U.S. patent application number 09/820016 was filed with the patent office on 2002-02-07 for compositions for the oxidation dyeing of keratinous fibers comprising at least one oxidation dye and at least one enzymatic oxidizing agent, and dyeing methods.
Invention is credited to Plos, Gregory.
Application Number | 20020013973 09/820016 |
Document ID | / |
Family ID | 8848677 |
Filed Date | 2002-02-07 |
United States Patent
Application |
20020013973 |
Kind Code |
A1 |
Plos, Gregory |
February 7, 2002 |
Compositions for the oxidation dyeing of keratinous fibers
comprising at least one oxidation dye and at least one enzymatic
oxidizing agent, and dyeing methods
Abstract
Compositions for oxidation dyeing of keratinous fibers, for
example, human keratinous fibers such as hair, comprising, in a
medium suitable for dyeing, at least one enzymatic oxidizing agent
and at least one oxidation dye chosen from the pyridine compounds
and acid addition salts, of formula (I) and processes comprising
such compositions.
Inventors: |
Plos, Gregory; (Paris,
FR) |
Correspondence
Address: |
Thomas L. Irving
FINNEGAN, HENDERSON, FARABOW,
GARRETT & DUNNER, L.L.P.
1300 I Street, N.W.
Washington
DC
20005-3315
US
|
Family ID: |
8848677 |
Appl. No.: |
09/820016 |
Filed: |
March 29, 2001 |
Current U.S.
Class: |
8/405 ; 8/406;
8/415; 8/416; 8/421; 8/423 |
Current CPC
Class: |
A61K 8/66 20130101; A61K
8/411 20130101; A61K 8/4926 20130101; A61K 8/415 20130101; A61Q
5/10 20130101 |
Class at
Publication: |
8/405 ; 8/406;
8/416; 8/415; 8/421; 8/423 |
International
Class: |
A61K 007/13 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 30, 2000 |
FR |
00 04061 |
Claims
What is claimed is:
1. Ready-to-use composition for the oxidation dyeing of keratinous
fibers, comprising, in a medium suitable for dyeing: (a) at least
one oxidation dye chosen from the pyridines of formula (I), and
acid addition salts thereof: 6 wherein: R.sub.1 is chosen from a
(C.sub.1-C.sub.4)alkyl group, a (C.sub.1-C.sub.4)monohydroxyalkyl
group, and a (C.sub.2-C.sub.4)polyhydroxyalkyl group, R.sub.2 is
chosen from a (C.sub.1-C.sub.4)alkoxy group, a
(C.sub.1-C.sub.4)monohydroxyalkoxy group, a
(C.sub.2-C.sub.4)polyhydroxyalkoxy group, an amino group, a
mono(C.sub.1-C.sub.4)alkylamino group, a
di-(C.sub.1-C.sub.4)alkylamino group, a monophenylamino group, a
monohydroxyphenylamino group, a monoalkoxyphenylamino group, a
monohydroxy(C.sub.1-C.sub.4)alkylamino group, a
dihydroxy-(C.sub.1-C.sub.4)alkylamino group, a
monohydroxy-(C.sub.2-C.sub.4)alkylamino group, a
dihydroxy-(C.sub.2-C.sub- .4)alkylamino group, a
(C.sub.1-C.sub.4)alkylmonohydroxy-(C.sub.1-C.sub.4)- alkylamino
group and a (C.sub.1-C.sub.4)alkylpolyhydroxy(C.sub.2-C.sub.4)a-
lkylamino group, R.sub.3 is chosen from a hydrogen atom, an amino
group, a mono(C.sub.1-C.sub.4)alkylamino group, a
monohydroxy(C.sub.1-C.sub.4)alky- lamino group and a
mono(polyhydroxy(C.sub.2-C.sub.4)alkyl)amino group; provided that:
when R.sub.2 is chosen form a (C.sub.1-C.sub.4)alkoxy group, a
(C.sub.1-C.sub.4)monohydroxyalkoxy group and a
(C.sub.2-C.sub.4)polyhydroxyalkoxy group, then R.sub.3 is a
hydrogen atom; and (b) at least one enzymatic oxidizing agent
chosen from: (i) a system comprising at least one 2-electron
oxidoreductase and its corresponding at least one donor, (ii) at
least one 4-electron oxidoreductase, and (iii) at least one
peroxidase.
2. A composition according to claim 1, wherein said at least one
oxidation dye of formula (I) is chosen from:
2,6-dimethoxy-3,5-diaminopyridine, 2,3-diamino-6-methoxypyridine,
2-methylamino-3-amino-6-methoxypyridine,
2-(2'-hydroxyphenyl)amino-3-amino-6-methoxypyridine,
2-(4'-hydroxyphenyl)amino-3-amino-6-methoxypyridine,
2-(4'-methoxyphenyl)amino-3-amino-6-methoxypyridine,
2-phenylamino-3-amino-6-methoxypyridine, and acid addition salts
thereof.
3. A composition according to claim 2, wherein said at least one
oxidation dye of formula (I) is chosen from
2,6-dimethoxy-3,5-diaminopyridine and at least one acid addition
salts thereof.
4. A composition according to claim 1, wherein said at least one
oxidation dye of formula (I) is present in an amount ranging from
0.0001 to 10% by weight relative to the total weight of the dye
composition.
5. A composition according to claim 4, wherein said at least one
oxidation dye of formula (I) is present in an amount ranging from
0.005 to 5% by weight relative to the total weight of the dye
composition.
6. A composition according to claim 1, further comprising at least
one oxidation base.
7. A composition according to claim 6, wherein said at least one
oxidation base is chosen from para-phenylenediamines, double bases,
para-aminophenols, orthoaminophenols and heterocyclic oxidation
bases.
8. A composition according to claim 7, wherein said
para-phenylenediamines are chosen from the compounds of formula
(II) and acid addition salts thereof: 7wherein: R.sub.4 is chosen
from a hydrogen atom, a (C.sub.1-C.sub.4)alkyl group optionally
substituted with a nitrogenous group, a
(C.sub.1-C.sub.4)monohydroxyalkyl group, a
(C.sub.2-C.sub.4)polyhydroxyalkyl group, a
(C.sub.1-C.sub.4)alkoxy(C.sub.- 1-C.sub.4)alkyl group, a phenyl
group and a 4'-aminophenyl group; R.sub.5 is chosen from a hydrogen
atom, a C.sub.1-C.sub.4 alkyl group optionally substituted with a
nitrogenous group, a C.sub.1-C.sub.4 monohydroxyalkyl group, a
C.sub.2-C.sub.4 polyhydroxyalkyl group, and a
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl group; R.sub.6 is
chosen from a hydrogen atom, a halogen atom, a
(C.sub.1-C.sub.4)alkyl group, a (C.sub.1-C.sub.4)monohydroxyalkyl
group, a (C.sub.1-C.sub.4)hydroxyalkoxy group, an
acetylamino(C.sub.1-C.sub.4) alkoxy group, a
(C.sub.1-C.sub.4)mesylaminoalkoxy group and a
carbamoylamino(C.sub.1-C.su- b.4)alkoxy group, R.sub.7 is chosen
from a hydrogen atom, a halogen atom and a C.sub.1-C.sub.4 alkyl
group.
9. A composition according to claim 8, wherein said nitrogenous
groups are chosen from amino, mono(C.sub.1-C.sub.4)alkylamino,
di(C.sub.1-C.sub.4)alkylamino, tri(C.sub.1-C.sub.4)-alkylamino,
monohydroxy(C.sub.1-C.sub.4)alkylamino, imidazolinium and ammonium
groups.
10. A composition according to claim 7, wherein said
para-phenylenediamines of formula (II) are chosen from
para-phenylenediamine, para-toluylenediamine,
2-chloro-para-phenylenediam- ine,
2,3-dimethyl-para-phenylenediamine,
2,6-dimethyl-para-phenylenediamin- e,
2,6-diethyl-para-phenylenediamine,
2,5-dimethyl-para-phenylenediamine,
N,N-dimethyl-para-phenylenediamine,
N,N-diethyl-para-phenylenediamine,
N,N-dipropyl-para-phenylenediamine,
4-amino-N,N-diethyl-3-methylaniline,
N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine,
4-amino-N,N-bis(.beta.-hydroxyethyl)-2-methylaniline,
4-amino-2-chloro-N,N-bis(.beta.-hydroxyethyl)aniline,
2-.beta.-hydroxyethyl-para-phenylenediamine,
2-fluoro-para-phenylenediami- ne,
2-isopropyl-para-phenylenediamine,
N-(.beta.-hydroxypropyl)-para-pheny- lenediamine,
2-hydroxymethyl-para-phenylenediamine,
N,N-dimethyl-3-methyl-para-phenylenediamine,
N,N-(ethyl-.beta.-hydroxyeth- yl)-para-phenylenediamine,
N-(.beta.,.gamma.-dihydroxypropyl)-para-phenyle- nediamine,
N-(4'-aminophenyl)-para-phenylenediamine,
N-phenyl-para-phenylenediamine,
2-.beta.-hydroxyethyloxy-para-phenylenedi- amine,
2-.beta.-acetylaminoethyloxy-para-phenylenediamine,
N-(.beta.-methoxyethyl)-para-phenylenediamine, and acid addition
salts thereof.
11. A composition according to claim 10, wherein said
para-phenylenediamines of formula (II) are chosen from
para-phenylenediamine, para-toluylenediamine,
2-isopropyl-para-phenylened- iamine,
2-.beta.-hydroxyethyl-para-phenylenediamine,
2-.beta.-hydroxyethyloxy-para-phenylenediamine,
2,6-dimethyl-para-phenyle- nediamine,
2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylened-
iamine, N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine,
2-chloro-para-phenylenediamine,
2-.beta.-acetylaminoethyloxy-para-phenyle- nediamine and acid
addition salts thereof.
12. A composition according to claim 7, wherein said double bases
are chosen from compounds of formula (III) and acid addition salts
thereof: 8wherein: a linker arm Y chosen from linear and branched
alkylene groups comprising from 1 to 14 carbon atoms optionally
substituted with at least one group chosen from hydroxyl and
(C.sub.1-C.sub.6)alkoxy groups, wherein said linear and branched
alkylene groups are optionally interrupted by or terminated by at
least one group chosen from nitrogenous groups and heteroatoms
chosen from oxygen, sulfur, and nitrogen atoms; Z.sub.1 and
Z.sub.2, which are identical or different, are each chosen from a
hydroxyl group and an amino group optionally substituted with a
group chosen from a (C.sub.1-C.sub.4)alkyl group and said linker
arm Y; R.sub.8 and R.sub.9 which are identical or different, are
each chosen from a hydrogen atom, a halogen atom, a
(C.sub.1-C.sub.4)alkyl group, a (C.sub.1-C.sub.4)monohydroxyalkyl
group, a (C.sub.2-C.sub.4)polyhydroxyalkyl group, a
(C.sub.1-C.sub.4)aminoalkyl group and said linker arm Y; R.sub.10,
R.sub.11, R.sub.12, R.sub.13, R.sub.14 and R.sub.15, which are
identical or different, are each chosen from a hydrogen atom, said
linker arm Y and a (C.sub.1-C.sub.4)alkyl group; provided that:
said compounds of formula (III) contain only one said linker arm Y
per molecule.
13. A composition according to claim 12, wherein said nitrogenous
groups are chosen from amino, mono(C.sub.1-C.sub.4)alkylamino,
di(C.sub.1-C.sub.4)alkylamino, tri(C.sub.1-C.sub.4)-alkylamino,
monohydroxy(C.sub.1-C.sub.4)alkylamino, imidazolinium and ammonium
groups.
14. A composition according to claim 12, wherein said double bases
of formula (III) are chosen from
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-a-
minophenyl)-1,3-diaminopropanol,
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-
-aminophenyl)ethylenediamine,
N,N'-bis(4-aminophenyl)tetramethylenediamine- ,
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediami-
ne, N,N'-bis(4-methylaminophenyl)-tetramethylenediamine,
N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine,
1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and addition salts
thereof.
15. A composition according to claim 14, wherein said double bases
of formula (III) are chosen from
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-a- minophenyl)-1,3-di
aminopropanol, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoct- ane, and
acid addition salts thereof.
16. A composition according to claim 7, wherein said
para-aminophenols are chosen from the compounds of formula (IV) and
acid addition salts thereof: 9wherein: R.sub.16 is chosen from a
hydrogen atom, a halogen atom, a (C.sub.1-C.sub.4)alkyl group, a
(C.sub.1-C.sub.4)monohydroxyalkyl group,
a(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl group, a
(C.sub.1-C.sub.4)aminoalkyl group and a
hydroxy(C.sub.1-C.sub.4)alkylamin- o(C.sub.1-C.sub.4)alkyl group,
R.sub.17 is chosen from a hydrogen atom, a halogen atom, a
(C.sub.1-C.sub.4)alkyl group, (C.sub.1-C.sub.4)monohydrox- yalkyl
group, (C.sub.2-C.sub.4)polyhydroxyalkyl group,
(C.sub.1-C.sub.4)aminoalkyl group, (C.sub.1-C.sub.4)cyanoalkyl
group and a (C.sub.1-C.sub.4)alkoxy-(C.sub.1-C.sub.4)alkyl group,
provided that: at least one of R.sub.16 and R.sub.17 is a hydrogen
atom.
17. A composition according to claim 16, wherein said
para-aminophenols are chosen from para-aminophenol,
4-amino-3-methylphenol, 4-amino-3-fluorophenol,
4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol,
4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol,
4-amino-2-aminomethylphenol,
4-amino-2-(.beta.-hydroxyethylaminomethyl)phenol,
4-amino-2-fluorophenol, and acid addition salts thereof.
18. A composition according to claim 7, wherein said
ortho-aminophenols are chosen from 2-aminophenol,
2-amino-5-methylphenol, 2-amino-6-methylphenol and
5-acetamido-2-aminophenol, and acid addition salts thereof.
19. A composition according to claim 7, wherein said heterocyclic
oxidation bases are chosen from pyridine derivatives, pyrimidine
derivatives, pyrazolopyrimidine derivatives, pyrazole derivatives
and acid addition salts thereof.
20. A composition according to claim 19, wherein said pyridine
derivatives are chosen from 2,5-diaminopyridine,
2-(4-methoxyphenyl)amino-3-aminopyri- dine,
2,3-diamino-6-methoxypyridine,
2-(.beta.-methoxyethyl)amino-3-amino-- 6-methoxypyridine
3,4-diaminopyridine, and acid addition salts thereof.
21. A composition according to claim 19, wherein said pyrimidine
derivatives are chosen from 2,4,5,6-tetraamino-pyrimidine,
4-hydroxy-2,5,6-triaminopyrimidine,
2-hydroxy-4,5,6-triaminopyrimidine,
2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and
acid addition salts thereof.
22. A composition according to claim 19, wherein said
pyrazolopyrimidine derivatives are chosen from
pyrazolo[1,5-a]pyrimidine-3,7-diamine,
2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine,
pyrazolo[1,5-a]pyrimidine-3,5-diamine,
2,7-dimethylpyrazolo[1,5-a]pyrimid- ine-3,5-diamine,
3-aminopyrazolo[1,5-a]pyrimidin-7-ol,
3-aminopyrazolo[1,5-a]pyrimidin-5-ol,
2-(3-aminopyrazolo[1,5-a]pyrimidin-- 7-ylamino)ethanol,
2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol,
2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxyethyl)amino]ethanol,
2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxyethyl)amino]ethanol,
5,6-dimethylpyrazolo[1,5-a]pyrimdine-3,7-diamine,
2,6-dimethylpyrazolo[1,- 5-a]pyrimidine-3,7-diamine,
2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine- -3,7-diamine and
3-amino-5-methyl-7-imidazolylpropylaminopyrazolo[1,5-a]py-
rimidine, a corresponding tautomeric form thereof, when a
tautomeric equilibrium exits, and acid addition salts thereof.
23. A composition according to claim 19, wherein said pyrazole
derivatives are chosen from 4,5-diamino-1-methylpyrazole,
3,4-diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)pyrazole,
4,5-diamino-1,3-dimethylpyrazole- ,
4,5-diamino-3-methyl-1-phenylpyrazole,
4,5-diamino-1-methyl-3-phenylpyra- zole,
4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1
-benzyl-4,5-diamino-3-me- thylpyrazole,
4,5-diamino-3-tert-butyl-1-methylpyrazole,
4,5-diamino-1-tert-butyl-3-methylpyrazole,
4,5-diamino-1-(.beta.-hydroxye- thyl)-3-methylpyrazole,
4,5-diamino-1-ethyl-3-methylpyrazole,
4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole,
4,5-diamino-1-ethyl-3-h- ydroxymethylpyrazole,
4,5-diamino-3-hydroxymethyl-1-methyl pyrazole,
4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,
4,5-diamino-3-methyl-1-i- sopropylpyrazole,
4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole,
3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,
3,5-diamino-1-methyl-4-methylaminopyrazole,
3,5-diamino-4-(.beta.-hydroxy- ethyl)amino-1-methylpyrazole, and
acid addition salts thereof.
24. A composition according to claim 6, wherein said at least one
oxidation base is present in an amount ranging from 0.0005 to 12%
by weight relative to the total weight of the ready-to-use dye
composition.
25. A composition according to claim 24, wherein said at least one
oxidation base is present in an amount ranging from 0.005 to 8% by
weight relative to the total weight of the ready-to-use dye
composition.
26. A composition according to claim 1, wherein said at least one
2-electron oxidases, lactate oxidases, pyruvate oxidases, uricases,
choline oxidases, sarcosine oxidases and bilirubin oxidases.
27. A composition according to claim 26, wherein said at least one
2-electron oxidoreductase is chosen from uricases of animal,
uricases of microbiological and uricases of biotechnological
origin.
28. A composition according to claim 27, wherein said at least one
2-electron oxidoreductase is chosen from uricases extracted from
boar's liver, Arthrobacter globiformis and Aspergillus flavus.
29. A composition according to claim 1, wherein said at least one
2-electron oxidoreductase is present in an amount ranging from 0.01
to 20% by weight relative to the total weight of the ready-to-use
dye composition.
30. A composition according to claim 29, wherein said at least one
2-electron oxidoreductase is present in an amount ranging from 0.1
to 10% by weight relative to the total weight of the ready-to-use
dye composition.
31. A composition according to claim 30, wherein said at least one
2-electron oxidoreductase is present in an amount ranging from 0.1
to 5% by weight relative to the total weight of the ready-to-use
dye composition.
32. A composition according to claim 1, wherein said at least one
2-electron oxidoreductase is present in an amount ranging from 10
to 108 units U per 100 g of ready-to-use dye composition.
33. A composition according to claim 1, wherein said at least one
donor is present in an amount ranging from 0.01 to 20% by weight
relative to the total weight of the ready-to-use dye
composition.
34. A composition according to claim 33, wherein said at least one
donor is present in an amount ranging from 0.1 to 5% by weight
relative to the total weight of the ready-to-use dye
composition.
35. A composition according to claim 1, wherein said at least one
4-electron oxidoreductase is chosen from at least one laccase, at
least one tyrosinase, at least one catechol oxidase and at least
one polyphenol oxidase.
36. A composition according to claim 35, wherein said at least one
4-electron oxidoreductase is chosen from at least one laccase.
37. A composition according to claim 36, wherein said at least one
laccase is chosen from laccases of plant origin, laccases of animal
origin, laccases of fungal origin and laccases of bacterial
origin.
38. A composition according to claim 36, wherein said at least one
laccase is chosen from laccases obtained by biotechnological
techniques.
39. A composition according to claim 37, wherein said at least one
laccase of plant origin is chosen from: Anacardiacea chosen from
Magnifera indica, Schinus molle and Pleiogynium timoriense;
Podocarpacea; Rosmarinus off.; Solanum tuberosum; Iris sp.; Coffea
sp.; Daucus carrota; Vinca minor; and Persea americana;
Catharanthus roseus;Musa sp.; Malus pumila; Gingko biloba;
Monotropa hypopithys (Indian pipe), Aesculus sp.; Acer
pseudoplatanus; Prunus persica and Pistacia palaestina.
40. A composition according to claim 37, wherein said at least one
laccase of fungal origin is chosen from Polyporus versicolor,
Rhizoctonia praticola, Rhus vernicifera, Scytalidium, Polyporus
pinsitus, Myceliophthora thermophila, Rhizoctonia solani,
Pyricularia orizae, Trametes versicolor, Fomes fomentarius,
Chaetomium thermophile, Neurospora crassa, Colorius versicol,
Botrytis cinerea, Rigidoporus lignosus, Phellinus noxius, Pleurotus
ostreatus, Aspergillus nidulans, Podospora anserina, Agaricus
bisporus, Ganoderma lucidum, Glomerella cingulata, Lactarius
piperatus, Russula delica, Heterobasidion annosum, Thelephora
terrestris, Cladosporium cladosporioides, Cerrena unicolor,
Coriolus hirsutus, Ceriporiopsis subvermispora, Coprinus cinereus,
Panaeolus papilionaceus, Panaeolus sphinctrinus, Schizophyllum
commune, Dichomitius squalens, and variants thereof.
41. A composition according to claim 37, wherein said at least one
laccase of fungal origin is obtained by biotechnological
techniques.
42. A composition according to claim 1, wherein said at least one
laccase is present in an amount ranging from 0.5 to 2000 Lacu per
100 g of ready-to-use dye composition.
43. A composition according to claim 1, wherein said at least one
4-electron oxidoreductase is present in an amount ranging from 0.01
to 20% by weight relative to the total weight of the ready-to-use
dye composition.
44. A composition according to claim 43, wherein said at least one
4-electron oxidoreductase is present in an amount ranging from 0.1
to 5% by weight relative to the total weight of the ready-to-use
dye composition.
45. A composition according to claim 1, wherein said at least one
peroxidase is chosen from NADH peroxidases having NADH as donor,
fatty acid peroxidases having a fatty acid as donor, NADPH
peroxidases having NADPH as donor, cytochrome-c peroxidases having
ferrocytochrome c as donor, iodide peroxidases having iodides as
donor, chloride peroxidases having chlorides as donor, L-ascorbate
peroxidases having L-ascorbate as donor and glutathione peroxidases
having glutathione as donor, catalases and simplex peroxidases.
46. A composition according to claim 45, wherein said at least one
peroxidase is chosen from simplex peroxidases.
47. A composition according to claim 46, wherein said simplex
peroxidases are present in an amount ranging from 0.1 to
5.times.10.sup.6 units per 100 g of the ready-to-use dye
composition.
48. A composition according to claim 1, wherein said at least one
peroxidase is chosen from peroxidases of plant origin, peroxidases
of animal origin, peroxidases of fungal origin and peroxidases of
bacterial origin.
49. A composition according to claim 1, wherein said at least one
peroxidase is chosen from peroxidases obtained by biotechnological
techniques.
50. A composition according to claim 1, wherein said at least one
peroxidase is present in an amount ranging from 0.0001 to 20% by
weight relative to the total weight of the ready-to-use dye
composition.
51. A composition according to claim 1, wherein said at least one
peroxidase is present in an amount ranging from 0.001 to 10% by
weight relative to the total weight of the ready-to-use dye
composition.
52. A composition according to claim 1, further comprising at least
one coupler chosen from meta-phenylenediamines, meta-aminophenols,
meta-diphenols, naphthols, heterocyclic couplers chosen from
pyrazolo[1,5-b]-1,2,4-triazoles,
pyrazolo[3,2-c]-1,2,4-triazoles,and pyrazol-5-ones, pyridines other
than the pyridines of formula (I) chosen from indoles, indolines,
indazoles, benzimidazoles, benzothiazoles, benzoxazoles,
1,3-benzodioxoles and quinolines.
53. A composition according to claim 52, wherein said at least one
coupler is chosen from 2-methyl-5-aminophenol,
5-N-(.beta.-hydroxyethyl)amino-2-m- ethylphenol, 3-aminophenol,
1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbe- nzene,
4-chloro-1,3-dihydroxybenzene,
2,4-diamino-1-(.beta.-hydroxyethylox- y)benzene,
2-amino-4-(.beta.-hydroxyethylamino)-1-methoxybenzene,
1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol,
.alpha.-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole,
4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline,
2,6-dihydroxy-4-methylpyridi- ne, 1-H-3-methylpyrazol-5-one,
1-phenyl-3-methylpyrazol-5-one, 2-amino-3-hydroxypyridine,
3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazole
2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, and acid addition salts
thereof.
54. A composition according to claim 52, wherein said at least one
coupler is present in an amount ranging from 0.0001 to 10% by
weight relative to the total weight of the ready-to-use dye
composition.
55. A composition according to claim 54, wherein said at least one
coupler is present in an amount ranging from 0.005 to 5% by weight
relative to the total weight of the ready-to-use dye
composition.
56. A composition according to claim 1 further comprising at least
one direct dye.
57. A composition according to claim 1, wherein said acid addition
salts are chosen from hydrochlorides, hydrobromides, sulphates,
tartrates, lactates and acetates.
58. A composition according to claim 1, wherein said medium
suitable for dyeing, is chosen from media comprising water; and
media comprising at least one organic solvent.
59. A composition according to claim 58, wherein said at least one
organic solvent is chosen from C.sub.1-C.sub.4 alkanols; glycerol;
glycols and glycol ethers; and aromatic alcohols.
60. A composition according to claim 59, wherein said
C.sub.1-C.sub.4 alkanols are chosen from ethanol and
isopropanol.
61. A composition according to claim 59, wherein said glycols and
glycol ethers are chosen from 2-butoxyethanol, propylene glycol,
propylene glycol monomethyl ether, diethylene glycol monoethyl
ether and monomethyl ether.
62. A composition according to claim 59, wherein said aromatic
alcohols are chosen from benzyl alcohol and phenoxyethanol.
63. A composition according to claim 58, wherein said at least one
organic solvent is present in an amount ranging from 1 to 40% by
weight relative to the total weight of the ready-to-use dye
composition.
64. A composition according to claim 63, wherein said at least one
organic solvent is present in an amount ranging from 5 to 30% by
weight relative to the total weight of the ready-to-use dye
composition.
65. A composition according to claim 1, wherein said composition
has a pH ranging from 5 to 11.
66. A composition according to claim 65, wherein said composition
has a pH ranging from 6.5 to 10.
67. A composition according to claim 65, further comprising at
least one agent for adjusting pH chosen from acidifying and
alkalinizing agents.
68. A composition according to claim 67, wherein said acidifying
agents are chosen from inorganic and organic acids.
69. A composition according to claim 68, wherein said inorganic and
organic acids are chosen from hydrochloric, orthophosphoric,
sulfuric, and carboxylic acids.
70. A composition according to claim 69, wherein said carboxylic
acids are chosen from acetic, tataric, citric, lactic and sulfonic
acids.
71. A composition according to claim 67, wherein said alkalinizing
agents chosen from aqueous ammonia, alkali metal carbonates,
alkanolamines, sodium hydroxides, potassium hydroxides and the
compounds of formula (VI) below: 10wherein: W is a propylene
residue, optionally substituted with a group chosen from a hydroxyl
group and a (C.sub.1-C.sub.4) alkyl group, R.sub.20, R.sub.21,
R.sub.22 and R.sub.23, which are identical or different, are each
chosen from a hydrogen atom, and a (C.sub.1-C.sub.4)alkyl and
(C.sub.1-C.sub.4)hydroxyalkyl groups.
72. A composition according to claim 71, wherein said alkanolamines
are chosen from mono-, di- and triethanolamine,
2-methyl-2-aminopropanol and derivatives thereof.
73. A composition according to claim 1, further comprising at least
one adjuvant used in hair dyeing compositions.
74. A composition according to claim 73, wherein said at least one
adjuvant is chosen from anionic, cationic, nonionic, amphoteric and
zwitterionic surfactants; anionic, cationic, nonionic, amphoteric
and zwitterionic polymers; inorganic and organic thickeners;
antioxidants; penetration agents; sequestering agents; fragrances;
buffers; dispersing agents; and conditioning agents.
75. A composition according to claim 74 wherein said conditioning
agents are chosen from modified and unmodified, non-volatile and
volatile silicones, film-forming agents, ceramides, preserving
agents and opacifying agents.
76. A composition according to claim 1, wherein said composition is
a liquid, a cream a gel, or any form suitable for dyeing keratinous
fibers.
77. A composition according to claim 76, wherein said keratinous
fibers are human hair.
78. A composition according to claim 1, wherein said composition is
free of gaseous oxygen.
79. A process for oxidation dyeing keratinous fibers comprising:
(1) applying to said fibers at least one ready-to-use dyeing
composition comprising, in a medium suitable for dyeing: (a) at
least one oxidation dye chosen from the pyridines of formula (I),
and acid addition salts thereof: 11wherein: R.sub.1 is chosen from
a (C.sub.1-C.sub.4)alkyl group, a (C.sub.1-C.sub.4)monohydroxyalkyl
group, and a (C.sub.2-C.sub.4)polyhydroxyalkyl group, R.sub.2 is
chosen from a (C.sub.1-C.sub.4)alkoxy group, a
(C.sub.1-C.sub.4)monohydroxyalkoxy group, a
(C.sub.2-C.sub.4)polyhydroxyalkoxy group, an amino group, a
mono(C.sub.1-C.sub.4)alkylamino group, a
di-(C.sub.1-C.sub.4)alkylamino group, a monophenylamino group, a
monohydroxyphenylamino group, a monoalkoxyphenylamino group, a
monohydroxy(C.sub.1-C.sub.4)alkylamino group, a
dihydroxy-(C.sub.1-C.sub.4)alkylamino group, a
monohydroxy-(C.sub.2-C.sub.4)alkylamino group, a
dihydroxy-(C.sub.2-C.sub- .4)alkylamino group, a
(C.sub.1-C.sub.4)alkylmonohydroxy-(C.sub.1-C.sub.4)- alkylamino
group and a (C.sub.1-C.sub.4)alkyl-polyhydroxy(C.sub.2-C.sub.4)-
alkylamino group, R.sub.3 is chosen from a hydrogen atom, an amino
group, a mono(C.sub.1-C.sub.4)alkylamino group, a
monohydroxy(C.sub.1-C.sub.4)al- kylamino group and a
mono(polyhydroxy(C.sub.2-C.sub.4)alkyl)amino group; provided that:
when R.sub.2 is chosen form a (C.sub.1-C.sub.4)alkoxy group, a
(C.sub.1-C.sub.4)monohydroxyalkoxy group and a
(C.sub.2-C.sub.4)polyhydroxyalkoxy group, then R.sub.3 is a
hydrogen atom; and (b) at least one enzymatic oxidizing agent
chosen from: (i) a system comprising at least one 2-electron
oxidoreductase and its corresponding at least one donor, (ii) at
least one 4-electron oxidoreductase, and (iii) at least one
peroxidase; (2) developing a color; and (3) rinsing said keratinous
fibers.
80. A process for oxidation dyeing keratinous fibers according to
claim 79, further comprising: washing said keratinous fibers with
shampoo; rinsing said keratinous fibers; and drying said keratinous
fibers.
81. A process for oxidation dyeing keratinous fibers according to
claim 79, wherein the time for developing a color ranges from 3 to
60 minutes.
82. A process for oxidation dyeing keratinous fibers according to
claim 81, wherein the time for developing a color ranges from 5 to
40 minutes.
83. A process for oxidation dyeing keratinous fibers comprising:
(1) storing a composition (A) comprising, in a medium suitable for
dyeing: at least one oxidation dye chosen from the pyridines of
formula (I), and acid addition salts thereof: 12wherein: R.sub.1 is
chosen from a (C.sub.1-C.sub.4)alkyl group, a
(C.sub.1-C.sub.4)monohydroxyalkyl group, and a
(C.sub.2-C.sub.4)polyhydroxyalkyl group, R.sub.2 is chosen from a
(C.sub.1-C.sub.4)alkoxy group, a (C.sub.1-C.sub.4)monohydroxyalkoxy
group, a (C.sub.2-C.sub.4)polyhydroxyalkoxy group, an amino group,
a mono(C.sub.1-C.sub.4)alkylamino group, a
di-(C.sub.1-C.sub.4)alkylamino group, a monophenylamino group, a
monohydroxyphenylamino group, a monoalkoxyphenylamino group, a
monohydroxy(C.sub.1-C.sub.4)alkylamino group, a
dihydroxy-(C.sub.1-C.sub.4)alkylamino group, a
monohydroxy-(C.sub.2-C.sub.4)alkylamino group, a
dihydroxy-(C.sub.2-C.sub- .4)alkylamino group, a
(C.sub.1-C.sub.4)alkylmonohydroxy-(C.sub.1-C.sub.4)- alkylamino
group and a (C.sub.1-C.sub.4)alkyl- polyhydroxy(C.sub.2-C.sub.4-
)alkylamino group, R.sub.3 is chosen from a hydrogen atom, an amino
group, a mono(C.sub.1-C.sub.4)alkylamino group, a
monohydroxy(C.sub.1-C.sub.4)al- kylamino group and a
mono(polyhydroxy(C.sub.2-C.sub.4)alkyl)amino group; provided that:
when R.sub.2 is chosen form a (C.sub.1-C.sub.4)alkoxy group, a
(C.sub.1-C.sub.4)monohydroxyalkoxy group and a
(C.sub.2-C.sub.4)polyhydroxyalkoxy group, then R.sub.3 is a
hydrogen atom; (2) storing, separately from said composition (A), a
composition (B) comprising, in a medium suitable for dyeing: at
least one enzymatic oxidizing agent chosen from: (i) a system
comprising at least one 2-electron oxidoreductase and its
corresponding at least one donor, (ii) at least one 4-electron
oxidoreductase, and (iii) at least one peroxidase; (3) mixing said
composition (A) and said composition (B) together just prior to use
to produce a mixture; (4) applying said mixture to said fibers; (5)
developing a color; and (6) rinsing said keratinous fibers.
84. A process for oxidation dyeing keratinous fibers according to
claim 83, further comprising: washing said keratinous fibers with
shampoo; rinsing said keratinous fibers; and drying said keratinous
fibers.
85. A process for oxidation dyeing keratinous fibers according to
claim 83, wherein the time for developing a color ranges from 3 to
60 minutes.
86. A process for oxidation dyeing keratinous fibers according to
claim 85, wherein the time for developing a color ranges from 5 to
40 minutes.
87. A kit comprising two compartments, wherein: (1) a first
compartment comprises in a medium suitable for dyeing keratinous
fibers: at least one oxidation dye chosen from the pyridines of
formula (I), and acid addition salts thereof: 13wherein: R.sub.1 is
chosen from a (C.sub.1-C.sub.4)alkyl group, a
(C.sub.1-C.sub.4)monohydroxyalkyl group, and a
(C.sub.2-C.sub.4)polyhydroxyalkyl group, R.sub.2 is chosen from a
(C.sub.1-C.sub.4)alkoxy group, a (C.sub.1-C.sub.4)monohydroxyalkoxy
group, a (C.sub.2-C.sub.4)polyhydroxyalkoxy group, an amino group,
a mono(C.sub.1-C.sub.4)alkylamino group, a
di-(C.sub.1-C.sub.4)alkylamino group, a monophenylamino group, a
monohydroxyphenylamino group, a monoalkoxyphenylamino group, a
monohydroxy(C.sub.1-C.sub.4)alkylamino group, a
dihydroxy-(C.sub.1-C.sub.4)alkylamino group, a
monohydroxy-(C.sub.2-C.sub.4)alkylamino group, a
dihydroxy-(C.sub.2-C.sub- .4)alkylamino group, a
(C.sub.1-C.sub.4)alkylmonohydroxy-(C.sub.1-C.sub.4)- alkylamino
group and a (C.sub.1-C.sub.4)alkyl-polyhydroxy(C.sub.2-C.sub.4)-
alkylamino group, R.sub.3 is chosen from a hydrogen atom, an amino
group, a mono(C.sub.1-C.sub.4)alkylamino group, a
monohydroxy(C.sub.1-C.sub.4)al- kylamino group and a
mono(polyhydroxy(C.sub.2-C.sub.4)alkyl)amino group; provided that:
when R.sub.2 is chosen form a (C.sub.1-C.sub.4)alkoxy group, a
(C.sub.1-C.sub.4)monohydroxyalkoxy group and a
(C.sub.2-C.sub.4)polyhydroxyalkoxy group, then R.sub.3 is a
hydrogen atom; and (2) a second compartment comprises in a medium
suitable for dyeing, a composition (B) comprising: at least one
enzymatic oxidizing agent chosen from: (i) a system comprising at
least one 2-electron oxidoreductase and its corresponding at least
one donor, (ii) at least one 4-electron oxidoreductase, and (iii)
at least one peroxidase.
Description
[0001] The invention relates to a ready-to-use composition for the
oxidation dyeing of keratinous fibers, such as, human keratinous
fibers, for example, hair, comprising, in a medium which is
suitable for dyeing, at least one oxidation dye chosen from
pyridines of formula (I), and at least one enzymatic oxidizing
agent, and the oxidation dyeing method for using them.
[0002] It is known to dye keratinous fibers, for example, human
hair, with dye compositions containing oxidation dye precursors,
such as, ortho- or para-phenylenediamines, ortho- or
para-aminophenols and heterocyclic bases, which are generally
referred to as oxidation bases. Oxidation dye precursors, or
oxidation bases, are colorless or weakly colored compounds which,
when combined with oxidizing products, can give rise to colored
compounds and dyes by an oxidative condensation process.
[0003] It is also known that it is possible to vary the shades
obtained with these oxidation bases by combining them with couplers
or color modifiers, the latter chosen, for example, from aromatic
meta-diamines, meta-aminophenols, meta-diphenols and certain
heterocyclic compounds such as, indoles, indolines and pyridine
derivatives (see, for example, patent applications DE 3 132 885 and
EP-A-0 106 987).
[0004] The variety of molecules used as oxidation bases and
couplers allows a wide rich palette of colors to be obtained.
[0005] The "permanent" colors obtained using these oxidation dyes
may moreover satisfy at least one of a number of objectives. Thus,
it should, for example, satisfy at least one of the following: be
without toxicological drawbacks, make it possible to obtain shades
in the desired intensity, and exhibit good resistance towards
external agents (at least one of light, adverse weather conditions,
washing, permanent waving, perspiration, and rubbing).
[0006] The dyes may also cover white and gray hair and, may also be
the least selective possible, that is to say, make it possible to
obtain the smallest possible differences in color right along the
same keratinous fiber, which may indeed be differently sensitised
(i.e. damaged) between its tip and its root.
[0007] Oxidation dyeing of keratinous fibers is generally carried
out in alkaline medium, in the presence of hydrogen peroxide.
However, the use of alkaline media in the presence of hydrogen
peroxide may possess the undesirable drawbacks of causing
appreciable degradation of the fibers, as well as, considerable
bleaching of the keratinous fibers.
[0008] Oxidation dyeing of keratinous fibers may also be carried
out using oxidizing systems other than hydrogen peroxide, for
example, enzymatic systems. Patent application EP-A-0,310,675, has
proposed dyeing keratinous fibers with compositions comprising an
oxidation base and optionally a coupler, in combination with
enzymes, such as, pyranose oxidase, glucose oxidase and uricase, in
the presence of a donor for the said enzymes. Although these
compounds are used under conditions which may diminish the
degradation of the keratinous fibers below the level of degradation
found by the dyes used in the presence of hydrogen peroxide, these
dyeing processes nevertheless lead to colors which are not entirely
satisfactory. For example, the processes may affect the intensity
(strength) of the colors or the colors' resistance to the various
attacking factors to which the hair may be subjected.
[0009] The inventor has now discovered that combination of at least
one oxidation dye chosen from the pyridines of formula (I), defined
below, and at least one enzymatic oxidizing agent make it possible
to obtain dye compositions leading to at least one of the following
advantages: intense colors without giving rise to any significant
degradation of the keratinous fibers, colors which are not very
selective, and properties of resistance to the various treatments
to which keratinous fibers, such as, hair may be subjected.
[0010] One embodiment of the invention is thus a ready-to-use
composition for the oxidation dyeing of keratinous fibers, and in
particular human keratinous fibers, for example, hair, comprising,
in a medium suitable for dyeing:
[0011] (a) at least one oxidation dye chosen from the pyridines of
formula (I), and acid addition salts thereof: 1
[0012] wherein:
[0013] R.sub.1 is chosen from a (C.sub.1-C.sub.4)alkyl group, a
(C.sub.1-C.sub.4)monohydroxyalkyl group, and a
(C.sub.2-C.sub.4)polyhydro- xyalkyl group,
[0014] R.sub.2 is chosen from a (C.sub.1-C.sub.4)alkoxy group, a
(C.sub.1-C.sub.4)monohydroxyalkoxy group, a
(C.sub.2-C.sub.4)polyhydroxya- lkoxy group, an amino group, a
mono(C.sub.1-C.sub.4)alkylamino group, a
di-(C.sub.1-C.sub.4)alkylamino group, a monophenylamino group, a
monohydroxyphenylamino group, a monoalkoxyphenylamino group, a
monohydroxy(C.sub.1-C.sub.4)alkylamino group, a
dihydroxy-(C.sub.1-C.sub.- 4)alkylamino group, a monohydroxy-
(C.sub.2-C.sub.4)alkylamino group, a dihydroxy-
(C.sub.2-C.sub.4)alkylamino group, a (C.sub.1-C.sub.4)alkylmon-
ohydroxy-(C.sub.1-C.sub.4)alkylamino group and a
(C.sub.1-C.sub.4)alkyl-po- lyhydroxy(C.sub.2-C.sub.4)alkylamino
group,
[0015] R.sub.3 is chosen from a hydrogen atom, an amino group, a
mono(C.sub.1-C.sub.4)alkylamino group, a
monohydroxy(C.sub.1-C.sub.4)alky- lamino group and a
mono(polyhydroxy(C.sub.2-C.sub.4)alkyl)amino group;
[0016] provided that: when R.sub.2 is chosen form a
(C.sub.1-C.sub.4)alkoxy group, a (C.sub.1-C.sub.4)monohydroxyalkoxy
group and a (C.sub.2-C.sub.4)polyhydroxyalkoxy group, then R.sub.3
is a hydrogen atom; and
[0017] (b) at least one enzymatic oxidizing agent chosen from:
[0018] (i) a system comprising at least one 2-electron
oxidoreductase and its corresponding at least one donor,
[0019] (ii) at least one 4-electron oxidoreductase, and
[0020] (iii) at least one peroxidase.
[0021] As indicated above, the colors obtained with the oxidation
dyeing composition comprising a pyridine of formula (I) according
to the invention, can be intense and can contribute to a palette of
highly chromatic colors. Such compositions may also exhibit
properties of resistance towards the action of various external
agents (at least one of light, adverse weather conditions, washing,
permanent waving and perspiration).
[0022] One embodiment of the invention is a method for the
oxidation dyeing of keratinous fibers using the ready-to-use dye
composition described above.
[0023] In one embodiment of the invention, the at least one
oxidation dye of formula (I) is chosen from
2,6-dimethoxy-3,5-diaminopyridine, 2,3-diamino-6-methoxypyridine,
2-methylamino-3-amino-6-methoxypyridine,
2-(2'-hydroxyphenyl)amino-3-amino-6-methoxypyridine,
2-(4'-hydroxyphenyl)amino-3-amino-6-methoxypyridine,
2-(4'-methoxyphenyl)amino-3-amino-6-methoxypyridine,
2-phenylamino-3-amino-6-methoxypyridine, and acid addition salts
thereof.
[0024] In another embodiment, the at least one oxidation dye of
formula (I) is chosen from 2,6-dimethoxy-3,5-diaminopyridine and
optionally, at least one acid addition salt thereof.
[0025] The at least one oxidation dye of formula (I) according to
the invention, may be present, for example, in an amount ranging
from 0.0001 to 10% by weight relative to the total weight of the
dye composition. In another embodiment of the invention, the at
least one oxidation dye of formula (I) is present in an amount
ranging from 0.005 to 5% by weight relative to the total weight of
the dye composition.
[0026] In addition to the at least one oxidation dye of formula (I)
above, the ready-to-use dye composition of the invention may
optionally contain at least one oxidation base and at least one
coupler.
[0027] According to one embodiment, the ready-to-use dye
composition further comprises at least one oxidation base.
[0028] The nature of the at least one oxidation base used in the
ready-to-use dye composition is not critical. The at least one
oxidation base, for example, may be chosen from
para-phenylenediamines, double bases, para-aminophenols,
ortho-aminophenols and heterocyclic oxidation bases.
[0029] Examples of the para-phenylenediamines which can be used as
oxidation bases in the dye compositions in accordance with the
invention, may be chosen from the compounds of formula (II) and
acid addition salts thereof: 2
[0030] wherein:
[0031] R.sub.4 is chosen from a hydrogen atom, a
(C.sub.1-C.sub.4)alkyl group optionally substituted with a
nitrogenous group, a (C.sub.1-C.sub.4)monohydroxyalkyl group, a
(C.sub.2-C.sub.4)polyhydroxyal- kyl group, a
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl group, a phenyl group
and a 4'-aminophenyl group;
[0032] R.sub.5 is chosen from a hydrogen atom, a C.sub.1-C.sub.4
alkyl group optionally substituted with a nitrogenous group, a
C.sub.1-C.sub.4 monohydroxyalkyl group, a C.sub.2-C.sub.4
polyhydroxyalkyl group, and a
(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl group;
[0033] R.sub.6 is chosen from a hydrogen atom, a halogen atom, a
(C.sub.1-C.sub.4)alkyl group, a (C.sub.1-C.sub.4)monohydroxyalkyl
group, a (C.sub.1-C.sub.4)hydroxyalkoxy group, an
acetylamino(C.sub.1-C.sub.4)-a- lkoxy group, a
(C.sub.1-C.sub.4)mesylaminoalkoxy group and a
carbamoylamino(C.sub.1-C.sub.4)alkoxy group,
[0034] R.sub.7 is chosen from a hydrogen atom, a halogen atom and a
C.sub.1-C.sub.4 alkyl group.
[0035] Examples of the above mentioned nitrogenous groups, are
chosen from amino, mono(C.sub.1-C.sub.4)alkylamino,
di(C.sub.1-C.sub.4)alkylamino, tri(C.sub.1-C.sub.4)-alkylamino,
monohydroxy(C.sub.1-C.sub.4)alkylamino, imidazolinium and ammonium
groups.
[0036] In one embodiment of the invention, examples of
para-phenylenediamines of formula (II) above, are chosen from
para-phenylenediamine, para-toluylenediamine,
2-chloro-para-phenylenediam- ine,
2,3-dimethyl-para-phenylenediamine,
2,6-dimethyl-para-phenylenediamin- e,
2,6-diethyl-para-phenylenediamine,
2,5-dimethyl-para-phenylenediamine,
N,N-dimethyl-para-phenylenediamine,
N,N-diethyl-para-phenylenediamine,
N,N-dipropyl-para-phenylenediamine,
4-amino-N,N-diethyl-3-methylaniline,
N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine,
4-amino-N,N-bis(.beta.-hydroxyethyl)-2-methylaniline,
4-amino-2-chloro-N,N-bis(.beta.-hydroxyethyl)aniline,
2-.beta.-hydroxyethyl-para-phenylenediamine,
2-fluoro-para-phenylenediami- ne,
2-isopropyl-para-phenylenediamine,
N-(.beta.-hydroxypropyl)-para-pheny- lenediamine,
2-hydroxymethyl-para-phenylenediamine,
N,N-dimethyl-3-methyl-para-phenylenediamine,
N,N-(ethyl-.beta.-hydroxyeth- yl)-para-phenylenediamine,
N-(.beta.,.gamma.-dihydroxypropyl)-para-phenyle- nediamine,
N-(4'-aminophenyl)-para-phenylenediamine,
N-phenyl-para-phenylenediamine,
2-.beta.-hydroxyethyloxy-para-phenylenedi- amine,
2-.beta.-acetylaminoethyloxy-para-phenylenediamine,
N-(.beta.-methoxyethyl)-para-phenylenediamine, and addition salts
thereof.
[0037] In another embodiment of the invention, the
para-phenylenediamines of formula (II) above, are chosen from
para-phenylenediamine, para-toluylenediamine,
2-isopropyl-para-phenylenediamine,
2-.beta.-hydroxyethyl-para-phenylenediamine,
2-.beta.-hydroxyethyloxy-par- a-phenylenediamine,
2,6-dimethyl-para-phenylenediamine,
2,6-diethyl-para-phenylenediamine,
2,3-dimethyl-para-phenylenediamine,
N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine,
2-chloro-para-phenylenediamine,
2-.beta.-acetylaminoethyloxy-para-phenyle- nediamine and acid
addition salts thereof.
[0038] According to the invention, the term double bases refers to
the compounds containing at least two aromatic rings comprising at
least one group chosen from amino and hydroxyl groups.
[0039] In one embodiment of the invention, the double bases which
can be used as oxidation bases in the dye compositions, are chosen
from compounds of formula (III) below, and acid addition salts
thereof: 3
[0040] wherein:
[0041] a linker arm Y chosen from linear and branched alkylene
groups comprising from 1 to 14 carbon atoms optionally substituted
with at least one group chosen from hydroxyl and
(C.sub.1-C.sub.6)alkoxy groups, wherein said linear and branched
alkylene groups are optionally interrupted by or terminated by at
least one group chosen from nitrogenous groups and heteroatoms
chosen from oxygen, sulfur, and nitrogen atoms;
[0042] Z.sub.1 and Z.sub.2, which are identical or different, are
each chosen from a hydroxyl group and an amino group optionally
substituted with a group chosen from a (C.sub.1-C.sub.4)alkyl group
and said linker arm Y;
[0043] R.sub.8 and R.sub.9 which are identical or different, are
each chosen from a hydrogen atom, a halogen atom, a
(C.sub.1-C.sub.4)alkyl group, a (C.sub.1-C.sub.4)monohydroxyalkyl
group, a (C.sub.2-C.sub.4)polyhydroxyalkyl group, a
(C.sub.1-C.sub.4)aminoalkyl group and said linker arm Y;
[0044] R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14 and
R.sub.15, which are identical or different, are each chosen from a
hydrogen atom, said linker arm Y and a (C.sub.1-C.sub.4)alkyl
group; provided that: said compounds of formula (III) contain only
one said linker arm Y per molecule.
[0045] In one embodiment of the invention, examples of the
nitrogenous groups of formula (III) may be chosen from amino,
mono(C.sub.1-C.sub.4)al- kylamino, di(C.sub.1-C.sub.4)alkylamino,
tri(C.sub.1-C.sub.4)alkylamino,
monohydroxy(C.sub.1-C.sub.4)alkylamino, imidazolinium and ammonium
groups.
[0046] In one embodiment of the invention, the double bases of
formula (III) are chosen from
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminophen-
yl)-1,3-diaminopropanol,
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminoph-
enyl)ethylenediamine,
N,N'-bis(4-aminophenyl)-tetramethylenediamine,
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4-aminophenyl)-tetramethylenediami-
ne, N,N'-bis(4-methylaminophenyl)tetramethylenediamine,
N,N'-bis-(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine,
1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and acid addition
salts thereof.
[0047] In another embodiment, the double bases of formula (III) are
chosen from
N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopr-
opanol, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and acid
addition salts thereof.
[0048] In yet another embodiment, the para-aminophenols which may
be used as oxidation bases in the dye compositions according to the
invention, are chosen from the compounds of formula (IV), and acid
addition salts thereof: 4
[0049] wherein:
[0050] R.sub.16 is chosen from a hydrogen atom, a halogen atom, a
(C.sub.1-C.sub.4)alkyl group, a (C.sub.1-C.sub.4)monohydroxyalkyl
group, a(C.sub.1-C.sub.4)alkoxy(C.sub.1-C.sub.4)alkyl group, a
(C.sub.1-C.sub.4)aminoalkyl group and a
hydroxy(C.sub.1-C.sub.4)alkylamin- o(C.sub.1-C.sub.4)alkyl
group,
[0051] R.sub.17 is chosen from a hydrogen atom, a halogen atom, a
(C.sub.1-C.sub.4)alkyl group, (C.sub.1-C.sub.4)monohydroxyalkyl
group, (C.sub.2-C.sub.4)polyhydroxyalkyl group,
(C.sub.1-C.sub.4)aminoalkyl group, (C.sub.1-C.sub.4)cyanoalkyl
group and a (C.sub.1-C.sub.4)alkoxy-(C- .sub.1-C.sub.4)alkyl group,
provided that: at least one of R.sub.16 and R.sub.17 is a hydrogen
atom.
[0052] In one embodiment of the invention, the para-aminophenols of
formula (IV) are chosen from para-aminophenol,
4-amino-3-methylphenol, 4-amino-3-fluorophenol,
4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol,
4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol,
4-amino-2-aminomethylphenol,
4-amino-2-(.beta.-hydroxyethylaminomethyl)phenol,
4-amino-2-fluorophenol, and acid addition salts thereof.
[0053] In another embodiment, ortho-aminophenols which can be used
as oxidation bases in the dye compositions according to the
invention, are chosen from 2-aminophenol, 2-amino-5-methylphenol,
2-amino-6-methylphenol, 5-acetamido-2-aminophenol, and acid
addition salts thereof.
[0054] Examples of heterocyclic bases which can be used as
oxidation bases in the dye compositions in according to the
invention, may be chosen from pyridine derivatives, pyrimidine
derivatives, pyrazolopyrimidine derivatives, pyrazole derivatives,
and acid addition salts thereof.
[0055] In one embodiment, the pyridine derivatives, may include
compounds described in patents GB 1,026,978 and GB 1,153,196,
incorporated by reference herein, such as, 2,5-diaminopyridine,
2-(4-methoxyphenyl)amino-- 3-aminopyridine,
2,3-diamino-6-methoxypyridine, 2-(.beta.-methoxyethyl)ami-
no-3-amino-6-methoxypyridine 3,4-diaminopyridine, and acid addition
salts thereof.
[0056] In another embodiment the pyrimidine derivatives, may
include compounds described in German patent DE 2,359,399, Japanese
patents JP 88-169,571 and JP 91-10659 and patent application WO
96/15765, all of which are incorporated by reference herein, such
as, 2,4,5,6-tetraamino-pyrimidine,
4-hydroxy-2,5,6-triaminopyrimidine,
2-hydroxy-4,5,6-triaminopyrimidine,
2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and
acid addition salts thereof.
[0057] Additionally, another embodiment of the invention employs
pyrazolopyrimidine derivatives disclosed in patent application
FR-A-2 750 048, incorporated by reference herein, such as,
pyrazolo[1,5-a]pyrimidine- -3,7-diamine,
2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine,
pyrazolo[1,5-a]pyrimidine-3,5-diamine,
2,7-dimethylpyrazolo[1,5-a]pyrimid- ine-3,5-diamine,
3-aminopyrazolo[1,5-a]pyrimidin-7-ol,
3-aminopyrazolo[1,5-a]pyrimidin-5-ol,
2-(3-aminopyrazolo[1,5-a]pyrimidin-- 7-ylamino)ethanol,
2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol,
2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxyethyl)amino]ethanol,
2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxyethyl)amino]ethanol,
5,6-dimethylpyrazolo[1,5-a]pyrimdine-3,7-diamine,
2,6-dimethylpyrazolo[1,- 5-a]pyrimidine-3,7-diamine,
2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine- -3,7-diamine and
3-amino-5-methyl-7-imidazolylpropylaminopyrazolo[1,5-a]py-
rimidine, a corresponding tautomeric form thereof, when a
tautomeric equilibrium exits, and acid addition salts thereof.
[0058] Another embodiment of the invention employs pyrazole
derivatives disclosed in German patents DE 3,843,892, and DE
4,133,957 and patent applications WO 94/08969, WO 94/08970,
FR-A-2,733,749 and DE 195 43 988 (all of which are incorporated by
reference herein), such as, 4,5-diamino-1-methylpyrazole,
3,4-diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)pyrazole,
4,5-diamino-1,3-dimethyl-pyrazol- e,
4,5-diamino-3-methyl-1-phenylpyrazole,
4,5-diamino-1-methyl-3-phenylpyr- azole,
4-amino-1,3-dimethyl-5-hydrazinopyrazole,
1-benzyl-4,5-diamino-3-me- thylpyrazole,
4,5-diamino-3-tert-butyl-1-methyl pyrazole,
4,5-diamino-1-tert-butyl-3-methylpyrazole,
4,5-diamino-1-(.beta.-hydroxye- thyl)-3-methylpyrazole,
4,5-diamino-1-ethyl-3-methylpyrazole,
4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole,
4,5-diamino-1-ethyl-3-h- ydroxymethylpyrazole,
4,5-diamino-3-hydroxymethyl-1-methylpyrazole,
4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,
4,5-diamino-3-methyl-1-i- sopropylpyrazole,
4-amino-5-(2'-aminoethyl)amino-1,3-dimethylpyrazole,
3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,
3,5-diamino-1-methyl-4-methylaminopyrazole,
3,5-diamino-4-(1-hydroxyethyl- )amino-1-methylpyrazole, and acid
addition salts thereof.
[0059] According to one embodiment of the invention, the at least
one oxidation base is chosen from para-phenylenediamines.
[0060] When present, the at least one oxidation base may be present
in an amount ranging from 0.0005 to 12% by weight relative to the
total weight of the ready-to-use dye composition. In another
embodiment, the at least one oxidation base may be present in an
amount ranging from 0.005 to 8% by weight relative to the total
weight of the ready-to-use dye composition.
[0061] Examples of the at least one 2-electron oxidoreductase which
may be used as an enzymatic oxidizing agent in the ready-to-use dye
composition of the invention, may be chosen from pyranose oxidases,
glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate
oxidases, uricases, choline oxidases, sarcosine oxidases and
bilirubin oxidases.
[0062] In one embodiment, the at least one 2-electron
oxidoreductase is chosen from uricases of animal, microbiological
and biotechnological origin.
[0063] Examples of these uricases comprise the uricase extracted
from boar's liver, the uricase from Arthrobacter globiformis and
the uricase from Aspergillus flavus.
[0064] In another embodiment, the at least one 2-electron
oxidoreductase may be used in pure crystalline form or in a form
diluted in a diluent which is inert with respect to the at least
one 2-electron oxidoreductase.
[0065] In one embodiment, the at least one 2-electron
oxidoreductase in accordance with the invention, may be present in
an amount ranging from 0.01 to 20% by weight relative to the total
weight of the ready-to-use dye composition. In another embodiment,
the at least one 2-electron oxidoreductase may be present in an
amount ranging from 0.1 to 10% by weight relative to the total
weight of the ready-to-use dye composition.
[0066] In yet another embodiment, the at least one enzymatic
oxidizing agent is at least one 2-electron oxidoreductase and may
be present in an amount ranging from 0.1 to 5% by weight relative
to the total weight of the ready-to-use dye composition.
[0067] The amount of the at least one 2-electron oxidoreductase may
also be defined as a function of its activity. Thus, the enzymatic
activity of the at least one 2-electron oxidoreductase can be
defined by the oxidation of the donor under aerobic conditions.
[0068] One unit U corresponds to the amount of the at least one
2-electron oxidoreductase which generates one .mu.mol of hydrogen
peroxide per minute at a pH of 8.5 and at a temperature of
25.degree. C.
[0069] In one embodiment, the at least one 2-electron
oxidoreductase is present in an amount ranging from 10 to 10.sup.8
units U per 100 g of ready-to-use dye composition.
[0070] According to the invention, the term "donor" means the
various substrates participating in the functioning of the at least
one 2-electron oxidoreductase.
[0071] The nature of the at least one donor (or substrate)
corresponding to the enzyme varies as a function of the nature of
the at least 2-electron oxidoreductase used. For example, in one
embodiment, donors for the pyranose oxidases, may comprise
D-glucose, L-sorbose and D-xylose; donors for the glucose oxidases
may comprise D-glucose; donors for the glycerol oxidases, may
comprise glycerol and dihydroxyacetone; donors for the lactate
oxidases may comprise lactic acid and its salts; donors for the
pyruvate oxidases may comprise pyruvic acid and its salts; donors
for the uricases may comprise uric acid and its salts; donors for
the choline oxidases may comprise choline and acid addition salts
thereof, such as, choline hydrochloride and betaine aldehyde;
donors for the sarcosine oxidases may comprise sarcosine,
N-methyl-L-leucine, N-methyl-D,L-alanine and N-methyl-D,L-valine;
and donors for the bilirubin oxidases may comprise bilirubin.
[0072] When utilized, the at least one donor (or substrate) is
present in an amount ranging from 0.01 to 20% by weight relative to
the total weight of the ready-to-use dye composition in accordance
with the invention. In another embodiment, the at least one donor
(or substrate) is present in an amount ranging from 0.1 to 5% by
weight relative to the total weight of the ready-to-use dye
composition.
[0073] In another embodiment the at least one 4-electron
oxidoreductase which may be used as an enzymatic oxidizing agent is
chosen from at least one laccase, at least one tyrosinase, at least
one catechol oxidase and at least one polyphenol oxidase
enzymes.
[0074] In one embodiment according to the invention, the at least
one 4-electron oxidoreductase used, is chosen from at least one
laccase.
[0075] The at least one laccase may be chosen from laccases of
plant origin, laccases of animal origin, laccases of fungal origin
(yeasts, molds or fungi) and laccases of bacterial origin, the
organisms of origin possibly being monocellular or
multicellular.
[0076] In another embodiment, the at least one laccase may be
obtained by biotechnological techniques.
[0077] Examples of the at least one laccase of plant origin which
may be utilized in accordance with the invention, are those
laccases produced by plants which carry out chlorophyll synthesis,
such as, those mentioned in patent application FR-A-2 694 018
(incorporated by reference, herein).
[0078] In one embodiment of the invention, the at least one laccase
is present in plant extracts chosen from: Anacardiacea, such as,
Magnifera indica, Schinus molle and Pleiogynium timoriense;
Podocarpacea; Rosmarinus off.; Solanum tuberosum; Iris sp.; Coffea
sp.; Daucus carrota; Vinca minor; Persea americana; Catharanthus
roseus; Musa sp.; Malus pumila; Gingko biloba; Monotropa hypopithys
(Indian pipe), Aesculus sp.; Acer pseudoplatanus; Prunus persica
and Pistacia palaestina.
[0079] Examples of at least one laccase of fungal origin,
optionally obtained by biotechnological techniques, which can be
used according to the invention, may comprise laccases obtained
from fungi chosen from Polyporus versicolor, Rhizoctonia praticola
and Rhus vernicifera as described, for example, in patent
applications FR-A-2 112 549 and EP-A-504 005 (incorporated by
reference, herein). Other examples of laccases obtained from fungal
origin comprise the laccases described in patent applications WO
95/07988, WO 95/33836, WO 95/33837, WO 96/00290, WO 97/19998 and WO
97/19999, incorporated by reference, herein, such as, the laccases
obtained from: Scytalidium, Polyporus pinsitus, Myceliophthora
thermophila, Rhizoctonia solani, Pyricularia orizae, and variants
thereof.
[0080] Additional examples may also comprise the laccases obtained
from: Trametes versicolor, Fomes fomentarius, Chaetomium
thermophile, Neurospora crassa, Colorius versicol, Botrytis
cinerea, Rigidoporus lignosus, Phellinus noxius, Pleurotus
ostreatus, Aspergillus nidulans, Podospora anserina, Agaricus
bisporus, Ganoderma lucidum, Glomerella cingulata, Lactarius
piperatus, Russula delica, Heterobasidion annosum, Thelephora
terrestris, Cladosporium cladosporioides, Cerrena unicolor,
Coriolus hirsutus, Ceriporiopsis subvermispora, Coprinus cinereus,
Panaeolus papilionaceus, Panaeolus sphinctrinus, Schizophyllum
commune, Dichomitius squalens, and variants thereof.
[0081] In one embodiment of the invention the at least one laccase
of fungal origin is optionally obtained by biotechnological
techniques.
[0082] In another embodiment of the invention, the enzymatic
activity of the at least one laccase comprising syringaldazine
among their substrates may be defined by the oxidation of
syringaldazine under aerobic conditions. One Lacu unit corresponds
to the amount of enzyme which catalyses the conversion of 1 mmol of
syringaldazine per minute at a pH of 5.5 and at a temperature of
30.degree. C. One U unit corresponds to the amount of enzyme which
produces an absorbance delta of 0.001 per minute at a wavelength of
530 nm, using syringaldazine as a substrate, at 30.degree. C. and
at a pH of 6.5.
[0083] Additionally, the enzymatic activity of the at least one
laccase used according to the invention may also be defined by the
oxidation of para-phenylenediamine. One ulac unit corresponds to
the amount of enzyme which produces an absorbance delta of 0.001
per minute at a wavelength of 496.5 nm, using para-phenylenediamine
as substrate (64 mM), at 30.degree. C. and at a pH of 5.
[0084] In another embodiment of the invention, the at least one
4-electron oxidoreductase is present in an amount ranging from 0.01
to 20% by weight relative to the total weight of the ready-to-use
dye composition. In another embodiment, the at least one 4-electron
oxidoreductase is present in an amount ranging from 0.1 to 5% by
weight relative to the total weight of the ready-to-use dye
composition.
[0085] When at least one laccase is used, the amount of the at
least one laccase present in the ready-to-use dye composition may
vary as a function of the nature of the laccase used. In one
embodiment of the invention, the at least one laccase is present in
an amount ranging from 0.5 to 2000 Lacu (i.e. between 10,000 to
40.times.10.sup.6 U units or alternatively between 20 to
20.times.10.sup.6 ulac units) per 100 g of ready-to-use dye
composition.
[0086] In one embodiment of the invention, the at least one
peroxidase which may be used as enzymatic oxidizing agent in the
ready-to-use dye composition can be chosen from enzymes belonging
to the subclass 1.11.1 described in the book Enzyme Nomenclature,
Academic Press Inc., 1984 (incorporated by reference, herein). Some
peroxidases belonging to this class require the presence of a donor
to function. This is the case, for example, for the NADH
peroxidases (1.11.1) having NADH as donor, the fatty acid
peroxidases (1.11.1.3) having a fatty acid, such as, palmitate as
donor, the NADPH peroxidases (1.11.1.2) having NADPH as donor, the
cytochrome-c peroxidases (1.11.1.5) having ferrocytochrome-c as
donor, the iodide peroxidases (1.11.1.8) having iodides as donor,
the chloride peroxidases (1.11.10) having chlorides as donor, the
L-ascorbate peroxidases (1.11.1.11) having L-ascorbate as donor and
the glutathione peroxidases (1.11.1.9) having glutathione as
donor.
[0087] Other examples of at least one peroxidase are those
peroxidases belonging to the subclass 1.11.1 function without a
donor other than the oxidation dye and are chosen from catalases
(1.11.1.6) and simplex peroxidases (1.11.1.7).
[0088] In one embodiment of the invention, simplex peroxidases
(1.11.1.7) are used.
[0089] All the peroxidases function in the presence of hydrogen
peroxide, which is provided in its native form or generated in situ
via an enzymatic route by at least one 2-electron oxidoreductase
and its corresponding at least one donor in the presence of
air.
[0090] The origin of the at least one peroxidase which may be used
in the ready-to-use dye composition in accordance with the
invention, is chosen from plant, animal, fungal and bacterial
origin. In one embodiment of the invention, the at least one
peroxidase may be obtained by biotechnological techniques.
[0091] Thus, the at least one peroxidase may be obtained, for
example, from the following sources: apple, apricot, barley, black
radish, beetroot, cabbage, carrot, corn, cotton, garlic, grape,
mint, rhubarb, soybean, spinach, inky cap, cow's milk and
microorganisms, such as, Acetobacter peroxidans, Staphylococcus
faecalis and Arthromyces ramosus.
[0092] The unit of activity of simplex peroxidase (1.11.1.7) can be
defined as being the amount of simplex enzyme forming 1 mg of
purpurogallin from pyrogallol in 20 s at pH 6 and at 20.degree. C.
By way of example, black radish peroxidase P6782 from Sigma.RTM.
has an activity of about 250 units per mg.
[0093] In one embodiment of the invention, the working
concentration of this type of enzyme thus ranges from 25 to
5.times.10.sup.6 units per 100 g of ready-to-use composition.
[0094] In one embodiment, the at least one peroxidase is present in
an amount ranging from 0.0001 to 20% by weight relative to the
total weight of the ready-to-use composition in accordance with the
invention. In yet another embodiment, the at least one peroxidase
is present in an amount ranging from 0.001 to 10% by weight
relative to the total weight of the ready-to-use composition.
[0095] According to one embodiment, the ready-to-use dye
composition in accordance with the invention contains at least one
4-electron oxidoreductase chosen from laccases.
[0096] The at least one coupler which may be present in the
ready-to-use composition in accordance with the invention is chosen
from the couplers conventionally used in oxidation dyeing, such as,
meta-phenylenediamines, meta-aminophenols, meta-diphenols,
naphthols and heterocyclic couplers, for example, chosen from
pyrazolo[1,5-b]-1,2,4-triazoles, pyrazolo[3,2-c]-1,2,4-triazoles,
pyrazol-5-ones, pyridines other than the pyridines of formula (I)
above, such as, indoles, indolines, indazoles, benzimidazoles,
benzothiazoles, benzoxazoles, 1,3-benzodioxoles and quinolines.
[0097] In one embodiment of the invention, the at least one coupler
is chosen from 2-methyl-5-aminophenol, 5-N-(.beta.-hydroxyethyl
)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene,
1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene,
2,4-diamino-1-(.beta.-hydroxyethyloxy)benzene,
2-amino-4-(.beta.-hydroxye- thylamino)-1-methoxybenzene,
1,3-diaminobenzene, 1,3-bis(2,4-diaminophenox- y)propane, sesamol,
.alpha.-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole,
4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline,
2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one,
1-phenyl-3-methylpyrazol-5-one, 2-amino-3-hydroxypyridine,
3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazol,
2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, and acid addition salts
thereof.
[0098] In one embodiment of the invention, the at least one coupler
is present in an amount ranging from 0.0001 to 10% by weight
relative to the total weight of the ready-to-use dye composition.
In another embodiment, the at least one coupler is present in an
amount ranging from 0.005 to 5% by weight relative to the total
weight of the ready-to-use dye composition.
[0099] In another embodiment of the invention, the ready-to-use dye
composition may further comprise at least one direct dye, used for
example, to modify the shades or to enrich them with glints.
[0100] In general, the acid addition salts which can be used in the
context of the dye compositions of the invention (pyridines of
formula (I), oxidation bases and couplers) are chosen, for example,
from hydrochlorides, hydrobromides, sulphates, tartrates, lactates
and acetates.
[0101] In one embodiment the medium which is suitable for dyeing
(or support) for the ready-to-use dye composition in accordance
with the invention comprises water. In another embodiment of the
invention, the medium suitable for dyeing comprises a mixture of
water and at least one organic solvent to dissolve the compounds
which would not be sufficiently soluble in water. By way of organic
solvents, mention may be made, for example, of C.sub.1-C.sub.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 and phenoxyethanol, similar products and mixtures
thereof.
[0102] In one embodiment, the at least one organic solvent may be
present in amount ranging from 1 to 40% by weight relative to the
total weight of the dye composition. In another embodiment, the at
least one organic solvent may be present in an amount ranging from
5 to 30% by weight relative to the total weight of the dye
composition.
[0103] The pH of the ready-to-use composition in accordance with
the invention is chosen such that the enzymatic activity of the
enzyme used is sufficient. In one embodiment of the invention, the
pH ranges from 5 to 11. In another embodiment of the invention, the
pH ranges from 6.5 to 10. The pH may be adjusted to the desired
value using acidifying and alkalinizing agents usually used for
dyeing keratinous fibers.
[0104] Among the acidifying agents, mention may be made, by way of
example, of inorganic and organic acids, chosen from hydrochloric
acid, orthophosphoric acid, sulphuric acid, carboxylic acids, such
as, acetic acid, tartaric acid, citric acid and lactic acid, and
sulfuric acids.
[0105] Among the alkalinizing agents, mention may be made, by way
of example, of alkalinizing agents chosen from aqueous ammonia,
alkali metal 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: 5
[0106] wherein:
[0107] W is a propylene residue, optionally substituted with a
group chosen from a hydroxyl group and a (C.sub.1-C.sub.4) alkyl
group, R.sub.20, R.sub.21, R.sub.22 and R.sub.23, which are
identical or different, are each chosen from a hydrogen atom, a
(C.sub.1-C.sub.4)alkyl group and a (C.sub.1-C.sub.4)hydroxyalkyl
group.
[0108] The ready-to-use dye composition in accordance with the
invention may also comprise at least one adjuvant used
conventionally in compositions for the dyeing of the hair, such as,
anionic, cationic, nonionic, amphoteric and zwitterionic
surfactants: anionic, cationic, nonionic, amphoteric and
zwitterionic polymers; inorganic and organic thickeners;
antioxidants; penetration agents; sequestering agents; fragrances;
buffers; dispersing agents; and conditioning agents, for example,
modified and unmodified, non-volatile and volatile silicones,
film-forming agents, ceramides, preserving agents and opacifying
agents.
[0109] Needless to say, a person skilled in the art may choose
these optional, complementary compounds such that the advantageous
properties intrinsically associated with the ready-to-use dye
composition in accordance with the invention are not substantially
adversely affected by the additions envisaged.
[0110] The ready-to-use dye composition in accordance with the
invention may be provided in various forms, such as, optionally
pressurized, liquids, creams, and gels, or in any other form
suitable for dyeing keratinous fibers, such as human hair. In one
embodiment of the invention, the at least one oxidation dye and the
at least one enzymatic oxidizing agent are present in the same
ready-to-use composition, and consequently the said composition
should be free of gaseous oxygen, so as to avoid any premature
oxidation of the oxidation dyes.
[0111] Another embodiment of the invention, is a method of
oxidation dyeing keratinous fibers, for example, human keratinous
fibers such as hair, using the ready-to-use dye composition as
defined above.
[0112] According to this method, at least one ready-to-use dye
composition, as defined above, may be applied to the fibers for a
period of time sufficient to develop the desired coloration, after
which the fibers may be rinsed, washed with shampoo, rinsed again
and dried.
[0113] In one embodiment, the time required to develop the
coloration on the keratinous fibers ranges from 3 to 60 minutes. In
another embodiment of the invention, the time required to develop
the coloration on the keratinous fibers ranges from 5 to 40
minutes.
[0114] According to one embodiment of the invention, the method
previously described may also include a preliminary step which
comprises separately storing, on the one hand, a composition (A)
comprising, in a medium suitable for dyeing, at least one oxidation
dye chosen from pyridines of formula (I) as defined previously,
and, on the other hand, a composition (B) comprising, in a medium
suitable for dyeing, at least one enzymatic oxidizing agent chosen
from a) at least one 2-electron oxidoreductase in the presence of
its corresponding at least one donor, b) at least one 4-electron
oxidoreductase, c) at least one peroxidase, and mixing said
composition A and said composition B together at the time of use,
and then applying this mixture to the keratinous fibers.
[0115] Another embodiment of the invention is a multi-compartment
dyeing device, dyeing "kit" or any other multi-compartment
packaging system, wherein a first compartment comprises composition
(A) as defined above and a second compartment comprises composition
(B) as defined above. These devices may be equipped with a means to
deliver the desired mixture to the hair, such as the devices
described in patent FR-2,586,913, which is incorporated by
reference herein.
[0116] Unless otherwise indicated, all numbers expressing
quantities of ingredients, properties such as molecular weight,
reaction conditions, and so forth used in the specification and
claims are to be understood as being modified in all instances by
the term "about". Accordingly, unless indicated to the contrary,
the numerical parameters set forth in the following specification
and attached claims are approximations that may vary depending upon
the desired properties sought to be obtained by the present
invention. At the very least, and not as an attempt to limit the
application of the doctrine of equivalents to the scope of the
claims, each numerical parameter should at least be construed in
light of the number of reported significant digits and by applying
ordinary rounding techniques.
[0117] The examples which follow are intended to illustrate the
invention without, however, limiting its scope.
DYEING EXAMPLES 1 to 9
[0118] Table 1 shows the prepared ready-to-use dye compositions
(contents in grams):
1TABLE 1 DYEING EXAMPLES 1-9 EXAMPLE 1 2 3 4 5 6 7 8 9
2,6-Dimethoxy-3,5-diaminopyridine 0.636 0.636 0.636 -- 0.636 -- --
-- -- dihydrochloride (oxidation dye of formula (I))
2-Methylamino-3-amino-6-methoxy- -- -- -- 0.732 0.732 -- -- -- --
pyridine (oxidation dye of formula (I))
2,3-Diamino-6-methoxypyridine -- -- -- -- -- 0.636 0.636 0.636
0.636 dihydrochloride (oxidation dye of formula (I))
para-Phenylenediamine (oxidation base) 0.324 -- -- -- -- 0.324 --
-- -- 2-Aminophenol (oxidation base) -- -- 0.327 0.327 -- -- -- --
0.327 para-Aminophenol (oxidation base) -- -- -- -- -- -- 0.327 --
-- 4,5-Diamino-1-ethyl-3-methylpyrazole -- 0.639 -- -- -- -- --
0.639 -- dihydrochloride (oxidation base) Common dye support (*)
(*) (*) (*) (*) (*) (*) (*) (*) pH agent (citric acid or
2-amino-2-methyl- pH 7 pH 7 pH 7 pH 7 pH 7 pH 7 pH 7 pH 7 pH 7
1-propanol) qs Distilled water qs 100 g 100 g 100 g 100 g 100 g 100
g 100 g 100 g 100 g (*) Common dye support
Common Dye Support Used in Examples 1-9 of Table 1
[0119]
2 Carboxymethylchitosan containing 84% active material 2.0 g (A.M.)
in water, sold under the name Olevasan .RTM. by the company
Sino-Lion Hydroxypropyl guar trimethylammonium chloride sold under
2.0 g the name Jaguar C13S .RTM. by the company Rhodia Chimie
Polyglyceryl monooleate (10 mol) sold under the name 1.0 g Decaglyn
10 .RTM. by the company Nikko N-Acetyl-L-cysteine 0.05 g Laccase
5.0 g
[0120] The amount of laccase used in the dye support corresponds to
5 360 000 ulac units per 100 g of ready-to-use dye composition.
[0121] The ready-to-use dye compositions described above were
applied to locks of natural grey hair containing 90% white hairs,
for 30 minutes at room temperature. The hair was then rinsed,
washed with a standard shampoo and then dried.
[0122] The hair was dyed in the shades listed in Table 2.
3TABLE 2 Shades of Dyed Hair EXAMPLE SHADE OBTAINED 1 Black-blue 2
Red-mahogany 3 Bronze-green 4 Slightly matt intense golden 5
Golden-green 6 Black-violet 7 Ash golden bronze-green 8 Intense
blue-green 9 Bronze green-golden
EXAMPLE 10
[0123] The ready-to-use composition below was prepared:
4 2,6-Dimethoxy-3,5-diaminopyridine dihydrochloride 0.726 g
(oxidation dye of formula (I)) para-Phenylenediamine (oxidation
base) 0.324 g Uric acid 1.0 g Uricase 1.0 g Oxyethylenated
methacrylic acid/ethyl acrylate/stearyl 2.5 g methacrylate
terpolymer sold under the name Aculyn 22 .RTM. by the company Rohm
& Haas Polyglyceryl monooleate (10 mol) sold under the name 1.0
g Decaglyn 10 .RTM. by the company Nikko N-Acetyl-L-cystein 0.1 g
2-Amino-2-methyl-1-propanol qs pH = 9.5 Distilled water qs 100
g
[0124] The amount of uricase used in this ready-to-use composition
corresponds to 20 000 U units per 100 g of ready-to-use
composition.
[0125] The ready-to-use dye composition described above was applied
to locks of natural grey hair containing 90% white hairs for 30
minutes at room temperature. The hair was then rinsed, washed with
a shampoo, rinsed again and then dried.
[0126] The hair was dyed in an intense ash-blue shade.
* * * * *