EP0637955A4 - Compositions de teinture pour les cheveux, composees de 5,6-dihydroxyindole et d'un oxydant a base de chlorite, et procedes de teinture a l'aide de ces compositions. - Google Patents

Compositions de teinture pour les cheveux, composees de 5,6-dihydroxyindole et d'un oxydant a base de chlorite, et procedes de teinture a l'aide de ces compositions.

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Publication number
EP0637955A4
EP0637955A4 EP93910638A EP93910638A EP0637955A4 EP 0637955 A4 EP0637955 A4 EP 0637955A4 EP 93910638 A EP93910638 A EP 93910638A EP 93910638 A EP93910638 A EP 93910638A EP 0637955 A4 EP0637955 A4 EP 0637955A4
Authority
EP
European Patent Office
Prior art keywords
hair
weight
amount
dhi
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP93910638A
Other languages
German (de)
English (en)
Other versions
EP0637955A1 (fr
Inventor
Gottfried Wenke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bristol Myers Squibb Co
Original Assignee
Bristol Myers Squibb Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/013,441 external-priority patent/US5413612A/en
Application filed by Bristol Myers Squibb Co filed Critical Bristol Myers Squibb Co
Publication of EP0637955A1 publication Critical patent/EP0637955A1/fr
Publication of EP0637955A4 publication Critical patent/EP0637955A4/fr
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • A61K8/492—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol
    • 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

Definitions

  • This invention concerns methods and compositions for dyeing human hair.
  • Modem hair dyeing methodology has developed from its initiation in the 1950s to the point where today it is the third largest product type in the hair care category, following shampoos and conditioners.
  • melanin One widely employed method for dyeing hair is based upon the production of the natural pigment melanin.
  • melanin The exact structure of melanin it not known. It is a polymer produced from tyrosine by a series of metabolic reactions the exact course of which remains to be clarified.
  • DHI 5,6- dihydroxyindole
  • DHICA 5,6-dihydroxyindole-2- carboxylic
  • Diacetoxyindole (DAI) is used by the art in its attempts to avoid these problems with DHI.
  • the practice has been to package DAI under mildly alkaline conditions in packages designed to protect the ingredients from air. Over the course of the time, between the initial packaging and the final use, the DAI is hydrolyzed to DHI. Since it is protected from air by the packaging, the DHI remains stable until it is ready for use.
  • oxidants has not been particularly successful with DHI, because oxidation takes place before the DHI penetrates the hair. Ideally, the DHI should penetrate the hair before oxidation takes place so that the pigment forms within the hair fiber. When the colorant forms in this manner, the color does not easily wash out. In contrast, if oxidation and melanin formation take place in the solution there is little or no dyeing effect. If oxidation takes place on the surface of the hair, the coloring is easily washed away during shampooing.
  • Dyeing with DHI is very attractive to many consumers, since its conversion to melanin is close to the natural pigmentation process.
  • One such disadvantage is that, while natural hair color comes in an inexhaustible variety of shades, many oxidants which are used in combination with DHI dye the hair only to a gray or black color with little or no warmth. Extensive research efforts have been undertaken to find ways to modify the final color result after dyeing with DHI.
  • a brown tonality is through use of hydrogen peroxide.
  • the hair is first dyed black through formation of melanin and then partially bleached to brown through destruction of part of the melanin.
  • A. clear disadvantage is the waste of DHI, which is supplied at the beginning. This is important, because DHI is an expensive raw material, and will control the price of the final product.
  • a second disadvantage is the fact that uneven and unpredictable results are often obtained due to the heterogeneity of living hair and the difference in its affinities for the dye, which vary from one person to another.
  • a third disadvantage is the likelihood of oxidative damage to the keratin of the hair as a result of the use of a product, containing peroxide - noticeable in a coarse feel of the hair.
  • hydrogen peroxide is normally used under alkaline conditions, with ammonia or an amine as the alkaline reagent. These alkaline reagents impart strong odors to the hair dyeing compositions and are unacceptable to many users.
  • a fourth disadvantage is that peroxide attacks and partly destroys the natural hair pigment. This weakens the hair and changes its feel and appearance.
  • Another object of the invention to provide a method to dye hair to a dark brown shade without using hydrogen peroxide.
  • sodium chlorite gives the darkest coloration on hair, and provides the most economic use of the DHI.
  • US 2,944,869 teaches dyeing of hair with o-diphenols and an oxidant, selected from ammonium and alkali metal iodates, periodates or persulfates.
  • an oxidant selected from ammonium and alkali metal iodates, periodates or persulfates.
  • these oxidants when used in a one-step treatment with DHI, give only weak colors on hair, since most of the DHI is oxidized and polymerized in solution, before it can penetrate the hair.
  • the art has long sought a suitable oxidizing agent which can be employed without the problems discussed above. More specifically, the art has sought dye compositions which will produce melanin in hair and give the hair a desirable color, with lasting wear qualities, in shorter periods of time, while avoiding the use of hydrogen peroxide and its resulting oxidative and bleaching damage to the hair.
  • Oxidative hair dyeing compositions and methods for their use have now been discovered which avoid many of the problems of prior art compositions.
  • These novel compositions are characterized by the use of sodium chlorite as the oxidizing agent.
  • the use of sodium chlorite, with 5,6-dihydroxyindoline, DHI or selected analogs, homologs or derivatives thereof, or with these compounds together with oxidizable primary intermediates and couplers, or together with DHICA or its lower alkyl esters, for example methyl to hexyl esters including straight chain and branched chain alkyl esters has not been specifically taught or suggested by any of the above citations nor, so far as the inventors are aware, by any other prior art.
  • DHI and DHI derivatives, analogs and homologs which may be employed in the practice of this invention include melanin forming compounds represented by the formula:
  • R represents hydrogen, alkyl, hydroxyalkyl, aminoalkyl, an alkyl group containing up to eight carbon atoms; aryl or substituted aryl containing up to three reaction inert substituents; R. represents hyrogen or alkyl containing up to six carbon atoms; and mixtures of said compounds.
  • the compound 5,6-dihydroxyindoline is also useful in this invention because under the conditions employed, it is oxidized to dopaminochrome which rearranges to DHI. The DHI then converts to melanin in accordance with the invention.
  • N-substituted compounds of the present invention are those of structure I where the N- substituent, R, is hydrogen, alkyl, hydroxyalkyl, aminoalkyl, containing 1 to about 8 carbon atoms in the moiety or a substituted or unsubstituted aryl wherein aryl substituents are reaction inert substituents such as OH, NH,, alkyl, alkoxyl, or N0 2 «
  • aryl substituents are reaction inert substituents such as OH, NH,, alkyl, alkoxyl, or N0 2 «
  • the most preferred compound is DHI.
  • DHI the invention will hereinafter be described principally with reference to DHI, but it should be remembered that the invention is applicable to all of the compounds within the scope of the above generic formula and their equivalents.
  • the various compounds may be used alone or in numerous mixtures, including mixtures with other oxidative dyes or with DHICA or its lower alkyl esters, to achieve a variety of
  • sodium chlorite imparts a dark brown color of natural appearance to the hair at relatively low concentrations of DHI and without the use of ammonia or other amines.
  • a further surprising aspect of the invention is the finding that DHICA and its lower alkyl esters or oxidizable primary intermediates and couplers can be employed in association with sodium chlorite and DHI to achieve a wider variety of tonalities in the treated hair.
  • compositions and methods of the invention there are many advantages to the compositions and methods of the invention. These include:
  • the dyeing procedure is simple (one-step) and fast.
  • the actual coloring of the hair can be performed at a pH which is at, or close to, neutrality.
  • the odor may be markedly reduced because ammonia or amines are omitted from the compositions.
  • compositions of this invention as applied to human hair comprise an aqueous vehicle which may contain a water miscible solvent, such as a lower alkanol, typically ethanol or isopropanol to aid solubility, together with DHI, or other compound(s) of the class defined above.
  • a water miscible solvent such as a lower alkanol, typically ethanol or isopropanol to aid solubility
  • Other compositions of the invention may contain DHI and/or a derivative, analog or ho olog together with DHICA or lower alkyl ester, or a primary intermediate/coupler combination. Of course, if such combination is employed, it may contain more than one intermediate or coupler to achieve a variety of shades.
  • a typical aqueous composition of the invention as applied to the hair may contain from about 0.1% to 3%, preferably 0.3% to 1.5% DHI or DHI analog, homolog or derivative, and from about 0.1% to 5%, preferably 0.5% to 4% of sodium chlorite. It is generally preferred to employ lower concentrations of the oxidizing agent when the concentration of DHI utilized is at the low end of the range.
  • the pH is normally from about 7 to 9, but some variation is acceptable.
  • the concentration of the DHI in the composition as applied to the hair is from about 0.1 to 2%. It was also noted above that DHI is rather unstable and subject to air oxidation. It is therefore normally packaged for commercial use in the form of DAI in a slightly alkaline solution, under conditions that substantially exclude air. On storage, under alkaline conditions, the DAI hydrolyzes to form DHI.
  • the molecular weight of DHI is about 60% lower than the molecular weight of DAI. Accordingly, the concentration of DAI in the original package will be higher than the ⁇ 5 concentration of DHI in the package as ready for use.
  • reactants oxidizable primary intermediates and couplers
  • the amounts of reactants will be about the same as utilized in conventional oxidant compositions.
  • the amounts which will be tinctorially effective will vary with the selected reactants, as is well known in the art. The skilled artisan will have no difficulty in selecting the reactants and the amounts to be employed. Generally each reactant will be present in an amount of from about 0.01 to 2%, preferably 0.01 to 0.5%.
  • DHICA or a lower alkyl ester of DHICA is employed in a formulation of the invention, the amount employed will typically be from about 0.1 to 1%.
  • a product of the invention may comprise a package containing two separate units of / ⁇ aqueous compositions, one containing the oxidant, the other containing DHI and, if employed, a primary intermediate and a coupler.
  • package* is used in the widest possible sense. It includes retail packages such as might be sold to an individual consumer with both compositions in the same box or other container. It includes also separate compositions in large amounts, such as might be sold to a beauty salon, whether or not the separate compositions are sold in the same container and are intended to be used together.
  • compositions of this invention are particularly adapted for co-dispensing from a compartmentalized package, such as the containers described in U.S. Pat. Nos. 3,241,722 and 4,103,772, the disclosures of which are incorporated herein by reference.
  • a compartmentalized package such as the containers described in U.S. Pat. Nos. 3,241,722 and 4,103,772, the disclosures of which are incorporated herein by reference.
  • the reactants are normally sealed in one compartment of the container and the hydrogen peroxide in another, and the container is constructed with means for mixing the separate ingredients in the container so that the resulting composition exits the container after such mixing.
  • There are two procedures for mixing which are normally employed.
  • One utilizes an aerosol package and valve adapted so that the compositions in the compartments mix as they pass through the valve.
  • the partition between the compartments is frangible and the container is formed with a mechanism which permits the partition to be pierced, or otherwise broken, so that the compositions mix prior to dispensing.
  • the resulting mixed composition can be dispensed under aerosol pressure, by simple pouring or by any other convenient method.
  • Couplers resorcinol m-aminophenol
  • compositions of the invention are preferably liquid solutions, but they may be in the form of emulsions, suspensions, lotions, or gels.
  • Surface active agents employed in the dyeing compositions of this invention can be amphoteric, anionic, nonionic or cationic.
  • surface active agents there can be mentioned: higher alkylbenzene sulfonates: alkylnaphthalen-sulfonates: sulfonated esters of alcohols and polybasic acids; taurates; fatty alcohol sulfates; sulfates of branched chain or secondary alcohols; alkyldimethyl-benzylammonium chlorides, salts of fatty acids or fatty acid mixtures; N-oxyalkylated fatty acid alkanolamides, and the like.
  • a thickening agent may also be incorporated in the dyeing composition of this invention which may be one or several of those commonly used in hair dyeing. These are exemplified by such products as sodium alginate or gum arabic, or cellulose derivatives, such as methylcellulose e.g.. Methocel 60 HG, or the sodium salt of carboxymethylcellulose, or hydroxyethylcellulose, e.g., Cellosize QP-40 or acrylic polymers, such as polyacrylic acid sodium salt, or inorganic thickeners, such as bentonite.
  • the quantity of this thickening agent can also vary over a wide range, even as high as 20%. Ordinarily it will range from about 0.5 to 5% by weight of the composition.
  • the viscosity of the composition may vary from about 1 cps to about 100,000 cps. For a typical lotion formulation, composition viscosity is from about 100 cps to about 10,000 cps.
  • antioxidants may also be useful to incorporate an antioxidant in the present dye compositions.
  • a variety of antioxidants are known in the prior art which would be useful for this purpose. Among these mention may be made of the inorganic sulfites, e.g., sodium sulfite, thioglycollic acid and other mercaptans, butylated hydroxytoluene, sodium dithionite, various forms of ascorbic acid and their derivatives, e.g., sodium ascorbate, erythorbic acid, ascorbyl palmitate, ascorbyl laurate, etc.
  • the quantity of antioxidant used can vary appreciably. However, the concentration will, in general, be up to about 1%, typically 0.001 to 1% by weight.
  • the dyeing compositions of this invention are preferably aqueous compositions.
  • aqueous composition is used herein in its usual generic sense as embracing any water-containing composition useful for the present purposes. This includes true solutions of cA2- the dye components aqueous medium, either alone or in conjunction with other materials, which are also dissolved or dispersed in the aqueous medium.
  • aqueous composition also encompasses any mixture of the chlorite and the dye forming reactants with the aqueous medium either alone or together with other ingredients.
  • the various components may be colloidally dispersed in the medium or may merely be intimately mixed therein.
  • the aqueous medium may comprise water or water and an additonal or auxiliary solvent.
  • Typical auxiliary solvents which may be used to enhance the solubility of the components include ethanol, carbitol, isopropanol, propylene glycol, ethylene glycol, diethylene glycol, diethylene glycol monoethyl ether, glycerine, etc.
  • aqueous dyeing compositions of this invention can be prepared by conventional methods used in the hair dyeing art. Thus, they can be prepared by dissolving or suspending the components in the selected media with adequate mixing. Preparation may take place at ambient temperatures, i.e., 20° to 35°C, but solubility and rate of preparation can be enhanced utilizing elevated temperatures, for example 40° to 100 C. 3
  • a suitable 3,4-dihydroxy-N-substituted phenethylamine material is converted by oxidative cyclization followed by chemical reduction to the N-su stituted- dihydroxyindole as per the method for preparation of N- methyl-5,6-dihydroxyindoles from epinephrine described by G.L. Mattok and R.A. Heacock in the Canadian Journal of Chemistry, Volume 42, p.284 (1964).
  • N-isopropyl-3, -dihydroxyphenethylamine (II) can be oxidized by an alkaline ferricyanide solution folllowed by reduction with ascorbic acid to give N-isopropyl-5,6-dihydroxyindole (III):
  • N- (4-aminobutyl) -5-6-dihydroxyindole (V) can be obtained from 3 , 4-dihydroxy-N- (4-nitrobutyl) - phenethylamine (IV) :
  • tristimulus values in the examples are standard Hunter chromacity values obtained by procedures well known to those skilled in the art.
  • the values recorded manifest the ability of the compositions of the invention to be usefully employed in hair coloring processes.
  • L is a measure of lightness and darkness that is, the depth of the color of the hair tress. The lower the value of L the darker the color.
  • a decrease in the value of L indicates a darkening of the hair tress.
  • a lowering of the value of L shows deposition of hair dye on the tress.
  • the a value is a measure of the greenness or redness of the hair's color. As the a value increases, the hair has a more prominent red tonality. A lowering in the a ⁇ £? value results in greener shades.
  • the b value is a measure of the yellow and blue color. Higher b values indicate a more yellow hue in the hair.
  • a DHI composition was prepared containing 1.85 parts by weight of DHI, 0.2 parts by weight thioglycolic acid (TGA -an antioxidant) and 78 parts by weight of water adjusted to pH 6.5 with hydrochloric acid. This solution was employed as a standard solution to determine the efficacy of a number of oxidizing agents including those reported in United States Patent 3,236,734.
  • the dyeing conditions (concentrations, dyeing time, pH etc.) are chosen such that the experimental conditions of US 3,236,734 are reproduced as closely as possible :
  • the concentration of DHI is equivalent, on a molar basis to the concentration of the hydrochloride of 2,4-dihydroxy phenylamine (Example 19 of US 3,236,734) and the concentration of the oxidants, sodium iodate, potassium persulfate, sodium perborate, is as described in this example.
  • Sodium bromate and sodium chlorate (listed in the patent without specification of conditions) were used at equimolar concentration as sodium iodate.
  • Perborate affords peroxide in aqueous solution. It is equivalent to aqueous peroxide itself - or to other peroxide sources, such as percarbonate, urea peroxide et cetera.
  • This example was conducted to show the unexpected superiority of sodium chlorite as an oxidant compared with hydrogen peroxide or other sources of peroxide, such as perborate.
  • Formulations were prepared, which contained DHI at a lower concentration than in Example 1 (DHI concentration 0.5% after mixing with oxidant) . This would be a preferred concentration for a commercial product, since DHI is an expensive raw material.
  • the formulations contain different alkaline agents to adjust the pH to the desired value. This is summarized in Table 3.
  • Entries 1 - 5 demonstrate, that, in contrast to sodium chlorite, peroxide, or its substantial equivalent perborate are only efficient as oxidants at alkaline pH.
  • Entry 11 illustrates the use of sodium chlorite.
  • the data demonstrate, that with peroxide as oxidant, the efficacy of sodium chlorite can be approached (but still not matched) only at high pH and high ammonia concentrations both of which are unacceptable because of the strong odor of ammonia and the likelihood of hair damage at the high pH.
  • Only sodium chlorite imparts a deep brown color at low pH, without ammonia, from solutions containing relatively low concentrations of DHI.
  • compositions were prepared: (as described in US 3,194,734)
  • Nonyl-Nonoxynol 49 was used instead of "Cemulsol 132", due to the unavailability of this component.
  • Cemulsol 132 is a non-ionogen condensation product of ethylene oxid and a naphthol compound.
  • Nonyl-Nonoxynol 49 is a non-ionogen condensation product of ethylene oxide and a benzene compound. Thi substitution has no effect on the described dyeing results.
  • the oxidant was added immediately before use t the formulation (ambient temperature) , applied to hair and left- f 20 minutes. The hair was rinsed with water, shampooed and dried. Hunter Tristimulus values were measured.
  • Tonality An example of Hunter Tristimulus values of natural dark and medium brown hair is the following:

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Cosmetics (AREA)
EP93910638A 1992-04-29 1993-04-12 Compositions de teinture pour les cheveux, composees de 5,6-dihydroxyindole et d'un oxydant a base de chlorite, et procedes de teinture a l'aide de ces compositions. Ceased EP0637955A4 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US87587492A 1992-04-29 1992-04-29
US875874 1992-04-29
US13441 1993-02-04
US08/013,441 US5413612A (en) 1992-04-29 1993-02-04 Composition and method for dyeing hair with indolic compounds in the presence of a chlorite oxidant
PCT/US1993/003630 WO1993021898A1 (fr) 1992-04-29 1993-04-12 Compositions de teinture pour les cheveux, composees de 5,6-dihydroxyindole et d'un oxydant a base de chlorite, et procedes de teinture a l'aide de ces compositions

Publications (2)

Publication Number Publication Date
EP0637955A1 EP0637955A1 (fr) 1995-02-15
EP0637955A4 true EP0637955A4 (fr) 1995-11-08

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP93910638A Ceased EP0637955A4 (fr) 1992-04-29 1993-04-12 Compositions de teinture pour les cheveux, composees de 5,6-dihydroxyindole et d'un oxydant a base de chlorite, et procedes de teinture a l'aide de ces compositions.

Country Status (8)

Country Link
EP (1) EP0637955A4 (fr)
JP (1) JPH07506359A (fr)
CN (1) CN1081874A (fr)
AU (1) AU4105993A (fr)
BR (1) BR9306301A (fr)
CA (1) CA2134461A1 (fr)
NZ (1) NZ247492A (fr)
WO (1) WO1993021898A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2751533B1 (fr) 1996-07-23 2003-08-15 Oreal Composition de teinture d'oxydation pour fibres keratiniques comprenant un polymere amphiphile non-ionique
FR2753093B1 (fr) 1996-09-06 1998-10-16 Oreal Composition de teinture d'oxydation pour fibres keratiniques comprenant un polymere amphiphile anionique
AU744697B2 (en) * 1997-05-02 2002-02-28 Rohm And Haas Company Hair dye compositions and method of thickening the same
DE19732975A1 (de) * 1997-07-31 1999-02-04 Henkel Kgaa Färbemittel
JP4955920B2 (ja) * 2004-12-08 2012-06-20 花王株式会社 染毛剤組成物
US7821580B2 (en) * 2006-08-15 2010-10-26 Lsi Corporation Contour free point operation for video skin tone correction
EP3173098A1 (fr) 2015-11-27 2017-05-31 Assistance Publique-Hopitaux De Paris Compositions immunostimulantes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2213169A (en) * 1987-12-30 1989-08-09 Oreal Dyeing keratinous fibres with an indole derivative and a direct nitro dye
EP0425345A1 (fr) * 1989-10-20 1991-05-02 L'oreal Procédés de teinture des fibres kératiniques avec des amino indoles, compositions et dispositifs de mise en oeuvre
US5073174A (en) * 1989-07-21 1991-12-17 L'oreal Dyeing process employing indole dyes and oxidation dye precursors and dyeing agents employed
WO1993013743A1 (fr) * 1992-01-16 1993-07-22 L'oreal Produit a base de particules minerales colorees comportant un pigment melanique, son procede de preparation et son utilisation en cosmetique

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4776857A (en) * 1986-11-21 1988-10-11 Repligen Corporation Use of hydroxylated indoles as dye precursors
US5032138A (en) * 1989-05-23 1991-07-16 Clairol Incorporated Chlorites as oxidants in hair coloring

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2213169A (en) * 1987-12-30 1989-08-09 Oreal Dyeing keratinous fibres with an indole derivative and a direct nitro dye
US5073174A (en) * 1989-07-21 1991-12-17 L'oreal Dyeing process employing indole dyes and oxidation dye precursors and dyeing agents employed
EP0425345A1 (fr) * 1989-10-20 1991-05-02 L'oreal Procédés de teinture des fibres kératiniques avec des amino indoles, compositions et dispositifs de mise en oeuvre
WO1993013743A1 (fr) * 1992-01-16 1993-07-22 L'oreal Produit a base de particules minerales colorees comportant un pigment melanique, son procede de preparation et son utilisation en cosmetique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9321898A1 *

Also Published As

Publication number Publication date
NZ247492A (en) 1995-04-27
AU4105993A (en) 1993-11-29
BR9306301A (pt) 1998-06-30
WO1993021898A1 (fr) 1993-11-11
CA2134461A1 (fr) 1993-11-11
CN1081874A (zh) 1994-02-16
EP0637955A1 (fr) 1995-02-15
JPH07506359A (ja) 1995-07-13

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