DE29912881U1 - Medium for coloring keratin colors - Google Patents

Description

Description Agent for coloring keratin colors

The present invention relates to agents for the oxidative coloration of keratin fibers, in particular human hair, based on a developer substance/coupler substance combination which contain certain 2,5-diamino-1-(phenyl)benzene derivatives as developer substance.

Oxidation dyes have become very important in the field of coloring keratin fibers, especially hair coloring. The color is created by the reaction of certain developer substances with certain coupler substances in the presence of a suitable oxidizing agent.

Oxidation dyes used to dye human hair must meet numerous additional requirements in addition to producing the desired intensity. The dyes must be safe from a toxicological and dermatological point of view and the hair dyes must be lightfast, permanent-wave-fast, acid-fast and rub-fast. In any case, such dyes must remain stable for a period of at least 4 to 6 weeks without exposure to light, friction and chemical agents. It is also necessary that a wide range of different color nuances can be produced by combining suitable developer substances and coupler substances.

However, with the dyes currently used it is not possible to meet all of the above requirements.

There is therefore still a need for new developing substances which meet the above-mentioned requirements to a particularly high degree.

It has now been found that certain 2,5-diamino-1-(phenyl)benzene derivatives according to the general formula (I) meet the requirements placed on developer components to a particularly high degree. Thus, using these developer components with certain coupler components, extremely strong color shades are obtained which are extraordinarily lightfast and washfast.

The present invention therefore relates to agents for the oxidative coloration of keratin fibers, such as wool, furs, feathers or hair, in particular human hair, based on a developer substance-coupler substance combination which contains (a) as developer substance 2,5-diamino-1-phenylbenzene derivatives of the general formula (I),

wherein
R1.R2

NH-N,

(I)

independently of each other hydrogen, a

halogen atom, a cyano group, a hydroxy group, a C1-C3-alkoxy group, a C1-C2-alkyl group, a C1-C2-alkylthioether group, an amino group, an alkylamino group, a dialkylamino group, a trifluoromethane group, a C1 _-C2 -hydroxyalkyl group, a C3-C4-dihydroxyalkyl group, a -C(O) _CH3 group or adjacent radicals R1 to R2 form an -O-CH2-O- bridge;

or their physiologically acceptable, water-soluble salts and (b) at least one coupling substance from the group consisting of 1,3-diaminobenzene, 2-amino-4-(2'-hydroxyethyl)amino-anisole, 1,3-diamino-4-(2'-hydroxyethoxy)benzene, 2,4-diamino-5-fluoro-toluene, 3-amino-2-methylamino-6-methoxy-pyridine, 3,5-diamino-2,6-dimethoxypyridine, 2,4-diamino-5-ethoxy-toluene, N-(3-dimethylamino)phenylurea, 1,3-bis(2,4-diaminophenoxy)propane, 3-amino-phenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methyl-phenol, S-amino^-fluor^-methylphenol, 1-naphthol, i-Acetoxy-2-methyl-naphthalene, 1,3-dihydroxy-benzene, 2-methyl-1,3-dihydroxy-benzene, 1-chloro-2,4-dihydroxy-benzene, 4-(2'-hydroxyethyl)amino-1,2-methylenedioxybenzene, 3,4-methylenedioxyphenol and 2-amino-5-methyl-phenol or their physiologically acceptable, water-soluble salts.

Examples of compounds of formula (I) which may be mentioned are: 2,5-diamino-1-(2-(2-hydroxyethyl)phenyl)benzene; 2,5-diamino-1-(2-aminophenyl)benzene; 2,5-diamino-1-(2-chlorophenyl)benzene; 2,5-diamino-1-(2-cyanophenyl)benzene; 2,5-diamino-1-(2-ethoxyphenyl)benzene; 2,5-diamino-1-(2-fluorophenyl)benzene; 2,5-diamino-1-(2-hydroxyphenyl)benzene; 2,5-diamino-1-(2-methoxyphenyl)benzene; 2,5-diamino-i-(2-methyl-

phenyl)benzene; 2,5-diamino-1-(2-trifluoromethyl-phenyl)benzene; 2,5- diamino-1-(3-(2-hydroxyethyl)-phenyl)benzene; 2,5-diamino-1-(3-annino-

cyanophenyl)benzene; 2,5-diamino-1-(3-ethoxy-phenyl)benzene; 2,5-diamino-1-(3-fluorophenyl)benzene; 2,5-diamino-1-(3-hydroxy-phenyl)benzene; 2,5-diamino-1-(3-methoxyphenyl)benzene; 2,5-diamino-1-(3-methylphenyl)benzene; 2,5-diamino-i-(3-trifluoromethyl-phenyl)benzene; 2,5-diamino-1-(4-(2-hydroxyethyl)phenyl)benzene; 2,5-diamino-1-(4-aminophenyl)benzene; 2,5-diamino-1-(4-chloro-phenyl)benzene; 2,5-diamino-1-(4-cyanophenyl)benzene; 2,5-diamino-1-(4-ethoxy-phenyl)benzene; 2,5-diamino-1-(4-fluorophenyl)benzene; 2,5-diamino-1-(4-hydroxy-phenyl)benzene; 2,5-diamino-1-(4-methoxy-phenyl)benzene; 2,5-diamino-1-(4-methylphenyl)benzene; 2,5-diamino-1-(4-trifluoromethyl-phenyl)benzene; 2,5-diamino-1-(2-methyl-3-fluoro-phenyl)benzene; 2,5-diamino-1-(2-methyl-3-hydroxy-phenyl)benzene; 2,5-diamino-1-(2-methyl-3-methoxyphenyl)benzene; 2,5-diamino-1-(2-methyl-3-methyl-phenyl)benzene; 2,5-diamino-1-(2-methyl-fluoro-phenyl)benzene; 2,5-diamino-1-(2-methylhydroxy-phenyl)benzene; 2,5-diamino-1-(2-methyl-methoxy-phenyl)benzene; 2,5-diamino-1-(2-methyl-methyl-phenyl)benzene; 2,5-Diamino-i-(2-methyl-4-fluoro-phenyl)benzene; 2,5-diamino-1-(2-methyl-4-hydroxy-phenyl)benzene; 2,5-diamino-1-(2-methyl-4-methoxyphenyl)benzene; 2,5-diamino-1-(2-methyl-4-methyl-phenyl)benzene; 2,5-diamino-1-(2-methyl-5-fluorophenyl)benzene; 2,5-diamino-1-(2-methyl-5-hydroxy-phenyl)benzene; 2,5-diamino-1-(2-methyl-5-methoxy-phenyl)benzene; 2,5-diamino-1-(2-methyl-5-methyl-phenyl)benzene; 2,5-diamino-1-(2-methyl-6-fluoro-phenyl)benzene; 2,5-diamino-1-(2-methyl-6-hydroxy-phenyl)benzene; 2,5-diamino-1-(2-methyl-6-methoxy-phenyl)benzene; 2,5-diamino-1-(2-methyl-6-methylphenyl)benzene; 2,5-diamino-1-(2-methoxy-3-fluorophenyl)benzene; 2,5-diamino-1-(2-methoxy-3-hydroxy-phenyl)benzene; 2,5-diamino-1-(2-

/VT

methoxy-3-methoxyphenyl)benzene; 2,5-diamino-1-(2-methoxy-3-methylphenyl)benzene; 2,5-diamino-1-(2-methoxy-4-fluoro-phenyl)benzene; 2,5-diamino-1-(2-methoxy-4-hydroxy-phenyl)benzene; 2,5-diamino-1-(2-methoxy-4-methoxy-phenyl)benzene; 2,5-diamino-1-(2-methoxy-4-methylphenyl)benzene; 2,5-diamino-1-(2-methoxy-5-fluorophenyl)benzene; 2,5-diamino-1-(2-methoxy-5-hydroxy-phenyl)benzene; 2,5-diamino-1-(2-methoxy-5-methoxy-phenyl)benzene; 2,5-diamino-1-(2-methoxy-5-methylphenyl)benzene; 2,5-diamino-1-(2-methoxy-6-fluoro-phenyl)benzene; 2,5-diamino-1-(2-methoxy-6-hydroxy-phenyl)benzene; 2,5-diamino-1-(2-methoxy-6-methoxy-phenyl)benzene; 2,5-diamino-1-(2-methoxy-6-methylphenyl)benzene; 2,5-diamino-1-(3-methyl-4-fluoro-phenyl)benzene; 2,5-diamino-1-(3-methyl-4-hydroxy-phenyl)benzene; 2,5-diamino-1-(3-methyl-4-methoxyphenyl)benzene; 2,5-diamino-1-(3-methyl-4-methyl-phenyl)benzene; 2,5-diamino-1-(3-methyl-5-fluoro-phenyl)benzene; 2,5-diamino-1-(3-methyl-5-hydroxy-phenyl)benzene; 2,5-diamino-1-(S-methyl-S-methoxyphenyl)benzene; 2,5-diamino-1-(3-methyl-5-methylphenyl)benzene; 2,5-diamino-1-(3-methyl-6-fluoro-phenyl)benzene; 2,5-diamino-1-(3-methyl-6-hydroxy-phenyl)benzene; 2,5-diamino-1-(3-methyl-6-methoxyphenyl)benzene; 2,5-diamino-1-(3-methyl-6-methyl-phenyl)benzene; 2,5-diamino-1-(2-fluoro-3-methylphenyl)benzene; 2,5-diamino-1-(2-fluoro-4-methylphenyl)benzene; 2,5-diamino-1-(2-fluoro-5-methyl-phenyl)benzene; 2,5-diamino-1-(2-fluoro-6-methyl-phenyl)benzene; 2,5-diamino-1-(2-chloro-3-chloro-phenyl)benzene; 2,5-diamino-1-(2-chloro-3-methyl-phenyl)benzene; 2,5-diamino-1-(2-chloro-4-chloro-phenyl)benzene; 2,5-diamino-1-(2-chloro-4-methyl-phenyl)benzene; 2,5-diamino-1-(2-chloro-5-chloro-phenyl)benzene; 2,5-diamino-1-(2-chloro-5-methyl-phenyl)benzene; 2,5-diamino-1-(2-chloro-6-chloro-phenyl)benzene; 2,5-diamino-1-(2-chloro-6-methyl-phenyl)benzene; 2,5-diamino-1-(2-acetyl-phenyl)benzene; 2,5-diamino-1-(3-acetylphenyl)benzene; 2,5-diamino-1-(4-acetyl-phenyl)benzene; 2,5-Diamino-1 -(3,4-

methylenedioxyphenyl)benzene; 2,5-Diamino-1-(2,3-methylenedioxyphenyl)benzene.

Preferred compounds of formula (I) are those in which R1 is hydrogen and R2 is methyl, chlorine, fluorine, methoxy, hydroxy, amino trifluoromethyl, or adjacent radicals R1, R2 form an -O-CH2-O- bridge.

Particularly suitable 2,5-diamino-1-(phenyl)benzene derivatives of the formula (I) are

2,5-diamino-1-phenyl-benzene;

2,5-diamino-1-(4-methoxy-phenyl)benzene; 2,5-diamino-1-(3-methoxyphenyl)benzene; 2,5-diamino-1-(4-amino-phenyl)benzene; 2,5-diamino-1-(2-methyl-phenyl)-benzene; 2,5-diamino-1-(3-methyl-phenyl)-benzene; 2,5-diamino-1-(4-methyl-phenyl)benzene; 2,5-diamino-1-(4-hydroxyphenyl)benzene; 2,5-diamino-1-(2-trifluoromethyl-phenyl)benzene; 2,5-diamino-1-(4-fluorophenyl)benzene and 2,5-diamino-1-(4-chlorophenyl)benzene, or their physiologically compatible salts.

The compounds of formula (I) can be used both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, such as hydrochloric acid, sulphuric acid, phosphoric acid, acetic acid, propionic acid, lactic acid or citric acid.

The 2,5-diamino-1-(phenyl)benzene derivative of formula (I) is contained in the colorant according to the invention in an amount of about 0.005 to 20 percent by weight, with an amount of about 0.01 to 10

Weight percent and especially 0.1 to 5 weight percent is preferred.

To achieve certain color nuances, other conventional coupler substances can be added to the agent according to the invention, such as, for example, 2,6-diaminopyridine, 2,4-diamino-1-methoxy-5-methylbenzene, 2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene, 2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene, 2,3-diamino-6-methoxypyridine, 2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 2,4-diamino-1,5-di(2-hydroxyethoxy)benzene, 1-(2-aminoethoxy)-2,4-diaminobenzene,2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene, 2,4-diaminophenoxyacetic acid, 3-[Di(2-hydroxyethyl)amino]-aniline, 4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxy-benzene, 5-methyl-2-(1-methylethyl)-phenol, 3-[(2-hydroxyethyl)amino]-aniline, 3-[(2-aminoethyl)-amino]-aniline, di(2,4-diaminophenoxy)-methane, 1, 3-Diamino-2,4-dimethoxy-benzene, 2,6-bis(2-hydroxyethyl)amino-toluene, 4-hydroxyindole, 3-dimethylamino-phenol, 3-diethylamino-phenol, 5-amino-4-methoxy-2-methyl-phenol, S-amino^-ethoxy^-methyl-phenol, 3-amino-2,4-dichlorophenol, 5-amino-2,4- dichlorophenol, S-amino^-methyl-phenol, 2-[(3-Hydroxyphenyl)amino]-acetamide, 5-[(2-hydroxyethyl)amino]-2-methyl-phenol, 3-[(2-hydroxyethyl)amino]-phenol, 3-[(2-methoxyethyl)-amino]-phenol, 5-amino-2-ethyl-phenol, 2-(4-amino-2-hydroxyphenoxy)-ethanol, 5-[(3- Hydroxypropyl)amino]-2-methyl-phenol, 3-[(2,3-dihydroxypropyl)amino]-2-methyl-phenol, 3-[(2-hydroxyethyl)amino]-2-methylphenol, 2-amino-3-hydroxy-pyridine, δ-amino^-chloro^-methyl-phenol, 1,5-dihydroxy-naphthalene, 1,7-dihydroxy-naphthalene, 2,3-dihydroxy-na phthalene, 2,7-dihydroxy-naphthalene, 1 ^-Dichloro-S.ö-dihydroxy^-methyl-benzene, 3,4-methylenedioxy-aniline, 6-bromo-1 -hydroxy-S^-methylenedioxy-benzene, 3,4-diamino-benzoic acid, 3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine, 6-

Amino-3,4-dihydro-1,4(2H)-benzoxazine, 3-methyl-1-phenyl-5-pyrazolone, 5,6-dihydroxyindole, 5,6-dihydroxyindoline, 5-hydroxyindole, 6-hydroxyindole,7-hydroxyindole and 2,3-indolindione may be added.

Although the advantageous properties of the diaminobenzene derivatives of the formula (I) described here suggest that they should be used as the sole developer, it is of course also possible to use the diaminobenzene derivatives of the formula (I) together with known developer substances, such as, for example, 1,4-diaminobenzene, 2,5-diaminotoluene, 2,5-diaminophenylethanol, 4-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4,5-diamino-1-(2'-hydroxyethyl)pyrazole, N,N-bis-(2'-hydroxyethyl)-p-phenylenediamine, 2,5-diamino-i ,V- biphenyl or tetraaminopyrimidines.

The coupler substances and developer substances can be contained in the colorant according to the invention individually or in a mixture with one another, the total amount of coupler substances and developer substances in the colorant according to the invention (based on the total amount of the colorant) being in each case about 0.005 to 20 percent by weight, preferably about 0.01 to 10 percent by weight and in particular 0.1 to 5 percent by weight.

The total amount of the developer substance-coupler substance combination contained in the dye described here is preferably about 0.01 to 25 percent by weight, with an amount of about 0.02 to 15 percent by weight and in particular 0.2 to 8.0 percent by weight being particularly preferred. The developer substances and coupler substances are generally used in approximately equimolar amounts; however, it is not disadvantageous if the developer substances

in this respect are present in a certain excess or deficiency (for example in a ratio (coupler: developer) of 1:2 to 1:0.5).

Furthermore, the colorant according to the invention can additionally contain other color components, for example 6-amino-2-methylphenol and 2-amino-5-methylphenol, as well as conventional direct dyes, for example triphenylmethane dyes such as 4-[(4'-aminophenyl)-(4'imino-2",5"-cyclohexadien-1"-ylidene)-methyl]-2-methylaminobenzene monohydrochloride (Cl. 42 510) and 4-[(4 ^l amino-3'-methyl-phenyl)-(4"-imino-3"-methyl-2" _I 5"cyclohexadien-1"-ylidene)-methyl]-2-methyl-aminobenzene monohydrochloride (Cl. 42 520), aromatic nitro dyes such as 4-(2'-hydroxyethyl)amino-nitrotoluene, 2-amino-4,6-dinitrophenol, 2-Amino-5-(2'-hydroxyethyl)amino-nitrobenzene, 6-chloro-2-(ethylamino)-4-nitrophenol, 4-chloro-N-(2-hydroxyethyl-2-nitroaniline, S-chloro^-hydroxy^-nitroaniline, 2-amino-6-chloro-4-nitrophenol and 1-[(2'-ureidoethyl)amino-4-nitrobenzene, azo dyes such as 6-[(4'-aminophenyl)azo]-5-hydroxy-naphthalene-1-sulfonic acid sodium salt (Cl. 14 805) or 2,6-diamino-3-((pyridin-3-yl)azo)pyridine and disperse dyes such as 1,4-diaminoanthraquinone, a mixture of N-hydroxyethyl and N-hydroxypropyl derivative of 1,4-diaminoanthraquinone. The colorants may contain these color components in an amount of about 0.1 to 4.0 percent by weight.

Of course, the coupler substances and developer substances as well as the other colour components, if they are bases, can also be used in the form of physiologically acceptable salts with organic or inorganic acids, such as hydrochloric acid or sulphuric acid, or - if they have aromatic OH groups -

in the form of salts with bases, for example as alkali phenolates.

In addition, if the dyes are to be used to dye hair, they can also contain other conventional cosmetic additives, for example antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite, as well as perfume oils, complexing agents, wetting agents, emulsifiers, thickeners and care substances. The preparation form of the dye according to the invention can be, for example, a solution, in particular an aqueous or aqueous-alcoholic solution. The particularly preferred preparation forms, however, are a cream, a gel or an emulsion. Their composition represents a mixture of the dye components with the additives customary for such preparations.

Common additives in solutions, creams, emulsions or gels are, for example, solvents such as water, lower aliphatic alcohols, for example ethanol, propanol or isopropanol, glycerin or glycols such as 1,2-propylene glycol, as well as wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or non-ionic surface-active substances such as fatty alcohol sulfates, oxyethylated fatty alcohol sulfates, alkyl sulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkyl betaines, oxyethylated fatty alcohols, oxyethylated nonylphenols, fatty acid alkanolamides and oxyethylated fatty acid esters, as well as thickeners such as higher fatty alcohols, starch, cellulose derivatives, petrolatum, paraffin oil and fatty acids, as well as care substances such as cationic resins, lanolin derivatives, cholesterol, pantothenic acid and betaine. The components mentioned are used in the amounts usual for such purposes, for example the wetting agents

and emulsifiers in concentrations of about 0.5 to 30 percent by weight, the thickeners in an amount of about 0.1 to 25 percent by weight and the care substances in a concentration of about 0.1 to 5.0 percent by weight.

Depending on the composition, the colorant according to the invention can react in a slightly acidic, neutral or alkaline manner. In particular, it has a pH value of 6.8 to 11.5, with the basic adjustment preferably taking place with ammonia. However, organic amines, for example monoethanolamine and triethanolamine, or inorganic bases such as sodium hydroxide and potassium hydroxide can also be used. Inorganic or organic acids, for example phosphoric acid, acetic acid, citric acid or tartaric acid, can be used for pH adjustment in the acidic range.

For use in the oxidative coloring of hair, the dye described above is mixed with an oxidizing agent immediately before use and a sufficient amount of this mixture for the hair coloring treatment, depending on the thickness of the hair, generally about 60 to 200 grams, is applied to the hair.

The oxidizing agents used to develop hair coloring are mainly hydrogen peroxide or its addition compounds with urea, melamine, sodium borate or sodium carbonate in the form of a 3 to 12 percent, preferably 6 percent, aqueous solution, but also atmospheric oxygen. If a 10 percent hydrogen peroxide solution is used as the oxidizing agent, the weight ratio between hair dye and oxidizing agent is 5:1 to 1:2, but preferably 1:1. Larger amounts of oxidizing agent

are used primarily when the dye concentration in the hair dye is higher, or when the hair is to be bleached more strongly. The mixture is left to act on the hair at 15 to 50 degrees Celsius for about 10 to 45 minutes, preferably 30 minutes, then the hair is rinsed with water and dried. If necessary, the hair is washed with a shampoo after this rinse and possibly rinsed with a weak organic acid, such as citric acid or tartaric acid. The hair is then dried.

The dyes according to the invention containing (a) diaminobenzene derivatives of formula (I) as developer substance and (b) certain coupler substances enable dyes with excellent color fastness, particularly with regard to light fastness, wash fastness and rubbing fastness. In terms of coloring properties, the dyes according to the invention offer a wide range of different color nuances, depending on the type and composition of the color components, which range from blonde to brown, purple, violet to blue and black shades. The shades are characterized by their particular color intensity. The very good coloring properties of the dyes according to the present application are also shown in the fact that these agents also enable gray hair that has not been chemically damaged to be colored easily and with good coverage.

The 2,5-diamino-1-phenylbenzene derivatives of formula (I) used in the agent according to the invention are readily soluble in water and, in combination with the coupler substances according to the invention, enable dyeings with high color intensity and

excellent colour fastness, particularly with regard to light fastness, wash fastness and rubbing fastness. They also have excellent storage stability, particularly as a component of the dyes described above.

The preparation of the 2,5-diamino-1-phenylbenzene derivatives of formula (I) according to the invention can be carried out using known synthesis methods.

The following examples are intended to illustrate the subject matter of the invention in more detail without limiting it thereto.

Examples Example 1 to 136: Oxidation hair dyes

Cream-shaped color mass

X g developer substance E1 of formula (I) according to

following tables
U g developer substance E2 to E9 according to the following

Tables

Y g Coupler substance K according to the following tables Z g Dye D according to the following tables 15.0 g Cetyl alcohol
0.3 g ascorbic acid

3.5 g sodium lauryl alcohol diglycol ether sulfate, 28% aqueous solution

3.0 g ammonia 22% aqueous solution 0.3 g sodium sulphite, anhydrous
ad 10Og water

Immediately before use, 30 g of the above coloring cream are mixed with 30 g of a 6% hydrogen peroxide solution. The mixture is then applied to the hair. After 30 minutes, the hair is rinsed with water, washed with a commercially available shampoo and dried. The coloring results can be seen in the tables below.

The abbreviations used in the following tables have the following meaning:

Developer substances 2,5-Diamino-i-phenyl-benzene hydrochloride E1 1,4-Diaminobenzene E2 2,5-diamino-phenylethanol sulfate E3 3-methyl-4-aminophenol E4 4-Amino-2-aminomethylphenol dihydrochloride E5 4-Aminophenol E6 N,N-Bis(2'-hydroxyethyl)-p-phenylenediamine sulfate E7 4,5-Diamino-1-(2'-hydroxyethyl)-pyrazole sulfate E8 2,5-Diaminotoluene sulfate E9

Couplers 1,3-Diaminobenzene K11 2-Amino-4-(2'-hydroxyethyl)aminoanisole sulfate K12 1,3-Diamino-4-(2'-Hydroxyethoxy)benzene sulfate K13 2,4-Diamino-5-fluoro-toluene sulfate K14 3-Amino-2-methylamino-6-methoxy-pyridine K15 S.S-Diamino^.e-dimethoxy-pyridine dihydrochloride K16 2,4-diamino-5-ethoxy-toluene sulfate K17 N-(3-Dimethylamino)phenylurea K18 1,3-Bis(2,4-diaminophenoxy)propane tetrahydrochloride K19 3-Aminophenol K21 5-Amino-2-methylphenol K22 S-Ammo^-chloro-ö-methyl-phenol K23 ö-Ammo^-fluoro^-methyl-phenol-sulfate K24 1-Naphthol K25 1 -Acetoxy^-methyl-naphthalene K26 1,3-Dihydroxybenzene K31 2-methyl-1,3-dihydroxybenzene K32 1-Chloro-2,4-dihydroxybenzene K33 4-(2'-Hydroxyethyl)amino-1,2-methylenedioxybenzene
hydrochlorid K34 3,4-methylenedioxyphenol K35 2-Amino-5-methyl-phenol K36

Direct dyes 2,6-Diamino-3-((pyridin-3-yl)azo)pyridine D1 ö-chloro^-ethylamino^-nitro-phenol D2 2-Amino-6-chloro-4-nitro-phenol D3

E.g. 1 2 3 4 5 6 Color
fabrics E1 2.71 0.19 0.067 0.4 4.67 0.112 K12 0.15 0.004 2.0 0.013 K21 0.32 0.003 0.7 0.02 K22 0.026 0.02 K25 0.03 K31 0.786 0.04 0.175 1.5 K32 0.04 0.15 D3 0.05 0.01 Color dark
brown bright
blond bright
aubergine warm
brown blue
black pearl silver-
blond

E.g. 7 8th 9 10 11 12 13 Color
fabrics E1 2.15 1.01 2.60 0.70 0.20 1.06 0.112 E4 0.52 0.036 0.01 0.165 0.01 0.01 0.01 K12 0.07 0.013 K16 0.068 K18 0.03 K21 0.06 0.418 0.76 0.016 0.02 K22 0.58 0.056 0.165 0.01 0.016 K25 0.03 K31 0.8 0.2 0.66 0.135 K32 0.316 0.06 0.451 K34 0.048 K35 0.03 K36 0.01 0.27 D1 0.01 D2 0.012 0.015 D3 0.16 0.02 Color dark-
maha-
goni purple
brown black
-brown chocolate
brown Sahara
brown color
do
brown silver
blond

E.g. 14 15 16 17 18 19 20 Color
fabrics E1 0.93 3.99 3.74 2.66 2.60 2.10 1.02 E4 0.25 0.1 0.03 0.55 0.015 0.16 0.01 K11 0.28 K13 0.23 0.075 K14 0.2 K15 0.02 0.065 K17 0.025 K19 0.15 K21 0.4 0.06 0.418 0.76 0.016 K23 0.15 0.57 0.16 K24 0.015 K31 0.10 1.05 0.8 0.66 0.135 K32 0.12 0.451 K33 0.72 K34 1.01 1.05 0.048 K36 0.17 0.27 D2 0.012 0.015 D3 0.16 Color frosted medium
brown dark
brown dark-
maha-
goni black
-brown chocolate
brown color
do
brown

E.g. 21 22 23 24 Color
fabrics E1 0.07 0.76 0.088 0.111 E4 0.01 0.16 0.01 0.01 K16 0.015 K17 0.015 0.01 K19 0.72 K21 0.02 0.76 0.02 0.025 K24 0.16 K25 0.03 K26 0.025 0.05 K31 0.135 K36 0.27 D2 0.012 Color silver
blond chocolate
brown silver
blond silver-
Blond

* 4 # φ # 4 · 4

E.g. 25 26 27 28 29 30 31 Color
fabrics E1 2.16 1.00 2.63 0.70 0.20 1.06 0.112 E5 0.89 0.062 0.017 0.28 0.017 0.016 0.015 K12 0.075 0.015 K16 0.07 K18 0.035 K21 0.07 0.42 0.75 0.018 0.02 K22 0.59 0.05 0.17 0.015 0.018 K25 0.035 K31 0.85 0.2 0.66 0.135 K32 0.315 0.065 0.45 K34 0.05 K35 0.033 K36 0.015 0.27 D1 0.015 D2 0.012 0.015 D3 0.16 0.025 Color dark-
maha-
goni purple
brown black
-brown chocolate
brown Sahara color
do
brown silver
blond

E.g. 32 33 34 35 36 37 38 Color
fabrics E1 2.15 1.01 2.60 0.70 0.20 1.06 0.112 E6 0.46 0.031 0.008 0.146 0.007 0.008 0.0075 K12 0.07 0.015 K16 0.07 K17 K18 0.03 K21 0.07 0.415 0.76 0.015 0.02 K22 0.59 0.05 0.165 0.01 0.016 K25 0.035 K31 0.85 0.25 0.65 0.14 K32 0.32 0.055 0.45 K34 0.049 K35 0.035 K36 0.015 0.275 D1 0.011 D2 0.015 0.015 D3 0.16 0.02 Color dark-
maha-
goni purple
brown black
-brown chocolate
brown Sahara
brown color
do
brown silver
blond

E.g. 39 40 41 42 43 44 45 Color
fabrics E1 0.94 3.99 3.74 2.66 2.61 2.10 1.02 E6 0.22 0.09 0.026 0.48 0.013 0.14 0.008 K11 0.28 K13 0.23 0.076 K14 0.2 K15 0.02 0.07 K17 0.025 K19 0.18 K21 0.39 0.06 0.415 0.75 0.02 K23 0.18 0.59 0.16 K24 0.015 K31 0.15 1.1 0.86 0.69 0.14 K32 0.125 0.452 K33 0.72 K34 1.05 1.05 0.048 K36 0.18 0.27 D2 0.012 0.018 D3 0.16 Color frosted medium
brown dark
brown dark-
maha-
goni black
-brown chocolate
brown color
do
brown

E.g. 46 47 48 49 Color
fabrics E1 0.07 0.76 0.088 0.111 E6 0.006 0.14 0.008 0.008 K16 0.015 K17 0.015 0.01 K19 0.74 K21 0.019 0.77 0.021 0.024 K24 0.16 K25 0.032 K26 0.025 0.05 K31 0.138 K36 0.27 D2 0.013 Color silver
blond chocolate
brown silver
blond silver
blond

E.g. 50 51 52 53 54 55 56 Color
fabrics E1 5.01 2.38 2.16 0.117 4.68 5.06 0.38 E7 0.1 0.6 0.5 1.6 0.5 2.2 0.8 K11 0.8 K12 0.2 K13 1.52 K14 0.8 K15 0.2 K16 4.96 K18 0.05 K19 0.2 K21 0.7 0.5 K22 1.43 0.5 K25 1.30 0.50 K31 1.66 1.98 K32 0.5 K33 0.72 K34 1.37 K35 0.35 K36 0.01 Color blue
black red
violet blue
green green medium
brown black cold
blue

E.g. 57 58 59 60 61 62 63 Color
fabrics E1 1.46 2.38 5.00 4.73 5.06 4.67 4.91 E7 3.19 0.6 0.1 0.5 2.2 0.49 2.15 K12 0.15 K13 0.145 K17 1.65 0.25 K19 0.31 K21 0.7 0.5 0.5 K23 2.5 0.38 0.4 K24 2.77 K26 0.69 0.7 K31 1.65 1.95 1.9 K32 0.55 0.48 K33 0.72 0.75 K34 1.37 1.4 K36 0.015 D1 0.01 D2 0.05 D3 0.1 Color warm
blue red
violet blue
black medium
brown black medium
brown black

E.g. 64 65 Color
fabrics E1 4,882 5,138 E7 2.2 2.0 K12 3.4 K19 K21 0.5 K24 1.55 K25 0.50 K31 1.98 1.04 Color blue
black blue
black

E.g. 66 67 68 69 70 71 72 73 Color
fabrics E1 3.27 0.59 0.06 2.02 3.25 0.584 0.059 2.03 E3 1.46 0.59 0.02 0.05 1.45 0.61 0.021 0.05 E4 0.01 0.01 0.10 0.01 E5 0.017 0.016 0.17 0.017 K11 0.20 0.21 K12 0.63 0.63 K13 0.30 0.32 K15 0.04 0.04 K16 0.01 0.01 K17 0.01 0.01 K18 0.50 0.5 K19 0.08 0.81 K21 0.30 0.03 0.02 0.32 0.03 0.025 K22 0.015 0.016 K23 0.312 0.315 K31 1.10 0.015 1.15 0.015 K32 0.05 0.08 0.25 0.052 0.085 0.26 K33 0.05 0.05 K34 0.01 0.011 K35 0.50 0.51 K36 0.03 0.03 Color schw
arz brown bright
blond dark
brown schw
arz brown bright
blond dark
brown

E.g. 74 75 76 77 78 79 80 Color
fabrics &Egr;1 2.16 3.24 0.59 0.059 2.03 3.71 3.64 &Egr;3 1.44 0.62 0.02 0.05 4.5 4.52 &Egr;6 0.008 0.008 0.087 0.008 0.007 0.008 &Egr;7 0.40 &Egr;8 0.01 0.82 0.81 &Kgr;11 0.80 0.2 &Kgr;12 0.63 &Kgr;13 0.31 &Kgr;14 0.25 0.24 &Kgr;15 0.01 0.04 &Kgr;16 0.01 &Kgr;17 0.01 &Kgr;18 0.5 &Kgr;19 0.81 &Kgr;21 0.32 0.031 0.025 &Kgr;22 0.016 4.55 4.5 &Kgr;23 0.325 &Kgr;24 &Kgr;25 1.35 0.55 &Kgr;26 0.77 &Kgr;31 1.25 0.016 &Kgr;32 0.051 0.085 0.26 &Kgr;33 0.05

K34 blue
green black 0.51 0.011 dark
brown red
violet red
violet K35 0.03 K36 brown Color bright
blond

E.g. 81 82 83 84 Dyes E1 3.62 3.62 3.68 3.64 E3 4.5 4.5 4.5 4.52 E4 0.01 0.01 E5 0.015 0.017 E8 0.81 0.81 0.82 0.81 K14 0.25 0.24 0.25 0.24 K22 4.5 4.5 4.52 4.5 K25 0.54 0.54 K26 0.75 0.77 Color red
violet red
violet red
violet red
violet

E.g. 85 86 87 88 89 90 91 92 Color
fabrics E1 3.27 0.59 0.059 2.03 3.25 0.58 0.059 2.03 E9 1.46 0.59 0.02 0.05 1.45 0.61 0.021 0.05 E4 0.01 0.01 0.10 0.01 E5 0.017 0.016 0.17 0.017 K11 0.20 0.21 K12 0.63 0.63 K13 0.30 0.32 K15 0.04 0.04 K16 0.01 0.01 K17 0.01 0.01 K18 0.50 0.5 K19 0.08 0.81 K21 0.30 0.03 0.02 0.32 0.03 0.025 K22 0.015 0.016 K23 0.312 0.315 K31 1.10 0.015 1.15 0.015 K32 0.05 0.08 0.25 0.052 0.085 0.26 K33 0.05 0.05 K34 0.01 0.011 K35 0.50 0.51 K36 0.03 0.03 Color schw
arz brown bright
blond dark
brown schw
arz brown bright
blond dark
brown

E.g. 93 94 95 96 97 98 99 Color
fabrics E1 2.16 3.24 0.59 0.059 2.03 3.71 3.64 E9 1.44 0.62 0.02 0.05 4.5 4.52 E6 0.008 0.008 0.087 0.008 0.007 0.008 E7 0.40 E8 0.01 0.82 0.81 K11 0.80 0.2 K12 0.63 K13 0.31 K14 0.25 0.24 K15 0.01 0.04 K16 0.01 K17 0.01 K18 0.5 K19 0.81 K21 0.32 0.031 0.025 K22 0.016 4.55 4.5 K23 0.325 K24 K25 1.35 0.55 K26 0.77 K31 1.25 0.016 K32 0.051 0.085 0.26 K33 0.05 K34 0.011

K35 blue
green black 0.51 bright
blond dark
brown red
violet red
violet K36 0.03 Color brown

E.g. 100 101 102 103 Dyes E1 3.62 3.62 3.68 3.64 E9 4.5 4.5 4.5 4.52 E4 0.01 0.01 E5 0.015 0.017 E8 0.81 0.81 0.82 0.81 K14 0.25 0.24 0.25 0.24 K22 4.5 4.5 4.52 4.5 K25 0.54 0.54 K26 0.75 0.77 Color red
violet red
violet red
violet red
violet

E.g. 104 blue 105 106 107 108 109 110 Color
fabrics E1 5.26 0.059 1.05 0.94 0.95 0.94 0.94 E8 0.05 2.24 1.2 1.12 1.0 1.26 0.7 K11 0.55 K15 0.35 K17 2.01 K19 2.6 K18 0.3 K21 0.1 K22 0.15 1.12 K23 1.5 K24 2.17 K26 1.11 K31 0.1 0.1 K32 0.2 K34 0.1 K35 1.15 K36 0.35 D2 0.55 Color red
orange boron
deaux boron
deaux dark
violet boron
deaux blue-
brown

E.g. 111 112 113 114 115 116 117 Color
fabrics E1 0.94 1.05 0.82 0.59 1.05 0.4 0.91 E8 1.0 1.2 1.1 1.0 0.9 2.0 0.16 K12 2.0 K13 1.6 K14 0.3 K16 0.1 K18 0.3 0.7 K21 0.1 K22 0.15 1.14 0.9 K23 0.95 K25 0.8 0.1 K32 0.2 K33 0.5 Color dark
violet boron
deaux blue
violet blue
violet blue
violet blue red dark
red
violet

E.g. 118 119 120 Color
fabrics E1 0.29 1.64 0.55 E8 1.3 0.3 0.5 K13 0.75 0.2 K22 0.15 0.5 0.15 K25 0.1 0.2 K31 0.12 0.2 0.1 K32 0.2 0.15 Color red
violet dark
blue
violet blue red

E.g. 121 122 123 124 125 126 127 128 Color
fabrics E1 0.391 0.59 0.91 0.73 0.38 E4 0.51 1.5 0.01 0.35 1.04 E5 0.038 0.25 0.55 E6 0.1 0.535 1.31 E8 0.5 0.01 0.2 0.05 0.1 0.1 0.06 0.01 K11 0.5 K15 0.013 K22 0.3 1.1 0.9 0.28 0.67 K23 0.52 0.02 K24 3.48 K26 0.138 K31 0.32 0.4 0.31 K32 0.33 0.22 0.5 0.2 K35 0.46 K36 0.15 D1 0.25 0.35 D2 0.49 D3 0.3 0.40 Color red
orange warm
it
yellow orange yellow-
orange yellow
orange dark
red-violet maha-
goni red
brown

E.g. 129 130 131 132 133 134 135 136 Color
fabrics E1 3.26 0.026 0.111 0.257 0.806 0.78 0.77 0.78 E2 1.0 0.015 0.4 0.29 0.1 E4 0.35 E5 0.6 E6 0.31 E8 0.05 2.24 1.25 1.12 1.02 0.06 0.06 0.06 K11 0.56 K15 0.36 K17 2.02 K18 0.35 K21 0.15 K22 0.155 K23 1.5 K24 2.15 0.55 0.544 0.546 K26 1.1 K31 0.155 0.42 0.41 K32 0.2 0.4 K35 1.15 K36 0.35 D2 0.55 D3 0.05 0.05 0.05 Color blue red
orange boron
deaux boron
deaux violet maha-
goni maha-
goni maha-
goni

38 Examples 137:

Hair dye solutions of the following composition are produced:

0.600 g developer substance of formula (I) according to Table

0.137 g 1,3-dihydroxybenzene

0.150 g 1-chloro-2,4-dihydroxybenzene

0.100 g 3-aminophenol

10,000 g potassium oleate (8% aqueous solution)

10,000 g ammonia (22% aqueous solution)

10,000 g ethanol

0.300 g ascorbic acid

ad 100,000 g water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6 percent hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 "Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyes are summarized in Table 1.

Table 1

Example Developer substance of formula (I) received
coloring 1a 2,5-Diamino-1-(phenyl)benzene*HCl medium blonde 1b 2,5-Diamino-1-(4-amino-phenyl)benzene*HCl medium blonde 1c 2,5-Diamino-1-(4-hydroxy-phenyl)benzene*HCl medium blonde 1d 2,5-Diamino-1-(4-fluoro-phenyl)benzene*HCl medium blonde

Examples 138:

Hair dye solutions of the following composition are produced:

0.600g 0.137g 0.150g 0.100g

10,000g 10,000g 10,000g 0.300g

up to 100,000 g

Developer substance of formula (I) according to table 1,3-dihydroxybenzene 1-chloro-2,4-dihydroxybenzene 5-amino-2-methylphenol Potassium oleate (8% aqueous solution) Ammonia (22% aqueous solution) Ethanol Ascorbic acid Water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6% hydrogen peroxide solution. The mixture is then applied to bleached hair. After an exposure time of 30 minutes at 40 Xelsius

The hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting colors are summarized in the table.

Table 2

Example Developer substance of formula (I) received
coloring 2a 2,5-Diamino-1-(4-methyl-phenyl)benzene*HCl medium blonde 2 B 2,5-Diamino-1-(3,4-methylenedioxy-
phenyl)benzene*HCI medium blonde 2c 2,5-Diamino-1-(2-trifluoromethyl-phenyl)benzene*HCl medium blonde

Examples 139:

Hair dye solutions of the following composition are produced:

0.40g 0.20g 0.05g 0.09g

10.00g 10.00g 10.00g 0.30g

to 100.00 g

Developer substance of formula (I) according to Table

1-Chloro-2,4-dihydroxybenzene

3-Aminophenol

1,3-Diamino-4-(2-hydroxyethoxy)benzene sulfate

Potassium oleate (8% aqueous solution)

Ammonia (22% aqueous solution)

Ethanol

Ascorbic acid

Water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6 percent hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 "Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyes are summarized in Table 3.

Table 3

Example Developer substance of formula (I) received
coloring 3a 2,5-Diamino-1-(phenyl)benzene*HCl blond 3b 2,5-Diamino-1-(4-amino-phenyl)benzene*HCl blond 3c 2,5-Diamino-1-(4-hydroxy-phenyl)benzene*HCl blond 3d 2,5-Diamino-1-(4-fluoro-phenyl)benzene*HCl blond

Examples 140:

Hair dye solutions of the following composition are produced:

0.40 g developer substance of formula (I) according to Table 4

0.20 g 1-chloro-2,4-dihydroxybenzene

0.05 g 2-amino-5-methylphenol

0.05 g N,N-Bis(2'-hydroxyethyl)-p-ohenylenediamine sulfate

10.00 g potassium oleate (8% aqueous solution)

10.00 g ammonia (22% aqueous solution) 10.00 g ethanol

42

0.30 g to 100.00 g

Ascorbic acid water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 10% hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 °C, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyes are summarized in Table 4.

Table 4

Example Developer substance of formula (I) received
coloring 4a 2,5-Diamino-1-(4-methyl-phenyl)benzene*HCl blond 4b 2,5-Diamino-1-(3,4-methylenedioxy-
phenyl)benzene*HCI blond 4c 2,5-Diamino-1-(2-trifluoromethyl-phenyl)benzene*HCl blond

Examples 141:

Hair dyes are produced in cream form with the following composition:

0.52g Developer substance of formula (I) according to Table 5 0.70g 5-Hydroxy-1,3-benzodioxole 0.05g 3-Aminophenol 15.00g Cetyl alcohol 3.00g Ammonia (22% aqueous solution) 3.50g Sodium lauryl alcohol diglycol ether sulfate, 28 percent aqueous solution 0.30g Sodium sulphite, anhydrous up to 100.00 g Water

Immediately before use, 30 g of the above coloring cream are mixed with 30 g of a 6% hydrogen peroxide solution. The mixture is then applied to bleached hair. After 30 minutes, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting colors are summarized in Table 5.

Table 5

Example Developer substance of formula (I) received
coloring 5a 2,5-Diamino-1-(phenyl)benzene*HCl medium blonde 5b 2,5-Diamino-1-(4-amino-phenyl)benzene*HCl medium blonde 5c 2,5-Diamino-1-(4-hydroxy-phenyl)benzene*HCl medium blonde 5d 2,5-Diamino-1-(4-fluoro-phenyl)benzene*HCl medium blonde

44
Examples 142:

Hair dyes are produced in cream form with the following composition:

0.52 g developer substance of formula (I) according to Table 6

0.70g 5-hydroxy-1,3-benzodioxole

0.05 g 3-amino-2-chloro-6-methylphenol

15.0 g cetyl alcohol

3.00 g ammonia (22% aqueous solution)

3.50 g sodium lauryl alcohol diglycol ether sulfate, 28 percent

aqueous solution

0.30 g sodium sulphite, anhydrous

ad 100.00 g water

Immediately before use, 30 g of the above coloring cream are mixed with 30 g of a 6% hydrogen peroxide solution. The mixture is then applied to bleached hair. After 30 minutes, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting colors are summarized in Table 6.

45

Table 6

Example Developer substance of formula (I) received
coloring 6a 2,5-Diamino-1-(4-methyl-phenyl)benzene*HCl medium blonde 6b 2,5-Diamino-1-(3,4-methylenedioxy-
phenyl)benzene*HCI medium blonde 6c 2,5-Diamino-1-(2-trifluoromethyl-phenyl)benzene*HCl medium blonde

Examples 143:

Hair dye solutions of the following composition are produced:

0.40g 0.20g 0.05g

0.10g

10.00g 10.00g 10.00g 0.30g

up to 100.00 g

Developer substance of formula (I) according to Table

5-((2-Hydroxyethyl)amino)-1,3-benzodioxole*HCl

3-Aminophenol

3-Amino-2-chloro-6-methylphenol

Potassium oleate (8% aqueous solution)

Ammonia (22% aqueous solution)

Ethanol

Ascorbic acid

Water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6% hydrogen peroxide solution. The mixture is then applied to bleached hair. After an exposure time of 30 minutes at 40 °Celsius

The hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting colors are summarized in Table 7.

Table 7

Example Developer substance of formula (I) received
coloring 7a 2,5-Diamino-1-(phenyl)benzene*HCl blond 7b 2,5-Diamino-1-(4-amino-phenyl)benzene*HCl blond 7c 2,5-Diamino-1-(4-hydroxy-phenyl)benzene*HCl blond 7d 2,5-Diamino-1-(4-fluoro-phenyl)benzene*HCl blond

Examples 144:

Hair dye solutions of the following composition are produced:

0.40g 0.20g 0.05g

0.10g

10.00g 10.00g 10.00g 0.30g

up to 100.00 g

Developer substance of formula (I) according to table 5-((2-hydroxyethyl)amino)-1,3-benzodioxole*HCl 5-amino-2-methylphenol 3-amino-2-chloro-6-methylphenol Potassium oleate (8% aqueous solution) Ammonia (22% aqueous solution) Ethanol Ascorbic acid Water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6 percent hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 "Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyes are summarized in Table 8.

Table 8

Example Developer substance of formula (I) received
coloring 8a 2,5-Diamino-1-(4-methyl-phenyl)benzene*HCl blond 8b 2,5-Diamino-1-(3,4-methylenedioxy-phenyl)-
benzene*HCI blond 8c 2,5-Diamino-1-(2-trifluoromethyl-phenyl)benzene*HCl blond

Examples 145:

Hair dyes are produced in cream form with the following composition:

1.02 g developer substance of formula (I) according to Table 9

0.50 g 1,3-dihydroxybenzene

0.09 g 3-aminophenol

0.01 g 2,4-diamino-1-1fluoro-5-methylbenzene sulfate

15.00 g cetyl alcohol

3.00 g ammonia (22% aqueous solution)

3.50 g sodium lauryl alcohol diglycol ether sulfate,

■a··»·

0.3Og
ad 100,0Og

28% aqueous solution of sodium sulphite, anhydrous water

Immediately before use, 30 g of the above coloring cream are mixed with 30 g of a 6 percent hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 "Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting colors are summarized in Table 9.

Table 9

Example Developer substance of formula (I) received
coloring 9a 2,5-Diamino-1-(phenyl)benzene*HCl brown 9b 2,5-Diamino-1-(4-amino-phenyl)benzene*HCl brown 9c 2,5-Diamino-1-(4-hydroxy-phenyl)benzene*HCl brown 9d 2,5-Diamino-1-(4-fluoro-phenyl)benzene*HCl brown

Examples 146:

Hair dyes are produced in cream form with the following composition:

1.02 g developer substance of formula (I) according to Table 10 0.50 g 1,S-dihydroxy^-methylbenzene 0.09 g 5-amino-2-methylphenol

0.01 g 2,4-diamino-1-1fluoro-5-methylbenzene sulfate

15.0Og cetyl alcohol

3.00 g ammonia (22% aqueous solution)

3.50 g sodium lauryl alcohol diglycol ether sulfate, 28 percent

aqueous solution

0.30 g sodium sulphite, anhydrous

ad 100.00 g water

Immediately before use, 30 g of the above coloring cream are mixed with 30 g of a 10% hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 °Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting colors are summarized in Table 10.

Table 10

Example Developer substance of formula (I) received
coloring 10a 2,5-Diamino-1-(4-methyl-phenyl)benzene*HCl brown 10b 2,5-Diamino-1-(3,4-methylenedioxy-phenyl)-
benzene*HCI brown 10c 2,5-Diamino-1-(2-trifluoromethyl-phenyl)-
benzene*HCI brown

50 Example 147: Hair dye

Hair dye solutions of the following composition are produced:

0.62 g developer substance of formula (I) according to Table

0.15 g 3-amino-6-methoxy-2-(methylamino)pyridine*2HCl

0.05 g 1,3-diamino-4-(2-hydroxyethoxy)benzene *HCl

0.30 g 1,3-dihydroxybenzene

0.10 g 4-amino-5-methylphenol

10.00 g potassium oleate (8% aqueous solution)

10.00 g ammonia (22% aqueous solution)

10.00 g isopropanol

0.30 g ascorbic acid

ad 100.00 g water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6 percent hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 "Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyes are summarized in Table 11.

Tables

Example Developer substance of formula (I) received
coloring 11a 2,5-Diamino-1-(phenyl)benzene*HCl reddish brown 11b 2,5-Diamino-1-(4-amino-phenyl)benzene*HCl reddish brown 11c 2,5-Diamino-1-(4-hydroxy-phenyl)benzene*HCl reddish brown 11d 2,5-Diamino-1-(4-fluoro-phenyl)benzene*HCl reddish brown

Example 148: Hair dye

Hair dye solutions of the following composition are produced:

0.62 g developer substance of formula (I) according to Table

0.05 g 3-amino-6-methoxy-2-(methylamino)pyridine*2HCl

0.30 g 1-chloro-2,4-dihydroxy-benzene

0.100 g 3-aminophenol

10.00 g potassium oleate (8% aqueous solution)

10.00 g ammonia (22% aqueous solution)

10.00 g isopropanol

0.30 g ascorbic acid

ad 100.0 g water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6% hydrogen peroxide solution. The mixture is then applied to bleached hair. After an exposure time of 30 minutes at 40 "Celsius

The hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting colors are summarized in the table.

Table 12

Example Developer substance of formula (I) received
coloring 12a 2,5-Diamino-1-(4-methyl-phenyl)benzene*HCl brown 12b 2,5-Diamino-1-(3,4-methylenedioxy-phenyl)-
benzene*HCI brown 12c 2,5-Diamino-1-(2-trifluoromethyl-phenyl)benzene*HCl brown

Example 149: Hair dye

Hair dye solutions of the following composition are produced:

0.50 g developer substance of formula (I) according to Table 13

0.20 g 5-methyl-2-(1-methylethyl)phenol

0.30 g 1,3-dihydroxybenzene

0.05 g 5-amino-2-methylphenol

10.00 g potassium oleate (8% aqueous solution)

10.00 g ammonia (22% aqueous solution)

10.00 g isopropanol

0.30 g ascorbic acid
ad 100.00 g water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6 percent hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 "Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyes are summarized in Table 13.

Table 13

Example Developer substance of formula (I) received
coloring 13a 2,5-Diamino-1-(phenyl)benzene*HCl blond 13b 2,5-Diamino-1-(4-amino-phenyl)benzene*HCl blond 13c 2,5-Diamino-1-(4-hydroxy-phenyl)benzene*HCl blond 13d 2,5-Diamino-1-(4-fluoro-phenyl)benzene*HCl blond

Example 150: Hair dye

Hair dye solutions of the following composition are produced:

0.62 g developer substance of formula (I) according to Table 14

0.06 g 5-methyl-2-(1-methylethyl)phenol

0.30 g 1,3-dihydroxybenzene

0.15g 1,3-dihydroxy-2-methylbenzene

10.00 g potassium oleate (8% aqueous solution)

10.00 g ammonia (22% aqueous solution)

10.00 g isopropanol

0.30g
ad 10O ₁ OOg

Ascorbic acid
Water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6 percent hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 "Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyes are summarized in Table 14.

Table 14

Example Developer substance of formula (I) received
coloring 14a 2,5-Diamino-1-(4-methyl-phenyl)benzene*HCl blond 14b 2,5-Diamino-1-(3,4-methylenedioxy-phenyl)-
benzene*HCI blond 14c 2,5-Diamino-1-(2-trifluoromethyl-phenyl)-
benzene*HCI blond

Examples 151:

Hair dyes are produced in cream form with the following composition:

3.02g Developer substance of formula (I) according to Table 15 1.50g 1,3-Dihydroxybenzene 1.50g 1,3-Diamino-4-(2-hydroxyethoxy)benzene sulfate 0.30g 3-Aminophenol 15.00g Cetyl alcohol 3.00g Ammonia (22% aqueous solution) 3.50g Sodium lauryl alcohol diglycol ether sulfate, 28 percent aqueous solution 0.30g Sodium sulphite, anhydrous up to 100.00 g Water

Immediately before use, 30 g of the above coloring cream are mixed with 30 g of a 6% hydrogen peroxide solution. The mixture is then applied to bleached hair. After 30 minutes, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting colors are summarized in Table 1.

Table 15

Example Developer substance of formula (I) received
coloring 15a 2,5-Diamino-1-(phenyl)benzene*HCl black 15b 2,5-Diamino-1-(4-amino-phenyl)benzene*HCl black 15c 2,5-Diamino-1-(4-hydroxy-phenyl)benzene*HCl black 15d 2,5-Diamino-1-(4-fluoro-phenyl)benzene*HCl black

56 Examples 152:

Hair dyes are produced in cream form with the following composition:

3.02g Developer substance of formula (I) according to Table 16 1.50g 1,3-Dihydroxybenzene 1.50g 5-((2-Hydroxyethyl)amino)-2-methoxyaniline sulfate 0.30g 3-Aminophenol 15.00g Cetyl alcohol 3.00g Ammonia (22% aqueous solution) 3.50g Sodium lauryl alcohol diglycol ether sulfate, 28 percent aqueous solution 0.30g Sodium sulphite, anhydrous up to 100.00 g Water

Immediately before use, 30 g of the above coloring cream are mixed with 30 g of a 6% hydrogen peroxide solution. The mixture is then applied to bleached hair. After 30 minutes, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting colors are summarized in Table 1.

Table 16

Example Developer substance of formula (I) received
coloring 16a 2,5-Diamino-1-(4-methyl-phenyl)benzene*HCl black 16b 2,5-Diamino-1-(3,4-methylenedioxy-phenyl)-
benzene*HCI black 16c 2,5-Diamino-1 -(2-trifluoromethyl-phenyl)-
benzene*HCI black

Example 153: Hair dye

Hair dye solutions of the following composition are produced:

0.30 g developer substance of formula (I) according to table 0.18 g 1-chloro^-dihydroxybenzene 0.30 g 4,5-diamino-i-(2'-hydroxyethyl)-1 H-pyrazole sulfate 0.30 g 1-naphthol

10.00 g potassium oleate (8% aqueous solution) 10.00 g ammonia (22% aqueous solution) 10.00 g isopropanol

0.30 g ascorbic acid
ad 100.00 g water

g of the above dye solution are mixed with 30 g of a 6% hydrogen peroxide solution immediately before use. The mixture is then applied to bleached hair

After an exposure time of 30 minutes at 40 °Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting colors are summarized in Table 17.

Table 17

Example Developer substance of formula (I) received
coloring 17a 2,5-Diamino-1-(phenyl)benzene*HCl reddish brown 17b 2,5-Diamino-1-(4-amino-phenyl)benzene*HCl reddish brown 17c 2,5-Diamino-1-(4-hydroxy-phenyl)benzene*HCl reddish brown 17d 2,5-Diamino-1-(4-fluoro-phenyl)benzene*HCl reddish brown

Example 154: Hair dye

Hair dye solutions of the following composition are produced:

0.30 g developer substance of formula (I) according to Table 18

0.18 g 1,3-dihydroxy-2-methylbenzene

0.30 g 4-amino-2-(aminomethyl)phenol hydrochloride

0.30 g 1-naphthol

10.00 g potassium oleate (8% aqueous solution)

10.00 g ammonia (22% aqueous solution)

10.00 g isopropanol

0.30 g ascorbic acid
ad 100.00 g water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6 percent hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 "Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyes are summarized in Table 18.

Table 18

Example Developer substance of formula (I) received
coloring 18a 2,5-Diamino-1-(4-methyl-phenyl)benzene*HCl reddish brown 18b 2,5-Diamino-1-(3,4-methylenedioxy-phenyl)-
benzene*HCI reddish brown 18c 2,5-Diamino-1-(2-trifluoromethyl-phenyl)-
benzene*HCI reddish brown

Example 155: Hair dye

Hair dye solutions of the following composition are produced:

0.30 g developer substance of formula (I) according to Table

0.18 g 1,3-dihydroxybenzene

0.30 g 4,5-diamino-1-(2'-hydroxyethyl)-1 H-pyrazole sulfate

0.30 g Acetic acid (methylnaphthalen-1-yl) ester

10.00 g potassium oleate (8% aqueous solution)

10.00 g ammonia (22% aqueous solution)

i ♦♦··

10.0Og

0.3Og

ad 100,0Og

isopropanol

Ascorbic acid

Water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6 percent hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 "Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyeings are summarized in Table 19.

Table 19

Example Developer substance of formula (I) received
coloring 19a 2,5-Diamino-1-(phenyl)benzene*HCl reddish brown 19b 2,5-Diamino-1-(4-amino-phenyl)benzene*HCl reddish brown 19c 2,5-Diamino-1-(4-hydroxy-phenyl)benzene*HCl reddish brown 19d 2,5-Diamino-1-(4-fluoro-phenyl)benzene*HCl reddish brown

Example 156: Hair dye

Hair dye solutions of the following composition are produced:

0.30 g developer substance of formula (I) according to Table 20 0.18 g 1,3-dihydroxybenzene
0.30 g 4-amino-3methylphenol

0.30 g Acetic acid (methylnaphthalen-1-yl) ester

10.00 g potassium oleate (8% aqueous solution)

10.00 g ammonia (22% aqueous solution)

10.00 g isopropanol

0.30 g ascorbic acid

ad 100.00 g water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6 percent hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 "Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyes are summarized in Table 20.

Table 20

Example Developer substance of formula (I) received
coloring 20a 2,5-Diamino-1-(4-methyl-phenyl)benzene*HCl reddish brown 20b 2,5-Diamino-1-(3,4-methylenedioxy-phenyl)-
benzene*HCI reddish brown 20c 2,5-Diamino-1-(2-trifluoromethyl-phenyl)-
benzene*HCI reddish brown

Example 157: Hair dye

Hair dye solutions of the following composition are produced:

1.30 g developer substance of formula (I) according to Table

0.08 g 5-amino-2-methylphenol

0.05 g 1,3-diamino-4-(2-hydroxyethoxy)-benzene*sulfate

0.01 g 3-aminophenol

0.50 g 1,3-dihydroxybenzene

0.10 g 4-amino-5-methylphenol

0.02 g 2-amino-5-methylphenol

0.02 g 2-amino-6-chloro-4-nitrophenol hydrochloride

10.00 g potassium oleate (8% aqueous solution)

10.00 g ammonia (22% aqueous solution)

10.00 g isopropanol

0.30 g ascorbic acid

ad 100.00 g water

Immediately before use, 100 g of the above dye solution are mixed with 30 g of a 6 percent hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 "Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyeings are summarized in Table 21.
Table 21

Example Developer substance of formula (I) obtained color 21a 2,5-Diamino-1-(phenyl)benzene*HCl brown 21b 2,5-Diamino-1-(4-amino-phenyl)benzene*HCl brown 21c 2,5-Diamino-1-(4-hydroxy-phenyl)benzene*HCl brown 21d 2,5-Diamino-1-(4-fluoro-phenyl)benzene*HCl brown

Examples 158:

Hair dye solutions of the following composition are produced:

0.60 g developer substance of formula (I) according to Table 22

0.30 g 1,3-dihydroxybenzene

0.01 g 5-amino-2-methylphenol

0.10 g 3-amino-2-chloro-6-methylphenol

0.05 g 2-chloro-6-(ethylamino)-4-nitrophenol

10.00 g potassium oleate (8% aqueous solution)

10.00 g ammonia (22% aqueous solution)

10.00 g ethanol

0.30 g ascorbic acid

ad 100.00 g water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6 percent hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 "Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyeings are summarized in Table 22.

·

64

Table 22

Example Developer substance of formula (I) received
coloring 22a 2,5-Diamino-1-(4-methyl-phenyl)benzene*HCl medium blonde 22b 2,5-Diamino-1-(3,4-methylenedioxy-phenyl)-
benzene*HCI medium blonde 22c 2,5-Diamino-1-(2-trifluoromethyl-phenyl)-
benzene*HCI medium blonde

Examples 159:

Hair dye solutions of the following composition are produced:

0.90g 0.40g 0.01g 0.10g 0.02g 0.01g

10.00g 10.00g 10.00g 0.30g

to 100.00 g

Developer substance of formula (I) according to Table

1,3-Dihydroxybenzene

2-Amino-5-methylphenol

3-Aminophenol

2-Amino-6-chloro-4-nitro-phenol hydrochloride

2-Amino-4,6-dinitrophenol

Potassium oleate (8% aqueous solution)

Ammonia (22% aqueous solution)

Ethanol

Ascorbic acid

Water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6 percent hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 "Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyeings are summarized in Table 23.

Table 23

Example Developer substance of formula (I) received
coloring 23a 2,5-Diamino-1-(phenyl)benzene*HCl brown 23b 2,5-Diamino-1-(4-amino-phenyl)benzene*HCl brown 23c 2,5-Diamino-1-(4-hydroxy-phenyl)benzene*HCl brown 23d 2,5-Diamino-1-(4-fluoro-phenyl)benzene*HCl brown

Examples 160:

Hair dye solutions of the following composition are produced:

0.90 g developer substance of formula (I) according to Table 24

0.40 g 1,3-dihydroxybenzene

0.40 g 1,S-dihydroxy^-methylphenol

0.10 g 5-amino-2-methylphenol

0.05 g 3-amino-2-chloro-6-methylphenol

0.40 g 2,5-diamino-phenylethanol sulfate

0.05 g 4-amino-3-methylphenol hydrochloride

ta-·

·

0.01g 0.07g

10.00g 10.00g 10.00g 0.30g

up to 100.00 g

66

2-Amino-4,6-dinitrophenol

6-Chloro-2-(ethylamino)-4-nitrophenol

Potassium oleate (8% aqueous solution)

Ammonia (22% aqueous solution)

Ethanol

Ascorbic acid

Water

Immediately before use, 30 g of the above dye solution are mixed with 30 g of a 6 percent hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 "Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyeings are summarized in Table 24.

Table 24

Example Developer substance of formula (I) received
coloring 24a 2,5-Diamino-1-(4-methyl-phenyl)benzene*HCl brown 24b 2,5-Diamino-1-(3,4-methylenedioxy-phenyl)-
benzene*HCI brown 24c 2,5-Diamino-1-(2-trifluoromethyl-phenyl)-
benzene*HCI brown

Examples 165:

Hair dye solutions of the following composition are produced:

0.90 g developer substance of formula (I) according to Table

0.50 g 2,5-diamino-toluene sulfate

0.40 g 1,3-dihydroxybenzene

0.40 g 4-amino-3-methylphenol

0.10 g 5-amino-2-methylphenol

0.10 g 5-((2-Hydroxyethyl)amino-2-methoxyaniline sulfate

0.10 g 3-aminophenol

0.05 g 1,3-diamino-4-(2-hydroxyethoxybenzene sulfate

0.07 g 2-amino-6-chloro-4-nitro-phenol hydrochloride

10.00 g potassium oleate (8% aqueous solution)

10.00 g ammonia (22% aqueous solution)

10.00 g ethanol

0.30 g ascorbic acid

ad 100.00 g water

Immediately before use, 100 g of the above dye solution are mixed with 30 g of a 6% hydrogen peroxide solution. The mixture is then applied to bleached hair. After a contact time of 30 minutes at 40 °Celsius, the hair is rinsed with water, washed with a commercially available shampoo and dried. The resulting dyeings are summarized in Table 25.

68

Table 25

Example Developer substance of formula (I) received
coloring 25a 2,5-Diamino-1-(phenyl)benzene*HCl brown 25b 2,5-Diamino-1-(4-amino-phenyl)benzene*HCl brown 25c 2,5-Diamino-1-(4-hydroxy-phenyl)benzene*HCl brown 25d 2,5-Diamino-1-(4-fluoro-phenyl)benzene*HCl brown

All percentages are by weight unless otherwise stated.

Claims (9)

1. Agent for the oxidative coloration of keratin fibers based on a developer substance-coupler substance combination, characterized in that it contains (a) as developer substance 2,5-diamino-1-phenylbenzene derivatives of the general formula (I),


wherein
R1, R2 independently of one another represent hydrogen, a halogen atom, a cyano group, a hydroxy group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₂ alkyl group, a C ₁ -C ₂ alkylthioether group, an amino group, an alkylamino group, a dialkylamino group, a trifluoromethane group, a C ₁ -C ₂ hydroxyalkyl group, a C ₃ -C ₄ dihydroxyalkyl group, a -C(O)CH ₃ group, or adjacent radicals R1 to R2 form an -O-CH ₂ - O bridge;
or their physiologically acceptable, water-soluble salts and b) at least one coupling substance from the group consisting of 1,3-diaminobenzene, 2-amino-4-( 2' -hydroxyethyl)aminoanisole, 1,3-diamino-4-( 2' -hydroxyethoxy)benzene, 2,4-diamino-5-fluorotoluene, 3-amino-2-methylamino-6-methoxypyridine, 3,5-diamino-2,6-dimethoxypyridine, 2,4-diamino-5-ethoxytoluene, N-( 3 -dimethylamino)phenylurea, 1,3-bis( 2,4 - diaminophenoxy)propane, 3-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 5-amino-4-fluoro-2-methylphenol, 1-naphthol, Contains 1-acetoxy-2-methyl-naphthalene, 1,3-dihydroxy-benzene, 2-methyl-1,3-dihydroxy-benzene, 1-chloro-2,4-dihydroxy-benzene, 4-( 2' -hydroxyethyl)amino-1,2-methylenedioxybenzene, 3,4-methylenedioxyphenol and 2-amino-5-methyl-phenol or their physiologically acceptable, water-soluble salts. 2. Agent according to claim 1, characterized in that in formula (I) R1 is hydrogen and R2 is methyl, chlorine, fluorine, methoxy, hydroxy, amino trifluoromethyl, or adjacent radicals R1, R2 form an -O-CH ₂ -O- bridge. 3. Agent according to claim 1 or 2, characterized in that the diaminobenzene derivative of the formula (I) is contained in an amount of 0.005 to 20.0 percent by weight. 4. Agent according to one of claims 1 to 3, characterized in that, in addition to the 1,4-diaminobenzene derivative of the formula (I), it additionally contains at least one further developer substance which is selected from 1,4-diaminobenzene, 2,5-diamino-toluene, 2,5-diaminophenylethanol, 4-aminophenol, 4-amino-3-methyl-phenol, 4-amino-2-aminomethylphenol, 4,5-diamino-1-( 2' -hydroxyethyl)-pyrazole, N,N-bis-(2'-hydroxyethyl)-p-phenylenediamine, 2,5-diamino-1,1'-biphenyl, tetraaminopyrimidines, or their physiologically acceptable salts. 5. Agent according to one of claims 1 to 4, characterized in that the developer substances and coupler substances are each contained in a total amount of 0.005 to 20 percent by weight, based on the total amount of the oxidation colorant. 6. Agent according to one of claims 1 to 5, characterized in that it additionally contains at least one direct dye. 7. Agent according to one of claims 1 to 6, characterized in that it has a pH value of 6.8 to 11.5. 8. Agent according to one of claims 1 to 7, characterized in that it is in the form of an aqueous or aqueous-alcoholic solution, a cream, a gel or an emulsion. 9. Agent according to one of claims 1 to 8, characterized in that it is a hair dye.