US3617167A

US3617167A - Methods and compositions containing 4-aminopyrazolones for the dyeing of human hair

Info

Publication number: US3617167A
Application number: US568750A
Authority: US
Inventors: Peter Berth; Karl-Josef Boosen
Original assignee: Therachemie Chemische Therapeutische GmbH
Current assignee: Therachemie Chemische Therapeutische GmbH
Priority date: 1965-08-05
Filing date: 1966-07-29
Publication date: 1971-11-02
Anticipated expiration: 1988-11-02
Also published as: BE688594A; DE1492198B2; IT942002B; DE1617876A1; DE1617876B2; DK113867B; DE1617876C3; AT272526B; SE342141B; DE1492198C3; FR1488169A; DE1492198A1; GB1146061A; NL6609633A

Abstract

WHEREIN R1 is a member selected from the group consisting of hydrogen, -CONH2, -COOH, -COOR'', alkyl having 1 to 10 carbon atoms, phenyl and nicotinoyl; R'' represents an alkyl having 1 to 4 carbon atoms; and R2 is a member selected from the group consisting of hydrogen, alkyl having 1 to 10 carbon atoms, phenyl and p-sulfonamidophenyl; and (b) a coupling component, said developer component compound being present in substantially equimolar to a slight excess with respect to said coupling component compound.

In the process of dyeing the living human hair which comprises treating the hair at a temperature of from 15* C. to 40* C. with an aqueous composition for dyeing human hair comprising an oxidation dyestuff and customary dyestuff adjuvants in the presence of an oxidizing agent, and thereafter rinsing the hair, the improvement which comprises utilizing as said oxidation dyestuff, from 0.1 percent to 5 percent by weight of an oxidation dyestuff combination of (a) a developer component compound having the formula

Description

l llmte States Patent 1 3,617,167

[72] Inventors Peter Berth OTHER REFERENCES nusseldol'f-nenlath; Vanieek et al., Collection of Czechoslovak Chemical Com- Karl-Josef Boosen, Dusseldorf-Holthausen, munications, Vol. 27, pp.2796 2800, 1962 of m ny Harry, The Principles and Practice of Modern Cosmetics, p. 1 pp 50 443, 1962. [22] Flled July 1966 Primary E.raminer-Albert T. Meyers [45] Patented Nov. 2, 1971 [73] Assignee Therachemie Chemisch Therapeutische j f Exammer Don Funderburk Gesellschafl "Lb-n. Henley-Hammond & Littell Dusseldorf, Germany [32] Prwmy 1965,9433 1966 ABSTRACT: In the process of dyeing the living human hair [33] Germany; Swltzerland which comprises treating the hair at a temperature of from [31] T 29157; 7253/66 C. to C. with an aqueous composition for dyeing human hair comprising an oxidation dyestuff and customary dyestuff adjuvants in the presence of an oxidizing agent, and thereafter 4 rinsing the hair, the improvement which comprises utilizing as [54] METHODS AND COMPOSITIONS CONTAINING 4- said oxidation dyestuff, 'from 0.] percent to 5 percent by AMINOPYRAZOLONES FOR THE DYEING OF weight of an oxidation dyestuff combination of (a) a HUMAN HAIR developer component compound having the formula 4 Claims, No Drawings R1'C=CNH3 [52] US. Cl. 8/l0.2,

424/62 [51] llnt.Cl A61k 7/12 N Field of Search 8/l0.2;

R is a member selected from the group consisting of [56] Cm hydrogen, coma. coon, -COOR', alkyl having 1 to 10 UNITED STATES PATENTS carbon atoms, phenyl and nicotinoyl; R represents an alkyl 2,9 /l K lOPiS i a l- 3/l0.2 having 1 to 4 carbon atoms consisting of hydrogen. alkyl hav- 3,01 1,858 l2/l96l Lantz et al. 8/l0.2 ing 1 to 10 carbon atoms, phenyl and p-sulfonamidophenyl; .12 .2 2 4/1 4 wilmsm nn et l.-

8/10.2 and (b) a coupling component, said developer component .2 /l 65 Lange 8/l0.2 X compound being present in substantially equimolar to a slight 3,253,980 /1966 Klinge et al 8/10.2 X excess with respect to said coupling component compound.

METHODS AND COMPOSITIONS CONTAINING 4- AMINOPYRAZOLONES FOR THE DYEING OF HUMAN HAIR Hair dyes utilizing oxidizing dyes are known, and phenylenediamines frequently are employed. It has also been proposed to use diaminopyridines. These compounds are converted into dyes on the hair by oxidation, either under the influence of atmospheric air or by the addition of oxidizers, for instance hydrogen peroxide. These hair dyeing agents are widely used, however, they have the grave disadvantage that they can be removed from the hair only with difficulty, if at all.

It now has been found that the hair dyes as described hereinbelow do not have this drawback because they can readily be removed from the hair while, on the other hand, exhibiting excellent coloring properties. These novel agents are characterized by a content of 4-aminopyrazolones having the generic formula In this formula, R and R individually may be hydrogen or an organic radical having no more than ten carbon atoms or coupling components known per se for dyes. The organic radical R of the 4-aminopyrazolone, for instance, may be an alkyl having one-l C-atoms or an aryl or a heterocyclic radical. Furthermore, functional groups may be present, such as -OH, -NH NHCH -N(Cl-l;,) or halogen, especially chlorine. As further organic radicals, the following groups should be named: -COOH, -COOR, -CONHR', CONRR", wherein R and R" are an alkyl or hydroxyalkyl having one to four carbon atoms.

The organic radical R in the above formula may be an alkyl having one to carbon atoms or an aryl or a heterocyclic radical, Functional groups may be present therein. Particularly to be named are hydrocarbon radicals having one to 10 C-atoms containing as functional groups -OH, -NH -COOH, CONH -SO H and -SO,NH

Particularly suitable as aromatic radical is phenyl. The same may contain alkyl or hydroxyalkyl groups having one to four carbon atoms or other substituents, such as NH OH, COOH, CONH SO H and SO NH Pyrazolones substituted with a radical R as named are produced by the reaction of beta-ketoacidesters with correspondingly substituted hydrazines, followed by nitrozation and reduction to the amino-compounds.

Numerous coupling components are known for hair dyeing agents. Suitable are amines, diamines, phenols, napthols, polyphenols and aminophenols. When using diamines, aminophenols and phenols, the orthoor meta-compounds are preferred. The following compounds are especially suited:

m-phenylenediamine o-phenylenediamine m-aminophenol o-aminophenol o-anisidine 2,4-diaminoanisol o-toluylenediamine m-toluylenediamine 2,4-diaminophenol pyrogallol resorcinol pyrocatechol aminoresorcinol 1,5-dihydroxynapthalene l,5-aminohydroxynaphthalene l ,8-aminohydroxynaphthalene alpha-naphthol The coupling components opportunely are employed in approximately molar quantities relative to the aminopyrazolones. However, no damage generally is incurred when the 4-aminopyrazolones are present in a certain excess.

lt furthermore has been found advantageous to use the 4- aminopyrazolones in the form of their salts, preferably the hydrochloride, since this lowers their sensitivity to air.

Coloring oftli hair with these agents cfii be az'cam nshed, as with other oxidizing dyes, by means of atmospheric oxygen or with chemical oxidizers, preferably hydrogen peroxide or its additives, especially on urea, melamine and sodium borate. The hair is dyed at temperatures ranging from 15 to 40 C preferably at room temperature.

The dyeing agents can be applied in aqueous solution but preferably as emulsion or as a cream or paste. For this purpose, the 4-aminopyrazolones and the coupling components can be admixed to any desired wetting agents or detergents, especially anionic or nonionic ones. Especially suitable detergents or wetting agents are alkylbenzenesulfonates, fatty alcohol sulfates, alkylsulfonates, fatty acid ethanolamines, ethylene additives on fatty acids or fatty alcohols.

The coloring properties of the dyes on the human hair are good also in mixture with the agents named. Hence, the hair dyeing agents can be produced in the form of shampoos, especially cream shampoos, which frequently is desirable in practice.

Moreover, the agents may contain thickeners, e.g. methylcellulose, starch, higher fatty alcohols, petrolatum (Vaseline), paraffin oil and fatty acids; also perfumes, i.e., essential oils; or hair treating agents such as pantothenic acid and cholesterol.

The additives named are applied in the quantities customary for these purposes. Detergents or wetting agents preferably are employed in amounts of -b 0.5-30 weight percent, thickeners in amounts of 0. l-25 percent, all calculated on the total composition. The concentration of the dyes, also calculated on the total composition, is up to 5 percent, and preferably 0.l to 2 percent by weight.

The hair dyeing agents can be applied in weakly acid, neutral or especially in alkaline pH range. The coloration of the hair thus attained has good light-, washand abrasion-resistance (rub-resistance) and can readily be removed again with reducing agents, e.g., sodium hydroxymethanesulfinate. This contrasts from the commonly known hair dyeing agents which greatly resist their removal, once applied to the hair.

The invention now will be further explained by the following examples. However, it should be understood that these are given merely by way of illustration, and not of limitation, and that numerous changes may be made in the details without departing from the spirit and the scope of the invention as hereinafter claimed.

Parts named in the examples are parts by weight; temperatures are degrees centigrade.

EXAMPLE I A solution was prepared from 2 parts 3-methyl-4-aminopyrazolone hydrochloride, 1 part resorcinol and 0.5 parts sodium sulfite in parts water. The pH was adjusted to 9.5 with ammonia, and the solution made up to 100 parts with water. Shortly before application, 4 parts H 0, (30 percent) were admixed thereto. This mixture was allowed to act on naturally grey living human hair at room temperature. After 20 minutes, the hair was rinsed and thoroughly shampooed. A strong red color was obtained. When, in lieu of the resorcinol, 1 part m-toluylenediamine was used, the hair assumed a redviolet color.

EXAMPLE 2 A solution was prepared as described in the preceding example except that 3 parts 4-aminopyrazolone-3-carboxylic acid amide hydrochloride were used instead of 3-methyl-4- aminopyrazolone. Under the conditions of example 1, a strong red color was obtained.

EXAMPLE 3 A solution consisting of 1.5 parts 4-aminopyrazolone hydrochloride, l part m-diaminoanisol, 1 part sodium sulfite, 5 parts of a thickener consisting of celluloseglycolate, in parts water was adjusted to a pH or nine with ammonia and made up to parts with water. The paste thus obtained dyed gray hair, after mixing with 8 parts melamine perhydrate, to a red-violet color within 30 minutes at room temperature.

EXAMPLE 4 A paste was prepared as described in example 3, except that, instead of the 4-aminopyrazolone, parts 3-phenyl-4- aminopyr-azolone were used, and the pH was held at 8. Living grey hair attained a red-violet color under the same conditions as given above.

EXAMPLE 5 An emulsion was prepared from parts fatty alcohol (C -C 10 parts fatty alcohol sulfate, 2 parts of the hydrochloride of 4-aminopyrazolone-3-carboxylic acid ethylester, 1 part alpha-naphthol and 77 parts water. The emulsion had a pH of 3.0 and was mixed with 10 parts sodiumperborate. This cream was applied to grey hair for minutes at C. and imparted thereto a deep blue color. This color could be completely removed again by a 20 minute treatment with a 3 percent aqueous Rongalit C solution (trade mark for sodium hydroxymethanesulfinate).

EXAMPLE 6 A cream was prepared as described in example 5, except that the alpha-naphthol used therein was replaced by 1 part of one of the coupling components listed in table 1. The color obtained under like conditions as in example 5, also is listed in table 1.

TABLE 1 Coupling Component Color resorcinol rcd-\iolct m-diaminoanisol blue-violet l,5-dihydroxynaplhalene blue o-aminophenol yellow EXAMPLE 7 EXAMPLE 8 Dyeing solutions were produced as described in example 1. However, in lieu of 3-methyl-4-pyrazolone hydrochloride as developer and resorcinol as coupling component, the compounds named in table 2 were used and imparted to the hair the color also listed in that table.

TABLE 2 Developer Coupling No. (as hydrochloride) component 1 l-phenyl-4-aminopyrazolone- Alpha-naphthol Blue-grey.

3-carboxylic acid.

2 1-pheny1-4-amiuopyrazolone- Resorcinol Blue- 3-carboxylic aeid amide. violet.

3 1-pheny1-4-aminopyrazolonem-Toluylenedia- Red- 3-carboxylic acid ethylester. mine. violet.

l-methyl-i-aminopyrazolone- Alpha-naphthol. B Inc-grey.

3-carboxylic acid ethylester.

5 1-n-hexy1-4aminopyrazolone- -do Do.

3-carboxylic acid ethylester.

6 l-(p-sullonamidophenyD-4- ....do Do.

aminopyrazolone-Ziearboxylic acid ethylester.

7 l-n-hexyli-aminopy-razolone- Rcsorcinol Red-violet.

3-carboxylic acid ethylester.

8 l-phenyH-aminopyrazolonem-Phenylenedia- Bluisli B-carboxylic acid ethylester. mine. re

9 l-phenyl-li-methyli-amino- AIDha-nephthOL... Bluegrey.

pyrazolone.

Whereas in the preceding examples the 4-aminopyrazolone hydrochlorides have been used, it should be noted that like results are obtained with the corresponding 4- aminopyrazolones themselves.

We claim as our invention:

improvement which comprises utilizin as said oxidation dyestuff, from 0.1 percent to 5 percent y weight, based on the total aqueous composition, of an oxidation dyestuff combination of (a) a developer component compound having the formula wherein R is a member selected from the group consisting of hydrogen, -COOH, COOR', alkyl having one to 10 carbon atoms, and phenyl; R represents an alkyl having one to four carbon atoms, and R is a member selected from the group consisting of hydrogen, alkyl having one to 10 carbon atoms, phenyl and p-sulfonamidophenyl; and (b) a coupling component compound selected from the group consisting of oand m-phenylenediamine, oand m-amino-phenyl, oand mtoluylenediamine, o-anisidine, 2,4-diaminoanisol, 2,4- diaminophenyl. pyrogalol, resorcinol, pyrocatechol, anaphthol, aminoresorcinol, l.S-dihydroxy-naphthalcne, l,5- aminohydroxynaphthalene and 1,8-amino-hydroxynaphthalene. said developer component compound being present in substantially equimolar amounts with respect to said coupling component compound.

2. The process of claim 1 wherein said oxidative dyestuff combination is present in an amount of from 0.1 percent to 2 percent by weight.

3. In the process of dyeing living human hair which comprises treating the hair at a temperature of from 15 C. to 40 C. for a time sufficient to effect dyeing with an aqueous composition for dyeing human hair comprising an oxidation dyestuff and customary dyestuff adjuvants in the presence ofa chemical oxidizing agent and thereafter rinsing the hair, the improvement which comprises utilizing as said oxidation dyestuff, from 0.] percent to 5 percent by weight, based on the total aqueous composition, of an oxidation dyestuff combination of 4-aminopyrazolone-3-carboxylic acid amide hydrochloride and resorcinol in substantially equimolar amounts.

4. In the process of dyeing living human hair which comprises treating the hair at a temperature of from l5 C. to 40 C. for a time sufficient to effect dyeing with an aqueous composition for dyeing human hair comprising an oxidation dyestuff and customary dyestuff adjuvants in the presence ofa chemical oxidizing agent and thereafter rinsing the hair, the improvement which comprises utilizing as said oxidation dyestuff, from O.l percent to 5 percent by weight, based on the total aqueous composition, of an oxidation dyestuff combination of 3-nicotinoyl-4-amino-pyrazolone hydrochloride and a-naphthol in substantially equimolar amounts.

Claims

2. The process of claim 1 wherein said oxidative dyestuff combination is present in an amount of from 0.1 percent to 2 percent by weight.
3. In the process of dyeing living human hair which comprises treating the hair at a temperature of from 15* C. to 40* C. for a time sufficient to effect dyeing with an aqueous composition for dyeing human hair comprising an oxidation dyestuff and customary dyestuff adjuvants in the presence of a chemical oxidizing agent and thereafter rinsing the hair, the improvement which comprises utilizing as said oxidation dyestuff, from 0.1 percent to 5 percent by weight, based on the total aqueous composition, of an oxidation dyestuff combination of 4-aminopyrazolone-3-carboxylic acid amide hydrochloride and resorcinol in substantially equimolar amounts.
4. In the process of dyeing living human hair which comprises treating the hair at a temperature of from 15* C. to 40* C. for a time sufficient to effect dyeing with an aqueous composition for dyeing human hair comprising an oxidation dyestuff and customary dyestuff adjuvants in the presence of a chemical oxidizing agent and thereafter rinsing the hair, the improvement which comprises utilizing as said oxidation dyestuff, from 0.1 percent to 5 percent by weight, based on the total aqueous composition, of an oxidation dyestuff combination of 3-nicotinoyl-4-amino-pyrazolone hydrochloride and a-naphthol in substantially equimolar amounts.