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. of ethyl ether-ammonia and a white precipitate formed. When alcohol was added through a dropping funnel to the solu the addition was complete, the flask containing the preci 20 tion of sodium hydroxide with continued stirring of the pitate was removed from the Dry Ice and allowed to warm thioglycolic acid solution. Simultaneously, ammonia gas to room temperature. It was then stoppered and placed in is bubbled through the sodium hydroxide solution; and, a Dry Ice chest overnight and the next morning it was during this gaseous infusion of ammonia and while the allowed to warm to room temperature. The precipitate stirring was continued, the thioglycolic acid solution was was separated, washed with dry ethyl ether and dried in a 25 introduced in small amounts extending over a period of 10 vacuum desiccator. The X-ray diffraction pattern of the minutes. With each addition of the acid a heavy white precipitate obtained by this process shows no evidence of precipitate formed that redissolved to form a cloudy solu crystallinity and it is an amorphous product. A 1.0 per tion. At the end of the addition of the acid a short period cent aqueous solution exhibits a pH of 9.0. of time passed in which a cloudy solution existed and then The dry preparation thus provided may have added to 30 a heavy granular precipitate formed. The precipitate it from 2% to 5% of dry crystalline sodium hydrosulfite was separated by filtration, washed with ether and dried The dry in situ basic ammonium thioglycolate, with or in a vacuum desiccator over calcium chloride. The prod without the sodium hydrosulfite, may be packaged in pill uct was a granular, free-flowing solid which, in a 1 percent form in sealed foils, capsules or ampules, envelopes or aqueous solution (distilled water), gave a pH of 11.1. packets, until ready for use, with little or no deterioration. 35 The foregoing reaction is accelerated by carrying out Where high humidity conditions may be encountered, a the reaction under refrigerated or chilled conditions. moisture occluding coating may be applied to the pills That is, the ethyl alcohol solution of sodium hydroxide similar to the enteric coatings found on some medicinal may be cooled to a temperature of about or below 10° C. preparations. Normally solid sulphonated oils providing and preferably, of from 0 to 5°C. a material in the nature of a detergent may be employed The precipitated product may be dried and packaged as coatings. If packaged in envelopes, the presence of or formed into a dry merchandizable product in accord the sodium hydrosulfite serves as a reducing agent for ance with the procedure heretofore described. This prod any oxidation product. uct may be mixed with the crystalline sodium sulfite be In use, 10 grams of the solid may be added to 100 cc. fore packaging. Where the dry preparation is made, the of water. I prefer, for the benefits hereinbefore indicated, 45 procedure hereinbefore described for solution in a carbo to use standard carbonated water, the beverage, or stand nated water should be followed. ardized carbonic acid solutions in which the demineralized Example III.-In this preparation, 10 grams thiogly water has been charged with carbonic acid to a pressure colic acid, 3 grams monoethanolamine and 1 gram so of five volumes of gas to one volume of water. This dium thioglycolate are dissolved in isopropyl ether (Dri formula will be effective in from 10 to 40 minutes, de erite treated) cooled to about 37 F. pending upon the nature of the hair. Stoichiometric amounts of ammonia gas may be in The procedure for cold waving may be to apply the fused into the chilled solution, calculated to make a solu freshly made solution in the carbonated water to the hair tion having a hydrogen ion concentration or pH 8.5 when and when saturated upon curlers, in accordance with a test sample is introduced into 100 cc. water. The pre standard procedure such as Croquignole or spiral wire 55 cipitated reaction product is dried to evaporate any resid curlers recirculation, preferably a loose wind, the proce ual ether. This compound may be hygroscopic and is dure varying in that the effervescing solution may be ap preferably mixed with the reducer or clearing salt pre plied directly to the hair without the necessity for pre viously described in the same ratio and packaged in liminarily rinsing or washing the same. Inter-facial ampules. The ampule packaged dry material may be gaseous agitation between the layer of the solution and the 60 employed in the process heretofore described for perma hair makes possible the elimination of wetting agents as nently waving hair in the cold, employing the procedure well as to cause the release of any adherent scale, dust before described, especially using carbonic acid charged and more intimately to bring the hair waving solution water. into contact with the hair. The hair may then be covered While I have described the preparation of a dry thio with additional quantities of the solution, such as by pads glycolate in which the base is the ammonia radical or a saturated with the solution, and the head is then desirably mixture of ammonia and alkali metal hydroxide such covered with some impervious cap such as by covering as sodium, I may prepare a dry preparation in which the entire head with a shower cap. an organic salt of thioglycolic acid is produced. Accord The hair may be left in this condition from thirty ingly, an organic base, such as guanidine, morpholine or minutes to eight to ten hours, depending upon the con 70 ethylene diamine may be reacted with thioglycolic acid. centration which is employed. A adjustment of the base to procure a thioglycolate which is normally dry and has. to the thioglycolate to provide pH about 9.5 to 9.6 and a in situ the self-contained reacted acid and base. concentration of the thioglycolate in water to about 8% The addition of stoichiometric amounts of the organic has been found to result in a preparation which, with bases to the thioglycolic acid is effected by dissolving the some types of hair, requires only a half hour contact for thioglycolic acid in an inert carrier such as isopropyl ether 3,990,336 S 6 or isopropanol. While the reaction mixture is chilled at dissolved in isopropy ether (dried as before described) a temperature below about 37 F. the reaction product and chilled to 0 C. s thrown out upon the addition of the organic base and A heavy, waxy precipitate is thrown out of solution. is filtered and vacuum-dried, as previously described. This precipitate is filtered, redissolved and recrystallized The quantity of the base may be to retain the pH below from water to provide a product having a melting point 9.6 and as low as pH 7. The addition of the base in of 78 C., with an assay of 99.83%. s excess of an amount to produce pH 9.6 may require care The dry super based morpholine thioglycolate and asso ful handling as to time and concentration as above pH ciated base may be dissolved in water which, when using 105 and as high as pH 13.0 may be secured to produce 6.5% (calculated as thioglycolic acid), gives a solution a depilatory if desired, with the proper control of time 10 having pH 9.5. This preparation gives a tighter curl, and concentration. with more lustrous sheen than sodium or ammonium thio The organic addition salts of thioglycolic acid, such glycolate at the same pH and concentration. as the guanidine thioglycolate, the morpholine thiogly Accordingly the dry product stripped from the ether colate or the ethylene diamine salt, where employed, are mixed with or coprecipitated with the added base or more desirable than the ammonium and sodium thio 15 morpholine to raise the pH within a range from 7.5 to glycolates in that as solutions they evidence practically 9.5 or above, may be packaged in accordance with any no offensive odors and may be employed in solutions of the procedure, heretofore described and may be em having a lower pH, i.e. pH 7.6, as compared with pH bodied in a carbonated water as a solvent, with the fea 9.5 for ammonium thioglycolate and in a concentration tures heretofore described for carrying out the hair wav of one half strength, i.e. 2%% solution as compared with 20 ing treatment. The added base in dry form may exceed 6.9% solution of ammonium thioglycolate. 9.5 where other than cold hair waving products are Example IV.-In this example 2 moles thioglycolic acid formed. (184 grams) are treated with 1 mole guanidine carbonate Example VII-1 mole of 70% ethylene diamine is (180 grams-equivalent to 2 moles of free guanidine added to 2 moles thioglycolic acid. Isopropyl alcohol base) in an ether solution. 25 chilled to a temperature of 3 C. (37 F.) is added to The mixture is allowed to stand under refrigerated show the formation of the organic salt of thioglycolic conditions (0 C.) for two hours until the reaction salt acid as a heavy precipitate. The salt is filtered and dried. which precipitates settles, whereupon it is filtered, dried, The thioglycolate is hygroscopic and does not give a dissolved in water and recrystallized. The dried salt sharp melting point, Analysis for the mercaptan value shows a melting point of 105-106 C., with an assay 30 shows the material to be 100% and corresponding to the of 99.8%. following formula: The guanidine thioglycolate which is thus formed may be dissolved in water to form a 6.8% solution (based on thioglycolic acid content), and then mixed with a base of pH 7.6. A cold wave made with this solution pro 35 vides a longer-lasting curl than sodium or ammonium thioglycolate solutions of equivalent strength having pH The thus formed ethylene diamine thioglycolate, which 9.5, in that the curl is tighter and persists upon drying, is separated, when formed in a solution of water in con rather than showing a tendency to loosen upon drying. centration of 5% calculated as thioglycolic acid and While most of the mercaptain compounds of sodium 40 added base to give pH 8.8 may be employed to wave and ammonia in alkaline media swell the hair fibres, hair and gives a better cold waving curl than the corre making it appear grayish, frizzy and losing at least 25% sponding salt of sodium, ammonium thioglycolate and of its original diameter of curl, the organic guanidine the mixed sodium and ammonium thioglycolate of high thioglycolate and base mixture, as here described, seems strength and pH value. v to contract the hair and give a curl that appears shiny, 45 Accordingly the ethylene diamine thioglycolate, either smooth and in effect at least 10% smaller in diameter coprecipitated or dry mixed with a base to provide a than the original curl. dry product, may be packaged or pill formed as above Example V-1 mole of guanidine carbonate is added, after the dry mercaptain salt and base are brought to with constant stirring, to a dry isopropyl ether solution gether to the desired pH. maintained at a temperature of 5 C. and containing 2 50 Example VIII-1 mole of thioglycolic acid is slowly moles of thioglycolic acid. A white coprecipitate in added to 1 mole of 70% ethylene diamine. Equal vol soluble product of guanidine thioglycolate forms in a ume of isopropyl alcohol is added and the mixture per menstrum of excess basic carbonate. This is filtered off mitted to stand in a refrigerator at 37 F. overnight. and dried. An aqueous layer consisting of guanidine The precipitate is separated and dried. The mercaptan thioglycolate and carbonate dissolved in the water of salt 55 analysis of the material showed an assay of 94.8% as formation also is obtained. This is separated from the ethylene diamine mono-thioglycolate. ether layer, the water evaporated off under vacuum and the dry super based guanidine thioglycolate and base re O covered from the water layer is mixed with the precipi NH-CH-CH-NE-O-C-CH-SH tate with added dry base to leave a dry product of pre 60 A 6% concentration solution (on a thioglycolic acid determined alkalinity. basis) with added base to give pH 9.5 may be prepared The aforesaid resulting guanidine thioglycolate and ad in water. mixed carbonate may be packaged dry, as in the prior A cold waving solution may be made in accordance examples, to be used by solution in water to make a 3% with the procedure previously outlined, preferably em concentration calculated as thioglycolic acid and pH 9.0. ploying the carbonated water. The curl, upon drying, The procedure for cold waving by dissolving in stand exhibits the properties heretofore described in connection ardized carbonated water, as previously described, may with the previously described organic salts of thioglycolic be also followed with the organic salt of thioglycolic acid acid and added base component. Accordingly the filtrate and base admixture. The dry curls made with this form described above may be mixed with a dry base to give of the thioglycolate mixture provides a tighter curl than the pH desired or, being dried, the base forming con ammonium and sodium thioglycolate, which has been stituent may be embodied and dried in situ. alkalinized to pH 9.5 with a 6.1% of thioglycolic acid While the guanidine thioglycolates and augmented base value in solution. mixture or coprecipitate as above described are useful Example VI.-2 moles of morpholine (174 grams) are and effective in cold waving, it will be observed that those added with constant stirring to 3 moles thioglycolic acid 75 hereinabove described may be used in depilatory creams 2,990,833 3. by the addition of a base to pH from 11.9 to 12.2, with a rate, chilled solutions which are mixed with agitation the said guanidine thioglycolate content of 6% based on or the base, when in gaseous form, may be infused into the thioglycolic acid. a chilled solution of the thioglycolic acid or alkyl thio Example IX.-8.5 grams thiolactic acid are suspended glycolate in the anhydrous organic liquid medium. It is in isopropyl ether chilled to a temperature of about 0° C. also possible to introduce the reactants into the anhydrous to which monoethanolamine is added in which a test Slam liquid medium and then subject the reaction mixture to ple shows pH 8. Thereupon ammonia gas is infused until the above refrigerated or chilled condition to precipitate a test sample shows pH 8.5. out the desired product. The reaction forms an aqueous and ether layer which The aforesaid dry powder, pill, capsulated or am may be decanted. The resultant salt which precipitates O pulated products in each of the examples are to be fur of lactic acid is vacuum dried. The presence of the nished to the trade to be used with neutralizer com monoethanolamine in this particular case may make a pounds furnished in dry form or with other known neu hygroscopic mixture and the dry preparation is desirably tralizer compounds. For purposes of exemplification maintained in ampules, to be used in one form of my in refer to sodium perborate. This perborate solution may vention with the carbonated water as previously de 5 have added to it immediately before use, after the hair scribed in applying the cold waving solution to the hair. treatment with the mercaptain compounds, solutions of A further formula is as follows: acetic acid or vinegar, tartaric acid or malic acid, in Example X-N-oxyethylthioglycolamide is made by order to produce a nascent hydrogen peroxide solution dehydrating a mixture of monoethanolamine and thiogly of acidified character. colic acid. The mixture is heated at about 140 C., at a 20 Where a dry mercaptain is made by the formation of pressure of 15 to 22 mm. until the proper computed an amide of extreme basic nature, it may be brought to amount of water is removed and collected. The resulting the lower pH's within the desired range and preferably product is ready for immediate use. about pH 9.5 or lower in the dry form by the addition Example XI-Isopropanolamine substituted for the of carbon dioxide gas. monoethanolamine under the same conditions as in Ex 25 Likewise, while I may reduce the pH of the basic ample X yields a corresponding product, similarly useful. thioglycolamide with carbon dioxide, I may do so by The product is N-oxypropylidithioglycolamide. adding an acid mercaptain in order to reduce the pH in Example XII-As another method for making a dry, the foregoing formula of a ratio of .1 mole of methyl self-contained thioglycolamide preparation, the following thioglycolate to .2 mole of ammonia, which will provide procedure is outlined: 30 an ester which has about pH 9.9. To 0.1 mole methyl thioglycolate (or 10 grams) in Other reaction products and mechanical inter mix refrigerated (37 F.) isopropyl ether there are intro tures will suggest themselves from my disclosure in my duced 0.2 mole ammonia gas (or 121 grams of NH4OH application Serial No. 437,628 with regard to the forma (28%)) until no more ester layer is visible. or it may be tion of a dry thioglycolate coprecipitated base and/or brought up by excess ammonia to give a thioglycolamide 35 basic admixture for use in forming a self-contained in situ of about pH 9.9. Then reduce the pH with carbon di precipitated thioglycolate or mercapto radical and base oxide gas to any pH desired, preferably pH 9.5, where a which optionally, upon the addition of the sulfite or clear reduction in pH is to be accomplished. Where a higher ing salt heretofore described, may be stored dry as a pH is desired, more ammonia gas is introduced into the powder, or in an anpule. Thus also the dry sodium batch. Decant the isopropyl ether layer and dry the salt 40 thioglycolate as an acidic component below pH 7 may be under vacuum. The resulting salt may then be packaged coprecipitated or mixed with ammonium carbonate, or for use with the carbonated water, as previously de guanidonium carbonate to above pH 7. scribed. The concentration in each charge or pili or pack These components or mixtures upon addition to age and its pH will be determined and instructions given charged or carbonated water in accordance with the in accordance with the time of treatment and hair to be standardized prescription for making the beverage, or in waved. a water extended paste result in the desirable cold hair Example XIII-60 ml. of ethyl thioglycolate was waving preparation heretofore described. The use of placed in a graduate and 20 ml. of 70 percent alcohol distilled water will give desirable results in each instance. was added. Dry ammonia gas was bubbled through the Likewise it will be understood that the aforesaid prep liquid, producing considerable turbulence. The addi 50 arations may be employed to crease-proof woolens and tion of ammonia gas was continued for about 12 hours like keratin containing products. (overnight), and a syrupy, semi-solid product was The Solution may also be employed for embossing ani formed that was readily soluble in water. Chilling the mal fibres. reaction mixture to 10° C. caused the product to con Increase of the added base to give a product of as geal to a pasty mass. Cooling in a Dry Ice bath gave 55 high as pH 13 makes the product valuable for depilation. a hard solid mass which, when warmed to room tem Likewise while I have described the preparation of the perature, became a waxy solid. This was dried under base-fortified dry mercaptain mixtures for use in pills, vacuum over calcium chloride and the product gave a capsules, ampules, packets, a cream may be made of pH of 6.9 in a 1 percent solution in distilled water. said preparations employing diglycol laurate-S. The dry It will be seen from the foregoing examples that 60 mercaptain compound may be used as a 3.5%-10% addi either thioglycolic acid or an alkyl thioglycolate may be tion to the water extended paste-like laurate compound. reacted with a base in an anhydrous liquid medium; such In general, the provision of the mercapto or thiogly as, for example, lower alcohols and lower ethers, to pro colate Salt, with either of the organic or inorganic bases, vide unique new products which, when dissolved in water, as herein described, assures predetermined strength and provide hair waving solutions having a pH not less than 65 standardized reaction after storage of a hair waving prep 6.5. It is essential that the reactions for preparing these aration, and is particularly valuable where the prepara novel products be carried out under chilled or refriger tion is dissolved in water charged with carbonic acid, as ated conditions (37 F.) or at lower temperatures, pref described, to provide a cold waving preparation in which erably at 0° C. and as low as -41° C. The reaction the resulting curl persists from the wet to and including proceeds slowly at temperatures above 0° C. and may 70 the fully dried condition without loss of curl curvature. take as long as from 12 to 24 hours to become com The utility of the product may be outlined as satis pleted. At temperatures of about 0° C. and lower factory not only for curling hair but likewise for straight (-4. C.) or in the range of from - 41 °-0° C., the ening hair. Also it may be used to crease proof fabrics reaction proceeds rapidly. In carrying out the reactions made of wool or to impart a permanent crease to arti it is possible to maintain one or both reactants in sep 5 cles of apparel, Such as pleating, embossing fabrics either 2,990,336 9 in the hot or cold, and likewise to soften hair and taize lar reaction product of a compound selected from the away its harshness or brittleness. It may be used to group consisting of thioglycolic acid and an alkyl thio soften nails or cuticles and also to modify or perma glycolate, and a base selected from the group consisting inentize the pile condition of fur, either to flatten or raise of ammonia, an amine, guanidine and morpholine, said it. Likewise the wide range of conditions which may be reaction product having been precipitated in an anhydrous emphasized will be clear in that I may treat Chinese organic liquid medium selected from the group consisting hair or horse hair, i.e. the tail and mane hairs as well as of lower alcohols and ethers chilled at a temperature not to soften and curl dog hair for example poodle, and re in excess of 37 F., said base being in an amount in ex lated uses in the veterinarian field. cess of the stoichiometric amount based on the amount I also consider forms of my invention as providing a O of said compound, said anhydrous organic liquid medium normally dry mercaptain compound which may be in the being maintained by said base at a pH in the range of acid form, in which event a quantity of base is added to 6.5-10 as determined when a test sample is introduced bring it to the upper required pH or, conversely, a dry into 100 cc. of water during said precipitation, said reac basic mercaptain may be reduced with a charge of carbon tion product providing upon dissolution in water, a hair dioxide to a range to pH 7. 15 waving solution having a pH of about 7.0. In emphasizing the merit of the dry preparation, it 6. The product of claim 5 wherein said reaction prod should be borne in mind that in making aqueous solu uct is precipitated in said anhydrous, organic liquid medi tions for the trade, it has been found necessary to allow um at a temperature in the range of from -41. C. to extra strength for deterioration by reason of oxidation about O' C. of mercaptain and evaporation of ammonia since this oc 20 7. The method of preparing a stable, dry, precipitated, curs either on the shelf or after the user has opened up solid granular reaction product which, upon dissolution the bottle for partial use. In that manner, instructions in water provides a hair waving solution, comprising dis for use cannot be uniformly followed whereas in accord ance with my invention, the dry preparation being con solving a compound selected from the group consisting Sumed immediately upon dilution, a predetermined con of thioglycolic acid and an alkyl thioglycolate and a base centration, and strength will dictate uniform instructions selected from the group consisting of ammonia, an amine, for use. guanidine and morpholine, said, reaction product being As a further distinguishing feature of my invention, it precipitated in an anhydrous organic liquid medium se is to be noted that it has been the practice to supply the lected from the group consisting of lower alcohols and trade with a greater concentration of the mercaptain com 30 ethers chilled to a temperature not in excess of 37 F., pound in order to allow for deterioration, with the result said base being in excess of the stoichiometric amount that when the fresh product is used it may have a delete based upon the amount of said compound and said an rious effect on the hair. hydrous organic liquid medium being maintained by said In the foregoing disclosure where I have specified base at a pH in the range of 6.5-10 as determined when the use of carbonated water and more particularly car 35 a test sample is introduced into 100 cc. of water, to pre bonated beverages as the materials which are to be cipitate a reaction product in a solid granular form; and employed for dissolving the dry, mercaptain compounds, recovering said reaction product from said anhydrous it has been found that the beverages existing on the organic liquid medium. market with a calcium content of about 8.0 parts per 8. In a method of imparting a permanent wave to million and a magnesium content of 1.5 parts per million 40 human hair including the steps of forming human hair are representative of the type of carbonated beverages into a desired configuration, applying an aqueous solu which may be used in accordance with my invention. tion of a hair-softening agent to said formed hair and The objective to be observed is to minimize as much as possible the use of an aqueous solute such as hard water fixing the configuration, the improvement which consists which carries into the hair an excessive amount of lime of providing said hair-softening agent by dissolving the or magnesium which, during the concentration which composition of claim 5 in water having a calcium content occurs in leaving the preparation on the hair, may have less than about 8.0 parts per million and a magnesium a deleterious effect on the hair. content less than 1.5 parts per million. I claim: 9. The process of claim 8 wherein the hair is neutral 1. A stable dry composition for imparting wave to ized by the application of a neutralizing agent after the human hair when dissolved in water and containing as 50 configuration of the hair has been fixed by application its essential active ingredient a dry, precipitated, solid, of the hair softening agent. granular reaction product of a compound selected from the group consisting of thioglycolic acid and an alkyl References Cited in the file of this patent thioglycolate and a base selected from the group con sisting of ammonia, an amine, guanidine- and morpholine, 55 UNITED STATES PATENTs said reaction product being precipitated in a chilled an hydrous organic liquid medium selected from the group 455,102 Hubener ------June 30, 1891 1,160,317 Perine ------Nov. 16, 1915 consisting of lower alcohols and ethers maintained by 1,616,202 Shook ------Feb. 1, 1927 said base at a pH in the range of 6.5-10 as determined 1987,526 Elbel et al. ------Jan. 8, 1935 when a test sample is introduced into 100 cc. of water, 2,183,894 Pye ------Dec. 19, 1939 said base being in an amount in excess of the stoichiomet 2,222,830 Moss ------Nov. 26, 1940 ric amount based on the amount of said compound, said 2,331,065 Willat ------Oct. 5, 1943 reaction product providing, upon dissolution in water, 2,389,755 Baker ------Nov. 27, 1945 a hair waving solution having a pH not less than 6.5. 65 2,412,282 Nelson ------Dec. 10, 1946 2. The product of claim 1 wherein said dry composi 2,418,664 Ramsey ------Apr. 8, 1947 tion is in the form of free-flowing granules. 2,465,346 Bodman ------Mar. 29, 1949 3. The product of claim 1 wherein said dry composi 2477,492 Moose ------July 26, 1949 tion is in the form of a compressed tablet body. 2,506,492 De Mytt ------May 2, 1950 4. The product of claim 3 wherein said compressed 2,594,030 Coons et al. ------Apr. 22, 1952 tablet body is provided with a coating of a solid detergent 2,600,624 Del Zoppo ------June 17, 1952 composition, 2,631965 Schnell ------Mar. 17, 1953 5. A stable dry composition for imparting wave to 2,660,568 Cunder ------Nov. 24, 1953 human hair when dissolved in water and containing as its essential active ingredient a dry, precipitated, solid granti Other references on following page) 2,990,888 2 FOREIGN PATENTS U.S. Disp, 24th ed., 1947, pp. 244, 245 and 768, (esp. &:675,870 GreatItalia. Britain ------EEE,July 16, 1952 p.in 244,of rt. .345.65colpar, beginning leftol, at bottonis 37. and ending at 499,807 Great Britain ------Jan. 30, 1939 Partington: "Textbook of Inorganic Chem...," Macmil 167,423 Germany ------Jan. 22, 1906 5 lan and Co., London, 6th ed., 1950, pp. 182-188. 1,003,963 France ------Nov. 21, 1951 Flinn et al.: "Waterworks Handbook," McGraw-Hill, . OTHER REFERENCES N.Y., 1916, pp. 716–718. f Beilstein: "Handbuch der Org. Chem." 4th ed., 1921 vol. 3, pp. 245, 257,258. 0

... ----...--, -...-...------a------v------...----...-- UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,990,336 June 27, 1961 Harry Martin It is hereby certified that error appears in the above numbered pat ent requiring correction and that the said Letters Patent should read as corrected below - Column l line 18 for "Patent No. 2,773,293" read -- abandoned --. Signed and sealed this 6th day of March 1962.

(SEAL) Attest: ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents