United States Patent (19) 11 Patent Number: 4,659,566 Petrow (45) Date of Patent: Apr. 21, 1987

(54) COMPOSITIONS AND METHODS FOR 1475971 6/1977 United Kingdom. PERMANENTLY WAVING OR STRAIGHTENING HAIR OTHER PUBLICATIONS Ebert, Chem. Abst. 47168p (1966), vol. 66. 76 Inventor: Henry G. Petrow, 32 Garfield Dr., Sagarin, Cosmetics. Science and Technology, pp. 618 and Watertown, Mass. 02172 1067 (1957). 21 Appl. No.: 642,921 Primary Examiner-Jerome D. Goldberg 22 Filed: Aug. 21, 1984 Assistant Examiner-F. Krosnick 51) Int. Cl...... A61K 7/09; A61K 7/11; Attorney, Agent, or Firm-Pennie & Edmonds A45D 7/00 57 ABSTRACT 52 U.S. Cl...... 424/71; 424/72; The invention relates to novel reducing compositions 132/7 for reducing the disulfide bonds of keratin, comprising a 58) Field of Search ...... 424/71, 72; 132/7 regenerable reducing agent, such as an iodide salt, ferro 56) References Cited cyanide salt, bromide salt and antimony(III) tartrate salt, capable of reducing the disulfide bonds of keratin, U.S. PATENT DOCUMENTS in combination with a consumable reducing agent, such 2,153,762 4/1939 Kritchevsky ...... 8/94.14 as a salt or ester of thioglycolic acid, or a sulfite, bisul 3,676,550 7/1972 Auzuino ...... 424/71 3,824,304 7/1974 Villanueva ...... 424/70 fite, hydrosulfite, metabisulfite or sulfoxylate salt, in 3,912,808 10/1975 Sokol ...... 424/71 which the consumable reducing agent is capable of 3,966,903 6/1976 Torii et al...... 424/72 regenerating the regenerable reducing agent by reduc 4,273,143 6/1981 Klemm et al. ... 424/71 ing the oxidized form of the regenerable reducing agent. 4,295,985 10/1981 Petrow ...... 252/105 Neutralizing compositions compatible with such reduc 4,366,827 1/1983 Madrange et al...... 424/71 ing compositions, as well as methods for permanently waving or straightening hair or fur, are also encom FOREIGN PATENT DOCUMENTS passed by the invention. 0037224 10/1981 European Pat. Off. . 57-2216 1/1982 Japan ...... 424/71 20 Claims, No Drawings 4,659,566 1. 2 ing agent in a second stage operation, referred to as a COMPOSITIONS AND METHODS FOR neutralization stage, to form new S-S linkages and to PERMANENTLY WAVING OR STRAIGHTENING impart the desired configuration to the hair. Generally HAR used neutralizing agents include hydrogen peroxide and sodium bromate (Robbins, Chemical and Physical Be TABLE OF CONTENTS havior of Human Hair, Van Nostrand Reinhold Com 1. Field of the Invention ... pany, New York (1979)). 2. Background of the Invention ... Conventional techniques, however, have suffered 2.1. Use of Iodine/Iodide ... from a number of disadvantages. In particular, thiol 3. Summary of the Invention ... 10 containing compositions suffer from a persistent dis 4. Detailed Description of the Invention ... agreeable sulfur odor. Other compositions suffer from 4.1. Reduction Systems ... the irritating odor of ammonia when utilized at alkaline 4.1.1. Sulfite or Bisulfite System ... values of pH. Sulfite and bisulfite systems when used for 4.1.2. Ammonium Thioglycolate System ... "home perms' require an extensively long period of 4.1.3. Monoethanolammonium Thioglycolate 15 time in contact with the hair, e.g., one hour or so, and System ... typically produce curls of less than professional stan 4.1.4. Glycerol Thioglycolate System ... dards. Additionally, since many of the other conven 4.2. Neutralization Systems ... tional ingredients are caustic to both hair and skin, 5. Examples: Preparation and Methods of Use... safety considerations do not allow for home use formu 5.1. Formulations ... 20 5.1.1. Bisulfite/Iodide ... lations as concentrated as typically used in professional 5.1.2. Ammonium Thioglycolate/Iodide ... salons. Consequently, such "home perm' systems are 5.1.3. Monoethanolammonium Thioglycolate/I- not as effective, i.e., curl is not as tight and does not last odide ... as long, as available professionally. More importantly, 5.1.4. Glycerol Thioglycolate/Iodide ... 25 the conventional systems tend to damage the hair (pre 5.2. Methods of Use... sumably through hydrolysis of peptide and amide link 5.3. Curling Hair Samples ... ages), particularly if left in contact with the hair for an 5.3.1. Bisulfite/Iodide Treatments ... extended time. The permed hair generally becomes 5.3.2. Ammonium Thioglycolate/Iodide Treat brittle, dry, and loses agreeable tactile quality. ments ... 30 2.1. USE OF ODINE/IODIDE 5.3.3. Monoethanolammonium Thioglycolate/I- odide Treatments ... Conventional techniques for hair waving or straight 5.3.4 Glycerol Monothioglycolate/Iodide Treat ening have not involved the use of water soluble-iodide Inents ... salts as described herein according to the preferred 6. Effect of Iodide Systems in Controlling Hair Dam 35 embodiment of the present invention. age ... Use of a mixture of iodine/iodide for treating hair for 7. Salon Tests on Hard-to Curl Hair ... other purposes has, however, been previously de 7.1. Fragile Hair ... scribed. In particular, Kritchensky (U.S. Pat. No. 7.2. Oriental Hair ... 2,153,762 issued Apr. 11, 1939) described use of a mix 7.3. Hard-to-Perm Caucasian Hair ... 40 ture of iodine, potassium iodide and sodium chloride as 8. Example: Straightening Hair... a first step prior to a lustering operation for improving 9. Claims the luster and decreasing the tendency of wool or hair to curl or spot when exposed to moisture. Kritchensky 1. FIELD OF THE INVENTION stated that absorption of the iodine in the mixture was The present invention is directed to new and im 45 necessary for reaction with unsaturated bonds in the proved methods of permanently waving hair, and novel hair to make the hair coarse and non-curling. compositions of matter useful in such improved meth U.S. Pat. No. 3,824,304, issued to Villanueva on July ods. The novel compositions may also be useful for 16, 1974, describes use of a tincture of iodine, i.e., a altering the shape of hair by relaxing or straightening mixture of iodine and sodium iodide in an alcoholic naturally or artifically waved hair. 50 solvent, to condition hair. 2. BACKGROUND OF THE INVENTION 3. SUMMARY OF THE INVENTION Conventional methods for permanently waving ke The present invention involves novel formulations ratinous fibers, particular hair, generally consist of a that are useful for permanently altering the shape or two stage process. Initially the hair is shampooed, and 55 configuration of keratinous fibers, particularly hair, or mechanically positioned into the configuration or shape fur. The formulations and methods of use described desired. Generally this is acheived by wrapping the hair herein are more efficient and represent distinct im around cylinders (termed "rollers') of the appropriate provements over conventional techniques of permanent size to either impart a curl or wave or to straighten hair or fur waving and relaxing. waved hair. 60 According to the present invention, a heretofore In the first stage of process, referred to as the reduc unusable reducing agent (RA), that has rapid kinetics tion stage, the disulfide linkages (S-S) of the keratin but not necessarily a useful equilibrium constant fortne fiber are opened (reduced to two mercaptain groups), cleavage of disulfide linkages in keratin, is combined with the aid of reducing agents, including thioglyco with a conventionally used reducing agent (RA2) that lates, sulfites, and bisulfites, etc. Depending upon the 65 has a usefully high equilibrium constant but not neces systems used, the hair is exposed either to acidic or sarily rapid reaction kinetics. According to the inven alkaline values of pH. Thereafter, the hair is rinsed tor's theoretical understanding of the chemistry in extensively and subsequently treated with a mild oxidiz volved, the primary agent for cleaving the disulfide 4,659,566 3 4 linkages is now RA1, which is very rapidly and substan tially completely regenerated from its oxidized form by 4.1. REDUCTION SYSTEMS RA2, which is consumed in the process. It is to be un According to the present invention in the first reduc derstood, however, that successful practice of the in ing stage of the two-stage process for hair treatment, a ventions described herein does not depend on the cor regenerable reducing agent (RA) that has rapid kinet rectness of such theoretical understanding, and that the ics, but not necessarily a useful equilibrium constant for invention shall not be limited to any particular chemical the reaction in which the disulfide linkages of keratin in mechanism. Practice of the methods described herein hair fibers are reduced, is combined with a consumable and use of the formulations of the invention result in the reducing agent (RA2) that has a usefully high equilib advantages described, independent of such theoretical O rium constant, but not necessarily rapid reaction kinet COCS. ics for the keratin reduction reaction. In the preferred embodiment of the present invention, By "useful' as applied to the equilibrium constant is the regenerable reducing agent is a water-soluble iodide meant that if the reaction were allowed to reach equilib salt including, but not limited to: simple salts such as rium, the amount of reduced keratin present, when potassium iodide, sodium iodide, and ammonium iodide. 15 subsequently oxidized (neutralized), would provide an In other embodiments, potassium ferrocyanide, sodium acceptable curl. In this context "useful' does not indi bromide and antimony (III) potassium tartrate may be cate that the reaction would occur within an acceptable used as the regenerable reducing agent, but they are less time frame for purposes of curling or straightening hair effective than iodides. or fur. Generally, an acceptable time frame would be The combinations of the present invention are useful 20 less than about one hour, preferably about ten to twenty in improving the kinetics of the reduction stage in per minutes. Conversely, a reaction which does not have a manent waving and hair straightening systems. When useful equilibrium constant would not, if allowed to used in systems containing sulfites or bisulfites, the im reach equilibrium, provide a sufficient amount of re provement is such that these odorless systems can pro duced keratin to impart an acceptable curl after subse duce professional quality permanent waves, which was 25 quent neutralization. not possible heretofore. By the term "rapid reaction kinetics” is meant that The combinations of the present invention when used the reduction reaction is fast enough to provide, within in thioglycolate systems have the very important and an acceptable time frame, sufficient reduced keratin surprising benefit of significantly reducing the usual which, after subsequent neutralization, would provide hair damage associated with waving, because: 30 an acceptable curl. Again, an acceptable time frame (a) The caustic thioglycolic reducing agents can be would be about one hour, preferably ten to twenty used at lower concentrations, because of the im minutes. proved kinetics. Based upon the inventor's proposed theoretical (b) If used at conventional concentrations, such caus mechanism of this reaction, it is presumed that the oxi tic agents can be left in contact with the hair for a 35 dized form of the regenerable reducing agent (RA1-ox) is shorter period of time, because of improved kinet rapidly and essentially completely reduced to RA1 by 1CS. the consumable reducing agent. While the consumable (c) Overprocessing is avoided because the consum reducing agent apparently does some useful work of able thioglycolate reducing agents are rapidly used cleaving disulfide bonds, the main work surprisingly up in the process of reducing iodine to iodide, seems to be accomplished by the regenerable reducing which reaction is favored over the thioglycolate agent, which by itself is not capable of cleaving the reaction with the hair. disulfide bonds in a detectable amount because of its (d) Most importantly and surprisingly, the regenera very low equilibrium constant for this reaction. (In fact ble reducing agent which is primarily responsible the reverse reaction, neutralization with iodine solution, for the disulfide cleavages is apparently very selec 45 proceeds very rapidly.) As shown in Table III (see tive for this reaction since it is innocuous at the Section 5.3.2), for example, ammonium thioglycolate concentrations used as far as hair damage is con systems, which on their own produce poor curls in five cerned. minutes, when combined with potassium iodide pro In addition, because of the improved kinetics of the duce very good curls in the same amount of time. reactions of this invention, the gentle and slow acting 50 Increased efficacy of formulations of the present in monoethanolammonium thioglycolate, which has here vention is conferred by the combination of a consum tofore been largely limited to home waves, can now able reducing agent with the regenerable reducing surprisingly be used in professional salon cold waves as agent. Specifically, according to the preferred embodi a practical substitute for the ammonia thioglycolate ment, a water-soluble iodide salt such as simple iodide system, thereby eliminating the irritating ammonia 55 salts including, but not limited to potassium iodide (KI), fumes associated with such systems. sodium iodide (NaI), or ammonium iodide (NH4), is utilized as the regenerable reducing agent. Combination 4. DETAILED DESCRIPTION OF THE of the regenerable and consumable reducing agents INVENTION enhances the efficacy of compositions containing only As described supra in Section 2, the conventional 60 the corresponding consumable reducing agent by per method for permanently waving hair fibers consists in a mitting the reduction of disulfide linkages of the keratin first reducing stage operation in which the disulfide to proceed at a faster rate. linkages (S-S) of the keratin fiber are broken with the Moreover, the hair is damaged less because the dam aid of a reducing agent. Thereafter, the hair is prefera aging consumable reducing agent in the combinations of bly rinsed well and subsequently treated in a second 65 the present invention: (a) can be in contact with the hair stage operation with a neutralizing agent to form new for a shorter period-of time; (b) may be used in lower or S-S linkages of the keratin to impart to the hair the more dilute concentrations; and (c) presumably is con desired configuration or shape. sumed rapidly by the oxidized-form of the regenerable 4,659,566 5 6 reducing agent which reacts more selectively. Hence, the combinations of the present invention inherently RA RA2 protect against overprocessing of the hair because the " RA - = A2K2(eg) x RA2-ox) (6) damaging consumable reducing agent is rapidly con sumed by the iodine in the process while the regenera Substitution of this ratio into expression (3) above ble reducing agent, which is primarily responsible for gives the disulfide cleavage, is apparently very selective for this reaction since it is innocuous at the concentrations Keratin-reduced RA2) (7) employed as far as hair damage is concerned. Other - Kai - = Ki(eg) x Kate) -ox advantages of specific embodiments are indicated infra. 10 The chemical reactions in the first reduction stage operation of hair treatment according to the present The equation for the reaction of the consumable re invention may be represented by the generalized equa ducing agent with keratin is tions as follows: 15 (8) Keratin + RA2 -NSS - Keratin-reduced + RA2 Ox 1 Keratin - RA1 -Elskeratin-reducedS - -- RA1-ox (1) 5 wherein the equilibrium constant for the reactions is K3(eq) and ks and k9 represent the forward and reverse wherein the equilibrium constant for the reaction is 20 reaction rate constants. K1(eq), and k4 and k5 represent the forward and reverse The equilibrium constant for the reaction of Equation reaction rate constants. "Keratin' represents the disul (8) may be computed as follows: fide-bound keratin protein, and "Keratin-reduced” rep resents reduced protein and "RA1-ox" represents the oxidized form of reducing agent RA1. 25 K3(eg) = Keratin-reduced)(RA2-ox (9)9 The equilibrium constant for the reaction of equation Keratin)RA2) (1) may be computed as follows: Equation (9) may be rewritten as

K(eg) = RA -ox)|Keratin-reduced k4 (2)2 30 Keratin-reduced) RA2 (10) - Rakai - = . Keratin) = K3(ed) IRA, . The expression (2) above may be rewritten such that Comparing Equations (7) and (10), it can be seen that 35 (11) K1(eq)xK2(eq)=K3(eq) Keratin-reduced RA) (3) Keratin) = Ki(eg) XR4 In addition to Equation (11), the constraints upon the If the value of RA1-o) is made very small, i.e., by choice of particular compounds for RA1 and RA2 in reduction by the consumable reducing agent, then the clude the following: corresponding value of As described above, RA2 has a useful equilibrium constant for the reduction of disulfide bonds, but the Keratin-reduced) reaction may not proceed rapidly enough. On the other Keratin) 45 hand, no matter how long one observes the reaction of the reduction of Keratin by RA1, it will not proceed to becomes usefully large, that is, the reaction of Equation an appreciable extent since the equilibrium constant is (1) would be "driven' in favor of Keratin-reduced, and so small. From effective conventional compositions sufficient amounts of reduced keratin would be formed containing a single reducing agent, such as thioglycol such that after neutralization an acceptable curl results. 50 ate, the equilibrium constant for reduction of Keratin The reaction of the regeneration of the regenerable may be estimated to be in the range of about 10- to 10. reducing agent by the consumable one is represented as Thioglycolate for example, has an equilibrium constant follows: of approximately 1. Since RA1 alone does not result in appreciable reduction of keratin, i.e., K1(eq) is very k6 (4) 55 small, for example, 10-10 to 10-20, K3eq is greater than RA1-ox + RA2 seRA, + RA2-ox K1(eq). wherein K2(eq) is the equilibrium constant for the reac In order to "drive' the reduction of Keratin by RA1 tion and ké and k7 represent the forward and reverse in favor of producing Keratin-reduced, the RA1-ox) reaction rate constants. must be reduced by the action of RA2 in accordance The equilibrium constant for the reaction of equation with Equation (4). Thus, kó must be very large relative (4) may be computed as follows: to k5. In accordance with Equation (11), when K3(eq)>K- RARA2-ox k6 65 1(eq) (i) above, then K2(eq.)>K1 (eq). Based upon the K2(eg)2(eg) =- (RAIR4- = k - . (5) relationships among the three equilibrium constants, K2(eq) would be expected to be very large, for example, Expression (5) above may be rewritten as in the range of to 1010 to 1020. 4,659,566 7 8 (iv) kecks All the samples were neutralized with 10% NaBrO3 The qualitative description for this constraint is that solution for 5 minutes, unrolled, rinsed, and allowed to the rate of regeneration of RA1 by RA2 is greater than air dry. the rate of reduction of Keratin by RA2. All the samples containing KI yielded professional (v) k4) k8 quality curl formation with no discernible hair damage. Both of constraints (iv) and (v) must be true in order The 5 samples treated without KI yielded curls of poor for one to observe an effect upon addition of RA1. If ks quality. The sixth sample without KI which was al were larger than k4 and ké, the reaction of k8 would be lowed to react for 30 minutes yielded a well-formed the fastest reaction and addition of RA1 would have no curl, but the hair showed discernible damage as evi effect. 10 denced by rough, stiff tactile qualities. Since the 'concentration' of disulfide bonds of kera In these experiments, the addition of KI increased the tin can not be accurately estimated, and since such a rate and quality of curl formation and eliminated hair figure would necessarily vary depending upon hair type damage. One can reasonably infer from these experi and from individual to individual, numbers for the equi ments that in the presence of KI and the thioglycolate librium constants K1(eq) and K3(eq) can only be ap 15 compound, the preferred reaction is the splitting of the proximated. disulfide bonds by the iodide-iodine regeneration reac The relationship of Equation (11) among the three tion. Thus, the thioglycolate would be consummed to equilibrium constants always holds by chemical law, regenerate iodide. and the critical factors are the kinetics of K1 (eq) and 20 This was confirmed in similar experiments in which K2(eq) relative to those of K3(eq). What is truly surpris data was obtained at various reaction times from 1.5 to ing is that the reaction of K1(eq) with its minute equilib 8 minutes. Analysis of these data establish that the reac rium constant should have a k4 that is greater than k8. tion rate in the presence of 0.3 MKI is 3 times as fast as According to the preferred embodiment of the pres is found with thioglycolate alone. That is, in the thio ent invention, the regenerable reducing agent (RA) is a 25 glycolate-iodide system 75% of the disulfide bond split water-soluble iodide salt such as simple iodide salts ting is a result of the iodide interaction. including potassium iodide (KI), sodium iodide (NaI), According to the present invention, the compounds or ammonium iodide (NH4I). When KI is utilized as listed in Table I (which should not be considered an RA1, the kinetics of expression (1) above are excellent exhaustive list) may be utilized as consumable reducing in that the reaction proceeds rapidly and iodide diffuses 30 agents. As illustrated in Table I, a number of these sub readily through the hair. stances may be used as reducing agents in the absence of Other salts which may be used as regenerable reduc a regenerable reducing agent. Enhanced results are ing agents include, but are not limited to: ferrocyanides, achieved when each of the listed compounds is com bromides, and antimony (III) tartrates. In comparison bined with a regenerable reducing agent as described with soluble iodide salts, the latter salts are far less 35 supra. In all the systems listed in Table I there is a sub effective being fair, weak and weak, respectively, rela stantial improvement when KI is used due to the im tive to iodide in their enhancing effects on hair waving provement in kinetics. compositions. Although potassium thiocyanate TABLE I (KSCN) is close in redox and electrolytic properties to 40 COMPOUNDS PROVIDING CONSUMABLE KI, KSCN is not effective at all in the compositions of REDUCINGAGENTS the present invention. Similarly, potassium chloride is Activity Without Regener not effective at all. Other common salts which also are Compound able Reducing Agent not effective include various sulfates and nitrates. Ammonium thioglycolate good To evaluate quantitatively the contribution of KI to Glycerol thioglycolate good (-- heat) 45 Monoethanolamnonium thioglycolate medium increasing the perming rate and degree of curl forma Sodium sulfite fair tion, the following experiments were performed. Ex Sodium bisulfite fair + actly 1 gm samples of untreated brown hair were sham Sodium hydrosulfite fair pooed, blotted dry, and wrapped on rollers. A total of Ammonium sulfite fair Ammonium bisulfite fair 10 samples were prepared in this way. Five of them 50 Potassium sulfite fair were impregnated with exactly 1 ml each of 1.0 M Potassium bisulfite fair - monoethanolammonium thioglycolate adjusted to pH Sodium formaldehyde bisulfite poor - 9.3 with monoethanolamine. The remaining glycolate Sodium formaldehyde sulfoxylate poor - solution was made 0.3 M in K and the five remaining indicates that heat activation is required. hair samples impregnated with exactly 1 ml each of this 55 solution. All 10 samples were allowed to react at ambi ent temperature (approx. 75' F) for 5 minutes and then 4.1.1. SULFITE OR BESULFITE SYSTEM quenched and allowed to soak in 600 ml of water. Each In one embodiment of the present invention, either sample was well agitated to thoroughly rinse out unre the sulfite (SO3F) or bisulfite (HSO3-) ion is utilized as acted agents. The amount of unreacted thioglycolate the consumable reducing agent (RA2). The useful con was determined by titration with standard iodine solu centration range of RA2 is about 0.3–2.0M, the prefera tion. For the five samples containing no KI, the average ble concentration being about 0.7 to 1.5 M. Preferred thioglycolate consumption was 36%. For the samples cations include: potassium (K), ammonium (NH4), containing KI, the average consumption was 54%. An sodium (Na+) and a mixture of Na+ and NH4+. The additional 2 samples were impregnated with 1.0 M thio 65 preferred regenerable reducing agent (RA) is the solu glycolate (pH 9.3) solution, one with and one without ble iodide ion. The useful concentration range for io KI, and allowed to set for 30 minutes. The thioglycolate dide is about 0.05-1.0 M, preferably about 0.15-0.4 M. consumption was 60% with KI and 63% without KI. Any of the cations as used for the RA2 may be utilized 4,659,566 9 10 for the RA1. The useful pH range for the combination rapidly consumed in the course of regenerating the of reducing agents is about 4-10, preferably about 6-7.5. iodide and cleaving disulfide bonds. This is particularly When either SO3 or HSO3 is used as the RA2, the important under all conditions of use contemplated for composition is useful particularly when employing a the composition, since the major negative side effect of heat-activated method of application. The heat may be permanent waving is hair damage. The present inven supplied by use of a dryer with a cap or by use of body tion also guards against aggravated hair damage result heat contained with a cap. In the latter instance, the ing from inexperience, carelessness, and too concen composition is allowed to remain on the hair for a some trated solutions. what longer period of time, e.g., about 15-30 minutes, compared to about 10-20 minutes when a dryer is used. 10 4.1.3. MONOETHANOLAMMONIUM A permanent wave that meets professional standards is THIOGLYCOLATE SYSTEM achieved. In another embodiment of the present invention the In practice, when K is utilized as the cation, the thioglycolate ion (HSCH2COO-) is also utilized as the composition of the present invention is substantially consumable reducing agent (RA2). The useful concen odorless at all values of pH in the preferred range, and 15 tration range of HSCH2COO is about 0.4-1.2M, pref has excellent diffusional properties so that the active erably about 0.7-1.2 M. The cation for RA2 in this em ingredients are rapidly delivered to the S-S linkage bodiment is the monoethanolammonium ion. The pre sites of the hair. Thus, this embodiment of the present ferred regenerable reducing agent (RA) is iodide. The invention offers a number of distinct additional advan useful concentration range for iodide is about 0.05-1.0 tages over conventional techniques, particularly: (a) 20 M, preferably 0.15-0.4 M. Useful cations for the RA1 lack of persistent unpleasant odor; and (b) more rapid include Na and K. The preferred composition reaction rate which reduces processing time and (c) should be adjusted to pH about 9.0-9.5 with monoetha most importantly and for the first time, enhanced curl nolamine. formation that is equivalent to that achieved by thiogly In practice, the monoethanolammonium thioglycol colic acid systems. 25 ate composition of this embodiment is particularly use In practice, when either NH4+ or a mixture of NH4+ ful when applied as a "cold wave', i.e., at ambient or and another cation such as Nat is utilized as the cation, room temperature. When thus used, the composition the disagreeable odor of sulfur dioxide is detected when can be used to achieve a permanent wave that meets used below the preferred range of pH, and the odor of professional standards and the objectionable, irritating ammonia is detected when used above the preferred 30 fumes of ammonia are eliminated. Heretofore, monoe range of pH. thanolammonium thioglycolate compositions have been 4.1.2. AMMONIUM THOGLYCOLATE SYSTEM largely restricted to home perms. In another embodiment of the present invention, the 4.14. GLYCEROL THIOGLYCOLATE SYSTEM thioglycolate (HSCH2COO-) ion is utilized as the con 35 In still another embodiment of the present invention, sumable reducing agent (RA2). The useful concentra the glycerine ester of thioglycolic acid, glycerol mono tion range is about 0.4-1.2 M, preferably about 0.5-1.0 thioglycolate, is utilized as the RA2. The preferred M. The preferred cation is NH4+. The preferred regen range for this RA2 is about 0.6-1.5 M. The preferred erable reducing agent (RA) is iodide. The useful con RA1 is the iodide ion which is utilized in the form of centration range of iodide is about 0.05-1.0 M, prefera soluble alkaline salts such as Na+, K, and NH4 and the ...bly about 0.15-0.4 M. The same cation as used for the like. In this system, the RA1 and RA2 must be mixed RA1 may be utilized for the RA2. The useful pH range together just prior to use because glycerol thioglycolate for this combination of reducing agents is about 9.0-9.5. hydrolyzes in water. The preferred pH range is about The composition has a distinct odor of ammonia at such 6.7-7.3, and aqueous ammonia is the preferred base used pH values. Also present is the characteristic odor of 45 to adjust the value of pH. sulfur of thioglycolate compositions. This thioglycolate In practice, the glycerol monothioglycolate composi odor persists for a substantial period of time post-treat tion of this embodiment may be advantageously be ment and is particularly noticeable and objectionable applied either as a "cold wave” or as a heat-activated when the hair is damp. formulation. Heretofore, this material was useful pri When ammonium thioglycolate is used as the RA2, 50 marily only when heat activated. and the pH adjusted to from 9.0-9.5 with ammonia, this composition is useful particularly when employed as a 4.2. NEUTRALIZATION SYSTEMS "cold wave' system. Thus, the composition is generally As explained previously, a second stage operation applied to and reacted with the hair at ambient or room comprising application of a neutralizing agent is neces temperature. 55 sary to form new S-S linkages of the keratin fibers in When iodide is used as the RA1, the composition is order to maintain the hair in the desired curled or allowed to remain on the hair for about 3-10 minutes. straight configuration. This represents a distinct advantage over conventional According to the present invention in the second ammonium thioglycolate systems which require contact stage of operation, the preferred neutralizing agent is with normal hair for about 10-30 minutes. aqueous sodium bromate (NaBrO3). The composition of this embodiment represents dis In practice, the neutralization stage of operation is tinct improvements over conventional ammonium thio performed as follows: after treatment of the hair with a glycolate systems because the thioglycolate (a) is in reducing composition, the hair is rinsed thoroughly to contact with the hair for a shorter time period; and/or remove the reducing agents, blotted, and a neutralizing (b) can be used at lower concentration (see Table III, 65 agent applied to the hair which is mechanically main Section 5.3.2). Moreover, the present composition of tained in the desired configuration. After about five fers inherent protection against overprocessing the hair minutes, the hair is briefly rinsed, released, i.e., un because the damaging ammonium thioglycolate is so wrapped from rollers, rinsed again, and allowed to dry. 4,659,566 11 12 When the hair has been treated with an alkaline compo -continued sition, it may initially be rinsed for about three minutes. Concentration When the hair has been treated with an acid composi Active ingredient (Molarity) tion, the hair is less porous and should be rinsed initially Ammonia (aqueous) for at least five minutes. USP Grade (E & F King) As a practical consideration, when an acid composi Added as reagent grade (28%) (Fischer Scientific) to adjust pH to 6.8. tion at a pH less than about 6.5-6.7 containing iodide as the regenerable reducing agent has been used, it is im portant to rinse thoroughly. For example, if a sulfite 5.1.2. AMMONIUM THIOGLYCOLATE/ODIDE composition described supra in Section 4.1.1 is used, a 10 Representative thioglycolate/iodide reduction sys small amount of iodine may be formed by oxidation of tems include: any residual iodide present. The presence of such iodine may be detected as a slight yellow color on any end Concentration papers used to wrap the hair. At pH about 6.7 or higher, 15 Active Ingredient (Molarity) such reaction does not occur with bromates. With the Ammonium thioglycolate 1. commonly used acidified hydrogen peroxide (H2O2) Potassium Iodide 0.3 neutralizers, iodine formation occurs. Ammonia (aqueous) Added as cosmetic grade, i.e., 60% contained thioglycolic acid (Evans Chemical). According to the present invention, other agents that Added as reagent grade (28%) (Fischer Scientific) to adjust pH to 9.3. can be utilized as neutralizing agents for the second 20 stage when iodide is used as the regenerable reducing agent include: sodium or potassium antimony (V) tar 5.1.3. MONOETHANOLAMMONIUM trate, and a composition comprising a solution of H2O2 THIOGLYCOLATE/IODIDE to which is introduced at the time of use a "protective' Representative monoethanolammonium thio reducing agent which reacts only slowly with H2O2 but 25 glycolate/iodide reduction systems include: rapidly with iodine. The protective reducing agent acts to reduce any iodine formed to iodide. Such reducing Concentration agents include ascorbic acid and carbazide. In practice, Active ingredient (Molarity) a solution of less than 3% H2O2 containing such reduc 30 Monoethanolamnonium 1.1 ing agent is used. In general, about 1-5% ascorbic acid thioglycolate or carbazide is sufficient. The useful pH range is about Potassium Iodide 0.3 1.5-3.8, preferably about 1.5-2.5. The preferred pH is Monoethanolamine Added as 39.2% contained thioglycolic acid (Evans Chemical). generally achieved by the addition of phosphoric acid. Reagent grade (Fischer Scientific) added to adjust pH to 9.3. The neutralizing compositions of the present inven 35 tion can also contain a thickening agent such as car boxymethyl cellulose, conditioning agents such as min 5.14. GLYCEROL THOGLYCOLATE/ODIDE eral oil, lanolin, or other suitable quaternary ammonium Representative glycerolthioglycolate/iodide reduc salts. Further the composition can also contain certain tion systems include: ...other conventional cosmetic adjuvants such as perfume, 40 ... : dyes, stabilizers, preservatives and surfactants. The following examples are given for the purpose of Concentration illustration and not by way of limitation on the scope of Active Ingredient (Molarity) the invention. Glycerol Monothioglycolate 1. 45 Potassium Iodide 0.3 5. EXAMPLES: PREPARATION AND METHODS Ammonia (aqueous) Added as cosmetic grade, i.e., 80% glycerol monothioglycolate in glycerine (Evans OF USE Chemical), 5.1. FORMULATIONS Added as reagent grade (28%) (Fischer Scientific) to adjust pH to 6.8. Examples presented below demonstrate formulations 50 for reducing compositions that were prepared as de 5.2. METHODS OF USE scribed supra in Section 4. The active ingredient listed The following experiments demonstrate methods of represents the initial starting ingredient used to prepare application and results obtained when using the compo the formulation. In each case, sodium laureth sulfate sitions according to the present invention. (Henkel Corp.) (0.5% by weight) was added to the 55 In each of the experiments 0.5gm of Caucasian hair composition as a wetting agent or surfactant. There (about 7 inches in length) (DeMeo Brothers, New York, was, however, nothing to indicate that such surfactant NY) was secured at one end with a plastic tab, sham is essential to the activity of the compositions. pooed using Purifying Shampoo TM (Eljenn Interna tional Corp., Newton, MA), rinsed with water, blotted 5.1.1. BISULFITE/ODIDE 60 and wrapped tightly, using end papers, around rollers (about 0.5 inch diameter). The appropriate reducing Representative bisulfite/iodide reduction systems composition was applied, allowed to react under condi include: tions of time and temperature as specified, and the hair was rinsed in running water for one minute. Concentration 65 Ambient or room temperature was about 75 F. Active Ingredient (Molarity) When experiments were performed at room tempera Sodium bisulfite 1.0 ture, the hair samples were not enclosed. When experi Potassium Iodide 0.3 ments were performed at higher temperatures, the hair 4,659,566 13 14 samples were enclosed in a plastic bag which was then warmed to the desired temperature using a salon-type TABLE II-continued hair dryer. APPLICATION OF BISULFITE/ODIDE In all cases, the neutralizing composition comprised a 2.0 0.3 6.8 NH3 Good 6 1.0 0.05 6.8 NH3 Fair 3-- commercially available aqueous solution of sodium 1.0 0.15 6.8 NH3 Fair 4 bromate (about 10%) at a pH of about 7.5 (AmeriBrom 1.0 0.30 6.8 NH3 Good 5 Co.). 1.0 0.45 6.8 NH3 Good 6 After the hair was rinsed, the sample was blotted, the 1.0 0.85 6.8 NH3 Good 6-- neutralizing composition applied and allowed to react 1.0 0.3 5.0 NH3 Good 6 with the hair for about 5 minutes. The hair was then 10 1.0 0.3 6.0 NH3 Very Good 7 1.0 0.3 6.5 NH3 Very Good 7 rinsed briefly, unwrapped and rinsed well in running 1.0 0.3 70 NH3 Good 6-- water. The unwrapped hair was then blotted and al 1.0 0.3 8.0 NH3 Good 5 lowed to air dry. 1.0 0.3 9.0 NH3 Fair 4. The "shape', "strength” and "springiness' oftne curl B. Temperature and Reaction Time Varied achieved was then evaluated. The "shape' of the curl 15 Hair type: Brown refers to the waved configuration perceptible in the hair Sodium Potas Bi- sium sample. The “strength' of the curl refers to persistence sulfite Iodide Value of the curl following a single shampooing 48 hours (Mo- (Mo- Final Temp Time Curl of post-treatment. The "springiness” of the curl refers to lar) lar) pH Base (F) (Min) Rating Curl 20 the liveliness with which a stretched curl springs back 1.0 0.3 6.8 NH3 75 30 Good 5 when released. o 1.0 0.3 6.8 NH3 88 30 Very 8 Each of the three parameters, shape, strength and Good springiness was evaluated post-treatment. Such evalua 1.0 0.3 6.8 NH3 98 20 Very 7 tion is necessarily subjective. In order to afford some Good 25 1.0 0.3 6.8 NH3 105 15 Excellent 9 objectivity to the evaluation, however, the results ob 1.0 0.3 6.8 NHs 115 15 Excellent 10 tained were rated and assigned a value from 0-10 ac cording to the following scale: Monoethanolamine used to adjust pH As previously explained, the curl or wave achieved Curl Rating Value of Curl 30 was evaluated and rated according to a scale of 0-10. Poor 0-2 For example, as illustrated in Table IIB, an excellent Fair 3-4 curl rating a curl value of 10 was obtained using 1.0 M Good 5-6 sodium bisulfite with 0.3 M potassium iodide at pH 6.8 Very Good 7-8 for 15 minutes at 115 F. The hair sample was reduced Excellent 9-10 in length about 2.5 inches, exhibiting a pronounced 35 springy curl. After a single shampooing, the curl per It should be noted that only curl ratings of about 8 to 10 sisted, with the hair increasing in length at most 0.25 meet cosmetically acceptable standards for professional inch. permanent waves. As demonstrated in Table IIA, the curl obtained was improved when the pH of the bisulfite system was re 5.3. CURLING HAIR SAMPLES duced from that conventionally used (e.g., Rave pH 5.3.1. BISULFITE/ODIDE TREATMENTS 10.1) to pH 6.8. Further, addition of the regenerable Tables IIA and IIB present results obtained when reducing agent, potassium iodide further improved re hair samples were treated with a bisulfite/iodide reduc sults. For example, a curl rating a curl value or 1 was ing composition. Because the conventional bisulfite 45 obtained using 0.7M sodium bisulfite with no potassium system is generally applied to human hair and then iodide at pH of 10.1. The wave was barely perceptible. covered with a plastic cap, experiments tabulated in Reduction in length of the hair sample was 0.25 inch. Table IIA were conducted at about 88 F., the approxi When 0.3 M potassium iodide was added, a curl rating mate temperature of hair on the human head when a value of 4 was obtained. The hair had a demonstrable moistened and covered with a plastic cap such as gener 50 wave. Reduction in length of the hair was about 1.25 ally used for "home' permanent wave systems. In all inch, which reduction persisted through a single sham cases the hair sample was allowed to react with the pooing. reducing compositions for 20 minutes (Table IIA) Increase of sodium bisulfite concentration from 0.7M about 1.0M, improved the rating of curl obtained. Fur g TABLE II 55 ther increase of sodium bisulfite concentration, how APPLICATION OF BISULFTE/ODIDE ever, to 2.0 M was no more effective than about 1.3 M. A. Temperature fixed at 88 F. The effect of varying the concentration of potassium Processing time 20 minutes iodide from 0.05 M to 0.85 M is also demonstrated Hair type: Brown Sodium Potassium Value (Table IIA). Above about 0.3 M potassium iodide did Bisulfite Iodide Final Curl of not improve the curl rating substantially. (Molarity) (Molarity) pH Base Rating Curl The effect of varying pH on the bisulfite system is 0.7 O 6.8 NH3 Fair 3 also demonstrated. As shown in Table IIA, reduction of 0.7 O 10.1 NH3 Poor 2 the pH to about 5.0, did not significantly affect the curl 0.7 O 6.8 MEA Poor 2 value obtained. As the pH falls below about 6.8, how 0.7 O 10. MEA Very Poor 65 0.7 0.3 10. MEA Fair 4 ever, an odor of sulfur dioxide becomes apparent. At 0.7 0.3 6.8 NH3 Good 6 pH about 6.8, the odor detection is minimal. Above pH 1.0 0.3 6.8 NH3 Very Good 7 7.0, the odor of ammonia becomes apparent. Moreover, 1.3 0.3 6.8 NH3 Very Good 7 at pH greater than 9.0, the value of the curl deteriorates. 4,659,566 15 16 Table IIB illustrates the effect of temperature and tion. In the presence of potassium iodide, a cosmetically time upon the curl obtained. As noted previously, the acceptable curl was achieved at room temperature bisulfite system is preferably used as a heat-activated (about 75 F). system. Cosmetically acceptable waves were obtained TABLE IV when the 1.0 M sodium bisulfite with 0.3 M potassium APPLICATION OF MONOETHANOLAMMONUM iodide was used at 88 F. for about 30 minutes or when THIOGLYCOLATE/IODDE used at elevated temperatures for about 15 minutes. Hair Type: brown Such temperatures are easily achieved using a salon Monoethanol type hair dryer. A respectable wave was obtained using ammonium Potassium the same system at ambient or room temperature (about 10 thioglycolate Iodide Final Time Curl Value 75' F.) for 30 minutes. (Molarity) (Molarity) pH (Min.) Rating of Curl In summary, the bisulfite/iodide composition can be 1.1 0.0 9.3 20 Good 6 used either as a "home' perm, i.e., either at ambient 1.1 0.3 9.3 20 Excellent 9 temperature or with a plastic cap over the hair (about Used monoethanolamine to adjust pH to 9.3. 88 F.), or as a professionally applied "salon-type' perm 15 using a hair dryer. Under both kinds of conditions a The monoethanolammonium thioglycolate composi cosmetically acceptable wave is achieved. Further, tion possesses all the unpleasant persistent odor of thio when the pH of the composition is adjusted to about glycolate and its decomposition products. No odor of 6.8-7.2, the composition is substantially odorless in the ammonia is detectable. absence of added fragrance. When the pH is lower than 20 this range, the odor of sulfur dioxide develops, and 5.3.4. GLYCEROL when the pH is above this range the odor of ammonia • MONOTHIOGLYCOLATE/ODIDE develops. Hair treated with compositions either above TREATMENTS or below the preferred pH range, acquires the odor of Table V illustrates results obtained using the glycerol the composition as well as the odor associated with the 25 monothioglycolate/iodide system. In the absence of breaking of disulfide bonds. These odors, however, potassium iodide, cosmetically acceptable curl could be disappear following the neutralization stage and do not achieved only when the composition was reacted with reappear when the hair is dampened. hair at about 115 F. for about 20 minutes. With 0.3 M 5.3.2. AMMONIUM THIOGLYCOLATE/IODIDE potassium iodide, an acceptable curl was aschieved at 30 both ambient and elevated temperatures. TREATMENTS The glycerol monothioglycolate/iodide composition Table III illustrates results obtained when hair sam has no ammonia odor, but does possess the unpleasant ples were treated with the ammonium thioglycolate/io persistent odor associated with thioglycolate. dide system. These experiments were conducted at TABLE V room temperature (about 75 F). 35 APPLICATION OF GLYCEROL TABLE III MONOTHIOGLYCOLATE/ODIDE APPLICATION OF THIOGLYCOLATE/ODIdE Treatment time: 20 minutes - Hair type Brown Hair type: Brown Ammonium- Potassium Glycerol mono- Potassium thioglycolate Iodide Final Tine Curl Value 40 thioglycolate Final Temp Curl Value (Molarity) (Molarity) pH (Min.) Rating of Curl iodide (Molarity) (Molarity) pH ("F.) Rating of Curl 1.1 0.0 9.3 5 Poor 2 1.1 0.0 9.3 20 Very Good 8 1.1 0.0 6.8 75 Fair 4. 1.1 0.3 9.3 5 Very Good 7 1.1 0.0 6.8 105 Good 5 i.1 0.3 9.3 10 Excellent ... 10 1.1 0.0 6.8 115 Very Good 8 1. 0.3 9.3 20 Excellent 10 45 1.1 0.3 6.8 75 Very Good 8 0.5 0.3 9.3 20 Very Good 7 0.9 0.3 6.8 105 Excellent 10 0.9 0.3 6.8 115 Excellent 10 Used aqueous solution of ammonia to adjust the value of pH. Used aqueous solution of ammonia to adjust the value of pH. As demonstrated, a cosmetically acceptable curl could be achieved using about 0.7-1.1 M ammonium 50 6. EFFECT OF ODIDE SYSTEMS IN thioglycolate with 0.3 M potassium iodide for about CONTROLLING HAIR DAMAGE 5-20 minutes. When no potassium iodide was added to the composition, an acceptable curl could be achieved Because conventional systems often leave the hair in only when the composition was reacted with hair for a dry, brittle, fragile condition, the extent of damage to about 20 minutes." 55 the treated hair was also evaluated. In these experi The thioglycolate/iodide composition when used at ments, particularly harsh treatment conditions were pH about 9.3 has an irritating odor of ammonia plus the employed, including the use of blonde hair which is characteristic sulfur odor of thioglycolate and its de more susceptible to damage, in order to demonstrate the composition products. Following neutralization and surprising differences using the iodide system. rinsing, the odor of ammonia disappears from the hair. 60 For example, a bisulfite/iodide composition was for The thioglycolate odor persists and is especially notice mulated as follows: 2.0 M sodium bisulfite, 0.3 M potas able when the hair is dampened. sium iodide, adjusted to pH 6.8 using an aqueous solu tion of ammonia. A sample of hair was treated as de 5.3.3. MONOETHANOLAMMONIUM scribed supra with the bisulfite/iodide composition for THIOGLYCOLATE/IODIDE TREATMENTS 65 30 minutes at 115 F. A control sample was treated Table IV illustrates the improvement of curl identically except no iodide was added. After neutral achieved by the addition of 0.3 M potassium iodide to ization and shampooing, very little observable damage 1.1 M monoethanolammonium thioglycolate composi to the test hair was apparent, and cosmetically accept 4,659,566 17 18 able curl was achieved. With the control, a poor curl was obtained, and the hair had a dry, frizzy, limp ap pearance. Concentration A thioglycolate/iodide composition was formulated Active Ingredient (Molarity) Sodium bisulfite 1.0 as follows: 1.1 M ammonium thioglycolate was com Potassium iodide 0.3 bined with 0.3 M potassium iodide, adjusted to pH 9.3 Monoethanolamine using ammonia. A sample of hair was treated as de Used to adjust pH to 6.8. scribed supra with the thioglycolate/iodide composi tion for 25 minutes at ambient temperature (about 75 Hair that had previously been tinted and whose ends F.). A control sample of hair was similarly treated ex 10 were "frosted' was shampooed, rinsed and wound cept that no potassium iodide was added to the control around rollers to give the hair the desired curled config composition. After neutralization and shampooing, uration. The composition was formulated as a lotion there was very little observable damage apparent in the and applied in situ to the hair using a heat-activated hair treated with the composition containing potassium 15 method of application. Heat was supplied by use of a iodide. There was, however, noticeable damage to the standard salon-type hair dryer at the "Normal” setting hair treated with the composition with no potassium for 18 minutes. The hair was then rinsed thoroughly, iodide. The latter hair sample appeared dry, brittle, and blotted, and a neutralizing composition comprising frizzy. about 2% H202 adjusted to the pH of about 2.0 using When the concentration of ammonium thioglycolate 20 phosphoric acid was then applied. In the absence of the was reduced to 0.7 M, there was very little observable preferred bromate neutralizing agent described in sec damage to hair samples treated with compositions with tion 4.2, there was noticeable iodine formation. This or without potassium iodide. The curl achieved, how iodine easily was rinsed out and did not persist. ever, when potassium iodide was not present in the The permed hair had a cosmetically acceptable, wavy composition did not meet professional standards. 25 curl, but did not feel like "permed' hair either to the A monoethanolammonium thioglycolate/iodide recipient, a licensed beautician herself, or to the opera composition was formulated as follows: 1.1 M monoe tor. There was no apparent additional damage to the thanolammonium thioglycolate, 0.3 M potassium io already fragile hair. Loss of curl two weeks post-treat ment was less than normal, according to the recipient. dide, adjusted to pH 9.3 using monoethanolamine. A 30 sample of hair was treated with the monoethanolam 7.2. ORIENTAL HAIR monium thioglycolate/iodide composition for 25 min In general it is more difficult to impart a permanent utes at ambient temperature (about 75 F). A control wave or curl to the hair of members of Oriental or sample of hair was similarly treated except that no po Asian races. tassium iodide was added to the composition. Very little 35 damage was noted in the test sample. However, the An odorless composition for stage one was prepared control sample showed demonstrable damage and had as follows: an inferior curl. A glycerol monothioglycolate/iodide composition Concentration was formulated as follows: 1.2 M glycerol monothio Ingredient (Molarity) glycolate, 0.3 M potassium iodide, adjusted to pH 6.8 Sodium bisulfite 1.0 using an aqueous ammonia solution. A sample of hair Potassium iodide 0.3 was treated as described supra with the glycerol mono Ammonia (aqueous) thioglycolate composition for 30 minutes at 115 F. A Used to adjust pH to 6.9 control sample of hair was similarly treated except that 45 no potassium iodide was added to the control composi Hair of a female Oriental was shampooed, rinsed and tion. After neutralization and shampooing, very little wound around rollers. The composition was formulated damage was apparent in the test sample. The control as a lotion and applied in situ to the hair using a heatac sample, however, had a noticeably "rougher" tactile tivated method of application. Heat was supplied by use 50 of a standard salon-type hair dryer at the "High' setting quality. Both samples had very good curls. for 15 minutes. The hair was then rinsed thoroughly, 7. SALON TESTS ON HARD-TO-CURL HAIR blotted and a peroxide neutralizing composition as de scribed in Section 4.2 supra was then applied. In the following examples, a composition prepared The treated hair exhibited a cosmetically acceptable according to the methods of the instant invention, was 55 wave, with no apparent signs of damage. (In the opinion applied in situ by experienced beauticians under normal of the recipient, her hair was marginally lightened to beauty-salon conditions. The remarks with respect to the same extent she has noticed with previous perms.) hair damage, curliness, texture and tactile quality of the This wave has persisted for 13 weeks. At 7 weeks hair represent the candid reactions and opinion of expe post-treatment, the hair was cut by a beautician, who rienced beauticians. stated the wave was "strong' and the hair exhibited no 7.1, FRAGILE HAIR apparent signs of damage or dryness. Hair that has been bleached, tinted, or treated to 7.3. HARD-TO-PERM CAUCASIAN HAIR change or lighten its natural color tends to become dry, The recipient, a Caucasian female with a history of - fragile, and difficult to treat with conventional perma 65 experiencing either severe hair damage from perms or nent waving systems. perms that did not last beyond a few weeks, was given An odorless composition for the reduction stage, was a wave with the following composition for the reduc prepared as described in Section 5.1.1, as follows: tion stage: 4,659,566 20 2. The reducing composition according to claim 1, in which the concentration of iodide salt is from about 0.15 Concentration to about 1 molar. Active Ingredient (Molarity) 3. The reducing composition according to claim 1, in Glycerol Monothioglycolate 0.85 5 which the concentration of the keratin reducing thio Potassium Iodide 0.3 glycolate salt is from about 0.5 to about 1 molar. Ammonia 4. The reducing composition according to claim 1, in Ingredients mixed just prior to use. which the keratin reducing thioglycolate salt is ammo Used to adjust pH to 6.8. nium thioglycolate. It should be noted that commercially available perms O 5. The reducing composition according to claim 1, in using glycerol monothioglycolate range from 1.1-1.2M which the keratin reducing thioglycolate salt is monoe thanolammonium thioglycolate. in concentration. 6. A reducing composition for reducing disulfide The hair was processed for 23 minutes under a salon bonds of keratin, comprising an aqueous solution of a hair dryer at the "Normal" setting. After rinsing for 5 is water soluble iodide salt and a water soluble, consum minutes, it was neutralized with sodium bromate (10%) able keratin reducing agent selected from the group with 5% urea added as a flame retardant. There was no consisting of salts of sulfites, bisulfites, hydrobisulfites, noticeable iodine formation. metabisulfites and sulfoxylates, in which the concentra The treated hair exhibited a cosmetically acceptable tion of the iodide salt is from about 0.15 to about 1 molar wave with small, springy curls and, according to the 20 and the concentration of the consumable reducing agent recipient and the beautician, the hair had a healthy, is from about 0.3 to about 2 molar. undamaged appearance and feel. 7. The reducing composition according to claim 6, in 8. EXAMPLE: STRAIGHTENING HAIR which the concentration of the consumable keratin reducing agent is from about 0.7 to about 2 molar. A composition for the reduction stage was prepared 25 8. The reducing composition according to claim 6, in as a lotion as follows: which the consumable keratin reducing agent is a sulfite salt. Concentration 9. The reducing composition according to claim 6, in Active Ingredient (Molarity) 30 which the consumable keratin reducing agent is a bisul Sodium bisulfite 1.0 fite salt. Potassium Iodide 0.3 10. A process for setting hair or fur, comprising: Ammonia (aqueous) (a) applying to hair or fur a reducing composition Used to adjust pH to 7.0 according to claim 1; 35 (b) allowing the hair or fur to stand in a desired con Samples of human hair (DeMeo Brothers, New York, figuration; N.Y.) that had previously been treated with a perma (c) applying to the hair or fur a sufficient amount of nent wave process were wet with water, shampooed an aqueous neutralizing composition to provide and wrapped around a large-bore cylinder. The lotion permanent waving or straightening of the hair or was applied using a heat-activated method. The hair 40 fur; and was maintained at about body temperature for 20 min (d) washing and drying the hair or fur. utes. Subsequently, the hair was thoroughly rinsed with 11. A process for setting hair or fur, comprising: water and treated with a neutralizing composition of (a) applying to hair or fur a reducing composition 10% cosmetic grade sodium bromate at pH 7.5. according to claim 6; Control samples of hair were treated using an identi- 45 (b) allowing the hair or fur to stand in a desired con cal process, except that potassium iodide was not added figuration; to the reducing composition. (c) applying to the hair or fur a sufficient amount of The hair samples treated with the composition con an aqueous neutralizing composition to provide taining potassium iodide achieved a cosmetically permanent waving or straightening of the hair or 50 fur; and straight configuration. Control samples, however, still (d) washing and drying the hair or fur. retained a portion of the curled or waved configuration 12. A reducing composition for reducing disulfide post-treatment. bonds of keratin, comprising an aqueous solution of a Having described the invention with particular refer water soluble iodide salt and glycerol monothioglyco ence to certain embodiments thereof, it will be obvious 55 late, in which the concentration of the iodide salt is to those skilled in the art to which the invention pertains from about 0.05 to about 1 molar and the concentration after understanding the invention, that various changes of the glycerol monothioglycolate is from about 0.6 and modifications may be made therein without depart about 1.5 molar. ing from the spirit and scope of the invention as defined 13. The reducing composition according to claim 2, by the claims appended hereto. 60 in which the concentration of the iodide salt is from What is claimed is: about 0.15 to about 1 molar. 1. A reducing composition for reducing disulfide 14. A process for setting hair or fur, comprising: bonds of keratin, comprising an aqueous solution of a (a) applying to hair or fur a reducing composition water soluble iodide salt and a water soluble keratin according to claim 12, reducing thioglycolate salt, in which the concentration 65 (b) allowing the hair or fur to stand in a desired con of the iodide salt is from about 0.05 to about 1 molar and figuration; the concentration of the thioglycolate salt is from about (c) applying to the hair or fur a sufficient amount of 0.4 to about 1.2 molar. an aqueous neutralizing composition to provide 4,659,566 21 22 permanent waving or straightening of the hair or permanent waving or straightening of the hair or fur; and fur; and (d) washing and drying the hair or fur. (d) washing and drying the hair or fur. 15. A process for setting hair or fur, comprising: 16. The process according to claim 10, 11, 14 or 15, in (a) applying to hair or fur a reducing composition which the neutralizing composition comprises sodium comprising an aqueous solution of a water soluble bromate. iodide salt and a water soluble, consumable keratin 17. The process according to claim 10, 11, 14 or 15, in reducing agent selected from the group consisting which the neutralizing composition comprises potas offulfilsifies suites, pilulites, nyarobisuhydrobisulfit metaDISulliesmetaisi 10 Sigimony18. The process (V) according arrate to claim 10, 11, 14 or 15, in and- sulfoxylates, in which the concentration of the which the neutralizing composition comprises hydro iodide salt is from about 0.05 to about 1 molar and gen peroxide with a sufficient amount of a protective the concentration of the consumable keratin reduc- reducing agent to reduce any iodine to iodide. ing agent is from about 0.3 to about 2 molar; 19. The process according to claim 18, in which the (b) allowing the hair or fur to stand in a desired con- 15 protective reducing agent is ascorbic acid. figuration; 20. The process according to claim 18, in which the (c) applying to the hair or fur a sufficient amount of protective reducing agent is carbazide. an aqueous neutralizing composition to provide 2k is : k sk

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