic effects such as good coloring strength to keratin fibers. Furthermore, the composition according to the invention has good stability and is easy to handle due to the appropriate viscosity range.

  Hereinafter, the composition according to the present invention will be described in detail.

[Surfactant]
The composition according to the invention comprises (a) 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 can be used.

  The surfactant used in the present invention can be selected from the group consisting of an anionic surfactant, an amphoteric surfactant, a cationic surfactant and a nonionic surfactant.

(a-1) Anionic surfactant The composition according to the present invention may comprise at least one surfactant. Two or more anionic surfactants may be used in combination.

Anionic surfactants, (C ₆ ~C ₃₀₎ alkyl sulfates, (C ₆ ~C ₃₀₎ alkyl ether sulfates, (C ₆ ~C ₃₀₎ alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates; (C ₆ ~C ₃₀₎ alkyl sulfonates, (C ₆ ~C ₃₀₎ alkylamide sulfonates, (C ₆ ~C ₃₀₎ alkylaryl sulfonates, alpha-olefin sulfonates, paraffin sulfonates; (C ₆ ~C ₃₀ ) alkyl phosphates; (C ₆ ~C ₃₀₎ alkyl sulfosuccinates, (C ₆ ~C ₃₀₎ alkyl ether sulfosuccinates, (C ₆ ~C ₃₀₎ alkyl amide sulphosuccinates; (C ₆ -C ₃₀₎ alkyl sulfoacetate; (C ₆ ~C ₂₄₎ acyl sarcosinates; (C ₆ ~C ₂₄₎ acyl glutamates; (C ₆ -C ₃₀₎ alkylpolyglycoside carboxylic acid ether; (C ₆ C ₃₀₎ alkyl polyglycoside sulphosuccinates; (C ₆ ~C ₃₀₎ alkyl sulfosuccinamates; (C ₆ ~C ₂₄₎ acyl isethionates; N- (C ₆ ~C ₂₄₎ acyl taurates; C ₆ -C ₃₀ fatty acid salts; coconut oil acid salts or hydrogenated coconut oil acid salts; (C ₈ ~C ₂₀₎ acyl lactylates; (C _{6 ~C 30)} alkyl -D- galactosideuronic salts; polyoxyalkylenated (C ₆ ~C ₃₀₎ alkyl ether carboxylates; polyoxyalkylenated (C ₆ ~C ₃₀₎ alkylaryl ether carboxylic acid salts; and polyoxyalkylenated (C ₆ ~C ₃₀₎ alkyl ether carboxylic acid salts; And preferably selected from the group consisting of the corresponding acid forms.

  In at least one embodiment, the anionic surfactant is in the form of a salt, such as an alkali metal, such as a sodium salt; an alkaline earth metal, such as a magnesium salt; an ammonium salt; an amine salt; and an amino alcohol salt. is there. Depending on the conditions, they may also be in the acid form.

Anionic surfactants include (C ₆ -C ₃₀ ) alkyl sulfates, (C ₆ -C ₃₀ ) alkyl ether sulfates or polyoxyalkylenated (C ₆ -C ₃₀ ) chlorinated or non-chlorinated. More preferably, it is selected from alkyl ether carboxylic acids.

(a-2) Amphoteric surfactant The composition according to the present invention may contain at least one amphoteric surfactant. Two or more amphoteric surfactants may be used in combination.

  Amphoteric or zwitterionic surfactants are, for example (non-limiting list), amine derivatives such as aliphatic secondary or tertiary amines, and optionally quaternized amine derivatives. Often, the aliphatic group is linear, containing from 8 to 22 carbon atoms and containing at least one water-solubilizing anionic group (e.g., carboxylate, sulfonate, sulfate, phosphate or phosphonate). Or it is a branched chain.

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

  The amphoteric surfactant is preferably selected from betaine surfactants.

Betaine type amphoteric surfactant, preferably, alkyl betaines, alkyl amido alkyl betaines, sulfobetaines, phosphobetaines, and alkyl amidoalkyl sulfobetaines, particularly (C ₈ ~C ₂₄₎ alkyl betaines, (C ₈ ~C ₂₄₎ The alkylamide (C ₁ -C ₈ ) alkylbetaine, sulfobetaine, and (C ₈ -C ₂₄ ) alkylamide (C ₁ -C ₈ ) alkylsulfobetaine are selected from the group consisting of. In one embodiment, the betaine-type amphoteric surfactants are (C ₈ -C ₂₄ ) alkyl betaines, (C ₈ -C ₂₄ ) alkylamides (C ₁ -C ₈ ) alkyl sulfobetaines, sulfobetaines, and phosphobetaines. Selected from.

  Non-limiting examples that may be mentioned include coco betaine, lauryl betaine, cetyl betaine, coco / oleamidopropyl betaine, cocamidopropyl betaine, palmitamidopropyl betaine, stearamide propyl betaine, alone or as a mixture , Cocamidoethylbetaine, Cocamidopropylhydroxysultain, Oleamidopropylhydroxysultain, Cocohydroxysultaine, Laurylhydroxysultaine, and Cocosultain under the name CTFA International Cosmetic Ingredient Dictionary & Handbook, 15th edition, 2014 The compounds classified in are included.

  Betaine-type amphoteric surfactants are preferably alkylbetaines and alkylamidoalkylbetaines, especially cocobetaine and cocamidopropylbetaine.

Among the amidoamine carboxylated derivatives are described in U.S. Pat.Nos. 2,528,378 and 2,781,354, sold under the name Miranol, CTFA dictionary, third edition under the names amphocarboxyglycinate and amphocarboxypropionate, Mention may be made of products classified in 1982 (the disclosures of which are incorporated herein by reference), each having the following structure:
^{_{R 1 -CONHCH 2 CH 2 -N +}} (R 2) (R 3) (CH 2 COO -) M + X - (B1)
[Where
R ₁ represents an alkyl group, heptyl, nonyl or undecyl group of the acid R ₁ -COOH present in the hydrolyzed coconut oil;
R ₂ represents a β-hydroxyethyl group,
R ₃ 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 ⁻ represents an organic or inorganic anionic ion such as halide ion, acetate ion, phosphate ion, nitrate ion, alkyl (C ₁ -C ₄ ) sulfate ion, alkyl (C ₁ -C ₄ )-or alkyl ( C ₁ -C ₄ ) aryl-sulfonate ions, in particular methyl sulfate ions and ethyl sulfate ions, or M ⁺ and X ⁻ are absent];
R ₁ '-CONHCH ₂ CH ₂ -N (B) (C) (B2)
[Where
R ₁ 'is an acid R ₁ present in coconut oil or hydrolysis linseed oil' alkyl _{-COOH, C 7, C 9,} C 11 or C ₁₃ alkyl group such as an alkyl group, C ₁₇ alkyl groups and An isoform, or an unsaturated C ₁₇ group,
B represents -CH ₂ CH ₂ OX '
C represents-(CH ₂ ) _z -Y ', z = 1 or 2,
X ′ represents a —CH ₂ —COOH group, —CH ₂ —COOZ ′, —CH ₂ CH ₂ —COOH, —CH ₂ CH ₂ —COOZ ′ or a hydrogen atom,
Y ′ represents —COOH, —COOZ ′, —CH ₂ —CHOH—SO ₃ Z ′, —CH ₂ —CHOH—SO ₃ H group or —CH ₂ —CH (OH) —SO ₃ —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
R _{a ''} -NH-CH (Y '')-(CH ₂ ) _n -C (O) -NH- (CH ₂ ) _{n '} -N (Rd) (Re) (B'2)
[Where
Y '' represents -C (O) OH, -C (O) OZ '', -CH ₂ -CH (OH) -SO ₃ H or -CH ₂ -CH (OH) -SO ₃ -Z '' Z '' represents a cationic ion derived from an alkali metal or alkaline earth metal such as sodium, an ion derived from an organic amine, or an ammonium ion;
Rd and Re represents a C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl group,
R _{a ''} represents an acid-derived C ₁₀ -C ₃₀ alkyl group or alkenyl group,
n and n ′ independently represent an integer of 1 to 3.]

Amphoteric surfactants having the formulas B1 and B2 are (C ₈ -C ₂₄ ) -alkyl anhomonoacetates, (C ₈ -C ₂₄ ) alkyl amphodiacetates, (C ₈ -C ₂₄ ) alkyl amhomonopropionates And (C ₈ -C ₂₄ ) alkylamphodipropionate.

  These compounds are: disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphopropionate, disodium caprylamphodipropionate, capryloan The names of disodium hodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid are classified in the CTFA dictionary, 5th edition, 1993.

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

  Among the compounds of the formula (B′2), mention may be made of diethylaminopropyl cocoa spartamide sodium (CTFA) marketed by the company CHIMEX under the designation CHIMEXANE HB.

(a-3) Cationic surfactant The composition according to the present invention may comprise at least one cationic surfactant. Two or more kinds of cationic surfactants may be used in combination.

  The cationic surfactant can be selected from the group consisting of primary, secondary or tertiary fatty amine salts, quaternary ammonium salts, and mixtures thereof that are optionally polyoxyalkylenated. .

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

[Where
R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different and contain 1 to 30 carbon atoms and optionally contain heteroatoms such as oxygen, nitrogen, sulfur and halogen. a straight-chain or branched aliphatic groups, e.g., alkyl, alkoxy, C ₂ -C ₆ polyoxyalkylene, alkylamido, (C ₁₂ ~C ₂₂₎ alkylamido (C ₂ ~C ₆₎ Selected from alkyl, (C ₁₂ -C ₂₂ ) alkylacetate and hydroxyalkyl groups, aliphatic groups; and aromatic groups such as aryl and alkylaryl, wherein X ⁻ is a halide ion, phosphate Selected from ions, acetate ions, lactate ions, (C ₂ -C ₆ ) alkyl sulfate ions, and alkyl- or alkylaryl-sulfonate ions];
A quaternary ammonium salt of imidazoline, for example of the following formula (B4):

[Where
R ₅ is selected from alkenyl and alkyl groups containing 8 to 30 carbon atoms, such as beef tallow or coconut fatty acid derivatives;
R ₆ is selected from hydrogen, C ₁ -C ₄ alkyl groups, and alkenyl and alkyl groups containing 8 to 30 carbon atoms;
R ₇ is selected from C ₁ -C ₄ alkyl groups;
R ₈ is selected from hydrogen and a C ₁ -C ₄ alkyl group;
X ⁻ is selected from halide ions, phosphate ions, acetate ions, lactate ions, alkyl sulfate ions, alkyl sulfonate ions, and alkyl aryl sulfonate ions. In one embodiment, R ₅ and R ₆ are, for example, a mixture of groups selected from alkenyl and alkyl groups containing 12 to 21 carbon atoms, such as beef tallow fatty acid derivatives, and R ₇ is methyl. , R ₈ is hydrogen. Examples of such products include quaternium-27 (CTFA, 1997) and quaternium-83 (CTFA, sold by Witco under the names `` Rewoquat® '' W75, W90, W75PG and W75HPG. 1997)), including but not limited to;
Di- or tri-quaternary ammonium salt of formula (B5):

[Where
R ₉ is selected from an aliphatic group containing 16 to 30 carbon atoms;
R ₁₀ is selected from hydrogen or 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, which} may be the same or different, are selected from hydrogen and an alkyl group containing 1 to 4 carbon atoms And
X ⁻ is selected from halide ion, acetate ion, phosphate ion, nitrate ion, ethyl sulfate ion, and 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 a quaternary ammonium salt containing at least one ester functional group, for example of the following formula (B6):

[Where
R ₂₂ is selected from C ₁ -C ₆ alkyl groups and C ₁ -C ₆ hydroxyalkyl and dihydroxyalkyl groups;
R ₂₃ is
The following groups:

Selected from linear and branched, saturated and unsaturated C _{1 to} C ₂₂ hydrocarbon-based groups R ₂₇ , and hydrogen;
R ₂₅ is
The following groups:

Selected from linear and branched, saturated and unsaturated C _{1 to} C ₆ hydrocarbon-based groups 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 to} 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 simple and complex, organic and inorganic anions, where the sum x + y + z ranges from 1 to 15 and when x is 0, R ₂₃ is R ₂₇ And if z is 0, R ₂₅ is conditional on R ₂₉ being shown. R ₂₂ can be selected from linear and branched alkyl groups. In one embodiment, R ₂₂ is selected from a linear alkyl group. In another embodiment, R ₂₂ 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 R ₂₃ is a hydrocarbon-based group R ₂₇ , it is a long chain and may contain 12 to 22 carbon atoms, or it may be a short chain and contain 1 to 3 carbon atoms. When R ₂₅ is a hydrocarbon group R ₂₉ it may contain, for example, 1 to 3 carbon atoms. By way of non-limiting example, in one embodiment, R ₂₄ , R ₂₆ , and R ₂₈ may be the same or different and are linear and branched, saturated and unsaturated C _11. -C ₂₁ hydrocarbon-based radical, for example, linear and branched, is selected from C ₁₁ -C ₂₁ alkyl and alkenyl groups, saturated and unsaturated. 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, for example equal to 2. The anion X ⁻ can be selected, for example, from halide ions, such as chloride ions, bromide ions and iodide ions; and C ₁ -C ₄ alkyl sulfate ions, such as methyl sulfate ions. However, methanesulfonate ion, phosphate ion, nitrate ion, tosylate ion, anions derived from organic acids, such as acetate and lactate ions, and all other anions compatible with ammonium containing ester functional groups 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 ion and methylsulfate ion].

In another embodiment, an ammonium salt of formula (B6) wherein:
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,
R ₂₃ is
The following groups:

Is selected from methyl, ethyl, and C ₁₄ -C ₂₂ hydrocarbon-based group, and hydrogen,
R ₂₅ is
The following groups:

And hydrogen,
R ₂₄ , R ₂₆ , and R ₂₈ may be the same or different and are linear and branched, saturated and unsaturated C _{13 to} C ₁₇ hydrocarbon-based groups such as linear Selected from straight and branched, saturated and unsaturated C ₁₃ -C ₁₇ alkyl and alkenyl groups.

  In one embodiment, the hydrocarbon-based group is linear.

  Non-limiting examples of compounds of formula (B6) that may be mentioned include diacyloxyethyl-dimethylammonium, diacyloxyethyl-hydroxyethyl-methylammonium, monoacyloxyethyl-dihydroxyethyl-methylammonium, triacyloxyethyl- Methylammonium, monoacyloxyethyl-hydroxyethyl-dimethyl-ammonium salts, such as chloride and methylsulfate, and mixtures thereof are included. 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. If the compound contains several acyl groups, these groups may be the same or different.

  These products, for example, directly esterify triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine, which are optionally oxyalkylenated, to fatty acids or to mixtures of fatty acids of plant or animal origin. Or by transesterification of their methyl esters. Following this esterification, alkyl halides such as methyl halide and ethyl halide; dialkyl sulfates such as dimethyl sulfate and diethyl sulfate; methyl methanesulfonate; methyl para-toluenesulfonate; glycol chlorohydrin; and glycerol chloro Quaternization may be achieved using an alkylating agent selected from hydrins.

  Such compounds are, for example, the names of Dehyquart® by Cognis, Stepanquat® by Stepan, Noxamium® by Ceca, and by Rewo-Goldschmidt. Sold under the name “Rewoquat® WE 18”.

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

  The above mentioned quaternary ammonium salts which can be used in the composition according to the invention include those corresponding to formula (I), for example tetraalkylammonium chloride, such as dialkyldimethylammonium chloride and alkyltrimethylammonium chloride ( The alkyl group contains from about 12 to 22 carbon atoms), e.g. behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride and benzyldimethylstearylammonium chloride; palmitylamidopropyltrimethylammonium chloride; and Van This includes, but is not limited to, stearamidopropyldimethyl (myristyl acetate) ammonium chloride sold by Dyk under the name “Ceraphyl® 70”.

  According to one embodiment, the cationic surfactants that can be used in the composition according to the invention are behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, quaternium-83, quaternium-87, quaternium-22, behenyl chloride. Selected from amidopropyl-2,3-dihydroxypropyldimethylammonium, palmitylamidopropyltrimethylammonium chloride, and stearamidopropyldimethylamine.

(a-4) Nonionic surfactant The composition according to the present invention may comprise at least one nonionic surfactant. Two or more nonionic surfactants may be used in combination.

Nonionic surfactants are compounds known per se (for example, in this regard, “Handbook of Surfactants”, by MR Porter, Blackie & Son Publishers (Glasgow and London), 1991, 116- (See page 178). They can therefore be selected, for example, from alcohols, α-diols, alkylphenols and esters of fatty acids, these compounds being ethoxylated, propoxylated or glycerolated, for example from 8 to 30 carbons. It can have at least one fatty chain containing atoms, the number of ethylene oxide or propylene oxide groups can range from 2 to 50, and the number of glycerol groups can range 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; for example polyethoxylated fatty amides containing 2 to 30 mol of ethylene oxide; for example 1.5 to 5, for example 1.5 to 4 fatty acid esters of polyethylene glycol; ethoxylated fatty acid esters of sorbitan containing from 2 ethylene oxide 30 mol; fatty acid esters of sucrose; ethoxylated oils of vegetable origin polyglycerolated fatty amides containing glycerol group glycerol (C ₆ ~C ₂₄₎ Polyethoxylated fatty acid mono- or diesters of alkyl polyglycosides; N- (C ₆ -C ₂₄ ) alkyl glucamine derivatives; amine oxides such as (C ₁₀ -C ₁₄ ) alkyl amine oxides or N- (C ₁₀ -C ₁₄ ) Acylaminopropylmorpholine oxide; Corn surfactant; and mixtures thereof can also be mentioned without limitation.

  The nonionic surfactant can preferably be selected from monooxyalkylenated, polyoxyalkylenated, monoglycerolated or polyglycerolated nonionic surfactants. More specifically, the oxyalkylene unit is an oxyethylene or oxypropylene unit, or a combination thereof, preferably an oxyethylene unit.

Examples of monooxyalkylenated or polyoxyalkylenated nonionic surfactants that may be mentioned include the following, alone or as a mixture:
Mono oxyalkylenated or polyoxyalkylenated (C ₈ ~C ₂₄₎ alkylphenols,
Saturated or unsaturated, linear or branched, mono oxyalkylenated or polyoxyalkylenated C ₈ -C ₃₀ alcohol,
Saturated or unsaturated, linear or branched, mono oxyalkylenated or polyoxyalkylenated C ₈ -C ₃₀ amides,
Saturated or unsaturated, esters of linear or branched C ₈ -C ₃₀ acid with polyalkylene glycols,
Saturated or unsaturated, mono-oxyalkylenated or polyoxyalkylenated esters of linear or branched C ₈ -C ₃₀ acids and sorbitol,
Saturated or unsaturated, monooxyalkylenated or polyoxyalkylenated vegetable oils,
In particular, condensates 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 comprises polyoxyethylenated fatty alcohol (polyethylene glycol ether of fatty alcohol) and polyoxyethylenated fatty ester (polyethylene glycol of fatty acid). Ester).

Examples of polyoxyethylenated saturated fatty alcohols that may be mentioned (or C ₈ -C ₃₀ alcohol), ethylene oxide adducts of lauryl alcohol, especially those containing from 5 to 50 oxyethylene units, and more particularly 7 Containing 12 to oxyethylene units (CTFA names are Laureth-7 to Laureth-12); behenyl alcohol ethylene oxide adducts, especially those containing 9 to 50 oxyethylene units (CTFA names are -9 to behenez-50); ethylene oxide adducts of cetearyl alcohol (mixture of cetyl alcohol and stearyl alcohol), especially those containing 10 to 50 oxyethylene units (CTFA names are ceteares-10 to ceteales-50) E.g. ceteares-33); ethylene oxide adducts of cetyl alcohol, Those containing 10 to 50 oxyethylene units (CTFA names from 10 to 50); stearyl alcohol ethylene oxide adducts, especially those containing 10 to 50 oxyethylene units (CTFA name) As steareth-10 to steareth-50, e.g. ceteareth-20); ethylene oxide adducts of isostearyl alcohol, especially those containing 10 to 50 oxyethylene units (as CTFA names are isosteares-10 to isosteares-50) As well as mixtures thereof.

Examples of polyoxyethylenated unsaturated fatty alcohols which may be mentioned (or C ₈ -C ₃₀ alcohol), ethylene oxide adducts of oleyl alcohol, especially those containing from 2 to 50 oxyethylene units, and more particularly Those containing 10 to 40 oxyethylene units (CTFA names Ores-10 to Ores-40); and mixtures thereof.

As examples of monoglycerolated or polyglycerolated nonionic surfactants, monoglycerolated or polyglycerolated C ₈ -C ₄₀ alcohols are preferably used.

In particular, monoglycerolated or polyglycerolated C ₈ -C ₄₀ alcohols correspond to the following formula:
RO- [CH ₂ -CH (CH ₂ OH) -O] _m -H or RO- [CH (CH ₂ OH) -CH ₂ O] _m -H
[Wherein R represents a linear or branched C ₈ -C ₄₀ , preferably C ₈ -C ₃₀ alkyl or alkenyl group, and m is in the range of 1 to 30, preferably 1.5 to 10. Represents a number].

  Examples of suitable compounds in the context of the present invention include lauryl alcohol containing 4 mol glycerol (INCI name: polyglyceryl-4 lauryl ether), lauryl alcohol containing 1.5 mol glycerol, oleyl containing 4 mol glycerol. Alcohol (INCI name: polyglyceryl-4 oleyl ether), oleyl alcohol containing 2 mol glycerol (INCI name: polyglyceryl-2 oleyl ether), cetearyl alcohol containing 2 mol glycerol, cetearyl alcohol containing 6 mol glycerol Mention may be made of olecetyl alcohol containing 6 mol of glycerol and octadecanol containing 6 mol of glycerol.

  Alcohol may represent a mixture of alcohols, just as the value of m represents a statistic, which means that in a commercial product several types of polyglycerolated fatty alcohols may coexist in the form of a mixture Means that.

Among the mono- or polyglycerolated alcohols, using C ₁₂ alcohol containing C ₈ / C ₁₀ alcohol containing glycerol 1mol, the C ₁₀ / C ₁₂ alcohol and 1.5mol containing glycerol 1mol glycerol It is preferable to do.

Mono- or polyglycerolated C ₈ -C ₄₀ fatty esters may correspond to the following formula:
R'O- [CH ₂ -CH (CH ₂ OR ''')-O] _m -R''orR'O- [CH (CH ₂ OR''')-CH ₂ O] _m -R ''
Wherein each of R ′, R ″ and R ′ ″ is independently a hydrogen atom or a linear or branched C ₈ -C ₄₀ , preferably C ₈ -C ₃₀ alkyl- Represents a CO- or alkenyl-CO- group, provided that at least one of R ′, R ″ and R ′ ″ is not a hydrogen atom, and m is from 1 to 30, preferably from 1.5. Represents a number in the range of 10.]

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

According to one embodiment of the present invention, the nonionic surfactant comprises a polyol and a saturated or unsaturated chain containing for example 8 to 24 carbon atoms, preferably 12 to 22 carbon atoms. Esters with fatty acids and their polyoxyalkylenated derivatives containing preferably 10 to 200, more preferably 10 to 100 oxyalkylene units, such as C ₈ -C ₂₄ , preferably C ₁₂ -C ₂₂ Glyceryl esters of fatty acids, and their polyoxyalkylenated derivatives containing preferably 10 to 200, more preferably 10 to 100 oxyalkylene units; of C _{8 to} C ₂₄ , preferably of C _{12 to} C ₂₂ fatty acids Sorbitol esters and their polyoxyalkylenated derivatives containing preferably 10 to 200, more preferably 10 to 100 oxyalkylene units; C ₈ -C ₂₄ , preferred Or sugar (sucrose, maltose, glucose, fructose and / or alkylglycose) esters of C _{12 to} C ₂₂ fatty acids, and those containing preferably 10 to 200, more preferably 10 to 100 oxyalkylene units A polyoxyalkylenated derivative of: a fatty alcohol ether; a sugar and a C _{8 to} C ₂₄ , preferably a C _{12 to} C ₂₂ fatty alcohol ether; and mixtures thereof.

  Examples of fatty acid glyceryl esters may include glyceryl stearate (mono-, di- and / or glyceryl tristearate) (CTFA name: glyceryl stearate), glyceryl laurate or glyceryl ricinoleate, and mixtures thereof. These polyoxyalkylenated derivatives include mono-, di- or triesters of fatty acids and polyoxyalkylenated glycerol (mono-, di- or triesters of fatty acids and polyalkylene glycol ethers of glycerol), Preferably, stearic acid (mono-, di- and / or tristearic acid) polyoxyethylenated glyceryl, for example stearic acid (mono-, di- and / or tristearic acid) PEG-20 glyceryl can be listed.

  Mixtures of these surfactants, for example products containing glyceryl stearate and PEG-100 stearate sold under the name ARLACEL 165 by Uniqema and stearin sold under the name TEGIN by Goldschmidt Products containing glyceryl acrylate (mono- and glyceryl distearate) and potassium stearate (CTFA name: glyceryl stearate SE) and the like can also be used.

Sorbitol esters and polyoxyalkylene derivatives thereof C ₈ -C ₂₄ fatty acids, sorbitan palmitate, esters of sorbitan isostearate, fatty containing sorbitan trioleate, and for example from 20 100 EO and alkoxylated sorbitan, e.g. Sorbitan monostearate sold under the name Span 60 by ICI (CTFA name: sorbitan stearate), sorbitan monopalmitate sold under the name Span 40 by ICI (CTFA name: sorbitan palmitate), And sorbitan tristearate 20 EO (CTFA name: polysorbate 65) sold under the name Tween 65 by ICI and marketed under the trade name Tween 20 or Tween 60 by Uniqema Select from currently used compounds It can be.

  Examples of fatty acid and glucose or alkyl glucose esters include glucose palmitate, alkyl glucose sesquistearate such as methyl glucose sesquistearate, alkyl glucose palmitate such as methyl glucose palmitate or ethyl glucose palmitate, methyl glucoside fatty ester, methyl Diesters of glucoside and oleic acid (CTFA name: dioleic acid methylglucose), mixed esters of methylglucoside and oleic acid / hydroxystearic acid mixture (CTFA name: dioleic acid / hydroxystearic acid methylglucose), methylglucoside and isostearic acid Esters (CTFA name: methylglucose isostearate), methyl glucoside and lauric acid ester (CTFA name: lauric acid methylglucose) ), Mixtures of monoesters and diesters of methyl glucoside and isostearic acid (CTFA name: methyl glucose sesqui-isostearate), mixtures of monoesters and diesters of methyl glucoside and stearic acid (CTFA name: methyl glucose sesquistearate), especially The products marketed under the name Glucate SS by AMERCHOL and the mixtures thereof can be listed.

  Examples of ethoxylated ethers of fatty acids and glucose or alkyl glucose include, for example, ethoxylated ethers of fatty acids and methyl glucose, especially polyethylene glycol ethers of diesters of methyl glucose and stearic acid having about 20 moles of ethylene oxide (CTFA name: PEG distearate). -20 methyl glucose), for example, the product marketed under the name Glucam E-20 distearate by the company AMERCHOL, polyethylene glycol ether (CTFA) of a mixture of mono- and diesters of methyl-glucose and stearic acid with about 20 mol of ethylene oxide (Name: PEG-20 methyl glucose sesquistearate), in particular the product marketed under the name Glucamate SSE-20 by the company AMERCHOL and those marketed under the name Grillocose PSE-20 by the company GOLDSCHMIDT, and mixtures thereof It is possible to enumerate the things.

  Examples of the sucrose ester include palmito-stearic acid saccharose, stearic acid saccharose, and monolauric acid saccharose.

  Alkyl polyglucosides can be used as sugar ethers, for example, decyl glucoside, such as the product marketed under the name MYDOL 10 by Kao Chemicals, the product marketed under the name PLATAREN 2000 by Henkel, And a product marketed under the name ORAMIX NS 10 by the company Seppic, such as caprylyl / capryl glucoside, for example the product marketed under the name ORAMIX CG 110 by the company Seppic or LUTENSOL GD 70 by the company BASF, lauryl glucoside, For example, products marketed under the names PLANTAREN 1200 N and PLANTACARE 1200 by Henkel, coco-glucoside, eg products sold under the name PLANTACARE 818 / UP by Henkel, optionally mixed with cetostearyl alcohol Cetostearyl glucoside, for example, Goldschmidt under the name MONTANOV 68 by Seppic Those sold under the name TEGO-CARE CG90 by Henkel and under the name EMULGADE KE3302 by Henkel, arachidyl glucoside, for example arachidyl and behenyl alcohol and arachidyl glucoside, which are marketed by Seppic under the name MOTANOV 202 In particular, cocoylethyl glucoside, for example in the form of a mixture (35/65) with cetyl and stearyl alcohol marketed under the name MOTANOV 82 by the company Seppic, and mixtures thereof can be mentioned in particular .

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

The nonionic surfactants according to the invention preferably contain alkenyl or branched C ₁₂ -C ₂₂ acyl chains, such as oleyl or isostearyl groups. More preferably, the nonionic 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 a copolymer of the formula:
HO (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c H
[Wherein a, b and c are integers such that a + c is in the range of 2 to 100 and b is in the range of 14 to 60], and mixtures thereof.

  According to one embodiment of the present invention, the nonionic surfactant can be selected from silicone surfactants. Non-limiting examples include those disclosed in documents US-A-5364633 and US-A-5411744.

  The silicone surfactant is preferably a compound of formula (I):

[Where
R ₁ , R ₂ and R ₃ are each independently a C _{1 to} C ₆ alkyl group or-(CH ₂ ) _x- (OCH ₂ CH ₂ ) _y- (OCH ₂ CH ₂ CH ₂ ) _z -OR ₄ Represents at least one of the R ₁ , R ₂ or R ₃ groups is not an alkyl group, R ₄ is a hydrogen, alkyl group or acyl group,
A is an integer ranging from 0 to 200;
B is an integer ranging from 0 to 50, provided that A and B are not equal to 0 at the same time,
x is an integer ranging from 1 to 6;
y is an integer ranging from 1 to 30,
z is an integer ranging from 0 to 5]
It may be.

  According to a preferred embodiment of the present invention, in the compound of formula (I), the alkyl group is a methyl group, x is an integer in the range of 2 to 6, and y is in the range of 4 to 30. It is an integer.

  Examples of silicone surfactants of formula (I) include compounds of formula (II):

[Wherein A is an integer in the range of 20 to 105, B is an integer in the range of 2 to 10, and y is an integer in the range of 10 to 20]
Can be mentioned.

Examples of silicone surfactants of formula (I) include compounds of formula (III):
H- (OCH ₂ CH ₂ ) _y- (CH ₂ ) ₃ -[(CH ₃ ) ₂ SiO] _{A '} -(CH ₂ ) _3- (OCH ₂ CH ₂ ) _y -OH (III)
[Wherein A ′ and y are integers ranging from 10 to 20].

  The compounds of the invention that can be used are those sold under the names DC 5329, DC 7439-146, DC 2-5695 and Q4-3667 by Dow Corning. Compounds DC 5329, DC 7439-146 and DC 2-5695 are each a compound of formula (II) wherein A is 22, B is 2 and y is 12; A is 103 and B is 10 A compound of formula (II) wherein y is 12; A is 27, B is 3, and y is 12.

  Compound Q4-3667 is a compound of formula (III) wherein A is 15 and y is 13.

  The surfactant used in the present invention is preferably selected from the group consisting of an anionic surfactant and a nonionic surfactant.

  The amount of (a) surfactant may be 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, based on the total weight of the composition according to the present invention, provided that (a) The amount of surfactant is subject to non-zero conditions. The amount of the (a) surfactant may be 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more based on the total mass of the composition.

  The amount of (a) surfactant in the composition according to the invention is from 0.1% by weight to 20% by weight, preferably from 0.5% by weight to 15% by weight, more preferably from 1% by weight, relative to the total weight of the composition. It may be in the range of 10% by weight.

[Fat substance]
The composition according to the invention comprises (b) at least one fatty substance. Two or more fatty substances may be used in combination. Thus, a single type of fatty substance or a combination of different types of fatty substances can be used.

  The term `` fatty substance '' means an organic compound that is insoluble in water (less than 5%, preferably less than 1%, more preferentially less than 0.1%) at room temperature (25 ° C.) and atmospheric pressure (760 mmHg). To do. The fatty material can contain in its structure at least one hydrocarbon-based chain containing an array of at least 2 siloxane groups, or at least 6 carbon atoms. In addition, the fatty substances may be soluble in organic solvents such as chloroform, ethanol, benzene or decamethylcyclopentasiloxane under the same temperature and pressure conditions.

(b) The fatty substance may be in liquid or solid form. As used herein, “liquid” and “solid” means that the fatty substance is in the form of a liquid or paste (non-solid) or solid at room temperature (25 ° C.) under atmospheric pressure (760 mmHg or 10 ⁵ Pa), respectively Means. The fatty substance preferably comprises at least one fatty substance in paste or solid form, preferably in solid form, at room temperature and atmospheric pressure. As an example of the fatty substance in solid form, for example, fatty alcohol can be mentioned.

  (b) The fatty substance is mainly composed of a fatty substance in a solid form. (b) The fatty substance is preferably a fatty substance in liquid form, less than 10% by weight, more preferably less than 5% by weight, preferentially less than 3% by weight, based on the total amount of the composition according to the invention, Preferably, it may be contained in an amount of less than 1% by mass, further less than 0.5% by mass, particularly less than 0.2% by mass. In one embodiment of the invention, the composition according to the invention does not contain (b) a fatty substance in liquid form.

  (b) Fatty substances are derived from oils of animal or vegetable origin, mineral oils, synthetic glycerides, fatty alcohols and / or fatty acid esters other than animal or vegetable oils and synthetic glycerides, fatty alcohols, fatty acids, silicone oils, and aliphatic hydrocarbons. Can be selected from the group consisting of These fatty substances may be volatile or non-volatile. Preferably, the fatty substance is selected from the group consisting of oils of animal or vegetable origin, synthetic glycerides, fatty esters other than animal or vegetable oils and synthetic glycerides, fatty alcohols, fatty acids, silicone oils, and aliphatic hydrocarbons. More preferably, (b) the fatty substance is selected from fatty alcohols, aliphatic hydrocarbons, preferably mineral oil, and mixtures thereof.

  Examples of aliphatic hydrocarbons include, for example, linear or branched hydrocarbons such as mineral oil (e.g., liquid paraffin), paraffin, petrolatum or petrolatum, naphthalene; hydrogenated polyisobutene, isoeicosane, polydecene, hydrogenated Mention may be made of polyisobutenes such as Parleam and decene / butene copolymers; and mixtures thereof.

Examples of other aliphatic hydrocarbons may also include linear or branched or optionally cyclic C ₆ -C ₁₆ lower alkanes. Examples which may be mentioned, hexane, undecane, dodecane, tridecane and isoparaffins include, for example, isohexadecane, isodecane, and C ₁₃ -C ₁₄ isoparaffin.

  Examples of synthetic glycerides are, for example, caprylic / capric triglycerides, such as those sold by Sterineries Dubois or sold under the names Miglyol® 810, 812 and 818 by Dynamit Nobel Can be mentioned.

  Examples of silicone oils include, for example, linear organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, etc .; cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane , Dodecamethylcyclohexasiloxane and the like; and mixtures thereof.

  Examples of vegetable oils include, for example, linseed oil, camellia oil, macadamia nut oil, sunflower oil, apricot oil, soybean oil, alara oil, hazelnut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, sausage oil. Mention may be made of flower oil, jojoba oil, almond oil, grape seed oil, sesame oil, peanut oil, and mixtures thereof.

  Examples of animal oils include, for example, squalene, perhydrosqualene, and squalane.

Examples of esters of fatty acids and / or fatty alcohols that are preferably different from the animal or vegetable oils and synthetic glycerides mentioned above include, inter alia, saturated or unsaturated, linear or branched C ₁ -C ₂₆ fats. Mention may be made of esters of group monoacids or polyacids with saturated or unsaturated, linear or branched C _{1 to} C ₂₆ aliphatic mono- or polyalcohols, the total number of carbons of the ester being 10 or more.

Among monoester, dihydroabietyl behenate; behenate octyldodecyl; behenate isocetyl; cetyl lactate; alkyl lactate (C ₁₂ -C _15); isostearyl lactate; lauryl lactate; lactic linoleyl; lactic oleyl; octanoic acid ( Iso) stearyl; isocetyl octoate; octyl octoate; cetyl octoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octoate; isonyl oleate; Methyl acetyl; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononanoate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl palmitate Isopropyl palmitate, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristate such as isopropyl myristate, butyl myristate, cetyl myristate, 2-octyldodecyl myristate, myristyl myristate or stearyl myristate, Mention may be made of hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate.

Further in connection with this variant, esters of C _{4 to} C ₂₂ dicarboxylic acids or tricarboxylic acids and C _{1 to} C ₂₂ alcohols and mono-, di- or tricarboxylic acids and C _{2 to} C ₂₆ di-, tri-, Esters with tetra- or pentahydroxy alcohols can also be used.

  Among others, mention may be made of: diethyl sebacate, diisopropyl sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, diisostearyl adipate, dioctyl maleate, glyceryl undecylate, stearoyl Octyldodecyl stearate, pentaerythrityl monolithinoleate, pentaerythrityl tetraisononanoate, pentaerythrityl tetrapelargonate, pentaerythrityl tetraisostearate, pentaerythrityl tetraoctanoate, propylene glycol dicaprylate, propylene glycol dicaprate Tridecyl erucate, triisopropyl citrate, triisostearyl citrate, glyceryl trilactate, glyceryl trioctanoate, citrate Liooctyl dodecyl, trioleyl citrate, propylene glycol dioctanoate, neopentyl glycol diheptanoate, diethylene glycol diisononanoate, and polyethylene glycol distearate.

  Among the esters mentioned above, ethyl palmitate, isopropyl palmitate, myristyl palmitate, cetyl palmitate or stearyl palmitate, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristate such as isopropyl myristate, myristine Butyl acid, cetyl myristate or 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate, dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, isononyl isononanoate, or cetyl octanoate It is preferable to use it.

The composition may also comprise sugar esters and diesters of C ₆ -C ₃₀ , preferably C ₁₂ -C ₂₂ fatty acids, as fatty esters. The term “sugar” means an oxygen-containing hydrocarbon-based compound that contains some alcohol functionality and at least 4 carbon atoms, with or without aldehyde or ketone functionality. These sugars may be monosaccharides, oligosaccharides or polysaccharides.

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

Sugar esters of fatty acids are, inter alia, esters or mixtures of the sugars described above with linear or branched, saturated or unsaturated C ₆ -C ₃₀ , preferably C ₁₂ -C ₂₂ fatty acids. Can be selected from the group comprising If they are unsaturated, these compounds can contain 1 to 3 conjugated or non-conjugated carbon-carbon double bonds.

  Esters according to this variant can also be selected from mono-, di-, tri-, tetraesters and polyesters, and mixtures thereof.

  These esters include, for example, oleic acid ester, lauric acid ester, palmitic acid ester, myristic acid ester, behenic acid ester, coconut fatty acid ester, stearic acid ester, linoleic acid ester, linolenic acid ester, capric acid ester and arachidonic acid ester. Or mixtures thereof, such as, among others, mixed esters of oleo-palmitic acid, oleo-stearic acid and palmito-stearic acid, among others.

  It is possible to use monoesters and diesters, especially mono- or dioleic acid esters of sucrose, glucose or methylglucose, stearic acid esters, behenic acid esters, oleopalmitic acid esters, linoleic acid esters, linolenic acid esters and oleostearic acid esters More particularly preferred.

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

Examples of esters or mixtures of esters of sugars and fatty acids that may be mentioned further include:
-73% monoester and 27% diester and triester, 61% monoester and 39% diester, triester and tetraester sold by Crodesta under the names F160, F140, F110, F90, F70 and SL40, respectively Palmis formed from 52% monoester and 48% diester, triester and tetraester, 45% monoester and 55% diester, triester and tetraester, 39% monoester and 61% diester, triester and tetraester Products showing sucrose tostearate and sucrose monolaurate,
-A product sold under the name Ryoto Sugar Esters, referred to for example in B370 and corresponding to sucrose behenate formed from 20% monoester and 80% di-triester-polyester,
-Mono-dipalmito-sucrose stearate sold under the name Tegosoft® PSE by the company Goldschmidt.

  The fatty substance may be at least one fatty acid, and two or more fatty acids may be used. Fatty acids should be in the acidic form (i.e. not salified to avoid soap), may be saturated or unsaturated, and have 6 to 30 carbon atoms, especially 9 to 30. Containing 1 carbon atom, optionally substituted with one or more hydroxyl groups (especially 1 to 4). If they are unsaturated, these compounds can contain 1 to 3 conjugated or non-conjugated carbon-carbon double bonds. They are more particularly selected from myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and isostearic acid. Preferably, the fatty substance is not a fatty acid.

  The fatty substance may be at least one fatty alcohol, and two or more fatty alcohols may be used.

The term “fatty alcohol” as used herein means any C ₈ -C ₃₀ fatty alcohol, saturated or unsaturated, straight-chain or branched, especially one or more Optionally substituted with hydroxyl groups (especially 1 to 4). If they are unsaturated, these compounds can contain 1 to 3 conjugated or non-conjugated carbon-carbon double bonds.

Among C ₈ -C ₃₀ fatty alcohols, for example, C ₁₂ -C ₂₂ fatty alcohols are used. Among these, lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, behenyl alcohol, linoleyl alcohol, undecylenyl alcohol, palmitoleyl alcohol, linolenyl alcohol, myristyl alcohol, arachidonyl alcohol and erucyl Mention may be made of alcohols, as well as mixtures thereof. In one embodiment, cetyl alcohol, stearyl alcohol or mixtures thereof (eg, cetearyl alcohol), and myristyl alcohol can be used as solid fatty substances. In another embodiment, isostearyl alcohol can be used as the liquid fatty substance.

  The fatty substance may be a wax. As used herein, “wax” means that the fatty material is in a substantially solid form at room temperature (25 ° C.) under atmospheric pressure (760 mmHg) and generally has a melting point of 35 ° C. or higher. As the waxy fatty substance, waxes generally used in cosmetics can be used alone or in combination.

For example, the wax may be carnauba wax, microcrystalline wax, ozokerite, hydrogenated jojoba oil, polyethylene wax, for example, wax sold under the name `` Performalene 400 Polyethylene '' by the company New Phase Technologies, silicone wax, for example poly ( C ₂₄ -C ₂₈₎ alkyl methyl dimethylsiloxane, such as the product sold under the name "Abil Wax 9810" by the company Goldschmidt, palm fat, stearic acid sold under the name "Kester Wax K82H" by Kester Keunen Inc. alkyl (C ₂₀ ~C _40), stearyl benzoate, may be selected from shellac wax, and mixtures thereof. For example, a wax selected from carnauba wax, candelilla wax, ozokerite, hydrogenated jojoba oil and polyethylene wax can be used. In at least one embodiment, the wax is preferably selected from candelilla wax and ozokerite, and mixtures thereof.

  (b) The fatty substance is particularly preferably a fatty alcohol. In particular, the (b) fatty substance comprises at least one fatty alcohol in solid form.

  (b) The amount of the fatty substance is 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, based on the total mass of the composition according to the present invention. Well, provided that (b) the amount of fatty substance is not zero. The amount of the (b) fatty substance may be 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more with respect to the total mass of the composition.

  The amount of (b) fatty substance in the composition according to the invention is from 1% to 50% by weight, preferably from 5% to 40% by weight, more preferably from 10% to 30%, based on the total weight of the composition. It may be in the range of mass%.

[Acrylic polymer]
The composition according to the invention comprises (c) at least one acrylic polymer. Two or more acrylic polymers may be used in combination. Thus, a single type of acrylic polymer or a combination of different types of acrylic polymers can be used.

  The (c) acrylic polymer according to the present invention may be any of an acrylic copolymer, an acrylic acid polymer, and another acrylic polymer including at least one monomer having a sulfonic acid group.

  Preferably, (c) the acrylic polymer is a hydrophilic acrylic polymer. According to the present invention, the term “hydrophilic acrylic polymer” means a non-hydrophobic and non-amphiphilic acrylic polymer.

(c-1) Acrylic polymer comprising at least one monomer having a sulfonic acid group According to a first embodiment, the (c) acrylic polymer used according to the invention comprises at least one sulfonic acid group having a sulfonic acid group Contains monomer.

  The polymers used in accordance with the present invention are homopolymers obtainable from at least one ethylenically unsaturated monomer having sulfonic acid groups, in free form or in partially or fully neutralized form. Good.

  Preferentially, the polymers according to the invention are inorganic bases (sodium hydroxide, potassium hydroxide or aqueous ammonia) or organic bases such as monoethanolamine, diethanolamine, triethanolamine, aminomethylpropanediol, N-methylglucamine. Partially or completely neutralized with basic amino acids, such as arginine and lysine, and mixtures of these compounds. They are generally neutralized.

  In the context of the present invention, the term “neutralized” means a polymer that is completely or almost completely neutralized, ie at least 90% neutralized.

  The polymers used in the compositions according to the invention generally have a number average molecular weight in the range from 1000 to 20000000 g / mol, preferably in the range from 20000 to 5000000 g / mol, more preferentially from 100000 to 150,000 g / mol.

  These polymers according to the invention may or may not be crosslinked.

Monomers having sulfonic acid groups of the polymers used in the compositions of the present invention include, among others, vinyl sulfonic acid, styrene sulfonic acid, (meth) acrylamide (C ₁ -C ₂₂ ) alkyl sulfonic acid, N- (C ₁ -C ₂₂₎ alkyl (meth) acrylamide (C ₁ -C ₂₂₎ alkylsulfonic acids, e.g. undecylacrylamide methanesulfonic acid is selected more thereof partially or completely neutralized form, and mixtures thereof The

According to a preferred embodiment of the present invention, the monomer having a sulfonic acid group is a (meth) acrylamide (C ₁ -C ₂₂ ) alkyl sulfonic acid, such as acrylamide methane sulfonic acid, acrylamide ethane sulfonic acid, acrylamide propane sulfonic acid. 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, 2-acrylamide-n-butanesulfonic acid, 2-acrylamide-2,4,4-trimethylpentanesulfonic acid, 2 -Selected from methacrylamide dodecyl sulfonic acid and 2-acrylamido-2,6-dimethyl-3-heptane sulfonic acid, as well as partially or fully neutralized forms thereof, and mixtures thereof.

  More particularly, 2-acrylamido-2-methylpropane sulfonic acid (AMPS®) or even a partially or fully neutralized form thereof is used.

  According to the present invention, 2-acrylamido-2-methylpropanesulfonic acid (AMPS®) monomer is preferably represented by the following general formula (1):

[Wherein X ⁺ represents a cationic counter ion, particularly an alkali metal or alkaline earth metal, or ammonium, preferably an alkali metal or ammonium ion, and R ₁ represents a hydrogen atom or a linear or branched group. C ₁ -C ₆ alkyl group, for example methyl, R ₁ preferably represents a hydrogen atom]
It corresponds to.

  If the polymer is cross-linked, the cross-linking agent can be selected from polyolefinic unsaturated compounds commonly used for cross-linking polymers obtained by free radical polymerization.

  Examples of crosslinking agents that may be mentioned include divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol di (meth) acrylate or tetraethylene glycol , Trimethylolpropane triacrylate, methylenebisacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth) acrylate, Allyl ethers of saccharide alcohols, or allyl or vinyl ethers of other polyfunctional alcohols, as well as phosphoric acid and / or It is included allyl esters of vinylphosphonic acid derivatives, or mixtures of these compounds.

  According to one preferred embodiment of the invention, the cross-linking agent is selected from methylene bisacrylamide, allyl methacrylate and trimethylolpropane triacrylate (TMPTA). The degree of cross-linking is generally in the range from 0.01 mol% to 10 mol%, more specifically from 0.2 mol% to 2 mol%, relative to the polymer.

  The homopolymer of a monomer having a sulfonic acid group may be crosslinked with one or more crosslinking agents.

These homopolymers are generally crosslinked and neutralized and have the following steps:
(a) dispersing or dissolving a monomer such as 2-acrylamido-2-methylpropanesulfonic acid in free form in a solution of tert-butanol or water and a solution of tert-butanol;
(b) the monomer solution or dispersion obtained in (a) in an amount that makes it possible to obtain a degree of neutralization of the sulfonic acid functionality of the polymer in the range of 90% to 100%. Neutralizing with an inorganic or organic base, preferably ammonia NH ₃ water;
(c) adding a crosslinking monomer to the solution or dispersion obtained in (b);
(d) performing standard free radical polymerization in the presence of a free radical initiator at a temperature in the range of 10 to 150 ° C., wherein the polymer is precipitated in a tert-butanol-based solution or dispersion; According to a preparation method including the steps.

Preferred AMPS® homopolymers are generally randomly distributed,
a) 90% to 99.9% by weight of the following general formula (2):

[Wherein X ⁺ represents a proton, an alkali metal cation, an alkaline earth metal cation or an ammonium ion, and 10 mol% or less of the cation X ⁺ is a proton H ⁺ in some cases]
Unit of
b) 0.01% to 10% by weight, comprising at least one monomer containing at least two olefinic double bonds, characterized in that the mass proportion is based on the total mass of the polymer It is prescribed.

  More particularly preferred homopolymers according to the invention comprise 98% to 99.5% by weight of units of the formula (2) and 0.2% to 2% by weight of crosslinking units.

  A polymer of this type that can be mentioned in particular is sold by Clariant under the name Hostacerin AMPS® (CTFA name: ammonium polyacryl dimethyl tauramide) or Simulgel 800 (CTFA name: polyacryloyl dimethyl taurine). Ammonium), a crosslinked and neutralized 2-acrylamido-2-methylpropanesulfonic acid homopolymer sold by the company Seppic.

  Other acrylic polymers comprising at least one monomer having a sulfonic acid group can include inter alia acryloyl dimethyl taurate polymers, preferably acryloyl dimethyl taurate copolymers. An acryloyl dimethyl taurate polymer is a polymer that includes acryloyl dimethyl taurate as a monomer, and an acryloyl dimethyl taurate copolymer is a copolymer that includes acryloyl dimethyl taurate and one or more other monomers as monomers. The acryloyl dimethyl taurate copolymer may include a copolymer of acryloyl dimethyl taurate and vinyl pyrrolidone (VP), such as acryloyl dimethyl taurate ammonium / VP copolymer sold under the name Aristoflex AVC by the company Clariant.

  In particular, the (c) acrylic polymer comprising at least one monomer having a sulfonic acid group may include an acrylamide / AMPS® copolymer.

  According to this embodiment, the acrylic polymer comprises (i) acrylamide (monomer 1), (ii) 2-acrylamido-2-methylpropane sulfonic acid, and (iii) comprises a crosslinker herein, at least It is a cross-linked anionic copolymer formed from units derived from a reaction with one type of polyolefinic unsaturated compound (monomer 3).

  The cross-linked anionic copolymer used in the context of the present invention is a product already known per se and its preparation is described inter alia in patent application EP-A-0503853 and therefore its contents Is incorporated herein by reference in its entirety.

  Thus, the above copolymer can be conventionally obtained from three different comonomers included in its construction according to emulsion polymerization techniques.

  The polyolefinic unsaturated monomers used as crosslinkers for the preparation of the copolymers according to the invention are preferably selected from the group formed by methylenebisacrylamide, allyl sucrose and pentaerythritol. More preferentially, methylenebisacrylamide is used.

  Preferably, the polyolefinic unsaturated compound is present in the copolymer at a concentration between 0.06 and 1 mmol per mole of monomer units as a whole.

  The ratio expressed in mol% between acrylamide and AMPS® is preferentially between 85/15 and 15/85, preferably between 70/30 and 30/70, more preferentially. Between 65/35 and 35/65, more specifically between 60/40 and 40/60. In addition, AMPS® is generally at least partially neutralized to the salt form, for example, with sodium hydroxide, potassium hydroxide or low molecular weight amines such as triethanolamine, or mixtures thereof. .

  Particularly preferred crosslinked copolymers in the context of the practice of the present invention correspond to those prepared in Example 1 of the above-mentioned patent application EP-A-0503853, which in this case is in the form of a water-in-oil inverse emulsion. It is. More precisely, this copolymer is formed from 60 mol% acrylamide and 40 mol% AMPS® sodium salt and is crosslinked with 0.22 mmol of methylene bisacrylamide per mole of total monomer mixture. The final water-in-oil inverse emulsion preferably contains about 40% by weight of the cross-linked copolymer as defined above and about 4% by weight of ethoxylated fatty alcohol with an HLB of about 12.5.

  More particularly used cross-linked copolymers according to the invention are Sepigel 305 (CTFA name: polyacrylamide / C13-14 isoparaffin / laureth 7) or Simulgel 600 (CTFA name: acrylamide / acryloyldimethyltaurine sodium copolymer sold by the company SEPPIC. / Isohexadecane / polysorbate 80) or Simulgel EG (CTFA name: sodium acrylate / acryloyldimethyltaurine sodium copolymer / isohexadecane / polysorbate 80).

  Other preferred examples of acrylic copolymers comprising at least one monomer having a sulfonic acid group include at least one monomer of 2-acrylamido-2-methylpropanesulfonic acid (AMPS®), a hydrophobic group. Mention may be made of AMPS® copolymers comprising at least one monomer having and at least one ethylenically unsaturated monomer that does not contain any hydrophobic groups.

  In the context of the present invention, the term “hydrophobic group” is a hydrocarbon-based, branched or unbranched, saturated or unsaturated fatty chain containing 6 to 50 carbon atoms. It is understood.

  In this embodiment, a 2-acrylamido-2-methylpropanesulfonic acid (AMPS (registered trademark)) monomer represented by the above general formula (1) can be preferably used.

  The AMPS® copolymer comprises at least one monomer having a hydrophobic group, which monomer is preferably 6 to 50 carbon atoms, preferably 6 to 22 and more particularly 12 to 18 Is an ethylenically unsaturated monomer containing at least one aliphatic hydrocarbon-based chain.

  The monomer having a hydrophobic group is preferably represented by the formula (3):

[Wherein R ₁ represents a hydrogen atom or a linear or branched C _{1 to} C ₆ alkyl group, preferably methyl, Y represents O or NH, and R ₂ represents 6 to 50 Of carbon atoms, more preferably 6 to 22 carbon atoms, still more preferably 12 to 18 carbon atoms, and x represents a number in the range of 0 to 100]
Selected from acrylates or acrylamides.

  According to one particular embodiment of the invention, in formula (3), Y represents an oxygen atom.

According to one particular embodiment of the invention, in formula (3), the R ₁ group represents methyl.

  According to one particular embodiment of the invention, x represents an integer between 3 and 25, and x is preferably equal to 4.

According to one particular embodiment of the invention, in formula (3), the R ₂ group represents an alkyl group containing 12 to 18 carbon atoms.

According to one particular embodiment of the present invention, the hydrophobic monomer of formula (3), wherein the Y group represents O, the R ₂ group represents an alkyl group containing 12 carbon atoms, x is Tetraethoxylated (4EO) lauryl methacrylate corresponding to a compound of formula (3) equal to 4.

  Preferably, the monomer having a hydrophobic group is tetraethoxylated lauryl methacrylate.

According to one particular embodiment of the invention, the AMPS® copolymer is such that x is equal to 0, Y represents an oxygen atom, R ₁ group represents methyl, R ₂ group represents 12 May comprise at least one monomer of formula (3) representing an alkyl group containing from 18 to 18 carbon atoms.

  In this embodiment, the monomer having a hydrophobic group is preferably lauryl methacrylate.

  Preferably, the AMPS® copolymer comprises lauryl methacrylate and tetraethoxylated lauryl methacrylate as monomers having hydrophobic groups.

  The AMPS® copolymer is also preferably of the following general formula (4):

[Wherein, R ₁ represents a hydrogen atom or a linear or branched C _{1 to} C ₄ alkyl group, R ₁ preferably represents a hydrogen atom, and R ₂ represents a linear or branched group. A branched C ₁ -C ₄ alkyl group, R ₃ represents a linear or branched C ₁ -C ₄ alkyl group, and R ₂ and R ₃ preferably represent methyl]
At least one ethylenically unsaturated monomer that does not contain any hydrophobic groups.

Ethylenically unsaturated monomers that do not contain any hydrophobic groups include (meth) acrylamides such as acrylamide, (meth) acrylic acid and its esters ((meth) acrylate esters) such as 2-hydroxyethyl acrylate, vinyl pyrrolidone, N- (C ₁ -C ₄ ) alkyl acrylamide, as well as N, N-di (C ₁ -C ₄ ) alkyl acrylamide, such as N, N-dimethylacrylamide, are selected.

  Preferably, the ethylenically unsaturated monomer that does not contain any hydrophobic groups is N, N-dimethylacrylamide.

  Preferably, the AMPS® copolymer is preferably crosslinked, preferably fully salified 2-acrylamido-2-methylpropane sulfonic acid, N, N-dimethylacrylamide, and tetraethoxylated methacrylic acid. A copolymer of lauryl acid and lauryl methacrylate is selected from, for example, a copolymer sold under the name Sepimax zen by the company Seppic and having an INCI name of polyacrylate crosspolymer-6.

(c-2) Acrylic acid polymers and other acrylic polymers Acrylic acid polymers and other acrylic polymers that can be used in accordance with the present invention can also include:
-Homopolymers or copolymers of acrylic acid or methacrylic acid or salts and esters thereof, for example the products sold by the company Novo under the names Carbopol 934, 940, 954, 981 and 980, Synthalen L (registered trademark) from 3V ), Sodium polymethacrylate sold under the name Darvan No. 7 (registered trademark) by Vanderbilt, products sold under the names Versicol F or Versicol K by Allied Colloid, Ultrahold 8 by Ciba Geigy and Synthalen K type polyacrylic acid,
-Polyacrylates and polymethacrylates, such as glyceryl acrylate polymers, especially copolymers of glyceryl acrylate and acrylic acid, such as Lubrajel® MS, Lubrajel® CG, Lubrajel® DV, by Guardian Laboratories, Products sold under the names Lubrajel (R) NP, Lubrajel (R) OIL, Lubrajel (R) Oil BG, Lubrajel (R) PF, Lubrajel (R) TW and Lubrajel (R) WA ,
A polyacrylic acid / alkyl acrylate copolymer, preferably a modified or unmodified carboxyvinyl polymer; the most particularly preferred copolymer according to the invention is an acrylate / C ₁₀ -C ₃₀ -alkyl acrylate copolymer (INCI name: acrylate / alkyl acrylate) (C _10-30 ) crosspolymer), for example, products sold by the company Lubrizol under the trade names Pemulen TR1, Pemulen TR2, Carbopol 1382 and Carbopol ETD 2020, more preferentially Pemulen TR-2,
-Alkyl acrylic acid / alkyl methacrylic acid copolymers and derivatives thereof, in particular salts and esters thereof, such as ethyl acrylate, methyl methacrylate and low content of quaternary ammonium groups offered by Evonik Degussa under the trade name EUDRAGIT RSPO A copolymer of methacrylates having
-Acrylate / vinyl alcohol copolymers, for example the product sold under the name Hydragen FN® by the company Cognis, as well as mixtures thereof.

  Preferably, the acrylic acid polymer may be a homopolymer of acrylic acid or methacrylic acid.

  The amount of (c) acrylic polymer may be 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less, based on the total weight of the composition according to the present invention, provided that (c) acrylic The amount of polymer is subject to non-zero. (c) The amount of the acrylic polymer may be 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more with respect to the total mass of the composition.

  The amount of (c) acrylic polymer in the composition according to the invention is from 0.01% to 20% by weight, preferably from 0.05% to 5% by weight, more preferably from 0.1% to 2%, based on the total weight of the composition. It may be in the range of mass%.

[Acid direct dye]
The composition according to the invention comprises (d) at least one acidic direct dye. Two or more acidic direct dyes may be used in combination. Thus, a single type of acid direct dye or a combination of different types of acid direct dyes can be used.

  Direct dye means a colored substance that does not require the use of an oxidizing agent to develop its color.

  The direct dye may be a natural direct dye or a synthetic direct dye.

  The expression "natural direct dye" is any naturally occurring and optionally produced by extraction (and optionally purification) from animals such as plant substrates or insects in the presence of natural compounds such as ash or ammonia. Is understood to mean a dye or a dye precursor.

  The natural direct dye is not limited as long as it is an acid direct dye. Natural direct dyes include quinone dyes (e.g., Lawson and juglone), alizarin, purpurin, lacaic acid, carminic acid, kermesic acid, purprogaline, protocatechualdehyde, indigoids such as indigo, sorghum, isatin, betanin, curcuminoids (e.g. curcumin) , Spinulosin, various types of chlorophyll and chlorophyllin, hematoxylin, hematein, brazilein, brazirine, safflower dyes (e.g., cartamine), flavonoids (e.g., rutin, quercetin, catechin, epicatechin, morin, apigenidine, and sandalwood), anthocyan (e.g., Apigeninidine and apigenin), carotenoids, tannins, orcein, santaline and cochineal carmine.

  Extracts or leachates containing natural acid direct dyes, especially henna-based extracts, curcuma longa extracts, sorghum leaf sheath extracts, haematoxylon campechianum extracts, green tea extracts, pine bark extracts, cacao extracts It is also possible to use products and logwood extracts.

  Natural acid direct dyes are curcuminoids, santalin, chlorophyllin, hematoxylin, hematein, brazilein, braziline, sorghum, lacqueric acid, lawson, juglone, alizarin, purpurin, carminic acid, kermesic acid, pulprogarine, protocatechaldehyde, indigoid, isatin, spinulosin Apigenin, orcein, betanin, flavonoid, anthocyan, and an extract or leachate containing these compounds are preferably selected.

  Alternatively, the natural acid direct dye can preferably be selected from, for example, hydroxylated quinones, indigoids, hydroxyflavones, santalines A and B, isatin and its derivatives, and brazirin and its hydroxylated derivatives.

  The hydroxylated quinone is preferably benzoquinone, naphthoquinone, and mono- or polyhydroxylated anthraquinone, which are optionally substituted with groups such as alkyl, alkoxy, alkenyl, chloro, phenyl, hydroxyalkyl and carboxyl .

  Naphthoquinone is preferably Lawson, juglone, flaviolin, naphthazarin, naphthopurine, rapacol, plumbagin, chloroplumbagin, droselone, shikonin, 2-hydroxy-3-methyl-1,4-naphthoquinone, 3,5-dihydroxy- 1,4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 2-methoxy-5-hydroxy-1,4-naphthoquinone and 3-methoxy-5-hydroxy-1,4-naphthoquinone.

  Benzoquinone is preferably spinulosin, atromentin, aurantiogliocladin, 2,5-dihydroxy-6-methylbenzoquinone, 2-hydroxy-3-methyl-6-methoxybenzoquinone, 2,5-dihydroxy-3 1,6-diphenylbenzoquinone, 2,3-dimethyl-5-hydroxy-6-methoxybenzoquinone and 2,5-dihydroxy-6-isopropylbenzoquinone.

  The anthraquinone is preferably alizarin, quinizarin, purpurin, carminic acid, chrysophanol, kermesic acid, rhein, aloe emodin, pseudopurpurin, quinizarin carboxylic acid, frangulaemodin, 2-methylquinizarin, 1-hydroxyanthraquinone And 2-hydroxyanthraquinone.

  Indigoids are preferably indigo, indirubin, isoindigo and tilian purple.

  Hydroxyflavones are preferably quercetin and morin.

  The expression “synthetic direct dye” is understood to mean any dye or dye precursor produced by chemical synthesis.

  The synthetic direct dye is not limited as long as it is an acidic direct dye. Examples of synthetic dyes include azo, methine, carbonyl, nitro (hetero) aryl type or tri (hetero) arylmethane direct dyes, alone or as a mixture.

  Acid direct dyes are also commonly known as “anionic direct dyes”. Anionic or acid dyes are known in the literature (e.g. `` Ullmann's Encyclopedia of Industrial Chemistry '', Azo Dyes, 2005, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002 / 14356007.a03 245, point 3.2. `` Ullmann's Encyclopedia of Industrial Chemistry '', Textile Auxiliaries, 2002, Wiley-VCH Verlag GmbH & Co.KGaA, Weinheim 10.1002 / 14356007.a26 227, and `` Ashford's Dictionary of Industrial Chemicals '', 2nd edition, p. 14- (See page 39, 2001). Anionic or acidic dyes cause less skin irritation compared to other direct dyes.

The term `` anionic direct dye '' means in its structure at least one sulfonate group SO ₃ ⁻ and / or at least one carboxylate group C (O) O ⁻ and / or at least one phosphonate group P. (= O) O ^- O ^- and optionally one or more anionic groups G ^- means any direct dyes containing, G ^-, which may be the same or different and alkoxides O ^-, Thioalkoxide S ⁻ , phosphonate, carboxylate and thiocarboxylate: represents an anionic group selected from C (Q) Q ′ ^{— where} Q and Q ′ may be the same or different, oxygen or represents a sulfur atom, preferably, G ^- represents a carboxylate, i.e., Q and Q 'represents an oxygen atom.

Preferred acidic direct dyes of the formulations of the present invention include acidic nitro direct dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes, anionic styryl dyes, and indigoids and acidic natural Selected from dyes, each of these dyes containing at least one sulfonate, phosphonate or carboxylate group having a cationic counter ion X ⁺ , where X ⁺ is preferably an alkali and alkaline earth metal Represents an organic or inorganic cationic counterion selected from e.g. Na ⁺ and K ⁺ .

Preferred acidic direct dyes are
a) Diaryl anionic azo dyes of the formula (IV) or (IV ′):

[In the formulas (IV) and (IV ′),
R ₇ , R ₈ , R ₉ , R ₁₀ , R ′ ₇ , R ′ ₈ , R ′ ₉ and R ′ ₁₀ may be the same or different and may be a hydrogen atom or
-Alkyl,
-Alkoxy, alkylthio,
-Hydroxyl, mercapto,
-Nitro,
-R ° -C (X) -X'-, R ° -X'-C (X)-, R ° -X'-C (X) -X ''-(R ° is a hydrogen atom or alkyl or Represents an aryl group, X, X ′ and X ″ may be the same or different and each represents an oxygen or sulfur atom or NR, and R represents a hydrogen atom or an alkyl group),
-(O) ₂ S (O ^- )-, X ⁺ , as defined above
- previously defined ^{(O) CO - -, X} +,
-(O) P (O ₂ ^- )-, 2X ⁺ , as defined above
-R ''-S (O) _2- (R '' represents a hydrogen atom or an alkyl, aryl, (di) (alkyl) amino or aryl (alkyl) amino group, preferably phenylamino or a phenyl group),
-R '''-S (O) _2- X'-(R '''represents an alkyl or optionally substituted aryl group, X' is as defined above),
-(Di) (alkyl) amino,
optionally substituted with one or more groups selected from i) nitro, ii) nitroso, iii) (O) ₂ S (O ⁻ ) —, X ⁺ , and iv) alkoxy with X ⁺ Aryl (alkyl) amino,
An optionally substituted heteroaryl, preferably a benzothiazolyl group,
-Cycloalkyl, especially cyclohexyl,
Ar-N = N- (Ar is optionally substituted aryl group, preferably one or more alkyl, (O) ₂ S (O ⁻ ) —, X ⁺ or phenylamino group optionally (Represents substituted phenyl)
Represents a group selected from
Or alternatively two adjacent groups R ₇ and R ₈ , or R ₈ and R ₉ , or R ₉ and R ₁₀ together form a condensed benzo group A ′, R ′ ₇ and R _'8 or R' ₈ and R _'9 or R,' ₉ and R _'10, taken together, fused benzo group B' to form a, a 'and B', i) nitro, ii) nitroso _{, iii) (O) 2 S} (O -) -, X +, iv) hydroxyl, v) mercapto, vi) (di) (alkyl) amino, vii) R ° -C (X ) -X '-, viii ) R ° -X'-C (X)-, ix) R ° -X'-C (X) -X ''-, x) Ar-N = N- and xi) optionally substituted aryl ( Optionally substituted with one or more groups selected from (alkyl) amino, X ⁺ , R °, X, X ′, X ″ and Ar are as defined above;
W is a sigma bond σ, an oxygen or sulfur atom, or a divalent group i) -NR- (R is as defined above) or ii) methylene-C (R _a ) (R _b )- R _a and R _{b, which} may be the same or different, each represents a hydrogen atom or an aryl group, or R _a and R _b together with the carbon atom having them represent a spiro Form cycloalkyl, preferably W represents a sulfur atom, or R _a and R _b together form a cyclohexyl,
Formulas (IV) and (IV ′) are represented by at least one sulfonate (O) ₂ S (O ⁻ ) —, X ⁺ or phosphonate (O) P (O ₂ ⁻ ) 2X ⁺ or carboxylate (O) C ( It is understood that the group O ⁻ ) −, X ⁺ is included in one of the rings A, A ′, B, B ′ or C, where X ⁺ is as defined above;
Examples of dyes of formula (IV) include Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37 , Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Food Red 17, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Acid Yellow 9, Acid Yellow 23, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 7, Acid Violet 14 , Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, and Pigment Red 57.
Examples of dyes of formula (IV ′) include Acid Red 111, Acid Red 134, and Acid yellow 38];
b) Anthraquinone dyes of formula (V) and (V ′):

[In the formulas (V) and (V ′),
R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ may be the same or different and may be a hydrogen or halogen atom or
-Alkyl,
-Hydroxyl, mercapto,
-Alkoxy, alkylthio,
-Optionally substituted, preferably substituted, with one or more groups selected from alkyl and (O) ₂ S (O ⁻ ) —, X ^{+, where} X ⁺ is as defined above. Aryloxy or arylthio,
Aryl (alkyl) optionally substituted with one or more groups selected from alkyl and (O) ₂ S (O ⁻ ) —, X ^{+, where} X ⁺ is as defined above amino,
-(Di) (alkyl) amino,
-(Di) (hydroxyalkyl) amino,
-(O) ₂ S (O ^- )-, X ⁺ (X ⁺ is as defined above)
Represents a group selected from
Z ′ represents a hydrogen atom or an NR ₂₈ R ₂₉ group, and R ₂₈ and R ₂₉ may be the same or different, a hydrogen atom or
-Alkyl,
-Polyhydroxyalkyl, for example hydroxyethyl,
-One or more groups, in particular i) alkyl, for example methyl, n-dodecyl, n-butyl, ii) (O) ₂ S (O ⁻ )-X ⁺ (X ⁺ is as defined above) ), Iii) R ° -C (X) -X'-, R ° -X'-C (X)-, R ° -X'-C (X) -X ''-(R °, X, X 'And X''are as defined above, preferably, R ° represents an alkyl group) optionally substituted aryl,
-Represents a group selected from cycloalkyl, especially cyclohexyl,
Z represents a group selected from hydroxyl and NR ′ ₂₈ R ′ ₂₉ , and R ′ ₂₈ and R ′ ₂₉ may be the same or different and may be the same as defined above for R ₂₈ and R ₂₉ Represents the same atom or group,
It is understood that formulas (V) and (V ′) contain at least one sulfonate group (O) ₂ S (O ⁻ ) —, X ⁺ , where X ⁺ is as defined above,
Examples of dyes of formula (V) include Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41 , Acid Violet 42, Acid Violet 43, Mordant Red 3, and EXT Violet 2.
Examples of dyes of formula (V ′) include Acid Black 48];
And
c) Quinoline-based dyes of the formula (VI):

[In the formula (VI)
R ₆₁ represents a hydrogen or halogen atom or an alkyl group,
R ₆₂ , R ₆₃ and R ₆₄ may be the same or different and each represents a hydrogen atom or a (O) ₂ S (O ⁻ ) —, X ⁺ group, and X ⁺ is as defined above. Or
R ₆₁ and R ₆₂ or R ₆₁ and R ₆₄ together represent a benzo group optionally substituted with one or more (O) ₂ S (O ⁻ ) —, X ⁺ groups. Form and X ⁺ is as defined above,
G represents an oxygen or sulfur atom or an NR _e group, R _e represents a hydrogen atom or an alkyl group, in particular, G represents an oxygen atom,
It is understood that formula (VI) contains at least one sulfonate group (O) ₂ S (O ⁻ ) −, X ⁺ , where X ⁺ is as defined above;
Examples of dyes of formula (VI) include Acid Yellow 2, Acid Yellow 3, and Acid Yellow 5]
You can choose from.

  The acid direct dye is preferably selected from the group consisting of Acid Orange 7, Acid Violet 43 and Acid Black 1.

  The amount of (d) acidic direct dye may be 5% by weight or less, preferably 3% by weight or less, more preferably 2% by weight or less, based on the total weight of the composition according to the present invention, provided that (d) The amount of acid direct dye is subject to non-zero. (d) The amount of the acid direct dye may be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total mass of the composition.

  The composition according to the present invention comprises (d) a direct dye in an amount of 0.001% to 5% by weight, preferably 0.01% to 3% by weight, more preferably 0.05% to 2% by weight, based on the total weight of the composition. You may contain in the quantity.

[water]
The composition according to the invention comprises (e) water.

  The amount of (e) water may be 90% by weight or less, preferably 80% by weight or less, more preferably 70% by weight or less based on the total weight of the composition according to the present invention, provided that (e) water The amount is subject to non-zero. (e) The amount of water may be 40% by mass or more, preferably 45% by mass or more, more preferably 50% by mass or more, based on the total mass of the composition.

  The amount of (e) water in the composition according to the invention is 40% to 90% by weight, preferably 45% to 80% by weight, more preferably 50% to 70% by weight relative to the total weight of the composition. It may be in the range of%.

[Other ingredients]
The composition according to the invention may further comprise at least one organic solvent. Two or more organic solvents may be used in combination. Thus, a single type of organic solvent or a combination of different types of organic solvents can be used. Organic solvents are different from (b) fatty substances.

  Suitable organic solvents can be selected from volatile and non-volatile organic solvents.

The organic solvent used in the present invention is preferably a liquid at room temperature, for example, 25 ° C. under atmospheric pressure (760 mmHg or 10 ⁵ Pa).

  Suitable organic solvents for use in the present invention are C1-C4 lower alcohols, glycols, polyols, and polyol ethers. Examples of organic solvents include, but are not limited to, ethanol, isopropyl alcohol, benzyl alcohol, phenylethyl alcohol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, glycerin, and mixtures thereof.

  Other suitable organic solvents include glycol ethers such as ethylene glycol and its ethers such as ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol and its ethers such as propylene glycol monomethyl ether, propylene Examples include glycol monopropyl ether, propylene glycol monobutyl ether, alkyl ethers of dipropylene glycol and diethylene glycol, such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and dipropylene glycol n-butyl ether.

  The amount of organic solvent in the composition according to the invention is from 0.5% to 30% by weight, preferably from 1% to 25% by weight, more preferably from 5% to 20% by weight, based on the total weight of the composition. It may be a range.

  Preferred examples of organic solvents include monoalcohols such as C2 to C4 monoalkanols (eg ethanol, isopropyl alcohol, butanol) and aromatic monoalcohols (eg benzyl alcohol), and mixtures thereof. Monoalcohol is different from (b) fatty substances.

  The amount of monoalcohol in the composition according to the invention is from 0.5% to 25% by weight, preferably from 1% to 20% by weight, more preferably from 5% to 15% by weight, based on the total weight of the composition. It may be a range.

  The composition according to the invention also contains various adjuvants conventionally used in compositions for dyeing hair, for example (c) anionic, nonionic, cationic, amphoteric or zwitterionic other than acrylic polymers. It may contain an ionic polymer or a mixture thereof, an antioxidant, a sequestering agent, a fragrance, a dispersing agent, a conditioning agent, a film forming agent, a ceramide, a preservative and an opacifier.

  The pH of the composition according to the invention can be adjusted to the desired value using acidifying or basifying agents commonly used in dyeing keratin fibers, or using conventional buffer systems.

  The composition according to the invention is preferably acidic. Accordingly, the pH of the composition is preferably 1 to 6, more preferably 2 to 5, and even more preferably 2 to 4.

  Among the acidifying agents, mention may be made, by way of example, of inorganic or organic acids such as hydrochloric acid, ortho-phosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.

  The acidifying or basifying agent is in an amount ranging from 0.001% to 15% by weight, preferably from 0.01% to 10% by weight, more preferably from 0.1% to 5% by weight relative to the total weight of the composition. Can be used.

  The viscosity of the composition according to the present invention is not particularly limited. Viscosity can be measured at room temperature by using a rheometer, for example a rotational viscometer RM180 (Mettler Toledo) equipped with a TV spindle. Preferably, the viscosity of the composition may range from 3600 to 9200 mPa · s, preferably from 5000 to 9150 mPa · s, more preferably from 6000 to 9100 mPa · s at room temperature and a shear rate of 200 1 / s.

  The form of the composition according to the present invention is not particularly limited as long as it is water-based, and can take various forms such as an emulsion (O / W or W / O type), an aqueous gel, and an aqueous solution. The composition according to the invention is preferably in the form of an O / W emulsion.

  The composition according to the invention has a structured phase of lamellar and vesicle structure. The structured phase of the present invention may be generated from the unique configuration of the present invention. Preferably, the composition has a lamellar structure.

  The composition according to the present invention is a composition for dyeing keratin fibers, preferably a cosmetic composition for dyeing keratin fibers. “Keratin fiber” as used herein means a fiber comprising at least one keratin material. It is preferable that at least a part of the surface of the keratin fiber is formed by the keratin fiber. Examples of keratin fibers include hair, eyebrows, eyelashes and the like. The composition according to the invention is preferably used for dyeing hair.

[Preparation]
The composition according to the invention can be prepared by mixing components (a) to (e) as essential components and the optional components described above.

  The methods and means for mixing the above essential and optional ingredients are not limited. Any conventional method and means for mixing the above essential and optional ingredients can be used to prepare the compositions according to the present invention.

  In one particular embodiment of the invention, the composition according to the invention comprises (1) mixing the fatty substance, surfactant and polyol (if present) at about 60-90 ° C. to prepare the mixture. (2) adding preheated water to the mixture and emulsifying the mixture; (3) adding pre-dissolved acidic direct dye and organic solvent (if present) to the mixture; and (4) the mixture. Cooling to about 20-50 ° C., (5) adding an acidifying agent and an organic solvent (if present), and then (6) adding an acrylic polymer to the mixture and mixing them. And can be prepared.

  The composition according to the invention is preferably a so-called one-part composition or a ready-to-use composition. For the purposes of the present invention, the expression “ready-to-use composition” is defined herein as a composition that is immediately applied to keratin fibers such as hair.

  Compared with so-called two-part compositions, so-called one-part compositions do not require mixing of the components in the composition before use. It is therefore easy for consumers to use the composition according to the invention for dyeing keratin fibers. Furthermore, the composition according to the present invention is capable of stable coloring of keratin fibers because the ingredients are mixed in the exact mixing ratio required for a two-part composition for dyeing keratin fibers. This is because there is no possibility of damage.

[Beauty method]
The present invention also relates to a cosmetic method for dyeing keratin fibers comprising the step of applying a composition according to the invention to keratin fibers.

  The step of applying the composition according to the invention to keratin fibers can be carried out by conventional applicators, for example brushes and combs, or even by hand.

  The keratin fibers coated with the composition according to the invention can be left for an appropriate time required to treat the keratin fibers. The length of time for treatment is not limited, but may be from 1 minute to 1 hour, preferably from 1 minute to 30 minutes, more preferably from 1 minute to 15 minutes. For example, the time for dyeing keratin fibers may be 1 to 20 minutes, preferably 5 to 15 minutes.

  Keratin fibers may be treated at room temperature. Alternatively, during the step of applying the composition according to the present invention to keratin fibers and / or the step of leaving the keratin fibers coated with the composition according to the present invention, the keratin fibers are allowed to move from 25 ° C to 65 ° C, preferably from 30 ° C. You may heat at 60 degreeC, More preferably, it is 35 to 55 degreeC, More preferably, you may heat at 40 to 50 degreeC.

  The keratin fibers may be rinsed after the step of applying the composition according to the present invention to the keratin fibers and / or after leaving the keratin fibers coated with the composition according to the present invention.

  The invention can also relate to the use of the composition according to the invention for dyeing keratin fibers such as hair.

  The invention is explained in more detail by means of examples. However, these examples should not be construed to limit the scope of the invention.

[Composition]
Each of the cosmetic compositions for dyeing hair according to Examples 1 to 3 (Examples 1 to 3) and Comparative Examples 1 to 5 (Comparative Examples 1 to 5) was prepared according to the following preparation protocol: did. The composition is shown in Table 1 below. Among the components, acrylamide / acrylamido-2-sodium-methylpropanesulfonic acid copolymer was obtained from SEPPIC, Inc. (product name: Sepigel 305 (TM), CTFA name: polyacrylamide / C ₁₃ -C ₁₄ isoparaffin / laureth - 7) Polyacrylate crosspolymer-6 was obtained from SEPPIC (product name: Sepimax Zen (registered trademark)), and carbomer was obtained from ASHLAND (product name: Ashland 980 MS Carbomer). All numerical values of the components are based on “mass%” as the active ingredient.

[Preparation protocol]
1) Fatty substances (cetyl alcohol and stearyl alcohol), surfactants (ceteales-33, steareth-20, and glyceryl stearate) and polyols (glycerin and butylene glycol) were mixed at 80 ° C. for 10 minutes.
2) Preheated water was slowly added to the mixture and emulsified at 80 ° C. for 15 minutes.
3) Predissolved acidic direct dyes (Acid Orange 7, Acid Violet 43, Acid Black 1, and Acid Yellow 23) and benzyl alcohol were added to the mixture and stirred for 15 minutes.
4) The mixture was cooled to a temperature below 40 ° C.
5) Lactic acid and ethanol were added to the mixture and stirred for 15 minutes.
6) The acrylic polymer (polyacrylamide / C ₁₃ -C ₁₄ isoparaffin / laureth-7, polyacrylate crosspolymer -6, or carbomer) or hydroxypropyl starch phosphate (if present) mixture was added slowly, 10 minutes Stir.
7) Finally, the pH of the mixture was adjusted to 2.7 with lactic acid.

[Evaluation]
(Structured phase)
The presence or absence of a structured phase in each of the compositions according to Examples 1-3 and Comparative Examples 1-5 was determined by microscopic observation in polarization mode. When Maltese crosses and multilayer patterns due to lamellar structure were observed, it was determined that a structured phase was present. On the other hand, if no Maltese cross or multilayer pattern was observed, it was determined that no structured phase was present.

(Hair color strength)
Each of the compositions according to Examples 1-3 and Comparative Examples 1-5 (4 g) was uniformly applied to 1 g of 100% white natural human hair. The samples were then left at 40 ° C. for 15 minutes, followed by washing with water, shampooing and drying. The color difference of the tuft before and after the above dyeing process was measured by using a Konica Minolta spectrocolorimeter CM-3600d. ΔE ^* (between the unstained original sample color and the stained sample color by the ΔL ^* a ^* b system) was calculated. The greater the ΔE ^* , the better the staining. The measured ΔE ^* was evaluated according to the evaluation criteria shown below.
Good: ΔE ^* is greater than 47.
Possible: ΔE ^* is 44 or more and 47 or less.
Bad: ΔE ^* is less than 44.

(Contamination intensity)
Each of the compositions according to Examples 1 to 3 and Comparative Examples 1 to 5 (0.1 ml) was applied to the surface of the artificial skin so that the application site was a circle with a diameter of 1 cm. The applied surface was left at 40 ° C. for 10 minutes, and then the composition was washed thoroughly with water and the surface was dried. The surface color difference before and after the above coating process was measured by using a Konica Minolta spectrocolorimeter CM-3600d. ΔE ^* (the surface color before application and the surface color after application by the ΔL ^* a ^* b system) was calculated. The smaller the ΔE ^* , the weaker the contamination. The measured ΔE ^* was evaluated according to the evaluation criteria shown below.
Good: ΔE ^* is less than 9.
Possible: ΔE ^* is 9 or more and 14 or less.
Bad: ΔE ^* is greater than 14.

(Thermal stability)
Each of the compositions according to Examples 1-3 and Comparative Examples 1-5 were stored in glass bottles at 45 ° C. for 2 months. Next, the state of the composition when the bottle was tilted to 45 degrees was observed at 45 ° C. Thermal stability was evaluated according to the evaluation criteria shown below.
Good: Most do not move and therefore remain rich.
Yes: Most move slightly, thus changing from rich to slightly fluid.
Bad: Most move substantially, thus changing from rich to liquid.

(Usability)
Usability of a composition for dyeing keratin fibers relates to its viscosity. If the viscosity is not within the proper range, it will be difficult to remove the composition from the container and apply it to the keratin fibers, for example with a comb. The viscosities of the compositions according to Examples 1-3 and Comparative Examples 1-5 were measured at a shear rate of 200 1 / s and room temperature using a rotational viscometer RM180 (Mettler Toledo) equipped with a TV spindle. did. Usability was evaluated according to the following evaluation criteria.
Good: Viscosity is 3600 to 9200 mPa · s.
Good: Viscosity is over 9200 mPa · s to 10200 mPa · s.
Poor: The viscosity is less than 3600 mPa · s or more than 10200 mPa · s.

  The results are shown in Table 1.

  As can be seen from Table 1, a combination of at least one surfactant, at least one fatty substance, at least one acrylic polymer, at least one acid direct dye, and water. Including the compositions according to each of Examples 1-3 can exhibit good hair color strength and improved stain strength, as well as good thermal stability and usability.

  On the other hand, the composition according to Comparative Example 1 containing a smaller amount of fatty substance than the present invention and lacking the acrylic polymer was inferior in hair color strength and thermal stability. The composition according to Comparative Example 2 containing the same amount of fatty substance as in the present invention but lacking the acrylic polymer had poor usability due to high viscosity. Similarly, the composition according to Comparative Example 3, which contained hydroxypropyl starch phosphate instead of the acrylic polymer of the present invention, had poor usability due to high viscosity. The composition according to Comparative Example 4, lacking fatty substances, did not have a structured phase and had poor hair color strength. The composition according to Comparative Example 5, lacking fatty substances and surfactants, did not have a structured phase and had poor stain strength.

  Thus, the composition according to the invention exhibits good stability and good usability, eg easy handling and excellent cosmetic effects, eg good color strength, while contamination of the scalp and other skin Can be prevented or reduced, it can be concluded that it can be highly preferred as a composition for dyeing keratin fibers.

Claims (15)

A composition for dyeing keratin fibers, preferably hair,
(a) at least one surfactant;
(b) at least one fatty substance;
(c) at least one acrylic polymer;
(d) at least one acid direct dye;
(e) A composition comprising water.   The composition according to claim 1, wherein (a) the surfactant is selected from a nonionic surfactant and an anionic surfactant.   3. The composition according to claim 1, wherein (b) the fatty substance contains at least one fatty alcohol.   4. The composition according to any one of claims 1 to 3, wherein (c) the acrylic polymer is selected from acrylic copolymers comprising at least one monomer having sulfonic acid groups, and acrylic acid polymers. A monomer having a sulfonic acid group of an acrylic copolymer has the following general formula (1):
[Wherein X ⁺ represents a cationic counter ion, particularly an alkali metal or alkaline earth metal, or ammonium, and R ₁ represents a hydrogen atom or a linear or branched C _{1 to} C ₆ alkyl group. Show]
The composition according to claim 4, wherein the composition is selected from monomers corresponding to: The acrylic copolymer is a monomer of acrylamide or formula (3):
[Wherein R ₁ represents a hydrogen atom or a linear or branched C _{1 to} C ₆ alkyl group, preferably methyl, Y represents O or NH, and R ₂ represents 6 to 50 Of carbon atoms, more preferably 6 to 22 carbon atoms, still more preferably 12 to 18 carbon atoms, and x represents a number in the range of 0 to 100]
The composition according to claim 4 or 5, further comprising a monomer represented by:   5. The composition according to claim 4, wherein the acrylic acid polymer is a homopolymer of acrylic acid or methacrylic acid.   (a) The amount of the surfactant is in the range of 0.1% to 20% by weight, preferably 0.5% to 15% by weight, more preferably 1% to 10% by weight, based on the total weight of the composition. 8. The composition according to any one of claims 1 to 7.   (b) the amount of fatty substance is in the range of 1% to 50% by weight, preferably 5% to 40% by weight, more preferably 10% to 30% by weight, relative to the total weight of the composition; 9. The composition according to any one of claims 1 to 8.   (c) The amount of the acrylic polymer is in the range of 0.01% to 20% by weight, preferably 0.05% to 5% by weight, more preferably 0.1% to 2% by weight, based on the total weight of the composition. 10. The composition according to any one of claims 1 to 9.   The composition according to any one of claims 1 to 10, further comprising (b) at least one organic solvent selected from monoalcohols other than fatty substances.   (b) The fatty substance is in the form of a liquid, less than 10% by weight, more preferably less than 5% by weight, preferentially less than 3% by weight, more preferably 1% by weight, based on the total amount of the composition. 12. Composition according to any one of the preceding claims, comprising less than, in particular less than 0.5% by weight.   The composition according to any one of claims 1 to 12, which has a lamellar structure.   (e) the amount of water ranges from 40% to 90% by weight, preferably from 45% to 80% by weight, more preferably from 50% to 70% by weight, relative to the total weight of the composition, Item 14. The composition according to any one of Items 1 to 13.   A method for dyeing keratin fibers, preferably hair, comprising the step of applying the composition according to any one of claims 1 to 14 to keratin fibers.