AU723806B2 - Composition for dyeing keratin fibres with a cationic direct dye and a thickening polymer - Google Patents

Description

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Applicant(s):

L'OREAL

Invention Title: COMPOSITION FOR DYEING KERATIN FIBRES WITH A CATIONIC DIRECT DYE AND A THICKENING POLYMER.

*c

C

C*

The following statement is a full description of this invention, including the best method of performing it known to me/us: COMPOSITION FOR DYEING KERATIN FIBRES WITH

A

CATIONIC DIRECT DYE AND A THICKENING

POLYMER

The invention relates to a: composition for dyeing keratin fibres, in particular human keratin fibres such as the hair, comprising, in a medium which is suitable for dyeing, at least one cationic direct dye of given formula and at least one specific thickening polymer.

The invention also relates to the dyeing 10 processes and dyeing devices using the said composition.

Two types of dyeing may be distinguished in the haircare sector.

The first is semi-permanent or temporary dyeing, or direct dyeing, which uses dyes capable of S:.giving the hair a natural coloration, a more or less pronounced colour change which may withstand shampooing several times. These dyes are also known as direct dyes; they can be used with or without an oxidizing agent. In the presence of an oxidizing agent, the aim is to obtain lightening dyeing. Lightening dyeing is carried out by applying a mixture, prepared at the time of use, of a direct dye and an oxidizing agent to the hair, and makes it possible in particular to obtain, by lightening the melanin in the hair, an advantageous effect such as a unified colour in the case of grey hair, or to bring out the colour in the case of naturally pigmented hair.

The second is permanent dyeing or oxidation dyeing. This is carried out with so-called "oxidation" dyes comprising oxidation dye precursors and couplers.

Oxidation dye precursors, commonly known as "oxidation bases", are compounds which are initially colourless or weakly coloured which develop their dyeing power on the hair in the presence of oxidizing agents added at the time of use, leading to the formation of coloured compounds and dyes. The formation of these coloured 10 compounds and dyes results either from an oxidative 0.

condensation of the "oxidation bases" with themselves or from an oxidative condensation of the oxidation bases with coloration-modifying compounds commonly known as "couplers", which are generally present in the dye compositions used in oxidation dyeing.

It is known practice to add direct dyes to oxidation dyes in order to vary the shades obtained with the said oxidation dyes or to enrich the shades with glints.

Among the cationic direct dyes available in the sector of dyeing keratin fibres, in particular human keratin fibres, the compounds whose structure is developed in the text hereinbelow are already known; nevertheless, these dyes lead to colorations which have characteristics that are still unsatisfactoryboth as regards the homogeneity of the colour distributed along the fibre, in which case the coloration is said to be too selective, and as regards the staying power, in terms of the resistance to the various attacking factors to which the hair may be subjected (light, bad weather, shampooing).

After considerable research conducted in this matter, the Applicant has now discovered that it is possible to obtain novel compositions for dyeing keratin fibres which are capable of giving less selective colorations which show good resistance to the various attacking factors to which the hair may be o 10 subjected, by combining at least one specific thickening polymer with at least one known cationic direct dye of the prior art, which have the respective *e* formulae defined below.

This discovery forms the basis of the present invention.

A first subject of the present invention is thus a composition for dyeing keratin fibres, and in particular human keratin fibres such as the hair, containing, in a medium which is suitable for dyeing, at least one cationic direct dye whose structure corresponds to formulae to (IV) defined below, characterized in that it also contains (ii) at least one specific thickening polymer.

The cationic direct dye which can be used according to the present invention is a compound chosen from those of formulae (III), (III') and (IV) below: 4 a) the compounds of formula below: A-D=D- N (I)

R,

in which: D represents a nitrogen atom or a -CH group, R, and which may be identical or different, 5 represent a hydrogen atom; a Cl-C 4 alkyl radical which can be substituted with a -CN, -OH or -NH, radical or form, with a carbon atom of the benzene ring, a heterocycle optionally containing oxygen or nitrogen, which can be substituted with one or more Ci-C 4 alkyl radicals; a 4'-aminophenyl radical,

R

3 and R' 3 which may be identical or different, represent a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a clano radical, or a Ci-C, alkyl, CI-C 4 alkoxy or acetyloxy radical, X- represents an anion preferably chosen from chloride, methyl sulphate and acetate, A represents a group chosen from the structures Al to A19 below: R4

-N

A,

R.

NZ

R4

S.

S.

S

S.

A

4

R

4 R 4

-N

4 N

I

R

4

A

7 R4

N-N+

R

4

A

5 4 N

A,

R4 /R4

N=N+

R ,R4 N-N

N

I

R

4

A,

R4 R4 N

I

R

4 Ag

R

4 0N+

N

4

/R

E N r R4

N-N+

S'

A13 4 s

R

R

Ala

A

17 A 1 and

R

4 in which R, represents a C 1

-C

4 alkyl radical which can be substituted with a hydroxyl radical and R 5 represents a Cl-C, alkoxy radical, with the proviso that when D represents -CH, when A represents A 4 or A, 1 and when R 3 is other than an alkoxy radical, then R, and R 2 do not simultaneously denote a hydrogen atom; b) the compounds of formula (II) below: B-N=N- (II) X- wc R9 in which:

R

6 represents a hydrogen atom or a Cl-C 4 alkyl radical, R, represents a hydrogen atom, an alkyl radical which can be substituted with a -CN radical or with an amino group, a 4'-aminophenyl radical or forms with RG a heterocycle optionally containing oxygen and/or nitrogen, which can be substituted with a Cz-C 4 alkyl radical, R. and R 9 which may be identical or different, represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine or fluorine, a C 1

-C

4 alkyl or 10 C 1

-C

4 alkoxy radical or a -CN radical, X- represents an anion preferably chosen from chloride, methyl sulphate and acetate, B represents a group chosen from the structures B1 to B6 below: Rioo Rio NN+ N- N+ N- o S S N S

R,,

B1 B2 B3

N+,

84 B5 Ro and B6 i

S

49 in which R 0 represents a Cz-C 4 alkyl radical, and

R,

2 which may be identical or different, represent a.

hydrogen atom or a C 1 alkyl radical; c) the compounds of formulae (III) and (III') below:

R

14 E-Dl D--N in which:

R,

3 represents a hydrogen atom, a C 1

-C

4 alkoxy radical, a halogen atom such as bromine, chlorine, iodine or fluorine, or an amino radical,

R

1 represents a hydrogen atom, a C 1

-C

4 alkyl radical or forms, with a carbon atom of the benzene ring, a heterocycle optionally containing oxygen and/or substituted with one or more C 1 alkyl groups,

R,

1 represents a hydrogen atom or a halogen atom such as bromine, chlorine, iodine or fluorine,

R

1 6 and R 17 which may be identical or different, represent a hydrogen atom or a Cl-C, alkyl radical, Di and D 2 which may be identical or different, represent a nitrogen atom or a -CH group, m 0 or 1, it being understood that when R 13 represents an unsubstituted amino group, then D, and D 2 simultaneously 10 represent a -CH group and m 0, X- represents an anion preferably chosen from chloride, methyl sulphate and acetate, E represents a group chosen from the structures El to E8 below:

R'-N+

SER'

E1 E2- 0 E3 0 N 1

N+

E4

S.

S

S* S S.

SO*

t5**

S

5.

S

S

S. 5

S.

5> 55 E6 E7 E8 and in which RI represents a C 1

C

4 alkyl radical; when m. 0 and when D, represents a nitrogen atom, then -10E can also denote a group of structure E9 below:

R!

N

E9 which R, represents a Cl-C 4 alkyl radical; d) the compounds of formula (IV) below: G-N -N -J in which: 11 the symbol G represents a group chosen from the structures G, to G 3 below: N+ N+ I X" I x- Rig

RIB

G, G 1M%4J: eM

G

3 in which structures G, to G 3 R denotes a Cz-C 4 alkyl radical, a phenyl radical which 5 can be substituted with a Cz-C, alkyl radical or a halogen atom chosen from chlorine, bromine, iodine and fluorine;

R,

9 denotes a Cz-C 4 alkyl radical or a phenyl radical;

R

20 and R 21 which may be identical or different, represent a C 1

-C

4 alkyl radical, a phenyl radical or together form, in G 1 a benzene ring substituted with one or more C 1

-C

4 alkyl, C 1

-C

4 alkoxy or NO 2 radicals or together form, in G 2 a benzene ring optionally substituted with one or more C 1

-C

4 alkyl, Cz-C 4 alkoxy or

NO

2 radicals;

R

20 can also denote a hydrogen atom; Z denotes an oxygen or sulphur atom or a group -NR 19 M represents a -CH, -CR (R denoting C.-C 4 alkyl) or

-NR

22 group; K represents a -CH, -CR (R denoting Ci-C, alkyl) or

-NR

22 group; P represents a -CH, -CR (R denoting alkyl) or

-NR

22 group; r denotes zero or 1;

R

22 represents an atom a C 1

-C

4 alkoxy radical or a Cl-C, alkyl radical;

R

23 and R 24 which may be identical or different, represent a hydrogen atom, a halogen atom chosen from Schlorine, bromine, iodine and fluorine, a CI-C 4 alkyl or alkoxy radical or an -NO 2 radical; SX- represents an anion preferably chosen from chloride, iodide, methyl sulphate, ethyl sulphate, acetate and perchlorate; o Swith the proviso that, o. if R 22 denotes then r denotes zero; if K or P or M denote Ci-C 4 -N-alkyl then R 23 or R 24 is other than a hydrogen atom; if K denotes -NR 22 then M=P= -CH, -CR; if M denotes -NR 2 then K=P= -CH, -CR; if P denotes -NR 22 then K=M and denote -CH or -CR; if Z denotes a sulphur atom with R 2 1 denoting Cl-C 4 alkyl, then R 20 is other than a hydrogen atom; if Z denotes -NR 22 with R, 1 denoting C 1

-C

4 alkyl, then at least one of the radicals R 18

R

2 0 or R 21 of G 2 is other than a CI-C, alkyl radical; the symbol J represents: a group of structure J 1 below:

RJ,

in which structure J 1

R

25 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a C--C, alkyl or Ci-C, alkoxy radical, a radical -OH, -NO 2

-NHR

28

-NR

29

R

30 -NHCO (C,-C 4 alkyl, or forms with R 26 a or 6-membered ring which may or may not contain one or 10 more hetero atoms chosen from nitrogen, oxygen and sulphur;

R

26 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a C,-C, alkyl or Ci-C, alkoxy radical or forms, with R 2 or R 2 a 15 5- or 6-membered ring which may or may not contain one or more hetero atoms chosen from nitrogen, oxygen and sulphur;

R

27 represents a hydrogen atom, an -OH radical, a radical -NHR 2 8 or a radical -NR 2 9

R

30

R

28 represents a hydrogen atom, a Cj-C 4 alkyl radical, a Cl-C, monohydroxyalkyl radical, a C 2

-C

4 polyhydroxyalkyl radical or a phenyl radical;

R

29 and R, 3 which may be identical or different, represent a alkyl radical, a C 1

-C

4 monohydroxyalkyl radical or a C 2 polyhydroxyalkyl radical; a 5- or 6-membered nitrogenous heterocyclic group which can contain other hetero atoms and/or carbonyl groups and which can be substituted with one or more Cl-C 4 alkyl, amino or phenyl -radicals, and in particular a group of structure J 2 below: (UNJ2

N

0 3 in which structure J 2

R

31 and R 32 which may be identical or different, represent a hydrogen atom, a C 1

-C

4 alkyl radical or a 10 phenyl radical;

CH

3 Y denotes the -CO- radical or the radical a.

n 0 or 1, with, when n denotes 1, U denoting a -COradical.

In the structures to (IV) defined above, the Ci-C, alkyl or alkoxy group preferably denotes methyl, ethyl, butyl, methoxy or ethoxy.

The cationic direct dyes of formulae (III) and (III') which can be used in the dye compositions in accordance with the invention are known compounds and are described, for example, in patent applications WO 95/01772, WO 95/15144 and EP-A-0,714,954. Those of formula (IV) which can be used in the dye compositions in accordance with the invention are known compounds and are described, for example, in patent applications FR-2,189,006, FR-2,285,851 and FR-2,140,205 and its Certificates of Addition.

Among the cationic direct dyes of formula (I) which can be used in the dye compositions in accordance with the invention, mention may be made more particularly of the compounds corresponding to the structures (II) to (154) below: t

C

C

+JH-CH

3 Cl.

CH3 CN CH3

N=N

-4 N+ CH3

CH

3 cl. (12) 0SSO

C

@0 C*O0

S

0* 5000 0

S*

U C 0@ *S S C

S

0050 C 00 00 S 0000

SO

S.

C

0005 em..

0 @400 50 S P 0 S. 0 0@

S.

H

3 C-N/ -CHCH N CH 3

CH

3 Cr (13) CH 3 CH CH

NH

CI. (14)

H

3 C-ND -CH-CH-/

CH

3

C

2

H

4

CN

/CH3

CH

3 CI* Cl. (16) Cl. (17)

CH

3 9 a.

CI* (19) CF (ll 18 N+H CAH N CF, (112) N

C

2

HS

CH3 NCl (13 N 4H -CN

CH

3 CH3 N=N

'NH

2 C 14

N-

CH3 -CH3 fj- N NH 2 CF, (115)

CH

3

C

CH

3

CH

3 .13 N= H /N

HH

HOj tHNHO\H0 +ND (OZI) .13 N N=N H N EHO Ho H O +ND .13 N N=N H N

HO

HOO

CR33 CD I c HO

_N

(8wi) .10 N=NK-i1 .0 cHO SHEO -P (LLI) .10 N -N=N /I

CHH

Ho

CH

3 IIiN=N N CI.

-a CH H-CN

NCH

3

CH

3 (122) (123) 3

KI

CH

3

CH

3

S

S. *S S S

S

S. S

S*

S

SS

S.

/CH 3

*N\

CH

3 (124) (125) (126)

CH

3 C/ NH 2 S -a 21

CH

3 /N CH 2

-CH

2

-CN

N=N -N s

CH

3 Cl (127)

,CH

3 0-CH 3 Ni- N= -0

NH

2 CH 30-CH 3 CN+

H

3 N- CH 3

CH

3 CH 3 H 3 C-N+ -N=N OI- (128) CI- (129) fCH3 Cl* (130)

CH

3

NH

2 CI* (131) ci. (132)

-CH

3 N.

CH

3 N CH 3 (133)

S*

S. S

S.

q S CHi-N+ Cl. (134) CI- (135) C1 (136)

S.

S S SSS S S. S 55

"CH

3 Cl. (137) CI* (t38)

CH

3 1

R

N H3

H

3 C-0 N=N

N

CH 3 O-CH3 99 4 4.99 94e9 9 4 9 9999 99 99 99 9 9 /CH 3 *N

CV

CH

3 3 C1* (140) 3 3 CI- (141) (139) 9 9..99 9* *9 9 99 S 9 49 9 9*

N+

N+ C"

CH

3 a a a. a N-'S C H 3 l -N=NN \C C (142)

H

3 C N 3

CH

3

CH

3

CN,

I /"NNO -N /NH cI (143)

CH

3

CH

3 CN+ CH 3 N= CF (144)

CH

3 H

CHCH

3 -N=N NH\ CI- (145)

ON

CFM

3 IS+ N CH3C (146) s

OH

3 0CH 3 /CH3

CH

3

OH

3

I

*.of

C

2

H

CN+ N=N N/ C3

CH

3 CI* (147)

CH

3 S0 4 (148)

CH

3 S0 4 (149) CI. (150) cI* (11)

CH

3 O-CH 3 ChN+ N=N

NH

2

CH

3

O-CH

3 CH 3 N=N N/ NC c1 (152)

CH

N CHN C (52)

CH,

CH

3 NN+ N=N N CH 3 S0 4 (153) S

CH

3

CH,

9 N+ CHf-CH,-CN (N=N N C" (154) -a S

CH,

structures (114) and (131) 5 Among the compounds of structures (Ii) to (154) described above, the ones most particularly preferred are the compounds corresponding to the o structures (114) and (131) Among the cationic direct dyes of formula (II) which can be used in the dye compositions in accordance with the invention, mention may be made more particularly of the compounds corresponding to the structures (II1) to (119) below: S Ci- (1|1) H3C CH 3 a a a. a a /CH 3 I

CH

CHO+ N=NN

CM

1 CH3

CH

IN 3

H

CN

CH

3

H

3 C N I

CH

3

CH

3 H

CH

3 (113) CI. (112) CI- (114)

CH

3 S0 4 (115)

CH

3

SO

4 (116)

CH

3

N+

CH 3

H

3 CH3

CH

3 S0 4 -(117) /CH 3

N

CH

3

CH

3 S0 4 -(118)

U

9

U

*5*e

U

*9*U

U

9. U and CH3 N*N+ NNN/CH 3

H

2 N CH 3 CH3so 4 (119) Among the cationic direct dyes of formula (III) which can be used in the dye compositions in accordance with the invention, mention may be made more 5 particularly of the compounds corresponding to the structures (1111) to (11118) below:

S

N

CH

3

CHN

CI. (1111) 0 HC\) O CH3 I C II CH 3 0 H3C\N)J +CH I

I

H

3 Clz CH;r 3 (1112) 9 9 *9 9 99 9 9*

H

3 C-ND' CH=N-N

CH

3 CH 3 S0 4 -(1114)

H

3 C-ND+ CH=N-N

OCH

3 Ior Cl, (1115)

CH

3 S0 4 (1116)

CH

3 S0 4 (1117)

H

3 CH~l C :1 (118

H

3 C-N+ -CH=N-N- CI

CH

3 *54* 9 9~9 9

CH

3 S0 4 N+ CH 3 CH 3 C CH=N-N( CH3S0 4 (11111) CH 3 C CH=N-N-

CH

3 S0 4 (11112) CH 3 H 3 -CH=N-N OCH 3

CH

3 SO4 (11113)

L

CH 3 KN N OCH 3 C" (11114)

CH

3

H

3 C-No -CH=CH NH 2

CH

3 COO (116 -a a i a a HC-NO+

CI-N-/"

CH

3

OH

CI o N=N-b C1 CI1 (11117) *and (11118) Among the specific compounds of structures (1111) to (11118) described above, the ones most particularly preferred are the compounds corresponding to the structures (1114), (1115) and (11113).

Among the cationic direct dyes of formula (III') which can be used in the dye compositions in accordance with the invention, mention may be made more particularly of the compounds corresponding to the structures (III'1) to (III'3) below: (111-1)

C

r C

C.

C. q C. C

C

CI (1112) ;and

CH

3

-N+

L I CI (1113) Among the cationic direct dyes of formula (IV) which can be used in the dye compositions in accordance with the invention, mention may be made more particularly of the compounds of structures (IV) 1 to below: 33 aNIN N N (IV), N+ N=N /\OH

(IV)

2 0

NHCOCH

3

S...H

N+ b N1%P (IV)4 N=N 2

I-

S 50

H

3 C N+ N=N NN IH 2

C

2

O

-a CH 2

CH-

2 0-H 0

H

3 C N+ N=N 'O \I~ I-

C

2

H

0

~,CH

3

H

3 0 N+ N=N N (IV)v 0 0 N+ N=

[V

I-

CH

0 N+ N=N N 3

CH

3 N+ N= N. HC2H (V1 'NCH0 0

CH

3 N+ N-N-

I-

0

H

3 C N+ N=N I 0

(IV)

13

(IV)

14

S

S S (IV)is

CKCH

N+ N=N /a C N 3 a.

C

NNI CH 3 N+N=N

I

CH 3 0 (tV) 17 CH3 NHCOCH 3 N+ N=N N IN MI I CH3 0 N+ N=N -N/3 I

CH/

0 4 [V 00 7

~CH

3 N+ N1- *C 2

H

5 ('V)21

H

N+ &>N(25 (IV) 22

~C

2

H

CH3 0 .OS HO t HO a-AHo~ I HO A) HO HO zHO N

N=N

HO HOHzHO 0

+N

9A1£HN N=N'-iII -0 vP(AI) HON0 NN4 H ND 1

IKIII

C~CH3 N+ N=N /NH 2 (v) 2 &H3 CH 3 S80 4

CH

3 9. I -CH2CH20H N+ N=N NH C2H (3

CH

3

CK

3 S0 4 N--a OH 3 3 1

CH

3 S0 4

XC

N+ N-N N 3 (IV)32 N+ N N ON

%%OH

3

CH

3 S0 4 39 H 3c N+ NN -Nz([V)U CH3SO:

H

3

C

CrN N=NNZ \(IV) 3 I H

CH

3

SO;

NHCOCH,

I N+ N-N N" CH 3 CH 3 3

CH

3 SO4;

N.SC

CH 3 (IV) 37 N+

CH

3

SO

4 CH 3

=N

rN CH 3 ('V)38

H

3 C N+ CH 3

SO

4

CH

3

H

3

C

N-N

CH

3

I.CH

3 (IV) 3 0 Ni CAHS0; -b *N CI

IV

N+

CH

3

SO

4

CH

3

CY=N

N+C

2

H

5

SO

T

0 2

H

H

3

C

N NN"

CH

3 ~~CH3 (I'I)43 a a a q a a a.

('V)44 0

CA

CHASO

('V)46

CH.

o 3 ('V)46

CH

3

,CH

3 N- NN

(IV)

47

CH

3 410 N+ N=(V) 2

CH

3

NOH

3 =N NHH 2 V4 s 0

H

3 C N= NH(tV) 5 0 6 10

OH

£1 p 43

S

N=N 1 N

CH

3

OH

(IV)

5 1 a a a a.

(IV)

52 N+ N=N

I-

0

CH

3 N+ OH NHCOCH 3 ('V)54 N+ N N (IV) 5 4 CH 3 0

CH

3 N=N /\OH (IV)6, 0

CH

3 N=N /\OH (IV)A8 4* 0 000C

CH

3 N-N (IV)6, I -a N CH 3 0

OH

CH

3 N+ N=N O0Hl~s

CH

3 N+1~1% N=N N I~o o CH 3 G 900*NO 2 *Cal N=N OH (IV) 62 N0 N= 00 3 ('V)6 4

CH

2

H

3 C N+ N=N OH (IV) 6 0

CH

3

CH

3

CH

3 N=N 'OH (IV)m 0

CH

3 CH3 N-N ,N\ CH IV)S7 I

NH

2

CH

3

SO

4 Cal N+ N- (IV)u 0 2-H0

N)

47

~C

3 HO N "N ii

CHASO;

NH

2 N+ N=N /\NH 2 0

CH

3 0

H

N

KN+ N=N 0I) 7 S OS0 0 CH3 N=N

NH-

2 I N+ (IV)n CH3

H

2

CH

2

OH

48

)CH

3 &CH0

~H

3

CH

3

SO;

(IV),

4 &3

CH

3

SO

4

CH

(IV)

76 /CH3

N=N-

kH CH 3

SO

4 The cationic direct dye(s) used according to the invention preferably represent(s) from 0.001 to by weight approximately relative to the total weight of the dye composition and even more preferably from 0.005 to 5% by weight approximately relative to this weight.

(ii) The thickening polymer which can be used according to the present invention is chosen from the group consisting of: 1- crosslinked acrylic acid homopolymers; 2- partially or totally neutralized 2-acrylamido-2-methylpropanesulphonic acid homopolymers and copolymers; 3- ammonium acrylate homopolymers and copolymers of ammonium acrylate and of acrylamide; 4- crosslinked copolymers of (meth)acrylic acid and of Cl-C 6 alkyl acrylate; 5- nonionic homopolymers and copolymers containing monomers containing ethylenic 9* unsaturation of ester and/or amide type.

Among the crosslinked acrylic acid homopolymers which may be mentioned, for example, are the products sold under the names Carbopols 980, 981, 954, 2984 and 5984 by the company Goodrich or the products sold under the names Synthalen M and 0* Synthalen K by the company 3 VSA.

Among the 2-acrylamido-2-methylpropanesulphonic acid homopolymers which may be mentioned are those described in patent application EP-A-0,815,828 (which forms an integral part of the content of the description). Mention may also be made of the product sold by the company Henkel under the name Cosmedia HSP 1160. Among the 2-acrylamido-2-methylpropanesulphonic acid copolymers which are partially or totally neutralized (with a base such as sodium hydroxide, potassium hydroxide or an amine), mention may be made in particular of the product described-in Example 1 of document EP-A-503,853 (which forms an integral part of the content of the description), and in particular the product sold by the company SEPPIC under the name Sepigel 305.

Among the ammonium acrylate homopolymers which may be mentioned are the product sold under the 10 name Microsap PAS 5193 by the company Hoechst. Among the copolymers of ammonium acrylate and of acrylamide which may be mentioned are the product sold under the name Bozepol C Nouveau or the product PAS 5193 sold by the company Hoechst (which are described and prepared 15 in documents FR 2,416,723, USP 2,798,053 and SUSP 2,923,692).

Among the crosslinked copolymers of (meth) acrylic acid and of C 1 -C alkyl acrylate which may be mentioned are the product sold under the name Viscoatex 538C by the company Coatex, which is a crosslinked copolymer of methacrylic acid and of ethyl acrylate as an aqueous dispersion containing 38% active material, or the product sold under the name Aculyn 33 by the company R6hm Haas, which is a crosslinked copolymer of acrylic acid and of ethyl acrylate as an aqueous dispersion containing 28% active material.

Among the nonionic homopolymers or copolymers containing monomers containing ethylenic unsaturation of ester and/or amide type, mention may be made of the products sold under the names: Cyanamer P250 by the company Cytec (polyacrylamide); PMMA MBX-8C by the company US Cosmetics (methyl methacrylate/ethylene glycol dimethacrylate copolymer); Acryloid B66 by the company R6hm Haas (butyl methacrylate/methyl methacrylate copolymer); BPA 500 by the company Kobo (polymethyl methacrylate).

According to the present invention, it is o 10 more particularly preferred to use the thickening polymers listed above in classes i.e.

those chosen from the group consisting of: 1- crosslinked acrylic acid homopolymers; 2- partially or totally neutralized 2-acrylamido-2-methylpropanesulphonic acid homopolymers and copolymers; 3- ammonium acrylate homopolymers and copolymers of ammonium acrylate and of acrylamide; 4- crosslinked copolymers of (meth)acrylic acid and of Cl-C, alkyl acrylate.

The thickening polymer(s) (ii) used according to the invention preferably represent(s) from 0.01 to by weight approximately relative to the total weight of the dye composition and even more preferably from 0.1 to 5% by weight approximately relative to this weight.

The medium which is suitable for dyeing (or support) generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which would not be sufficiently watersoluble. As organic solvents, mention may be made, for example, of lower alkanols such as ethanol and isopropanol; aromatic alcohols such as-benzyl alcohol, as well as similar products and mixtures thereof.

The solvents can be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

The pH of the dye composition in accordance with the invention is generally approximately between 2 and 11 and preferably approximately between 5 and It can be adjusted to the desired value using acidifying or basifying agents usually used for dyeing S S 15 keratin fibres.

Among the acidifying agents, mention may be [-made, by way of example, of inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, *5 tartaric acid, citric acid and lactic acid, and sulphonic acids.

Among the basifying agents, mention may be made, by way of example, of aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula below: NW-N (V) Rs/ R3 in which W is a propylene residue optionally substituted with a hydroxyl group or a Cl-CG alkyl radical; R 33

R

34

R

3 s and R 36 which may be identical or different, represent a hydrogen atom or a alkyl or Cz-C 6 hydroxyalkyl radical.

In addition to the cationic direct dye(s) (i) defined above, the dye composition in accordance with the invention can contain one or more additional direct dyes which can be chosen, for example, from nitrobenzene dyes, anthraquinone dyes, naphthoquinone dyes, triarylmethane dyes, xanthene dyes and azo dyes which are non-cationic.

When it is intended for oxidation dyeing, the dye composition in accordance with the invention contains, in addition to the cationic direct dye(s) one or more oxidation bases chosen from the oxidation bases conventionally used for oxidation dyeing and among which mention may be made in particular of para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, orthoaminophenols and heterocyclic bases.

When they are used, the oxidation base(s) preferably represent(s) from 0.0005 to 12% by weight approximately relative to the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately relative to this weight.

When it is intended for oxidation dyeing, the dye composition in accordance with the -invention can also contain, in addition to the cationic direct dye and the thickening polymer (ii) as well as the oxidation bases, one or more couplers so as to modify the shades obtained or to enrich them with glints, by using the cationic direct dye(s) and the oxidation base(s).

The couplers which can be used in the dye composition in accordance with the invention can be chosen from the couplers used conventionally in oxidation dyeing and among which mention may be made in particular of meta-phenylenediamines, metaaminophenols, meta-diphenols and heterocyclic couplers.

When it is (they are) present, the coupler(s) preferably represent(s) from 0.0001 to 10% by weight approximately relative to the total weight of the dye :composition, and even more preferably from 0.005 to by weight approximately relative to this weight.

The dye composition in accordance with the invention can also contain various adjuvants conventionally used in compositions for dyeing the hair, such as antioxidants, penetrating agents, sequestering agents, fragrances, buffers, dispersing agents, surfactants, film-forming agents, ceramides, preserving agents, screening agents and opacifiers.

Needless to say, a person skilled in the art will take care to select this (these) optional complementary compound(s) such that the advantageous properties intrinsically associated with the dye composition in accordance with the invention are not, or are not substantially, adversely affected by the addition(s) envisaged.

The dye composition according to the invention can be in various forms, such as in the form of liquids, shampoos, creams or gels or any other form 10 which is suitable for dyeing keratin fibres, and in particular human hair. It can be obtained by mixing, at the time of use, a composition, which may be pulverulent, containing the cationic direct dye(s) with a composition containing the specific thickening 15 polymer.

When the combination of the cationic direct dye and the thickening polymer (ii) according to the invention is used in a composition intended for

S.

oxidation dyeing (in which case one or more oxidation bases are used, optionally in the presence of one or more couplers) or when it is used in a composition intended for lightening direct dyeing, then the dye composition in accordance with the invention also comprises at least one oxidizing agent chosen, for example, from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, and enzymes such as peroxidases, lactases and two-electron oxidoreductases. It is particularly 56 preferred to use hydrogen peroxide or enzymes.

Another subject of the invention is a process for dyeing keratin fibres, and in particular human keratin fibres such as the hair, using the dye composition as defined above.

According to a first variant of this dyeing process in accordance with the invention, at least one dye composition as defined above is applied to the fibres, for a period which is sufficient to develop the

S.

e• 10 desired coloration, after which the fibres are rinsed, r O optionally washed with shampoo, rinsed again and dried.

The time required to develop the coloration :sea*, eSe* S"on the keratin fibres is generally between 3 and minutes and even more specifically between 5 and minutes.

According to a second variant of this dyeing t. process in accordance with the invention, at least one sees dye composition as defined above is applied to the fibres, for a period which is sufficient to develop the .C desired coloration, without final rinsing.

According to one specific embodiment of this dyeing process, and when the dye composition in accordance with the invention comprises at least one oxidation base and at least one oxidizing agent, the dyeing process comprises a first step which consists in separately storing, on the one hand, a composition (Al) comprising, in a medium which is suitable for dyeing, at least one cationic direct dye as defined above and at least one oxidation base, and, on the other hand, a composition (BI) comprising, in a medium which is suitable for dyeing, at least one oxidizing agent, and then in mixing them together at the time of use, after which this mixture is applied to the keratin fibres, the composition or the composition (Bi) containing the thickening polymer (ii) as defined above.

According to another specific embodiment of 10 this dyeing process, and when the dye composition in accordance with the invention comprises at least one oxidizing agent, the dyeing process comprises a first step which consists in separately storing, on the one hand, a composition (A2) comprising, in a medium which is suitable for dyeing, at least one cationic direct dye as defined above, and, on the other hand, a composition (B2) comprising, in a medium which is suitable for dyeing, at least one oxidizing agent, and then in mixing them together at the time of use, after which this mixture is applied to the keratin fibres, the composition (A2) or the composition (B2) containing the thickening polymer as defined above.

Another subject of the invention is a multicompartment dyeing device or dyeing "kit" or any other multi-compartment packaging system, a first compartment of which comprises the composition (Al) or (A2) as defined above and a second compartment of which comprises the composition (Bi) or (B2) as defined above. These devices can be equipped with means for dispensing the desired mixture onto the hair, such as the devices described in patent FR 2,586,913 in the name of the Applicant.

The examples which follow are intended to illustrate the invention without, however, limiting its scope.

EXAMPLES

EXAMPLES 1 to 4: 10 The four direct dyeing compositions given in the table below were prepared: (all contents expressed in grams) Example Example Example Example 1 2 3 4 Cationic direct dye of formula 0.2 (I1) Cationic direct dye of formula 0.2 (114) Cationic direct dye of formula 0.1 (IV) 27 Cationic direct dye of formula 0.2 (IV) o Crosslinked polyacrylic acid sold under the name Carbopol 2984 by the company Goodrich 1.0 AM* Ammonium acrylate/ acrylamide copolymer sold under the name Bozepol C Nouveau by the company Hoechst 1.0 AM* a a a a. a i Crosslinked methacrylic acid/ethyl acrylate copolymer sold as an aqueous dispersion containing 38% active material, 10 under the name Viscoatex 538C by the company Coatex 1.0 AM* Crosslinked 15 acrylic acid/ethyl acrylate ~copolymer sold as •g an aqueous dispersion Scontaining 28% a "active material, under the name Aculyn 33 by the company R6hm Haas 1.0 AM* Ethanol 10 10 10 2-Amino-2-methyl- pH 9 pH 9 pH 9 pH 9 1-propanol qs Demineralized 100 100 100 100 water qs AM* denotes active material 61 The above compositions were each applied for minutes to locks of natural grey hair containing white hairs. The locks of hair were then rinsed, washed with a standard shampoo and then dried.

The locks were dyed in the following shades: Examples Shades obtained 1 Bright red 2 Bright orange 3 Bright purple 4 Bright red .9 .r i a a a For the purposes of this specification it will be clearly understood that the word "comprising" means "including but not limited to", and that the word "comprises" has a corresponding meaning.

Claims (7)

1. Composition for dyeing keratin fibres, including, in a medium which is suitable for dyeing, at leat one compound chosen from compounds of formulae (II), (III), III') or (IV) below: a) the compounds of formula below: R'3 A-D=D /N (1) X"R R3 in which: D represents a nitrogen atom or a -CH group, R and R 2 which may be identical or different represent a hydrogen atom; a C 1 -Ca alkyl radical which can be S: substituted with a -CN, -OH or -NH 2 radical or form, with a carbon atom of the benzene ring, a heterocycle optionally containing oxygen or nitrogen, which can be substituted with one or more C 1 -C 4 alkyl radicals; a 4'-aminophenyl radical, R 3 and R' 3 which may be identical or different, represent 25 a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a cyano radical, or a C-C 4 alkyl, CI-C 4 alkoxy or acetyloxy radical, X- represents an anion H:\VC1 arke\Keep\pecis\36777.99 L'oreA Idoc 4/07/00 63 A represents a group chosen from the structures Al to A19 below: A, R. R;-N N R 4 S a S S S A 4 R 4 ,R 4 R 4 N I R4 Al R 4 A 1 0 ,R4 N-N+ R N R 4 As 4 N R 4 As R, N-N N R 4 A6 RN7 R; N K 4 Aq /R 4 N=N. All R 4 N. A12 N 1 /R4 tI- S /R, N -N+ S H:\PCIarke\Keep\ epecis\36777.99 L'oreal .doc 4/07/00 64 R 4 R 4 N+ 4N |N+ N R S S R 4 A, 7 A, and R4 N N+ ,N+ A 99 R 4 in which R 4 represents a C 1 -C 4 alkyl radical which can be substituted with a hydroxyl radical and R represents a C1-C 4 alkoxy radical, with the proviso that 5 when D represents -CH, when A represents A 4 or A 13 and when R 3 is other than an alkoxy radical, then R 1 and R 2 do not simultaneously denote a hydrogen atom; b) the compounds of formula (II) below: RRe B-N=N N (II) x" R7 9R in which: R 6 represents a hydrogen atom or a C 1 -C 4 alkyl radical, R 7 represents a hydrogen atom, an alkyl radical which 65 can be substituted with a -CN radical or with an amino group, a 4'-aminophenyl radical or forms with R 6 a heterocycle optionally containing oxygen and/or nitrogen, which can be substituted with a CI-C 4 alkyl radical R 8 and R 9 which may be identical or different, represent a hydrogen atom, a halogen atom selected from bromine, chlorine, iodine, fluorine, a CI-C 4 alkyl, C 1 -C 4 alkoxy radical or a -CN radical, X- represents an anion, B represents a group chosen from the structures B1 to B6 below: S *a a *a a a N+ N- -N+ R, R 1 -N+-RI :R1~~s K12 No RIO N+ R 'S R10 and H:\PClarke\Keep\specis\36 7 7 7 .99 L'oreal.doc 4/07/00 66 in which Rio represents a C 1 -C 4 alkyl radical, R 11 and R 1 2, which may be identical or different, represent a hydrogen atom or a Ci-C 4 alkyl radical; c) the compounds of formulae (III) and (III') below: 4 E-D,=D 2 Dy-(N) X R X' R 5 R K16 in which: R 13 represents a hydrogen atom, a Cz-C 4 alkoxy radical, a halogen atom selected from bromine, chlorine, iodine or fluorine, or an amino radical, R represents a hydrogen atom, a C-C 4 alkyl radical or forms, with a carbon atom of the benzene ring, a 20 heterocycle optionally containing oxygen and/or substituted with one or more C 1 -C 4 alkyl groups, R 1 5 represents a hydrogen atom or a halogen atom selected from bromine, chlorine, iodine or fluorine, ooe R 16 and R 17 which may be identical or different, represent 25 a hydrogen atom or a C 1 -C 4 alkyl radical, o* a H:\fClarke\Keep\specis\36 77 7 9 9 L'oreal.doc 4/07/00 67 Di- and D 2 which may be identical or different, represent a nitrogen atom or a -CH group, m 0 or 1 it being understood that when R3. 3 represents an unsubstituted amino group, then D, and D 2 simultaneously represent a -CH group and m 0, X- represents an anion, E represents a group chosen from the structures El to E8 below: *Po 0** El E2 0 E3 0 E4 HAPFClarke\Keep\specis\36777.99 L'oreal.doc 4/07/00 N) K' E7 R' N+ N \R and in which R' represents a C 1 -C 4 alkyl radical; a. when m 0 and when D 1 represents a nitrogen atom, then E can also denote a group of structure E9 below: R' N E9 N+ R' 5 in which R' represents a C 1 -C 4 alkyl radical; d) the compounds of formula (IV) below: G-N N--J (IV) in which: the symbol G represents a group chosen from the structures G 1 to G 3 below: 69 <N //v I I" X RI 2 N, G G P' 4 PM M G, in which structures G 1 to G 3 R 18 denotes a C 1 -C 4 alkyl radical, a phenyl radical which can be substituted with a CI-C 4 alkyl radical or a halogen atom chosen from chlorine, bromine, iodine and 5 fluorine; R 19 denotes a C 1 -C 4 alkyl radical or a phenyl radical; SR 2 0 and R 2 1 which may be identical or different, represent a C 1 -C 4 alkyl radical, a phenyl radical or together form, in G 1 a benzene ring substituted with one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy or NO 2 radicals or together form, in G 2 a benzene ring optionally substituted with one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy or NO 2 radicals; can also denote a hydrogen atom; Z denotes an oxygen or sulphur atom or a group -NR 19 M represents a -CH, -CR (R denoting Ci-C 4 alkyl) or 70 -NR 2 2 (X)r group; K represents a -CH, -CR (R denoting Cj-C 4 alkyl) or -NR 22 group; P represents a -CH, -CR (R denoting Cl-C 4 alkyl) or -NR 2 2 group; r denotes zero or 1; R 2 2 represents an atom a Cl-Cj alkoxy radical or a C 1 -C 4 alkyl radical; R 2 3 and R 2 4 which may be identical of different, represent a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a Ci-Cd alkyl or C 1 -C 4 alkoxy radical or an -NO 2 radical; X- represents an anion with the proviso that, R 2 2 denotes then r denotes zero; if K or P or M denote Cj-C 4 -N-alkyl then R 2 3 or R 2 4 is other than a hydrogen atom; **if K denotes -NR 22 then M=P= -CH, -CR; if M denotes -NR 22 then K=P= -CH, -CR; *if P denotes -NR 2 2 then K=M and denote -CH or -CR; if Z denotes a sulphur atom with R 2 1 denoting CI-C 4 alkyl, then R 2 0 is other than a hydrogen atom; 0* if Z denotes -R 2 with R 19 denoting C,- 4 akl hna 25 least one of the radicals R 18 R 2 0 or R 2 1 of G 2 is other than a Cj-C 4 alkyl radical; H:\r-clarke\Keep\specis\3677 7 .9 9 b'oreal.doc 4/07/00 the symbol J represents: a group of structure J 1 below: in which structure J 1 R 25 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl or CI-C 4 alkoxy radical, a radical -OH, -NO 2 -NHR 28 -NR 29 R 30 -NHCO (Cl-C 4 alkyl, or forms with R 26 S'a 5- or 6-membered ring which may or may not contain one or more hetero atoms chosen from nitrogen, oxygen 10 and sulphur; R 26 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a Ci-C4 alkyl or C 1 -C 4 alkoxy radical or forms, with R 2 7 or R 2 8 a 5- or 6-membered ring which may or may not contain one or more hetero atoms chosen from nitrogen, oxygen and sulphur; S" R 27 represents a hydrogen atom, an -OH radical, a radical -NHR 2 8 or a radical -NR 2 9 R 3 0; R 2 8 represents a hydrogen atom, a C 1 -C 4 alkyl radical, a CI-C 4 monohydroxyalkyl radical, a C 2 -C 4 polyhydroxyalkyl radical or a phenyl radical; R 2 9 and R 3 0 which may be identical or different, represent a C 1 -C 4 alkyl radical, a CI-C4 monohydroxyalkyl radical or a C 2 -C 4 polyhydroxyalkyl radical; 72 a 5- or 6-membered nitrogenous heterocyclic group which can contain other hetero atoms and/or carbonyl groups and which can be substituted with one or more C 1 -C 4 alkyl, amino or phenyl radicals, and in particular a group of structure J 2 below: N -N\ 0 R 32 in which structure J 2 R and R 32 which may be identical or different, R31 32 represent a hydrogen atom, a Cl-C 4 alkyl radical or a phenyl radical; CH Y denotes the -CO- radical or the radical C **to n 0 or 1, with, when n denotes 1, U denoting a -CO- radical, the said composition further including (ii) at least one thickening polymer chosen from the group comprising: 1- crosslinked acrylic acid homopolymers;

2- partially or totally neutralized 2-acrylamido-2-methylpropanesulphonic acid homopolymers and copolymers;

3- ammonium acrylate homopolymers and 73 copolymers of ammonium acrylate and of acrylamide;

4- crosslinked copolymers of (meth) acrylic acid and of CI.-C 6 alkyl acrylate;

5-nonionic homopolymers and copolymers containing monomers containing etliylenic unsaturat ion of ester and/or amide type. 2. Composition according to claim 1, in which the compound of formula is a cationic direct dye and the cationic direct dyes of formula are chosen from the compounds corresponding to the structures (Ii) to (154) below: CH 3 N [f NN=N 'O NH-CH 3 CU (i CH 3 H' \PC Irke\ Keep\ SPelis\36 7 7 7l.99 L'orea I.doc 4/07/00 74 ci. (12) CHCH/ CH 3 H3 -N3'I- H C -ON\ CKH CV, (13) cI, (14) 0 :0,04, /CH 3 H 3 C-No CHCHO N N C 2 4 C CI, CI 16 0@ H 3 C-N -CH-( Cr .(17) CH 3 1' CF 18 CI- (9 'CH 3 a. a a. a. a .q a. a a. a. a a a S a. S aVfl a p a, a a SSb C a. a S aaa S. a a a a. CH 3 N= -0 NH 2 N CH 3 C1, (110) (mI) CH 3 C 2 H N=N -N N C 2 H CH. 3 C1, (112) CH 3 H O CN C 2 H 4 -CN CH 3 (113) CH 3 N- CH 3 CH 3 NN-PNH 2 N- CH 3 cI cI. (114) .e Jj N=N- -NH 2 OH 3 H 3 C H H I N=N N H 3 C -C 2 H 8 (115) CIl (16 (117 CI (118) .CH. CH 3 CN H ,C /N\ N- C 2 H CH 3 (119) H N Cl- CH 2 -CH 2 -NH 2 H -N CF, CH 2 -CH 2 -OH H CHz-CH 2 -CN (120) (121) CH 3 (122) 78 CH 3 CH3 Ni. >N=N CI* (123) N -CH 3 CH 3 OCH 3 CH 3 N=N N c (124) N -H CH 3 \CH CH 3 CH 3 F I N=N N /CF, (125) /IN+ N CH 3 CH3 V *H CH 3 3 7 -N H 2 ci* (126) CH 3 CH 2 -CH.-CN /N N= CV (127) CH 3 OH 3 0-OH 3 -N=N -NH 2 N- OH 3 0-OH 3 OH 3 0-OH 3 N -CH 3 OH 3 OH 3 01. (128) CI. (129) I H C-N+ -N=N NCI, OH 3 OH 3 C/ N+- OH 3 (130) CF (131) ci- (132) 11 1. /CH 3 CH 3 (133) CI.* (134) en. C C C C C* C. C p *C C C C CCC. C CC. C C. CI. (135) CI- (136) CI (137) *CH. 3 /CH 3 N=N+ H 3 CO\ N H cr' (138) H 3 C c N=NN\ CH 3 CH 3 .N/ CH 3 H 3 CI* (139) H3 CI. (140) CI. (141) 3 CH 3 CH 3 N S =N I H 3 C -Cl CH 3 (6 11 NH NH CI. (143) CH 3 CN+ CH 3 N=NN S CH 3 CH 3 CN+ CH 3 N'\ S- CH 3 CN a a a a. a a a a a a CI- (144) CI. (145) Cl- (146) CI- (147) CH 3 IN cc> ,6 11 CH3 IN CH 3 N=N S- CH 3 cl CA CN+ CH 3 s CHS CH 3 S0 4 (148) CH 3 S0 4 (149) S. S S S S S* S S CH 3 KI CF, (150) -N 1 (152) WH 3 84 CH 3 N 'NI N 1 CH S 0 4 (153) -CH3 CH 2 -CH 2 -CN CI (154) S -H 3. Composition according to claim 2, in which the cationic direct dyes correspond to the structures (II), (114) and (13). Composition according to claim 1, in which the compounds of formula (II) are cationic direct dyes and the cationic direct dyes of formula (II) are chosen from the compounds corresponding to the structures (Ml) to (119) below: 3 Ci'. C CM( 1 1 =s CH 3 H~C N- NN N CI (112) CH 3 CH H:\P~clarke\Keep\specis\367 7 7 .9 9 L'1oreal .doc 4/07/00 CH 3 CNi-N+ N=N N CH 3 CH 3 /3 CH 3 N=N /\N s CCN (113) CI (114) .9 @999 .9 et 9 0 @09@ *99~ ~9 9) 9 97999 9 C @9 *0 9* 0 97 .9

97. 9 Ot 0 09 09 CH 3 H/ CH 3 N= N-0 N\ S CH 3 I CH N N+ H N\ H 3 C CH 3 CH 3 N'NI CH 3 N= N H N )l CH 3 CH 3 CH 3 S0 4 CH 3 S0 4 (116)- CH 3 S0 4 -(IM7 86 CH3 N N+ H 3 C N S CH 3 SO 4 (118) and CH 3 N=N N ZEIS ICH 3 CH 3 S0 4 (119) H 2 N Composition according to claim 1, in which the compounds of formula (III) are cationic direct dyes and the cationic direct dyes of formula (III) are chosen from the compounds corresponding to the structures (I111) to (11118) below: V CH3 H 5 C CK 2 N N [Nzz CH=-N-N/ CH 3 0 HC)'J CH3 N CN N- H 3 C) I -N- CH3 CI, (1111) CI. (1112) CI. (1113) HA\F'Clarke\Keep\specis\36 7 7 7.99 L'orealdoc 4/07/00 H 3 0-No'-CH=N-N 'o CH 3 CH3S0 4 -(1114) (1115) (1116) H3C-No -CH=N-N CH 3 S0 4 CH 3 S0 4 (1117) CF, (1118) Cl (1119) CH 3 S 0 4 (1111 *9 9 -Ct CK 3 S0 4 CH 3 CH 3 S0 4 (11113) cI- (11114) CH- 3 C00 -(11) -89- HC-N C=H N 2 CH 3 COO (116 H C-No CH=N-N- /C1 (111W7) CH 3 and OH 10C1 N=N- CF (11118) H 3 C--"N CH 3 6. Composition according to claim 5, in which the cationic direct dyes of formula (III) are chosen from the compounds corresponding to the structures (1114), (1115) and (11113). 7. Composition according to claim 1, in which the compounds of formula (III') are cationic direct dyes and the cationic direct dyes of formula (III,) are chosen from the compounds corresponding to the structures (III'1) to (111'3) below: N N N+CH 3 NH H;\PC1ai-ke\KeeP\S~~eCis\36 7 7 7 9 9 L'orea1 .doc 4/07/00 90 CHiN+_ 0" C (1112) NH ;.and CH 3 NN N= Cl (tl3 CH3 CH 3 8. Composition according to claim 1, in which the compounds of formula (IV) are cationic direct dyes and the cationic direct dyes of formula (IV) are chosen from the compounds corresponding to the structures (IVh. to (IV) 7 7 below: N+ N=N N (I) I- C N=N OH (IV) 2 0 NHCOCH 3 CH toN+ N=N CH (IV)a H:\PC1arke\KeeP\SPeCis\ 3 67 7 7 .99 L'oread .doc 4/07/00 CHO C 0 1. H' 0 0 N NN +N 0 H 0 H0 H 'HO, I% I (Al)N NN +N O HO~S E lCH 3 (V 1 CHH3 I C N+ N=N C~N 2 H C 2 11 CH 3 N=N 12 I -CH 2 CH 2 0H CH 3 N+ N=N /\NH 2 (iV),3 11 3 C" N+ N=N NH 2 1 4 0 93 CH3 I CH 3 (V 1- 3 C N+ N=N N NH 3 N I- CH 3 0 .4 ~CH3 I- CH 3 4 0 H* NHCOCH 3 N-N CH 3 (v 1 0 44 4K-A. H 3 I- N= CH 3 20 0 N+ N-N N 2S('V)21 ~C 2 H N+ N=N NV2 *cI H 3 C N. =NCH3 (IV)23 0 ~r~CH3 H N+N=N ('V)24 0 *.3 S.N=N ~CH 3 2 N"C 2 C 2 (I) 1 ~CK 2 CH 2 OH I 0 CH3(IV) ICI CH CH 3 SO4j *too N+ N=N N2(V UNH 2

999. I- CH3 CH 3 S0 4 @060 N+ N=N NN-) I -a H 2 (IV) OH3 CH SO.- a N NI 31 I C 2 HS %A1 3 CH 3 SO 4 CHC N+ N=N NN H 32 I CH3 CMH3 CH 3 S0 4 H3N+ NN AV(r4 -CH 3 S0 4 -c ~CH 3 N+ N=N 3 3 CHH3 CH 3 S0 4 NHCOCK 3 CHH3 CH 3 .S0 4 CH 3 *s N=N N. N( (IV) 3 7 [L.J CH 3 1 CH 3 SO~m CH3 CH. 3 ::H 3 C N+ CH 3 s0 4 m S.3 ~C 3 N+ C 2 HS0O CAI ~CH 3 NCH (IV)O N+ CH 3 S0 4 CH 3 *.3 N "H \H /Pt) 4 2 N* 9SO [IT CH' ('V)4 3 N+ B OH 3 N+ N=N N ('V)44 OCH 3 0 N4 CH 3 so; a 6 0I H N/ *(tV) 1 N=N N\o N* A N+ N-=N N 0CH 3 I ia H 3 ('V)46 OH 3 -N IIN- OH 3 t 4 i 1 100 II V) N+ N =(V NI-1 CH 3 CH N N NH 2 2 )4 H~C N+ N=N 'N (V)SO aa I C104 OH 0 3 OH 1 101 OH Nj+ N N -o NI-i 2 5 3 I- 0 OCH 3 N+ N=N OH ([V)U 0 NHCOCH 3 OH 3 N+ N-N -o NH 2 I N+ N=N N ,H NH 2 102 CH 3 N+ N=N OH ('V)57 0 OH 3 N+ N=N OH ([V)W 0 1-130 OH N+ N=N P N'l% 0. H 3 OH OH 3 N=N OH 0 CH 3 103 CH 3 NO 2 N+ N=N -OH ('V)62 0 0 2 N N+ N=N N ,H (IV)6 -CH O 3 OCHH3 *CH 3 SO 4 NO *woo 9 CH 104 CH 3 N CH 3 N+ N=N OH (IV)66 0 CH 3 N. N=N N CH 3 CH.. I NH 2 (V 6 CH 3 CH 3 SO 4 N N 0 HO%:a. CH 3 SO 105 2 u N H 2 V 7 N+ N=N /\NH 2 -(V 7 I 0 CH 3 0 H N N=N (V 0. N 0 CH 3 /\NH 2 0 CH 2 CH 2 0H CH 3 C 3 0 N=N -O NH 2 N* H2 7 4 CI CH 3 S0 4 106 CH, N NN NH 2 N CNH 2 v I CH 3 SO 4 T CH 3 CH 3 CH, rIS N+ N=N NH 2 (V) 76 1. 0 NH 2 CH 3 N=N N N 1 CH 3 N V) I CH 3 SO 4 NO, CH 3 9. Composition according to any one of the preceding claims, in which the cationic direct dye(s) of formula (III), (III') or (IV) represent(s) from 0.001 to by weight relative to the total weight of the composition. Composition according to claim 9, in which the cationic direct dye(s) of formula (III), (III') 25 or (IV) represent(s) from 0.005 to 5% by weight relative to e: the total weight of the composition. 11. Composition according to any one of claims 1 to 1. 0 in which the thickening polymer of class is a crosslinked copolymer of methacrylic acid and of ethyl acrylate. 12. Composition according to any one of claims 1 to in which the thickening polymer of class is a crosslinked copolymer of acrylic acid and of ethyl acrylate. H:\FClarke\Keep\specis\36777.99 L'oreal.doc 4/07/00 107 13. Composition according to any one of claims 1 to 12 in which the thickening polymer (ii) represents from 0.01 to 10% by weight relative to the total weight of the composition. 14. Composition according to claim 13, in which the thickening polymer (ii) represents from 0.1 to 5% by weight relative to the total weight of the composition. Composition according to any one of the preceding claims, in which the medium which is suitable for dyeing (or support) includes water or of a mixture of water and at least one organic solvent. 16. Composition according to any one of the preceding claims in which the composition has a pH of between 2 and 11. 17. Composition according to claim 16 in which the composition has a pH of between 5 and 18. Composition according to any one of the preceding claims, which is intended for oxidation dyeing and which 25 contains one or more oxidation bases chosen from para- phenylenediamines, bis(phenyl)alkylenediamines, para- aminophenols, ortho-aminophenols or heterocyclic bases. 19. Composition according to claim 18, in which the oxidation base(s) are present in an amount of from 0.0005 to 12% by weight relative to the total weight of the dye composition. Composition according to claim 19, in which the oxidation base(s) is present in an amount of from 0.005 to 6% by weight relative to the total weight of the dye Scomposition. H:\PClarke\Keep\specis\36777.99 L'oreal.doc 4/07/00 108 21. Composition according to any one of claims 18 to further including one or more couplers chosen from meta-phenylenediamines, meta-aminophenols, meta- phenylenediamines, meta-aminophenols, meta-diaphenols or heterocyclic couplers. 22. Composition according to claim 21, in which the coupler(s) are present in an amount of from 0.0001 to by weight relative to the total weight of the dye composition. 23. Composition according to claim 22, in which the coupler(s) are present in an amount of from 0.005 to 5% by weight relative to the total weight of the dye composition. 24. Composition according to any one of the preceding claims, which is intended for oxidation dyeing or lightening direct dyeing and which contains at least one oxidizing agent. Composition according to any one of the preceding claims in which the keratin fibres are human keratin 0 Sfibres. 25 26. Composition according to claim 25 in which the human keratin fibres are hair. 27. Composition according to any preceding claim in which the amine represented by X- is chosen from chloride, 30 methyl sulfate or acetate. 28. Composition according to any preceding claim in which the amine represented by X- in the compounds of formula (iv) represented by the symbol G is selected from chloride, iodide, methyl sulfate, ethyl sulfate, acetate, or perchlorate. H: \PCIarke\Keep\secs\3 6 777 9 9 L'orea I.doc 4/07/00 109 29. Process for dyeing keratin fibres including applying to the fibres at least one dye composition as defined in any one of claims 1 to 28 for a period which is sufficient to develop the desired coloration, after which the fibres are rinsed, optionally washed with shampoo, rinsed again and dried. Process for dyeing keratin fibres, including applying at least one dye composition as defined in any one of claims 1 to 23 to the fibres, for a period which is sufficient to develop the desired coloration, without final rinsing. 31. Process for dyeing keratin fibres including a first step which includes separately storing, on the one hand, a composition (Al) comprising, in a medium which is suitable for dyeing,- at least one cationic direct dye (i) as defined in any one of claims 1 to 10 and at least one oxidation base, and, on the other hand, a composition (BI) comprising, in a medium which is suitable for dyeing, at least one oxidizing agent, and then in mixing them together at the time of use, after which this mixture is applied to the keratin fibres, wherein the composition (Al) or the composition (Bl) contains the thickening polymer (ii) as 25 defined in any one of claims 1 or 11 to 14. 32. Process for dyeing keratin fibres, including a first step which includes separately storing, on the one hand, a composition (A2) comprising, in a medium which is suitable for dyeing, at least one cationic direct dye (i) as defined in any one of claims 1 to 10 and, on the other hand, a composition (B2) comprising, in a medium which is suitable for dyeing, at least one oxidizing agent, and then in mixing them together at the time of use, after which this mixture is applied to the keratin fibres, wherein the composition (A2) or the composition (B2) contains the thickening polymer (ii) as defined in any one of claims 1 H:\FClarike\Keep\specis\36777.99 L'oreal.doc 4/07/00 110 or 11 to 14. 33. Process for dyeing keratin fibres according to any one of claims 29 to 32 in which the keratin fibres are human keratin fibres. 34. A process according to claim 33 in which the human keratin fibres are hair. 35. Multi-compartment dyeing device or multi- compartment dyeing "kit", including a first compartment which comprises the composition (Al) or (A2) as defined in any one of claims 31 or 32 and a second compartment which comprises the composition (Bl) or (B2) as defined in claim 31 or 32. 36. Composition for dyeing keratin fibres substantially as herein described with reference to the **b accompanying examples. 37. Process for dyeing keratin fibres substantially as herein described with reference to the accompanying as S.examples. 25 38. Multi-compartment dyeing device substantially as herein described with reference to the accompanying examples. Dated this 4th day of July 2000 L'OREAL By their Patent Attorneys GRIFFITH HACK Fellows Institute of Patent and Trade Mark Attorneys of Australia H:\FClarke\Keep\spcis\36777.99 L'oreal.doc 4/07/00