EP1227785A2

EP1227785A2 - Process for producing a hairdye composition

Info

Publication number: EP1227785A2
Application number: EP00940800A
Authority: EP
Inventors: Takeshi Onuki; Mutsumi Noguchi; Joji Mitamura
Original assignee: Lion Corp
Current assignee: Lion Corp
Priority date: 1999-06-22
Filing date: 2000-06-22
Publication date: 2002-08-07
Also published as: AU5567500A; WO2000078273A2; WO2000078273A3

Abstract

In producing an oxidative hairdye composition of a single aerosol preparation type by dissolving an oxidation dye and an oxidase in water, charging the resulting solution in an aerosol container and charging a propellant in this aerosol container, a process for the production of a hairdye composition which is characterized in that whole of the said aerosol container is shaken during or immediately after the said propellant is charged into the said aerosol container.

Description

DESCRIPTION PROCESS FOR PRODUCING A HAIRDYE COMPOSITION

Technical Field of the Invention

The present invention relates to a process for producing an oxidative hairdye composition of a single aerosol preparation type wherein an oxidase such as laccase is compounded. More particularly, it relates to a process for producing an oxidative hairdye composition of a single aerosol preparation type wherein the stability with a lapse of time is good and an excellent hair-dyeing effect is available even after preserved for a long period.

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 its liquid property 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 ) .

However, when a hairdye composition of a single preparation type, particularly that of a single aerosol preparation type, is produced by mixing with oxidase, the oxidase reacts with the oxidation dye in the composition during preservation due to unstable property of the oxidase whereby insoluble aggregates are formed. Formation of such insoluble aggregates in the product is a big problem as a hairdye which is a kind of quasi-drugs . Thus, there is a big problem that, unless such insoluble matters are suppressed, it is not possible to put it into a market especially as an aerosol product.

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 a process for producing an oxidation hairdye composition of a single aerosol preparation type where stability of the oxidase is good and an excellent hair-dyeing action is achieved even after preservation for a long period.

The present inventors have conducted an intensive study for achieving the above-mentioned object and have found that, in producing an oxidative hairdye composition of a single aerosol preparation type by dissolving an oxidation dye and an oxidase in water, charging the resulting solution in an aerosol container and charging a propellant in this aerosol container, formation of insoluble matters in the above solution can be suppressed, stability of the composition with a lapse of time is improved, formation of the insoluble matters even after preserved for a long period is not substantially noted and the hair-dyeing effect by the above components can be effectively achieved provided that the whole aerosol container is shaken during or immediately after charging the propellant into the aerosol container.

It has been found that stability during preservation is further improved in that case when dissolving of the oxidation dye and the oxidase into water and charging of the resulting solution and the propellant into the aerosol container are carried out in vacuo or in an atmosphere of inert gas .

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 oxidase as an oxidizing agent. Examples of the oxidase used in the present invention are laccase, peroxidase, uricase and tyrosinase. 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 Myceliophthora sp. , e. g. M. thermophila , a strain of Rhizoctonia sp. , in particular a strain of Rh. praticola or Rh. solani , a strain of Pyricularia sp, in particular P. oryzae , or a strain of Scytalidium, such as S. thermophilium . The laccase may also be from a plant such as Rhus sp . , e.g. Rhus vernicifera ,

In specific embodiments of the invention the oxidoreductase is a laccase such as a Polyporus sp. laccase, especially the Polyporus pinisi tus laccase (also called Trametes villosa laccase) described in WO 96/00290 (from Novo Nordisk Biotec Inc. ) or a Myceliophthora sp. laccase, especially the Myceliophthora thermophila laccase described in WO 95/33836 (from Novo Nordisk Biotech Inc. ) .

Further, the laccase may be a Scytalidium sp. laccase such as the S. thermophilium 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 Coprinus sp. laccase, such as a C. cinereus laccase , especially a C. cinereus IFO 30116 laccase, or a Rhizoctonia 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 Collybia , Fomes , Lentinus , Pleurotus, Aspergillus, Neurospora , Podospora , Phlebia , e . g. P. radiata (WO 92/01046), Coriolus sp., e. g. C. hirsi tus ( JP 2-238885), or Botrytis.

Bilirubin oxidase may preferably be derived from a strain of Myrothecium sp., such as M. verrucaria .

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 Trichoderma sp. such as Trichoderma harzianu , such as the L-amino acid oxidase described in WO 94/25574 (from Novo Nordisk

A/S) , or Trichoderma viride.

A suitable glucose oxidase may originate from Aspergillus sp. , such as a strain of Aspergillus niger , or from a strain of

Cladosporium sp . in particular Cladosporium oxysporum. Hexose oxidases from the red sea-weed Chondrus crispus

(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 composition 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 preferred to use not less than 0.0005% (% by weight; hereinafter, used in the same sense) or, particularly, not less than 0.005%. When the amount is too small, a sufficient effect is not resulted. Although there is no particular limitation for the upper limit, no increase in the effect proportional to an increase in the compounding amount is available even if compounded too much and, in view of the above, it is recommended to use not more than 10%, preferably not more than 5%, more preferably not more than 1% and further preferably not more than

0.5%.

In the hairdye composition of the present invention, an oxidation dye is used as a component which takes place a color 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-l , 4- quinonediimine, o-aminophenol sulfate, 2 , 4-diaminophenyl 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 , 1 -amino-4-methylaminoanthraquinone , nitro-p-phenylenediamine hydrochloride, 1,4- diaminoanthraquinone , nitro-p-phenylenediamine, picramic acid, sodium picramate, 2-amino-5-nitrophenol sulfate, 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:

NH₂ in which

R¹ represents a hydrogen atom, C₁-C₄-alkyl, C₁-C₄- monohydroxyalkyl , C₂-C₄-polyhydroxyalkyl, (C_x-

C₄)alkoxy(C₁-C₄)alkyl, C_j-C^alkyl substituted with a nitrogen-containing group, phenyl or 4 ' -aminophenyl; R² represents a hydrogen atom, C₁-C₄-alkyl, C^ C₄monohydroxyalkyl , C₂-C₄polyhydroxyalkyl, (C^ C₄)alkoxy(C₁-C₄)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, C- C₄monohydroxyalkyl , C₁-C₄hydroxyalkoxy, C_λ- C₄acetylaminoalkoxy, C^^mesylaminoalkoxy or C_:- C₄carbamoylaminoalkoxy , R⁴ represents a hydrogen atom, a halogen atom or C₁-C₄- alkyl .

Among the nitrogen-containing groups in the above formula (1), amino, mono(C₁-C₄ )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-hydroxyethyl) 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 C^C^alkoxy groups; R⁵ and R⁶ represents a hydrogen or halogen atom, C₁-C₄alkyl, C₄aminoalkyl or a bridging group Y;

R⁷, R⁸, R⁹, R¹ 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, tri(C₁- C₄)alkylamino, monohydroxy( C^C, )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) tetramethylenediamine, 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 , C^C. nonohydroxyalkyl , ( C₁-C₄ ) alkoxy ( C₁-C₄ ) alkyl , C-^- C₄aminoalkyl or ( C₁-C₄ ) hydroxyalkyl ( C₁-C₄ ) aminoalkyl . R¹⁴ represents a hydrogen or halogen atom, C₁-C₄alkyl, C₁-C₄monohydroxyalkyl, C₂-C₄polyhydroxyalkyl, C_λ- C₄aminoalkyl, C₁-C₄cyanoalkyl or (C₁-C₄)alkoxy( C₁-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 1 026 978 and GB-PS 1 153 196 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 4 133 957 and in the Patent Applications WO 94/08969, WO 94/08970, FR-A-2733 749 and DE 19543988 can in particular be mentioned: 4 , 5-diamino 1-methyl pyrazole, 3,4-diamino pyrazole, 4,5-diamino l-(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 , R¹ R¹⁷ and R¹⁸, which are identical or differ. represent a hydrogen atom, C₁-C₄alkyl, aryl, C_λ- C₄hydroxyalkyl , C₂-C₄polyhydroxyalkyl, (C₁-C₄)alkoxy(C₁- C₄) alkyl, C₁-C₄aminoalkyl (where the amine can be protected by an acetyl, ureido or sulfonyl group) , (C₁-C₄)alkylamino (C_j-C alkyl, di- [ (C₁-C₄) alkyl] amino C_α-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_λ-C₄ ) alkyl ] -amino C_λ-C₄alky1 ; - the groups X, which are identical or differ, represent a hydrogen atom, C₁-C₄alkyl, aryl , C₁-C₄hydroxyalkyl, C₂-C₄polyhydroxyalkyl, amino C₁-C₄alkyl, (C^ C₄) alkyl (C₁-C₄)aminoalkyl, di- [ (C^C,,) alkyl] aminoCi- C₄alkyl (where the dialkyl groups can form a carbon ring or a heterocyclic ring with 5 or 6 members), hydroxy C_j^-C_t) alkyl or di- [ hydroxy( -C₄ ) alkyl ] amino-C_x-C₄alkyl , amino, C₁-C₄alkyl or di- [ (C_j-C,,) alkyl ] -amino, a halogen atom, a carboxylic 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 + q is 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 furthermore 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. DeMendoza, 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, l-H-3- methyl-pyrazole-5-on, l-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^ 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, or C₂-C₄polyhydroxyalkoxy;

R²⁵ represents a hydrogen atom, C₁-C₄alkoxy, C_:- C₄aminoalkoxy, C₁-C₄mono-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-l-ethyl-2-methoxybenzene, 3,5-diamino- 2-methoxy- 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-1- ( β-hydroxy-ethyloxy) -4-methylamino-benzene,

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

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-1 , 3-dihydroxy-benzene , 4-chloro-l , 3-dihydroxybenzene, 2-chloro-l , 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_λ 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 that : 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:

R₇ represents a hydroxyl group, an amino group, a C_x-

C₄-alkylamino group, a C^^monohydroxyalkylamino group or a C₂-C₄polyhydroxyalkylamino group,

R₈ represents a hydrogen atom, a halogen atom or a C_λ-

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 2075583, EP-A-119860, EP-A-285274, 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 pyrazolof 1 , 5-b] -1 , 2 , 4-triazole,

- 2-isopropyl pyrazolof 1 , 5-b] -1 , 2 , 4-triazole,

- 2-phenyl pyrazolof 1 , 5-b] -1 , 2 , 4-triazole ,

- 2,6-dimethyl pyrazolof 1 , 5-b] -1 , 2 , 4-triazole, - 7-chloro-2 , 6-dimethylpyrazolo[ 1 , 5-b] -1 , 2 , 4-triazole,

- 3 , 6 -dimethyl-pyrazolof 3 , 2-c] -1 , 2 , 4-triazole,

- 6-phenyl-3-methylthio- pyrazolof 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 5256526, EP-A-557851, EP-A-578248, EP-A-518 238. EP-A-456226, EP-A-488909, EP-A-488248 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; and Rec. Trav. Chim. 1961, 80, 1075, 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:

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-ethoxycarbony1 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 5 441 863, JP 62-279 337, JP 06-236 Oil and JP 07-092632, 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 07-244 361 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 , -1rimethy1- benzeneaminium chloride (also called Basic Blue 99 or Arianor Steel Blue 306004 in Color Index), 7-hydroxy-8- [ ( 2- methoxyphenyl ) azo ] -N , N , N- rimethyl-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- 1-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.

R,, and R' which are identical or differ, each represents a hydrogen atom or a halogen atom selected from chlorine, bromine, iodine and fluorine, cyano , C₁-C₄-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:

wherein R₂₂ represents a C₁-C₄alkyl group , which can be substituted with a hydroxyl group , and R₂₃ represents a C₁-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 R₂₄ 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

B 1 - B6 :

B4 B5 B6 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'):

(VII) (VTT) 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,

D_: 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, D_: and D₂ represent simultaneously a group -CH, and m = 0,

E represents a group selected from the following struc tures E1-E8:

E6 E7 E8 in which R₃₆ represents a C₁-C₄alkyl group; when m = 0 and O₁ 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 (VII'), 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:

CH,

CH₃

CH,

CH, CH₃

CH,

/

CH,

/

CH,

/

CH,

CI

CH,

/

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,

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 (VII18) can in particular be mentioned:

CH,

H₃SO₄ ^" (VII13)

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 (VII ') , which are applicable in the ready-to-use dye compositions according to the invention, the compounds with the following structures (VII' 1) to (VII' 3) can in par ticular be mentioned:

CH₃

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.

The hairdye composition of the present invention is prepared into a single aerosol type and any of propellant such as liquefied propane gas (LPG), dimethyl ether (DME), nitrogen gas and carbon dioxide gas may be used although LPG is best in view of production of foams after spraying.

According to the present invention, in producing an oxidative hairdye composition of an single aerosol preparation type by dissolving an oxidation dye, an oxidase in water and the above-mentioned optional components upon necessity, charging the resulting solution in an aerosol container and charging a propellant in this aerosol container, the whole aerosol container is shaken during or immediately after charging the propellant into the aerosol container.

This shaking operation is to compulsorily consume the residual oxygen in the container and to suppress the formation of a dye precursor. Since the operation is done in a tightly-closed aerosol container, no polymerization occurs. Thus, in the system, neither insolubilization nor aggregation of the oxidation dye takes place and stability becomes good. With regard to a method for the shaking, any of modes of up-and-down, horizontal, turning, in the shape of the figure 8, etc. may be carried out and there is no particular limitation therefor . Time for shaking depends upon the type and is from 10 seconds to 30 minutes or, preferably, 1-10 minute(s).

The stage for the shaking is immediately after compounding with the enzyme, during the charging of the propellant and immediately thereafter and, as a result of such an operation, formation of insoluble matters can be suppressed. It is preferred in the present invention that compounding of the above-mentioned oxidation dye, oxidase and other optional components and dissolution thereof into water are carried out either in vacuo or in the atmosphere of inert gas such as nitrogen gas , carbon dioxide gas and rare gas where the method therefor may be free and there is no particular limitation. Examples are a method where vacuation is conducted, substitution with nitrogen gas is conducted or, after vacuation, substitution with inert gas is conducted. Charging of the propellant may be carried out in air although it is preferred to charge in vacuo or in an atmosphere of inert gas such as nitrogen gas , carbon dioxide gas and rare gas. With regard to a method for the charging, any method will do and there is no particular limitation therefor. As to an aerosol container, known one may be used.

Examples 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.

[Examples and Comparative Examples]

The components shown in Table 1 were used and made into an aerosol form by a conventional method. Compounding of the components, their charging into an aerosol container and atmosphere during the charging of a propellant into the aerosol container are as shown in Table 2. With regard to an aerosol container, an Aerosol Test Bottle (manufactured by Tokyo Kobunshi KK) was used.

With regard to the stage of shaking the aerosol container, it was carried out immediately after charging of the propellant and an up-and-down shaker (60 shakings per minute) was used. Incidentally, the aerosol container was not shaken in any of the Comparative Examples. The resulting hairdye compositions of a single aerosol type were subjected to the following tests and evaluations. The result is shown in Table 2.

Whether or not the Insoluble Matters were Formed:

Formation of insoluble matters or aggregates in the composition was judged by visual observation immediately after compounding and after allowing to stand for one month at 25°C and 45°C. OO: nothing at all

O: noted a little

Δ: somewhat noted x: considerably 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. Table 1

Compositions

Components (%) 1 2 3 4 p-Phenylenediamine - 1.5 1.5 1 p-Aminophenol 0.1 0.1 0.1 0.1 m-Aminophenol 0.08 - - 0.08

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

Resorcinol - - - 0.1

Ethanol 5 5 5 5

POE Lauryl ether sodium sulfate (p = 3) 0.2 0.2 0.2 0.2

Oxidase 0.03 0.1 0.01 0.05

(Laccase) (Peroxidase) (Uncase) (Laccase)

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

LPG (4 kg/cm²) 4 4 4 4

Pure water b b b b

Total 100.0 100.0 100.0 100.0

PH 7.0 7.0 7.0 7.0

Table 2 Examples Comp.Ex.

1 2 3 4 5 6 7 8 9 1 2 [Atmosphere at the Stage of Compounding] Air o

Vacuum o o o o o o o

Nitrogen gas o o

Argon gas o o [Atmosphere at the Stage of Filling]

Air o o

Vacuum o o o o

Nitrogen gas o o o

Argon gas o Carbon dioxide gas o

Nitrogen after Vacuation o

Shaking Operation Y Y Y Y Y Y Y Y Y N N N

[Composition 1] Insoluble Matters

Immediately after compounding oo oo oo oo oo oo oo oo oo oo oo oo After kept at 25°C for 1 month o o oo oo oo oo oo oo oo x Δ-X Δ~X After kept at 45°C for 1 month o o oo oo oo oo oo oo oo x Δ-X Hair-dyeing property(ΔE) 27 28 32 30 31 31 32 31 30 20 22 21

[Compositions 2 and 3] Insoluble Matters

Immediately after compounding oo oo oo 00 00 00 00 00 After kept at 25°C for 1 month o o oo oo 00 x Δ~x Δ~x After kept at 45°C for 1 month o o oo 00 00 X X Δ~x Hair-dyeing property(ΔE) 27 29 33 31 31 19 22 20

[Composition 4] Insoluble Matters

Immediately after compounding oo oo oo oo oo oo oo oo

After kept at 25°C for 1 month o o oo oo oo Δ~χ Δ~χ

After kept at 45°C for 1 month o o oo oo oo x x Δ~X Hair-dyeing property(ΔE) 26 28 31 32 30 21 20 21

Y: carried out; N: not carried out

According to the present invention, it is now possible to give a hairdye composition of a single aerosol preparation type wherein the stability with a lapse of time is improved.

Claims

, L4 I f

1. In producing an oxidative hairdye composition of a single aerosol preparation type by dissolving an oxidation dye and an oxidase in water, charging the resulting solution in an aerosol container and charging a propellant in this aerosol container, a process for the production of a hairdye composition which is characterized in that whole of the said aerosol container is shaken during or immediately after the said propellant is charged into the said aerosol container.

2. The process for the production according to claim 1, wherein dissolving of the above oxidation dye and oxidase into water and charging of the resulting solution and the propellant into the aerosol container are carried out in vacuo or in an atmosphere of inert gas .