US2876781A

US2876781A - Hair waving lotion of alkali metal and ammonium salts of an aliphatic mercaptan carboxylic acid

Info

Publication number: US2876781A
Application number: US276883A
Authority: US
Inventors: Martin Harry
Original assignee: Permanent Hair Waving Corp
Current assignee: Permanent Hair Waving Corp
Priority date: 1942-04-04
Filing date: 1952-03-15
Publication date: 1959-03-10
Anticipated expiration: 1976-03-10

Description

United States HAIR WAVIN G LOTION F ALKALI METAL AND AMMONIUM SALTS OF AN ALIPHATIC MER- CAPIAN CARBOXYLIC ACID Harry Martin, Monroe, N. Y., assignor, by mesne assignments, to Permanent Hair Waving Corporation, Norfolk, Va., a corporation of Virginia No Drawing. Original application April 4, 1942, Serial No. 437,628. Divided and this application March 15, 1952, Serial No. 276,883

20 Claims. (Cl. 132-7) This invention relates to compositions suitable for hair curling, and is herein disclosed in some detail as embodied in compositions suitable for cold hair waving. This application is a division of my application Serial No. 437,628, filed April 4, 1942, now abandoned, which latter is in part a continuation of my prior application Serial N0. 383,204, filed March 13, 1941, now Patent No. 2,350,178 of May 30, 1944.

It has been found possible in the past, it dangers and unpleasantness were ignored, to efiect the cold waving of hair with inorganic sulfides or hydrosulfides, but some people seem to have been fatally poisoned by solutions of those inorganic materials, and, moreover, the odor of the substances used was highly ofiensive and nauseous.

It has been hitherto proposed to use the hydrochloride of the sulfur-bearing amino acid cysteine, but that is commercially prohibitive and was used at pH of about 11, which irritated the operatorshands and the scalp carrying the treated hair.

Other substances have been tried, but had to be so strongly alkaline when used that they stung the hands of the operator or the scalp of the person whose hair was being curled, and for that reason, were practically worthless for most purposes.

According to the present invention, the foregoing and other difiiculties are overcome, and a curling solution is provided which is highlyeffective in the cold, is harrn less, is economical to prepare, is safe in unskilled hands, is so nearly odorless that its odor is easily covered up, leaves notoxic or otherwise objectionable residue, does not injure the hands of an operator or the scalp of a person whose hair is being curled, and does not act as a depilatory;' Moreover, the solution is in every way suitable to put into the hands of the average housewife. Modified solutions may be used hot, if weaker, or may be useful when speed is desired.

In one form of the invention, ten grams of sodium thioglycolate were dissolved in 100 cc. of water, making a'solution of pH 6 to 7, and applied to the hair wound on a rod at room temperature. In the course of an hour to three hours, the still wound hair was washed with warm water, say below 125 F. The hair appeared unharmed and waved permanently to the wound shape.

depending on the texture and condition of the hair, or,

for bleached or dyed hair, ten minutes, and wet with a solution made by mixing 500 cc. of 20 volume hydrogen peroxide with 500 cc. water and 30 grams tartaric acid. This neutralizes the alkalinity of the ammonia-containing solution and, incidentally raises the hair to 125 F.

Evaporation of the water from the chemicals used Patented Mar. 10, 1959 10 grams thiglycolic acid 7 grams sodium hydroxide 20 cc. 26 B. aqua ammonia 100 cc. water or witch-hazel 2 drops synthetic oil (to give a positive odor) of pine.

This formula was effective on fine hair (which yields slowly to treatment), as well as on bleached dyed and coarse hair, the time varying from five to thirty minutes, when cold.

For domestic use by unskilled persons modified formulas were the best, using 4% to 10% of a soluble thioglycolate and a pH between 7 and 9.5. Above pH 10, a depilatory action shows itself in partial or incipient destruction of the hair fibre. Occasionally a 3% solution is advisable, and as high as 15% is usable by a skilled operator under some conditions.

It is usually most satisfactory to make the solution alkaline by aqua ammonia, but alkali metal salts give a tighter curl on some types of hair. Many common salts, even sodium chloride, sodium sulphate, and ammonium acetate, when present, exert definitely deleterious effects.

Often the best effects are obtained by adding an organic base to replace part of the sodium as:

10 grams thioglycolic acid 3 grams monoethanol amine 1 gram sodium thioglycolate were dissolved in less than 100 cc. water, 26 B. aqua ammonia wa sadded to make pH 8.5 and water added to make 100 cc.

Another material was made with 6.5 grams thioglycolic acid cc. water Monoethanolamine to make pH 7 Aqua ammonia to make pH 9.05 Water to make cc.

Solutions with a pH of 9.02, which is obviously about 9, have proved the most satisfactory compromise solution for all around use, considering fineness of hair, temperature, time and other considerations of beauty parlor practice. One such solution was 7 grams thioglycolic acid 100 cc. water Sodium or potassium hydroxide solution 8.5 grams thiolactic acid 90 cc. water Monoethanolamine added to make pH 8 Then 26 B. aqua ammonia to make pH 8.5 diluted to 100 cc.

Where a curling solution was found to be used promptly so that no deterioration occurred by standing, the best results were obtained by using appropriate solutions of thiocarbarnate salts. These thiocarbamate salts were easily made by mixing for example, two moles of monocthanolamine with one mole of carbon disulphide.

The reaction was instantaneous so that the carbon disulphide should be usually added slowly to avoid spattering.

The resulting dithiocarbamate in suitable solution, curled hair rapidly and safely and was easily washed out, to fix the curl. As little as a 4% solution was found useful especially in the cold. The product may be called a solution of monoethanolammonium-N-oxyethyldithiocarbamate. It was stable over a period of some weeks.

When isopropanolamine was substituted for the monoethanolamine, it yielded a parallel product of about equal utility. That product may be called isopropanolammonium dithiocarbamate. It was possible to use ammonium dithiocarbamate made in the same way, by using an excess of ammonium hydroxide, although its odor made it less useful.

Other useful results were obtained by producing amides and treating hair withthem in solution, thus avoiding any uncertainty or difficulty arising from the possible instability of the thiocarbamate.

N-oxyethylthioglycolamide was made by dehydrating a mixture of monoethanolamine and thioglycolic acid. The mixture was heated at about 140 C. at a pressure of 15 to 22 mm. until the proper computed amount of water was removed and collected. The resulting product was ready for immediate use, when in proper solution.

lsopropanolamine substituted for the monoethanolamine under the same conditions, yielded a corresponding product similarly useful. The product was N-oxypropyldithioglycolamide.

When butanolamine was substituted for the monoethanolarnine under the same conditions, it yielded a corresponding product similarly useful.

Monothioglycolates of glycols or other polyhydroxyl alcohols were also found useful in hair curling, but not equal to the amides. These were made as follows:

To thioglycolic acid, containing about a fraction of 1% of sulphuric acid, was added slowly with intermittent cooling, a slight excess of ethylene oxide yielding a viscous liquid, ready to use in hair curling when in suitable solution after removal of the sulphuric acid as by barium carbonate. The product in solution was ethyleneglycolmonothioglycolate.

Propylene oxide substituted for the ethylene oxide yielded the corresponding propyleneglycol product which was about equally useful in hair curling. Glycidol when substituted for the ethylene oxide yielded the corresponding glyccryl monothioglycolate, which also proved usein] in hair curling.

Monothioglycerine and thiosalicylic acid were found to be usable in suitable concentrations though inferior to most of the other materials named above.

It was found that many of these materials were effective on the other animal fibres and were useful in treating woolen textiles, for example, to make them crease resistant and make them hold creases, as for instance in men's trousers.

A pink flannel made by Botany Worsted Mills E. B. was wet with a 4% solution of monoethanolammonium-N-oxyethyldithiocarbamate with aqua ammonia added to make a pH of about 9, and heated with a crease for 5 to seconds to 200 F. on a flat surface with an electric iron, washed with very dilute acetic acid and then with very dilute hydrogen peroxide.

The material was hung up and dried. It dried with the crease ironed in at one line, but dried flat elsewhere where treated and the crease was permanent. The untreated area wrinkled. The color was slightly affected, but this may be allowed for in dyeing. The feel of the treated portion was improved to that of a much more expensive flannel. I

A purple soft fine womans wear wool with a tendency to crepe when wetted made by the same company was similarly treated with the same solution, at a temperature of about 180 F. with a crease. The color was slightly altered, which could be allowed for in the dyeing. The material retained its crease where treated and dried fiat where treated, but became crepe-like elsewhere.

A blue mans worsted cloth, like a summer alpaca made by the same people was similarly treated at F. The crease was permanent and the treated area re.- mained flat.

It will be noted that most of the named compounds contain both a hydroxyl and a mercapto group and com tain an organic radical either in the acid or the basic element. 7

Having thus described my invention and illustrated its use, what I claim as new and desire to secure by Letters Patent is:

1. A hair waving lotion consisting essentially of an aqueous solution of at least 4% thioglycolic acid, by weight of the solution, the solution having been neutralized to a pH of about 8 with an alkali metal hydroxide to attain the equivalence point for the resulting thioglycolate salt, and having then been brought to a pH in the range of about pH 9 to about pH 10 by the addition of ammonia.

2. A hair waving lotion consisting essentially of an aqueous solution of at least 4% thioglycolic acid, by weight of the solution, sufiicient alkali metal alkali to produce a pH of about 8 with this thioglycolic acid concentration, and sufiicient ammonia to give an ultimate pH in the range of about pH 9 to about pH 10.

3. A hair waving lotion consisting essentially of an aqueous solution of thioglycolate, equivalent: to 1 to 15% thioglycolic acid by weight of the solution, sufiicient alkali metal alkali to produce a pH of about 8 with this thioglycolic acid concentration, and sufficient ammonia to give an ultimate pH in the range of about pH 9 to about pH 10.

4. A hair waving lotion consisting essentially of an aqueous solution of at least 4% thioglycolic acid, by weight of the solution, sufficient alkali metal alkali to produce a pH of at least 6 with this thioglycolic acid concentration, and sufficient ammonia to give an ultimate pH of about 7 to about 9.5.

5. A hair waving lotion consisting essentially of an aqueous solution of l to 15% thioglycolic acid by weight of the solution, sufiicient alkali metal alkali to produce a pH of at least 6 with this thioglycolic acid concentration, and sulficient ammonia to give an ultimatepH of about 7 to about 9.5.

6. A hair waving lotion consisting essentially of an aqueous solution of 4 to 10% thioglycolic acid by weight of solution, sufiicient alkali metal alkali to produce a pH of about 8 with this thioglycolic acid, concentration, and sufiicient ammonia to give an ultimate pH in the range of about 9 to about 10.

7. A hair Waving lotion consisting essentially of, an aqueous solution of 4 to 10% thioglycolic acid by weight of solution, sufiicient alkali metal alkali to produce a pH of at least 6 with this thioglycolic acid concentration, and suflicient ammonia to give an ultimate pH of about 7 to about 9.5.

8. A hair waving lotion consisting essentially of an aqueous solution of alkali metal and ammonium salts of an aliphatic mercaptan carboxylic acid of not more than three carbon atoms, equivalent to from 1 to 15% aliphatic mercaptan carboxylic acid by weight of solution, having a pH in the range of about pH 9 to about pH 10, the proportion of said alkali metal salt being such that it would produce a pH of at least 6 with this concentration of said acid in the absence of ammonia.

9. The product of claim 8 wherein at least a part of the alkali metal is substituted by a lower alkanolamine.

10. The method of permanently changing the configuration of hair on the living human scalp including the steps of treating the hair with the permanent waving solution of claim 8 and then fixing said configuration.

11. The method of permanently changing the configuration of hair on the living human scalp including the steps of treating the hair with the permanent waving solution of claim 9 and then fixing said configuration.

12. A hair waving lotion consisting essentially of an aqueous solution of alkali metal thioglycolate and ammonium thioglycolate, equivalent to at least 4% thioglycolic acid by weight of solution, having a pH in the range of about pH 9 to about pH 10, the alkali metal proportion of alkali metal thioglycolate being such that it would produce a pH of about 8 with this thioglycolic acid concentration in the absence of ammonia.

13. The method of permanently changing the configuration of hair on the living human scalp including the steps of treating the hair with the permanent waving solution of claim 12 and then fixing said configuration.

14. A hair waving lotion consisting essentially of an aqueous soultion of an alkali metal thioglycolate and ammonium thioglycolate, equivalent to from 1 to 15% thioglycolic acid by weight of solution, having a pH in the range of about pH 9 to about pH 10, the proportion of alkali metal thioglycolate being such that it would produce a pH of at least 6 with this thioglycolic acid concentration in the absence of ammonia.

15. The method of permanently changing the configuration of hair on the living human scalp including the 6 steps of treating the hair with the permanent waving solution of claim 14 and then fixing said configuration.

16. A hair waving lotion consisting essentially of an aqueous solution of an alkali metal thioglycolate and ammonium thioglycolate, equivalent to from 3 to 15% thioglycolic acid by weight of solution, having a pH of about 7 to about 9.5, the proportion of alkali metal thioglycol'ate being such that it would produce a pH of at least 6 with this thioglycolic acid concentration in the absence of ammonia.

17. A hair waving lotion consisting essentially of an aqueous solution of sodium thioglycolate and ammonium thioglycolate, equivalent to from 4 to 10% thioglycolic acid by weight of solution, having a pH of about 7 to about 10, the proportion of sodium thioglycolate being such that it would produce a pH of at least 6 with this thioglycolic acid concentration in the absence of ammonia.

18. A hair waving lotion comprising about 10 grams of thioglycolic acid, about 7 grams of sodium hydroxide, about 20 cc. of aqua ammonia of about 26 B. dissolved in about 100 cc. of water.

19. The method of permanently changing the configuration of hair on the living human scalp including the steps of treating the hair with the permanent waving solution of claim 18, the hair being physically contoured to the desired configuration, and then fixing said configuration.

20. The method of permanently changing the configuration of hair on the living human scalp including the steps of treating the hair with the permanent waving solution of claim 18, the hair being physically contoured to the desired configuration, varying the time of treatment from five to thirty minutes, according tothe type of hair treated, and then fixing said configuration.

References Cited in the file of this patent UNITED STATES PATENTS Speakman May 21, 1940 Evans June 27, 1944 OTHER REFERENCES

Claims

1. A HAIR WAVING LOTION CONSISTING ESSENTIALLY OF AN AQUEOUS SOLUTION OF AT LEAST 4% THIOGLYCOLIC ACID BY WEIGHT OF THE SOLUTION, THE SOLUTION HAVING BEEN NEUTRALIZED TO A PH OF ABOUT 8 WITH AN ALKALI METAL HYDROXIDE TO ATTAIN THE EQUIVALENCE POINT FOR THE RESULTING THIOGLYCOLATE SALT, AND HAVING THEN BEEN BROUGHT TO A PH IN THE RANGE OF ABOUT PH 9 TO ABOUT PH 10 BY THE ADDITION OF AMMONIA

18. A HAIR WAVING LOTION COMPRISING ABOUT 10 GRAMS OF THIOGLYCOLIC ACID. ABOUT 7 GRAMS OF SODIUM HYDROXIDE, ABOUT 20 CC. OF AMMONIA OF ABOUT 26* BE DISSOLVED IN ABOUT 100 CC. OF WATER