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Publication numberUS3148126 A
Publication typeGrant
Publication dateSep 8, 1964
Filing dateMar 30, 1953
Priority dateApr 4, 1942
Publication numberUS 3148126 A, US 3148126A, US-A-3148126, US3148126 A, US3148126A
InventorsHarry Martin
Original AssigneePermanent Hair Waving Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Compositions suitable for hair curling
US 3148126 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,148,126 COMPOSITIONS SUITABLE FOR HAIR CURLING Harry Martin, Monroe, N.Y., assignor, by mesne assignments, to Permanent Hair Waving Corporation, Norfolk, Va., a corporation of Virginia No Drawing. Original application Apr. 4, 1942, Ser. No. 437,628. Divided and this application Mar. 30, 1953, Ser. No. 345,701

4 Claims. (Cl. 16787.1)

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 No. 383,204, filed March 1'3, 1941, now Patent No. 2,350,178, of May 30, 1944.

It has been found possible in the past, if dangers and unpleasantness were ignored, to elfect 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 oflensive and nauseous.

It hast 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 operators hands 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 difficulties are overcome, and a curling solution is provided which is highly effective in the cold, is harmless, is economical to prepare, is safe in unskilled hands, is so nearly odorless that its odor is easily covered up, leaves no toxic 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 suit able 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.

The same solution, in the hands of a skilled operator, with the further addition of 15 cc. of 26 B aqua ammonia, making a solution of pH 11.6 waved the hair in one and one-half to two hours, and was washed out the same way.

A more rapid procedure was to wet the rolled-up hair with the same solution, leave for fifteen minutes or more, 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 appears to be an effective agent in this process. The oxygen of the air seems to convert the thioglycolate to a dithiodiglycolate which is inert and comparatively odorless.

It was found that oxygen gas delivered under a helmet covering the scalp was highly effective in arresting action 3,148,126 Patented Sept. 8, 1964 of the thioglycolate and destroying its odor and giving the best interior curl.

One solution deodorized by witch-hazel was well adapted to professional use, as follows:

10 grams thioglycolic 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.

Ofter 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 was added 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 have proved the most satisfactory compromise solution for all round 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 to make pH 8, then 26 B. aqua ammonia to make pH 9.9, then dilute to cc.

A 1% alkaline solution of the thioglycolic acid curled hair at 212 F.

Other acids and salts containing not more than three carbon atoms in the acid radical were usable. Thus 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 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 monoethanolarnmonium-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 with them in solution, thus avoiding any uncertainty or difiiculty 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.

Isopropanolamine substitued for the monoethanolamine under the same conditions, yielded a corresponding product similarly useful. The product was N-oxypropyldithioglyeolamide.

When butanolamine was substituted for-the monoethanolarnine under the same conditions, it yielded a corre- 3 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 glyceryl monothioglycolate, which also proved useful 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 mens trousers.

A pink flannel made by Botany Worsted Mills 404/ 1068/ 13444 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 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 allowedfor in dyeing. The feel of the treated portion was improved to that of a much more expensive flannel;

A purple soft fine womans wear wool with a tendency to crepe wh'n wetted made by the same company 114/ /6649 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 flat where treated, but became crepelike elsewhere.

A blue mans worsted cloth, like a summer alpaca 48/ 1/ 179 made by the same people was similarly treated at F. The crease was permanent and the treated area remained flat.

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

Reference is made to the companion application Serial No. 276,883, filed March 15, 1952, now US. Patent No. 2,876,781 from which application claims have been transferred.

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

1. The process of giving permanent shape to hair which comprises arranging'the hair in the desired form and treating it with an alkaline solution containing an alkanolamide of an aliphatic mercaptan carboxylic acid of not more than three carbon atoms, the amount of said mercaptan compound by weight being from about 1% to 15%, said solution having a pH of from about 7 to about 9.5, and thereafter. eliminating such solution from the hair in order to set the latter.

2. The process of giving permanent shape to hair which comprises arranging the hair in the desired form and treating it with an alkaline solution of N-oxyethylthioglycolamide, the amount of said N-oxyethylthioglycolamide by weight being from about 1% to 15%, said solution having a pH of from about 7 to about 9.5, andthereafter eliminating such solution from the hair in order to set the latter.

3. A hair-waving lotion having as its principal ingredient an N-alkanolamide of an aliphatic mercaptan carboxylic acid of not more than three carbon atoms, the amount of said mercaptan compound by weight being from about 1 to 15 said lotion containing free alkali to give a pH of from about 7 to about 9.5 and containing also an aqueous carrier for said compound and said alkali, said lotion being useful to impart a permanent wave to hair in the cold.

4. A hair-waving lotion having as its principal ingredient N-oxyethylthioglycolamide, the amount of said N- oxyethylthioglycolamide by weight being from about 1 to 15%, said lotion containing free alkali to give a pH of from about 7 to about 9.5 and containing also an aqueous carrier for said N-oxyethylthioglycolamide and said alkali, said lotion being useful to impart a permanent wave to hair in the cold.

References Cited in the file of this patent UNITED STATES PATENTS 2,736,323 McDonough Feb. 28, 1956

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2736323 *Aug 13, 1949Feb 28, 1956Tide Water Patent Dev CompanyPermanent waving solutions and method
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4192863 *Jun 17, 1975Mar 11, 1980Tokuzo KondoCompletely one-step permanent wave solution and a method for using the same
US4832948 *Dec 28, 1987May 23, 1989Tokuzo KondoPermanent wave solution
US5041286 *Jul 25, 1989Aug 20, 1991Yasmin Products Pty. LimitedProcess for reconfiguring keratin fibre
US5091573 *Aug 27, 1990Feb 25, 1992Rohm And Haas CompanyThiol-terminated hydroxyamides
US5247125 *Feb 28, 1991Sep 21, 1993Rohm And Haas CompanyThiol-terminated hydroxyamides
U.S. Classification132/203, 8/127.6, 132/204, 424/70.5
International ClassificationA61Q5/04, A61K8/46, A61K8/30
Cooperative ClassificationA61Q5/04, A61K8/46
European ClassificationA61K8/46, A61Q5/04