DE3348135C2 - - Google Patents

Description

The invention relates to an aqueous colorant for dyeing keratinic fibers, especially hair.

The invention is based on the object, aqueous colorants for Dyeing of keratinic fibers, especially hair available deliver, wherein the dyes and the hair dyes are opposite to the characterized her known dyes and hair dyes characterized that they are known from the prior art disadvantages avoid and dyeings with high lightfastness, high friction speed and extraordinarily good wash fastness also have a very good storage stability.

Subject matter of the invention are aqueous colorants for dyeing Keratinic fibers, in particular hairs according to claims 1 to 5.

As examples of those falling under the general formula (I) 4-amino-3-nitro phenols

wherein R has the meaning alkyl, hydroxyalkyl or dihydroxyalkyl having 1 to 6 carbon atoms, which are straight-chain or branched to ordered, and the condition is that R is not methyl or beta-hydroxyethyl, are called:
3-nitro-4-ethylaminophenol,
3-nitro-4- (n-propyl) aminophenol,
3-nitro-4- (n-pentyl) aminophenol,
3-nitro-4- (α-methyl-β-hydroxyethyl) aminophenol,
3-nitro-4- (α-ethyl-β-hydroxyethyl) aminophenol,
3-nitro-4- (β-hydroxypropyl) aminophenol,
3-nitro-4- (γ-hydroxypropyl) aminophenol,
3-nitro-4- (β, γ-dihydroxypropyl) aminophenol,
3-nitro-4- (β-hydroxy-n-butyl) aminophenol,
3-nitro-4- (β-hydroxy-n-hexyl) aminophenol.

The preparation of the compounds of general formula (I) can carried out analogously to known methods. Below are general methods of preparation exemplifying the compounds of the formula (I).

General manufacturing process A

By reacting compounds of the formula (II)

with chloroformic acid haloalkyl esters of the formula (III).

wherein R 'is a straight-chain or branched alkyl radical having 2 to 6 Carbon atoms, which is a beta or gamma-halogen atom, preferably chlorine or bromine, in the presence of bases  to compounds of the formula (IV)

and by subsequent intramolecular alkylation (to cyclic Carbamates, which are generally not isolated) and decar Boxylierung of these intermediates by means of base, the Ver obtained compounds of formula (I). (The production of the partly still Chloroformic acid haloalkyl not described in the literature ester of formula (III) takes place by reaction accordingly halogenated hydroxyalkanes with phosgene at temperatures around 0 ° C, optionally in the presence of catalysts.) The implementation is usually two-stage, but can also be used as a one-pot be accomplished.

Step 1:

As bases here are z. B. usable: alkali and alkaline earth carbonates and bicarbonates, alkaline earth oxides, triethylamine and similar organic bases. It becomes organic in the presence Solvent worked, such. As toluene, chlorobenzene, dioxane, Dimethoxyethane and the like, which are inert in the reaction behavior. Optionally, these solvents can also with  Water are combined. The temperature is about 70 ° C or higher until the reflux of the solvent used. in this connection is the starting compound with the base (in slight excess) submitted in demm solvent, at 70 ° C then the chlorine formic acid haloalkyl ester is added dropwise. For workup will optionally filtered hot and the filtrate is either concentrated or poured onto water, whereupon the intermediates of the Formula (IV) in each case fail.

Level 2:

As bases, alkali or alkaline earth hydroxides are useful. When Solvents are water or ethanol or mixtures thereof ver applies. The 1st stage intermediate is reacted with 4 to 4.5 moles of base combined at room temperature and then to about 60-80 ° C. heated. After neutralization the product precipitates directly or becomes by concentration (with removal of salts) won.

General manufacturing process B

By reacting halogenated nitrophenols of the formula (V)  

wherein X is halogen, preferably fluorine or chlorine, with alkyl, Hydroxyalkyl or dihydroxyalkylamines which are present in the alkyl, Hydroxyalkyl or Dihydroxyalkylrest 1 to 6 carbon atoms ent hold and straight-chain or branched, the verbin compounds of the formula (I) are produced. The starting compound is with an excess of one of said amines and with a Base (in question are alkali and alkaline earth hydroxides, carbonates and hydrogencarbonates, triethylamine and similar organic amines) Room temperature and then, optionally in An the presence of a catalyst such. B. copper (I) chloride in one Bath heated to 100-140 ° C bath temperature. After a few hours is cooled, with z. Hydrochloric acid and acidified with a extracted organic solvent (eg., Methylene chloride, vinegar ester, benzene or the like). The organic phase then contains unumge set starting material. The aqueous phase is now neutralized and extracted again. In these organic extracts is the desired product, obtained by concentration and given if purified by recrystallization.

Hereinafter, compounds of the formula (I) and their Her described in examples without the choice of Examples should be a limitation.  

Example 1 Preparation of 4- (γ-hydroxypropyl) amino-3-nitrophenol

Step a) Preparation of γ-chloropropyl-N- (2-nitro-4-hydroxyphenyl) carbamate

77 g (0.5 mol) of 3-nitro-4-aminophenol are dissolved in 200 ml of dimethoxyethane, with 27 g of calcium carbonate and at 70 ° C dropwise with 80 g (0.51 mol) Chloroformic acid γ-chloropropyl ester used. After an hour will be the reaction mixture is filtered hot and the filtrate in 700 ml of ice water stirred, whereupon 128 g (93%) of the desired compound precipitated. The enamel point is 103-105 ° C, after recrystallization from toluene 106 ° C.

Stage b) Preparation of 4- (γ-hydroxypropyl) amino-3-nitrophenol

110 g (0.4 mol) the compound described in step a) are added to a mixture of 180 g 40% aqueous sodium hydroxide and 400 ml of ethanol at room temperature portions added wisely. The reaction mixture is then heated to reflux, with salt acid adjusted to pH 6 and concentrated completely. For the separation of the salts is the residue taken up in ethanol, filtered and again largely concentrated. The precipitated product is squeezed off, dried and can be made from water, ethanol or ethyl acetate are recrystallized.

Yield: 71 g (84%), melting point: 110-111 ° C

Analysis for C₉H₁₂N₂O₄:
calculated: C 50.94; H 5.70; N 13.20%;
Found: C 51.00; H 5.50; N 13.10%.

UV / VIS: λ _max = 478 nm (ε = 5335)

example 2 Preparation of 3-nitro-4- (n-propyl) aminophenol

34.7 g (0.2 mol) of 4-chloro-3-nitrophenol, 21 g of sodium carbonate, 0.1 g of copper (I) - chloride and 20 g of n-propylamine are dissolved in a bath at room temperature up to heated to a bath temperature of 120 ° C. After 5 hours, the reaction taken up with water, acidified with hydrochloric acid (pH 2) and three extracted with ethyl acetate to remove unreacted starting material NEN. The aqueous phase is again after neutralizing with three times Extracted vinegar. After drying and concentration, these extracts provide the desired product in the form of a red oil.

UV / VIS: λ _max = 480 nm (ε = 5490)

example 3 Preparation of 4- (β-hydroxypropyl) amino-3-nitrophenol

Stage a) Preparation of β-chloropropyl-N- (2-nitro-4-hydroxyphenyl) carbamate

To 77 g (0.5 mol) of 4-amino-3-nitrophenol and 27 g of calcium carbonate in 250 ml Dioxane are at 70 ° C 85 g (0.54 mol) of chloroformic acid-α-methyl-β-chloro added ethyl ester. After 2 hours at 90 ° C gets hot from the anorga filtered off with sodium salts and the filtrate was concentrated completely. The wished Intermediate product is in the form of a reddish oil and is so in the following stage used.

Stage b) Preparation of 4- (β-hydroxypropyl) amino-3-nitrophenol

The total amount of oil recovered in the precursor is dissolved in 300 ml of ethanol taken and added to 200 g of a 40% aqueous sodium hydroxide solution. subsequently, The mixture is refluxed for one hour, adjusted to pH 6.5 with hydrochloric acid set and narrowed down completely. After boiling the residue with vinegar ester, filtering off the salts and concentration to the recrystallization necessary volumes are obtained on cooling 65 g of the desired product.

Yield over both stages: 61%
Melting point: 146 ° C

Analysis for C₉H₁₂N₂O₄:
calculated: C 50.94; H 5.70; N 13.20%;
Found: C 50.90; H 5.60; N 13.20%.

UV / VIS: λ _max = 474 nm (ε = 5218)

The compounds of the formula (I) can be used both in basic and in neutral or acidic hair dyes and used because of their stability in oxidation dyes. Furthermore, they may also be present in hair dyes containing other direct coloring dyes in which dye precursors may or may not be present. A variety of direct dyes and color precursors, which are useful for this purpose is known from previous publishers Publications, z. B.
Ullmann; Balm and sagarin; Cosmetics, Science and Technology, Vol. 2, pp. 308-10 J. Corbett; VII Congress JFSCC, Hamburg 1972, pp. 559-599 J. Corbett; Hair Coloring; Rev. Prog. Coloration, 1973, vol. 4, pp. 3-7 Black, Kravitz, D'Angelo; Laboratory evaluation of some oxidation hair color intermediates; Cosmetics and Toiletries 1979, Vol. 94, p. 47

The pH of the aqueous colorant according to the invention for dyeing keratinic fibers, especially hair may vary z. B. from un dangerous 2.5 to 12 and preferably from 3.5 to 10. When dyeing in alka can be made of a compatible alkalizing agent can be used to give the desired pH. The amount of angewen alkalizing agent may vary within a wide range, the dye and the specially used alkalizing agent and the desired pH depends. By way of illustration, it is stated that alkalisia from less than about 0.1 to about 15%, and preferably from about 0.25 to about 8% by weight of the composition tion, may vary.

The alkalizing agent is selected so as not to be used Dye is acting (i.e., it is compatible with it) and it does not precipitate. If human hair is to be dyed, the alkalizer may be used be neither toxic nor in its highest under the conditions of use damage to the scalp applied in the composition. On Preliminary test can be done with the alkalizers to their compatibility with the dye to show or the possibility of Reveal toxicity or harmfulness.

In dyeing human hair, ammonium hydroxide is a suitable alka as it is economical and within a large area is nontoxic. However, instead of or together with ammonia, any another ammonia derivative can be used as the alkalizing agent, such as an alkylamine, for example ethylamine or triethylamine, an alkanediamine, such as 1,3-diaminopropane, an alkanolamine such as ethanolamine, a polyalkylene poly amine, such as diethyltriamine or a heterocyclic amine. As alkalization may also be an alkali or alkaline earth metal hydroxide having a concentration, which does not precipitate with any of the components of the composition, be applied. These compounds can also be used in human dyeing Hair applied as far as their concentration in the final dye solution is below that which could possibly irritate the scalp.

The preferred alkalizing agent is water-soluble organic amines Volatility (boiling point greater than approximately 50 ° C) less than 12  Carbon atoms, such as isobutylamine, 2-ethylbutylamine, diethylamine, triethyl amine. As alkalizing agents, the following are particularly suitable:

• (A) ammonia,
• (b) Primary aliphatic diamines, such as
  Ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, diethylenetriamine, triethylenetetramine, 2,2'-iminodipropylamine,
• (c) alkanolamines, such as
  Ethanolamine, isopropanolamine, triethanolamine, triisopropanolamine, N-methyldiethanolamine, diisopropylethanolamine, dimethylisopropanolamine, 2-amino-2-methylpropane-1,3-diol, tri (hydroxymethyl) methylamine.

The pH of the agent may be with an inorganic or organic acid or an acidic salt compatible with the agent. As examples of acids or acid salts may be mentioned: sulfur acid, formic acid, acetic acid, lactic acid, citric acid or tartaric acid or ammonium sulfate, sodium dihydrogen phosphate or potassium bisulfate.

There may also be water-soluble surfactants in the he Be used colorants used. These can be anionic, nonionic or cationic. To explain different types what water-soluble surfactants may be mentioned: Higher alkyl benzenesulfonates, alkylnaphthalenesulfonates, sulfonated esters of alcohols and polybasic acids, taurates, fatty alcohol sulfates, branched sulfates chain or secondary alcohols, alkyldimethylbenzylammonium chlorides and As examples of special wetting agents can be mentioned: Lauryl sulfate, polyoxyethylene lauryl ester, myristyl sulfate, glyceryl monostearate, the sodium salt of polmitin methyltaurine, cetylpyridinium chloride, laurylsul fonate, myristylsulfonate, lauric acid diethanolamine, polyoxyethylene stearate, Stearyldimethylbenzylammonium chloride, dodecylbenzene sodium sulfonate, nonyl naphthalene sodium sulfonate, dioctyl sodium sulfosuccinate, sodium N-methyl N-oleyl taurate, Oleic acid esters of sodium isethionate, sodium dodecylsulfate, the sodium salt of 3,9-diethyltridecanol-6-sulfate and the like. The amount of water-soluble surfactant can be used within a wide range, such as from 0.01 to 40% by weight of the composition, especially riieren.  

In addition to other materials such. B. emulsifiers can also be a thickening be incorporated into the present agent. advantageously, For example, one or more of these may be commonly used in hair dyes needed agents such as sodium alginate or gum arabic or cellulose derivatives, such as methyl cellulose or the sodium salt of carboxymethylcellu loose, or acrylic polymers, such as the sodium salt of polyacrylic acid, or on organic thickeners, such as bentonite, are used. The amount of Thickening agent can vary within a wide range, such as from 0.1% to 20% by weight, and preferably from about 0.5% 5 weight percent.

The proportions of dyes of the formula (I) in the agents according to the invention may also vary within a wide range, as described by unge about 0.001% to more than about 10%. The agent preferably contains one dyeing proportion of color varying from about 0.001 to 10% can. The water content of the composition is generally the Main ingredient and can also be found within a large area strong dependence on the amount of other additives vary. So can the water content is only 10% and preferably about 50 to 90%.

The colorants of the invention are aqueous agents. The expression "Aqueous medium" is used here in its usual general sense det, comprising any agent containing water according to the invention. To include true solutions of dyes in an aqueous medium, either alone or in combination with other substances, which are also aqueous Medium have been dissolved or dispersed. The term "aqueous co tel "also detects any mixture of dye with the aqueous medium either alone or together with other components. The dye can colloidally dispersed in the medium or only intimately mixed therein.

As used herein, the term "aqueous medium" encompasses any medium contains the water. The aqueous medium can therefore be an aqueous-alkaline, aqueous-neutral or aqueous-acidic medium. In addition, that can aqueous medium water and a solvent such as aliphatic alcohols, aro matic alcohols, Ethylenglykoldidalkylether u. Ä. Included. The latter can be used as a solubilizer to dissolve the dye and / or another material.  

The aqueous colorants of the invention can take many forms. So royal In the form of thin or thick, flowable liquids, pastes, emulsions ions, jellies, etc. are present.

Typical colorants that are particularly suitable for dyeing human hair are suitable are given below:

1. Alkaline agent

Among the dyes, at least one dye of the formula (I) be contained. However, other direct dyes can also be added be present in addition. Surfactants, alkalis, thickeners and their combination may be as in the table immediately above given proportions are needed. Direct Rising Dyes, which are considered To sentences are suitable, z. As described in: Ullman; Balm and sagarin; Cosmetics, Science and Technology, Vol. 2, pp. 308-10 J. Corbett; VII Congress JFSCC, Hamburg 1972, pp. 559-599 J. Corbett; Hair Coloring; Rev. Prog. Coloration, 1973, vol. 4, pp. 3-7 Black, Kravitz, D'Angelo; Laboratory evaluation of some oxidation hair color intermediates; Cosmetics and Toiletries 1979, Vol. 94, p. 47

2. Acid agent

The acidic agents are similar to the above alkaline agents with the Exception that the alkali is omitted and acid up to a pH of 2.5 to 7, preferably from 3.5 to 6.5 is added. The wetting agent may be anionic, ka be cationic or non-ionic or consist of suitable mixtures thereof, and any of the above-mentioned substances can be used. The choice of Ver Thickener is somewhat more limited, so on alkylcellulosics, such as methyl cellulose and inorganic agents. In certain cases, the wetting agents even act as a thickener.  

Oxidation dye compositions

The dyes of the formula (I) used according to the invention are in general compatible with oxidation dyes. Accordingly, they can be in oxidation color substances which are particularly suitable for dyeing human hair, be applied. Useful agents contain 1 to 5% ammonia, 1 to 6% Hydrogen peroxide or urea peroxide (in the ready-to-use preparation), 0.005 to 2% oxidation dye 0.001 to 3% of the compounds indicated in formula (I) above binding, as well as wetting agents, thickeners, etc. The oxidation dye components can eg. For example, p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene Resorcinol, hydroquinone, p-aminophenol, 2,4-diaminoanisole, p-aminodiphenylamine, 4,4'-diaminodiphenylamine and all other known for this purpose development be ment and coupling components. In addition, in the oxidation dye composition also directly dyeing dyes such. 45 nitro 2-aminophenol, 2-nitro-p-phenylenediamine, 4-nitro-o-phenylenediamine and all white For this purpose known compounds may be present. Suitable development and coupling components and direct dyes are, for example be wrote in the literature mentioned above.

The aqueous colorants according to the invention can according to usual on this area used methods are produced. So they can solve by solving or Sus pend the dye in water in the desired concentration Herge be presented. Water-miscible organic solvents can be used det to facilitate the dissolution of the dyes; in this case can the dye is first dissolved in the solvent and then diluted with water become. The dispersing of the various ingredients can be accomplished by heating the composition to temperatures between 40 and 110 ° C ent neither before dilution nor afterwards, also relieved.

The aqueous colorants according to the invention can according to usual on this area used techniques are applied to the hair. At a For example, use on live hair on the human head the means with a brush, a sponge or other means to the state Apply a touch, such as dipping, be applied until the hair with the composition is completely saturated.

The reaction time or the time for the contact of the colorant with the Hair is not critical and can be used on a larger hair coloring range, such as time periods of about 5 minutes to unt about 2 hours, and preferably from about 5 minutes to about 60 minutes.  

The temperature of dyeing can also be, as is customary in this field, lie within wide limits. Thus the temperature during dyeing can vary from about room temperatures, e.g. B. about 20 ° C to about 60 ° C upwards and preferably from about 20 ° C to about 45 ° C.

The color compositions of the invention are especially useful for dyeing human hair on the head useful.

Any compounds which fall under the formula (I) may be related be applied with the present invention. However, for explanation the following special compounds are mentioned: 4- (γ-hydroxy-n-propyl) amino-3-nitrophenol, 3-nitro-4- (n-propyl) aminophenol, 4- (β-hydroxy-n-propyl) amino-3-nitrophenol.

The dyes used in the compositions according to the invention can be prepared analogously to various known methods, as already has been explained above.

The following examples illustrate the dyeing of hair with the invention aqueous colorants for dyeing keratinic fibers, in particular of Hair. The procedures used for dyeing can be repeated as follows are given:

Dyeing process A Dyeing hair with agents in the alkaline range (pH 7 to about 12)

Using certain amounts of the following components becomes a mixture manufactured:

dye prescribed amount solvent prescribed amount emulsifier prescribed amount Surfactant prescribed amount thickener prescribed amount Alkaline agent for setting the prescribed pH value

The dye is wetted with the solvent, the agents listed above and 30 ml of water are added. The mixture is stirred for approx. Heated to 60 ° C until the formation of a uniform dispersion. Then the Diluted with water to 100 ml and the prescribed pH of 7 or set higher.  

The resulting dye is on natural hair, gray hair, lasting Wavy hair and bleached hair applied and with the hair for 20 minutes keep in touch for a long time. Thereafter, the hair is rinsed with clean water and put in shape as usual.

Dyeing process B Dyeing hair with acidic agents (pH 7 to about 3)

A mixture is made from the following components:

dye prescribed amount solvent prescribed amount emulsifier prescribed amount Surfactant prescribed amount thickener prescribed amount Acid agent to set the prescribed pH

The dye is wetted with the solvent, the other ingredients individually added; it is filled up with water and with stirring to about 50 ° C. heated to form a uniform dispersion. The hair will be with this Means colored as described under method A.

Dyeing process C Dyeing hair from a peroxide bath

The following agent is made:

Dye u. dye precursor depending on the nuance fatty alcohol 26.5 g Surfactant 5.0 g fatty acid 1.0 g 25% ammonia 10.0 g ethylenediaminetetraacetic 0.3 g Water on 100 g

A 40 g portion of this agent is mixed with 40 g of 6% hydrogen peroxide, and the mixture turns to natural, permed graying and bleached Hair is applied, and allowed to remain there for 30 minutes at 30 ° C. The hair is then rinsed with clear water, shampooed and dried.  

Application Example 1

Be 0.3 g of the dye of Example 1 according to the method A in a Agents applied as described in Application Example 1 are given gray or pale blond hair a strong cherry red color.

Application Example 2

Are 0.15 g of dye from Example 1, 0.1 g of p-phenylenediamine and 0.05 g Resorcinol incorporated into a composition as described in the dyeing method C, and applied on natural gray hair, you get one reddish light blonde tone.

Application Example 3

0.7 g of the dye of Example 3 are prepared by the method A under Ver use of 1.2 g of methylcellulose, 5 g of monoethanolamine lauryl sulfate, 2 g Cetylstearyl alcohol, 5 g Diethylglykolmonoethylether dyed on hair. The pH of the agent is adjusted to 9.0. Light brown hair gets one strong burgundy tone.

Application Example 4

0.6 g of dye from Example 2 are incorporated into a composition such as described in Application Example 6 and applied to light brown hair, so this gets a strong shade of red.

Application Example 5

Be 0.9 g of the dye of Example 3 and 0.4 g of 1,4,5,8-tetraamino Anthraquinone incorporated into a means as in Application Example 6 beschrie ben and applied to light to medium brown hair, this receives one strong eggplant tone.

Claims (5)

1. An aqueous colorant for dyeing keratinic fibers, in particular hair, which contains as the dye at least one compound of the general formula (I) wherein R is alkyl, hydroxyalkyl or dihydroxylalkyl having 1 to 6 carbon atoms arranged straight-chain or branched, with the proviso that R is not methyl or β-hydroxyethyl. 2. Composition according to claim 1, characterized in that the Compound of the general formula (I) 0.001 to 5 weight percent of the total funds. 3. Composition according to one of claims 1 or 2, characterized by gekenn records that further dyes and dye precursors are included. 4. Composition according to one of claims 1 to 3, characterized gekennzeich net, that the pH of the agent in the range of about 2.5 to about 12 lies.   5. Composition according to one of claims 1 to 4, characterized that it is common in hair color-changing preparations Additives, such as wetting agents, surfactants, emulsifiers, Solubilizer, thickener and the like contains.