EP1165027A1

EP1165027A1 - Hairdye composition of single preparation type containing an oxidase

Info

Publication number: EP1165027A1
Application number: EP00911409A
Authority: EP
Inventors: Takeshi Onuki; Mutsumi Noguchi; Joji Mitamura
Original assignee: Lion Corp
Current assignee: Lion Corp
Priority date: 1999-03-30
Filing date: 2000-03-28
Publication date: 2002-01-02
Also published as: WO2000059459A1; AU3329500A

Abstract

An oxidative hairdye composition of a single preparation type containing an oxidase and a process for producing the same, characterized in that, (i) the composition is filled in a container in such a state that the oxygen concentration at the headspace is made 1 % by weight or less or (ii) a mixing operation of the components containing the oxidase is carried out in the absence of oxygen and the filling of the resulting composition into the container is carried out in the absence of oxygen.

Description

DESCRIPTION

HAIRDYE COMPOSITION OF SINGLE PREPARATION TYPE CONTAINING AN OXIDASE

Technical Field of the Invention

The present invention relates to an oxidative hairdye composition of a single preparation type wherein an oxidase is compounded and also to a process for producing the same. More particularly, it relates to an oxidative hairdye composition of a single preparation type wherein the oxidase has a good stability with a lapse of time and an excellent hair-dyeing effect is available.

Background Art In an oxidative hairdye, it is usual that an oxidation dye (the first preparation) and an oxidizing agent (the second preparation) are mixed upon use to react them and are applied to hair whereby white hair is dyed.

In that case, the first preparation contains an oxidation dye such as p-phenylenediamine and p-aminophenol and is usually alkaline. Therefore, there has been a problem that skin irritation to scalp is resulted due to the alkali.

On the other hand, in the second preparation, hydrogen peroxide has been used as an oxidizing agent. However, it has been known that hydrogen peroxide damages the hair and that its continued use for a long term shows a bad effect such as that hair is damaged or, after dyeing, the dyed hair is discolored.

In view of the above, investigations have been made for the first preparation to make the liquid neutral (Japanese Laid-Open Patent Hei-8/217652 ) while, for the second preparation, an art of using an oxidase in place of hydrogen peroxide has been proposed as an attempt of reducing the damage of hair by hydrogen peroxide . Examples of such an art are the use of a peroxide as an oxidase (Japanese Laid-Open Patents Sho-47/10400 and Sho-53/32132 ) , the use of laccase (U. S. Patent 3,251,742 and Japanese Laid-Open Patent Hei-6/172145 ) and the use of uricase (Japanese Laid-Open Patent Sho- 63/246313) . Incidentally, in the common hair-dyeing method at present, there is no means other than the mixing of the first and the second preparations and a fundamental problem that "mixing is troublesome" still remains.

Accordingly, an oxidative hairdye of a single preparation type where oxidation dye and oxidase causing no damage of hair are previously mixed is an ideal product.

However, when a hairdye composition of a single preparation type is produced using oxidase, the oxidase reacts with the oxidation dye in the composition during preservation due to unstable property of the oxidase which is a protein whereby insoluble aggregates are formed. Therefore, it is a very big problem as a hairdye that the action of the oxidase upon use is not fully achieved but such aggregates are formed in the product. Thus, there is a big problem that, unless the resulting aggregates are suppressed, it is not possible to put it into a market as a hairdye product of a single preparation type.

With regard to an art for improving the stability of preservable period of oxidase, that for catalase (Japanese Laid-Open Patent Hei-8/175935) and that for uricase (Japanese Laid-Open Patent Hei-8/217652 ) have been disclosed but, in the art disclosed as such, it is essential to add a reducing agent to the composition and there is a possibility that the action of oxidase is reduced by a suppressing action of the reducing agent.

Disclosure of Invention Accordingly, an object of the present invention is to offer an oxidation hairdye composition of a single preparation type containing an oxidase where stability of the oxidase is high, production of the aggregates is suppressed and action by the oxidase is effectively achieved and also to offer a process for producing the same.

In order to achieve the above-mentioned object, the present inventors have conducted an intensive study for achieving the above-mentioned object and accomplished the present invention.

Thus , the present invention offers :

(1) a hairdye composition, characterized in that, it is an oxidation hairdye composition of a single preparation type containing an oxidase and is filled in a container in such a state that the oxygen concentration at the headspace is made 1% by weight or less; and

(2) a process for the production of a hairdye composition which is characterized in that, in the production of the hairdye composition mentioned in the above ( 1) , a mixing operation of the components containing the oxidase is carried out in the absence of oxygen and a filling operation of the resulting composition into the container is carried out in the absence of oxygen.

The oxidase-containing hairdye composition in accordance with the present invention greatly improves the stability of the oxidase with a lapse of time and significantly suppresses the production of aggregates with the oxidation dye even when prepared as a single preparation type whereby an excellent hair-dying effect is achieved.

Best Mode for Carrying Out the Invention The present invention will now be illustrated in detail as follows . The hairdye composition of the present invention uses laccase, peroxidase, uricase, catalase, tyrosinase, etc. as an oxidizing agent. They may be used independently of their source.

Particularly preferred enzymes are laccases and related enzymes, the term "laccases and related enzymes" including enzymes comprised by the enzyme classification E.C. 1.10.3.2 (laccases) and catechol oxidase enzymes comprised by E.C. 1.10.3.1, bilirubin oxidase enzymes comprised by the enzyme classification E.C. 1.3.3.5 and mono-phenol mono- oxygenase enzymes comprised by the enzyme classification E.C. 1.14.99.1. Laccases are multi-copper containing enzymes that catalyze the oxidation of phenols and aromatic amines. Laccase-mediated oxidations result in the production of aryloxy-radical intermediates from suitable phenolic substrates; the ultimate coupling of the intermediates so produced provides a combination of dimeric, oligomeric, and polymeric reaction products .

The laccase may be derived from a microorganism, e.g. a fungus or a bacteria, or a plant. Preferably, the laccase employed is derived from a fungus. More preferably, it is derived from a strain of Polyporus sp. , in particular a strain of P. pinsi tus or P. versicolor , a strain of Mycellophthora sp. , e. g. M. thermophila , a strain of Rhlzoctonia sp. , in particular a strain of Rh. praticola or Rh. solani , a strain of Pyricularia sp, in particular P. oryzae , or a strain of Scytalldlum, such as S. thermophlllum. The laccase may also be from a plant such as Rhus sp., e.g. Rhus vernlclfera ,

In specific embodiments of the invention the oxidoreductase is a laccase such as a Polyporus sp. laccase, especially the Polyporus plnlsl tus laccase (also called Trametes vlllosa laccase) described in WO 96/00290 (from Novo Nordisk Biotec Inc.) or a Myceliophthora sp. laccase, especially the Myceliophthora thermophlla laccase described in WO 95/33836 (from Novo Nordisk Biotech Inc.). Further, the laccase may be a Scytalldlum sp. laccase such as the S. thermophlllum laccase described in WO 95/33837 and WO 97/19998 (from Novo Nordisk Biotech Inc. ) , the contents of which is incorporated herein by reference , or a Pyricularia sp. laccase, such as the Pyricularia oryzae laccase which can be purchased from SIGMA under the trade name SIGMA No. L5510, or a Coprlnus sp. laccase, such as a C. clnereus laccase , especially a C. clnereus IFO 30116 laccase, or a Rhlzoctonla sp. laccase, such as a Rh. solani laccase, especially the neutral Rh. solani laccase described in WO 95/07988 (from Novo Nordisk A/S) having a pH optimum in the range of from 6.0 to 8.5.

The laccase may also be derived from a fungus such as Collybla , Fomes , Lentlnus , Pleurotus , Asperglllus , Neurospora , Podospora , Phlehla, e. g. P. radlata (WO 92/01046) , Corlolus s . , e. g. C. hlrsl tus ( JP 2-238885), or Botrytls . Bilirubin oxidase may preferably be derived from a strain of Myrotheclum sp., such as M. verrucarla .

Oxidases yielding peroxide (H₂0₂) are typically used in combination with a peroxidase to remove or at least reduce the peroxide produced.

Suitable oxidases include glucose oxidase (E.C.

1.1.3.4), hexose oxidase (E.C. 1.1.3.5), L-amino-acid oxidase

(E.C. 1.4.3.2), xylitol oxidase, galactose oxidase (E.C.

1.1.3.9), pyranose oxidase (E.C. 1.1.3.10) and alcohol oxidase (E.C. 1.1.3.13).

If an L-amino acid oxidase is used, it may be derived from a Trlchoderma sp. such as Trlchoderma harzlanum, such as the L-amino acid oxidase described in WO 94/25574 (from Novo Nordisk A/S), or Trlchoderma vlrlde. A suitable glucose oxidase may originate from Aspergillus sp. , such as a strain of Asperglllus nlger , or from a strain of Cladosporlum sp . in particular Cladosporlum oxysporum .

Hexose oxidases from the red sea-weed Chondrus crlspus (commonly known as Irish moss ) (Sullivan and Ikawa, (1973), Biochim. Biophys. Acts, 309, p. 11-22; Ikawa, (1982), Meth. in Enzymol. 89, Carbohydrate Metabolism Part D, 145-149) oxidise a broad spectrum of carbohydrates, such as D-glucose, D- galactose, maltose, cellobiose, lactose, D-glucose 6-phosphate, D-mannose, 2-deoxy-D-glucose, 2-deoxy-D-galactose, D-fructose, D-glucuronic acid, and D-xylose.

The compounding amount of the oxidase used in the present invention in the preparation may vary depending upon the form, the frequency of use and the applying time of the preparation and also upon the titer of the enzyme preparation but, usually, it is recommended to compound 0.0005-10% (% by weight; hereinafter, used in the same sense) or, preferably, 0.005-5%. When the amount is less than 0.0005%, a sufficient effect is not resulted while, even when it is compounded in more than 10%, there is a tendency that an increase in the effect proportional to an increase in the compounding amount is not available .

In the hairdye composition of the present invention, an oxidation dye is used as a component which takes place in a coloring reaction with the oxidase and there is no particular limitation for type and compounding amount of the oxidation dye used in the present invention but the dye may be selected from known ones. For example, those which are described in "Standards for Materials for Quasi-Drugs" such as 5-amino- o-cresol, o-aminophenol, m-aminophenol, p-aminophenol, 2,6-diaminopyridine , 5- ( 2-hydroxylethylamino ) -2- methylphenol , N,N-bis ( β-hydroxyl ) -p-phenylenediamine sulfate, p-nitro-o-phenylenediamine, p-phenylenediamine, m-phenylenediamine , N-phenyl-p-phenylenediamine, resorcinol, 2-hydroxyl-5-nitro- 2 ' , 4 ' -diaminoazobenzene sodium sulfate. toluene-2 , 5-diamine, 5-amino-o-cresol sulfate, p- aminophenol sulfate, o-chloro-p-phenylenediamine sulfate, 4,4' -diaminodiphenylamine sulfate, p-methylaminophenol sulfate, p-phenylenediamine sulfate, m-phenylenediamine sulfate, toluene-2, 5-diamine sulfate, 2,4- diaminophenoxyethanol hydrochloride , toluene-2 , 5-diamine hydrochloride , m-phenylenediamine hydrochloride, 2,4- diaminophenol hydrochloride, 3 , 3 ' -iminodiphenol, p- phenylenediamine hydrochloride, N-phenyl-p-phenylenediamine hydrochloride, N-phenyl-p-phenylenediamine acetate, 1,5- dihydroxynaphthalene , toluene-3 , 4-diamine, p- methylaminophenol , N,N'-bis(4-aminophenyl) -2 , 5-diamino- 1, 4-quinonediimine, o-aminophenol sulfate, 2,4- diaminophenol sulfate and m-aminophenol sulfate may be used in an appropriate amount either solely or jointly by combining two or more .

Further, direct materials which are frequently used together with such oxidation dyes such as 2-amino-4- nitrophenol, 2-amino-5-nitrophenol, l-amino-4- methylaminoanthraquinone , nitro-p-phenylenediamine hydrochloride, 1 , 4-diaminoanthraquinone, nitro-p- phenylenediamine , picramic acid, sodium picramate, 2- amino-5-nitrophenol sulfate, resorcinol, nitro-p- phenylenediamine sulfate, p-nitro-o-phenylenediamine sulfate and p-nitro-m-phenylenediamine sulfate may be used as well .

Particularly preferred oxidation dyes among them are p-phenylenediamine or salt thereof, toluene-2 , 5-diamine or salt thereof, p-aminophenol, 5-amino-o-cresol, m-aminophenol, p-nitro-o-phenylenediamine, 2 , 6-diaminopyridine, resorcinol, o-aminophenol and m-phenylenediamine.

The compounding concentration of the oxidation dye may be appropriately selected depending upon the frequency of use of the hairdye and the form of the preparation but, usually, it is recommended to compound in an amount of 0.01-10% or, preferably, 0.1-5% of the total composition.

WO 99/36034, WO 99/36035, WO 99/36036, WO 99/36037, WO 99/36038, WO 99/36039, WO 99/36040, WO 99/36041, WO 99/36042, WO 99/36043, WO 99/36044, WO 99/36045 and WO 99/36046 in the name of L^'Oreal discloses different kind of oxidizing dyes (developed substances or oxidation bases) and coupling components (coupling agents) which can also be used according to the present invention and which are hereby incorporated by reference. The oxidation bases can in particular be selected among para-phenylenediamines , double bases, para-aminophenols , ortho-aminophenols and heterocyclic oxidation bases.

Among the para-phenylenediamines suitable as oxidation bases in the dye compositions according to the invention, the following compounds of the formula ( 1 ) and their addition salts with an acid can in particular be mentioned:

in which

R¹ represents a hydrogen atom, C₁-C₄-alkyl, C₁-C₄- monohydroxyalkyl , C₂ - C₄ - polyhydroxy alkyl , (C_λ- C₄)alkoxy( C^C alkyl, C₁-C₄-alkyl substituted with a nitrogen-containing group, phenyl or 4 ' -aminophenyl; R² represents a hydrogen atom, C₁-C₄-alkyl, C^ C₄monohydroxyalkyl , C₂-C₄polyhydroxyalkyl, (C_x-

C₄) alkoxy (C^C alkyl or C₁-C₄alkyl substituted with a nitrogen-containing group;

R³ represents a hydrogen atom, a halogen atom such as chlorine, bromine, iodine or fluorine, C₁-C₄alkyl,

C₁-C₄hydroxyalkoxy , C_x-

C₄acetylaminoalkoxy , C^C^esylaminoalkoxy or C_x- C₄carbamoylaminoalkoxy,

R⁴ represents a hydrogen atom, a halogen atom or C_x- C₄- alkyl.

Among the nitrogen-containing groups in the above formula (1), amino, mono ( C^C,, )alkylamino, di(C₁-C₄)alkylamino, tri(C₁-C₄)alkylamino, monohydroxy(C₁-C₄)alkylamino, imidazolinium and ammonium can in particular be mentioned. More particularly among the para-phenylenediamines of the above formula (1), the following para-phenylenediamines can be mentioned: para-phenylenediamine, paratoluylenediamine , 2-chloro para-phenylenediamine, 2,3- dimethyl para-phenylenediamine, 2, 6-dimethyl para- phenylenediamine, 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-methyl aniline, N,N-bis(β-hydroxy-ethyl) para-phenylenediamine, 4-N,N-bis- (β-hydroxyethyl) amino 2-methyl aniline, 4-N,N- bis- (β-hydroxyethyl)amino 2-chloro aniline, 2-β-hyroxyethyl para-phenylenediamine, 2-fluoro para-phenylenediamine, 2- isopropyl para-phenylenediamine, N- (β-hydroxypropyl) para- phenylenediamine , 2-hydroxymethyl para-phenylenediamine, N,N-dimethyl 3-methyl para-phenylenediamine, N,N- (ethyl, β-hydroxyethyl) para-phenylenediamine, N-(β, 7 dihydroxypropyl) para-phenylenediamine, N- ( 4 * -aminophenyl) para-phenylenediamine, N-phenyl para-phenylene-diamine, 2- β-hydroxyethyloxy para-phenylenediamine, 2-β- acetylaminoethyloxy para-phenylenediamine, N-(β- methoxyethyl ) para-phenylenediamine and their addition salts with an acid.

Among the para-phenylenediamines of the above formula (1), the following are especially preferred: para- phenylenediamine , paratoluylenediamine , 2-isopropyl para- phenylenediamine, 2-β-hydroxyethyl para-phenylenediamine, 2-β-hydroxyethyloxy para-phenylenediamine, 2,6-dimethyl para-phenylenediamine, 2,6-diethyl para-phenylenediamine, 2,3-dimethyl para-phenylenediamine, N,N-bis-(β- hydroxyethyl) para-phenylenediamine, 2-chloro para- phenylenediamine, 2-β-acetylaminoethyloxy para- phenylenediamine and their addition salts with an acid.

By double bases is, according to the invention, meant such compositions which include at least two aromatic nuclei carrying amino and/or hydroxyl groups.

Among the double bases suitable as oxidation bases in the dye compositions according to the invention, the compounds of the following formula (2) and their addition salts with an acid can in particular be mentioned:

in which

Z¹ and Z², which are identical or differ, represent a hydroxyl group or -NH₂, which can be substituted with a C₁-C₄alkyl group or with a bridging group Y; the bridging group Y is a linear or branched alkylene chain with 1 to 14 carbon atoms, which can be interrupted or terminated by one or more nitrogen- containing groups and/or one or more hetero atoms, such as oxygen, sulphur or nitrogen atoms, and optionally be substituted with one or more hydroxyl groups or _x-C₆-alkoxy groups ;

R⁵ and R⁶ represents a hydrogen or halogen atom, C^ C₄alkyl, C₁-C₄mono-hydroxyalkyl, C₂-C₄polyhydroxyalkyl , C₁-C₄aminoalkyl or a bridging group Y; - R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹², which are identical or differ, represent a hydrogen atom, a bridging group Y or a C₁-C₄alkyl group; whereby it should be understood that the compounds of the formula (2) only include a single bridging group Y per molecule.

Among nitrogen-containing groups of the above formula (2), the following can in particular be mentioned: amino, mono(C₁-C₄)alkylamino, di(C₁-C₄) alkyl-amino, tτi ( C₁- C₄)alkylamino , monohydroxy(C₁-C₄)alkylamino, imidazolinium and ammonium.

Among the double bases of the above formula ( 2 ) , the following can more particularly be mentioned: N,N=-bis-(β- hydroxyethyl) N,N' -bis- ( 4 ' -aminophenyl) 1,3-diamino propanol, N,N=-bis- (β-hydroxyethyl) N,N=-bis- ( 4 ' - aminophenyl) ethylenediamine, N,N=-bis- (4-aminophenyl) tetra ethylenediamine , N,N' -bis- (β-hydroxyethyl) N,N'-bis- (4-aminophenyl) tetramethylenediamine, 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 their addition salts with an acid.

Particularly preferred double bases of the formula (2) are N,N' -bis- (β-hydroxyethyl) N,N' -bis- ( 4 ' -aminophenyl) 1,3-diamino propanol, 1 , 8-bis- ( 2 , 5-diamino-phenoxy) -3 , 5- dioxaoctane or one of their addition salts with an acid.

Among the para-aminophenols suitable as oxidation bases in the dye compositions according to the invention, the compounds of the following formula ( 3 ) and their addition salts with an acid can especially be mentioned:

in which

R¹³ represents a hydrogen or halogen atom , C₁-C₄alkyl , Ci-Cmonohydroxyalkyl , ( _x - C₄ ) alkoxy ( C^C alkyl , C_x- C₄aminoalkyl or ( C₁-C₄ ) hydroxyalkyl ( C^C,, ) aminoalkyl , R¹⁴ represents a hydrogen or halogen atom , C₁-C₄alkyl , C₁-C₄monohydroxyalkyl , C₂-C₄polyhydroxyalkyl , C_x- C₄aminoalkyl , C₁-C₄cyanoalkyl or ( C^-C alkoxy(C_:-

C₄)alkyl, whereby it should be understood that at least one of the groups R¹³ or R¹⁴ represents a hydrogen atom.

Among the para-aminophenols of the above formula (3), the following can in particular be mentioned: para- aminophenol , 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4-amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2-(β- hydroxyethyl aminomethyl) phenol, 4-amino 2-fluoro phenol and acid addition salts thereof.

Among the ortho-aminophenols suitable as oxidation bases in the dye compositions according to the invention, the following can in particular be mentioned: 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol , 5-acetamido

2-amino phenol and acid addition salts thereof.

Among the heterocyclic bases suitable as oxidation bases in the dye compositions according to the invention, the following can in particular be mentioned: pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, pyrazolo-pyrimidine derivatives and acid addition salts thereof .

Among the pyridine derivatives , the compositions described for instance in the patents GB-PS 1026978 and GB-PS 1153196 can in particular be mentioned: 2 , 5-diamino pyridine , 2- ( 4-methoxyphenyl)amino 3-amino pyridine, 2,3-diamino 6- methoxy pyridine, 2- (β-methoxyethyl)amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine and the addition salts thereof . Among the pyrimidine derivatives, the compositions described for instance in the German patent DE 2 359 399 or the Japanese patents JP 88-169571 and JP 91-333495 or in the Patent Application WO 96/15765 can in particular be mentioned: 2, 4, 5, 6-tetra-aminopyrimidine, 4-hydroxy 2,5,6- triaminopyrimidine , 2-hydroxy 4 , 5 , 6-triaminopyrimidine, 2 , 4-dihydroxy 5 , 6-diaminopyrimidine , 2,5,6- triaminopyrimidine and their addition salts with an acid.

Among the pyrazole derivatives , the compounds described for instance in the patents DE 3 843 892 and DE 4 133957 and in the Patent Applications WO 94/08969 , WO 94/08970 , FR-A-2733749 and DE 19543988 can in particular be mentioned: 4,5-diamino 1-methyl pyrazole, 3,4-diamino pyrazole, 4,5- diamino 1- ( 4 ' -chlorobenzyl) pyrazole, 4,5-diamino 1,3- dimethyl pyrazole, 4,5-diamino 3-methyl 1-phenyl pyrazole, 4,5-diamino 1-methyl 3-phenyl pyrazole, 4-amino 1,3-dimethyl 5-hydrazino pyrazole, 1-benzyl 4,5-diamino 3-methyl pyrazole, 4,5-diamino 3-tert-butyl 1-methyl pyrazole, 4,5-diamino 1- tert-butyl 3-methyl pyrazole, 4,5-diamino 1- (β-hydroxyethyl)

3-methyl pyrazole, 4,5-diamino 1-ethyl 3-methyl pyrazole, 4,5-diamino 1-ethyl 3- ( 4 ' -methoxyphenyl) pyrazole, 4,5- diamino 1-ethyl 3-hydroxymethyl pyrazole, 4,5-diamino 3- hydroxymethyl 1-methyl pyrazole, 4,5-diamino 3-hydroxymethyl 1-isopropyl pyrazole, 4,5-diamino 3-methyl 1-isopropyl pyrazole, 4-amino 5- ( 2 ' -aminoethyl) amino 1,3-dimethyl pyrazole, 3 , 4 , 5-triamino pyrazole, 1-methyl 3 , 4 , 5-triamino pyrazole, 3, 5-diamino 1-methyl 4-methylamino pyrazole, 3, 5-diamino 4-( β-hydroxyethyl)amino-1-methyl pyrazole and their acid addition salts .

Among the pyrazolo pyrimidine derivatives , the following can in particular be mentioned: the pyrazolo- [ 1 , 5-a] -pyrimidines of the formula (4) shown below, their addition salts with an acid or base and their tautomeric forms when a tautomeric equilibrium exists:

in which

R¹⁵, R¹⁶, R¹⁷ and R¹⁸ , which are identical or differ, represent a hydrogen atom, C₁-C₄alkyl, aryl, C_x- C₄hydroxyalkyl , C₂-C₄polyhydroxyalkyl, (C_x- C₄) alkoxy(C^C,,) alkyl, C₁-C₄aminoalkyl (where the amine can be protected by an acetyl, ureido or sulfonyl group) , (Ci-C alkylamino ( C^C alkyl , di- [ (C^C,)alkyl] amino C₁-C₄alkyl (where the dialkyl groups can form a carbon ring or a heterocyclic ring with 5 or 6 members ) , hydroxy-C₁-C₄alkyl or di- [hydroxy(C^C alkyl] -amino

Ci-C.alkyl; the groups X, which are identical or differ, represent a hydrogen atom, C₁-C₄alkyl, aryl, C₁-C₄hydroxyalkyl,

C₂-C₄polyhydroxyalkyl, amino C₁-C₄alkyl, (C₁-

C₄ ) alkyl (C₁-C₄) aminoalkyl, di- [ (C₁-C₄) alkyl] aminoCi-

C₄alkyl (where the dialkyl groups can form a carbon ring or a heterocyclic ring with 5 or 6 members ) , hydroxy (C₁-C₄)alkyl or di- [hydroxy(C^C alkyl] amino -C_x-

C₄alkyl, amino, C₁-C₄alkyl or di- [ (C^C alkyl] -amino , a halogen atom, a earboxylic acid group or a sulfonic acid group; i is 0, 1, 2 or 3; - p is 0 or 1; q is 0 or 1, n is 0 or 1 with the proviso that the sum p + q differs from 0 ; - when p + qis 2, n has the value 0 , and the groups NR¹⁵R¹⁶ and NR¹⁷R¹⁸ occupy the positions (2,3); (5,6); (6,7);

(3,5) or (3,7); when p + q is 1 , n has the value 1 , and the group NR¹⁵R¹⁶ (or NR¹⁷R¹⁸) and the group OH occupy the positions (2,3) ; (5,6); (6,7); (3,5) or (3,7) . When the pyrazolo- [ 1 , 5-a] -pyrimidines of the above formula ( 4 ) are such which include a hydroxyl group in one of the positions 2, 5 or 7 in the α-position to a nitrogen atom, a tautomeric equilibrium exists which for instance can be indicated by the following reaction scheme.

Among the pyrazolo- [ 1 , 5-a] -pyrimidines of the above formula (4), the following can be mentioned in particular: - pyrazolo- [ 1 , 5-a] -pyrimidine-3 , 7-diamine;

2,5-dimethyl pyrazolo- [ 1 , 5-a] -pyrimidine-3 , 7- diamine ; pyrazolo- [ 1 , 5-a] -pyrimidine-3 , 5-diamine;

2 , 7-dimethyl pyrazolo- [ 1 , 5-a] -pyrimidine-3 , 5- diamine;

3-amino pyrazolo- [ 1 , 5-a] -pyrimidine-7-ol;

3-amino pyrazolo- [ 1 , 5-a] -pyrimidine-5-ol;

2- (3-amino pyrazolo- [ 1 , 5-a] -pyrimidine-7-ylamino) - ethanol ; - 2-(7-amino pyrazolo- [ 1 , 5-a] -pyrimidine-3-ylamino) - ethanol; 2- [ (3-amino-pyrazolo[ 1 , 5-a]pyrimidine- 7 -yl) - ( 2- hydroxy-ethyl) -amino] ethanol;

2- [ (7 -amino-pyrazolo [ 1 , 5-a]pyrimidine-3-yl) - ( 2- hydroxy-ethyl) -amino] ethanol; - 5,6-dimethyl pyrazolo- [ 1 , 5-a] -pyrimidine-3 , 7- diamine ;

2, 6-dimethyl pyrazolo- [ 1 , 5-a] -pyrimidine-3 , 7- diamine ;

2,5, N 7, N 7-tetramethyl pyrazolo- [ 1 , 5-a] - pyrimidine-3 , 7-diamine; and their addition salts and tautomeric forms, provided a tautomeric equilibrium exists.

The pyrazolo- [ 1 , 5-a] -pyrimidines of the above formula (4) can be prepared by way of cyclisation of an aminopyrazole according to the syntheses described in the following references :

EP 628559 BEIERSDORF-LILLY

R. Vishdu, H. Navedul , Indian J. Chem., 34b (6), 514,

1995. - N.S. Ibrahim, K.U. Sadek, F.A. Abdel-Al, Arch. Pharm. ,

320, 240, 1987.

R.H. Springer, M.B. Scholten, D.E. O'Brien, T. Novinson,

J.P. Miller, R.K. Robins, J. Med. Chem., 25, 235, 1982.

T. Novinson, R.K. Robins, T.R. Matthews, J. Med. Chem., 20, 296, 1977. US 3907799 ICN PHARMACEUTICAL

The pyrazolo- [ 1 , 5-a] -pyrimidines of the above formula ( 4 ) can f rthermore be produced by cyclisation from a hydrazine according to the syntheses described in the following references :

A. McKillop, R.J. Kobilecki, Heterocycles , 6(9), 1355,

1977.

E. Alcade, J. De Mendoza, J.M. Marcia-Marquina, C.

Almera, J. Elguero , J. Heterocyclic Chem. , 11(3), 423, 1974.

K. Saito, I. Hori, M. Higarashi, H. Midorikawa, Bull.

Chem. Soc. Japan, 47(2), 476, 1974.

The oxidation base or bases represent preferably between approximately 0.0005% and approximately 12% by weight of the total weight of the dye composition according to the invention, especially between approximately 0.005% and approximately 6% by weight.

The coupling agent or coupling agents suitable in the ready-to-use dye compositions according to the invention are such which are conventionally used in oxidation dye composition, viz. metaphenylene diamines , metaaminophenols , metadiphenols , heterocyclic coupling agents and their addition salts with an acid.

These coupling agents can especially be selected among 2-methyl- 5-amino-phenol, 5-N- (β-hydroxyethyl) -amino-2- methyl-phenol, 3-amino-phenol, 1 , 3-dihydroxybenzene , 1,3- dihydroxy-2-methyl-benzene , 4-chloro-l , 3-dihydroxy-benzene , 2 , 4-diamino-l- (β-hydroxyethyloxy) -benzene, 2-amino-4- (β- hydroxyethylamino ) -1-methoxy-benzene, 1 , 3-diamino-benzene, 1, 3-bis- (2,4-diaminophenoxy) -propane, sesamol, α-naphtol, 6-hydroxy-indole, 4-hydroxy-indole , 4-hydroxy-N-methyl- indole, 6-hydroxy-indolin, 2 , 6-dihydroxy-4-methyl-pyridine, 1-H-3-methyl-pyrazole-5-on , 1-phenyl-3-methyl-pyrazole-5- one, 2 , 6-dimethyl-pyrazolo- [ 1 , 5-b] -1 , 2 , 4-triazole, 2,6- dimethyl- [3 , 2-c] -1 , 2 , 4-triazole, 6-methyl-pyrazolo- [ 1 , 5- a] -benzimidazole and acid addition salts thereof.

The meta-aminophenol or meta-aminophenols applicable as coupling agents in the ready-to-use dye composition according to the invention is/are preferably selected from compounds of the following formula (5) and acid addition salts thereof :

in which

R¹⁹ represents a hydrogen atom, C₁-C₄-alkyl, C^ C₄monohydroxyalkyl or C₂-C₄polyhydroxyalkyl, R²⁰ represents a hydrogen atom, C₁-C₄alkyl, C₁-C₄alkoxy or a halogen atom selected from chlorine, bromine and fluorine, - R²¹ represents a hydrogen atom, C₁-C₄alkyl, C₁-C₄alkoxy, C^^mono-hydroxyalkyl, C₂-C₄polyhydroxyalkyl, C_λ- C₄monohydroxyalkoxy or C₂-C₄poly-hydroxyalkoxy. Among the meta-aminophenols of the above formula (5), the following can be mentioned in particular: meta- aminophenol, 5-amino-2-methoxy phenol, 5- amino-2-(β- hydroxyethyloxy) -phenol, 5-amino-2-methyl phenol, 5-N-(β- hydroxyethyl) amino-2-methyl phenol, 5-N-(β- hydroxyethyl) amino-4-methoxy-2-methyl phenol , 5-amino-4- methoxy-2-methyl phenol, 5-amino-4-chloro-2-methyl phenol, 5-amino-2 , 4-dimethoxy phenol, 5- (γ-hydroxypropylamino) -2- methyl phenol and acid addition salts thereof.

The meta-phenylenediamine or meta-phenylenediamines applicable as coupling agents in the ready-to-use dye composition according to the invention is/are preferably selected from compounds of the following formula (6) and acid addition salts thereof: in which

R²² represents a hydrogen atom, C₁-C₄alkyl, C_x- C₄monohydroxyalkyl or C₂-C₄polyhydroxyalkyl; - R²³ and R²⁴ , which are identical or differ, each represents a hydrogen atom, C₁-C₄alkyl, C_x- C₄monohydroxyalkoxy or C₂-C₄polyhydroxyalkoxy; R²⁵ represents a hydrogen atom, C₁-C₄alkoxy, C^ C₄aminoalkoxy, C^C^ono-hydroxyalkoxy, C₂- C₄polyhydroxyalkoxy or 2 , 4-diaminophenoxyalkoxy .

Among the meta-phenylenediamines of the above formula (6), the following can in particular be mentioned: 2,4- diamino- benzene, 3 , 5- diamino- 1- ethyl- 2 -methoxybenzene,

3, 5 -diamino -2 -me thoxy- 1-methyl benzene, 2 , 4-diamino-l- ethoxybenzene, 1 , 3-bis- (2 , 4-diaminophenoxy) propane, bis- (2, 4-diaminophenoxy) -methane, 1- (β-aminoethyloxy) -2,4- diamino- benzene, 2-amino-l- (β-hydroxy-ethyloxy) -4- methylamino -benzene, 2 , 4-diamino-l-ethoxy 5 -methyl-benzene,

2 , 4 -diamino- 5- (β-hydroxyethyloxy ) -1-methylbenzene, 2,4- diamino-1- (β,γ-dihydroxy-propyloxy) benzene, 2,4-diamino-

1- (β-hydroxyethyloxy) -benzene, 2-amino-4-N- (β- hydroxyethyl) -amino- 1-methoxy-benzene and acid addition salts thereof.

The meta-diphenol or meta-diphenols applicable as coupling agents in the ready-to-use dye composition according to the invention is/are preferably selected from the compounds of the following formula (7) and acid addition salts thereof:

in which - R²⁶ and R²⁷, which are identical or differ, each represents a hydrogen atom, C₁-C₄alkyl or a halogen atom selected from chlorine, bromine and fluorine. Among the meta-diphenols of the above formula (7), the following can in particular be mentioned: 1 , 3-dihydroxy- benzene, 2-methyl-l , 3-dihydroxy-benzene, 4-chloro-l , 3- dihydroxy-benzene , 2-chloro- 1 , 3-dihydroxybenzene, and acid addition salts thereof.

Among the heterocyclic coupling agents applicable in the ready-to-use dye composition according to the invention, derivatives of benzimidazole, derivatives of benzomorpholine, derivatives of sesamol, pyrazolo-azol derivatives. pyrrolo-azole derivatives, imidazolo-azole derivatives, pyrazolo-pyrimidine derivatives, derivatives of pyrazoline-3 , 5-diones , pyrrolo- [ 3 , 2-d]oxazole derivatives, pyrazolo- [ 3 , 4-d] -thiazole derivatives, thiazolo-azole S- oxide derivatives, thiazolo-azole S,S-dioxide derivatives and their addition salts with an acid can in particular be mentioned.

Among the benzimidazole derivatives applicable as heterocyclic coupling agents in the dye composition according to the invention, the compounds of the following formula (I) and their acid addition salts can in particular be mentioned:

in which:

R_x represents a hydrogen atom or C₁-C₄-alkyl, R₂ represents a hydrogen atom, C₁-C₄alkyl or phenyl, R₃ represents a hydroxyl, amino or methoxy group, R₄ represents a hydrogen atom, a hydroxyl group, a methoxy group or C₁-C₄alkyl group, with the proviso tha : when R₃ is an amino group, it is in position 4, when R₃ is in position 4, R₄ is in position 7, when R₃ is in position 5, R₄ is in position 6. Among the benzimidazole derivatives of the above formula (I), the following can in particular be mentioned: 4-hydroxy benzimidazole, 4-amino benzimidazole, 4-hydroxy- 7-methyl benzimidazole, 4-hydroxy-2-methyl benzimidazole, 1-butyl-4-hydroxy benzimidazole, 4-amino-2-methyl benzimidazole, 5 , 6-dihydroxy benzimidazole, 5-hydroxy-6- methoxy benzimidazole, 4 , 7-dihydroxy benzimidazole, 4,7- dihydroxy-1-methyl benzimidazole, 4 , 7-dimethoxy benzimidazole, 5 , 6-dihydroxy- 1-methyl benzimidazole, 5,6- dihydroxy-2-methyl benzimidazole, 5 , 6-dimethoxy benzimidazole and their addition salts with an acid.

Among the benzomorpholine derivatives applicable as heterocyclic coupling agents in the ready-to-use dye composition according to the invention, the compounds of the following formula (II) and their addition salts with an acid can in particular be mentioned:

in which

R₅ and R₆, which are identical or differ, each represents a hydrogen atom or C₁-C₄-alkyl, and Z represents a hydroxyl group or an amino group.

Among the benzomorpholine derivatives of the above formula (II) the following can in particular be mentioned:

6-hydroxy 1 , 4-benzomorpholine, N-methyl 6-hydroxy 1,4- benzomorpholine, 6-amino 1 , 4-benzomorpholine and their acid addition salts.

Among the derivatives of sesamol applicable as heterocyclic coupling agents in the ready-to-use dye composition according to the invention, the compounds of the following formula (III) and their addition salts with an acid can in particular be mentioned:

in which

R₇ represents a hydroxyl group, an amino group, a C₁-C₄-alkylamino group, a C^^monohydroxyalkylamino group or a C₂-C₄polyhydroxyalkylamino group, R₈ represents a hydrogen atom, a halogen atom or a C₁-₄alkoxy group.

Among the derivatives of sesamol of the above formula (III), the following can in particular be mentioned: 2-bromo 4 , 5-methylenedioxy phenol, 2-methoxy 4 , 5-methylenedioxy aniline, 2- (β-hydroxyethyl) amino 4 , 5-methylenedioxy benzene and their acid addition salts.

Among the pyrazolo-azole derivatives applicable as heterocyclic coupling agents in the ready-to-use dye composition according to the invention, the compounds can in particular be mentioned which are described in the following Patents and Patent Applications: FR 2 075 583, EP-A-119 860, EP-A-285 274, EP-A-244 160, EP-A-578 248, GB 1 458 377, US 3 277 554, US 3 419 391, US 3 061 432, US 4 500 630, US 3 725 067, US 3 926 631, US 5 457 210, JP 84/99437, JP 83/42045, JP 84/162548, JP 84/171956, JP 85/33552, JP 85/43659, JP 85/172982, JP 85/190779 as well in the following publications: Chem. Ber. 32, 797, (1899), Chem. Ber. 89, 2550, (1956), J. Chem. Soc. Perkin trans I, 2047, (1977), J. Prakt. Chem., 320, 533, (1978), the subject matter of which constitute an integrated part of the present application.

As the pyrazolo-azole derivatives, the following can in particular be mentioned:

- 2-methyl pyrazolo [ 1 , 5-b] -1 , 2 , 4-triazole, - 2-ethyl pyrazolo [ 1 , 5-b] -1 , 2 , 4-triazole,

- 2-isopropyl pyrazolo[ 1 , 5-b] -1 , 2 , 4-triazole,

- 2-phenyl pyrazolo[ 1 , 5-b] -1 , 2 , 4-triazole,

- 2,6-dimethyl pyrazolo[ 1 , 5-b] -1 , 2 , 4-triazole ,

- 7-chloro-2 , 6-dimethylpyrazolo[ 1 , 5-b] -1 , 2 , 4-triazole, - 3, 6-dimethyl-pyrazolo [ 3 , 2-c] -1, 2, 4-triazole, - 6-phenyl-3-methylthio- pyrazolo[ 3 , 2-c] -1 , 2 , 4-triazole ,

- 6-amino-pyrazolo[ 1 , 5-a]benzimidazole, and their addition salts with an acid.

Among the pyrrolo-azole derivatives applicable as heterocyclic coupling agents in the ready-to-use dye composition according to the invention, the compounds can in particular be mentioned which are described in the following Patents and Patent Applications: US 5 256 526, EP-A-557 851, EP-A-578 248, EP-A-518 238, EP-A-456 226, EP-A-488 909, EP-A-488 248 and in the following publications: D.R. Liljegren Ber. 1964, 3436; E.J. Browne, J.C.S., 1962, 5149; P. Magnus, J.A.C.S., 1990, 112, 2465; P. Magnus, J.A.C.S., 1987, 109, 2711; - Angew. Chem. 1960, 72, 956; andRec. Trav. Chim. 1961, 80, 1075, the subject matter of which constitute an integrated part of the present application.

5-cyano-4-ethoxycarbonyl-8-methyl pyrrolo [1,2-b]- 1,2, 4-triazole,

5-cyano-8-methyl- 4 -phenyl pyrrolo [l,2-b]-l,2,4- triazole, - 7-amido-6-ethoxycarbonyl pyrrolo [1,2-a]- benzimidazole , and their addition salts with an acid.

Among the imidazolo-azole derivatives applicable as heterocyclic coupling agents in the ready-to-use dye composition according to the invention, the compounds can in particular be mentioned which are described in the following Patents and Patent Applications: US 5441863, JP 62-279337, JP 06-236 Oil and JP 07-092 632, the subject matter of which constitute an integrated part of the present application. As the imidazolo-azole derivatives, the following can in particular be mentioned:

7 , 8-dicyano-imidazolo- [ 3 , 2-a] -imidazole, 7 , 8-dicyano-4-methyl-imidazolo- [3 , 2-a] -imidazole, and their addition salts with an acid. Among the pyrazolo-pyrimidine derivatives applicable as heterocyclic coupling agents in the ready-to-use dye composition according to the invention, the compounds can in particular be mentioned which are described in the following Patent Application: EP-A-304-001, the subject matter of which constitute an integrated part of the present application.

As the pyrazolo-pyrimidine derivatives, the following can in particular be mentioned: pyrazolo- [ 1 , 5-a] -pyrimidine-7-one , 2, 5-dimethyl pyrazolo [1,5-a] pyrimidine-7-one , - 2-methyl-6-ethoxycarbonyl pyrazolo [1,5-a] pyrimidine-7-one ,

2-methyl-5-methoxymethyl pyrazolo [1,5-a] pyrimidine-7-one ,

2-tert-butyl-5-trifluoromethyl pyrazolo [1,5-a] pyrimidine-7-one ,

2, 7-dimethyl pyrazolo [1,5-a] pyrimidine-5-one, and their addition salts with an acid.

Among the pyrazoline-3 , 5-diones derivatives applicable as heterocyclic coupling agents in the ready- to-use dye composition according to the invention, the compounds can in particular be mentioned which are described in the following Patents and Patent Applications : JP 07-036159 , JP 07-084348 and US 4 128 425, and in the following publications : - L. WYZGOWSKA, Acta. Pol. Pharm. 1982, 39 (1-3), 83. E. HANNIG, Pharmazie, 1980, 35 (4), 231 M.H. ELNAGDI, Bull. Chem. Soc . Jap., 46(6), 1830, 1973 G. CARDILLO, Gazz. Chim. Ital. 1966, 96, (8-9), 973, the subject matter of which constitute an integrated part of the present application.

As the derivatives of pyrazolin-3 , 5-diones , the following can in particular be mentioned: 1,2-diphenyl pyrazoline-3 , 5-dione, 1,2-diethyl pyrazoline-3 , 5-dione, and their addition salts with an acid. Among the pyrrolo- [ 3 , 2-d] -oxazole derivatives applicable as heterocyclic coupling agents in the ready- to-use dye composition according to the invention, the compounds can in particular be mentioned which are described in the Patent Application JP 07-325 375, the subject matter of which constitute an integrated part of the present application.

Among the pyrazolo- [ 3 , 4-d] -thiazole derivatives applicable as heterocyclic coupling agents in the ready- to-use dye composition according to the invention, the compounds can in particular be mentioned which are described in the Patent Application JP 07-244361 and in J. Heterocycl. Chem. 16, 13, (1979).

Among the thiazolo-azole S-oxide derivatives and thiazolo-azole S,S-dioxide derivatives applicable as heterocyclic coupling agents in the ready-to-use dye composition according to the invention, the compounds can in particular be mentioned which are described in the following documents : - JP 07-098 489;

Khim. Geterotsilk. Soedin, 1967, p. 93; J. Prakt. Chem., 318, 1976, p. 12; Indian J. Heterocycl. Chem. 1995, 5(2), p. 135; Acta. Pol. Pharm. 1995, 52(5), 415; - Heterocycl. Commun. 1995, 1(4), 297; Arch. Pharm. (Weinheim, Ger.), 1994, 327(12), 825. These coupling agents constitute preferably between approximately 0.0001% and approximately 10% by weight of the ready-to-use dye composition, especially between approximately 0.005% and approximately 5% by weight.

The cationic direct dye(s) applicable in the ready- to-use dye composition according to the invention is/are preferably selected among cationic amino-anthraquinone dyes, cationic mono or di-azo dyes and cationic naphtoquinone dyes. Examples of the above are especially [8-[(p- aminophenyl) azo ] -7-hydroxy-2-naphtyl ] trimethylammonium chloride (also called Basic Brown 16 or Arianor Mahogany 306002 in Color Index), 3- [ ( 4-amino-6-bromo-5 , 8-dihydro-l- hydroxy-8-imino- 5-oxo-2-naphtalenyl )amino ] -N, ,N- trimethyl-benzeneaminium chloride (also called Basic Blue 99 or Arianor Steel Blue 306004 in Color Index), 7-hydroxy-8- [ ( 2-methoxyphenyl ) azo] -N , N , N-trimethyl-2-naphtaleneaminium chloride (also called Basic Red 76 or Arianor Madder Red in Color Index), [ 8- [ ( 4-amino-2-nitrophenyl)azo] -7-hydroxy-2- naphtyl] trimethylammonium chloride (also called Basic Brown 17 or Arianor Sienna Brown 306001 in Color Index) and 3- [ ( 4 , 5-dihydro-3-methyl-5-oxo-l-phenyl-lH-pyrazol-4- yl)azo] -N,N,N-trimethyl-benzenaminium chloride (also called Basic Yellow 57 or Arianor Straw Yellow 306005 in Color Index) . The cationic direct dye(s) can furthermore be selected among : a ) Compounds of the formula (V) :

in which

D represents a nitrogen atom or a group -CH,

R₁₉ and R₂₀, which are identical or differ, each represents a hydrogen atom, a C₁-C₄alkyl group, which can be substituted with one of the groups -CN, -OH or -NH₂ or together with a carbon atom in the benzene ring form an optionally oxygen-containing or nitrogen-containing heterocyclic group, which can be substituted with one or more C₁-C₄alkyl groups; or a 4'- aminophenyl group , R₂₁ and R'₂₁, which are identical or differ, each represents a hydrogen atom or a halogen atom selected from chlorine, bromine, iodine and fluorine, cyano, C^C,,-alkoxy or acetyloxy, X^" represents an anion, preferably selected from chloride, methylsulphate and acetate,

A represents a group selected from the following structures A1-A19:

A, A,

10 A„ *«

13 4 *1S

16 *17 A_1β and

wherein R₂₂ represents a C₁-C₄alkyl group, which can be substituted with a hydroxyl group, and R₂₃ represents a C_x- C₄alkoxy group; b) compositions of the formula (VI):

in which

R₂₄ represents a hydrogen atom or a C₁-C₄alkyl group,

R₂₅ represents a hydrogen atom, an alkyl group, which can be substituted with a group -CN or with an amino group, or

4 '-aminophenyl , or R₂₅ represents together with R₂ an optionally oxygen and/or nitrogen-containing heterocyclic group, which can be substituted with a C₁-C₄alkyl group,

R₂₆ and R₂₇, which are identical or differ, represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine or fluorine, C₁-C₄alkyl, C₁-C₄alkoxy or the group -CN,

X^" represents an anion, preferably selected from chloride, methylsulphate and acetate,

B represents a group selected from the following structures

B1-B6:

B4 B5 Bβ

in which R₂₈ represents a C₁-C₄alkyl group, and R₂₉ and R₃₀, which are identical or differ, each represents a hydrogen atom or a C₁-C₄alkyl group; c) compounds of the following formulae (VII) and (VII'):

in which

R₃₁ represents a hydrogen atom, a C₁-C₄alkoxy group, a halogen atom such as bromine, chlorine, iodine or fluorine, or an amino group ,

R₃₂ represents a hydrogen atom or a C₁-C₄alkyl group, or R₃₂ together with a carbon atom in the benzene ring forms a heterocyclic group, which optionally includes an oxygen atom and/or is substituted with one or more C₁-C₄alkyl groups,

R₃₃ represents a hydrogen atom or a halogen atom such as bromine, chlorine, iodine or fluorine,

R₃₄ and R₃₅, which are identical or differ, each represents a hydrogen atom or a C₁-C₄alkyl group, O_x and D₂, which are identical or differ, represent a nitrogen atom or a group -CH, m = 0 or 1 , whereby it should be understood that when R₃₁ represents a non-substituted amino group, Ω_x and D₂ represent simultaneously a group -CH, and m = 0, X^" represents an anion, preferably selected from chloride, methylsulphate and acetate,

E represents a group selected from the following structures

E1 -E8 :

in which R₃₆ represents a C₁-C₄alkyl group; when m = 0 and O_x represents a nitrogen atom, E can also represent a group with the following structure E9 :

in which R₃₆ represents a C₁-C₄alkyl group.

The cationic direct dyes of the formulae (V), (VI), (VII) and (VII¹ ) , which are applicable in the ready-to-use dye compositions according to the invention, are compositions known per se, which are described for instance in the Patent

Applications WO 95/01772, WO 95/15144 and EP-A-0 714 954.

Among the cationic direct dyes of the formula (V) , which are applicable in the ready-to-use dye compositions according to the invention, the compounds of the following structures (VI) to (V52) can in particular be mentioned:

and

Among the above compounds with the structures (VI) to (V52), the compounds with the structures (VI), (V2), (V4), (VI4) and (V31) are particularly preferred.

Among the cationic direct dyes of the formula (VI), which are applicable in the ready-to-use dye compositions according to the invention, the compounds with the following structures (VII) to (VI12) can in particular be mentioned:

CH_jSO,^' (VI11) and

Among the cationic direct dyes of the formula (VII), which are applicable in the ready-to-use dye compositions according to the invention, the compounds with the following structures (VIII) to (VI18) can in particular be mentioned:

H₃C— N r+ — CH=N- CH₃S0₄ ^' (VII6)

CH₃SO₄ ^" (VII10)

\ CH,

CH_j

CH₃COO^" (VIM6)

Among the above particular compositions with the structures (VIII) to (VII18), the compounds with the structures (VII4), (VII5) and (VII13) are particularly preferred.

Among the cationic direct dyes of the formula (VII¹), which are applicable in the ready-to-use dye compositions according to the invention, the compounds with the following structures (VII'l) to (VII '3) can in particular be mentioned:

The cationic direct dye or dyes used according to the invention represent preferably between approximately 0.001% and approximately 10% by weight of the total weight of the ready-to-use dye composition, especially between approximately 0.05% and approximately 5% by weight.

In general, the acid addition salts suitable within the scope of the dye compositions according to the invention (oxidation bases and coupling agents) are especially selected from hydrochlorides , hydrobromides , sulphates , tartrates , lactates and acetates .

Further, in addition to the above-mentioned components, it is also possible, if necessary, to add pH buffers, surface-active agents, thickeners such as hydroxyethyl cellulose and xanthan gum, perfumes, antiseptics, ultraviolet ray absorbers, antioxidants, bactericides , pearling agent, etc. With regard to the surface-active agents among the above, any of anionic ones such as α-olefinsulfonates , alkanesulfonates , fatty acid alkyl ether carboxylates , N- acylamino acids and C₁₂.₁₈ saturated and unsaturated fatty acid acylglutamates ; amphoteric ones such as alkylbetaines , alkylamidobetaines and hydroxysulfobetaines ; cationic ones such as mono- or di-alkyl quaternary ammonium salts; and nonionic ones such as polyoxyethylene alkyl ethers and fatty acid alkylolamides may be used.

In order to improve the feel or touch of the hair, it is also possible to compound silicone derivatives such as dimethylpolysiloxane , amino-modified silicone and polyether-modified silicone.

The pH of the hairdye of the present invention is preferably 5.0-9.0 or, more preferably, 6.0-8.0. When the pH is too high, skin irritation causes a problem and that is not preferred. In a hairdye composition which is the first feature of the present invention, the above-mentioned components are mixed to give a single preparation type product wherein the oxidative hairdye composition of a single preparation type containing oxidase is filled in a container in such a state that oxygen concentration in the headspace is made 1% or less.

When the oxygen concentration in the headspace area of the container is reduced as such, it is now possible to give an oxidative hairdye of a single preparation type compounded with an oxidase and to give an oxidative hairdye composition of a single preparation type in which stability of the oxidase per se and the product with the lapse of time is good and also the hair-dyeing effect is excellent.

The oxygen concentration in the headspace area is 1% or less and, more preferably, 0.5% or less or, particularly preferably, 0.1% or less.

There is no particular limitation for the container in which the composition is filled but the container may be appropriately selected depending upon the form of the product . In the case of an aerosol form, it is preferably filled in an aerosol container made of metal while, in the case of a cream or gel form, it is preferably filled in a container, particularly a tube, having a high oxygen-barrier property.

There is no particular limitation for a method for making the oxygen concentration in the headspace 1% or less and a method of filling the composition in a container in the absence of oxygen as in the case of the second feature of the present invention which will be mentioned later may be effectively adopted. It is preferred that the composition filled in a container is mixed in the absence of oxygen and that the oxygen concentration in the composition is 0.00015% or less.

In the second feature of the present invention where the hairdye composition of the above-mentioned first feature is produced, a mixing operation of the components including oxidase is carried out in the absence of oxygen and a filling operation of the resulting composition in a container is carried out in the absence of oxygen.

With regard to the state of absence of oxygen, an atmosphere containing substantially no oxygen or, to be more specific , vacuum or an inert gas atmosphere such as nitrogen gas , carbon dioxide gas or rare gas may be adopted and the above-mentioned components may be mixed and filled in a container under such an atmosphere . Any method may be used for attaining the above-mentioned atmosphere and there is no particular limitation therefor. For example, a vacuating method, a method of substituting with nitrogen and a method where vacuation is conducted and then substitution with inert gas is done may be used. When the product is produced by such a method, it is now possible to suppress the catalytic reaction (i.e. , aggregation of the oxidation dye) of the enzyme with the oxidation dye by the oxygen dissolved in the composition or by oxygen in the headspace of the container.

Incidentally, it is preferred that mixing of the composition filled in the container is carried out in such a manner that the oxygen concentration therein is made 0.00015% or less.

In accordance with the present invention as mentioned hereinabove, it is now possible, instead of the conventional permanent hairdyes of a mixed type where the first and the second preparations are mixed, to offer a form of a single preparation type where such a mixing operation is not necessary and the usability for consumers is very high. In any of the forms such as aerosol, cream, gel, liquid, etc., stability of the product is now very good such as that aggregation of the oxidation dye in the product can be prevented.

The present invention will now be more specifically illustrated by way of the following Examples and Comparative Examples although the present invention is not limited thereto. Incidentally, % in the following examples is that by weight. Methods for the evaluation of the properties in the following examples are as follows . Production of aggregates :

Production of the aggregates in the composition was checked by naked eye immediately after the compounding and also after allowing to stand for one month at 25°C and at 45°C. OO: no aggregate was noted at all O: aggregates were noted a little Δ: some aggregates were noted x: considerable aggregates were noted Hair-dying property (ΔE):

About 10 g of a dried tuft of white hair of goat were shampooed, water was removed therefrom (weight of the tuft after removing the water was 17 g) and each 3 g of the compositions to be evaluated (the products immediately after the compounding) were applied thereto quickly and uniformly. This was allowed to stand at 30°C for a predetermined period, rinsed, dried, shampooed and air-dried and a hair-dyeing property to the hair of goat was evaluated. With regard to the hair-dyeing property (ΔE), the L, a and b values of the dyed tuft were measured by a color difference meter (SE2000 manufactured by Nippon Denshoku) and the color difference (ΔE) from the hair which was not dyed was calculated whereby the hair-dyeing property was evaluated. Incidentally, the more the ΔE , the better the hair dyeing property.

Color staining:

A tuft (about 10 g) of human black hair was dyed by a predetermined method using each of the compositions to be evaluated (the products of immediately after the compounding) , shampooed and dried using a dried white towel and the color stained onto the towel was judged by visual observation.

OO: no staining at all

O: staining noted if carefully observed Δ: staining was well noted x: staining was so much that the towel was unable to be used

Examples 1-8 and Comparative Examples 1-8. The components as shown in Tables 1 and 2 were prepared into an aerosol form and filled in an aerosol container. Vacuation was carried out so that the oxygen concentration in the headspace was adjusted to an extent as shown in Tables 1 and 2. Results of the evaluations are shown in Tables 1 and

Table 1 Examples Comparative Examples

Components (%) 1 2 3 1 2 3 4

p-Phenylenediamine 1.5 1.5 - 1 1.5 1.5 - 1 p-Aminophenol 0.1 0.1 0. 0.1 0.1 0.1 0.1 0.1 m-Aminophenol 0.08 0.08 - - 0.08 0.08

Toluene-2,5-diamine sulfate 2 2 - - 2 2 m-Phenylenediamine 0.15 0.15 - - 0.15 0.15 -

Resorcinol 0.1 - - 0.1 Laccase 3 0.1 1 5 3 0.1 1 5

Sodium hydroxide q.s. q.s. q.s q.s. q.s q.s. q.s q.s.

Pure water b b b b b b b b

LPG (4.0kg/cm²) 4 4 4 4 4 4 4 4

Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 pH 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0

Oxygen concn in headspace(%) 0.5 0.01 0.1 0.01 21 10

Aggregates Immediately after compounding OO OO OO OO Δ Δ Δ

After kept at 25°C for 1 month OO OO OO OO Δ~x x Δ~χ After kept at 45°c for 1 month OO OO OO OO Hair-dyeing property(ΔE)^* 29 32 30 34 24 27 25 28 Color staining^* OO OO OO OO O O

^*: for a product immediately after compounding; b: balance Table

Exampl ιes Comparative Examples

Components (%) 5 6 7 8 5 6 7 8

p-Phenylenediamine 15 15 - 1 15 15 1 p-Aminophenol 01 01 01 01 01 01 01 01 m-Aminophenol - - 008 008 - - 008 008

Toluene-2,5-dιamιne sulfate - - 2 2 - - 2 2 m-Phenylenediamine 015 015 - - 015 015 -

Resorcinol - - - 01 - - - 01

Oxidase uri per cat tyr uri per ca tyr

1 01 05 1 1 01 05 1

Sodium hydroxide qs qs qs qs qs qs qs qs

Pure water b b b b b b b b

LPG (4 Okg/cm²) 4 4 4 4 4 4 4 4

Total 1000 1000 1000 1000 1000 1000 1000 1000

PH 70 70 70 70 70 70 70 70

Oxygen concn in headspace(%) 05 001 01 001 21 5 10

Aggregates

Immediately after compounding OO OO OO OO X Δ Δ Δ

After kept at 25°c for 1 month OO OO OO OO X Δ~x X Δ~x

After kept at 45°c for 1 month OO OO OO OO X X X x

Hair-dyeing property(ΔE)^* 28 30 29 30 22 25 23 26

Color staining^* OO OO OO OO O O Δ Δ *: for a product immediately after compounding b: balance uri: uricase per: peroxidase cat: catalase tyr: tyrosinase

Examples 9-13 and Comparative Example 9.

A hairdye composition of the following formulation was compounded under an atmosphere as shown in Table 3 and filled in a glass bottle as a container under an atmosphere as shown in Table 3. Concentration of oxygen dissolved in the composition and that at the headspace at that time are shown in Table 3. Results of evaluations of each of the compositions are shown in Table 3 as well. -Phenylenediamine 1. ,5% p-Aminophenol 0. .1 m-Phenylenediamine 0. .15

Laccase 0. .01 Sodium hydroxide q. ,S.

Pure water balance

Total 100.0% pH 7. .0 Table 3

Comp.Ex. Examples

9 9 10 11 12 13

[Atmosphere at the Stage of Compounding] Air O

Vacuum O O O

Nitrogen gas O

Argon gas O

[Atmosphere at the Stage of Filling] Air O

Vacuum O

Nitrogen gas O

Argon gas O

Carbon dioxide gas O Nitrogen gas after Vacuation O

Oxygen Concn (%) Dissolved in Compn 0.008 0.00005 0.0001 0.00003 o.oooos o.oooos Oxygen Concn (%) in Headspace 3 0.07 0.1 0.01 0.5 0.01

Aggregates

Immediately after compounding Δ OO OO OO OO OO

After kept at 25°c for 1 month Δ~^χ OO OO OO OO OO

After kept at 45°c for 1 month X OO OO OO OO OO

Hair-dyeing property(ΔE)^* 28 32 30 33 29 32

Color staining^* Δ OO OO OO OO OO *: for a product immediately after compounding

Examples 14-18 and Comparative Example 10.

A hairdye composition of the following formulation was compounded under an atmosphere as shown in Table 4 and filled in a glass bottle as a container under an atmosphere as shown in Table 4. Concentration of oxygen dissolved in the composition and that at the headspace at that time are shown in Table 4. Results of evaluations of each of the compositions are shown in Table 4 as well. p-Phenylenediamine 1.5% p-Aminophenol 0.1 m-Phenylenediamine 0.15

Uricase or Peroxidase 0.1 Sodium hydroxide q.s.

Pure water balance

Total 100.0% pH 7.0

Table 4

Comp.Ex. Examples

10 14 15 16 17 18

Oxidase uricase uricase ^■ -peroxidase- -

[Atmosphere at the Stage of Compounding]

Air O

Vacuum O O O

Nitrogen gas O

Argon gas O [Atmosphere at the Stage of Filling]

Air O

Vacuum O

Nitrogen gas O

Argon gas O Carbon dioxide gas O

Nitrogen gas after Vacuation O

Oxygen Concn (%) Dissolved in Compn 0.008 0.00005 0.0001 0.00001 0.00008 0.00008 Oxygen Concn (%) in Headspace 3 0.07 0.1 0.01 0.5 0.01

Aggregates

Immediately after compounding Δ OO OO OO OO OO

After kept at 25°c for 1 month Δ~χ OO OO OO OO OO

After kept at 45°c for 1 month X OO OO OO OO OO Hair-dyeing property(ΔE)* 28 30 33 30 31 29 Color staining^* Δ OO OO OO OO OO

^*: for a product immediately after compounding

Examples 19-23 and Comparative Example 11. A hairdye composition of the following formulation was compounded under an atmosphere as shown in Table 5 and filled in a glass bottle as a container under an atmosphere as shown in Table 5. Concentration of oxygen dissolved in the composition and that at the headspace at that time are shown in Table 5. Results of evaluations of each of the compositions are shown in Table 5 as well . p-Aminophenol 0.1% m-Aminophenol 0.08

Toluene-2, 5-diamine sulfate 2 Catalase or Tyrosinase 0.03

Sodium hydroxide q.s.

Pure water balance

Total 100.0% pH 7.0

Table 5 Comp.Ex. Examples 11 19 20 21 22 23

Oxidase catalase - catalase - - - - -tyrosinase- -

[Atmosphere at the Stage of Compounding]

Air O

Vacuum O O O

Nitrogen gas O

Argon gas O [Atmosphere at the Stage of Filling]

Air O

Vacuum O

Nitrogen gas O

Argon gas O Carbon dioxide gas O

Nitrogen gas after Vacuation O

Aggregates

Immediately after compounding Δ OO OO OO OO OO

After kept at 25°c for 1 month Δ~χ OO OO OO OO OO

After kept at 45°c for 1 month X OO OO OO OO OO

Hair-dyeing property(ΔE)* 28 30 33 30 31 29 Color staining^* Δ OO OO OO OO OO

^*: for a product immediately after compounding

Examples 24-26 and Comparative Example 12. A hairdye composition of the following formulation was compounded under an atmosphere as shown in Table 6 and filled in a glass bottle as a container under an atmosphere as shown in Table 6. Concentration of oxygen dissolved in the composition and that at the headspace at that time are shown in Table 6. Results of evaluations of each of the compositions are shown in Table 6 as well. p-Phenylenediamine 1% p-Aminophenol 0.1 m-Aminophenol 0.08 Toluene-2 , 5-diamine sulfate 2

Resorcinol 0.1

Laccase 0.05

Sodium hydroxide q.s.

Pure water balance Total 100.0% pH 7.0 Table

Comp.Ex. Examples

12 24 25 26

[Atmosphere at the Stage of Compounding]

Air O

Vacuum O

Nitrogen gas O

Argon gas O

[Atmosphere at the Stage of Filling]

Air O

Vacuum Nitrogen gas Argon gas O Carbon dioxide gas O

Nitrogen gas after Vacuation O

Oxygen Concn (%) Dissolved in Compn 0.008 0.00005 0.0001 0.00008 Oxygen Concn (%) in Headspace 3 0.07 0.04 0.01

Aggregates

Immediately after compounding Δ OO OO OO

After kept at 25°c for 1 month Δ~χ OO OO OO

After kept at 45°c for 1 month X OO OO OO

Hair-dyeing property(ΔE)* 28 33 31 33

Color staining* Δ OO OO OO *: for a product immediately after compounding

According to the present invention, it is now possible to give a hairdye composition of a single preparation type wherein an aggregating reaction of oxidase with oxidation dye is greatly suppressed so that stability with a lapse of time is improved and, in addition, a high hair-dyeing effect is achieved.

Claims

1. A hairdye composition, characterized in that, it is an oxidative hairdye composition of a single preparation type containing an oxidase and is filled in a container in such a state that the oxygen concentration at the headspace is made

1% by weight or less.

2. A process for the production of a hairdye composition which is characterized in that, in the production of the hairdye composition mentioned in claim 1, a mixing operation of the components containing the oxidase is carried out in the absence of oxygen and a filling operation of the resulting composition into the container is carried out in the absence of oxygen .