US2776668A - Method and preparations for the permanent dyeing of keratinous material - Google Patents

Method and preparations for the permanent dyeing of keratinous material Download PDF

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US2776668A
US2776668A US234156A US23415651A US2776668A US 2776668 A US2776668 A US 2776668A US 234156 A US234156 A US 234156A US 23415651 A US23415651 A US 23415651A US 2776668 A US2776668 A US 2776668A
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solution
hair
minutes
water
thioglycolic acid
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William E Morgan
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Parbel of Florida Inc
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Parbel of Florida Inc
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    • 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
    • A61Q5/10—Preparations for permanently dyeing 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/30—Material containing basic nitrogen containing amide groups furs feathers, dead hair, furskins, pelts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing
    • Y10S8/917—Wool or silk

Definitions

  • a further object of the invention is to provide a method for permanently dyeing keratinous material, and' particula'rly humanhain-under suitable conditions withnon i toxic coal-tar dyes, in--such a manner that the color is' securely fixed in the dyed materialandcannot b removed by rubbing, washing or shampooingi-
  • a still further object of the-invention is to providea method 1 for permanently dyeing human hair with nontoxic dyes in-a manner to permit permanenbwaving'bf' the dyed hair without change of the "color imparted -to the hair and without hair damage.
  • a still further object of theinvention is to providefa method forpermanently dyeing human hair with entirely non-toxic and harmless dyes, which methodis ea'sy'and" safe 'in its application, satisfactory in its results; and does not require either a pre-treatrnent or an-after-treatment" ofthe hair; i p
  • Still'a further object of the invention is to provide'a method of permanently dyeing human hair by means of the dyes which areknown as certified colors and Which heretofore have not been successfully used for this'pui pose; l
  • Still anotherobject of the invention is to produce a preparation for the permanent dyeing of keratino'usmaterialg andparticularly' of human hair; which can be applied to-the"*hair in a simple manner and which pro prisesth'e desired coloringeasily andsafely andwithout undesirable or harmful side eflec'ts or after'effectsi
  • a special object of the invention is to produce a preparation-forthe-permanent dyeing of keratinousmaterial, andparticularly of-human hair, which consists of two" separate solutions to be mixed immediatelybefore appli-' cation to thematerial to be' dyed, and which yields a mixture producing the desired coloring effect by'means" of-cer'tifiedcolors'in a reliable, safe'and permanent man-'
  • Another specialobject of the invention is to produce" a preparationfor"the permanent dyeing of 'ker'atinous" materiaL particularly of human hair, which consists-of a dry, powdery mixture of several water-solublein gredients which, on
  • the dyeing method according to my invention comprises the steps of treating the material to be dyed "with a freshly prepared neutral to mildly alkaline, aqueous solution containing a small percentage of a water-soluble mercapto compound and, as sole coloring agent, a dyestufi of the group consisting of the Ext. D & C, D & C and F D & C certified colors and mixtures thereof, washing the dyed material with an aqueous medium, and drying'it.
  • certified colors could be used for the perm'anent' dyeing of keratinous matter only in strongly acid or" strong salt solutions, and at elevated temperatures.
  • The'pr esent'invention is based on my discovery that the Ext. D & C, D & C and F D & C certified, non-toxic coal tar dyes are suitable for the permanent dyeing of keratinous material at moderate temperatures and in neutral or mildly alkaline solutions, if a relatively small percentage of water-soluble mercapto compounds is added to the dye solutions immediately before they are used.
  • Myinvention makes it possible to dye human hair in a simple manner permanently with dye preparations containing" exclusively completely harmless and safe ingredientsand to produce natural, predictable color shades which arefast to rubbing, washing, shampooing and permanent waving.
  • the substances migrating with the water or transported thereby become effectively trapped or imbedded in the hair substance and are not subject to removal by customary treatments, such as rubbing, toweling, washing, shampooing or permanent Waving; Microscopic examination has shown the hair fibers to be uniformly stained over the areas between the imbrications.
  • dye solutions suitable for the dyeing of keratinous material according to my invention may contain preferably between about 0.033 and 6.2% by weight of the solution of such dyestuffs.
  • the water-soluble mercapto compounds to be used in the dye solutions according to my invention are particularly the water-soluble mercapto compounds of the general type useful for hair waving and depilatory purposes. Suitable examples are thioglycolic and thiosalicylic acids in the form of their water-soluble salts, thioglycol, thioglycerol and thiophenol. At present, I prefer in most cases to use thioglycolic acid because it is readily available, has no intense objectionable odor, and is ordinarily entirely harmless in the concentrations in which it is used according to my invention, but I do not limit my invention either to this or to any other particular mercapto compound.
  • the water-soluble mercapto compounds are present in my dye solutions in quantities equivalent with respect to S H group to about 0.1 to 6% by Weight of the solutions of thioglycatic acid.
  • a mercapto compound content equivalent with respect to S H group to between about 1.2% and about 6% by weight of the solution of thioglycolic acid has been found to give most favorable results.
  • the temperatures used in my dyeing processes may vary between about 50 and about 110 F. Temperatures of between about 60 and about 80 F. are preferred, particularly in the use of my invention for the permanent dyeing of human hair.
  • the dye solutions according to my invention are applied to the keratinous material at a pH value between about 6.6 and about 11.3 and preferably at a pH value of between about 9 and 10.2.
  • a pH value between about 6.6 and about 11.3 and preferably at a pH value of between about 9 and 10.2.
  • I have successfully used concentrated aqueous ammonia, sodium hydroxide, sodium carbonate in the presence of ammonium chloride, ethylene diamine, and triethanolamine. Other alkalies could undoubtedly be employed.
  • Useful effects in coloring hair are accomplished at temperatures of between about 60 F. and about 80 F. with relatively weak solutions of mercapto compounds and usually at mild alkalinities. I have found adequate, for example, up to about 4% by weight of the solution of thioglycolic acid at alkalinities corresponding to pH values of not more than about 10.5 during 15 to 25 minutes. Many of my successful hair dyeings, accomplished without evidence of any resultant hair damage have been performed with less than 2.6% by weight of the solution of thioglycolic acid in the form of its sodium salt, with excess of ammonia as free base at pH values of about 9 to 10 at a temperature of about 68 F. within about to minutes. This combination of conditions lies well within allowable extremes and may be adopted as normal.
  • alkalinity should be adjusted to a lower pH value, for instance, 9.4 or less to preclude irreversible hair damage.
  • a high temperature such as, for example, 110 F.
  • a moderate concentration of mercapto compound for instance, in the range of up to about 2.5% by weight of the solution of thioglycolic acid, may require lowering of the pH value below 9.3 in order to preclude hair damage.
  • very good hair coloration without any evidence of hair damage, may be effected with 2.5% by weight of the solution of thioglycolic acid acting upon hair at 110 F. during 15 minutes at a pH of 8.0. Decrease below normal of any of the three factors diminishes the risk of hair damage but weakens correspondingly the resultant coloration.
  • coloring action is appreciably less than at 60 to F. for 1.4% by weight of the solution of thioglycolic acid at a pH of 9.4 acting during 20 minutes.
  • coloring action is appreciably less than with 1.4% by weight of the solution of thioglycolic acid, other conditions remaining the same for both cases.
  • coloring action is appreciably less than at a pH of 8.5 for 2.5% by weight of the solution of thioglycolic acid at 70 F. during 20 minutes.
  • Minima for concentration of mercapto compound, pH, and temperature are not imposed like maxima, by the susceptibility of hair to damage, but are chosen when low values for one or more factors require considerable increase above normal in one or more of the remaining factors for good and intense coloring of the hair.
  • the solutions have a pH value between 6.6 and 10.4 but not higher than 9.4 when the mercapto concentration is equivalent to at least 3% by weight of the solution of thioglycolic acid and not higher than 9.15 when the mercapto concentration is equivalent to at least 5.6% by weight of the solution of thioglycolic acid.
  • the solution is applied to the hair at a temperature of between about 50 F. and F. but not less than 70 F. when both mercapto concentration and pH value approach their minimum values and not higher than 80 F. when both mercapto concentration and pH value approach their maximum values.
  • Mild oxidizing agents such as hydrogen peroxide, and acids, such as acetic acid, may be used in these cases, which :are within thebroad scope of my inventiomfor after-treatment of the dyed hair.
  • My invention also covers the new preparations for the permanent dyeing of keratinous material to be .used in...
  • Such preparation maybe, for instance, a'
  • Preparations which are intended for the dyeing of human hair contain preferably a quantity of: wateresoluble mercapto compound equivalent withrespect to SH' group toabout 1.2%"to6%-' by weight-of the solution-of' thioglycolic acid and have a pH value of "between*6.6 to 10.4 but not higher than 9.4 when the mercaptoconcentration is equivalentioat least 3%- by weight of the. solution of thioglycolic acid and not higher than:.9.15. when the mercapto. concentrationis equivalent to at least 5.6%..by weight of the solution of thioglycolicacid.
  • a preparation of :the dyeing of keratinous .material,. and particularlyrof human hair may comprisea' of. the two solutions,; the total-quantity of solvent in both solutions and the relative proportionsof the solutions being such that the resulting mixture is neutral or mildly alkaline and contains a small percentage ofa watersoluble mercapto compound.
  • a preparation for the dyeing of keratinous materiaLand particularly of human hair may be a substantially dry powder mixture comprising a dry, water-soluble solid mercapto compound, an ammonium salt, a dry, weakly alkaline, water-soluble salt of an alkali-metal, and,:'as:
  • a dry, wateresolubledyestuff selected from the group consisting of. the Ext. D & .C,.D;& Cand.
  • a dye solution which contains a small percentage of mercapto compound and is neutral or mildly alkaline.
  • Example -I Firm textured, nearly colorless human hair was immersed for 15 minutes-at a temperature of F., with exclusion of air, in a solution carrying,0.920g.. of a dyestufi'mixture consisting of:
  • Example [I Firm textured, nearly colorless human hair was satu- Y rated for 3 minutes in a solution containing 3.89 g. of a dyestuff mixture consisting of:
  • the hair was in part merely rinsed and blotted, then dried, in part well-shampooed, then rinsed, blotted and dried.
  • the rinsed hair retained a pale pink-violet coloration,- the shampooed hair a distinctly paler pink-violet coloration; Most of the pale color adhering' to the merely rinsed hair was located superficially and-was removable by shampooing. The hair .was not permanently dyed.
  • the thioglycolic acid content amounted to 2.6% by weight of the solution, the dyestutf content to about 4% by weight of the solution.
  • hair of the same character was similarly saturated for 3 minutes and then exposed wet for 15 minutes to the atmosphere under identical temperature conditions estimated on the average to be about 60 F.
  • the hair was in part merely rinsed and blotted, then dried, in part well shampooed, then rinsed, blotted and dried.
  • the merely rinsed hair retained a strong violet-brown coloration
  • the shampooed hair likewise a strong violet-brown coloration, hardly distinguishable from that of the merely rinsed hair.
  • the hair was substantially dyed.
  • Example III A solution was prepared containing:
  • This mixture was immediately applied at a temperature of 68 F. to uucolored human hair, conveniently by a brush.
  • the wet hair was allowed to remain exposed to the atmosphere for 20 minutes at a temperature at which the wet solution was maintained substantially constant at 60 F. Thereafter, the dark excess of dye was rinsed from the hair with Warm water until the washings were substantially colorless.
  • the hair was then gently toweled and finally dried with a warm air current. The hair retained a natural and pleasing dark auburn coloration. It was subsequently gently shampooed with only an insignificant change of hair coloration resulting from even the first shampooing.
  • Example IV 0.800 g. D & C Black #1 (C. 1. 246) 0.600 g. D & C Orange #3 (C. I. 27)
  • the mixture was immediately applied at a temperature of about 77 to uucolored hair conveniently by a brush.
  • Thejwet hair was allowed to remain exposed to the atmosphere for 20 minutes at a temperature at which the evaporation of the water caused some cooling down of the solution.
  • the average temperature of 20. minutes exposure time was estimated to be about 75 F.
  • Example V A mixture was prepared of:
  • Example V1 2.4 g D & c Black #1 c. I. 246) 1.7 g. D & 0 Orange #3 c. I. 27 21 g. Ext. D & c Red #13 c. I. 252
  • Example VII 3 yes utlv ixtur aving the. amecomposition as in the preceding example were dissolved in a solvent containing:
  • Example VIII 6.2 g. of -a dye mixture 1 having the; same. composition as in the preceding, two exampleswere dissolvedin a solvent; containing:
  • A- solution was preparedqcarryingz 0.50 g. D & C Violet #1 (C. I. 697) 2.5 0 g. thioglycolic acid 1.1 g. sodium hydroxide 7.41 ml.” concentrated ammonia aqua q. s. water to make 100 mLpH' 10.4
  • the average temperature of the solution was about 64 F. Thereafter, the hairwas well rinsed'and dried. It re-. tained apermanent pronounced bluecoloration;
  • Example X A solution was prepared'carrying:
  • the solution throughout the total exposure time of 23 minutes was estimated to be about 68 F
  • the hair waswellrinsed and dried.
  • the hair retained a pronounced blue .colora tion, slightly, duller-and a little more reddish than the.
  • Example XI A solution was prepared carrying:
  • the fresh solution was chilled to 50 F. and firm.
  • Example XII A solut-ion was prepared, carrying 1.65 g. of adyestufif: mixture; having the same composition as in- Ex: ample XI; and
  • Example XIII 1 A solution was prepared carrying 1.56 g. ofadyestulf mixture having the same-composition as in Example XII, and d 25.0 ml. propylene glycol 2.5 g. thioglycolic acid.
  • Example XIV A solutionv was prepared containing:
  • Example XV A mixture, in powder form, consisting of:
  • Example XVI A solution was prepared carrying:
  • the hair was rinsed and dried. It retained a reddish blond coloration.
  • Example XIX A solution was prepared containing 1.65 g. of a dye mixture having the same composition as in Example XIX, and:
  • Example XX A solution was prepared containing:
  • the wool was incipiently, but weak- 1y, dyed, at ordinary temperatures with'the weakly alkaline mixture of dyestufis.
  • Example XXI A solution was prepared carrying 0.300 g. D& Black #1 (c. 1.246 0.088 g. D'& 0 Brown #1 c. I. 234 0.113 g. Ext. 13a 0 Red #13 o. I. 252
  • Example Example XXII Wool was treated with the solution and by the method described in Example XXI at 50 F. for 15 minutes. After subsequent rinsing and drying, the wool retained a pronounced permanent, medium gray coloration without any evident alteration of the texture or strength.
  • Example XXIII Wool was treated with the solution and in the manner described in Example XXI at pH 8, and at a temperature of 110 F.', for 15 'minutes. After rinsing and drying,
  • the wool retained abeautiful velvet black. It had been permanently dyed. No wool damage was evident. The dyed fabric remained soft and pliable.
  • Example XXIV' Wool was dyed in the solution and by the process described inExample XXI at pH 6.6, and at a temperature of 110 F., for 15 -minutes. Afterrinsing and drying, the wool retained a permanent, very dark reddish brown coloration, noticeably lighter than the velvet black retained after the identical procedure with a corresponding solution at pH 8.0 as described in Example XXIII.
  • a method forthe permanent dyeing of keratinousmaterial which comprises treating the material to be dyed with a freshly prepared aqueous solution containing a quantity of a water soluble mercapto compound oflow" toxicity equivalent .with. respect to, SH group to aboutture-between about 50 F. and 110 F;
  • n&' c, D & .C and FD & c certified colors larld mixtures thereof the solution having a pI-I valu'e between 6.6 and 10.4 butnot higher than 9.4 when the mercapto'concentration is equivalent to at least 3 by weight .of the solution of thioglycolic acid and not higher than'f9,15 whenthe mercapto concentration is equivalent tofat least 5.6% byjweight of the solution of thioglycolic acid,'then washingthe dyed hair with an aqueous medium and drying the same.
  • a method for the permanent dyeing. of human hair which comprises the steps of treating the hair to be dyed with afreshly'pjrepared aqueous solution of a quantityof a water-soluble mercapto compound of the group consisting of thioglycolic acid, thiosalicylic acid in the form, of its water-solublesalts, thioglycol, thioglycerol and thiophenol equivalent withrespect to SH group to about 1.2%
  • a method for the permanent dyeing of human hair which consists of the steps of treating the hair to be dyed at a temperature of between about 50 F. and 110 F. with a freshly prepared aqueous solution of a quantity of a water-soluble mercapto compound of the group consisting of thioglycolic acid, thiosalicylic acid in the form of its water-soluble salts, thioglycol, thioglycerol and thiophenol equivalent with respect to SH group to about 1.2% to 4% by Weight of the solution of thioglycolic acid and containing, as sole coloring agent, about 0.033% to about 6.2% by weight of the solution of a dyestutf of the group consisting of the Ext.
  • D & C, D & C and F D & C certified colors and mixtures thereof said solution having a pH value of between 6.6 and 10.4 but not higher than 9.4 when the mercapto concentration is equivalent to at least 3% by weight of the solution of thioglycolic acid, then Washing the dyed hair with an aqueous medium and drying the same.
  • a method for the permanent dyeing of human hair which consists of the steps of treating the hair to be dyed at a temperature between about 50 F. and 110 F. with a freshly prepared aqueous solution of a quantity of a Water-soluble mercapto compound of the group consisting of thioglycolic acid, thiosalicylic acid in the form of its water-soluble salts, thioglycol, thioglycerol and thiophenol equivalent with respect to SH group to about 4% to 6% by weight of the solution of thioglycolic acid and containing, as sole coloring agent, about 0.033% to about 6.2% by weight of the solution of a dyestuff of the group consisting of the Ext, D & C, D & C and F D & C certified colors and mixtures thereof, said solution having a pH value between 6.6 and 9.4 but not higher than 9.15 when the mercapto concentration is equivalent to at least 5.6% by weight of the solution of thioglycolic acid, then treating the
  • a water-soluble mercapto compound selected from the group consisting of thioglycolic acid, thiosalicylic acid in the form of its water-soluble salts, thioglycol, thioglycerol and thiophenol equivalent with respect to SH group to about 1.2% to 6% by Weight of the solution of thioglycolic acid and, as sole
  • D & C, D & C and F D & C certified colors and mixtures thereof said solution having a pH value between 6.6 and 10.4 but not higher than 9.4 when the mercapto concentration is equivalent to at least 3% by Weight of the solution of thioglycolic acid and not higher than 9.15 when the mercapto concentration is equivalent to at least 5.6% by weight of the solution of thioglycolic acid.
  • a preparation for the permanent dyeing of keratinous material in the form of a substantially dry powdered mixture comprising a dry water-soluble solid mercapto compound of low toxicity, an ammonium salt, a dry, weakly alkaline water-soluble salt of an alkali metal, and, as sole coloring agent, a dry dyestuff selected from the group consisting of the Ext.
  • D & C, D & C and F D & C certified colors and mixtures thereof the several ingredients being present in such proportions that, on addition of the dry powdered mixture to a predetermined quantity of water, a dye solution is formed which contains about 0.033% to about 6.2% by weight of the solution of dyestutf and a quantity of mercapto compound equivalent with respect to SH group to about 0.1% to about 6% by weight of the solution of thioglycolic acid and which has a pH value of between about 6.6 and 11.3.
  • a preparation for the permanent dyeing of human hair in the form of a substantially dry powdered mixture comprising a dry water-soluble salt of thioglycolic acid, an ammonium salt, a dry, weakly alkaline watersoluble salt of an alkali metal, and, as sole coloring agent, a dry dyestuff selected from the group consisting of the Ext. D & C, D & C and F D & C certified colors and mixtures thereof, the several ingredients being present in such proportions that, on addition of the dry powdered mixture to a predetermined quantity of water, a dye solution is formed containing about 0.033 to 6.2% b. w.
  • a method for the permanent dyeing of keratinous material which comprises the steps of preparing separately an aqueous dye solution containing, as sole coloring agent, a dyestufi selected from the group consisting of the Ext. D & C, D & C and F D & C certified colors and mixtures thereof and a water solution of a Watersoluble mercapto compound, the respective pH values of the two solutions, the total quantity of solvent in both solutions, the relative proportions of the solutions, the concentration of mercapto compound in the mercapto solution and the concentration of dyestufi in the dye solution being such that a mixture of the two solutions contains about 0.033% to about 6.2% by weight of the solution of dyestuff and a quantity of mercapto compound equivalent with respect to SH group to about 0.1% to about 6% by weight of the solution of thioglycolic acid and has a pH value between about 6.6 and about 11.3, combining the two separate solutions to form such mixture, applying the freshly prepared mixture to the keratinous material to be
  • a method for the permanent dyeing of human hair which comprises the steps of preparing separately an aqueous dye solution containing, as sole coloring agent, a dyestutf selected from the group consisting of the Ext. D & C, D & C and F D & C certified colors and mixtures thereof and a Water solution of a water-soluble mercapto compound of the group consisting of thioglycolic acid, thiosalicylic acid in the form of its watersoluble salts, thioglycol, thioglycerol and thiophenol, the respective pH values of the two solutions, the total quantity of solvent in both solutions, the relative proportions of the solutions, the concentration of mercapto compound in the mercapto solution and the concentration of dyestuff in the dye solution being such that a mixture of the two solutions contains about 0.033% to about 6.2% by weight of the solution of dyestutr and a quantity of mercapto compound equivalent with respect to SH group to about 1.2% to about 6% by weight of

Description

United States Patent 2,776,663 METHQD AND PREPARATIGNSFOR THE PERMA NENT DYEING 0F KERATINOUSMATERIAL William E. Morgan, Ridgefield, N. 1., assignor to Helena Rubinstein, Inc., New-York, N.- Y., a corporation of New York No Drawing. Ap lication'June'ZS, 195i, Serial No. 234,156
1 18 Claims. (Cl. 132-7) for human skin and with neutral or moderately alkaline" solutions which are=harmless to the-hair as wellas to the skin.
A further object of the invention is to provide a method for permanently dyeing keratinous material, and' particula'rly humanhain-under suitable conditions withnon i toxic coal-tar dyes, in--such a manner that the color is' securely fixed in the dyed materialandcannot b removed by rubbing, washing or shampooingi- A still further object of the-inventionis to providea method 1 for permanently dyeing human hair with nontoxic dyes in-a manner to permit permanenbwaving'bf' the dyed hair without change of the "color imparted -to the hair and without hair damage.
A still further object of theinvention is to providefa method forpermanently dyeing human hair with entirely non-toxic and harmless dyes, which methodis ea'sy'and" safe 'in its application, satisfactory in its results; and does not require either a pre-treatrnent or an-after-treatment" ofthe hair; i p
Still'a further object of the invention is to provide'a method of permanently dyeing human hair by means of the dyes which areknown as certified colors and Which heretofore have not been successfully used for this'pui pose; l
Still anotherobject of the invention is to produce a preparation for the permanent dyeing of keratino'usmaterialg andparticularly' of human hair; which can be applied to-the"*hair in a simple manner and which pro ducesth'e desired coloringeasily andsafely andwithout undesirable or harmful side eflec'ts or after'effectsi A special object of the invention is to produce a preparation-forthe-permanent dyeing of keratinousmaterial, andparticularly of-human hair, which consists of two" separate solutions to be mixed immediatelybefore appli-' cation to thematerial to be' dyed, and which yields a mixture producing the desired coloring effect by'means" of-cer'tifiedcolors'in a reliable, safe'and permanent man-' Another specialobject of the invention is to produce" a preparationfor"the permanent dyeing of 'ker'atinous" materiaL particularly of human hair, which consists-of a dry, powdery mixture of several water-solublein gredients which, on dissolution in a predetermined amount 2,776,668 Patented Jan. E, 12957 of water, yield'a dye solution applicable directly to the material to be dyed to produce the desired coloring by means of certified colors in a simple and safe manner.
These" and other objects, which will appear in more detail as the description proceeds, are accomplished according to my invention by the methods and preparations described hereafter and defined in the appended claims.
Throughout the following description the term by weight of the solution" is used to indicate that a specified number' of parts by Weight of solute is present in parts by'weight of solution. 7
Generally, the dyeing method according to my invention comprises the steps of treating the material to be dyed "with a freshly prepared neutral to mildly alkaline, aqueous solution containing a small percentage of a water-soluble mercapto compound and, as sole coloring agent, a dyestufi of the group consisting of the Ext. D & C, D & C and F D & C certified colors and mixtures thereof, washing the dyed material with an aqueous medium, and drying'it.
Heretofore, certified colors could be used for the perm'anent' dyeing of keratinous matter only in strongly acid or" strong salt solutions, and at elevated temperatures. As 'a result, difficulties arose in the use of such dyes for some purposes and, particularly, they could not be employed' for the permanent dyeing ofthe hair of living persons unless the hair was subjected to complicated pretreatments or after-treatments.
The'pr esent'inventionis based on my discovery that the Ext. D & C, D & C and F D & C certified, non-toxic coal tar dyes are suitable for the permanent dyeing of keratinous material at moderate temperatures and in neutral or mildly alkaline solutions, if a relatively small percentage of water-soluble mercapto compounds is added to the dye solutions immediately before they are used. Myinvention makes it possible to dye human hair in a simple manner permanently with dye preparations containing" exclusively completely harmless and safe ingredientsand to produce natural, predictable color shades which arefast to rubbing, washing, shampooing and permanent waving.
While I do not wish to be bound by any specific theory, my experiments seem to indicate that the mercapto compoundsfacilitate the transport of the dyestuffs directly into the cell structure of the keratinous material to be dyed and thusinsure a thorough penetration and fixation of the dyes in the material to be colored.
I havefound that hair substance itself, under the action of dissolved mercapto compounds in neutral or weakly alkaline aqueous solutions, absorbs not only water, but other substances dissolved in the aqueous mixture, such as dissolved dyestufis. The size of the dyestufi molecules and'the diffusion velocities of the dissolved substances seem to have little or no influence on their transportation. Even'in the presence of relatively small proportions of mercapto compounds, the dyestuffs do not form merely a filter cake 'on the exterior of the hair shaft, which is removable by rubbing or washing, but pass with the liquid into the interior of the hair. The substances migrating with the water or transported thereby become effectively trapped or imbedded in the hair substance and are not subject to removal by customary treatments, such as rubbing, toweling, washing, shampooing or permanent Waving; Microscopic examination has shown the hair fibers to be uniformly stained over the areas between the imbrications.
The expressions Ext. D & C, D & C and F D & C certified colors or simply certified colors as used in myspecification and claims is intended to designate the coal tar dyes which are certified as permissible and pure by the Federal Food and Drug Administration. Such colors are certified as F D & C where they are per- 3 missible in Foods, Drugs and Cosmetics, as D & C where they are permissible in Drugs and Cosmetics, and as Ext. D & C where they are permissible in Drugs and Cosmetics for external application only.
It has been found that dye solutions suitable for the dyeing of keratinous material according to my invention may contain preferably between about 0.033 and 6.2% by weight of the solution of such dyestuffs.
The water-soluble mercapto compounds to be used in the dye solutions according to my invention are particularly the water-soluble mercapto compounds of the general type useful for hair waving and depilatory purposes. Suitable examples are thioglycolic and thiosalicylic acids in the form of their water-soluble salts, thioglycol, thioglycerol and thiophenol. At present, I prefer in most cases to use thioglycolic acid because it is readily available, has no intense objectionable odor, and is ordinarily entirely harmless in the concentrations in which it is used according to my invention, but I do not limit my invention either to this or to any other particular mercapto compound. The water-soluble mercapto compounds are present in my dye solutions in quantities equivalent with respect to S H group to about 0.1 to 6% by Weight of the solutions of thioglycatic acid. For hair dyeing purposes, a mercapto compound content equivalent with respect to S H group to between about 1.2% and about 6% by weight of the solution of thioglycolic acid has been found to give most favorable results.
The temperatures used in my dyeing processes may vary between about 50 and about 110 F. Temperatures of between about 60 and about 80 F. are preferred, particularly in the use of my invention for the permanent dyeing of human hair.
The dye solutions according to my invention are applied to the keratinous material at a pH value between about 6.6 and about 11.3 and preferably at a pH value of between about 9 and 10.2. As basis for the establishment and maintenance of the desired pH values, I have successfully used concentrated aqueous ammonia, sodium hydroxide, sodium carbonate in the presence of ammonium chloride, ethylene diamine, and triethanolamine. Other alkalies could undoubtedly be employed. For most purposes, I prefer to use concentrated aqueous ammonia and sodium hydroxide either separately or in suitable mixtures.
In general, I have found predominantly aqueous solutions of dyestuffs and mercapto compounds well adapted for color transportation into and color fixation in hair. Small additions of water miscible organic solvents, such as propylene glycol, ethyl alcohol, tetra-hydrofurfuryl alcohol or the like may be advantageous in order to improve the solubility of the coal tar dyes.
Useful effects in coloring hair are accomplished at temperatures of between about 60 F. and about 80 F. with relatively weak solutions of mercapto compounds and usually at mild alkalinities. I have found adequate, for example, up to about 4% by weight of the solution of thioglycolic acid at alkalinities corresponding to pH values of not more than about 10.5 during 15 to 25 minutes. Many of my successful hair dyeings, accomplished without evidence of any resultant hair damage have been performed with less than 2.6% by weight of the solution of thioglycolic acid in the form of its sodium salt, with excess of ammonia as free base at pH values of about 9 to 10 at a temperature of about 68 F. within about to minutes. This combination of conditions lies well within allowable extremes and may be adopted as normal. Increase above normal in any of the three principal factors, namely, concentration of mercapto compound, alkalinity in pH terms, and temperature, intensifies not only the resultant coloration, but also the action of the remaining unaltered factors upon the hair substance. With increase toward higher extremes of these factors, and particularly when large increases in two factors occur together, hair substance may tend to absorb excessive amounts of water with undesirable swelling, distortion and softening of the hair. The fiber may thereby be weakened and actual disintegration of the hair may occur unexpectedly on washing or combing. An unfavorable result caused by the elevation of one factor above normal may often be forestalled by expedient lowering below normal of one or more of the other factors. If considerably high concentrations of mercapto compounds are employed, such as, for instance amounts equivalent with respect to S H group to 4.5 to 6% by weight of the solution of thioglycolic acid, then alkalinity should be adjusted to a lower pH value, for instance, 9.4 or less to preclude irreversible hair damage. If a high temperature is employed, such as, for example, 110 F., then a moderate concentration of mercapto compound, for instance, in the range of up to about 2.5% by weight of the solution of thioglycolic acid, may require lowering of the pH value below 9.3 in order to preclude hair damage. For example, very good hair coloration, without any evidence of hair damage, may be effected with 2.5% by weight of the solution of thioglycolic acid acting upon hair at 110 F. during 15 minutes at a pH of 8.0. Decrease below normal of any of the three factors diminishes the risk of hair damage but weakens correspondingly the resultant coloration. Thus with color solutions, for instance, in the neighborhood of 50 F., coloring action is appreciably less than at 60 to F. for 1.4% by weight of the solution of thioglycolic acid at a pH of 9.4 acting during 20 minutes. With 0.5% by weight of the solution of thioglycolic acid, coloring action is appreciably less than with 1.4% by weight of the solution of thioglycolic acid, other conditions remaining the same for both cases. At a pH value of 7.7, coloring action is appreciably less than at a pH of 8.5 for 2.5% by weight of the solution of thioglycolic acid at 70 F. during 20 minutes. Minima for concentration of mercapto compound, pH, and temperature are not imposed like maxima, by the susceptibility of hair to damage, but are chosen when low values for one or more factors require considerable increase above normal in one or more of the remaining factors for good and intense coloring of the hair.
Contact between hair and dye solution should be maintained for at least several minutes. A period as short as above five minutes may produce appreciable coloration of the hair, but with tinting action during six minutes, the resulting coloring is appreciably weaker than with tinting action during fifteen minutes for 2.5% by weight of the solution of thioglycolic acid at 70 F. and a pH value of 9.4. Ordinarily, it is not necessary or desirable to maintain the hair in contact with the dye solution for more than a maximum time of thirty-five minutes. However, where the pH value of the solution is low or the temperature used is below 70 F., contact times of from 1 to 2 hours may have no detrimental effect on the hair, although generally, after the first thirty minutes, no significant increase in intensity of coloration has been observed.
I have found that in the dyeing of human hair, it is preferable to use solutions containing, in addition to the dissolved dyestuffs, an amount of mercapto compound equivalent with respect to S H group to about 1.2% to 6% by weight of the solution of thioglycolic acid.
Preferably the solutions have a pH value between 6.6 and 10.4 but not higher than 9.4 when the mercapto concentration is equivalent to at least 3% by weight of the solution of thioglycolic acid and not higher than 9.15 when the mercapto concentration is equivalent to at least 5.6% by weight of the solution of thioglycolic acid. The solution is applied to the hair at a temperature of between about 50 F. and F. but not less than 70 F. when both mercapto concentration and pH value approach their minimum values and not higher than 80 F. when both mercapto concentration and pH value approach their maximum values.
According to a preferred embodiment of my invenarm-see.
tion, the mercapto content of, thensolution .is. kept below aboutj4%.,by weightsof the solution. This .hasthQadVan-x tage that thehairiswnot appreciablyafiiected bythereduce.
ing action of themercapto, compounds and, consequently, no oxidizing after-treatment of thedyed materialris necessary. After the dy'feing operation.itself,..the ,dyed. ma: terial is sirhplylrinsed with-water to remove the..excess dye in order to. producea permanent coloringwhich is .fastagainst rubbing; or shampooing. However, .it .is possible,
to, use solutionsncontaining morezthan about 4%. and .up to..about,6% by weight of the solution of water-soluble mercaptocompounds. In these cases the dyed material,
afterapplication of thedye solution thereto,.is preferably treatedwith a, mild oxidizing. agent,: such ashydrogen peroxide.
While. most of thecertifiedcolors when used in accordance withmy invention. willproduce ,the desired-color values on. hair-with hair coloring. effects which. are "fast to. rubbing,.,washing, shampooing and permanent waving without any after-treatment, in some .cases it may. be-usee.
ful to apply to the dyed hair an after-treatment for the purpose of color development, color intensification or improved color fixation. Mild oxidizing agents; suchas hydrogen peroxide, and acids, such as acetic acid, may be used in these cases, which :are within thebroad scope of my inventiomfor after-treatment of the dyed hair.
My invention also covers the new preparations for the permanent dyeing of keratinous material to be .used in...
my method. Such preparation maybe, for instance, a'
neutral or mildly alkaline solution containingsin am aqueous solvent a small percentage of a water-soluble: mercapto compound and, as sole coloring agent, a dye-r stufi of the group consisting of the Ext. DI&,C, D1 8: C. andF D"&' C certifiedcolors and mixtures thereof Preparations which are intended for the dyeing of human hair contain preferably a quantity of: wateresoluble mercapto compound equivalent withrespect to SH' group toabout 1.2%"to6%-' by weight-of the solution-of' thioglycolic acid and have a pH value of "between*6.6 to 10.4 but not higher than 9.4 when the mercaptoconcentration is equivalentioat least 3%- by weight of the. solution of thioglycolic acid and not higher than:.9.15. when the mercapto. concentrationis equivalent to at least 5.6%..by weight of the solution of thioglycolicacid.
Sincemany of the certified colors may deteriorate if they remain in a solution containing-mercapto compounds for any. length of time, it is essential that-the dye com ponents of the solutions are combined with the-mercapto components immediately before application. to the keratinous material to be dyed. Preferably, the dye mercapto solutions are freshly prepared from two sepae' rate starting solutions immediately before they are used. Thus, a preparation of :the dyeing of keratinous .material,. and particularlyrof human hair, may comprisea' of. the two solutions,; the total-quantity of solvent in both solutions and the relative proportionsof the solutions being such that the resulting mixture is neutral or mildly alkaline and contains a small percentage ofa watersoluble mercapto compound.
According to another embodiment of my invention, .a preparation for the dyeing of keratinous materiaLand particularly of human hair, may be a substantially dry powder mixture comprising a dry, water-soluble solid mercapto compound, an ammonium salt, a dry, weakly alkaline, water-soluble salt of an alkali-metal, and,:'as:
sole coloring agent, a dry, wateresolubledyestuff selected from the group consisting of. the Ext. D & .C,.D;& Cand.
F D & C certified .colors andmixturesrthereof, the-several ing edients. being, present. in .such. proportions that, an. addition thereof 'to a predetermined.quantitywof water;
a dye solution is formed which contains a small percentage of mercapto compound and is neutral or mildly alkaline.
The following examples are intendedto illustrate the invention without limiting its scope, and to show clearly, the absence of transport ofdissolveddyesuifs" into the hair and other keratinous material "in the absence of mercapto compounds in contrast to the immediateactiva tion of such .transportof dyestuifs'in the presence of small percentages of mercapto compounds under otherwise identical conditions.
Example -I Firm textured, nearly colorless human hair was immersed for 15 minutes-at a temperature of F., with exclusion of air, in a solution carrying,0.920g.. of a dyestufi'mixture consisting of:
D &.C.Black. #1 (0.1. 246) D. &.C.Brown #1 (C. L234) Ext.-.D:& C:Reds.#.13 (01.252)
4.0 mLconcentrated ammonia water q. s. water to make 102 ml.
After 15 minutes the. hair was next immersed for .15 minutes in 20 volume 'hydrogen'peroxide in 7 percent acetic acid, then finallytshampooed and'toweled. The hair retained a pale'grjay coloration; No appreciabledyeing of the hair hadbeen accomplished.
10 ml. of ammoniacal thioglycolate solution were then." added to the previously described solution, the resulting, mixture having substantially the following composition? 0.920 g. dyestutf mixture 1.4 g.-thioglycolic acid 6.0 ml. concentrated ammonia water q. s. water to make 112ml. pH-9.5
The thioglycolic acid content of the mixture'amount ed by weight of the solution and the" dyestuif content amounted to-0.8% by weight of the solution.
For comparison,- hair 'of the same character was simi larly immersed for 15 minutes at 70 F. with exclusion' of airain this solution After 15 minutes, the hair was next. immersed for 15 minutes in 20 volume hydrogen: peroxide in 7 percent acetic acid, then finally shampooed and .toweled. The hair retained a moderate ash blonde coloration, approachingtbrown, but lacking warmth or redness. A permanent dyeing had resulted.
Example [I Firm textured, nearly colorless human hair was satu- Y rated=for 3 minutes in a solution containing 3.89 g. of a dyestuff mixture consisting of:
D & C Black #1 (CT. 246) F D & C Yellow #5 (C. I. 640)* Ext. D & C Red #8 (Cl. 176) D & C Red #33 (C. I. 30)
4.0 ml. concentrated ammonia water q. s. Water to make 86 ml.
The hair was then exposed for 15 minutes to the atmosphere While wet. Cooling of the solution during the exposure period took place, the average temperature being estimated to be about 60 F.
After 15 minutes the hair was in part merely rinsed and blotted, then dried, in part well-shampooed, then rinsed, blotted and dried. The rinsed hair retained a pale pink-violet coloration,- the shampooed hair a distinctly paler pink-violet coloration; Most of the pale color adhering' to the merely rinsed hair was located superficially and-was removable by shampooing. The hair .was not permanently dyed.
Upon addition of 10 ml. of ammoniacal thioglycolate 7 solution to this dye solution, a mixture resulted which had the following composition:
3.89-g. of dyestuff mixture 2.5 g. thioglycolic acid 1.1 g. sodium hydroxide 7.41 ml. concentrated ammonia aqua q. s. water to make 96 ml. pH9.25
In this mixture, the thioglycolic acid content amounted to 2.6% by weight of the solution, the dyestutf content to about 4% by weight of the solution.
For comparison, hair of the same character was similarly saturated for 3 minutes and then exposed wet for 15 minutes to the atmosphere under identical temperature conditions estimated on the average to be about 60 F. After 15 minutes, the hair was in part merely rinsed and blotted, then dried, in part well shampooed, then rinsed, blotted and dried. The merely rinsed hair retained a strong violet-brown coloration, the shampooed hair likewise a strong violet-brown coloration, hardly distinguishable from that of the merely rinsed hair. The hair was substantially dyed.
Example III A solution was prepared containing:
0.320 g. D & C Black #1 (C. I. 246) 0.800 g. D & C Orange #3 (C. I. 27) 0.700 g. Ext. D & C Red #13 (C. I. 252) Total 1.820 g. dyestuff mixture 25.0 ml. propylene glycol q. s. water to make 90 ml.
To this solution was added immediately before use ml. of ammoniacal sodium thioglycolate solution containing:
2.5 g. thioglycolic acid 1.1 g. sodium hydroxide 3.4 ml. concentrated ammonia aqua The resulting 100 ml. solution had a pH of 10.1. The thioglycolic acid content was 2.5% by weight of the solution.
This mixture was immediately applied at a temperature of 68 F. to uucolored human hair, conveniently by a brush. the wet hair was allowed to remain exposed to the atmosphere for 20 minutes at a temperature at which the wet solution was maintained substantially constant at 60 F. Thereafter, the dark excess of dye was rinsed from the hair with Warm water until the washings were substantially colorless. The hair was then gently toweled and finally dried with a warm air current. The hair retained a natural and pleasing dark auburn coloration. It was subsequently gently shampooed with only an insignificant change of hair coloration resulting from even the first shampooing.
Example IV 0.800 g. D & C Black #1 (C. 1. 246) 0.600 g. D & C Orange #3 (C. I. 27)
0.500 g. F D & C Yellow #6 (a dyestutf obtained by coupling diazotized sulfanilic acid with 2-naphthol-6-sulfonic acid) 1.000 g. Ext. D & C Red 13 (C. I. 252) Total 3.900 g. dyestuff mixture 25.0 ml. propylene glycol 1.1 g. sodium hydroxide 1.7 ml. of concentrated ammonia aqua were dissolved with water in a volume of 90 mls., pI-I12.15
To this solution was added, immediately before use, 10 ml. of substantially neutral ammonium thioglycolate solution, carrying 2.5 g. thioglycolic acid to make 100 ml. solution having a pH of 9.7.
The mixture was immediately applied at a temperature of about 77 to uucolored hair conveniently by a brush. Thejwet hair was allowed to remain exposed to the atmosphere for 20 minutes at a temperature at which the evaporation of the water caused some cooling down of the solution. The average temperature of 20. minutes exposure time was estimated to be about 75 F.
After 20 minutes, the dark excess of dye was rinsed from the hair with warm water until the washings were substantially colorless. The hair thereafter was gently toweled and finally dried with a warm air current. The hair maintained a permanent, dark brown, very natural coloration.
In some cases, where very intense hair coloration is desired, not all of the dyestuffs participating in the. final color-quality remain reliably compatible in high concentrations. In such cases a repeated treatment of the hair with a weaker dye mixture may be convenient, employing in each treatment a dye mixture, with a smaller proportion of mercapto compound. This may be illustrated by the following:
Example V A mixture was prepared of:
2.4 g. D & C Black #1 (C. I. 246) 1.7 g. D & C Orange #3 (C. I. 27) 2.1 g. Ext. D & C Red #13 (C. I. 252) Total 6.2 g. dyestufi mixture 25.0 ml. propylene glycol q. s. water to make 93 ml.
To this mixture is added, immediately before use, 7.0
ml. of ammoniated sodium thioglycolate solution, carry- The mixture was at once applied to uucolored hair, conveniently by brief immersion thereof, and the wet hair allowed to remain exposed to the atmosphere at a temperature of 66 F. for 20 minutes. Thereafter, the dark excess of color was rinsed from the hair with warm water, until the washings were substantially colorless. The hair was then gently toweled and dried in a warm air current. The hair retained a dark brown coloration, nearly a black. Immediately thereafter, a portion of the dyed and dried hair was identically treated with an identical mixture of the same quantities of the same dyes as above, freshly mixed with 7 ml. of the same sodium thioglycolate solution. After 20 minutes exposure of the wet hair to the atmosphere at 66 F., the hair was simi-, larly rinsed as above, toweled and dried. The hair retained a black coloration. No hair damage was evident.
Example V1 2.4 g D & c Black #1 c. I. 246) 1.7 g. D & 0 Orange #3 c. I. 27 21 g. Ext. D & c Red #13 c. I. 252
Total 6.2 g. dyestutl mixture was dissolved in a solvent containing:
25.0 ml. propylene glycol 1.5 g. sodium hydroxide 4.0 g. thioglycolic acid 2.86 ml. concentrated ammonia aqua q. s. water to make ml. pH-9.45
In the fresh mixture, firm textured, nearly colorless human hair was saturated for 3 minutes at a temperature of about 74 F. and then exposed to the room atmosphere for 20 minutes in Wet condition. Over the entire contact period of 23 minutes, the solution had on the average a t mperature of about 66F. At theend of the- 20 m utep iold. he i Was s ifi edwwi h Warm wa er n r d-Y he. h r. e imi a e ut fu a k. w brown coloration,,and;there was. no indication of damage to; the hair.
' Example VII 3 yes utlv ixtur aving the. amecomposition as in the preceding example were dissolved in a solvent containing:
25.0 ml. propylene glycol 2.0 g. sodium hydroxide 5.5 g. thioglycolic acid 3.86 ml. concentratedammonia aquav q. s.. water. to make 100 ml.
In the fresh' mixture .firmtextured,.nearly colorless human hair wassaturated forfi minutes at about. "74 F., then exposed to room temperature for 20 minutes in wet condition. The over all temperature of thesolution throughout the contact time of 23 minutes was about 66 F. At the expiration of the 20.."minuteperiod, the hair was, -rinsed,, then treated for. 10 .minutes at a. temperature of about 68 F. with 5 volumes hydrogen peroxide solution carrying 3% of-aceticacid. After lfinal rinsing and drying, the hair retainedea very. darkbrown coloration,
almost a black. No indication of hair damage appeared at .any stageof treatment.
Example VIII 6.2 g. of -a dye mixture 1 having the; same. composition as in the preceding, two exampleswere dissolvedin a solvent; containing:
25.0 ml. propylene glycol 2.2 g. sodium hydroxide.
6.0 g. thioglycolic acid 4.21 ml. concentrated ammonia. aqua q.. s. water to .malge 100 mlpH-9.15
In the fresh mixture, firm textured, nearly colorless human hair was saturated for 3 minutesat79 F. and then exposed. to the room atmosphere-for 20-minutes in' wet condition. The average temperature over theentire 23 minutes of contactwas about 66 F;
At the end of 20 -minutes--exposure, the hair was rinsed, then treated for minutes at room temperature with 5 volumes of hydrogen-peroxide= solution carrying 3% of acetic acid; finally rinsed and dried. The-hair retained a very dark, drabbrown coloration, almost a black. There was noindication of hairdamage apparent atany stage ofthe treatment.-
Example .IX.
A- solution was preparedqcarryingz 0.50 g. D & C Violet #1 (C. I. 697) 2.5 0 g. thioglycolic acid 1.1 g. sodium hydroxide 7.41 ml." concentrated ammonia aqua q. s. water to make 100 mLpH' 10.4
In the fresh solution firm textured, uncolored human hair was saturatedfor 3 minutes at. abouty73 F., then exposed in. wet ,condition to. the. room-=;atmospl1ere1 for minutes. During the entire contact time of 23 minutes,
the average temperature of the solution was about 64 F. Thereafter, the hairwas well rinsed'and dried. It re-. tained apermanent pronounced bluecoloration;
Example X A solution was prepared'carrying:
0.50 g. D & C Violet #1 (C. I. 697) 2.50 g. thioglycolic acid 2.55 ml. concentrated ammonia aqua q. s.. water to make100. ml. pH-.8. 52,
In the fresh mixture, firm textured, colorless human. hair was saturated for 3 minutes at a temperature of about.
76 F. and then exposed in wet condition to the. room atmosphere for 20 minutes. The average, temperature of.
the solution throughout the total exposure time of 23 minutes was estimated to be about 68 F At the end of "the 201minutes, the hair waswellrinsed and dried. The hair: retained a pronounced blue .colora tion, slightly, duller-and a little more reddish than the.
final blue ofExample- IX.
Example XI A solution was prepared carrying:
0.250 g. D & C Black #1 (C. I. 246) 0.600 g. D &C Orange-#3'(C. I. 27)
0.500 g. F D & C Yellow #64 a dyestutf obtained by coupling diazotized sulfanilic acid with 2-naphth0l-6-sulfonic acid) 0.300g. Ext. D"& C Red #13 (C. 1.252) Total 1.650 g. dyestufi mixture- 25.0:m1. propylene glycol 2.5 gl; thioglycolic acid 1.1 g. sodium hydroxide 3.41 ml. concentrated ammonia aqua q. s. water to make ml. pH9.40
The fresh solution was chilled to 50 F. and firm.
textured, uncolored human hair was immediately immersed therein at 50 F. for 15 minutes. Thereafter the hair was rinsed, blotted, and 'dried. The hair retainedapale, golden blonde coloration, very natural.
Example XII A solut-ion was prepared, carrying 1.65 g. of adyestufif: mixture; having the same composition as in- Ex: ample XI; and
2510 ml. propylene glycol 2.5 g. thioglycolic acid,
2.95 ml. concentrated ammonia water q. s. water to make 100 iml.pH- 8'.0
The fresh solutionwas-warmedto F., and.; firm textured, uncolored human hairwas immediately immersed therein at 110 F. for. 15 minutes. Thereafter the hair was rinsed, blotted and dried. The hair retained a dark, Warm brown color, very natural. No evidence appeared of hair damage.
Example XIII 1 A solution was prepared carrying 1.56 g. ofadyestulf mixture having the same-composition as in Example XII, and d 25.0 ml. propylene glycol 2.5 g. thioglycolic acid.
1.95 ml. concentrated ammonia-aqua. q. s. waterto make 100 ml..pH-6.60
Example XIV A solutionv was prepared containing:
0.160 g. D & C Black #1 (C. I. 246) 0.750 g. D & c Orange-#3 c. 1. 27 0.600 g. F D & C Yellow #6 (a dyestulf obtained by coupling diazotized sulfanilic acid With- 2-naphthol-6-sulfonic acid) 0.140 g. Ext; D*&-*C"Red #13 (CI. 252) :-Total 1.650 g. dyestufiimixture 25.0 ml. propylene glycol 2.5 g. thioglycolic acid 1.1 g. sodium hydroxide 3.41 ml. concentrated ammonia squa q. s. water to make 100 ml. pH9.40
Firm textured, uncolored human hair was dipped in this solution at 68 F. for three minutes and then exposed to the atmosphere for minutes at 66 F. The hair was then rinsed, blotted and dried. A permanent dyeing of the hair to a light, ash blonde, was obtained.
Repeating the same procedure with exposure times of 10, 20 and 30 minutes respectively, the final coloration became progressively more intense, until, with 30 minute exposure, a very natural, dark ash-blonde with red overtones was obtained.
Example XV A mixture, in powder form, consisting of:
0.250 g. D & C Black #1 (C. I. 246) 0.600 g. D & C Orange #3 (C. I. 27)
0.500 g. F D & C Yellow #6 (a dyestufi obtained by coupling diazotized sulfanilic acid with 2-naphthol-6-sulfonic acid) 0.300 g. Ext. D & C Red #13 (C. I. 252) Total 1.650 g. dyestutf mixture 3.9 g. calcium thioglycolate, equivalent to 2.4 g. thioglycolic acid 4.5 g. sodium carbonatec. p., anhydrous 3.0 g. ammonium chloride, U. S. P. was shaken to solution in water to make 100 ml. having a pH=9.4.
In the fresh mixture, firm textured uncolored human hair was saturated for 3 minutes at 70 F., then exposed in wet condition to the room atmosphere for 20 minutes, the average temperature of the solution for the entire contact time being estimated as 66 F. At the end of the 20 minutes, the hair was well rinsed and dried. It retained a beautiful, very natural dark brown coloration.
Example XVI A solution was prepared carrying:
1.0 g. F D & C Green #2 (C. I. 670) 1.0 g. D & C Red #33 (C. I. 30)
Total 2.0 g. dyestuff mixture 1.23 g. ethylene diamine 2.14 g. 2-mercapto-ethanol (equivalent to 2.53 g. of
thioglycolic acid) q. s. water to make 100 mL; pH=9.6
Firm textured, uncolored human hair was saturated briefly in the fresh solution and then exposed in wet condition to the room atmosphere for 15 minutes at a temperature to retain the solution at about 66 F. throughout the exposure period. Thereafter, the hair was immersed for 15 minutes in 4% acetic acid solution, finally shampooed, rinsed and dried. The hair retained a strong bluish red permanent coloration.
Example XVII A solution was prepared carrying:
0.40 g. D & C Red #33 (C. I. 30)
0.40 g. F D & C Blue #1 (C. I. 671 is the ammonium salt) 1.60 g. D & C Orange #3. (C. I. 27)
0.25 g. Ext. D & C Red #13 (C. I. 252) Total 2.65 g. dyesturf mixture 25.0 ml. propylene glycol 2.63 g. monothioglycerol (1 mcrcapto-2,3 propane diol),
(equivalent to 2.24 g. of thioglycolic acid) 3.14 ml. concentrated ammonia aqua q. 5. water to make 100 ml. pH=9.8
Firm textured, uncolored human hair was saturated in the fresh solution at 70 C. for 3 minutes, then exposed in wet condition to the room atmosphere for 20 minutes. During the entire contact period of 23 minutes the temperature of the solution averaged about 66 F. At the end of the 20 minutes, the hair was shampooed, rinsed and dried. The hair retained a coppery red coloration.
Example XVIII A solution was prepared carrying:
0.250 g. D & C Black #1 (C. I. 246) 0.600 g. D & C Orange #3 (C. I. 27)
0.500 g. F D & C Yellow #6 (a dyestufi obtained by coupling diazotized sulfanilic acid with 2-naphthol-6-sulfonic acid) 0.300 g. Ext. D & C Red #13 (C. I. 252) Total 1.650 g. dyestuff mixture 25.0 ml. propylene glycol 3.0 g. thiophenol (equivalent to 2.5 g. of thioglycolic acid) 3.44 ml. concentrated ammonia aqua q. s. Water to make 100 ml. pH=9.5
Firm textured, uncolored human hair was saturated in the fresh solution at about 74 F. for 3 minutes and then exposed in wet condition to the room atmosphere for 20 minutes. The average temperature during the entire contact time of 23 minutes was about 66 F.
At the end of 20 minutes, the hair was rinsed and dried. It retained a reddish blond coloration.
Example XIX A solution was prepared containing 1.65 g. of a dye mixture having the same composition as in Example XIX, and:
25.0 ml. propylene glycol 4.18 g. thiosalicylic acid (equivalent to 2.5 g. of thioglycolic acid) 5.3 ml. concentrated ammonia aqua q. s. water to make 100 ml. pH=9.6
Firm textured, uncolored human hair was saturated in the fresh solution for 3 minutes at 74 F. and then exposed in wet condition to the room atmosphere for 20 minutes. The average temperature of the solution throughout the exposure period of 23 minutes was about 66 F.
After 20 minutes, the hair was rinsed and dried. It retained a light, coppery brown color which was permanent.
In numerous other instances, both with mixtures of certified colors and with single certified colors, I have established by similar comparative tests that a negligible to slight fixation in hair of color from neutral or alkaline solutions in the absence of mcrcapto compounds, can be transformed into strong and useful fixation in hair of the same colors merely by the added presence in the color solutions of mcrcapto-compounds. Such further instances include:
Ext. D & C Blue #1 (Methylene Blue) C. I. 922
D & C Violet #1 (Wool Violet SBN) C. I. 697
D & C Orange #5 Dibromofluorescein Ext. D & C Yellow #3 (Fast Light Yellow) C. I. 636 F D & C Red #1 (Ponceau 3R) C. I.
F D & C Red #2 (Amaranth) C. I. 184
D & C Red #19 (Rhodamine B) C. I. 759
D & C Red #27 (Tetrachlorotetrabromofluorescein) The following examples are intended to show that Wool can also be permanently dyed with my dye preparations at ordinary temperatures;
Example XX A solution was prepared containing:
0.300 g. D & C Black #1 (C. I. 246) 0.088 g. D & C Brown #1 I. 234,) 0.113 g. Ext. D & C Red.#13 (C. I. 252) Total0.501 g. of dyestufi mixture 1.0 g. Dupanol .C (sodium lauryl sulfate) q. s. water to make 85 m1. pH=6.25
In this mixture there was immersed for 20 minutes. at
80 F. a strip of white all wool fabric, which was thereafter rinsed to nearly colorless with water. Wool is not dyed by brief contact at ordinary temperatures with the nearly neutral dyestui'f mixture To the nearly neutral dye-mixture were next added and Well-mixed 2.5 .mLof
concentrated ammoniaaqua to malre 87-88 ml. 11.3. A duplicate strip of White, all-wool fabric wa's immersed.
therein for 20 minutes at 76 F. The wooLwas thereafter briefly dippedin 5 percent acetic acid solution, and finally rinsed with warm tap water. The wool retained a faint grayish color. The wool is incipiently, but weak- 1y, dyed, at ordinary temperatures with'the weakly alkaline mixture of dyestufis.
To the ammoniacal dye mixture was next added, and
well mixed, 5 ml. of ammoniacal sodium thioglycolate: 30
solution carryingi 1.4 g. thioglycolic acid. 0.6 g, sodium hydroxide 0.4 m1. concentrated ammonia aqua, to make 93 ml.
A triplicate strip-of white, all wool fabric was immersed for 20 minutes at 76 F. The wool was thereafter briefly dipped in 5% acetic acid solution, then shampooed warm, and warm rinsed. The wool retained an intense, dull black color. Wool is deeply dyed at ordinary temperatures by brief contact with the combination ofalkaline mercapto compound with the dyestuffs.
Example XXI A solution was prepared carrying 0.300 g. D& Black #1 (c. 1.246 0.088 g. D'& 0 Brown #1 c. I. 234 0.113 g. Ext. 13a 0 Red #13 o. I. 252
Total 0.501 g. of dyestuff mixture 1 1.0 g. Dupanol C (sodium lauryl sulfate) 2.64 ml. concentrated ammonia aqua 0.1 g. thioglycolic acid 0.03 g. sodium hydroxide q. s. water to make 100ml.
In the fresh mixture a strip of whit e, all wo ol fabric was immersed for 20v minutes at .66? FL, thereafter dipped.
for minutes in 5% aqueous acetic acid at 66 F., finally shampooed in warm water, rinsed, and dried. The wool thioglycolate used in Example Example XXII Wool was treated with the solution and by the method described in Example XXI at 50 F. for 15 minutes. After subsequent rinsing and drying, the wool retained a pronounced permanent, medium gray coloration without any evident alteration of the texture or strength.
Example XXIII Wool was treated with the solution and in the manner described in Example XXI at pH 8, and at a temperature of 110 F.', for 15 'minutes. After rinsing and drying,
the wool retained abeautiful velvet black. It had been permanently dyed. No wool damage was evident. The dyed fabric remained soft and pliable.
Example XXIV' Wool was dyed in the solution and by the process described inExample XXI at pH 6.6, and at a temperature of 110 F., for 15 -minutes. Afterrinsing and drying, the wool retained a permanent, very dark reddish brown coloration, noticeably lighter than the velvet black retained after the identical procedure with a corresponding solution at pH 8.0 as described in Example XXIII.
What is claimedis:
.1. A method forthe permanent dyeing of keratinousmaterial, which comprises treating the material to be dyed with a freshly prepared aqueous solution containing a quantity of a water soluble mercapto compound oflow" toxicity equivalent .with. respect to, SH group to aboutture-between about 50 F. and 110 F;
3.; Method as claimed=in claiml, in. which the pH value of the solution. is maintained ,betweenB. and. 10.2.
4. A method, for the permanent dyeingof human hair.
which comprises, the. steps of treating the hairto be dyed,
at -.a temperature of between. about F. and 110 F,
with afreshly prepared aqueoussolutionofa quantity of a water-solublemercapto compound .of the group consisting of thioglycolic acid, thiosalicylicacid in the form of its water soluble salts, thioglycol, thioglycerol and thiophenol equivalenuwith;respecttoSI-Lgroup to about 1.2% to 6% retained a distinct, even, gray color, appreciably stronger. than the faint grayish color obtained intheentire absence. of thioglycolate, and much weaker, than the du ll black color obtained in the presence of the 1415 times stronger by weight of the solution ofthioglycolic acid and containing, as sole coloringagent, about 0.033%, to about 6,2 by weight of the solution of a dyestulfof the group consisting f theExt. n&' c, D & .C and FD & c certified colors larld mixtures thereof, the solution having a pI-I valu'e between 6.6 and 10.4 butnot higher than 9.4 when the mercapto'concentration is equivalent to at least 3 by weight .of the solution of thioglycolic acid and not higher than'f9,15 whenthe mercapto concentration is equivalent tofat least 5.6% byjweight of the solution of thioglycolic acid,'then washingthe dyed hair with an aqueous medium and drying the same.
5. A method. as claimed inclaim 4, in which the pH- value ofthe solutionis maintainedbetween. 9 and 10.2.;
6. A method as claimed in claim 4, in which the mercapto compound used is thioglycolic acid.
7. A method for the permanent dyeing. of human hair which comprises the steps of treating the hair to be dyed with afreshly'pjrepared aqueous solution of a quantityof a water-soluble mercapto compound of the group consisting of thioglycolic acid, thiosalicylic acid in the form, of its water-solublesalts, thioglycol, thioglycerol and thiophenol equivalent withrespect to SH group to about 1.2%
to 6% by weight ofthe solution of thioglycolic acid and, containing, as sole coloring agent, about 0.033% to about 6.2% by weightof the solution of, a dyestuif of the group consisting of the Ext. D & C, D & C and F D &-C certified colors and mixtures thereof, said solution having a pH value between 6.6 and 10.4 but not higher than 9.4 when the mercapto concentration is equivalent to at least 3% by weight of the solution of thioglycolic acid and not higher than 9.15 when the mercapto concentration is equivalent to at least 5.6% by weight of the solution of thioglycolic acid, said solution being applied to the hair at a tempera- 15 ture of between about 50 F. and 110 F. but not less than 70 F. when both mercapto concentration and pH value approach their minimum values and not higher than 80 F. when both mercapto concentration and pH value approach their maximum values.
8. A method as claimed in claim 7, in which the pH value of the solution is maintained between 9 and 10.2.
9. A method as claimed in claim 7, in which the dye solution is left in contact with the hair for a period of about minutes to about 35 minutes,
10. A method for the permanent dyeing of human hair which consists of the steps of treating the hair to be dyed at a temperature of between about 50 F. and 110 F. with a freshly prepared aqueous solution of a quantity of a water-soluble mercapto compound of the group consisting of thioglycolic acid, thiosalicylic acid in the form of its water-soluble salts, thioglycol, thioglycerol and thiophenol equivalent with respect to SH group to about 1.2% to 4% by Weight of the solution of thioglycolic acid and containing, as sole coloring agent, about 0.033% to about 6.2% by weight of the solution of a dyestutf of the group consisting of the Ext. D & C, D & C and F D & C certified colors and mixtures thereof, said solution having a pH value of between 6.6 and 10.4 but not higher than 9.4 when the mercapto concentration is equivalent to at least 3% by weight of the solution of thioglycolic acid, then Washing the dyed hair with an aqueous medium and drying the same.
11. A method for the permanent dyeing of human hair which consists of the steps of treating the hair to be dyed at a temperature between about 50 F. and 110 F. with a freshly prepared aqueous solution of a quantity of a Water-soluble mercapto compound of the group consisting of thioglycolic acid, thiosalicylic acid in the form of its water-soluble salts, thioglycol, thioglycerol and thiophenol equivalent with respect to SH group to about 4% to 6% by weight of the solution of thioglycolic acid and containing, as sole coloring agent, about 0.033% to about 6.2% by weight of the solution of a dyestuff of the group consisting of the Ext, D & C, D & C and F D & C certified colors and mixtures thereof, said solution having a pH value between 6.6 and 9.4 but not higher than 9.15 when the mercapto concentration is equivalent to at least 5.6% by weight of the solution of thioglycolic acid, then treating the dyed hair with a mild oxidizing agent, washing the hair with an aqueous medium and drying the hair.
12. A preparation for the permanent dyeing of keratinous material in the form of an aqueous solution having a pH between about 6.6 and about 11.3 and containing a quantity of a water-soluble mercapto compound of low toxicity equivalent with respect to SH group to about 0.1 to about 6% by weight of the solution of thioglycolic acid and, as sole coloring agent, about 0.033 to about 6.2% by weight of the solution of a dyestuff of the group consisting of the Ext. D & C, D & C and F D & C certified colors and mixtures thereof.
13. A preparation for the permanent dyeing of human hair in the form of a freshly prepared aqueous solution containing an amount of a water-soluble mercapto compound selected from the group consisting of thioglycolic acid, thiosalicylic acid in the form of its water-soluble salts, thioglycol, thioglycerol and thiophenol equivalent with respect to SH group to about 1.2% to 6% by Weight of the solution of thioglycolic acid and, as sole coloring agent, about 0;033% to about 6.2% by weight of the solution of a dyestuff of the group consisting of the Ext. D & C, D & C and F D & C certified colors and mixtures thereof, said solution having a pH value between 6.6 and 10.4 but not higher than 9.4 when the mercapto concentration is equivalent to at least 3% by Weight of the solution of thioglycolic acid and not higher than 9.15 when the mercapto concentration is equivalent to at least 5.6% by weight of the solution of thioglycolic acid.
14. A preparation as claimed in claim 13, in which the solution has a pH value of between about 9 and 10.2.
15. A preparation for the permanent dyeing of keratinous material in the form of a substantially dry powdered mixture comprising a dry water-soluble solid mercapto compound of low toxicity, an ammonium salt, a dry, weakly alkaline water-soluble salt of an alkali metal, and, as sole coloring agent, a dry dyestuff selected from the group consisting of the Ext. D & C, D & C and F D & C certified colors and mixtures thereof, the several ingredients being present in such proportions that, on addition of the dry powdered mixture to a predetermined quantity of water, a dye solution is formed which contains about 0.033% to about 6.2% by weight of the solution of dyestutf and a quantity of mercapto compound equivalent with respect to SH group to about 0.1% to about 6% by weight of the solution of thioglycolic acid and which has a pH value of between about 6.6 and 11.3.
16. A preparation for the permanent dyeing of human hair in the form of a substantially dry powdered mixture comprising a dry water-soluble salt of thioglycolic acid, an ammonium salt, a dry, weakly alkaline watersoluble salt of an alkali metal, and, as sole coloring agent, a dry dyestuff selected from the group consisting of the Ext. D & C, D & C and F D & C certified colors and mixtures thereof, the several ingredients being present in such proportions that, on addition of the dry powdered mixture to a predetermined quantity of water, a dye solution is formed containing about 0.033 to 6.2% b. w. of dyestufi and about 1.2% to 6% by weight of the solution of thioglycolic acid and which has a pH value of between about 6.6 and 10.4 but not higher than 9.4 when the thioglycolic acid concentration is at least 3% by weight of the solution and not higher than 9.15 when the thioglycolic acid concentration is at least 5.6% by weight of the solution.
17. A method for the permanent dyeing of keratinous material, which comprises the steps of preparing separately an aqueous dye solution containing, as sole coloring agent, a dyestufi selected from the group consisting of the Ext. D & C, D & C and F D & C certified colors and mixtures thereof and a water solution of a Watersoluble mercapto compound, the respective pH values of the two solutions, the total quantity of solvent in both solutions, the relative proportions of the solutions, the concentration of mercapto compound in the mercapto solution and the concentration of dyestufi in the dye solution being such that a mixture of the two solutions contains about 0.033% to about 6.2% by weight of the solution of dyestuff and a quantity of mercapto compound equivalent with respect to SH group to about 0.1% to about 6% by weight of the solution of thioglycolic acid and has a pH value between about 6.6 and about 11.3, combining the two separate solutions to form such mixture, applying the freshly prepared mixture to the keratinous material to be dyed, washing the dyed material with an aqueous medium and drying the same.
18. A method for the permanent dyeing of human hair, which comprises the steps of preparing separately an aqueous dye solution containing, as sole coloring agent, a dyestutf selected from the group consisting of the Ext. D & C, D & C and F D & C certified colors and mixtures thereof and a Water solution of a water-soluble mercapto compound of the group consisting of thioglycolic acid, thiosalicylic acid in the form of its watersoluble salts, thioglycol, thioglycerol and thiophenol, the respective pH values of the two solutions, the total quantity of solvent in both solutions, the relative proportions of the solutions, the concentration of mercapto compound in the mercapto solution and the concentration of dyestuff in the dye solution being such that a mixture of the two solutions contains about 0.033% to about 6.2% by weight of the solution of dyestutr and a quantity of mercapto compound equivalent with respect to SH group to about 1.2% to about 6% by weight of the mixed solution of thioglycolic acid and has a pH value of between about 6.6 to 10.4 but not higher than 9.4 when the mercapto concentration in the mixture is equivalent to at least 3% by Weight of the mixed solution of thioglycolic acid and not higher than 9.15 when the mercapto concentration of the mixture is equivalent to at least 5.6% by weight of the mixed solution of thioglycolic acid, combining the two separate solutions to form such a mixture, applying the fresh mixture to the hair to be dyed at a temperature about 50 and 110 F., washing the dyed hair with an aqueous medium and drying the same.
References Cited in the file of this patent UNITED STATES PATENTS 1,917,101 Niederhausern July 4, 1933 2,201,929 Speakrnan May 21, 1940 2,405,166 Reed Aug. 6, 1946 2,418,664 Ramsey Apr. 8, 1947 2,464,281 Peterson Mar. 15, 1949 2,501,184 Michaels Mar. 21, 1950 2,577,710 McDonough Dec. 4, 1951 2,610,941 Schueller Sept. 16, 1952 18 2,643,211 Den Beste June 23, 1953 2,653,121 Schnell Sept. 22, 1953 FOREIGN PATENTS 171,725 Austria June 25, 1952 117,071 Australia June 3, 1943 OTHER REFERENCES Windus et al.: The Unhairing Problem, Journal American Leather Chem. Association, volume 33, 1938, pages 246 to 253.
Hall: The Monthly Review of Current Textile Progress, Textile Colorist, February 1942, pp. 63 to 65.
Hollenberg: Cold wave formulation, Drug and Cosmetic Industry, June 1950, pgs. 664, 665 765-767, and 769, pg. 766; The coloring of the wave solution presents a parallel problem with the great variety of certified approved colors at our disposal, there are only a few that stand up in these solutions 167-871 Speakman: Constitution, properties and uses of wool, The Textile Manufacturer, April 1940, page 160.
Evans: Drug and Cosmetic Industry, June 1950, page 648.
Herriott: Advances in Protein Chemistry, vol. III, 1947, pages 182 and 183.

Claims (1)

1. THE METHOD FOR THE PERMANENT DYEING OF KERATINOUS MATERIAL, WHICH COMPRISES TREATING THE MATERIAL TO BE DYED WITH A FRESHLY PREPARED AQUEOUS SOLUTION CONTAINING A QUANTITY OF A WATER SOLUBLE MERCAPTO COMPOUND OF LOW TOXICITY EQUIVALENT WITH RESPECT TO SH GROUP TO ABOUT 0.1 TO ABOUT 6% BY WEIGHT OF THE SOLUTION OF THIOGLYCOLIC ACID AND, AS SOLE COLORING AGENT, ABOUT 0.033 TO ABOUT 6.2% BY WEIGHT OF THE SOLUTION OF A DYESTUFF OF THE GROUP CONSISTING OF THE EXT. D & C, D & C, AND F D & C CERTIFIED, COLORS AND MIXTURES THEREOF, THE SOLUTION HAVING A PH VALUE BETWEEN ABOUT 6.6 AND ABOUT 11.3, THEN WASHING THE DYED MATERIAL WITH AN AQUEOUS MEDIUM AND DRYING THE SAME.
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CH350076D CH350076A (en) 1951-06-28 1957-01-04 Process for dyeing non-textile keratin materials such as human hair, natural furs, etc., and composition for carrying out this process

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Cited By (12)

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US2904385A (en) * 1956-07-17 1959-09-15 Oreal Dyeing animal fibres and compositions therefor
US2983651A (en) * 1955-12-10 1961-05-09 Oreal Dyeing of animal fibres
US2988091A (en) * 1956-09-04 1961-06-13 Long S Hair Conditioner Inc Mechanism for permanently conditioning hair
US3041244A (en) * 1957-09-17 1962-06-26 Jerome A Feit Quinone hair dye compositions
DE1212684B (en) * 1963-09-04 1966-03-17 Therachemie Chem Therapeut Preparations for coloring hair
DE1212683B (en) * 1963-09-04 1966-03-17 Therachemie Chem Therapeut Preparations for coloring hair
US3399682A (en) * 1963-08-05 1968-09-03 Hoyu Shokai Kk Method of simultaneously permanently dyeing and waving human hair
US5356439A (en) * 1992-09-14 1994-10-18 Shiseido Co., Ltd. Non-oxidative permanent dye formulation for hair and synthetic fibers
US5942009A (en) * 1997-03-28 1999-08-24 Brg, Ltd. Same-day waving and coloring of hair
US20070134184A1 (en) * 2005-12-13 2007-06-14 Stephen Pheiffer Organic therapeutic and cosmetic preparation
US20090123406A1 (en) * 2005-12-13 2009-05-14 Stephen Pheiffer Organic therapeutic and cosmetic preparation
WO2012038114A3 (en) * 2010-09-20 2012-10-18 Henkel Ag & Co. Kgaa Colour preservation by means of conditioning agents containing reducing agents

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DE1257358B (en) * 1963-04-24 1967-12-28 Partipharm A G Process for coloring human hair

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US2201929A (en) * 1934-12-10 1940-05-21 Speakman John Bamber Treatment of fibers or fibrous materials containing keratin
US2405166A (en) * 1942-02-11 1946-08-06 Raymond Lab Inc Process for waving hair
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US1917101A (en) * 1928-04-26 1933-07-04 Firm Of Durand & Huguenin S A Production of fast dyeings with ester-salts of leuco vat-dyestuffs
US2201929A (en) * 1934-12-10 1940-05-21 Speakman John Bamber Treatment of fibers or fibrous materials containing keratin
US2577710A (en) * 1941-06-16 1951-12-04 Procter & Gamble Permanent waving compositions and methods
US2405166A (en) * 1942-02-11 1946-08-06 Raymond Lab Inc Process for waving hair
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US2464281A (en) * 1945-03-07 1949-03-15 Raymond Lab Inc Cream hair treating preparations
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US2643211A (en) * 1949-11-30 1953-06-23 Rayette Inc Hair color-rinse concentrate
AT171725B (en) * 1949-12-22 1952-06-25 Albrecht Dr Maier Thioglycolic acid or similar Agent containing active organic sulfhydryl compounds for producing cold permanent waves

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2983651A (en) * 1955-12-10 1961-05-09 Oreal Dyeing of animal fibres
US2904385A (en) * 1956-07-17 1959-09-15 Oreal Dyeing animal fibres and compositions therefor
US2988091A (en) * 1956-09-04 1961-06-13 Long S Hair Conditioner Inc Mechanism for permanently conditioning hair
US3041244A (en) * 1957-09-17 1962-06-26 Jerome A Feit Quinone hair dye compositions
US3399682A (en) * 1963-08-05 1968-09-03 Hoyu Shokai Kk Method of simultaneously permanently dyeing and waving human hair
DE1212684B (en) * 1963-09-04 1966-03-17 Therachemie Chem Therapeut Preparations for coloring hair
DE1212683B (en) * 1963-09-04 1966-03-17 Therachemie Chem Therapeut Preparations for coloring hair
US5356439A (en) * 1992-09-14 1994-10-18 Shiseido Co., Ltd. Non-oxidative permanent dye formulation for hair and synthetic fibers
US5942009A (en) * 1997-03-28 1999-08-24 Brg, Ltd. Same-day waving and coloring of hair
US20070134184A1 (en) * 2005-12-13 2007-06-14 Stephen Pheiffer Organic therapeutic and cosmetic preparation
US20090123406A1 (en) * 2005-12-13 2009-05-14 Stephen Pheiffer Organic therapeutic and cosmetic preparation
WO2012038114A3 (en) * 2010-09-20 2012-10-18 Henkel Ag & Co. Kgaa Colour preservation by means of conditioning agents containing reducing agents

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FR1169087A (en) 1958-12-22

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