AU730455B2 - Dye composition containing a cationic direct dye and a pyrazolo(1,5-a)pyrimidine as oxidation base, and dyeing processes - Google Patents

Description

AUSTRALIA

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

L'OREAL

Invention Title: DYE COMPOSITION CONTAINING A CATIONIC DIRECT DYE AND A PYRIMIDINE AS OXIDATION BASE, AND DYEING

PROCESSES

The following statement is a full description of this invention, including the best method of performing it known to me/us: '1 -I l1o The invention relates to a composition for the oxidation dyeing of keratin fibres, containing at least one cationic direct dye and at least one as oxidation base, as well as to the oxidation dyeing process using this composition.

It is known practice to dye keratin fibres, and in particular human hair, with dye compositions containing oxidation dye precursors, in particular ortho- or para-phenylenediamines, ortho- or paraaminophenols, bis(phenyl)alkylenediamines or heterocyclic compounds, which are generally referred to as oxidation bases. Oxidation dye precursors, or oxidation bases, are colourless or weakly coloured compounds which, when combined with oxidizing products, 15 can give rise to coloured compounds and dyes by a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or coloration modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds.

The variety of molecules used as regards the oxidation bases and the couplers allows a wide range of colours to be obtained.

2 The so-called "permanent" coloration obtained by means of these oxidation dyes must moreover satisfy a certain number of requirements. Thus it must have no toxicological drawbacks, it must be able to give shades of the desired intensity and it must be able to withstand external agents (light, bad weather, washing, permanent-waving, perspiration, rubbing).

The dyes must also be able to cover white hair and, lastly, they must be as unselective as possible, i.e. they must give the smallest possible coloration differences along the same length of keratin fibre, which may in fact be differently sensitized S. damaged) between its tip and its root.

It is has already been proposed, in S. 15 particular in patent application FR-A-2,750,048, to use as oxidation bases, alone or in combination .with one or more couplers. However, the colorations obtained are not always sufficiently intense, chromatic or resistant to the various attacking factors to which the hair may be subjected.

The Applicant has now discovered, entirely surprisingly and unexpectedly, that the combination of at least one pyrazolo[1,5-a]pyrimidine as oxidation base and at least one cationic direct dye defined below makes it possible to obtain intense colorations which moreover have improved properties of resistance with 1.' 3 respect to the various attacking factors to which the hair may be subjected (shampoo, light, bad weather, permanent-waving, perspiration, rubbing, etc.).

These discoveries form the basis of the present invention.

A first subject of the invention is thus a composition for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair, characterized in that it contains, in a medium which is suitable for dyeing: at least one pyrazolo[l1,5-a]pyrimidine as oxidation base; and at least one cationic direct dye; the said composition being free of any enzymatic system capable of bringing about the oxidation of the As indicated above, the dye composition in accordance with the invention leads to intense colorations which moreover have excellent properties of resistance with respect to the action of various external agents (light, bad weather, washing, permanent-waving, perspiration and rubbing).

A subject of the invention is also a process for the oxidation dyeing of keratin fibres using this dye composition.

4 The pyrazolo[l,5-a]pyrimidines which can be used as oxidation bases in the dye composition in accordance with the invention are preferably chosen from the compounds of formula below, and the addition salts thereof with an acid or with a base: NN 3 [NR 3 3 R J 5 R3p 6 N.

(V)

7

[NR

3 5

R

3 6 q in which:

R

33

R

34

R

35 and R 36 which may be identical or different, denote a hydrogen atom, a Ci-C 4 alkyl 1 0 radical, an aryl radical, a CI-C 4 hydroxyalkyl radical, a C 2

-C

4 polyhydroxyalkyl radical, a (Ci-C 4 )alkoxy- (Ci-C 4 )alkyl radical, a Ci-C 4 aminoalkyl radical (it being possible for the amine to be protected with an acetyl, ureido or sulphonyl radical), a (C 1

-C

4 )alkylamino(Ci-C 4 alkyl radical, a di[ (Ci-C4)alkyl]amino- (Ci-C 4 )alkyl radical (it being possible for the dialkyls to form a 5- or 6-membered aliphatic or heterocyclic ring), a hydroxy(Cl-C 4 )alkyl- or di[hydroxy- (Ci-C 4 alkyl] amino (Ci-C 4 alkyl radical; the radicals R, which may be identical or different, denote a hydrogen atom, a Ci-C 4 alkyl radical, an aryl radical, a Ci-C 4 hydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a Ci-C 4 aminoalkyl radical, a

(C

1

-C

4 )alkylamino(C 1

-C

4 )alkyl radical, a di (C 1

-C

4 )alkyl]amino(C 1

-C

4 alkyl radical (it being possible for the dialkyls to form a 5- or 6-membered aliphatic or heterocyclic ring), a hydroxy(Ci-C 4 )alkylor di[hydroxy(C 1

-C

4 )alkyl]amino(C 1

-C

4 )alkyl radical, an amino radical, a (Ci-C 4 )alkyl- or di[ (C-C 4 )alkyl]amino radical; a halogen atom, a carboxylic acid group or a sulphonic acid group; i is equal to 0, 1, 2 or 3; p is equal to 0 or 1; q is equal to 0 or 1; n is equal to 0 or 1; with the proviso that: the sum p q is other than 0; 15 (ii) when p q is equal to 2, then n is equal to 0 and the groups NR 33

R

34 and NR 35

R

36 occupy the or positions; (iii) when p q is equal to 1, then n is equal to 1 and the group NR 33

R

34 (or NR 35

R

36 and the OH group occupy the or (3,7) positions.

The pyrazolo[l,5-a]pyrimidines of formula (V) above are known compounds which are described in particular in patent application FR-A-2,750,048, the content of which forms an integral part of the present patent application.

Among the pyrazolo~l.,5-alpyrimidines of formula which can be used as oxidation bases in the dye compositions in accordance with the invention, mention may be made in particular of: pyrazololll,5-alpyrimidine-3,7-diamine; 2-methylpyrazolo[l, S-alpyrimidine-3,7-diamine; 2, 5-dimethylpyrazolo[1, S-alpyrimidine-3,7-diamine; pyrazolo[1,5-a]pyrirnidine-3,5-diamine; 2 7 -dimethylpyrazolo1,5-alpyrimdine.3,5-.diamine; 3-aminopyrazolo[1.,5-alpyrimidin-7-ol; 3 -amino- 5-methylpyrazolo 5-a pyrimdin-7 .ol; 3-aininopyrazolo[1, 2-(3-aminopyrazolo[1, 5-alpyrilnidin-7--ylamino) ethanol; 3 -amino-7-f 3 15 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo- [1,5 -pyrimidine; (7-aminopyrazolo(1, 5-alpyrimidin-3-ylamino) ethanol; (3-aminopyrazolo[1, 5-alpyrimidin-7-yl)-(2-hydroxyethyl) amino) ethanol; (7-aminopyrazolo[1,5-alpyrimidin-3-yl)-(2-hydroxyethyl) aminol ethanol; 5, 6-dimethylpyrazolo[1, 5-alpyrimidine-3,7-diamine; 2,6-dimethylpyrazolo(l, 5-alpyrimidine-3,7-diamine; 2,5,N7,N7-tetramethylpyrazolo[1,57a]pyrimidine-3,7diamine; and the addition salts thereof with an acid or with a base.

The cationic direct dye(s) which can be used in the dye composition in accordance with the invention is (are) preferably chosen from cationic aminoanthraquinones, cationic mono- or diazo compounds and cationic naphthoquinones.

As examples, mention may be made in particular of [8-f (p-aminophenyl)azo]-7-hydroxy- 2 -naphthylIt rime thyl1ammonium chloride (also known as Basic Brown 16@ or Arianor Mahogany 3060b2& in the color Index), the combination of 3- -amino- 6-bromo- 8-dihydro-l-hydroxy-8-imino-5-oxo-2-naphthyl) amino] .~.N,N,N-trimethylbenzenaminium chloride and of 3-f 6-dibromo-5,8-dihydro-l-hydroxy-8-imino-5-oxo- 3-naphthyl) amino] N-trimethylbenzenaninium chloride (also known as Basic Blue 99@ or Arianor Steel Blue 306004@ in the Color Index), 7-hydroxy-8-[(2-rnethoxyphenyl) azo] -N,N,N-trimethyl-2-naphthalenamininn chloride (also known as Basic Red 760 or Arianor Madder Red® in the Color Index), [8-[H4-amino-2-nitrophenyl)- 20 azo] -7-hydroxy-2-naphthyl] trimethylaunonium chloride (also known as Basic Red 1180 or Arianor Bordeaux 306006@ in the Color Index), the combination of [8-f(4amino-3-nitrophenyl) azo] -7-hydroxy-2-naphthyl] trimethylamrnonium chloride and of (8-((4-amino-2-nitrophenyl) azo] -7-hydroxy-2-naphthyl] trimethylammonium chloride (also known as Basic Brown 170 or Arianor Sienna Brown 306001@ in the Color Index), dihydro-3-methyl-5-oxo-l-phenyl-lH-pyrazol-4-yl)azo]- N,N,N-trimethylbenzenaminium chloride (also known as Basic Yellow 57® or Arianor Straw Yellow 306005® in the Color Index), 1-(y-aminopropyl)aminoanthraquinone hydrochloride, 1-N- (methylmorpholiniumpropyl) amino-4hydroxyanthraquinone methyl sulphate and Basic Orange 690 (Color Index name).

The cationic direct dye(s) used in the dye composition in accordance with the invention can also be chosen from the compounds of formulae (II), (III), (III') and (IV) below: a) compounds of formula

S'

3

R

1 A-D D N N (I) X

R

R,

in which: D represents a nitrogen atom or a -CH group,

R

1 and R 2 which may be identical or different, represent a hydrogen atom; a C 1

-C

4 alkyl radical which can be substituted with a -CN, -OH or -NH 2 radical or form, with a carbon atom of the benzene ring, a 9 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 a hydrogen atom or a halogen atom chosen from chlorine, bromine, iodine and fluorine, or a cyano,

C

1

-C

4 alkoxy or acetyloxy radical, X- represents an anion preferably chosen from chloride, methyl sulphate and acetate, A represents a group chosen from structures Ai to A 19 below: t o

S

of 0 5

S

/R4 I- N R4

A

1 R

R

4 R4

N-N+

RN

4 R4 N-N

I

4 S. S *5

R

4 ,R 4 N

R

4

A

7

R

4 R4 N R4 Ag N

R

4

A

10

N+

R4

A

1 3 /R4

N=N+

R

All R4

N+

S

A

14 0- A 12 R4

N-N-'

Sit- A 1 R4

A

18

N+

R 4 and in which R 4 represents a Cl-C 4 alkyl radical which can be substituted with a hydroxyl radical and R 5 represents a Cl-C 4 alkoxy radical, with the proviso that when D represents -CH, A represents A 4 or A 13 and R 3 is other c 11 than an alkoxy radical, then Ri and R 2 do not simultaneously denote a hydrogen atom; b) compounds of formula (II):

R

8 S\

/R"

B-N=N N (I) RR7

R

9 in which:

R

6 represents a hydrogen atom or a Ci-C 4 alkyl radical,

R

7 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 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, 15 represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine or fluorine, a Ci-C 4 alkyl or

C-C

4 alkoxy radical or a -CN radical, X- represents an anion preferably chosen from chloride, methyl sulphate and acetate, 20 B represents a group chosen from structures B1 to B6 below: Rio ,Rio /Rio N 10

N-N

t S R S 10 /Rio

N-N

R,,

N

Rio and in which Rio represents a Cz-C 4 alkyl radical and R 11 and

R

12 which may be identical or different, represent a hydrogen atom or a Cz-C 4 alkyl radical; c) compounds of formulae (III) and (III'): E-D =D 2

X"

E-D 0 (Ill') in which: Ri3 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, 13

R

14 represents a hydrogen atom, a Ci-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 Ci-C 4 alkyl groups,

R

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

R

1 6 and R 1 7 which may be identical or different, represent a hydrogen atom or a CI-C 4 alkyl radical,

D

1 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 DI and D 2 simultaneously 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 structures El to E8 below: N C

NR'

El E2 0 N

N

E3 0 R' R'

N

RE4 E4 and in which R' represents a Ci-C 4 alkyl radical; when m 0 and Di represents a nitrogen atom, then E can also denote a group of structure E9 below:

R'

E9 N

R'

in which R' represents a Ci-C 4 alkyl radical; d) compounds of formula (IV): G-N N--J (IV) in which G represents a group chosen from structures Gi to G 3 below:

R

20 ,1 R2 R24 Z K N R N P x I x

M

R

18 R 8 G, G2 G3 in which:

R

18 denotes a C 1

-C

4 alkyl radical, a phenyl radical, a phenyl radical substituted with a C 1

-C

4 alkyl radical or a halogen atom chosen from chlorine, bromine, iodine and fluorine;

R

19 denotes a C 1

-C

4 alkyl radical or a phenyl radical;

R

20 and R 21 which may be identical or different, represent a Ci-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, Ci-C 4 alkoxy or NO 2 radicals, or together form, in G 2 a benzene ring optionally 15 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 -NR1 9 M represents a -CH, -CR" denoting C 1

-C

4 alkyl) or -NR22(X-)r group; K represents a -CH, -CR" denoting Ci-C 4 alkyl) or -NR22(X-)r group; P represents a -CH, -CR" denoting Ci-C 4 alkyl) or -NR22(X-)r group; r denotes zero or 1;

R

22 represents an atom a Ci-C 4 alkoxy radical or a

C

1

-C

4 alkyl radical;

R

23 and R 24 which may be identical or different, represent a hydrogen atom or halogen atom chosen from chlorine, bromine, iodine and fluorine., a Ci-C 4 alkyl or C 1

-C

4 alkoxy radical or an -NO 2 radical; X- represents an anion preferably chosen from chloride, iodide, methyl sulphate, ethyl sulphate, acetate and perchlorate; with the proviso that: if R 22 denotes then r denotes zero; if K or P or M denotes an -N-(Ci-C 4 )alkyl X- group, then at least one of the radicals R 23 and R 24 is other than a hydrogen atom; if K denotes -NR22(X)r, then M P -CH or -CR"; S 20 if M denotes -NR 22 then K P -CH or -CR"; if P denotes -NR22(X-)r, then K M and denote -CH or

-CR;

alkyl radical, then R 20 is other than a hydrogen atom; 25 if Z denotes -NR 22 and R 19 denotes a C 1

-C

4 alkyl

R

20 in the group of structure G 2 is other than a C 1

-C

4 alkyl radical; J represents: either a group of structure J1 below:

R

27

J

1 in which:

R

25 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a C 1

-C

4 alkyl or C 1

-C

4 alkoxy radical, a radical -OH, -NO 2

-NHR

28

-NR

29

R

30 or -NHCO(Cz-C 4 )alkyl, or forms, with R 26 a 5- or 6-membered ring which may or may not contain one or more hetero atoms chosen from nitrogen, oxygen and sulphur;

R

2 6 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a Cz-C 4 alkyl or C 1

-C

4 alkoxy radical, or forms, with R 27 or R 28 Sa 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, an

•-NHR

28 radical or an -NR 29

R

30 radical; 18

R

28 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

29 and R 30 which may be identical or different, represent a Ci-C 4 alkyl radical, a Ci-C 4 monohydroxyalkyl radical or a C 2

-C

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

N

R3 in which: 15 R 31 and R 32 which may be identical or different, represent a hydrogen atom, a Ci-C 4 alkyl radical or a phenyl radical; Y denotes a -CO- radical or the radical -*c

H

3 19 n 0 or 1, it being understood that when n 1, then U denotes a -CO- radical.

In the structures to (IV) defined above, the CI-C 4 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 the patent applications WO 95/01772, WO 95/15144 and EP-A-0,714,954. The cationic direct dyes of formula (IV) which can be used in the dye compositions in accordance with the invention are also known compounds and are described, for example, in patent applications FR-A-2,189,006, FR-A-2,285,851 and FR-A-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 structures (Il) to (152) below:

CH

3

N+

OH

3

OH

3

N

-NH-CH

3 /OH 3 N cI

CH

3 (I11) (12)

H

3

QC-

CV, (13) 3 cI. (14) CH3

*N\

OH

3 CI* CI* (16) /Cl-

CH

3

H

3 C-ND+ OH CI.- (17) *0 a a.

CH

3 CH 3 CH 3 OH 3 CH CV, (19)

C-

3 N CH 3

OH

3 OH3 N N=N /H 2 NH 2 (110) OH 3 OH3

N+

OH

3 O0H 3

CH

3 N

-C

2

H

CH 3

HOH

/C

2

H

4

-N

OH 3

CH

3 IIN N=N NH 2 CV, (114)

OH

3

OH

3 N=N NH 2 CV (115)

H

OH

3 N=N NH 2 CV (116)

O

3

N

COH

3

H

3 0

H

CH

H

j/ N=N N Ct (117) HC C 2

H

H

3

OH

3 N N=N+ Ci (118)

N

C H 3 N H 3

OH

3 N H X N=N ON \CI. (119) N-

C

2

H

CH 3

OH

3 N /H N \CV (120) CH 2

-CH

2

-NH

2

OH

3

OH

3

OH

3

IH

N H 'N CV (121)

OH

3

OH

3 N

H

it, N=N ON CV (122)

-CH

2 -0H 2

-ON

OH

3 N+ CH N=N /N \01- (123) N

OH

3

H

3

OCH

3 (124) O H 3 =N ON N

H

(125)

OH

3 IIIIII NH 2 (126)

OH

3 NI /0H 2 -OH2-ON 2

H

CI (127) a a.

CH

3

OH

3 OH3

N+

OH

3

NH

2 0-OH 3 cI- 01* (128) (129) 0-OH 3 a a a. a a a.

a a.

OH

3 cI- (130)

-NH

2 CI.- (131) CI- (132)

CH

3 /OH 3 N-<2 N \OH 3 (133) a a.

a a a. a *9

NCH

CHi--N+ I/

H

3

-T

N- N CF (134)

OH

3

OH

3 O H3 N /CH 3

H

3 0-O\ N=N N\C3.CF' (135) r 0/

N

CHO

N N=N /0* HO 0 (ot'i)-t N1 N= 0- H 00 (6c1 c O N N=N

HHO

O

(sl) lo ID HN N=N Z N a. a a HOO0 (9t) lo HO N N=N.

HO

+N

HOj *H aS (9t7) .13 N N=N c HO

+N

NHO

N N=N

CHO

HO

CHO

HN N N=N

N

HOj (zir) Cl* (147) CH 3 S0 4 (4

OH

3

IN

(148)

CAH

CN+ OH3

OH

3 CH 3

SO

4 (149) cIl (150) CIl (11

OH

3 se 0 000 0 .0000 0 00

ICH

3 0-O.H

CN+

KIN N=N NH 2

CH

3 0-OH 3 and CH3 O-CH3 N+

CH

CH

3 CH 3 Among the compounds of structures (Ii) to (152) described above, the ones most particularly preferred are the compounds corresponding to 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 structures (II) to (1112) below: 3

C

H CH 3

//CH

SN=N CH Cl (112) N* I CH33 (113)

CH

3

CH/

(114)

OH

3 /OH3

N

CH

3 (115) OH3

N+

CH

3 S0 4 (116)

OH

3 N

I-N

CH

3 S0 4 (117) 3 IN /H3

CH

3 S0 4 -(118)

OH

3

OH

3 /N CH 2

-CH

2

-CN

/N=N N\ C1 (119) S

OH

3 OH3 N-N+ NN--N N H

CH

3 S0 4 (1110)

H

3 C N H 3 CHH3 CH CH 3 N-NN CH N3 C 3 0 4 (ii NH

C

3 and a I N CH 3 S0 4 -(1112) Hq 2 N CH 3 Among the cationic direct dyes of formula (III) which can be used in the dye compos itions in accordance with the invention, mention may be made more particularly of the compounds corresponding to structures (III1) to (11118) below:

N+'

CH

3

-CH=N-N

I-

'OH

3 (1111) 0 CH=N-N CH 3 (1112) 0 Hc N

CH

3

LCH=N-

CI, (1113)

CH

3

SO

4 -(1114) -OCH- CV (1115)

H

3

C-

CH

3

SO

4 (1116)

CH

3 SO4 (1117)

H

3

C-

H

3 C-N+ CH= H C-N+01= cI, (1118) C, ci- (1119)

CH

3

S.

S S 55.* 5

S

5555**

CH

3 S0 4 -(11110)

CH

3

SO

4 (11) ICH 3 S0 4 (11112) OCH CH 3 S0 4 '(113 N OCH 3 (11114)

CH

3 000 (11115)

H

3 C-N+ D- CH=CH NH 2

CH

3 000 (11116) (11117) ;and (11118) Among the compounds of structures (1111) to (11118) described above, the ones most particularly preferred are the compounds correspfnding to 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 structures (III'l) to (III'3) below: (111'1) CH-N+ CH=CH (111'2) and (11'3)

CH

3

IH

CH3 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 corresponding to structures (IV) 1 to (IV) 77 below: 0 N- NN OH(V) I-

(V)

N

38 N

NHCOCH

3

~'CH

3 N+ N=N N"CHC 2 H I b CH3 CH 2

OH

0 N N=N

N

2 (tV) CHC 0 aN+ N=N -H O

N

7 *I I -CH CH OH

H

3 CN-' N=N 2 2 7 H C CH 2

CH

2 0H (V) 3 1 C 2

H

5 I8 0 OH3 HO CN+ N=N N 7 ~(tV) 9 3 K

OH

3 0 UO ~N=N -N O 0

-I

NAOHN-& N=N, +NO ZH -0.

"L(AI) HN_& N=N HOH ON I' HOzHO zHO N /N=N 9 z 0 HN N=N+N 0 "I(Al) N N N +N

,-CH

3 H 3

OH

N+ N= N3 17

OH

3 C H 3

NHCOCH

3 I OH3

H

3

O

I 7

CH

3 ('1 0 0: I H 3 O H 3 N N=N N0 2 ,H

IV

2 o o 0 Nf N =N N' (V)

~HO

t

Z(AI)

c0 HO N N

N)

HO

I

U U U. U U U 9

NAI)

HO0zHO z HOIN HO z HO N 0

(AI)

c HO- Cr(AI) -0 ~HO NN

H

~CH3 I N+ NN N NH 2 ('V)29

UH

3

CH

3 S0 4

OH

3 2 OH N+ N=N N N 2 HH 30

OH

3 NCH CH OH

CH

3 s0 4 I N+ N=N N N 2H 31 OH -a0 2

H

0H 3 S0 4 N+ N=N NO3 (I'V)32 CH SO 4 N Cl OH3 I 3 0H 3 S0 4 1~ ~H

H

3 CN4 N=N N" ('V)34

CH

3 CH304 43

H

3

C

N+ N=N -CH 3 Cn\ N 1-

CH

3 ('V)3

CH

3 S0 4 N NHCOCH 3 Ia N=N /H

'V

I CH3

OH

3

CH

3 S0 4 IN

H

3 37

CH

3

SO

4

CH

3 V.

V

V

V.

V V

V.

V

V

*V4.

V

V

V. V V 7

CH

3 CH 3 3

H

3

C

CH

3

SO

4

CH

3

H

3 0 NN=N OH 3 (IV6 3 O2H C~ H~ S- C H C H 3

SO

4

OH

3 41

CH

3 S0 4

OH

3

NHCOCH

3 "'IICH 3

(IV)

42 C H SO-

S

**5R *5 S S

S

SS

*5 S S 9S 5

S

5.5.55 S. S I S 5*

H-CH

~N=N N Br 0 4

H

9 N+ NN

H

3 aN N 00H 3 0 N

CH

3 SO 0 6

H

(I'1)43 ('V)44 N0 /n I N+ N N 4 I

N

0

H

0 N+L NN

,,CH

3 I /H N')4

CH

3 C10 4 3

CH

3 S N+-kN =N CH 3

(IV)

47 CH3 I N+ N-N 0000 *sees. H 2 N .00::NH 2 .00.

SOS. SCH 3 2 49 11ees OH 3

NH

2 000-) H C N+<N =N NH(I), so .5104

O

S 0- C N± NN \NH

(IV)

5

OH

3 OH

OH

N N =N o NH

(V)

5 2 010 N OH 3 N+ N=N /H 2 OH(V) 0

NHOCH

3 N H 3 aN N OH 0 C104

NH

2 47 CH 3 I N+ N=N OH (IV)57 I 0 0 CH 3 I 0 1 O H 3 .0

OH

oo*

CH

N+ N N OH(I) ooo ~I 0 0 0H 000 N+ N=N N' 0.0

O-H

3 0 NO NO 2 01 N N N O H (V 62 I 0 0 2Nr I+ N

N=

N

I-

OCH

3

CH

3

SO

4 H 3 C N= N 0

OH

3

N\

OH

3

(IV)

64 ([V)6

-N

(IV)

66

N=N

/CH 3

""H

3

(IV)

6 7

CH

3

SO

4

NN

N 6 8 N0 N4 N=N -s(V) 69 O0H 3 HO

NH

CH

3

SO

4

NH

2 aN+ N=N O NH 2 70 0

CH

3 0

H

N

I N+ N=N 0 71 N CH 3 N N=N

NH

2 7 2

/CH

2

CH

2

OH

*9.N=N -ON CH2OH2OH N+ -(tV) 7 3

CH

3

CH

3

SO

4

OCH

3 .9N=N -ONH 2

CHS

4

NH

2 ('V)74

OH

3 I

CH

3 N N

HNH

2 N+

NH

2 (7V)7 I CH 3

SO

4

CH

3

CH

3

CH

3 N+ N= N

NH

2 (IV) 76 I

O

NH

2 and

CH

3

CH,

N+ H (IV)T 1 CH 3 SO4 NO 2

CH

3 The pyrazolo[l,5-a]pyrimidine(s) of formula in accordance with the invention and/or the addition salt(s) thereof with an acid or with a base 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% a by weight approximately relative to this weight.

"The cationic direct dye(s) used according to 0 the invention preferably represent(s) from 0.001 to by weight approximately relative to the total weight of

I

the dye composition and even more preferably from 0.005 to 5% by weight approximately relative to this weight.

The medium which is suitable for dyeing (or the support) generally consists of water or of a mixture of water and at least one organic solvent in order to dissolve the compounds which would not be sufficiently soluble in water. By way of organic solvent, mention may be made, for example, of Ci-C 4 alkanols such as ethanol and isopropanol; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and aromatic alcohols such as benzyl alcohol or phenoxyethanol, 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.

20 The pH of the dye composition in accordance with the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value using acidifying or basifying agents commonly used for 25 dyeing 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, tartaric acid, citric acid or 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 triethanolamines, 2-methyl-2-aminopropanol and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (Vi) below: R3 R3 N-W-N (VI) /R3

R,

in which W is a propylene residue optionally 15 substituted with a hydroxyl group or a Ci-C 6 alkyl radical; R 36

R

37

R

38 and R 39 which may be identical or different, represent a hydrogen atom or a Ci-C 6 alkyl or

C-C

6 hydroxyalkyl radical.

The dye composition in accordance with the invention can also contain one or more couplers which can be chosen from the couplers used conventionally in oxidation dyeing and among which mention may be made in particular of meta-phenylenediamine meta-aminophenols, meta-diphenols and heterocyclic couplers such as, for example, indole derivatives, indoline derivatives, pyridine derivatives and pyrazolones, and the addition salts thereof with an acid.

These couplers are chosen more particularly from 2-methyl-5-aminophenol, 5-N- (p-hydroxyethyl)amino- 2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-l,3-dihydroxy-* benzene, 2,4-diamino-l-(P-hydroxyethyloxy)benzene, 2-amino-4- (-hydroxyethylamino)-l-methoxybenzene, 1,3diaminobenzene, 1, 3-bis (2,4-diaminophenoxy)propane, sesamol, a-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one and l-phenyl-3-methylpyrazol-5-one, and the addition salts thereof with an acid.

When they are present, these couplers preferably represent from 0.0001 to 10% by weight S. approximately relative to the total weight of the dye composition, and even more preferably from 0.005 to 20 by weight approximately relative to this weight.

The dye composition in accordance with the invention can also contain one or more additional oxidation bases other than a and/or one or more non-cationic direct dyes, in 4~ 54 particular in order to modify the shades or to enrichthen! with glints.

Among the additional oxidation bases which can be used in the dye compositions in accordance with the invention, mention may be made of para-phenylenediamines, bis (phenyl) alkylenedianines, para-aminophenols, ortho-aminophenols and heterocyclic bases.

Among the para-phenylenediamines, mention may be made more particularly, by way of example, of paraphenylenediamine, para-toluylenediamine, 2-chloro-paraphenylenediamine, 2,3 -dimethyl-para-phenylenediamine, 2, 6-dimethyl-para-phenylenediamine, 2, 6-diethyl-paraphenylenediamine, 2, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-paraphenylenediamine, N, N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis (phydroxyethyl) -para-phenylenedianine, 4-N, N-bis hydroxyethyl) amino-2-methylaniline, 4-N,N-bis (fhydroxyethyl) amino-2-chloroaniline, 2-f-hydroxyethylpara-phenylenedianine, 2-f luoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (j-hydroxypropyl) para-phenylenediamine, 2 -hydroxymethyl-paraphenylenediamine, N, N-dimethyl-3-methyl-paraphenylenediamine, N-ethyl-N- (J-hydroxyethyl) -paraphenylenediamine, N- (f,y-dihydroxypropyl) -paraphenylenediamine, N- -aminophenyl) -para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-f3-hydroxyethyloxy-para-phenylenediamine, 2 -f-acetylaminoethyloxy-para-phenylenediamine and N- (-methoxyethyl) para-phenylenediamine, and the addition salts thereof with an acid.

Among the para-phenylenediamines mentioned above, para-phenylenedi amine, para- toluylenediamine, 2--sopropyl-para-phenylenediamine, 2-p3-hydroxyethylpara-phenylenediamine, 2 -p-hydroxyethyloxy-paraphenylenediamine, 2, 6-dimethyl-para-phenylenediamine, 2, 6-diethyl-para-pheny-efldiamfine, 2, 3-dimethyl-paraphenylenediamine, N,N-bis (f-hydroxyethyl) -paraphenylenediamine, 2 -chioro-para-phenylenediamine and 2-f-acetylaminoethyloxy-para-phenylenediamine and the addition salts thereof with an acid are most particularly preferred.

Among the bis (phenyl) alkylenediamines, mention may be made more particularly, by way of 20 example, of N,N'-bis(f3-hydroxyethyl)-N,N'-bis(4'-amilophenyl) 3-diaminopropanol, N,N' -bis (P-hydroxyethyl) N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4aminophenyl) tetramethylenediamine, N,N' -bis (f-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediamine, 56 N,N'-bis(4-methylaminophenyl)tetramethylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,5dioxaoctane, and the addition salts thereof with an acid.

Among the para-aminophenols, mention may be made more particularly, by way of example, of paraaminophenol, 4-amino-3-methylphenol, 4-amino-3fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(p-hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol, and the addition salts thereof with an acid.

Among the ortho-aminophenols, mention may be made more particularly, by way of example, of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6methylphenol and 5-acetamido-2-aminophenol, and the addition salts thereof with an acid.

20 Among the heterocyclic bases, mention may be made more particularly, by way of example, of pyridine derivatives, pyrimidine derivatives other than the compounds of formula in accordance with the invention and pyrazole derivatives.

25 Among the pyridine derivatives, mention may be made more particularly of the compounds described, f or example, -in patents GB 1, 026, 978 and GB 1, 153, 196, such as 2, 5 -diaminopyri dine, 2- (4-methoxyphenyl) amino- 3 -aminopyri dine, 2, 3 -di amino- 6-me thoxypyridine, 2- (fmeth oxyethyl) amino-3-amino-6-methoxypyridine and 3,4diaminopyridine, and the addition salts thereof with an acid.

Among the pyrimidine derivatives, mention may be made more particularly of, the compounds described, for example, in German patent DE 2,359,399 or Japanese patents JP 88-169,571 and JP 91-10659 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2, 5, 6-triarrinopyrimidine, 2hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5, 6diaminopyrimidine and 2, 5, 6-triaminopyrimidine.

Among the pyrazole derivatives, mention may be made more particularly of the compounds described in patents DE 3,843,892, DE 4,133,957 and patent applications WO 94/08969, WO 94/08970, FR-A-2,733,749 and DE 195 43 988, such as 20 pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4'chlorobenzyl)pyrazole, 4, 5-diamino-1, 3-dimethylpyrazole, 4, 5-diamino-3-methyl-l-phenylpyrazole, diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3dimethyl-5-hydrazinopyrazole, 1-benzyl-4, 5-diamino-3- *ehlyaoe *,-imn--et-uy--eh 5 eypyrazole, 4,5-diamino-3-tert-butyl- l-methylyzl 4,5-diamino-1-(P-hydroxyethyl)-3-methylpyrazole, diamino-l-ethyl-3-methylpyrazole, 3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-l-ethyl-3hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-lmethylpyrazole, 4,5-diamino-3-hydroxymethyl-l-isopropylpyrazole, 4,5-diamino-3-methyl-l-isopropylpyrazole, 4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5triaminopyrazole, 3,5-diamino-l-methyl-4-methylaminopyrazole and 3,5-diamino-4-(P-hydroxyethyl)amino-lmethylpyrazole, and the addition salts thereof with an acid.

When they are used, these additional oxidation bases preferably represent 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.

In general, the addition salts with an acid which can be used in the context of the invention (compounds of formula additional oxidation bases and couplers) are chosen in particular from the hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates. The addition salts with a base which can be used in the 59 context of the dye compositions of the invention (compounds of formula are, in particular, those obtained with sodium hydroxide, potassium hydroxide, aqueous ammonia or amines.

The dye composition in accordance with the invention can also contain various adjuvants used conventionally in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickening agents such as, for example, nonionic guar gums, antioxidants, penetrating agents, sequestering agents, fragrances, buffers, dispersing agents, conditioners such as, for example, volatile or non-volatile, modified or unmodified silicones, film-forming agents, ceramides, preserving agents and opacifiers.

Needless to say, a person skilled in the art will take care to select this or these optional 20 additional compounds such that the advantageous properties intrinsically associated with the oxidation dye composition in accordance with the invention are •not, or are not substantially, adversely affected by the addition(s) envisaged.

25 The dye composition according to the invention can be in various forms, such as in the form of liquids, powders, creams or gels or any other form which is suitable for dyeing keratin fibres, and in particular human hair.

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

According to this process, at least one dye composition as defined above is applied to the fibres, the colour being developed at acidic, neutral or alkaline pH using a non-enzymatic oxidizing agent which is added to the dye composition only at the time of use or which is present in an oxidizing composition that is applied simultaneously or sequentially.

1According to one preferred embodiment of the dyeing process of the invention, the dye composition described above is preferably mixed, at the time of 9* use, with an'oxidizing composition containing, in a medium which is suitable for dyeing, at least one non- 20 enzymatic oxidizing agent present in an amount which is sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibres and is S"left to stand on the fibres for 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, after which the fibres are rinsed, washed with shampoo, rinsed again and dried.

61 The oxidizing agent present in the oxidizing composition as defined above can be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratin fibres, and among which mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromates, peracids and persalts such as perborates and persulphates. Hydrogen peroxide is particularly preferred.

The pH of the oxidizing composition containing the oxidizing agent as defined above is such that, after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibres preferably ranges between 3 and 12 approximately, and.

even more preferably between 5 and 11. It is adjusted to the desired value with the aid of acidifying or basifying agents commonly used for dyeing keratin fibres and as defined above.

The oxidizing composition as defined above can also contain various adjuvants conventionally used 20 in compositions for dyeing the hair and as defined above.

The composition which is finally applied to the keratin fibres can be in various forms, such as in .the form of liquids, creams or gels or any other form which is suitable for dyeing keratin fibres, and in particular human hair.

Another subject of the invention is a multicompartment dyeing device or multi-compartment dyeing "kit" or any other multi-compartment packaging system, a first compartment of which contains the dye composition as defined above and a second compartment of which contains the oxidizing composition as defined above. These devices can be equipped with a means for applying the desired mixture to the hair, such as the devices described in patent FR-2,586,913 in the name of the Applicant.

The example which follows is intended to illustrate the invention without thereby being limiting in nature.

OOOOO

o* EXAMPLE OF DYEING IN ALKALINE MEDIUM The dye composition below, in accordance with the invention, was prepared: Pyrazolo[l,5-a]pyrimidine-3,7-diamine dihydrochloride (oxidation base) 0.333 g Cationic direct dye of formula (12) 1 g 960 ethyl alcohol 18 g Pentasodium salt of diethylenetriaminepentaacetic acid 1.1 g Aqueous ammonia containing 20% NH 3 10.0 g Demineralized water qs 100 g The above dye composition was mixed weight for weight, at the time of use, with a hydrogen peroxide solution by weight) of pH 3.

The mixture obtained was applied to locks of natural grey hair containing 90% white hairs, for minutes. The locks were then rinsed, washed with a 20 standard shampoo, rinsed again and then dried.

The hair was dyed in an intense fuchsia shade.

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 (9)

1. Composition for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair, characterized in that it contains, in a medium which is suitable for dyeing: at least one pyrazolo[1,5-a]pyrimidine as oxidation base; and at least one cationic direct dye; the said composition being free of any enzymatic system capable of bringing about the oxidation of the

2. Composition according to Claim 1, characterized in that the is (are) chosen from the compounds of formula (V) below, and the addition salts thereof with an acid or with a base: N 2 [NRRJp e, N 2 (V) 7 [NRR3SFq in which: 20 R 33 R 34 R 35 and R 36 which may be identical or different, denote a hydrogen atom, a C 1 -C 4 alkyl radical, an aryl radical, a Ci-C 4 hydroxyalkyl radical, a C 2 -C 4 polyhydroxyalkyl radical, a (Ci-C 4 )alkoxy- (C 1 -C 4 )alkyl radical, a Ci-C 4 aminoalkyl radical (it being possible for the amine to be protected with an acetyl, ureido or sulphonyl radical), a (C-C 4 )alkyl- amino (C 1 -C 4 )alkyl radical, a di (C 1 -C 4 alkyl] amino- (Ci-C 4 )alkyl radical (it being possible for the dialkyls to form a 5- or 6-membered aliphatic or heterocyclic ring), a hydroxy(C 1 -C 4 alkyl- or di [hydroxy-(C 1 -C 4 alkyl] amino (Ci-C 4 alkyl radical; the radicals R, which may be identical or different, denote a hydrogen atom, a Ci-C 4 alkyl radical, an aryl radical, a Ci-C 4 hydroxyalkyl radical, a C 2 -C 4 poly- hydroxyalkyl radical, a Ci-C 4 aminoalkyl radical, a (CI-C 4 )alkylamino(C 1 -C 4 )alkyl radical, a di[ (Ci-C 4 alkyl]amino(Cl-C 4 )alkyl radical (it being possible for the dialkyls to form a 5- or 6-membered aliphatic or heterocyclic ring), a hydroxy(C 1 -C 4 )alkyl- or di [hydroxy(C 1 -C 4 )alkyl] amino(C-C 4 alkyl radical, an amino radical, a (C 1 -C 4 )alkyl- or di[ (C-C 4 )alkyl] amino radical; a halogen atom, a carboxylic acid group or a 20 sulphonic acid group; i is equal to 0, 1, 2 or 3; p is equal to 0 or 1; q is equal to 0 or 1; n is equal to 0 or 1; 25 with the proviso that: the sum p q is other than 0; (ii) when p q is equal to 2, then n is equal to 0 and the groups NR 33 R 3 4 and NR 35 R 36 OCCUPY the 3); or positions; (iii) when p q is equal to 1, then n is equal to 1 and the group NR 33 R 34 (or NR 3 5 R 3 6 and the 01H group occupy the or positions.

3. Composition according to Claim 2, characterized in that the pyrazolo[l,5-alpyrimidines of formula are chosen from: pyrazolo[1,5-alpyrimidine-3, 7-diamine; 2-rethylpyrazoloEl, 5-alpyrimidine-3,7-diamine; 2,5-dimethylpyrazolo[1,5-alpyrimidine-3,7-diamine; pyrazolo[l,5-a]pyrimidine-3, 2,7-dimethylpyrazolol,5-alpyrirnidine-3, 3-aminopyrazolo[1, 5-alpyrimidin-7-ol; 3-amino-5--methylpyrazololil,5-alpyrimidin-7-ol; 3-aminopyrazolo[l, *too 2- (3-aminopyrazolo Il, 5-alpyrimidin-7-ylamino)ethanol; 3-amino-7-f-hydroxyethylamino-5-methylpyrazolo- -methyl-7-imidazolylpropylamino pyrazolo- [1 -pyrimidine; (7-aminopyrazolotl, 5-alpyrimidin-3-ylamino)ethanol; (3-arinopyrazoloti, 5-alpyrimidin-7-yl)-(2-hydroxY- 6 ethyl) amino] ethanol; -5,6-dimethylpyrazolo(l, 5-alpyrimidine-3,7-diamine; 67 2, 6-dimethylpyrazolofi, 5-allpyrimidine-3 ,7-diamine; 2,5,N7,N7-tetramethylpyrazolo[1,5-alpyrimidine-3,7- diamine; and the addition salts thereof with an acid or with a base.

4. Composition according to any one of the preceding claims, characterized in that the cationic direct dye(s) is (are) chosen from cationic aminoanthraquinones, cationic mono- or diazo compounds and cationic naphthoquinones. Composition according to Claim 4, characterized in that the cationic direct dyes Are chosen from F(p-aminophenyl) azo] -7-hydroxy- 2-naphthyl] trimethylammonium chloride, the combination of 3-F (4-axino-6-bromo-5,B-dihydro-l-hydroxy-8-imino-5- oxo-2-naphthyl) amino] N-trimethylbenzenaminium chloride and of 3- 6-dibromo-5, 8-dihydro-1-hydroxy-

8-imino-5-oxo-3-naphthyl) amino] N,N-trimethyl- benzenaminium chloride, 7-hydroxy-8- F(2-methoxy- phenyl) azo] -N,N,N-trimethyl-2-napht halenaminium chloride, (8-F (4-amino-2-nitrophenyl'lazo] -7-hydroxy-2.-- eo naphthylltrimethylaimonium chloride, the combination'of [8-f (4-amino-3-nitrophenyl)azo] -7-hydroxy-2- o: naphthylltrimethylarnmonium. chloride and of amino-2-nitrophenyl) azo) -7-hydroxy-!2-naphthyl] trimethylammonium chloride, 3-F 5-dihydro-3-methyl-5- 68 oxo-l-phenyl-:H-pyrazol-4-yl)azo]-N,N,N-trimethyl- benzenaminium chloride, 1-(y-aminopropyl)aminoanthra- quinone hydrochloride, l-N-(methylmorpholiniumpropyl)- amino-4-hydroxyanthraquinone methyl sulphate and Basic Orange 69®. 6. Composition according to any one of Claims 1 to 3, characterized in that the cationic direct dye(s) is (are) chosen from the compounds of formulae (III), (III') and (IV) below: a) compounds of formula R' 3 R A -D=D N (I) X- R, R 3 in which: D represents a nitrogen atom or a -CH group, RI and R 2 which may be identical or different, represent a hydrogen atom; a Ci-C 4 alkyl radical which can be substituted with a -CN, -OH or -NH 2 radical or o* 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 20 radicals; a 4'-aminophenyl radical, R 3 and R' 3 which may be identical or different, represent a hydrogen atom or a halogen atom chosen from chlorine, bromine, iodine and fluorine, or a cyano, C 1 -C4 alkoxy or acetyloxy radical, X- represents an anion preferably chosen from chloride, methyl sulphate and acetate, A represents a group chosen from structures A 1 to A 19 below: /R 4 N +iN +N +N N R 4 R 4 R +Z ox N-N 4 R 4 N-N N I R4 -N+ 4 N A 7 IF R4 N RN N=N+ R 5 All N+ A 1 2 C--N+ R4 4 F IN ISI'lI" N-N+ A1 3 A 1 4 p R N+ N,S A16 N /~R4 .1 M4 and R4 R4 N N+ R4 in which R 4 represents a Ci-C 4 alkyl radical which can be substituted with a hydroxyl radical and Rs represents a Ci-C 4 alkoxy radical, with the proviso that when D represents -CH, A represents A 4 or A 13 and R 3 is other than an alkoxy radical, then Ri and R 2 do not simultaneously denote a hydrogen atom; 10 b) compounds of formula (II): B-N=N N (II) RR 7 X- T R 7 in which: R 6 represents a hydrogen atom or a Ci-C 4 alkyl radical, R 7 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 R 6 a heterocycle, optionally containing oxygen and/or nitrogen, which can be substituted with a C 1 -C 4 alkyl radical, R 8 and R9, 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 CI-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 structures B1 to B6 below: Ro Ro /Rio R 10 ^Ro10 N--N N N-N SI I I I I R S N S RK12 B1 B2 B3 nl/ (I 73 RRio oRi aN and I I R 0 S R /o B4 B5 B6 in which R 1 o represents a C 1 -C 4 alkyl radical and R 11 and R 12 which may be identical or different, represent a hydrogen atom or a CI-C 4 alkyl radical; c) compounds of formulae (III) and (III'): R14 R 14 E-D =D2 j~N)E D, R E--D X1 X. R 17 N X" R1s I R (1I) (III') in which: R 13 represents a hydrogen atom, a Ci-C 4 alkoxy radical, 10 a halogen atom such as bromine, chlorine, iodine or fluorine or an amino radical, R 14 represents a hydrogen atom, a CI-C 4 alkyl radical or forms, with a carbon atom of the benzene ring, a heterocycle optionally containing oxygen and/or 15 substituted with one or more Ci-C 4 alkyl groups, II 74 R 15 represents a hydrogen atom or a halogen atom such as bromine, chlorine, iodine or fluorine, R 16 and R 17 which may be identical or different, represent a hydrogen atom or a C 1 -C 4 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 Di and D 2 simultaneously 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 structures El to E8 below: g R'-N N R El E2 15 OH R' R' N N4' N N N* E3 E4 R' o eg *0I R' and I I\ R' R' R' E6 E7 E8 in which R' represents a Ci-C 4 alkyl radical; when m 0 and Di represents a nitrogen atom, then E can also denote a group of structure E9 below: R' N E9 R' in which R' represents a C1-C 4 alkyl radical; d) compounds of formula (IV): N -J (IV) in which: 10 G represents a group chosen from structures GI to G3 below: 0 1 R 20 N ~-Z R, N RP N I X X M R18 R 18 G, G 2 G 3 in which: R 1 8 denotes a C 1 -C 4 alkyl radical, a phenyl radical, a phenyl radical substituted with a C 1 -C 4 alkyl radical or a halogen atom chosen from chlorine, bromine, iodine and fluorine; R 19 denotes a Ci-C 4 alkyl radical or a phenyl radical; R 20 and R 21 which may be identical or different, represent a Ci-C 4 alkyl radical, a phenyl radical or 10 together form, in G 1 a benzene ring substituted with *..one or more Ci-C 4 alkyl, CI-C 4 alkoxy or NO 2 radicals, or together form, in G 2 a benzene ring optionally substituted with one or more Ci-C 4 alkyl, Ci-C 4 alkoxy or NO 2 radicals; R 20 can also denote a hydrogen atom; 15 Z denotes an oxygen or sulphur atom or a group -NR 1 9; M represents a -CH, -CR" denoting Ci-C 4 alkyl) or -NR 22 group; K represents a -CH, -CR" denoting Ci-C 4 alkyl) or -NR22(X group; -NR 22 group; 77 P represents a -CH, -CR" denoting Ci-C 4 alkyl) or -NR22(X-)r group; r denotes zero or 1; R 22 represents an atom a C 1 -C 4 alkoxy radical or a C 1 -C 4 alkyl radical; R 23 and R 24 which may be identical or different, represent a hydrogen atom or halogen atom chosen from chlorine, bromine, iodine and fluorine, a Ci-C 4 alkyl or Ci-C 4 alkoxy radical or an -NO 2 radical; X- represents an anion preferably chosen from chloride, iodide; methyl sulphate, ethyl sulphate, acetate and perchlorate; with the proviso that: if R 22 denotes then r denotes zero; if K or P or M denotes an (C 1 -C 4 )alkyl X- group, then at least one of the radicals R 23 and R 24 is other than a hydrogen atom; if K denotes -NR 2 2(X)r, then M P -CH or -CR"; if M denotes -NR22(X-)r, then K P -CH or -CR"; if P denotes -NR 2 2 then K M and denote -CH or 20 -CR; if Z denotes a sulphur atom and R 21 denotes a Ci-C 4 alkyl radical, then R 20 is other than a hydrogen atom; if Z denotes -NR 2 2 and R 19 denotes a Ci-C 4 alkyl S" radical, then at least one of the radicals R 18 R 19 or R 20 in the group of structure G 2 is other than a Ci-C 4 alkyl radical; S4. I, 78 J represents: either a group of structure J 1 below: P 27 J 6 in which: R 25 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a Ci-C 4 alkyl or Ci-C 4 alkoxy radical, a radical -OH, -NO 2 -NHR 28 -NR 29 R 30 or -NHCO(Ci-C 4 )alkyl, or forms, with R 26 a 5- or 6-membered ring which may or may not contain one or 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 1 -C 4 alkyl or Ci-C 4 alkoxy radical, or forms, with R 27 or R 28 S 15 A 5- or 6-membered ring which..may or may not contain .o one or more hetero atoms chosen from nitrogen, oxygen and sulphur; R 27 represents a hydrogen atom, an -OH radical, an -NHR 28 radical or an -NR 29 R 3 o radical; 20 R 28 represents a hydrogen atom, a Ci-C 4 alkyl radical, a C 1 -C 4 monohydroxyalkyl radical, a C 2 -C 4 polyhydroxyalkyl radical or a phenyl radical; 79 R 29 and R 30 which may be identical or different, represent a C 1 -C 4 alkyl radical, a C1-C 4 monohydroxyalkyl radical or a C 2 -C 4 polyhydroxyalkyl radical; or a 5- or 6-membered heterocyclic group containing nitrogen, which can contain other hetero atoms and/or carbonyl groups and 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 J N 0 F2 in which: 0@ R31 and R 32 which may be identical or different, represent a hydrogen atom, a Ci-C 4 alkyl radical or a 00 phenyl radical; 15 Y denotes a -CO- radical or the radical c CH 3 S n 0 or 1, it being understood that when n 1, then U denotes a -CO- radical. 7. Composition according to Claim 6, characterized in that the cationic direct dyes of formula are chosen from the compounds corresponding to structures (Il) to (152) below: OH 3 N+ OH 3 NH-OH 3 CI" (11) *00* 00009

9.. 0 9* .9 H 3 C /CH 3 N CH 3 (12) CF (13) CIl (14) CI. 3 CIl (16) 3 Cl (17) HO-H 4 Cj--N+ CH CH OH OH 3 0 N=N N CH (18) OH 3 C H CH 3 3 NN N CHH3 OH 3 N=N NH 2 OF (110) OH 3 0H O 3 N+/ N=N NH O2 (112 N 0H OH 3 83 CH 3 CN+ C 2 H 4 -CN II -N=N ON /CL* (113) N C 2 H 4 -CN CH 3 OH 3 lN. N=N -NH 2 c 14 OH 3 C NH -N 2 CL, (115) OH 3 CI OH3 OH 3 N+' N=N NH 2 01,- (116) H 3 N OH 3 H 3 N /H N+ NN I' N CL, (117) I.c HO 3 0 2 84 CH 3 N' N+ N=N 0CL, (1 18) NI N CH 3 CH 3 13 CH 3 CH 3 KN=N N cl, (119) N+ CAH CH 3 CH 3 Fr N=N N CL (120) N- CH 2 -CH 2 -NH 2 OH 3 CH 3 CH H N=N. N CL, (121) CH -0H 2 7OH CH 3 CH 3 i~ N=N ON /CL (122) N+ CH 2 -CH 2 -CN CH 3 OH 3 OH NN+ N CH3 OH 3 CH 3 N=N N CH3 'IN+ N CH OH 3 OH OH 3 OH 3 O CH/3 N=NN N+ OHN= H 3 CH 3 N+ /0CH 2 -0H 2 -CN Cs N=N ON\ H (123) (124) (125) (126) CV (127) /CH 3 0H 3 CH 3 0-OH 3 CH3 CN+ CI' cI CH3 *N\ CH 3 N C H 3 H 3 C-N+ -NN-N\ CH 3 CH 3 N+ CH 3 NN ~NHI, (128) (129) CI. (13 0) C1 (131) CI. (132) AC CH H 3 N-;N I CH 3 OH 3 CH N N=NC -N\ CH 3 OH 3 3 O H 3 N N+ O H3 H 3 C-O N=N N N H Ci- (133) 01- (134) OF' (135) O. H 3 S.O. 000. o CI- (136) 01 (137) O 3 CHO £HO H HOvI N=N N c HO (LtHO.1 +N \N N=N HO (OVI) _0 ~N N=N HOs CHO ~HO\ N- (6 0I .10 HON N=N HO O-H CHO (gel) .10 \N N=N 0-O cH £HO +N=N HO (143) CH3 Cl (144) OH3 N+ CH 3 NN (145) OH3 NS C3 N OH 3 01- (146) 01- (147) OH 3 N+ 0? OH 3 OH 3 N+ OCH *N\ CH 3 CNi N=N -N/C ~CH 3 CH N=N 0~ N OH 3 OH 3 0-OH 3 N. N=N NH 2 OH 3 0O 3 CH3 0-CH 3 LN=N -N N CH 3 OH 3 OH 3 0H 3 S0 4 CH 3 S0 4 01 (150) (148) (149) ~0 (151) ,and (152) 8 S. S 8 *4 8. Composition according to Claim 6, characterized in that the cationic direct dyes of formula (II) are chosen from the compounds corresponding to structures (Ml) to (1112) below: H 3 C, OH 3 N O- N\ CH/ OH 3 CokrjJ+N=N -N N N+ \CH 3 OH 3 3 OH3 .3 OH 3 j~N 0I1 CI- 01 C1, (112) (114) egos S.00 66* C 3 OH3 C, N=N N S OH 3 O N CI (115) 4 (OLIO (611) (81 "OS'CHO CHO zNH CHO N HO4 \N, +N c/ CHO (LIi) Svos c HO CHO S \N N c O/ /N CHO c HO-9 \N /N=N cH/ +N C Ho/ OH CHO (911) .tOS cHO 93 CH 3 CH 3 M N+ NH CH3 N N+ N CH 3 SO4 (1111) and CH 3 SO,' (1112) 9. Composition according to Claim 6, characterized in that the cationic direct dyes of formula (III) are chosen from the compounds corresponding to structures (III1) to (III11118) below: C C C. C C. C u f I I /CH=N-N cv, (1111) N+I OH 3 OH 3 0 H 3 .CH 3 N N CH=N-N Cl (1112) OH 3 H 3 C NA' ,CH 3 CH=N-N-- CI (1113) H 3 C 'I- OH3 CH 3 SO 4 -(1114) Il (1115) H 3 c H 3 C-N+ -CH=N-N I CH 3 S0 4 (1116) CH 3 S0 4 (1117) H C-N -CH=N CF (1118) H 3 C- -CI CI (1119) -N CH 3 CH 3 S0 4 (11110) CH 3 SO 4 (111 Cl CH 3 S0 4 (11112) CH 3 S0 4 (11113) CH 3 CI CH 3 (11114) NH 2 CH 3 CO (11115) H 3 C-N+ CH=CH NH 2 CH 3 COO (116 H 3 C-N+ I -N- CH 3 C1 (11117) and Cl-aN=N (11118) a 4I a a a

10. Composition according to Claim 6, characterized in that the cationic direct dyes of formula (III,) are chosen from the compounds corresponding to structures (III'l) to (11113) below: CH3 NH OH 3 CHi-N+ D-C H=CH (112 NH and CH 3 N~NNN ICI (1113) N N OH 3 I (OHr 3

11. Composition according to Claim 6, characterized in that the cationic direct dyes of formula (IV) are chosen from the compounds corresponding to structures (IV) 1 to (IV) 7 .7 below: aN+ N N N (IV) 1 I- C H 3 03 (N N+ N N OH (IV) 2 NHCOCH 3 I CH 3 (IV) 3 I N+ N =N H2C 2O I- -CH 2 CH 2 OH (V) 0 N+ N NH 2 (tV) 0 I H H N N=N \H 2 H2 CH CH O CH 3 HCN+ N=N NZ' K ~CHCHH .3 0 100 CH 3 N+ N=N 1- -0 O*1H 3 (tv) 1 CH 3 N+ N=N -0 2 H CH 3 CH OH N+ N=N N 2 0H 2 0 0 CH 2 CH 2 0H (V CH 3 N+ N=N NH 2 (V) 13 0 CH 3 *CH 3. H =NN 3 1 0 1% H3(I 0 101 ClN+ N=N N' tV 1 I- OH 3 (V, N H 3 N+ N=N NI 7 IC 3 I -<:CH3(V 1 0 CH3 NHOH 3 I N =N -b NN 7 3 (IV) 18 HOC N 3 H3OH C N N =N N ",(V2 0 NH3(V 1 7 0H N+ NN N /NS (tV) 2 0 C*N N=N, N 7 2 (V) 2 2 C HI 2 102 .0t N=N H 3 C 3 N OH3 I N- N=N 71N.-, O H N=N 3 I 0 N=N Nl--CH 2 CH 2 OH I I CH2 CH 2 OH (I'I)23 (IV) 24 2 a. a a a. a a. (I'/)26 ('V)27 IaN=N N/ NC 3 CH 3 S0 4 N+ N=N NH 2 CH 3 S0 4 (I'I)28 I Ifos cHO c O£ CHO '£C(Al) 7C(A,) CHO c HO. HO 9 9 9* 9 9*9*99 9 9 9 9.9. *9 9 9 9999 *9. 9. 99 9 9999 99 99 9 9999 9 9999 9

99.. 99 9* 9 ~HO "(Al) ~OS HO HOHOR HO HO HO HO N O(AI) 9AI) H N Q HO I EOT 104 I H 11 3 CN+ N=N -N"('V)34 CH 3 S0 4 H1 3 0 N N=N Dil NIV)' OH 3 3 CH 3 S0 4 NHCOCH 3 N+ N N-N I (IV) 3 6 CH 3 CH 3 S0 4 N=CNIA (IV) 37 SOC CH 3 N=N C- NH3 CICH O 3 At 105 H C~ 1 4 C 2 H i .CH 3 C3 39 CH 3 INC3 I CH SO 4 CH 3 CH 3 S0 4 (CH 3 41 42 es S S POO* be*** *S. C 2 HS0; C. 2 H N.N=N U 4 H 9 4 3 106 N OH 3 N+1 N=N N (IV)4 OC N CH 3 SO CalH 4H N0 H I N;N N 0" 0 NH I C10_ CH 3 (IV) 4 6 C/"3H C3 0- N NI N= CH 3 47 H 3 C104 ~/N 2 N* NH 0 N N=N NH2-V4 I I COH 3 107 H- 3 C N~ N =N NH C104 O OH N+ N=N NH (tV) 5 1 OH 3 OH S 0 INe:- N=N -O NH ('V)52 C104 OH NH 2 N=N NH (V 1 2 (VS OCH 3 OH 3 N+ N OH (IV)54 0 OCOH 3 C 4 NH 2 108 OH 3 I 0 OJH 3 I- aN+ N=N P OH (IV)58 I 0 1HC -CH *I 0 IH I. N+ N=N CHN (tV)e 9 I~ H 3 0 OH2 109 N+ N=N 2 OH ('V)62 I 0 I 1 N 0 2 N, CH3 N+ N=N N N''Vr, I CH 3 I N CH 3 00H 3 O 3 6 CH 3 SO 4 NO 2 N OH 3 H C N+ NN OH (V 6 OH3 OH 3 N OH 3 N+ N=N OH(I) 0 OH 3 N=NN C H 3 V 6 I ~NH2(V 6 H 3 2 CH 3 SO) 4 110 NN (IV) 68 0 HOa NH C N= N 6 9 00H 3 HO 'NH CH 3 SO 4 NH 2 Nat- N N O NH 2 70 0 OH 3 0 H 'N 0 N N=N 71 0. CH 3 I 'N N=N NH (NY (V) 7 3 I U11 C 3S OCH 3 NHH N2 (IV) 74 IH CH 3 SO 4 UOH 3 N =NN NH 2 IN) H 3 O NH 2 A(IV) 7 OH 3 N OH N=N NH2 (IV) 76 NH2 and N N=NN I ~CH'1 *N NO (IV)T7 *I CH 3 SO4 N 2 OH 3 12. Composition according-.to any one of the preceding claims, characterized in that the **pyrazolo(1,5-alpyrimidine(s) and/or the addition salt(s) thereof with an acid or with a base represent(s) from 0.0005 to 12% by weight relative to the total weight of the dye composition. 112 13. Composition according to Claim 12, characterized in that the and/or the addition salt(s) thereof with an acid or with a base represent(s) from 0.005 to 6% by weight relative to the total weight of the dye composition. 14. Composition according to any one of the preceding claims, characterized in that the cationic direct dye(s) represent(s) from 0.001 to 10% by weight relative to the total weight of the dye composition. 15. Composition according to Claim 14, characterized in that the cationic direct dye(s) represent(s) from 0.005 to 5% by weight relative to the total weight of the dye composition. 16. Composition according to any one of the 15 preceding claims, characterized in that it contains one or more couplers chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers such as, for example, indole derivatives, indoline derivatives, pyridine derivatives and 20 pyrazolones, and the addition salts thereof with an acid. 17. Composition according to any one of the preceding claims, characterized in that it contains one or more additional oxidation bases other than a pyrazolo[l,5-alpyrimidine and/or one or more non- cationic direct dyes. 4* 113 Composition according to Claim 17, characterized in that the additional oxidation base(s) is (are) chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho- aminophenols and heterocyclic bases. 19. Composition according to any one of the preceding claims, characterized in that the addition salts with an acid are chosen from the hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates, and in that the addition salts with a base are chosen from those obtained with sodium hydroxide, potassium hydroxide, aqueous ammonia or amines. 20. Process for the oxidation dyeing of 15 keratin fibres, and in particular of human keratin fibres such as the hair, characterized in that at least one dye composition as defined in any one of Claims 1 to 19 is applied to the said fibres, and in that the colour is developed at acidic, neutral or alkaline pH 20 using a non-enzymatic oxidizing agent which is added to the dye composition only at the time of use or which is present in an oxidizing composition that is applied simultaneously or sequentially. 21. Process according to Claim characterized in that the oxidizing agent is chosen from 114 hydrogen peroxide, urea peroxide, alkali metal bromates, peracids and persalts. 22.. Multi-compartment dyeing device or multi-compartment dyeing "kit", a first compartment of which contains a dye composition as defined in any one of Claims 1 to 19 and a second compartment of which contains an oxidizing composition containing a non- enzymatic oxidizing agent. Dated this 21st day of October 1999 L'OREAL By their Patent Attorneys GRIFFITH HACK Fellows Institute of Patent and Trade Mark Attorneys of Australia o 4* 06