Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/10—Preparations for permanently dyeing the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
  • A61K8/66—Enzymes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/42—Colour properties
  • A61K2800/43—Pigments; Dyes

Definitions

• 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.
• 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.
• 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.
• 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.
• the present inventors have conducted an intensive study for achieving the above-mentioned object and accomplished the present invention.
• the present invention offers :
• 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;
• 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.
• 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.
• laccases and related 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.
• 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 ,
• 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.).
• 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.
• a Pyricularia sp. laccase such as the Pyricularia oryzae laccase which can be purchased from S
• 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 are typically used in combination with a peroxidase to remove or at least reduce the peroxide produced.
• Suitable oxidases include glucose oxidase (E.C.
• an L-amino acid oxidase 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.
• 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.
• 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%.
• 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 .
• 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.
• 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-pheny
• 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 .
• 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.
• R 1 represents a hydrogen atom, C 1 -C 4 -alkyl, C 1 -C 4 - monohydroxyalkyl , C 2 - C 4 - polyhydroxy alkyl , (C ⁇ - C 4 )alkoxy( C ⁇ C alkyl, C 1 -C 4 -alkyl substituted with a nitrogen-containing group, phenyl or 4 ' -aminophenyl;
• R 2 represents a hydrogen atom, C 1 -C 4 -alkyl, C ⁇ C 4 monohydroxyalkyl , C 2 -C 4 polyhydroxyalkyl, (C x -
• R 3 represents a hydrogen atom, a halogen atom such as chlorine, bromine, iodine or fluorine, C 1 -C 4 alkyl,
• R 4 represents a hydrogen atom, a halogen atom or C x - C 4 - alkyl.
• amino, mono ( C ⁇ C,, )alkylamino, di(C 1 -C 4 )alkylamino, tri(C 1 -C 4 )alkylamino, monohydroxy(C 1 -C 4 )alkylamino, imidazolinium and ammonium can in particular be mentioned.
• 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( ⁇ -hydroxy-ethyl) para-phenylenediamine, 4-N,N-bis- ( ⁇ -hydroxyethyl) amino 2-methyl aniline, 4-N,N- bis- ( ⁇ -hydroxyethyl)
• para-phenylenediamines of the above formula (1) the following are especially preferred: para- phenylenediamine , paratoluylenediamine , 2-isopropyl para- phenylenediamine, 2- ⁇ -hydroxyethyl para-phenylenediamine, 2- ⁇ -hydroxyethyloxy para-phenylenediamine, 2,6-dimethyl para-phenylenediamine, 2,6-diethyl para-phenylenediamine, 2,3-dimethyl para-phenylenediamine, N,N-bis-( ⁇ - hydroxyethyl) para-phenylenediamine, 2-chloro para- phenylenediamine, 2- ⁇ -acetylaminoethyloxy para- phenylenediamine and their addition salts with an acid.
• double bases is, according to the invention, meant such compositions which include at least two aromatic nuclei carrying amino and/or hydroxyl groups.
• Z 1 and Z 2 which are identical or differ, represent a hydroxyl group or -NH 2 , which can be substituted with a C 1 -C 4 alkyl 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 -C 6 -alkoxy groups ;
• R 5 and R 6 represents a hydrogen or halogen atom, C ⁇ C 4 alkyl, C 1 -C 4 mono-hydroxyalkyl, C 2 -C 4 polyhydroxyalkyl , C 1 -C 4 aminoalkyl or a bridging group Y; - R 7 , R 8 , R 9 , R 10 , R 11 and R 12 , which are identical or differ, represent a hydrogen atom, a bridging group Y or a C 1 -C 4 alkyl group; whereby it should be understood that the compounds of the formula (2) only include a single bridging group Y per molecule.
• nitrogen-containing groups of the above formula (2) the following can in particular be mentioned: amino, mono(C 1 -C 4 )alkylamino, di(C 1 -C 4 ) alkyl-amino, t ⁇ i ( C 1 - C 4 )alkylamino , monohydroxy(C 1 -C 4 )alkylamino, imidazolinium and ammonium.
• N,N -bis-( ⁇ - hydroxyethyl) N,N' -bis- ( 4 ' -aminophenyl) 1,3-diamino propanol
• N,N -bis- (4-aminophenyl) tetra ethylenediamine
• Particularly preferred double bases of the formula (2) are N,N' -bis- ( ⁇ -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.
• R 13 represents a hydrogen or halogen atom , C 1 -C 4 alkyl , Ci-Cmonohydroxyalkyl , ( x - C 4 ) alkoxy ( C ⁇ C alkyl , C x - C 4 aminoalkyl or ( C 1 -C 4 ) hydroxyalkyl ( C ⁇ C,, ) aminoalkyl
• R 14 represents a hydrogen or halogen atom , C 1 -C 4 alkyl , C 1 -C 4 monohydroxyalkyl , C 2 -C 4 polyhydroxyalkyl , C x - C 4 aminoalkyl , C 1 -C 4 cyanoalkyl or ( C ⁇ -C alkoxy(C : -
• 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-( ⁇ - hydroxyethyl aminomethyl) phenol, 4-amino 2-fluoro phenol and acid addition salts thereof.
• 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
• 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 .
• 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- ( ⁇ -methoxyethyl)amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine and the addition salts thereof .
• 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.
• 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
• 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:
• R 15 , R 16 , R 17 and R 18 which are identical or differ, represent a hydrogen atom, C 1 -C 4 alkyl, aryl, C x - C 4 hydroxyalkyl , C 2 -C 4 polyhydroxyalkyl, (C x - C 4 ) alkoxy(C ⁇ C,,) alkyl, C 1 -C 4 aminoalkyl (where the amine can be protected by an acetyl, ureido or sulfonyl group) , (Ci-C alkylamino ( C ⁇ C alkyl , di- [ (C ⁇ C,)alkyl] amino C 1 -C 4 alkyl (where the dialkyl groups can form a carbon ring or a heterocyclic ring with 5 or 6 members ) , hydroxy-C 1 -C 4 alkyl or di- [hydroxy(C ⁇ C alkyl] -amino
• Ci-C.alkyl the groups X, which are identical or differ, represent a hydrogen atom, C 1 -C 4 alkyl, aryl, C 1 -C 4 hydroxyalkyl,
• C 4 alkyl (where the dialkyl groups can form a carbon ring or a heterocyclic ring with 5 or 6 members ) , hydroxy (C 1 -C 4 )alkyl or di- [hydroxy(C ⁇ C alkyl] amino -C x -
• 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;
• 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 :
• 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 :
• 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- ( ⁇ -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- ( ⁇ -hydroxyethyloxy) -benzene, 2-amino-4- ( ⁇ - hydroxyethylamino ) -1-methoxy-benzene, 1 , 3-diamino-benzene, 1, 3-bis- (2,4-diaminophenoxy) -propane, sesamol, ⁇ -naphtol, 6-hydroxy-indole, 4-hydroxy-indole , 4-hydroxy-N-methyl- indole, 6-hydroxy-indolin, 2 , 6-dihydroxy-4-methyl-pyridine, 1-H
• 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 :
• R 19 represents a hydrogen atom, C 1 -C 4 -alkyl, C ⁇ C 4 monohydroxyalkyl or C 2 -C 4 polyhydroxyalkyl
• R 20 represents a hydrogen atom, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or a halogen atom selected from chlorine, bromine and fluorine
• - R 21 represents a hydrogen atom, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C ⁇ mono-hydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, C ⁇ - C 4 monohydroxyalkoxy or C 2 -C 4 poly-hydroxyalkoxy.
• meta-aminophenols of the above formula (5) the following can be mentioned in particular: meta- aminophenol, 5-amino-2-methoxy phenol, 5- amino-2-( ⁇ - hydroxyethyloxy) -phenol, 5-amino-2-methyl phenol, 5-N-( ⁇ - hydroxyethyl) amino-2-methyl phenol, 5-N-( ⁇ - 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- ( ⁇ -hydroxypropylamino) -2- methyl phenol and acid addition salts thereof.
• 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
• R 22 represents a hydrogen atom, C 1 -C 4 alkyl, C x - C 4 monohydroxyalkyl or C 2 -C 4 polyhydroxyalkyl; - R 23 and R 24 , which are identical or differ, each represents a hydrogen atom, C 1 -C 4 alkyl, C x - C 4 monohydroxyalkoxy or C 2 -C 4 polyhydroxyalkoxy; R 25 represents a hydrogen atom, C 1 -C 4 alkoxy, C ⁇ C 4 aminoalkoxy, C ⁇ C ⁇ ono-hydroxyalkoxy, C 2 - C 4 polyhydroxyalkoxy or 2 , 4-diaminophenoxyalkoxy .
• 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,
• 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:
• - R 26 and R 27 which are identical or differ, each represents a hydrogen atom, C 1 -C 4 alkyl or a halogen atom selected from chlorine, bromine and fluorine.
• a halogen atom selected from chlorine, bromine and fluorine.
• 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.
• 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.
• R x represents a hydrogen atom or C 1 -C 4 -alkyl
• R 2 represents a hydrogen atom, C 1 -C 4 alkyl or phenyl
• R 3 represents a hydroxyl, amino or methoxy group
• R 4 represents a hydrogen atom, a hydroxyl group, a methoxy group or C 1 -C 4 alkyl group, with the proviso tha : when R 3 is an amino group, it is in position 4, when R 3 is in position 4, R 4 is in position 7, when R 3 is in position 5, R 4 is in position 6.
• 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.
• R 5 and R 6 which are identical or differ, each represents a hydrogen atom or C 1 -C 4 -alkyl, and Z represents a hydroxyl group or an amino group.
• 6-hydroxy 1 4-benzomorpholine, N-methyl 6-hydroxy 1,4- benzomorpholine, 6-amino 1 , 4-benzomorpholine and their acid addition salts.
• R 7 represents a hydroxyl group, an amino group, a C 1 -C 4 -alkylamino group, a C ⁇ monohydroxyalkylamino group or a C 2 -C 4 polyhydroxyalkylamino group
• R 8 represents a hydrogen atom, a halogen atom or a C 1 - 4 alkoxy group.
• 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.
• 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.
• 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.
• the imidazolo-azole derivatives the following can in particular be mentioned:
• 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 ,
• 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.
• 1,2-diphenyl pyrazoline-3 , 5-dione, 1,2-diethyl pyrazoline-3 , 5-dione, and their addition salts with an acid 1,2-diphenyl pyrazoline-3 , 5-dione, 1,2-diethyl pyrazoline-3 , 5-dione, and their addition salts with an acid.
• 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.
• 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).
• the compounds can in particular be mentioned which are described in the following documents : - JP 07-098 489;
• 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 chlor
• D represents a nitrogen atom or a group -CH
• R 19 and R 20 which are identical or differ, each represents a hydrogen atom, a C 1 -C 4 alkyl group, which can be substituted with one of the groups -CN, -OH or -NH 2 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 C 1 -C 4 alkyl groups; or a 4'- aminophenyl group , R 21 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:
• R 24 represents a hydrogen atom or a C 1 -C 4 alkyl group
• R 25 represents a hydrogen atom, an alkyl group, which can be substituted with a group -CN or with an amino group, or
• R 25 represents together with R 2 an optionally oxygen and/or nitrogen-containing heterocyclic group, which can be substituted with a C 1 -C 4 alkyl group,
• R 26 and R 27 which are identical or differ, represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine or fluorine, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or the group -CN,
• X " represents an anion, preferably selected from chloride, methylsulphate and acetate,
• R 28 represents a C 1 -C 4 alkyl group
• R 29 and R 30 which are identical or differ, each represents a hydrogen atom or a C 1 -C 4 alkyl group
• R 31 represents a hydrogen atom, a C 1 -C 4 alkoxy group, a halogen atom such as bromine, chlorine, iodine or fluorine, or an amino group ,
• R 32 represents a hydrogen atom or a C 1 -C 4 alkyl group, or R 32 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 C 1 -C 4 alkyl groups,
• R 33 represents a hydrogen atom or a halogen atom such as bromine, chlorine, iodine or fluorine,
• E represents a group selected from the following structures
• R 36 represents a C 1 -C 4 alkyl group
• E can also represent a group with the following structure E9 :
• R 36 represents a C 1 -C 4 alkyl group.
• the cationic direct dyes of the formulae (V), (VI), (VII) and (VII 1 ) 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
• the compounds with the structures (VI), (V2), (V4), (VI4) and (V31) are particularly preferred.
• compositions with the structures (VIII) to (VII18) are particularly preferred.
• 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.
• the acid addition salts suitable within the scope of the dye compositions according to the invention are especially selected from hydrochlorides , hydrobromides , sulphates , tartrates , lactates and acetates .
• any of anionic ones such as ⁇ -olefinsulfonates , alkanesulfonates , fatty acid alkyl ether carboxylates , N- acylamino acids and C 12 .
• 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.
• 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.
• 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.
• the container in which the composition is filled may be appropriately selected depending upon the form of the product .
• the container in which the composition is filled, 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• the hair-dyeing property ( ⁇ E) 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 ( ⁇ E) from the hair which was not dyed was calculated whereby the hair-dyeing property was evaluated.
• SE2000 color difference meter manufactured by Nippon Denshoku
• 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.
• 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
• 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
• 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
• 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
• 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
• 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 .
• 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
• 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.
• Oxygen Concn (%) Dissolved in Compn 0.008 0.00005 0.0001 0.00008 Oxygen Concn (%) in Headspace 3 0.07 0.04 0.01
• 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.

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