DE20206612U1 - Agent for the oxidative dyeing of keratin fibers - Google Patents

Description

Description Agent for oxidative coloring of keratin fibers

The present invention relates to special aldehyde-containing agents for the oxidative dyeing of keratin fibers.

Oxidation dyes have become very important in the field of coloring keratin fibers, especially hair coloring. The coloring is created by the reaction of certain developer substances with certain coupler substances in the presence of a suitable oxidizing agent. The developer substances used in particular are 2,5-diaminotoluene, 2,5-diaminophenylethyl alcohol, p-aminophenol, 1,4-diaminobenzene and 4,5-diaminopyrazole-1-(2-hydroxyethyl), while the coupler substances used are, for example, resorcinol, 2-methyl-resorcinol, 1-naphthol, 3-aminophenol, m-phenylenediamine, 2-amino-4-(2'-hydroxyethyl)amino-anisole, 1,3-diamino-4-(2'-hydroxyethoxy)benzene and 2,4-diamino-5-fluoro-toluene.

Oxidation dyes used to dye human hair must meet numerous additional requirements in addition to the desired intensity. The dyes must be safe from a toxicological and dermatological point of view and the hair dyes must have good lightfastness, perm fastness, acid fastness and rubbing fastness. In any case, such dyes must remain stable for a period of at least 4 to 6 weeks without the influence of light, rubbing and chemical agents. It is also necessary that a combination of suitable

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A wide range of different colour nuances can be produced using developing substances and coupler substances.

To achieve a satisfactory coloring result, the exposure time of common hair dyes is 20 to 40 minutes. This can be shortened by using heat. However, there are practical limits with regard to the tolerable temperature and uniformity of the heat exposure. Shorter application times can also be achieved with the same color result by increasing the initial concentration of the dye precursors, although such an increase in concentration is undesirable in terms of the solubility, toxicology and dermatology of the ingredients and, not least, for cost reasons. There is therefore still a need for new agents and processes which, compared to conventional oxidation dyes, require a significantly shorter time to achieve a good coloring result, while also avoiding color shifts.

It has now been found that by adding certain aldehydes according to the general formulas (I) and (II) to conventional oxidative hair dyes, these requirements can be met to a particularly high degree. By using small amounts of suitable aldehydes, the exposure times required to achieve a given shade depth can be significantly shortened.

The autocondensation of p-phenylenediamines to oligomers in the presence of aldehydes is known from the literature. F. Feigel describes it in Spot Tests in Organic Analysis ( ^7th ed. Elsevier, New York, 1966)

a method for detecting aldehyde groups in which diluted hydrogen peroxide and p-phenylenediamine reagents are added to an unknown substance in a neutral or acidic solution. If the unknown substance contains aldehyde functions, a black color or precipitate is formed. This type of reaction was kinetically investigated by JC Thompsen and HA Mottola (Anal. Chem. 1984, 56, 2834-2836) at pH=5 on a system containing p-phenylenediamine, hydrogen peroxide and glutaraldehyde. Quantitative methods for measuring formaldehyde based on this type of reaction were described by NP Evmiridis and MI Karayannis (Analyst 1987, 112, 831-835) and NP Evmiridis, NC Sadiris and MI Karayannis (Analyst 1990, 115, 1103-1107). In addition to the self-condensation of p-phenylenediamine, the analogous reaction of p-phenylenediamines substituted with N-methyl was also investigated. In both cases, the analysis methods showed the best detection limits and reproducibility in the weakly acidic range (pH 5.5-6.0). The use of cinnamaldehydes and hydroxybenzaldehydes in oxidation hair dyes is also known from the literature, although a shortening of the exposure time by adding aldehydes is not described. In this context, reference is made to US-PS 5034014, EP-OS 0820759, EP-OS 0820760, DE-AS 2830497 and DE-AS 29 32489.

It has now been found that certain aldehydes not only promote the self-condensation of p-phenylenediamines but also - particularly in neutral and basic environments - the reaction of developing substances with coupler substances in oxidative dye systems.

accelerate. By adding aldehydes, the exposure time until a certain color depth is achieved can be significantly reduced.

The present invention therefore relates to agents for the oxidative coloration of keratin fibers based on developer substances and coupler substances which contain at least one aldehyde of the general formula (I) or (II),

R1 ^R6 ^V R5 R3^ &Uacgr; R4

R—CHO

(D

R1, R2, R3, R4, R5 independently of one another represent hydrogen, a carboxyl group, an aldehyde group, a halogen atom (F ₁ Cl, Br, I), a cyano group, a hydroxyl group, a C^C^alkyloxy group, a C ₂ -C ₄ -hydroxyalkoxy group, a C _r C ₆ -alkyl group, a nitro group, a C^C^alkylamino group, a di(C _r C ₄ )alkylamino group, a (C ₂ -C ₄ -dihydroxyalkyl)amino group, a (C ₁ -C ₄ -hydroxyalkyl)-(C ₁ -C ₄ )alkylamino group, a trifluoromethane group, a C _r C ₄ -hydroxyalkyl group or a C ₂ -C ₄ -dihydroxyalkyl group, or two adjacent radicals R1 to R5 form an -O-CH2-O- bridge; R6 represents a -CH=CH-CHO group, a -CHO group or a -X-(Y) _r -Z-CHO group (with r = O or 1); R represents a -CRZRSRQ group, a saturated, optionally substituted cycloalkane radical having 3 to 10 atoms in the ring, where the ring

&idigr;&iacgr;... : &igr;&igr; · &iacgr; :· :

may contain up to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur, or an optionally substituted cycloalkene radical having 3 to 10 atoms in the ring, where the ring may contain up to three cumulative or non-cumulative double bonds and up to heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur;

R7, R8 and R9 can be the same or different and are independently hydrogen, a saturated cycloalkane radical having 3 to 10 atoms in the ring, where the ring can contain up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulfur, a cycloalkene radical having 3 to 10 atoms in the ring, where the ring can contain up to three cumulative or non-cumulative double bonds and up to heteroatoms from the group consisting of nitrogen, oxygen and sulfur, a branched or unbranched alkyl chain -(CH ₂ ) _n - with η equal to an integer from 1 to 20, a branched or unbranched alkene chain -(CH ₂ ) _m -(CH=CH) _p -(CH ₂ ) _q - with m and q independently of one another equal to an integer from 0 to 20 and ρ is an integer from 1 to 5, or a branched or unbranched alkyne chain -(CH ₂ ) _m -(CsQ _p -(CH ₂ ) _q - with m and q independently of one another being an integer from 0 to 20 and ρ is an integer from 1 to 3, where the abovementioned radicals are optionally substituted by one or more halogen atoms, hydroxyl groups, sulfonic acid groups, carbonyl groups (keto groups or aldehyde groups), carboxy groups, ester groups, amide groups, thioester groups, ether groups, thioether groups, nitro groups, cyano groups, amino groups, di(C _r C ₄ )alkylamino groups, (dihydroxy(C ₂ -C ₄ )alkyl)amino groups, (C _r C ₄ -hydroxyalkyl)-

C^C^alkylamino groups, trifluoromethane groups or phosphate groups;

X and Z can be the same or different and are independently equal to a branched or unbranched alkyl chain -(CH ₂ ) _n - with η equal to an integer from 1 to 20, a branched or unbranched alkene chain -(CH ₂ ) _m -(CH=CH) _p -(CH ₂ ) _q - with m and q independently equal to an integer from 0 to 20 and ρ equal to an integer from 1 to 5, or a branched or unbranched alkyne chain -(CH ₂ ) _m -(C^C) _p -(CH ₂ ) _q - with m and q independently equal to an integer from 0 to 20 and ρ equal to an integer from 1 to 3; and

Y is -O-, -S-, -NH-, NR- or a group -C(O)-O-, -O-C(O)-, -C(O)-NH- or -O-C=NH-;

where the group -X-(Y) _r -Z can also represent a saturated cycloalkane ring with up to 7 atoms in the ring, whereby depending on the ring size up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulfur can be contained, a cycloalkene ring with up to two cumulated or non-cumulated double bonds and 3 to 7 atoms in the ring, whereby depending on the ring size up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulfur can be contained.

Keratin fibres within the meaning of the present application are, for example, wool, silk or hair, in particular human hair.

Preferred are compounds of formula (I) in which R6 represents an X-(Y) _r -Z-CHO group (with r = 0 or 1), where the X-(Y) _r -Z group is equal to a branched or unbranched alkyl chain

-(CH ₂ ) _n - with &eegr; equal to an integer from 1 to 12, a branched or unbranched alkene chain -(CH ₂ ) _m -(CH=CH) _p -(CH ₂ ) _q - in which the sum of m and q is less than or equal to 20 and &rgr; is equal to an integer from 1 to 3, or a branched or unbranched alkyne chain -(CH ₂ ) _m -(CsC) _p -(CH ₂ ) _q - in which the sum of m and q is less than or equal to 20 and &rgr; is equal to an integer from 1 to 3, or the group -X-(Y) _n -Z represents a saturated cycloalkane ring with 3 to 7 atoms in the ring, where, depending on the ring size, up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur can be contained, or a cycloalkene ring with up to two cumulated or non-cumulated double bonds and 3 to 7 atoms in the ring, where, depending on the ring size, up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur can be contained; where the aforementioned radicals may optionally be substituted by one or more halogen atoms, hydroxyl groups, sulfonic acid groups, carbonyl groups, carboxy groups, ester groups, amide groups, thioester groups, ether groups, thioether groups, nitro groups, cyano groups, amino groups, di ₍ C 1 -C ₄ )alkylamino groups, (dihydroxy(C ₂ -C ₄ )alkyl)amino groups, (C ₁ -C ₄ -hydroxyalkyl)-C ₁ -C ₄ -alkylamino groups, trifluoromethane groups or phosphate groups.

Preference is given to compounds of the formula (II) in which R is a saturated, optionally substituted cycloalkane radical having 3 to 10 atoms in the ring, where the ring can contain up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur, or an optionally substituted cycloalkene radical having 3 to 10 atoms in the ring, where the ring can contain up to three cumulative or non-cumulative

double bonds and up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur, or a -CR7R8R9 group with R7, R8 and R9 independently of one another being hydrogen, a saturated cycloalkane ring with 3 to 7 atoms in the ring, where, depending on the ring size, up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur can be contained, a cycloalkene ring with up to two cumulated or non-cumulated double bonds and 3 to 7 atoms in the ring, where, depending on the ring size, up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur can be contained, a branched or unbranched alkyl chain -(CH ₂ ) _n - with &eegr; is an integer from 1 to 16, a branched or unbranched alkene chain -(CH ₂ ) _m -(CH=CH) _p -(CH ₂ ) _q - in which the sum of m and q is less than or equal to 20 and &rgr; is an integer from 1 to 3, or a branched or unbranched alkyne chain -(CH ₂ ) _m -(CsQ _p -(CH ₂ ) _q - in which the sum of m and q is less than or equal to 20 and ρ is an integer from 1 to 3, where the aforementioned radicals may optionally be substituted by one or more halogen atoms, hydroxyl groups, sulfonic acid groups, carbonyl groups, carboxy groups, ester groups, amide groups, thioester groups, ether groups, thioether groups, nitro groups, cyano groups, amino groups, di(C _r C ₄ )alkylamino groups, (dihydroxy(C ₂ -C ₄ )alkyl)amino groups, (C _r C ₄ -hydroxyalkyl)-C _r C ₄ -alkylamino groups, trifluoromethane groups or phosphate groups.

Particularly preferred are compounds of formula (I) in which R6 represents a -X-(Y) _r -Z group (with r = 0 or 1) which is equal to a branched

*· t*t

«♦ * t«

or unbranched alkyl chain -(CH ₂ ) _n - with &eegr; equal to an integer from 1 to 10, a branched or unbranched alkene chain -(CH ₂ ) _m -(CH=CH) _p -(CH ₂ ) _q - in which the sum of m and q is less than or equal to 12 and &rgr; is equal to an integer from 1 to 3, or a branched or unbranched alkyne chain -(CH ₂ ) _m -(C^C) _p -(CH ₂ ) _q - in which the sum of m and q is less than or equal to 12 and &rgr; is equal to an integer from 1 to 3, or the group -XYZ- represents a saturated cycloalkane ring with 5 or 6 atoms in the ring, where, depending on the ring size, up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur can be contained, or a cycloalkene ring with up to two cumulated or non-cumulated double bonds and 5 or 6 atoms in the ring, where, depending on the ring size, up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur can be contained, where the aforementioned radicals can optionally be replaced by one or more halogen atoms, hydroxyl groups, sulphonic acid groups, carbonyl groups, carboxy groups, ester groups, amide groups, thioester groups, ether groups, thioether groups, nitro groups, cyano groups, amino groups, di(C ₁ -C ₄ )alkylamino groups, (dihydroxy(C ₂ -C ₄ )alkyl)amino groups, (C ₁ -C ₄ -hydroxyalkyl)-C ₁ -C ₄ -alkylamino groups, trifluoromethane groups or phosphate groups.

Particularly preferred compounds of formula (II) are those in which R is a saturated, optionally substituted (preferably substituted with one or more C1 to C4 alkyl groups) cycloalkane radical having 5 or 6 atoms in the ring, where the ring can contain up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur, or an optionally substituted (preferably substituted with a

or more C1- to C4-alkyl groups) cycloalkene radical with 5 or 6 atoms in the ring, where the ring can contain up to three cumulative or non-cumulative double bonds and up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur, or a -CR7R8R9 group with R7, R8 and R9 independently of one another being hydrogen, a saturated cycloalkane ring with 5 or 6 atoms in the ring, where, depending on the ring size, up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur can be contained, a cycloalkene ring with up to two double bonds and 5 or 6 atoms in the ring, where, depending on the ring size, up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur can be contained, a branched or unbranched alkyl chain -(CH ₂ ) _n - with &eegr; is an integer from 1 to 10, a branched or unbranched alkene chain -(CH ₂ ) _m -(CH=CH) _p -(CH ₂ ) _q - in which the sum of m and q is less than or equal to 12 and &rgr; is an integer from 1 to 3, or a branched or unbranched alkyne chain -(CH ₂ ) _m -(CsC) _p -(CH ₂ ) _q - in which the sum of m and q is less than or equal to 12 and &rgr; is equal to an integer from 1 to 3, where the aforementioned radicals may optionally be substituted by one or more halogen atoms, hydroxyl groups, sulfonic acid groups, carbonyl groups, carboxy groups, ester groups, amide groups, thioester groups, ether groups, thioether groups, nitro groups, cyano groups, amino groups, di(C ₁ -C ₄ )alkylamino groups, (dihydroxy(C ₂ -C ₄ )alkyl)amino groups, (C ₁ -C ₄ -hydroxyalkyl)-C ₁ -C ₄ -alkylamino groups, trifluoromethane groups or phosphate groups.

Suitable compounds of formula (I) include in particular: 3-phenylbutyraldehyde, p-tert-butyl-a-methylhydrocinnamaldehyde,

Heliotropin, 2-methyl-3-(4'-ethylphenyl)-propionaldehyde, 2-(phenylmethylene)-heptanal, 3-(3'-isopropylphenyl)-butanal, 2-methyl-3-(4'-isopropylphenyl)propionaldehyde, 2-(Phenylmethylene)octanal and phenylethanal.

Suitable compounds of formula (II) are in particular: acetaldehyde, propionaldehyde, butanal, pentanal, isopentanal, hexanal, heptanal, octanal, malondialdehyde, glutaraldehyde, 2,4-dimethyl-3-cyclohexene-carboxaldehyde, cyclohexanal, 3,7-dimethyl-7-hydroxy-octanal, cis/trans-5-dimethyl^e-octadienal, 3,7-dimethyl-6-octenal, (E,Z)-2,6-nonadienal, dimethyloctahydro-2-naphthaldehyde, 2-methylpentanal, 5-hydroxy-pentanal, 2-ethylhexanal, 3,5,5-trimethylhexanal, 2-ethylbutyraldehyde, 3,3-dimethylbutyraldehyde, 2-ethylbutyraldehyde, 2-methylbutyraldehyde, isobutyraldehyde, hydroxyisohexyl 3-cyclohexene-carboxaldehyde, 2,6,6-trimethyl-1,3-cyclohexadiene-1-carboxaldehyde and pinoacetaldehyde.

Substances which contain so-called masked or capped aldehyde functions can also be used as compounds of formula (I) or (II). These are compounds which are converted into molecules of general formula (I) or (II) by spontaneous removal of protective groups. Examples of protective groups which can be mentioned are hydrates of aldehyde functions, acetals and hemiacetals, anils, Schiff bases with aliphatic and aromatic amines or sulfite adducts. Also suitable are compounds of the diazolidinyl type, hydantoin type or imidazoidinyl type as well as oligomeric and polymeric forms of the individual aldehydes.

The aldehyde compounds according to formula (I) or (II) are contained in the colorant according to the invention (based on the ready-to-use preparation) in a total amount of about 0.005 to 20 percent by weight, with an amount of about 0.05 to 5 percent by weight and in particular 0.025 to 2.5 percent by weight being preferred.

The developer substances used in particular are 1,4-diaminobenzene (p-phenylenediamine), 1^-diamino^-methyl-benzene (p-toluenediamine), 1^-diamino^.e-dimethyl-benzene, 1^-diamino-S .ö-diethyl-benzene, 1 ^-diamino^.ö-dimethyl-benzene, 1 ^-diamino^.S-dimethyl-benzene, 2-ChIoM ,4-diaminobenzene, 1,4-diamino-2-(thiophene- 2-yl)benzene, 1,4-diamino-2-(thiophen-3-yl)benzene, 1,4-diamino-2-(pyridin-3-yl)benzene, 2,5-diaminobiphenyl, 1^-diamino ^-methoxymethyl-benzene, 1,4-diamino-2-aminomethyl-benzene, 1 ^-Diamino^-hydroxymethyl-benzene, 1,4-diamino-2-(2-hydroxyethoxy)-benzene, 2-(2-(acetylamino)ethoxy)-1,4-diamino-benzene, 4-phenylamino-aniline, 4-Dimethylaminoaniline, 4-Diethylaminoaniline, 4-Dipropylaminoaniline, 4-[Ethyl(2-hydroxyethyl)amino]aniline, 4-[Di(2-hydroxyethyl)amino]aniline, 4-[ Di(2-hydroxyethyl)-amino]-2-methyl-aniline, 4-[(2-methoxyethyl)amino]-aniline, 4-[(3-hydroxypropyl)amino]-aniline, 4-[(2,3- Dihydroxypropyl)amino]aniline, 1,4-diamino-2-(i-hydroxyethyl)benzene, 1,4-diamino-2-(2-hydroxyethyl)-benzene, 1,4-diamino-2-(1-methylethyl)-benzene, 1,3-bis[(4-aminophenyl)-(2-hydroxyethyl)amino ]-2-propanol, 1,4-bis[(4-aminophenyl)amino]-butane, 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, 4-aminophenol, 4-amino -3-methyl-phenol, 4-amino-3-(hydroxymethyl)-phenol, 4-amino-3-fluorophenol, 4-methylamino-phenol, 4-amino-2-(aminomethyl)-phenol,

4-Amino-2-(hydroxymethyl)-phenol, 4-amino-2-fluoro-phenol, 4-amino-2-[(2-hydroxyethyl)-amino]methyl-phenol, 4-amino-2-methyl-phenol , 4-amino-2-(methoxymethyl)-phenol, 4-amino-2-(2-hydroxyethyl)-phenol, 5-amino-salicylic acid, 2,5-diaminopyridine, 2,4,5,6-tetraamino -pyrimidine, 2,5,6-triamino-4-(1H)-pyrimidone, 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole, 4,5-diamino-1-(1- methylethyl)-1H-pyrazole, 4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazole, 1 -[(4-Chlorophenyl)methyl]-4,5-diamino-1H-pyrazole, 4,5-diamino-i-methyl-IH-pyrazole, 2-amino-phenol, 2-amino-6-methyl-phenol, 2-Amino-5-methyl-phenol and 1,2,4-trihydroxybenzene are considered.

Particular coupler substances are N-(3-dimethylamino-phenyl)-urea, 2,6-diaminopyridine, 2-amino-4-[(2-hydroxyethyl)amino]-anisole, 2,4-diamino-1-fluorine -5-methyl-benzene, 2,4-diamino-1-methoxy-5-methylbenzene, 2,4-diamino-1-ethoxy-5-methyl-benzene, 2,4-diamino-1-(2-hydroxyethoxy) -5-methyl-benzene, 2,4-Di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene, 2,3-diamino-6-methoxy-pyridine, 3-amino-6-methoxy-2-( methylamino)-pyridine, 2,6-diamino-3,5-dimethoxy-pyridine, 3,5-diamino-2,6-dimethoxy-pyridine, 1,3-diamino-benzene, 2,4-diamino-1-(2-hydroxyethoxy)-benzene, 1,3-diamino-4-(2,3-dihydroxypropoxy)-benzene, 1,3-diamino-4- (3-hydroxypropoxy)-benzene, 1,3-diamino-4-(2-methoxyethoxy)-benzene, 2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene, 1-(2-aminoethoxy) -2,4-diaminophenoxy-benzene, 2-amino-1-(2-hydroxyethoxy)-4-methylamino-benzene, 2,4-diaminophenoxy-acetic 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, 1,3-Di(2,4-diaminophenoxy)-propane, Di(2,4-diaminophenoxy) -methane, 1,S-diamino^^-dimethoxy-benzene, 2,6-bis(2-hydroxy-

ethyl)amino-toluene, 4-hydroxyindole, 3-dimethylamino-phenol, 3-diethylamino-phenol, S-amino^-methyl-phenol, 5-amino-4-fluoro-2-methylphenol, S-amino^-methoxy^ -methyl-phenol, ö-amino^-ethoxy^-methylphenol, S-amino^^-dichloro-phenol, S-amino^^-dichloro-phenol, 3-amino-2-methyl-phenol, S-amino^- chloro-e-methyl-phenol, 3-amino-phenol, 2-[(3-hydroxyphenyl)amino]-acetamide, 5-[(2-hydroxyethyl)amino]-4-methoxy-2-methyl-phenol, 5- [(2-Hydroxyethyl)amino]-2-methyl-phenol, 3-[(2-hydroxyethyl)amino]-phenol, 3-[(2-methoxyethyl)amino]-phenol, 5-amino-2-ethyl-phenol , δ-Amino^-methoxy-phenol, 2-(4-amino-2-hydroxy-phenoxy)-ethanol, 5-[(3-hydroxypropyl)amino]-2-methyl-phenol, 3-[(2,3- Dihydroxypropyl)amino]-2-methyl-phenol, 3-[(2-hydroxyethyl)-amino]-2-methyl-phenol, 2-amino-3-hydroxy-pyridine, 2,6-dihydroxy-3,4-dimethylpyridine , S-amino^-chloro^-methyl-phenol, 1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxy-naphthalene, 1,7-dihydroxy-naphthalene, 2,3-dihydroxy-naphthalene, 2 ,7-Dihydroxy-naphthalene, 2-methyl-1-naphthol acetate, (m-dihydroxy-phenyl)-acrylamide, i-chloro^^-dihydroxy-benzene, 2-chloro- (m-Dihydroxy-phenyl)-acrylamide, 1,2-DiChIOr-S,5-dihydroxy-4-methyl-benzene, 1,S-Dichlor^^-dihydroxy-benzene, 1,3-Dihydroxy-2-methylbenzene, 3,4-methylenedioxy-phenol, 3,4-methylenedioxy-aniline, 5-[(2-hydroxyethyl)amino]-1,3-benzodioxole, 6-bromo-1-hydroxy-3,4-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-dihydroxy-indole, 5,6-dihydroxy-indoline, 5-Hydroxy-indole, 6-Hydroxy-indole, 7-Hydroxy-indole and 2,3-indolindione.

The coupler substances and developer substances can be used in the dyeing agent according to the invention individually or in a mixture

·· fct ·4 « M ··

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 ready-to-use colorant) being in each case about 0.005 to 20 percent by weight, preferably about 0.01 to 5 percent by weight and in particular 0.1 to 2.5 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 20 percent by weight (based on the ready-to-use dye), with an amount of about 0.02 to 10 percent by weight and in particular 0.2 to 6 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 are present in a certain excess or deficiency in this regard.

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 from the group of acidic or basic dyes, triphenylmethane dyes, aromatic nitro dyes, azo dyes and disperse dyes. The colorants according to the invention can contain these color components (based on the ready-to-use colorant) in an amount of about 0.1 to 4 percent by weight.

Of course, the coupler substances and developer substances as well as the other color 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 sulfuric acid, or - if they have aromatic OH groups - in the form of salts with bases, for example as alkali phenolates.

In addition, if the dye is a hair dye, it may also contain other common cosmetic additives, for example antioxidants such as ascorbic acid, thioglycolic acid or sodium sulphite, as well as perfume oils, complexing agents, wetting agents, emulsifiers, thickeners and care substances.

The preparation form of the colorant 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.

The agents according to the invention can be used both in the form of a "single-component preparation" consisting of a color carrier mass containing the compounds of formula (I) to (III), which is mixed with an oxidizing agent before use or is oxidized in air by atmospheric oxygen ("air oxidation"), and in the form of a "multi-component preparation" in which the compounds of formula (I) or (II) and the other constituents of the

Color carrier mass are present separately from one another and are only mixed together immediately before application (if necessary with the addition of an oxidizing agent).

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 customary 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 30 percent by weight and the care substances in a concentration of about 0.1 to 10 percent by weight.

Depending on the composition, the colorant according to the invention can react slightly acidic, neutral or alkaline. In particular, it has a pH value of 6.5 to 11.5. The basic setting is preferably carried out with ammonia, but organic amines, for example monoethanolamine or triethanolamine, or

Inorganic bases, such as sodium hydroxide or potassium hydroxide, can be used. Inorganic or organic acids, such as phosphoric acid, acetic acid, citric acid or tartaric acid, can be used to adjust the pH 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 color 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 3 to 6 percent hydrogen peroxide solution is used as the oxidizing agent, the weight ratio between hair dye and oxidizing agent is 5:1 to 1:5, preferably about 2:1 to 1:3 and especially 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 at the same time. The addition of other oxidizing agents, such as salts of peroxydisulfate, is in principle just as possible as the use of atmospheric oxygen as the oxidizing agent.

The mixture is left to act on the hair at 15 to 50 degrees Celsius for about 10 to 45 minutes, preferably 10 to 20 minutes, then the hair is rinsed with water and dried. After this rinse, the hair can also be washed with a shampoo and, if necessary, rinsed with a weak organic acid such as citric acid or tartaric acid. Finally, the hair is dried.

The dye according to the invention enables hair to be dyed with excellent color fastness within a very short time, particularly with regard to light fastness, wash fastness and rubbing fastness. In terms of coloring properties, the hair dyes according to the invention offer a wide range of different color nuances, depending on the type and composition of the color components, ranging 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 enable gray, chemically undamaged keratin fibers, especially human hair, to be colored easily and with good coverage.

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

20 Examples

Example 1: Hair dye solution

Hair dye solutions of the following composition are produced:

0.01 mol 4-amino-3-methyl-phenol

0.01 mol 3-amino-6-methyl-phenol

0.3 g ethylenediaminoteraacetate disodium salt

0.3 g ascorbic acid

2.8 g lauryl ether sulfate

8.0 g ethanol, 96%

9.0 g ammonia, 25% aqueous solution

ad 100.0 g water

Immediately before use, 20 g of the above dye solution are mixed with 20 g of a 6% aqueous hydrogen peroxide solution and 1.0 g of an "accelerator solution" according to Table 1. The mixture thus obtained (pH = 9.5-10) is applied to bleached hair and rinsed with water after an exposure time of 10 minutes at 40 ⁰ C. The hair is then washed with a commercially available shampoo and then dried.

The staining results obtained are summarized in Table 1.

Table 1:

"Accelerator solution" L* a* b* a) Water (not according to the invention) 56.0 30.1 24.6 b) 5% acetaldehyde in ethanol/water 1:1 39.3 38.6 26.2 c) 5% hexanal in ethanol/water 1:1 43.8 37.2 26.6 d) 2% glutaraldehyde in water 40.3 38.4 27.0 e) 5% hydroxycitronellal in ethanol/water 1:1 42.5 38.9 25.5 f) 5% 3-phenylbutyraldehyde in ethanol 45.3 44.3 29.3

The color measurement values in Table 1 clearly show that when the aldehyde according to the invention is added, a more color-intensive coloration (smaller L value) is achieved than with a non-inventive agent.

Example 2: Hair dye solution

Hair dye solutions of the following composition are produced:

0.01 mol developer substance according to Table 2

Coupler substance according to Table 2 Ethylenediaminoteraacetate disodium salt Ascorbic acid Lauryl ether sulfate Ethanol, 96% Ammonia, 25% aqueous solution Water

0.01 mol 0.3 g 0.3 g 2.8 g 8.0 g 9.0 g ad 100.0 g

·

Immediately before use, 20 g of the above dye solution are mixed with 20 g of a 6% aqueous hydrogen peroxide solution and (A) 1.0 g of water (not according to the invention) or (B) 1.0 g of a 1% aqueous glutaraldehyde solution (according to the invention). The mixture thus obtained (pH = 9.5-10) is applied to bleached hair and rinsed with water after an exposure time of 10 minutes at 40 ⁰ C. The hair is then washed with a commercially available shampoo and then dried. The dyeing results obtained are summarized in Table 2.

Table 2: (A) never
inventive
L* ht-
young
a* measure
b* (B)
inventive
L* young
a* measure
b* 44.6 2.6 18.6 36.5 2.9 17.0 Developer substance-
Coupler substance-
combination 49.3 43.4 35.6 44.6 45.9 36.8 a) 1,4-diamino-2-methyl-
benzene/ resorcinol 45.3 4.7 3.8 38.4 6.2 1.8 b)4,5-Diamino-1-(2-
hydroxyethyl)-1 H-pyrazole/
3-Amino-6-methylphenol 59.1 28.2 22.8 42.7 37.1 27.3 c) 1,4-diamino-2-
hydroxymethyl-benzene/
3-Aminophenol 30.9 20.0 -6.8 24.3 17.0 -5.0 d) 4-Amino-3-methyl-
phenol/ 3-Amino-6-
methylphenol e) 1,4-diamino-2-methyl-
benzene/ 3-amino-6-
methylphenol

49 ·&id; ·· ·

The color measurement values in Table 2 clearly show that when the aldehyde according to the invention is added, a more color-intensive coloration (smaller L value) is achieved than with an agent not according to the invention, regardless of the developer substance-coupler substance combination used.

Example 3: Hair dye cream

A hair dye cream with the following composition is used 0.002mol 2-Amino-4-hydroxyethylaminoanisole manufactured: 0.016mol 4-Amino-3-methylphenol 0.011mol 3-Amino-6-methylphenol 0.002mol 1-Naphthol 10.8g Cetylstearyl alcohol 2.5g Lauryl ether sulfate 0.3g ethylenediaminotetraacetic acid Disodium salt 0.3g Ascorbic acid 18.0g Ethanol, 96% 7.5g Ammonia, 25% aqueous solution to 100.0 g Water

20 g of the above dye solution are mixed immediately before use with 20 g of a 6% aqueous hydrogen peroxide solution and (A) 0.4 g water (not according to the invention) or

(B) 0.4 g of a 10% aqueous glutaraldehyde solution (according to the invention) is mixed. The mixture thus obtained (pH = 9.5-10) is applied to bleached hair and rinsed with water after an exposure time of 20 minutes or 30 minutes at 40 ⁰ C. The hair is then washed with a commercially available shampoo and then dried.

The staining results obtained are summarized in Table 3.

Table 3: Exposure time

(A) not according to the invention

L*

(B) according to the invention

20 minutes

33.0

29.6

17.46

28.3

26.2

14.8

30 minutes

29.3

27.1

15.1

24.8

24.1

12.5

The color measurement values in Table 3 clearly show that when the aldehyde according to the invention is added, a more intense color (smaller L value) is achieved after an exposure time of just minutes than with a non-inventive agent after 30 minutes.

The Lab values contained in Tables 1 to 3 were measured using a Minolta CR-200 colorimeter. The L value represents the brightness (i.e. the lower the L value, the greater the color intensity), while the a value is a measure of the red component (i.e. the higher the a value, the greater the red component). The b value is a measure of the blue component of the color, with the blue component being greater the more negative the b value is.

All percentages contained in this application are by weight unless otherwise stated.

Claims (13)

1. Agent for the oxidative coloration of keratin fibers based on developer substances and coupler substances, which contains at least one aldehyde of the general formula (I) or (II),


wherein
R1, R2, R3, R4, R5 independently of one another represent hydrogen, a carboxyl group, an aldehyde group, a halogen atom (F, Cl, Br, I), a cyano group, a hydroxyl group, a C ₁ -C ₄ alkoxy group, a C ₂ -C ₄ hydroxyalkoxy group, a C ₁ -C ₅ alkyl group, a nitro group, a C ₁ -C ₄ alkylamino group, a di(C ₁ -C ₄ )alkylamino group, a (C ₂ -C ₄ dihydroxyalkyl)amino group, a (C ₁ -C ₄ hydroxyalkyl)-(C ₁ -C ₄ )alkylamino group, a trifluoromethane group, a C ₁ -C ₄ hydroxyalkyl group or a C ₂ -C ₄ dihydroxyalkyl group, or two adjacent radicals R1 to R5 form an -O-CH ₂ -O- bridge;
R6 represents a -CH=CH-CHO group, a -CHO group or a X-(Y) _r -Z-CHO group (with r = 0 or 1);
R represents a -CR7R8R9 group, a saturated, optionally substituted cycloalkane radical having 3 to 10 atoms in the ring, where the ring can contain up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulfur, or an optionally substituted cycloalkene radical having 3 to 10 atoms in the ring, where the ring can contain up to three cumulative or non-cumulative double bonds and up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulfur;
R7, R8 and R9 can be the same or different and are each independently hydrogen, a saturated cycloalkane radical with 3 to 10 atoms in the ring, where the ring can contain up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur, a cycloalkene radical with 3 to 10 atoms in the ring, where the ring can contain up to three cumulative or non-cumulative double bonds and up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur, a branched or unbranched alkyl chain -(CH ₂ ) _n - with n equal to an integer from 1 to 20, a branched or unbranched alkene chain -(CH ₂ ) _m -(CH=CH) _p -(CH ₂ ) _q - with m and q independently equal to an integer from 0 to 20 and p equal to an integer from 1 to 5, or a branched or unbranched alkyne chain -(CH ₂ ) _m -(C~C) _p -(CH ₂ ) _q - with m and q independently of one another being an integer from 0 to 20 and p being an integer from 1 to 3, where the aforementioned radicals may optionally be substituted by one or more halogen atoms, hydroxyl groups, sulfonic acid groups, carbonyl groups, carboxy groups, ester groups, amide groups, thioester groups, ether groups, thioether groups, nitro groups, cyano groups, amino groups, di(C ₁ -C ₄ )alkylamino groups, (dihydroxy(C ₂ -C ₄ )alkyl)amino groups, (C ₁ -C ₄₄ -hydroxyalkyl)-C ₁ -C ₄ -alkylamino groups, trifluoromethane groups or phosphate groups;
X and Z may be the same or different and are independently equal to a branched or unbranched alkyl chain -(CH ₂ ) with n being an integer from 1 to 20, a branched or unbranched alkene chain -(CH ₂ ) _m -(CH=CH)p-(CH ₂ )q- with m and q being independently equal to an integer from 0 to 20 and p being an integer from 1 to 5, or a branched or unbranched alkyne chain -(CH ₂ ) _m -(C~C) _p -(CH ₂ ) _q - with m and q being independently equal to an integer from 0 to 20 and p being an integer from 1 to 3; and
Y is -O-, -S-, -NH-, NR- or a group -C(O)-O-, -OC(O)-, -C(O)-NH- or -OC = NH-;
where the group -X-(Y) _r -Z can also represent a saturated cycloalkane ring with 3 to 7 atoms in the ring, whereby, depending on the ring size, up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulfur can be contained, a cycloalkene ring with up to two cumulated or non-cumulated double bonds and 3 to 7 atoms in the ring, whereby, depending on the ring size, up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulfur can be contained. 2. Agent according to claim 1, characterized in that in formula (I) R6 represents a -X-(Y) _r -Z group (with r = 0 or 1) which is equal to a branched or unbranched alkyl chain -(CH ₂ ) _n - with n equal to an integer from 1 to 10, a branched or unbranched alkene chain -(CH ₂ ) _m -(CH=CH) _p -(CH ₂ ) _q - in which the sum of m and q is less than or equal to 12 and p is equal to an integer from 1 to 3, or a branched or unbranched alkyne chain (CH ₂ ) _m -(C~C) _p -(CH ₂ ) _q - in which the sum of m and q is less than or equal to 12 and p is equal to an integer from 1 to 3, or the group -XYZ- is a saturated cycloalkane ring with 5 or 6 atoms in Ring, where, depending on the ring size, up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur can be contained, or a cycloalkene ring with up to two cumulated or non-cumulated double bonds and 5 or 6 atoms in the ring, where, depending on the ring size, up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur can be contained, where the aforementioned radicals can optionally be substituted by one or more halogen atoms, hydroxyl groups, sulphonic acid groups, carbonyl groups, carboxy groups, ester groups, amide groups, thioester groups, ether groups, thioether groups, nitro groups, cyano groups, amino groups, di(C ₁ -C ₄ )alkylamino groups, (dihydroxy(C ₁ -C ₄ )alkyl)amino groups, (C ₁ -C ₄ -hydroxyalkyl)-C ₁ -C ₄ -alkylamino groups, trifluoromethane groups or phosphate groups. 3. Agent according to claim 1, characterized in that in formula (II) R is a saturated, optionally substituted cycloalkane radical with 5 or 6 atoms in the ring, where the ring can contain up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulfur, or an optionally substituted cycloalkene radical with 5 or 6 atoms in the ring, where the ring can contain up to three cumulative or non-cumulative double bonds and up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulfur, or a -CR7R8R9- group with R7, R8 and R9 independently of one another equal to hydrogen, a saturated cycloalkane ring with 5 or 6 atoms in the ring, where, depending on the ring size, up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulfur can be contained, a cycloalkene ring with up to two double bonds and 5 or 6 atoms in the ring, where, depending on the ring size, up to 3 heteroatoms from the group consisting of nitrogen, oxygen and sulphur, a branched or unbranched alkyl chain -(CH ₂ )- with n equal to an integer from 1 to 10, a branched or unbranched alkene chain -(CH ₂ ) _m -(CH=CH) _p -(CH ₂ ) _q - in which the sum of m and q is less than or equal to 12 and p is equal to an integer from 1 to 3, or a branched or unbranched alkyne chain (CH ₂ ) _m -(C~C) _p -(CH ₂ ) _q - in which the sum of m and q is less than or equal to 12 and p is equal to an integer from 1 to 3, where the abovementioned radicals are optionally substituted by one or more halogen atoms, hydroxyl groups, sulphonic acid groups, carbonyl groups, carboxy groups, ester groups, amide groups, thioester groups, ether groups, thioether groups, nitro groups, cyano groups, Amino groups, di(C ₁ -C ₄ )alkylamino groups, (dihydroxy(C ₂ -C ₄ )alkyl)amino groups, (C ₁ -C ₄ -hydroxyalkyl)-C ₁ -C ₄ -alkylamino groups, trifluoromethane groups or phosphate groups. 4. Agent according to one of claims 1 to 3, characterized in that the compound of formula (I) or (II) is selected from 3-phenylbutyraldehyde, p-tert.butyl-α-methylhydrocinnamic aldehyde, heliotropin, 2-methyl-3-( 4' -ethylphenyl)propionaldehyde, 2-(phenylmethylene)heptanal, 3-( 3' -isopropylphenyl)butanal, 2-methyl-3-( 4' -isopropylphenyl)propionaldehyde, 2-(phenylmethylene)octanal, phenylethanal, acetaldehyde, propionaldehyde, butanal, pentanal, isopentanal, hexanal, heptanal, octanal, malondialdehyde, glutaraldehyde, 2,4-dimethyl-3-cyclohexenecarboxaldehyde, cyclohexanal, 3,7-Dimethyl-7-hydroxy-octanal, cis/trans-3,7-dimethyl-2,6-octadienal, 3,7-dimethyl-6-octenal, (E,Z)-2,6-nonadienal, dimethyloctahydro-2-naphthaldehyde, 2-methylpentanal, 5-hydroxy-pentanal, 2-ethylhexanal, 3,5,5-trimethylh exanal, 2-ethylbutyraldehyde, 3,3-dimethylbutyraldehyde, 2-ethylbutyraldehyde, 2-methyl-butyraldehyde, isobutyraldehyde, hydroxyisohexyl 3-cyclohexene-carboxaldehyde, 2,6,6-trimethyl-1,3-cyclohexadiene-1-carboxaldehyde and pinoacetaldehyde. 5. Agent according to one of claims 1 to 4, characterized in that the compounds of formula (I) or (II) are contained in the ready-to-use colorant in a total amount of 0.005 to 20 percent by weight. 6. Agent according to one of claims 1 to 5, characterized in that the developer substance is selected from the group consisting of 1,4-diaminobenzene, 1,4-diamino-2-methylbenzene, 1,4-diamino-2,6-dimethylbenzene, 1,4-diamino-3,5-diethylbenzene, 1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,3-dimethylbenzene, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2-(thiophen-2-yl)benzene, 1,4-diamino-2-(thiophen-3-yl)benzene, 1,4-diamino-2-(pyridin-3-yl)benzene, 2,5-diaminobiphenyl, 1,4-diamino-2-methoxymethylbenzene, 1,4-diamino-2-aminomethylbenzene, 1,4-diamino-2-hydroxymethyl-benzene, 1,4-diamino-2-(2-hydroxyethoxy)-benzene, 2-(2-(acetylamino)ethoxy)-1,4-diamino-benzene, 4-phenylamino-aniline, 4-dimethylamino-aniline, 4-diethylamino-aniline, 4-Dipropylaminoaniline, 4-[Ethyl( 2 -hydroxyethyl)amino)aniline, 4-[Di(2-hydroxyethyl)amino]aniline, 4-[Di( 2 -hydroxyethyl)amino)-2-methylaniline, 4-[( 2 -Methoxyethyl)amino]aniline, 4-[( 3 -Hydroxypropyl)amino)aniline, 4-[( 2 , 3 -Dihydroxypropyl)amino]-aniline, 1,4-diamino-2-( 1 -hydroxyethyl)-benzene, 1,4-diamino-2-( 2 -hydroxyethyl)-benzene, 1,4-diamino-2-(1-methylethyl)-benzene, 1,3-bis[( 4 -aminophenyl)-( 2 -hydroxyethyl)amino]-2-propanol, 1,4-bis[( 4 -aminophenyl)amino]-butane, 1,8-bis( 2,5-diaminophenoxy)-3,6-dioxaoctane, 4-amino-phenol, 4-amino-3-methyl-phenol, 4-amino-3-(hydroxymethyl)-phenol, 4-amino-3-fluoro-phenol, 4-methylamino-phenol, 4-amino-2-(aminomethyl)-phenol, 4-amino-2-(hydroxymethyl)-phenol, 4-amino-2-fluoro-phenol, Amino-2-[( 2 -hydroxyethyl)- amino]methyl-phenol, 4-Amino-2-methyl-phenol, 4-Amino-2-(methoxymethyl)-phenol, 4-Amino-2-( 2 -hydroxyethyl)-phenol, 5-Amino-salicylsäure, 2,5-Diamino-pyridin, 2,4,5,6-Tetraamino-pyrimidin, 2,5,6-Triamino-4-( 1 H)- pyrimidon, 4,5-Diamino-1-( 2 -hydroxyethyl)-1H-pyrazol, 4,5-Diamino-1-(1- methylethyl)-1H-pyrazol, 4,5-Diamino-1-[( 4 -methylphenyl)methyl]-1H- pyrazol, 1-[( 4 -Chlorphenyl)methyl]-4,5-diamino-1H-pyrazol, 4,5-Diamino-1 - methyl-1H-pyrazol, 2-amino-phenol, 2-amino-6-methyl-phenol, 2-amino-5-methyl-phenol and 1,2,4-trihydroxybenzene. 7. Agent according to one of claims 1 to 6, characterized in that the coupler substance is selected from N-(3-dimethylaminophenyl)urea, 2,6-diaminopyridine, 2-amino-4-[( 2- hydroxyethyl)amino]anisole, 2,4-diamino-1-fluoro-5-methylbenzene, 2,4-diamino-1-methoxy-5-methylbenzene, 2,4-diamino-1-ethoxy-5-methylbenzene, 2,4-diamino-1-( 2 -hydroxyethoxy)-5-methylbenzene, 2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene, 2,3-diamino-6-methoxypyridine, 3-amino-6-methoxy-2-(methylamino)pyridine, 2,6-diamino-3,5-dimethoxypyridine, 3,5-Diamino-2,6-dimethoxy-pyridin, 1,3-Diaminobenzol, 2,4-Diamino-1-( 2 -hydroxyethoxy)-benzol, 1,3-Diamino-4-(2,3- dihydroxypropoxy)-benzol, 1,3-Diamino-4-( 3 -hydroxypropoxy)-benzol, 1,3-Diamino-4-( 2 -methoxyethoxy)-benzol, 2,4-Diamino-1,5-di(2- hydroxyethoxy)-benzol, 1-( 2 -Aminoethoxy)-2,4-diamino-benzol, 2-Amino- 1-( 2 -hydroxyethoxy)-4-methylamino-benzol, 2,4-Diaminophenoxyessigsäure, 3-[Di( 2 -hydroxyethyl)amino]-anilin, 4-Amino-2-di[(2- hydroxyethyl)amino]-1-ethoxy-benzol, 5-Methyl-2-( 1 -methylethyl)-phenol, 3-[( 2 -Hydroxyethyl)amino]-anilin, 3-[( 2 -Aminoethyl)-amino]-anilin, 1,3-Di( 2 , 4 -diaminophenoxy)-propan, Di( 2 , 4 -diaminophenoxy)-methan, 1,3-Diamino-2,4-dimethoxy-benzol, 2,6-Bis( 2 -hydroxyethyl)amino-toluol, 4-Hydroxyindol, 3-Dimethylamino-phenol, 3-Diethylamino-phenol, 5-Amino-2-methyl-phenol, 5-Amino-4-fluor-2-methyl-phenol, 5-Amino-4- methoxy-2-methyl-phenol, 5-Amino-4-ethoxy-2-methyl-phenol, 3-Amino- 2,4-dichlor-phenol, 5-Amino-2,4-dichlor-phenol, 3-Amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol, 3-amino-phenol, 2-[( 3 -Hydroxyphenyl)-amino]-acetamide, 5-[( 2 -Hydroxyethyl)amino]-4-methoxy-2-methyl-phenol, 5-[( 2 -Hydroxyethyl)amino]-2-methyl-phenol, 3-[( 2 - Hydroxyethyl)amino]-phenol, 3-[( 2 -Methoxyethyl)amino]-phenol, 5-amino-2-ethyl-phenol, 5-amino-2-methoxy-phenol, 2-(4-amino-2-hydroxy-phenoxy)-ethanol, 5-[( 3 -Hydroxypropyl)amino]-2-methyl-phenol, 3-[( 2 , 3 -Dihydroxypropyl)-2 -methyl-phenol, 3-[( 2 -Hydroxyethyl)-amino]-2-methyl-phenol, 2-Amino-3-hydroxy-pyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 5-Amino-4- chlor-2-methyl-phenol, 1-Naphthol, 2-Methyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,7-Dihydroxy-naphthalin, 2,3-Dihydroxy-naphthalin, 2,7-Dihydroxy-naphthalin, 2-Methyl-1-naphthol-acetat, (m-Dihydroxyphenyl)-acrylamid, 1-Chlor-2,4-dihydroxy-benzol, 2-Chlor- (m-Dihydroxyphenyl)-acrylamid, 1,2-Dichlor-3,5-dihydroxy-4-methyl-benzol, 1,5-Dichlor- 2,4-dihydroxy-benzol, 1,3-Dihydroxy-2-methyl-benzol, 3,4-Methylendioxyphenol, 3,4-Methylenedioxy-aniline, 5-[( 2 -Hydroxyethyl)amino]-1,3-benzodioxole, 6-bromo-1-hydroxy-3,4-methylenedioxy-benzene, 3,4-diaminobenzoic acid, 3,4-dihydro-6-hydroxy-1,4( 2 H)-benzoxazine, 6-amino-3,4-dihydro-1,4 ( 2H )-benzoxazine, 3-methyl-1-phenyl-5-pyrazolone, 5,6-dihydroxy-indole, 5,6-dihydroxy-indoline, 5-hydroxy-indole, 6-hydroxy-indole, 7-hydroxy-indole and 2,3-indolindione. 8. Agent according to one of claims 1 to 7, characterized in that the developer substances and coupler substances are used in the ready-to-use dye in a total amount of 0.005 to 20 percent by weight each. 9. Agent according to one of claims 1 to 8, characterized in that it can additionally contain at least one direct dye. 10. Agent according to one of claims 1 to 9, characterized in that it has a pH value of 6.5 to 11.5. 11. Agent according to one of claims 1 to 10, characterized in that it is a hair dye. 12. Ready-to-use agent for the oxidative dyeing of hair, characterized in that it contains at least one aldehyde compound of formula (I) or (II) according to one of claims 1 to 4 and an oxidizing agent. 13. Agent according to claim 12, characterized in that the oxidizing agent is hydrogen peroxide.