DE20213695U1 - Agent for coloring keratin fibers - Google Patents

Description

The present invention relates to non-oxidative dyes for keratin fibers, such as hair, silk or wool, based on certain non-oxidative anthraquinone dyes.

Hair coloring is subject to a wide variety of trends these days. While hair used to be colored primarily to cover up gray hair, today there is a growing desire to integrate hair color into current fashion and as an expression of personality.

There are still two methods available for coloring hair. Firstly, there is oxidative hair coloring, which leads to a very permanent coloring result. Secondly, there is the option of coloring the hair with non-oxidative or direct dyes (often referred to as tinting agents). With both coloring methods, it is particularly desirable to achieve a high color density on the hair while at the same time only causing minimal skin coloring.

Although the direct dyes used in tints are usually optimized in terms of both their coloring performance and the durability of the color, the tinting results gradually become weaker with each wash, so that depending on the product used and the hair type, such dyes usually last a maximum of 10 washes. Another problem with the durability of the dyes is that the dyes

sometimes wash out at different speeds, which causes the colour tone to change uncontrollably as a result of the stronger washing out of one or more dyes.

Cationic dyes with aryl or heteroarylazo groups as well as anthraquinone or naphthoquinone systems have proven to be particularly suitable for use in tinting agents, whereby the cationic group can be either delocalized or localized. In this context, the widely used so-called "Arianor® dyes" should be mentioned, for example, which not only have good coloring properties, but also result in very little skin coloring. Model formulations with "Arianor® dyes" can be found, for example, in the monograph by K. Schrader, "Fundamentals and formulations of cosmetics", 2nd edition (1989), pages 811-815. The "Arianor® dyes" consist mainly of cationic azo dyes, only the blue dye ("Arianor® Steel-Blue") is a naphthoquinone derivative. In contrast to the other "Arianor® dyes", this blue dye is not a uniform compound with a constant composition due to the manufacturing process. Rather, the composition of this dye varies depending on the manufacturer and process conditions, so that every delivery batch of this dye must be checked for color consistency in order to ensure a constant color tone of the colorants produced with this dye.

A number of attempts have already been made to optimise the known dyeing systems based on direct dyes. Among others, EP-OS 1 006 153 and

EP-OS 1 006 154 and EP-OS O 758 547 propose the use of certain cationic aminoanthraquinones in non-oxidative colorants.

However, there was still a great need for non-oxidative dyes based on direct dyes, which do not have the aforementioned problems - especially with regard to the blue dye - and enable excellent and, above all, very permanent coloring of keratin fibers across all common shades.

Surprisingly, it has now been found that this problem can be solved by using certain direct anthraquinone dyes.

The present invention therefore relates to an agent for coloring keratin fibers - in particular hair - which is characterized in that it contains a combination of
a) at least one anthraquinone dye of the general formula (I),

OH OH'

(iii)

with R1 and R2 independently equal to a -CH2CH2OH group or a -CH2CH2CH2OH group, and

b) contains at least one other natural, nature-identical or synthetic direct dye.

The total content of the dyes of the formula (I) in the colorant according to the invention is preferably about 0.001 to 8 percent by weight, with an amount of 0.005 to 4 percent by weight being particularly preferred.

Natural direct dyes include plant dyes such as henna or indigo.

Synthetic direct dyes that can be mentioned are anionic or cationic dyes/nitro dyes, azo dyes, triphenylmethane dyes or quinone dyes, such as 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, 4-(di(2-hydroxyethyl)amino)-2-nitro-1-phenylamino-benzene;

1-Amino-4-[(2-hydroxyethyl)amino]-2-nitrobenzene (HC Red No. 7), 2-amino-4,6-dinitro-phenol, 1^-diamin^-nitrobenzene (CI76070), 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)-methylannino)-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, 3 -Nitro-4-(hydroxyethylamino)-phenol, 4-[(2-nitrophenyl)-amino]phenol (HC Orange No. 1), 1-[(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-ChIoM,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-nitrophenol, 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, 1,2,3,4-tetrahydro-6-nitroquinoxaline, 7 -Amino-3,4-dihydro-6-nitro-2H-1,4-benzoxazine (HC Red No. 14); 1,2-Diamino-4-nitrobenzene (CI76020), 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, i-Amino^-methyl-ö-nitrobenzene, 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-trifluoromethyl-benzene, (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, 2,4-dinitro-1-hydroxy-naphthalene; 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), i-Amino^-hydroxy-g.iO-anthraquinone (CI60710, Disperse Red 15), 1-hydroxy- 4-[(4-methyl-2-sulfophenyl)amino]-9,10-anthraquinone, 7-beta-

2-anthracenecarboxylic acid (CI75470, Natural Red 4), 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^-diamino^-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), 1,4-diamino-9,10-

anthraquinone (CI61100, Disperse Violet No. 1), 1-amino-4-(methylamino)-9,10-anthraquinone (CI61105, Disperse Violet No. 4, Solvent Violet No. 12), 2-hydroxy-3-methoxy- 1,4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 2-hydroxy-3-methyl-1,4-naphthoquinone, N-(6-((3-chloro-4-(methylamino)phenyl) imino)-4-methyl-3-oxo-1,4-cyclohexadien-1-yl)urea (HC Red No. 9), 2-((4-(Di(2-hydroxyethyl)amino)phenyl)-amino) -5-((2-hydroxyethyl)amino)-2,5-cyclohexadiene-1,4-dione (HC Green No. 1), 5-Hydroxy-1,4-naphthoquinone (CI75500, Natural Brown No. 7), 2-Hydroxy-1,4-naphthoquinone (CI75480, Natural Orange No. 6), 1,2-Dihydro-2-(1,3 -dihydro-3-oxo-2H-indol-2-ylidene)-3H-indol-3-one (CI73000), 1,3-bis(dicyanomethylene)indane; 9-(Dimethylamino)-benzo[a]-phenoxazin-7-ium chloride (CI51175; Basic Blue No. 6), di[4-(diethylamino)phenyl][4-(ethylamino)naphthyl]carbenium chloride (CI42595 ; Basic Blue No. 7), di-(4-(dimethylamino)phenyl)-(4-(methyl-phenylamino)-naphthalen-1-yl)carbenium 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-hydroxyethyl)amino)-phenyl)azo]-6-methoxy-3-methyl-benzothiazolium methylsulfate (CU 1154; Basic Blue No. 41), Basic Blue No. 77, S-Amino^-bromo-S-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), tri(4-amino-3-methylphenyl)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), 1-[(4-aminophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (Cl 12250; Basic Brown No. 16), 3-[(4-Amino-2,5-dimethoxyphenyl)azo]-N,N,N-trimethylbenzolaminium chloride (CM 12605, Basic Orange No. 69), 1-[(4 -Amino-3-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (Cl 12251; Basic Brown No. 17), 2-((4-aminophenyl)azo)-1,3-dimethyl -1H-imidazole-3-ium chloride (Basic Orange No. 31), 3,7-Diamino-2,8-dimethyl-5-phenylphenazinium chloride (CI50240; Basic Red No. 2), 1,4-Dimethyl-5-[(4-(dimethylamino)-phenyl)azo]-1, 2,4-triazolium chloride (CM 1055; Basic Red No. 22), 1,3-dimethyl-2-((4-dimethylamino)phenyl)azo-1H-imidazol-3-ium chloride (Basic Red No. 51), 2-hydroxy-1-[(2-methoxyphenyl)azo]-7-(trimethylammonio)naphthalene chloride (CI12245; Basic Red No. 76), 2-[2-((2,4- Dimethoxyphenyl)amino)ethenyl]-1,3,3-trimethyl-3H-indol-1-ium chloride (CI48055; Basic Yellow No. 11), 3-Methyl-1-phenyl-4-[(3-(trimethyl-ammonio)phenyl)azo]-pyrazole-5-one chloride (Cl 12719; Basic Yellow No. 57), di[4-(dimethylamino)phenyl]iminomethane hydrochloride (CI41000; Basic Yellow No. 2), 1-methyl-4-((methyl-phenylhydrazono)-methyl)-pyridinium methyl sulfate (Basic Yellow No. 87 ), bis[4-(diethylamino)phenyl]phenylcarbenium hydrogen sulfate (1:1) (CI42040; Basic Green No. 1), di(4-(dimethylamino)phenyl)phenylmethanol (CI42000; Basic Green No. 4) , 1-(2-morpholiniumpropylamino)-4-hydroxy-9,10-anthraquinone methyl sulfate, 1-[(3-(dimethyl-propylaminium)propyl)amino]-4-(methyl-amino)-9,10-anthraquinone -chloride;1-[Di(2-hydroxyethyl)amino]-3- methyl-4-[(4-nitrophenyl)azo]-benzene (CU 1210, Disperse Red No. 17), 1 -[Di(2-hydroxyethyl)amino]-4-[(4-nitrophenyl)azo]-benzene ( Disperse Black No. 9), 4-[(4-Aminophenyl)azo]-1-[di(2-hydroxyethyl)amino]-3-methylbenzene (HC Yellow No. 7), 2,6-Diamino-3-[ (pyridin-3-yl)azo]-pyridine,

♦ · · · t · t t t · · t · t 9·

2-((4-(Acetylamino)phenyl)azo)-4-methylphenol (Cl 11855; Disperse Yellow No. 3); 2-((4-(Ethyl(2-hydroxyethyl)amino)-2-methylphenyl)azo)-5-nitro-1,3-thiazole (CU 11935; Disperse Blue No. 106); 6-Hydroxy-5-[(4-sulfophenyl)azo]-2-naphthalenesulfonic acid disodium salt (CI15985; Food Yellow No. 3; FD&C Yellow No. 6), 2,4-dinitro-1-naphthol-7-sulfonic acid disodium salt ( CU0316; Acid 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. 3), 5-hydroxy-1-(4-sulfophenyl)-4-[(4-sulfophenyl)azo]pyrazole-3-carboxylic acid trisodium salt Food Yellow No. 4; 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 (CH 3015, Acid Yellow No. 9), 5-[(2,4-Dinitrophenyl)amino]-2-phenylamino-benzenesulfonic acid sodium salt (CM 0385; Acid Orange No. 3), 4-[(2,4 -Dihydroxyphenyl)azo]-benzenesulfonic acid monosodium salt (Cl 14270; Acid Orange No. 6), 4-[(2-Hydroxynaphth-1-yl)azo]-benzenesulfonic acid sodium salt (Cl 15510; Acid Orange No. 7), 4-((2-Hydroxy-naphthalen-1-yl)azo)-3-methylbenzenesulfonic acid sodium salt (Cl 15575; Acid Orange No. 8), 4-[(2,4-dihydroxy-3-[(2,4-dimethylphenyl)azo]phenyl)azo]-benzenesulfonic acid sodium salt (CI20170; Acid Orange No. 24), 3',6'-dihydroxy -4',5'-diiodospiro(isobenzofuran-1 (3H)-9'-(9H)xanthene)-3-one (CI45425, D&C Orange No. 10), 4-Hydroxy-3-[(4-sulfonaphth- 1-yl)azo]-1-naphthalenesulfonic acid disodium salt (Cl 14720; Acid Red No. 14), 4-hydroxy-3-[(2-methoxyphenyl)azo]-1-naphthalenesulfonic acid monosodium salt (Cl 14710; Acid Red No .4), 6-Hydroxy-5-[(4-sulfonaphth-1-yl)azo]-2,4-naphthalene disulfonic acid trisodium salt (Cl 16255; Ponceau 4R; Acid Red No. 18),

♦·

3-Hydroxy-4-[(4-sulfonaphth-1-yl)azo]-2,7-naphthalene-disulfonic acid trisodium salt (Cl 16185; Acid Red No. 27), 8-amino-1-hydroxy-2-(phenylazo) -3,6-naphthalene-disulfonic acid disodium salt (Cl 17200; Acid Red No. 33), 5-(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) , N-[6-(Diethylamino)-9-(2,4-disulfophenyl)-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',4',5',7'-tetrabromo-3', 6'-dihydroxyspiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one disodium salt (CI45380; Acid Red No. 87), 2',4',5',7'-tetrabromo- 4,5,6,7-tetrachloro-3',6'-dihydroxyspiro[isobenzofuran- !(SH^'PHlxanthenl-S-on-dinatrium salt (CI45410; Acid Red No. 92), 3 ^l ,6 ^l -Dihydroxy-4',5'-diiodospiro[isobenzofuran-1(3H),9 ^I (9H) -xanthene]-3-one disodium salt (CI45425; Acid Red No. 95), 2-hydroxy-3-((2-hydroxynaphth-1-yl)azo)-5-nitrobenzenesulfonic acid monosodium salt (CM 5685; Acid Red No. 184), (2-sulfophenyl)di[4-(ethyl( (4-sulfophenyl)methyl)-amino)phenyl]-carbenium disodium salt, betaine (CI42090; Acid Blue No. 9; FD&C Blue No. 1), 3-hydroxy-4-((4-methyl-2-sulfophenyl) azo)-2-naphthalenecarboxylic acid disodium salt (Cl 15850; D&C Red No. 6), 6-hydroxy-5-((2-methoxy-5-methyl-4-sulfophenyl)azo)-2-naphthalenesulfonic acid disodium salt (Cl 16035 ;FD&C Red 40), 1,4-Bis[(2-sulfo-4-methylphenyl)amino]-9,10-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), i-Amino^cyclohexylamino^ iO-anthraquinone^- sulfonic acid sodium salt (CI62045; Acid Blue No. 62), 3,3-bis(3,5-dibromo-4-hydroxyphenyl)-4,5,6,7-tetrabromo-2,1(3h )-benzoxathiol-1,1-dioxide, 1-amino-4-(phenylamino)-9,10-anthraquinone-2-sulfonic acid (CI62055; Acid Blue No. 25), 2-(1,3-Dihydro-3-oxo-5-sulfo-2H-indol-2-ylidene)-2,3-dihydro-3-oxo-1H-indole-5-sulfonic acid disodium salt (CI73015; Acid Blue No. 74), 9-(2-carboxyphenyl)-3-[(2-methylphenyl)amino]-6-[(2-methyl-4-sulfo-phenyl)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]-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) (CH 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) or 3-hydroxy- 4-(3-methyl-5-oxo-1 -phenyl-4,5-dihydro-1 H-pyrazol-4-ylazo)-naphthalene-1 sulfonic acid sodium salt, chromium complex (Acid Red No. 195).

Preferably, the following direct dyes (alone or in combination with each other) are used as component b): 2,6-diamino-3-((pyridin-3-yl)azo)-pyridine, 2-amino-6-chloro-4-nitrophenol,

4-[(2-Hydroxyethyl)amino]-3-nitro-1-methylbenzene, 3-nitro-4-(hydroxyethylamino)-phenol, 9-(dimethylamino)-benzo[a]phenoxazin-7-ium chloride (C.I. 51175; Basic Blue No. 6), di[4-(diethylamino)phenyl][4-(ethylamino)-naphthyl-carbenium chloride (Cl. 42595; Basic Blue No. 7), 3,7-di(dimethylamino- )phenothiazine-5-ium chloride (C.I. 52015; Basic Blue No. 9), di[4-(dimethyl-amino)phenyl]-[4-(phenyl-amino)naphthyl]-carbenium chloride (Cl. 44045; Basic Blue No. 26), 2-[(4-(Ethyl(2-hydroxyethyl)amino)-phenyl)azo]-6-methoxy-3-methyl-benzothiazolium methyl sulfate (Cl. 11154; Basic Blue No. 41), 2,8-dimethyl-7- (dimethylamino)-3-imino-3H-phenoxazine monohydrochloride (Basic Blue No. 151), 7-(dimethylamino)-3-imino-2-methoxy-3H-phenoxazine monohydrochloride (Basic Blue No. 124), Bis[ 4-(dimethylamino)-phenyl]-[4-(methylamino)-phenyl]carbenium chloride (Cl. 42535; Basic Violet No. 1), 4-[(4-amino-3-methylphenyl)(4-imino- 3-methyl-2,5-cyclohexadien-1-ylidene)methyl]-2-methylbenzenamine hydrochloride (Cl. 42520, Basic Violet No. 2), Tris[4-(dimethylamino)phenyl]-carbenium chloride (Cl. 42555; Basic Violet No. 3), 2-[3,6-(diethylamino)-dibenzopyranium-9-yl]-benzoic acid chloride ( C.1.45170; Basic Violet No. 10), di(4-aminophenyl)-(4-amino-3-methylphenyl)carbenium chloride (Cl. 42510; Basic Violet No. 14), 1,3-bis[(2 ,4-diamino-5-methylphenyl)azo]-3-methylbenzene (Cl. 21010; Basic Brown No. 4), 1-[(4-aminophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride ( Cl 12250; Basic Brown No. 16), 1-[(4-Amino-3-nitrophenyl)azo]-7-(trimethylammonio)-2-naphthol chloride (Cl 12251; Basic Brown No. 17), 3,7-diamino-2,8-dimethyl -5-phenyl-phenazinium chloride (Cl. 50240; Basic Red No. 2), 1,4-dimethyl-5-[(4-(dimethylamino)-phenyl)azo]-1,2,4-triazolium chloride (Cl . 11055; Basic Red No. 22), 3(or5)-[[4-[benzyl-methylamino]phenyl]azo]-1,2-(or 1,4)-dimethyl-1,2,4-triazolium- bromide (Cl. Basic Red No. 46), 2-{[4-(dimethyl-

amino)phenyl]azo}-1,3<limethyl-1H-imidazol-3-ium-chloride (Basic Red No. 51), 2-Hydroxy-1 -[(2-methoxyphenyl)azo]-7-(trimethyl- ammonio)-naphthalene chloride (Cl 12245; Basic Red No. 76), 5-{[4-(dimethylamino)-phenyl]azo}-1,2-dimethyl-1 H-pyrazol-2-ium chloride, 1 ,3-Dimethyl-2-{[4-(methylamino)-phenyl]azo}-1H-imidazol-3-ium chloride (Basic Red No. 109), 2-[(4-amino-phenyl)azo]- 1,3-dimethyl-1 H-imidazol-3-ium chloride, 4-{[4-(dimethyl-amino)phenyl]azo}-1-methylpyridinium chloride, N,N-Dimethyl-4-[(E)-(1-oxido-4-pyridinyl)diazenyl]aniline,4-((4-(Dimethylamino)phenyl)azo)-pyridine-N-oxide, 2-[2 -((2,4-Dimethoxyphenyl)amino)-ethenyl]-1,3,3-trimethyl-3H-indol-1-ium chloride (C.I. 48055; Basic Yellow No. 11), 3-methyl-1-phenyl -4-[(3-(trimethyl-ammonio)phenyl)azo]-pyrazol-5-one chloride (CI12719; Basic Yellow No. 57), 1-methyl-4-{[methyl(phenyl)-hydrazono]methyl }pyridinium chloride (Basic Yellow No. 87), 1-Methyl-4-{(E)-[methyl(4-methoxy-phenyl)-hydrazono]methyl}pyridinium chloride, 1-methyl-4-({methyl[4-methoxy-phenyl]hydrazono}methyl)pyridinium methyl sulfate (Basic Yellow No. 91) and bis[4-(diethylamino)phenyl]-phenyl carbenium hydrogen sulfate (1:1) (C.I. 42040; Basic Green No. 1), 4-[Ethyl-(2-hydroxyethyl)amino]-1-[ (2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Blue No. 12), 1-amino-5-chloro-4-[(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 10) , 5-chloro-1,4-[di(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 11) and 1-amino-4-[di(2-hydroxyethyl)amino]-2- nitrobenzene hydrochloride (HC Red No. 13).

The total content of natural, nature-identical and/or synthetic non-oxidative dyes in the colorant according to the invention is about 0.01 to 15 percent by weight, in particular about 0.1 to 12 percent by weight.

To increase the color intensity, the carriers commonly used in cosmetic systems can be added. Suitable compounds are described, for example, in DE-OS 196 18 595, to which reference is hereby expressly made. Particularly suitable carriers are, for example, benzyl alcohol, vanillin and isovanillin.

The agent according to the invention for coloring keratin fibers can be in the form of a solution, in particular as an aqueous-alcoholic solution, a cream, a gel or an emulsion. In addition to water, solvents that can be mentioned include lower aliphatic monohydric or polyhydric alcohols, their esters and ethers, or mixtures of these solvents with one another or with water. The maximum boiling point of the above-mentioned suitable solvents is about 400 ^° C, with a boiling point of 20 ^° C to 250°C being preferred.

It is also possible to remove the agent according to the invention from a pressure container as an aerosol spray or as an aerosol foam with the aid of an atomizer or other suitable pumping devices or spraying devices or in a mixture with conventional propellants liquefied under pressure.

Furthermore, if the ingredients are solids, the agent can be in the form of a powder or granules dedusted by adding a dedusting agent (for example an inert oil). Such an agent is dissolved in water or an aqueous preparation before use.

·

·

·

The pH of the colorant according to the invention is 2 to 11, with a pH of about 5 to 9 being particularly preferred. An alkaline pH is preferably set using ammonia, but it is also possible to use organic amines, such as monoethanolamine or triethanolamine, instead of ammonia. However, an organic or inorganic acid, such as hydrochloric acid, sulfuric acid, phosphoric acid, ascorbic acid, glycolic acid or lactic acid, can be used to set an acidic pH.

Of course, the dye described above may optionally contain other additives customary for dyes for keratin fibers, such as care substances, wetting agents, thickeners, plasticizers, preservatives and perfume oils, as well as other additives listed below.

Furthermore, the coloring agent according to the invention can contain wetting agents or emulsifiers from the classes of anionic, amphoteric, nonionic or zwitterionic surface-active substances such as fatty alcohol sulfates, alkanesulfonates, alkylbenzenesulfonates, alkylbetaines, a-olefinsulfonates, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid alkanolamines, ethoxylated fatty acid esters, fatty alcohol polyglycol ether sulfates, alkylpolyglucosides, thickeners such as higher fatty alcohols, starch, alginates, bentonites, cellulose derivatives, Vaseline, paraffin oil and fatty acids, water-soluble polymeric thickeners such as natural gums, guar gum, xanthan gum, locust bean gum, pectin, dextran, agar-agar, amylose, amylopectin, dextrins, clays or fully synthetic hydrocolloids such as polyvinyl alcohol, as well as

Care substances such as lanolin derivatives, cholesterol, pantothenic acid, water-soluble polymers, protein derivatives, provitamins, vitamins, plant extracts, sugar and betaine, excipients such as humectants, electrolytes^, antioxidants, fatty amides, sequestering agents, film-forming agents and preservatives.

The coloring agent described above can also contain natural or synthetic polymers or modified polymers of natural origin, whereby the keratin fiber is strengthened at the same time as the coloring. Such agents are generally referred to as tint fixatives or color fixatives. Examples of synthetic polymers known for this purpose in cosmetics include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol or polyacrylic compounds such as polyacrylic acid or polymethacrylic acid, polyacrylonitrile, polyvinyl acetates and copolymers of such compounds, such as polyvinylpyrrolidone-vinyl acetate; while natural polymers or modified natural polymers can be used, for example, chitosan (deacetylated chitin) or chitosan derivatives.

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 25 percent by weight and the care substances in an amount of about 0.1 to 5 percent by weight. The aforementioned polymers can be used in the agent according to the invention in the amount customary for such agents, in particular in an amount of about 1 to 5 percent by weight.

·&diams;·*· iiii si**

The agent according to the invention for coloring keratin fibers is particularly suitable for coloring hair. The colorant according to the invention is applied to the hair in the usual way in an amount sufficient to color the hair, generally about 50 to 150 grams. After a contact time sufficient to color the hair, which is usually about 10 to 45 minutes at 20 to ⁰ C, preferably about 15 to 30 minutes at about 40 ⁰ C, the hair is rinsed with water, optionally washed with a shampoo and/or rinsed with an aqueous solution of a weak organic acid, such as citric acid or tartaric acid, and dried.

The dye with additional fixing is applied in the known and usual way by moistening the hair with the fixing product, styling the hair and then drying it.

With the dye according to the invention, shades can be achieved both in the natural tone range and in the fashionable range (for example, highly fashionable, bright shades). In addition to the tones mentioned, it is also possible to achieve a range of brilliant color reflections across the entire visible color range. Due to the very high color strength of the dyes and the good absorption properties, the original color of the fiber can be covered in an excellent manner. This also fully meets the desire mentioned at the beginning to integrate hair color into fashion and as an expression of personality. The excellent properties of the new dye are particularly evident in

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18

hair damaged by light and weather or on permed hair. The resulting colors are particularly characterized by their very good durability and resistance to washing out.

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

Examples Examples 1-13: non-oxidative hair dyes

A colour mass of the following composition is prepared: 10.00 g ethanol
1.00 g hydroxyethyl cellulose

&khgr; g dyes according to table ad 100.00 g water, demineralized

The pH of the mass is adjusted to 8 by adding ethanolamine

set.

The dye is applied to bleached hair and after a

After 20 minutes exposure time at 40 ^° C, rinse with water.

The hair is then dried.

The dyes used and the dyeing results obtained are shown in

Table 1 summarizes.

All percentages are by weight unless otherwise stated.

Table 1:

Example 1 2 3 4 5 6 7 8th 9 10 11 12 13 Connection of the
Formula (I) 0.199 0.149 0.054 0.181 0.011 0.102 0.050 0.100 0.040 0.079 0.102 0.153 0.151 2,6-Diamino-3-
((pyridin-3-yl)azo)-
pyridine 0.005 0.005 Basic Violet No. 2 0.122 0.101 3-Nitro-4-(hydroxy-
ethylamino)-phenol 0.303 0.303 2-Amino-6-chloro-4-
nitrophenol 0.119 0.119 HC Red No. 13 0.071 0.070 HC Red No. 10/
HC Red No. 11 0.401 0.401 4-[(2-Hydroxyethyl)-
amino]-1-methyl-3-
nitrobenzene 0.100 0.104 HC Blue No. 12 0.118 0.120 Basic Yellow No. 57 0.020 0.022 Basic Red No. 76 0.104 0.100 Basic Brown No. 17 0.051 0.052 Basic Brown No. 16 0.051 0.050 Color result red
violet red
brown yellow
green green
yellow purple red
blue yellow
green blue turquoise
green Red Blue
brown dark
green dark
brown brown
red

Claims (7)

1. Agent for coloring keratin fibers, characterized in that it contains a combination of a) at least one anthraquinone dye of the general formula (I),


with R1 and R2 independently equal to a -CH2CH2OH group or a -CH2CH2CH2OH group, and b) contains at least one other natural, nature-identical or synthetic direct dye. 2. Agent according to claim 1, characterized in that the direct dye of component b) is selected from 2,6-diamino-3-((pyridin-3-yl)azo)-pyridine, 2-amino-6-chloro-4-nitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene, 3-nitro-4-(hydroxyethylamino)-phenol, 9-(dimethylamino)-benzo[a]phenoxazin-7-ium chloride (C. I. 51175; Basic Blue No. 6), di[4-(diethylamino)phenyl][4-(ethylamino)-naphthyl]-carbenium chloride (C. I. 42595; Basic Blue No. 7), 3,7-di(dimethylamino)-phenothiazin-5-ium chloride (C. I. 52015; Basic Blue No. 9), Di[4-(dimethylamino)phenyl]-[4-(phenyl-amino)naphthyl]-carbenium chloride (C.I. 44045; Basic Blue No. 26), 2-[(4-(Ethyl(2-hydroxyethyl)amino)-phenyl)azo]-6-methoxy-3-methyl-benzothiazolium-methylsulfate (C.I. 11154; Basic Blue No. 41), 2.8 -Dimethyl-7-(dimethylamino)-3-imino-3H-phenoxazine monohydrochloride (Basic Blue No. 151), 7-(Dimethylamino)-3-imino-2-methoxy-3H-phenoxazine monohydrochloride (Basic Blue No. 124), Bis[4-(dimethylamino)-phenyl]-[4-(methylamino)-phenyl]carbenium chloride (C.I. 42535 ;Basic Violet No. 1) (Diethylamino)-dibenzopyranium-9-yl]-benzoic acid chloride (C.I. 45170; Basic Violet No. 10), di(4-aminophenyl)-(4-amino-3-methylphenyl)carbenium chloride (C.I. 42510; Basic Violet No. 14), 1,3-bis[(2,4-diamino-5-methylphenyl)azo]-3-methylbenzene ( C.I. 21010; Basic Brown No. 4) -2,8-dimethyl-5-phenyl-phenazinium chloride (C.I. 50240; Basic Red No. 2), 1,4-dimethyl-5-[(4-(dimethylamino)-phenyl)azo]-1,2,4-triazolium chloride (C.I. 11055; Basic Red No. 22), 3(or 5)-[[4-[Benzyl-methylamino]phenyl]azo]-1,2-(or 1,4)-dimethyl-1,2,4-triazolium bromide (C.I. Basic Red No. 46) ), 4-{[4-(Dimethylamino)phenyl]azo}-1-methylpyridinium-chlorid, N,N-Dimethyl-4-[(E)-(1-oxido-4-pyridinyl)diazenyl]anilin, 4-((4-(Dimethylamino)phenyl)azo)-pyridin-N-oxid, 2-[2-((2,4-Dimethoxyphenyl)amino)- ethenyl]-1,3,3-trimethyl-3H-indol-1-ium-chlorid (C. I. 48055; Basic Yellow No. 11), 3-Methyl-1-phenyl-4-[(3-(trimethyl-ammonio)phenyl)azo]-pyrazol- 5-on-chlorid (C. I. 12719; Basic Yellow No. 57), 1-Methyl-4-{[methyl(phenyl)- hydrazono)methyl}pyridinium-chlorid (Basic Yellow No. 87), 1-methyl-4-{(E)-[methyl(4-methoxy-phenyl)-hydrazono]methyl}pyridinium chloride, 1-methyl-4-({methyl[4-methoxy-phenyl)hydrazono}methyl)pyridinium methyl sulfate (Basic Yellow No. 91) and bis[4-(diethylamino)phenyl]-phenyl-carbenium hydrogen sulfate (1: 1) (C.I. 42040; Basic Green No. 1), 4-[ethyl-(2-hydroxyethyl)amino]-1-[(2-hydroxyethyl)amino]-2-nitrobenzene hydrochloride (HC Blue No. 12), 1-amino-5-chloro-4-[(2,3-dihydroxypropyl )amino)-2-nitrobenzene (HC Red No. 10), 5-chloro-1,4-[di(2,3-dihydroxypropyl)amino]-2-nitrobenzene (HC Red No. 11) and 1-amino-4-[di(2-hydroxyethyl)amino)-2-nitrobenzene hydrochloride (HC Red No. 13). 3. Agent according to claim 1 or 2, characterized in that the dye of formula (I) is contained in an amount of 0.001 to 8 percent by weight. 4. Agent according to one of claims 1 to 3, characterized in that the direct dye of component b) is contained in a total amount of 0.01 to 15 percent by weight. 5. Agent according to one of claims 1 to 4, characterized in that it additionally contains a carrier 6. Agent according to one of claims 1 to 5, characterized in that it additionally contains at least one natural or synthetic polymer or modified polymer of natural origin and is in the form of a tint fixative or color fixative. 7. Agent according to one of claims 1 to 6, characterized in that it is a hair dye.