JP7301867B2 - Cosmetic composition comprising cationic polymer, anionic direct dye, dimethylsulfone and ethylhydroxypyrone, method and use thereof - Google Patents

Description

The present invention relates to compositions comprising one or more cationic polymers, one or more anionic direct dyes, and at least dimethylsulfone and/or at least ethylhydroxypyrone.

The invention also relates to a method for treating keratin fibres, in particular human keratin fibres, such as hair, comprising at least the step of applying a composition according to the invention to said keratin fibres.

The present invention also relates to the use of the composition according to the invention for treating keratinous fibres, in particular human keratinous fibres, such as hair.

It is known to dye keratin fibers by direct coloring or semi-permanent coloring. Direct or semi-permanent coloring involves imparting color via coloring molecules that either adsorb onto the surface of the hair or penetrate the hair. Therefore, the method conventionally used in direct dyeing is to apply a direct dye, which is a colored dye molecule that has an affinity for said fiber, to the keratin fiber, bring the fiber into contact with the dye molecule, and then the fiber. It is to wash away. Generally, this technique results in chromatic coloring.

These hair dyeing compositions certainly have good tinctorial strength, but are particularly sensitive to sensitive hair, i.e. generally to the action of external atmospheric agents such as light, weather and/or brushing, combing. The cosmetic properties imparted by these hair compositions are even more improved when applied to hair damaged or weakened by the action of mechanical or chemical treatments such as, dyeing, bleaching, permanenting and/or straightening. need to Therefore, it is common to resort to hair care compositions that employ auxiliary cosmetic agents known as conditioning agents to improve the cosmetic properties of sensitized hair. These conditioning agents can of course also improve the cosmetic behavior of natural hair.

In addition, sensitized blonde hair has been found to become dull and yellowish over time, especially at the ends.

However, these hair coloring compositions are not always satisfactory and can be improved even further, especially with respect to selectivity from root to tip of the hair, direct dye deposition on the keratin fibers. .

Furthermore, prior art hair compositions are generally poor in terms of quality of use (good spreadability and distribution of the composition, ease of rinsing) or residual to various external agents (e.g. shampoo, light, pollution). In terms of sexuality, it does not lead to increased satisfaction.

EP-A-0 337 354 FR-A-2 270 846 FR-A-2 383 660 FR-A-2 598 611 FR-A-2 470 596 FR-A-2 519 863 French Patent No. 2 505 348 French Patent No. 2 542 997 EP-A-080 976 French Patent No. 2 077 143 French Patent No. 2 393 573 French Patent No. 2 162 025 French Patent No. 2 280 361 French Patent No. 2 252 840 French Patent No. 2 368 508 French Patent No. 1 583 363 U.S. Patent No. 3 227 615 U.S. Patent No. 2 961 347 French Patent No. 2 080 759 French Patent No. 2 190 406 French Patent No. 2 320 330 French Patent No. 2 270 846 French Patent No. 2 316 271 French Patent No. 2 336 434 French Patent No. 2 413 907 U.S. Patent No. 2 273 780 U.S. Patent No. 2 375 853 U.S. Patent No. 2 388 614 U.S. Patent No. 2 454 547 U.S. Patent No. 3 206 462 U.S. Patent No. 2 261 002 U.S. Patent No. 2 271 378 U.S. Patent No. 3 874 870 U.S. Patent No. 4 001 432 U.S. Patent No. 3 929 990 U.S. Patent No. 3 966 904 U.S. Patent No. 4 005 193 U.S. Patent No. 4 025 617 U.S. Patent No. 4 025 627 U.S. Patent No. 4 025 653 U.S. Pat. No. 4 026 945 U.S. Patent No. 4 027 020 EP-A-122 324 French Patent No. 1 492 597 U.S. Patent No. 4 131 576 U.S. Patent No. 3 589 578 U.S. Patent No. 4 031 307 French Patent Application No. 2 589 476 US-A-4 957 732 EP 186 507 EP-A-412,704 EP-A-412,707 EP-A-640,105 WO95/00578 EP-A-582,152 WO93/23009 U.S. Patent No. 4,693,935 U.S. Patent No. 4,728,571 U.S. Patent No. 4,972,037 US 4 185 087 EP-A 0 530 974 US-A-4 874 554 US-A-4 137 180

CTFA Dictionary the Color Index (published by The Society of Dyers and Colourists, P.O. Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JB, England) Walter Noll, Chemistry and Technology of Silicones (1968), Academic Press Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics

Therefore, after one or more applications, the keratin fibers are not charged or weighed down, while maintaining good quality of use (good spreadability of the composition on the hair, ease of rinsing). A composition with good dyeing properties that dyes with low root-to-tip selectivity, good color absorption and good intensity, conditions keratin fibers and can also impart improved cosmetic properties to keratin fibers. Developing things is really needed.

These objects are achieved by the present invention, one of the subjects of interest being
a. one or more cationic polymers;
b. One or more anionic direct dyes; and
c. A composition comprising at least dimethylsulfone and/or at least ethylhydroxypyrone.

The compositions according to the invention make it possible to dye keratin fibers with a good long-lasting quality while at the same time achieving the desired properties, especially in terms of strength, quality and cosmetic properties of the keratin fibers.

In particular, the compositions according to the invention make it possible to obtain good dyeings with low selectivity, in particular blond hair tips that are shiny, not dull and have beautiful shadows as well as the roots.

It has also been found that the compositions according to the invention are capable of dyeing hair with good color absorption and good intensity.

Furthermore, the compositions according to the invention condition the keratin fibers well, while maintaining good application qualities (good spreadability of the composition on the hair, ease of rinsing) without charging or weighing the hair. It is possible to

Other features and advantages of the invention will emerge more clearly on reading the following description and examples.

In this specification, unless otherwise specified:
- the limits of a range of values are included within this range, especially in the expressions "between" and "range from".
- As used herein, the expression "at least one" is equivalent to and may be replaced by the expression "one or more".

Cationic Polymer According to the present invention, the composition comprises one or more cationic polymers.

The term "cationic polymer" means any polymer containing cationic groups and/or groups that can be ionized into cationic groups, preferably non-silicon polymers.

The cationic polymers that can be used according to the invention are any of those known per se for conditioning hair, namely in particular patent application EP-A-0 337 354 and French patent application FR-A-2 270. 846, FR-A-2 383 660, FR-A-2 598 611, FR-A-2 470 596 and FR-A-2 519 863.

Preferred cationic polymers that may be used in compositions according to the present invention are primary , containing units containing secondary, tertiary and/or quaternary amine groups.

The weight average molecular weight of the cationic polymer is preferably above 10 ⁵ , preferably above 10 ⁶ , more preferably between 10 ⁶ and 10 ⁸ .

Among the cationic polymers that can be used according to the invention, mention may be made in particular of polyamine, polyaminoamide and polyquaternary ammonium type polymers.

Polymers of the polyamine, polyaminoamide and polyquaternary ammonium type which can be used in the composition according to the invention are in particular those described in FR 2 505 348 and FR 2 542 997. .

Among these polymers, mention may be made in particular of:

(式中、
- R₃及びR₄は、同一であっても異なっていてもよく、水素原子、又は1～6個の炭素原子を含有するアルキル基、好ましくはメチル若しくはエチル基を表し、
- R₅は、同一であっても異なっていてもよく、水素原子又はCH₃基を示し、
- Aは、同一であっても異なっていてもよく、1～6個の炭素原子、好ましくは2個若しくは3個の炭素原子を有する直鎖状若しくは分岐状のアルキル基、又は1～4個の炭素原子を含むヒドロキシアルキル基を表し、
- R₆、R₇及びR₈は、同一であっても異なっていてもよく、1～18個の炭素原子を含有するアルキル基、又はベンジル基、好ましくは1～6個の炭素原子を含有するアルキル基を表し、
- X^-は、鉱酸又は有機酸に由来するアニオン、好ましくは、メトスルフェートのアニオン、又はハロゲン化物イオン、更に良好には塩化物イオン又は臭化物イオンを示す)。 (1) Homopolymers or copolymers derived from esters or amides of acrylic or methacrylic acid and containing at least one unit of the following formulas (VIII), (IX), (X) and (XI):

(In the formula,
- R ₃ and R ₄ , which may be the same or different, represent a hydrogen atom or an alkyl group containing 1 to 6 carbon atoms, preferably a methyl or ethyl group;
- _R5 , which may be the same or different, represents a hydrogen atom or a _CH3 group;
- A, which may be the same or different, are linear or branched alkyl groups having 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or 1 to 4 represents a hydroxyalkyl group containing carbon atoms of
- _R6 , _R7 and _R8 , which may be the same or different, are alkyl groups containing 1 to 18 carbon atoms or benzyl groups, preferably containing 1 to 6 carbon atoms represents an alkyl group that
^-X- denotes an anion derived from a mineral or organic acid, preferably the anion of methosulfate, or a halide ion, better still chloride or bromide).

Copolymers of family (1) also include acrylamide, methacrylamide, diacetoneacrylamide, acrylamide and methacrylamide substituted at the nitrogen atom with lower (C ₁ -C ₄ )alkyl, acrylic or methacrylic acid or esters thereof, vinyl It can also contain one or more units derived from comonomers, which can be selected from the family of vinyllactams, such as pyrrolidone or vinylcaprolactam, as well as vinyl esters.

Thus, among these copolymers of family (1), mention may be made of:
- copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or dimethyl halide, for example the products sold under the name Hercofloc by the company Hercules,
- copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride, e.g. described in patent application EP-A-080 976 and sold under the name Bina Quat P 100 by Ciba Geigy,
- copolymers of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate, sold under the name Reten by the company Hercules,
- quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, e.g. products sold under the name Gafquat by the company ISP, e.g. Gafquat 734 or Gafquat 755, or Copolymers 845, 958 and Product known as 937. These polymers are detailed in FR 2 077 143 and FR 2 393 573,
- dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymer, e.g. the product sold under the name Gaffix VC 713 by the company ISP,
- in particular the vinylpyrrolidone/methacrylamidopropyldimethylamine copolymer sold under the name Styleze CC 10 by the company ISP,
- quaternized vinylpyrrolidone/dimethylaminopropyl methacrylamide copolymers, such as the product sold under the name Gafquat HS 100 by the company ISP, and
- crosslinked polymers of methacryloyloxy( _C1 - _C4 )alkyltri( _C1 - _C4 )alkylammonium salts, e.g. by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride or with acrylamide, Polymers obtained by copolymerization with dimethylaminoethyl methacrylate quaternized with methyl chloride, homopolymerization or copolymerization followed by crosslinking with olefinically unsaturated compounds, especially methylenebisacrylamide polymer. More particularly, said copolymer can be used in the form of a dispersion containing 50% by weight of a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in mineral oil. This dispersion is sold under the name Salcare® SC 92 by the company Ciba. Crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer (INCI name Polyquaternium-37), for example the polymer sold by Cognis under the name Cosmedia Ultragel 300, or as a dispersion in mineral oil or liquid ester is used. These dispersions are sold under the names Salcare® SC 95 and Salcare® SC 96 by the company Ciba.

(2) piperazinyl units and divalent alkylene or hydroxyalkylene groups containing straight or branched chains, optionally interrupted by oxygen, sulfur or nitrogen atoms, or aromatic or heterocyclic rings; , polymers formed from divalent alkylene or hydroxyalkylene groups, as well as oxidation and/or quaternization products of these polymers. Such polymers are described in particular in FR 2 162 025 and FR 2 280 361.

(3) Water-soluble polyaminoamides, especially prepared by polycondensing acidic compounds with polyamines. These polyaminoamides may also be crosslinked with epihalohydrins, diepoxides, dianhydrides, unsaturated dianhydrides, bis-unsaturated derivatives, bis-halohydrins, bis-azetidiniums, bis-haloacyldiamines, bis-alkyl halides. well or alternatively with oligomers resulting from the reaction of difunctional compounds reactive with bis-halohydrins, bis-azetidiniums, bis-haloacyldiamines, bis-alkyl halides, epihalohydrins, diepoxides or bis-unsaturated derivatives. may be used, and the cross-linking agent is used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide. These polyaminoamides can be alkylated or, if they contain one or more tertiary amine functional groups, may be quaternized. Such polymers are described in particular in FR 2 252 840 and FR 2 368 508.

(4) Polyaminoamide derivatives obtained by condensing a polyalkylenepolyamine with a polycarboxylic acid followed by alkylation with a difunctional agent. For example, mention may be made of adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl groups contain from 1 to 4 carbon atoms, preferably denoting methyl, ethyl or propyl. Such polymers are described in particular in FR 1 583 363.

Among these derivatives, mention may be made in particular of the adipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold under the names Cartaretine F, F4 or F8 by the company Sandoz.

(5) polyalkylenepolyamines containing two primary amine groups and at least one secondary amine group and dicarboxylic acids selected from diglycolic acid and saturated aliphatic dicarboxylic acids having 3 to 8 carbon atoms; A polymer obtained by reaction with an acid. The molar ratio between the polyalkylenepolyamine and the dicarboxylic acid is between 0.8:1 and 1.4:1 and the resulting polyaminoamide has a molar ratio of epichlorohydrin to secondary amine groups of the polyaminoamide. React with epichlorohydrin in a ratio between 0.5:1 and 1.8:1. Such polymers are described inter alia in US Pat. No. 3,227,615 and US Pat. No. 2,961,347.

Polymers of this kind are sold in particular by the company Hercules Inc. under the name Hercosett 57 or, in the case of adipic acid/epoxypropyl-diethylenetriamine copolymers, by the company Hercules under the names PD 170 or Delsette 101.

(式中、k及びtは、0又は1に等しく、和k+tは1に等しく；R₁₂は、水素原子又はメチル基を示し；R₁₀及びR₁₁は、互いに独立して、1～6個の炭素原子を含有するアルキル基、アルキル基が好ましくは1～5個の炭素原子を含有するヒドロキシアルキル基、低級(C₁～C₄)アミドアルキル基を示し、又は、R₁₀及びR₁₁は、それらが結合している窒素原子と一緒になって、ピペリジル若しくはモルホニル等の複素環基を示すことができ；Y^-は、臭化物イオン、塩化物イオン、酢酸イオン、ホウ酸イオン、クエン酸イオン、酒石酸イオン、硫酸水素イオン、亜硫酸水素イオン、硫酸イオン、又はリン酸イオン等のアニオンである)。これらのポリマーは、特に、仏国特許第2 080 759号及びその追加特許である仏国特許第2 190 406号に記載されている。 (6) Cyclopolymers of alkyldiallylamines or dialkyldiallylammoniums, e.g. homopolymers or copolymers containing units corresponding to formula (XII) or formula (XIII) as main constituents of the chain:

(wherein k and t are equal to 0 or 1 and the sum k+t is equal to 1; R ₁₂ represents a hydrogen atom or a methyl group; R ₁₀ and R ₁₁ an alkyl group containing 6 carbon atoms, the alkyl group preferably represents a hydroxyalkyl group containing 1 to 5 carbon atoms, a lower (C ₁ -C ₄ ) amidoalkyl group, or R ₁₀ and R ₁₁ together with the nitrogen atom to which they are attached can represent a heterocyclic group such as piperidyl or morphonyl; Y ⁻ can represent bromide, chloride, acetate, borate, citrate anions such as acid, tartrate, bisulfate, bisulfite, sulfate, or phosphate). These polymers are described in particular in FR 2 080 759 and its addition FR 2 190 406.

R ₁₀ and R ₁₁ independently of each other denote an alkyl group preferably having 1 to 4 carbon atoms.

Among the polymers defined above, in particular dimethyldiallylammonium chloride homopolymer and its homologues with lower weight average molecular weights, sold under the name Merquat 100 by the company Nalco, and diallyl, sold under the name Merquat 550 Copolymers of dimethylammonium chloride and acrylamide may be mentioned.

(式中、
- R₁₃、R₁₄、R₁₅及びR₁₆は、同一であっても異なっていてもよく、1～20個の炭素原子を含有する脂肪族基、脂環式基若しくはアリール脂肪族基、又は低級ヒドロキシアルキル脂肪族基を表し、或いはR₁₃、R₁₄、R₁₅及びR₁₆は、一緒に又は別々に、それらが結合している窒素原子と、窒素以外の第2のヘテロ原子を任意選択により含有する複素環を構成し、或いはR₁₃、R₁₄、R₁₅及びR₁₆は、ニトリル、エステル、アシル若しくはアミド基、又はCOOR₁₇D基若しくはCONHR₁₇D基(式中、R₁₇はアルキレンであり、Dは第四級アンモニウム基である)で置換されている直鎖状又は分岐状C₁～C₆アルキル基を表し、
- A₁及びB₁は、2～20個の炭素原子を含有するポリメチレン基を表し、これは、直鎖状又は分岐状であってよく、飽和又は不飽和であってよく、主鎖に連結した又は挿入された、1個若しくは複数個の芳香族環、又は1個若しくは複数個の酸素若しくは硫黄原子、若しくはスルホキシド、スルホン、ジスルフィド、アミノ、アルキルアミノ、ヒドロキシル、第四級アンモニウム、ウレイド、アミド若しくはエステル基を含有してもよく、
- X^-は、鉱酸又は有機酸に由来するアニオンを示す)。 (7) Quaternary diammonium polymers, especially containing repeat units corresponding to formula (XIV):

(In the formula,
- R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ , which may be the same or different, are aliphatic, cycloaliphatic or arylaliphatic groups containing 1 to 20 carbon atoms, or represents a lower hydroxyalkylaliphatic group, or R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ together or separately optionally the nitrogen atom to which they are attached and a second heteroatom other than nitrogen; or R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are nitrile, ester, acyl or amide groups, or COOR ₁₇ D or CONHR ₁₇ D groups, where R ₁₇ is an alkylene and D is a quaternary ammonium group) represents a linear or branched C ₁ -C ₆ alkyl group substituted with
- A ₁ and B ₁ represent a polymethylene group containing 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated and linked to the main chain one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or may contain an ester group,
^-X- indicates an anion derived from a mineral or organic acid).

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

In addition, when A ₁ represents a linear or branched, saturated or unsaturated, alkylene or hydroxyalkylene group, B ₁ is (CH ₂ ) _n -CO-D-OC-(CH ₂ ) _p - It may also indicate a group,
n and p are integers ranging from approximately 2 to 20;
where D denotes:
a) Glycol residue of formula: -OZO-, where Z refers to a straight or branched hydrocarbon-based group or a group corresponding to one of the following formulae:
-( _CH2 - _CH2 -O) _x - _CH2 - _CH2- ,
-[ _CH2 -CH( _CH3 )-O] _y - _CH2 -CH( _CH3 )-
(Wherein, x and y represent an integer from 1 to 4 representing a defined specific degree of polymerization, or an arbitrary number from 1 to 4 representing an average degree of polymerization)),
b) bis-secondary diamine residues, such as piperazine derivatives,
c) Formula: -NH-Y-NH-, where Y is a straight or branched hydrocarbon group or a divalent _-CH2 - _CH2- SS- _CH2 - _CH2- group ) of the bis-primary diamine residue,
d) A ureylene group of the formula -NH-CO-NH-.

Preferably X ⁻ is an anion such as chloride or bromide.

The number average molecular weight of these polymers is generally between 1000 and 100,000.

Polymers of this kind are described in particular in FR 2 320 330, FR 2 270 846, FR 2 316 271, FR 2 336 434 and FR 2 413 907 and US 2 273 780, US 2 375 853, US 2 388 614, US 2 454 547, US 3 206 462, US 2 261 002, US 2 271 378, US 3 874 870, US 4 001 432, US 3 929 990, US 3 966 904, US 4 005 193 US 4 025 617, US 4 025 627, US 4 025 653, US 4 026 945 and US 4 027 020.

(式中、R₁₈、R₁₉、R₂₀及びR₂₁は、同一であっても異なっていてもよく、およそ1～4個の炭素原子を含有するアルキル又はヒドロキシアルキル基を示し、r及びsは、およそ2から20までの範囲の整数であり、X^-は、鉱酸又は有機酸に由来するアニオンである)。 More specifically, polymers formed from repeat units corresponding to formula (XV) can be used:

(wherein R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ , which may be the same or different, represent an alkyl or hydroxyalkyl group containing approximately 1 to 4 carbon atoms, and r and s is an integer ranging from approximately 2 to 20 and X ⁻ is an anion derived from a mineral or organic acid).

A particularly preferred compound of formula (XV) is the compound in which R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ represent a methyl group, r=3, s=6 and X=Cl, according to the INCI nomenclature (CTFA) called hexadimethrin chloride.

(式中、
- R₂₂、R₂₃、R₂₄及びR₂₅は、同一であっても異なっていてもよく、水素原子、又はメチル、エチル、プロピル、β-ヒドロキシエチル、β-ヒドロキシプロピル、若しくは-CH₂(OCH₂CH₂)_pOH基を表し、
ここで、pは、0に等しいか、又は1から6の間の整数に等しいが、但し、R₂₂、R₂₃、R₂₄及びR₂₅は、同時に水素原子を表さず、
- t及びuは、同一であっても異なっていてもよく、1から6の間の整数であり、
- vは、0に等しいか、又は1から34の間の整数に等しく、
- X^-は、ハロゲン化物イオン等のアニオンを表し、
- Aは、ジハライド基を示すか、又は好ましくは-CH₂-CH₂-O-CH₂-CH₂-を表す)。 (8) Polyquaternary ammonium polymers, especially formed from units of formula (XVI):

(In the formula,
- _R22 , _R23 , _R24 and _R25 , which may be the same or different, are hydrogen atoms, or methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl, or _-CH2 ( OCH ₂ CH ₂ ) _p OH group,
wherein p is equal to 0 or equal to an integer between 1 and 6 with the proviso that R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ do not simultaneously represent a hydrogen atom;
- t and u, which may be the same or different, are integers between 1 and 6;
- v is equal to 0 or equal to an integer between 1 and 34;
^-X- represents an anion such as a halide ion,
-A represents a dihalide group or preferably _-CH2 - _CH2 -O- _CH2 - _CH2- ).

Such compounds are described in particular in patent application EP-A-122 324.

Among these, mention may be made, for example, of the products Mirapol® A15, Mirapol® AD1, Mirapol® AZ1 and Mirapol® 175 sold by the company Mirapol.

(9) Quaternary polymers of vinylpyrrolidone and/or vinylimidazole, for example the products sold under the names Luviquat® FC 905, FC 550 and FC 370 and Luviquat Excellence by BASF.

(10) Cationic polysaccharides, preferably cationic cellulose and galactomannan gums.

Among the cationic polysaccharides, mention may be made in particular of cellulose ether derivatives containing quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with water-soluble quaternary ammonium monomers, and cationic galactomannan gums. can.

Cellulose ether derivatives containing quaternary ammonium groups (INCI name Polyquaternium-10) are described in French Patent No. 1 492 597 and given the name "UCARE POLYMER JR" (JR 400 LT, JR 125 and JR 30M), or the polymers sold under “LR” (LR 400, LR 30M). These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose reacted with epoxides substituted with trimethylammonium groups.

Cationic cellulose copolymers or cellulose derivatives grafted with water-soluble quaternary ammonium monomers are described inter alia in U.S. Pat. Hydroxyalkylcelluloses, such as hydroxymethyl, hydroxyethyl or hydroxypropylcellulose, grafted with dimethyldiallylammonium salts.

A cationic cellulose polymer that may be mentioned in particular is Polyquaternium-4, which is a copolymer of hydroxyethylcellulose and dimethyldiallylammonium chloride.

Associative celluloses such as alkylhydroxyethyl celluloses quaternized with _C8 - _C30 fatty chains, for example the product Quatrisoft LM 200® (INCI name Polyquaternium-24) by Amerchol/Dow Chemical Company and Croda Company. Crodacel QM® (INCI name PG-Hydroxyethylcellulose Cocodimonium Chloride), Crodacel QL® (C ₁₂ Alkyl) (INCI name PG-Hydroxyethylcellulose Lauryldimonium Chloride), and Crodacel QS® (INCI name PG-Hydroxyethylcellulose Lauryldimonium Chloride) Trademark) (C ₁₈ alkyl) (INCI name PG-hydroxyethylcellulose stearyldimonium chloride) may also be mentioned.

Other fatty chain hydroxyethyl cellulose derivatives such as the commercial product Softcat Polymer SL® manufactured by Amerchol/Dow chemical under the INCI name Polyquaternium-67, e.g. SL-100, SL-60, SL-30 and SL. -5 can also be mentioned.

Cationic galactomannan gums are described in more detail in US Pat. No. 3,589,578 and US Pat. No. 4,031,307, in particular guar gums containing cationic trialkylammonium groups. For example, guar gum modified with salts such as 2,3-epoxypropyltrimethylammonium chloride is used.

(11) Cationic proteins or cationic protein hydrolysates, polyalkyleneimines, especially polyethylenimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines with epichlorohydrin, quaternary polyureylenes and chitin. derivative.

Cationic proteins or protein hydrolysates are in particular chemically modified polypeptides with quaternary ammonium groups or grafted quaternary ammonium groups at the ends of the chains. Their molecular weight can vary, for example, from 1500 to 10,000, in particular from approximately 2,000 to 5,000. Among these polymers, mention may be made in particular of:
- Collagen hydrolysates with triethylammonium groups, e.g. the product sold under the name Quat-Pro E by the company Maybrook, referred to in the CTFA dictionary as Triethonium Hydrolyzed Collagen Ethosulfate ,
- Collagen hydrolysates with trimethylammonium chloride and trimethylstearylammonium chloride groups, e.g. the product sold under the name Quat-Pro S by the company Maybrook, Steartrimonium Hydrolyzed Collagen in the CTFA dictionary. is called
- animal protein hydrolysates with trimethylbenzylammonium groups, e.g. the product sold under the name Crotein BTA by the company Croda, referred to in the CTFA dictionary as Benzyltrimonium hydrolyzed animal protein; to be
- A protein hydrolyzate having a quaternary ammonium group in the polypeptide chain, said ammonium group containing at least one alkyl group having 1 to 18 carbon atoms.

Among these protein hydrolysates, mention may be made, inter alia:
- Croquat L (quaternary ammonium groups containing _C12 alkyl groups),
- Croquat M (quaternary ammonium groups containing _C10 - _C18 alkyl groups),
- Croquat S (quaternary ammonium groups containing _C18 alkyl groups),
- Crotein Q (the quaternary ammonium group contains at least one alkyl group with 1 to 18 carbon atoms).

These various products are marketed by Croda.

(式中、X^-は、有機酸又は鉱酸のアニオンであり、Aは、コラーゲンタンパク質加水分解物に由来するタンパク質残基を示し、R₂₆は、最大30個の炭素原子を含む親油基を示し、R₂₇は、1～6個の炭素原子を有するアルキレン基を表す)。例えば、名称Lexein QX 3000でInolex社により販売されており、CTFA辞典でココトリモニウムコラーゲン加水分解物(Cocotrimonium Collagen Hydrolysate)と称される製品を挙げることができる。 Other quaternized proteins or hydrolysates are for example those corresponding to formula (XVII):

(Where X ^- is an anion of an organic or mineral acid, A represents a protein residue derived from a collagen protein hydrolyzate, and _R26 is a lipophilic group containing up to 30 carbon atoms. and R ₂₇ represents an alkylene group having 1 to 6 carbon atoms). Mention may be made, for example, of the product marketed by the company Inolex under the name Lexein QX 3000 and referred to in the CTFA dictionary as Cocotrimonium Collagen Hydrolysate.

Quaternized vegetable proteins such as wheat, maize or soy proteins may also be mentioned, for example quaternized wheat proteins. The name Hydrotriticum WQ or QM, referred to as cocodimonium hydrolyzed wheat protein in the CTFA dictionary, the name Hydrotriticum QL, referred to as lauryldimonium hydrolyzed wheat protein in the CTFA dictionary, or the name Hydrotriticum QL referred to in the CTFA dictionary as stearyldimonium hydrolyzed wheat protein. and sold by Croda under the name Hydrotriticum QS.

(12) Polyamines such as Polyquart RH sold by Cognis, under the name polyethylene glycol (15) tallow polyamine in the CTFA dictionary.

(13) Polymers containing in their structure:
(a) one or more units corresponding to formula (A) below:
_{CH2CHNH2 (} A)
(b) optionally one or more units corresponding to formula (B) below:
_CH2CHNHCOH (B)

In other words, these polymers can in particular be chosen from homopolymers or copolymers comprising one or more units derived from vinylamine and optionally one or more units derived from vinylformamide.

Preferably, these cationic polymers have, in their structure, 5 mol % to 100 mol % of units corresponding to formula (A) and 0 to 95 mol % of units corresponding to formula (B), preferentially is selected from polymers containing 10 mol % to 100 mol % of units corresponding to formula (A) and 0 to 90 mol % of units corresponding to formula (B).

These polymers can be obtained, for example, by partial hydrolysis of polyvinylformamide.

This hydrolysis can be carried out in an acidic or basic medium.

The weight-average molecular weight of said polymer may range from 1000 to 3000000 g/mol, preferably from 10000 to 1000000 g/mol, more particularly from 100000 to 500000 g/mol, determined by light scattering.

The cationic charge density of these polymers can vary from 2-20 meq/g, preferably 2.5-15 meq/g, more particularly 3.5-10 meq/g.

Polymers comprising units of formula (A) and optionally units of formula (B) are sold in particular by BASF under the name Lupamin, for example, without limitation, under the names Lupamin 9095, Lupamin 5095, Lupamin 1095, Lupamin 9030 , and Lupamin9010.

Preferably, the cationic polymer is from polymers of families (1), (2), (7) and (10) above, more preferably from families (1) and (10) above, even more preferably is selected from the above family (1) polymers.

According to a preferred embodiment of the present invention, the cationic polymer is a crosslinked polymer of a methacryloyloxy(C ₁ -C ₄ )alkyltri(C ₁ -C ₄ )alkylammonium salt, a cellulose ether derivative containing quaternary ammonium groups, and mixtures thereof, more preferably polyquaternium-37, polyquaternium-10, and mixtures thereof, even more preferably polyquaternium-37.

Preferably, the cationic polymer in the composition according to the invention represents 0.01-5% by weight, more preferably 0.05-3% by weight, even more preferably 0.1-2% by weight, relative to the total weight of the composition. do.

Anionic Direct Dyes According to the present invention, the composition comprises one or more anionic direct dyes.

The anionic direct dyes of the present invention are dyes commonly referred to as "acidic" direct dyes for their affinity with alkaline substances. The term "anionic direct dye" means that the structure has at least one _CO2R or _SO3R substituent, where R is a hydrogen atom or a cation derived from a metal or an amine, or an ammonium ion. are understood to mean any direct dye, including Anionic dyes can be selected from acid nitro direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoids, and acid natural dyes.

Acid dyes according to the present invention include the following formulas (a-II), (a-II'), (a-III), (a-III'), (a-IV), (a-IV'), Dyes a-V), (a-V'), (a-VI), (a-VII), (a-VIII) and (a-IX) may be mentioned:

(式(a-II)及び(a-II')中、
・R₇、R₈、R₉、R₁₀、R'₇、R'₈、R'₉及びR'₁₀は、同一であっても異なっていてもよく、水素原子、又は：
- アルキル；
- アルコキシ、アルキルチオ；
- ヒドロキシル、メルカプト；
- ニトロ、ニトロソ；
- R°-C(X)-X'-、R°-X'-C(X)-、R°-X'-C(X)-X''-(式中、R°は、水素原子又はアルキル若しくはアリール基を表し、X、X'及びX''は、同一であっても異なっていてもよく、酸素若しくは硫黄原子又はNR(式中、Rは、水素原子又はアルキル基を表す)を表す)；
- (O)₂S(O^-)-M⁺ (式中、M⁺は、水素原子又はカチオン性対イオンを表す)；
- (O)CO^--M⁺ (式中、M⁺は、上で定義した通りである)；
- R''-S(O)₂- (式中、R''は、水素原子、アルキル基、又はアリール、(ジ)(アルキル)アミノ若しくはアリール(アルキル)アミノ基、好ましくはフェニルアミノ又はフェニル基を表す)；
- R'''-S(O)₂-X'- (式中、R'''は、任意選択により置換されていてもよいアリール又はアルキル基を表し、X'は上で定義した通りである)；
- (ジ)(アルキル)アミノ；
- i) ニトロ、ii) ニトロソ、iii) (O)₂S(O^-)-M⁺、及び、iv) アルコキシ (式中、M⁺は上で定義した通りである) から選ばれる1個又は複数個の基で任意選択により置換されていてもよい、アリール(アルキル)アミノ；
- 任意選択により置換されていてもよいヘテロアリール、好ましくはベンゾチアゾリル基；
- シクロアルキル、特にシクロヘキシル；
- Ar-N=N- (式中、Arは、任意選択により置換されていてもよいアリール基、好ましくは、1個又は複数個のアルキル、(O)₂S(O^-)-M⁺又はフェニルアミノ基で任意選択により置換されていてもよいフェニルを表す)；
から選ばれる基を表し、
- 或いは、2個の隣接する基であるR₇とR₈、又はR₈とR₉、又はR₉とR₁₀は、一緒になって、縮合ベンゾ基A'を形成し、R'₇とR'₈、又はR'₈とR'₉、又はR'₉とR'₁₀は、一緒になって、縮合ベンゾ基B'を形成し、A'及びB'は、i) ニトロ、ii) ニトロソ、iii) (O)₂S(O^-)-M⁺、iv) ヒドロキシル、v) メルカプト、vi) (ジ)(アルキル)アミノ、vii) R°-C(X)-X'-、viii) R°-X'-C(X)-、ix) R°-X'-C(X)-X''-、x) Ar-N=N-、及びxi) 任意選択により置換されていてもよいアリール(アルキル)アミノ (式中、M⁺、R°、X、X'、X''及びArは、上で定義した通りである)から選ばれる1個又は複数個の基で任意選択により置換されていてもよく；
・Wは、シグマσ結合、酸素若しくは硫黄原子、又は二価の基i) -NR- (式中、Rは、上で定義した通りである) 若しくはii) メチレン-C(R_a)(R_b)-を表し、R_a及びR_bは、同一であっても異なっていてもよく、水素原子若しくはアリール基を表すか、或いは、R_a及びR_bは、それらを有する炭素原子と一緒になって、スピロシクロアルキルを形成し、好ましくは、Wは、硫黄原子を表すか、又はR_a及びR_bは、一緒になって、シクロヘキシルを形成し；
式(a-II)及び(a-II')は、A、A'、B、B'、又はC環の1個上に、少なくとも1個のスルホネート基(O)₂S(O^-)-M⁺又は1個のカルボキシレート基(O)CO^--M⁺、好ましくはスルホン酸ナトリウムを含むことが理解される)。 a) diaryl anionic azo dyes of formula (a-II) or (a-II'):

(In the formulas (a-II) and (a-II'),
- _R7 , _R8 , _R9 , _R10 , _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, Nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (where R° is a hydrogen atom or an alkyl or aryl group, and X, X' and X'' may be the same or different, and are an oxygen or sulfur atom or NR (wherein R represents a hydrogen atom or an alkyl group) represents);
- (O) _2S (O ^- )-M ⁺ , where M ⁺ represents a hydrogen atom or a cationic counterion;
- (O)CO ^- -M ⁺ , where M ⁺ is as defined above;
- R''-S(O) ₂ - (wherein R'' is a hydrogen atom, an alkyl group, or an aryl, (di)(alkyl)amino or aryl(alkyl)amino group, preferably phenylamino or phenyl represents a group);
- R'''-S(O) ₂ -X'-, where R''' represents an optionally substituted aryl or alkyl group and X' is as defined above. be);
- (di)(alkyl)amino;
- i) nitro, ii) nitroso, iii) (O) _2S (O ^- )-M ⁺ , and iv) alkoxy, wherein M ⁺ is as defined above, or aryl(alkyl)amino optionally substituted with multiple groups;
- an optionally substituted heteroaryl, preferably a benzothiazolyl group;
- cycloalkyl, especially cyclohexyl;
- Ar-N=N- (wherein Ar is an optionally substituted aryl group, preferably one or more alkyl, (O) _2S (O ^- )-M ⁺ or represents phenyl optionally substituted with a phenylamino group);
represents a group selected from
- Alternatively, two adjacent groups, _R7 and _R8 , or _R8 and _R9 , or _R9 and _R10 , together form a fused benzo group A', _R'7 and R' ₈ , or R' ₈ and R' ₉ , or R' ₉ and R' ₁₀ together form a fused benzo group B', A' and B' being i) nitro, ii) nitroso, iii) (O) _2S (O ^- )-M ⁺ , 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 optionally one or more groups selected from aryl(alkyl)amino (wherein M ⁺ , R°, X, X′, X″ and Ar are as defined above); optionally substituted by;
- W is a sigma σ bond, an oxygen or sulfur atom, or a divalent group i) -NR- (wherein 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, represent a hydrogen atom or an aryl group, or R _a and R _b together with the carbon atom bearing them together form spirocycloalkyl, preferably W represents a sulfur atom, or R _a and R _b together form cyclohexyl;
Formulas (a-II) and (a-II') have at least one sulfonate group (O) ₂ S(O ^- )- on one of the A, A', B, B', or C rings. M ⁺ or one carboxylate group (O)CO ^- -M ⁺ , preferably sodium sulfonate).

Examples of dyes of formula (a-II) are Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, 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, Food Yellow 3, or Sunset Yellow. can be mentioned,
Acid Red 111, Acid Red 134, Acid Yellow 38 can be mentioned as examples of dyes of formula (a-II').

(式(a-III)及び(a-III')中、
・R₁₁、R₁₂及びR₁₃は、同一であっても異なっていてもよく、水素若しくはハロゲン原子、又はアルキル若しくは-(O)₂S(O^-)M⁺基 (式中、M⁺は、上で定義した通りである) を表し；
・R₁₄は、水素原子、アルキル基、又は-C(O)O^-M⁺基 (式中、M⁺は、上で定義した通りである)を表し；
・R₁₅は、水素原子を表し；
・R₁₆は、オキソ基を表し、この場合にR'₁₆は不在であり、或いは、R₁₅とR₁₆は、一緒になって、二重結合を形成し；
・R₁₇及びR₁₈は、同一であっても異なっていてもよく、水素原子、又は：
- (O)₂S(O^-)-M⁺ (式中、M⁺は、上で定義した通りである)；
- Ar-O-S(O)₂- (式中、Arは、任意選択により置換されていてもよいアリール基、好ましくは、1個又は複数個のアルキル基で任意選択により置換されていてもよいフェニルを表す)；
から選ばれる基を表し；
・R₁₉及びR₂₀は、一緒になって、二重結合、又は任意選択により置換されていてもよいベンゾ基D'のいずれかを形成し；
・R'₁₆、R'₁₉及びR'₂₀は、同一であっても異なっていてもよく、水素原子又はアルキル若しくはヒドロキシル基を表し；
・R₂₁は、水素原子又はアルキル若しくはアルコキシ基を表し；
・R_a及びR_bは、同一であっても異なっていてもよく、上で定義されており、好ましくは、R_aは水素原子を表し、R_bはアリール基を表し；
・Yは、ヒドロキシル基又はオキソ基のいずれかを表し；
・ - - - - は、Yがオキソ基である場合、単結合を表し、Yがヒドロキシル基を表す場合、二重結合を表し；
式(a-III)及び(a-III')は、D又はE環のいずれかの上に、少なくとも1個のスルホネート基(O)₂S(O^-)-M⁺又は1個のカルボキシレート基-C(O)O^-M⁺、好ましくはスルホン酸ナトリウムを含むことが理解される)。 b) pyrazolone anionic azo dyes of formula (a-III) or (a-III'):

(In the formulas (a-III) and (a-III'),
· R ₁₁ , R ₁₂ and R ₁₃ may be the same or different and are hydrogen or halogen atoms, or alkyl or -(O) ₂ S(O ^- )M ⁺ groups (wherein M ⁺ is , as defined above);
- R ₁₄ represents a hydrogen atom, an alkyl group, or a -C(O)O ^- M ⁺ group, where M ⁺ is as defined above;
- R ₁₅ represents a hydrogen atom;
- R ₁₆ represents an oxo group in which R' ₁₆ is absent or R ₁₅ and R ₁₆ together form a double bond;
- R ₁₇ and R ₁₈ , which may be the same or different, are a hydrogen atom, or:
- (O) ₂ S(O ^- )-M ⁺ , where M ⁺ is as defined above;
- Ar-OS(O) ₂ - (wherein Ar is an optionally substituted aryl group, preferably a phenyl optionally substituted with one or more alkyl groups represents);
representing a group selected from;
- R ₁₉ and R ₂₀ together form either a double bond or an optionally substituted benzo group D';
- R' ₁₆ , R' ₁₉ and R' ₂₀ , which may be the same or different, represent a hydrogen atom or an alkyl or hydroxyl group;
- R ₂₁ represents a hydrogen atom or an alkyl or alkoxy group;
- R _a and R _b , which may be the same or different and are defined above, preferably R _a represents a hydrogen atom and R _b represents an aryl group;
- Y represents either a hydroxyl group or an oxo group;
- - - - represents a single bond when Y is an oxo group and a double bond when Y represents a hydroxyl group;
Formulas (a-III) and (a-III') have at least one sulfonate group (O) ₂ S(O ^- )-M ⁺ or one carboxylate group on either the D or E ring. is understood to include the group -C(O)O ^- M ⁺ , preferably sodium sulfonate).

Examples of dyes of formula (a-III) are Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and examples of dyes of formula (a-III') are Acid Yellow 17. can be mentioned.

(式(a-IV)及び(a-IV')中、
・R₂₂、R₂₃、R₂₄、R₂₅、R₂₆及びR₂₇は、同一であっても異なっていてもよく、水素若しくはハロゲン原子、又は：
- アルキル；
- ヒドロキシル、メルカプト；
- アルコキシ、アルキルチオ；
- 任意選択により置換されていてもよいアリールオキシ又はアリールチオ、好ましくは、アルキル及び(O)₂S(O^-)-M⁺ (式中、M⁺は、上で定義した通りである)から選ばれる1個又は複数個の基で置換されているアリールオキシ又はアリールチオ；
- アルキル及び(O)₂S(O^-)-M⁺ (式中、M⁺は、上で定義した通りである)から選ばれる1個又は複数個の基で任意選択により置換されていてもよいアリール(アルキル)アミノ；
- (ジ)(アルキル)アミノ；
- (ジ)(ヒドロキシアルキル)アミノ；
- (O)₂S(O^-)-M⁺ (式中、M⁺は、上で定義した通りである)；
から選ばれる基を表し、
・Z'は、水素原子又はNR₂₈R₂₉基を表し、R₂₈及びR₂₉は、同一であっても異なっていてもよく、水素原子又は：
- アルキル；
- ヒドロキシエチル等のポリヒドロキシアルキル；
- 1個又は複数個の基、特にi) アルキル、例えばメチル、n-ドデシル、n-ブチル、ii) (O)₂S(O^-)-M⁺ (式中、M⁺は、上で定義した通りである)、iii) R°-C(X)-X'-、R°-X'-C(X)-、又はR°-X'-C(X)-X''- (式中、R°、X、X'及びX''は、上で定義した通りであり、好ましくは、R°は、アルキル基を表す) で任意選択により置換されていてもよいアリール；
- シクロアルキル、特にシクロヘキシル；
から選ばれる基を表し；
・Zは、ヒドロキシル及びNR'₂₈R'₂₉(式中、R'₂₈及びR'₂₉は、同一であっても異なっていてもよく、上で定義したR₂₈及びR₂₉と同じ原子又は基を表す) から選ばれる基を表し；
式(a-IV)及び(a-IV')は、少なくとも1個のスルホネート基(O)₂S(O^-)-M⁺又は1個のカルボキシレート基-C(O)O^-M⁺、好ましくはスルホン酸ナトリウムを含むことが理解される)。 c) Anthraquinone dyes of formulas (a-IV) and (a-IV'):

(In the formulas (a-IV) and (a-IV'),
- _R22 , _R23 , _R24 , _R25 , _R26 and _R27 , which may be the same or different, are hydrogen or halogen atoms, or:
- alkyl;
- hydroxyl, mercapto;
- alkoxy, alkylthio;
- optionally substituted aryloxy or arylthio, preferably selected from alkyl and (O) _2S (O ^- )-M ⁺ , where M ⁺ is as defined above aryloxy or arylthio substituted with one or more groups;
- optionally substituted with one or more groups selected from (O) _2S (O ^- )-M ⁺ , wherein M ⁺ is as defined above. good aryl(alkyl)amino;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino;
- (O) ₂ S(O ^- )-M ⁺ , where M ⁺ is as defined above;
represents a group selected from
- Z' represents a hydrogen atom or an _NR28R29 group, _{wherein R28} and _R29 may be the same or different, and a hydrogen atom or:
- alkyl;
- polyhydroxyalkyls such as hydroxyethyl;
- one or more groups, in particular i) alkyl, such as methyl, n-dodecyl, n-butyl, ii) (O) _2S (O ^- )-M ⁺ , where M ⁺ is defined above iii) R°-C(X)-X'-, R°-X'-C(X)-, or R°-X'-C(X)-X''- (formula wherein R°, X, X' and X'' are as defined above, preferably R° represents an alkyl group, optionally substituted aryl;
- cycloalkyl, especially cyclohexyl;
representing a group selected from;
- Z is hydroxyl and NR' ₂₈ R' ₂₉ (wherein R' ₂₈ and R' ₂₉ may be the same or different and are the same atoms or groups as R ₂₈ and R ₂₉ defined above) represents a group selected from;
Formulas (a-IV) and (a-IV') have at least one sulfonate group (O) ₂ S(O ^- )-M ⁺ or one carboxylate group -C(O)O ^- M ⁺ , is understood to preferably include sodium sulfonate).

Examples of dyes of formula (a-IV) are 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, EXT violet No. 2,
Acid Black 48 can be mentioned as an example of a dye of formula (a-IV').

(式(a-V)及び(a-V')中、
・R₃₀、R₃₁及びR₃₂は、同一であっても異なっていてもよく、水素若しくはハロゲン原子、又は：
- アルキル；
- 1個若しくは複数個のヒドロキシル基で任意選択により置換されていてもよいアルコキシ、1個若しくは複数個のヒドロキシル基で任意選択により置換されていてもよいアルキルチオ；
- ヒドロキシル、メルカプト；
- ニトロ、ニトロソ；
- ポリハロアルキル；
- R°-C(X)-X'-、R°-X'-C(X)-、又はR°-X'-C(X)-X'''- (式中、R°、X、X'及びX''は、上で定義した通りである)；
- (O)₂S(O^-)-M⁺ (式中、M⁺は、上で定義した通りである)；
- (O)CO^--M⁺ (式中、M⁺は、上で定義した通りである)；
- (ジ)(アルキル)アミノ；
- (ジ)(ヒドロキシアルキル)アミノ；
- ヘテロシクロアルキル、例えば、ピペリジノ、ピペラジノ又はモルホリノ；
から選ばれる基を表し、
特に、R₃₀、R₃₁及びR₃₂は、水素原子を表し；
・R_c及びR_dは、同一であっても異なっていてもよく、水素原子又はアルキル基を表し；
・Wは、上で定義した通りであり、Wは、特に-NH-基を表し；
・ALKは、二価の直鎖状又は分岐状C₁～C₆アルキレン基を表し、特に、ALKは、-CH₂-CH₂-基を表し；
・nは、値1又は2を有し；
・pは、両端を含む1から5の間の整数を表し；
・qは、両端を含む1から4の間の整数を表し；
・uは、値0又は1を有し；
・nが、値1を有する場合、Jは、ニトロ又はニトロソ基、特にニトロ基を表し；
・nが、値2を有する場合、Jは、酸素若しくは硫黄原子、又は二価の-S(O)_m-基 (式中、mは、整数1又は2を表す) を表し、好ましくは、Jは、-SO₂-基を表し；
・M'は、水素原子又はカチオン性対イオンを表し；
・存在するか又は存在しない

は、上で定義した1個又は複数個のR₃₀基で任意選択により置換されていてもよいベンゾ基を表し；
式(a-V)及び(a-V')は、少なくとも1個のスルホネート基(O)₂S(O^-)-M⁺又は1個のカルボキシレート基-C(O)O^-M⁺、好ましくはスルホン酸ナトリウムを含むことが理解される)。 d) Nitro dyes of formulas (aV) and (a-V'):

(In the formulas (aV) and (a-V'),
- _R30 , _R31 and _R32 , which may be the same or different, are hydrogen or a halogen atom, or:
- alkyl;
- alkoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups;
- hydroxyl, mercapto;
- Nitro, Nitroso;
- polyhaloalkyl;
- R°-C(X)-X'-, R°-X'-C(X)-, or R°-X'-C(X)-X'''- (where R°, X , X' and X'' are as defined above);
- (O) ₂ S(O ^- )-M ⁺ , where M ⁺ is as defined above;
- (O)CO ^- -M ⁺ , where M ⁺ is as defined above;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino;
- heterocycloalkyl, such as piperidino, piperazino or morpholino;
represents a group selected from
In particular _R30 , _R31 and _R32 represent a hydrogen atom;
- R _c and R _d may be the same or different and represent a hydrogen atom or an alkyl group;
- W is as defined above, W especially represents a -NH- group;
- ALK represents a divalent linear or branched _C1 - _C6 alkylene group, in particular ALK represents a _-CH2 - _CH2- group;
- n has the value 1 or 2;
- p represents an integer between 1 and 5, inclusive;
- q represents an integer between 1 and 4, inclusive;
- u has the value 0 or 1;
- when n has the value 1, J represents a nitro or nitroso group, especially a nitro group;
- when n has the value 2, J represents an oxygen or sulfur atom or a divalent -S(O) _m - group (wherein m represents an integer 1 or 2), preferably J represents a _-SO2- group;
- M' represents a hydrogen atom or a cationic counterion;
- exists or does not exist

represents a benzo group optionally substituted with one or more R ₃₀ groups as defined above;
Formulas (aV) and (a-V') have at least one sulfonate group (O) ₂ S(O ^- )-M ⁺ or one carboxylate group -C(O)O ^- M ⁺ , preferably understood to include sodium sulfonate).

Examples of dyes of formula (a-V) include Acid Brown 13, Acid Orange 3, and examples of dyes of formula (V') are Acid Yellow 1, 2,4-dinitro-1-naphthol-7- sodium salts of sulfonic acids, 2-piperidino-5-nitrobenzenesulfonic acid, 2-(4'-N,N-(2''-hydroxyethyl)amino-2'-nitro)anilineethanesulfonic acid, or 4-( β-Hydroxyethylamino)-3-nitrobenzenesulfonic acid, EXT D&C yellow 7 may be mentioned.

(式(a-VI)中、
・R₃₃、R₃₄、R₃₅及びR₃₆は、同一であっても異なっていてもよく、水素原子、又は、アルキル、任意選択により置換されていてもよいアリール、及び任意選択により置換されていてもよいアリールアルキル、特に、アルキル基、及び(O)_mS(O^-)-M⁺基 (式中、M⁺及びmは、上で定義した通りである) で任意選択により置換されていてもよいベンジル基から選ばれる基を表し；
・R₃₇、R₃₈、R₃₉、R₄₀、R₄₁、R₄₂、R₄₃及びR₄₄は、同一であっても異なっていてもよく、水素原子、又は：
- アルキル；
- アルコキシ、アルキルチオ；
- (ジ)(アルキル)アミノ；
- ヒドロキシル、メルカプト；
- ニトロ、ニトロソ；
- R°-C(X)-X'-、R°-X'-C(X)-、又はR°-X'-C(X)-X''- (式中、R°は、水素原子、又はアルキル若しくはアリール基を表し、X、X'及びX''は、同一であっても異なっていてもよく、酸素若しくは硫黄原子又はNR(式中、Rは、水素原子又はアルキル基を表す) を表す)；
- (O)₂S(O-)-M⁺ (式中、M+は、水素原子又はカチオン性対イオンを表す)；
- (O)CO^--M⁺ (式中、M⁺は、上で定義した通りである)；
から選ばれる基を表し、
- 或いは、2個の隣接する基であるR₄₁とR₄₂、又はR₄₂とR₄₃、又はR₄₃とR₄₄は、一緒になって、縮合ベンゾ基I'を形成し、I'は、i) ニトロ、ii) ニトロソ、iii) (O)₂S(O^-)-M⁺、iv) ヒドロキシル、v) メルカプト、vi) (ジ)(アルキル)アミノ、vii) R°-C(X)-X'-、viii) R°-X'-C(X)-、ix) R°-X'-C(X)-X''- (式中、M⁺、R°、X、X'、及びX''は、上で定義した通りである) から選ばれる1個又は複数個の基で任意選択により置換されていてもよく；
特に、R₃₇～R₄₀は、水素原子を表し、R₄₁～R₄₄は、同一であっても異なっていてもよく、ヒドロキシル又は(O)₂S(O^-)-M⁺基を表し、R₄₃とR₄₄が、一緒になって、ベンゾ基を形成する場合、好ましくは(O)₂S(O^-)-基で置換されており；
G、H、I、又はI'環の少なくとも1個は、少なくとも1個のスルホネート基(O)₂S(O^-)-又は1個のカルボキシレート基-C(O)O^-、好ましくはスルホネートを含むことが理解される)。 e) triarylmethane dyes of formula (a-VI):

(In formula (a-VI),
- R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ may be the same or different and may be a hydrogen atom, alkyl, optionally substituted aryl, and optionally substituted optionally substituted with arylalkyl, particularly alkyl groups, and (O) _m S(O ⁻ )-M ⁺ groups, where M ⁺ and m are as defined above. represents a group selected from a benzyl group;
- _R37 , _R38 , _R39 , _R40 , R41, _{R42 , R43} and _R44 , which may be the same or different, are hydrogen atoms, or:
- alkyl;
- alkoxy, alkylthio;
- (di)(alkyl)amino;
- hydroxyl, mercapto;
- Nitro, Nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, or R°-X'-C(X)-X''-, where R° is hydrogen represents an atom, or an alkyl or aryl group, X, X' and X'' may be the same or different and represents an oxygen or sulfur atom or NR (wherein R represents a hydrogen atom or an alkyl group represents);
- (O) _2S (O-)-M ⁺ , where M+ represents a hydrogen atom or a cationic counterion;
- (O)CO ^- -M ⁺ , where M ⁺ is as defined above;
represents a group selected from
- or two adjacent groups R ₄₁ and R ₄₂ or R ₄₂ and R ₄₃ or R ₄₃ and R ₄₄ together form a fused benzo group I', wherein I' is i) nitro, ii) nitroso, iii) (O) _2S (O ^- )-M ⁺ , iv) hydroxyl, v) mercapto, vi) (di)(alkyl)amino, vii) R°-C(X) -X'-, viii) R°-X'-C(X)-, ix) R°-X'-C(X)-X''- (where M ⁺ , R°, X, X' , and X'' are as defined above) optionally substituted with one or more groups selected from;
In particular, R ₃₇ to R ₄₀ represent hydrogen atoms, R ₄₁ to R ₄₄ , which may be the same or different, represent hydroxyl or (O) ₂ S(O ⁻ )—M ⁺ groups, When R ₄₃ and R ₄₄ together form a benzo group, it is preferably substituted with a (O) ₂ S(O ^- )- group;
At least one of the G, H, I, or I' rings is at least one sulfonate group (O) ₂ S(O ^- )- or one carboxylate group -C(O)O ^- , preferably sulfonate (understood to include

Examples of dyes of formula (a-VI) include Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 9, Acid Violet 49, Acid green 3, Acid green 5, Acid Green 50.

(式(a-VII)中、
・R₄₅、R₄₆、R₄₇及びR₄₈は、同一であっても異なっていてもよく、水素原子又はハロゲン原子を表し；
・R₄₉、R₅₀、R₅₁及びR₅₂は、同一であっても異なっていてもよく、水素若しくはハロゲン原子、又は：
- アルキル；
- アルコキシ、アルキルチオ；
- ヒドロキシル、メルカプト；
- ニトロ、ニトロソ；
- (O)₂S(O^-)-M⁺ (式中、M⁺は、水素原子又はカチオン性対イオンを表す)；
- (O)CO^--M⁺ (式中、M⁺は、上で定義した通りである)；
から選ばれる基を表し、
特に、R₅₃、R₅₄、R₅₅及びR₄₈は、水素又はハロゲン原子を表し；
・Gは、酸素若しくは硫黄原子、又はNR_e基(式中、R_eは、上で定義した通りである)を表し、特に、Gは酸素原子を表し；
・Lは、アルコキシドO^-M⁺、チオアルコレートS^-M⁺、又はNR_f基 (式中、R_fは、水素原子又はアルキル基を表し、M⁺は、上で定義した通りであり、特にM⁺は、ナトリウム又はカリウムである) を表し；
・L'は、酸素若しくは硫黄原子、又はアンモニウム基：N⁺R_fR_g (式中、R_f及びR_gは、同一であっても異なっていてもよく、水素原子、又は、任意選択により置換されていてもよいアリール若しくはアルキル基を表す) を表し、特に、L'は、酸素原子、又は、1個又は複数個のアルキル若しくは(O)_mS(O^-)-M⁺基 (式中、m及びM⁺は、上で定義した通りである) で任意選択により置換されていてもよいフェニルアミノ基を表し；
・Q及びQ'は、同一であっても異なっていてもよく、酸素又は硫黄原子を表し、特に、Q及びQ'は、酸素原子を表し；
・M⁺は、上で定義した通りである)。 f) Dyes derived from xanthenes of formula (a-VII):

(In the formula (a-VII),
- _R45 , _R46 , _R47 and _R48 , which may be the same or different, represent a hydrogen atom or a halogen atom;
- _R49 , _R50 , _R51 and _R52 , which may be the same or different, are hydrogen or halogen atoms, or:
- alkyl;
- alkoxy, alkylthio;
- hydroxyl, mercapto;
- Nitro, Nitroso;
- (O) _2S (O ^- )-M ⁺ , where M ⁺ represents a hydrogen atom or a cationic counterion;
- (O)CO ^- -M ⁺ , where M ⁺ is as defined above;
represents a group selected from
In particular _R53 , _R54 , _R55 and _R48 represent a hydrogen or halogen atom;
- G represents an oxygen or sulfur atom or a NR _e group, wherein R _e is as defined above, in particular G represents an oxygen atom;
L is an alkoxide O ⁻ M ⁺ , thioalcoholate S ⁻ M ⁺ , or NR _f group, wherein R _f represents a hydrogen atom or an alkyl group, M ⁺ is as defined above, in particular M ⁺ is sodium or potassium);
· L' is an oxygen or sulfur atom, or an ammonium group: N ⁺ R _f R _g (wherein R _f and R _g may be the same or different, a hydrogen atom, or optionally represents an optionally substituted aryl or alkyl group), in particular L′ is an oxygen atom or one or more alkyl or (O) _m S(O ⁻ )-M ⁺ groups (formula in, m and M ⁺ represent a phenylamino group optionally substituted with ) as defined above;
- Q and Q', which may be the same or different, represent an oxygen or sulfur atom, in particular Q and Q' represent an oxygen atom;
• M ⁺ is as defined above).

Examples of dyes of formula (a-VII) include Acid Yellow 73, Acid Red 51, Acid Red 52, Acid Red 87, Acid Red 92, Acid Red 95, Acid Violet 9.

(式(a-VIII)中、
・R₅₃、R₅₄、R₅₅、R₅₆、R₅₇、R₅₈、R₅₉及びR₆₀は、同一であっても異なっていてもよく、水素原子、又は：
- アルキル；
- アルコキシ、アルキルチオ；
- ヒドロキシル、メルカプト；
- ニトロ、ニトロソ；
- R°-C(X)-X'-、R°-X'-C(X)-、又はR°-X'-C(X)-X''- (式中、R°は、水素原子又はアルキル若しくはアリール基を表し、X、X'及びX''は、同一であっても異なっていてもよく、酸素若しくは硫黄原子又はNR(式中、Rは、水素原子又はアルキル基を表す) を表す)；
- (O)₂S(O^-)-M⁺ (式中、M⁺は、水素原子又はカチオン性対イオンを表す)；
- (O)CO^--M⁺ (式中、M⁺は、上で定義した通りである)；
から選ばれる基を表し、
・Gは、酸素若しくは硫黄原子又はNR_e基 (式中、R_eは、上で定義した通りである) を表し、特に、Gは酸素原子を表し；
・R_i及びR_hは、同一であっても異なっていてもよく、水素原子又はアルキル基を表し；
式(a-VIII)は、少なくとも1個のスルホネート基(O)₂S(O^-)-M⁺又は1個のカルボキシレート基-C(O)O^-M⁺、好ましくはスルホン酸ナトリウムを含むことが理解される)。 g) Dyes derived from indoles of formula (a-VIII):

(In the formula (a-VIII),
- _R53 , _R54 , _R55 , _R56 , _R57 , _R58 , _R59 and _R60 , which may be the same or different, are hydrogen atoms, or:
- alkyl;
- alkoxy, alkylthio;
- hydroxyl, mercapto;
- Nitro, Nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, or R°-X'-C(X)-X''-, where R° is hydrogen represent an atom or an alkyl or aryl group, and X, X' and X'' may be the same or different and represent an oxygen or sulfur atom or NR (wherein R represents a hydrogen atom or an alkyl group ) represents );
- (O) _2S (O ^- )-M ⁺ , where M ⁺ represents a hydrogen atom or a cationic counterion;
- (O)CO ^- -M ⁺ , where M ⁺ is as defined above;
represents a group selected from
- G represents an oxygen or sulfur atom or a NR _e group, wherein R _e is as defined above, in particular G represents an oxygen atom;
- R _i and R _h may be the same or different and represent a hydrogen atom or an alkyl group;
Formula (a-VIII) contains at least one sulfonate group (O) ₂ S(O ^- )-M ⁺ or one carboxylate group -C(O)O ^- M ⁺ , preferably sodium sulfonate is understood).

Acid Blue 74 can be mentioned as an example of a dye of formula (a-VIII).

(式(a-IX)中、
・R₆₁は、水素若しくはハロゲン原子又はアルキル基を表し；
・R₆₂、R₆₃及びR₆₄は、同一であっても異なっていてもよく、水素原子又は(O)₂S(O^-)-M⁺基 (式中、M⁺は、水素原子又はカチオン性対イオンを表す) を表し；
・或いはR₆₁とR₆₂、又はR₆₁とR₆₄は、一緒になって、1個又は複数個の(O)₂S(O^-)-M⁺基 (式中、M⁺は、水素原子又はカチオン性対イオンを表す) で任意選択により置換されていてもよいベンゾ基を形成し；
式(a-IX)は、少なくとも1個のスルホネート基(O)₂S(O^-)-M⁺、好ましくはスルホン酸ナトリウムを含むことが理解される)。 h) Dyes derived from quinolines of formula (a-IX):

(In formula (a-IX),
- 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 are hydrogen atoms or (O) ₂ S(O ^- )-M ⁺ groups (wherein M ⁺ is a hydrogen atom or a cation represents the sex counterion);
or R ₆₁ and R ₆₂ or R ₆₁ and R ₆₄ together are one or more (O) ₂ S(O ^- )-M ⁺ groups, where M ⁺ is a hydrogen atom or representing a cationic counterion) to form a benzo group optionally substituted with
It is understood that formula (a-IX) contains at least one sulfonate group (O) ₂ S(O ^- )-M ⁺ , preferably sodium sulfonate).

Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5 can be mentioned as examples of dyes of formula (a-IX).

More specifically, the dyes of formulas (a-II) to (a-VII) used in the present invention are selected from the table below:

Most of these dyes are described inter alia in the Color Index, published by The Society of Dyers and Colourists, P.O. Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JB, England.

Even more preferred anionic dyes are code C.I. 58005 (monosodium salt of 1,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid), C.I. 60730 (2-[(9,10-dihydro-4-hydroxy -9,10-dioxo-1-anthracenyl)amino]-5-methylbenzenesulfonic acid monosodium salt), C.I. 15510 (4-[(2-hydroxy-1-naphthyl)azo]benzenesulfonic acid monosodium salt) ), C.I. 15985 (disodium salt of 6-hydroxy-5-[(4-sulfophenyl)azo]-2-naphthalenesulfonic acid), C.I. 17200 (5-amino-4-hydroxy-3-(phenylazo)-2 ,7-naphthalenedisulfonic acid, disodium salt), C.I. 19140 (5-Hydroxy-1-(4-sulfonatophenyl)-4-[(E)-(4-sulfonatophenyl)diazenyl]-1H-pyrazole- 3-carboxylate trisodium), C.I. 20470 (disodium salt of 1-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-3,6-naphthalenedisulfonic acid), C.I. 42090 ( N-Ethyl-N-[4-[[4-[ethyl[(3-sulfophenyl)methyl]amino]phenyl]-(2-sulfophenyl)methylene]-2,5-cyclohexadien-1-ylidene]- 3-sulfobenzenemethanaminium hydroxide disodium salt, inner salt) and C.I. 61570 (2,2'-[(9,10-dihydro-9,10-dioxo-1,4-anthracenediyl)diimino ]bis[5-methyl]benzenesulfonic acid disodium salt) is a dye listed in the Color Index.

Compounds corresponding to mesomeric forms or tautomers of structures (a-II) through (a-IX) can also be used.

Preferably, the anionic direct dyes are diaryl anionic azo dyes of formula (a-II), pyrazolone anionic azo dyes of formula (a-III), triarylmethane dyes of formula (a-VI), mesomeric forms, tautomers thereof, and mixtures thereof.

More preferably, the anionic direct dye is from a mixture of a diaryl anionic azo dye of formula (a-II), a pyrazolone anionic azo dye of formula (a-III) and a triarylmethane dye of formula (a-VI) To be elected.

According to a preferred embodiment of the present invention, the composition comprises Acid Blue 9 (C.I. 42090, N-ethyl-N-[4-[[4-[ethyl[(3-sulfophenyl)methyl]amino]phenyl]-( 2-Sulfophenyl)-methylene]-2,5-cyclohexadien-1-ylidene]-3-sulfobenzenemethanaminium hydroxide disodium salt, inner salt), Acid Red 33 (C.I. 17200, 5-amino- 4-Hydroxy-3-(phenylazo)-2,7-naphthalenedisulfonic acid disodium salt), Acid Yellow 23 (C.I. 19140, 5-Hydroxy-1-(4-sulfonatophenyl)-4-[(E) -(4-sulfonatophenyl)diazenyl]-1H-pyrazole-3-carboxylate trisodium), and mixtures thereof, preferably the composition comprises , at least Acid Blue 9 (C.I. 42090, N-ethyl-N-[4-[[4-[ethyl[(3-sulfophenyl)methyl]amino]phenyl]-(2-sulfophenyl)-methylene]-2, 5-Cyclohexadien-1-ylidene]-3-sulfobenzenemethanaminium hydroxide disodium salt, inner salt), at least Acid Red 33 (C.I. 17200, 5-amino-4-hydroxy-3-(phenylazo)- 2,7-naphthalenedisulfonic acid disodium salt) and at least Acid Yellow 23 (C.I. 19140, 5-Hydroxy-1-(4-sulfonatophenyl)-4-[(E)-(4-sulfonatophenyl ) diazenyl]-1H-pyrazole-3-carboxylate trisodium).

Preferably, the anionic direct dyes in the composition according to the invention represent 0.001 to 20% by weight, preferably 0.005 to 10% by weight, more preferably 0.01 to 5% by weight, relative to the total weight of the composition. .

Preferably, the composition according to the invention comprises at least one diaryl anionic azo dye of formula (a-II), at least one pyrazolone anionic azo dye of formula (a-III) and at least one When comprising triarylmethane dyes of formula (a-VI), the total content of anionic direct dyes in the composition according to the invention is 0.001 to 20% by weight, more preferably It corresponds to 0.005 to 10% by weight, even more preferably 0.01 to 5% by weight.

More preferably, if the composition according to the invention comprises at least Acid Blue 9 (C.I. 42090), at least Acid Red 33 (C.I. 17200) and at least Acid Yellow 23 (C.I. 19140), the anions in the composition according to the invention The total content of sexual direct dyes corresponds to 0.001 to 20% by weight, more preferably 0.005 to 10% by weight, even more preferably 0.01 to 5% by weight, relative to the total weight of the composition.

Preferably, the composition according to the invention has a weight ratio of cationic polymer content to anionic direct dye content of between 0.01 and 20, more preferably between 0.5 and 15, inclusive. Preferably between 1 and 12 inclusive, even better between 1.5 and 10 inclusive.

Preferably, the composition according to the invention comprises a diaryl anionic azo dye of formula (a-II), a pyrazolone anionic azo dye of formula (a-III) and a content of cationic polymer of formula (a-VI ) to the total triarylmethane dye content is between 0.01 and 20, more preferably between 0.5 and 15, inclusive, still more preferably between 1 and 12, inclusive. is between 1.5 and 10 inclusive.

Preferably, the composition according to the invention has a weight ratio of the content of the cationic polymer to the total content of Acid Blue 9 (C.I. 42090), Acid Red 33 (C.I. 17200) and Acid Yellow 23 (C.I. 19140) , between 0.01 and 20, more preferably between 0.5 and 15 inclusive, even more preferably between 1 and 12 inclusive, even better between 1.5 and 10 inclusive.

More preferably, the composition according to the invention has a weight ratio of the content of Polyquaternium-37 to the total content of Acid Blue 9 (C.I. 42090), Acid Red 33 (C.I. 17200) and Acid Yellow 23 (C.I. 19140). is between 0.01 and 20, more preferably between 0.5 and 15 inclusive, even more preferably between 1 and 12 inclusive, even better between 1.5 and 10 inclusive.

Dimethylsulfone and EthylHydroxypyrone According to the present invention, the composition comprises at least dimethylsulfone and/or at least ethylhydroxypyrone.

Ethylhydroxypyrone can also be named 2-ethyl-3-hydroxy-4H-pyran-4-one, or ethyl maltol.

Preferably, the compositions of the invention comprise at least dimethylsulfone and at least ethylhydroxypyrone.

Preferably, the total content of dimethylsulfone and/or ethylhydroxypyrone is 0.001-20% by weight, more preferably 0.005-10% by weight, even more preferably 0.01-5% by weight, relative to the total weight of the composition. corresponds to

Preferably, the total content of dimethylsulfone and ethylhydroxypyrone corresponds to 0.001-20% by weight, more preferably 0.005-10% by weight, even more preferably 0.01-5% by weight, relative to the total weight of the composition. do.

Preferably, the composition according to the invention has a weight ratio of the total content of dimethylsulfone and/or ethylhydroxypyrone to the content of anionic direct dyes between 0.01 and 10, more preferably from 0.1 inclusive. Between 10, more preferably between 1 and 10 inclusive, even better between 1 and 6 inclusive.

Preferably, the composition according to the invention has a weight ratio of the total content of dimethylsulfone and ethylhydroxypyrone to the content of the anionic direct dye between 0.01 and 10, more preferably between 0.1 and 10 inclusive. between, more preferably between 1 and 10 inclusive, even better between 1 and 6 inclusive.

Preferably, the composition according to the invention comprises a total content of dimethylsulfone and/or ethylhydroxypyrone of diaryl anionic azo dyes of formula (a-II), pyrazolone anionic azo dyes of formula (a-III), and the weight ratio of the triarylmethane dye of formula (a-VI) to the total content is between 0.01 and 10, more preferably between 0.1 and 10 inclusive, even more preferably between 1 and 10 inclusive between, and better still between 1 and 6 inclusive.

More preferably, the composition according to the invention has a total content of Acid Blue 9 (C.I. 42090), Acid Red 33 (C.I. 17200) and Acid Yellow 23 (C.I. 19140) in the total content of dimethylsulfone and ethylhydroxypyrone. mass to mass ratio between 0.01 and 10, more preferably between 0.1 and 10 inclusive, better between 1 and 10 inclusive, even better between 1 and 6 inclusive is.

Silicones According to the present invention, the composition may optionally further comprise one or more silicones.

Silicones can be selected in particular from non-aminosilicones, aminosilicones, and mixtures thereof.

In the present invention, the term "silicone" is obtained according to what is generally accepted by the polymerization and/or polycondensation of suitably functionalized silanes, the silicon atoms of which are linked together via oxygen atoms (siloxane bonds -Si-O-Si-), optionally substituted with a hydrocarbon-based group directly linked to said silicon atom via a carbon atom. is intended to refer to any organosilicon polymer or oligomer of linear or cyclic, branched or crosslinked structure of reasonable molecular weight. The most common hydrocarbon-based radicals are alkyl radicals, especially C ₁ -C ₁₀ alkyl radicals, especially methyl, fluoroalkyl radicals whose alkyl portion is C ₁ -C ₁₀ , and aryl radicals, especially phenyl. is.

According to the present invention, the term "non-aminosilicone" denotes any silicone that does not contain at least one primary, secondary or tertiary amine group or quaternary ammonium group.

Non-aminosilicones, which can be used in the composition according to the invention, are in particular polyorganosiloxanes, which can be in the form of oils, waxes, resins or gums.

Organopolysiloxanes are further defined in Walter Noll, Chemistry and Technology of Silicones (1968), Academic Press.

Silicones may be volatile or non-volatile.

The silicone, if volatile, is more particularly selected from those having a boiling point between 60° C. and 260° C., and even more particularly selected from:

(i) Cyclic silicones containing 3 to 7, preferably 4 to 5, silicon atoms.

These are, for example, octamethylcyclotetrasiloxane, sold inter alia under the name Volatile Silicone 7207 by the company Union Carbide or Silbione 70045 V2 by the company Rhodia, Volatile Silicone 7158 by the company Union Carbide and Silbione 70045 V5 by the company Rhodia. commercially available decamethylcyclopentasiloxane, as well as mixtures thereof.

であるものを挙げることもできる。 Cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as Volatile Silicone FZ 3109 sold by Union Carbide, having the chemical structure:

You can also mention what is.

Mixtures of cyclic silicones and organosilicon compounds, such as mixtures of octamethyl-cyclotetrasiloxane and tetrakis(trimethylsilyl)pentaerythritol (50/50), and octamethylcyclotetrasiloxane and oxy-1,1'-bis(2, Mixtures of 2,2′,2′,3,3′-hexatrimethylsilyloxy)neopentanes may also be mentioned;

(ii) A linear volatile silicone containing 2 to 9 silicon atoms and having a viscosity of 5×10 ^-6 m ² /s or less at 25°C. An example is the decamethyltetrasiloxane sold especially under the name SH 200 by the company Toray Silicone. Silicones belonging to this class are also described in an article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics.

When the silicone is nonvolatile, preferably polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, and polyorganosiloxanes modified with organofunctional groups, and mixtures thereof are used. .

These silicones are more particularly chosen from polyalkylsiloxanes, especially having a viscosity at 25° C. of 5×10 ⁻⁶ to 2.5 m ² /s, preferably 1×10 ⁻⁵ to 1 m ² /s. , polydimethylsiloxanes containing trimethylsilyl end groups (dimethicone by the CTFA name). The viscosity of silicones is measured at 25° C., for example, according to ASTM Standard 445 Appendix C.

Among these polyalkylsiloxanes, mention may be made, without limitation, of the following commercial products:
- Silbione oils of the 47 and 70 047 series sold by Rhodia, or Mirasil oils, such as oil 70 047 V 500 000,
- the Mirasil series of oils sold by Rhodia,
- 200 series oils from Dow Corning, for example more particularly DC200 with a viscosity of 60000 cSt,
- Viscasil oils from General Electric and certain oils from the SF series (SF 96, SF 18) from General Electric.

Mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups (dimethiconol by the CTFA name), for example oils of the 48 series from Rhodia.

Mention may be made, for example, of dimethiconol emulsions containing anionic surfactants and preferably having a low particle size of less than 500 nm, preferably less than 200 nm.

Mention may also be made of polydimethylsiloxanes containing α,ω-silanol groups.

In this class of polyalkylsiloxanes, one may also mention the products sold by the company Goldschmidt under the names Abil Wax 9800 and 9801, which are poly(C ₁ -C ₂₀ )alkylsiloxanes.

Polyalkylarylsiloxanes are in particular linear and/or branched polydimethylmethylphenylsiloxanes and polydimethyldiphenylsiloxanes with viscosities of 1×10 ⁻⁵ to 5×10 ⁻² m ² /s at 25° C. selected from

Among these polyalkylarylsiloxanes, examples that may be mentioned include the products sold under the following names:
- 70 641 series Silbione oil from Rhodia,
- Rhodorsil 70 633 and 763 series oils from Rhodia,
- oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning,
- PK series silicones from Bayer, e.g. product PK20,
- PN and PH series silicones from Bayer, e.g. products PN1000 and PH1000,
- Certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.

Silicone gums which may be present in the composition according to the invention are in particular polydiorganosiloxanes with a high number average molecular weight between 200,000 and 1,000,000, used alone or as a mixture in a solvent. This solvent can be selected from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane and tridecane, or mixtures thereof.

More specifically, the following products can be mentioned:
- polydimethylsiloxane gum,
- polydimethylsiloxane/methylvinylsiloxane gum,
- polydimethylsiloxane/diphenylsiloxane gum,
- polydimethylsiloxane/phenylmethylsiloxane gum,
- Polydimethylsiloxane/diphenylsiloxane/methylvinylsiloxane gum.

Products that can be used are more particularly mixtures of:
- a mixture formed from a chain-end hydroxylated polydimethylsiloxane (known as dimethiconol according to the CTFA dictionary nomenclature) and a cyclic polydimethylsiloxane (known as cyclomethicone according to the CTFA dictionary nomenclature), For example the product Q2 1401 sold by Dow Corning,
- mixtures formed from polydimethylsiloxane gums and cyclic silicones, for example the product SF 1214 Silicone Fluid from General Electric. This product is a SF 30 gum equivalent to dimethicone with a number average molecular weight of 500000 dissolved in an oil SF 1202 Silicone Fluid equivalent to decamethylcyclopentasiloxane.
- A mixture of two PDMS with different viscosities, more particularly a mixture of PDMS gum and PDMS oil, for example the product SF 1236 from General Electric. Product SF 1236 is a mixture of gum SE 30 with a viscosity of 20 m ² /s and oil SF 96 with a viscosity of 5×10 ⁻⁶ m ² /s as defined above. This product preferably contains 15% gum SE 30 and 85% oil SF 96.

Organopolysiloxane resins that may be present in the compositions according to the invention are represented by the following units: R2SiO2 _{/2 , R3SiO1 /} 2, RSiO3 _/2 and SiO4 _/2 , where R is It is a crosslinked siloxane system containing a hydrocarbon group containing from 1 to 16 carbon atoms, or a phenyl group. Among these products, particularly preferred are those in which R represents a C ₁ -C ₄ alkyl group, more particularly methyl, or a phenyl group.

Among these resins, mention may be made of the product sold under the name Dow Corning 593 or the products sold under the names Silicone Fluid SS 4230 and SS 4267 by General Electric, which are dimethyl/trimethylsiloxanes. The structure is silicone.

Mention may also be made in particular of the trimethylsiloxysilicate type resins sold by Shin-Etsu Chemical Co., Ltd. under the names X22-4914, X21-5034 and X21-5037.

Organomodified silicones that may be present in the compositions according to the invention are silicones as defined above, containing one or more organic functional groups attached to these structures via hydrocarbon-based groups.

Among the organically modified silicones, mention may be made of:
- Polyorganosiloxanes containing polyethyleneoxy and/or polypropyleneoxy groups optionally containing _C6 - _C24 alkyl groups, for example dimethicone copolyols sold under the name DC 1248 by Dow Corning or oils by Union Carbide The products known as Silwet L 722, L 7500, L 77 and L 711 and the (C ₁₂ )alkylmethicone copolyols sold under the name Q2 5200 by Dow Corning or, in particular, the INCI name PEG-12 dimethicone. silicones, such as the product XIAMETER OFX-0193 FLUID by Dow Corning,
- polyorganosiloxanes containing thiol groups, e.g. the products sold by the company Genesee under the names GP 72 A and GP 71,
- polyorganosiloxanes containing alkoxylated groups, for example the products sold under the name Silicone Copolymer F-755 by the company SWS Silicones and Abil Wax 2428, 2434 and 2440 by the company Goldschmidt,
- polyorganosiloxanes containing hydroxylated groups, e.g. polyorganosiloxanes containing hydroxyalkyl functional groups as described in French Patent Application No. 2 589 476;
- polyorganosiloxanes containing acyloxyalkyl groups, such as those described in patent US-A-4 957 732;
- Polyorganosiloxanes containing anionic groups of carboxylic acid type, e.g. the products described in patent EP 186 507 from Chisso Corporation, or anionic groups of alkylcarboxyl type, e.g. from Shin-Etsu Chemical Co., Ltd. 2-hydroxyalkyl sulfonates, 2-hydroxyalkyl thiosulfates, such as the products sold under the names Abil S201 and Abil S255 by the company Goldschmidt, as in product X-22-3701E.

According to the present invention there is also a silicone comprising a polysiloxane moiety and a non-silicone organic chain moiety, one of these two moieties making up the backbone of the polymer and the other being grafted onto said backbone. can be used. These polymers are described, for example, in EP-A-412,704, EP-A-412,707, EP-A-640,105 and WO95/00578, EP-A-582,152 and WO93/23009, and US Pat. 4,728,571 and US Pat. No. 4,972,037, the disclosures of which are specifically incorporated herein by reference. These polymers are preferably anionic or nonionic.

Such polymers are, for example, copolymers, which are obtainable by radical polymerization from monomer mixtures comprising:
a) 50-90% by weight of tert-butyl acrylate;
b) 0-40% by weight acrylic acid, 5-40% by weight silicone macromer of the formula:
(In the formula,
V is a number ranging from 5 to 700 and the mass percentage is calculated relative to the total mass of the monomers).

Other examples of grafted silicone polymers are, inter alia, polydimethylsiloxanes grafted with mixed polymer units of poly(meth)acrylic acid type and polyalkyl(methyl)acrylate type via thiopropylene type linking chains. (PDMS) and polydimethylsiloxane (PDMS) grafted with polyisobutyl (meth)acrylate type polymer units via thiopropylene type linking chains.

Non-amino silicones can be used in the present invention, but preferably have a viscosity equal to 60000 cst at 25° C. and a shear rate of 1 s ⁻¹ .

Viscosity can be measured at 25° C. with a viscometer or rheometer, preferably with cone-plate geometry.

The silicones used in the compositions of the invention can also be chosen from aminosilicones.

For purposes of the present invention, the term "aminosilicone" means any silicone containing at least one primary, secondary or tertiary amine group or quaternary ammonium group.

Aminosilicones ^suitable for ^use in accordance with the present invention include, but ^are not limited to ^, Volatile and nonvolatile, cyclic, linear and branched aminosilicones having

Preferably, the aminosilicones that can be used in the cosmetic composition according to the invention are chosen from:

(式中、x'及びy'は、独立して、質量平均分子量(Mw)が約5,000から500,000の間になるような整数である)； (i) a polysiloxane corresponding to formula (A):

(where x' and y' are independently integers such that the weight average molecular weight (Mw) is between about 5,000 and 500,000);

(ii) an aminosilicone corresponding to formula (B):
_{R'aG (3-a)} -Si( _OSiG2 ) _n- ( _OSiGbR ' _(2-b) ) _m -O-SiG _(3-a') R'a _' (B)
(In the formula,
G independently represents a hydrogen atom, or a phenyl, OH, or a C1-C8 alkyl group such as methyl, or a C1-C8 alkoxy group such as methoxy;
a and a' independently represent the number 0 or an integer from 1 to 3, especially 0;
b represents 0 or 1, especially 1;
m and n are numbers such that the sum (n+m) is in the range of 1 to 2,000, especially 50 to 150; n is a number from 0 to 1,999, especially 49 to 149; , capable of indicating a number from 1 to 2,000, especially from 1 to 10;
R' independently represents a monovalent group having the formula _-CqH2qL , where q is a number ranging from 2 to 8 and _L is selected from the following groups: , an optionally quaternized amino group:
-NR''-QN(R'') ₂
-N(R'') ₂
-N ⁺ (R'') _3A ^-
-N ⁺ H(R'') _2A ^-
-N ⁺ _H2 (R'') ^A-
-NR'^' -QN ⁺ _R''H2A-
-NR''-QN ⁺ (R ^' ') _2HA-
-NR''-QN ⁺ (R'') _3A ^- ,
(In the formula,
R'' independently represents hydrogen, phenyl, benzyl, or a saturated monovalent hydrocarbonaceous group such as a C1-C20 alkyl group;
Q represents a linear or branched C _r H _2r group, r being an integer ranging from 2 to 6, preferably from 2 to 4;
A ⁻ represents cosmetically acceptable ions, in particular halide ions such as fluoride, chloride, bromide or iodide ))).

(式中、n及びmは、式Bに上述した意味を有する)。 One group of aminosilicones corresponding to this definition (B) is represented by a silicone called "trimethylsilyl amodimethicone" having formula (C):

(wherein n and m have the meanings given above for Formula B).

(式中、
m及びnは、和(n+m)が、1～1,000、特に50～250、より詳細には100～200の範囲でありうるような数であり、nが、0～999、特に49～249、より詳細には125～175の数を示すこと、mが、1～1,000、特に1～10、より詳細には1～5の数を示すことが可能であり；
R₁、R₂、R₃は、独立して、ヒドロキシ又はC1～C4アルコキシ基を表し、ここでR1～R3基の少なくとも1個は、アルコキシ基を示す)。 Another group of aminosilicones falling within this definition is represented by silicones having the following formula (D) or (E):

(In the formula,
m and n are numbers such that the sum (n+m) can range from 1 to 1,000, especially from 50 to 250, more particularly from 100 to 200, and n is from 0 to 999, especially from 49 to 249, more particularly 125 to 175, m may represent a number from 1 to 1,000, especially from 1 to 10, more particularly from 1 to 5;
R ₁ , R ₂ , R ₃ independently represent hydroxy or C1-C4 alkoxy groups, wherein at least one of the R1-R3 groups represents an alkoxy group).

Alkoxy groups are preferably methoxy groups.

The hydroxy/alkoxy molar ratio preferably ranges from 0.2:1 to 0.4:1, preferably from 0.25:1 to 0.35:1 and more particularly equals 0.3:1.

The weight average molecular weight (Mw) of the silicone preferably ranges from 2,000 to 1,000,000, more particularly from 3,500 to 200,000.

(式中、
p及びqは、和(p+q)が、1～1,000、特に50～350、より詳細には150～250の範囲になるような数であり、pが、0～999、特に49～349、より詳細には159～239の数を示すこと、qが、1～1,000、特に1～10、より詳細には1～5の数を示すことが可能であり；
R₁及びR₂は、独立して、ヒドロキシル又はC₁～C₄アルコキシ基を表し、ここでR₁又はR₂基の少なくとも1個は、アルコキシ基を示す)。

(In the formula,
p and q are numbers such that the sum (p+q) is in the range from 1 to 1,000, especially from 50 to 350, more particularly from 150 to 250, and p is from 0 to 999, especially from 49 to 349 , more particularly denoting a number from 159 to 239, q denoting a number from 1 to 1,000, particularly from 1 to 10, more particularly from 1 to 5;
R ₁ and R ₂ independently represent hydroxyl or C ₁ -C ₄ alkoxy groups, wherein at least one of the R ₁ or R ₂ groups represents an alkoxy group).

Alkoxy groups are preferably methoxy groups.

The hydroxy/alkoxy molar ratio generally ranges from 1:0.8 to 1:1.1, preferably from 1:0.9 to 1:1 and more particularly equals 1:0.95.

The weight average molecular weight (Mw) of the silicone preferably ranges from 2,000 to 200,000, more particularly from 5,000 to 100,000, more particularly from 10,000 to 50,000.

Commercial products corresponding to these silicones having structure (D) or (E) contain in their compositions one or more other amino acids whose structure differs from that of formula (D) or (E). It can contain silicones.

A product containing an aminosilicone having structure (D) is sold under the name BELSIL ADM 652 by Wacker.

A product containing an aminosilicone having structure (E) is sold by the company Wacker under the name FLUID WR 1300®.

(式中、
m及びnは、和(n+m)が、1～2,000、特に50～150の範囲になるような数であり、nが、0～1,999、特に49～149の数を示すこと、mが、1～2,000、特に1～10の数を示すことが可能であり；
Aは、4～8個の炭素原子、好ましくは4個の炭素原子を含有する、直鎖状又は分岐状のアルキレン基を示す。この基は、好ましくは直鎖状である)。 Another group of aminosilicones falling within this definition is represented by formula (F) below:

(In the formula,
m and n are numbers such that the sum (n+m) is in the range of 1 to 2,000, especially 50 to 150; n is a number from 0 to 1,999, especially 49 to 149; , capable of indicating a number from 1 to 2,000, especially from 1 to 10;
A represents a linear or branched alkylene group containing 4 to 8 carbon atoms, preferably 4 carbon atoms. This group is preferably linear).

The weight average molecular weight (Mw) of these aminosilicones preferably ranges from 2,000 to 1,000,000, more particularly from 3,500 to 200,000.

A preferred silicone of formula (F) is amodimethicone sold under the trade name XIAMETER® MEM-8299 Cationic Emulsion by Dow Corning.

(式中、
m及びnは、和(n+m)が、1～2,000、特に50～150の範囲になるような数であり、nが、0～1,999、特に49～149の数を示すこと、mが、1～2,000、特に1～10の数を示すことが可能であり；
Aは、4～8個の炭素原子、好ましくは4個の炭素原子を含有する、直鎖状又は分岐状のアルキレン基を示す。この基は、好ましくは分岐状である)。 Another group of aminosilicones falling within this definition is represented by formula (G) below:

(In the formula,
m and n are numbers such that the sum (n+m) is in the range of 1 to 2,000, especially 50 to 150; n is a number from 0 to 1,999, especially 49 to 149; , capable of indicating a number from 1 to 2,000, especially from 1 to 10;
A represents a linear or branched alkylene group containing 4 to 8 carbon atoms, preferably 4 carbon atoms. This group is preferably branched).

The weight average molecular weight (Mw) of these aminosilicones preferably ranges from 500 to 1,000,000, more particularly from 1,000 to 200,000.

A silicone having this formula is, for example, DC2-8566 Amino Fluid from Dow Corning.

(式中、
R₅は、独立して、1～18個の炭素原子を含有する一価の炭化水素系基、特にC₁～C₁₈アルキル基又はC₂～C₁₈アルケニル基、例えばメチルを表し；
R₆は、SiC結合を介してSiに連結している、二価の炭化水素系基、特に、C₁～C₁₈アルキレン基、又は二価のC₁～C₁₈、例えばC₁～C₈アルキレンオキシ基を表し；
Q^-は、ハロゲン化物イオン、特に塩化物イオン等のアニオン、又は有機酸塩(例えば酢酸塩)であり；
rは、2～20、特に2～8の平均統計値を表し、
sは、20～200、特に20～50の平均統計値を表す)。 (iii) Aminosilicones corresponding to formula (H):

(In the formula,
R ₅ independently represents a monovalent hydrocarbon-based group containing 1 to 18 carbon atoms, especially a C ₁ -C ₁₈ alkyl group or a C ₂ -C ₁₈ alkenyl group, such as methyl;
R ₆ is a divalent hydrocarbon-based group, in particular a C ₁ -C ₁₈ alkylene group, or a divalent C ₁ -C ₁₈ , such as C ₁ -C ₈ , linked to Si via a SiC bond. represents an alkyleneoxy group;
Q ⁻ is an anion such as a halide ion, especially chloride ion, or an organic acid salt (e.g. acetate);
r represents the mean statistic from 2 to 20, especially from 2 to 8;
s represents the average statistic between 20 and 200, especially between 20 and 50).

Such aminosilicones are described in more detail in patent US Pat. No. 4,185,087.

(式中、
R₇は、独立して、1～18個の炭素原子を含有する一価の炭化水素系基、特に、C₁～C₁₈アルキル基、C₂～C₁₈アルケニル基、又は5個若しくは6個の炭素原子を含有する環、例えばメチルを表し；
R₆は、独立して、SiC結合を介してSiに連結している、二価の炭化水素系基、特に、C₁～C₁₈アルキレン基、又は二価のC₁～C₁₈、例えばC₁～C₈アルキレンオキシ基を表し；
R₈は、独立して、水素原子、1～18個の炭素原子を含有する一価の炭化水素系基、特に、C₁～C₁₈アルキル基、C₂～C₁₈アルケニル基又は-R₆-NHCOR₇基を表し；
X^-は、ハロゲン化物イオン、特に塩化物イオン等のアニオン、又は有機酸塩(例えば酢酸塩)であり；
rは、2～200、特に5～100の平均統計値を表す)。 (iv) a quaternary ammonium silicone having formula (bI):

(In the formula,
R ₇ is independently a monovalent hydrocarbon-based group containing 1 to 18 carbon atoms, especially a C ₁ -C ₁₈ alkyl group, a C ₂ -C ₁₈ alkenyl group, or 5 or 6 represents a ring containing carbon atoms of e.g. methyl;
R ₆ is independently a divalent hydrocarbon-based group, particularly a C ₁ -C ₁₈ alkylene group, or a divalent C ₁ -C ₁₈ , such as C represents a ₁ - _C8 alkyleneoxy group;
R ₈ is independently a hydrogen atom, a monovalent hydrocarbon group containing 1 to 18 carbon atoms, especially a C ₁ -C ₁₈ alkyl group, a C ₂ -C ₁₈ alkenyl group or -R ₆ -NHCOR ₇ represents the group;
X ⁻ is an anion such as a halide ion, especially chloride ion, or an organic acid salt (e.g. acetate);
r represents an average statistic between 2 and 200, especially between 5 and 100).

These silicones are described, for example, in patent application EP-A 0 530 974.

(式中、
R₁、R₂、R₃及びR₄は、独立して、C₁～C₄アルキル基又はフェニル基を示し；
R₅は、C1～C4アルキル基又はヒドロキシ基を示し；
mは、1から5までの範囲の整数であり；
nは、1から5までの範囲の整数であり；
ここで、xは、アミン価が0.01から1meq/gの間であるように選ばれる)。 (v) an aminosilicone having formula (J):

(In the formula,
R ₁ , R ₂ , R ₃ and R ₄ independently represent a C ₁ -C ₄ alkyl group or a phenyl group;
R ₅ represents a C1-C4 alkyl group or a hydroxy group;
m is an integer ranging from 1 to 5;
n is an integer ranging from 1 to 5;
where x is chosen such that the amine value is between 0.01 and 1 meq/g).

(vi) Multiblock polyoxyalkylenated aminosilicones of type (AB) _n , where A is a polysiloxane block and B is a polyoxyalkylenated block containing at least one amine group.

Said silicone is preferably composed of repeating units having the following general formula:
_[ -( _SiMe2O ) _{xSiMe2 -} RN(R'')-R'-O( _C2H4O ) _a ( _C3H6O ) _b -R' _- N(H)-R-]
or
_[ -( _SiMe2O ) _{xSiMe2 -} RN(R'' ₎ -R'-O( _C2H4O ) _a ( _C3H6O ) _b- ]
(In the formula,
a is an integer greater than or equal to 1, preferably in the range from 5 to 200, more particularly in the range from 10 to 100;
b is an integer ranging from 0 to 200, preferably from 4 to 100, more particularly from 5 to 30;
x is an integer ranging from 1 to 10,000, more particularly from 10 to 5,000;
R'' is a hydrogen atom or methyl;
R independently represents a divalent linear or branched C ₂ -C ₁₂ hydrocarbon-based radical which may optionally contain one or more heteroatoms such as oxygen, preferably R independently represents an ethylene group, a _linear or branched _propylene group, a linear or branched butylene group, or a _{-CH2CH2CH2OCH} (OH) _CH2- group, preferentially in which R independently represents a _{-CH2CH2CH2OCH (} OH) _CH2- group _;
R′ independently represents a divalent linear or branched C ₂ -C ₁₂ hydrocarbon-based radical optionally containing one or more heteroatoms such as oxygen, preferably , R′ represents an ethylene group, a linear or branched propylene group, a linear or branched butylene group, or a —CH ₂ CH ₂ CH ₂ OCH(OH)CH ₂ — group, preferentially , R' represents -CH( _CH3 ) _-CH2- ).

The siloxane blocks are preferably between 50 and 95 mol %, more particularly between 70 and 85 mol % of the total mass of silicone.

The amine content is preferably between 0.02 and 0.5 meq, more particularly between 0.05 and 0.2 meq per gram of copolymer in a 30% solution in dipropylene glycol.

The weight average molecular weight (Mw) of the silicone is preferably between 5,000 and 1,000,000, more particularly between 10,000 and 200,000.

Particular mention may be made of the silicone sold by the company Momentive under the name SILSOFT A-843 or SILSOFT A+.

(式中、
R、R'及びR''は、独立して、C₁～C₄アルキル又はヒドロキシ基を表し、
Aは、C₃アルキレン基を表し、m及びnは、化合物の質量平均分子量がおよそ5,000から500,000の間になるようなものである)； (vii) Alkylaminosilicones corresponding to the following formulas (K' and K):

(In the formula,
R, R' and R'' independently represent _C1 - _C4 alkyl or hydroxy groups,
A represents a _C3 alkylene group, m and n are such that the weight average molecular weight of the compound is approximately between 5,000 and 500,000);

(式中、
x及びyは、1から5,000までの範囲の数であり、好ましくは、xは、10～2,000、特に100～1,000の範囲であり、好ましくは、yは、1～100の範囲であり；
R₁及びR₂は、独立して、好ましくは同一であり、6～30個の炭素原子、好ましくは8～24個の炭素原子、特に12～20個の炭素原子を含む、直鎖状又は分岐状で飽和又は不飽和のアルキル基であり；
Aは、2～8個の炭素原子を含有する直鎖状又は分岐状のアルキレン基を示す)。

(In the formula,
x and y are numbers ranging from 1 to 5,000, preferably x ranging from 10 to 2,000, especially from 100 to 1,000, preferably y ranging from 1 to 100;
R ₁ and R ₂ are independently preferably identical and contain 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, especially 12 to 20 carbon atoms, linear or a branched, saturated or unsaturated alkyl group;
A represents a linear or branched alkylene group containing 2 to 8 carbon atoms).

Preferably A contains 3 to 6 carbon atoms, especially 4 carbon atoms, preferably A is branched.

Particular mention may be made of _the following divalent radicals _{: -CH2CH2CH2-} , and _-CH2CH ( _CH3 ) _CH2- .

Preferably, R ₁ and R ₂ are independently linear saturated alkyl groups containing 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, especially 12 to 20 carbon atoms and in particular dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals, preferentially R1 and R2 being the same or different, hexadecyl ( cetyl) and octadecyl (stearyl) groups.

Preferentially, the silicone is of formula (K), wherein:
x ranges from 10 to 2,000, in particular from 100 to 1,000;
y ranges from 1 to 100;
A contains 3 to 6 carbon atoms, especially 4 carbon atoms, preferably A is branched, more particularly A is selected from the following divalent radicals: CH _{2 CH2CH2} and _-CH2CH ( _CH3 ) _{CH2- ;}
R1 and R2 are independently linear saturated alkyl groups containing 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms, especially 12 to 20 carbon atoms, in particular selected from dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals, preferentially R1 and R2 being the same or different, hexadecyl (cetyl) and octadecyl (stearyl) selected from the base.

A preferred silicone of formula (K) is bis-cetearyl amodimethicone.

Particular mention may be made of the silicones sold under the name SILSOFT AX by the company Momentive.

Aminosilicones of the present disclosure also include polydimethylsiloxanes containing primary amine groups at the chain ends or on side chains, e.g., aminopropyl ends or side groups, such as formulas (A'), (B') or may be chosen from those in (C'):

In formula (A'), the value of n is such that the weight average molecular weight of the silicone is between 500 and 55,000. As examples of aminosilicones (A'), mention should be made of those sold by the company Gelest under the names DMS-A11, DMS-A12, DMS-A15, DMS-A21, DMS-A31, DMS-A32 and DMS-A35. can be done.

In formula (B'), the values of n and m are such that the weight average molecular weight of the silicone is between 1,000 and 55,000. Examples of silicones (B') are sold by Gelest under the names AMS-132, AMS-152, AMS-162, AMS-163, AMS-191 and AMS-1203 and by Shin-Etsu Chemical Co., Ltd. under KF-8015. I can list what is being done.

In formula (C'), the value of n is such that the weight average molecular weight of the silicone is between 500 and 3,000. As examples of silicones (C'), mention may be made of those sold by the company Gelest under the names MCR-A11 and MCR-A12.

Preferably, the aminosilicone according to the invention is amodimethicone, for example amodimethicone sold under the name KF 8020 by the supplier Shin-Etsu Chemical Co., Ltd. or under the trade name SILSOFT 253 by the supplier MOMENTIVE PERFORMANCE MATERIALS. be. Another preferred aminosilicone is amodimethicone of formula (F) sold under the trade name XIAMETER® MEM-8299 Cationic Emulsion by Dow Corning.

In another embodiment, the aminosilicones according to the invention are selected from bis-cetearyl amodimethicones (sold under the name SILSOFT AX by Momentive).

Another preferred aminosilicone that can be used in the compositions of the present invention is aminopropyl dimethicone, eg aminopropyl dimethicone sold by Shin-Etsu Chemical Co., Ltd. under the name KF-8015.

Preferably, the silicone is selected from the aminosilicones mentioned above.

Preferably, when silicones are present in the composition, the total content of silicones is 0.01 to 15% by weight, better still 0.05 to 10% by weight, even better corresponds to 0.1 to 5% by mass.

Preferably, when aminosilicone is present in the composition, the total content of aminosilicone is 0.01 to 15% by weight, better still 0.05 to 10% by weight, even better corresponds to 0.1 to 5% by mass.

According to a preferred embodiment of the present invention, the composition comprises one or more silicones, more preferably the silicones are amodimethicone of formula (F) as described above, polydimethylsiloxane gums as described above. , cationic emulsions of polydimethylsiloxane, and mixtures thereof.

According to this embodiment, the total content of silicones corresponds to 0.01-15% by weight, better still 0.05-10% by weight, even better 0.1-5% by weight, relative to the total weight of the composition. do.

Cationic Surfactants According to the present invention, the composition may optionally further comprise one or more cationic surfactants.

The term "cationic surfactant" means a surfactant that is positively charged when included in the composition according to the invention. This surfactant can have one or more permanent positive charges or can contain one or more functional groups that can be cationized in the composition according to the invention.

The cationic surfactant is preferably from primary, secondary or tertiary fatty amines or salts thereof, and quaternary ammonium salts, optionally polyoxyalkylenated, and mixtures thereof To be elected.

Aliphatic amines generally contain at least one _C8 - _C30 hydrocarbon-based chain, preferably a _C12 - _C22 alkyl chain.

As an example of an aliphatic amine, mention may be made of stearamidopropyldimethylamine.

Examples of quaternary ammonium salts that may be mentioned in particular include:

(式中、
R₈～R₁₁は、同一であっても異なっていてもよく、1～30個の炭素原子を含む直鎖状若しくは分岐状脂肪族基、又はアリール若しくはアルキルアリール等の芳香族基を表し、R₈～R₁₁基の少なくとも1個が、12～22個の炭素原子、好ましくは16～22個の炭素原子を含むことが理解され；及び
X^-は、有機又は無機のアニオン性対イオン、例えば、ハロゲン化物イオン、酢酸イオン、リン酸イオン、硝酸イオン、(C₁～C₄)アルキル硫酸イオン、(C₁～C₄)アルキル又は(C₁～C₄)アルキルアリールスルホン酸イオンから選ばれるものを表す)。 - quaternary ammonium salts of general formula (IV):

(In the formula,
R ₈ to R ₁₁ , which may be the same or different, represent a linear or branched aliphatic group containing 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, It is understood that at least one of the R ₈ -R ₁₁ groups contains 12-22 carbon atoms, preferably 16-22 carbon atoms; and
X ⁻ is an organic or inorganic anionic counterion such as halide, acetate, phosphate, nitrate, (C ₁ -C ₄ )alkyl sulfate, (C ₁ -C ₄ )alkyl or ( C ₁ -C ₄ ) represent those selected from alkylarylsulfonate ions).

Aliphatic groups may contain heteroatoms such as oxygen, nitrogen, sulfur and halogens, among others. Aliphatic groups are, for example, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, polyoxy(C ₂ -C ₆ )alkylene, C ₁ -C ₃₀ alkylamido, (C ₁₂ -C 22 )alkylamido (C 12 -C ₂₂ )alkylamido (C ₂ -C ₆ )alkyl, (C ₁₂ -C ₂₂ )alkylacetate, and C ₁ -C ₃₀ hydroxyalkyl groups, and X ^- is halide, phosphate, acetate, lactate, (C ₁ to C ₄ ) alkyl sulfate ions and (C ₁ to C ₄ ) alkyl or (C ₁ to C ₄ ) alkyl aryl sulfonate ions.

Among the quaternary ammonium salts of formula (IV), preferred are on the one hand tetraalkylammonium salts, such as dialkyldimethylammonium or alkyltrimethylammonium salts, wherein the alkyl groups are approximately 16-22 containing carbon atoms and in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium or benzyldimethylstearylammonium salts or, on the other hand, palmitylamidopropyltrimethylammonium salts, stearamidopropyltrimethylammonium salts, stearamidopropyl dimethyl cetearyl ammonium salt or stearamidopropyl dimethyl(myristyl acetate) ammonium salt sold under the name Ceraphyl® 70 by the company Van Dyk. Particular preference is given to using the chloride salts of these compounds.

(式中、R₁₂は、例えば獣脂脂肪酸に由来する、8～30個の炭素原子を含むアルキル又はアルケニル基を表し、R₁₃は、水素原子、C₁～C₄アルキル基、又は8～30個の炭素原子を含むアルキル若しくはアルケニル基を表し、R₁₄は、C₁～C₄アルキル基を表し、R₁₅は、水素原子又はC₁～C₄アルキル基を表し、X^-は、ハロゲン化物イオン、リン酸イオン、酢酸イオン、乳酸イオン、アルキル硫酸イオン、アルキル又はアルキルアリールスルホン酸イオンからなる群から選ばれるアニオンであり、ここでアルキル及びアリール基は、それぞれ好ましくは、1～20個の炭素原子及び6～30個の炭素原子を含む)。 - quaternary ammonium salts of imidazolines, e.g. of formula (V):

(wherein R ₁₂ represents an alkyl or alkenyl group containing 8-30 carbon atoms, for example derived from tallow fatty acid, R ₁₃ represents a hydrogen atom, a C ₁ -C ₄ alkyl group, or an 8-30 represents an alkyl or alkenyl group containing 1 carbon atom, R ₁₄ represents a C ₁ -C ₄ alkyl group, R ₁₅ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, X ^- is a halide anion selected from the group consisting of ions, phosphate, acetate, lactate, alkylsulphate, alkyl or alkylarylsulphonate ions, wherein the alkyl and aryl groups each preferably have 1 to 20 carbon atoms and 6-30 carbon atoms).

R ₁₂ and R ₁₃ preferably represent a mixture of alkyl or alkenyl groups containing 12 to 21 carbon atoms, for example derived from tallow fatty acid, R ₁₄ preferably represents a methyl group, R ₁₅ , preferably represents a hydrogen atom. Such a product is for example sold under the name Rewoquat® W 75 by the company Rewo.

(式中、R₁₆は、任意選択により、ヒドロキシル化されている及び/又は1個又は複数個の酸素原子により中断されていてもよい、およそ16～30個の炭素原子を含むアルキル基を示し、R₁₇は、水素、及び1～4個の炭素原子を含むアルキル基、及び(R_16a)(R_17a)(R_18a)N-(CH₂)₃基から選ばれ、R_16a、R_17a、R_18a、R₁₈、R₁₉、R₂₀及びR₂₁は、同一であっても異なっていてもよく、水素、及び1～4個の炭素原子を含むアルキル基から選ばれ、X^-は、ハロゲン化物イオン、酢酸イオン、リン酸イオン、硝酸イオン、及びメチル硫酸イオンの群から選ばれるアニオンである)。 - in particular di- or tri-quaternary ammonium salts of formula (VI):

(wherein R ₁₆ represents an alkyl group containing approximately 16-30 carbon atoms, optionally hydroxylated and/or interrupted by one or more oxygen atoms; , R ₁₇ is selected from hydrogen and alkyl groups containing 1 to 4 carbon atoms, and (R _16a )(R _17a )(R _18a )N-(CH ₂ ) ₃ groups, R _16a , R _17a , R _18a , R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ , which may be the same or different, are selected from hydrogen and alkyl groups containing 1 to 4 carbon atoms, and X ^- is anions selected from the group consisting of halide ions, acetate ions, phosphate ions, nitrate ions, and methyl sulphate ions).

Such compounds are, for example, Finquat CT-P (Quaternium 89) available from Finetex and Finquat CT (Quaternium 75) available from Finetex.

(式中、
R₂₂は、C₁～C₆アルキル基及びC₁～C₆ヒドロキシアルキル又はジヒドロキシアルキル基から選ばれ；
R₂₃は、以下から選ばれ：
- 以下の基：

- 直鎖状又は分岐状で飽和又は不飽和のC₁～C₂₂炭化水素系基である、R₂₇基、
- 水素原子；
R₂₅は、以下から選ばれ：
- 以下の基：

- 直鎖状又は分岐状で飽和又は不飽和のC₁～C₆炭化水素系基である、R₂₉基、
- 水素原子；
R₂₄、R₂₆及びR₂₈は、同一であっても異なっていてもよく、直鎖状又は分岐状で飽和又は不飽和のC₇～C₂₁炭化水素系基から選ばれ；
r、s及びtは、同一であっても異なっていてもよく、2から6までの範囲の整数であり；
yは、1～10の範囲の整数であり；
x及びzは、同一であっても異なっていてもよく、0から10までの範囲の整数であり；
X^-は、単純又は錯体の、有機又は無機のアニオンであり；
但し、和x+y+zは、1～15であり、xが0の場合、R₂₃はR₂₇を示し、zが0の場合、R₂₅はR₂₉を示す)。 - quaternary ammonium salts containing at least one ester function, such as those of formula (VII):

(In the formula,
R ₂₂ is selected from C ₁ -C ₆ alkyl groups and C ₁ -C ₆ hydroxyalkyl or dihydroxyalkyl groups;
R ₂₃ is chosen from:
- The following groups:

- an _R27 group which is a linear or branched, saturated or unsaturated _C1 - _C22 hydrocarbon-based group,
- hydrogen atoms;
R ₂₅ is chosen from:
- The following groups:

- an _R29 group which is a linear or branched, saturated or unsaturated _C1 - _C6 hydrocarbon-based group,
- hydrogen atoms;
R ₂₄ , R ₂₆ and R ₂₈ , which may be the same or different, are selected from linear or branched, saturated or unsaturated C ₇ to C ₂₁ hydrocarbon-based radicals;
r, s and t, which may be the same or different, are integers ranging from 2 to 6;
y is an integer ranging from 1 to 10;
x and z, which may be the same or different, are integers ranging from 0 to 10;
X ⁻ is a simple or complex, organic or inorganic anion;
provided that the sum x+y+z is from 1 to 15, and when x is 0, R ₂₃ indicates R ₂₇ , and when z is 0, R ₂₅ indicates R ₂₉ ).

The alkyl group R ₂₂ may be linear or branched, more particularly linear.

Preferably R ₂₂ represents a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, more particularly a methyl or ethyl group.

Advantageously, the sum x+y+z is between 1 and 10.

When R ₂₃ is a hydrocarbon-based group R ₂₇ , this group may contain at most 12 to 22 carbon atoms or at least 1 to 3 carbon atoms. good.

When R ₂₅ is a hydrocarbon-based group R ₂₉ , this group preferably contains 1 to 3 carbon atoms.

Advantageously, R ₂₄ , R ₂₆ and R ₂₈ , which may be the same or different, are selected from linear or branched, saturated or unsaturated C ₁₁ -C ₂₁ hydrocarbon-based radicals, More particularly, it is selected from linear or branched, saturated or unsaturated C ₁₁ -C ₂₁ alkyl and alkenyl groups.

Preferably, x and z are the same or different and equal to 0 or 1.

Advantageously, y is equal to one.

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

The anion X ⁻ is preferably a halide ion (chloride, bromide or iodide) or an alkylsulphate, more particularly methylsulphate. However, methanesulfonate, phosphate, nitrate, tosylate, anions derived from organic acids such as acetate or lactate, or any other anion compatible with ammonium containing ester functional groups. can be used.

The anion X ⁻ is more particularly chloride or methylsulphate.

- メチル、エチル、又はC₁₄～C₂₂炭化水素系基；
- 水素原子；
R₂₅は、以下から選ばれ：
- 以下の基：

- 水素原子；
R₂₄、R₂₆及びR₂₈は、同一であっても異なっていてもよく、直鎖状又は分岐状で飽和又は不飽和のC₁₃～C₁₇炭化水素系基から選ばれ、好ましくは、直鎖状又は分岐状で飽和又は不飽和のC₁₃～C₁₇アルキル及びアルケニル基から選ばれる。 More particularly, in the composition according to the invention an ammonium salt of formula (VII) is used, wherein:
R ₂₂ represents a methyl or ethyl group;
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 chosen from:
- The following groups:

- methyl, ethyl or _C14 - _C22 hydrocarbon-based radicals;
- hydrogen atoms;
R ₂₅ is chosen from:
- The following groups:

- hydrogen atoms;
R ₂₄ , R ₂₆ and R ₂₈ , which may be the same or different, are selected from linear or branched, saturated or unsaturated C ₁₃ -C ₁₇ hydrocarbon-based radicals, preferably linear It is selected from linear or branched, saturated or unsaturated C ₁₃ -C ₁₇ alkyl and alkenyl groups.

The hydrocarbon-based radicals are advantageously straight-chain.

For example, compounds of formula (VII) such as diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium, monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium, and monoacyloxyethylhydroxyethyldimethylammonium salts ( chloride or methyl sulfate), as well as mixtures thereof. Acyl groups preferably contain 14 to 18 carbon atoms and are more particularly derived from vegetable oils such as palm oil or sunflower oil. If the compound contains several acyl groups, these groups may be the same or different.

These products are, for example, triethanolamines, triisopropanolamines, alkyldiethanolamines, optionally oxyalkylenated with C ₁₀ -C ₃₀ fatty acids of vegetable or animal origin or with mixtures of C ₁₀ -C ₃₀ fatty acids. Alternatively, it can be obtained by directly esterifying an alkyldiisopropanolamine, or by transesterifying these methyl esters. After this esterification, alkyl halide (preferably methyl halide or ethyl halide), dialkyl sulfate (preferably methyl sulfate or ethyl sulfate), methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydride Quaternization using an alkylating agent such as phosphorus or glycerol chlorohydrin follows.

Such compounds are known, for example, by Henkel under the name Dehyquart®, by Stepan under the name Stepanquat®, by Ceca under the name Noxamium® or by Rewo-Witco under the name Rewoquat®. (registered trademark) WE 18.

A composition according to the invention may, for example, contain a mixture of mono-, diester and triester salts of quaternary ammonium, with the diester salt being the majority of the mass.

Ammonium salts containing at least one ester function, described in patents US-A-4 874 554 and US-A-4 137 180, can also be used.

The behenoylhydroxypropyltrimethylammonium chloride provided by Kao Corporation under the name Quatarmin BTC 131 can be used.

Preferably, an ammonium salt containing at least one ester function contains two ester functions.

Among the quaternary ammonium salts containing at least one ester function that may be used, it is preferred to use the dipalmitoylethylhydroxyethylmethylammonium salt.

Preferably, the cationic surfactant is selected from quaternary ammonium salts of general formula (IV), and mixtures thereof.

Even better, the cationic surfactant is selected from behentrimonium chloride, cetrimonium chloride, and mixtures thereof.

Preferably, when cationic surfactants are present in the composition, the total content of cationic surfactants is 0.1-10% by weight, more preferably 0.5-8% by weight, relative to the total weight of the composition. %, better still 1 to 5% by weight.

According to a preferred embodiment of the present invention, the composition comprises one or more cationic surfactants, more preferably said cationic surfactants are cetyltrimethylammonium salts, behenyltrimethylammonium salts, di selected from palmitoylethyl hydroxyethyl-methylammonium salts, and mixtures thereof, more particularly behenyltrimethylammonium chloride or methosulfate, cetyltrimethylammonium chloride or methosulfate, dipalmitoylethyl-hydroxyethylmethylammonium chloride or methosulfate, and chosen from mixtures thereof, better still the total content of cationic surfactants is from 0.1 to 10% by weight, better from 0.5 to 8% by weight, more preferably from 0.5 to 8% by weight, relative to the total weight of the composition Even better it corresponds to 1 to 5% by weight.

Fatty Substances According to the present invention, the composition may optionally further comprise one or more fatty substances.

According to the invention, the fatty substance optionally present in the composition is non-silicone (contains no silicon atoms).

By “fatty substance” is meant an organic compound that is insoluble in water at normal temperature (25° C.) and atmospheric pressure (760 mmHg, i.e. 1.013×10 ⁵ Pa), i.e. the solubility is less than 5%, preferably 1%. less than, more preferably less than 0.1%.

Fatty substances are generally soluble in organic solvents such as chloroform, ethanol, benzene, liquid petrolatum or decamethylcyclopentasiloxane under the same conditions of temperature and pressure.

The fatty substances that can be used in the composition according to the invention are generally not oxyalkylenated and preferably do not contain the carboxylic acid function COOH.

Preferably, the fatty substance is selected from hydrocarbons, fatty alcohols, fatty acid esters, fatty ethers, and mixtures thereof.

Even more preferentially, the fatty substance is selected from fatty alcohols, fatty acid esters and mixtures thereof.

Hydrocarbon means a hydrocarbon, of mineral or vegetable origin or synthetic, composed exclusively of carbon atoms and hydrogen.

More particularly, the hydrocarbon is selected from:

- _C6 - _C16 alkanes, which may be linear or branched and cyclic.

Examples include hexane, undecane, dodecane, tridecane, and isoparaffins such as isohexadecane, isododecane and isodecane, and mixtures thereof.

- straight or branched hydrocarbons of animal or synthetic mineral origin with more than 16 carbon atoms, e.g. paraffin or petrolatum oil, liquid petrolatum, polydecene, hydrogenated polyisobutene, e.g. commercialized by NOF Corporation Squalene, sold under the name Parleam®.

In a preferred variant, the one or more hydrocarbons are selected from linear or branched, optionally cyclic C ₆ -C ₁₆ alkanes.

The term "fatty alcohol" means non-glycerolated and non-oxyalkylenated fatty alcohols which are preferably liquid at normal temperature (25° C.) and atmospheric pressure (760 mm Hg, or 1.013×10 ⁵ Pa).

Preferably, the fatty alcohols of the present invention contain 8-30 carbon atoms, more preferably 8-20 carbon atoms.

The fatty alcohols of the invention may be saturated or unsaturated.

The saturated fatty alcohols are preferably branched. They may or may not optionally contain at least one aromatic ring in their structure. Preferably they are acyclic.

More particularly, the saturated fatty alcohol of the present invention is selected from octyldodecanol, isostearyl alcohol and 2-hexyldecanol.

Octyldodecanol is particularly preferred.

Unsaturated fatty alcohols have at least one double or triple bond, preferably one or more double bonds, in their structure. If several double bonds are present, they are preferably 2 or 3 and may be conjugated or unconjugated.

These unsaturated fatty alcohols may be linear or branched.

They may or may not optionally contain at least one aromatic ring in their structure. Preferably they are acyclic.

More particularly, the unsaturated fatty alcohols of the present invention are selected from oleic (or oleyl) alcohol, linoleic (or linoleyl) alcohol, linolenic (or linolenyl) alcohol and undecylenic alcohol.

Oleyl alcohol is particularly preferred.

Fatty acid ester means an ester derived from fatty acids and/or fatty alcohols.

Esters are preferably esters of linear or branched, saturated or unsaturated C ₁ -C ₂₆ aliphatic mono- or polyacids and linear or branched, saturated or unsaturated C ₁ - Esters of _C26 aliphatic monohydric alcohols or polyhydric alcohols, the total number of carbon atoms in the ester is 10 or more.

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

Among monoesters of monoacids and monoalcohols, ethyl palmitate and isopropyl palmitate, alkyl myristates such as isopropyl myristate or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl neopentanoate , and isostearyl neopentanoate.

Also esters of C4 _{- C22} di- or tricarboxylic acids and _C1 - _C22 alcohols, and esters of mono-, di- or tricarboxylic acids and di-, tri-, tetra- or penta-hydroxylated C4- _C26 non-sugar alcohols _. , can be used.

In particular, diethyl sebacate, diisopropyl sebacate, di(2-ethylhexyl) sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, 2-ethylhexyl diadipate, diisostearyl adipate, malein di(2-ethylhexyl) acid, triisopropyl citrate, triisocetyl citrate, triisostearyl citrate, glyceryl trilactate, glyceryl trioctanoate, citrate ester of trioctyldodecyl, trioleyl citrate, neopentyl glycol diheptanoate, and diethylene glycol diisononanoate.

The composition may also contain, as fatty acid esters, esters and diesters of sugars with C ₆ -C ₃₀ fatty acids, preferably C ₁₂ -C ₂₂ fatty acids. "Sugar" is understood to mean an oxidized hydrocarbon compound containing at least 4 carbon atoms, with some alcohol functionality and with or without an aldehyde or ketone functionality. It is recalled that These sugars can be monosaccharides, oligosaccharides or polysaccharides.

Suitable sugars include, for example, sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and alkylated derivatives thereof such as methylglucose.

Esters of sugars and fatty acids are in particular the group comprising esters or ester mixtures of the sugars mentioned above with C ₆ -C ₃₀ fatty acids, preferably linear or branched, saturated or unsaturated C ₁₂ -C ₂₂ fatty acids. You can choose from When unsaturated, these compounds may contain 1-3 carbon-carbon double bonds and may be conjugated or unconjugated.

Esters according to this variant are also selected from mono-, di-, tri- and tetra-esters, polyesters and mixtures thereof.

These esters are, for example, oleates, laurates, palmitates, myristates, behenates, coconut fatty acid esters, stearates, linoleates, linolenates, caprates, arachidonates. esters, and mixtures thereof, such as mixed esters of oleo-palmitic acid, oleostearic acid, and palmito-stearic acid, among others.

More particularly mono- and diesters, especially mono- or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates, oleostearates, sucrose, glucose or methylglucose to use.

As an example, we may mention the product sold under the name Glucate® DO by the company Amerchol, which is methyl glucose dioleate.

Finally, it is also possible to use natural or synthetic esters of monoacids, diacids or triacids with glycerol.

Among these, mention may be made of vegetable oils.

As vegetable oils or synthetic triglycerides for use as fatty acid esters in the compositions of the invention, mention may be made, for example:
- Triglyceride oils of vegetable or synthetic origin, such as liquid triglycerides of fatty acids containing 6 to 30 carbon atoms, such as heptanoic or octanoic triglycerides, or e.g. sunflower, maize, soybean, pumpkin, grape seed , sesame, hazelnut, apricot, macadamia nut, arara, sunflower, castor oil, avocado, olive, rapeseed, copra, wheat, sweet almond, apricot, safflower, bancoulier nut, camellia, tamanu, babassu and plakasy oils, Triglycerides of caprylic/capric acid, such as those sold by the company STEARINERIES DUBOIS or those sold by the company DYNAMIT NOBEL under the names Miglyol® 810, 812 and 818, jojoba oil, shea butter oil.

Preferably, the esters according to the invention are fatty acid esters derived from monoalcohols, in particular myristate esters or isopropyl palmitate, or natural or synthetic esters of mono-, di- or triacids with glycerol, in particular vegetable oils. It is possible to use

Aliphatic ethers are selected from dialkyl ethers such as dicaprylyl ether.

Preferably, the fatty substance is selected from the aforementioned fatty alcohols and fatty acid esters, and mixtures thereof.

Preferably, when fatty substances are present in the composition, the total content of fatty substances is 0.5 to 25% by weight, better still 1 to 15% by weight, even better corresponds to 4 to 12% by mass.

According to a preferred embodiment of the present invention, the composition comprises one or more fatty substances, more preferably said fatty substances are selected from fatty alcohols, fatty acid esters and mixtures thereof, Preferably, the total content of fatty substances corresponds to 0.5-25% by weight, better still 1-15% by weight, even better 4-12% by weight, relative to the total weight of the composition. .

Preferably, the composition according to the invention comprises:
a. one or more selected from crosslinked polymers of methacryloyloxy(C ₁ -C ₄ )alkyltri(C ₁ -C ₄ )alkylammonium salts, cellulose ether derivatives containing quaternary ammonium groups, and mixtures thereof; a cationic polymer of the species;
b. diaryl anionic azo dyes of formula (a-II), pyrazolone anionic azo dyes of formula (a-III), triarylmethane dyes of formula (a-VI), their mesomeric forms, their tautomers and mixtures thereof;
c. At least dimethylsulfone, and at least ethylhydroxypyrone.

More preferably, the cationic polymer is selected from crosslinked polymers of methacryloyloxy(C ₁ -C ₄ )alkyltri(C ₁ -C ₄ )alkylammonium salts.

More preferably, the anionic direct dye is Acid Blue 9 (C.I. 42090, N-ethyl-N-[4-[[4-[ethyl[(3-sulfophenyl)methyl]amino]phenyl]-(2-sulfo Phenyl)-methylene]-2,5-cyclohexadien-1-ylidene]-3-sulfobenzenemethanaminium hydroxide disodium salt, inner salt), Acid Red 33 (C.I. 17200, 5-amino-4-hydroxy -3-(Phenylazo)-2,7-naphthalenedisulfonic acid disodium salt), Acid Yellow 23 (C.I. 19140, 5-Hydroxy-1-(4-sulfonatophenyl)-4-[(E)-(4 -sulfonatophenyl)diazenyl]-1H-pyrazole-3-carboxylate trisodium), and mixtures thereof.

According to a preferred embodiment of the present invention, the composition comprises at least one cationic surfactant selected from quaternary ammonium salts of general formula (IV) and mixtures thereof, more preferably said The cationic surfactant is selected from cetyltrimethylammonium salts, behenyltrimethylammonium salts, dipalmitoylethylhydroxyethyl-methylammonium salts, and mixtures thereof, more particularly behenyltrimethylammonium chloride or methosulfate, cetyltrimethyl ammonium chloride or methosulfate, dipalmitoylethyl-hydroxyethylmethylammonium chloride or methosulfate;

According to another preferred embodiment of the invention, the composition comprises at least one silicone, more preferably the silicone is chosen from aminosilicones.

The composition may contain a cosmetically acceptable medium. A cosmetically acceptable medium that can be used in the compositions of the present invention can comprise water, one or more organic solvents, or mixtures thereof.

Preferably, the compositions according to the invention are aqueous.

According to this selection, the water content is 5-98% by weight, more preferably 15-95% by weight, even more preferably 25-90% by weight, relative to the total weight of the composition. can vary from 30 to 85% by mass.

Examples of organic solvents are especially those which are liquid at 25° C., especially at 1.013×10 ⁵ Pa, especially those which are water-soluble, such as C ₁ -C ₇ alcohols, especially C ₁ -C ₇ aliphatics or Aromatic monoalcohols, C ₃ -C ₇ polyols, and ethers of C ₃ -C ₇ polyols can be used, and thus can be used alone or mixed with water. Advantageously, the organic solvent can be chosen from ethanol, isopropanol and mixtures thereof.

Preferably, the pH of the composition is between 1.5 and 11, more preferably between 2 and 7, even more preferably between 2.5 and 6.5, even better between 3 and 4.5.

The pH of these compositions can be adjusted to the desired value with alkalizing or acidifying agents. Alkalizing agents that may be mentioned are, for example, ammonia, alkanolamines or inorganic or organic hydroxides. Acidifying agents may include, for example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acid, and the like.

The compositions according to the invention may also contain cosmetic additives such as thickeners, preservatives, fragrances, nonionic surfactants, amphoteric polymers, pearlescent agents.

These additives can be present in the composition according to the invention in amounts ranging from 0 to 20% by weight, relative to the total weight of the composition.

Those skilled in the art will carefully choose these optional additives and their amounts so as not to adversely affect the properties of the composition according to the invention.

Compositions according to the invention may be in the form of creams, lotions or milks.

The compositions can be applied to damp or dry hair in a rinse-off or leave-on manner.

A subject of the present invention is also a method for treating keratin fibers, in particular human keratin fibers such as hair, comprising at least the step of applying a composition according to the invention as described above to said keratin fibers. .

Preferably, the method according to the invention is a method for improving the yellowish mottling of said keratin fibers.

According to a preferred embodiment of the invention, the step of washing out said keratin fibers is performed after the step of applying the composition according to the invention to said keratin fibers.

The step of drying the keratin fibers is provided in the method according to the invention, in particular by heating means such as a hair dryer, a straightening iron, a steam iron or a heating helmet, the heating means being between 150°C and 230°C. , preferably at a temperature of 200°C to 220°C.

The present invention also relates to the use of a composition according to the invention as described above for treating keratin fibers, in particular human keratin fibers such as hair.

Preferably, the composition according to the invention as described above is used to ameliorate the yellowish mottling of said keratin fibres.

The following examples are illustrative of the invention and should not be construed as limiting its scope.

A composition containing the following ingredients was prepared. All amounts are expressed as weight percent active relative to the total weight of each composition.

0.4 grams of Compositions A and B were each applied to a 1 gram lock of Asian bleached and sensitized hair (SA 20).

The tress was gently massaged from root to tip about 6 times with two fingers for 15 seconds.

The tress was then washed off, squeezed with a finger and finally dried at 60°C for 10 minutes.

It is observed that there is better color absorption and lower selectivity in the tresses treated with composition A according to the invention than in the tresses treated with comparative composition B.

Claims (9)

a. One or more cationic polymers selected from crosslinked polymers of methacryloyloxy(C ₁ -C ₄ )alkyltri(C ₁ -C ₄ )alkylammonium salts;
b. One or more anionic direct dyes; and
c . containing dimethylsulfone and ethylhydroxypyrone ;
the cationic polymer corresponds to 0.1 to 2% by weight relative to the total weight of the composition;
Anionic direct dyes represent 0.01 to 5% by weight relative to the total weight of the composition, and
the total content of dimethylsulfone and ethylhydroxypyrone corresponding to 0.01 to 5% by weight relative to the total weight of the composition;
The weight ratio of the cationic polymer content to the anionic direct dye content is between 1 and 12, inclusive; and
A composition wherein the mass ratio of the total content of dimethylsulfone and ethylhydroxypyrone to the content of the anionic direct dye is between 1 and 6, inclusive. 2. Composition according to claim 1 , characterized in that the cationic polymer is Polyquaternium-37. diaryl anionic azo dyes of formula (a-II) below, pyrazolone anionic azo dyes of formula (a-III) below, triarylmethane dyes of formula (a-VI) below, their mesomeric forms, A composition according to claim 1 or 2 , characterized in that it comprises one or more anionic direct dyes selected from the tautomers of and mixtures thereof:

(In formula (a-II),
_R7 , _R8 , _R9 , _R10 , _R'7 , _R'8 , _R'9 and _R'10 , which may be the same or different, are hydrogen atoms, or:
- alkyl;
- alkoxy, alkylthio;
- hydroxyl, mercapto;
- Nitro, Nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- (wherein R° is a hydrogen atom or represents an alkyl or aryl group, and X, X' and X'' may be the same or different and represents an oxygen or sulfur atom or NR (wherein R represents a hydrogen atom or an alkyl group) represents);
- (O) _2S (O ^- )-M ⁺ , where M ⁺ represents a hydrogen atom or a cationic counterion;
- (O)CO ^- -M ⁺ , where M ⁺ is as defined above;
- R''-S(O) ₂ - (wherein R'' represents a hydrogen atom, an alkyl group , an aryl, a (di)(alkyl)amino or aryl(alkyl)amino group , or a phenylamino group ) ;
- R'''-S(O) ₂ -X'-, wherein R''' represents a substituted or unsubstituted aryl or alkyl group and X' is as defined above;
- (di)(alkyl)amino;
- i) nitro, ii) nitroso, iii) (O) _2S (O ^- )-M ⁺ , and iv) alkoxy, wherein M ⁺ is as defined above, or aryl(alkyl)amino , substituted or unsubstituted with multiple groups;
- a substituted or unsubstituted heteroaryl group ;
- cycloalkyl;
- Ar-N=N- (wherein Ar represents a substituted or unsubstituted aryl group );
represents a group selected from
- Alternatively, two adjacent groups, _R7 and _R8 , or _R8 and _R9 , or _R9 and _R10 , together form a fused benzo group A', _R'7 and R' ₈ , or R' ₈ and R' ₉ , or R' ₉ and R' ₁₀ together form a fused benzo group B', A' and B' being i) nitro, ii) nitroso, iii) (O) _2S (O ^- )-M ⁺ , 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) substituted or unsubstituted aryl ( alkyl)amino (wherein M ⁺ , R°, X, X′, X″ and Ar are as defined above) substituted or unsubstituted is a substitution ;
Formula (a-II) has at least one sulfonate group (O) ₂ S(O ⁻ )-M ⁺ or one carboxyl group on one of the A, A′, B, B′, or C rings. is understood to include the rate group (O)CO ^- -M ⁺ );

(In formula (a-III),
· R ₁₁ , R ₁₂ and R ₁₃ may be the same or different and are hydrogen or halogen atoms, or alkyl or -(O) ₂ S(O ^- )M ⁺ groups (wherein M ⁺ is , as defined above);
- R ₁₄ represents a hydrogen atom, an alkyl group, or a -C(O)O ^- M ⁺ group, where M ⁺ is as defined above;
- R ₁₅ represents a hydrogen atom;
- R ₁₆ represents an oxo group, in which case R' ₁₆ is absent, or R ₁₅ and R ₁₆ together form a double bond;
- R ₁₇ and R ₁₈ , which may be the same or different, are a hydrogen atom, or:
- (O) ₂ S(O ^- )-M ⁺ , where M ⁺ is as defined above;
- Ar-OS(O) ₂ - (wherein Ar represents a substituted or unsubstituted aryl group );
representing a group selected from;
- R ₁₉ and R ₂₀ together form either a double bond or a substituted or unsubstituted benzo group D';
- R' ₁₆ , R' ₁₉ and R' ₂₀ , which may be the same or different, represent a hydrogen atom or an alkyl or hydroxyl group;
- Y represents either a hydroxyl group or an oxo group,
- - - - represents a single bond when Y is an oxo group and a double bond when Y represents a hydroxyl group;
Formula (a-III ) has at least one sulfonate group (O) ₂ S(O ^- )-M ⁺ or one carboxylate group -C(O)O on either the D or E ring. ^- understood to include M ⁺ );

(In formula (a-VI),
- R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ may be the same or different and may be a hydrogen atom, alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted arylalkyl represents a group selected from;
- _R37 , _R38 , _R39 , _R40 , R41, _{R42 , R43} and _R44 , which may be the same or different, are hydrogen atoms, or:
- alkyl;
- alkoxy, alkylthio;
- (di)(alkyl)amino;
- hydroxyl, mercapto;
- Nitro, Nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, or R°-X'-C(X)-X''-, where R° is hydrogen represent an atom or an alkyl or aryl group, and X, X' and X'' may be the same or different and represent an oxygen or sulfur atom or NR (wherein R represents a hydrogen atom or an alkyl group ) represents );
- (O) _2S (O ^- )-M ⁺ , where M ⁺ represents a hydrogen atom or a cationic counterion;
- (O)CO ^- -M ⁺ , where M ⁺ is as defined above;
represents a group selected from
- or two adjacent groups R ₄₁ and R ₄₂ or R ₄₂ and R ₄₃ or R ₄₃ and R ₄₄ together form a fused benzo group I', wherein I' is i) nitro, ii) nitroso, iii) (O) _2S (O ^- )-M ⁺ , iv) hydroxyl, v) mercapto, vi) (di)(alkyl)amino, vii) R°-C(X) -X'-, viii) R°-X'-C(X)-, ix) R°-X'-C(X)-X''- (where M ⁺ , R°, X, X' , and X'' are as defined above) substituted or unsubstituted with one or more groups selected from;
At least one of the G, H, I, or I' rings may contain at least one sulfonate group (O) _2S (O ^- )- or one carboxylate group -C(O) ^O- . understood). Acid Blue 9 (CI 42090, N-ethyl-N-[4-[[4-[ethyl[(3-sulfophenyl)methyl]amino]phenyl]-(2-sulfophenyl)-methylene]-2,5- Cyclohexadien-1-ylidene]-3-sulfobenzenemethanaminium hydroxide disodium salt, inner salt), Acid Red 33 (CI 17200, 5-amino-4-hydroxy-3-(phenylazo)-2,7 -disodium salt of naphthalenedisulfonic acid), Acid Yellow 23 (CI 19140, 5-Hydroxy-1-(4-sulfonatophenyl)-4-[(E)-(4-sulfonatophenyl)diazenyl]-1H- trisodium pyrazole-3-carboxylate), and mixtures thereof, comprising one or more anionic direct dyes. Composition. 5. Composition according to any one of claims 1 to 4 , characterized in that it comprises one or more silicones. 6. Composition according to any one of claims 1 to 5 , characterized in that it comprises one or more cationic surfactants. 7. Composition according to any one of claims 1 to 6 , characterized in that it comprises one or more fatty substances selected from fatty alcohols, fatty acid esters and mixtures thereof . A method for treating keratinous fibres , comprising at least the step of applying a composition according to any one of claims 1 to 7 to said keratinous fibres. Use of a composition according to any one of claims 1 to 7 for treating keratin fibres .