WO2000052100A1

WO2000052100A1 - Agents for colouring fibres

Info

Publication number: WO2000052100A1
Application number: PCT/EP2000/001024
Authority: WO
Inventors: Thomas Kripp; Thomas Czigler; Pascal André SEMADENI
Original assignee: Wella Aktiengesellschaft
Priority date: 1999-02-27
Filing date: 2000-02-09
Publication date: 2000-09-08

Abstract

The invention relates to non-oxidative colouring agents which can be obtained by reacting one or more carbonyl compounds with thiobarbituric acid or derivatives thereof. The invention also relates to a method for producing said colouring agents, to colourants containing them and to a method for colouring and later decolouring hair using said colourants.

Description

Means for dyeing fibers

The present application relates to new dyes obtainable by reacting thiobarbituric acid with one or more carbonyl compounds, a process for the preparation of these dyes and an agent for dyeing fibers, in particular hair, and a method for dyeing and later decoloring fibers using this agent.

For the dyeing of keratin-containing fibers, such as hair, wool or furs, either direct synthetic or vegetable dyes or oxidation dyes, which result from the oxidative coupling of so-called developer substances with so-called coupler substances, are generally used. Although a large number of dyestuffs are known, only a few dyestuffs are suitable for use in dyes for keratin fibers, since these have to meet a multitude of conditions which in other areas of dyeing (dyeing synthetic fibers or foodstuffs) only have to be partially fulfilled . For example, a dye for keratin fibers must be able to dye the hair, be toxicologically harmless, enable coloring under mild conditions (low temperatures etc.), cause as little skin staining as possible, be water-soluble, largely sweat-resistant and washable, apply evenly to the fiber ( particularly important for dye mixtures), evenly (ie without changing the color) washed out, have the highest possible coverage, damage the fiber as little as possible and do not interfere with other hair treatment methods (e.g. permanent wave treatment)

Because of the multitude of requirements, only a few substances are ultimately suitable for dyeing hair and compromises are indispensable for individual requirements.

Each of these two dye systems (direct dyes, oxidation dyes) has specific advantages and disadvantages, which have different degrees of weight depending on the requirements of the consumer. Gentle hair coloring is generally possible with direct dyes, but direct dyes are only suitable for covering gray hair to a limited extent due to the significantly lower hiding power, whereby a satisfactory coloring result can no longer be achieved with a proportion of gray of more than 30% with non-oxidative direct pullers .

Table 1 gives an overview of the basic strengths and weaknesses of the two systems used so far:

There is therefore a great need for a gentle, non-oxidative agent for the semi-permanent dyeing of fibers, in particular keratin fibers such as human hair, which enables intensive and permanent dyeing of the fiber in a multitude of colors and shades, this dyeing being desired if desired - should be easy to remove at any time. Table 1: Comparison of various properties of direct and oxidative dyes

Surprisingly, it has now been found that the aforementioned object is achieved by means of special new dyes obtainable by reacting thiobarbituric acid or its salts with one or more carbonyl compounds.

From the literature, Journal of the American Chemical Society 38 (1916), pages 2164-2166, it has long been known that the implementation of Carbonyl compounds with thiobarbituric acid lead to color reactions, but the targeted synthesis of dyes suitable for hair dyeing by reacting carbonyl compounds with thiobarbituric acid and the use of the dyes prepared in this way for dyeing hair is not described in the prior art.

The present invention therefore relates to the reaction of (a) thiobarbituric acid and / or its derivatives, for example the alkali metal or alkaline earth metal salts of thiobarbituric acid, with (b) one or more carbonyl compounds from the group consisting of saturated dialdehydes, saturated diketones, saturated ketoaldehydes , unsaturated dialdehydes, unsaturated diketones, unsaturated ketoaldehydes, monoaldehydes with one or more chromophoric groups, monoketones with one or more chromophoric groups and quinones, available non-oxidative dyes and a process for the preparation of these dyes.

The following are particularly suitable as carbonyl compounds

To name connections:

(i) unsaturated or saturated dialdehydes, for example glutacodialdehyde or glutacondialdehyde monoenolate, gemsteinedialdehyde,

Fumaric dialdehyde, glutaraldehyde, glyoxal, malondialdehyde, mucodialdehyde, o-phthalaldehyde or terephthalaldehyde;

(ii) unsaturated or saturated diketones, for example diacetyl,

Acetylacetone or isatin;

(iii) unsaturated or saturated keto aldehydes, mono aldehydes with one or more chromophoric groups or monoketones with one or several chromophoric groups, for example 2,3,4-trihydroxybenzaldehyde, 3-oxobutyraldehyde, acrolein, acetaldehyde, benzaldehyde and its derivatives (for example p-dimethylaminobenzaldehyde), dimethylamino-phenylpentadienal, ethylvanillin, glyceraldehyde, isovanillin, methylfurfural , o-vanillin, stilbenaldehyde, vanillin, cinnamaldehyde and its derivatives (for example p-dimethylamino-cinnamaldehyde, p-nitro-cinnamaldehyde or o-nitro-cinnamaldehyde), benzophenone or 2,3-deoxy-ribose; and

(iv) Quinones, for example p-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone (coenzyme Q ₀ ) or 5-hydroxy-1,4-naphthoquinone (juglone).

The new dyes can be prepared in a simple manner by heating an aqueous solution containing one or more suitable carbonyl compounds and a 1 to 2-fold molar excess (based on the number of aldehyde, ketone or quinone groups in the carbonyl compound) on thiobarbituric acid or its derivatives with a pH value of less than / equal to 3 to at least 50 ° C, the reaction mixture being preferably stirred. The desired pH is adjusted by adding a suitable organic or inorganic acid, with the use of hydrochloric acid being particularly preferred. With less reactive carbonyl compounds, higher temperatures (approx. 80 ° C) and / or longer reaction times (1-2 hours) are required. The reaction mixture is then cooled and the precipitated dye is filtered off. If necessary, the dye thus obtained can be cleaned again. For this purpose, 1 g of the dye is fine in a grater pulverized, the powder obtained is then heated in 200 ml of 0.6 N hydrochloric acid for 40 minutes, then cooled to 60 ° C and filtered through a glass frit with a slight vacuum. The powder obtained is washed again with 100 ml of 0.6 N hydrochloric acid, then with 25 ml of cold water, 25 ml of ethanol and finally with 100 ml of diethyl ether. It is then dried in vacuo at 60 ° C. to constant weight.

The following compounds can be mentioned as examples of dyes according to the invention:

Table 2: Dyes obtained by reacting saturated or unsaturated dialdehydes with thiobarbituric acid

- "= Increased basic absorption without a characteristic maximum. Table 3: Dyes obtained by reacting diketones or ketolactams with thiobarbituric acid

Table 4: Dyes obtained by reacting monoketones with chromophore and thiobarbituric acid

Table 5: Dyes obtained by reacting monoaldehydes with chromophore and thiobarbituric acid

"~" = Increased basic absorption without a characteristic maximum.

Table 6: Dyes obtained by reacting quinones with thiobarbituric acid

= Increased basic absorption without a characteristic maximum.

While, as expected, the shift of the absorption maximum into the longer-wave region can be produced in the case of divalent carbonyl compounds by increasing the number of conjugated double bonds, the second thiobarbituric acid group can can also be replaced by a corresponding chromophoric system for monovalent carbonyl compounds (example: benzaldehyde <vanillin <p-dimethylaminobenzaldehyde). In the case of dyes, a broadband absorption behavior with high extinction coefficients can generally be observed.

Based on the manufacturing process and the spectroscopic investigations from the manufacturing examples, the following structure of the dyes obtained is assumed: either

Thiobarbituric acid dialdehyde, inventive

Diketone, dye (suspected

Ketoaldehyde structure)

Quinone

or

Thiobarbituric acid monoaldehyde, inventive

Monoketone dye (suspected

Structure) The dyes have a high dyeing capacity and very good sweat and wash fastness without containing azo groups or metal salts and have a number of advantages over conventional non-oxidative dyes (so-called direct draws) (see Table 7).

Table 7: Comparison of various properties of conventional direct drawers with the dyes according to the invention

The present invention therefore further relates to an agent for dyeing or tinting fibers containing at least one of the dyes according to the invention described above. The fibers in particular are keratin fibers, for example wool, silk, furs or hair (in particular human hair), but also non-keratin fibers, for example cotton, linen, hemp textiles, Breness fibers, viscose, acetyl cellulose, cellulose triacetate or polyamide fibers.

The agent for dyeing fibers according to the invention can be present, for example, in the form of a solution, in particular as an aqueous alcohol solution, a cream, a gel or an emulsion. In addition to water, for example, lower aliphatic monohydric or polyhydric alcohols, their esters and ethers, or else mixtures of these solvents with one another or with water can be used as solvents. The maximum boiling point of the abovementioned suitable solvents is approximately 400 ° C., a boiling point of 20 ° C. to 250 ° C. being preferred. It is also possible to remove the agent according to the invention with the aid of an atomizer or other suitable pump devices or spray devices or in a mixture with conventional propellants liquefied under pressure as an aerosol spray or as an aerosol foam from a pressure container.

The dye is contained in the colorant according to the invention in an amount of 0.001 to 10 percent by weight, preferably 0.01 to 3 percent by weight. The pH of the colorant according to the invention can vary from 0 to 14, depending on the fiber to be colored, over the entire pH range. The pH is preferably about 2 to 10, with an acidic pH of 2 to 7 being particularly preferred, particularly when coloring human hair. An alkaline pH is preferably adjusted with ammonia or sodium hydroxide solution, but it is also possible to use organic amines, such as monoethanolamine or triethanolamine, instead of ammonia. On the other hand, an organic or inorganic acid, such as, for example, hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, tartaric acid, glycolic acid or lactic acid, can be used to set an acidic pH.

Of course, the colorant according to the invention can additionally contain other additives customary for such colorants, such as care agents, thickeners, plasticizers, preservatives, wetting agents or emulsifiers, for example from the classes of anionic, amphoteric, nonionic or zwitterionic surface-active substances such as fatty alcohol sulfates, alkane sulfonates, Alkylbenzenesulfonates, alkylcarnitines, acyl-carnitines, alkylbetaines, α-olefinsulfonates, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid aeanolamines, ethoxylated fatty acid esters, fatty alcohol polyglycol ether sulfates, alkyl polyglucosides, thickeners such as higher fatty alcohol cellulose, paraffin oil, benton oil, benton derivatives, starch 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, auxiliaries such as humectants, electrolytes, antioxidants, fatty amides, sequestering agents, film-forming agents and preservatives. The colorant according to the invention can furthermore contain natural or synthetic polymers or modified polymers of natural origin, whereby a strengthening of the keratin fiber is achieved simultaneously with the coloring. Of the synthetic polymers known for this purpose in cosmetics, for example 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, are mentioned; while, for example, chitosan (deacetylated chitin) or chitosan derivatives can be used as natural polymers or modified natural polymers.

The ingredients 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 weight percent. The abovementioned polymers can be used in the amount customary for such agents, in particular in an amount of about 1 to 5 percent by weight. The agent according to the invention for dyeing fibers can additionally have coloring herbal components, for example henna leaves, indigo, chamomile flowers, curcuma roots, rot tree bark, olive leaves, Canadian blood root, turmeric root, yellow wood, red wood, red sandalwood, blue wood, madder root, in order to achieve special shades. Black elderberry or black apple, and / or customary, physiologically harmless, direct dyes from the group of nitro dyes, azo dyes, quinone dyes and triphenylmethane dyes, alone or in combination with one another. The substantive dyes mentioned can be contained in an amount of about 0.01 to 4 percent by weight.

The colorant according to the invention enables uniform, wash-stable dyeings of fibers, in particular keratin fibers, such as human hair, which do not show any significant difference from the original color even after 20 washes with a shampoo, with virtually any color tone being obtainable by varying the dyes used. Furthermore, there is little, if any, hair coloring on the scalp.

Depending on which of the dyes according to the invention described above is used, the agent according to the invention can also be used to add a multitude of different fashionable or natural shades, for example purple-violet to black, red, orange, yellow, blue, violet, without the addition of other dyes or brown shades can be achieved (see Table 8). Table 8: Dyes obtained by reacting thiobarbituric acid with various carbonyl compounds, sorted by color

The dyeing with the colorant according to the invention is carried out by applying an amount sufficient for dyeing the hair, generally about 50 to 150 grams, to the hair after an exposure time sufficient for hair dyeing, which is usually about 3 to at 20 to 50 ° C. 60 minutes, preferably 5 to 30 minutes, the hair is rinsed with water, optionally washed with a shampoo and / or rinsed and dried with an aqueous solution of a weak organic acid, such as citric acid or tartaric acid. In a special embodiment of the present invention, the intensity of the dyes can also be adjusted by weakening the concentration of the dyes, which can be achieved step by step by repeated use of the method (due to the particularly gentle method of dyeing, this is possible without restrictions) Add final color. This is the first time that a discreet, step-by-step approach to a target hair color is possible, for example from white or gray hair to dark hair.

By dispensing with aggressive chemicals while maintaining high coverage and abrasion resistance, the colorants according to the invention are also particularly suitable for dyeing near the eyes. For example, one of the blue dyes can be used in a shampoo for gray hair in very low concentrations («0.1%) to compensate for the frequently occurring yellow tinge. After the first dye treatment, the hair appears light gray or gray-brown and the color is completely resistant to abrasion. If desired, the color tone can be intensified in the manner described above by repeated application of the colorant to the desired color.

Although the hair dyed with the colorant according to the invention has a coloration which is extremely stable to the effects of sweat and air, it can be preferably at any desired time at an acidic or alkaline pH with a suitable reducing agent, such as, for example, sulfites, pyrosulfites or hydrogen sulfites Alkali sulfites (e.g. sodium sulfite), alkali hydrogen sulfites (e.g. sodium hydrogen sulfite) or alkali pyrosulfites (e.g. sodium or potassium pyrosulfite), ammonium sulfite or ammonium hydrogen sulfite, or a suitable oxidizing agent, such as hydrogen peroxide and / or commercially available bleaching agents containing persulfates, are completely removed again. The bleaching agents generally have a content of 5 to 50 percent by weight, preferably 15 to 30 percent by weight, of ammonium persulfate and / or alkali persulfates. The decolorization is preferably carried out reductively in an alkaline medium using the aforementioned decolorizing agents (in particular with ammonium sulfite or ammonium hydrogen sulfite), the use of the aforementioned sulfites, hydrogen sulfites and pyrosulfites in combination with other reducing agents, such as reductones and / or thiols, being particularly preferred.

The exposure time of the decolorizer is 5 to 45 minutes, in particular 5 to 30 minutes, depending on the color to be decolorized, depending on the pH of the decolorization agent and the temperature (about 20 to 50 degrees Celsius), the decolorization process being accelerated by the application of heat. After the exposure time of the decolorizing agent has ended, the hair is rinsed with water, optionally washed with a shampoo and / or treated with a neutral or weakly acidic rinse and then dried, where both the shampoo and the rinse can contain a reductone, for example ascorbic acid . A further, particularly hair-friendly variant of the decolorization consists in the use of alkaline, low-percentage sulfite solution, as described in DE OS 19737987.

The coloring agent according to the invention and the corresponding decolorizing agent can expediently also be packed together in a two-component kit.

Since the dyeing can be decolourized, any permanent wave treatment that may be required must always be carried out before the dyeing treatment, since normal (reductive) permanent wave treatment destroys the dyes. Since the colorants according to the invention have a very good shelf life and do not cause any additional damage to the hair, they are particularly suitable for coloring hair after the permanent wave treatment, although the coloring may only be carried out after the permanent wave treatment. It is particularly advantageous here that if the perm has to be renewed, it is also necessary to supplement the dyeing, this dyeing then taking place automatically on a hair material which has been decolourized evenly by the permanent wave treatment.

The following examples are intended to explain the subject in more detail without restricting it to these examples. Examples

Manufacturing examples

Example 1: 5- [3- (4-Dimethylamino-phenyl) allylidene] -2-thioxodihydro-pyrimidine-4,6-dione

2.88 g (20 mmol) of thiobarbituric acid and 1.75 g (10 mmol) of 4-dimethylamino cinnamaldehyde are heated in 400 ml of water with 12% HCl until a

Precipitation arises. It is then cooled to about 5 ° C. The precipitated dye is filtered off and washed with a 0.5 N HCl solution and dried at 60 ° C. under reduced pressure (vacuum drying cabinet). A violet-blue solid is obtained.

Yield: 85% of theory (contains 2.24% (0.33 mol) water)

Melting point:> 200 ° C

¹ H-NMR (500 MHz, DMSO-d _g ): δ = 3.11 (s, N-CH ₃ , 2x3H); 6.81 (d, Ar-H,

1 H); 7.58 (d, Ar-H, 1H); 7.72 (d, CH, 1H); 8.01 (d, CH, 1H); 8.21 (dxd, CH,

1 H); 12.05 (s, NH, 2x1 H)

IR (film): 3056m, 1683m, 1644s, 1610s, 1573m, 1468vs, 1379s, 1320s,

1289s, 1238s, 1180vs, 995s, 941s

MS (m / z; relative intensity): 330 (8, M ⁺ ), 316 (2), 302 (28), 273 (2), 245 (2),

231 (2), 201 (4), 187 (14), 159 (100), 148 (27), 134 (22).

UV: (DMSO): λ _max (ε) = 566 nm (23761)

CHN analysis:

(C ₁₅ H ₁₅ N ₃ 0 ₂ S) CHNS calculated: 59.78 5.02 13.94 10.64 found: 59.79 4.95 13.90 10.72 Example 2: 5-furan-2-yl-methylene-2-thioxodihydro-pyrimidine-4,6-dione

2.88 g (20 mmol) thiobarbituric acid and 0.96 g (10 mmol) furfural are heated in 400 ml water with 12% HCl until a precipitate forms.

It is then cooled to about 5 ° C. The precipitated dye is filtered off and washed with a 0.5 N HCl solution and dried at 60 ° C. under reduced pressure (vacuum drying cabinet). A brown-yellow solid is obtained.

Yield: 76% of theory.

Melting point:> 230 ° C (decomp.)

¹ H NMR (500 MHz, DMSO-d _§ ): δ = 6.91 (s, CH, 1 H); 8.05 (s, CH, 1H);

8.31 (d, C-H, 1H); 8.51 (d, C-H, 1H); 12.45 (s, NH, 2x1H).

CHN analysis:

(C ₉ H ₆ N ₂ O ₃ S) CHNS calculated: 48.65 2.72 12.61 14.43 found: 48.50 2.33 12.50 14.52

Example 3: 5- (4-Dimethylamino-benzylidene) -2-thioxo-dihydropyrimidine-4,6-dione

2.88 g (20 mmol) of thiobarbituric acid and 1.49 g (10 mmol) of 4-dimethylaminobenzaldehyde are heated in 400 ml of water with 12% HCl until a precipitate forms. It is then cooled to about 5 ° C. The precipitated dye is filtered off and washed with a 0.5 N HCl solution and dried at 60 ° C. under reduced pressure (vacuum drying cabinet). A pink-red solid is obtained. Yield: 95% of theory (contains 78% (1, 3 mol) water) Melting point:> 200 ° C

¹ H NMR (500 MHz, DMSO-dg): δ = 3.10 (s, N-CH ₃ , 2x3H); 6.81 (d, Ar-H,

2H); 8.17 (s, C-H, 1H); 8.41 (d, Ar-H, 2H); 12.07 (s, NH, 2x1H).

IR (film): 3116m, 1640vs, 1495vs, 1377s, 1303m, 1233m, 1169s, 1011w,

943w.

UV (DMSO): λmax (ε) = 566 nm (36874).

CHN analysis:

(C ₁₃ H ₁₃ N ₃ 0 ₂ S x 2H ₂ O) CHNS calculated: 50.15 5.46 13.50 10.30 found: 49.32 4.79 14.92 12.83

Example 4: 5- [3- (6-Hydroxy-4-oxo-2-thioxo-1, 2,3,4-tetrahydro-pyrimidin-5-yl) allylidene] -2-thioxo-dihydro-pyrimidin-4 , 6-dione

11.5 g (80 mmol) of thiobarbituric acid and 3.3 g (20 mmol) of 1, 1, 3,3-tetramethoxypropane are heated in 800 ml of water with 12% HCl until a precipitate forms. It is then cooled to about 5 ° C. The precipitated dye is filtered off and washed with a 0.5 N HCl solution and dried at 60 ° C. under reduced pressure (vacuum drying cabinet). A purple solid is obtained. Yield: 81% of theory (contains 11.0% (2 mol) water) Melting point:> 220 ° C.

¹ H-NMR (500 MHz, DMSO-d _§ ): δ = 4.81 (s br, OH, 2x1 H); 7.72 (d, CH, 2x1H); 8.56 (t-like dxd, CH, 1H); 11.52 (s br, NH, 3x1 H). UV (DMSO): λ _max (ε) = 531 nm (23761). IR (film): 3128s, 1628s, 1498s, 1366s, 1297s, 1223s, 1134s, 1010m,

779m, 761m, 678w.

MS (m / z; relative intensity): 325 (16, M ⁺ ), 307 (42), 277 (44), 215 (78), 201

(80), 185 (100), 149 (64), 123 (31), 93 (99), 75 (97), 57 (99).

CHN analysis:

(C _Ϊ ^ ₄ 0 ^ ₂ X 2 ^ 0) CHNS calculated: 36.67 3.36 15.55 17.80 found: 35.90 3.63 14.90 17.32

Example 5: 5- [5- (6-Hydroxy-4-oxo-2-thioxo-1, 2,3,4-tetrahydropyrimidin-5-yl) penta-2,4-dienylidene] -2-thioxo -dihydro-pyrimidine-4,6-dione

5.8 g (40 mmol) of thiobarbituric acid and 3.57 g (10 mmol) of tetrabutylammonium glutaconaldehyde are heated in 600 ml of water with 12% HCl until a precipitate forms. It is then cooled to about 5 ° C.

The precipitated dye is filtered off and washed with a 0.5 N HCl solution and dried at 60 ° C. under reduced pressure (vacuum drying cabinet). A black solid is obtained.

Yield: 45% of theory.

Melting point:> 230 ° C.

¹ H-NMR (500 MHz, DMSO-d _§ ): δ = 4.81 (s br, OH, 2x1 H); 7.55 (m, CH,

1 H); 7.68 (m, C-H, 1H); 8.01 (m, C-H, 1H); 8.52 (m, C-H, 1H); 8.89 (m,

C-H, 1H); 12.11 (s br, NH, 3x1 H).

IR (film): 2885m, 1624s, 1439s, 1352s, 1 1 18s, 1019s, 954s.

UV: (DMSO): λ _max (ε) = 628 nm (119760), 530 nm (88666). MS (m / z; relative intensity): 329 (9, M ⁺ ), 295 (12), 279 (19), 237 (53), 215 (27), 207 (66), 197 (21), 185 (100), 165 (9), 149 (29), 123 (15), 115 (99).

Example 6: 5- [4- (4-Hydroxy-6-oxo-2-thioxo-1, 6-dihydro-2H-pyrimidin-5-ylidene) but-2-enylidene] -2-thioxo-dihydro-pyrimidine - 4,6-dione

2.88 g (20 mmol) of thiobarbituric acid and 0.88 g (5 mmol) of fumaric dialdehyde are heated in 400 ml of water with 12% HCl until a precipitate forms. It is then cooled to about 5 ° C. The precipitated dye is filtered off and washed with a 0.5 N HCl solution and dried at 60 ° C. under reduced pressure (vacuum drying cabinet). A brown solid is obtained. Yield: 41% of theory. Melting point:> 230 ° C.

Coloring examples

Example 7: Hair dye

An acidic solution (pH = 2-4), which contains 0.01-3.0% of a dye according to Examples 1 to 6, is applied directly to the hair. After a contact time of 10-20 minutes - if necessary with warming to 30 to 40 ° C - the hair is rinsed with water and washed twice with a shampoo and rinsed again with water. Instead of an aqueous solution, it is optionally also possible to use a customary cosmetic preparation, for example a shampoo, an emulsion, a cream, a lotion, a gel, a foam, a spray or a

Mascara product.

Depending on the dye used, the following color results are obtained:

Dye according to the color result

Example 1 blue

Example 2 yellow

Example 3 red

Example 4 pink-red

Example 5 black

Example 6 brown

Example 8: Hair dye

0.603 g 3- (2- (4- (1,3-dibutyltetrahydro-4,6-dioxo-2-thioxo-

5 (2H) -pyrimidinylidene-propanesulfonic acid -} - 2-butenylidene) - (2H) -benzoxazol-3-yl) sodium salt

1,000 g of isopropanol

0.500 g lactic acid to 10,000 g water

The coloring is carried out in the manner described in Example 7. The hair gets a dark blonde color. Example 9: Hair dye

0.603 g of 5- {4- [bis- (2-hydroxyethyl) amino] benzylidene} -2 thioxodihydropyrimidine-4,6-dione

1,000 g of isopropanol

0.500 g lactic acid to 10,000 g water

The coloring is carried out in the manner described in Example 7. The hair gets a pink color.

Example 10: Re-shading of oxidation hair dye

23.00 g cetyl alcohol

10.00 g of lauryl alcohol diglycol ether sulfate sodium salt (28% aqueous solution)

0.30 g ascorbic acid

0.40 g sodium sulfite

0.02 g of 4-amino-3-methylphenol

0.03 g 1,4-diamino-2- (hydroxyethyl) benzene sulfate (1: 1)

0.01 g 1,3-di (2,4-diaminophenoxy) propane tetrahydrochloride

0.01 g of 5-amino-2-methylphenol

0.02 g 5 - ((2-hydroxyethyl) amino) -2-methoxyaniline sulfate (1: 1))

0.01 g 1,3-diamino-4- (2-hydroxyethoxy) benzene

0.01 g of 4-amino-2- (aminomethyl) phenol dihydrochloride

0.02 g of 5-amino-2-methylphenol

0.03 g of 3-aminophenol

0.29 g 1,3-dihydroxybenzene 0.03 g 1,3-dihydroxy-2-methylbenzene

0.60 g 1,4-diamino-2-methyl-benzene

0.01 g sodium hydroxide

0.40 g of isopropyl alcohol

7.60 g ammonia (25% aqueous solution) ad 100.00 g water, fully desalinated

50 g of the above oxidation hair dye are mixed with 50 g of hydrogen peroxide solution (6% strength aqueous solution) immediately before use and applied to bleached hair. After an exposure time of 30 minutes at 40 ° C, the hair is rinsed with water and shampooed.

The dyed hair is then "re-shaded" (ie changed in color) by using a 0.6% 5- [3- (6-hydroxy-4-oxo-2-thioxo-1, 2,3,4-tetrahydro-pyrimidine -5-yl) -allylidene] -2-thioxodihydro-pyrimidine-4,6-dione, the hair dye composition according to the invention is applied to this hair and after an exposure time of 30 minutes, the hair is rinsed with water, shampooed and dried.

The hair is given a dark brown color due to the refinement.

Example 11: Re-shading of oxidation hair dye

23.00 g cetyl alcohol

10.00 g of lauryl alcohol diglycol ether sulfate sodium salt

(28% aqueous solution)

0.30 g ascorbic acid

0.40 g sodium sulfite

0.03 g 1,4-diamino-2- (hydroxyethyl) benzene sulfate (1: 1)

0.01 g 1,3-di (2,4-diaminophenoxy) propane tetrahydrochloride

0.02 g 5 - ((2-hydroxyethyl) amino) -2-methoxyaniline sulfate (1: 1))

0.01 g 1,3-diamino-4- (2-hydroxyethoxy) benzene

0.01 g of 4-amino-2- (aminomethyl) phenol dihydrochloride 0.01 g of 2,4-diamino-1,5-di (2-hydroxyethoxy) benzene

0.01 g of 4-amino-2 - (((2-hydroxyethyl) amino) methyl) phenol

0.01 g of 2,4-diamino-1-fluoro-5-methyl-benzenesulfate hydrate

0.03 g 1,3-dihydroxy-2-methylbenzene

0.01 g sodium hydroxide

0.40 g of isopropyl alcohol

7.60 g ammonia (25% aqueous solution) ad 100.00 g water desalted

50 g of the above oxidation hair dye are mixed with 50 g of hydrogen peroxide solution (6% strength aqueous solution) immediately before use and applied to bleached hair. After an exposure time of 30 minutes at 40 ° C, the hair is rinsed with water and shampooed. The dyed hair is then "re-shaded" (ie changed in color) by using a 0.6% 5- [5- (6-hydroxy-4-oxo-2-thioxo-1, 2,3,4-tetrahydro-pyrimidine -5-yl) -penta-2,4-dienylidene] -2-thioxo-dihydro-pyrimidine-4,6-dione, the hair dye composition according to the invention which is applied to this hair and, after an exposure time of 30 minutes, the hair is rinsed with water, shampooed and dries. The hair is given a black-blue-violet color through the refinement.

Example 12: Hair dye with direct dyes

0.158 g of 5- [5- (6-hydroxy-4-oxo-2-thioxo-1, 2,3,4-tetrahydropyrimidin-5-yl) penta-2,4-dienylidene] -2-thioxo- dihydropyrimidine-4,6-dione 0.525 g 1-chloro-4 - [(2-hydroxyethyl) amino] -3-nitrobenzene 0.080 g 4- (di- (2-hydroxyethyl) amino) -N- (2- hydroxyethyl) -2-nitroaniline 0.074 g 4- (di (2-hydroxyethyl) amino) -2-nitroaniline hydrochloride 10,000 g isopropanol

10,000 g of lauryl alcohol diglycol ether sulfate sodium salt (28% aqueous solution) to 100,000 g of water

The coloring is carried out in the manner described in Example 7. The hair gets a brown color. Example 13: Hair dye with direct dyes

0.090 g of 5- [3- (6-hydroxy-4-oxo-2-thioxo-1, 2,3,4-tetrahydro-pyrimidin-5-yl) allylidene] -2-thioxo-dihydro-pyrimidin-4, 6-dione 0.490 g (2 - ((4-nitrophenyl) amino) ethyl) urea 0.709 g 4- (ethyl- (2-hydroxyethyl) amino) -N- (2-hydroxyethyl) -2-nitroaniline 0.040 g 5- Chloro-4 - ((2,3-dihydroxypropyl) amino) -2-nitroaniline 0.088 g 1 - ((4-aminophenyl) -azo) -2-hydroxy-7- (trimethyl-ammonium) -naphthalene 10,000 g isopropanol

10,000 g of lauryl alcohol diglycol ether sulfate sodium salt (28% aqueous solution) to 100.00 g of water

The coloring is carried out in the manner described in Example 7. The hair gets a brown color.

Unless otherwise stated, all percentages mentioned in the previous application represent percentages by weight.

Claims

Patent claims

1. A process for the preparation of non-oxidative dyes, characterized in that one or more carbonyl compounds which are selected from saturated dialdehydes, saturated diketones, saturated ketoaldehydes, unsaturated dialdehydes, unsaturated diketones, unsaturated ketoaldehydes, monoaldehydes with one or more chromophoric groups, monoketones with one or more chromophoric groups and quinones, at least 50 ° C and a pH of less than / equal to 3 with a 1 to 2-fold molar excess of thiobarbituric acid or its derivatives, then the reaction mixture is cooled and the precipitated dye is filtered off becomes.

2. The method according to claim 1, characterized in that the carbonyl compound is selected from glutacone dialdehyde, glutacondialdehyde monoenolate, amber dialdehyde, fumardialdehyde, glutardialdehyde, glyoxal, malondialdehyde, mucon dialdehyde, o-phthalodialdehyde, terephthalaldaldehyde, acetylacetyl, diacetone, diacetone Isatin, 2,3,4-tri-hydroxybenzaldehyde, 3-oxo-butyraldehyde, acrolein, acetaldehyde, benzaldehyde, p-dimethylaminobenzaldehyde, dimethylamino-phenylpentadienal, ethylvanillin, glyceraldehyde, isovanillin, methylfurfural, o-vanillin, stilbenaldehyde, Vanillin, cinnamaldehyde, p-dimethylamino-cinnamaldehyde, p-nitro-cinnamaldehyde, o-nitrocinnamaldehyde, benzophenone, 2,3-deoxy-ribose, p-benzoquinone, 2,3-dimethoxy-5-methyl-1, 4-benzoquinone and 5-hydroxy-1,4-naphthoquinone.

3. Dye obtainable by reacting (a) thiobarbituric acid and / or its derivatives with (b) one or more carbonyl compounds from the group consisting of saturated dialdehydes, saturated diketones, saturated ketoaldehydes, unsaturated dialdehydes, unsaturated diketones, unsaturated ketoaldehydes, monoaldehydes with one or more chromophoric groups, monoketones with one or more chromophoric groups and quinones.

4. Dye according to claim 3, characterized in that it is selected from the group consisting of 5- [3- (4-dimethylamino-phenyl) allylidene] -2-thioxo-dihydro-pyrimidine-4,6-dione, 5 -Furan-2-yl-methylene-2-thioxo-dihydro-pyrimidine-4,6-dione, 5- (4-dimethylamino-benzylidene) -2-thioxo-dihydro-pyrimidine-4,6-dione, 5- [ 3- (6-Hydroxy-4-oxo-2-thioxo-1, 2,3,4-tetrahydro-pyrimidin-5-yl) allylidene] -2-thioxo-dihydro-pyrimidin-4,6-dione, 5 - [5- (6-Hydroxy-4-oxo-2-thioxo-1, 2,3,4-tetrahydro-pyrimidin-5-yl) penta-2,4-dienylidene] -2-thioxo-dihydro-pyrimidine -4,6-dione and 5- [4- (4-Hydroxy-6-oxo-2-thioxo-1, 6-dihydro-2H-pyrimidin-5-ylidene) - but-2-enylidene] -2-thioxo dihydro-pyrimidine-4,6-dione.

5. Agent for dyeing fibers, characterized in that it contains at least one dye according to claim 3 or 4.

6. Composition according to claim 5, characterized in that the dye is contained in an amount of 0.001 to 10 weight percent.

7. Composition according to claim 5 or 6, characterized in that it has a pH of 2 to 10.

8. Agent according to one of claims 5 to 7, characterized in that it is a hair dye.

9. A method for dyeing and bleaching hair, characterized in that a sufficient amount of an agent according to claim 8 is applied to the hair and after an exposure time of 3 to 60 minutes at 20 to 50 ° C, the hair is rinsed with water, if appropriate washed with a shampoo and / or rinsed with the aqueous solution of a weak organic acid and then dried, and the colored hair is decolorized at a later time with the aid of a reducing agent or oxidizing agent.

10. The method according to claim 9, characterized in that alkali sulfites, alkali hydrogen sulfites, alkali pyrosulfites, ammonium sulfite or ammonium hydrogen sulfite, alone or in combination with reductones and / or thiols are used as reducing agents.

11. The method according to claim 9, characterized in that the oxidizing agent used is hydrogen peroxide alone or a combination of hydrogen peroxide and ammonium persulfates and / or alkali persulfates bleaching powder.