US3920384A - Autoxidizable hair dye containing preparations - Google Patents
Autoxidizable hair dye containing preparations Download PDFInfo
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- US3920384A US3920384A US489317A US48931774A US3920384A US 3920384 A US3920384 A US 3920384A US 489317 A US489317 A US 489317A US 48931774 A US48931774 A US 48931774A US 3920384 A US3920384 A US 3920384A
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- hair
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- autoxidizable
- coloring
- triol
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Classifications
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- 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
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
-
- 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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/347—Phenols
-
- 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
-
- 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
- Y10S424/00—Drug, bio-affecting and body treating compositions
- Y10S424/01—Aerosol hair preparation
-
- 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
- Y10S424/00—Drug, bio-affecting and body treating compositions
- Y10S424/02—Resin hair settings
Definitions
- This invention relates to a process for gradually col- 5 2,975,101; 710,134; 754,948; 754,949; 745,532; oring hair over a relatively long period of time using, as 824,519; 827,439.
- Other references of interest relating the coloring agent, autoxidizable organic compounds. to the hydrolysis of 1,2,4-triacetoxybenzene are as fol- It also concerns certain compositions of matter that are lows: Ber. 31', (1898) p.” 1247; Ber. 32 (1899) ,p. 282 useful for this purpose and to a method for preparing and 'J .C.S.- 1934 p. 1625. However, none of these referthese' compositions. ences suggest the claimed compositions or processes.
- compositions containing other oxidation intermediates I N,N-bis( 2-hydroxyethyl)-ptoxic when ingested and therefore, do present some haphenylenediamine sulfate or 1,2,4-benzenetriol) or zard in use. compositions containing other oxidation intermediates.
- Gray hair swatches were inpregnated with each multaneously be colored and groomed during the applicomposition four times at room temperature (.twice a cation of these compositions. day for 2 days), then shampooed, rinsed and air dried.
- an autoxidizable hair coloring composinificance tion giving natural looking, drab and long-wearing hair color
- a composition V N;i', y comprising a mixture of N,N-bis(2-hydroxyethyl)-pphenylenediamin?
- Sulfate phenylenediamine or an acid addition salt thereof (e.g. g gfg ig g zi'sxgi sulfate, chloride, etc.) and 1,2,4-benzenetriol.
- the color produced with the combination of BBB and Benz T is drabber than the 3 than PPD or PTD initially and is much more stable after exposure to room air.
- PPD and PTD continue to slowly oxidize after the swatch is shampooed which means that a person using either as an autoxidizable hair color would not know what the final color of his hair would be.
- triols are preferably prepared just prior to use in preparing the present composition by storing the triacetate at room temperature to 50C for 12 to 24 hours with ethanol and dilute sulfuric acid.
- Each trio] is formed by transesterification as follows:
- reaction mixture is then added in its entirety without separation to the rest of the formulation, where the pH is adjusted with a suitable alkali.
- composition of the present invention is'most conveniently applied in the form of a hair grooming composition which will simultaneously groom and color the hair.
- the autoxidizable compounds are usually contained in solution in the composition.
- enough composition is applied to thoroughly wet hair (approximately g. on the average), followed by simple combing into the desired style.
- No shampooing or rinsing is required after application as is the case for the usual hair coloring product.
- the extent of the hair coloring is determined by the concentration of the autoxidizable organic compoundsand the number of applications, the latter determined at the discretion of the user.
- N,N-bis( 2-hydroxyethyl)-pphenylenediamine sulfate and triol may vary somewhat. In general, however, the former (i.e. BHE) will comprise between about 0.05% to 1.0% by weight and preferably between about 0.1% to 0.5% of the composition, while the latter (i.e. the triol) will comprise between 0.02% and 1.0% by weight and preferably between about 0.05% to 0.2%.
- the present composition will preferably contain a hair grooming agent.
- a hair grooming agent Some typical materials that may serve this purpose are the quaternized vinyl-pyrrolidone copolymers, carboxyvinyl polymers, etc.
- Plasticizers, conditioners and slip agents may also be chosen from a variety of compounds such as polyoxyethylene lauryl 4 ether, polyoxyethylene fatty alcohol, stearyldimethylbenzylammonium chloride, silicone copolymer, etc.
- ingredients are chosen to make a liquid or gel type of composition.
- an aerosol foam is particularly suitable since the ingredients are protected against degradation by air.
- Common Freons such as 12, 114 or 152A are suitable as well as hydrocarbon propellants.
- the pH of the composition is ordinarily adjusted to the range 4 to 11 and preferably 6 to 8 with an alkalizing agent, e.g. ethanolamine, diethanolamine, triethanolamine, disodium hydrogen phosphate, sodium carbonate, etc.
- an alkalizing agent e.g. ethanolamine, diethanolamine, triethanolamine, disodium hydrogen phosphate, sodium carbonate, etc.
- An antioxidant is useful to prevent premature oxidation of the intermediates during shelf storage. This may be chosen from such things as sodium sulfite, ascorbic acid, sodium hydrosulfite, etc.
- the level of antioxidant can vary between 0.03 to 1%to be determined by storage stability needs. The quantity and type of antioxidant also determine the rate of the hair coloring reaction.
- Water is ordinarily the major constituent of the composition and can vary over a wide range dependent in large measure on the quantity of other additives.
- the water content may vary between 50 to An alcohol, glycol or derivative thereof is added as a solubilizing agent in the range of 0 to 30% depending on the rest of the composition.
- Gafquat 755 quaternized vinylpyrrolidone copolymer; has a minimum of 19% solids in a water vehicle and have an average M.W. over 1,000,000.
- Emulphor AM 650 polyoxyethylated (l0) isostearyl alcohol (10 moles of ethyleneoxide).
- Silicone SF-l066 dimethyl polysiloxane/polyethyleneoxide/polypropyleneoxide copolymer vis. 1200 1500 centistokes at 25C.; s.g. at 20C. 1.04.
- BHE N, N, bis (2-hydroxyethyl)-p-phenylenediamine sulfate.
- Propellant 152 a l, l difluoroethane.
- Propellant 114 1,2 -dichloro -1,l,2,2-tetrafluoroethane.
- Propellant l2 dichlorodifluoromethane.
- Carbopol 941 A water soluble polymer of acrylic acid crossed linked with about 1% of a polyallyl ether of sucrose having an average of 5.8 allyl groups for each sucrose molecule (M.W. of the order of 1,000,000).
- UCON-LB-l7l5 Polypropylene glycol butyl ether viscosity is 1715 Saybolt universal seconds at F.
- UCON LB-3000 polypropylene glycol butyl ether viscosity is 3000 Saybolt universal seconds at 100F.
- EXAMPLE 1 AEROSOL FOAM a.
- the triol is prepared by weighing 1.26 g. 1,2,4-benzenetriacetate, 30 g. ethyl alcohol (approx.), 0.4 g. conc. sulfuric acid into a container which should have little or no headspace remaining.
- composition after being applied twice'a day for two days (total of four) to gray hair gives a naturallooking medium drab brown shade.
- composition after being applied twice a day for two days to gray hair gives a natural-looking drab "brown shade.
- EXAMPLE 3, LIQUID a. The trio] is prepared by weighing 2.8 g. 1,2,4-benzenetriacetate, 50 g. ethyl alcohol (95%), l g. conc. sulfuric acid into a container which should have little or no headspace remaining. Cap the container and place in a 50 oven for 18 hours (approx) A clear solution 6 will result containing 1.4 g. triol, 2.94 g. ethyl acetat and excess alcohol. Set aside until step (e).
- An autoxidizable hair preparation capable of 001- I acid addition. salt thereof and a triol selected from the group consisting of 1,2 ,4-benzenetriol and 2,4,5-trihydroxytoluene; said p-phenylenediarnine and said triol being present in tinctorially effective amounts.
- preparation according to claim 1 in the form of an aqueous solution.
- the preparation according to claim 1 also including a hair grooming agent.
- a method for gradually coloring hair which comprises applying to said hair at multiple spaced intervals of time the composition of claim 1 and permitting said composition applied to said hair to be exposed to the atmosphere after each application whereby a gradual build-up of color is developed in said hair.
- An autoxidizable hair preparation capable of coloring hair when applied thereto and exposed to the atmosphere comprising an aqueous hair dye carrier containing from about 0.05% to 1.0% by weightof N,N- bis( 2-hydroxyethyl)-p-phenylenediamine or an acid addition salt thereof and from about 0.02% to 1% by weight of a triol selected from the group consisting of 1,2,4-benzenetriol and 2,4,4-trihydroxytoluene.
Abstract
An autoxidizable hair preparation capable of coloring hair when applied thereto and exposed to the atmosphere comprising N,Nbis(2-hydroxyethyl)-p-phenylenediamine or an acid addition salt thereof and a triol selected from the group consisting of 1,2,4benzenetriol and 2,4,5-trihydroxytoluene. The preparation is applied at multiple spaced intervals of time until the desired color build-up is attained. Also prepares the composition by preforming a solution of the triol by storing the corresponding triacetate in acid solution for a period of time then adding the N,N-bis(2-hydroxyethyl)-p-phenylenediamine.
Description
' Feinland et al.
[ AUTOXIDIZABLE HAIR DYE CONTAINING PREPARATIONS [75] Inventors: Raymond Feinland, Stamford,
Conn.; Sigmund Iscowitz, Flushing; Milos S. Bil, Forest Hills, both of NY.
[73] Assignee: Clairol'lncorporated, New York,
[22] Filed: July 17, 1974 [21] Appl. No.: 489,317
424/D1G. 1; 424/D1G. 2; 424/70 [51] Int. Cl. A61K 7/13 [58] Field of Search 8/102, 11, 32
[56] References Cited I UNITED STATES PATENTS 2,162,458 6/1939 Lehmann 8/l0 2 2,733,186 1/1956 Brye 8/10.2 2,975,101 3/1961 Charle et al. 8/102 3,167,478 l/1965 Charle et al. 8/l0.2
[ Nov. 18, 1975 3,337,411 8/1967 Wilmsmann et al. 8/10.2
FOREIGN PATENTS 0 APPLICATIONS 12,902 4/1900 United Kingdom 8/10.2
Primary Examiner-Albert T. Meyers Assistant Examiner-Vera C. Clarke Attorney, Agent, or Firmlrving Woltzman; George A. Mentis; David J. Mugford ABSTRACT An autoxidizable hair preparation capable of coloring hair when applied thereto and exposed to the atmosphere comprising N,N-bis(2-hydroxyethyl)-pphenylenediamine or an acid addition salt thereof and a trio] selected from the group consisting of 1,2,4- benzenetrio] and 2,4,5-trihydr0xytoluene. The preparation is applied at multiple spaced intervals of time until the desired color build-up is attained. Also prepares the composition by preforming a solution of the trio] by storing ,the corresponding triacetate in acid solution for a period of time then adding the N,N-bis(2- hydroxyethyl')-p phenylenediamine.
8*Claims, No Drawings Several references in the prior art'have suggested the useof ben'z enetriols in hair coloring compositions. In this connection, attention is invited;to US. Pat. Nos. 2,162,458; 3,214,472; .3,236,734;, 2,733,186;
This invention relates to a process for gradually col- 5 2,975,101; 710,134; 754,948; 754,949; 745,532; oring hair over a relatively long period of time using, as 824,519; 827,439. Other references of interest relating the coloring agent, autoxidizable organic compounds. to the hydrolysis of 1,2,4-triacetoxybenzene are as fol- It also concerns certain compositions of matter that are lows: Ber. 31', (1898) p." 1247; Ber. 32 (1899) ,p. 282 useful for this purpose and to a method for preparing and 'J .C.S.- 1934 p. 1625. However, none of these referthese' compositions. ences suggest the claimed compositions or processes.
It is known in the prior art that human hair can be V To compare. the relative merits of autoxidation dyecoloredover a periodof time through the use of certain ing properties of the present compositions on hair samlead salt compositions. However, these lead salt comples as to depth of shade and the -lasting qualities of the positions (so-called color restorers") have an inherent colorings, the experiments described below were carlimitation in the shade quality that can be achieved ried out. The results obtained with the present compowith them. This isa weak yellow or yellow-orange colsition were compared with the results obtained from oration and is dependent on theformation of lead sulthe autoxidation of the individual components of this fide. Furthermore, lead salts are known to be highly composition (i.e. I N,N-bis( 2-hydroxyethyl)-ptoxic when ingested and therefore, do present some haphenylenediamine sulfate or 1,2,4-benzenetriol) or zard in use. compositions containing other oxidation intermediates.
It has now been found that a gradual coloration of the The following test conditions were employed in this hair over a period of time, and particularly grey hair, study: may be effectively accomplished by means of repeated a. All the compositions employed were aqueous soluapplications of a composition containing autoxidizable tions containing 0.014M of each test compound, 0.03% organic compounds in solution. These materials may sodium sulfite, and 1.5% triethanolamine; the pH of also be incorporated in a composition which can also each composition was adjusted to 8 using'sulfuric acid. serve as a hair grooming agent so that the hair may sib. Gray hair swatches were inpregnated with each multaneously be colored and groomed during the applicomposition four times at room temperature (.twice a cation of these compositions. day for 2 days), then shampooed, rinsed and air dried.
It is accordingly an object of the present invention to 39 Color readings were taken immediately'and again after provide a safe method for gradually coloring hair over exposure of the swatches to the atmosphere for four a period of time. months. 9
It is also an object of the present invention to provide b. The color readings of L, a, b were obtained with a composition that is useful in carrying out the afore- Hunter Color/Difference Meter D25D2. said process. The results of these tests are summarized in the Table It is a further object of this invention to provide a below. The color results are given visually as well as in method for preparing said composition. Hunter units L, a, b where L is lightness (0 black, 100
Other and more detailed objects of this invention will white), +a is red, --a is green, +b is'yellow and '-b is be apparent from the following description and claims. blue. w I
It has been found, in accordance with the present in- 40 The abbreviations in the Table have the following sigvention, that an autoxidizable hair coloring composinificance: tion giving natural looking, drab and long-wearing hair color can be obtained by employing a composition V N;i', y comprising a mixture of N,N-bis(2-hydroxyethyl)-pphenylenediamin? Sulfate: phenylenediamine or an acid addition salt thereof (e.g. g gfg ig g zi'sxgi sulfate, chloride, etc.) and 1,2,4-benzenetriol. In place Benz T 1,2,4 benzenetriol of the said benzenetriol, there may also be employed TABLE I Compounds 1 a b Visual'Observation BHE, original 29.l +0.8 8.2 Light yellow brown BHE, after 4 months 28.8 +1.4 7.5 Slightly redder PPD, original 37.6 +0.5 +l0.8 Very light yellow brown PPD, after 4 months 28.3 +1.9 6.8 Redder and much darker PTD', original 37.0 +1.7 +l0.6 Very light orange brown PTD, after 4 months 29.8 +410 9.0 Much redder and darker Benz T, original 28.4 +2.2 7.2 Light red brown Benz T, after 4 months "29.3 +2.6 7.0 Unchanged U BI-IE Benz T, original 19.8 0.2 2.7 Dark drab brown BHE Benz T, after 4 mos. 20.6 -0.3 2.8 Unchanged PPD Benz T, original 17.2 +0.5 3.5 1 Dark brown PPD Benz T, after 4 mos. 17.4 +1.4 v 3.2 Slightly redder PTD Benz T, original 17.7 +0.7 3.7 Dark brown 'PTD Benz T, after 4 mos. 17.9 +1.3 3.5
"Slightly redder 2,4,5'-trihydroxytoluene. It has been further found that after the desired drab color is developed on-hair through the use of these compositions, the hair maintains these desired drab shades for relatively long periods of time even on exposure to the air in a room.
Ascan be seen from Table I, the color produced with the combination of BBB and Benz T is drabber than the 3 than PPD or PTD initially and is much more stable after exposure to room air. Apparently, PPD and PTD continue to slowly oxidize after the swatch is shampooed which means that a person using either as an autoxidizable hair color would not know what the final color of his hair would be.
Because of the tendency of the triols to rapidly oxidize, in accordance with the present invention, they are preferably prepared just prior to use in preparing the present composition by storing the triacetate at room temperature to 50C for 12 to 24 hours with ethanol and dilute sulfuric acid. Each trio] is formed by transesterification as follows:
2,4,5-trihydroxytoluene The reaction mixture is then added in its entirety without separation to the rest of the formulation, where the pH is adjusted with a suitable alkali.
The composition of the present invention is'most conveniently applied in the form of a hair grooming composition which will simultaneously groom and color the hair. The autoxidizable compounds are usually contained in solution in the composition. In a typical application, enough composition is applied to thoroughly wet hair (approximately g. on the average), followed by simple combing into the desired style. No shampooing or rinsing is required after application as is the case for the usual hair coloring product. The extent of the hair coloring is determined by the concentration of the autoxidizable organic compoundsand the number of applications, the latter determined at the discretion of the user.
The quantity of N,N-bis( 2-hydroxyethyl)-pphenylenediamine sulfate and triol that may be employed may vary somewhat. In general, however, the former (i.e. BHE) will comprise between about 0.05% to 1.0% by weight and preferably between about 0.1% to 0.5% of the composition, while the latter (i.e. the triol) will comprise between 0.02% and 1.0% by weight and preferably between about 0.05% to 0.2%.
In addition to the reactive autoxidizable ingredients, the present composition will preferably contain a hair grooming agent. Some typical materials that may serve this purpose are the quaternized vinyl-pyrrolidone copolymers, carboxyvinyl polymers, etc. Plasticizers, conditioners and slip agents may also be chosen from a variety of compounds such as polyoxyethylene lauryl 4 ether, polyoxyethylene fatty alcohol, stearyldimethylbenzylammonium chloride, silicone copolymer, etc.
The above ingredients are chosen to make a liquid or gel type of composition. For repeated use, an aerosol foam is particularly suitable since the ingredients are protected against degradation by air. Common Freons such as 12, 114 or 152A are suitable as well as hydrocarbon propellants.
The pH of the composition is ordinarily adjusted to the range 4 to 11 and preferably 6 to 8 with an alkalizing agent, e.g. ethanolamine, diethanolamine, triethanolamine, disodium hydrogen phosphate, sodium carbonate, etc.
An antioxidant is useful to prevent premature oxidation of the intermediates during shelf storage. This may be chosen from such things as sodium sulfite, ascorbic acid, sodium hydrosulfite, etc. The level of antioxidant can vary between 0.03 to 1%to be determined by storage stability needs. The quantity and type of antioxidant also determine the rate of the hair coloring reaction.
Water is ordinarily the major constituent of the composition and can vary over a wide range dependent in large measure on the quantity of other additives. Thus, the water content may vary between 50 to An alcohol, glycol or derivative thereof is added as a solubilizing agent in the range of 0 to 30% depending on the rest of the composition.
The following Examples are given to further illustrate the present invention. The following terms used in these Examples or elsewhere have the meaning ascribed to them below.
Gafquat 755: quaternized vinylpyrrolidone copolymer; has a minimum of 19% solids in a water vehicle and have an average M.W. over 1,000,000.
Emulphor AM 650: polyoxyethylated (l0) isostearyl alcohol (10 moles of ethyleneoxide).
Brij 35: polyoxyethylated (23) lauryl ether (23 moles of ethyleneoxide).
Silicone SF-l066: dimethyl polysiloxane/polyethyleneoxide/polypropyleneoxide copolymer vis. 1200 1500 centistokes at 25C.; s.g. at 20C. 1.04.
BHE: N, N, bis (2-hydroxyethyl)-p-phenylenediamine sulfate.
Propellant 152 a: l, l difluoroethane.
Propellant 114: 1,2 -dichloro -1,l,2,2-tetrafluoroethane.
Propellant l2: dichlorodifluoromethane.
Carbopol 941: A water soluble polymer of acrylic acid crossed linked with about 1% of a polyallyl ether of sucrose having an average of 5.8 allyl groups for each sucrose molecule (M.W. of the order of 1,000,000).
UCON-LB-l7l5: Polypropylene glycol butyl ether viscosity is 1715 Saybolt universal seconds at F.
UCON LB-3000: polypropylene glycol butyl ether viscosity is 3000 Saybolt universal seconds at 100F.
EXAMPLE 1, AEROSOL FOAM a. The triol is prepared by weighing 1.26 g. 1,2,4-benzenetriacetate, 30 g. ethyl alcohol (approx.), 0.4 g. conc. sulfuric acid into a container which should have little or no headspace remaining.
Cap the container and place in a 50 C oven for 16 hours (approx.). A clear solution will result containing 0.63 g. triol, 1.323 g. ethyl acetate and excess alcohol. Set aside until step (h).
b. Mix at room temperature 140 g. water, 200 g. ethyl alcohol and g. Gafguat 755 until uniform.
c. Mix at 50 C 0.53 g. Emulphor AM 650, 0.40 g. Brij 35 and 0.13 g. perfume until a clear solution is obtained.
d. Add (b) to (c) and mix until uniform.
e. Add 0.67 g. stearyldimethylbenzylammonium chloride and mix until lumps dissolve.
f. Add 0.53 g. Silicone SF 1066 to batch and mix until uniform.
. g. Add 1.47 g. of BHE and 0.60 g. sodium sulfite and mix until uniform.
h. Add triol solution and mix until uniform.
i. Adjust pH with triethanolamine to 7.8 8.1 (4 to 5 g.).
j. Q.S. with water to 1,000 g.
A clear, colorless solution is obtained with the following composition:
BHE 0.147% 1,2,4-benzenetriol 0.063 ethyl acetate 0.132 sodium sulfite 0.060 triethanolamine 0.4 ethyl alcohol (95%) 23 Gafquat 755 2.000 Emulphor AM 650 0.053 perfume 0.013 stearyldirnethylbenzylammonium chloride i 0.067 vSilicone SF-1066 0.053 Brij 35 0.04 water q.s.
To 94 g. of above composition, 6 g. of a propellant blend of l52A/l 14/12 (/35/35) is added to obtain a quick breaking aerosol foam.
The composition after being applied twice'a day for two days (total of four) to gray hair gives a naturallooking medium drab brown shade.
EXAMPLE 2, GEL
ing temperature to 4050 C, cool down to room temperature when smooth dispersion is obtained, continue stirring.
c. Add 4 g. BHE and 1.2 g. sodium sulfite.
(1. Mix 0.13 g. perfume into 0.4 g. Brij and add to :main solution.
e. Add triol solution.
f. Add 43 g. triethanolamine, and adjust pH with triethanolamine and sulfuric acid to 7.9-8.l.
g. Q.S. with water to 1,000 g. to form a soft gel.
The composition after being applied twice a day for two days to gray hair gives a natural-looking drab "brown shade.
" EXAMPLE 3, LIQUID a. The trio] is prepared by weighing 2.8 g. 1,2,4-benzenetriacetate, 50 g. ethyl alcohol (95%), l g. conc. sulfuric acid into a container which should have little or no headspace remaining. Cap the container and place in a 50 oven for 18 hours (approx) A clear solution 6 will result containing 1.4 g. triol, 2.94 g. ethyl acetat and excess alcohol. Set aside until step (e).
b. Mix together 100 g. UCON LB-1715,
A clear near colorless solution is obtained with the following composition.
2,4,5 trihydroxytoluene 0.140% N,N bis (2-hydroxyethyl) p-phenylene diamine sulfate 0.147
sodium sulfite 0.120 triethanolamine 0.100 UCON LB-l7l5 10.00 UCON LB-3000 10.000 Brij 35 0.04 perfume 0.013 ethyl alcohol (95%) 50.00 ethyl acetate 0.294
DI. Water- In any of the" above examples the perfume may be ter.
What is claimed is:
1'. An autoxidizable hair preparation capable of 001- I acid addition. salt thereof and a triol selected from the group consisting of 1,2 ,4-benzenetriol and 2,4,5-trihydroxytoluene; said p-phenylenediarnine and said triol being present in tinctorially effective amounts.
2. preparation according to claim 1 in the form of an aqueous solution.
3. The preparation according to claim 1 in the form of an aerosol composition also containing a propellant system.
4. The preparation according to claim 1 also including a hair grooming agent.
5. The preparation according to claim 4 wherein the grooming agent comprises about 0.1% to 50% by weight based on the total weight of the composition.
6. A method for gradually coloring hair which comprises applying to said hair at multiple spaced intervals of time the composition of claim 1 and permitting said composition applied to said hair to be exposed to the atmosphere after each application whereby a gradual build-up of color is developed in said hair.
7. The method according to claim 6 wherein the hair is neither shampooed nor rinsed directly after the hair coloring operation.
8. An autoxidizable hair preparation capable of coloring hair when applied thereto and exposed to the atmosphere comprising an aqueous hair dye carrier containing from about 0.05% to 1.0% by weightof N,N- bis( 2-hydroxyethyl)-p-phenylenediamine or an acid addition salt thereof and from about 0.02% to 1% by weight of a triol selected from the group consisting of 1,2,4-benzenetriol and 2,4,4-trihydroxytoluene.
g.- UCON LB-3000, 500 g. ethyl alcohol, and 200 g. water eliminated and replaced with an equal quantity of wa-
Claims (8)
1. AN AUTOXIDIZABLE HAIR PREPARATION CAPABLE OF COLORING HAIR WHEN APPLIED THERETO AND EXPOSED TO THE ATMOSPHERE COMPRISING AN AQUEOUS HAIR DYE CARRIER AND N,N-BIS(2-HYDROXYETHYL)-P-PHENYLENEDIAMINE OR AN ACID ADDITION SALT THEREOF AND A TRIOL SELECTED FROM THE GROUP CONSISTING OF 1,2,4-BENZENETRIOL AND 2,4,5-TRIHYDROXYTOLUENE; SAID P-PHENYLENEDIAMINE AND SAID TRIOL BEING PRESENT IN TINCTORIALLY EFFECTIVE AMOUNTS.
2. preparation according to claim 1 in the form of an aqueous solution.
3. The preparation according to claim 1 in the form of an aerosol composition also containing a propellant system.
4. The preparation according to claim 1 also including a hair grooming agent.
5. The preparation according to claim 4 wherein the grooming agent comprises about 0.1% to 50% by weight based on the total weight of the composition.
6. A method for gradually coloring hair which comprises applying to said hair at multiple spaced intervals of time the composition of claim 1 and permitting said composition applied to said hair to be exposed to the atmosphere after each application whereby a gradual build-up of color is developed in said hair.
7. The method according to claim 6 wherein the hair is neither shampooed nor rinsed directly after the hair coloring operation.
8. An autoxidizable hair preparatIon capable of coloring hair when applied thereto and exposed to the atmosphere comprising an aqueous hair dye carrier containing from about 0.05% to 1.0% by weight of N,N-bis(2-hydroxyethyl)-p-phenylenediamine or an acid addition salt thereof and from about 0.02% to 1% by weight of a triol selected from the group consisting of 1,2,4-benzenetriol and 2,4,4-trihydroxytoluene.
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US489317A US3920384A (en) | 1974-07-17 | 1974-07-17 | Autoxidizable hair dye containing preparations |
US05/570,675 US4054413A (en) | 1974-07-17 | 1975-04-23 | Autoxidizable hair dye containing preparations |
CA229,789A CA1044600A (en) | 1974-07-17 | 1975-06-20 | Autoxidizable hair dye containing preparations |
AU82866/75A AU489008B2 (en) | 1975-07-09 | Autoxidizable hair dye containing preparations | |
JP50085415A JPS6039645B2 (en) | 1974-07-17 | 1975-07-14 | Autooxidizing hair dye and its manufacturing method |
MX159599A MX144048A (en) | 1974-07-17 | 1975-07-15 | A AUTOOXIDABLE COMPOSITION TO HAVE HAIR |
GB29858/75A GB1491980A (en) | 1974-07-17 | 1975-07-16 | Autoxidizable hair dye containing preparations |
AR259608A AR214709A1 (en) | 1974-07-17 | 1975-07-16 | SELF-RESISTANT COMPOSITION FOR THE HAIR AND PROCESS FOR THE PREPARATION OF THE HAIR |
DE19752532036 DE2532036A1 (en) | 1974-07-17 | 1975-07-17 | AUTOXIDIZABLE HAIR COLOR COMPOSITION AND HAIR COLOR PROCEDURE |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US489317A US3920384A (en) | 1974-07-17 | 1974-07-17 | Autoxidizable hair dye containing preparations |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/570,675 Continuation-In-Part US4054413A (en) | 1974-07-17 | 1975-04-23 | Autoxidizable hair dye containing preparations |
Publications (1)
Publication Number | Publication Date |
---|---|
US3920384A true US3920384A (en) | 1975-11-18 |
Family
ID=23943346
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US489317A Expired - Lifetime US3920384A (en) | 1974-07-17 | 1974-07-17 | Autoxidizable hair dye containing preparations |
Country Status (2)
Country | Link |
---|---|
US (1) | US3920384A (en) |
AR (1) | AR214709A1 (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2352542A1 (en) * | 1976-05-28 | 1977-12-23 | Combe Inc | HAIR DYING PROCESS IN WHICH THE INTENSITY OF THE COLORING IS GRADUALLY INCREASED DURING SUCCESSIVE TREATMENTS |
US4104021A (en) * | 1976-05-28 | 1978-08-01 | Combe Incorporated | Process for dyeing hair in which the depth of shade is gradually increased in successive treatments |
US4170452A (en) * | 1976-01-19 | 1979-10-09 | L'oreal | Dye composition containing diphenylamine and polyhydroxybenzene |
US4226595A (en) * | 1977-12-27 | 1980-10-07 | Henkel Kommanditgesellschaft Auf Aktien | Oxidation hair-coloring preparation based upon N,N-bis-(β-hydroxyethyl)-m-phenylenediamines |
US4297098A (en) * | 1976-08-26 | 1981-10-27 | Alberto-Culver Company | Method for gradual coloring of hair to a light brown shade and preparations for use therein |
US4381920A (en) * | 1979-08-03 | 1983-05-03 | Michael-David Laboratories | Method and composition for dyeing human hair |
US5350424A (en) * | 1992-10-13 | 1994-09-27 | Combe Incorporated | Dyestuff composition for the gradual dyeing of hair by atmospheric oxidation and process using the same |
US5685882A (en) * | 1994-07-22 | 1997-11-11 | L'oreal | Use of guar gum in non-rinsed compositions for the dyeing of keratin fibers |
US5741337A (en) * | 1994-05-09 | 1998-04-21 | L'oreal | Process for the oxidative dyeing of keratinous fibres with a composition which contains an oxidation dye precursor, a coupler, and an oxidant at an acidic pH |
EP1062939A1 (en) * | 1999-10-02 | 2000-12-27 | Basler Haar-Kosmetik GmbH | Hair dyeing process and suitable compositions |
WO2011111054A1 (en) | 2010-03-09 | 2011-09-15 | Cavinkare Pvt. Ltd, | Improved hair dye composition |
WO2015112789A1 (en) | 2014-01-24 | 2015-07-30 | Combe International Ltd. | Gradual haircolor compositions and methods of using the same |
US9889080B2 (en) | 2015-05-07 | 2018-02-13 | Celeb LLC | Color depositing shampoo |
US10245221B2 (en) | 2015-05-07 | 2019-04-02 | Celeb LLC | Stabilized color depositing shampoo |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2162458A (en) * | 1936-05-08 | 1939-06-13 | Winthrop Chem Co Inc | Hair dye |
US2733186A (en) * | 1951-04-19 | 1956-01-31 | Compositions for the dyeing of hair | |
US2975101A (en) * | 1957-01-22 | 1961-03-14 | Oreal | Dyeing of hair and other keratinous materials |
US3167478A (en) * | 1958-01-08 | 1965-01-26 | Oreal | Color stabilized hair dye composition of ammonia and trihydroxybenzene |
US3337411A (en) * | 1961-10-26 | 1967-08-22 | Interpal S A | Oxidation dyestuffs with ascorbic acid or salts thereof for dyeing living human hair |
-
1974
- 1974-07-17 US US489317A patent/US3920384A/en not_active Expired - Lifetime
-
1975
- 1975-07-16 AR AR259608A patent/AR214709A1/en active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2162458A (en) * | 1936-05-08 | 1939-06-13 | Winthrop Chem Co Inc | Hair dye |
US2733186A (en) * | 1951-04-19 | 1956-01-31 | Compositions for the dyeing of hair | |
US2975101A (en) * | 1957-01-22 | 1961-03-14 | Oreal | Dyeing of hair and other keratinous materials |
US3167478A (en) * | 1958-01-08 | 1965-01-26 | Oreal | Color stabilized hair dye composition of ammonia and trihydroxybenzene |
US3337411A (en) * | 1961-10-26 | 1967-08-22 | Interpal S A | Oxidation dyestuffs with ascorbic acid or salts thereof for dyeing living human hair |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4170452A (en) * | 1976-01-19 | 1979-10-09 | L'oreal | Dye composition containing diphenylamine and polyhydroxybenzene |
FR2352542A1 (en) * | 1976-05-28 | 1977-12-23 | Combe Inc | HAIR DYING PROCESS IN WHICH THE INTENSITY OF THE COLORING IS GRADUALLY INCREASED DURING SUCCESSIVE TREATMENTS |
US4104021A (en) * | 1976-05-28 | 1978-08-01 | Combe Incorporated | Process for dyeing hair in which the depth of shade is gradually increased in successive treatments |
US4297098A (en) * | 1976-08-26 | 1981-10-27 | Alberto-Culver Company | Method for gradual coloring of hair to a light brown shade and preparations for use therein |
US4226595A (en) * | 1977-12-27 | 1980-10-07 | Henkel Kommanditgesellschaft Auf Aktien | Oxidation hair-coloring preparation based upon N,N-bis-(β-hydroxyethyl)-m-phenylenediamines |
US4381920A (en) * | 1979-08-03 | 1983-05-03 | Michael-David Laboratories | Method and composition for dyeing human hair |
US5350424A (en) * | 1992-10-13 | 1994-09-27 | Combe Incorporated | Dyestuff composition for the gradual dyeing of hair by atmospheric oxidation and process using the same |
US5741337A (en) * | 1994-05-09 | 1998-04-21 | L'oreal | Process for the oxidative dyeing of keratinous fibres with a composition which contains an oxidation dye precursor, a coupler, and an oxidant at an acidic pH |
US5685882A (en) * | 1994-07-22 | 1997-11-11 | L'oreal | Use of guar gum in non-rinsed compositions for the dyeing of keratin fibers |
EP1062939A1 (en) * | 1999-10-02 | 2000-12-27 | Basler Haar-Kosmetik GmbH | Hair dyeing process and suitable compositions |
WO2011111054A1 (en) | 2010-03-09 | 2011-09-15 | Cavinkare Pvt. Ltd, | Improved hair dye composition |
WO2015112789A1 (en) | 2014-01-24 | 2015-07-30 | Combe International Ltd. | Gradual haircolor compositions and methods of using the same |
US9237993B2 (en) | 2014-01-24 | 2016-01-19 | Combe Incorporated | Gradual haircolor compositions and methods of using the same |
CN105916482A (en) * | 2014-01-24 | 2016-08-31 | 酷姆国际公司 | Gradual haircolor compositions and methods of using the same |
US9474704B2 (en) | 2014-01-24 | 2016-10-25 | Combe Incorporated | Gradual haircolor compositions and methods of using the same |
JP2017503848A (en) * | 2014-01-24 | 2017-02-02 | コーム インターナショナル リミテッドCombe International Ltd. | Stepwise hair color composition and method of use |
US10022312B2 (en) | 2014-01-24 | 2018-07-17 | Combe Incorporated | Gradual haircolor compositions and methods of using the same |
US9889080B2 (en) | 2015-05-07 | 2018-02-13 | Celeb LLC | Color depositing shampoo |
US10245221B2 (en) | 2015-05-07 | 2019-04-02 | Celeb LLC | Stabilized color depositing shampoo |
Also Published As
Publication number | Publication date |
---|---|
AR214709A1 (en) | 1979-07-31 |
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