DE29919706U1 - Fiber dyeing preparations - Google Patents

Description

The present invention relates to an agent for coloring fibers, in particular keratin fibers (e.g. silk, wool and hair, in particular human hair), which contains a combination of at least one rhodanine, 2-thioxo-4-imidazolidinone or 2-thioxo-4-oxazolidinone of the formula (I) and at least one carbonyl compound.

Depending on the original hair color to be dyed and the desired end result, hair dyes are mainly divided into oxidation dyes or tints.

Oxidation hair dyes are ideal for covering higher levels of grey hair. The oxidation dyes used for grey hair up to 50% are generally referred to as oxidative tints, while the oxidation dyes used for grey hair over 50% or for "lightening" are generally referred to as so-called oxidative colours.

Direct dyes are mainly contained in non-oxidative dyes (so-called tinting agents). Some direct dyes, such as nitro dyes, can penetrate the hair due to their small size and - at least in the outer layers -

* · • * » · · * •

- dye directly. Such tints are very gentle on the hair and usually last 6 to 8 washes.

Direct dyes, especially nitro dyes, are also frequently used in oxidative dyes to produce certain nuances or to intensify the color.

It is known that colored polymers produced in the hair through oxidation are generally very durable against external influences such as water, shampoo or light. Depending on the coloring technique, they are so firmly anchored that they remain in the hair until the next haircut. However, the use of hydrogen peroxide - especially in an alkaline environment - has a detrimental effect on the hair structure.

The use of certain carbonyl compounds in combination with certain amines or CH-acidic compounds for coloring keratin fibers is known from the prior art. For example, DE-OS 197 45 292 describes the use of a combination of malonaldehyde derivatives, such as malonaldehyde bis-dialkyl acetals, and certain amines or CH-acidic compounds for coloring hair without the addition of oxidizing agents, while DE-OS 197 17 223 and DE-OS 197 17 224 describe colorants in which a combination of certain amines or CH-acidic compounds with aminovinyl aldehydes or certain unsaturated non-aromatic aldehydes is described. DE-OS 197 17 280 also describes the use of a combination of certain heterocyclic aldehydes and amines or CH-acidic compounds for coloring hair without the addition of

Oxidizing agents are known. DE-OS 197 45 356 also describes the use of a combination of certain onium aldehydes or onium ketones (e.g. 4-formyl-i-methyl-pyridinium benzene sulfate) and certain amines or CH-acidic compounds for coloring hair without the addition of oxidizing agents. Although the above-mentioned combinations enable hair to be colored more gently than oxidizing dyes, their coloring properties are still not satisfactory.

There is therefore still a great need for dyes that enable both intensive and gentle coloring with a wide range of shades under mild conditions.

Surprisingly, it has now been found that this task can be accomplished in an outstanding manner by using a combination of certain rhodanines, 2-thioxo-4-imidazolidinones or 2-thioxo-4-oxazolidinones
of formula (I) with carbonyl compounds, in particular aromatic carbonyl compounds. The compounds mentioned react with the carbonyl compounds under mild conditions and colorations with excellent brilliance and color depth are obtained.

The present invention therefore relates to an agent for coloring fibers, in particular keratin fibers, such as wool, silk and hair, in particular human hair, which is obtained by mixing two components, wherein one component (component (b)) contains at least one carbonyl compound, in particular an aromatic aldehyde compound, and the other component (component (a)) contains at least one compound of the formula (I) or its

contains physiologically acceptable salts,

■ /

(I)

in which R is hydrogen, a C1-C3-alkyl group, a C1-C3-alkylene group, a C1-03-alkoxy-CI-CS-alkyl group, a C1-C3-hydroxyalkyl group, an amino group, a dimethylamino group or a carboxymethyl group and X is S, O or NR1, with R1 being hydrogen or a C1-C3-alkyl group; provided that the carbonyl compound of component (b) is an aromatic, non-heterocyclic carbonyl compound, if in formula (I) R is hydrogen or a carboxymethyl group and X is S. Among the compounds of formula (I), the following compounds are particularly preferred: rhodanine, rhodanine-3-acetic acid, 3-ethylrhodanine, 3-allylrhodanine, 3-methylrhodanine, 3-aminorhodanine, 2-thioxo-4-imidazolidinone, 3-methyl-2-thioxo-4-oxazolidinone and 3-ethyl-2-thioxo-4-oxazolidinone.

Some of the compounds of formula (I) are commercially available. However, the compounds of formula (I) can also be prepared by conventional synthesis processes known from the literature, for example analogously to the process described in Beilstein Vol. 27, E1, 302d for 3-alkyl-2-thioxo-4-oxazolidinone, the process described in Beilstein Vol. 27, E1, 309c for alkylrhodanines or the process described by I. Arenal, M. Bernabe and E. Fernandez Alvarez in Ann. Quim., Ser. C (1984), 80(2), pages 190-192 and H.C. Beyerman, L. Maat, A. Sinnema and A. Van Veen in Reel. Trav. Chim. Pays-Bas (1968), 87(1), pages 11-23 for 3-alkyl-2-thioxo-4-imidazolidinones and 1,3-dialkyl-2-thioxo-4-imidazolidinones.

The following carbonyl compounds of component (b) can be mentioned: syringaldehyde, vanillin (4-hydroxy-3-methoxybenzaldehyde), isovanillin (3-hydroxy-4-methoxy-benzaldehyde), 3,4-dihydroxy-benzaldehyde, 4-hydroxybenzaldehyde, 3 ,5-Dimethoxy-4-hydroxy-benzaldehyde, 4-dimethylaminobenzaldehyde, 4-methyl-5-imidazolecarboxaldehyde, 4-dimethylaminocinnamaldehyde, 4-hydroxy-2-methoxy-benzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 4 -Dimethylamino-2-methoxybenzaldehyde, 2-hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 4-dimethyiamino-1-naphthaldehyde, 4'-hydroxy-biphenyl-1-carbaldehyde, 2-hydroxy- 3-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-Dihydroxy-benzaldehyde, 2,5-Dihydroxybenzaldehyde, 2,3,4-Trihydroxybenzaldehyde, 3,4,5-Trihydroxybenzaldehyde, 2,4,6-Trihydroxybenzaldehyde, 2,4-Dimethoxybenzaldehyde, 2,3-Dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, indole-3-carbaldehyde, benzene-1,4-dicarbaldehyde, 4-ethoxybenzaldehyde, 2-methyl-1,4-naphthoquinone, 4-carboxybenzaldehyde, 4-Hydroxy-3-methoxycinnamaldehyde, 3,5-dimethoxy-4-hydroxycinnamaldehyde, 3-methoxy-4-(i-pyrrolidinyl)-benzaldehyde, 4-diethylamino-3-methoxybenzaldehyde, 1,2-phthaldialdehyde, Pyrrole-2-carbaldehyde, Thiophene-2-carbaldehyde, Thiophene-3-carbaldehyde, Chromone-3-carboxaldehyde, 6-Methyl-4-oxo-1 (4H)-benzopyran-3-carbaldehyde, N-Methylpyrrole-2- carbaldehyde, 5-methylfurfural, e-hydroxy-chromene-S-carboxaldehyde, 6-methylindole-3-carboxaldehyde, 4-dibutylaminobenzaldehyde, N-ethylcarbazole-3-carbaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 3,4-dimethoxy- 5-hydroxybenzaldehyde, 5-(4-(diethylamino)phenyl)-2,4-pentadienal, 2,3-

Thiophene dicarboxaldehyde, 2,5-thiophenedicarboxaldehyde, 2-methoxy-1-naphthaldehyde, S-ethoxy^-hydroxybenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, formylsalicylic acid, 2,4-dimethoxy-3-methylbenzaldehyde, 2 ,6-Dimethoxy-4-hydroxybenzaldehyde, 2,6-dimethoxy-4-hydroxybenzaldehyde,4-hydroxy-3-methylbenzaldehyde, 6-methoxy-2-naphthaldehyde, 4-(1-pyrrolidino)-benzaldehyde, 4-diethylaminobenzaldehyde, 4 -Methylthiobenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, isophthaldialdehyde, 5-bromovanillin, 4-hydroxy-3-nitro-benzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-Dimethylamino-e-methyl-benzene-I.S-dicarbaldehyde^-Hydroxy-S-methoxy-5-nitrobenzaldehyde, 2-dimethylamino-5-nitro-benzaldehyde, quinoline-4-carbaldehyde, 4-antipyrinecarboxaldehyde and 4-dimethylamino-2 -nitrobenzaldehyde.

Among these compounds are aromatic carbonyl compounds, especially vanillin (4-hydroxy-3-methoxybenzaldehyde), isovanillin (3-hydroxy-4-methoxy-benzaldehyde), 3,4-dihydroxy-benzaldehyde, 4-hydroxybenzaldehyde, 3,5-dimethoxy- 4-hydroxy-benzaldehyde, 4-dimethylaminobenzaldehyde, 4-hydroxy-2-methoxy-benzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, syringaldehyde, 2-hydroxybenzaldehyde, 4-hydroxy-1- naphthaldehyde, 4-methoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 4'-hydroxy-biphenyl-1-carbaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 2,4-dihydroxy-benzaldehyde, 3,4-dihydroxybenzaldehyde , 2,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,3-dimethoxy-benzaldehyde, 2,5-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 3,4-Dimethoxybenzaldehyde, Benzene-1,4-dicarbaldehyde, 4-Ethoxy-benzaldehyde, 2-Methyl-1,4-

naphthoquinone, 4-carboxy-benzaldehyde, 4-diethylamino-3-methoxybenzaldehyde, 1,2-phthaldialdehyde, 4-dibutylaminobenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 3,4-dimethoxy-5-hydroxybenzaldehyde, 2-methoxy-1- naphthaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, formylsalicylic acid, 2,4-dimethoxy-3-methylbenzaldehyde, 2,6-dimethoxy-4-hydroxy-benzaldehyde, 2,6- Dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 6-methoxy-2-naphthaldehyde, 4-diethylamino-benzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, isophthaldialdehyde, 5-Bromovanillin, 4-Hydroxy-3-nitro-benzaldehyde, 4-Dimethylamino-2-methylbenzaldehyde, 4-Dimethylamino-6-methyl-benzene-1,3-dicarbaldehyde, 4-Hydroxy-3-methoxy-5-nitrobenzaldehyde, 2-Dimethylamino-5-nitro-benzaldehyde and 4-dimethylamino-2-nitro-benzaldehyde, particularly preferred.

The compound of formula (I) and the carbonyl compound are kept separate until shortly before use. They can also be stored in the same packaging if they are in solid form and are mixed with the other components of the colorant shortly before use.

The dye according to the invention generally consists of a mixture of components (a) and (b), namely a dye carrier mass (a) which contains the compounds of formula (I) and optionally direct dyes, and a further dye carrier mass (b) which contains the carbonyl compound and optionally direct dyes. Components (a) and (b) are mixed immediately before use to form a ready-to-use dye and then applied to the fiber to be dyed.

The compounds of formula (I) and the carbonyl compounds are each contained in the respective color carrier mass (component (a) or component (b)) in a total amount of about 0.02 to 20 percent by weight, preferably 0.2 to 10 percent by weight, wherein the compound of formula (I) and the carbonyl compound are each contained in a total amount of about 0.01 to 10 percent by weight, preferably 0.1 to 5 percent by weight, in the ready-to-use colorant obtained by mixing components (a) and (b).

Furthermore, the colorant according to the invention can optionally
additionally contain common, physiologically harmless, direct dyes from the group of nitro dyes, azo dyes, quinone dyes and triphenylmethane dyes, for example
1,4-Bis[(2-hydroxyethyl)amino]-2-nitrobenzene, 1-(2-hydroxyethyl)amino-2-nitro-4-[di(2-hydroxyethyl)amino]-benzene (HC Blue No. 2),
1-Amino-3-methyl-4-[(2-hydroxyethyl)amino]-6-nitrobenzene (HC Violet No. 1), 4-[Ethyl-(2-hydroxyethyl)amino]-1 -[(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride
(HC Blue No. 12), 4-[Di(2-hydroxyethyl)amino]-1-[(2-methoxyethyl)amino]-2-nitrobenzene (HC Blue No. 11),
1-[(2,3-Dihydroxypropyl)amino]-4-[methyl-(2-hydroxyethyl)amino]-2-nitrobenzene
(HC Blue No. 10), 1-[(2,3-Dihydroxypropyl)amino]-4-[ethyl-(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Blue No. 9),
1-(3-Hydroxypropylamino)-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene (HC Violet No. 2), 1-methylamino-4-[methyl-(2,3-dihydroxypropyl)amino]-2-nitrobenzene
(HC Blue No. 6), 2-((4-amino-2-nitrophenyl)amino)-5-dimethylamino-benzoic acid
(HC Blue No. 13), 1-(2-Aminoethylamino)-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene,1-Amino-4-[(2-hydroxyethyl)-
amino]-2-nitrobenzene (HC Red No. 7), 2-amino-4,6-dinitro-phenol,

• J • * · r * · ■ ··» ♦ ·· • # ·· • 0

4-Amino-2-nitro-diphenylamine (HC Red No. 1), 1-amino-4-[di(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Red No. 13), 1-amino- 5-chloro-4-[(2-hydroxyethyl)amino]-2-nitrobenzene, 4-amino-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 3), 4-((2 -Hydroxyethyl)methylamino)-1-(methylamino)-2-nitrobenzene, 1-amino-4-((2,3-dihydroxypropyl)amino)-5-methyl-2-nitrobenzene, 1 -amino-4-(methylamino) -2-nitrobenzene, 4-amino-2-nitro-1 -((prop-2-en-1 yl)amino)-benzene, 4-amino-3-nitrophenol, 4-[(2-Hydroxyethyl)amino]-3-nitrophenol1-[(2-Aminoethyl)amino]-4-(2-hydroxyethoxy)-2-nitrobenzene (HC Orange No. 2), 4-(2,3- Dihydroxypropoxy)-1-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Orange No. 3), 1-amino-5-chloro-4-[(2,3-dihydroxypropyl)amino]-2-nitrobenzene ( HC Red No. 10), 5-Ch!oro-1,4-[di(2,3-dihydroxypropyl)amino] -2-nitrobenzene (HC Red No. 11), 2-[(2-Hydroxyethyl)amino] -4,6-dinitro-phenol, 4-ethylamino-3-nitrobenzoic acid, 2-[(4-amino-2-nitrophenyl)amino]-benzoic acid, 2-chloro-6-ethylamino-4-nitrophenol, 2-amino-6-chloro-4-nitγophenol, 4-[(3-hydroxypropyl)amino]-3-nitrophenol, 2,5-diamino-6-nitropyridine , 6-Amino-3-((2-hydroxyethyl)-amino)-2-nitropyridine, 3-amino-6-((2-hydroxyethyl)amino)-2-nitropyridine, 3-amino-6-(ethylamino)- 2-nitropyridine, 3-((2-Hydroxyethyl)amino)-6-(methylamino)-2-nitropyridine, 3-amino-6-(methylamino)-2-nitropyridine, 6-(ethylamino)-3-((2 -hydroxyethyl)amino)-2-nitropyridine, 1^,S^-tetrahydro-ö-nitroquinoxaline, /-Amino-S^-dihydro-e-nitro^H-i ,4-benzoxazine (HC Red No. 14), 1-amino-2-[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 5 ), 1-(2-Hydroxyethoxy)-2-[(2-hydroxyethyl)-amino]-5-nitrobenzene (HC Yellow No. 4), 1-[(2-Hydroxyethyl)amino]-2-nitrobenzene (HC Yellow No. 2), 2-(Di(2-hydroxyethyl)amino)-5-nitrophenol, 2-[(2-hydroxyethyl)amino]-1-methoxy-5-nitrobenzene, 2-amino-3-nitrophenol, 1 - (2-Hydroxyethoxy)-3-methylamino-4-nitrobenzene,

2,3-(Dihydroxypropoxy)-3-methylamino-4-nitrobenzene, 2-[(2-Hydroxyethyl)amino]-5-nitrophenol (HC Yellow No. 11), 3-[(2-Aminoethyl)amino]-1 -methoxy-4-nitrobenzene hydrochloride (HC Yellow No.9), 1-[(2-Ureidoethyl)amino]-4-nitrobenzene, 4-[(2,3-dihydroxypropyl)-amino]-3-nitro-1 -trifluoromethyl-benzene (HC Yellow No. 6), 1-chloro-2,4-bis[(2-hydroxyethyl)amino]-5-nitrobenzene (HC Yellow No. 10), 1-amino-4-((2 -aminoethyl)amino)-5-methyl-2-nitrobenzene, 4-[(2-hydroxyethyl)amino]-3-nitro-1 -methylbenzene, 1 -Chloro-4-[(2-hydroxyethyl)amino]-3-nitrobenzene (HC Yellow No. 12), 4-[(2-hydroxyethyl)amino]-3-nitro-1-trifluoromethylbenzene (HC Yellow No. 13) , 4-[(2-Hydroxyethyl)amino]-3-nitro-benzonitrile (HC Yellow No. 14), 4-[(2-Hydroxyethyl)amino]-3-nitro-benzamide (HC Yellow No. 15), 3 -((2-Hydroxyethyl)amino)-4-methyl-1-nitrobenzene, 4-chloro-3-((2-hydroxyethyl)amino)-1 -nitrobenzene, 1,4-Di[(2,3-dihydroxypropyl) amino]-9,10-anthraquinone, 1-[(2-Hydroxyethyl)amino]-4-methylamino-9,10-anthraquinone (CI61505, Disperse Blue No. 3), 2-[(2-Aminoethyl)amino]-9,10-anthraquinone (HC Orange No. 5), 1-Hydroxy-4-[(4-methyl-2-sulfophenyl)amino]-9,10- anthraquinone, 1-[(3-aminopropyl)-amino]-4-methylamino-9,10-anthraquinone (HC Blue No. 8), 1-[(3-aminopropyl)amino]-9,10-anthraquinone (HC Red No. 8), 1,4-diamino-2-methoxy-9,10-anthraquinone (CI62015, Disperse Red No. 11, Solvent Violet No. 26), 1,4-dihydroxy-5,8-bis[(2 -hydroxyethyl)amino]-9,10-anthraquinone (CI62500, Disperse Blue No. 7, Solvent Blue No. 69), 9-(Dimethylamino)-benzo[a]phenoxazin-7-ium chloride (CI511 75; Basic Blue No. öJ.Di^-idiethylaminoJphenylJ^-iethylaminoJnaphthylJcarbenium chloride (CI42595; Basic Blue No. 7), Di-(4-( dimethylamino)phenyl)-(4-(methyl-phenylamino)naphthalene-i-yOcarbenium chloride (CI42563; Basic Blue No. 8), 3,7-di(dimethylamino)phenothiazine-5-ium chloride (CI52015; Basic Blue No. 9), di[4-(dimethylamino)phenyl][4-(phenylamino)naphthyl]-carbenium chloride (CI44045; Basic Blue No. 26), 2-[(4-(Ethyl(2-hydroxy-

ethyl)amino)phenyl)azo]-6-methoxy-3-methyl-benzothiazolium methyl sulfate (CM 1154; Basic Blue No. 41), e-Amino^-bromo-ö-hydroxy^- imino-6-[(3-( trimethylammonio)phenyl)amino]-1(4H)-naphthalinone chloride (CI56059; Basic Blue No. 99), bis[4-(dimethylamino)phenyl][4-(methylamino)phenyl]carbenium chloride (CI42535; Basic Violet No. 1), Tris(4-amino-3-methyl-phenyl)carbenium chloride (CI42520; Basic Violet No. 2), Tris[4-(dimethylamino)phenyl]carbenium chloride (CI42555; Basic Violet No. 3 ), 2-[3,6-(Diethylamino)dibenzopyranium-9-yl]-benzoic acid chloride (CI45170; Basic Violet No. 10), di(4-aminophenyl)(4-amino-3-methylphenyl)carbenium chloride (CI42510; Basic Violet No. 14), 1,3-bis[(2,4-diamino -5-methylphenyl)azo]-3-methylbenzene (CI21010; Basic Brown No. 4), i-^-aminophenyOazoJ-Z-itrimethylammonio^-naphthol chloride (Cl 12250; Basic Brown No. 16), 1-[( 4-Amino-2-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (Basic Brown No. 17), i-^-Amino-S-nitrophenyOazol^-itrimethylammonio^-naphthol chloride (Cl 12251 ;Basic Brown No. 17), SJ-Diamino^.e-dimethyl-S-phenylphenazinium chloride (CI50240; Basic Red No. 2), 1,4-Dimethyl-5-[(4-(dimethylamino)phenyl)azo]-1,2 ,4-triazolium chloride (CH 1055; Basic Red No. 22), 2-hydroxy-1 -[(2-methoxyphenyl)azo]-7-(trimethylammonio)-naphthalene chloride (Cl 12245; Basic Red No. 76 ), 2-[2-((2,4-Dimethoxyphenyl)amino)ethenyl]-1,S.S-trimethyl-SH-indol-i-ium chloride (CI48055; Basic Yellow No. 11), 3-Methyl-1 -phenyl-4-[(3-(trimethylammonio)-phenyl)azo]-pyrazole-5-one chloride (CI12719; Basic Yellow No. 57), di(4-(dimethylamino)phenyl)iminomethane hydrochloride (CI41000; Basic Yellow No. 2), bis[4-(diethylamino)phenyl]phenyl carbenium hydrogen sulfate (1:1) (CI42040; Basic Green No. 1), Di(4-(dimethylamino)-phenyl)-phenylmethanol (CI42000; Basic Green No. 4), 1-[Di(2-hydroxyethyl)amino]-3-methyl-4-[(4 -nitrophenyl)azo]-benzene (CM 1210, Disperse

Red No. 17) roxy-5-[(4-sulfophenyl)azo]-2-naphthalenesulfonic acid disodium salt (CU 5985; Food Yellow No. 3; FD&C Yellow No. 6), 2,4-dinitro-1-naphthol-7-sulfonic acid disodium salt (Cl 10316; Acid Yellow No. 1; Food Yellow No. 1), 2-(lndan-1,3-dione-2-yl) quinoline-x,x-sulfonic acid (Mixture of mono- and disulfonic acid) (CI47005; D&C Yellow No. 10; Food Yellow No. 13; Acid Yellow No. 3), 5-Hydroxy-1-(4-sulfophenyl)-4-[^-sulfophenyOazoJpyrazole-S-carboxylic acid trisodium salt (Cl 19140; Food Yellow No. 4; Acid Yellow No. 23), 9-(2 -Carboxyphenyl)-6-hydroxy-3H-xanthen-3-one (CI45350; Acid Yellow No. 73; D&C Yellow No. 8), 4-((4-Amino-3-sulfophenyl)azo)benzenesulfonic acid disodium salt (CM 3015, Acid Yellow No. 9), 5-[(2,4-Dinitrophenyl)amino]-2-phenylaminobenzenesulfone acid sodium salt (Cl 10385; Acid Orange No. 3), 4-[(2,4-Dihydroxyphenyl)azo]-benzolsulfonsäure-mononatriumsalz (Cl 14270; Acid Orange No. 6), 4-[(2-Hydroxynaphth-1-yl)azo]-benzolsulfonsäurenatriumsalz (Cl 15510; Acid Orange No. 7), 4-[(2,4-Dihydroxy-3-[(2,4-dimethylphenyl)azo]phenyl)azo]-benzolsulfonsäure-natriumsalz (CI20170; Acid Orange No. 24), 4-Hydroxy-3-[(4-sulfonaphth-1-yl)azo]-1-naphthalinsulfonsäure-dinatriumsalz (CI14720; Acid Red No. 14), 6-Hydroxy-5-[(4-sulfonaphth-1-yl)azo]-2,4-naphthalin-disulfonsäure-trinatriumsalz (Cl 16255; Ponceau 4R; Acid Red No. 18) Acetylamino)-4-hydroxy-3-[(2-methylphenyl)azo]-2,7-naphthalene-disulfonic acid disodium salt (Cl 18065; Acid Red No. 35), 2-(3-hydroxy-2,4,5,7-tetraiodo-dibenzopyran-6-one-9-yl)-benzoic acid disodium salt (CI45430; Acid Red No. 51 ),

ft ft

I« ft « ft · · ft · ft « · ·*

N-[6-(Diethylamino)-9-(2,4-disulfophenyI)-3H-xanthene-3-ylidene]-N-ethylethanammonium hydroxide, inner salt, sodium salt (CI45100; Acid Red No. 52), 8- [(4-(Phenylazo)phenyl)azo]-7-naphthol-1,3-disulfonic acid disodium salt (CI27290; Acid Red No. 73), 2 ¹ ,4',5 ¹ ,7 ^I -tetrabromo-3 ¹ ,6 ^t dihydroxyspiro[isobenzofuran-1(3H),9'-[9H]xanthen3-3-one disodium salt (CI45380; Acid Red No. 87), 2 ^I ,4 ¹ ,5\7 ^I -tetrabromo-4,5,6 ,7-tetrachloro-3 ¹ ,6 ^I -dihydroxyspiro[isobenzofuran-1(3H),9'[9H]xanthene]-3-one disodium salt (CI45410; Acid Red No. 92), S'^'-Dihydroxy^'.S'-diiodospiro-[isobenzofuran- 1(3H),9'(9H)-xanthene]-3-one disodium salt (CI45425; Acid Red No. 95), 2-hydroxy-3-((2-hydroxynaphth-1-yl)azo)-5- nitrobenzenesulfonic acid monosodium salt (Cl 15685; Acid Red No. 184), (2-sulfophenyl)di[4-(ethyl((4-sulfophenyl)methyl)amino)phenyl]-carbenium disodium salt, betaine (CI42090; Acid Blue No. 9; 1,4-Bis[(2-sulfo-4-methylphenyl)amino]-9,1O-anthraquinone disodium salt (Cl 61570; Acid Green No. 25), bis[4-(dimethylamino)phenyl]-(3,7- disulfo-2-hydroxynaphth-1 -yl)carbenium inner salt, monosodium salt (CI44090; Food Green No. 4; Acid Green No. 50), Bis[4-(diethylamino)phenyl](2,4-disulfophenyl)carbenium inner salt, sodium salt (2:1) (CI42045; Food Blue No. 3; Acid Blue No. 1), Bis[4- (diethylamino)phenyl](5-hydroxy-2,4-disulfophenyl)carbenium inner salt, calcium salt(2:1) (CI42051; Acid Blue No. 3), 1-amino-4-(cyclohexylamino^.iO-anthraquinone^- sulfonic acid sodium salt (CI62045; Acid Blue No. 62), 2-(1,3-dihydro-3-oxo-5-sulfo-2H-indol-2-ylidene)-2,3-dihydro-3-oxo-1 H-indole-5-sulfonic acid disodium salt (CI73015; Acid Blue No. 74), 9-(2-Carboxyphenyl)-3-[(2-methylphenyl)amino]-6-[(2-methyl-4-sulfophenyl)amino]xanthylium inner salt, monosodium salt (CI45190; Acid Violet No. 9), 1 -Hydroxy-4-[(4-methyl-2-sulfophenyl)-amino]-9,10-anthraquinone sodium salt (CI60730; D&C Violet No. 2; Acid Violet No. 43), Bis[3-nitro-4- [(4-phenylamino)-3-sulfo-phenylamino]-

,4» . &iacgr;

i#ft ft· ··* ···

phenyl]-sulfone (Cl 10410; Acid Brown No. 13), 5-amino-4-hydroxy-6-[(4-nitrophenyl)azo]-3-(phenylazo)-2,7-naphthalene-disulfonic acid disodium salt ( CI20470; Acid Black No. 1), 3-Hydroxy-4-[(2-hydroxynaphth-1-yl)azo]-7-nitro-1-naphthalene-sulfonic acid chromium complex (3:2) (CU 5711; Acid Black No. 52), 3-[(2,4-Dimethyl-5-sulfophenyl)azo]-4-hydroxy-1-naphthalenesulfonic acid disodium salt (CI14700; Food Red No. 1; Ponceau SX; FD&C Red No. 4), 4-(Acetylamino)-5-hydroxy-6-[(7-sulfo-4-[(4-sulfophenyl)azo]naphth-1 -yl)azo]-1,7-naphthalene disulfonic acid tetrasodium salt (CI28440; Food Black No. 1 ), 3-Hydroxy-4-(3-methyl-5-oxo-1 -phenyl-4,5-dihydro-1 H-pyrazole-4-ylazo)-naphthalene-1 -sulfonic acid sodium salt, chromium complex (Acid Red No . 195), 4-((5-((2-Hydroxyethyl)amino-1-methyl-1H-pyrazol-4-yl)imino)-4,5-dihydro-5-((2-hydroxyethyl)imino)- 1 -methyl-1 H-pyrazole monosulfate, 5-hydroxy-1,4-naphthoquinone (CI75500, Natural Brown No. 7), 2-Hydroxy-1,4-naphthoquinone (CI75480, Natural Orange No. 6) and 1,2-dihydro-2-(1,3-dihydro-3-oxo-2H-indol-2-ylidene)-3H-indole -3-on (CI73000).

The direct dyes can be used in component (a) and component (b) in a total amount of about 0.02 to 20 percent by weight, preferably 0.2 to 10 percent by weight, the total amount of direct dyes in the ready-to-use colorant obtained by mixing components (a) and (b) being about 0.01 to 10 percent by weight, preferably 0.1 to 5 percent by weight.

Component (a) and component (b), as well as the ready-to-use colorant, are preferably present independently of each other

in the form of a solution, in particular an aqueous or aqueous-alcoholic solution, a cream, a gel, an emulsion or an aerosol foam.

Component (a) and component (b) can contain all substances which are customary and known for such preparations, for example solvents such as water, lower aliphatic alcohols, for example ethanol, n-propanol and isopropanol or glycols such as glycerin and 1,2-propanediol, furthermore wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or non-ionic surface-active substances such as fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid alkanolamides, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid alkanolamides, ethoxylated fatty acid esters, furthermore thickeners such as higher fatty alcohols, starch or cellulose derivatives, perfumes, hair pretreatment agents, conditioners, hair swelling agents, Preservatives, Vaseline, paraffin oil and fatty acids as well as care substances such as cationic resins, lanolin derivatives, cholesterol, pantothenic acid and betaine. The aforementioned substances 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 (each based on component (a) or component (b)), the thickeners in an amount of about 0.1 to 25 percent by weight (each based on component (a) or component (b)) and the care substances in a concentration of about 0.1 to 5.0 percent by weight (each based on component (a) or component (b))

The pH of the ready-to-use colorant is adjusted by mixing component (a) containing the compounds of formula (I) with component (b) containing the carbonyl compound - preferably acidic - and is about 3 to 11, preferably 4 to 10. In a particularly preferred embodiment of the invention, component (a) and/or the ready-to-use preparation have a pH of 4 to 9, whereby the acidic or neutral pH of component (b) can optionally only be adjusted shortly before mixing with component (a) by adding an acidic component (c).

To adjust the pH value suitable for coloring, alkalizing agents such as alkanolamines, ammonia, alkylamines, alkali hydroxides or alkaline earth hydroxides, alkali carbonates or alkaline earth carbonates, ammonium carbonates and in particular ammonia or ammonium hydroxide, or acids such as lactic acid, acetic acid, tartaric acid, phosphoric acid, hydrochloric acid, citric acid, ascorbic acid and boric acid can be used.

The two components are mixed immediately before use and applied to the fiber, preferably human hair. Depending on the desired color depth, this mixture is left to act for 5 to 60 minutes, preferably 15 to 30 minutes, at a temperature of 20 to 50 degrees Celsius, especially at 30 to 40 degrees Celsius. The fiber is then rinsed with water, washed with a shampoo if necessary, and then dried.

The compounds of formula (I) and the carbonyl compound are generally used in an equimolar ratio in the ready-to-use dye. Depending on the desired shade, a single

or the compounds of formula (I) are mixed with one or more carbonyl compounds, whereby a wide spectrum of different nuances can be produced.

The dyes according to the invention provide excellent coloring of keratin fibers, in particular human hair, but also wool or silk, in yellow to brown shades.

The following examples are intended to illustrate the subject in more detail without limiting it to these examples.

Examples Examples 1 to 76: Hair dyes

Component (a) containing compound of formula (I)

Compound of formula (I) Quantities according to Table 1

direct dye quantities according to Table 1

Ethanol 25.0g

Lauryl ether sulfate, 28% aqueous solution 10.0 g

Water, fully demineralized ad 100.0 g

The compound of formula (I) is dissolved in the above mixture at room temperature or with gentle heating. The pH of the solution is 4.5 to 5. If necessary, direct dyes can be added to this mixture. Depending on the direct dye, the pH can be increased by adding a base to improve the dyeing result.

Carbonyl-containing component (b)

Carbonyl compound quantities according to Table 1

Lauryl ether sulfate, 28% aqueous solution 10.0 g

Ethanol 25.0g

Water, fully demineralized ad 100.0 g

The carbonyl compound is dissolved in the above mixture at room temperature or with gentle heating. The pH of the solution is adjusted to 4.0 with 10% aqueous lactic acid.

1 g of component (a) is mixed with 1 g of component (b). The resulting ready-to-use hair dye is then applied to a strand of hair and evenly distributed with a brush. After an exposure time of 30 minutes at 40 ⁰ C, the hair is washed with a shampoo, then rinsed with lukewarm water and then dried.

The obtained stainings are summarized in Table 1 below.

Tabel 1: Color results

No. Compound (I) containing Aldehyde-containing component (a) component (b)

Color tone after dyeing

Color measurement values Lab

Aminorhodanine 1.71%

Aminorhodanine 1.71%

Aminorhodanine 1.71%

Aminorhodanine 1.71%

Aminorhodanine 1.71%

Aminorhodanine 1.71%

3,4,5-Trihydroxybenzaldehyde 1.99% Syringaldehyde 2.1%

3,4-Dihydroxybenzaldehyde 1.99%

4-Hydroxy-3-methoxybenzaldehyde 1.75% 5-Formylsalicylic acid 1.92%

2,4-Dimethyoxy-3-methylbenzaldehyde 2.07% fox red

orange-brown
dark orange

After dyeing: +36.1;+39.5; +33.1 After dyeing: +47.6; +39.5; +47.7

After dyeing: +53.2; +30.3; +57.6 bright orange After dyeing: +59.8;+37.8; +67.0 After dyeing: +77.2;-2.6; +80.9

After dyeing: +77.0;-4.1; +72.2

sunny yellow

CO

Tabel 1: (Continued)

No. Compound (I) containing component (a)

Aldehyde-containing component (b) Color tone after dyeing

Color measurement values Lab

Aminorhodanine 1.71%

Aminorhodanine 1.71%

Aminorhodanine 1.71%

Aminorhodanine 1.71%

Aminorhodanine 1.71%

Aminorhodanine 1.71%

2,6-Dimethoxy-4-

hydroxybenzaldehyde 2.1%

4-Hydroxy-3-methyl-

benzaldehyde1.57%

2,3,4-Trihydroxy-

benzaldehyde1.78%

3-(3,5-Dimethoxy-4-hydro-

xy-phenyl)-propenal 2.40 %

6-Methoxy-2-naphthaldehyd

2.15%

4-Dimethylamino-2-meth-

oxybenzaldehyde 2.07 % yellow-orange

yellow-orange

orange-brown

orange-brown

After dyeing: +69.0;+18.5; +85.5 After dyeing: +70.6;+13.1; +79.0 After dyeing: +55.7;+28.3; +63.4 After dyeing: +43.6;+30.6; +44.4 After dyeing: +73.8; +3.93; +80.1 bright orange After dyeing: +57.5; +45.4; +68.0

Table 1: (Continuation)

No. Compound (I) containing Aldehyde-containing component (a) component (b)

Color after dyeing

Color measurement values Lab

Aminorhodanine 1.71%

Aminorhodanine 1.71%

Aminorhodanine 1.71%

Aminorhodanine 1.71%

Aminorhodanine 1.71%

Aminorhodanine 1.71%

2-Methoxynaphthaldehyde 2.15%

3,5-Dimethyl-4-hydroxybenzaldehyde 1.73%

3,4-Dimethyoxy-5-hydroxybenzaldehyde2.10%

4-Diethylamino-2-hydroxybenzaldehyde 2.23%

4-Dibutylaminobenzaldehyde 2.69%

4-Diethylaminobenzaldehyde 2.04%

yellow-orange orange-yellow yellow orange

orange-orange

After dyeing: +71.4;+8.43; +83.9 After dyeing: +68.6;+21.5; +70.6 After dyeing: +76.2,-3.5; +69.1

After dyeing: +67.9;+28.1; +64.3

After dyeing: +66.9; +29.7; +62.8 After dyeing: +59.8;+45.1; +67.3

Table 1: (Continuation)

No. Compound (I) containing component (a)

Aldehyde-containing component (b)

Color after dyeing

Aminorhodanine 1.71% Aminorhodanine 1.71% Aminorhodanine 1.71% Aminorhodanine 1.71% Aminorhodanine 1.71%

4-Dimethylaminobenzaldehyde 1.72%

orange

4-Methoxy-1-naphthaldehyde yellow-orange 2.15%

3-Ethoxy-4-hydroxy-orange benzaldehyde 1.92%

Isophthalaldehyde 1.55% yellow

1,2-Phthalaldehyde 1.55% ochre

Color measurement values Lab

After dyeing: +53.7;+52.3; +63.3

After dyeing: +68.6; 13.9; +81.6

After dyeing: ro
ro • »■
· #· * +58.9; +34.4; +65.6 4 &agr;
·%·* β ■ ·
• ■ ■ After dyeing: +78.8;-3.5; +65.6 &phgr; After dyeing: +48.0; +14.9; +46.5

Table 1: (continued )

No. Compound (I) containing Aldehyde-containing compo Color according to Color measurements Component (a) nent (b) dyeing Lab 24 Aminorhodanine 1.71% 4-Hydroxy-2-methoxy- yellow-orange After dyeing: benzaldehyde 1.76 % +66.7;+24.0; +81.6 25 Rhodanine-N-acetic acid 4-Dimethylamino- orange After dyeing: 2.2% benzaldehyde 1.72 % +68.1;+39.42; +82.4 26 Rhodanine 1.54% 4-Dimethylamino- orange After dyeing:

N-Methylrhodanine 1.70%

N-Ethylrhodanine 1.86%

Benzaldehyde 1.72% 4-Dimethylaminobenzaldehyde 1.73%

4-Dimethylaminobenzaldehyde 1.73%

orange

orange

+59.6;+46.3; +72.3 After dyeing: +54.8;+47.5; +65.9 After dyeing: +56.9; +48.5; +67.78

r o ω

· •••&bgr;

Table 1: (continued)

No. Compound (I) containing Component (a)

Aldehyde-containing component (b)

Color tone after dyeing

Color measurement values Lab

N-Allylrhodanine 2.00%

Rhodanine 1.54%

N-Methylrhodanine 1.70%

N-Ethylrhodanine 1.86%

N-Allylrhodanine 2.00%

Rhodanine-3-acetic acid
2.21%

4-Dimethylaminobenzaldehyde 1.73% 3,4,5-Trihydroxybenzaldehyde 1.99% 3,4,5-Trihydroxybenzaldehyde 1.99% 3,4,5-Trihydroxybenzaldehyde 1.99%

3,4,5-Trihydroxybenzaldehyde 1.99%

3,4,5-Trihydroxybenzaldehyde 1.99% orange
dull gold

forest snail orange

forest snail orange

forest snails-

orange

gold-orange

After dyeing: +52.0;+45.7; +59.4 After dyeing: +57.8; +26.4; +60.7 After dyeing: +39.3;+41.2; +38.3 After dyeing: +40.3;+43.3; +40.5

After dyeing: +40.8;+42.2; +40.4

After dyeing: +58.6;+24.1; +64.7

Table 1: (Continuation)

No. Compound (I) containing component (a)

Aldehyde-containing compo Color according to Color measurements Oil •
• nent (b) dyeing Lab I
•
• 3,5-Dimethyl-4-hydroxy- light yellow After dyeing: • benzaldehyde 1.73% +74.0;+1.74; +66.0 •
• 3,5-Dimethyl-4-hydroxy- light yellow After dyeing: *
• benzaldehyde 1.73% +68.8;+17.5; +69.2 3,5-Dimethyl-4-hydroxy- golden yellow After dyeing: benzaldehyde 1.73% +61.2;+28.0; +66.7 3,5-Dimethyl-4-hydroxy- golden yellow After dyeing: benzaldehyde 1.73% +68.1;+24.5; +74.3 3,5-Dimethyl-4-hydroxy- yellow After dyeing: benzaldehyde 1.73% +76.9; +3.9; +76.8 4-Hydroxy-2-methoxy- yellow-orange After dyeing: benzaldehyde 1.76% +73.1;+11.5; +89.0

35 Rhodanine 1.54%

36 N-Methylrhodanine 1.70%

37 N-Ethylrhodanine 1.86%

38 N-Allylrhodanine 2.00%

39 Rhodanine-3-acetic acid 2.21%

40 Rhodanine 1.54%

&phgr;
φ · 41 45 φφφ··
• Compound (I) containing Aldehyde-containing compo Color according to Color measurements Table 1: (continued) • :...:. 46 Component (a) nent (b) dyeing Lab No. • ΦI ^: 42 N-methylrhodanine 1.70% 4-Hydroxy-2-methoxy- yellow-orange After dyeing: benzaldehyde 1.76% +68.2;+20.5; +83.9 ·
•&phgr;* · :...:. 43 N-Ethylrhodanine 1.86% 4-Hydroxy-2-methoxy- yellow-orange After dyeing: · ·
· · benzaldehyde 1.76 % +70.7;+22.4; +88.9 •
··· ·
·.: 44
···· N-Allylrhodanine 2.00% 4-Hydroxy-2-methoxy- yellow-orange After dyeing: ·
· benzaldehyde 1.76% +68.9;+21.4; +86.9 Rhodanine-3-acetic acid 4-Hydroxy-2-methoxy- yellow After dyeing: 2.21% benzaldehyde 1.76% +78.3;+3.36; +96.3 Rhodanine 1.54% 4-Dimethylamino-2-meth- bright orange After dyeing: oxy-benzaldehyde 2.07% +62.1;+41.5; +72.5 N-Methylrhodanine 1.70% 4-Dimethylamino-2-meth- bright orange After dyeing: oxy-benzaldehyde 2.07% +52.9;+47.6; +60.8

•
•
····
· 4
· i 47 · ·
· ·
· · · Compound (I) containing Aidehyde-containing compo Color according to Color measurements Table 1: (continued) :...:. 49 Component (a) nent (b) dyeing Lab No. B B
·· «
· *
·· 48 ·
· ·
· ·
·· ·· N-Ethylrhodanine 1.86% 4-Dimethylamino-2-meth- bright orange After dyeing: •&Bgr; ·
· ■
···
·· "·. : 50
·· oxybenzaldehyde 2.07 % +56.6;+49.6; +67.5 ·· ·
·
·
·· · N-Allylrhodanine 2.0% 4-Dimethylamino-2-meth- bright orange After dyeing: *·■·
^: .. ^{: :} 51 oxybenzaldehyde 2.07% +56.6;+46.9; +66.8 ··· ·
•
• Rhodanine-3-acetic acid 4-Dimethylamino-2-meth- orange After dyeing: ·· ···
. . 52 2.21% oxy-benzaldehyde 2.07% +66.6;+34.0; +74.6 3-Ethyl-2-thioxo-4- 4-Dimethylamino- golden yellow After dyeing: oxazolidinone 1.67% benzaldehyde 1.72 % +79.7;+4.32; +83.0 3-Ethyl-2-thioxo-4- 3,4,5-Trihydroxy ash yellow After dyeing: oxazolidinone 1.67% benzaldehyde 1.99% +72.6;+4.61; +52.6 3-Ethyl-2-thioxo-4- 4-Hydroxy-2-methoxy- yellow After dyeing: oxazolidinone 1.67% benzaldehyde 1.76% +80.0;-9.86; +68.8

Table 1: (Continuation)

No. Compound (I) containing Component (a)

Aldehyde-containing component (b)

Color after dyeing

Color measurement values Lab

3-Ethyl-2-thioxo-4-oxazolidinone
1.67%

2-Thioxo-4-imidazolidinone
1.34%

2-Thioxo-4-imidazolidinone
1.34%

2-Thioxo-4-imidazolidinone
1.34%

2-Thioxo-4-imidazolidinone
1.34%

4-Dimethylamino-2-methoxybenzaldehyde 2.07%

4-Dimethylaminobenzaldehyde 1.72% 3,4,5-Trihydroxybenzaldehyde 1.99%

4-Hydroxy-2-methoxybenzaldehyde 1.76% 4-Dimethylamino-2-methoxybenzaldehyde 2.07%

orange

golden yellow
ash yellow

bright yellow, orange

After dyeing: +77.37; +7.95; +72.5

After dyeing: +74.9;+8.49; +82.2 After dyeing: +74.0;+1.33; +58.7 After dyeing: +80.0;-9.46; +70.2 After dyeing: +74.27;+11.9; +70.4

OO

Table 1: (continued) Compound (I) containing
Component (a) 1.54% Aldehyde-containing compo
nent (b) Color according to
dyeing Color measurements
Lab ϕ · ϕ
φ φ φφφ
ϕ ϕ ϕ
ϕ ϕ ϕ No. Rhodanine 5-Bromovanillin 2.67% bright orange After dyeing: 58 1.54% +69.1;+33.1; +61.1 ϕ ϕ
ϕ ϕ
ϕ ϕ ϕ Rhodanine 4-Hydroxy-3- bright orange After dyeing: φφφφφ
φ · ^: 59 1.54% nitrobenzaldehyde 1.93 % +59.4;+42.0; +72.1 φφφφφ Rhodanine 4-Dimethylamino-2- orange After dyeing: ϕ ϕ 60 1.54% methylbenzaldehyde 1.88% +64.2; +37.7; +63.4 ϕ ϕ
ϕ ϕ ·
ϕ ϕ ■
φφφφφ Rhodanine 4-Dimethylamino-6- yellow-orange After dyeing: &phgr;
φφφφ φ
ϕ ϕ
ϕ ϕ 61 methylbenzene-1,3- +67.8;+23.8; +80.5 φφφφφ
ϕ ϕ
ϕ ϕ
φφφ· 1.54% dicarbaldehyde 2.21% φφφφφ
ϕ ϕ ϕ
ϕ ϕ ϕ
φφ Rhodanine 4-Hydroxy-3-methoxy-5- orange After dyeing: φ φ φ φ φ 62 1.54% nitrobenzaldehyde 2.27 % +62.1;+29.2; +65.8 ΦΦΦΦ·
φ · Rhodanine 4-Dimethylamino-1- orange After dyeing: 63 naphthaldehyde 2.3% +62.3; +25.4; +58.6

φ φφφ • φφφ φ φ

Φ; Φ; Φ; Φ; Φ;

&phgr;&phgr;&phgr;&phgr; φ

Table 1: (continued)

No. Compound (I) containing component (a)

Aldehyde-containing component (b)

Color tone after dyeing

Color measurement values Lab

64 Rhodanine 1.54%

65 Rhodanine 1.54%

66 Rhodanine 1.54%

HC Blue No. 12 1.54% (pH 9.51)

67 Rhodanine 1.54% HC Blue No. 2 1.54% (pH 7.7)

68 Rhodanine 1.54% Basic Blue No. 12 1.54% (pH 7.2)

2-Dimethylamino-5-nitrobenzaldehyde 2.24% 4-Dimethylamino-2-nitrobenzaldehyde 2.24% Vanillin 1.76%

Vanillin 1.76%

Vanillin 1.76%

bright lemon yellow
matte orange

brown

moss green

After dyeing: +79.0;-1.9; +74.9 After dyeing: +69.1;+16.1; +52.7 After dyeing: +35.6;+7.9; +7.4

After dyeing: +3.0;+5.9; +12.6

bright blue- After dyeing: green +44.7;-27.4; +6.5

Table 1: (Continuation)

No. Compound (I) containing component (a)

Aldehyde-containing component (b)

Color tone after dyeing

Color measurement values Lab

Rhodanine 1.54%

Acid Violet No. 9 1.54% (pH 7.3)

Rhodanine 1.54%

HC Blue No. 12 1.54% (pH 7.6)

Rhodanine 1.54% HC Blue No. 2 1.54% (pH 7.3)

Rhodanine 1.54% Basic Blue No. 12 1.54% (pH 9.9)

Vanillin 1.76%

4-DimethyIamino-2-methoxy-benzaldehyde 2.07%

4-Dimethylamino-2-methoxy-benzaldehyde 2.07%

4-Dimethylamino-2-methoxy-benzaldehyde 2.07%

orange

red-brown

red-brown

moss green

After dyeing: +54.6;+34.8; +42.0

After dyeing: +33.7;+10.3; +3.0

After dyeing: +33.6;+11.8; +4.1

After dyeing: +35.4;-9.8; +26.4

CaJ

Table 1: (Continuation)

No. Compound (I) containing component (a)

Aldehyde-containing component (b)

Color tone after dyeing

Color measurement values Lab

Rhodanine 1.54%

Acid Violet No. 9 1.54% (pH 5.1)

Rhodanine 1.54% HC Blue No. 2 1.54% (pH 7.0)

Rhodanine 1.54% Basic Blue No. 12 1.54% (pH 3.0)

Rhodanine 1.54%

Acid Violet No. 9 1.54% (pH 3.0)

4-Dimethylamino-2-methoxy-benzaldehyde 2.07%

3,4,5-Trihydroxybenzaldehyde 1.98%

3,4,5-Trihydroxybenzaldehyde 1.98%

3,4,5-Trihydroxybenzaldehyde 1.98%

Red orange

brown

Red orange

After dyeing: +48.7;+43.6; +20.3

After dyeing: +29.3;+13.5; +17.5

After dyeing: +39.7; -22.4; +14.8

After dyeing: +47.0;+35.3; +37.7

The L*a*b* color measurement values given in the present examples were determined using a Minolta Chromameter II 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 in this application are by weight unless otherwise stated.

Claims (8)

1. An agent for dyeing fibres which is obtained by mixing two components, characterised in that one component (component (b)) contains at least one carbonyl compound, in particular an aromatic aldehyde compound, and the other component (component (a)) contains at least one compound of formula (I) or physiologically acceptable salts thereof,


in which R is hydrogen, a C1-C3 alkyl group, a C1-C3 alkylene group, a C1-C3 alkoxy-C1-C3 alkyl group, a C1-C3 hydroxyalkyl group, an amino group, a dimethylamino group or a carboxymethyl group and X is S. O or NR1, with R1 being hydrogen or a C1-C3 alkyl group; provided that the carbonyl compound of component (b) is an aromatic, non-heterocyclic carbonyl compound, when in formula (I) R is hydrogen or a carboxymethyl group and X is S. 2. Agent according to claim 1, characterized in that the compound of formula (I) is selected from rhodanine, rhodanine-3-acetic acid, 3-ethylrhodanine, 3-allylrhodanine, 3-methylrhodanine, aminorhodanine, 2-thioxo-4-imidazolidinone, 3-methyl-2-thioxo-4-oxazolidinone and 3-ethyl-2-thioxo-4-oxazolidinone. 3. Agent according to claim 1 or 2, characterized in that the carbonyl compound is selected from vanillin, isovanillin, 3,4-dihydroxybenzaldehyde, 4-hydroxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, syringaldehyde, 2-hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 4'-hydroxybiphenyl-1-carbaldehyde, 2-hydroxy-3-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, benzene-1,4-dicarbaldehyde, 4-ethoxybenzaldehyde, 2-methyl-1,4-naphthoquine on, 4-carboxy-benzaldehyde, 4-diethylamino-3-methoxybenzaldehyde, 1,2-phthaldialdehyde, 4-dibutylaminobenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 3,4-dimethoxy-5-hydroxy-benzaldehyde, 2-methoxy-1-naphthaldehyde, 3-ethoxy-4-hydroxy-benzaldehyde, 2-nitrobenzaldehyde, 3-Ni trobenzaldehyde, 4-nitrobenzaldehyde, formylsalicylic acid, 2,4-Dimethoxy-3-methylbenzaldehyde, 2,6-dimethoxy-4-hydroxy-benzaldehyde, 2,6-dimethoxy-4-hydroxy-benzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 6-methoxy-2-naphthaldehyde, 4-diethylamino-benzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, isophthaldialdehyde, 5-bromovanillin, 4-Hydroxy-3-nitro-benzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-dimethylamino-6-methyl-benzene-1,3-dicarbaldehyde, 4-hydroxy-3-methoxy-5-nitrobenzaldehyde, 2-dimethylamino-5-nitro-benzaldehyde and 4-dimethylamino-2-nitro-benzaldehyde. 4. Agent according to one of claims 1 to 3, characterized in that the compound of formula (I) is contained in component (a) in an amount of 0.02 to 20 percent by weight. 5. Agent according to one of claims 1 to 4, characterized in that the carbonyl compound is contained in component (b) in an amount of 0.01 to 20 percent by weight. 6. Agent according to one of claims 1 to 5, characterized in that the compound of formula (I) and the carbonyl compound are each contained in the ready-to-use agent in an amount of 0.01 to 10 percent by weight. 7. Agent according to one of claims 1 to 6, characterized in that the ready-to-use preparation obtained by mixing components (a) and (b) has a pH of 3 to 11. 8. Agent according to one of claims 1 to 7, characterized in that it additionally contains direct dyes.