DE2830497B1 - Process for dyeing human hair and means for carrying it out - Google Patents

Description

The invention also relates to an agent for coloring human hair for carrying out the process, consisting of a) a hydroxybenzaldehyde in solution, b) optionally a dye precursor known for hair dyes, c) optionally a substantive dye and d) customary additives, characterized in that that the hydroxybenzaldehyde is a compound of the formula is wherein R1 represents a hydrogen atom or an OH group.

Dye precursors known for hair dyes are aromatic di- or polyfunctional amines with at least one primary amino group and a further functional group in the m-, o- or p-position or heterocyclic amino compounds or di- or polyfunctional phenols, e.g. a p-phenylenediamine of the general formula II and / or at least one acid addition salt of these compounds, where in the formula R1, R2 and R3 are identical or different and each represent a hydrogen atom or an alkyl or alkoxy radical having 1 or 2 carbon atoms, and R4 and Rs are identical or different and each represent a Hydrogen atom or an alkyl, hydroxyalkyl, alkoxyalkyl (where the alkoxy radical has 1 or 2 carbon atoms), carbamylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl or carbethoxyaminoalkyl radical (the alkyl radicals in R4 and Rs have 1 to 3 carbon atoms), represent, with the proviso that R1 or R3 is a hydrogen atom when R4 and Rs are not hydrogen atoms.

Such p-phenylenediamines are: p-phenylenediamine, p-tolylenediamine, 2-methyl-5-methoxy-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-dimethyl-3-methoxy-p-phenylenediamine, 4- (N-methoxyethylamino) aniline, 4- (N-ethyl-N-carbamylmethylamino) aniline and / or 4-N, N-di-, 8-hydroxyethylamino) aniline.

A preferred embodiment of the agent contains the dye precursor p-aminophenol or 2-methyl-4-aminophenol.

Other special dye precursors are compounds of the type 4-Hydroxy-4'-aminodiphenylamine and / or 4,4'-dihydroxydiphenylamine and / or their Derivatives, in particular 2-acetamido-3,5-dimethyl-4,4'-dihydroxydiphenylamine, 2-acetamido-3,5-dimethyl-4,4'-dihydroxy-2-chlorodiphenylamine, 2-acetamido -5-methyl-4,4'-dihydroxy-2'-chlorodiphenylamine, 2-ureido-3,5-dimethyl-4,4'-dihydroxy-2'-chlorodiphenylamine, 2-ureido-4-hydroxy-4'-aminodiphenylamine, 2-acetamido-4-hydroxy-4'-aminodiphenylamine, 2,5-dihydroxy-4,4'-diEbis (2-hydroxyethyl) amino] diphenylamine, 2-methoxy-4-amino-2 ', 5-dihydroxy-4' - (2-hydroxyethyl) aminodiphenylamine, 2-acetamido-4-hydroxy-5,3 ', 5'-trimethyl-4'-aminodiphenylamine, 2-acetamido-4,4'-dihydroxy-5-methoxy-2'-chlorodiphenylamine, 2-ureido-4,4'-dihydroxy-5-methoxy 2'-chlorodiphenylamine, 2-ureido-4,4'-dihydroxy-5-methoxy-2'-chlorodiphenylamine, 2-ureido -4-hydroxy-5-methyl-4'-chloro-3'-methylaminodiphenylamine, 2-ureido-4-hydroxy-5-methyl4'-N-ethyl-N-ureidoaminodiphenylamine.

Also mentioned as dye precursors are: resorcinol, m-aminophenol, 2-methyl-5-aminophenol, methyl-5- (N-, B-hydroxyäthylamino) -phenol, 6-hydroxybenzomorpholine, 2,6-dimethyl-5-acetylaminophenol, 2-methyl-5-carbethoxyaminophenol, 2-methoxy-5-carbethoxyaminophenol and / or 2-methyl-5-ureidophenol.

A polyaminophenol, monoaminodiphenol, Diaminodiphenol and / or polyphenol, preferably trihydroxybenzene, can be used.

The hair dye can be nitro dyes as substantive dyes included, e.g. B.

2,4-Dinitronaphthol (1) sulfonic acid (7) disodium salt, 2,4-Dinitro4'-hydroxy-diphenylamine, 4-nitro-4'-aminoazobenzene, 2,4-dinitro-3'-sulfo-4'-phenylaminodiphenylamine Na salt, 2-methyl-4-bis (2-hydroxyethyl) amino-4'-nitroazobenzene, (2-hydroxy-5-nitrophenyl-1 -azo-oc-acetacetic anilide =) 2-Hydroxy-5-nitrophenyl- 1 -azo-3-butan-2-one-1-acid anilide, 1, 2-diamino-4-nitrobenzene, 1, 4-diamino-2-nitrobenzene, 1-hydroxy-2-amino-4-nitrobenzene, 1 -hydroxy-2-amino-5-nitrobenzene, 1 -hydroxy-2-amino-4,6-dinitrobenzene, 1 -hydroxy-2-nitro-4-aminobenzene, 1-amino-2-nitro-4- (bis (2-hydroxyethyl) aminobenzene, 1-amino-2-nitro-4-methylaminobenzene, 2-nitro-4'-hydroxydiphenylamine, 2-nitro-4-aminodiphenylamine, 1-hydroxy-3-nitro-4-aminobenzene.

In one embodiment, the agent contains at least one excipient from the group consisting of penetrants, foaming agents, thickeners, Antioxidants, alkalis or acids (for pH adjustment), perfumes, sequestering agents and film makers.

In a special embodiment of the agent, its pH is in the range from 8 to 11.5, preferably from 9 to 10.

At least one compound selected from the group can be used as alkali from ammonia, the alkylamines, alkanolamines, ammonium derivatives, sodium and potassium hydroxide as well as sodium and potassium carbonate can be used.

Furthermore, the agent according to the invention can be water-soluble, anion-active, Incorporate cationic, non-ionic or amphoteric surface-active substances Examples of particularly suitable surface-active substances are compounds selected from the group consisting of alkylbenzenesulfonates, alkylnaphthalene sulfonates, Fatty alcohol sulfates, fatty alcohol ether sulfates, alkyl sulfonates, quaternary ammonium salts, preferably trimethylcetylammonium bromide or cetylpyridinium chloride, cetylpyridinium bromide, Diethanolamides of fatty acids, polyethoxylated acids and alcohols as well as polyethoxylated ones Alkyl phenols. The surface-active substances are in the agent according to the invention preferably in a proportion of 0.5 to 30% by weight, in particular from 4 to 25% by weight, contain.

The agent according to the invention can also be used with organic solvents add to solubilize the insufficiently water-soluble compounds.

Examples of advantageous solvents are ethanol, isopropanol, Glycerin, glycols such as butyl glycol, ethylene glycol, propylene glycol, diethylene glycol monoethyl ether or monomethyl ether and analogous compounds. The solvents can in the invention Colorants with advantage in an amount of 1 to 40 wt .-%, preferably from 5 to 30% by weight.

Examples of advantageous thickeners, which the invention Colorants that can be incorporated are sodium alginate, gum arabic, cellulose derivatives, such as methyl cellulose or the sodium salt of carboxymethyl cellulose, and acrylic acid polymers; mineral thickeners such as bentonite can just as well be used. The proportion of thickeners is preferably 0.5 to 5% by weight, in particular 0.5 to 3% by weight, based on the total colorant.

Examples of antioxidants are potassium metabisulphite, sodium dithionite, Sodium sulfite, thioglycolic acid, sodium bisulfite and ascorbic acid. The proportion of Antioxidants can contain 0.05 to 1% by weight, based on the total weight of the colorant, turn off.

In the dyeing process according to the invention, oxidizing agents such as Hydrogen peroxide, urea peroxide or persalts, e.g. B. ammonium persulfate is used An advantageous oxidizing agent is the aqueous solution, which in general Contains 3-10 wt.% H202, or use urea peroxide or sodium perborate.

The compounds of formula (I) are in the colorant according to the invention generally in a proportion of 0.01 to 5.0% by weight, based on the total weight of the coloring agent.

The colorant of the invention can be as a solution, paste, cream or Jelly or in the form of any other preparation suitable for coloring suitable for human hair and z. B. as hair dyes, hair tinting agents, tint fixers and color detergent is commercially available to show that dilute solutions of the compounds of formula (I) even in the absence of oxidizing agents allow human hair to be dyed, the following tests were carried out, with particular It is noteworthy that here the colorations in the pH range from about 5 to about 11 can be carried out.

Test 1 for human streak coloring with salicylaldehyde salicylaldehyde was in various concentrations in a solution of 47 wt .-% water, 47 % By weight 2-propanol, 6% by weight NH3 (25%) dissolved and the strand of human hair in each case treated with it at room temperature for 30 minutes. The results are in the table I reproduced: Table I Concentration of the staining result (in the absence of salicylaldehyde an oxidizing agent) 0.1% by weight slightly yellow 0.2% by weight slightly more weak yellow 0.5% by weight stronger yellow 1.0% by weight good yellow 2.0% by weight yellow 5.0% by weight yellow (like 2 wt .-% solution) With 2 wt .-% salicylaldehyde in the solution used the optimal saturation limit of the coloration has been reached.

Additional studies have shown that with salicylaldehyde im neutral area, the yellow colorations can also be achieved, but can be washed off. It is therefore preferred to use salicylaldehyde in the alkaline range up to pH 11 To dye hair.

Further studies have shown that when using 2,5-dihydroxybenzaldehyde As a hair dye, the desired coloration of the hair already in the neutral or weak acidic range up to about pH 5 occurs, but the hair also in the alkaline range up to about pH 11 can be colored with it.

The following tests show that dilute solutions of salicylaldehyde or 2-5-dihydroxybenzaldehyde, also in combination with oxidizing agents for coloring of human hair are suitable.

Test 2 for human streak coloring with salicylaldehyde and hydrogen peroxide The procedure was as stated in test 1, but the solution also contained 3% by weight hydrogen peroxide.

The results obtained are shown in Table II below: Tabel II Concentration of the coloring result (in the presence of salicylaldehyde, an oxidizing agent) 0.1% by weight light brown 0.2% by weight more brown 0.5% by weight more brown (similar to as when using 0.2% by weight salicylaldehyde) 1.0% by weight / a light brown 2.0% by weight light medium brown 5.0% by weight medium brown Was the salicylaldehyde through in test 2 2,5-dihydroxybenzaldehyde, similar staining results were obtained.

Test 3 for human streak coloring with salicylaldehyde, 2-aminophenol and hydrogen peroxide It was worked as indicated in test 1, but contained the solution also contains the amount of 2-aminophenol given below in Table III and 3% by weight of hydrogen peroxide.

The results obtained are shown in Table III below: Table III Concentration in Concentration in Coloring Result Salicylaldehyde 2-aminophenol (with oxidizing agent) 0.3% 0.9% strong red-brown 0.6% 0.6% yellow-red-brown 0.9% 0.3% yellow-brown To prove that the salicylaldehyde with further dye precursors find use in the presence of oxidizing agents for dyeing human hair test 4 was performed.

Test 4 for human hair staining with salicylaldehyde, various Dye precursors in the presence of oxidizing agent It was stated as in test 1, worked, but the salicylaldehyde concentration was adjusted to 0.5 wt .-%. The hydrogen peroxide content was 3% by weight.

The results obtained are shown in Table IV below: Table IV Dye precursor Dyeing result + hydrogen peroxide + salicylaldehyde 2,5-Diaminotoluenesulfat green blond 2,5-Diaminoanisolsulfat green blond 2,4-Diaminotoluene light brown 1,2-diamino4-chlorobenzene yellow-brown Dye precursor Dyeing result + Hydrogen peroxide + salicylaldehyde 2,4-diaminoanisole sulfate medium brown 1,2,4-triaminobenzene- dark red-brown dihydrochloride N, N-dimethyl-p-phenylenediamine very light brown N-methyl-p-phenylenediamine- green blond dihydrochloride 2-aminophenol light brown 3-aminophenol yellow-brown 4-aminophenol red-brown 4-amino-o-cresol light brown 4-amino-m-cresol medium brown 2-amino-p-cresol dark yellow-brown 6-amino-m-cresol yellow-brown pyrocatechol light brown resorcinol light brown 1,2,4-trihydroxybenzene medium brown pyrogallol yellow brown aFNaphthol light brown 4-methylaminophenol sulfate light brown 4-amino-3-methylphenol yellow-brown 4-amino-2-methylphenol sulfate medium brown 3-dimethylaminophenol medium brown 2-aminoresorcinol hydrochloride medium yellow brown 2,5-diaminophenol medium brown 4-dimethylaminobenzaldehyde medium brown 4-amino-diphenylamine medium blonde 4,4'-diaminodiphenylamine sulfate light blond 8-aminoquinoline red-brown 6-aminoquinoline hydrochloride medium brown monohydrate 4-aminosalicylic acid test 5 for human hair coloration with 2,5-dihydroxybenzaldehyde with various dye precursors in the presence an oxidizing agent The procedure was as indicated in test 1, but was adjusted the 2,5-dihydroxybenzaldehyde concentration to 0.5 wt .-%. The concentration of the dye precursor was in each case 0.5% by weight. The results obtained are Table V gives a summary of the following: Table V Dyestuff precursor, dyeing result + 2,5-Dihydroxybenzaldehyd + hydrogen peroxide 2,5-Diaminotoiuolsulfat green blond 2,4-diaminoanisole sulfate light brown 2,4-diaminoanisole sulfate light brown 2-aminophenol yellow-brown Continuation of dye precursor, dyeing result + 2,5-dihydroxybenzaldehyde + Hydrogen peroxide 3-aminophenol light brown 4-aminophenol red brown pyrocatechol light brown resorcinol light brown pyrogallol medium brown 4-aminodiphenylamine medium blond Example 1 A. A hair coloring cream is made. A mixture consisting of Cetyl stearyl alcohol mixture 27.00 g sodium lauryl sulfate 11.40 g water 11.60 g emulsified and homogenized to a cream.

B. The following are incorporated into the cream obtained: Salicylaldehyde 0.30 g 2-aminophenol 0.90 g 2-propanol 15.00 g water 13.80 g C. In the next steps of the description are in the batch obtained above potassium metabisulphite 0.50 g of water 5.00 g incorporated.

D. Then ammonium hydroxide (25%) 6.00 g are incorporated.

E. The whole is supplemented with water to 100.00 g and the pH value set to 10.5 to 11.0.

The hair coloring cream obtained is filled into tubes.

F. The hair coloring cream is made with aqueous hydrogen peroxide solution (6%) mixed in a weight ratio of 1: 1 and applied to 95% gray hair.

Contact time at 20 ° C: 30 minutes The hair is then rinsed, shampooed and dried.

The hair is golden.

Example 2 The procedure is as indicated in Example 1, but are used: A. Cetyl stearyl alcohol mixture 27.00 g sodium lauryl sulfate 11.40 g water 11.60 g B. salicylaldehyde 1.00 g 2-aminophenol 1.00 g 2,5-diaminotoluene sulfate 1.50 g 2-propanol 15.00 g water 11.50 g C. Potassium metabisulfite 0.50 g water 5.00 g D. ammonium hydroxide (25%) 6.00 g E. supplemented with water to 100.00 g The pH value is set to 10.5 to 11.0.

The hair is dark blonde-gold after the treatment.

The original hair was 95% gray.

Example 3 A. Cetyl Stearyl Alcohol Mixture 27.00 g of sodium lauryl sulfate 11.40 g water 11.60 g B. salicylaldehyde 0.10 g 2-aminophenol 0.10 g 4-aminophenol 0.30 g 2-propanol 15.00 g water 14.50 g C. Potassium metabisulphite 0.50 g water 5.00 g of D. ammonium hydroxide (25%) 6.00 g supplemented with water to 100.00 g The pH value is set to 10.5 to 11.0.

The hair is light brown after the treatment.

The original hair was light blonde.

Example 4 It becomes a tint set according to the following formulation produced as a liquid preparation: isopropyl alcohol 30,000 g copolymer of Vinyl pyrrolidone and vinyl acetate 2.000 g polyethylene glycol MW 1400-1600 0.200 g lauryl pyridinium chloride 0.200 g perfume 0.300 g demineralized water 67.165 g Basic Blue 99 (Color Index 56059) 0.025 g Basic Red 22 (Color Index 11055) 0.010 g 2,5-dihydroxybenzaldehyde 0.100 g 100.00 g The pH is adjusted to 5.5.

After shampooing and rinsing the hair, then 15 to 20 Apply ml of the tinting agent to towel-dampened hair. Then the hair - depending on the desired hairstyle - rolled on a water wave curler. The hair turns 30 Dried under the dryer for minutes and then styled. The hair then lies medium brown tinted before.

Example 5 A tint is made from the following formulation: 2,5-dihydroxybenzaldehyde 0.70 g Basic Blue 99 (Color Index 56059) 0.20 g Basic Brown 16 (Color Index 12250) 0.50 g Basic Red 22 (Color Index 11055) 0.10 g 2-propanol 10.00 g Hydroxyethyl cellulose 1.00 g glycerine DAB 7 3.00 g monoethanolamine 1.00 g potassium hydroxide solution (51%) 2.00 g perfume 0.30 g deionized water 81.20 g 100.00 g The pH is adjusted to 8.0 to 8.5.

The above tinting agent can be in a known manner in aerosol cans be filled using a propellant. The tint is used sprayed on the hair, tinting it reddish brown.

Example 6 A toning agent is made from the following formulation: Salicylaldehyde 0.70 g Basic Blue 99 (Color Index 56059) 0.20 g 2-propanol 10.00 g hydroxyethyl cellulose 1.00 g glycerin DAB 7 3.00 g monoethanolamine 1.00 g potassium hydroxide solution (51%) 2.00 g perfume 0.30 g deionized water 81.80 g 100.00 g The pH value is set to 8.0 to 8.5.

The tinting agent can, as indicated in Example 5, bottled and be applied. As a result, the hair is tinted green blonde, so that the tint acts as an anti-red agent.

DE-AS 11 06 925 discloses a method for dyeing human hair described, in which an agent is used which, as an active ingredient, is an ortho-dihydroxybenzene compound contains, with protocatechualdehyde being preferred as the active ingredient there (cf.

Col. 2, lines 49-52, Col. 5, example 6) and the coloring by alkali and / or ammonium periodate and / or ammonium persulfate as an oxidizing agent will. In DE-AS 11 06925 the use of salicylaldehyde and of 2,5-dihydrobenzaldehyde alone or in combination with an oxidizing agent to achieve coloring on human hair not previously described and also not Suggested It is surprising that in the present invention there is no oxidizing agent yellowing with salicylaldehyde and / or 2,5-dihydroxybenzaldehyde on human hair can be generated, while protocatechualdehyde does not under these conditions Staining causes Even more surprising is that protocatechualdehyde is present in the presence of oxidizing agents only under very special conditions (oxidizing agents and pH value) red-brown resp.

medium brown hair dye supplies; among these for protocatechualdehyde necessary conditions can, however, with salicylaldehyde or 2,5-dihydroxybenzaldehyde no brown hair coloring can be achieved.

The following table is intended to show the surprising results of the comparative tests clarify.

Comparative studies by dyeing tests on human hair as evidence the technical progress achieved taking into account DE-AS 1106 925 No. Concentration addi- tion of Oxyda- pH value active ingredient according to active ingredient according to tion of tion medium invention DE-AS 1106925 solution in% salicylaldehyde protocatechualdehyde 1) 1 without 4 light yellow no coloring 2) 0.5 sodium iodate 3% 4 light yellow red-brown 3) 1 without 10 yellow no coloration 4) 0.5 sodium iodate 3% 10 yellow no coloration 5) 0.5 ammonium peroxy 4 light yellow no color disulphate 3% 6) 0.5 ammonium peroxy 10 yellow medium brown disulfate 3% 7) 0.5 H2 ° 2 3% 4 yellow no color 8) 0.5 H202 3% 10 brown no staining

Claims (3)

Claims: 1. Process for dyeing human hair using a) a hydroxybenzaldehyde in solution, b) optionally an oxidizing agent, c) optionally a dye hair product known for hair dyes, d) optionally a substantive dye and e) customary additives, characterized in that a compound of the formula (I) is used as the hydroxybenzaldehyde used in which R1 represents a hydrogen atom or the OH group. 2. Agent for coloring human hair, consisting of a) a hydroxybenzaldehyde in solution, b) optionally a dye hair product known for hair dyes, c) optionally a substantive dye and d) conventional additives, characterized in that the hydroxybenzaldehyde is a compound of the formula is, wherein R1 represents a hydrogen atom or an OH group. Means for changing the hair color by means of bleaching (bleaching) and dyeing are known and such are e.g. B. in Ullmanns Encyklopadie dertechnischen Chemie, 4th Edition, Volume 12, pages 435-441 described. The object of the present invention is to provide a versatile process and to provide means for coloring human hair which permit To color human hair light yellow to yellow and brown to reddish brown, the means through special physiological compatibility and toxicological harmlessness should distinguish. Another object is that by combining with direct dyes or by combination with dye precursors and Oxidizing agents any desired hair coloration can be produced. The new method and the new means should also be very versatile be applicable. They should therefore permit 1. Human hair to be yellow to brown directly to color without using oxidizing agents. and / or needing dye precursors, it is desirable that the hair color is in the alkaline range up to pH 11 and should be feasible in the acidic range up to pH 5. Further is to achieve further coloring options the possibility of combining with direct hair dyes desired to produce any desired hair coloration. 2. The new funds should be based on the usual oxidizing agents based on hydrogen peroxide can be combined to achieve brown hair coloring. 3. The new funds are said to contain dye precursors and hydrogen peroxide be combinable in order to be able to produce any desired colorations both darker and lighter shades compared to the initial state. The invention relates to a process for dyeing human hair using a) a hydroxybenzaldehyde in solution, b) optionally an oxidizing agent, c) optionally a dye precursor known for hair dyes, d) optionally a substantive dye and e) customary additives, characterized in that that a compound of the formula (I) is used as the hydroxybenzaldehyde is used, where R1 represents a hydrogen atom or the OH group.