Permanent hair shaping composition and method for using the same
United States Patent Wajaroff 5] Apr. 29, 1975 PERMANENT HAIR SHAPING [56] References Cited COMPOSITION AND METHOD FOR USING UMTED STATES PATENTS THE SAME 3.109.777 ll/l963 Zviak v. 132/7 Inventor: Theodor wajaroff Darmstadt i ZViZlk Germany 1 Primary Examiner-G. E. McNeil [73} Assignee. Wella Aktlengesellschaft, Darmstadt. Attorney. Agent or Firm Michae] S. Striker Germany [22] Filed: Dec. 26, 1973 57 ABSTRACT [21] Appl. N0.: 428,406 A two step permanent hair shaping composition comprising a component A to be used in the first step comprising a salt of a mercapto carboxylic acid and a [30] Formal Apphcauon Pr&#39;omy Data component B to be used in the second step comprising Dec. 23. I972 Germany 2263203 3 n f a mercapto cal-boxylic acid and a hydrophmc mercapto carboxylic acid ester wherein said ester is [52] US. Cl 132/7; 424/72 added just prior to use and a method for using the [51] Int. Cl A45d 7/00 Same [58] Field of Search 132/7; 424/72 16 Claims, 2 Drawing Figures I I0 i 20 PERMANENT HAIR SHAPING COMPOSITION AND METHOD FOR USING THE SAME BACKGROUND OF THE INVENTION:  
  This invention relates to a two component permanent hair shaping composition and a method for using the same.  
  The shaping of human hair has conventionally been carried out by utilizing as active agent a water soluble salt of a mcrcaptocarbosylic acid. for example an ammonium thioglycolate and the known preparations have been in the form of liquids or thickened preparations i.e.. creams and gels. The shaping treatment has generally been conducted by applying the shaping composition to the hair and permitting it to act on the hair for a sufficient time to produce the shaping. This results in a reductive splitting of the disulfide bridges in the hair keratin to form HS groups. The hair shaping agent is then washed out with water and the hair treated with an oxidation agent containing setting composition. preferably with a solution containing hydrogen peroxide. This treatment causes an oxidative crosslinking of the HS groups to reform the disulfide bridges.  
  If a permanent wave is vented. the hair is prewet with a portion of the shaping composition and the prewet hair wound up onto permanent wave rollers. After the shaping composition has acted on the hair for about Ill-2U minutes that is. about the time necessary for winding the hair on rollers. the remaining portion ofthe shaping composition is applied. After a period of 5 to minutes. the hair is washed for removal of the shaping composition and the hair then subjected to an oxidative fixing or setting treatment.  
  If a permanent straightening ofthe hair is desired. the shaping composition in thickened form. for instance as a cream. is applied to the hair and evenly distributed throughout the hair for example by combing. After the shaping composition has acted on the hair for about 10-21] minutes. during which the hair is combed more or less continuously. the shaping agent is washed out with water. The hair is then fixed or set in the known manner. i.e.. with a setting composition containing an osidative agent.  
  The above-described hair shaping agents on the basis of mercaptocarboxylie acid salts are only effective in the alkaline pH range and are therefore made up only in the pH ranges of at least 7.0 to 9.6. Already at the lower end of the pH range. the keratin softening activity and therewith the shaping capability is relatively weak. While there is an increased activity at the upper end of the pH range. there is also an increased stressing. i.e.. wear and tear on the hair and the skin of the scalp. Further as the degree ofthe shaping is dependent on the working time of the shaping agent. there must from time to time during the shaping treatment be interruptions during which a strand of hair is unwound from a roller and examined to determine whether the desired degree of shaping has already been reached.  
  in this situation. whether permanent waving or straightening is involved. it sometimes happens that the necessary or requisite time is csceeded. There then results in the former case an over curling of the hair and in addition both here and in the case of the hair straightening a certain amount of damage to the hair and the scalp.  
  it has already been proposed to carry out permanent shaping with acid made up agents which contain as the shaping substance hydrophilic esters of mercaptocarboxylic acids. In this connection. there come into con sideration such compounds. as for evample. monothioglycolic acid-glycol ester or -glycerine ester. which through the presence of hydrophilic groups in their molecule have an increased water solubility. As. however. these hydrophilic esters are in aqueous medium gradually saponified they cannot be kept for a long period under such conditions without decomposition of the preparation taking place. It is therefore necessary that the pure compound as such be added just shortly before the shaping treatment with an acid adjusted aqueous liquid. The hair shaping process is otherwise carried in the exact same manner as when the shaping agent is a mercaptocarboxylic acid salt. The result is however only a relatively poor permanent waving of the hair.  
  The disadvantages of the aforcdescribed shaping processes arise from the fact that the activity of the shaping agents scarcely changes so that their effectiveness during the entire working period on the hair remains substantially constant. it is only through the use of easily volatile substances such as ammonia for the alkalinization of the shaping agent that a small decrease in the activity as a consequence of the volatilization is brought about. If however this is not brought about or not to a sufficient degree than all of the abovedescribed disadvantages are observed.  
  lt has now been found in accordance with the invention that the above disadvantages can be avoided and hair permanently shaped i.e.. waved or straightened without the danger ofover curling and with no damage to the hair or scalp. the waving being characterized by a substantial improvement in regard to permanency of the shaping and condition of the hair.  
  In accordance with the invention there is provided a process comprising in a first step applying to the hair a permanent shaping i.e.. waving or straightening composition which is alkaline in nature and preferably weakly alkaline. comprising a mercaptocarboxylic acid salt and thereafter in a second step applying a shaping composition. preferably a further portion of the shaping composition used in the first step to which there has been added a hydrophilic mercaptocarbosylic acid ester just prior to use.  
  lf the purpose of the treatment is to permanently wave the hair. then the hair is in a first step wet with the first-mentioned shaping composition preferably in the form ofa solution. and then the hair is rolled up on permanent wave rollers. There is then added to a further portion of the hair waving composition as used in the first stage a hydrophilic mercaptocarboxylic acid ester and this solution applied onto the rolled up hair. After a period of about 5 to 20 minutes. the hair is thoroughly washed with water and then treated in the known manner with a fixing agent. for example with a hydrogen peroxide solution i.e.. the hair is oxidatively set.  
  lfa straightening ofcurly hair is to be carried out in accordance with the invention. then the abovedescribed first step shaping agent in thickened form. i.e.. as a cream or gel is applied onto the hair. uniformly distributed and allowed to act on the hair for about 5 to ltl minutes. There is then added to a similar amount of the same composition. a pure hydrophilic mercaptocarbosylic acid ester and this mixture applied onto the hair. After a period of about ltl-ZO minutes during which the hair is thoroughly combed to facilitate the straightening effect. the hair is thoroughly washed with water and fixed in the known manner.  
  If desired a shortening ofthe time for shaping the hair may be obtained by application of heat from an external source during the second step as for example by using a drying hood while the shaping agent is acting on the hair.  
  Because of the weakly alkaline nature of the shaping agent used in the first stage. the softening of the hair keratin is achieved and the desired shaping of the hair facilitated.  
  After applying the shaping mixture in the second treatment step onto the hair. a strong increase in the keratin softening effect sets in. which is clearly traceable to the fact that the hydrophobic region of the hair keratin has been reached. After a short time. the action quickly. by itself and within the treatment period drops off.  
  The sharp increase in the keratin softening and therewith the shaping action through the treatment on the basis that the action of the mercaptocarboxylic acid salt is considerably increased because of the hydrophilic esters which are very shaping active in the alkaline pH range. In the alkaline mixture, however. there sets in an increased saponification of the esters. liberating free mercaptocarboxylic acid which continuously neutralizes the free alkali through salt formation. The decrease in the alkalinity and therewith the pH value of the composition determines that in spite of the increasing concentration of mercaptocarboxylic acid. the shaping effect of the mixture with increasing ester saponification rapidly falls off.  
 From FIG. I ofthe drawing. the dependence on time of the saponification effected splitting of the monothioglycolic acid-glycerine ester can be seen. Three aqueous solutions were prepared for comparison purposes. each containing 1 lg of the hydrophilic ester per 100 g solution. At room temperature the pH of the solutions has. with a 5 percent aqueous ammonia solution. been adjusted to a pH value of 7.0. 7.5 and 8.0 respectively and is thereafter maintained constant with continuous addition of 5 percent aqueous ammonia. Through the continuous ammonia addition there is provided a measure for the free thioglycolic acid formed by saponification of the hydrophilic ester.  
  FIG. 2 there is shown the pH pattern during a shaping treatment carried out in accordance with Example 1 of the application as can be seen. at first the pH value of the shaping liquid is slightly increased on account of the escape of CO: (from 8.2 to 8.5). After 15 minutes (completion of the winding) when the addition of the hydrophilic ester takes place. there is observed a rapid pH decrease in the second treatment step liquid preparation.  
  The proccss of the invention makes possible a strong and durable shaping of the hair. which is particularly suitable for hair which is shaped only with difficulty. In spite of this strong shaping activity. and on account of the self-initiated fall off in activity. the condition of the hair and the scalp are considerably improved. In addition the permanent shaping hair process of the invention does not result in a situation where over curling of the hair can take place.  
  For carrying out the process of the invention it is most advantageous if a batch of shaping composition (ill containing the mercaptocarbosylic acid salt is made up and if about one-halfofthis is used for the first step and if the remaining half is reserved for use in the second step following addition ofthe hydrophilic ester. ln gen eral it is possible to split the batch of shaping composition so that the amounts used in the first and second steps fall with the ratio of one-third to one-half: twothirds to one-half.  
  As mercaptocarboxylic acid salt there can be used the known water-soluble compounds, which as cation contain for example. the ammonium. sodium or potassium ion and as anion. the thioglycolate or thiolactate ion. Most preferred is the ammonium salt of thioglycolic or thiolactic acid. The salt is advantageously used in a starting concentration of about 5 to 10 weight percent (calculated as acid).  
  ln addition to the mercaptocarboxylic acid salt. the shaping composition can also contain the conventional cosmetic additives as for instance. emulsifiers. surface active agents. thickeners. perfume oils. penetration agents and the like.  
  The hydrophilic esters of mercaptocarboxylic acids. as set out above are used in accordance with the invention in pure form and are added to the shaping composition just before use in the second step of the shaping treatment. Illustrative of the esters which are suitable for use herein are the glycol. glycerine and methoxyethanol ester. Most preferred are such esters of thioglycolic and thiolactic acid. The amount of hydrophilic ester added to shaping composition prior to its use in the second step of the process is generally in the range of 2-5g hydrophilic ester to 40g of shaping composition.  
 In accordance with the process ofthe invention there may be utilized in the compositions for the hair shaping. the known combination of the enzyme urease and urea and therewith the pH value and also the activity of the mercaptocarboxylic acid salt can be increased. Thus in accordance with an embodiment of the invention there can be added to the shaping composition comprising a neutral urea containing preparation prior to its use in the first step. an enzyme i.e.. urease and thereafter prior to the use of the shaping composition in the second step there is added the hydrophilic mercaptocarboxylic acid ester. In accordance with a further embodiment of the invention there may be introduced into the compositions ester splitting enzymes such as for example. pancreatin. the same facilitating the saponifying-splitting of the hydrophilic esters. This latter type of enzyme can be introduced into the composition initially or just prior to the addition of the hydrophilic ester i.e.. before the use of the composition in the second step.  
  The following Examples will further illustrate the invention but are in no way to be considered as being a limitation thereof. All percentages reported in the Examples are percentages by weight.  
 EXAMPLE I Human hair was prewet with 40 g of a permanent wave solution having a pH of 8.2 and the following composition:  
 aqueous ammonium thioglycolatc solution til) t ammonium bicarbonate ammonium carbonate urea perfume oil IIIJ  Continued 0.4 g oleic acitl pentaer thrile pohglycol ether fill g water The prewet hair was then wound up on permanent wave rollers. 4.0 g monothioglvcolic acid glycerine ester was then added to the remaining 40 g of permanent wave solution and it was then used to wet the wound up hair. After l-l5 minutes had elapsed. the hair was washed with water and further treated in the conventional manner with a known fixing or setting agent. as for example. with hydrogen peroxide solution.  
 EXAMPLE 2 Human hair was prewet with 30 g of a permanent wave solution having a pH of 8.8 and the following composition:  
 aqueous ammonium thiolactate solution [509? ammonium bicarbonate ammonium carbonate perfume oil polyethylenegl col-sorbitan-oleie acid ester 44.5 g water EXAMPLE 3 40 g ofa permanent wave solution having a pH of 9.0 and the following composition were used to prewet human hair:  
  aqueous ammonium thiolactate solution (50% ammonium carbonate formamidc perfume oil poleth \lene glycol-sorbitan-oleic acid ester WillLl&#39; The prewet hair was then wound up on permanent wave rollers. 5.0 g thiolactic acid methoxyethylester were added to the balance (40g) of permanent wave solution and the wound up hair wet with this solution. After a working period of 8-15 minutes. the hair was washed with water and fixed in the conventional manner.  
 EXAMPLE 4 Human hair was prewet with 60 g of a permanent wave solution having a pH of 7.6 and the following composition and then wound up on permanent wave rollers:  
  aqueous ammonium thiogl \colulc solution (50&#39;; ammonium bicarbonate perfume oil 0.11 g oct \lphenol 20 mols ethylcneoxide 93.3 g water lzllll g 20.0 g 5.4 g 0.7 g  
  There were then added to the remaining 60g of solution 7.5 g monothioglycolic acid-glycerine ester and 2.25 g pancreatin and the resultant solution used to wet the wound up hair. After a working time of about 20 minutes. the pH had dropped to 7.0 (without pancreatin but in the same time the pH had dropped only to 7.3.). The hair was thoroughly washed out with water and fixed in the known manner. The pancreatin can be added to the prewetting solution with the same results.  
 EXAMPLE 5 Human hair was wet with 40 g of a permanent wave solution having a pH of 7.0 and the following composition which had just prior to use had added thereto 1.5 g of a mixture of urease and panereatin l:l  
 l5.6 g aqueous ammonium thioglycolate solution (50% l 2.8 g urea 0.2 g perfume oil 03 g oetylphenol 20 mol ethyleneoxide H) g aqueous solution of a l&#39;att aeid&#39;albumin condensate (35% I marketed under the tradename Lamepon S&#34; h Chemische Fabrik (irunan lllertissen no.1 g water son g The thusly wet hair was then wound up onto permanent wave rollers. In the time taken to complete the winding up of the hair. due to the presence of ureasc and urea in the solution. there is formed ammonium carbonate which increases the alkalinity of the solution. Thereafter, there was added to the remaining -10 g of permanent wave solution 3 g monothioglycolic acid glycerine ester and the hair moistened with this solution. After acting on the hair for about 20 minutes. the hair was washed with water and fixed in the known manner.  
 EXAMPLE 6 For straightening human hair. 50 g of a cream having a pH of 9.0 and the following composition was applied onto the hair and uniformly distributed thereover:  
  After a period of about It) minutes. there were added to the remaining 50 g of cream. 2 g monothioglycolic acid-glycerine ester and this mixture applied onto the hair and worked into the already present cream. After a period of about 5-15 minutes. the hair was repeatedly combed. then washed with water and fixed in the known manner.  
  As fixing agent there can for instance be used in the foregoing Examples an acid 2 percent aqueous hydrogen peroxide.  
 1 claim:  
  1. Process for permanently shaping human hair comprising in a first step applying to the hair a neutral or alkaline shaping composition containing a mercap tocarhoxylic acid salt. permitting said shaping eomposi tion to act on the hair. thereafter in a second step applying a further quantity of the composition used in step 1 to which there has now been added a hydrophilic mercaptocarhoxylic acid ester. permitting said composition to act on the hair. washing said compositions off from the hair and then applying to the hair a setting composition for permanently setting the hair.  
  2. Process according to claim I wherein said shaping composition as used in said first step contains urease.  
  3. Process according to claim I wherein following said first step. the hair is rolled up on permanent wave rollers and thereafter the second step is carried out.  
  4. Process according to claim l wherein the hair shaping composition is permitted to act on said hair in the second step for about 5 to 20 minutes.  
  5. Process according to claim 1 wherein said mercaptocarhoxylic acid salt is a water soluble salt of thioglycolic or thiolactic acid.  
  6. Process according to claim 5 wherein said salt is an ammonium. sodium or potassium salt.  
  7. Process according to claim I wherein said hydrophilic mercaptocarboxylic acid ester is a glycol. glycerine or methoxyethanol ester.  
 8. Process according to claim 1 wherein an ester 8 splitting enzyme is present in said composition for accelerating the splitting of said hydrophilic mercaptocarboxylic acid ester.  
  9. Process according to claim 8 wherein said enzyme is pancreatin.  
  10. Process according to claim I wherein said shaping is for the purpose of straightening the hair.  
  ll. Process according to claim 1 wherein said shaping is for the purpose of waving the hair.  
  12. Process according to claim 1 wherein the hair shaping composition is permitted to act on said hair in the first step for from 5 to 10 minutes and in said step for about l0 to 20 minutes.  
  l3. Process according to claim 1 wherein said salt is present in said composition in an amount of 5 to It) wt. percent calculated as acid.  
  14. Process according to claim 1 wherein said ester is present in said composition in an amount of about 5 to about l0 wt. percent.  
  15. Process according to claim 10 wherein said composition is applied in the form of a cream or gel.  
  16. Process according to claim ll wherein said composition is applied in the form of a liquid solution or emulsion.