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Publication numberUS3066077 A
Publication typeGrant
Publication dateNov 27, 1962
Filing dateMay 8, 1961
Priority dateMay 8, 1961
Publication numberUS 3066077 A, US 3066077A, US-A-3066077, US3066077 A, US3066077A
InventorsDe Mytt Louis E, Yung Hsiung Du
Original AssigneeGillette Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Alpha, alpha'-dimercaptoadipic hair waving compositions
US 3066077 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

tit

3,000,777 Patented Nov. 27, 1952 3,066,077 ALPI-IA,ALPHA'-DIMERCAPTOADIPIC HAIR WAVING CGMPOSITIONS Louis E. De Mytt, Chicago, and Du Yung Hsiung, Park Forest, Ill., assignors to The Gillette Company, Boston, Mass, a corporation of Delaware No Drawing. Filed May 8, 1961, Ser. No. 108,312

8 Claims. (Cl. 167-871) This invention relates to the cold permanent waving of hair and pertains more specifically to a hair Waving composition comprising alpha,alpha'-dimercaptoadipic acid and derivatives thereof.

Although a variety of mercaptans has hitherto been proposed for use in the cold permanent waving of hair (by which is meant hair waving without the external application of heat to the hair), those mercaptans containmg two carboxyl groups in the molecule, such as mercaptosuccinic acid and dimercaptosuccinic acid, have been found to be ineffective as waving agents, failing to produce satisfactory waves. Dimercaptosuccinic acid is also very unstable in aqueous solution.

'. It has now been found, surprisingly enough, that the homologous alpha,alpha'-dimercaptoadipic acid, its salts,

esters and amides are effective waving agents for the cold permanent waving of hair. Since this member of the series of dicarboxylic acids has also been found to be non-toxic (Danielli et al., Biochemical Journal, 41, 325 (1947)), is is unique in its utility as an agent for the cold permanent waving of hair. Moreover, dimercaptoadipic' acid and its derivatives are stable in dry solid form, making it possible to provide hair waving compositions either in the form of aqueous lotions or as dry solid compositions adapted to be dispersed or dissolved in an aqueous alkaline medium to form a lotion.

In addition to alpha,alpha-dimercaptoadipic acid itself, the derivatives of dimercaptoadipic acid which may be employed in the present invention include those which are soluble in aqueous alkaline media; for example, the monoand disalts of alkali metals such as sodium or potassium and including ammonium salts, salts of alkaline earth metals such as calcium and magnesium salts, and salts with organic amines such as monoethanoalamine, diethanolamine, monoisopropanolamine, diisopropanolamine, 2 amino 2 methylpropanediol 1,3, etc. Other derivatives which may be employed include both monoand diesters of lower alkyl alcohols containing up to 4 carbon atoms such as methyl, ethyl, propyl, butyl, as well as of alkoxyalkyl alcohols containing as many as 7 carbon atoms; for example, methoxyethyl, isopropoxypropyl, etc. In addition to salts and esters of dimercaptoadipic acid as aforesaid, there may also be employed monoand di-amides of this acid, including not only the amides made from ammonia but those made from hydrazine and/ or primary and/ or secondary lower alkyl amines containing from 1 to 4 carbon atoms such as methyl, ethyl, N-propyl, and butyl amine and alkanolamines such as monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine, etc. It will be understood that mixed compounds of these types are also included; for example, compounds in which one carboxyl group is neutralized to form a salt and the other is esterified or ammonolyzed, as well as compounds in which one car boxyl group is esterified and the other is ammonolyzed.

When provided in dry solid form adapted to be dissolved in aqueous media to form a permanent waving lotion, the compositions of the present invention contain in combination with dimercaptoadipic acid or a derivative thereof as described above a solid, non-volatile, watersoluble, alkaline material such as sodium carbonate or a non-volatile solid amine; for example, Z-amino-Z-methylpropanediol-1,3. There should be present a moderate excess of alkaline material over and above the amount required to neutralize any acidic groups present in the dimercaptoadipic acid or derivative, the excess amountmg to 0.3 to 1.5 equivalent weight for each equivalent weight of dimercaptoadipic acid or derivative thereof.

The compositions of the present invention instead of being provided in dry solid form may also be supplied to the consumer in the form of a stable lotion or aqueous solution. In this case volatile alkaline materials such as ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, moncethanolamine, and the like may replace part or all of the solid non-volatile amine or of the sodium carbonate.

When in the form of an aqueous lction ready for use in hair waving, the concentration of mercaptan in the solution preferably is from 0.3 to 1.2 gram equivalent weight per liter, best results usually being obtained with concentrations from 0.5 to 0.8 gram equivalent per liter. The composition may be used together with other waving agents, for example, an aqueous ammonium thioglycolate solution, if desired.

Particularly satisfactory results are obtained when the alphaapha-.dimercaptoadipic acid and derivatives thereof are employed in conjunction with a water-solub'e salt of thioglycolic acid. When the composition is provided in dry, solid form magnesium thioglycolate is preferred as the salt, although sodium or potassium thioglycolate may also be used. When the composition is in the form of an aqueous solution or lotion, there may be used in ad- .dition to or in place of the foregoing salts ammonium thioglycolate or salts of thioglycolic acid with such amines as mono-, di-, and tri-ethanolamine, mono-, di-, and triisoprcpanolamine, or mixtures thereof. The relative proportions of the water-soluble thioglycolate and of the alpha,alpha'-dimercaptoad-ipic acid or derivative thereof are not critical, but best results are obtained when 0.05 to 1.0 equivalent weight of thiog'ycolate is used for each equivalent weight of alpha,alpha'-dimercaptoadipic acid or derivative.

In use, the .dry solid waving composition may be dissolved in the desired quantity of an aqueous medium such as water to form a lotion of the desired concentration. This lotion, or a previously prepared lotion if the composition is supplied to the consumer in the form of an aqueous solution, may be applied in the usual manner to a tress of hair which is thereupon wound upon a conventional curling rod and again saturated, if desired, with the aqueous solution. The hair is then permitted to process for a period of time ranging from fifteen minutes to an hour or more, whereupon it becomes soft and gradua ly conforms to its wound shape. After the d:sfred period of processing, the hair is neutralized to set it or harden it in its wound configuration either by pouring though the hair an aqueous solution of a conventional neutralizer or oxidizing agent such as sodium bromate or sodium perborate, or by simply rinsing with water then subjecting it to aerial oxidation by exposing it to the oxygen of the atmosphere for a period of time from two to six hours or more. In the latter case aerial oxidation may be supplemented, if desired, by the use of an aqueous neutralizer solution.

In the case Where the permanent waving composition is supplied to the consumer in the form of a dry solid composition, it may also be employed by securing or aflixing it in any desired manner to a device for holding it in place on or within the wound tress of hair in position to be leached out by an aqueous medium which is subsequently applied to the hair so as to form an aqueous Waving lotion in situ, the remainder of the procedure being as described above. For example, the composition may be secured in dry solid form to a curler or to an end paper on which or with which the hair is wound.

It will be understood that any of the usual additives such as perfumes, opacifying agents, dyes, hair conditioners, etc., may be added to the lotion or to the dry solid waving composition if desired.

The following specific examples are intended to illustrate more clearly the nature of the present invention without imposing any limitation upon the scope thereof.

Example 1 A waving composition was prepared by mixing 0.5 equivalent weight of diamrnonium alpha,alpha'-dimercaptoadipate with 0.65 equivalent weight of anhydrous sodium carbonate to form a pulverulent, dry, solid mass. This composition was found to be highly stable upon storage for a period of several months at room temperature. Upon dissolution in the appropriate quantity of water to form a solution containing 1.0 gram equivalent of dimercaptoadipate per liter, the lotion was employed for permanent waving of hair by applying it to a hair tress which was then wound upon a curler and resaturated with the solution. After being allowed to process for fifteen minutes, the hair tress was thoroughly rinsed with water and allowed to stand exposed to the atmosphere for thirty minutes to initiate aerial oxidation of the reduced hair, whereupon neutralization or oxidation of the hair was completed by pouring through it an aqueous solution (1% to 3% by weight) of sodium perborate tetrahydrate neutralizer. A satisfactory permanent wave was obtained. Even better results were achieved when the use of the aqueous solution of sodium perborate was dispensed with, the neutralization of the hair being completely by exposure to atmospheric oxygen overnight.

Example 2 A dry solid composition was prepared containing 0.8 equivalent weight diamrnonium dimercaptoadipate, 0.2 equivalent weight magnesium thioglycolate, and 0.66 equivalent weight 2-amino-2-methylpropanediol-1,3. This mixture, which was stable upon storage at room temperature, formed a highly satisfactory permanent waving lotion when dissolved in the appropriate quantity of water to form a solution containing the stated number of gram equivalents per liter. Particularly good results were obtained when this lotion was employed in the first procedure described in Example 1 above.

Example 3 Alpha,alpha'-dirnercaptoadipic acid itself, a stable, white, solid material, was dissolved in the appropriate quantity of an aqueous alkaline medium to form a solution containing 0.8 to 1.0 gram equivalent per liter. The solution contained suflicient alkaline material to neutralize the dimercaptoadipic acid together with an excess amounting to 0.3 to 0.6 gram equivalent per liter. Satisfactory results were obtained using ammonia, monoethanolamine, diisopropanolamine, and 2-amin'o-2-methylpropanediol-l,3 as well as mixtures thereof as the alkaline material when the resulting lotions were employed in the second procedure described in Example 1 above.

Example 4 A dry powdered composition containing 1.0 equivalent of diamrnonium dimercaptoadipate together with 1.2 equivalent sodium carbonate was prepared by mixing the solid powdered constituents. When dissolved in the appropriate quantity of water to provide a lotion containing the stated quantities of gram equivalents per liter, the solution was found to provide a satisfactory cold permanent wave when employed according to any of the procedures described above.

Example 5 There was suspended in one liter of absolute ethanol a mixture of 210 g. of dimercaptoadipic acid together with 5 g. of p-toluene sulfonic acid. To the mixture was added 300 ml. of benzene. The reaction mixture was refluxed, whereupon the dimercaptoadipic acid slowly dissolved with the resultant production of water as a byproduct, approximately sixteen hours being required for completion of the esterification reaction.

The reaction mixture was poured into water and the ester which separated was extracted with ether, the ether solution washed with a saturated aqueous sodium bicarbonate solution and finally with water, then dried and the ether evaporated at reduced pressure. The residual oil solidified and was recrystallized from ethanol to give stable, white, crystalline diethyl dimercaptoadipate melting at 5l52 C. It was readily dissolved in an aqueous solution of ammonia to form an aqueous hair waving lotion containing 0.7 gram equivalent of the diethyl ester per liter togther with 0.5 gram equivalent of free ammonia. This lotion, when employed in accordance with any of the procedures described above, provided a satisfactory permanent wave.

Example 6 There were dissolved in 400 ml. of methoxyethanol, 429 g. of dimercaptoadipic acid. To the reaction mixture were added 400 ml. of benzene and 4 ml. of concen trated sulfuric acid. The reaction mixture was then refiuxed for about three hours until production of the water by-product ceased. The reaction mixture was cooled, washed with a l0% aqueous sodium carbonate solution, then with water. The benzene was removed by distillation to yield dimethoxyethyl dimercaptoadipate in the form of a yellow oil having a purity as determined iodimetrically of 96.7%. This product could readily be dissolved in an aqueous alkaline medium as described in Example 5 to form a hair waving lotion. This lotion, when used according to any of the procedures described above, provided a satisfactory permanent wave.

Example 7 To 306 g. of dimethoxyethyl dimercaptoadipate there were added slowly and with stirring 850 ml. of aqua ammonia, dissolution of the ester being accompanied by an increase in temperature and the formation of a white solid precipitate. The reaction mixture was stirred for two hours at 5060 C., then cooled and the solid product removed by filtration. The product was recrystal= lized from hot water to yield bisdimercaptoadipamide in the form of a white crystalline solid melting at l8l C.

The bisamide was readily dissolved in an aqueous solution of ammonia to form a hair waving lotion as described in Example 5 above. The lotion provided satisfactory permanent waves when employed in accordance with any of the procedures described above.

Example 8 There were added to 266 g. of diethyl dimercaptoadipate slowly and with stirring 244 g. of monoethanolamine. An exothermic reaction occurred, and the mixture was allowed to stand for three hours, whereupon it was dissolved in one liter of water and treated with an acid ion exchange resin until a pH of 6 was achieved. The resin was removed by filtration and the filtrate-containing the product was concentrated under reduced pressure until a solid precipitate appeared which was removed by filtration. The resultant solid bis-N(beta-hydroxyethyl)- dimercaptoadipamide was recrystallized from absolute ethanol, the pure product appearing as a white crystalline solid melting at l62-l63 C.

The bisamide was readily dissolved in an aqueous solution of ammonia to form a hair waving lotion as described in Example 5 above. This lotion provided satisfactory permanent waves when employed in accordance with any of the procedures described above.

Example 9 There were dissolved in 400 ml. of methanol at 50 C. 133 g. of diethyl dimercaptoadipate. To this solution there were added slowly and with stirring 125 g. of hydrazine hydrate, the temperature being maintained at 50 C. A white solid product precipitated from the reaction mixture, whereupon the reaction mixture was cooled and the solid product separated by filtration and washed with methanol. The product, S,S-dihydrazinobisdimercaptohydrazide, melted at 18018l C. It was readily dissolved in an aqueous solution of ammonia to form a hair waving lotion as described in Example 5 above. This lotion provided satisfactory permanent waves when employed in accordance with any of the procedures described above.

Example Alpha,alpha-dimercaptoadipic acid was dissolved in an aqueous solution of ammonia to form a solution containing 0.88 gram equivalent per liter of the mercaptan, the ammonia being present in an amount in excess of that required to neutralize the carboxyl groups to form diammonium alpha,alpha'-dimercaptoadipate, the amount of excess being 0.67 gram equivalent per liter. In this solution was dissolved 0.1 gram equivalent of ammonium thioglycolate. The resulting lotion was employed to wave hair by the first procedure described in Example 1 above, with satisfactory results.

Similar results were obtained with an aqueous lotion containing 0.78 gram equivalent of diammonium alpha, alpha'-dimercaptoadipate, 0.2 gram equivalent of ammonium thioglycolate, and 0.70 gram equivalent of excess free ammonia per liter, when used in the same procedure.

Example 11 An aqueous lotion was prepared containing 0.90 gram equivalent of diammonium alpha,alpha-dimercaptoadipate, 0.10 gram equivalent of ammonium thioglycolate, and 0.73 gram equivalent of free diisopropanolamine per liter. Satisfactory results were obtained in waving hair by the first procedure described in Example 1 above using this lotion.

Similar results were obtained using an aqueous lotion containing 0.80 gram equivalent of diammonium alpha,alpha'-dimercaptoadipate, 0.20 gram equivalent of ammonium thioglycolate, and 0.68 gram equivalent of free diisopropanolamine per ilter in the same procedure.

Example 12 An aqueous lotion was prepared containing 0.82 gram equivalent of the monoethanolamine salt of alpha,alpha'- dimercaptoadipic acid and 0.50 gram equivalent of free diisopropanolamine per liter.

A tress of hair was wound on a curling rod using an end paper (for confining the ends of the hair tress) which carried a dry solid deposit consisting of 0.38 gram milliequivalent of magnesium thioglycolate and 0.26 gram milliequivalent of 2-amino 2 methylpropanediol 1,3. The lotion was then used to saturate the wound tress, dissolving or leaching out the solid deposit carried by the paper. The procedure followed was the same as the first procedure described in Example 1 above, and the results were very satisfactory.

This application is a continuation-in-part of our copending application Serial No. 648,781, filed March 27, 1957, now abandoned.

Although specific embodiments of the invention have been described herein, it is not intended to limit the invention solely thereto, but to include all of the obvious variations and modifications within the spirit and scope of the appended claims.

We claim:

1. An aqueous hair waving lotion consisting essentially of (1) water, (2) a member of the class consisting of (A) alpha,alpha'-dimercaptoadipic acid, (B) monoand disalts thereof with a member of the class consisting of alkali metals, alkaline earth metals, and organic amines, (C) monoand diesters thereof with a member of the class consisting of lower alkyl alcohols and alkoxy alkyl alcohols containing up to 7 carbon atoms, (D) monoand diamides thereof with a member of the class consisting of ammonia, hydrazine, pri mary and secondary lower alkylamines and lower alkanolamines and mixtures thereof, and (3) a Water-soluble alkaline material selected from the class consisting of sodium carbonate, ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, and organic amines, said alkaline material being present in an amount in excess of that required to neutralize any acidic material present, the amount of said excess being from 0.3 to 1.5 equivalent weight for each equivalent weight of said member.

2. A lotion as defined in claim 1 containing, in addition to the ingredients specified in claim 1, a thioglycolate.

3. A dry solid composition soluble in an aqueous medium to form a hair waving lotion as defined in claim 1 in which said alkaline material is non-volatile.

4. A composition as defined in claim 3 in which said alkaline material is 2-amino-Z-methylpropanediol-1,3.

5. A composition as defined in claim 3 containing, in addition to the ingredients specified in claim 3, a solid water-soluble salt of thioglycolic acid.

6. A dry solid composition soluble in an aqueous medium to form a hair waving lotion consisting essentially of alpha,alpha'-dimercapt0adipic acid together with 2- arnino-2-methylpropanediol-1,3, said last-named material being present in excess of the amount reactive with said acid, the amount of said excess being from 0.3 to 1.5 equivalent weight for each equivalent weight of said acid.

7. An aqueous hair waving lotion consisting essentially of water, alpha,alpha-dimercaptoadipic acid, and a water-soluble non-volatile amine, said amine being present in an amount in excess of that required to neutralize said acid, the amount of said excess being from 0.3 to 1.5 equivalent weight for each equivalent weight of said acid.

8. An aqueous hair waving lotion consisting essentially of water, alpha,alpha'-dimercaptoadipic acid, and ammonia, said ammonia being present in an amount in excess of that required to neutralize said acid, the amount of said excess being from 0.3 to 1.5 equivalent weight for each equivalent weight of said acid.

References Cited in the file of this patent UNITED STATES PATENTS 2,577,710 McDonough Dec. 4, 1951 2,719,814 Haefele Oct. 4, 1955 2,751,327 Deadman June 19, 1956 2,847,351 Brown et a1 Aug. 12, 1958 2,869,559 Moore Jan. 20, 1959 OTHER REFERENCES Danielli et al.: Biochemical Journal, vol. 41 (1947), pp. 325-333.

Harry: Modern Cosmeticology, 4th ed., Leonard Hill Ltd. London (1955), pp. 453-4.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2577710 *Jun 16, 1941Dec 4, 1951Procter & GamblePermanent waving compositions and methods
US2719814 *Sep 10, 1953Oct 4, 1955Procter & GambleHair waving lotion
US2751327 *Sep 12, 1952Jun 19, 1956Ashe Lab LtdPreparation of hair treating compositions in solid form
US2847351 *Nov 8, 1955Aug 12, 1958Gillette CoHair waving composition comprising a disulfide and either a non-corresponding mercaptan or thiourea dioxide
US2869559 *Oct 7, 1957Jan 20, 1959Procter & GambleNon-volatile mercaptan and hydroxyamine impregnated end wrap and method of use
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3215605 *Apr 25, 1962Nov 2, 1965RevlonMethod for coloring hair and other keratinaceous fibers with metal salts
US4292326 *Dec 1, 1978Sep 29, 1981Nazzaro Porro MarcellaProcess for treatment of hyperpigmentary dermatoses
US4898726 *Aug 24, 1988Feb 6, 1990Johnson Products Co., Inc.Initiated hair straightening composition and system
US5378813 *May 29, 1992Jan 3, 1995President And Fellows Of Harvard CollegeMeso-2,5-dimercapto-N,N,N'N'-tetramethyladipamide
US7118736Feb 22, 2001Oct 10, 2006L'orealHair relaxer compositions comprising at least one hydroxide compound and at least one activating agent, and methods of using the same
US7195755Aug 20, 2001Mar 27, 2007L'oreal S.A.Compositions comprising at least one hydroxide compound and at least one reducing agent, and methods for relaxing hair
US7468180Aug 20, 2001Dec 23, 2008L'oreal, S.A.Compositions comprising at least one hydroxide compound and at least one oxidizing agent, and methods to straighten curly hair
Classifications
U.S. Classification424/70.4, 564/151, 564/154, 424/70.5, 252/188.2, 562/594, 560/147
International ClassificationA61K8/46, A61Q5/04, A61K8/30
Cooperative ClassificationA61Q5/04, A61K8/46
European ClassificationA61Q5/04, A61K8/46