Office 2,990,336 Paterated June 27, 196 2 step of employing the hair waving components com 2,990,336 prising water soluble mercaptains in carbon dioxide gen PROCESS OF HAR WAVING ANB) erating solutions, such as carbonic acid water whereby Harry Martin,PREPARATION Monroe, N.Y., THEREFOR assignor, by direct and introduction of harmful minerals in the hair waving mesne assignments to Permanent Hair Waving Corpo 5 preparation is minimized and the introduction of oxidiz ration, Norfolk, Va., a corporation of V ing components retarded, if not completely eliminated. No Drawing. Filed Oct. 16, 1959, Ser. No. 846,818 Still more particularly it is contemplated by my in 9 Clains. (C.167-87.) vention to provide a hair waving preparation which is This invention relates to compounds and methods for self contained in the relationship of the mercaptain radical hair waving and preparations therefor. 10 to the base, which may be stored under any climatic con Known to me are the methods for waving hair in the ditions without deterioration so as not to require special cold by the use of mercapto products and more particu packaging prescriptions but which is arranged to be larly such products as thioglycerine, thioglycolic acid and brought into solution in an aqueous medium when re a wide range of mercaptain containing materials disclosed quired by the addition of the aqueous solvent, whereby in my prior applications Serial No. 383,204, now Patent 15 the formation of the undesirable by-products and ob No. 2,350,178, and Serial No. 437,628, filed April 4, 1942, noxious odors is minimized, if not completely avoided, now Patent No. 2,773,293. This application is a con- . and upon solution in the carbonated aqueous medium, tinuation-in-part of my application Serial No. 326,593, ofassures components a standardized which maystrength deleteriously without the affect introduction the hair filed December 17, 1952, now abandoned, that is, in turn, 20 in the process of conducting the hair waving operation, a continuation-in-part of my application Serial No. 437 whether in the cold or by associated application of ex 628, filed April 4, 1942, and the subject matter of the ternal heat. latter application is included in my application Serial No. Still further, in accordance with my invention, I have 255,725, filed November 9, 1951. All of these prepara discovered that novel mechanical as well as chemical tions which have been found commercially feasible are 25 procedural benefits are obtained in cold hair waving by supplied on the open market for hair waving in solutions directly applying a cold hair waving preparation of water in which a water medium is supplied, adjusted to a pre soluble mercaptain compounds dissolved in a carbonic determined hydrogen ion concentration of pH, which is acid releasing solution, such as carbonic acid solutions, calculated to minimize damage of toe hair, or to stabilize and applying the solution so made to the hair, whereby the product in accordance with the use to be made in 30 initial rinsing or washing of the hair may be avoided, a the hands of a professional hair technician or chemist. predetermined strength of mercaptain is applied and an In accordance with my discovery, these products are inter-facial agitation secured between the solution and subject to objection by reason of the prescription to wash the hair to cause an efficient hair waving operation in the hair before the application of the cold waving prep which the curl which results is effected in the wet and aration and afterward. While this procedure may seem 85 persists after drying with highly desirable results, evi to be innocuous, it has been my experience that lack of dencing little or no dulling or embrittlement of the hair attention to the nature of the diluting agent, rinsing agent when dry. or washing agent has resulted in damage to the hair, and Still more particularly it is an object of my inven has made for unpredictable results, especially in the hands tion to provide a hair waving preparation which is self of the unskilled. This I attribute to the fact that in the 40 contained with regard to the relationship of the acidic use of hard water, such as is found in various portions factor to the base factor, to cause a relaxation of the of the world, including various mid-western and western hair component, to produce a highly desirable wave which states of the United States, there is a sufficient presence persists in the transitory stage from a wet curl to a dry of calcium compounds and the alkaline earth compounds, curl, and has predetermined strength by reason of its in such as magnesium or lime, to combine with the thio 45 activity when stored dry, characterized by its predeter glycolic acid radical or various mercaptains to form un mined strength when it is employed to wet the hair in desirable reactions, even to the point of forming a depila the procedure for carrying out cold waving operations tion component. This latter reaction product is especial in the presence of water charged with carbonic acid gas ly harmful to the hair if the hair waving solution is per and further, characterized by exerting inter-facial agita mitted to dry on the hair or stay in contact with the hair 50 tion on contact with the hair whereby initial rinsing or for long periods, such as overnight, in which event there washing operations are omitted and deleterious side ef occurs at least a superficial concentration of the calcium fects overcome. in combination with the mercaptain employed, to form a Further novel inherent aspects of my preparation and depilation compound, dulling or weakening the hair. the process of producing hair waving will become ap In accordance with one form of my invention, I have 55 parent and be more clearly outlined as this description found that if the solvent for the water soluble mercaptan proceeds. compounds is brought together with these mercaptain For a clearer understanding of my invention, I refer compounds on the hair under conditions minimizing, if sto the following: - not completely excluding, the presence of minerals found Example I-Preparation of dry ammonium thiogly in hard water, such as the alkaline earth materials, of 60 colate hair waving preparation. which magnesium and lime are examples, and under con Thioglycolic acid is dissolved into chilled isopropyl ditions minimizing the presence of adsorbed air or oxy ether. Into this solution maintained at a temperature be gen, that standard procedure may be adapted for hair low about 37 F. there is then introduced ammonia gas waving, particularly in the cold, to secure highly desirable by bubbling the same into it. Additions of the ammonia hair waving operations with minimum hair dulling ef 65 gas are charged into the ether solution of thioglycolic acid, fects, and thereby to secure a standardized time factor in in accordance with the alkalinity of the end product which the exposure of the hair to the hair waving mixture. is desired. More specifically, in accordance with my invention, Desirably the introduction of the ammonia gas may be I have discovered that hair waving, particularly in the the point where the separated ammonium thioglycolate cold, may be carried out, with controlled time factors 70 evidences pH between 9.5 and 9.6. When a precipitated and without harmful effects, and more particularly with product that is soluble in the Drierite treated ether begins out initially rinsing or washing the hair, by the procedural to evolve, additions of ammonia gas serve to raise the 2,990,338 3 4. alkalinity until, at optimum charge, pH 9.5 or 9.6 by test inducing the desired wave. Adjustments may be found is reached. Separation is effected by decanting the ethereali necessary in the time and concentration as different types layer. The precipitate is dried, preferably under vacuum, of hair are required to be treated, it being observed that to achieve dry ammonium thioglycolate, with a self-con the greater the concentration and pH, the lower the time . tained or in situ deposited base which may evidence a pH factor and, conversely, the more dilute the solution and of 6.5 to as high as pH 10.5. the lower the pH, the longer will be the time necessary The ether employed in the foregoing and subseqently to effect the desired wave. Therefore the amount of time described examples is that which has been dehydrated as for treatment will be a factor of concentration and pH. by Drierite (a calcium sulfate dehydrating or like agent). The hair, after treatment and removal from the form In carrying out this reaction, it is preferred to prepare 0. which holds it curled, is rinsed with water. Preferably a 200 ml, 0.39 molar solution of thioglycolic acid in butyi an acid shampoo or detergent is used, and benzyldimethyl ether which is placed in a flash and then cooled with Dry ammonium chloride (phemerol chloride) is suggested. Ice (-40 C.). A second flask containing 175 ml. of Example II.-For the preparation of a composite thio ethyl ether was cooled to -40° C. by means of a Dry Ice glycolate in situ mixed base, the dry preparation may be bath; and, while so chilled, ammonia gas was introduced 5 as follows: into and condensed in the ethyl ether until 34 grams of Seven grams of sodium hydroxide are dissolved in 150 ammonia had been added. The chilled solution of thio ml. of ethyl alcohol with stirring. A solution of 10 grams glycolic acid was added by a dropping funnel to the ethyl of vacuum distilled thioglycolic acid in 50 ml.