DE19719605A1 - Oxidation hair dyes - Google Patents

Abstract

Coupler components for oxidation dyes containing standard developer compounds, used to dye keratin fibres comprise 3-hydroxydiphenylamine derivatives of formula (I) or their salts, where R<1>-R<4> = H, 1-4C (hydroxy)alkyl, allyl, 1-4C (hydroxy)alkoxy or halogen, with the provision that at least one of R<1>-R<4> is not H. Oxidation hair dyes comprising oxidation dye precursors in a carrier, containing 0.01-10 mmoles (I) per 100 g dye, in addition to standard developer compounds and optional standard coupler components, are also claimed. R<1>-R<4> are H, methyl or methoxy. The carrier is a cream emulsion containing 1-25 wt.% emulsifiable fat component, or it is a gel containing 1-20 wt.% soap, both with respect to the hair dye.

Description

The invention relates to the use of 3-hydroxydiphenylamine derivatives as Coupling components in oxidation dyes that are used to color Keratin fibers are suitable.

For the coloring of keratin fibers, especially human hair, they play so-called oxidation dyes because of their intense colors and good realness properties play a preferred role. Such colorants contain oxidation dye precursors, so-called developer components and coupler components th. The developer components form under the influence of oxidizing agents or of atmospheric oxygen with one another or under coupling with an or several coupler components make up the actual dyes.

Good oxidation dye precursors must first and foremost be the following Fulfill settlements: You must have the desired in the oxidative coupling Develop color nuances with sufficient intensity and authenticity. You must also have a good ability to be absorbed by the fiber, in particular with human hair no noticeable differences between stressed and may survive freshly regrown hair (leveling power). You should be be constantly against light, heat and the influence of chemical reducing agents, e.g. B. against permanent wave fluids. After all, they should - if used as a hair dye coming into use - do not stain the scalp too much, and above all they should be harmless from a toxicological and dermatological point of view.

Primary aromatic amines are usually used as developer components another, in the para or ortho position, free or substituted Hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and aminopyrimidines and their derivatives are used.

Special representatives are, for example, p-phenylenediamine, p-tolylenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-pheny lenediamine, 2- (2,5-diaminophenyl) -ethanol, 2- (2,5-diaminophenoxy) -ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolone-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihy droxy-5,6-diaminopyrimidine, 2,5,6-triaminohydroxypyrimidine and 1,3-N, N'- Bis (2'-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -diamino-propan-2-ol.

As a rule, m-phenylenediamine derivatives, naph thols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols ver turns. Particularly suitable coupler substances are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, Resorcinol, resorcinol monomethylether, m-phenylenediamine, 1-phenyl-3-methyl pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-4- hydroxypyndin, 2-methylresorcinol and 5-methylresorcinol.

With regard to other customary dye components, reference is expressly made to the Co lipa list, published by the body care and detergent industry association, Frankfurt, referred to.

Alone with a developer component or a special coupler / developer As a rule, the combination does not succeed in creating one that looks natural on the hair To preserve color nuance. In practice, therefore, combinations are usually used various developer components and coupler components are used. It there is therefore a constant need for new, improved dye components.

It was therefore the object of the present invention to provide new developer components nents to find which the oxidation dye precursors to be presented to meet requirements to a particularly high degree.

3-Hydroxydiphenylamine has long been used as an oxidation dye precursor, e.g. B. from DE 3 34 011 (1916), known.

It has now been found that 3-hydroxydiphenylamine derivatives, at least another substituent, e.g. B. an alkyl group, an alkoxy group or Carrying chlorine, in its coloring properties, especially in the color absorption, in the wash and lightfastness, are significantly better.

The invention therefore relates to the use of 3-hydroxydiphenylamine derivatives of the formula I.

in which the groups R ¹ , R ² , R ³ and R ^{4 are} independently hydrogen, alkyl or hydroxyalkyl groups with 1-4 C atoms, allyl groups, alkoxy or hydroxyalkyloxy groups with 1-4 C atoms or halogen atoms, with the proviso that at least one of the groups R ¹ to R ^{4 is} not hydrogen, or their salts as coupler components in oxidation colorants with a content of customary developer compounds for coloring keratin fibers.

Some of the compounds of the formula I are known from the literature, some of which are not Derivatives known from the literature are based on synthesis processes known per se accessible. The synthesis of a compound of formula I unknown from the literature is described in the example section.

The new coupler components deliver with a large number of known ones Developer compounds a wide range of interesting oxidation colors in the Range of light brown to purple nuances, which are due to the good color absorption on keratin fibers and their good fastness properties especially for those Suitable for hair coloring.

The compounds of the formula I in which the groups R ¹ , R ² , R ³ and R ^{4 are} hydrogen, methyl or methoxy groups or chlorine are preferred - in particular because of their good accessibility.

Furthermore, those compounds of the formula I are preferred which have a further substituent other than hydrogen. The position of the groups R ² , R ³ and R ⁴ on the respective aromatic nucleus has no fundamental influence on the coloring properties. However, R ² should preferably be in the ortho or meta position to the hydroxyl group.

Keratin fibers include fur, wool, feathers, and especially human Understand hair. Although the oxidation colorants according to the invention in are primarily suitable for dyeing keratin fibers, is in principle one Use also in other areas, especially in color photography, nothing against.

The present invention also relates to oxidation hair dyes containing oxidation dye precursors in a carrier and 3-hydroxydiphenylamine derivatives of the formula I according to claim 1 as couplers in an amount of 0.05 to 10 millimoles per 100 grams of the hair dye as well Customary developer components and, if appropriate, customary coupler components contain.

Regarding the other developer and coupler components, see the The substances listed at the beginning of the description are referred to as the preferred represent further dye components.

Preferred further developer components are 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 1- (2-hydroxyethyl) -2,5-diaminobenzene, p-phenylenediamine, p-tolylenediamine, o- and p- Aminophenol, 3-methyl-4-aminophenol, 2,5-diaminophenoxyethanol, 2-hydroxy methyl-p-aminophenol and 2-aminomethyl-p-aminophenol. 4-amino-2- (2- hydroxyethoxy) phenol and 1,3-N, N'-bis (2'-hydroxyethyl) -N, N'-bis (4'-amino phenyl) -diamino-1,3-propan-2-ol are also developer components that be are preferably combined with the developer components according to the invention can.

Very particularly preferred further developer components are 2,4,5,6-tetrami nopyrimidine, 1- (2-hydroxyethyl) -2,5-diaminobenzene, 3-methyl-4-aminophenol, o- Aminophenol, 2-aminomethyl- and 2-hydroxymethyl-p-aminophenol.

Preferred coupler components are 1-naphthol, resorcinol and 2-methyl-5-amino phenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chloro-6-methyl-3-aminophenol, 3- Amino-6-methoxy-2-methylaminophenol, 2-hydroxy-4-aminophenoxyethanol, 2- Amino-3-hydroxypyridine, 4-chlororesorcinol, 2,4-diaminophenoxyethanol, 2,6- Dimethyl-3-aminophenol, 2,4-dichloro-3-aminophenol, 3,4-methylenedioxy phenol, 2-methyl-resorcinol, m-aminophenol, 2-methyl-5- (2-hydroxyethylamino) - phenol, 2,6-dihydroxy-3,4-dimethylpyridine, 3-amino-2-methylamino-6-methoxy pyridine, 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene, 2,6-bis (2- hydroxyethylamino) toluene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene.

Particularly preferred coupler components are 1-naphthol, resorcinol, 1,3- Bis (2,4-diaminophenoxy) propane, 2-hydroxy-4-aminophenoxyethanol, 4-chloro resorcinol, 2,4-diaminophenoxyethanol, 2-methyl-resorcinol, 2-methyl-5 (2-hydroxy ethylamino) phenol, 3-amino-2-methylamino-6-methoxypyridine.

These further developer and coupler components are usually used in used in free form. In the case of substances with amino groups, however, it can be preferred they are in salt form, especially in the form of hydrochlorides and sulfates, to use.

The totality of those contained in a hair dye according to the invention Oxidation dye precursors usually make up 0.005 to 20% by weight, but preferably only 0.1 to 5% by weight of the hair dye. Be there Developer and coupler components generally in approximately molar amounts used to each other. Even if the molar use proves to be expedient has been shown to be a certain excess of individual oxidation dye precursors not disadvantageous, so that developer and coupler com components in a molar ratio of 1: 0.5 to 1: 3, in particular from 1: 1 to 1: 2, can be included.

To further modify the color shade, the inventive Hair dyes additionally customary substantive dyes, e.g. B. from the group the nitrophenols, the nitrophenylenediamines, the anthraquinones or the Contain indophenols, such as. B. those under the international names resp. Trade names HC Yellow 2, HC Yellow 4, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, Nitro Blue, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16, picric acid and Rodol 9 R known compounds, in an amount of 0.01 to 20 wt .-%, based on the total oxide tion hair dyes. 4-amino-2-nitro-diphenylamine-2'-carboxylic acid, 6-nitro 1,2,3,4-tetrahydroquinoxaline, Rodol 9 R and HC Red BN are according to the invention particularly preferred substantive dyes.

It is not necessary that the oxidation dye precursors or the given Any substantive dyes contained in each case are uniform compounds represent. Rather, in the hair colorants according to the invention, conditional by the manufacturing process for the individual dyes, in subordinate Amounts of other components may also be included, if these do not Adversely affect the dyeing result or for other reasons, e.g. B. toxicological, must be excluded.

Oxidation dyes are used to produce the colorants according to the invention material precursors incorporated into a suitable water-containing carrier. To the Hair coloring purposes are such carriers, for. B. creams, emulsions, gels or also surfactant-containing foaming solutions, e.g. B. shampoos, foam aerosols or other preparations suitable for use on the hair.

Powdered carriers are also suitable for those preparations that are before Application to be dispersed in water.

Usual components of such cosmetic carriers are, for. B .:

• - Wetting and emulsifying agents of the anionic, nonionic, zwitterionic, ampholytic or cationic surfactants,
• - thickeners, e.g. B. of the type of water-soluble polymers to which natural products such as starch, vegetable gums, gelatine or biopolymers (e.g. xanthan gum), semi-synthetic products such as B. cellulose ether or Guar derivatives or fully synthetic polymers. like polyvinylpyrrolidone, Polyvinyl alcohol, polyethylene glycol, crosslinked polyacrylic acids or their co polymers include,
• - emulsified fatty substances, e.g. B. fatty alcohols, fatty acids, fatty acid esters such. B. Fatty acid monoglycerides, fatty acid alkanolamides, paraffins or silicones,
• - soaps, e.g. B. Sodium, ammonium or alkanolammonium soaps of C ₁₂ -C ₁₈ fatty acids for the production of aqueous gels,
• - solvents such as B. ethanol, propylene glycol or glycerine,
• - Hair cosmetic, nourishing or setting additives such as B. cationic Polymers, protein derivatives, glucose, maleic acid, lecithins, panthenol or Pantothenates, vitamins, plant extracts, anti-dandruff ingredients, allantoin and light stabilizers,
• - electrolytes, pH adjusters and buffer salts (e.g. ammonium salts),
• - Complexing agents and antioxidants to stabilize the dye precursors (e.g. sodium sulfite, ascorbic acid),
• - fragrance.

The ingredients of the cosmetic carrier are used to produce the Hair colorants according to the invention in amounts customary for these purposes used, e.g. B. can emulsifiers in amounts of 0.5 to 30 wt .-% and Thickener in amounts from 0.1 to 25% by weight of the total colorant be included.

Particularly suitable as a carrier is, for. B. a cream emulsion (Oil-in-water emulsion) with a content of 1 to 25% by weight of an emulsified Fat component and 0.5 to 30 wt .-% of an emulsifier from the group of anionic, cationic, zwitterionic, ampholytic and nonionic Surfactants or a gel with a content of 1 to 20% by weight of a soap are preferred Ammonium oleate.

The oxidative development of the color can in principle with atmospheric oxygen take place. However, preference is given to using a chemical oxidizing agent, especially if there is a lightening effect on human hair in addition to the coloring is desired. As oxidizing agents come persulfates, chlorites and in particular Hydrogen peroxide or its addition products with urea, melamine as well as sodium borate in question. It is also possible to carry out the oxidation with the aid of Catalyzing enzymes. The enzymes can be used to transfer Atmospheric oxygen on the developer component or to intensify the effect serve small amounts of oxidizing agents present. An example of a enzymatic method consists in getting the effect of small amounts (e.g. 1% and less, based on the total agent) hydrogen peroxide through Increased peroxidases.

Finally, the oxidative development can also be caused by the addition of salts bivalent metals or iodides are catalytically promoted.

Appropriately, the preparation of the oxidizing agent is carried out immediately the hair coloring with the preparation from the oxidation dye precursors mixed. The resulting ready-to-use hair dye preparation should be used before tend to have a pH in the range from 6 to 10. It is particularly preferred the use of hair dyes in a weakly alkaline environment. the Application temperatures can range between 15 and 40 ° C. After an exposure time of about 30 minutes, the hair dye will through Rinse away from hair to be colored. The rewash with one Shampoo is not required if a strong surfactant carrier, e.g. B. a coloring shampoo, was used.

The following examples are intended to explain the subject matter of the invention in more detail.

Examples 1. Production examples

The following coupler components were prepared according to the literature:
K1: 3-hydroxy-3'-chlorodiphenylamine according to FR 1 173 121 A1 (Chem. Abstr. 56: 479 df)
K2: 3-hydroxy-4'-methoxy-diphenylamine according to FR 1 173 121 A1 (Chem. Abstr. 56: 479 df)
K3: 3-hydroxy-5-methyl-diphenylamine according to J. pr. 33,539
K4: 2-methyl-3-hydroxy-diphenylamine

Manufacturing

30 g of phosphoric acid (85%) were added to a mixture of 50.5 g of aniline and 125 g of water were added dropwise. The mixture was made with 62 g of 2-methylresorcinol, 50 g Water and 24.5 g aniline are added and the autoclave is kept for 12 hours (under pressure) heated to 160 ° C.

After cooling and releasing the pressure, the reaction mixture became alkaline adjusted and excess aniline removed by steam distillation.

After neutralization (with hydrochloric acid), the precipitated product was filtered off and recrystallized twice from water. There were white crystals with a Melting point of 136 ° C obtained.

2. Examples of use

Hair colorants according to the invention were prepared in the form of a hair color and cream emulsion of the following composition:

Cream base 50 wt% Developer component (E) 7.5 mmol Coupler component (K) 7.5 mmol Na ₂ SO ₃ (inhibitor) 1.0 wt% (NH ₄ ) ₂ SO ₄ 1.0 wt% conc. Ammonia solution ad pH = 10 water ad 100% by weight

The cream base is composed as follows:

Sebum alcohol 17.0% by weight Coconut fatty alcohol C ₁₂ -C ₁₈ 4.0% by weight Texapon®N28 (1) 40.0% by weight Dehyton®K (2) 25.0% by weight Eumulgin B2 (3) 1.5 wt% least. water 12.5% by weight

The following commercial products were used:
Texapon®N28: sodium lauryl ether sulfate, 28%
CTFA name: Sodium Lareth Sulfate
Dehyton®K: amide betaine surfactant, 30%
CTFA name: Cocoamidopropyl Betaine
Eumulgin®B2: cetyl / stearyl alcohol + 20 mol EO
CTFA name: Ceteareth 20

The following compounds were used as developer component (E):
E1: 3-methyl-4-aminophenol
E2: 2-aminomethyl-4-aminophenol
E3: 2- (2,5-diaminophenoxy) ethanol
E4: 4-hydroxy-2,5,6-triaminopyrimidine
E5: 2,4,5,6-tetraaminopyrimidine
E6: p-aminophenol
E7: p-tolylenediamine
E8: 2-hydroxyethyl-p-phenylenediamine

The 3-hydroxydiphenyl according to the invention were used as coupler compounds amine derivatives K1 to K4 are used.

The ingredients were mixed together in sequence. After adding the Oxidation dye precursors and the inhibitor was initially concentrated trated ammonia solution, the pH of the emulsion was adjusted to 10, then was made up to 100 g with water.

The oxidative development of the color was measured with 3% hydrogen peroxide solution solution carried out as an oxidizing solution. For this purpose, 100 g of the emulsion were added 50 g hydrogen peroxide solution (3%) are added and mixed.

The coloring cream was standardized to approx. 5 cm long strands, 90% gray, but not specially pretreated human hair is applied and leave there for 30 minutes at 32 ° C. After the dyeing process was finished the hair rinsed, washed with a standard shampoo and on finally dried.

The results of the hair coloring tests are shown in the following table:

Claims (4)

1. Use of 3-hydroxydiphenylamine derivatives of the formula I.
in which the groups R ¹ , R ² , R ³ and R ^{4 are} independently hydrogen, alkyl or hydroxyalkyl groups with 1-4 carbon atoms, allyl groups, alkyloxy or hydroxyalkyloxy groups with 1-4 carbon atoms or halogen atoms, with the Provided that at least one of the groups R ¹ to R ^{4 is} not hydrogen, or their salts as coupler components in oxidation colorants with a content of customary developer compounds for coloring keratin fibers. 2. Use according to claim l, characterized in that the groups R ¹ , R ² , R ³ and R ^{4 are} hydrogen, methyl or methoxy groups or chlorine. 3. Oxidation hair dyes, containing oxidation dye precursors in one Carrier, characterized in that 3-hydroxydiphenylamine derivatives of Formula I according to claim 1 as a coupler in an amount of 0.01 to 10 milli mol per 100 g of the hair dye and customary developer components and optionally customary coupler components are included. 4. Hair dye according to claim 3, characterized in that a carrier Cream emulsion with a content of 1-25% by weight of an emulsified Fat component or a gel with a content of 1-20% by weight of a soap, each based on the total hair dye, is included.