DE19820894A1 - Two-component fiber dyeing agent, especially for use on hair - Google Patents

Abstract

A two-component agent for fiber dyeing consists of: (a) a first component containing thiobarbituric acid and/or derivative; and (b) a second component containing a carbonyl compound which is a saturated or unsaturated dialdehyde, diketone or ketoaldehyde, a mono-aldehyde or -ketone containing one or more chromophoric groups, or a quinone.

Description

The present invention relates to a process for dyeing fibers, especially keratin fibers, using thiobarbituric acid and / or their derivatives and special carbonyl compounds and a Means for performing this dyeing process.

For dyeing fibers containing keratin, e.g. hair, wool or furs, generally come either directly synthetic or vegetable dyes or oxidation dyes that by oxidative coupling of so-called developer substances with so-called coupler substances arise for use. Although A variety of dyes are known, only a few are known for the use in colorants for keratin fibers suitable, since this one Variety of conditions must be met simultaneously in others Areas of dyeing technology (dyeing of synthetic fibers or Food) must only be partially fulfilled. So a dye for Stain keratin fibers to the hair can be toxicologically harmless, a coloration under mild Conditions (low temperatures etc.) allow one to be as possible cause slight skin staining, be readily water-soluble, largely be lightfast and washable, apply evenly to the fiber (particularly important with dye mixtures), evenly (without change of the color) are washed out, the highest possible coverage  have as little damage to the fiber and other hair treatment methods of treatment (e.g. perm treatment).

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

Each of these two coloring systems (direct dyes, oxidati ons dyes) has specific advantages and disadvantages, depending on the Demand of the consumer is of varying importance.

Direct dyes are generally gentler Hair coloring possible, but direct dyes are suitable due to the significantly lower hiding power only to a limited extent cover gray hair, with a gray content of more than 30% non-oxidative direct drawers no longer have a satisfactory staining result can be achieved.

Table 1 gives an overview of the basic strengths and Weaknesses of both systems:  

Table 1

Comparison of various properties of direct and oxidative dyes

There is therefore a great need for a gentle, preferably Non-oxidative, process for optionally also removable Permanent dyeing of fibers, especially human hair, that a coloring of the fiber in a variety of colors and shades enables, as well as a means of performing this method.  

Surprisingly, it has now been found that a new Process for gentle, optionally also removable Permanent dyeing of fibers, especially human hair Use a special 2-component agent to color the Fibers in a variety of colors and shades as well as intense Dyes with high light fastness and wash resistance, in particular uniform and intense black coloring with high light fastness and wash resistance.

The present invention therefore relates to a two-component Agent for dyeing fibers consisting of (a) a thiobarbituric acid and / or their derivatives-containing 1st component and (b) a Carbonyl compound which is selected from saturated dialdehydes, saturated diketones, saturated ketoaldehydes, unsaturated Dialdehydes, unsaturated diketones, unsaturated ketoaldehydes, Monoaldehydes with one or more chromophoric groups, mono ketones with one or more chromophoric groups and quinones, containing 2nd component, and a method for dyeing Fibers using this agent.

In particular, keratin fibers come as fibers, for example Wool, silk, furs or hair (especially human hair), however also non-keratin fibers, such as cotton, linen, Hemp textiles, nettle fibers, viscose, acetyl cellulose, cellulose triacetate or polyamide fibers.  

In a special embodiment of this invention can be the weakening of the concentrations also at different intensities Adjust hues or shades of gray that result from repeated use of the process (due to the particularly hair-friendly coloring method this is possible without restrictions) to a gradual approach Add the color to the desired final color. So that is with hair coloring for the first time a subtle, gradual introduction to a target hair color, for example from white or gray hair to jet black hair, possible.

The thiobarbituric acid and / or its derivatives, for example the alkali salts or alkaline earth salts of thiobarbituric acid, are in the 1st compo nente in a total amount of 0.01 to 20 percent by weight, preferably example, 0.1 to 5 weight percent, in particular 0.1 to 1 weight percent, used while the carbonyl compounds in the 2. component in a total amount of 0.001 to 10 percent by weight, preferably 0.003 to 3 percent by weight.

Unsaturated or saturated come as carbonyl compounds Dialdehydes, for example glutacondialdehyde or glutacondialdehyde Monoenolate, amber dialdehyde, fumardialdehyde, glutardialdehyde, Glyoxal, malondialdehyde, mucondialdehyde, o-phthaldialdehyde or Therephthaldialdehyde; unsaturated or saturated diketones, for example wise diacetyl, acetylacetone or isatin; unsaturated or saturated Ketoaldehydes, monoaldehydes or monoketones with one or more chromophoric groups, for example 2,3,4-trihydroxybenzaldehyde, 3-oxo-butyraldehyde, acrolein, acetaldehyde, benzaldehyde and its  Derivatives (e.g. p-dimethylaminobenzaldehyde), dimethylamino phenylpentadienal, ethylvanillin, glyceraldehyde, isovanillin, Methylfurfural, o-vanillin, stilbenaldehyde, vanillin, cinnamaldehyde and its Derivatives (for example p-dimethylamino-cinnamaldehyde, p-nitrocinnamaldehyde or o-nitrocinnamaldehyde), benzophenone or 2,3-deoxyribose; and Quinones, for example p-benzoquinone, 2,3-dimethoxy-5-methyl-1,4- benzoquinone (coenzyme Q0) or 5-hydroxy-1,4-naphthoquinone (jugion) into consideration.

Both the 1st component and the 2nd component of the invention appropriate agents for dyeing fibers can, for example, in the form a solution, especially as an aqueous-alcoholic solution, a cream, a gel or an emulsion. Can as a solvent in addition to water, for example, lower aliphatic monovalent or more valuable alcohols, their esters and ethers, or mixtures of these Solvents can be called with each other or with water. Of the maximum boiling point of the aforementioned suitable solvents about 400 ° C, with a boiling point of 20 ° C to 250 ° C being preferred.

It is also possible to use one or both components of the invention appropriate means with the help of an atomizer or other suitable pumping devices or spraying devices or in a mixture with conventional propellants liquefied under pressure as aerosol spray or can be removed as aerosol foam from a pressure vessel.

The pH of the two components of the dyeing according to the invention means and the mixture of these two components can depend in  of the fiber to be dyed over the entire pH range from 0 vary to 14. Preferably the pH is about 2 to 10, with an acidic pH of 2 to 7 is particularly preferred. The setting an alkaline pH is preferably with ammonia, it is however, also possible instead of ammonia organic amines, such as Example to use monoethanolamine or triethanolamine. For the Setting an acidic pH value, however, can be an organic or inorganic acid, such as hydrochloric acid, sulfuric acid, Phosphoric acid, citric acid, tartaric acid, glycolic acid or lactic acid, be used.

Of course, both the 1st component and the 2nd com component of the agent according to the invention for dyeing fibers if necessary, other additives customary for colorants for keratin fibers, such as for example care substances, wetting agents, thickeners, plasticizers, preservatives Detergents and perfume oils as well as others, listed below led additives included.

Furthermore, both in the 1st component and the 2nd compo Nente of the agent for dyeing fibers wetting agent or emulsifiers from the classes of anionic, amphoteric, not ionogenic or zwitterionic surfactants such as fat alcohol sulfates, alkane sulfonates, alkyl benzene sulfonates, alkyl carnitines, acyl carnitines, alkyl betaines, α-olefin sulfonates, ethoxylated fatty alcohols, oxyethylated nonylphenols, fatty acid alkanolamines, oxyethylated fatty acid esters, fatty alcohol polyglycol ether sulfates, alkyl polyglucosides, thickeners medium such as higher fatty alcohols, starch, alginates, bentonites, cellulose  derivatives, petroleum jelly, paraffin oil and fatty acids, water-soluble polymers Thickeners such as natural types of rubber, guar gum, xanthan gum, locust bean gum, pectin, dextran, agar-agar, amylose, Amylopectin, dextrins, clays or fully synthetic hydrocolloids like 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, auxiliary substances such as moist halide agents, electrolytes, antioxidants, fatty amides, sequestrants, film-forming agents and preservatives.

Both the 1st component and the 2nd component of the invention appropriate means for dyeing fibers can continue natural or synthetic polymers or modified natural polymers Lichen origin may be included, which means at the same time as the coloring the keratin fiber is strengthened. Of those used for this purpose synthetic polymers known in cosmetics, for example Polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol or polyacrylic bonds such as polyacrylic acid or polymethacrylic acid, polyacrylonitrile, Polyvinyl acetates and copolymers of such compounds, such as for example, polyvinyl pyrrolidone vinyl acetate mentioned; while as natural Liche polymers or modified natural polymers such as Chi tosan (deacetylated chitin) or chitosan derivatives can.

The components mentioned are in the usual for such purposes Amounts used, for example the wetting agents and emulsifiers in Kon concentrations of about 0.5 to 30 percent by weight, the thickeners in one  Amount from about 0.1 to 25 percent by weight and the care substances in one Amount from about 0.1 to 5 percent by weight. The aforementioned polymers can in the usual amount for such agents, especially in a Amount of about 1 to 5 percent by weight can be used.

The agent for dyeing fibers according to the invention can be used to achieve this of special color shades additionally coloring herbal components, such as henna leaves, indigo, chamomile flowers, curcuma roots, Rotten tree bark, olive leaves, Canadian blood root, turmeric, yellow wood, redwood, red sandalwood, blue wood, madder root, black elder or black apple, and / or usual, physiologically harmless Liche direct dyes from the group of nitro dyes, azo dyes, quinone dyes and triphenylmethane dyes, alone or in Combination with each other.

The agent according to the invention enables uniform, wash-out stable Dyeing of fibers, in particular keratin fibers, for example human hair, which can also be washed after 20 washes with a Shampoo no discernible difference from the original color show, practically everyone by varying the carbonyl component any color tone can be achieved. Furthermore, hair coloration occurs when at all, only a slight staining of the scalp.

Analogous to the oxidative coloring, the dye is only formed in the fiber itself (but without oxidation), which is apparently an intense Penetration of the fiber and thus a high dyeing performance and great fastness to washing.  

The color is probably due to the combination according to the invention nation of thiobarbituric acid and carbonyl compounds on formation a condensation product with a conjugated system on both sides of u electrons. Depending on the carbonyl compound used, the agent according to the invention a variety of different fashionable or natural shades can be obtained; for example black ones (p-benzoquinone, glutacondialdehyde or glutacondialdehyde monoenolate), red (for example malondialdehyde, acetaldehyde, dimethylamino-phenyl pentadienal, p-dimethylamino-benzaldehyde), orange (e.g. Diacetyl, acetylacetone, isatin, 2,3,4-trihydroxybenzaldehyde, ethylvanillin, Glyceraldehyde, stilbenaldehyde, p-nitrocinnamaldehyde, vanillin, 2,3-deoxyribose), yellow (for example amber dialdehyde, Glutardi aldehyde, o-phthalaldehyde, terephthalaldehyde, 3-oxobutyraldehyde, Benzaldehyde, isovanillin, methylfurfural, o-nitrocinnamaldehyde, o-vanillin, Cinnamaldehyde, benzophenone), blue (e.g. p-dimethylamino cinnamaldehyde), violet (e.g. mucondialdehyde) or brown (e.g. acrolein, glyoxal, fumaric dialdehyde, 2,3-dimethoxy-5- methyl-1,4-benzoquinone, 5-hydroxy-1,4-naphthoquinone) shades.

Examples of that through different combinations of thiobarbitur acid and carbonyl compounds (being based on the total number of Carbonyl groups in the respective carbonyl compound a 1.5: 1 molar Ratio of thiobarbituric acid to carbonyl compound used colorations obtained are in Tables 2 to 6 below (divided according to the carbonyl compound used) summarized.  

Here, in the column for the extinction _maximum ("λ _max "), insofar as this has been determined, the sign "∼" stands for an increased basic absorption without a characteristic extinction _maximum .

Table 2

Saturated and unsaturated dialdehydes + thiobarbituric acid

Table 3

Diketones and ketolactams + thiobarbituric acid

Table 4

Monoaldehydes with chromophore + thiobarbituric acid

Table 5

Monoketones with chromophore + thiobarbituric acid

Table 6

Quinones + thiobarbituric acid

While with divalent carbonyl compounds (dialdehydes, Diketonen, Ketoaldehyden) as expected the shift of the absorption maximum in the longer-wave range can be that the number of conjugated double bonds increases is, the use of monovalent carbonyl compounds second thiobarbituric acid group also by a corresponding one chromophores system to be replaced.  

The two-component agent according to the invention can be different Way of dyeing fibers, especially human hair, be used.

So the two components (component 1 and component 2) are mixed with each other immediately before use and the preparation obtained immediately applied to the fiber to be dyed become. After an exposure time of 5 to 60 minutes at about 20 to 80 ° C, preferably 30 to 50 ° C, the fiber is rinsed with water and optionally washed with a shampoo and then ge dries.

It is also possible to successively apply the two components to the Apply fiber, applying the two components beforehand preferably with a time interval of 5 to 15 minutes (preferably at room temperature). Here, the 1st component can be both as well as after the 2nd component. It is also possible to use the fiber between the individual treatment steps Rinse out water or wash with a shampoo. After a Exposure time from 5 to 60 minutes at about 20 to 80 ° C, preferably 30 to 50 ° C, the fiber is rinsed with water and optionally with washed with a shampoo and then dried.

In both methods, the application temperature can also change over time the coloring treatment can be changed, for example by the Temperature in the course of the coloring treatment of room temperature (20 ° C) to about 30 to 80 ° C, preferably 30 to 50 ° C; is increased.  

The thiobarbituric acid or its derivative can be - based on the sum of the carbonyl components - in principle both equimolar as well as in a molar excess or deficit present; expediently, however, it should be in a molar excess shot, preferably at least 1.3 times, in particular at least 1.5 times the molar excess over the total all carbonyl groups of the carbonyl contained in the 2nd component Connections are used, with a 1.5 to 300 times excess on thiobarbituric acid - based on the sum of all carbonyl groups carbonyl compounds contained in the second component - especially is preferred.

The 2-component colorant according to the invention is suitable especially for coloring hair. Another subject of The present invention is therefore the use of the above wrote 2-component agent for dyeing hair, in particular their human hair.

Although colored with the 2-component agent according to the invention Hair has a color that is extremely stable to light and air , it can be used with an acidic or alkaline pH suitable reducing agents, such as sulfites, pyrosulfites or Hydrogen sulfites, for example alkali sulfites, alkali hydrogen sulfites or Alkali pyrosulfites (such as sodium sulfite, sodium pyrosulfite, Potassium pyrosulfite), ammonium sulfite or ammonium bisulfite, or a suitable oxidizing agent, such as hydrogen peroxide  and / or commercially available bleaching powders containing persulfates are constantly discolored. The bleaching powder usually have one Content of 5 to 50 weight percent, preferably 15 to 30 weight percent, of ammonium persulfate or alkali persulfates or a Mi mixture of ammonium persulfate and alkali persulfates. The discoloration is preferably carried out reductively in an alkaline medium using the aforementioned decolorizing agents (in particular with ammonium sulfite or Ammonium bisulfite), the use of the aforementioned Reducing agents in combination with other reducing agents, such as Example reductones and / or thiols, is particularly preferred.

The exposure time of the decolorizing agent is dependent on this of the pH of the decolorizing agent depending on the color to be decolorized and Temperature (about 20 to 50 degrees Celsius) 5 to 45 minutes, in particular 5 to 30 minutes, with the decolorization process by adding heat can be accelerated. After the exposure time of the Ent the hair is rinsed with water, if necessary with a Washed shampoo and / or a conditioner, preferably a neutra len or weakly acidic rinse, treated and then dried, whereby both the shampoo and the conditioner are a reduction, such as Example may contain ascorbic acid.

Since the coloring can be decolorized, a permanent wave must be used always be carried out before the coloring treatment.

The two-component agent according to the invention for dyeing fibers, in particular human hair, and the dyeing according to the invention  Processes have a number of advantages over conventional ones Oxidation colorants. A comparison of the two staining systems is in summarized in Table 7 below.

Table 7

Comparison of the properties of oxidation colorants with the 2-component colorant according to the invention

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

Examples example 1 One-step hair coloring

100 ml of a thiobarbituric acid solution saturated at room temperature (approx. 0.72 percent = 50 mmol) are mixed with a solution for the ge desired coloring required amount of malondialdehyde (in the form of Diacetals; depending on the desired color intensity between 0.01% (pale red) and 1% (dark red) - each based on the total amount of the aqueous Solution) in 20 ml of water (using citric acid to a pH of 3 set) mixed.

The mixture thus obtained is immediately applied to the hair. After an exposure time of 10 to 15 minutes at room temperature Hair for 5 minutes using a hair dryer or dryer to 40 to Heated 50 ° C and then rinsed with water and twice with washed with a shampoo.

The color achieved varies depending on the amount of carbonyl used component from pale red to dark red. Even after 20 washes a shampoo shows no fading of the color.

Example 2 Two-step hair coloring

100 ml of a thiobarbituric acid solution saturated at room temperature (approx. 0.72 percent = 50 mmol) are applied to the hair and 10 left to act for up to 15 minutes at room temperature. Then will  a solution with a total content of 10 mmol malondialdehyde in 100 ml of 1% citric acid solution applied to the hair. After a Exposure time of a further 10 minutes at room temperature is the Hair dry for 5 to 10 minutes with a hair dryer or dryer Heated to 40 to 50 ° C and then rinsed with water and two washed with a shampoo.

The hair treated in this way has a red color. Even after 20 hairs washing with a shampoo does not fade the color tone put.

Example 3 Two-step hair coloring

A solution of 0.45 g (25 mmol) of ethyl vanillin in 100 ml of 1% Citric acid is applied to the hair and added for 10 to 15 minutes Left to act at room temperature. Then (under incl pull the surrounding scalp areas) with lukewarm water rinses. Then 100 ml of a saturated solution of thiobarbitur acid (approx. 0.72 percent = 50 mmol) applied to the hair. After an exposure time of another 10 minutes at room temperature the hair for 5 to 10 minutes with a blow dryer or a dryer hood heated to 40 to 50 ° C and then rinsed with water and washed twice with a shampoo.

The hair treated in this way has an orange color. Even after 20 shampoos with a shampoo is not a fade in color ascertain.  

Example 4 Two-step hair coloring (black)

100 ml of a thiobarbituric acid solution saturated at room temperature (approx. 0.72 percent = 50 mmol) are applied to the hair and 10 left to act for up to 15 minutes at room temperature. Then will a solution containing (a) 0.036 g (0.1 mmol) of glutacondi aldehyde monoenolate tetrabutylammonium salt or (b) 0.2 g (1.85 mmol) p-Benzoquinone in 100 ml of 1% citric acid applied to the hair. After an exposure time of another 10 minutes at room temperature the hair for 5 to 10 minutes with a blow dryer or a Drying hood heated to 40 to 50 ° C and then with water rinsed out and washed twice with a shampoo.

The hair has a deep black (a) or brown-black (b) staining which is completely abrasion resistant. Even after 20 washes with shampoo there is no fading of the color tone.

Example 5 Two-step, gradual hair coloring (black)

100 ml of a thiobarbituric acid solution saturated at room temperature (approx. 0.72 percent = 50 mmol) are applied to the hair and 10 left to act for up to 15 minutes at room temperature. Then will a solution containing (a) 0.0036 g (0.01 mmol) of glutacondi aldehyde monoenolate tetrabutylammonium salt or (b) 0.02 (0.185 mmol) p-Benzoquinone in 100 ml of 1% citric acid applied to the hair.  

After an exposure time of another 10 minutes at room temperature the hair for 5 to 10 minutes with a blow dryer or a Drying hood heated to 40 to 50 ° C and then with water rinsed out and washed twice with a shampoo.

The hair appears light gray after the first dyeing treatment (a) or gray-brown (b) and the color is completely resistant to abrasion. With repeated repetition of the above-described dyeing treatment The shade of gray deepens, so that in this way, over one applied for a reasonable period of time, a subtle gradual one Approximation of the current hair color to the target color (up to Pitch black) can be achieved.

All the percentages mentioned in the present application represent unless otherwise stated, weight percent.

Claims (12)

1. 2-component agent for dyeing fibers consisting of (a) a 1st compo containing a thiobarbituric acid and / or its derivatives nente and (b) a carbonyl compound which is selected from saturated dialdehydes, saturated diketones, saturated keto aldehydes, unsaturated dialdehydes, unsaturated diketones, uns saturated ketoaldehydes, monoaldehydes with one or more chromophoric groups, monoketones with one or more chromo phoren groups and quinones, containing the second component. 2. Composition according to claim 1, characterized in that the thio barbituric acid and / or its derivatives in the 1st component in one Amount of 0.01 to 20.0 percent by weight are included. 3. Means according to claim 1, characterized in that the Carbonyl compound is selected from glutacondialdehyde or Glutacondialdehyde monoenolate tetrabutylammonium salt, amber dialdehyde, fumaric dialdehyde, glutaraldehyde, glyoxal, malondialdehyde, Mucondialdehyde, o-phthaldialdehyde, therephthaldialdehyde, diacetyl, Acetylacetone, isatin, 2,3,4-trihydroxy-benzaldehyde, 3-oxo-butyraldehyde, Acrolein, acetaldehyde, benzaldehyde or its derivatives, dimethyl amino-phenyl-pentadienal ethyl vanillin, glyceraldehyde, isovanillin, Methylfurfural, o-vanillin, stilbenaldehyde, vanillin, cinnamaldehyde or its derivatives, benzophenone, 2,3-deoxyribose, p-benzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone and 5-hydroxy-1,4- naphthoquinone.   4. Means according to claim 1 or 3, characterized in that the Carbonyl compound in the 2nd component in an amount of 0.001 to 10.0 percent by weight is included. 5. Agent according to one of claims 1 to 4, characterized that the 1st component and the 2nd component each have a pH of 2 to 10. 6. Agent according to one of claims 1 to 5, characterized in that it is a means of dyeing hair. 7. Process for dyeing fibers using a 2-component agent in which the 1st component and the 2. Component mixed together immediately before use then the preparation obtained is applied to the fiber and after an exposure time of 5 to 60 minutes at 20 to 80 ° C Rinse fiber with water and, if necessary, with a shampoo is washed, characterized in that an agent according to one of the Claims 1 to 6 is used. 8. Process for dyeing fibers using a 2- component agent in which the 1st component before or after the 2. component is applied to the fiber and after a Exposure time of 5 to 60 minutes at 20 to 80 ° C with the fiber  Rinsed water and if necessary washed with a shampoo, characterized in that an agent according to any one of claims 1 to 6 is used. 9. The method according to claim 8, characterized in that the Apply the two components at intervals of 5 to 15 Minutes. 10. The method according to claim 8 or 9, characterized in that between the individual treatment steps remove the fiber with water rinsed or washed with a shampoo. 11. The method according to any one of claims 7 to 10, characterized records that in the course of the treatment the temperature of 20 ° C 30 to 80 ° C is increased. 12. The method according to any one of claims 7 to 11, characterized records that the thiobarbituric acid or its derivatives in the 1st Kompo at least 1.3 times, in particular at least one 1.5-fold molar excess over the sum of all carbonyl groups of the carbonyl compounds contained in the second component is used.