JP2001510782A - Use of di- and oligoacylaromatics to dye keratin-containing fibers - Google Patents

Abstract

(57) [Summary] The present invention relates to a compound represented by the formula (1): Wherein R ¹ and R ² are each a lower (C _1-4 ) alkyl group, aryl or heteroaryl group, and R ³ , R ⁴ and R ⁵ are each hydrogen, halogen, C _1-4- It is an alkyl group, a C _1-4 -alkoxyl group or a hydroxy- (C _1-4 ) -alkoxyl group, a hydroxyl group, a nitro group, an amino group, or a C _1-4 acyl group. Primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, amino acids 2 to 9 of aromatic di- and oligoacyl compounds which are not 1,2-diacetylbenzenes Keratin-containing compounds in the presence of at least one primary or secondary amino or hydroxyl group-containing compound selected from the group consisting of oligopeptides and aromatic hydroxy compounds, and / or at least one CH-active compound. It relates to the use for dyeing fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention relates to an aromatic diene for dyeing keratin-containing fibers (particularly human hair).
And use of an oligoacyl compound, a preparation containing an aromatic di- and oligoacyl compound for dyeing keratin-containing fibers, and a method for dyeing keratin-containing fibers.

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, p-aminophenol, o-aminophenol, 1- (2′-hydroxyethyl) -2,5-diaminobenzene, N, N-bis -(2-hydroxyethyl) -p-phenylenediamine,
2- (2,5-diaminophenoxy) -ethanol, 1-phenyl-3-carboxamido-4-amino-5-pyrazolone, 4-amino-3-methylphenol,
2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6 -Diaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2-hydroxyethylaminomethyl-4-aminophenol, 4,4'-diaminodiphenylamine, 4-amino-3-fluorophenol, 2 -Aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, bis- (2-hydroxy-5-aminophenyl) -methane, 1,4-bis- (4-aminophenyl) -diazacyclo Heptane, 1,3-bis- (N- (2-hydroxyethyl) -N- (4-aminophenylamino))-2-propanol, 4-amino-2- (2-hydro (Xyethoxy) -phenol, and EP074
4,74-Diaminopyrazole derivatives according to 0741 or WO 94/08970, for example 4,5-diamino-1- (2'-hydroxyethyl) pyrazole.

[0004] The second intermediates are typically m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, and m-aminophenols. Particularly suitable second intermediates are 1-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, o-aminophenol, 5-amino-2-methylphenol, m-aminophenol , Resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-aminophenol, 1,3
-Bis- (2,4-diaminophenoxy) -propane, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2-amino-3-hydroxypyridine, 2,6-dihydroxy-3,4-diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 4-amino-2-hydroxytoluene, 2,6-bis- (2-hydroxyethylamino) -toluene, 2,4-diaminophenoxyethanol, 1-methoxy-2-amino-4- (2-hydroxyethylamino (No) -benzene, 2-methyl-4-chloro-5-aminophenol, 6-methyl-1,2,3,4-tetrahydro Quinoxaline, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 2,6-dimethyl-3-aminophenol, 3-amino-6-methoxy-2-methylaminophenol, 2-hydroxy-4 -Aminophenoxyethanol, 2-methyl-5- (2-hydroxyethylamino) -phenol, and 2,6-dihydroxy-3,4-dimethylpyridine.

For dyes suitable for use in the hair coloring and coloring preparations according to the invention, reference is also made in particular to: Zviak, The Science of Hair Care, Chapter 7 (pp. 248-250; direct dyes) and Chapter 8 (pp. 264-267; oxidation dye precursors) [published as Volume 7 in the "Dermatology" series. Things (Ch
. Culnan and H.C. Maibach), Marcel Dekker Inc. , New York / Basel, 1986], and "Europaeische Inventar der Kosmetik-Ro"
hstoffe ”(published by Europaeische Gemeinschaft and bundled in disc form
sverband Deutscher Industrie- und Handelsunternehmen fuer Arzneimitt
el, 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. US Pat. No. 3,158,542 describes a system for dyeing keratin-containing fibers containing a combination of 1,2-diacetylbenzene or an aliphatic 1,2-diacetyl compound and an amine (eg an amino acid and an aliphatic or aromatic amine). ing. However, the system has the disadvantage of having a limited range of shades and, when used in humans, the aromatic 1,2-diacetylated compounds stain the scalp excessively.

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 which can provide a wide range of colors. Skin staining should be avoided. Furthermore, the dyes of the present invention, if irritating, are very low.

(Solution method) [0008] The present invention provides the following formula (1):

Embedded image [Wherein, R ¹ and R ² are each a lower (C _1-4 ) alkyl group, aryl or heteroaryl group, and R ³ , R ⁴ and R ⁵ are each hydrogen, halogen, C _1-4 alkyl A C _1-4 alkoxyl group or a hydroxy- (C _1-4 ) -alkoxyl group, a hydroxyl group, a nitro group, an amino group, or a C _1-4 acyl group. And a primary or secondary aliphatic or aromatic amine, a nitrogen-containing heterocyclic compound, an amino acid, an amino acid 2 to an aromatic di- or oligoacyl compound which is not a 1,2-diacetylbenzene. 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 relates to the use for dyeing of contained fibers.

Surprisingly, it has been found that the combination of the aromatic di- and oligoacyl compounds with an amine or a CH-active compound 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. Basically an oxidizing agent may be present, but is not essential. 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 invention also encompasses the use of substances whose individual components are the products of reaction with one another.

The present invention provides a preparation for dyeing keratin-containing fibers (particularly human hair), comprising: (A) one or more di- and oligoacyl compounds represented by the above formula (1); ) At least one primary or secondary selected from primary or secondary aliphatic or aromatic amines, nitrogen-containing heterocyclic compounds, amino acids, oligopeptides consisting of 2 to 9 amino acids and aromatic hydroxy compounds; It also relates to formulations containing compounds containing secondary amino or hydroxyl groups and / or at least one CH-active compound.

Suitable compounds (1) that can be used as component A include 1,3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2-benzoylacetophenone, 2- ( 4-methoxybenzoyl) -acetophenone, 2-
(2-furoyl) -acetophenone, 2- (2-pyridoyl) -acetophenone, and 2- (3-pyridyl) -acetophenone, and mixtures thereof. 1,4-Diacetylbenzene, 2- (2-furoyl) -acetophenone, and 2- (3-pyridoyl) -acetophenone are preferred.

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-, m-toluylenediamine, 2,5-diaminotoluene, -phenol, -Phenetol, 4-amino-3-methylphenol, 2- (2,5-diaminophenyl) -ethanol, 2- (2,4-diaminophenoxy) -ethanol, 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 Phenol, 4-amino-2-hydroxymethylphenol, 1,3-diamino-2,4-dimethoxybenzene,
-, 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-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 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, further represented by formula (II) Aromatic aniline and phenol having an aromatic group:

[0013]

Embedded imageIn the formula (II), R⁶Is 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).⁷, R⁸, R⁹, R^TenAnd R¹¹Is a hydrogen, hydroxyl, or amino group (the amino group is a C_1-4Alkyl, C_1-4Hydroxyalkyl, C_1-4Aminoalkyl or C_1-4Alkoxy-C_1-4-May be substituted with an alkyl group),
X 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, NR¹²Group (R¹²Is hydrogen, C_1-4Alkyl
Or hydroxy-C_1-4-Alkyl group), the group O- (CH_Two) p-NH or NH- (C
H_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 salt or disodium salt, 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, , 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 amino acids, examples of which are
An amino acid obtained by hydrolysis of a plant or animal protein (eg, collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein). Either acidic or alkaline amino acids may be used. Preferred amino acids are arginine, histidine, tyrosine, phenylalanine, DOPA (dihydroxyphenylalanine), ornithine, lysine and tryptophan.

[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-tetramethylindolinium-p-toluene Sulfonate, 1,2,3,3-tetramethyl-3H-indolium methanesulfonate, Fischer base (1,3,3-trimethyl-2-methylindoline), 2,
3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium-p-toluenesulfonate, rhodanine, rhodanin-3-acetic acid, 1-ethyl-2-quinaldinium iodide, 1-methyl-2 -Quinaldinium iodide, barbituric 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 plurality of different components selected from the group consisting of a primary or secondary amino group-containing compound, a nitrogen-containing heterocyclic compound, an aromatic hydroxy compound and an amino acid may be used in combination. (When the auxiliary action of the added substance is not impaired). When using aromatic di- and oligoacyl compounds 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 formulations of the present invention to obtain a lighter color than the keratin-containing fibers to be dyed. The oxidizing agent is usually used in an amount of 0.01 to 6% by weight, based on the solution applied. 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-orange to brown-black. Good color durability and very low irritation. In a preferred embodiment, the dyes according to the invention contain, in addition to the compounds used according to the invention, customary direct dyes in order to further adjust the shade. Direct dyes, for example, nitrophenylenediamines, nitroaminophenols, azo dyes,
Select from anthraquinones or indophenols. Preferred direct dyes are the compounds known under the following international or trade names: HC Yellow 2, HC Yellow
low 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse
Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue
2, HC Blue 12, Disperse Blue 3, Basic Blue 99, HC Violet
1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, B
asic Brown 16, Basic Brown 17, and 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitrotoluidine, picramic acid , 2-
Amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid, and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. The formulations according to this aspect of the invention contain the direct dye, preferably in an amount of 0.01 to 20% by weight, based on the total dye formulation.

Furthermore, the preparations according to the invention may contain naturally occurring dyes such as henna red, henna red
It may also contain neutral, henna black, chamomile flowers, sandalwood, black tea, ilex bark, sage, sapwood, rapeseed root, catechu, Sedre and alkanet. Other dye components that may be present in the dyes of the present invention are indoles and indolines and their physiologically compatible salts. Preferred examples are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,
6,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 6-hydroxyindole, 6-aminoindole, and 4-aminoindole; 5,6-dihydroxyindolin , N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-
Dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 6-hydroxyindoline, 6-aminoindoline, and 4-aminoindoline.

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 highly pure 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 dyestuffs according to the invention may also contain known active substances, additives and auxiliaries usually 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.

Suitable anionic surfactants 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; formula: RO— (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 (having 10 to 18 carbon atoms in the alkyl group and 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.

[0028] 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 dialkylammonium methosulfate and methylhydroxyalkyldialkyloxyalkylammonium methosulfate (commercially available under the trade name Stepantex®) are also readily available. It is 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, 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 below: 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, acacia, indian gum, carob 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 conventional amounts 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 dye preparation is usually in the range of 2 to 11, preferably 5 to 9. For dyeing keratin-containing fibers (especially human hair), dyes are usually
It is applied to the hair as a formulation in a 0 g quantity of a water-containing cosmetic carrier and left for about 30 minutes before rinsing or washing off with a commercial shampoo. The compounds of component A and component 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.

The components A and B of the formulations of the present invention may be stored separately or together and may 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 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 a Dyeing Solution Suspension of a dyeing component (10 mmol), amine (10 mmol), sodium acetate (10 mmol) and a 20% fatty alkyl ether sulfate solution (1 drop) in 100 ml of water A liquid was prepared. 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. Table 1 shows the colors and color depths.

The color depth 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

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

[Table 5]

[0050]

[Table 6]

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Horst Hefkes D-40595 Düsseldorf, Germany, Carlo-Schmidt-Strär No. 113 F-term (reference) 4C083 AB411 AC151 AC211 AC311 AC471 AC531 AC532 AC551 AC552 AC581 AC781 AC791 AC792 AC811 AC851 AC852 AC861 AD411 BB04 BB05 BB07 BB47 CC36 EE26

Claims (9)

[Claims] (1) Formula (1): [Wherein, R ¹ and R ² are each a lower (C _1-4 ) alkyl group, aryl or heteroaryl group, and R ³ , R ⁴ and R ⁵ are each hydrogen, halogen, C _1-4 alkyl A C _1-4 alkoxyl group or a hydroxy- (C _1-4 ) -alkoxyl group, a hydroxyl group, a nitro group, an amino group, or a C _1-4 acyl group. And a primary or secondary aliphatic or aromatic amine, a nitrogen-containing heterocyclic compound, an amino acid, an amino acid 2 to an aromatic di- or oligoacyl compound which is not a 1,2-diacetylbenzene. 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. 2. A preparation for dyeing keratin-containing fibers, especially human hair,
(A) Formula (1): [Wherein, R ¹ and R ² are each a lower (C _1-4 ) alkyl group, aryl or heteroaryl group, and R ³ , R ⁴ and R ⁵ are each hydrogen, halogen, C _1-4 alkyl A C _1-4 alkoxyl group or a hydroxy- (C _1-4 ) -alkoxyl group, a hydroxyl group, a nitro group, an amino group, or a C _1-4 acyl group. One or more aromatic di- and oligoacyl compounds which are not 1,2-diacetylbenzenes, and (B) a primary or secondary aliphatic or aromatic amine, At least one compound containing a primary or secondary amino or hydroxyl group selected from a ring compound, an amino acid, an oligopeptide consisting of 2 to 9 amino acids and an aromatic hydroxy compound, and / or at least one CH- Preparations containing the active compound. 3. Component A comprises 1,3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2-benzoylacetophenone,
3. The composition of claim 2, wherein the composition is selected from the group consisting of 2- (4-methoxybenzoyl) -acetophenone, 2- (2-furoyl) -acetophenone, 2- (2-pyridyl) -acetophenone, and 2- (3-pyridyl) -acetophenone. A formulation as described. 4. The preparation according to claim 2, wherein component B is selected from the group consisting of the following compounds: a primary or secondary amine, wherein 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-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 tetrahydrochloride, 2,4,5-triaminophenol trihydrochloride, pentaaminobenzene pentahydrochloride, hexaaminobenzene hexa Hydrochloride, 2,4,6-triaminoresorcinol trihydrochloride, 4,5-diaminopyrocatechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5-diamino-4-hydroxypyrocatechol. Sulfates, aromatic anilines and phenols with additional aromatic groups, for example 4,4'-diamido Stilbene 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 ', 4,4'-Tetraaminobenzophenone, 1,3-bis- (2,4-diaminophenoxy) -propane tetrahydrochloride, 1,8-bis- (2,5-diaminophenoxy) -3,6 -Dioxaoctane-tetrahydrochloride, 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 trihydrochloride; a nitrogen-containing heterocyclic compound, -, 3-, 4-amino, 2-amino-3-
Hydroxy-, 3-amino-2-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-,
, 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 physiologically compatible salts (preferably salts with inorganic acids); aromatic hydroxy compounds, 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. 5. The compounds of components A and B each comprise 100 g of the total dye preparation
Formulation according to any of claims 2 to 4, used in an amount of from 0.03 to 65 mmol, in particular from 1 to 40 mmol, per mol. 6. The preparation according to claim 2, wherein the oxidizing agent is used in an amount of 0.01 to 6% by weight, based on the applied solution. 7. The preparation according to claim ₂ , wherein H ₂ O ₂ is used as the oxidizing agent. 8. The preparation according to claim 2, wherein an anionic, zwitterionic and / or nonionic surfactant is used. 9. A method for dyeing keratin-containing fibers, comprising: (A) formula (1): [Wherein, R ¹ and R ² are each a lower (C _1-4 ) alkyl group, aryl or heteroaryl group, and R ³ , R ⁴ and R ⁵ are each hydrogen, halogen, C _1-4 alkyl A C _1-4 alkoxyl group or a hydroxy- (C _1-4 ) -alkoxyl group, a hydroxyl group, a nitro group, an amino group, or a C _1-4 acyl group. One or more aromatic di- and oligoacyl compounds which are not 1,2-diacetylbenzenes, and (B) a primary or secondary aliphatic or aromatic amine, At least one primary or secondary amino or hydroxyl group-containing compound selected from a ring compound, an amino acid, an oligopeptide consisting of 2 to 9 amino acids and an aromatic hydroxy compound, and / or at least one CH-active compound As well as applying a dye preparation containing conventional cosmetic ingredients to the keratin-containing fibers, leaving it for a certain period of time (usually about 30 minutes) and then rinsing or shampooing.