Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/04—Preparations for permanent waving or straightening the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q9/00—Preparations for removing hair or for aiding hair removal
  • A61Q9/04—Depilatories

Definitions

• hair waving particularly in the cold, may be carried out with controlled time factors and without harmful effects, and more particularly without initially rinsing or washing the hair, by the procedural Patented June 27, 196i 2 step of employing the hair waving components comprising water soluble mercaptans in carbon dioxide generating solutions, such as carbonic acid water whereby introduction of harmful minerals in the hair waving preparation is minimized and the introduction of oxidizing components retarded, if not completely eliminated.
• my in vention to provide a hair waving preparation which is self contained in the relationship of the mercaptan radical to the base, which may be stored under any climatic conditions without deterioration so as not to require special packaging prescriptions but which is arranged to be brought into solution in an aqueous medium when required by the addition of the aqueous solvent, whereby the formation of the undesirable by-products and obnoxious (M1018 is minimized, if not completely avoided, and upon solution in the carbonated aqueous medium, assures a standardized stren without the introduction of components which may deleteriously affect the hair in the process of conducting the hair waving operation, whether in the cold or by associated application of external heat.
• a hair waving preparation which is self contained in the relationship of the mercaptan radical to the base, which may be stored under any climatic conditions without deterioration so as not to require special packaging prescriptions but which is arranged to be brought into solution in an aqueous medium when required by the addition of the aqueous solvent
• ahair waving preparation which is selfoontained with regard tothe relationship of the acidic factor to the base factor, to cause a relaxation of the hair component, to produce a highly desirable wave which persists in the transitory stage from a wet curl to a dry curl, and has predetermined strength by reason of its in activity when stored dry, characterized by its predetermined strength when it is employed to wet the hair in the procedure for carrying out cold waving operations in the presence of water charged with carbonic acid gas and furthercharacterized by exerting inter-facial agitation on contact with the hair whereby initial rinsing or washing operations are omitted and deleterious side ef-. fects overcome.
• Example I Preparation of dry ammonium thioglyeolate hair waving preparation.
• Thioglycolic acid is dissolved into chilled isopropyl ether. Into this solution maintained at a temperature below about 37 F. there is then introduced ammonia gas by bubbling the same into it. Additions of the ammonia" gas are charged into the ether solution of thioglycolic acid, in accordance with the alkalinity of the end product which is desired.
• the introduction of the ammonia gas may be the point where the separated ammonium thioglycolate evidences pH between 9.5 and 9.6.
• additions of ammonia gas serve to raise the 3 alkalinity until, at optimum charge, pH 9.5 or 9.6 by test is reached. Separation is effected by decanting the ethereal layer.
• the precipitate is dried, preferably under vacuum, to achieve dry ammonium thioglycolate, with a self-com tained or in situ deposited base which may evidence a pH of 6.5 to as high as pH 10.5.
• the ether employed in the foregoing and subseqently described examples is that which has been dehydrated as by Drieritc (a calcium sulfate dehydrating or like agent).
• the flask containing the precipitate was removed from the Dry Ice and allowed to warm to room temperature. It wasthen stoppered and placed in a Dry Ice chest overnight and the next morning it was allowed to warm to room temperature. The precipitate was separated, washed with dry ethyl ether and dried in a vacuum desiccator.
• the X-ray difiraction pattern of the precipitate obtained by this process shows no evidence of crystallinity audit is an amorphous product.
• a 1.0 percent aqueous solution exhibits a pH of 9.0.
• the dry preparation thus provided may have added to it from 2% to 5% of dry crystalline sodium hydrosulfite
• the dry in situ basic ammonium thioglycolate, with or without the sodium hydrosulfite may be packaged in pill form in sealed foils, capsules or ampules, envelopes or packets, until ready for use, with little or no deterioration. Where high humidity conditions may be encountered, a moisture occluding coating may be applied to the pills similar to the enteric coatings found on some medicinal preparations. Normally solid sulphonated oils providing a material in the nature of a detergent may be employed ascoatings. If packaged in envelopes, the presence of the sodium hydrosulfite serves as a reducing agent for any oxidation product.
• grams of the solid may be added to 100 cc. of water.
• the procedure for cold waving may be to apply the freshly made solution in the carbonated water to the hair and when saturated upon curlers, in accordance with standard procedure such as Croquignole or spiral wire curlers recirculation, preferably a loose wind, the procedure varying in that the efiervescing solution may be applied directly to the hair without the necessity for preliminarily rinsing or washing the same. Inter-facial gaseous agitation between the layer of the solution and the hair makes possible the elimination of wetting agents as well as to cause the release of any adherent scale, dust and more intimately to bring the hair waving solution into contact with the hair.
• the hair may then be covered with additional quantities of the solution, such as by pads saturated with the solution, and the head is then desirably covered with some impervious cap such as by covering the entire head with a shower cap.
• the hair may be left in this condition from thirty minutes to eight toten hours, depending upon the concentration which is employed.
• a adjustment of the base to the thioglycolate to provide pH about 9.5 to 9.6 and a concentration of the thioglycolate in water to about 8% has been found to result in a preparation which, with some types of hair, requires only a half hour contact for inducing the desired wave.
• Adjustments may be found necessary in the time and concentration as different types of hair are required to be treated, it being observed that the greater the concentration and pH, the lower the time factor and, conversely, the more dilute the solution and the lower the pH, the longer will be the time necessary to effect the desired wave. Therefore the amount of time for treatment will be a factor of concentration and pH.
• an acid shampoo or detergent is used, and benzyldirnethylammonium chloride (phemerol chloride) is suggested.
• Example II Form the preparation of a composite thioglycolate in situ mixed base, the dry preparation may be as follows:
• the foregoing reaction is accelerated by carrying out the reaction under refrigerated or chilled conditions. That is, the ethyl alcohol solution of sodium hydroxide may be cooled to a temperature of about or below 10 C. and preferably, of from 0 to 5C.
• the precipitated product may be dried and packaged or formed into a dry merchandizable product in accordance with the procedure heretofore described.
• This prod-' uct may be mixed with the crystalline sodium sulfite before packaging.
• the procedure hereinbefore described for solution in a carbonated water should be followed.
• Example III In this preparation, 10 grams thioglycolic acid, 3 grams monoethanolamine and 1 gram so dium thioglycolate are dissolved in isopropyl ether (Drierite treated) cooled to about 37 F.
• Stoichiometric amounts of ammonia gas may be infused into the chilled solution, calculated to make a solution having a hydrogen ion concentration or pH 8.5 when a test sample is introduced into cc. water.
• the precipitated reaction product is dried to evaporate any residual ether.
• This compound may be hygroscopic and is preferably mixed with the reducer or clearing salt previously described in the same ratio and packaged in ampules.
• the ampule packaged dry material may be employed in the process heretofore described for permanently waving hair in the cold, employing the procedure before described, especially using carbonic acid charged water.
• the quantity of the base may be to retain the pH below 9.6 and as low as pH 7.
• the addition of the base in excess of an amount to produce pH 9.6 may require careful handling as to time and concentration as above pH 10.5 and as high as pH 13.0 may be secured to produce a depilatory if desired, with the proper control of time and concentration.
• the organic addition salts of thioglycolic acid such as the guanidine thioglycolate, the morpholine thioglycolate or the ethylene diamine salt, where employed, are more desirable than the ammonium and sodium thioglycolates in that as solutions they evidence practically no offensive odors and may be employed in solutions having a lower pH, i.e. pH 7.6, as compared with pH 9.5 for ammonium thioglycolate and in a concentration of one half strength, i.e. 2Vz% solution as compared with 6.9% solution of ammonium thioglycolate.
• Example I V In this example 2 moles thioglycolic acid (184 grams) are treated with 1 mole guanidine carbonate (180 grams-equivalent to 2" moles of free guanidine base) in an ether solution.
• the mixture is allowed to stand under refrigerated conditions C.) for two hours until the reaction salt which precipitates settles, whereupon it is filtered, dried, dissolved in water and recrystallized.
• the dried salt shows a melting point of IDS-106 C., with an assay of 99.8%.
• the guanidine thioglycolate which is thus formed may be dissolved in water to form a 6.8% solution (based on thioglycolic acid content), and then mixed with a base of pH 7.6.
• a cold wave made with this solution provides a longer-lasting curl than sodium or ammonium thioglycolate solutions of equivalent strength having pH 9.5, in that the curl is tighter and persists upon drying, rather than showing a tendency ,to loosen upon drying.
• Example V --l mole of guanidine'carbonate is added, with constant stirring, to a dry isopropyl ether solution maintained at a temperature of 5 C. and containing 2 moles of thioglycolic acid.
• a white coprecipitate insoluble product of guanidine thioglycolate forms in a menstrum of excess basic carbonate. This is filtered oil and dried.
• An aqueous layer consisting of guanidine thioglycolate and carbonate dissolved in the water of salt formation also is obtained. This is separated from the other layer, the water evaporated off under vacuum and the dry super based guanidine thioglycolate and base recovered from the water layer is mixed with the precipitate with added dry base to leave a dry product of predetermined alkalinity.
• the aforesaid resulting guanidine thioglycolate and admixed carbonate may be packaged dry, as in the prior examples, to be used by solution in water to make a 3% concentration calculated as thioglycolic acid and pH 9.0.
• the procedure for cold waving by dissolving in standardized carbonated water, as previously described, may be also followed with the organic salt of thioglycolic acid and base admixture.
• the dry curls made with this form of the thioglycolate mixture provides a tighter curl than ammonium and sodium thioglycolate, which has been alkalinized to pH 9.5 with a 6.1% of thioglycolic acid value in solution.
• Example VI.2 moles of morpholine (174 grams) are added with constant stirring to 3 moles thioglycolic acid dissolved in isopropyl ether (dried as before described) and chilled to 0 C. r
• a heavy, waxy precipitate is thrown out of solution. This precipitate is filtered, redissolved and recrystallized from water to provide a product having a melting point of 78 C., with an assay of 99.83%.
• the dry super based morpholine thioglycolate and associated base may be dissolved in water which, when using 6.5% (calculated as thioglycolic acid), gives a solution having pH 9.5. This preparation gives a tighter curl, with more lustrous sheen than sodium or ammonium thioglycolate at the same pH and concentration.
• the dry product stripped from the ether mixed with or coprecipitated with the added base or morpholine to raise the pH within a range from 7.5 to 9.5 or above may be packaged in accordance with any of the procedure, heretofore described and may be em- .bodied in a carbonated water as a solvent, with the features heretofore described for carrying out the hair waving treatment.
• the added base in dry form may exceed 9.5 where other than cold hair waving products are formed.
• Example VII l mole of 70% ethylene diamine is added to 2 moles thioglycolic acid. Isopropyl alcohol chilled to a temperature of 3 C. (37 F.) is added to show the formation of the organic salt of thioglycolic acid as a heavy precipitate. The salt is filtered and dried.
• the thioglycolate is hygroscopic and does not give a sharp melting point.
• Analysis for the mercaptan value shows the material to be and corresponding to the following formula:
• ethylene diamine thioglycolate which is separated, when formed in a solution of water in concentration of 5% calculated as thioglycolic acid and added base to give pH 8.8 may be employed to wave hair and gives a better cold waving curl than the corresponding salt of sodium, ammonium thioglycolate and the mixed sodium and ammonium thioglycolate of high strength and pH value.
• the ethylene diamine thioglycolate either coprecipitated or dry mixed with a base to provide a dry product, may be packaged or pill formed as above after the dry mercaptan salt and base are brought together to the desired pH.
• Example VIII -l mole of thioglycolic acid is slowly added to 1 mole of 70% ethylene diamine. Equal volume of isopropyl alcohol is added and the mixture permitted to stand in a refrigerator at 37 F. overnight. The precipitate is separated and dried. The mercaptan analysis of the material showed an assay of 94.8% as ethylene diamine mono-thioglycolate.
• a 6% concentration solution (on a thioglycolic acid basis) with added base to give pH 9.5 may be prepared in water.
• a cold waving solution may be made in accordance with the procedure previously outlined, preferably employingthe carbonated water.
• the curl upon drying, exhibits the properties heretofore described in connection with the previously described organic salts of thioglycolic accuses 'l by the addition of a base to pH from 11.9 to 12.2, with the said guanidine thioglycolate content of 6% based on the thioglycolic acid.
• Example IX --8.5 grams thiolactic acid are suspended in isopropyl ether chilled to a temperature of about C. to which monoethanolaminc is added in which a test sample shows pH 8. Thereupon ammonia gas is infused until a test sample shows pH 8.5.
• the reaction forms an aqueous and ether layer which may be decanted.
• the resultant salt which precipitates of lactic acid is vacuum dried.
• the presence of the monoethanolamine in this particular case may make a hygroscopic mixture and the dry preparation is desirably maintained in ampules, to be used in one form of my invention with the carbonated water as previously described in applying the cold waving solution to the hair.
• Example X .N-oxyethylthioglycolamide is made by dehydrating a mixture of monoethanolamine and thioglycolic acid. The mixture is heated at about 140 C., at a pressure of to 22 mm. until the proper computed amount of water is removed and collected. The resulting product is ready for immediate use.
• Example Xl.lsopropanolamine substituted for the monoethanolamine under the same conditions as in Example X yields a corresponding product, similarly useful.
• the product is N-oxypropyldithioglycolamide.
• Example XIII.60 ml. of ethyl thioglycolate was placed in a graduate and ml. of 70 percent alcohol was added. Dry ammonia gas was bubbled through the liquid, producing considerable turbulence. The addition of ammonia gas was continued for about l2 hours (overnight), and a syrupy, semi-solid product was formed that was readily soluble in water. Chilling the reaction mixture to 10 C. caused the product to congeal to a pasty mass. Cooling in a Dry Ice bath gave a hard solid mass which, when warmed to room temperature, became a waxy solid. This was dried under vacuum over calcium chloride and the product gave a pH of 6.9 in a 1 percent solution in distilled water.
• thioglycolic acid or an alkyl thioglycolate may be reacted with a base in an anhydrous liquid medium; such as, for example, lower alcohols and lower ethcrs. to provide unique new products which, when dissolved in water. provide hair waving solutions having a pH not less than 6.5. It is essential that the reactions for preparing these novel products be carried out under chilled or refrigerated conditions (37 F.) or at lower temperaturesfprcferably at 0 C. and as low as -4l C. The reaction proceeds slowly at temperatures above 0 C. and may take as long as from 12 to 24 hours to become completed. At temperatures of about 0 C.
• reaction proceeds rapidly.
• chilled solutions which are mixed with agitation or the base, when in gaseous form. may be infused into a chilled solution of the thioglycolic acid or alkyl thioglycolate in the anhydrous organic liquid medium. It is also possible to introduce the reactants into the anhydrous liquid medium and then subject the reaction mixture to the above refrigerated or chilled condition to precipitate out the desired product.
• the aforesaid dry powder, pill, capsulated or ampulated products in each of the examples are to be furnished to the trade to be used with neutralizer compounds furnished in dry form or with other known neu tralizer compounds.
• neutralizer compounds furnished in dry form or with other known neu tralizer compounds for purposes of exemplification I refer to sodium perborate.
• This perborate solution may have added to it immediately before use, after the hair treatment with the mercaptan compounds, solutions of acetic acid or vinegar, tartaric acid or malic acid, in order to produce a nascent hydrogen peroxide solution of acidified character.
• a dry mercaptan is made by the formation of an amide of extreme basic nature, it may be brought to the lower pHs within the desired range and preferably about pH 9.5 or lower in the dry form by the addition of carbon dioxide gas.
• I may reduce the pH of the basic thioglycolamide with carbon dioxide
• I may do so by adding an acid mercaptan in order to reduce the pH in the foregoing formula of a ratio of .1 mole of methyl thioglycolate to .2 mole of ammonia, which will provide an ester which has about pH 9.9.
• the solution may also be employed for embossing animal fibres.
• a cream may be made of said preparations employing diglycol laurate-S.
• the dry mercaptan compound may be used as a 3.5%-l0% addition to the water extended paste-like laurate compound.
• the provision of the mercapto or thioglycolate salt, with either of the organic or inorganic bases, as herein described assures predetermined strength and standardized reaction after storage of a hair waving preparation, and is particularly valuable where the preparation is dissolved in water charged with carbonic acid, as described, to provide a cold waving preparation in which the resulting curl persists from the wet to and including the fully dried condition without loss of curl curvature.
• the utility of the product may be outlined as satisfactory not only for curling hair but likewise for straightening hair. Also it may be used to crease proof fabrics made of wool or to impart a permanent crease to articlcs of apparel, such as pleating, embossing fabrics either abscess in the hot or cold, and likewise to soften hair and taire away its harshness or brittleness. It may be used to soften nails or cuticles and also to modify or permanentize the pile condition of fur, either to flatten or raise it. Likewise'the wide range of conditions which may be emphasized will be clear in that I may treat Chinese hair or horse hair, i.e. the tail and mane hairs as well as to soften and curl dog hair for example poodle, and related uses in the veterinarian field.
• forms of my invention as providing a normally dry mercaptan compound which may be in the acid form, in which event a quantity of base is added to bring it to the upper required pH or, conversely, a dry basic mercaptan may be reduced with a charge of carbon dioxide to a range to pH 7.
• said reaction prodact is precipitated in said anhydrousorganic liquid medi um at a temperature in the range of from 41 C. to about 0' C.
• the method of preparing a stable, dry, precipitated, solid granular reaction product which, upon dissolution in water provides a hair waving solution, comprising dissolving a compound selected from the group consisting of thioglycolic acid and an alkyl thioglycolate and a base selected from the group consisting of ammonia, an amine, guanidine and morpholinc, said reaction product being precipitated in an anhydrous organic liquid medium selected from the group consisting of lower alcohols and ethers chilled to a temperature not in excess of 37 F., said base being in excess of the stoichiomet-ric amount based upon the amount of said compound and said anhydrous organic liquid medium being maintained by said base at a pH in the range of 6.5-10 as determined when a test sample is introduced into cc. of water, to precipitate a reaction product in a solid granular form; and recovering said reaction product from said anhydrous organic liquidmedium.
• a method of imparting" a permanent wave to human hair including the steps of. forming human hair into a desired configuration, applying an aqueous solution of a hair-softening agent tosaid formed hair and fixing the configuration, the improvement which consists of providing said hair-softening agent by dissolving the composition of claim 5 in water having a calcium content less than about 8.0 parts-per million and .a magnesium content less than 1.5 parts per million.

Landscapes

• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Veterinary Medicine (AREA)
• Birds (AREA)
• Epidemiology (AREA)
• Dermatology (AREA)
• Cosmetics (AREA)

Priority Applications (3)

Applications Claiming Priority (1)

Publications (1)

Family

ID=25299027

Family Applications (1)

Country Status (3)

Cited By (5)

Families Citing this family (1)

Citations (21)

• 1959
  • 1959-10-16 US US846818A patent/US2990336A/en not_active Expired - Lifetime
• 1960
  • 1960-10-15 FR FR841302A patent/FR1273508A/fr not_active Expired
  • 1960-10-17 DE DEM46858A patent/DE1186581B/de active Pending

Patent Citations (21)

Also Published As

Similar Documents