US3853464A - Human hair dyeing compositions containing diphenylamines - Google Patents

Abstract

Hair dye and hair-setting lotion compositions contain a diphenylamine of the formula

WHEREIN Z represents amino, acylamino or hydroxy, R1, R2 and R3 represent hydrogen or lower alkyl, R4 represents hydrogen, lower alkyl or together with R1 and the nitrogen atom to which R4 is attached form a dihydro-oxazine or pyrroline heterocycle and R5 represents hydrogen, lower alkyl or together with R2 and the nitrogen atom to which R5 is attached form a dihydro-oxazine or pyrroline heterocycle and the acid salts of said diphenylamine.

Description

United States Patent [191 Kalopissis et a].

[451 Dec. 10, 1974 1 HUMAN HAIR DYEING COMPOSITIONS CONTAINING DIPHENYLAMINES [75] Inventors: Gregoire Kalopissis, Paris; Andree Bugaut, Boulogne-sur-Seine; Francoise Estradier, Paris, all of France [73] Assignee: Societe Anonyme dite: LOreal, Paris, France [22] Filed: July 11, 1972 [21] Appl. No.: 270,633

Related US. Application Data [63] Continuation-impart of Ser. No. 61,833, Aug. 6,

1970, Pat. No. 3,792,090.

[30] Foreign Application Priority Data Aug. 11, 1969 Luxembourg 59265 [52] US. Cl 8/11, 8/10.1, 8/102, 8/32, 260/244, 260/247.5, 260/247.7,

[51] Int. Cl D061) 1/32 [58] Field of Search 8/10.1, 10.2, 11, 32; 260/571, 244 R, 247.5 B, 326.5 L, 247.7,

[56] References Cited UNITED STATES PATENTS 1/1964 Lecher et al 10/1965 Charle et a1. 260/571 Klinge et a1 3,253,980 5/1966 v 8/10.2 X 3,274,249 9/1966 Brunner et a1... 8/10.2 X

3,516,778 6/1970 Brunner 8/10 2 3,561,913 2/1971 Munakata et al... 8/32 3,697,644 10/1972 Laiderman 8/10.1 X

Primary ExaminerThomas J. Herbert, Jr. Assistant ExaminerBruce H. Hess Attorney, Agent, or FirmCushman, Darby & Cushman [57] ABSTRACT Hair dye and hair-setting lotion compositions contain a diphenylamine of the formula Ru R Z N NH Q OH 15 Claims, No Drawings HUMAN HAIR DYEING COMPOSITIONS CONTAINING DIPHENYLAMINES This application is a continuation-in-part of our application Ser. No. 61,833, filed Aug. 6, 1970, now US. Pat. No. 3,792,090.

This invention relates to novel leuco derivatives of indoanilines, a process for preparing the same and to novel cosmetic compositions containing these leuco derivatives for dyeing keratinic fibers such as human hair. The leuco derivatives of indoanilines of this invention are colorless compounds which, when applied in an aqueous solution to the fibers to be dyed, oxidize in the air or in the presence of another oxidizing agent, thereby giving the corresponding indoanilines, which on the other hand are colored compounds directly responsible for dyeing of the fiber. The dyeings thus obtained present qualities of fastness and intensity of dyeing superior to those dyeings obtained by direct application of indoanilines, because of the better solubility of the leucoderivatives of these compounds.

More specifically the present invention relates to novel dyeing compositions for keratinous fibers, in particular for human hair, characterized in that they contain in an aqueous or dilute alcohol solution at least one leucoderivative, i.e., a diphenylamine of the formula wherein Z represents a member selected from the group consisting of amino, acylamino and hydroxy', R R and R each independently represent a member selected from the group consisting of hydrogen and lower alkyl containing from 1 to 4 carbon atoms; R, represents a member selected from the group consisting of the hydrogen, lower alkyl containing l-4 carbon atoms.

and together with R1 and the nitrogen atom to which R; is attached form a heterocycle selected from the group consisting of dihydro-oxazine and pyrroline; and R represents a member selected from the group consisting of hydrogen, lower alkyl containing 1-4 carbon atoms and together with R and the nitrogen atom to which R, is attached form a heterocycle selected from the group consisting of dihydro-oxazine and pyrroline; or a salt formed by this leucoderivative with an organic or inorganic acid, particularly. oxalic acid, hydrochloric acid and tartaric acid.

The dyeing compositions according to the invention can contain only the compounds of formula (I), in which case they make it possible to obtain an extremely rich range of shades including violets, blues, greens, reds and pinks, and a great variety of more or less ash, golden or copper blonds. These colorings can develop on the fibers under the sole action of the oxygen in the air, or again under the action of another oxidizing agent such as hydrogen peroxide, the latter being able to be incorporated in the compositions of this invention at the time of their application to the hair.

Because of their affinity for keratinous fibers and the power of the colorings to which they give rise, the compounds of formula (I) can be used in the compositions according to the invention in extremely slight concentrations. These concentrations can vary between 0.002

and 2% by weight and are generally between 0.005 and 0.5% by weight.

The pH of the dye compositions according to the invention can vary between 4 and l 1. To regulate this pH at the desired value, it is possible to use as alkalizing agents, ammonia, mono-, dior triethanolamine and as acidifying agents, phosphoric acid, acetic acid or lactic acid.

The dye compositions according to the invention can be in aqueous solutions to which, if desired, there can be added low molecular weight alcohols such as ethanol or isopropanol, in amounts of 20 to by weight, or again glycols such as propyleneglycol or butylglycol, in amounts of l to 6% by weight. These alcohols and glycols facilitate the use of the diphenylamines of formula (I).

The dye compositions according to the invention can also contain other known leucoderivatives of indoanilines, indamines or indophenols, or again oxidation dyes such as orthoor paraphenylenediamines or orthoor para-aminophenols. They can also contain direct dyessuch as nitro dyes of the benzene series, azo dyes, anthraquinone dyes, oxazines or azines.

Further the compositions according to the invention can contain various ingredients usually used in capillary cosmetics, such as, wetting agents, dispersing agents, penetrating agents, thickeners or perfumes. They can, on the other hand, be in the form of creams or gels, or packaged under pressure in aerosol bombs or containers, together with a. conventional aerosol propellant such as dichlorodifluoromethane, trichloromonofluoromethane and their mixtures. Obviously other conventional aerosol propellants can be used.

Dyeing of keratinous fibers, in particular human hair, with the dye compositions according to the invention, can be performed in the usual way, by application of the composition to the fibers to be dyed, the composition being left in contact with the fibers for a time varying from 10 to 30 minutes. Following this application, the fibers can be rinsed and if desired washed. Thereafter, the thus treated fibers are dried. If desired, there can be added to the composition, before its application, either 20 to 60 percent by weight of the composition of hydrogen peroxide at 20 volumes or equivalent quantities of another oxidizing agent, especially if it is desired to achieve a simultaneous bleaching of the fiber.

In another embodiment of the present invention, the novel diphenylamines can also be employed in the production of capillary hair-setting lotions. These lotions comprise an aqueous alcohol solution, at least one diphenylamine of Formula l or a salt thereof and at least one cosmetic resin. The amount of diphenylamine or its salt' present in the hair-setting lotion according to this invention can be extremely slight. Such an amount generally varies between 0.002 and 1% by weight and preferably between 0.002 and 0.5% by weight, of the total hair-setting lotion composition, the pH of which generally lies between 5 and 8.

Representative cosmetic resins that can be employed in the hair-setting lotions of the present invention include, for instance, polyvinyl pyrrolidone having a molecular weight of 40,000-400,000, copolymer of crotonic acid and vinyl acetate, said copolymer having a molecular weight ranging from about 10,000 to 70,000, copolymer of vinyl pyrrolidone and vinyl acetate wherein the ratio of PVP to VA ranges between 5070:50-30, said copolymer having a molecular weight ranging from about 30,000 to 200,000 and maleic anhydride-butylvinyl ether copolymers, a l solution of which in methylethyl ketone has a viscosity of O. l-3.5 cps at 25C. These resins are used in a proportion of l to 3% by weight of the hair-setting lotion composition.

The alcohols suitable for the preparation of the hairsetting lotions according to the invention are low molecular weight alkanols, such as ethanol or isopropanol which are present in amounts of about 20 to 70% by weight of the total hair-setting lotion composition.

The hair-setting lotions of the present invention impart to the hair a great variety of hues located in the ash blond, golden blond or copper blond tones, and which can even be shaded violet, mauve, blue, green or pink. The colorings obtained are characterized by a pearly appearance and a great richness of glints and by their regularity, even in the case of application of irregularly bleached hair.

The hair-setting lotions according to the invention are usually employed by application to wet hair, previously washed and rinsed, followed by rolling the hair up on curlers and drying the hair.

Certain of the compounds of formula (I) are novel, and these novel compounds are also a part of the present invention. Thus, the present invention also has as an object. the provision of compounds of the formula wherein Z represents a member selected from the group consisting of amino, acylamino and hydroxy; R R and R each independently are selected from the group consisting of hydrogen and lower alkyl contain ing 1-4 carbon atoms; R, represents a member selected from the group consisting of hydrogen, lower alkyl containing 1-4 carbon atoms and together with R and the nitrogen atom to which R, is attached form a heterocycle selected from the group consisting of dihydrooxazine and pyrroline; and R represents a member selected from the group consisting of hydrogen, lower alkyl containing 1-4 carbon atoms and together with R, and the nitrogen atom to which R is attached form a heterocycle selected from the group consisting of dihydro-oxazine and pyrroline; with the proviso that at least two of R R R;,, R, and R are other than hydrogen when 2 is other than acylamino; and a salt formed by this compound with an organic or inorganic acid, particularly, oxalic acid. hydrochloric acid and tartaric acid.

The compounds represented by Formula I, above can be prepared by reducing an indoaniline having the formula wherein R, to R and Z have the meanings given above, in an aqueous or dilute aqueous alcohol medium having an alkaline pH in the range of about 9 to 12 and in the presence of effective amounts of a reducing agent selected from the group consisting of sodium hydrosulfite or an alkaline sulfide such as ammonium sulfide. The amount of reducing agent can vary but generally it will be present in amounts such that the mole ratio of indoaniline being reduced to reducing agent ranges between l:l.5 to I13. This reducing reaction is generally carried out at ambient pressure and at a temperature ranging from about 25 to 50C.

Alternatively the reduction of the above indoaniline can be carried out in a solvent selected from the group consisting of ethanol and ethyl acetate by catalytic hydrogenation at ordinary pressure and a temperature of 20 to 50C in the presence of catalytic amounts of palladium on a substrate selected from the group consisting of barium sulfate and carbon. Generally the amounts of the catalyst, i.e. the palladium on said substrate, ranges between about 10 to 25 percent by weight of indoaniline being reduced.

The following examples are intended to illustrate the present invention. Unless otherwise specified, all parts and percentages are by weight and all temperatures are expressed in degrees centrigrade.

EXAMPLE l 4-hydroxy 2-amino 4-N,N-dimethylamino diphenylamine is prepared according to the following reaction:

0.0028 mol (0.550 g) of N-[(2'-amino 4'- dimethylamino) phenyl] benzoquinoneimine is dissolved in 200 cc of absolute ethyl alcohol. To the resulting solution, there is added mg. of palladium on carbon 10% Pd on C ofEngelhard Industries) as the catalyst and the product is reduced in the usual way by hydrogen at normal pressure and a temperature of 30C. After 10 minutes, the reaction medium is colorless. The solution is then filtered to recover the catalyst and the thus filtered solution is concentrated under vacuum and nitrogen up to 50 cc. Then 50 cc of water, saturated with carbon dioxide gas, is added and the above diphenylamine which has precipitated, is filtered therefrom. After drying under vacuum, the above compound exhibits a melting point of 197C.

Molecular weight calculated for C H N O 243.

Molecular weight found by potentiometric determination in acetic acid by perchloric acid 245 Analysis Calculated for Found CHHHNJO C7r 69.ll 69.02 69.23

hairmen wt Pd on a" EXAMPLE 2 Molecular weight calculated for C H N O 2 HCl,

Molecular weight found by potentiometric determination in water with 0.] N soda solution 332.

4-hydroxy 3', 5'-dimethyl 2', 4'-diamino diphenyl amine and its dihydrochloride, monohydrate are prepared according to the following reaction:

CH N11 S O Na EH 13 M N 0 3 H 0 I NEG W 3 CH3 NHQ I Q NH OH To 150 cc of a 1.25 N soda solution containing 0.05 20 EXAMPLE 3 mole 14 g) of sodium hydrosulfite of 75% purity, there N-[7-(6'-amino l'-oxa 4'-aza l',2',3',4'-tetrah is gradually added, with good stirring, while keeping dro)-naphthyl] 4-amin0 phenol is prepared in accorthe reaction mixture in the vicinity of 0.02 mole dance with the following reaction:

III GQ NH H 2 s o ua 21-1 0 2 NaOH 0 (5.90 g) of N-([2',4'-diamino 3',5'-dimethyl) phenyl] 0.05 mole (14 g) of sodium hydrosulfite of 75% pubenzoquinoneimine trihydrate partially dissolved in 30 4O rity is dissolved in 160 cc of 1.25 N soda solution. cc of 95 ethanol. When the addition is completed, the There is then adde gr ually, with g ig ring, hile reaction mixture is colorless. It is filtered and acetic keeping the temperature n h i ini y of acid is added to pH 7 to precipitate the above diphenylmole (5.82 g) of N-[7-(6-amino l'-oxa 4-aza l',2',3- amine. After filtering, washing with water and drying ',4-tetrahydro)-naphthyl] benzoquioneimine hydrounder vacuum at 80 for 5 hours, the above diphenylchloride in 30 cc of ethanol and 10 cc of water. When amine exhibits a melting point of 220. the addition is completed, the reaction mixture is al- Molecular weight calculated for 'C l-l N O 243. lowed be become colorless. It is cooled, neutralized Molecular weight found by potentiometric determiwith acetic acid and the above compound, which has nation in acetic acid by perchloric acid =24l. precipitated, is filtered therefrom. After washing with water, saturated with carbon dioxide gas. followed by a recrystallization in a dimethylformamidewater mixture and drying under vacuum for 5 hours at 80, the above compound exhibits a melting point of 215C.

Analysis caiculated for Fmmd Molecular weight calculated for C H N O .0.5 H O u n n 266 a; 2 4 3-8; 3-52 Molecular weight found by potentiometric determi- N% 17.27 17.05 17.14 mum in acetic acid by perchloric acid =262.

0 Analysis Calculated for Found c H N o 0.5 H 0 1 I C% 63.15 63.53 63.44 1 g of the above diphenylamine thus obtained is dlS- H% 602 6.05 6.07 N% 15.79 15.83 l5.63

solved in 10 cc of 2 N hydrochloric solution. The solution is cooled to l0, then 10 cc of hydrochloric acid at 2213 are added. The 4-hydroxy 3,5-dimethyl 2',4'- es EXAMPLE 4 diamino diphenylamine dihydrochloride, monohydrate -[7'-(6'- yd y crystallizes. After filtering and drying under vacuum, tetrahydro) -naphthyl] 4-amino phenol monohydrate is the product melts with decomposition at 209. prepared in accordance with the following reaction:

M S Na -2 H2O N N O H2O To 75 cc of 1.25 N soda solution, in which there has colorless, it is cooled to 0, then neutralized with acetic been dissolved 0.040 mole (10.9 g) sodium hydrosulacid to precipitate the above compound. This comfite of 75% purity, there is added gradually, with good pound is then filtered under nitrogen, washed with stirring, while keeping the reaction mixture in the vicinwater saturated with carbon dioxide gas and dried for ity of 00 mole g) of N-[7-(6'-hydroxy l- 3 days under vacuum on phosphoric anhydride. It melts oxa 4-aza l,2',3,4-tetrahydro)-naphthyl] bent 217, zoquinoneimine monohydrate in suspension in 15 cc in M l l i h l l d f C I-N 0 257,

ethanol. When the reaction mixture is colorless, it is neutralized with carbonic anhydride to precipitate the M l l i h f d b potentiometric d iabove compound. After filtering and drying under vacnation i g i id b hl i i 25 uum on phosphoric anhydride for 3 days, the above compound exhibits a melting point of 329C.

Analysis Calculated for Found n m a z' 07 65.37 65.02 65.]8 H(/( 5.83 5.87 5.92 N71 l6.34 l6.45 16.37 Analysis Calculated for Found H20 60 93 61 03 C? 60.86 i 534 594 2.5 g of the thus obtained diphenylamine are intro- 1014 10-18 duced in 5 cc of hydrochloric acid (d l.19) at -l0. After 5 minutes of stirring and after washing with 2 cc of iced hydrochloric acid (d= 1.19) and drying under vacuum on potash, 3 g of 4-hydroxy 2'-acetylamino 4'- 40 amino diphenylamine dihydrochloride are recovered, EXAMPLE 5 the said dihydrochloride melting with decomposition at 4-hydroxy 2-acetylamino 4'-amino diphenylamine 263. and its dihydrochloride are prepared in accordance Molecular weight calculated for C H N O 2 HC] with the following reaction: 330

NHCOCH r s OuNa H O H N N O HC]. 2

2 ""'1i'a'oa 9 NHCOCH 3 -n 1-I Nfl oa t In 100 cc ofa normal soda solution, there is dissolved Molecular weight found by potentiometric determi- 0.028 mole (8.1 g) of sodium hydrosulfite of 75% punation in water with N soda Solution rity. To this solution, there is gradually added, while keeping the temperature in the vicinity of 30, 0.01 EXAMPLE 6 mole (2.91 g) of N-[(2'-acetylamino 4-amino)phenyl] 4-hydroxy 2-acetylamino 4'-N,N-dimethylamino dibenzoquinoneimine hydrochloride in 20 cc of ethyl alphenylamine is prepared in accordance with the followcohol and 5 cc of water. When the reaction mixture is ing reaction:

NHCOCH3 H c w 3 I 0.025 mole (7 g) of sodium hydrosulfite of 75% purity Analysis g f g g g H O Fmmd is dissolved in 80 cc of 0.1 N soda solution. To this solu- 3 g M44 6416 tion there is gradually added, with good stirring, while H% 3 6.44 6.52

keeping the reaction mixture in the vicinity of 25, 0.01 mole (3.37 g) of N-[(2'-acetylamino 4'- dimethylamino) phenyl] benzoquinoneimine monohy- EXAMPLE 3 drochloride monohydrate in cc of 50% dilute ethyl 20 alcohol solution. When the reaction mixture has become colorless, it is cooled to 0 then neutralized with 2 l dlphenylamme descnbed m acetic acid to precipitate the above compound which 0.009 mole (2.65 g) of N [(2,,4, diamin0 15 then filtered under nitrogen, washed with water saturated with carbonic gas and dried under vacuum on phosphoric anhydride. It melts at 204.

Molecular weight calculated for C H N O 285 Molecular weight found by potentiometric determination in acetic acid by perchloric acid 282 Alternative method for preparing the 4-hydroxy 3',

dimethyl) phenyl] benzoquinoneimine trihydrate is dissolved in 120 cc of water and 250 cc of 95 ethanol. To this solution there are added, drop by drop, at 25, with stirring, 10 cc of an ammonia solution at 16 Be, previously saturated with hydrogen sulphide. The resulting solution is concentrated under nitrogen to a volume of 150 cc, then cooled to 0. The above compound is then Analysis Calculated for Found filtered from the reaction mass, washed with water and cmHmNao2 then recrystallized in a dimethylformamide-water mixg; 62.22 22% 2-23 ture. After drying under vacuum at 80 for 5 hours, the 14173 4172 14:64 above compound exhibits a melting point of 220 (no lowering of the melting point is observed when used in mixture with the product prepared in Example 2).

EXAMPLE 7 4-hydroxy 2'-acetylamino 4'-amino 5'-methyl diphenylamine is prepared in accordance with the following EXAMPLE 9 reaction: A hair dye composition is prepared as follows:

NHCOCH s o tta 2 H o H N N O H01 2 2 2 I NaOH 5 H FHCOCH 2 NH-@ OH o. 5 H 0 In 100 cc of normal soda solution, there is dissolved gf gif 1 gg 0.028 mole (8.1 g) of sodium hydrosulfite of 75% pu- ,.f,;, '"fl 100 g rity. To this solution there is gradually added, while nia at 22Be.q- -p. pH 9.5 keeping the temperature in the vicinity of 30, 0.01

mole (3.05 g) of N-[(2'-acetylamino 4'-amino 5- This dye composition when applied for 20'minutes at methyl) phenyl] benzoquinoneimine hydrochloride in ambient temperature to 95% naturally white hair, im- 20 cc of ethyl alcohol and 5 cc of water. When the reparts thereto after rinsing and shampooing, an intense action mixture is colorless, it is cooled to 0, then neu- Parme Shadetralized with acetic acid to precipitate the above compound which is then filtered under nitrogen, washed EXAMPLE 10 with carbon dioxide gas and dried under vacuum of P 0 it melts at 187.

Molecular weight calculated for c,,H,,N,0 0.5

H20: 280 Compound of Example I 0.025 g Molecular weight found by potentiometric determi- 96 20 g Water. q.s.p. 100 nation in acetic acid by perchloric acid 277 Ammonia at 22Be. q.s.p. pH 10 The following hair dye composition is prepared:

This dye composition when applied for minutes at ambient temperature to 95% naturally white hair, imparts thereto, after rinsing and shampooing, a pearly pink beige shade.

EXAMPLE ll The following hair dye composition is prepared:

Compound of Example l 0.05 g 20 volume hydrogen peroxide 50 g Water. q.s.p. 100 g Ammonia at 22Be, q.s.p. pH ID This dye composition when applied for minutes at ambient temperature to 95% naturally white hair, imparts thereto after rinsing and shampooing, an intense violet shade.

EXAMPLE 12 The following hair-setting lotion composition is prepared: 20

Compound of Example I 0.05 g

Vinyl aeetate-erotonic acid polymer (90% vinyl acetate, 10% erotonic acid, molecular weight 45,000 to 50.000) 1 g 2 Ethyl alcohol, 96 titer g Water, q.s.p. 100 g Triethanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair, imparts thereto a light pearly parme shade.

EXAMPLE 13 The following hair dye composition is prepared:

' Compound of Example 2 0.3 g Ethyl alcohol, 96 titer 30 g Water, q.s.p. l00 g V1" lactic acid, q.s.p. pH 4 This hair dye composition when applied for 20 minutes at ambient temperature to bleached hair, imparts thereto after rinsing and shampooing, a very luminous golden pink shade.

EXAMPLE 14 The following hair dye composition is prepared:

Compound of Example 2 0.2 g

Ethyl alcohol, 96 titer 25 g Water, q.s.p. 100 g Ammonia at 22Be, q.s.p. pH 9 This hair dye composition when applied for 20 minutes at ambient temperature to 95% naturally white hair, imparts thereto after rinsing and shampooing, an intense cyclamen pink shade. 5

EXAMPLE 15 The following hair dye composition is prepared:

Compound of Example 2 0.005 g Ethyl alcohol, 96 titer 20 g Water, q.s.p. 100 g EXAMPLE 16 The following hair-setting lotion composition is prepared:

Compound of Example 2 0.] g Vinyl acetate-crotonic acid copolymer vinyl acetate, I07! crotonic acid, molecular weight 45,000 to 50,000) 2 g Ethyl alcohol, 96 titer 50 g Water, q.s.p. l00 g Ammonia at 22Be, q.s.p. pH 7.5

This hair-setting lotion when applied to bleached hair, imparts thereto a golden pink shade.

EXAMPLE 17 The following hair dye composition is prepared:

Compound of Example 3 0.25 g Ethyl alcohol, 96 titer 40 g Water, q.s.p. 100 g Ammonia at 22Be, q.s.p. pH It) This hair dye composition when applied for l0 minutes at ambient temperature to naturally white hair, imparts thereto, after rinsing and shampooing, a very luminous pearly pink beige shade.

EXAMPLE 18 The following hair-setting lotion composition is prepared:

Compound of Example 3 0.05 g Vinyl acetate-crotonic acid copolymer (90% vinyl acetate, 10% crotonic acid, molecular weight 45,000 to 50,000) 2 g Ethyl alcohol, 96 titer 50 g Water, q.s.p. g

Ammonia at 22Be, q.s.p. pH 8.5

This hair-setting lotion when applied to bleached hair, imparts thereto an intense golden shade with pink glints,

EXAMPLE 1) The following hair-setting lotion composition is prepared:

Compound of Example 4 0.25 g Vinyl acetate-crotonic acid copolymer (90% vinyl acetate, l0% crotonic acid, molecular weight 45,000 to 50,000) 2 g Ethyl alcohol, 96 titer 50 g Water, q.s.p. l00 g Triethanolamine, q.s.p. pH 7.5

This hair-setting lotion when applied to bleached hair, imparts thereto a golden green shade.

EXAMPLE 20 The following hair-setting lotion composition is prepared:

Compound of Example 4 0.08 g N-[(4-hydroxy 3',5'-dimethyl) phenyl] 3,5

dimethyl benzoquinoneimine 0.04 g Vinyl acetate-crotonic acid copolymer (90% vinyl acetate, 10% crotonie acid, molecular weight 45,000 to 50.000) 2 g Ethyl alcohol, 96 liter 50 g Water. q.s.p. l00 g Triethanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair, imparts thereto an extremely luminous golden blond shade.

EXAMPLE 21 The following hair dye composition is prepared:

Compound of Example 3 0.05 g Z-amino 4-methoxy phenol hydrochloride 0.166 g lsopropyl alcohol, 96 titer 30 g Water, q.s.p. 100 g Ammonia at 22Be, q.s.p. pH 8.5

This hair dye composition when applied for minutes at ambient temperature to 95% naturally white hair, imparts thereto, after rinsing and shampooing, a copper blond shade.

EXAMPLE 22 The following hair dye composition is prepared:

Compound of Example 3 g 2,6-diamino 4-N.N-diethylamino-phenol trihydrochloride 0.03 g lsopropyl alcohol. 96 titer g Water. q.s.p. 100 g Ammonia at 22Be. q.s.p. pH 9.5

This hair dye composition when applied for 20 minutes at ambient temperature to 95% naturally white hair, imparts thereto, after rinsing and shampooing, a

light bronze shade.

EXAMPLE 23 The following hair dye composition is prepared:

Compound of Example 2 0.025 g Nitrometaphenylenediamine 0.075 g Ethyl alcohol, 96 titer g Water, q.s.p. 100 g Ammonia at 22Be, q.s.p. pH 10 This hair dye composition when applied for 20 minutes at ambient temperature to 95% naturally white hair, imparts thereto, after rinsing and shampooing, a very luminous intense golden shade.

EXAMPLE 24 The following hair dye composition is prepared:

Compound of Example 5 0.4 g Butylglycol 5 g Lauryl alcohol oxyethylenated with 10.5

moles of ethylene oxide 5 g Water, q.s.p. 100 g The final pH of this solution is 5.

This hair dye composition when applied for 20 minutes at ambient temperature to 95% naturally white hair, imparts thereto, after rinsing and shampooing, a silvery eucalyptus green shade.

EXAMPLE 25 The following hair dye composition is prepared:

Compound of Example 6 0.1 g Butylglycol 5 g Lauryl alcohol oxyethylenated with 10.5

moles of ethylene oxide 5 g Ammonia at 22Be, q.s.p. pH 6 Water, q.s,p. 100 g This hair dye composition when applied for 20 minutes at ambient temperature to bleached hair, imparts thereto, after rinsing and shampooing, a pearly pale green blue shade.

EXAMPLE 26 The following hair dye composition is prepared:

Compound of Example 7 0,2 g Ethyl alcohol, 96 titer 25 Water, q.s.p. 100 g Ammonia at 22Be, q.s.p. pH 8 This hair dye composition when applied for 20 minutes at ambient temperature to naturally white hair, imparts thereto, after rinsing and shampooing, a silvery pale green shade.

EXAMPLE 27 The following hair-setting lotion composition is prepared:

Compound of Example 5 I 0.2 g Vinyl acetate-crotonic acid copolymer (90% vinyl acetate, 10% crotonic acid, molecular weight 45,000 m 50,000) r 2 g Ethyl alcohol, 96 titer 50 g Water, q.s.p. g

100 Triethanolamine, q.s.p. pH 7 This hair-setting lotion when applied to bleached hair, imparts thereto a very intense turquoise blue shade.

EXAMPLE 28 The following hair-setting lotion composition is prepared:

Compound of Example 6 0.3 Vinyl acetate-crotonic acid copolymer (90% g vinyl acetate, 10% crotonic acid, molecular weight 45,000 to 50,000) 2 g Ethyl alcohol, 96 titer 50 g Water, q.s.p. 100 g Ammonia at 22Be, q.s.p. pH 6 This hair-setting lotion when applied to bleached hair, imparts thereto a golden pale green shade.

EXAMPLE 29 The following hair-setting lotion composition solution is prepared:

Compound of Example 4 0.15 g 4-hydroxy-2,4'diamino-5 methyl diphenylamine hydrochloride 0.06 g Vinyl acetate-crotonic acid copolymer (90% vinyl acetate, 10% crotonic acid, molecular weight 45,000 to 50,000) 2 g Ethyl alcohol, 96 titer 50 g Water, q.s.p. 100 g Ammonia at 22Be, q.s.p. pH 8.5

u R1 2 I \N NH OH wherein Z represents a member selected from the group consisting of amino and acylamino R R and R each independently represent a member selected from the group consisting of hydrogen and lower alkyl containing l-4 carbon atoms; R represents a member selected from the group consisting of hydrogen, lower alkyl containing l-4 carbon atoms and together with R, and the nitrogen atom to which R, is attached form a heterocycle selected from the group consisting of dihydro-oxazine and pyrroline; and R represents a member selected from the group consisting of hydrogen, lower alkyl containing l-4 carbon atoms and together with R and the nitrogen atom to which R is attached from a heterocycle selected from the group consisting of dihydro-oxazine and pyrroline; and (b) an acid salt of said diphenylamine.

2. The composition of claim 1, wherein said diphenylamine is the salt of an acid selected from the group consisting of oxalic acid, hydrochloric acid and tartaric acid.

3. The composition of claim 1 which also includes another dye selected from the group consisting of another oxidation dye and a direct dye.

4. The composition of claim 3, wherein said another dye is selected from the group consisting of orthoand paraphenylenediamine, orthoand paraaminophenol, and other indoaniline, indamine and indophenol leucoderivatives.

5. The composition of claim 3 which also includes a dye selected from the group consisting of nitro dye of the benzene series, azo dye, anthraquinone dye, oxazine and azines.

6. The composition of claim 1 which also includes a glycol in amounts of about l to 6% by weight of the tota].

7. The composition of claim 6, wherein said glycol is selected from the group consisting of propyleneglycol and butylglycol.

8. The composition of claim 1 wherein said solvent is an aqueous lower alkanol solution wherein the low molecular weight alkanol is present in amounts of about 20 to by weight of the total.

9. The composition of claim 8, wherein said alkanol is selected from the group consisting of ethanol and isopropanol.

10. The composition of claim 8 which also includes a cosmetic resin in amounts of about 1 to 3% by weight of the total.

11. The composition of claim 10, wherein said cosmetic resin is selected from the group consisting of polyvinylpyrrolidone, copolymer of crotonic acid-vinyl acetate, copolymer of vinylpyrrolidone-vinyl acetate and copolymer of maleic anhydride-butylvinvyl ether,

12. A process of dyeing human hair, comprising impregnating said fibers to be dyed with the composition of claim 1, permitting said composition to remain in contact with said fibers for a period ranging from 10 to 30 minutes, rinsing said fibers and drying said fibers 13. A process for dyein'g and setting human hair, comprising applying to previously washed and rinsed hair the composition of claim 10 and subsequently rolling said hair up on curlers and drying said hair.

14. The composition of claim 1 wherein the diphenylamine of (a) is selected from the group consisting of 4-hydroxy-2'-amino-4'-N,N-dimethylamino diphenylamine, 4-hydroxy-3,5'-dimethyl-2',4-diamino diphenylamine,

dimethylamino diphenylamine.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORREQTIUN Patent No. ,853,464 Dated December 10, 1974 Inventor(s) Gregoire Kalc pissis, Andree Bugaut and Francoise Estradier It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the Heading:

Under [30] add July 14, 1971 Luxembourg 63526 Ehgncd and gwizd this twenty-second Day July 1975 [SEAL] Anest:

RUTH C. MASON C. MARSHALL DANN AIHSIIng Officer Commissioner of Parents and Trademarks

Claims (15)

1. A DYE COMPOSITION FOR HUMAN HAIR, COMPRISING A SOLUTION IN A SOLVENT SELECTED FROM THE GROUP CONSISTING OF WATERAND AN AQUEOUS LOWER ALKANOL SOLUTION OF 0.002 TO 2% BY WEIGHT OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF (A) A DIPHENYLAMINE OF THE FORMULA

2. The composition of claim 1, wherein said diphenylamine is the salt of an acid selected from the group consisting of oxalic acid, hydrochloric acid and tartaric acid.

3. The composition of claim 1 which also includes another dye selected from the group consisting of another oxidation dye and a direct dye.

4. The composition of claim 3, wherein said another dye is selected from the group consisting of ortho- and paraphenylenediamine, ortho- and paraaminophenol, and other indoaniline, indamine and indophenol leucoderivatives.

5. The composition of claim 3 which also includes a dye selected from the group consisting of nitro dye of the benzene series, azo dye, anthraquinone dye, oxazine and azines.

6. The composition of claim 1 which also includes a glycol in amounts of about 1 to 6% by weight of the total.

7. The composition of claim 6, wherein said glycol is selected from the group consisting of propyleneglycol and butylglycol.

8. The composition of claim 1 wherein said solvent is an aqueous lower alkanol solution wherein the low molecular weight alkanol is present in amounts of about 20 to 70% by weight of the total.

9. The composition of claim 8, wherein said alkanol is selected from the group consisting of ethanol and isopropanol.

10. The composition of claim 8 which also includes a cosmetic resin in amounts of about 1 to 3% by weight of the total.

11. The composition of claim 10, wherein said cosmetic resin is selected from the group consisting of polyvinylpyrrolidone, copolymer of crotonic acid-vinyl acetate, copolymer of vinylpyrrolidone-vinyl acetate and copolymer of maleic anhydride-butylvinvyl ether.

12. A process of dyeing human hair, comprising impregnating said fibers to be dyed with the composition of claim 1, permitting said composition to remain in contact with said fibers for a period ranging from 10 to 30 minutes, rinsing said fibers and drying said fibers.

13. A process for dyeing and setting human hair, comprising applying to previously washed and rinsed hair the composition of claim 10 and subsequently rolling said hair up on curlers and drying said hair.

14. The composition of claim 1 wherein the diphenylamine of (a) is selected from the group consisting of 4-hydroxy-2''-amino-4''-N,N-dimethylamino diphenylamine, 4-hydroxy-3'',5''-dimethyl-2'',4''-diamino diphenylamine, N-(7''-(6''-amino-1''-oxa-4''-aza-1'',2'',3'',4''-tetrahydro)-naphthyl)-4-amino phenol, 4-hydroxy-2''-acetylamino-4''-amino diphenylamine, 4-hydroxy-2''-acetylamino-4''-N,N-dimethylamino diphenylamine and 4-hydroxy-2''-acetylamino-4''-amino-5''-methyl diphenylamine.

15. The composition of claim 14 wherein said diphenylamine of (a) is 4-hydroxy-2''-amino-4''-N,N-dimethylamino diphenylamine.