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    • 专利摘要:
    The present invention relates to ready-to-use compositions for dyeing keratin fibers, in particular human keratin fibers, such as hair, containing the following on a support suitable for dyeing keratin fibers: (a) at least one laccase type enzyme; (b) one or more solvents selected from specific polyols and ethers or polyethers thereof; And (c) at least one oxidation dye. The present invention also relates to a method of dyeing hair using the composition.
    公开号:KR20010034066A
    申请号:KR1020007007675
    申请日:1999-01-12
    公开日:2001-04-25
    发明作者:랑제라르；꼬떼레쟝
    申请人:조지안느 플로；로레알；
    IPC主号:
    专利说明:

    Oxidative dye composition of keratin fibers containing laccase, and dyeing method using the composition {MIXTURE FOR THE OXIDATION TINTING OF KERATIN FIBRES CONTAINING A LACCASE AND TINTING METHOD USING SAID MIXTURE}
    The present invention provides dyeing compositions for keratinous fibers containing at least one laccase type enzyme, at least one solvent selected from certain polyols or ethers or polyethers thereof, and at least one oxidizing dye, and dyeing keratinous fibers, in particular human hair It is about a use.
    Dyeing compositions containing oxidizing dye precursors, in particular ortho- and para-phenylenediamine, ortho- or para-aminophenol, a heterocyclic base commonly referred to as an oxidizing base, are known for dyeing keratinous fibers, in particular human hair. . An oxidizing dye precursor or oxidizing base is a colorless or slightly colored compound which, when combined with an oxidation product, generates dyes and colored compounds by oxidation condensation methods.
    The color tone obtained with the oxidizing base can be changed by combining the oxidizing base with a coupling agent or, in particular, a color modifier selected from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds. It is also known.
    The variety of molecules used in the oxidation base and coupling agent allows a rich color range to be obtained.
    In addition, the so-called "permanent" colors obtained by the oxidizing dye must satisfy many requirements. Therefore, it should not be flawed from a toxicological point of view, it should be possible to obtain a hue of the desired intensity and exhibit good resistance to external factors (light, bad climatic conditions, washing, perm wavering, sweating, rubbing).
    In addition, the dye should be able to cover gray hair, thereby minimizing discernment. In other words, it should be possible to minimize possible differences in color across the same keratin fibers, which can actually be differentiated (ie, damaged) between their ends and hair roots.
    Oxidative dyeing of keratinous fibers is usually carried out in alkaline media in the presence of hydrogen peroxide. However, the use of alkaline media in the presence of hydrogen peroxide has the drawback of causing substantial degradation of the fibers as well as discoloration of the keratin fibers, which is not always desirable.
    In addition, oxidative staining of keratin fibers may be performed using an oxidizing system different from hydrogen peroxide, such as an enzyme system. Thus, dyeing keratin fibers using a composition containing one or more oxidizing dyes in combination with laccase-type enzymes is described in US Pat. No. 3,251,742, patent applications FR-A-2,112,549, FR-A-2,694,018, EP-A-. 0,504,005, WO95 / 07988, WO95 / 33836, WO95 / 33837, WO96 / 00290, WO97 / 19998 and WO97 / 19999 are already disclosed and the composition is brought into contact with atmospheric oxygen. The dyeing formulations are used under conditions that do not cause degradation of keratinous fibers as compared to those caused by dyeing performed in the presence of hydrogen peroxide, but in terms of color uniformity ("match") and chromaticity distributed along the fibers In terms of lightness and dyeing power, still inadequate color is obtained.
    It is an object of the present invention to solve the above mentioned problems.
    Applicant surprisingly has the presence of oxidizing dye (s) (oxidation bases and / or coupling agents) as oxidative systems, as novel compositions containing at least one laccase type enzyme and at least one specific solvent, which will be defined in more detail below. Under immediate use, it results in a more uniform, more intense, more dyeable color without causing significant degradation or discoloration of the keratinous fibers and exhibits low selectivity and good resistance to various attacks the hair may receive A composition was found that could constitute a possible dye formulation.
    The finding forms the basis of the present invention.
    Accordingly, a first subject of the invention is a ready-to-use composition for human keratin fibres, more particularly human hair, in a carrier suitable for dyeing keratin fibres, comprising:
    (a) at least one laccase type enzyme;
    (b) at least one solvent selected from:
    Branched or unbranched C 3 -C 8 αω-diol;
    Branched or unbranched C 5 -C 8 1,2-1,4-1,5-2,3-2,4-2,5-2,6-2,7-2,8-3,4- 3,5-3,6 diols;
    Branched or unbranched C 6 -C 8 1,3-diol;
    C 4 -C 8 triols;
    Diethylene glycol and dipropylene glycol;
    C 3 -C 8 monoalkyl ethers of C 3 -C 9 glycols; C 5 -C 9 monoalkyl ethers of ethylene glycol; C 1 -C 2 monoalkyl ethers of C 5 -C 9 glycols; C 2 monoalkyl ethers of 1,2-1,3-1,4-2,3-butanediol; Monoalkyl ethers of glycols having a total carbon number of 5;
    C 1 -C 9 dialkyl ethers of C 2 -C 9 glycols;
    Phenyl ether of C 3 -C 9 glycol;
    (c) at least one oxidation dye.
    The laccase (s) used in the ready-to-use dye compositions according to the invention are, in particular, organisms which may be of plant origin, animal origin, fungal origin (yeast, filamentous fungus, fungus) or bacterial origin, mono- or multi-cell origin. It can be selected from laccases of. They can be obtained by biotechnology.
    Among laccases of plant origin that can be used according to the invention, for example, lactose, such as extracts of Mango (Magnifera indica), Schinus molle or Pleiogynium timoriense ( Extract of Anacardiaceae, Podocarpaceae, Rosmarinus off., Solanum tuberosum, Iris sp., Coffee sp., Carrot (Daucus) carrota, Vinca minor, Avocado (Persea americana), Catharenthus roseus, Banana (Musa sp.), Apple (Malus pumila), Gingko biloba, Monotropa hippo From extracts of Monotropa hypopithys (Indian pipe), Aesculus sp., Acer pseudoplatanus, Prunus persica, Pistacia palaestina As indicated in patent application FR-A-2,694,018, as found It may be mentioned laccase dehydratase produced by plants performing chlorophyll synthesis like.
    Among the laccases of fungal origin, optionally obtained by biotechnology, which can be used according to the present invention, Polyporus versicolor as disclosed in patent applications FR-A-2,112,549 and EP-A-504005 ), Laccase (s) derived from Rhizoctonia practicola and Rhus vernicifera, patent applications WO 95/07988, WO 95/33836, WO 95, which are incorporated herein by reference. The laccase (s) described in / 33837, WO 96/00290, WO 97/19998 and WO 97/19999, for example Scytalidium, Polyporus pinsitus, Micellolioptera Laccase (s) derived from Thermophila thermophila, Rhizoctonia solani, Pyricularia orizae, or variants thereof. In addition, Tramates versicolor, Pomes fomentarius, Caetomium thermophile, Neurospora crassa, Coriolus versicol (Coriolus versicol), Botrytis cinerea, Rigidoporus lignosus, Pelinus noxius, Pleurotus ostreatus, Aspergillus Aspergillus nidulans, Podospora anserina, Agaricus bisporus, Ganoderma lucidum, Glomerella singulata, Lactarius pipera Lactarius piperatus, Russula delica, Heterobasidion annosum, Telephora terrestris, Cladosporium Cladosporiodes m cladosporiodes, Cerrena unicolor, Coriolus hirsutus, Ceriporiopsis subvermispora, Coprinus cinereus, Panaole Those derived from Panaeolus papilionaceus, Panaeolus sphinctrinus, Schizophyllum commune, Dichomitius squalens and their variants Can be mentioned.
    The laccases of fungal origin, optionally obtained by biotechnology, are preferably selected.
    Among their substrates, the enzymatic activity of the laccases of the present invention, with syringaldazine, can be determined from the oxidation of cyringalazine under aerobic conditions. The lacu unit corresponds to the amount of enzyme that catalyzes the conversion of 1 mmol of cyringalazine per minute at 30 ° C. and pH 5.5. Unit u corresponds to the amount of enzyme that exhibits a delta absorbance of 0.001 per minute at 530 nm, using cyringalazine as the substrate at 30 ° C. and pH 6.5.
    In addition, the enzymatic activity of the laccases of the invention can be defined from the oxidation of para-phenylenediamine. The lacu unit corresponds to the amount of enzyme exhibiting a delta absorbance of 0.001 per minute at 496.5 nm using para-phenylenediamine as substrate (64 mM) at 30 ° C. and pH 5. In the present invention, it is preferable to obtain enzyme activity in units of lacu.
    The amount of laccase used in the composition of the present invention varies depending on the nature of the selected laccase. Preferably, the amount varies from 0.5 to 2000 lacu, or 1000 to 4 × 10 7 u units, or 20 to 2 × 10 6 lacu units, per 100 g of the composition.
    Polyols are, for the purposes of the present invention, polymers of saturated or unsaturated, straight, branched or cyclic alkyl type having at least two -OH functional groups on the alkyl chain, and polymers of said polyhydrylated alkyl compounds (polyethers) Indicates.
    In branched or unbranched C 3 -C 8 αω-diol, αω is understood to be for the longest carbon chain in the case of side chain compounds.
    Among the above compounds, for example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol (or 2,3-dimethyl-1,3 -Propanediol).
    Branched or unbranched C 5 -C 8 1,2-1,4-1,5-2,3-2,4-2,5-2,6-2,7-2,8-3,4-3 2,5-hexanediol, 2,4-pentanediol (or amylene glycol), 2-methyl-2,4-pentanediol (or hexylene glycol), 2,3 among 5,3,6 diols -Dimethyl-2,3-butanediol (or pinacol) is mentioned.
    Among the C 4 -C 8 triols, in particular 1,2,4-butanetriol and 1,2,6-hexanetriol can be mentioned.
    Among the monoalkyl ethers of glycols having a total carbon number of 5, there may be mentioned monoethyl ethers of propylene glycol.
    C 3 - C 9 of glycol C 3 - C 8 of the mono alkyl ether, the monobutyl ether of propylene glycol.
    Among the C 5 -C 9 monoalkyl ethers of ethylene glycol, monohexyl ethers of ethylene glycol are mentioned.
    Among the C 1 -C 2 monoalkyl ethers of C 5 -C 9 glycols, monomethyl ether of dipropylene glycol, monomethyl ether of isoprene glycol, and monomethyl ether of tripropylene glycol can be mentioned.
    Among the C 2 monoalkyl ethers of 1,2-1,3-1,4-2,3-butanediol, monomethyl ethers of 2,3-butanediol are mentioned.
    Among the C 1 -C 9 dialkyl ethers of C 2 -C 9 glycol, dibutyl ether of propylene glycol can be mentioned.
    Among the phenyl ethers of C 3 -C 9 glycols, in particular monophenyl ethers of propylene glycol and monophenyl ethers of diethylene glycol are mentioned.
    In the present invention, it is preferable to use the following as a solvent:
    Branched or unbranched C 3 -C 8 αω-diol;
    Diethylene glycol and dipropylene glycol;
    C 3 -C 8 monoalkyl ethers of C 3 -C 9 glycols;
    C 1 -C 2 monoalkyl ethers of C 5 -C 9 glycols.
    The polyols or ethers or polyethers thereof are present in the dyeing compositions according to the invention in a proportion of usually 0.1 to 40% by weight, more preferably 0.5 to 20% by weight relative to the total weight of the composition.
    The nature of the oxidative dye (s) used in the readily available dyeing compositions is not limited.
    The oxidation base can in particular be selected from para-phenylenediamine, double bases, para-aminophenols, ortho-aminophenols and heterocyclic oxidation bases.
    Among the para-phenylenediamines which can be used as the oxidation base in the dyeing compositions according to the invention, in particular the compounds of the formula (I), and acid addition salts thereof, are mentioned:
    (Wherein
    R 1 is a hydrogen atom, a C 1 -C 4 alkyl radical, a monohydroxy (C 1 -C 4 alkyl) radical, a polyhydroxy (C 2 -C 4 alkyl) radical, (C 1 -C 4 ) alkoxy ( C 1 -C 4 ) alkyl radical, a C 1 -C 4 alkyl radical substituted with a nitrogen-containing group, a phenyl radical or a 4′-aminophenyl radical;
    R 2 is a hydrogen atom, a C 1 -C 4 alkyl radical, a monohydroxy (C 1 -C 4 alkyl) radical, a polyhydroxy (C 2 -C 4 alkyl) radical, (C 1 -C 4 ) alkoxy ( C 1 -C 4 ) alkyl radical or C 1 -C 4 alkyl radical substituted with a nitrogen-containing group;
    R 3 is a hydrogen atom, a halogen atom such as chlorine, bromine, iodine or fluorine atom, C 1 -C 4 alkyl radical, monohydroxy (C 1 -C 4 alkyl) radical, hydroxy (C 1 -C 4 alkoxy ) Radicals, acetylamino (C 1 -C 4 alkoxy) radicals, mesylamino (C 1 -C 4 alkoxy) radicals or carbamoylamino (C 1 -C 4 alkoxy) radicals;
    R 4 represents hydrogen or a halogen atom or a C 1 -C 4 alkyl radical.
    Among the nitrogen-containing groups of the above formula (I), in particular amino, mono (C 1 -C 4 ) alkylamino, (C 1 -C 4 ) dialkylamino, (C 1 -C 4 ) trialkylamino, monohydroxy (C 1 -C 4 ) alkylamino, imidazolinium and ammonium radicals.
    Among the para-phenylenediamines of the above formula (I), more particularly para-phenylenediamine, para-tolylenediamine, 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-methylaniline, N, N-bis (β-hydroxyethyl ) -Para-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (β-hydroxypropyl) -para-phenylene Diamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl-β- Hydroxyethyl) -para-phenylenediamine, N- (β, γ-dihydroxypropyl) -para-phenylenediamine, N- (4'-aminophenyl) -para-phenylenediamine, N-phenyl- Para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, N- (β-methoxyethyl) -para-phenylene Diamine and their acid addition salts.
    Among the para-phenylenediamines of the above formula (I), most particularly preferred are para-phenylenediamine, para-tolylenediamine, 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 acid addition salts thereof.
    In the present invention, "double base" is understood to mean a compound containing two or more aromatic rings with amino and / or hydroxyl groups.
    Among the dual bases which can be used as oxidation bases in the dyeing compositions according to the invention, in particular the compounds corresponding to the following formula (II), and acid addition salts thereof:
    (Wherein
    Z 1 and Z 2 are the same or different and represent a hydroxyl or —NH 2 radical which may be substituted with a C 1 -C 4 alkyl radical or a bond Y;
    The bond Y may be interrupted or interrupted by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms, optionally with one or more hydroxyl or C 1 -C 6 alkoxy radicals A C 1 -C 14 straight or branched alkylene chain which may be substituted;
    R 5 and R 6 are hydrogen or halogen atoms, C 1 -C 4 alkyl radicals, monohydroxy (C 1 -C 4 alkyl) radicals, polyhydroxy (C 2 -C 4 alkyl) radicals, amino (C 1 -C 4 alkyl) radical or bond Y;
    R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are the same or different and represent a hydrogen atom, a bond Y or a C 1 -C 4 alkyl radical);
    It is understood that the compound of formula II contains only one binding segment Y per molecule.
    Among the nitrogen-containing groups of the above formula (II), in particular amino, mono (C 1 -C 4 ) alkylamino, (C 1 -C 4 ) dialkylamino, (C 1 -C 4 ) trialkylamino, monohydroxy (C 1 -C 4 ) alkylamino, imidazolinium and ammonium radicals.
    Among the double bases of formula II, more particularly N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropanol, 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 acid addition salts Can be mentioned.
    Among the double bases of Formula II, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropanol, 1,8-bis Particular preference is given to (2,5-diaminophenoxy) -3,5-dioxaoctane, or one of their acid addition salts.
    Among the para-aminophenols which can be used as the oxidation base in the dyeing compositions according to the invention, in particular the compounds corresponding to the formula III, and their acid addition salts are mentioned:
    (Wherein
    R 13 is hydrogen or a halogen atom, C 1 -C 4 alkyl, monohydroxy (C 1 -C 4 alkyl), (C 1 -C 4 ) alkoxy (C 1 -C 4 ) alkyl, amino (C 1- C 4 alkyl) or hydroxy (C 1 -C 4 ) alkylamino (C 1 -C 4 alkyl) radicals,
    R 14 is hydrogen or a halogen atom, C 1 -C 4 alkyl, monohydroxy (C 1 -C 4 alkyl), polyhydroxy (C 2 -C 4 alkyl), amino (C 1 -C 4 alkyl), A cyano (C 1 -C 4 alkyl) or (C 1 -C 4 ) alkoxy (C 1 -C 4 ) alkyl radical,
    At least one of the radicals R 13 or R 14 is understood to represent a hydrogen atom).
    Among the para-aminophenols of formula III, more particularly para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4- Amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxy Ethylaminomethyl) phenol, 4-amino-2-fluorophenol, and their acid addition salts.
    Among the ortho-aminophenols which can be used as the oxidation base in the dyeing compositions according to the invention, more particularly 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido 2-aminophenol and those acid addition salts are mentioned.
    Among the heterocyclic bases which can be used as the oxidation base in the dyeing compositions according to the invention, more particularly pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives, and acid addition salts thereof are mentioned.
    Among the pyridine derivatives, more particularly, for example, the compounds described in patents GB 1,026,978 and GB 1,153,196, such as 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino-3-aminopyridine, 2, 3-diamino-6-methoxypyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxypyridine, 3,4-diaminopyridine, and their acid addition salts are mentioned. .
    Among the pyrimidine derivatives, more particularly, for example, the compounds described in German patent DE 2,359,399 or Japanese patents JP 88-169,571 and JP 91-333,495 or patent application WO 96/15765, such as 2,4,5,6- Tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-dia Minopyrimidines, 2,5,6-triaminopyrimidines, and their acid addition salts.
    Among the pyrazole derivatives, more particularly compounds described in patent DE 3,843,892, DE 4,133,957 and patent applications WO 94/08969, WO 94/08970, FR-A-2,733,749 and DE 195 43 988, such as 4,5-diamino -1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5-diamino-1,3-dimethylpyrazole , 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyra Sol, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl -3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5 -Diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxy Hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino- 3-methyl-1-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3 , 4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyra Sol and their acid addition salts.
    Among pyrazolopyrimidine derivatives, more particularly pyrazolo [1,5-a] pyrimidine of the formula (IV), its acid or base addition salt, and its tautomeric form, when present, are present :
    (Wherein
    R 15 , R 16 , R 17 and R 18 are the same or different and represent a hydrogen atom, a C 1 -C 4 alkyl radical, an aryl radical, a C 1 -C 4 hydroxyalkyl radical, a C 2 -C 4 polyhydroxy Alkyl radicals, (C 1 -C 4 ) alkoxy (C 1 -C 4 alkyl) radicals, C 1 -C 4 aminoalkyl radicals (which makes it possible for the amine to be protected with acetyl, ureido or sulfonyl radicals), (C 1 -C 4 ) alkylamino (C 1 -C 4 alkyl) radicals, di-[(C 1 -C 4 ) alkyl] amino (C 1 -C 4 alkyl) radicals (dialkyl radicals are carbon-containing rings, or 5 Or alternatively to form a 6-membered heterocycle), hydroxy (C 1 -C 4 ) alkyl- or di- [hydroxy (C 1 -C 4 ) alkyl] amino (C 1 -C 4 alkyl) Represent radicals;
    -X radicals are the same or different and are hydrogen atom, C 1 -C 4 alkyl radical, aryl radical, C 1 -C 4 hydroxyalkyl radical, C 2 -C 4 polyhydroxyalkyl radical, C 1 -C 4 amino Alkyl radical, (C 1 -C 4 ) alkylamino (C 1 -C 4 alkyl) radical, di-[(C 1 -C 4 ) alkyl] amino (C 1 -C 4 alkyl) radical (dialkyl is carbon- It is possible to form a containing ring or a 5- or 6-membered heterocycle), hydroxy (C 1 -C 4 ) alkyl or di- [hydroxy (C 1 -C 4 ) alkyl] -amino (C 1- C 4 alkyl) radical, amino radical, (C 1 -C 4 ) alkyl- or di-[(C 1 -C 4 ) alkyl] -amino radical; Halogen atom, carboxylic acid group, 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;
    only,
    the sum of p + q is not zero;
    when p + q is 2, n is 0 and the NR 15 R 16 and NR 17 R 18 groups are (2,3); (5,6); (6,7); Occupies the position of (3,5) or (3,7);
    when p + q is 1, n is 1 and the NR 15 R 16 (or NR 17 R 18 ) and OH groups are (2,3); (5,6); (6,7); Occupies the position of (3,5) or (3,7)).
    When the pyrazolo [1,5-a] pyrimidine of Formula IV includes a hydroxyl group at one of the positions 2, 5 or 7 at the α position with respect to the nitrogen atom, for example, There is an equilibrium of tautomers represented by:
    Among the pyrazolo [1,5-a] pyrimidines of the general formula (IV), in particular when the following compounds, addition salts thereof, and tautomeric equilibrium are present, their tautomeric forms are mentioned:
    Pyrazolo [1,5-a] pyrimidine-3,7-diamine;
    2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
    Pyrazolo [1,5-a] pyrimidine-3,5-diamine;
    2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine;
    3-aminopyrazolo [1,5-a] pyrimidin-7-ol;
    3-aminopyrazolo [1,5-a] pyrimidin-5-ol;
    2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;
    2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;
    2-[(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) (2-hydroxyethyl) amino] ethanol;
    2-[(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) (2-hydroxyethyl) amino] ethanol;
    5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
    2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
    2,5, N7, N7-tetramethylpyrazolo [1,5-a] pyrimidine-3,7-diamine.
    The pyrazolo [1,5-a] pyrimidines of the formula IV can be prepared by cyclization from aminopyrazoles according to the synthesis 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 PHARMACEUTICALS.
    In addition, pyrazolo [1,5-a] pyrimidines of the formula IV can be prepared by cyclization from hydrazine according to the synthesis described in the following references:
    A. McKillop and R.J. Kobilecki, Heterocycles, 6 (9), 1355, 1977.
    E. Alcade, J. De Mendoza, J.M. Marcia-Marquina, C. Almera, J. Elguero, J. Heterocyclic Chem., 11 (3), 423, 1974.
    -K. Saito, I. Hori, M. Higarashi, H. Midorikawa, Bull. Chem. Soc. Japan, 47 (2), 476, 1974.
    The oxidation base (s) according to the invention preferably represent approximately 0.0005 to 12% by weight, even more preferably approximately 0.005 to 6% by weight of the total weight of the immediately available dyeing composition.
    Coupling agent (s) which can be used in the ready-to-use dyeing compositions according to the invention are those usually used in oxidative dyeing compositions, ie meta-phenylenediamine, meta-aminophenol, meta-diphenol, sesamol and the like Derivatives, mono- or polyhydroxylated derivatives of naphthalene, heterocyclic compounds such as indole derivatives, indolin derivatives, benzimidazole derivatives, benzomorpholine derivatives, sesamol derivatives, pyrazoleazole derivatives, pyrroloazole derivatives, Imidazoloazole derivatives, pyrazolopyrimidine derivatives, 3,5-pyrazolindione, pyrrolo [3,2-d] oxazole derivatives, pyrazolo [3,4-d] oxazole derivatives, thiazoloazole S -Oxide derivatives, thiazoloazole S, S-dioxide derivatives, and acid addition salts thereof.
    The coupling agent. Especially 2-methyl-5-aminophenol, 5-N- (β-hydroxyethyl) amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy- 2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (β-hydroxyethyloxy) benzene, 2-amino-4- (β-hydroxyethylamino ) -1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis (2,4-diaminophenoxy) propane, sesamol, α-naphthol, 6-hydroxyindole, 4-hydroxy Indole, 4-hydroxy-N-methylindole, 6-hydroxyindolin, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl- 3-methylpyrazol-5-one, 2,6-dimethyl-pyrazolo [1,5-b] -1,2,4-triazole, 2,6-dimethyl [3,2-c] -1, 2,4-triazole, 6-methylpyrazolo [1,5-a] benzimidazole, and their acid addition salts.
    The coupling agent preferably represents approximately 0.0001 to 10% by weight, even more preferably approximately 0.005 to 5% by weight of the total weight of the immediately available dyeing composition.
    Usually, acid addition salts (oxidation bases and coupling agents) that can be used in the area of the dyeing compositions of the invention are especially chosen from hydrochlorides, bromates, sulfates and tartarates, lactates and acetates.
    In addition, the dyeing composition of the present invention can improve the dimness of the color tone by directly containing the dye in addition to the oxidizing dye as defined above. The direct dye may be chosen in particular from nitro, azo or anthraquinone dyes.
    Subject of the invention is also a method of dyeing keratin fibers, in particular human keratin fibers, such as hair, using the readily available dyeing compositions as defined above.
    According to the method, the one or more readily available dyeing compositions as defined above are applied to the fibers for a time sufficient to give the desired color, followed by rinsing, optionally washing with shampoo, again rinsing and drying.
    The time required for the development of the keratinous fibers is usually 3 to 60 minutes, even more precisely 5 to 40 minutes.
    According to one particular embodiment of the invention, the process comprises, on the one hand, a composition (A) containing at least one oxidative dye as defined above in a medium suitable for dyeing, on the other hand, in a medium suitable for dyeing, After storing the composition (B) containing the above laccase type enzyme and at least one solvent selected from polyol or ether or polyether thereof as defined above, before applying the mixture to keratin fibers, A preliminary step consisting of mixing the above in use.
    According to one particular embodiment of the present invention, a solvent [olyol (s) or ether or polyether thereof] may be incorporated into the composition (A).
    Another subject of the invention is a multicompartment apparatus or dyeing (kit) or other multicompartment packaging system in which the first compartment has the composition (A) as defined above and the second compartment has the composition (B) as defined above. . The device may be equipped with means to enable delivery of the desired mixture to the hair, as described in patent FR-2,586,913 in the applicant's name.
    Suitable media (or carriers) for the keratinous fibers of the ready-to-use dyeing compositions for keratinous fibers according to the invention usually comprise water and mixtures of one or more polyols or ethers or polyethers thereof as defined above. It may additionally contain organic solvent (s) different from the polyols or ethers or polyethers thereof used according to the invention, so as to dissolve compounds which are not sufficiently soluble in the medium. As the organic solvent, for example, aromatic alcohols such as benzyl alcohol, as well as C 1 -C 4 alkanols such as ethanol and isopropanol, similar products and mixtures thereof can be mentioned.
    The organic solvent may preferably be present in a proportion of about 0.5 to 40% by weight, even more preferably about 1 to 20% by weight relative to the total weight of the dyeing composition.
    The pH of the ready-to-use dyeing composition for keratinous fibers according to the invention is chosen such that the enzymatic activity of laccases is not impaired. It usually varies from about 4 to 11, more preferably about 6 to 9.
    The ready-to-use dyeing compositions according to the invention also contain anionic, cationic, nonionic, zwitterionic or zwitterionic surfactants or mixtures thereof, polymers, thickeners, antioxidants, laccases used according to the invention. And different enzymes, such as peroxidases or oxidoreductases containing two electrons, penetrants, metal ion blockers, perfumes, buffers, dispersants, membrane-forming agents, screening agents, vitamins, preservatives or opacifying agents Can be.
    Of course, those skilled in the art are cautious in selecting such optional addition compounds so that the advantageous properties inherent in the readily available dyeing compositions according to the invention are not damaged or substantially damaged by the envisioned adduct (s). You will have to.
    The ready-to-use dyeing compositions according to the invention can be provided in various forms, such as in the form of liquids, creams, gels, or any other form suitable for dyeing keratin fibers, in particular human hair, optionally pressurized.
    In the dyeing compositions of the present invention, the oxidizing dye (s) and laccase (s) are present in the composition which should be free of gaseous oxygen to avoid both premature oxidation of the oxidizing dye (s).
    Now, specific embodiments are given to illustrate the present invention.
    In the following description or description, unless otherwise indicated, percentages are expressed in weight.
    The following examples illustrate the invention without any limitation.
    Examples 1 and 2: Dyeing Compositions
    The following ready-to-use dyeing compositions were prepared (content g):
    FurtheranceOne2 Lactase obtained from Rhus vernicifera, containing 180 units / mg, sold by SIGMA1.81.8 Para-phenylenediamine0.2540.254 2,4-diaminophenoxyethanol. 2HCl0.2600.260 Nonionic Surfactant: Alkyl polyglucoside in aqueous solution containing 60% active substance (AS), sold under the trade name ORAMIX CG110 by SEPPIC.4.800 (AS)4.800 (AS) Polyol according to the invention2020 pH agent qs pH6.56.5 Demineralized water qs100100
    Composition (1): 1,4-butanediol,
    Composition (2): monobutyl ether of propylene glycol.
    The ready-to-use dye composition is applied to a natural gray hair stage where 90% is white at 30 ° C. for 40 minutes. The hair is then rinsed, washed with standard shampoo and dried. In both cases the hair is dyed bluish grey.
    In the above examples, 1.8% of 180 units / mg of Rhus vernicifera laccase was added to I.C.N. It can be replaced with 1% of 100 units / mg of Pyricularia Orizae laccase sold by the company.
    权利要求:
    Claims (22)
    [1" claim-type="Currently amended] A ready-to-use composition for dyeing keratin fibers, in particular human keratin fibers, such as hair, comprising in a carrier suitable for dyeing keratin fibers:
    (a) at least one laccase type enzyme;
    (b) at least one solvent selected from:
    Branched or unbranched C 3 -C 8 αω-diol;
    Branched or unbranched C 5 -C 8 1,2-1,4-1,5-2,3-2,4-2,5-2,6-2,7-2,8-3,4- 3,5-3,6 diols;
    Branched or unbranched C 6 -C 8 1,3-diol;
    C 4 -C 8 triols;
    Diethylene glycol and dipropylene glycol;
    C 3 -C 8 monoalkyl ethers of C 3 -C 9 glycols; C 5 -C 9 monoalkyl ethers of ethylene glycol; C 1 -C 2 monoalkyl ethers of C 5 -C 9 glycols; C 2 monoalkyl ethers of 1,2-1,3-1,4-2,3-butanediol; Monoalkyl ethers of glycols having a total carbon number of 5;
    C 1 -C 9 dialkyl ethers of C 2 -C 9 glycols;
    Phenyl ether of C 3 -C 9 glycol;
    (c) at least one oxidation dye.
    [2" claim-type="Currently amended] The composition of claim 1, wherein the laccase (s) is selected from laccases of plant origin, animal origin, fungal origin, bacterial origin or obtained by biotechnology.
    [3" claim-type="Currently amended] The composition of claim 1 or 2, wherein the laccase is selected from those produced by plants that perform chlorophyll synthesis.
    [4" claim-type="Currently amended] The method of claim 3, wherein the laccase is Anacardiaceae or Podocarpaceae, Rosmarinus off., Solanum tuberosum, Iris sp., Coffee (Coffea) sp., Carrot (Daucus carrota), Vinca minor, Avocado (Persea americana), Catharenthus roseus, Banana (Musa sp.), Apple (Malus pumila), Bank (Gingko biloba), Monotropa hypopithys (Indian Pipe), Aesculus sp., Acer pseudoplatanus, Prunus persica, Pistasia A composition selected from those extracted in Pistacia palaestina.
    [5" claim-type="Currently amended] The method of claim 2, wherein the laccase is Pyricularia orizae, Polyporus versicolor, Rhizoctonia praticola, Rhus vernicifera , Scytalidium, Polyporus pinsitus, Miceliophtora thermophila, Rhizoctonia solani, Tramates versicolor, Po Mess fomentarius, Caetomium thermophile, Neurospora crassa, Coriolus versicol, Botrytis cinerea , Rigidoporus lignosus, Pelinus noxius, Pleurotus ostreatus, Aspergillus nidulans, Grapespora anselina (Podospora anserina), Agaricus bisporus, Ganoderma lucidum, Glomerella cingulata, Lactarius piperatus, Rucura delica (Russula delica) ), Heterobasidion annosum, Telephora terrestris, Cladosporium cladosporioides, Serena unicolor, Coriolus hirsutus (Coriolus hirsutus), Ceriporiopsis subvermispora, Coprinus cinereus, Panaeolus papilionaceus, Panaeolus spink trinus (Coriolus hirsutus) Panaeolus sphinctrinus, Schizophyllum commune, Dichomitius squalens, and those derived from their variants. Composition.
    [6" claim-type="Currently amended] 6. The laccase (s) according to claim 1, wherein the laccase (s) is provided in an amount ranging from 0.5 to 2000 lacu or 1000 to 4 × 10 7 or from 20 to 2 × 10 6 lacu per 100 g of the composition. The composition characterized in that.
    [7" claim-type="Currently amended] The composition according to any one of claims 1 to 6, wherein the solvent is selected from the following:
    Branched or unbranched C 3 -C 8 αω-diol;
    Diethylene glycol and dipropylene glycol;
    C 3 -C 8 monoalkyl ethers of C 3 -C 9 glycols;
    C 1 -C 2 monoalkyl ethers of C 5 -C 9 glycols.
    [8" claim-type="Currently amended] 8. Composition according to any one of the preceding claims, wherein the solvent according to the invention is present in a proportion of 0.1 to 40% by weight, preferably 0.5 to 20% by weight, relative to the total weight of the composition. .
    [9" claim-type="Currently amended] 9. The composition according to claim 1, wherein the oxidative dye (s) are selected from an oxidizing base and / or a coupling agent.
    [10" claim-type="Currently amended] 10. The method of claim 9, wherein the oxidizing base is selected from ortho- or para-phenylenediamine, bisphenylalkylenediamine, ortho- or para-aminophenol and heterocyclic bases, and acid addition salts of the compounds. Composition.
    [11" claim-type="Currently amended] The composition of claim 9 or 10, wherein the oxidation base is present at a concentration ranging from 0.0005 to 12% by weight relative to the total weight of the composition.
    [12" claim-type="Currently amended] 10. The composition of claim 9, wherein the coupling agent is selected from meta-phenylenediamine, meta-aminophenol, meta-diphenol, heterocyclic coupling agents, and acid addition salts of the compounds.
    [13" claim-type="Currently amended] 13. A composition according to claim 9 or 12, wherein the coupling agent is present in a concentration ranging from 0.0001 to 10% by weight relative to the total weight of the composition.
    [14" claim-type="Currently amended] 14. A composition according to any one of claims 9 to 13, wherein the acid addition salts of the oxidizing base and the coupling agent are selected from hydrochlorides, bromates, sulfates, tartarates, lactates and acetates.
    [15" claim-type="Currently amended] The composition according to any one of claims 1 to 14, which further contains a direct dye.
    [16" claim-type="Currently amended] The method according to any one of claims 1 to 15, wherein the medium (or carrier) suitable for the keratin fibers comprises a mixture of water and one or more solvents selected from those defined in claims 1 or 7. Characterized by a composition.
    [17" claim-type="Currently amended] 17. The composition of claim 16, wherein the medium additionally contains one or more organic solvents.
    [18" claim-type="Currently amended] 18. The composition according to any one of the preceding claims, wherein the pH varies from 4 to 11, preferably from 6 to 9.
    [19" claim-type="Currently amended] 19. The surfactant, polymer, thickener, antioxidant, enzyme different from laccase, penetrant, metal ion sequestrant, perfume, buffer, dispersant, membrane-forming agent, screening agent according to any one of claims 1 to 18. And at least one cosmetic adjuvant commonly used in hair dyeing compositions, selected from the group consisting of vitamins, preservatives or opacifying agents.
    [20" claim-type="Currently amended] 20. A keratinous fiber, in particular hair, characterized in that one or more readily available dyeing compositions as defined in any of claims 1 to 19 are applied to keratinous fibers for a time sufficient to give a desired color. Same method of dyeing human keratin fibers.
    [21" claim-type="Currently amended] The composition (A) according to claim 20, which, on the one hand, contains at least one oxidizing dye as defined in any one of claims 9 to 14 in a medium suitable for dyeing, on the other hand, keratin In a medium suitable for the fiber, a composition (B) containing an enzyme of at least one laccase type as defined in any of claims 1 to 6 is stored in a separate form, and then the mixture is added to the keratin fibers. A preliminary step consisting in mixing the above at the time of application before use, wherein the composition (A) or composition (B) comprises a solvent as defined in claim 1.
    [22" claim-type="Currently amended] A multicompartment apparatus or dyeing comprising a first compartment having a composition (A) as defined in claim 21 and a second compartment having a composition (B) as defined in claim 21. Kit ".
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    同族专利:
    公开号 | 公开日
    EP1041956A1|2000-10-11|
    BR9907205A|2000-08-29|
    CA2317944A1|1999-07-22|
    RU2224501C2|2004-02-27|
    AU1974099A|1999-08-02|
    DE69927783D1|2005-11-24|
    DE69927783T2|2006-10-19|
    FR2773475B1|2001-02-02|
    EP1041956B1|2005-10-19|
    FR2773475A1|1999-07-16|
    JP2002509096A|2002-03-26|
    AT306890T|2005-11-15|
    PL341714A1|2001-04-23|
    CN1202803C|2005-05-25|
    US6551359B1|2003-04-22|
    WO1999036044A1|1999-07-22|
    AU734426B2|2001-06-14|
    CN1292677A|2001-04-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-01-13|Priority to FR98/00,252
    1998-01-13|Priority to FR9800252A
    1999-01-12|Application filed by 조지안느 플로, 로레알
    1999-01-12|Priority to PCT/FR1999/000037
    2001-04-25|Publication of KR20010034066A
    优先权:
    申请号 | 申请日 | 专利标题
    FR98/00,252|1998-01-13|
    FR9800252A|FR2773475B1|1998-01-13|1998-01-13|Tinctorial composition and methods for dyeing keratinic fibers using the same|
    PCT/FR1999/000037|WO1999036044A1|1998-01-13|1999-01-12|Mixture for the oxidation tinting of keratin fibres containing a laccase and tinting method using said mixture|
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