US3506389A

US3506389A - Hair dyeing with couplers and a 1-amino-4-substituted-alkylaminobenzene

Info

Publication number: US3506389A
Application number: US383937A
Authority: US
Inventors: Roger Charle; Gregoire Kalopissis; Jean Gascon
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1963-08-01
Filing date: 1964-07-20
Publication date: 1970-04-14
Anticipated expiration: 1987-04-14
Also published as: DE1794383C3; AT264017B; GB1025916A; IT965508B; FR1403633A; DE1492069B2; DE1794383B2; DE1492069A1; BE650836A; CH438585A; DE1794383A1; NL6408654A

Description

United States Patent Int. 01. A61k 7/12 US. Cl. 8--10.2 10 Claims ABSTRACT OF THE DISCLOSURE The invention relates to dyeing hair with a 1-amino-4- substituted alkyl amino benzene and a coupler selected from the group consisting of substituted phenols, R5COCHZCOR5, and

wherein R is methyl; R is selected from the group consisting of methyl and ethoxy; R is phenyl; R is selected from the group consisting of p-carboxyphenylarnino and m-carboxyphenylamino; and Y is selected from the group consisting of phenyl, p-sulfophenyl, m-sulfophenyl and 2- chloro-S- sulfophenyl.

. This invention relates to a method of dyeing hair using paradiaminobenzene derivatives and couplers, and to compositions for use in that method.

' It is well known in the art of dyeing hair to use primary para-diamine's in conjunction with couplers to obtain various shades of color. However, the prior procedures were not satisfactory, because the colors obtained were not fast to light. Moreover, it was diflicult to produce a predtermined shade by reason of the fact that the final shade results from the superimposition of two dyes, namely the amine used and a second dye obtained by interaction of the amine with the coupler.

The present invention relates to a new method of dyeing hair which has not the aforesaid disadvantages because the dyes formed have exceptional fastness to light, at least in regard to the times, of the order of one year, which are relevant to hair dyeing. On the other hand, the amine employed does not in itself possess any satisfactory coloring power, so that the shade obtained results from the interaction of the coupler with the amine.

The method of the present invention comprises applying to the hair:

(a) An aminet of the formula:

in whichR represents a hydrogen atom, or a methyl, ethyl or propyl radical and X is selected from the group consisting of 3,506,389 Patented Apr. 14, 1970 in which R is selected from the group consisting of methyl, ethyl and propyl, and R is selected from the group consisting of CH CONH -CH COOH,

. CH CH NHSO CH CH CON(C H (2) N-piperidyl; and (3) N-morpholyl.

(b) One or more couplers of one of the following formulas:

in which R represents methoxy;

in which R is selected from the group consisting of CH --NHCOCH -NHCH CONH and -NHCOCH N(C H and R is selected from the group consisting of hydrogen and methyl;

in which R is methyl and R is selected from the group consisting of methyl and ethoxy;

in which R is phenyl and R is selected from the group consisting of p-carboxyphenylamino and m-carboxyphenylamino; 7

in which Y is selected from the group consisting of phenyl, p-sulfonphenyl, m-sulfophenyl and 2-chloror5-sulfophenyl; and

(0) An oxidizing agent; allowing sufficient time to elapse after the application for the dyeing effect to be obtained, then removing any unwanted excess of components (a), (b) or (c) from the hair.

The amine and coupler can be used, where appropriate, in the form of their salts.

The method can conveniently be carried out by applying the said amine and the said coupler in the form of aqueous solution in consecutive order to the hair, and the oxidizing agent can be conveniently in either the solution of amine or coupler.

The solutions can contain other dyestuffs which may be employed under the same conditions as direct dyes, for example azo dyes. They can also contain wetting agents, dispersing agents, penetration agents and other ingredients generally employed in hair dyeing.

A great variety of shades of color can be obtained using the method of the invention. When utilized with one or several amines, the couplers of Formula II provide shades of blue, the couplers of Formula HI provide shades of yellow and the couplers of Formula 1V provide shades of red.

It is therefore possible to obtain a very considerable range of colors by associating a given coupler with a given amine, but-and this is one of the most important features of the inventionit is possible when using a given amine and a mixture of two couplers belonging to two of the Formulae II, III or IV to obtain, by varying the proportions of couplers, all shades between the colors obtained with each of the two couplers used by itself. Similarly, by using a given coupler, a variety of colors can be obtained, although to a smaller degree, by using various amines of the Formula I.

It will be seen that by using a limited number of amines and couplers it is possible to cover the whole range of shades appropriate for hair dyes.

The dyes obtained using the method of this invention have proved to have exceptional resistance to light as compared with dyes hitherto used for hair dyeing. Moreover, a study of the toxicity of the dyes provided by the present invention has shown, contrary to what might have been expected, that they are probably less toxic, and in any case, not more toxic, than the dyes based upon p-phenylenediamine which are at present in use for hair dyeing, which themselves produce appreciable allergy reactions only in extremely rare cases.

Finally, the amines of Formula I have the advantage that they do not impart any color to the hair when applied in the absence of couplers. By virtue of this property, the colors obtained using the present invention result essentially from the combination of the amine and of the coupler and not from the superimposition of two dis-' tinct colors, as is the case in the majority of dyeing solutions hitherto employed. This property is most valuable in practice, because it has been observed that the shades obtained in the earlier processes vary from one person to another and even from one place to another on the same hair by reason of a selectivity in the taking of the amines and the couplers on the hair, which disadvantage is avoided with the invention since the color obtained results only from the amine-coupler association.

The invention is illustrated by the following examples:

EXAMPLE 1 There is prepared a solution having the following composition:

4-amino-3-methyl-N-ethyl-N- ,8- methylsulphamido) ethyl]aniline sulphate2.9 g. 2,5-dimethylphenol-1.22 g. Sodium hydroxide-0.2 g. Ethyl alcohol cc. Ammonia solution (22 B.)6 cc.

Water q.s. for 50 cc. The pH of this solution is 10.5.

The solution, which can be kept without deteriorating, is mixed at the time of use with an equal volume of hydrogen peroxide vol.), and when applied to white hair dyes it blue. The method of dyeing in this and in the folowing examples consisted of applying the dyeing solution to the hair at ambient temperature, leaving the hair for 20 minutes and then successively rinsing, shampooing, rinsing again and drying.

EXAMPLE 2 There is prepared a solution having the following composition: 4-amino-3-methyl-N-ethyl-N-carbamyl methylaniline sulphate-1.28 g. 3-N-acetamino-6-methyl-phenol1.65 g. Ammonia solution (22 B.)-6 cc. Water q.s. for 50 cc.

The pH of this solution is 10.6. When mixed with an equal volume of hydrogen peroxide (20 vol.) and applied to white hair it gives a moderate blue color.

4 EXAMPLE 3 There is prepared a' solution having the following composition:

4-amino-N-ethyl-N-carbamylmethylaniline-0.97 g. 4-methoxyphenol1.25 g.

Ammonia solution (22 Be'.)'6 cc.

Water q.s. for cc.

The pH of this solution is 10.6. When mixed with an equal volume of hydrogen peroxide (20' vol.) and applied to grey hair, it gives a greenish-greyish blue color.

EXAMPLE 4 There is prepared a first solution A having the following composition:

N-(4-aminophenyl)morpholine sulphate2.59 g. 3-acetaminophenol3 g. Ammonia solution (22 B.)-6 cc. Water q.s. for 50 cc.

This solution has a pH of 10.6.

There is also prepared a solution B having the following composition:

N-(4-aminophenyl)morpholine sulphate-2.59 g. 3-N-(carbamylmethylamino)phenol--2.32 g. Ammonia solution (22 B.)-6 cc.

Water q.s. for 50 cc.

EXAMPLE 5 There are prepared a solution C, identical to that described in Example 3, and a solution D having the following composition:

4-amino-N-ethyl-N-carbamylmethylanilineO.97 g. 1-phenyl-3-methyl-5-pyrazolone-0.88 g. Ammonia solution (22 B .)6 cc.

Water q.s. for 50 cc.

This solution D has a pH of 10.6

To 50 cc. of a mixture of these two solutions C and D are added 50 cc. of hydrogen peroxide (20' vol.).

Depending upon the proportions of the mixture of C and D, there are obtained upon dyeing grey hair colors ranging from purplish grey to blackish blue. Thus, with 40 volumes of C and volumes of D a dark violet-grey is obtained; with 60 volumes of C and 40 volumes of D a dark bluish-grey is obtained; and with volumes of C and 20 volumes of D a blackish-blue is, obtained.

EXAMPLE 6 There is prepared a solution having the following composition:

4-amino-3-methyl-N-ethyl-N [[3- (methylsulphamido) ethyl] aniline sulphate2.9 g. 4-benzoylacetaminobenzoic acid11.3 g. Ammonia solution (22 B.)-25 cc. Water q.s. for 50 cc.

This solution, which has a pH of 10, can be kept well without decomposition. It is mixed with an equal volume of hydrogen peroxide (20' vol.) and appled immediately to white hair, giving a deep orange-yellow color.

EXAMPLE 7 There is prepared a solution having the following composition:

N-(4-aminophenyl) piperidine sulphate-2.39 g. 1-phenyl-3-methyl-5-pyrazolone1.75 g.

Ammonia solution (22 B.)8 cc. Water q.s. for 50 cc.

This solution, which has a pH of 10.7, can be kept well without decomposition. An equal volume of hydrogen peroxide (20 vol.) is added to the solution, and the mixture is applied immediately to white hair giving a dark purplish-red color.

EXAMPLE 8 There is prepared a solution having the following composition:

N-methyl-N-(4-aminophenyl)-u-aminoacetic acid- 3-methyl-1-(p-sulphophenyl)-pyrazol-5-one sulphonic acid-2.55 g.

Ammonia solution (22 B.)8 cc.

Water q.s. for 50 cc.

This solution, which has a pH of 10.5, can be kept well without decomposition. By adding thereto an equal volume of hydrogen peroxide (20 vol.) and applying it to white hair, a pale reddish-purple color is obtained.

EXAMPLE 9 There are prepared three solutions E, F and G, each containing: 4-amino-3-methyl-N-ethyl-N-[fl-(methylsulphamido) ethyl] aniline sulphate2.9 g.

and respectively- For E:

3-acetaminophenol1.5 g.

Ammonia solution (22 B.)6 cc.

For F:

4-benzoylaceta minobenzoic acid-11.3 g. Ammonia solution (22 B.)25 cc.

For G:

1-phenyl-3-methyl-5-pyrazolone1.75 g. Ammonia solution (22 B.)-8 cc.

Each of these solutions is thereafter diluted with water to bring its volume to 50 cc. Two of these solutions are mixed in any proportions and there is added at the time of use a volume of hydrogen peroxide (20 vol.) equal to the volume of this mixture. Depending upon the proportions of the two solutions employed, the following results are obtained on white hair:

E+F: All shades ranging from dark greenish-blue to deep orange-yellow;

F+G: All shades ranging from deep orange-yellow to dark purple-red;

G+E: All shades ranging from purple-red to dark greenish-blue.

EXAMPLE 10 There are prepared a solution H, identical to that described in Example 2, and a solution I containing:

4,4-dihydroxy-2-aminoazobcnze-O.50 g. Disodium phosphate (dihydrate)0.9 g. Caustic soda q.s. for pH 10.

Water q.s. for 50 cc.

To 50 cc. of a mixture of solutions H and J is added an equal volume of hydrogen peroxide (20 vol.). Depending upon the ratios of the volumes of solutions H and J, there are obtained on application of the mixture to white hair colors ranging from greenish-grey to bright orange-yellow.

EXAMPLE 11 There is prepared a solution K, having the following composition:

4-amino-N-ethyl-N-carbamylmethylaniline-1.93 g. Solution of ammonia (22 B.)6 cc. Water q.s. for 100 cc.

6 The pH of this solution K is 11. This solution is applied to grey hair at ambient temperature and after 20 minutes the hair is then rinsed with water.

There was also prepared a solution L containing:

3-acetaminophenol-2.25 g. Ammonia solution (22 B.)-6 cc. Water q.s. for cc.

The pH of this solution L is 10.6. Solution L is then applied for 20 minutes at ambient temperature to the hair previously treated with solution K, and after 20 minutes the hair is rinsed.

Finally, there is applied at ambient temperature to the hair, treated with solutions K and L, a solution M composed of:

Cc. Hydrogen peroxide (50 vol.) 5O Ammonia solution (22 B) 6 Water q.s. for 100 cc.

20 minutes after the application of solution M, the hair is rinsed, washed and dried. There is thus obtained a moderate blue color in the hair.

EXAMPLE 12 There is prepared a solution N having the following composition:

3-acetaminophenol--2.25 g. Ammonia solution (22 B.)--6 cc. Hydrogen peroxide (20 vol.)50 cc. Water q.s. for 100 cc.

The pH of this solution is 10.6. Solution N is applied to the grey hair previously treated by solution K, as described in Example 11, and the same color is obtained as in Example 11.

EXAMPLE 13 There is prepared a solution containing:

4-amino-N-ethyl-N-carbamylmethylaniline1.93 g. Solution N of Example 12 q.s. for 100 cc.

Application to grey hair for 20 minutes gives a color identical to that obtained in accordance with Examples 11 and 12.

EXAMPLE 14 White hair is treated by a solution containing:

3-06- (N',N'-diethyl amino-acetamino-phenol1 .11 g. Aqueous solution of ammonia at 22 B.6 cc. Water q.s.p. 100 cc.

Solution of ammonia in Water at 22 B.6 cc. Water q.s.p. 100 cc.

The coloring obtained is grey-greenish.

EXAMPLE 16 A solution is prepared as follows: 4-amino, [N-ethyl,N- (N'-diethyl) -carbamylmethyl] aniline chlorhydrate-1.45 g. 6-methyl, 3-(N-carbamylmethyDarnino, phenol-222 g.

8 Aqueous solution of ammonia at 22 B.6 cc. (b) a coupler selected from the group consisting of Water q.s.p. 50 cc. (1) on The pH of said solution is 10.5 V

Said solution utilized in the same conditions as Example 1 with H produces a dark-blue coloring. 0

EXAMPLE 17 A solution is prepared as follows: in which R2 represents methoxy, 4-amino, 3-methyl[N-ethyl, N-(N'-diethyl)-carbamyl- 1O (2) methyl] aniline chlorhydratel.50 g. 011 B-acetamino, phenol3 g. Aqueous solution of ammonia at 22 B.-6 cc. RF Water q.s.p. 50 cc. 15 The pH of said solution is 10.6 R

Said solutifm applied in Same conditiol. as for in which R is selected from the group consisting of Example 1 with hydrogen peroxlde produces a light blue- NHCOCH3 NHCH2CONH2, greenish hue.

NHCH CON C H EXAMPLE 1:; 2 2 h and NHCOCH N(C H and R is selected A Solutlon prepared as follows from the group consisting of hydrogen and methyl; 4 (Emailing),ilglzthyhN-carbamylmethyl)an1l1ne chlorhy- (3) 3-[(N-diethyl)carbamylmethyl1-amino, phenol2.22 g. in which R5 methyl and 6 is Selected from the Aqueous solution of ammonia at 22 B.6 cc. group cohslshhg of methyl and ethoxy; Water q.s.p. 100 cc. (4) R COCH COR The p of Said Solution is in which R, is phenyl and R is selected from the When said solution is applied in the same conditions group consisting of P-Cafhoxyphehylammo and as mentioned for Example 2 with hydrogen peroxide, a yp y and crimson-grey hue is obtained. (5)

EXAMPLE 19 f ff A solution is prepared as follows: 0:0 N 4 amino,(N-ethyl,N-carbamylmethyl)-aniline chlorhydrate-l.l5 g. Y 6 methyl,3 y y y l amino, in which Y is selected from the group consisting of phenol2.36 g. 40 Phenyl, p-sulfophenyl, m-sulfophenyl and 2-chloro- Aqueous solution of ammonia at 22 B'.6 cc. 5-sulfophenyl; and Water q.s.p. 100 cc. (c) an oxidizing agent; The pH of said solution is 10.6. (H) Permitting the fi (a), (b) (c) remain on the hair for a time sufiicient to dye Said solution applied in the same conditions as meni h d honed in Example 1 With hydrogen Peroxide, a dark 49 (III) removing the excess of said mixture from crimson-grey hue is obtained. the hair.

A Shown in the above examples, the method of the 2. The method as claimed in claim 1, in which the oxidizpresent invention is not limited to the application to the i agcnt i h d id hair of a solution containing together the amine, the cou- 3 Th thod as l i d i l i 2, i hi h the aid pler or couplers and hydrogen peroxide, but includes the 50 hydrogen peroxide is applied to the hair in an aqueous successive application of different solutions each containl ti f th id i ing one or more of the iugerdicnts. 4. The method as claimed in claim 2, in which the hy- What We claim 1s: drogen peroxide is applied to the hair in an aqueous solu- 1. A method of dyeing hair, which comprises the steps tio of th aid coupler, of pp y h to the hail effective dyeing amounts of! 5. A composition of matter for dyeing hair which coman amine of the formula prises an aqueous solution having a pH of 9 to 11 and NH2 hair coloring amounts of (a) a colorless amine having the formula R1 NHz .R I X in which R is selected from the group consisting of hydrogen, methyl, ethyl and propyl, and X is selected f th 0 t f (1) mm 6 gr up consls i 1n whlch R 18 selected from the group consisting of hydrogen, methyl, ethyl and propyl, and X is selected from the group consisting of 1 R in which R is selected from the group consisting of methyl, ethyl and propyl, and R is selected from the group consisting of CH CONH CH COOH, OH CH NHSO CH -CH CON(C H (2) N- in which R is selected from the group consisting of piperidyl; and (3) N-morpholyl; methyl, ethyl and propyl, and R is selected from 9 the group consisting of CH CONH -CH COOH, CH CH NHSO CH CH CON(C H (2) N- piperidyl; and (3) N-morpholyl; and (b)a colorless coupler selected from the group consisting of I R2 in which R represents methoxy;

in which R is selected from the group consisting of CH NHCOCH NHCH CONH group consisting of p-carboxyphenylamino and mcarboxyphenylamino; and

in which Y is selected from the group consisting of phenyl, p-sulfophenyl, m-sulfophenyl and 2-chloro-5- sulfophenyl. 6. The composition as claimed in claim 5 further comprising an oxidizing agent.

7. The composition as claimed in claim 6, in which the oxidizing agent is hydrogen peroxide.

8. The composition for dyeing hair of claim 5, wherein said amine is selected from the group consisting of 4- amino 3 methyl-N-ethyl-N-(,B-methyl-sulfamidoethyl)- aniline sulfate, 4 amino-3-methyl-N-ethyl-N-carbamylmethyl-aniline sulfate; 4-amino-N-ethyl-N-carbamylmethylaniline; 4-amino-N-ethyl N carbamylmethylaniline chlorhydrate; N-(4-aminophenyl)-morpholine sulfate; N- (4-aminophenyl) pipe ridine sulfate; N-methyl-N-(4'- aminophenyl)- 3-aminoacetic acid; 4-amino-[N-ethyl-N- (N'-diethyl)-carbamylrnethyl]aniline chlorhydrate; and 4- amino-3-methyl-[N-ethyl N (N diethyD-carbamylmethyl]aniline chlorhydrate.

9. The composition for dyeing hair of claim 5, wherein said coupler is selected from the group consisting of 6- methyl 3 [(N'-diethyl)carbamylmethyl]aminophenol; 2,5-dimethylphenol; N-acetamino-3-methyl-6-phenol; 4- methoxyphenol; 3-acetaminophenol; 3-N- (carbamyl-methylamino)phenol; 1-phenyl-3-methyl-5-pyrazo1one; 4-benzoylacet-aminobenzoic acid; 3-methyl-(l-p-sulfophenylpyrazol-5-one) sulfonic acid; 3-[a-(N'-diethyl)amino] acct aminophenol; 6-methyl-3-[a-(N-diethyl)-amino] acetaminophenol; 6 methyl 3 (N-carbamylmethyl)- aminophenol; and 3-[ (N'-diethyl) carbamylmethyl] amino phenol.

10. The composition of claim 5 wherein said pH is between 10 and 10.7.

References Cited UNITED STATES PATENTS 1,102,028 6/ 19 14 Fischer 96100 1,969,479 8/ 1934 Seymour 96100 X 2,113,330 4/1938 Mannes et a1 96-100 X 2,369,929 2/1945 Vittum et a1. 96100 X 2,436,130 2/ 1948 Weissberger et al. 96100 X FOREIGN PATENTS 158,989 5/1952 Australia.

371,677 4/ 1932 Great Britain.

653,053 5/1951 Great Britain.

830,446 3/ 1960 Great Britain. 1,292,212 3/1962 France.

OTHER REFERENCES Ofiicial Gazette, vol. 652, Nov. 6, 1951, pp. 289-290, 167-88.

ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner US Cl. X.R. 8-11