US3893803A - Hair dyeing premixes containing peroxidase enzymes stabilized with heme complexing agents - Google Patents

Hair dyeing premixes containing peroxidase enzymes stabilized with heme complexing agents Download PDF

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US3893803A
US3893803A US296465A US29646572A US3893803A US 3893803 A US3893803 A US 3893803A US 296465 A US296465 A US 296465A US 29646572 A US29646572 A US 29646572A US 3893803 A US3893803 A US 3893803A
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peroxidase
group
enzyme
oxidation dye
dye precursor
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Emil Thomas Kaiser
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
    • 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
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
    • A61K8/66—Enzymes

Definitions

  • ABSTRACT Premixes for dyeing hair comprising a peroxidase enzyme, an aromatic oxidation dye precursor, an antioxidant, and a heme complexing agent. The premix is combined with hydrogen peroxide on the hair whereupon a dye is formed and the hair is colored.
  • the present invention relates to enzyme-activated hair dyeing premixes with improved stability.
  • Hair dyeing premixes containing a peroxidase enzyme, an aromatic oxidation dye precursor, and an anti oxidant such as sodium sulfite are known in the art. See, for example, West German Pat. No. 2,155,390 which issued in 1971.
  • solutions of such premixes have a shelf life of at most only a few days because the anti-oxidant which preserves the dye precursor also deactivates the enzyme.
  • hair dyeing premixes must have a shelf life longer than a few days in order to be commercially feasible, there is a need in the prior art for some means of stabilizing the enzyme against the anti-oxidant.
  • the present invention satisfies this need.
  • peroxidase has one ferriprotoporphyrin group per molecule and that certain substances will combine with B ferriprotoporphyrin to form complex compounds. It is also known that peroxidase reacts with hydrogen peroxide to give a series of complexes in consecutive reactions in each of which a substrate is oxidized to a free radical. Further, an article by I. Fridovich entitled The Stimulation of Horseradish Peroxidase by Nitrogenous Ligands in the Journal of Biological Chemistry, Vol. 238, No. 12, 1963, pp.
  • the present invention lies in the discovery that peroxidase enzymes in combination with certain nitrogenous ligands are stabilized against some anti-oxidizing agents without loss of enzymatic activity.
  • the present invention further lies in the discovery that a peroxidase enzyme-activated hair dyeing premix solution comprising peroxidase enzyme, at least one oxidation dye precursor and an anti-oxidant can be stabilized by certain nitrogenous ligands so that when combined with hydrogen peroxide on the hair after months of storage, the premix will be effective to form a dye and color the hair. Without the stabilizing effect of the nitrogenous ligand, the enzyme of the premix is deactivated in a few days by the reducing action of the anti-oxidant, resulting in an ineffective premix solution.
  • the peroxidase enzyme-activated hair dyeing premix of the present invention comprises:
  • A from about 0.005 ppm to about 500 ppm ofa peroxidase enzyme; B. from about 0.01 to about 1% of a nitrogenous 1igand; C. from about 0.001 to about 6% by weight of at least one aromatic compound which is an oxidation dye precursor;
  • the enzyme of the premix is stabilized against the reducing action of the anti-oxidant by the heme complexing agent, resulting in longer shelf life for the premix solution. It is intended idazole and 0.5% sodium dithionite. However, horseradish peroxidase retains only 0.7% of its original activity after 3 days in the presence of 0.5% sodium dithionite alone. Similarly, in Table II, horseradish peroxidase is stabilized against sodium sulfite by 0.1% benzimidazole.
  • the enzyme samples consisted of horseradish peroxidase enzyme with an R2 value of 114 in Table I and 1.1 in Table II, a pH 6, 0.1 M phosphate buffer and thn.- nitrogenous ligand and/or anti-ox1dant as shown in Tables I and II. Samples were stored at 80F. and yellow light was employed to prevent any photoinactivation.
  • Peroxidase enzymes suitable for use in the present invention are those which catalyze the oxidation of various materials (including the oxidation dye precursors herein) by hydrogen peroxide.
  • Peroxidase enzymes can be derived by known methods from a variety of plants, e.g., apples, apricots, barley, horseradish roots, beets, cabbage, carrots, corn, cotton garlic, grapefruit, mint. rhubarb, soybeans and spinach, and peroxidase enzymes can also be isolated from animal sources, e.g., bovine milk, or from bacterial sources, e.g., Acetobacter peroxidans.
  • NAD peroxidase which is derived, for example, from Staphylococcus faecalis
  • NADP peroxidase which is derived, for example, from casei
  • fatty acid peroxidase which is derived, for example, from peanuts
  • cytochrome peroxidase which is derived, for example, from bakers yeast
  • peroxidase which is derived, for example, from the horseradish root
  • iodinase which is derived, for example, from thyroid gland tissue
  • glutathione peroxidase which is derived, for example, from liver and blood.
  • NAD peroxidase (1.11.1.1), NADP peroxidase (1.11.1.2), fatty acid peroxidase (1.11.1.3), cytochrome peroxidase (1.11.1.5), peroxidase (1.11.1.7), iodinase (1.11.1.8) and glutathione peroxidase (1.11.1.9).
  • the preferred peroxidase enzyme is the one called horseradish peroxidase. It has the classification number 1.11.1.7 and is sometimes simply called peroxidase. It is the most readily available of all the peroxidases.
  • the peroxidase enzymes herein can be used in their pure crystalline form, which is obtained by isolating the enzymes from other materials present during their preparation, or they can be used in a diluted form where the enzyme is present in a composition along these materials and/or added inert diluents.
  • enzyme preparations normally contain the enzyme in combination with inert diluent and carrier materials such as carbohydrates, agglutinating proteins, inorganic salts such as sodium sulfate, calcium sulfate, and the like.
  • the enzyme constitutes a minor component and comprises from about 1 to about 50% by weight of the preparation. The remaining 50 to 99% is comprised of the hereinbefore described diluents and carriers.
  • the commercially available enzyme-containing preparations are preferred as sources of enzyme herein as they are more readily available than the pure crystalline enzyme and provide known, pre-determined and desirable levels of enzyme activity.
  • the peroxidase enzyme is used at concentrations of from about 0.005
  • the oxidation dye precursors which are used in the compositions and processes herein include aromatic diamines, various substituted phenols, amino phenols and derivatives of these aromatic compounds (e.g., N- substituted derivatives of the amines and ethers of the phenols).
  • the oxidation dye precursors useful herein can be classified as primary oxidation dye precursors and secondary oxidation dye precursors, as detailed hereinafter.
  • oxidation hair dye precursors include those monomeric aromatic compounds which, on oxidation, form oligomers or polymers having extended conjugated systems of electrons in their molecular structure. Because ofthe new electronic structure, the resultant oligomers and polymers exhibit a shift in their electronic spectra to the visible range and appear colored.
  • oxidation dye precursors capable of forming colored polymers include materials such as various aromatic amines having a single functional group and which, on oxidation, form a series of conjugated imines and quinoid dimers, trimers, etc. ranging in color from green to black.
  • Compounds, such as p-phenylenediamine, which have two functional groups are capable of oxidative polymerization to yield higher molecular weight colored materials having extended conjugated electron systems, i.e., the so-called Bandrowskis Base type of dye compound.
  • Color modifiers such as those detailed hereinafter as secondary oxidation dye precursors, can optionally be used in conjunction with the primary oxidation dye precursors herein and are thought to interpose themselves in the colored polymers during their formation and to cause shifts in the electronic spectra thereof, thereby resulting in changes in color and/or color intensity.
  • peroxidase enzymes disclosed herein are suitable for use (in conjunction with a peroxide source, e.g., H 0 as detailed herein) with all manner of primary and secondary oxidation dye precursors.
  • oxidation dye precursors suitable for use herein are found in Sagarin, Cosmetic Science and Technology, lnterscience, pages 504 and 508, and the dye precursors detailed below are only by way of example and are not intended to limit the compositions and processes herein. Additional oxidation dye precursors useful herein are described in French application Pat. No. 1,318,072 and Fr. Addition 90,633, Jan. 19, 1968, to Schwarzkopf; British Pat. No. 1,127,080, Sept. 1 l, 1968, to Kalopissis and Bugaut; and Netherlands Application No. 6,609,833, Feb. 6, 1967, to Therachemie Chemisch Therapeutician G.m.b.l-l., incorporated herein by reference. Pyridine, quinoline, isoquinoline oxidation dye precursors such as those disclosed by Bergwein, Reichst., Aromen, Koerperpracticm. 17 (14) 136-8 (1967), are also suitable herein.
  • the oxidation dye precursors.which are used in the process of the present invention can be divided into two classes, primary and secondary.
  • the primary oxidation dye precursors are essential to the practice of the invention and include those aromatic diamines, polyhydric phenols. aminophenols and derivatives of these aromatic compounds (e.g., N-substituted derivatives of the amines. and ethers of the phenols) which produce color formation in the following test, which is performed at room temperature (about 18 to 28C.).
  • aromatic diamines, polyhydric phenols, aminophenols, and derivatives thereof, described above as primary oxidation dye precursors can also have additional substituents on the aromatic ring, e.g., halogen, aldehyde. carboxylic acid, nitro, sulfonic acid and substituted and unsubstituted hydrocarbon groups, as well as additional substituents on the amino nitrogen, and on the phenolic oxygen, e.g., substituted and unsubstituted alkyl and aryl groups.
  • aromatic diamines and derivatives thereof aminophenols and derivatives thereof and polyhydric phenols and derivatives thereof, respectively, are compounds having the general formulas (A), (B) and (C) below:
  • X is hydrogen, halogen, (etg. fluorine, chlorine, bromine or iodine), nitro, amino, hydroxyl,
  • aromatic amines and phenolic compounds, and derivatives thereof, including aromatic diamines and polyhydric phenols of the types described by formulas (A), (B) and (C) above, but which are found by the above test not to be suitable primary oxidation dye precursors, are suitable as secondary dye precursors if they are capable of modifying the color, shade or intensity of color produced by primary oxidation dye precursors in the following test, which is conducted at room temperature (about 18 to 28C.).
  • aromatic amines and phenols and derivatives described above as secondary oxidation dye precursors can also have additional substituents on the aromatic ring, e. g., halogen, aldehyde, carboxylic acid, nitro, sulfonyl and substituted and unsubstituted hydrocarbon groups, as well as additional substituents on the amino nitrogen, or phenolic oxygen, e.g., substituted and unsubstituted alkyl and aryl groups.
  • Rl N R 2 wherein Z is hydrogen, C to C alkyl, halogen (e.g., fluorine, chlorine, bromine or iodine) nitro,
  • the choice of a single oxidation dye precursor or of a particular combination of oxidation dye precursors will be determined by the color, shade and intensity of coloration which is desired.
  • the total concentration of oxidation dye precursor in the coloring solution can be from about 0.001% to about 6% by weight and is preferably from about 0.01% to about 2.0% by weight.
  • the heme complexing agents contemplated by the present invention are characterized by an unshared pair of electrons on a nitrogen atom. It is believed that the nitrogen atom forms a complex with the ferric iron of the heme group of the peroxidase enzyme resulting in protection of the ferric iron from the reducing action of the anti-oxidant. Peroxidase enzyme is inactivated,
  • Preferred heme complexing agents are imidazole and benzimidazole'but many other heme complexing agents are effective to stabilize peroxidase enzymes in accordance with the present invention.
  • Examples of other effective heme complexing agents are pyridine and its derivatives, ammonia, where the substituent is an alkyl group of from 1 to 3 carbon atoms, substituted imidazoles where the substituent is an alkyl group of from l,to 3 carbon atoms, benzotriazole, substituted benzotriazoles, where the substituent is an alkyl group of from 1 to 3 carbon atoms, 1,2,3-triazole, 1,2,4-triazole, pyrazole, Z-isoimidazole, pyrrole, and compounds of the general formula wherein R,, R and R are the same or different from each other, are selected from the group consisting essentially of hydrogen, alkyl groups of from 1 to 3 carbon atoms, hydroxyalkyl groups of from 1 to 3 carbon atom
  • anti-oxidant agents contemplated by the present invention are those anti-oxidants which are more easily substituted benzimidazoles oxidized than the dye precursor but which will not displace the nitrogenous ligand which has formed a complex with the enzyme.
  • anti-oxidants of the present invention are sodium sulfite, sodium dithionite, thioglycolate, and ascorbic acid.
  • Preferred antioxidants are sodium sulfite and sodium dithionite.
  • a solution of this invention comprises from about 0.1% to about 1% by weight of an anti-oxidant compound.
  • Hair coloring products employing oxidation hair dyes are typically marketed in kit form, i.e., a package comprising an individually packaged oxidizing component and an individually packaged oxidation dyeing component.
  • the oxidizing component comprises an aqueous solution of from about 0.1% to about 6% by weight of hydrogen peroxide
  • the oxidation dyeing premix component comprises from about 0.001% to about 6% by weight of one or more primary oxidation dye precursors or one or more secondary oxidation dye precursors or a mixture thereof, from about 0.005 ppm to about 500 ppm of a heme peroxidase enzyme, from about 0.1% to about 1% by weight of an anti-oxidant selected from the group consisting essentially of sodium sulfite, sodium dithionite, thioglycolate and ascorbic acid, and from about 0.01% to about 1% by weight of a nitrogenous ligand.
  • the oxidizing component and the oxidation dyeing premix component are mixed by the user on the hair
  • EXAMPLE I This example illustrates the coloring of human hair with a composition of the present invention. All percentages are by weight. 60 grams of a dilute hydrogen peroxide solution buffered to pH 6 are prepared by dissolving 2 grams of an aqueous 30% hydrogen peroxide solution in 58 grams of an aqueous NaH PO /Na HPO buffer solution, which is 0.1 M in phosphate.
  • a dye base premix composition of the invention consisting of 1% p-phenylenediamine, 0.005% horseradish peroxidase, 0.25% sodium sulfite, 0.1% benzimidazole, 5% ethanol (solvent and wetting agent), 0.2% Dow Corning EF-l3574A (a cationic polysiloxane conditioner from the Dow Corning Company), Varion CDG (a coco betaine surfactant from the Northern Petrochemical Company), 1% JR-IL (a cationic cellulose derivative thickener from Union Carbide Company having the structure wherein R is a residue of an anhydrous glucose unit wherein y is an integer of 50 to 20,000 and wherein each R individually represents a substituent of the general formula wherein m is an integer ofO to 10, n is an integer from 0 to 3, and p is an integer from 0 to 10.
  • n is from 0.35 to 0.45 and the sum of m p is from 1 to 2) and the balance water containing a pH 6 buffer as described above.
  • the premix composition is combined with hydrogen peroxide on the hair of a human female subject having naturally light brown hair by working it into a rich lather which remains on the hair and does not run down the neck and forehead. After working the mixture for 1 minute (to insure uniform application to all of the hair), the foamy lather is allowed to remain on the hair an additional 3 minutes. The subject then rinses her hair thoroughly with tap water and allows it to dry. It is observed that the hair has changed from its original light brown color to a medium brown shade.
  • the horseradish peroxidase is replaced by an equivalent amount of NAD peroxidase, NADP peroxidase, fatty acid peroxidase, soybean hull peroxidase, cytochrome peroxidase, iodinase, and glutathione peroxidase, respectively, and equivalent results are secured.
  • the p-phenylenediamine is replaced by an equivalent amount of ophenylenediamine, 2,4-toluenediamine, N-phenyl-pphenylenediamine, N,N-dimethyLp-phenylenediamine, 4-nitro-o-phenylenediamine, o-hydroxyphenol, phydroxyphenol, 3,4-dihydroxybenzaldehyde, 2- methoxy-4-(l-propenyl)phenol, 4-methoxyphenol, pmethoxyaniline, N,N-dimethyl-p-phenylenediamine, 4-hydroxy-3-methoxycinnamic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2-nitri-paminophenol, 2-amino-l-phenol-4-sulfonic acid, and mixtures thereof, respectively, and shampoo-fast hair colors are secured.
  • benzimidazole is replaced by an equivalent amount of imidazole, pyridine, ammonia, benzotriazole, 1,2,3-triazole, 1,2,4-triazole, pyrazole, 2-isoimidazole, and pyrrole and equivalent results are obtained.
  • EXAMPLE II 60 grams of a dilute hydrogen peroxide solution buffered to pH 6 are prepared as in Example I. 60 grams of a dye base premix composition of the invention are prepared consisting of 1% nitro-p-phenylenediamine, 1% p-aminophenol, 0.015% soybean hull peroxidase, 0.1% imidazole, 10% Miranol S2M (a dicarboxylic capric imidazoline which is an amphoteric surfactant from the Miranol Chemical Company having the structure) 0.5% sodium sulfate, and 2% Klucel G (a hydroxypropyl cellulose thickener from Hercules, Inc.
  • a dye base premix composition of the invention consisting of 1% nitro-p-phenylenediamine, 1% p-aminophenol, 0.015% soybean hull peroxidase, 0.1% imidazole, 10% Miranol S2M (a dicarboxylic capric imidazoline which is an amphoter
  • Example I having the structure) OH
  • the premix is combined with hydrogen peroxide on the hair of a human female subject having naturally light brown hair as in Example I. The subject then rinses her hair thoroughly with tap water and allows it to dry whereupon it is observed that the hair has changed from .its original color to an auburn color.
  • a premix solution for dyeing hair comprising:
  • a nitrogenous ligand which is a heme complexing agent selected from the group consisting of imidazole, benzimidazole, pyridine, ammonia, benzotriazole, 1,2,3- triazole. 1.2,4-triazole, pyrazole, 2-isoimidazole and pyrrole;
  • an anti-oxidant selected from the group consisting of sodium sulfite, sodium dithionite, thioglycolate and ascorbic acid;
  • E. balance. water said composition having a pH of from about 4 to about 10.
  • the peroxidase enzyme is selected from the group consisting of NAD peroxidase, fatty acid peroxidase. NADP peroxidase, cytochrome peroxidase. horseradish peroxidase, iodinase, glutathione peroxidase. and soybean hull peroxidase.
  • a premix for dyeing hair according to claim 1 wherein the anti-oxidant is selected from the group consisting of sodium sulfite and sodium dithionite.
  • N R R and R5 N R R wherein X is selected from the group consisting of hydrogen, halogen, nitro, amino, hydroxyl,
  • R R and R are each selected from the group consisting of hydrogen, C, to C alkyl and alkenyl and aryl, alkaryl, and aralkyl having 6 to 9 carbon atoms
  • R. is selected from the group consisting of hydrogen, alkyl and alkenyl groups having from 1 to 4 16 carbon atoms
  • Z is selected from the group consisting of hydrogen, C to C alkyl, halogen, nitro
  • M is hydrogen or an alkali or alkaline earth metal, ammonium or substituted ammonium wherein one or more hydrogens on the ammonium ion is replaced with a l to 3 carbon atom alkyl or hydroxyalkyl radical.
  • a hair dyeing composition comprising:
  • a nitrogenous ligand which is a heme complexing agent selected from the group consisting of imidazole, benzimidazole, pyridine, ammonia, benzotriazole, 1,2,3- triazole, 1,2,4-triazole, pyrazole, 2-isoimidazole and pyrrole;
  • an anti-oxidant selected from the group consisting of sodium sulfite, sodium dithionite, thioglycolate, and ascorbic acid;
  • balance water said composition having a pH of from about 4 to about 10.

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Cited By (43)

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FR2400359A1 (fr) * 1977-08-19 1979-03-16 Oreal Compositions tinctoriales a base de colorants directs contenant un acide (2,5-dihydroxyphenyl) carboxylique ou l'un de ses sels
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WO2000037032A1 (fr) * 1998-12-22 2000-06-29 Lion Corporation Compositions de coloration capillaire
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FR2794364A1 (fr) * 1999-06-01 2000-12-08 Oreal Composition de teinture d'oxydation des fibres keratiniques et procede de teinture mettant en oeuvre cette composition
US6231621B1 (en) * 1996-10-08 2001-05-15 Novozymes A/S Diaminobenzoic acid derivatives as dye precursors
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RU2174387C2 (ru) * 1997-10-03 2001-10-10 Л'Ореаль Окисляющая композиция и ее применение для окрашивания, придания новой постоянной формы или для обесцвечивания кератиновых волокон
FR2808680A1 (fr) * 2000-05-15 2001-11-16 Oreal Composition oxydante et utilisations pour la teinture, pour la deformation permanente ou pour la decoloration des fibres keratiniques
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WO2002096901A3 (de) * 2001-05-25 2003-03-13 Wella Ag 1,3-dihydroxybenzol-derivate und diese verbindungen enthaltende färbemittel
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US20040194233A1 (en) * 1997-10-03 2004-10-07 Mettrie Roland De La Oxidizing composition and uses for dyeing, for permanently reshaping or for bleaching keratin fibres
US20040200012A1 (en) * 1997-10-03 2004-10-14 L'oreal S.A. Oxidizing composition and uses for dyeing, for permanently reshaping or for bleaching keratin fibres
US20040244122A1 (en) * 1997-10-03 2004-12-09 L'oreal S.A. Oxidizing composition and uses for dyeing, for permanently reshaping or for bleaching keratin fibres
US20050150060A1 (en) * 1997-10-03 2005-07-14 L'oreal S.A. Oxidizing composition and uses for dyeing, for permanently reshaping or for bleaching keratin fibres
US20090260164A1 (en) * 1999-12-30 2009-10-22 L'oreal S.A. Compositions for oxidation dyeing keratin fibers comprising at least one thickening polymer comprising at least one fatty chain and at least one fatty alcohol chosen from monoglycerolated fatty alcohols and polyglycerolated fatty alcohols
US20140335038A1 (en) * 2011-12-12 2014-11-13 Conopco, Inc., D/B/A Unilever Method of strengthening hair fibres

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US4065255A (en) * 1975-06-26 1977-12-27 L'oreal 2-Methyl-5-N-hydroxyalkylaminophenol in an oxidation dye composition and method of using the same
US4213960A (en) * 1977-03-02 1980-07-22 L'oreal Cosmetic compositions for treating the hair
FR2400358A1 (fr) * 1977-08-19 1979-03-16 Oreal Compositions tinctoriales a base de colorants d'oxydation comprenant un acide (2,5-dihydroxyphenyl) alcanoique ou l'un de ses sels a titre d'antioxydant
FR2400359A1 (fr) * 1977-08-19 1979-03-16 Oreal Compositions tinctoriales a base de colorants directs contenant un acide (2,5-dihydroxyphenyl) carboxylique ou l'un de ses sels
US4840639A (en) * 1978-07-20 1989-06-20 Wella Aktiengesellschaft Agent for dyeing hair
EP0007537A1 (de) * 1978-07-20 1980-02-06 Wella Aktiengesellschaft Mittel zur Färbung von Haaren
WO1980000214A1 (en) * 1978-07-20 1980-02-21 Wella Ag Preparation for hair coloration
US4325704A (en) * 1979-08-24 1982-04-20 Henkel Kommanditgesellschaft Auf Aktien Hair dyes
US4391603A (en) * 1980-04-17 1983-07-05 L'oreal Hydroxyl derivatives of benzaldehyde for coloring keratin fibres in the absence of oxidizing agent
US4575377A (en) * 1982-09-10 1986-03-11 Henkel Kommanditgesellschaft Auf Aktien Oxidation hair dyes comprising resorcinol derivatives as coupling components
US4976742A (en) * 1985-07-08 1990-12-11 Henkel Kommanditgesellschaft Auf Aktien META-aminophenols useful as oxidation hair dye couplers
EP0226197A3 (de) * 1985-12-20 1988-03-09 Henkel Kommanditgesellschaft auf Aktien Haarfärbemittel mit direktziehenden Azomethinfarbstoffen
US5084067A (en) * 1988-03-03 1992-01-28 L'oreal 3-substituted para-amino phenols and their use as oxidation dye precursors in compositions for dyeing kerafinous fibers
US5364413A (en) * 1988-03-03 1994-11-15 L'oreal 3-substituted para-aminophenols, process for preparing them, their use for dyeing keratinous fibres and the intermediate compounds used in the preparation process
US5503640A (en) * 1988-03-03 1996-04-02 L'oreal 3-substituted para-aminophenols, process for preparing them, their use for dyeing keratinous fibres and the intermediate compounds used in the preparation process
US5047066A (en) * 1988-06-08 1991-09-10 Kao Corporation Dye composition for keratinous fibers containing a 2-substituted 4-aminophenol compound as a developer, and a coupling substance
US5560750A (en) * 1990-05-08 1996-10-01 Preemptive Advertising, Inc. Compositions and methods for altering the color of hair
EP0548620A1 (de) * 1991-12-20 1993-06-30 GOLDWELL GmbH Verfahren zum oxidativen Färben von menschlichen Haaren und Mittel zur Durchführung dieses Verfahrens
US5538517A (en) * 1992-06-25 1996-07-23 L'oreal Method for dyeing keratin fibers with indole or indoline derivatives, hydrogen peroxide and a peroxidase
WO1994012620A1 (en) * 1992-12-01 1994-06-09 Novo Nordisk A/S Enhancement of enzyme reactions
WO1994012621A1 (en) * 1992-12-01 1994-06-09 Novo Nordisk Enhancement of enzyme reactions
WO1994012619A1 (en) * 1992-12-01 1994-06-09 Novo Nordisk A/S Enhancement of enzyme reactions
US5700769A (en) * 1992-12-01 1997-12-23 Novo Nordisk A/S Enhancement of enzyme reactions
US5965510A (en) * 1992-12-01 1999-10-12 Novo Nordisk A/S Enhancement of enzyme reactions
US5391488A (en) * 1993-04-19 1995-02-21 Enzymol International, Inc. Biocatalytic oxidation of a reactive primary alcohol using soybean peroxidase
US5972042A (en) * 1995-12-22 1999-10-26 Novo Nordisk A/S Method for dyeing a material with a dyeing system which contains an enzymatic oxidizing agent
EP0795313A3 (de) * 1996-03-16 1997-10-22 Wella Aktiengesellschaft Mittel und Verfahren zum oxidativen Färben von Keratinfasern
US5849041A (en) * 1996-03-16 1998-12-15 Wella Aktiengesellschaft Oxidation hair dye composition and method of dyeing hair using same
US5925148A (en) * 1996-08-02 1999-07-20 Novo Nordisk A/S Enzymatic method for overdyeing warp dyed denim textiles
US6231621B1 (en) * 1996-10-08 2001-05-15 Novozymes A/S Diaminobenzoic acid derivatives as dye precursors
EP0946133A4 (en) * 1996-12-23 2001-08-29 Procter & Gamble HAIR COLORING AGENT
EP0952811A4 (en) * 1996-12-23 2001-08-29 Procter & Gamble COMPOSITIONS FOR HAIR COLORANTS
EP0951270A4 (en) * 1996-12-23 2001-08-29 Procter & Gamble COMPOSITIONS FOR HAIR COLORANTS
EP0957894A4 (en) * 1996-12-23 2001-08-29 Procter & Gamble HAIR COLORING AGENT
US20040194233A1 (en) * 1997-10-03 2004-10-07 Mettrie Roland De La Oxidizing composition and uses for dyeing, for permanently reshaping or for bleaching keratin fibres
US20050150060A1 (en) * 1997-10-03 2005-07-14 L'oreal S.A. Oxidizing composition and uses for dyeing, for permanently reshaping or for bleaching keratin fibres
US6241784B1 (en) 1997-10-03 2001-06-05 L'oreal S.A. Oxidizing composition and uses for dyeing, for permanently setting or bleaching keratin fibres
US20060080789A2 (en) * 1997-10-03 2006-04-20 L'oreal S.A. Oxidizing composition and uses for dyeing, for permanently reshaping or for bleaching keratin fibres
US20040244122A1 (en) * 1997-10-03 2004-12-09 L'oreal S.A. Oxidizing composition and uses for dyeing, for permanently reshaping or for bleaching keratin fibres
US20040200012A1 (en) * 1997-10-03 2004-10-14 L'oreal S.A. Oxidizing composition and uses for dyeing, for permanently reshaping or for bleaching keratin fibres
FR2769216A1 (fr) * 1997-10-03 1999-04-09 Oreal Composition oxydante et utilisations pour la teinture, pour la deformation permanente ou pour la decoloration des fibres keratiniques
RU2174387C2 (ru) * 1997-10-03 2001-10-10 Л'Ореаль Окисляющая композиция и ее применение для окрашивания, придания новой постоянной формы или для обесцвечивания кератиновых волокон
WO1999017721A1 (fr) * 1997-10-03 1999-04-15 L'oreal Composition oxydante et utilisations pour la teinture, pour la deformation permanente ou pour la decoloration des fibres keratiniques
US20040194232A1 (en) * 1997-10-03 2004-10-07 L'oreal S.A. Oxidizing composition and uses for dyeing, for permanently reshaping or for bleaching keratin fibers
WO2000037032A1 (fr) * 1998-12-22 2000-06-29 Lion Corporation Compositions de coloration capillaire
WO2000037031A1 (fr) * 1998-12-22 2000-06-29 Lion Corporation Compositions de coloration capillaire
FR2794364A1 (fr) * 1999-06-01 2000-12-08 Oreal Composition de teinture d'oxydation des fibres keratiniques et procede de teinture mettant en oeuvre cette composition
EP1062938A1 (fr) * 1999-06-01 2000-12-27 L'oreal Composition de teinture d'oxydation des fibres kératiniques et procédé de teinture
US6730133B1 (en) 1999-09-24 2004-05-04 L'oreal S.A. Compositions for oxidation dyeing of at least one keratinous fibre and dying processes using these compositions
US6695887B2 (en) * 1999-12-30 2004-02-24 L'oreal S.A. Compositions for oxidation dyeing keratin fibers comprising at least one fatty alcohol having more than twenty carbon atoms and at least one oxyalkylenated nonionic surfactant with an hlb greater than 5
US20090260164A1 (en) * 1999-12-30 2009-10-22 L'oreal S.A. Compositions for oxidation dyeing keratin fibers comprising at least one thickening polymer comprising at least one fatty chain and at least one fatty alcohol chosen from monoglycerolated fatty alcohols and polyglycerolated fatty alcohols
US7771492B2 (en) 1999-12-30 2010-08-10 L'oreal S.A. Compositions for oxidation dyeing keratin fibers comprising at least one thickening polymer comprising at least one fatty chain and at least one fatty alcohol chosen from monoglycerolated fatty alcohols and polyglycerolated fatty alcohols
FR2808680A1 (fr) * 2000-05-15 2001-11-16 Oreal Composition oxydante et utilisations pour la teinture, pour la deformation permanente ou pour la decoloration des fibres keratiniques
EP1157684A3 (fr) * 2000-05-15 2002-12-11 L'oreal Composition oxydante et utilisations pour la teinture, pour la déformation permanente ou pour la décoloration des fibres kératiniques
US20020163109A1 (en) * 2001-04-03 2002-11-07 Raytheon Company Conformal firing of ceramic radomes
US20040016063A1 (en) * 2001-05-25 2004-01-29 Laurent Chassot 1,3-Dihydroxybenzene derivatives and colorants containing said compounds
WO2002096901A3 (de) * 2001-05-25 2003-03-13 Wella Ag 1,3-dihydroxybenzol-derivate und diese verbindungen enthaltende färbemittel
US7125428B2 (en) 2001-05-25 2006-10-24 Wella Ag 1,3-Dihydroxybenzene derivatives and colorants containing said compounds
US20140335038A1 (en) * 2011-12-12 2014-11-13 Conopco, Inc., D/B/A Unilever Method of strengthening hair fibres

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