DE4139675A1 - Oxidn. dye compsn. - contains 1,3-di:hydro:indole-2-one as coupler, giving, strong, fast red and brown shades - Google Patents

Abstract

Oxidn. dye compsn. contains the usual developer components as oxidn. dye pre-prod. cosmetic carrier, and coupler, 1,3-dihydroindole-2-one of formula (I). In (I), R1, R2, R3, R4 = 1-4C alkyl or 2-4C hydroxyalkyl, and R2, R3, R4 may = halogen. More specifically, R1 = H or Me; R2, R3, R4 = H or one of these = Cl or F and the other = H. Pref. the amt. of (I) s 0.05-10 mmols/100g of dye compsn. The carrier is cream emulsion contg. 1-25 wt. % of emulsified fat component and 0.5-30 % of an emulsifier comprising an anionic, nonionic, amphelytic or zwitterionic tenside or a gel with 1-20 % of a soap, pref. NH4 oleate. ADVANTAGE - Strong, fast, uniform, red and brown shades are obtd. In an example, an emulsion was prepd. contg. 10g of 12-18C fatty alcohol, 25g of 12-14C fatty alcohol ethoxylate sulphate (as Na salt 2 EO), 60g of water, 7.5 mmols of p-toluylene diamine, 7.5 mmols of 1,3-dihydroindole-2-one, 1g of Na2SO3 and concn. NH4OH to pH 9.5; these components were mixed followed by addn. of water to 100g. Mixt. of 100g of the emulsion and 50g of 3% H202 was applied to hair (90% grey) for 30 mins. at 27 deg.C followed by rinsing, washing and drying, giving a dark brown shade.

Description

The invention relates to the use of 1,3-dihydroindol-2-ones as coupler-type oxidation dye precursors in oxidation colorants containing conventional developer compounds for the dyeing of keratin fibers, in particular of human Hair.

Oxidative dyes become oxidative coupling one or more developer components (or oxidation bases) with each other or with one or more coupler components (color modifier) provides. For the coloring of keratin fibers, in particular of human hair, these oxidation dye precursors are in a cosmetic carrier suitable for use on the hair incorporated, which allows easy application and distribution of color substances on the hair. Such carriers are z. Creams, Emulsions, gels, shampoos, foam aerosols or others are preferred aqueous preparations.

As developer substances are usually primary aromatic Amines with another, in para- or orthoposition located Hydroxy or amino group used under the influence of a Oxidizing agent form ortho- and parachinoid structures and  can react to dye molecules. Other than developers or oxidation base suitable compounds are for. B. Diaminopyridines, heterocyclic hydrazones, 4-aminopyrazolones, 2,4,5,6-tetraaminopyrimidines, 4,5-diamino-2,6-dihydroxypyrimidine and 6-hydroxy-2,4,5-triaminopyrimidines.

The dyes obtainable by this oxidative self-coupling are usually unsatisfactory. By coupling with phenols or others aromatic amines and aminophenols, in particular those with metastatischen hydroxy or amino groups, but can usually be Produce high intensity and brilliance dyeings.

One of the most important fields of application for oxidation dyes is the field of hair dye. Good oxidation Hair dye precursors must first and foremost the following You must comply with the oxidative coupling ge wished to develop color shades in sufficient intensity. you must also have a good absorption on human hair be sit without staining the scalp too much. Also, the color should be uniform, d. H. the more stressed hair Tips should not be dyed stronger than the little geschä damaged hairline. The dyeings produced with it have to be high Stability against heat, light and used in the Dauerwellung Have chemicals. Finally, the Oxidation hair dye precursors in toxicological and be dermatologically harmless.

There is therefore a constant need for Oxidation dye precursors with improved application and toxicological properties, esp Of Huppler compounds, which with the well-known color bases of Type of aromatic diamines and tetraaminopyrimidines red bis  to create reddish-brown shades that are particularly intense and intense uniform staining of the hair from the hairline to the hair tip even with heavily damaged hair allow.

It has now been found that oxidation colorants consisting of Oxidation dye precursors and a cosmetic carrier, the conventional oxidation components as oxidation dye precursors which meet the requirements to a high degree, if they are 1,3-dihydroindol-2-ones of the formula I as coupler components

in which R ¹ , R ² , R ³ and R ^{4 are} independently hydrogen, alkyl groups having 1-4 C atoms or hydroxyalkyl groups having 2-4 C atoms and R ² , R ³ and R ^{4 may} also be halogen atoms.

The present invention suitable coupler components of the formula I. form with a variety of common developer components in intensive oxidation dyeings in the range of red and brown shades, characterized by high authenticity and by a particularly uniform Distinguish color lift.

As developers, z. B. aromatic amines having one or more other para or ortho-standing NH ₂ groups, NH-R groups, NR ² groups, wherein R is an alkyl group having 1-4 C-atoms, an optionally substituted aminoalkyl group with 2 Represents 4 C atoms, o- and p-aminophenols, amino phenol ethers, diaminopyridines, 2,4,5,6-tetraaminopyridine and its derivatives, 4,5-diamino-2,6-dihydroxypyrimidine and 4-hydroxy-2, 5,6-triaminopyrimidines. Specially suitable developer components are given in the examples as E1 to E14.

Particularly suitable coupler components according to the invention are, above all because of their ready availability, those compounds of the formula I in which R ^{1 is} hydrogen or a methyl group and R ² , R ³ and R ^{4 are} hydrogen or one of the groups R ² , R ³ and R ^{4 are} chlorine or fluorine and the remaining hydrogen.

The coupler compounds suitable according to the invention are literaturbe known; if individual compounds are not known from the literature, they can be analogous to literature methods produce the known 1,3-dihydroindol-2-ones. The new Kupp Component components are well-known for color modification for all th oxidation bases (developer compounds). Some specifically suitable Nete developer components are in the example part as component E1 to E14 listed.

Another patent object is a hair dye with a content on oxidation dye precursors in a cosmetic carrier, the 1,3-dihydroindol-2-ones of the formula I as a coupler in an amount from 0.05-10 millimoles per 100 grams of the hair dye as well as usual Developer components and optionally conventional coupler components contain. In the hair dye invention, the Kupp Lerkomponenten of formula I preferably used in free form.

The hair colorants according to the invention, in addition to the new Kupp lerkomponenten of formula I, other known coupler substances  included to modify the color nuances and to generate natural shades are required. Such conventional couplers connections are z. B. m-phenylenediamines, m-aminophenols, resor cine, naphthols or pyrazolones.

Optionally, other known developer components (Oxidation bases) and direct dyes for further Modification of color shades can be used. Such direktzie existing dyes are z. Nitrophenylenediamines, Nitroaminophenols, anthraquinone dyes or indophenols.

It is also not necessary that the new coupler components of formula I are uniform compounds. Rather, you can too Mixtures of different compounds of formula I can be used.

In the hair colorants according to the invention are developer compo nenten and coupler components generally in about molar amounts used to each other. Even if the molar use as has proved appropriate, so is a certain excess of individual Oxidation dye precursors not disadvantageous, so that development Lersubstanzen and couplers in a molar ratio of 1: 0.5 can be included up to 1: 2.

For the preparation of the hair dye according to the invention are Oxidation dye precursors in a suitable cosmetic Carrier incorporated. Such carriers are z. As creams, emulsions, Gels or surfactant-containing, foaming solutions, eg. Shampoos, Foam aerosols or other preparations intended for use the hair are suitable.

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

• - wetting and emulsifying agents such as anionic, nonionic or ampholytic surfactants, e.g. B. fatty alcohol sulfates, alkanesulfo nate, α-olefinsulfonates, fatty alcohol polyglycol ether sulfates, Ethylene oxide addition products to fatty alcohols, to fatty acids, on alkylphenols, on sorbitan fatty acid esters, on fatty acid partial glycerides and fatty acid alkanolamides,
• - Thickeners, such as. As fatty alcohols, fatty acids, paraffin fin oils, fatty acid esters and other fatty components in emul gated form,
• - Water-soluble, polymeric thickeners, such. Methyl or hydroxyethyl cellulose, starch, vegetable gums, water-soluble synthetic polymers, water-soluble Biopolymers (eg xanthan gum),
• - hair-care additives, such as. B. water-soluble, cationic Polymers, protein derivatives, pantothenic acid, vitamins, plants extracts, cholesterol and sugar,
• - Electrolyte and buffer salts, pH adjusters, complexing agents and Perfume oils,
• - Reducing agent for stabilizing the dye, for. B. Na triumsulfite or ascorbic acid.

The ingredients of the cosmetic carriers are used to prepare the Hair colorants according to the invention in customary for this purpose Quantities used; z. B. become emulsifiers in concentrations from 0.5 to 30% by weight and thickener in concentrations of 0.1 to 25 wt .-% of the total colorant used.  

Particularly suitable as a carrier is a cream emulsion (oil-in-oil). Water emulsion) containing 1 to 25 wt .-% of an emul gelled fat component and 0.5 to 30 wt .-% of an emulsifier from the group of anionic, nonionic, ampholytic or zwitterionic surfactants or a gel with a content of 1 to 20 % By weight of a soap, preferably ammonium oleate.

The oxidation dye precursors are in amounts of from 0.2 to 5 Wt .-%, preferably 1 to 3 wt .-%, of the total colorant in the carrier mixed.

The oxidative development of the staining can basically be done with air oxygen take place. However, preferred is a chemical Oxidati Onsmittel used, especially if in addition to the coloring a Whitening effect on the hair is desired. Come as an oxidizing agent in particular hydrogen peroxide or its addition products Urea, melamine or sodium borate and mixtures of such Hydrogen peroxide addition products with potassium peroxide disulfate in Consideration.

Suitably, the preparation of the oxidizing agent is immediate before hair dyeing with the preparation Oxidation dye precursors and carriers mixed. That here The resulting ready-to-use hair dye preparation should be preferred have a pH in the range of 6 to 10. Especially before zugt is the application of the hair dye in a weak alka English milieu. The application temperatures can be in one range between 15 and 40 ° C lie. After an exposure time of approx. 30 Minutes the hair dye by rinsing of the dye to removed hair. The washing with a shampoo is no longer necessary, if a strong surfactant-containing carrier, for. B. a coloring shampoo, was used.

Hair dyes according to the invention were in the form of a hair dye Be cream emulsion of the following composition:

Fatty alcohol C _12-18 | 10.0 g Fatty alcohol C₁₂-C₁₄ + 2 EO sulfate, Na salt, 28% pure 25.0 g water 60.0 g Developer component (component E) 7.5 mmol Coupler component (component K) 7.5 mmol Na₂SO₃ (inhibitor) 1.0 g concentrated ammonia solution to pH = 9.5 water ad 100 g

As the developer component (component E), the following Ver used:

E 1: p-toluenediamine
E 2: 2-chloro-p-phenylenediamine
E 3: N-methyl-p-phenylenediamine
E 4: 2,5-diaminobenzyl alcohol
E 5: 2- (2-hydroxyethyl) -p-phenylenediamine
E 6: N- (2-hydroxyethyl) -p-phenylenediamine
E 7: N, N-bis- (2-hydroxyethyl) -p-phenylenediamine
E 8: N- (2-methoxyethyl) -p-phenylenediamine
E 9: 3-Chloro-6-methyl-p-phenylenediamine
E10: N, N-diethyl-p-phenylenediamine
E11: p-aminophenol
E12: 2,5-diaminopyridine
E13: N-methylpyrrolidone-2-hydrazone
E14: 2,4,5,6-tetraaminopyrimidine

As coupler component according to the invention (component K) were the the following compounds are used:

K1: 1,3-dihydroindol-2-one
K2: 5-fluoro-1,3-dihydroindol-2-one (known from US 38 82 236)
K3: 6-chloro-1,3-dihydroindol-2-one (known from US 38 82 236)
K4: N-methyl-1,3-dihydroindol-2-one (known from Can. J. Chem. 46 (1968), 2189)
K5: N-methyl-5-chloro-1,3-dihydroindol-2-one (known from US 41 60 632)
K6: 3-chloro-1,3-dihydroindol-2-one (known from J. Het. Chem., 17 II (1980), 1533)

The ingredients were mixed together in order. To Addition of the oxidation dye precursors and the inhibitor was initially using concentrated ammonia solution the pH of the Emulsion adjusted to 9.5, then it was with water to 100 g filled.

The oxidative development of the staining was with 3% water stoffperoxidlösung performed as an oxidizing agent. For this purpose were 100 g of the emulsion with 50 g of hydrogen peroxide solution (3%) ver sets and mixes.

The staining cream was standardized to about 5 cm strands, 90% gray, but not very pre-treated people applied and left there for 30 minutes at 27 ° C. After Be After completion of the dyeing process, the hair was rinsed, with an over washed out hair wash and then dried.  

The results of hair dyeing tests are in the following table shown.

table

Claims (4)

1. oxidation dye, consisting of oxidation dye precursors and a cosmetic carrier, which contain the usual development as Oxidationsfarbstoffprodukte developer compo, characterized in that as Kupplerkompo components 1,3-dihydroindol-2-one of the formula I are included, wherein R ¹ , R ² , R ³ and R ^{4 are} independently hydrogen, alkyl groups having 1-4 C atoms or hydroxyalkyl groups having 2-4 C atoms and R ² , R ³ and R ^{4 may} also be halogen atoms. 2. oxidation dye according to claim 1, characterized in that R ^{1 is} hydrogen or a methyl group and R ² , R ³ and R ^{4 are} hydrogen or one of the groups R ² , R ³ and R ^{4 are} chlorine or fluorine and the remaining hydrogen. 3. hair dye containing Oxidation dye precursors in a cosmetic carrier, characterized in that 1,3-dihydroindole-2-ones of the formula I according to claim 1 as a coupler in an amount of 0.05 to 10 millimoles per 100 grams of the hair dye as well as usual  Developer components and optionally conventional Kupplerkompo are included. 4. hair dye according to claim 3, characterized in that as Carrier a cream emulsion with a content of 1-25 wt .-% an emulsified fat component and 0.5-30% by weight of a Emulsifier from the group of anionic, nonionic, ampholytic or zwitterionic surfactants or a gel with a content of 1-20% by weight of a soap, preferably ammonium oleate, is included.