WO2018115791A1

WO2018115791A1 - Hair dyeing method using acid dyes comprising a pretreatment using a cationic polymer

Info

Publication number: WO2018115791A1
Application number: PCT/FR2017/053824
Authority: WO
Inventors: Marie Giafferi; Mickaël AGACH; Leila Hercouet
Original assignee: L'oreal
Priority date: 2016-12-22
Filing date: 2017-12-22
Publication date: 2018-06-28
Also published as: FR3061005B1; FR3061005A1

Abstract

The present invention concerns a method for dyeing keratinous fibres, in particular human keratinous fibres such as hair, that comprises the application of one or more cationic polymers, followed by the application of one or more anionic direct dyes. The invention also concerns a dyeing kit comprising a composition A comprising one or more cationic polymers and a composition B comprising one or more anionic direct dyes. It also concerns the use of one or more cationic polymers in a pretreatment before dyeing the hair using direct acid dyes, in order to reduce staining of the scalp. This method for dyeing the hair in two steps helps obtain intense, chromatic colouring that is wash-resistant and that does not stain the scalp after the application of anionic direct dyes.

Description

A method of hair dyeing from acid dyes comprising pretreatment using a cationic polymer

The present invention relates to a hair dyeing process from one or more acid dyes comprising a pretreatment using one or more cationic polymers, the pretreatment being implemented before the application of the anionic direct dye (s).

It is known to dye keratinous fibers, and in particular human hair, with dyeing compositions containing direct dyes. The standard dyes that are used are in particular nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine, triarylmethane or natural dyes.

These dyes may be nonionic, anionic, cationic or amphoteric. These dyes are colored molecules or dyes having an affinity for keratinous fibers. These compositions containing one or more direct dyes are applied to the keratinous fibers for a time necessary to obtain the desired coloration, and then rinsed. The colorations that result are particularly chromatic colorations that are however temporary or semi-permanent because the nature of the interactions that bind the direct dyes to the keratinous fiber, and their desorption of the surface and / or the core of the fiber are responsible for their low dyeing power and their poor resistance to light, washing, or perspiration.

On the other hand, the use of acid dyes usually results in undesirable scalp coloring.

Acid dyes are good for coloring hair because they are usually cheap. Moreover, at the concentrations generally used, they have little or no sensitization. Nevertheless, these dyes stain the scalp a lot. They are therefore used at low concentrations which does not always achieve good coverage of white hair.

There is therefore still some progress to be made in this field, especially from acid dyes to provide powerful, resistant dyes that respect the nature of the hair and that do not cause scalp coloring.

This object is achieved by the present invention which relates to a process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, which comprises the application of a composition A having a basic pH comprising one or more polymers cationic agents chosen from quaternary diammonium polymers comprising recurring units of formula (I) below, followed by the application of one or more anionic direct dyes R 13 R 15

in which :

- 13, R14, R15 and R16, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or hydroxyalkylaliphatic C1-C12 radicals,

or R13, R14, R15 and R16, together or separately, together with the nitrogen atoms to which they are attached, constitute heterocycles optionally comprising a second heteroatom other than nitrogen

or else R13, R14, R15 and R16 represent a linear or branched C1-C6 alkyl radical substituted with a nitrile, ester, acyl or amide group or -CO-O-R17-D or -CO-NH-R17-D where R17 is alkylene and D is a quaternary ammonium group;

A1 and B1 represent divalent polymethylenic groups comprising from 2 to 20 carbon atoms, linear or branched, saturated or unsaturated, and which may contain, bound to or intercalated in the main chain, one or more aromatic rings, or one or more atoms oxygen, sulfur or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and

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

it being understood that A1, R13 and R15 can form with the two nitrogen atoms to which they are attached a piperazine ring;

in addition, if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 may also denote a (CH2) n -CO-D-OC- (CH2) p- group, with n and p, which are identical or different, being integers varying from 2 to 20, and D denoting:

a) a glycol residue of formula -OZO-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas: - (CH 2 CH 2 O) x -CH 2 CH 2 - and - [CH 2 CH (CH 3) O] wherein x and y denote an integer of 1 to 4, representing a defined and unique degree of polymerization or any number of 1 to 4 representing an average degree of polymerization;

b) a bis-secondary diamine residue such as a piperazine derivative; c) a bis-primary diamine residue of formula -NH-Y-NH- where Y denotes a linear or branched hydrocarbon radical, or the divalent radical -CH2-CH2-SS-CH2-CH2-;

d) a ureylene group of formula -NH-CO-NH-.

The subject of the invention is also a dyeing kit comprising a composition A comprising one or more cationic polymers as defined above and a composition B comprising one or more anionic direct dyes.

It also relates to the use of one or more cationic polymers in pretreatment of a hair coloring from acid direct dyes to reduce the scalp tachage.

This two-step hair dyeing process provides an intense, chromatic, wash-resistant coloration that does not stain the scalp after the application of anionic direct dyes.

Preferably, the composition A has a basic pH, preferably a pH between 9 and 10. The dye composition B which contains the anionic direct dyes generally has an acidic pH.

Anionic direct dyes

The anionic direct dyes useful in the process of the invention are dyes commonly called "acid" direct dyes for their affinity with alkaline substances. By anionic direct dyes is meant any direct dye comprising in its structure at least one CO2R or SO3R substituent with R denoting a hydrogen atom or a cation derived from a metal or an amine, or an ammonium ion. The anionic dyes may be chosen from acidic nitro dyes, acidic azo dyes, acidic azine dyes, triarylmethane acid dyes, acidic indoamine dyes, acidic anthraquinone dyes, indigoids and acidic natural dyes.

As acid dyes according to the invention, mention may be made of the dyes of formulas (II), (IV), (III), (IV), (IV), (IV), (V), (V), (VI), (VII), (VIII) and (IX):

a) the diaryl anionic azo dyes of formula (II) or (II '):

formula (II) and (II ') in which:

R ₇ , R ₉ , R ₁₀ , R ' ₇ , R' e, R '9 and R' 10, which may be identical or different, represent a hydrogen atom or a group chosen from:

alkyl;

alkoxy, alkylthio;

hydroxy, mercapto;

nitro, nitroso;

- R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X "- with R ° representing a hydrogen atom, a alkyl or aryl group X, X 'and X ", identical or different, representing an oxygen atom, sulfur or NR with R representing a hydrogen atom or an alkyl group;

(0) 2S (0 ^" ) -, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;

(O) CO ^" -, IVT with IVT as defined above;

R "-S (O) 2-, with R" representing a hydrogen atom, an alkyl group, an aryl, (di) (alkyl) amino, aryl (alkyl) amino group; preferentially a phenylamino or phenyl group;

R "'- S (O) 2 -X'- with R'" representing an optionally substituted alkyl, aryl group, X 'as defined above;

(di) (alkyl) amino;

aryl (alkyl) amino optionally substituted with one or more groups selected from i) nitro; ii) nitroso; iii) (O) 2 S (O ^" ) -, M ⁺ and iv) alkoxy with M ⁺ as previously defined;

optionally substituted heteroaryl; preferentially a benzothiazolyl group;

cycloalkyl; in particular cyclohexyl, Ar-N = N- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl groups, (O) 2 S (O ^" ) -, M ⁺ or phenylamino;

- or two contiguous groups R7 with Re or Re with Rg or

Rg with R10 together form a fused group benzo A '; and R ' ₇ with R'e or R'e with R'g or R'g with R'10 together form a fused group benzo B'; with A 'and B' optionally substituted with one or more groups selected from i) nitro; ii) nitroso; iii) (0) 2S (O ^" ) -, M ⁺ ; iv) hydroxy; 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) aryl (alkyl) amino optionally substituted, with M ⁺ , R 0, X, X ', X" and Ar as defined previously;

W represents a sigma bond σ, an oxygen atom, sulfur atom, or a divalent radical i) -NR- with R as defined above, or ii) methylene -C (R _a ) (Rb) - with R _a and Rb, which are identical or different, representing a hydrogen atom or an aryl group, or else R _a and Rb together with the carbon atom carrying them form a cycloalkyl spiro; preferentially W represents a sulfur atom or R _a and Rb together form a cyclohexyl;

it being understood that the formulas (II) and (II ') comprise at least one (O) 2S (O ^" ) -, M ⁺ sulfonate radical or a carboxylate (O) CO ^" -, IVT radical on one of the A, A rings ', B, B' or C; preferentially sodium sulphonate;

By way of example of dyes of formula (II), mention may be made of: 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 73, Acid Red 135, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 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 13, Acid Blue 17, 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;

and by way of example of dyes of formula (II ') that may be mentioned: Acid Red 1 1 1, Acid Red 134, Acid yellow 38;

b) the azo anionic pyrrazolone dyes of formula (III) and (ΙΙΙ '):

formulas (III) and (ΙΙΙ ') in which:

11, R12 and R13, which may be identical or different, represent a hydrogen atom, a halogen atom, an alkyl group or - (O) 2S (O ^" ), M ⁺ with M ⁺ as defined above;

Ru represents a hydrogen atom, an alkyl group or a - C (O) O ^{- group} , IVT with IVT as defined above;

R15 represents a hydrogen atom;

R16 represents an oxo group in which case R'16 is absent, or else R15 with R16 together form a double bond;

R17 and Rie, identical or different, represent a hydrogen atom, or a group chosen from:

(0) 2S (O ^" ) -, M ⁺ with M ⁺ as defined above; Ar-O-S (O) 2- with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted by one or more alkyl groups ;

R19 and R20 together form either a double bond or an optionally substituted benzo D 'group;

R'16, R'19 and R'20, identical or different, represent a hydrogen atom or an alkyl group, or hydroxy;

R21 represents a hydrogen atom, an alkyl group, or alkoxy; ^■ R _a and R _a, identical or different, are as defined above, preferably R _a represents a hydrogen atom and Rb represents an aryl group;

^■ Y represents either a hydroxyl group or an oxo group;

■ represents a single bond when Y is oxo group; and represents a double bond when Y represents a hydroxyl group; it being understood that the formulas (III) and (ΙΙΓ) comprise at least one sulfonate radical (O) 2S (O ^" ) -, M ⁺ or a carboxylate radical -C (O) O ^" , IVT on one of the rings D or E ; preferentially sodium sulphonate;

By way of example of dyes of formula (III), mention may be made of: Acid Red 195, Acid

Yellow 23, Acid Yellow 27, Acid Yellow 76, and by way of example of dyes of formula (ΙΙΓ), mention may be made of: Acid Yellow 17;

c) anthraquinone dyes of formula (IV) and (IV):

^■ R22, R23, R24, R25, R26 and R27, identical or different, represent a hydrogen or halogen atom or a group chosen from:

alkyl;

hydroxy, mercapto;

alkoxy, alkylthio;

aryloxy or optionally substituted arylthio, preferably substituted by one or more groups selected from alkyl and (0) 2S (O ^" ) -, M ⁺ with M ⁺ as defined above; aryl (alkyl) amino optionally substituted with one or more groups selected from alkyl and (0) 2S (O ^" ) -, M ⁺ with M ⁺ as defined above;

(di) (alkyl) amino;

(Di) (hydroxyalkyl) amino

(0) 2S (0 ^" ) -, M ⁺ with M ⁺ as previously defined;

^■ Z represents a hydrogen atom or a group N R28 29 with R2s and R29, identical or different, represent a hydrogen atom or a group chosen from:

alkyl;

polyhydroxyalkyl such as hydroxyethyl;

aryl optionally substituted by one or more groups particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (0) 2S (O ^" ) -, M ⁺ with M ⁺ as defined above, iii) R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X "- with R °, X, X 'and X" as defined previously, preferably R ° represents an alkyl group;

cycloalkyl; in particular cyclohexyl;

^■ Z, represents a group chosen from hydroxy and NR'2sR'29 with R'28 and R'29, identical or different, represent the same atoms or groups as R28 and R29 as defined above;

it being understood that the formulas (IV) and (IV) comprise at least one sulfonate (O) 2 S (O ^" ) -, M ⁺ radical or a carboxylate radical -C (O) O ^" , M ⁺ ; preferentially sodium sulphonate;

By way of example of dyes of formula (IV), mention may be made of Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140 and Acid Blue 251, Acid Green. 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; Purple EXT # 2;

and by way of example of dyes of formula (IV), mention may be made of: Acid Black 48; d) nitro dyes of formula (V), (V) and (V "):

formulas (V) and (V) in which:

30, R31 and R32, which may be identical or different, represent a hydrogen or halogen atom or a group chosen from:

alkyl;

aikoxy optionally substituted with one or more hydroxyl groups, alkylthio optionally substituted with one or more hydroxyl groups;

hydroxy, mercapto;

nitro, nitroso;

polyhaloalkyl;

- R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X "- with R ° X, X 'and X" as defined above;

(0) 2S (0 ^" ) -, M ⁺ with M ⁺ as previously defined; (O) CO ^" -, IVT with IVT as defined above;

(di) (alkyl) amino;

(di) (hydroxyalkyl) amino;

heterocycloalkyl such as piperidino, piperazino or morpholino; particularly R 30, R 31 and R 32 represent a hydrogen atom;

R _c and Rd, identical or different, represent a hydrogen atom or an alkyl group;

W is as defined previously; W is particularly -NH-; ALK represents a divalent alkylene group, linear or branched, C1-C6; particularly ALK represents a -CH2-CH2- group;

n is 1 or 2;

p represents an integer inclusive of between 1 and 5;

q represents an integer inclusive of between 1 and 4;

u is 0 or 1;

when n is 1, J represents a nitro or nitroso group; especially nitro;

when n is 2, J represents an oxygen atom, sulfur, or a divalent radical -S (0) _m - with m representing an integer 1 or 2; preferably J represents a radical -SO2-;

M 'represents a hydrogen atom or a cationic counterion;

Present or absent represents a benzo group optionally substituted with one or more R30 groups as defined above; it being understood that the formulas (V) and (V) comprise at least one sulfonate (O) 2 S (O ^" ) -, M ⁺ radical or a carboxylate radical -C (O) O ^" , M ⁺ ; preferentially sodium sulphonate;

By way of example of dyes of formula (V), mention may be made of: Acid Brown 13;

Orange Acid 3; by way of example of dyes of formula (V), mention may be made of: Acid Yellow 1, 2,4-dinitro-1-naphthol-7-sulfonic acid sodium salt, 2-piperidino 5-nitro benzene sulfonic acid , 2 (4'-N, N (2 "-hydroxyethyl) amino-2'-nitro) aniline ethanesulfonic acid, 4-p-hydroxyethylamino-3-nitrobenzene sulfonic acid, EXT D & C yellow 7, d) triarylmethane dyes of formula (VI):

formula (VI) in which:

^■ R33, R34, R35 and R36, identical or different, represent a hydrogen atom or a group selected from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl and benzyl group optionally substituted with a group (O) _m S (O ^" ) -, M ⁺ with M ⁺ and m as defined above;

^■ R37, R38, R39, R40, R41, R42, R43 and R44, identical or different, represent a hydrogen atom or a group chosen from:

alkyl;

alkoxy, alkylthio;

(di) (alkyl) amino;

hydroxy, mercapto;

nitro, nitroso;

(O) CO ^" -, IVT with IVT as defined above;

or two contiguous groups R41 with R42 or R42 with R43 or R43 with R44 together form a fused group benzo: I '; with I 'optionally substituted with one or more groups selected from i) nitro; ii) nitroso; iii) (O) 2 S (O ^" ) -, M ⁺ ; iv) hydroxy; v) mercapto; vi) (di) (alkyl) amino; vii) R ° -C (X) -X'-; viii) R ° - X'-C (X) -; ix) R ° -X'-C (X) -X "-; with M ⁺ , R 0, X, X ', X "as previously defined;

R 37 to R 40 represent a hydrogen atom, and R 41 to R 44, which are identical or different, represent a hydroxyl or (O) 2 S (O ^" ) -, M ^{+ group} , and when R 43 with R 44 together form a benzo group, it is preferentially substituted with a group (O) 2S (0 ^" ) -;

it being understood that at least one of the G, H, I or Γ rings comprises at least one (O) 2 S (O ^" ) sulfonate radical or a -C (O) O ^" carboxylate radical; preferentially sulphonate; By way of example of dyes of formula (VI), mention may be made of: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid green 3; Acid green 5; Acid Green 50;

e) the dyes derived from xanthene of formula (VII):

formula (VII) in which:

^■ R45, ₄ 6, 47 and R ₄ 8, identical or different, represent a hydrogen atom or a halogen atom;

^■ R49, R50, R51 and R52, identical or different, represent a hydrogen or halogen atom or a group chosen from:

alkyl;

alkoxy, alkylthio;

hydroxy, mercapto;

nitro, nitroso;

- (0) 2S (0 ^" ) -, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;

(O) CO ^" -, IVT with IVT as defined above;

especially R53 R54, R55 and R ₄ 8représentent a hydrogen or halogen atom;

"G represents an oxygen atom, sulfur atom or a group NR _e with R _e as defined above, particularly G represents an oxygen atom;

^■ L is O alkoxide ^"M ^+; S ^{thioalkoxide"} M ⁺ or NRf group, with R representing a hydrogen atom or an alkyl group and M ⁺ as hereinbefore defined; M ⁺ is especially sodium or potassium;

L 'represents an oxygen atom, sulfur atom or an ammonium group:

NTRfRg, with R f and R _g, which are identical or different, representing a hydrogen atom, an alkyl group, optionally substituted aryl; The represents particularly an oxygen atom or a phenylamino group optionally substituted with one or more alkyl groups or (0) _m S (O ^" ) -, M ⁺ with m and M ⁺ as defined above;

^■ Q and Q \ identical or different, represent an oxygen or sulfur atom; particularly Q and Q 'represent an oxygen atom;

^■ M ⁺ is as defined previously;

By way of example of dyes of formula (VII), mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52, Acid Red 87; Acid Red 92; Acid Red 95; Purple Acid 9;

f) the dyes derived from indole of formula (VIII):

R 53, R 54, R 55, 56, R 57, R 58, R 59 and R 60, which may be identical or different, represent a hydrogen atom or a group chosen from:

alkyl;

alkoxy, alkylthio;

hydroxy, mercapto;

nitro, nitroso;

(O) CO ^" -, IVT with IVT as defined above;

G represents an oxygen atom, sulfur atom or a group NR _e with R _e as defined above; especially G represents an oxygen atom; R, and Rh, identical or different, represent a hydrogen atom or an alkyl group; it being understood that formula (VIII) comprises at least one (O) 2S (O ^" ) -, M ⁺ sulfonate radical or a carboxylate radical -C (O) O ^" , M ⁺ ; preferentially sodium sulphonate

By way of example of dyes of formula (VIII), mention may be made of: Acid Blue 74. g) quinoline-derived dyes of formula (IX):

^■ R6i represents a hydrogen atom, halogen or alkyl;

^■ 62, 63, and R64, identical or different, represent a hydrogen atom or a group (0) 2S (0 ^" ) -, M ⁺ with M ⁺ representing a hydrogen atom or a cationic counterion;

^■ or when R6i with R62 or with R64 R6i, together form a benzo group optionally substituted by one or more group (0) 2S (0 ^") -, M ⁺ with M ⁺ representing a hydrogen atom or an-ion against cationic;

it being understood that the formula (IX) comprises at least one sulfonate radical (O) 2 S (O ^" ) -, M ⁺ preferentially sodium sulphonate.

By way of example of dyes of formula (IX), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

More particularly, the dyes of formula (II) to (VII) useful for the invention are chosen from:

(C.I. 45380) Acid Red 87 (VII)

(CI 10316) 2,4-Dinitro-1-naphthol-7-sulfonic acid sodium salt (V)

(CI 10383) Orange Acid 3 (V)

(CI 13015) Acid Yellow 9 / Food Yellow 2 (II)

(CI 14780) / Direct Red 45 / Food Red 13 (II)

(Cl 1371 1) Acid Black 52 (II)

(Cl. 13065) Acid Yellow 36 (II)

(CI 14700) 1-Hydroxy-2- (2 ', 4'-xylyl-5-sufonatoazo) -naphthalene-4-sulfonic acid sodium salt / Food Red 1 (11)

(CI 14720) Red Acid 14 / Food Red 3 / Blue Mordant 79 (II) (C. 1. 14805) 4-Hydroxy-3 - [(2-methoxy-5-nitrophenyl) diaza] -6- (phenylamino) naphthalene-2-sulphonic acid / Acid Brown 4 sodium salt (II) )

(CI 15510) Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 (II)

(CI 15985) Food Yellow 3 / Pigment Yellow 104 (II)

(C.I. 16185) Acid Red 27 / Food Red 9 (II)

(CI 16230) Orange Acid 10 / Food Orange 4 (II)

(Cl 16250) Acid Red 44 (II)

(CI 17200) Acid Red 33 / Food Red 12 (II)

(C.I. 15685) Acid Red 184 (II)

(CI 19125) Acid Violet 3 (II)

(C.I. 18055) 1-Hydroxy-2- (4'-acetamido phenylazo) -8-acetamido-naphthalene-3,6-disulphonic acid sodium salt / Acid Purple 7 / Food Red 1 1 (II)

(C.I. 18130) Acid Red 135 (II)

(C.I. 19130) Acid Yellow 27 (III)

(C.I. 19140) Acid Yellow 23 / Food Yellow 4 / Yellow 5 / Trisodium salt of 5-hydroxy-1- (4-sulfonatophenyl) -4- (4-sulfonatophenylazo) -H-pyrazole-3-carboxylic acid ( III)

(Cl. 20170) 4 '- (Sulfonato-2 ", 4" -dimethyl) -bis- (2,6-phenylazo) -1,3-dihydroxybenzene /

Orange Acid 24 (II)

(CI 20470) 1-Amino-2- (4'-nitrophenylazo) -7-phenylazo-8-hydroxy-naphthalene-3,6-disulfonic acid / Acid Black 1 (II) sodium salt

(C 23266) (4 - ((4-methylphenyl) sulfonyloxy) -phenylazo) 2,2'-dimethyl-4 - ((2-hydroxy-5,8-disulfonato) naphthylazo) biphenyl / Acid Red 111 (II ') )

(CI 27755) Food Black 2 (II)

(C-25440) 1- (4'-sulfonatophenylazo) -4 - ((2 "-hydroxy-3" -acetylamino-6 ", 8" -disulfonato) naphthylazo) -6-sulfonatonaphthalene (tetrasodium salt) / Food Black 1 (II)

(Cl 42090) Acid Blue 9 (VI)

(Cl 60730) Acid Violet 43 (IV)

(Cl 61570) Acid Green 25 (IV)

(Cl 62045) Sodium salt of 1-amino-4-cyclohexylamino-9,10-anthraquinone

2-sulfonic acid / Acid Blue 62 (IV)

(Cl 62105) Acid Blue 78 (IV) (CI 14710) 4-Hydroxy-3 ((2-methoxyphenyl) azo) -1-naphthalenesulfonic acid / Acid Red 4 (II) sodium salt

2-Piperidino 5-nitro benzene sulfonic acid (V)

Acid 2 (4'-N, N (2 "-hydroxyethyl) amino-2'-nitro) aniline ethanesulfonic acid (V)

4-p-hydroxyethylamino-3-nitrobenzene acid

Sulfonic (V)

(Cl 42640) Acid Violet 49 (VI)

(Clot 42080) Acid Blue 7 (VI)

(CI 58005) Sodium salt of 1,2-dihydroxy-3-sulpho-anthraquinone / Mordant Red 3

(IV)

(Cl 62055) 1-Amino-9,10-dihydro-9,10-dioxo-4- (phenylamino) -2-anthracenesulfonic acid / Acid Blue 25 (IV) sodium salt

(CI 14710) 4-Hydroxy-3 - ((2-methoxyphenyl) azo) -1-naphthalenesulfonic acid / Acid Red 4 (II) sodium salt

16255) Acid Red 18/7-Hydroxy-8 - [(4-Sulfo-1-Naphthalenyl) Azo] -1,3-Naphthalenedisulfonic acid (II) trisodium salt

Most of these dyes are described in particular in the Color Index published by The Society of Dyers and Colorists, PO Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JBN England.

The more particularly preferred anionic dyes are the dyes designated in the Color Index under the code CI. 58005 (monosodium salt of 1, 2-dihydroxy-9,10-anthraquinone-3-sulfonic acid), CI. 60730 (2- [(9,10-dihydro-4-hydroxy-9,10-dioxo-1-anthracenyl) amino] -5-methyl-benzenesulfonic acid, monosodium salt), Cl. 15510 (monosodium salt of 4 - [(2-hydroxy-1-naphthalenyl) -azo] -benzene sulfonic acid), CI. 15985 (disodium salt of 6-hydroxy-5 - [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid), Cl. 17200 (disodium salt of 5-amino-4-hydroxy-3- (phenylazo) -2,7-naphthalene disulfonic acid), CI. 20470 (disodium salt of 1-amino-2- (4'-nitrophenylazo) -7-phenylazo-8-hydroxy-3,6-naphthalene disulfonic acid), Cl. 42090 (disodium salt of N-ethyl-N- [4 - [[4- [ethyl [3-sulphophenyl) methyl] amino] phenyl] (2-sulphophenyl) methylene] -2,5-cyclohexadien-1 -ylidene] -3-sulfobenzenemethanaminium hydroxide, internal salt), Cl. 61570 (disodium salt of 2,2 '- [(9,10-dihydro-9,10-dioxo-1, 4-anthracenediyl) diimino] -bis- [5-methyl] benzene sulfonic acid, C. I 19140 (Trisodium salt of 5-hydroxy-1- (4-sulfonatophenyl) -4- (4-sulfonatophenylazo) -H-pyrazole-3- acid carboxylic acid), (Cl. 16255) 7-Hydroxy-8 - [(4-Sulfo-1-Naphthalenyl) Azo] -1,3-naphthalenedisulfonic acid, trisodium salt, (Cl 60730) Acid Violet 43.

Compounds corresponding to the mesomeric, tautomeric forms of structures (II) to (IX) can also be used.

The anionic direct dye (s) are generally applied to the fibers from a composition B whose total content of anionic direct dyes is between 0.001% to 20% by weight relative to the total weight of composition B and preferably from 0.005% to 10% in weight. More particularly, the anionic dye (s) in the composition B represent from 0.01 to 5% by weight. The pH of the composition B which contains the anionic dye (s) is generally less than 7, preferably acid of between 2 and 6.5, better still between 1.8 and 6.

Cationic polymers

The process of the invention comprises the application of one or more cationic polymers.

The term "cationic polymer", any polymer comprising cationic groups and / or ionizable groups of cationic groups at pH greater than 7.

Preferably, the cationic polymer or polymers according to the invention do not comprise anionic groups and / or ionizable groups in anionic groups.

Cationic polymers that may be used preferably have an average molar mass by weight (Mw) between 500 and approximately 5.10 ^s, preferably between 10 ³ and 3.10 ⁶ approximately. Quaternary diammonium polymers comprising recurring units of formula:

N + -A, -N +

R X- X-

14 16

in which :

- 13, R14, R15 and R16, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or hydroxyalkylaliphatic C1-C12 radicals, or R13, R14, R15 and R16, together or separately, together with the nitrogen atoms to which they are attached, constitute heterocycles optionally comprising a second heteroatom other than nitrogen

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

b) a bis-secondary diamine residue such as a piperazine derivative;

c) a bis-primary diamine residue of formula -NH-Y-NH- where Y denotes a linear or branched hydrocarbon radical, or the divalent radical -CH 2 -CH 2 -S-S-CH 2 -CH 2 -;

d) a ureylene group of formula -NH-CO-NH-.

Preferably, X ^" is an anion such as chloride or bromide These polymers have a number average molecular weight (Mn) generally between 1000 and 100,000.

Mention may be made more particularly of polymers which consist of repeating units corresponding to the formula:

in which R1, R2, R3 and R4, identical or different, denote an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms, n and p are integers ranging from 2 to 20, and X- is an anion derived from a mineral or organic acid.

A particularly preferred compound of formula (IV) is that for which R 1,

R2, R3 and R4 represent a methyl radical, n = 3, p = 6 and X = Cl, called Hexadimethrine chloride according to the INCI nomenclature (CTFA).

Preferably, the cationic polymers are chosen from cationic polymers of formula (II).

According to a preferred embodiment, the cationic polymer or polymers are the polymers of formula (IV) of family (8), in particular the compound of formula (II) which is particularly preferred is that for which R1, R2, R3 and R4 represent a methyl radical, n = 3, p = 6 and X = Cl, called Hexadimethrine chloride according to the INCI nomenclature (CTFA).

Composition A may comprise from 0.1 to 25% by weight, preferably from 1 to 20% by weight, better still from 5 to 15% by weight, of one or more cationic polymers relative to the total weight of composition A.

The pH of the composition A which contains the cationic polymer or polymers is basic, more preferably greater than or equal to 8, more preferably between 8 and 1 1, more preferably between 9 and 10.5.

In the process of the invention, a composition A comprising the cationic polymer (s) is applied in pretreatment, before application of the anionic direct dye (s).

The essays :

Compositions A or B that are useful in the process of the invention generally comprise water or a mixture of water and one or more organic solvents or a mixture of organic solvents.

By organic solvent is meant an organic substance capable of dissolving or dispersing another substance without chemically modifying it. Examples of organic solvents that may be mentioned are lower C 1 -C ₄ alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, dimethyl sulfone, and aromatic alcohols such as benzyl alcohol or phenoxyethanol .

The organic solvents are present in proportions preferably of between 0.5 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 0.5 and 30% by weight approximately.

The additives :

Compositions A and B which are useful in the dyeing process according to the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants. or mixtures thereof, polymers other than those previously described, thickeners, in particular anionic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, agents dispersants, conditioning agents.

Typically, compositions A and / or B generally contain surfactants and / or thickeners.

The adjuvants above are generally present in an amount for each of them between 0.01 and 40% by weight relative to the weight of the composition, preferably between 0.1 and 20% by weight relative to the weight of the composition.

Compositions A and B useful in the present invention may be in various galenic forms, such as a powder, a lotion, a mousse, a cream, a gel or in any other form suitable for dyeing keratinous fibers. They can also be packaged in a pump bottle without propellant or under pressure in an aerosol bottle in the presence of a propellant and form a foam.

The pH of these compositions can be adjusted to the desired value by means of basifying agents or from acidifying agents usually used for dyeing keratin fibers or else using conventional buffer systems. Among the acidifying agents of the compositions used in the invention, mention may be made, for example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid and carboxylic acids as defined above. such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.

These alkalinizing agents are bases for increasing the pH of the compositions in which it is located. The basifying agent is a Bronsted, Lowry or Lewis base. It can be mineral or organic.

As alkalinizing agents, mention may be made of: i) (bi) carbonates, ii) ammonia, iii) alkanolamines such as mono-, di- and triethanolamines and their derivatives iv) ethylenediamines oxyethylenated and / or oxypropylenes, v) mineral or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii) amino acids such as arginine, lysine, ornithine, citruline and histidine, glycine and viii) the compounds of formula (XVII) below:

N - W - N c ^d (XVII)

Formula (XVII) wherein W is a divalent (C 1 -C 8) alkylene radical optionally substituted by at least one hydroxyl group or at least one (C 1 -C 4) alkyl radical and / or optionally interrupted by at least one heterotatome such as oxygen, sulfur or by a group -N (R _e ) -; R _a , Rb, R _c , Rd and R _e , identical or different, represent a hydrogen atom, a (C 1 -C 4) alkyl or hydroxy (C 1 -C 4) alkyl radical, preferably W represents a propylene radical.

Staining process

According to a first particular embodiment of the invention, the dyeing method implements the application of one or more cationic polymers, followed by the application of one or more anionic dyes. The implementation can be carried out by the application of a composition A which contains one or more cationic polymers followed by the application of a coloring composition B which contains one or more anionic direct dyes.

The application of composition A may be followed by rinsing with water before application of coloring composition B.

According to the process of the invention, the cationic polymer (s) is applied, then, optionally after a laying time, the anionic direct dye (s) are applied.

After application of the cationic polymer (s) or composition A containing them, the exposure time may be between 1 minute and 2 hours, more particularly between 2 minutes and 1 hour, preferably between 3 and 30 minutes.

The application and the laying of compositions A and B are generally carried out at a temperature of between 20 ° C. and 150 ° C., preferably between room temperature (25 ° C.) and 100 ° C. To implement the hair coloring at high temperatures for example between 50 and 100 ° C, it is for example possible to treat the hair with a straightener after application of the coloring composition. Preferably, the anionic direct dye (s) are applied directly after the application of the cationic polymer (s), without the laying time and with an intermediate rinsing between the two steps of the dyeing process. The dyeing process of the invention may be followed by a rinsing and / or washing step with one or more shampoos, followed by one or more rinsing with water of the keratin fibers and optionally followed by drying by heating. preferably at a temperature of between 30 and 60 ° C.

Heating drying products include a hair dryer, a hair helmet, a hair straightener, a hair curling iron, an infrared ray dispenser and other conventional heaters.

The following examples serve to illustrate the invention without being limiting in nature.

EXAMPLES OF COLORING

Example 1

The following compositions are prepared in the proportions indicated in grams:

Aqueous composition A containing the cationic polymer (A),

Coloring composition B comprising the acid direct dyes

Ingredients (INCI Name) (Y (B) (g%)

GLYCINE 1

LACTIC ACID 2 ma

DIMETHYL SULFONE 6

Cl 19140 0.01

Cl 15510 0.2

Cl 60730 0.07

Cl 16255 0.05

ACID BLACK 1 (Cl 20470) 0.07

PH ENOXYETH ANOL 0.5

BENZYL ALCOHOL 5

CARBOMER 2,5

POLYACRYLAMIDE (and) C13-14 ISOPARAFFIN

2

(and) LAURETH-7 (*)

DIPROPYLENE GLYCOL 2

ETHANOL 7

WATER 71.4 ( ^* ) Sepigel 305 (Seppic)

The pH of composition B is 3.5.

The method for dyeing keratinous fibers is implemented according to the following procedure.

Pretreatment:

The composition (A) is applied to a lock of 90% white Caucasian hair previously washed with Elsève multivitamin shampoo. The ratio of bath Composition A / Wick is 1/1 (by weight)

- After an exposure time of 5 min at 33 ° C, the wick is rinsed with water.

Coloring:

The coloring composition B described above is applied to the rinsed wick. The bath ratio Composition B / Wick is 4/1 (by weight). After a laying time of 15min / 40 ° C, the lock is rinsed and washed with Elsève multivitamin shampoo.

Example 2 (comparative)

The composition B described in Example 1 is applied to a lock of 90% white Caucasian hair previously washed with Elsève multivitamin shampoo and which has not been pretreated with the composition A.

The bath ratio composition B / wick is 4/1 (by weight). After a laying time of 15min / 40 ° C, the lock is rinsed and washed with Elsève multivitamin shampoo.

Color results

The color of the locks was evaluated in the CIE L ^* a ^* b ^{* system} using a Minolta Spectrophotometer CM3600D colorimeter. In this system L ^* a ^* b ^* , the three parameters denote respectively for L ^* the intensity of the color, a ^* the green / red color axis and b ^* the blue / yellow color axis.

The color is evaluated by the color difference ΔΕ between the wick before treatment and the wick after staining: the higher the value of ΔΕ, the greater the power of the hair coloring is important. This value is calculated from the following equation:

ΔE = - L ₀ ^* ) ² + (a ^* - a ₀ ^* ) ² + (b ^* - b ₀ ^* ) ² In which L ^* , a ^* and b ^* represent the values measured on locks of hair after staining , and Lo ^* , ao ^* and bo ^* represent the values measured on wicks before treatment.

As shown in the table below, the wick pre-treated with composition A followed by a staining step with composition B exhibits more intense staining, as well as a larger increase in color than wick. not having undergone pretreatment (Example 2).

Example 3: Comparative

The procedure of Example 1 is repeated by substituting the polymer of Example 1 for a composition containing poly dimethyl diallyl ammonium chloride in 40% water (Polyquaternium-6 sold under the name Merquat 100 © by Lubrizol). The coloration obtained on the fibers is then measured according to the method described above. We obtain the results below.

These results show that with the process of the invention, a coloration superior to that obtained with a composition containing polyquaternium-6 is obtained.

EXAMPLE 4

The following compositions were made (% by weight). The evaluation of the skin tachage was performed according to the protocol below.

Aqueous composition A4 containing the cationic polymer (A),

it is so p = 5

B4 coloring composition comprising acid direct dyes (% by weight and active material)

Each of the compositions A4 and A4C is applied pre-treatment on a skin sample. After a pose of 5 min, the composition is rinsed. The composition B4 which contains anionic direct dyes is then applied to the 2 skin samples which have been pre-treated previously and to a skin sample which has not undergone pre-treatment.

After 10 minutes of exposure, the 3 skin samples on which the dye composition is applied are washed with a shampoo and then dried with a towel.

The intensity of the skin coloration is then visually assessed.

The intensity of the coloration is much greater on the skin sample that has not been pre-treated with the composition A4 or A4C.

The intensity of the staining is substantially lower when the skin sample has been treated with the A4 composition than that obtained with a pretreatment with the A4C composition.

These results show that the hair dyeing method according to the invention makes it possible to reduce the scalp tachage during hair dyeing by means of anionic direct dyes.

Claims

REVE NDI CATIO NS

1. A process for dyeing keratin fibers which comprises the application of a composition A having a basic pH comprising one or more cationic polymers chosen from quaternary diammonium polymers comprising recurring units of the following formula (I), followed by application of one or more anionic direct dyes,

R 1 3 R 15

N + - A ₁ - NH- B.

II ¹

R <^ † 4 X- <1 "8 ^x"

(I)

in which :

- R13, R14, R15 and R16, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or from C1-C12 hydroxyalkylaliphatic radicals,

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

it being understood that A1, R13 and R15 can form with the two nitrogen atoms to which they are attached a piperazine ring; in addition, if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 may also denote a (CH2) n -CO-D-OC- (CH2) p- group, with n and p, which are identical or different, being integers varying from 2 to 20, and D denoting:

a) a glycol residue of formula -O-Z-O-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas:

(CH 2 CH 2 O) x-CH 2 CH 2 - and - [CH 2 CH (CH 3) O] y -CH 2 CH (CH 3) - where x and y denote an integer of 1 to 4, representing a defined and unique degree of polymerization or any number of 1 at 4 representing an average degree of polymerization;

b) a bis-secondary diamine residue such as a piperazine derivative; c) a bis-primary diamine residue of formula -NH-Y-NH- where Y denotes a linear or branched hydrocarbon radical, or the divalent radical -CH 2 -CH 2 -S-S-CH 2 -CH 2 -;

d) a ureylene group of formula -NH-CO-NH-.

2. The method of dyeing according to claim 1 above wherein the cationic polymer or polymers are chosen from quaternary diammonium polymers comprising recurring units of formula (II):

in which R1, R2, R3 and R4, identical or different, denote an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms, n and p are integers ranging from 2 to 20, and X- is an anion derived from an inorganic or organic acid, preferably the polymer in which R 1, R 2, R 3 and R 4 represent a methyl radical, n = 3, p = 6 and X = Cl, called Hexadimethrine chloride according to the INCI nomenclature (CTFA).

3. Coloring process according to any one of the preceding claims, in which the acid direct dye (s) are chosen from acidic nitro dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes and acidic indoamine dyes. acidic anthraquinone dyes, indigoids and acidic natural dyes.

4. The method of dyeing according to any one of the preceding claims wherein the composition A which contains the cationic polymer or polymers has a pH greater than or equal to 8, more preferably between 8 and 1 1, more preferably between 9 and 10, 5.

5. The method of dyeing according to any one of the preceding claims wherein the composition B which contains the anionic direct dye (s) has an acidic pH, preferably between 2 and 6.5, better still between 2.5 and 6.

6. Coloring method according to any one of the preceding claims wherein the anionic direct dye or dyes are applied after application of the cationic polymers after an exposure time of between 1 minute and 2 hours, more particularly between 2 minutes and 1 hour, preferably between 3 and 30 minutes h, A dyeing method according to any one of the preceding claims, wherein the composition A is an aqueous composition which comprises from 0.1 to 25% by weight, preferably from 1 to 20% by weight, better from 5 to 15% by weight of one or more cationic polymers, relative to the total weight of composition A.

The method of coloring according to any one of the preceding claims, wherein the composition B is an aqueous composition which comprises between 0.001 to 20% by weight, preferably from 0.005 to 10% by weight, more preferably from 0.01 to 5% by weight. weight of one or more anionic direct dyes relative to the total weight of composition B.

8. Use of one or more cationic polymers in pretreatment of hair coloring from anionic direct dyes to reduce tachage of the scalp.

9. A hair dyeing kit comprising a composition A comprising one or more cationic polymers as defined in any one of the preceding claims and a composition B comprising one or more anionic direct dyes as defined in any one of the preceding claims. .