DE4335624A1 - Hair dye compsn. contg. substd. quinone cpd. - Google Patents

Abstract

A dye compsn. for keratinous fibres, esp. human hair, comprises: (A) a quinone cpd. of formula (I); (B) either (i) at least one aminoacid or an oligopeptide made up of 2-9 aminoacids, (ii) at least one aniline deriv., (iii) at least one aliphatic amine, (iv) at least one phenol deriv., or (v) at least one benzoic acid deriv.; and (C) an aq. carrier. R<1>-R<4> = H, halogen, 1-4C alkyl, 1-4C alkoxy, hydroxy, nitro or an amino gp. (opt. substd. by 1-4C alkyl or 2-4 C hydroxyalkyl); or R<3>+R<4> = condensed aromatic ring that may be substd. by halogen, 1-4C alkyl, amino or OH gps.; provided that at least one of R<1>-R<4> = OH or halogen.

Description

The invention relates to agents for dyeing keratin-containing Fa Serums that certain quinones in combination with amino acids, oligopep tides, aniline derivatives, phenol derivatives or benzoic acid derivatives contain.

For dyeing keratin fibers, e.g. B. hair, wool or Furs generally come with either substantive dyes or oxidation dyes, which by oxidative coupling or several developer components with each other or with one or several coupler components are created for use. With Oxidati ons dyes can be intense dyeings with good fastness Achieve properties, the development of the color happens however under the influence of strong oxidizing agents such. B. H₂O₂, which often results in damage to the fiber. Direct pull existing dyes are applied under gentler conditions, their disadvantage, however, is that the colorations are often only about have inadequate fastness properties.  

Colorants based on quinones, where the use of additional oxidizing agents can be dispensed with here an alternative. From the German patent DE 32 44 454 is the use of 1,2-naphthoquinone sulfonic acid as a hair dye medium known. The European patent application EP 0 376 776 A2 and EP 0 460 996 A1 disclose hair colorants which, besides be agreed quinones contain hydroxy or amino indoles.

Surprisingly, it has now been found that certain quinones also in combination with amino acids, oligopeptides, aniline derivatives, Phenol derivatives and benzoic acid derivatives are excellent for dyeing of keratin-containing fibers are suitable, with colorations of yellow, orange, brown, violet black, blue black to deep black will hold.

As keratin fibers come z. B. wool, furs, skins and human hair into consideration. The color specified in more detail below In principle, agents can also be used for dyeing other natural fibers, such as B. cotton, jute, sisal, linen or silk, modified Natural fibers, such as B. regenerated cellulose, nitro, alkyl or Hy droxyalkyl or acetyl cellulose and synthetic fibers, such as. B. Polyamide, polyacrylonitrile, -, polyurethane and polyester fibers ver be applied.

The invention relates to agents for dyeing keratin-containing Containing fibers, especially human hair

• - a quinone of formula I.
• - in which R¹, R², R³ and R⁴ are hydrogen atoms, halogen atoms, C₁-C₄ alkyl, C₁-C₄ alkoxy, hydroxy, nitro or given optionally substituted with C₁-C₄-alkyl or C₂-C₄-hydroxyalkyl ized amino groups, but at least one the radicals R¹, R², R³, R⁴ for a hydroxyl group or a Halogen atom, and R³ and R⁴ together also for one optionally with halogen atoms, C₁-C₄-alkyl, amino or Hydroxy-substituted fused aromatic ring can stand
• - at least one amino acid or one of 2 to 9 amino acids built oligopeptide
• - And a water-based carrier.

Suitable quinones are e.g. B. 2-hydroxybenzoquinone, 2-hydroxy-5-chloro, 2,4-dichloro, 2,3,5-trichloro, 2-hydroxy-5-methyl, 2,5-dimethyl-3- hydroxy, 2,3-, 2,5-dihydroxy, 2,3,5,6-tetrahydroxy, 2,5-dianili no-3,6-dichloro-, 2,5-bis- (4-methoxyanilino) -3,6-dichlorobenzoquinone, Chloranil, chloranilic acid, nitranilic acid, 2-hydroxy-, 2,3-, 2,5-di hydroxy-, 2,3-dichloro-1,4-naphthoquinone and the sodium, potassium and Ammonium salts of the hydroxy substituted compounds.

All naturally occurring and synthetic come as amino acids Amino acids in question, e.g. B. by hydrolysis from vegetable or animal proteins, e.g. B. collagen, keratin, casein, elastin, Sun. Japanese protein, wheat gluten or almond protein accessible amino acids. Both acidic and alkaline amino acids are used, e.g. B. tyrosine, histidine, phenylalanine, DOPA, Ar ginin and tryptophan. Suitable oligopeptides are all natural occurring and synthetic amino acids built oligopeptides. The oligopeptides can be naturally occurring or synthetic oligopeptides, but also those in polypeptide or protein hydro  lysates contained oligopeptides, provided that they have one for the Use sufficient in the colorants of the invention have solubility. As examples are e.g. B. glutathione or the in the hydrolyzates of collagen, keratin, casein, elastin, soy protein, wheat gluten or almond protein containing oligopeptides call.

Another object of the invention are agents for dyeing kera containing fibers containing tin, in particular human hair

• a quinone of the formula I according to claim 1,
• - at least one aniline derivative
• - And a water-based carrier.

Suitable aniline derivatives are the aniline derivatives substituted one or more times by lower C _1-4 alkyl, hydroxyalkyl, alkoxy, acyloxy groups, carboxyl, carboxylate, sulfo, sulfonate, amino or aminoalkyl groups, amino functions by lower C _1-4 alkyl, hydroxyalkyl, aminoalkyl or carboxyalkyl may be substituted, e.g. B. 2-, 3-, 4-aminophenol, o-, m-, p-phenylenediamine, 2,5-diaminotoluene, -phenol, -anisole, -phenethol, 2-chloro-p-phenylene-diamine, 4-methylamino- , 3-, 4-dimethylamino-, 3,4-methylenedioxy aniline, 3-amino-2,4-dichloro-, 4-methylamino-, 2-methyl-5-amino-, 3-methyl-4-amino-, 2-methyl-5- (2-hydroxyethylamino) -, 2-methyl-5-amino-6-chloro, 2-methyl-5-amino-4-chloro, 2-methyl-5-amino-6-chloro -, 5- (2-Hydroxyethylamino) -4-methoxy-2-methyl-, 4-amino-2-aminomethylphenol, 1,3-diamino-2,4-dimethoxybenzene, 2-, 3-, 4- Amino benzoic acid, phenylacetic acid, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-diamino noboic acid, 4-, 5-aminosalicylic acid, 3-amino-4-hydroxy-, 4 -Ami no-3-hydroxy-benzoic acid, 2-, 3-, 4-aminobenzenesulfonic acid, 3-amino no-4-hydroxybenzenesulfonic acid, 1-amino-8-hydroxy-3,6-naphthalenedi sulfonic acid disodium salt, 1,3, 5-, 1,2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene tetrahydrochloride, 2,4,5-triaminophenol trihydrochloride, pentaaminobenzene pentahydrochloride, hexamaminobenzene hexahydrochloride, 2,4, 6-triaminoresorcinol trihydrochloride, 4,5-diamino catechol sulfate, 4,6-diaminopyrogallol dihydrochloride, 3,5-di amino-4-hydroxycatechol sulfate, 4,4′-diamino-diphenylamine sulfate, 4, 4'-diamino-diphenylamine-2-sulfonic acid, 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane × 4 HCl, 1,3-bis (2,4-diaminophenoxy) propane × 4 HCl, N, N'-bis (2-hydroxyethyl) -p-phenylenediamine × 2 HCl, 2- (2,5-diaminophenyl) ethanol × 2 HCl.

Another object of the invention are agents for dyeing kera containing fibers containing tin, in particular human hair

• a quinone of the formula I according to claim 1,
• - At least one aliphatic amine
• - And a water-based carrier.

Suitable aliphatic amines are e.g. B. 2-aminoethanol, 2-methoxy, 2-ethoxyethylamine, 2- (2-aminoethoxy) ethanol, 2-, 3-aminopropanol, 2,3-dihydroxypropylamine, 4-hydroxypropylamine, 2-aminopropane-1,3- diol, 2-amino-2-methylpropanol, 2-amino-2-methylpropane-1,3-diol, 2-amino-2-hydroxymethylpropane-1,3-diol, tetrahydroxypentylamine, Pentahydroxyhexylamine (e.g. glucamine), diamines such as 1,2-diamino ethane, 1,2-, 1,3-diaminopropane, 1,3-diamino-2-propanol, 2- (2-ami noethylamino) ethylamine, ethanol, 3- (2-aminoethylamino) propyl amine, propanol.

Another object of the invention are agents for dyeing kera containing fibers containing tin, in particular human hair

• a quinone of the formula I according to claim 1,
• - at least one phenol derivative
• - And a water-based carrier.

Suitable phenol derivatives are e.g. B. resorcinol, 2-, 4-methylresorcinol, Pyrogallol, 1,3,5-, 1,2,4-trihydroxybenzene, 2,5-dimethylresorcinol, 1,3-, 1,5-, 1,8-, 2,3-dihydroxynaphthalene.  

Another object of the invention are agents for dyeing kera containing fibers containing tin, in particular human hair

• a quinone of the formula I according to claim 1,
• - At least one benzoic acid derivative
• - And a water-based carrier.

Suitable benzoic acid derivatives are e.g. B. 2,4-, 3,5-dihydroxy, 2,4,6-, 3,4,5-trihydroxybenzoic acid, 4-, 5-aminosalicylic acid.

In all colorants according to the invention, several ver different quinones of formula I are used together. Especially preferred are tetrahydroxy-p-benzoquinone, chloranilic acid and Chloranil.

The colorants according to the invention already result in physiological tolerable temperatures of below 45 ° C intense colorings. she are therefore particularly suitable for dyeing human hair. For use on human hair, the inventive Colorants incorporated into a water-based cosmetic carrier be tested. Suitable water-containing cosmetic carriers are e.g. B. Creams, emulsions, gels or even foaming solutions containing surfactants such as B. shampoos or other preparations suitable for use are suitable on the hair.

In addition, the addition of solubilizers such as ethylene, 1,3- Propylene, 1,2-propylene, 1,2-butylene glycol, glycerin, ethanol, tert. Butanol, 2-propanol or phenethol in amounts of 2-50% to be useful.

The water-containing cosmetic carrier usually contains wetting agents and Emulsifiers such as anionic, nonionic or ampholytic ten side, e.g. B. fatty alcohol sulfates, alkane sulfonates, α-olefin sulfonates, Fatty alcohol polyglycol ether sulfates, alkyl glycosides, ethylene oxide plant  products on fatty alcohols, on fatty acids, on alkylphenols Sorbitan fatty acid esters, on fatty acid partial glycerides and fatty acid alkanolamides; Thickeners, e.g. B. fatty alcohols, fatty acids, Paraffin oils, fatty acid esters and other fat components in emulsified ter form; water-soluble polymeric thickeners such as natural ones Gums, e.g. B. gum arabic, karaya gum, guar gum, locust beans bread kernel flour, linseed gums and pectin, biosynthetic gums, e.g. B. xanthan gum and dextrans, synthetic gums, e.g. B. Agar Agar and algin, starch fractions and derivatives such as amylose, amylo pectin and dextrins, modified cellulose molecules, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, clays such as B. bentonite or fully synthetic hydrocolloids, e.g. B. Poly vinyl alcohol or polyvinyl pyrrolidone, hair care additives, such as e.g. B. water-soluble cationic polymers, anionic polymers, nonionic polymers, amphoteric or zwitterionic polymers, Pantothenic acid, vitamins, plant extracts or cholesterol, pH Adjusting agents, complexing agents and perfume oils as well as reducing agents Stabilization of the ingredients, e.g. B. ascorbic acid, finally can also use dyes to color the cosmetic preparations be included.

The quinones of formula I and the amino acids, oligopeptides, aniline derivatives, aliphatic amines, phenol derivatives or benzoic acid derivatives vate are preferably in an amount of 0.3 to 65 each 6 to 20 mmol, in each case based on 100 g of the total colorant, contain.

For the coloring result it can be advantageous to use the coloring agents Add ammonium or metal salts. Suitable metal salts are e.g. B. the carbonates, halides, sulfates, nitrates, acetates, lactates, Glycolate, Formiate, Valeriate, Capronate, Tartrate, Citrate, Glu conate, propionate, phosphate, sulfonate and phosphonate of potash um, sodium, lithium, magnesium, calcium, strontium, barium,  Manganese, iron, cobalt, copper, zinc, lanthanum; are preferred Lithium bromide, calcium bromide, calcium gluconate, strontium chloride, Strontium nitrate, aluminum chloride, aluminum lactate, zinc chloride, Zinc sulfate, magnesium chloride, magnesium sulfate, lanthanum nitrate, Am monium carbonate, chloride and acetate, which in the given case in egg ner amount of 0.3 to 65, preferably 6 to 20 mmol, based on 100 g of the total colorant are included.

The pH value of the ready-to-use coloring preparations is between 2 and 11, preferably between 5 and 9.

For dyeing hair, the colorants according to the invention are in the form of water-containing cosmetic carrier in an amount of 100 g hair applied, left there for about 30 minutes and then out rinses or washed out with a commercially available hair shampoo.

The two reactive components (quinone of formula I and amino acid right, oligopeptide, aniline derivative, aliphatic amine, phenol derivative or benzoic acid derivative) can either on the hair at the same time be applied or one after the other, it does not matter plays which of the two components is applied first; between The application of the first and second components can take up to 30 minutes apart.

The two reactive components can be separated and separated the water-free or already stored in the finished formulation become. When stored separately, the reactive components only intimately mixed with one another immediately before use. There is a defined amount of warm (50-80 ° C) during dry storage Add water and create a homogeneous mixture len.

Examples Preparation of a coloring solution

A 10 mmole slurry of a quinone of formula I 10 mmol of the second component according to the invention, 10 mmol of sodium acetate and a drop of a 20% Texapon-N25 solution in 100 ml Prepares water. The slurry was heated to boiling temperature and filtered after cooling, the pH was then raised to 6 set (variant A). According to another method of preparation the two components were separated in 50 ml of water slurries and the mixture heated to boiling, to room temperature cooled and only now combined, filtered and the solution to pH 6 set (variant B) (see the following table).

90% of this staining solution was grayed at 30 ° C for 30 minutes human hair that has not been pretreated. The respective Dyeing temperatures, dyeing times, shades and depths are the Tables 1 and 2.

The color depth was rated on the following scale:

-: no or very pale color
(+): weak intensity
+: medium intensity
+ (+): medium to strong intensity
++: strong intensity
++ (+): strong to very strong intensity
+++: very strong intensity

Claims (10)

1. Means for dyeing keratin fibers, especially human hair containing

• - a quinone of formula I.
• - In the R¹, R², R³ and R⁴ represent hydrogen atoms, halogen atoms, C₁-C₄-alkyl, C₁-C₄-alkoxy, hydroxy, nitro or optionally substituted with C₁-C₄-alkyl or C₂-C₄-hydroxyalkyl amino groups , but at least one of the radicals R¹, R², R³, R⁴ represents a hydroxyl group or a halogen atom, and R³ and R⁴ together also represent a fused aromatic ring optionally substituted with halogen atoms, C₁-C₄ alkyl, amino or hydroxyl groups can,
• - At least one amino acid or an oligopeptide composed of 2 to 9 amino acids
• - And a water-based carrier.

2. Containing compositions for dyeing fibers containing keratin, in particular human hair

• a quinone of the formula I according to claim 1,
• - at least one aniline derivative
• - And a water-based carrier.

3. Containing agents for dyeing keratin fibers, in particular human hair

• a quinone of the formula I according to claim 1,
• - At least one aliphatic amine
• - And a water-based carrier.

4. Containing agents for dyeing keratin fibers, in particular human hair

• a quinone of the formula I according to claim 1,
• - at least one phenol derivative
• - And a water-based carrier.

5. Containing agents for dyeing keratin fibers, in particular human hair

• a quinone of the formula I according to claim 1,
• - At least one benzoic acid derivative
• - And a water-based carrier.

6. Composition according to claim 1, characterized in that a quinone of formula I in an amount of 0.3 to 65, preferably 6 to 20 mmol, and at least one amino acid or one of 2 to 9 Amino acid built oligopeptide in an amount from 0.3 to 65, preferably 6 to 20 mmol, in each case based on 100 g of the entire colorant are included. 7. Composition according to claim 2, characterized in that a quinone of formula I in an amount of 0.3 to 65, preferably 6 to 20 mmol, and at least one aniline derivative in an amount of 0.3 to 65, preferably 6 to 20 mmol, in each case based on 100 g of the entire colorant are included.   8. Composition according to claim 3, characterized in that a quinone of formula I in an amount of 0.3 to 65, preferably 6 to 20 mmol, and at least one aliphatic amine in an amount from 0.3 to 65, preferably 6 to 20 mmol, in each case based on 100 g of the total colorant are included. 9. Composition according to claim 4, characterized in that a quinone of formula I in an amount of 0.3 to 65, preferably 6 to 20 mmol, and at least one phenol derivative in an amount of 0.3 to 65, preferably 6 to 20 mmol, in each case based on 100 g of the entire colorant are included. 10. Composition according to claim 5, characterized in that a quinone of formula I in an amount of 0.3 to 65, preferably 6 to 20 mmol, and at least one benzoic acid derivative in an amount from 0.3 to 65, preferably 6 to 20 mmol, in each case based on 100 g of the total colorant are included.