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Publication numberUS3536436 A
Publication typeGrant
Publication dateOct 27, 1970
Filing dateJul 6, 1966
Priority dateJul 7, 1965
Also published asDE1492175A1
Publication numberUS 3536436 A, US 3536436A, US-A-3536436, US3536436 A, US3536436A
InventorsLange Fritz-Walter
Original AssigneeHans Schwarzkopf
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Hair dyeing composition and method
US 3536436 A
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Description  (OCR text may contain errors)

3,536,436 HAIR DYEING COMPOSITION AND METHOD Fritz-Walter Lange, Gauting, Germany, assignor t Hans Schwarzkopf, Hamburg-Altona, Germany No Drawing. Filed July 6, 1966, Ser. No. 563,087 Claims priority, application Germany, July 7, 1965,

Sch 37,337

Int. Cl. A43d 75/00 US. Cl. 8-102 3 Claims ABSTRACT OF THE DISCLOSURE Oxidation hair dyeing composition Comprises a liquid carrier in which there is distributed an alkali hydroxide or ammonium hydroxide as alkalizing agent and an effective amount of one of the following Z-methyl-hydroxyethyl-amino--aminopyridine, 2 cyclohexylamino-S-aminopyridine, 2 (-methoxypropylamino)-5-aminopyridine, 2-(-dimethylamino-propylamino) 5 aminopyridine, 2- phenylamino-5-aminopyridine or Z-hydroXyethylamino-S- aminopyridine-hydrochloride.

The present invention relates to a composition and method for dyeing hair and, more particularly, the present invention is concerned with imparting to hair a red to brownish-reddish purple, reddish-brown or bluish-reddish brown color or color component which is frequently desirable for modifying other dye components in order to give the hair the desired final color.

For the dyeing of hair, dye intermediates may be used which, upon oxidation, will be developed tc form the effective dye. Usually, oxidation of the dye intermediate is carried out shortly before or during the dyeing of the hair. In many cases, the dye intermediates are aromatic amines which in an alkaline, preferably ammoniacal medium and possibly with the addition of an oxidizing agent will give to the hair the desired color.

It is an object of the present invention to provide a new hair dyeing composition and a method of applying the same, which per se, or in combination with other hair dyeing agents, will permit coloring the hair, particularly in the range of reddish or orange nuances.

Other objects and advantages of the present invention will become apparent from a further reading of the description and of the appended claims.

With the above and other objects in view, the present invention contemplates a composition of matter suitable for use in the oxidative dyeing of hair which comprises a carrier material adapted for application to human hair and having distributed therethrough an alkalizing agent and an effective amount of at least one substance selected from the group consisting of compounds of the general formula:

wherein R is selected from the group consisting of hydrogen, aryl, cyclohexyl, hydroxyalkyl, aminoalkyl, methoxyalkyl and alkoxyalkyl, and R is selected from the group consisting of aryl, cyclohexyl, hydroxyalkyl, aminoalkyl, methoxyalkyl and alkoxyalkyl, and the hydrochlorides thereof.

Preferably, the alkoxyalkyl will be ethoxyalkyl.

Preferred substances according to the present invention are 2-methyl-hydroxyethyl-amino-5-aminopyridine, 2-cyclohexylamino-5-aminopyridine, 2-('y-methoxypropylamino)-5-aminopyridine, 2-(7-dimethylamino-propylamino)- United States Patent 0 3,536,436 Patented Oct. 27, 1970 S-aminopyridine, 2-phenylamino-5-aminopyridine and 2- hydroxyethylamino-5-aminopyridine-hydrochloride.

It is also within the scope of the. present invention and frequently preferred to include at least one oxidation hair dye intermediate in the hair dyeing composition, and preferably a hair dye intermediate selected from the group consisting of p-phenylenediamine, p-toluylenediamine, mphenylenediamine, m-toluylenediamine, p-aminophenol,

p-amino-N-dimethylaniline, 4,4 diamino-diphenylamine,

m-diaminoanisole, m-diethylaminophenol, 2,3-diaminopyridine, 2,6-diaminopyridine, m-aminophenol, o-aminophenol, alpha-naphthol, 2,6-dioxypyridine, resorcinol, catechol, pyrogallol, hydroquinone, phloroglucinol and 2,7-dioxynaphthalene.

According to a preferred method of carrying out the present invention, there is applied to the hair a first sub stance which comprises a carrier material adapted for application to human hair and having distributed therethrough an alkalizing agent and a dye intermediate such as described above; and adapted to be oxidized into a dye, and also a second substance which comprises a carrier material adapted for application tohuman hair and having distributed therethrough the above described composition of matter of the present invention and an oxidizing agent, such as hydrogen peroxide.

Surprisingly, it has been found that the nuances in the hair coloring which are obtained in accordance with the present invention are particularly desirable and advantageous either as coloring of hair per se, or in order to influence the shade or nuance achieved with other hair dyeing compositions.

The hair coloring obtained according to the present invention is very stable and, once it is obtained, will not be changed by subsequent mechanical or chemical treatment of the hair.

Particularly, the hair colorings achieved in accordance with the present invention are wash-fast, light-fast and diffusion-fast and stable at various pH and achieve an evenness of coloration which is far superior to What can be obtained by using the nitro-dyestuffs which conventionally are employed for obtaining red and orange hair colorings.

The compounds of the present invention may either be used singly or in combination with each other or in combination with per se known benzoid oxidation dyestuffs or other pyridine oxidation dyes.

Whereas by using non-substituted 2,5-diamino-pyridine it is only possible to get a single type of red coloration of the hair, the compounds of the present invention permit the dyeing of the hair in great number of new nuances and, as pointed out above, the dyed hair retains its color under substantially all conditions to which the hair conventionally might be exposed.

Without limiting the invention to any specific theoretical explanation, it may be assumed that the influence of constituents at the second amino group of the 2,5-diamino-pyridine is such that the bathochromic efiect rises from orange via red towards bluish violet, in the following sequence of constituents:

CH reddishorange -r -N-GH -CHz-OH, N-CH2'CHz-CH2-N I i 1 1 CH3 N-CHg-CH2-OH, reddish-violet N NHz blue-violet brown 4 ble, they will serve to describe the effect achieved by replacing the 2-hydroxyethylaminopyridine-hydrochloride of Example I with the compounds of the respective examples and by proceeding otherwise in accordance with Ex- H 5 amples I and II.

TABLE I f fi p Structural formula, Hair color obtained 3 2-methyl-hydroxy-ethyl-amino-5-aminopyridine Brownish red-violet.


C211 O H 4 Z-cycloh exylamino-5-aminop yridine D HzN- N N I A 2-(y-meth0Xypropy1-amin0)-5-aminopyridine Reddish brown.


CHz.CH2.CHz.O CH3 6 2-(y-dimethylamino-propyl-amino) -5-aminopyridinc.. Bluish red-brown.

/H 'N CH3 N CH2.CH2.CHg.N

7 2-pl1eny1amino-5-aminopyric1ine Brownish red-violet.

The methods of producing the substituted 2,5-diaminopyridines of the present invention are known per se and thus need not be described in detail herein.

The, per se, colorless pyridine derivatives may be developed on the hair to dyes, either by the influence of the oxygen of the air without application of an oxidizing agent such as hydrogen peroxide or, if stronger coloring is desired, the developing of the dye may be carried out by application of hydrogen peroxide or the like to the hair.

The following examples are given as illustrative only, without, however, limiting the invention to the specific details of the examples.

The well-known conventional additives such as thickening agents, emulsifiers and the like have been omitted from the examples in order to stress the inventive features.

EXAMPLE I 2.2 grams of 2 hydroxyethylamino-S-aminopyridinehydrochloride are dissolved in 4.0 grams aqueous ammonia and 94.0 grams water.

Upon applying the thus formed solution to blond colored hair and allowing contact between the solution and the hair for about minutes, followed by rinsing and drying, it will be found that the hair has obtained a beautiful purple-red color tone of high wet fastness.

EXAMPLE II 70 grams of the solution obtained according to Example I are mixed with 30 ml. 6% hydrogen peroxide and the mixture is applied to the hair. After allowing contact between the mixture and the hair for 20 minutes, at room or body temperature, followed by rinsing, a strong and highly stable purple-red hair color is obtained.

EXAMPLES IIIVII Examples III-VII are summarized in the following ta- EXAMPLE VIII 1.0 gram p-toluylenediamine sulfate and 1.0 gram 2- methyl-hydroxyethylamino-5-aminopyridine are dissolved in 94.0 grams water, 4.0 grams of 25% aqueous ammonia solution are added. Upon applying this solution as described in Example II, a light chestnut brown coloration of the hair will be achieved.

EXAMPLE IX 2.0 grams 2-hydroxyethylamino-5-aminopyridine-hydrochloride and 0.1 gram 2,6-diaminopyridine are dissolved in 93.9 grams water and 4.0 grams 25% aqueous ammonia are added thereto.

Upon applying this solution in the manner described in Example I, the hair will be colored in a very natural looking ash-blond color. In this case the 2,6-diaminopyridine serves as a modifier.

What is claimed as new and desired to be secured by Letters Patent is:

1. A composition of matter suitable for use in the oxidative dyeing of hair which comprises a liquid carrier material adapted for application to human hair and having distributed therethrough an alkalizing agent selected from the group consisting of alkali hydroxides and ammonium hydroxide and an effective amount of a member selected from the group consisting of 2-methyl-hydroxyethyl-amino-S-aminopyridine, 2-cyclohexylamino-S-aminopyridine,

2-('y methoxypropylamino) 5 aminopyridine, Z-(y-dimethylamino propylamino) S-aminopyridine, 2-phenylamino-S-aminopyridine and 2-hydroxyethylamino5-aminopyridine-hydrochloride.

2. A composition of matter as defined in claim 1 and additionally including at least one other oxidation hair dye intermediate selected from the group consisting of pphenylenediamine, p toluylenediamine, m phenylenediamine, m-toluylenediamine, parninophenol, p-amino-N- dimethylaniline, 4,4-diamino-diphenylamine, m-diaminoanisole, m-diethylaminophenol, 2,3-diaminopyridine, 2,6- diaminopyridine, m-aminophenol, o-aminophenol, alphanaphthol, 2,6-dioxypyridine, resorcinol, catechol, pyrogal- 101, hydroquinone, phloroglucinol and 2,7-dioXynapl1 thaline.

3. A method of dyeing hair comprising the step of applying to the hair a liquid carrier material adapted for application to human hair and having distributed therethrough an alkalizing agent selected from the group consisting of alkali hydroxides and ammonium hydroxide, an effective amount of a member selected from the group consisting of Z-methyl-hydroxyethyl-amino-5-aminopyridine, Z-cyclo-hexylarnino-5-aminopyridine, 2-('y-methoxypropylamino)-5-aminopyridine, 2-( -dimethylamino-propylamino)-5-aminopyridine, 2-phenylamino-S-aminopyridine and 2 hydroxyethylamino S-aminopyridine-hydrochloride, and another oxidation hair dyeing intermediate selected from the group consisting of p-phenylenediamine, p-toluylenediamine, m-phenylenediamine, m-toluylenediamine, p-aminophenol, p-amino-N-dimethylaniline,v 4,4- diamino-diphenylamino, m-diaminoanisole, m-diethylaminophenol, 2,3-diaminopyridine, 2,6-diaminopyridine, maminophenol, o-aminophenol, alpha-naphthol, 2,6- dioxypyridine, resorcinol, catechol, pyrogallol, hydroquinone, phloroglucinol and 2,7-dioxynaphthaline.

References Cited UNITED STATES PATENTS 3,082,200 3/1963 Moore et a1 260-296 X ALBERT T. MEYERS, Primary Examiner D. M. STEPHENS, Assistant "Examiner

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3082200 *Sep 30, 1958Mar 19, 1963Gen Aniline & Film CorpAminopyridinediazonium salts
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3838965 *Jul 7, 1971Oct 1, 1974OrealDyeing keratinous fibers with azaindoanilines
US4003699 *Nov 22, 1974Jan 18, 1977Henkel & Cie G.M.B.H.Oxidation hair dyes based upon tetraaminopyrimidine developers
US4046503 *Apr 5, 1976Sep 6, 1977Henkel & Cie GmbhDeveloper-coupler hair dyes based on alkoxy-triamino-pyrimidines
US4169703 *Aug 3, 1978Oct 2, 1979Syntex (U.S.A.) Inc.A mixture of 1-naphthol, p-aminophenol, a modifier, and a coupler
US4172703 *Aug 3, 1978Oct 30, 1979Syntex (Usa) Inc.1,5-dihydroxynaphthalene, m-aminophenol, p-aminodiphenylamine, modifier, coupler, and base
US4661115 *Feb 6, 1986Apr 28, 1987Ruetgerswerke AktiengesellschaftHair dyeing agents
US5283338 *Apr 1, 1992Feb 1, 1994Bayer AktiengesellschaftReacting 2-amino-5-methylpyridine with nitrosyl chloride in a hydrogen chloride saturated aqueous solution and gas phase
US6730789Oct 18, 2000May 4, 2004L'oreal S.A.Radiation resistance, weatherproof, washfastness, colorfastness; hair dyes
US7300472Jun 19, 2006Nov 27, 2007Henkel Kommanditgesellschaft Auf AktienFor freshening up the color or nuancing fibers containing keratin which have already been colored
US7326259Jun 22, 2005Feb 5, 2008L'oreal S.A.Use of polycationic compounds in the dyeing of keratinous fibres
USRE30199 *Oct 23, 1978Jan 29, 1980Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa)Oxidation hair dyes based upon tetraaminopyrimidine developers
WO2001035917A1 *Oct 18, 2000May 25, 2001Veronique BiraultCompositions for dyeing keratinous fibres containing 3-amino pyrazolo-[1,5-a]-pyridines, dyeing method, novel 3-amino pyrazolo-[1,5-a]-pyridines
U.S. Classification8/409
International ClassificationA61K8/41, A61K8/30, A61K8/49, A61Q5/10
Cooperative ClassificationA61K8/4926, A61Q5/10, A61K8/413
European ClassificationA61Q5/10, A61K8/49C4, A61K8/41F