US 3649158 A
A process and composition for dyeing keratinic fibers, particularly, human hair, in which tetrazolium salts are applied to the fibers in a colorless oxidized state and reduced to colored insoluble formazanes by reducing agents. The reducing agents are used so that the keratinic bonds are not disrupted and can be used at the same time that a permanent wave process is applied. Also, various shades can be obtained using leuco derivative dyes which become oxidized when functioning as reducing agents.
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Description (OCR text may contain errors)
United States Patent Kalopissis et a].
[ 1 Mar. 14, 1972  PROCESS FOR DYEING LOCKS OF HUMAN HAIR WITH TETRAGOLIUM SALTS lnventors: Gregoire Kalopissis, Paris; Andree Bugaut,
Boulogne, both of France Assignee: Societe Anonyme dite: LOreal Filed: Aug. 5, 1968 Appl. No.: 749,958
Foreign Application Priority Data Aug. 8, 1967 Luxembourg ..54,267 Dec. 4, 1967 Luxembourg ...55,016
8/17, 8/l27.51, 8/41 B, 8/46, 260/308 D, 260/193 Int. Cl ..D06p 3/04, D06p 3/08 Field ofSearch ..8/127.51,10,10.1,4l,46,
 References Cited UNITED STATES PATENTS 3 ,297,709 1/1967 Davis ..260/ 308 3,185,567 5/1965 Rogers ..96/3 3,257,205 6/ 1966 Cassiers et a1. ..96/95 X 3,396,736 8/1968 Shansky ..8/10 X Primary ExaminerGeorge F. Lesmes Assistant Examiner-Patricia C. lves Attorney-Holcombe, Wetherill & Brisebois  ABSTRACT 6 Claims, No Drawings PROCESS FOR DYEING LOCKS OF HUMAN HAIR WITH TETRAGOLIUM SALTS In a known method of dyeing keratinic fibers, compositions are used which contain compounds which are colorless and soluble in water when in a reduced state, but capable of being transformed, when oxidized, into colored pigments which are insoluble in water.
Among these coloring compositions are those based on oxidation dyes and on vat dyes.
The present invention relates to the use of compounds for dyeing keratinic fibers which, in contradistinction to those heretofore in use, are colorless and soluble in water when oxidized, but are insoluble or nearly so in water, and very strongly colored when reduced.
The dyes of this type have several advantages when used to dye keratinic fibers, and particularly human hair. When in their colorless, oxidized form, they penetrate the keratinic fibers very well and have a great afiinity for them, so that the hair may be washed immediately after impregnation with one of these colorless dyeing compositions, and the color then developed by reduction.
It is an object of the present invention to provide a new method of dyeing keratinic fibers and especially human hair characterized by the step of impregnating the hair with a composition containing at least one tetrazolium salt responding to the formula:
n is a whole number equal to 1 or 2,
R and R" represent aromatic radicals which may be substituted by groups such as nitro, methoxy and halogen groups;
R, regardless of the value of n, represents hydrogen, an
alkyl radical, an aromatic radical, which may be substituted by such groups as nitro, methoxy, or halogen groups, a heterocyclic remainder or an N=N-Ar remainder in which Ar represents an aromatic group;
hydrogen, when n=l or a radical responding to the formula when n=2.
A represents an anion, such for example, as a halide,
methosulfate, sulfate, or acetate.
After rinsing the fibers or the hair, if desired, thecolor is brought out by applying a reducing solution which transforms the said tetrazolium salt or salts into colored insoluble formazanes, according to the reaction:
The reducing agents which may be used in accordance with 75 I 3,3 .929 tent r the s e sy whis h e y qit e vsi tion potentials lower than those of formazane/tetrazolium salt systems.
The reducing agents which may be used in carrying out the invention may be those which do not have any effect on the structure of the keratin of the hair, and specifically not on the S-S bonds, that is to say, soft reducing agents such as ascorbic acid, hydrazine, dithionic acids, and the reductones.
It is also possible to use reducing agents such as thiols or borohydrides, which can disrupt the SS bonds of the keratin, but preferably in such weak concentrations, that they have practically no chemical effect on the hair.
Colorless compounds which do not react with the keratin and which are transformed into colored compounds by oxidation, such as leuco derivatives, or oxidation dyes may also be used as reducing agents.
In this method the reducing agents of the leuco-derivative type or the oxidation dyes may act as shade varying means.
In accordance with the present invention a colored permanent wave may be effected by utilizing the properties of tetrazolium salts.
In one alternative method, the hair may first be treated with a conventional reducing agent, rinsed, and treated with a solution of tetrazolium salt which, by reacting with the reducing groups in the hair, are transformed into formazane and develop a color. If so desired, an oxidizing agent may then be applied to carry out the second step of a conventional permanent.
In a second alternative method a solution of tetrazolium salts is applied to the hair, after which a conventional permanent waving process is carried out, that is to say, a reducing solution is applied, which transforms the tetrazolium salts into forrnazanes and so develops the color. The second step of a permanent waving process, that is to say, the application of a conventional oxidizing agent, may then be carried out, if desired.
A further object of the invention is to provide a hair dyeing composition characterized by the fact that it contains at least one tetrazolium salt, as above defined.
Among the tetrazolium salts which may be used in accordance with the present invention are the following, but this list is not exhaustive:
3-para nitrophenyl-2,5 diphenyl tetrazolium chloride responding to the formula:
MGM Q 3,3'-para (di-orthomethoxy) diphenylene-2,2', 5,5-
tetraphenyl-ditetrazolium dichloride responding to the formula:
ew 4) CH; CH:
,3"-para (di-orthomethoxy) diphenylene-Z ,2'-diphenyl- -paradiphenylene-2,2',5,5tetraphenyl-ditetrazolium e rqnsiq tqtt fe s e 11506- l c-ciHr [01-12 In a preferred embodiment of the invention the composition contains from 0.1 to 10 percent of tetrazolium salts.
In one specific embodiment the pH value of the composition is basic, that is to say, greater than 7.
The composition according to the invention may also contain any additives which are conventionally used in dyeing solutions. They may take the form of aqueous or hydroalcoholic solutions, creams, gels, or aerosols.
Among the tetrazolium salts which may be used in carrying out the invention, a certain number have the characteristic of forming photosensitive formazanes, that is to say formazanes which are unstable in the presence of light. in this particular case the colors obtained are transient and make it possible to apply shades to the hair which are of short duration, and are then eliminated without any need to resort to a bleach.
The transient dyeing compounds according to the invention have the advantage over those transient dyeing compounds heretofore known that they degrade progressively with out changing the color of the hair, their disappearance being evidenced only by a progressive decrease in the intensity of the color.
In order that the object of the invention may be better understood, several methods of carrying it out will now be described, purely by way of illustration and example.
EXAMPLE 1 The following solution is prepared:
3-p-nitrophenyl2.5'diphenyl tetrazaliurn chloride 3.8 g Nl-l OH q.s.p. pH l0 water, q.s.p. [00 cc.
This solution is applied to 90 percent white hair, and left to act for 15 minutes, after which the hair is rinsed.
10 cc. of 3 percent sodium ascorbate is then applied and left to act for 15 minutes.
The hair is then rinsed and shampooed.
The result is a violet red shade.
EXAMPLE 2 A solution A having the following composition is prepared:
Jpara nitrophenyl-lj-diphenyl tetrazolium chloride water, q.s.p.
EXAMPLE 3 A lock of bleached hair is impregnated with the abovepregnated with the following reducing solution for pennanent waving:
thioglycnlic acid 5 g. ammonia q.s.p. pH 7.7 water q.s.p. 100 g.
This is left to act for 7 minutes. The hair is then rinsed with described solution A for 15 minutes, as indicated in Example 6 5 1. It is then rinsed in clear water, and a spraying solution having the following composition is prepared:
A deep red color is produced at once, and resists subsequent shampooings.
clear water, the permanent fixed with solution A for 5 minutes, and rinsed.
The result is a lock which is curly and deep red in color. Both the color and the curl resist subsequent shampooing.
EXAMPLE 5 The following solutions are prepared:
Solution l: 3-para nitro phcnyblfi diphen yl tetrazoliurn chloride 0.39 5. water, q.s.p. 100 3.
Solution 2: hydrazine 0.3 5. water. q.s.p. 100 g.
The two above solutions are mixed in equal quantities and a lock of bleached hair is immediately colored. in this mixture the 3-para nitro phenyl-2,5-diphenyl tetrazolium chloride and the hydrazine are in equimolecular proportions. The pH of the mixture is near neutrality. The solution is left to act for IS minutes and the hair is rinsed and shampooed. An orange red coloration results.
EXAMPLE 6 The following dyeing composition is prepared:
LIV-para (di-orthornethoxy) diphenylenc-2,2', 5 ,5'-tetraphenyl ditcu'azoliurn chloride 1 5. water, q.s.p. 100 g.
This solution is applied to percent white hair, and left to act for 15 minutes, and the hair rinsed. The lock is not colored. The following solution is then prepared:
fonnamidine rulfinic acid (Manofast) l 5. Nil NaOH solution q.s.p. pH 10 water q.l.p. g.
This is left to act for 5 minutes. The hair is then rinsed and shampooed. A gray violet color results.
EXAMPLE 7 The following solutions are prepared:
Solution l: 3,3'-para (di-orthornethoxy) diphenylene-LZ ',S,S -tetmv phenyl-ditctrazolium dichloride lwater q.s.p. N30 Solution 2: alloxantine 0.32 g.
5 N NaOH q.a.p. pH 10 water. q.r.p. I00 5.
When about to dye, the two solutions are mixed in equal quantities, so that they are in equimolecular proportions.
A lock of 90 percent white hair is impregnated with this mixture for 15 minutes, rinsed, and shampooed. The result is a giayg violet a little more intense and more violet than in Exam-, p e
The following composition is prepared:
A lock of 90 percent white hair is impregnated with this solution, and left to act for 15 minutes. The hair is then rinsed.
A 3 percent solution of sodium hydrosulfite, brought to pH by the addition of sodium hydroxide is then applied. This is left to act for 5 minutes, after which the hair is rinsed and shampooed. A deep blue grey results.
EXAMPLE 9 The following solutions are prepared:
Just before application to the hair, the two solutions are mixed in equal quantities, i.e., in equimolecular proportions. The mixture has a pH value of about 7.
This mixture is applied to 90 percent white hair, and left to act for minutes. The hair is then rinsed and shampooed. A deep grey black results.
What is claimed is:
l. A process for dyeing locks of human hair, which comprises the step of impregnating the hair with at least one composition containing from about 0.1 to 10 percent of a tetrazolium salt responding to the formula:
n is a whole number between 1 and 2 inclusive,
R is a radical selected from the group consisting of phenylene and a phenylene substituted by a substituent selected from the group consisting of nitro and methoxy radicals;
R" is a radical selected from the group consisting of phenyl and a phenyl substituted by a substituent selected from the group consisting of nitro and methoxy radicals;
R is selected from the group consisting of hydrogen, phenyl, and a phenyl radical substituted by a substituent selected from the group consisting of nitro and methoxy radicals;
Y is selected from the group consisting of hydrogen, when n=1, and, when n=2,
a radical corresponding to the following formula:
and developing the color by reducing the tetrazolium salt in the hair with a reducin solution or H 0;.
2. A process accor ing to claim f, in WhlCh the reducing solution contains a reducing agent selected from the group consisting of ascorbic acid, hydrazine, dithionic acids, reductones, borohydrides, thiols, sodium ascorbates, forrnamidine sulfinic acid, alloxanthine, aminohydroquinone hydrobromide, and sodium hydrosulfite.
3. A process according to claim 1, in which the hair is rinsed with water before applying the reducing solution.
4. A process according to claim 1, in which the tetrazolium salt is mixed, immediately before applying to the hair, with the solution containing the reducing agent.
5. A process according to claim 1, in which the dyeing of the hair is combined with a permanent waving process, the hair being first impregnated with a reducing agent, conventionally used in the first step of a permanent waving process, rinsed, and then treated with the tetrazolium salt and then neutralized.
6. A process according to claim 1, in which the dyeing of the hair is combined with a permanent waving process, the hair being first impregnated with the composition containing the tetrazolium salt and then treated with a reducing agent conventionally used in the first step of a permanent waving process and then the hair is neutralized.