JP2001519372A - Dehydroascorbic acid-containing composition for dyeing keratin-containing fibers - Google Patents

Abstract

(57) The present invention provides a compound of the formula (I): And a primary or secondary aliphatic or aromatic amine, a nitrogen-containing heterocyclic compound, an α- or ω-amino acid, an oligopeptide consisting of 2 to 9 amino acids, and an aromatic hydroxy compound And / or at least one CH-active compound for dyeing keratin-containing fibers, the composition comprising at least one primary or secondary amino or hydroxyl group-containing compound and / or at least one CH-active compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention relates to a composition for dyeing keratin-containing fibers, which contains a combination of dehydroascorbic acid and a reactive component, use of the composition for dyeing keratin-containing fibers, and keratin-containing fibers And a method for staining the same.

BACKGROUND OF THE INVENTION Keratin-containing fibers, such as hair, wool or fur, are usually dyed with direct dyes or oxidation dyes. Oxidation dyes comprise one or more first intermediates (E
ntwicklerkomponent) or the first intermediate and one or more second intermediates (Kupplerkomponenten) are formed by oxidative coupling. The first and second intermediates are also known as oxidation dye precursors. Commonly used first intermediates are primary aromatic amines further having a free or substituted hydroxy or amino group at the para or ortho position, diaminopyridine derivatives,
Heterocyclic hydrazones, 4-aminopyrazolone derivatives, and 2,4,5,6-tetraaminopyrimidine and derivatives thereof.

Examples are p-phenylenediamine, p-toluylenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis- (2-hydroxyethyl) -p- Phenylenediamine, 2- (2,5-diaminophenyl) -ethanol, 2- (2,5-diaminophenoxy) -ethanol, 1-phenyl-3-carboxyamido-4-amino-5-pyrazolone, 4- Amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-
Aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, and 2,5,6-triamino-4-hydroxypyrimidine.

[0004] The second intermediates are typically m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, and m-aminophenols. Particularly suitable second intermediates are α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-
Aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-aminophenol, 1.3
-Bis- (2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, and 5-methylresorcinol.

With respect to other conventional dye components, reference is particularly made to: “Dermatology”
Series (ed. By Ch. Culnan and H. Maibach), Marcel Dekker Inc. New York / Basel, 1986, Vol. 7, Ch. Zviak, The Science of
Hair Care, Chapter 7 (pp. 248-250; direct dyes) and Chapter 8 (chapter 26).
Pages 4-267; oxidation dyes) and "Europaeische Inventar der Kosmetik-Rohstoffe" 1996 (published by the European Commission and in the form of a disc in Bundesverband Deutscher Industrie- und Handelsunternehmen fuer Ar.
zneimittel, Reformwaren und Koerperpflegemittel e.V. , Mannheim, Germany).

[0006] Oxidation dyes provide high-purity colors with good durability, but the development of such colors is usually carried out under the action of oxidizing agents (eg H ₂ O ₂ ). Oxidants can damage fibers. In addition, certain oxidation dye precursors or mixtures of oxidation dye precursors often irritate people with sensitive skin.
Direct dyes are applied under milder conditions, but have the disadvantage that the durability of the resulting colors is often inadequate.

DISCLOSURE OF THE INVENTION Technical Problem to be Solved by the Invention An object of the present invention is to provide a dye for keratin fibers (particularly human hair), which has a strong color, a gray hiding property, and An object of the present invention is to provide a dye having performance not less than that of a conventional oxidative hair dye in terms of durability and not necessarily containing an oxidizing agent (for example, H ₂ O ₂ ). Another object of the present invention was to provide a dye capable of providing a wide range of shades without staining the skin. Furthermore, the dyes of the present invention, if irritating, are very low.

The solution It has been surprisingly found that the combination of dehydroascorbic acid and at least one other component is very suitable for dyeing keratin-containing fibers. Such a combination results in very vivid and deep colors, leading to a wide range of shades. The use of an oxidizing agent is not necessary, but in principle does not preclude it.

That is, the present invention provides a composition for dyeing a keratin-containing fiber, wherein (A) a formula (I):

Embedded image And (B) a primary or secondary aliphatic or aromatic amine, a nitrogen-containing heterocyclic compound, an α- or ω-amino acid, an oligopeptide comprising 2 to 9 amino acids, and an aromatic compound. At least one primary or secondary amino or hydroxyl group-containing compound selected from group hydroxy compounds, and / or at least one CH
-A composition containing the active compound.

In the context of the present invention, keratin-containing fibers are understood to include wool, fur, feathers, and especially human hair. However, basically, the dyes of the present invention can be used in other natural fibers (eg, cotton, jute, sisal, linen or silk), modified natural fibers (eg, regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetal cellulose), and synthetic fibers. It may be used for dyeing fibers (eg, polyamide, polyacrylonitrile, polyurethane and polyester fibers).

The composition of the present invention comprises the compounds of components A and B,
It is contained in an amount of preferably 0.03 to 65 mmol, more preferably 1 to 40 mmol, per 0 g. The invention also encompasses embodiments containing the reaction products of the individual components A and B. The dehydroascorbic acid used as component A is a known compound, is commercially available, and its synthesis method is described in the literature.

Examples of suitable compounds containing primary or secondary amino groups (eg primary aromatic amines) as component B are: N, N-dimethyl-, N, N-diethyl -, N- (2-hydroxyethyl) -N-ethyl-, N, N-bis- (2-hydroxyethyl)-, N- (2-methoxyethyl)-, 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline dihydrobromide, 2-, 3-, 4-
Aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, o-, p-phenylenediamine, o-toluylenediamine, 2,5-diaminotoluene, -phenol, -phenetol, 4-amino-3-methylphenol, 2- (2,5-diaminophenyl) -ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy)-
Ethanol, 4-methylamino-, 3-amino-4- (2'-hydroxyethyloxy)-, 3,4-methylenediamino-, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro -, 4-methylamino-, 2-methyl-5-amino-, 3-methyl-4-amino-, 2-methyl-5- (2-hydroxyethylamino)-, 6-methyl-3-amino- 2-chloro-, 2-methyl-5-amino-4-chloro-, 3,4-methylenedioxy-, 5- (2-hydroxyethylamino) -4-methoxy-2-methyl-, 4-amino- 2-hydroxymethylphenol, 1,3-diamino-2,4-dimethoxybenzene, 2-, 3-, 4-aminobenzoic acid, -phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-diaminobenzoic acid, 4-, 5-amido Salicylic acid, 3-amino-4-hydroxy -, 4
-Amino-3-hydroxybenzoic acid, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6-amino -7-hydroxynaphthalene-2
-Sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-
Amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-
Naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-, 1,2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene, 2,4,5-
Triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,
6-triaminoresorcinol, 4,5-diaminopyrocatechol, 4,6-diaminopyrogallol, 3,5-diamino-4-hydroxypyrocatechol, an aromatic compound having an additional aromatic group represented by the formula (II) Aniline and phenol:

[0013]

Embedded imageIn the formula (II), R¹Is a hydroxyl group or an amino group (this amino group is_1-4Alkyl, C _1-4 Hydroxyalkyl, or C_1-4Alkoxy-C_1-4Which may be substituted with an alkyl group).^Two, R^Three, R^Four, R^FiveAnd R⁶Is a hydrogen, hydroxyl, or amino group (this amino group is_1-4Alkyl, C_1-4Hydroxyalkyl, C_1-4Aminoalkyl or C_1-4Alkoxy-C_1-4-Optionally substituted with an alkyl group),
Z is a direct bond, saturated or unsaturated C_1-4Carbon chains (which may be hydroxy substituted), carbonyl, sulfonyl or imino groups, oxygen
Or a sulfur atom, or formula (III): Z- (CH_Two-Y-CH_Two—Z ′) o (III) wherein Y is a direct bond, CH_TwoOr a CHOH group, wherein Z and Z ′ are each an oxygen atom, NR⁷Group (R⁷Is hydrogen, C_1-4Alkyl
Is hydroxy-C_1-4-Alkyl group), the group O- (CH_Two) p-NH or NH- (CH _Two ) p'-O (p and p 'are 2 or 3), and o is a number of 1-4. ] It is a group shown by these.

Examples of compound (II) include 4,4′-diaminostilbene, 4,4′-diaminostilbene-2,2′-disulfonate monosodium or disodium salt, 4-amino-4′-dimethyl Aminostilbene, 4,4'-diaminodiphenylmethane, -sulfide, -sulfoxide, -amine, 4,4'-diaminodiphenylamine-2
-Sulfonic acid, 4,4'-diaminobenzophenone, -diphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl, 3,3', 4,4'-tetraaminobenzophenone, 1,3-bis -(2,4-diaminophenoxy) -propane, 1,8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane, 1,3-bis- (4
-Aminophenylamino) -propane, 2-propanol, 1,3-bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis- [2- ( 4-aminophenoxy) -ethyl] -methylamine and N-phenyl-1,4-phenylenediamine. The compounds may be used in free form or as physiologically compatible salts, especially with inorganic acids such as hydrochloric acid or sulfuric acid.

Examples of suitable nitrogen-containing heterocyclic compounds are: 2-, 3-, 4-amino, 2,
-Amino-3-hydroxy-, 2,6-diamino-, 2,5-diamino-, 2,3-diamino-, 2-dimethylamino-5-amino-, 2-methylamino-3-amino-6 Methoxy-2,3-diamino-6-methoxy-2,6-dimethoxy-3,5-diamino-2,4,5-triamino-2,6-dihydroxy-3,4-dimethylpyridine, , 4-Dihydroxy-5,6-diamino-, 4,5,6-triamino-, 4-hydroxy-2,5,6-triamino-, 2-hydroxy-4,5,6-triamino-, 2,4 , 5,6-tetraamino-, 2-methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino-, 2-amino-4-methoxy-6-methylpyrimidine, 3 , 5-Diaminopyrazole, -1,2,4-triazole, 3-amino-, 3-amido No-5-hydroxypyrazole, 2-, 3-,
8-aminoquinoline, 4-amino-quinaldine, 2-, 6-aminonicotinic acid,
5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-aminobenzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline, and indole and indoline derivatives such as 4-, 5-, 6
-, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. The compounds may be used in free form or as physiologically compatible salts, especially with inorganic acids such as hydrochloric acid or sulfuric acid.

Suitable amino acids are any natural and synthetic α-amino acids, examples of which are plant or animal proteins such as collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. It is an amino acid obtained by hydrolysis. Either acidic or alkaline amino acids may be used. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine and tryptophan. Other amino acids, such as 6-aminocaproic acid, may be used.

[0017] Oligopeptides are natural or synthetic oligopeptides and oligopeptides present in polypeptides or protein hydrolysates that have sufficient water solubility to be used in the dyes of the present invention. . Examples of such polypeptides are glutathione and oligopeptides present in hydrolysates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein. Such oligopeptides are preferably used with compounds containing primary or secondary amino groups or with aromatic hydroxy compounds.

Examples of suitable aromatic hydroxy compounds are: 2-, 4-, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, Phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino-, 2- (2-hydroxyethyl)-, 3,4-methylenedioxyphenol, 2,4-, 3, 4-dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 2,4,6
-Trihydroxybenzoic acid, -acetophenone, 2-, 4-chlororesorcinol, 1-naphthol, 1,5-, 2,3-, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalene Sulfonic acid, 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

The following are examples of CH-active compounds: 1,2,3,3-tetramethyl-3H-indolinium iodide, 1,2,3,3-tetramethyl-3H-indolium-p -Toluenesulfonate, 1,2,3,3-tetramethyl-3H-indolium methanesulfonate, Fischer base (1,3,3-trimethyl-2-methyleneindoline), 2,3-dimethylbenzothiazolium iodide 2,2,3-dimethylbenzothiazolium-p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-ethyl-2-quinaldinium iodide, 1-methyl-2-quinaldinium iodide, barbitur Acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, diethylthiobarbituric acid, oxindole, 3-indoxyl acetate, Coumaranone and 1-methyl-3-phenyl-2-pyrazolinone.

In any of the dyes, a plurality of different dyeing substances may be used in combination. Further, a primary or secondary amino group-containing compound, a nitrogen-containing heterocyclic compound,
A plurality of different components selected from the group of aromatic hydroxy compounds or amino acids may be used in combination.

It has proved advantageous to add alkali metal or ammonium salts of C _1-6 carboxylic acids or C _1-6 hydroxycarboxylic acids and carbonic acids to the compositions according to the invention. Examples of such salts are formate, acetate, propionate, butyrate, valerate, caproate, glycolate, lactate and carbonate. As the ammonium cation, a hydroxyalkyl ammonium cation may be used.

When using dehydroascorbic acid according to the present invention, an oxidizing agent (eg, H ₂ O ₂ ) need not be present. However, in some cases, it may be desirable to add hydrogen peroxide or other oxidizing agents to the compositions of the present invention to obtain a lighter color than the keratin-containing fibers to be dyed. The oxidizing agent is typically added to the solution to be applied in an amount of about 0.1%.
It is used in an amount of from 01 to 6% by weight. A preferred oxidizing agent for human hair is H ₂ O ₂ . The dyes of the present invention provide a wide range of shades ranging from yellow to yellow-brown, orange, brown-orange, medium-brown, dark brown, violet, dark violet to black. Good color durability and very low irritation.

In a preferred embodiment, the dyes according to the invention comprise, in addition to the compounds used according to the invention, customary direct dyes in order to further adjust the shade. Direct dyes are selected, for example, from nitrophenylenediamines, nitroaminophenols, anthraquinones or indophenols. Examples of direct dyes are compounds known by the following international or trade names: HC Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76. , HC Blue 2, Disperse Blue 3, Basi
c Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, Basic Brown 17, and picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-amino- 2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,
4-tetrahydroquinoxaline, 4-N-ethyl-1,4-bis- (2'-hydroxyethylamino) -2-nitrobenzene hydrochloride, and 1-methyl-3-nitro-4- (2'-hydroxy Ethyl) -aminobenzene. The compositions of this embodiment of the invention contain the direct dye, preferably in an amount of from 0.01 to 20% by weight, based on the total dye composition.

Further, the compositions of the present invention may include naturally occurring dyes such as henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, ilex bark, sage, soka tree, rapeseed root, catechu , Sedre and Alcanet. The optional oxidation dye precursor or direct dye need not be a single compound. The hair dye of the present invention may contain a small amount of other components resulting from the method of producing each dye, which may adversely affect the dyeing result, or other reasons (for example, toxicological reasons).
May be included as long as it is not necessary to exclude them.

The dyes of the present invention produce high purity colors even at physiologically acceptable temperatures below 45 ° C. Accordingly, the dyes of the present invention are particularly suitable for dyeing human hair. For application to human hair, the dyes are typically combined in a water-containing cosmetic carrier. Suitable water-containing cosmetic carriers are, for example, creams, emulsions, gels or surfactant-containing effervescent solutions (eg shampoos) or other formulations suitable for application to keratin-containing fibers. Dyes may be combined in a water-free carrier.

The dyes according to the invention may also contain known active substances, additives and auxiliaries normally present in such formulations. Dyes often contain at least one surfactant. In principle, any of the anionic, zwitterionic, amphoteric, nonionic and cationic surfactants are suitable. However, in many cases it has proven advantageous to choose from anionic, zwitterionic or nonionic surfactants.

[0027] Anionic surfactants suitable for the formulations of the present invention are anionic surfactants suitable for use on the human body. Such materials have a water-solubilizing anionic group, such as a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, esters, ethers, amides and hydroxyl groups can also be present in the molecule. Sodium, potassium and ammonium salts and mono-,
The following are examples of suitable anionic surfactants in the form of di- and trialkanol ammonium salts (2 or 3 carbon atoms in the alkanol group):

A straight-chain fatty acid (soap) having 10 to 22 carbon atoms; a formula: R—O— (CH ₂ —CH ₂ O) _x —CH ₂ —COOH wherein R is 10 carbon atoms
-22, wherein x = 0 or 1-16. An acyl carboxylic acid having 10 to 18 carbon atoms in an acyl group, an acyl tauride having 10 to 18 carbon atoms in an acyl group, an acyl isethionate having 10 to 18 carbon atoms in an acyl group, an alkyl group Mono- and dialkyl sulfosuccinates having 8 to 18 carbon atoms, and monoalkyl polyoxyethyl sulfosuccinate having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups; and linear alkane having 12 to 18 carbon atoms. sulfonates, linear α- olefin sulfonates, of-carbon atoms from 12 to 18 fatty α- sulfo fatty acid methyl ester-12 to 18 carbon atoms, - _{formula: R-O- (CH 2 -CH} 2 O) x -SO ₃ H [wherein, R is preferably a linear alkyl group having 10 to 18 carbon atoms, and x = 0 or 1 to 12. Alkyl sulfates and alkyl polyglycol ether sulfates according to DE-A-3725030, mixtures of surface-active hydroxysulfonates, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-3723354. A sulfonate of an unsaturated fatty acid having 12 to 24 carbon atoms / 1 to 6 double bonds according to DE-A-3926344; and about 2 to 15 molecules of ethylene oxide and / or propylene oxide in a fatty alcohol having 8 to 22 carbon atoms. Esters of tartaric acid and citric acid with the alcohol in the form of an added product.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids (alkyl groups having from 10 to 18 carbon atoms, up to 12 glycol ether groups in the molecule), and especially And salts of saturated and especially unsaturated _C8-22 carboxylic acids such as oleic, stearic, isostearic and palmitic acids.

[0030] In the present invention, zwitterionic surfactants, at least one quaternary ammonium group and at least one -COO ^- or -SO ₃ ^- is a surface-active compound having a group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N, N-dimethylammonium glycinate (for example coconut oil alkyldimethylammonium glycinate), N-acylaminopropyl-N, N-dimethyl. Ammonium glycinate (for example, coconut oil acylaminopropyldimethylammonium glycinate) and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazoline having 8 to 18 carbon atoms in the alkyl or acyl group; Oil acylaminoethyl hydroxyethyl carboxymethyl glycinate. Preferred zwitterionic surfactants are CT
It is a fatty acid amide derivative known as FA name Cocamidopropyl Betaine.

The amphoteric surfactant has, in addition to a C _8-18 alkyl or acyl group, at least one free amino group and at least one —COOH or —SO ₃ H group in the molecule. It is a surfactant compound that can form a salt. Examples of suitable amphoteric surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyl Taurine, N-alkyl sarcosine,
2-alkylaminopropionic acid and alkylaminoacetic acid (the alkyl group having about 8 to 18 carbon atoms). Particularly preferred amphoteric surfactants are N-coconut alkylaminopropionate, coconut acylaminoethylaminopropionate,
And C _12-18 acyl sarcosine.

The nonionic surfactant has, for example, a polyol group, a polyalkylene glycol ether group, or a combination of a polyol / polyglycol ether group as a hydrophilic group. Examples of such compounds are:-straight chain fatty alcohols having 8 to 22 carbons, fatty acids having 12 to 22 carbons, and alkyl phenols having 8 to 15 carbons in the alkyl group, ethylene oxide 2-3.
0 mol and / or propylene oxide 0-5 moles adducts, ethylene oxide 1 to 30 mole adducts of glycerol, C _12-22 fatty mode monoester and diesters, & C _8-22 alkyl mono - and oligoglycosides and their Ethoxylated analogs, 5-60 moles of ethylene oxide adduct of castor oil and hydrogenated castor oil, ethylene oxide adduct of sorbitan fatty acid ester, ethylene oxide adduct of fatty acid alkanolamide.

Examples of suitable cationic surfactants for use in the hair treatment formulations of the present invention include:
Among others, quaternary ammonium compounds. Preferred quaternary ammonium compounds are ammonium halides such as: alkyltrimethylammonium chloride, dialkyldimethylammonium chloride and trialkylmethylammonium chloride such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride , Lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Other cationic surfactants suitable for use in accordance with the present invention are quaternized protein hydrolysates.

The following cationic silicone oils are also suitable for use in accordance with the invention: commercial products Q2-7224 (manufacturer: Dow Corning; stabilized trimethylsilyl amodimethicone), Dow Corning 929 Emulsion (A
containing hydroxyamino-modified silicone, also known as modimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer:
Wacker), and Abil ™ -Quat 3270 and 3272 (manufacturer: Th.
Goldschmidt; diquaternary polydimethylsiloxane, Quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines, such as Tego Amid (
Stearylamidopropyldimethylamine, available under the trade name S18, exhibits a favorable conditioning effect and is particularly readily biodegradable. Quaternary ester compounds, so-called "esterquats", such as methylhydroxyalkyldialkyloxyalkylammonium methosulfate (commercially available under the trade name Stepantex ™), are also readily biodegradable.

An example of a quaternary sugar derivative suitable for use as a cationic surfactant is Glucquat ™ 100 (CTFA name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride), a commercial product. The compound having an alkyl group used as a surfactant may be a single compound. However, typically such compounds are prepared from natural plant or animal sources and are thus obtained as a mixture of compounds having different alkyl chain lengths depending on the source.

Surfactants that are ethylene oxide and / or propylene oxide adducts of fatty alcohols, or derivatives of such adducts, may have products with “normal” homolog distribution and products with narrow homolog distribution Any of the objects may be used.
Products having a "normal" homolog distribution are homolog mixtures obtained by reacting fatty alcohols with alkylene oxides using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. On the other hand, a narrow homolog distribution is obtained, for example, when hydrotalcite, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalyst. It may be advantageous to use products with a narrow homolog distribution.

Other active substances, auxiliaries and additives are exemplified by: nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymer, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymer, and polysiloxanes Water-soluble polymers such as quaternized cellulose ethers, quaternary group-containing polysiloxanes, dimethyldiallylammonium chloride polymer, acrylamide / dimethyldiallylammonium chloride copolymer, dimethylaminoethyl methacrylate / vinylpyrrolidone copolymer quaternized with diethyl sulfate , Vinylpyrrolidone / imidazolinium metochloride copolymer, and quaternized polyvinyl alcohol; zwitterionic and amphoteric polymers, such as Amidopropyl-trimethylammonium chloride / acrylate copolymer, and octylacrylamide / methyl methacrylate / t-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymer; anionic polymers such as polyacrylic acid, cross-linked polyacrylic acid, vinyl acetate / croton Acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers, and acrylic acid / ethyl acrylate / Nt-butylacrylamide terpolymers,

Thickeners, such as agar, guar gum, alginate, xanthan gum, gum arabic, indian gum, locust bean flour, linseed gum, dextran, cellulose derivatives (eg methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose), starch fractions and derivatives (eg Amylose,
Amylopectin and dextrin), clay (e.g., bentonite), or pure synthetic hydrocolloid (e.g., polyvinyl alcohol); Structures, e.g., glucose, and maleic acid; Hair conditioning compounds, e.g., phospholipids (e.g., soy lecithin, egg lecithin and kephalin) Hydrolysates, especially elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, condensation products of them with fatty acids, and quaternized protein hydrolysates)

Perfume oils, dimethyl isosorbide and cyclodextrin; solubilizing agents, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol; antidandruff agents, such as Piloctone Olamine and Zinc Omadine; Active substances, such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acid and its salts, plant extracts and vitamins, cholesterol, UV absorbers,

• Consistency factors, such as sugar esters, polyol esters or polyol alkyl ethers; • Fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, • Fatty acid alkanolamides, • Complexing agents Swelling and penetrating agents such as glycerol, propylene glycol monoethyl ether, carbonate, hydrogen carbonate, guanidines, ureas, primary, secondary and tertiary phosphates, imidazoles, tannins , pyrrole, - opacifiers, such as latex, & pearlescent agent such as ethylene glycol mono - and distearate, - propellants, such as propane / butane mixtures, N ₂ O, dimethyl ether, CO ₂ Oyo Air, as well as, anti-oxidants.

To prepare the dyestuffs of the present invention, the components of the water-containing carrier are used in amounts customary for that purpose. For example, the emulsifier is used at a concentration of 0.5 to 30% by weight and the thickener is used at a concentration of 0.1 to 25% by weight, based on the whole dye. The addition of ammonium or metal salts to the dye can be advantageous to the dyeing results. Examples of suitable metal salts are formate, alkali metal (eg, potassium, sodium or lithium), alkaline earth metals (eg, magnesium, calcium, strontium or barium), aluminum, manganese, iron, cobalt, copper, or zinc. , Carbonate, halide, sulfate, butyrate, valerate, caproate,
Acetate, lactate, glycolate, tartrate, citrate, gluconate, propionate, phosphate and phosphonate. Preferred are sodium acetate, lithium bromide, calcium bromide, calcium gluconate, zinc chloride, zinc sulfate, magnesium chloride, magnesium sulfate, ammonium carbonate, ammonium chloride and ammonium acetate. Such salts are preferably present in an amount of 0.03 to 65 mmol, more preferably 1 to 40 mmol, per 100 g of total dye.

The pH value of the ready-to-use dyeing composition is usually in the range from 2 to 11, preferably from 5 to 9. The invention relates to compounds of formula (I) in aqueous or organic-aqueous solutions:

Embedded image Of dehydroascorbic acid, a primary or secondary aliphatic or aromatic amine, a nitrogen-containing heterocyclic compound, an α- to ω-amino acid, an amino acid 2 to
Keratin in the presence of at least one primary or secondary amino or hydroxyl group-containing compound selected from 9 oligopeptides and aromatic hydroxy compounds, and / or at least one CH-active compound It also relates to the use for dyeing of the contained fibers.

The present invention also relates to a method for dyeing keratin-containing fibers, wherein a dye containing dehydroascorbic acid and the compound of component B is used as a dye component. To carry out the process according to the invention, the dyestuffs are usually applied to the hair as a formulation in a 100 g quantity of a water-containing cosmetic carrier, left for about 30 minutes and then rinsed off or washed off with a commercial shampoo.

The components A and B may be applied to the hair simultaneously or sequentially.
In the latter case, either of the two components may be applied first. The optional ammonium or metal salt may be added to either the first component or the second component. There may be an interval of up to 30 minutes between the application of the first component and the application of the second component. The fibers may be pretreated with a salt solution.

Component A and Component B of the composition of the present invention may be stored separately or together,
It can be stored as a liquid or paste-like formulation (aqueous or water-free) or as a dry powder. When the components are stored together as a liquid formulation, the formulation is:
It should be substantially water-free to avoid reaction of the components. If the reactive components are stored separately, mix well immediately before application. If the components are stored as a dry powder, a homogenous mixture is usually prepared by adding a predetermined amount of warm water (50-80 ° C) before application.

Example Preparation of Dyeing Solution Dehydroascorbic acid (10 mmol), component B (10
(Mmol), sodium acetate (10 mmol), and a 20% fatty alkyl ether sulfate solution (1 drop). The suspension was briefly heated to about 80 ° C., filtered after cooling and then adjusted to pH6. Unpretreated 90% gray human hair tufts were placed in the above staining solution at 30 ° C. for 30 minutes. Thereafter, the dyed human tufts are rinsed with warm water for 30 seconds, and a warm air stream (30-40)
C) and then passed through a comb. The color was evaluated visually under sunlight. The following table shows the colors and color depths.

The color strength was evaluated according to the following criteria: −: very light even with color (+): low purity +: medium purity + (+): medium to high purity ++: high purity ++ ( +): High or ultra-high purity +++: Ultra-high purity

[0049]

[Table 1]

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Horst Hefkes D-40595 Düsseldorf, Germany, Carlo-Schmidt-Strär 113, F-term (reference) 4C083 AB311 AB411 AC231 AC232 AC301 AC471 AC472 AC531 AC551 AC552 AC581 AC621 AC782 AC791 AC841 AC842 AC851 AC852 AD411 AD641 AD642 BB04 BB05 CC36 DD23 EE26

Claims (9)

[Claims] 1. A composition for dyeing keratin-containing fibers, comprising: (A) a compound of the formula (I): And (B) a primary or secondary aliphatic or aromatic amine, a nitrogen-containing heterocyclic compound, an α- or ω-amino acid, an oligopeptide comprising 2 to 9 amino acids, and an aromatic compound. At least one primary or secondary amino or hydroxyl group-containing compound selected from group hydroxy compounds, and / or at least one CH
-A composition containing the active compound. 2. The composition according to claim 1, wherein component B is selected from the group consisting of the following compounds: primary or secondary amines, N- (2-hydroxyethyl) -N-ethyl-, N- (2-methoxyethyl)-, 2,3-, 2,4-, 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, N, N-bis- (
2-hydroxyethyl) -p-phenylenediamine, 2,5-dihydroxy-4-
Morpholinoaniline dihydrobromide, 2-, 3-, 4-aminophenol,
o-, p-phenylenediamine, 2,4-diaminophenoxyethanol, 2- (
2,5-diaminophenyl) -ethanol, 2,5-diaminotoluene, -phenol, -phenetol, 4-methylamino-, 3-amino-4- (2'-hydroxyethyloxy)-, 3,4 -Methylenediamino-, 3,4-methylenedioxyaniline, 3-amino-2,4-dichloro-, 4-methylamino-, 3,4-methylenedioxy-, 3-methyl-4-amino-, 2-methyl-5- (2-hydroxyethylamino)-, 6-methyl-3-amino-2-chloro-, 5- (2-hydroxyethylamino) -4-methoxy-2-methyl-, 4-amino -2-aminomethylphenol, 4-amino-2-hydroxymethylphenol, 3,4-methylenedioxyphenol, 1,3-diamino-2,4-dimethoxybenzene, 2-,
3-, 4-aminobenzoic acid, -phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,
4-, 3-, 5-diaminobenzoic acid, 4-, 5-aminosalicylic acid, 3-amino-4-hydroxy-, 4-amino-3-hydroxybenzoic acid, 2-, 3-, 4-aminobenzenesulfonic acid , 3-amino-4-hydroxybenzenesulfonic acid, 4
-Amino-3-hydroxynaphthalenesulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7 -Disulfonic acid, 3
-Amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1
, 3,5-, 1,2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene tetrahydrochloride, 2,4,5-triaminophenol trihydrochloride, pentaaminobenzene Pentahydrochloride, hexaaminobenzene
Hexahydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminopyrocatechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5-diamino-4-hydroxypyrocatechol Sulfates, aromatic anilines with additional aromatic groups and phenols, such as 4,4'-diaminostilbene dihydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid sodium salt, 4,4'- Diaminodiphenylmethane, -sulfide, -sulfoxide, -amine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, -diphenyl ether, 3,3 ', 4,4'-tetraaminodiphenyl. Tetrahydrochloride, 3,3 ', 4
, 4'-Tetraaminobenzophenone, 1,3-bis- (2,4-diaminophenoxy) -propane tetrahydrochloride, 1,8-bis- (2,5-diaminophenoxy) -3,6-dioxa Octane tetrahydrochloride, 1,3-bis- (4-
Aminophenylamino) -propane, 2-propanol, 1,3-bis- [N- (
4-aminophenyl) -2-hydroxyethylamino] -2-propanol, selected from the group consisting of N, N-bis- [2- (4-aminophenoxy) -ethyl] -methylamine trihydrochloride; A nitrogen-containing heterocyclic compound, comprising 2-, 3-, 4-amino, 2-amino-3-
Hydroxy, 2,6-diamino-, 2,5-diamino-, 2,3-diamino-, 2-dimethylamino-5-amino-, 3-amino-2-methylamino-6-methoxy-, 2, 3-diamino-6-methoxy-, 3,5-diamino-2,6-dimethoxy-, 2,4,5-triamino-, 2,6-dihydroxy-3,4-dimethylpyridine, 4,5,6 -Triamino-, 2-hydroxy-4,5,6-triamino-, 4
-Hydroxy-2,5,6-triamino-, 2,4,5,6-tetraamino-, 2-methylamino-4,5,6-triamino-, 2,4-, 4,5-diamino-, 2-amino-4-methoxy-6-methylpyrimidine, 2,3,4-trimethylpyrrole,
2,4-dimethyl-3-ethylpyrrole, 3,5-diaminopyrazole, -1,2,
4-triazole, 3-amino-, 3-amino-5-hydroxypyrazole, 2
-, 3-, 8-aminoquinoline, 4-aminoquinaldine, 2-, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-, 6-aminoindazole, 5-, 7-
Aminobenzimidazole, -benzothiazole, 2,5-dihydroxy-4-morpholinoaniline, and indole and indoline derivatives such as 4-,
5-, 6-, 7-aminoindole, 4-, 5-, 6-, 7-hydroxyindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline, and their physiological compatibility Aromatic hydroxy compounds, selected from the group consisting of acidic salts (preferably salts with inorganic acids); 2-, 4-, 5-methylresorcinol;
2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-, 3-, 4-methoxy-, 3-dimethylamino-, 2- ( 2-hydroxyethyl)-, 3,4-methylenedioxyphenol, 2,4-, 3,4
-Dihydroxybenzoic acid, -phenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, -acetophenone, 2-, 4-chlororesorcinol, 1-naphthol, 1,5-, 2,3-, 2, 7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid, 3,6-dihydroxy-2,7
Selected from the group consisting of -naphthalenesulfonic acids; CH-active compounds, 1,2,3,3-tetramethyl-3H-indolymium iodide, 1,2,3,3-tetramethyl-3-indo Lium-p-toluenesulfonate, 1,2,3,3-tetramethyl-3-indolium methanesulfonate, 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium- p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1-ethyl (methyl) -2-quinaldinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethyl (ethyl) thiobarbituric acid, A member selected from the group consisting of oxindole, coumaranone and 1-methyl-3-phenyl-2-pyrazolinone. 3. The compounds of components A and B each contain 100% of the total dye composition.
3. The composition according to claim 1, wherein the composition is present in an amount of from 0.03 to 65 mmol per gram. 4. The method according to claim 1, which comprises an alkali metal salt, an ammonium salt and / or a hydroxyalkyl-substituted ammonium salt of C _1-6 carboxylic acid, C _1-6 hydroxycarboxylic acid and / or carbonic acid. A composition as described. 5. The composition according to claim 1, wherein the oxidizing agent is used in an amount of from 0.01 to 6% by weight, based on the applied solution. 6. The composition according to claim 1, wherein H ₂ O ₂ is used as the oxidizing agent. 7. The composition according to claim 1, wherein an anionic, zwitterionic and / or nonionic surfactant is used. 8. A compound of formula (I) in an aqueous or organic-aqueous solution: Of dehydroascorbic acid, a primary or secondary aliphatic or aromatic amine, a nitrogen-containing heterocyclic compound, an α- to ω-amino acid, an amino acid 2 to
Keratin in the presence of at least one primary or secondary amino or hydroxyl group-containing compound selected from 9 oligopeptides and aromatic hydroxy compounds, and / or at least one CH-active compound Use for dyeing of contained fibers. 9. A method for dyeing keratin-containing fibers, comprising: (A) a method of formula (I): And (B) a primary or secondary aliphatic or aromatic amine, a nitrogen-containing heterocyclic compound, an α- or ω-amino acid, an oligopeptide comprising 2 to 9 amino acids, and an aromatic compound. A dye composition containing at least one primary or secondary amino or hydroxyl group-containing compound selected from group III hydroxy compounds, and / or at least one CH-active compound, and a usual cosmetic ingredient; A method comprising applying and leaving for a period of time (typically about 30 minutes), followed by rinsing or shampooing.