US3869454A - Novel diazamerocyanines and their use for dyeing keratinous fibers - Google Patents
Novel diazamerocyanines and their use for dyeing keratinous fibers Download PDFInfo
- Publication number
- US3869454A US3869454A US259689A US25968972A US3869454A US 3869454 A US3869454 A US 3869454A US 259689 A US259689 A US 259689A US 25968972 A US25968972 A US 25968972A US 3869454 A US3869454 A US 3869454A
- Authority
- US
- United States
- Prior art keywords
- hair
- dihydro
- methyl
- dye
- prepared
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/16—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms
- C09B23/162—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms only nitrogen atoms
- C09B23/166—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms only nitrogen atoms containing two or more nitrogen atoms
-
- 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
- A61K8/413—Indoanilines; Indophenol; Indoamines
-
- 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
-
- 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
- A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
-
- 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
- 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
- oxidation dyes or bases associated with dyeing modifiers or couplers which can be aromatic metadiamines or metaaminophenols, or pyrazolones or diketones.
- an oxidizing agent as hydrogen peroxide is added to the mixture of bases and couplers selected which has been previously alkalized.
- R is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, or R and R,,, taken together with the carbon atoms to which they are linked, form a benzene ring, a halogen-substituted benzene ring, a benzene ring substituted with lower alkyl having 14 carbon atoms, a benzene ring substituted with lower alkoxy having 14 carbon atoms or a nitrosubstituted benzene ring;
- B is selected from the group consisting of (i) a nitrogen-containing heterocycle different from the nitrogen containing heterocycle of A; (ii) a cycle of the formula wherein Y is a member selected from the group consisting of oxygen and wherein R and R each independently represent a member selected from the group consisting of hydrogen, lower alkyl having 1-4 carbon atoms and phenyl; and Z is an anion derived from
- the above-described hair dyeing compositions according to the present invention are aqueous solutions, to which most often have been added low molecular weight alcohols such as ethanol or isopropanol, or glycols such as propylene glycol or butylglycol, the alcohol or glycol facilitating the solution of the dye in the composition.
- alcohols such as ethanol or isopropanol
- glycols such as propylene glycol or butylglycol
- These solutions are easily prepared by dissolving one or more compounds of Formula I in water or in a water-alcohol mixture.
- the proportion of alcohol used is generally between and 70% by weight, while the proportion of glycol is generally between 1 and 6% by weight.
- the concentration of the dye or dyes of Formula I in the dyeing compositions according to the present invention can vary in broad limits, because of the great affinity of these compounds for keratinous fibers. This concentration is generally between about 0.001 and about 0.5% by weight and preferably between about 0.002 and about 2% by weight.
- the pH of the compositions according to the present invention is generally between about 2,5 and l0 and preferably between about 3 and 8.
- the pH is adjusted to the desired value by addition of an acid such as orthophosphoric acid, lactic acid or acetic acid or a base such as mono-, dior triethanolamine or ammonia.
- compositions according to the present invention can contain only one or more of the dyes of Formula I, in which case they make it possible to obtain on the hair shades rich in glints that go from yellow to blue, covering the light spectrum.
- the composition according to the invention can, however, contain other direct dyes, for example, azo or anthraquinone dyes, nitro dyes of the benzene series, indoanilines, indophenols or indamines.
- the hair-dyeing compositions according to the present invention can also contain various adjuvants and ingredients customarily used in capillary cosmetics, for example, wetting agents, dispersing agents, swelling agents, penetrating agents, thickeners, softeners or perfumes. They can also be packaged under pressure in aerosol bombs or containers, together with a conventional aerosol propellant such as dichlorodifluoromethane, trichloromonofluoromethane and their mixtures. Of course, other conventional aerosol propellants can be used.
- a conventional aerosol propellant such as dichlorodifluoromethane, trichloromonofluoromethane and their mixtures.
- other conventional aerosol propellants can be used.
- Dyeing of keratinous fibers, particularly human hair, with the dye compositions according to the invention can be performed in the usual way, by application at ambient temperature of the composition to the fibers to be dyed, the composition being left in contact for a period varying from 3 to 30 minutes. Following this application, the fibers are rinsed and, if desired, washed. Thereafter the treated fibers are dryed.
- the compounds of Formula I can be employed in the production of capillary setting lotions.
- These lotions comprise an aqueous dilute alcohol solution, at least one cosmetic resin and at least a compound of Formula I or a salt thereof as defined above.
- the setting lotions according to the invention generally contain from 20 to by weight of the total hairsetting lotion composition, of a low molecular weight alkanol such as ethanol or isopropanol and from i to 3% by weight of cosmetic resin.
- Representative cosmetic resins that can be employed in the hair-setting lotions of the present invention include, for instance, polyvinyl pyrrolidone having a molecular weight of 40,000-400,000, copolymer of crotonic acid and vinyl acetate, said copolymer having a molecular weight ranging from about 10,000 to 70,000, copolymer vinyl pyrrolidone and vinyl acetate, wherein the ratio of PVP to VA ranges between 50-70: 5030, said copolymer having a molecular weight ranging from about 30,000 to 200,000 and maleic anhydridebutylvinyl ether copolymers, a 1% solution of which is methylethyl ketone has a viscosity of 0.1-3.5 cps at 25C. These resins are used in a proportion of l to 3% by weight of the hair-setting lotion composition.
- the pH of the hair setting lotions according to the invention is generally between 3 and 8. As stated above, it is possible to regulate the pH to the desired value by using mono or di or triethanolamine and an acidifying agents, acetic acid or lactic acid.
- the setting lotions according to the invention can contain only the dyes of Formula I, in which case they constitute what is known as shading compositions.
- the hair-setting lotions of this invention can also contain other direct dyes such as anthraquinone dyes, nitro dyes of the benzene series and those mentioned above.
- the hair-setting lotions can also contain various ingredients usually'used in capillary cosmetics, for example, wetting agents, dispersing agents, swelling agents, penetrating agents, thickeners, softeners or perfumes, as mentioned above.
- the hair-setting lotions disclosed herein are used in the customary manner by applying at ambient temperature to wet hair that has been previously washed and rinsed, followed by rolling the hair up on curlers and drying of the hair.
- the dyes of Formula I can also be used in the production of hair lacquers.
- These lacquers contain in alcohol solution at least one cosmetic resin and at least a compound of Formula I.
- the alcohols suitable for the preparation of the hair lacquers according to the invention are low molecular weight alcohols, such as ethanol or isopropanol.
- resin there may be used one or more of polyvinyl pyrrolidone, copolymer of crotonic acid and. vinyl acetate, copolymer of vinyl pyrrolidone and vinyl acetate, copolymer of maleic anhydride and butylvinyl ether, all as described above.
- the amount of dye of Formula I ranges from about 0.00l to about 0.5% by weight and the amount of cosmetic resin used is between about 1 and 3% by weight.
- the hair lacquers of the present invention are conveniently packaged in pressurized containers or aerosol bombs of the type described above.
- the hair lacquers are conveniently applied directly to the hair, preferably in the form of a spray at ambient temperature.
- the present invention in the composition of matter aspect thereof, includes novel diazamerocyanines and salts thereof of the formula A N N B (1') wherein A is a nitrogen heterocycle as defined above and B is a residue corresponding to one of the following formulae:
- X represents an anion derived from an inorganic or organic acid
- R is selected from the group consisting of hydrogen or lower alkyl having 1-4 carbon atoms
- R is hydrogen, lower alkyl having 1-4 carbon atoms. lower alkyl having 14 carbon atoms substituted by an amine. lower alkyl having l-4 carbon atoms substituted by an amide, and
- W is selected from the group consisting of oxygen and sulfur. and R is selected from the group consisting of amino and lower alkyl of l-4 carbon atoms, R1, and R each independently represent a member selected from the group consisting of hydrogen and lower alkyl having 14 carbon atoms; Y represents a member selected from the group consisting of wherein R, and R each independently represent a member selected from the group consisting of hydrogen and lower alkyl having l-4 carbon atoms, and Z is an anion derived from an inorganic or organic acid. such as halide. perchlorate, fluoborate. acetate. bisullate and sulfate;
- R represents a member selected from the group consisting of hydrogen and wherein W represents a member selected from the group consisting of oxygen and sulfur, and R represents a member selected from the group consisting of amino and lower alkyl having 1-4 carbon atoms, R and R each independently represent a member selected from the group consisting of hydrogen, lower alkyl having l-4 carbon atoms and methoxy, provided that R represents hydrogen when R',, R and R,-, represent hydrogen, R and R together with the carbon and nitrogen atoms to which they are attached, represent a member selected from the group consisting of a saturated heterocycle containing 5 ring atoms, an unsaturated heterocycle containing 5 ring atoms, a saturated heterocycle containing 6 ring atoms, an unsaturated heterocycle containing 6 ring atoms, in which case R represents hydrogen and R represents a member selected from the group consisting of hydrogen and lower alkyl having l-4 carbon atoms;
- R and R together with the nitrogen atoms to which they are attached represent a member selected from the group consisting of a saturated heterocycle containing 5 ring atoms, an unsaturated heterocycle containing 5 ring atoms, a saturated heterocycle containing 6 ring atoms, an unsaturated heterocycle containing 6 ring atoms, in which case R represents hydrogen and R represents a member selected from the group consisting of hydrogen, lower alkyl having l-4 carbon atoms and acyl having 2 to 5 carbon atoms.
- Y designates a residue -NHR or kaline medium or an acid medium, in case it is desired to obtain a compound with a quaternary ammonium group.
- the acid used can be that corresponding to the desired salt, or a different acid, in which case the condensation is followed by an addition to the reaction medium ofa salt of the acid corresponding to the desired diazamerocyanine salt that is more soluble in water than said diazamerocyanine salt, which is then isolated by filtering.
- This method of preparation has been generally described by S. Hunig in Angewandte Chemie, International Edition, Volume 7, pages 335-344 (1968), the disclosure of which is hereby incorporated by reference.
- Example 2 In a manner similar to that of Example 1. but using 2,6-dimeth vl phenol for the 2-amino-6-methyl phenol, the above-indicated dye is obtained in form of a bright red solid with a melting point of236. Molecular weight was calculated in a similar manner as Example 1 and found by potentiometric determination to be 300 (theory: 297).
- a red product is obtained with a melting point of 238.
- a red product is obtained with a melting point of 240.
- a product with green glints is obtained with a melting point of 230.
- a product with green glints is obtained with a melting point of 242.
- the dye is obtained in the form of a reddish violet solid with a melting point of 180 (decomposition).
- ANN-116 is prepared in a manner identical with that of Example 9, except that 1,3-diamino 2.6-dimethyl phenol is cmployed.
- the dye is isolated in the form of a reddish violet solid with a melting point of 170 (decomposition).
- Example 2 is prepared in a manner identical with that of Example 1 1, except that 1,3-dimethyl 2,3-dihydro benzimidazolone hydrazone is employed.
- the dye is isolated in the form of a reddish orange product with a melting point of 268.
- EXAMPLE l3 1,2-dimethyl 2,3-dihydro 2:4'-azino indazole l'- phenyl 3'-methyl 4-pyrazolone of the below formula ii N 01/ Jana is prepared in a manner similar to that of-Example 11.
- the dye is obtained in the form of a brownish orange product with a melting point of 264.
- EXAMPLE l4 4-methyl 3-phenyl 2,3-dihydro 2:4-azino thiazole lphenyl 3-methyl 4'-ylidene 5-pyrazolone of the below formula is prepared in a manner as described by S. Huenig in Liebigs Annalen der Chemie,' Vol 636, p. 27, the disclosure of which is hereby incorporated by reference.
- a dye is obtained in the form of a deep violet solid with a melting point of 213.
- the dye is obtained in the form of a solid with green glints with a melting point of 225.
- N-CHa 2.12 g of 1,2-dimethyl 3-indaz0lone hydrazone hydrochloride are dissolved in cc ofwater. At ambient temperature a solution of 1.5] g of 6-hydroxy benzomorpholine in 80 cc of water is added, then, with stirring, in 15 minutes a solution of 4.56 g of ammonium persulfate and 12 cc of ammonia at 22Be is added. Stirring is continued for 30 minutes, followed by filtering, washing with cold water and drying of the precipitate thus obtained on phosphoric anhydride. The product obtained is a brownish red dye with a melting point of 230.
- Example 17 is prepared in a manner identical with that described in Example 17.
- the dye is obtained in the form ofa brown solid with green glints having a melting point of 184.
- Example 17 is prepared in a manner identical with that described in Example 17.
- the dye is obtained in the form of a brown solid with a melting point of 195.
- EXAMPLE 21 7 "-(6 hydroxy benzomorpholine) 2-az o 3-methyl benzothiazolium perchlorate'is obtained by dissolving of the chloride prepared in Example 20 in a suitable quantity of acetic acid and reprecipitation by sodium perchlorate.
- the melting point was found to be 240C (decomposition).
- EXAMPLE 22 3.45 g (0.01 mole) of 4-methyl 3-phenyl thiazolone benzene sulfonylhydrazone and 1.51 g (0.01 mole) of 6-hydroxy benzomorpholine are dissolved in cc of crystallizable acetic acid. Thereafter, in 15 minutes about 2.28 g (0.01 mole) of ammonium persulfate in 10 cc of water is added and the solution takes on a violet tint. The reaction mixture is stirred for 30 minutes, then 5 cc of sodium perchlorate dissolved in 20 cc of water are added. The reaction mixture is again stirred for 1 hour, then filtered and dried under vacuum on phosphoric anhydride.
- the product is purified by dissolving in a suitable quantity of dichlorethane, filtering of the insoluble material and reprecipitation by carbon tetrahydrochloride.
- a powder with green glints is obtained with a melting point of 230.
- the product is purified by dissolving in a sufficient quantity of dichlorethane and precipitation by carbon tetrachloride, there being obtained crystals with green glints with a melting point of C.
- EXAMPLE 24 25 10 g (0.04 mole) of N,N-dimethyl benzimidazolone hydrazone dihydrochloride and 6.04 g (0.04 mole) of -hydroxy benzomorpholine are dissolved in 250 cc of acetic acid. g of sodium acetate dissolved in 100 cc of acetic acid are added and then, in about 30 minutes, 30 18.24 g (0.08 mole) of ammonium persulfate dissolved in 100 cc of water are added. The mixture is allowed to react for 30 minutes, then the inorganic salts are separated by filtering and the product is precipitated by addition of 20 g of sodium perchlorate dissolved in 300 cc of water. 9 g of the product are collected, corresponding to a yield of 70%, which is purified by extraction with methanol and concentration. The melting point was found to be 240C.
- This hair-setting lotion when applied to hair dyed brown, imparts thereto a purplish brown shade.
- Example 7 0.1 g Vinyl acetate-crotonic acid copolymer (vinyl acetate-90% crotonic acid- 10 7!, molecular weight 45,000 50,000)
- Example 7 Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 7:, vinyl acetate 30 7:, molecular weight Ethyl alcohol, 96 titer 200 volume hydrogen peroxide Orthophosphoric acid, q.s.p.
- This hair-setting lotion is applied at ambient temperature to naturally light brown hair. After setting and drying, the hair is lightly brightened and imparts thereto a pearly glint,
- Dye of Example 7 0.0015 g Ethyl alcohol, 96 titer 50 cc 200 volume hydrogen peroxide 5 g Orthophosphoric acid, q.s.p. pH 3 Water, q.s.p. 100 cc This composition is applied to naturally dark blond hair. After setting and drying the hair is lightlybrightened up and the lotion imparts thereto anash rose glint.
- EXAMPLE 29 The following dyeing composition is prepared Dye of Example 1 0.0006 g Dye of Example 8 0.0006 g Vinyl acetate-crotonic acid copolymer (vinyl acetate /z. crotonic acid 10 7(, molecular weight 45,000 50,000) 2 g Ethyl alcohol, 96 titer 55 cc 200 volume hydrogen peroxide 5 g Orthophosphoric acid, q.s.p. pH 3 Water, q.s.p. 100 cc This lotion is applied to natural blond hair. After setting and drying, the hair is brightened and presents an ash pearly blond shade.
- EXAMPLE 30 The following dyeing composition suitable for packaging in an aerosol container is prepared:
- Example 4 Dye of Example 1 Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 60 vinyl acetate- 40 7:, molecular weight 45,000 60,000) 3 g Ethyl alcohol, 96 titer. q.s.p. 100 cc
- This composition packaged in an aerosol container with dichlorodifluoromethane as the propellant and 20 g of water are added to 20 g of the solution thus sprayed in the form of a lacquer gives natural blond prepared. A gel is obtained which, applied at ambient hair luminous golden glints.
- Dye of Example 1 I 0.005 g Dye of Example l 0.01 g Dye of Example 8 0.00] g Vinyl pyrrolidone-Vin l acetate copolymer (Vinyl pyrrolidone 7:, vinyl acetate 40 71, molecular weight Ethyl alcohol, 96 titer 50 cc Triethanolamine, q.s.p. pH 7 Water, q.s.p. I00 cc This hair-setting lotion when applied to freshly bleached hair, imparts thereto a light silvery shade EXAMPLE 32 The following dyeing composition is prepared:
- Dye of Example 17 0.2 Butylcellosolre 8 g Propylene glycol 8 g Alkylphenol polyethoxyether sold under the name "Remcopal 334" by the Gerland company 22 g Alkylphenol polyethoxyether sold under the name Remcopal 349- by the Gerland company 22 g Ammonia at 22Be 10 g Water. q.s.p. l00 g g g g 20 g of water are added to 20 g of the solution thus temperature for l0 minutes to previously bleached hair, imparts to the hair an iridescent blond shade.
- Example 24 0,0l0 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 7O 71, vinyl acetate 30 /t, molecular weight 35,000 45,000) 2.0 g Ethyl alcohol, 96 titer cc 45 Triethanolamine, q.s.p. pH 7 Water, q.s.p. 100 cc
- This hair-setting lotion when applied to hair dyed golden blond, imparts thereto a luminous and aesthetic 5O pearl glint.
- a gel is obtained which, applied to brown hair at ambient temperature for 15 minutes, imparts to the hair, after rinsing, a dark auburn brown shade.
- This hair-setting lotion when applied to bleached hair, imparts thereto a very luminous light pink blond shade.
- EXAMPLE 40 The following hair-setting lotion is prepared:
- Example 22 Dye of Example 22 i 0.010 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 70 7, vinyl acetate 30 molecular weight 35,000 45.000) 2.0 g Ethyl alcohol, 96 titer 50 cc Triethanolamine. q.s.p. pH 7 N-[(4'-amino 2-methoxy 3'.5-dintethyl) phenyl] 2.5-dimethyl benzoquinoneimine 0.010 g Water. q.s.p 100 cc This hair-setting lotion, when applied to light blond hair, imparts thereto a pearl ash shade.
- Example 23 Dye of Example 23 0.007 g N-(4'-amino 2-methoxy 3,5'-dimethyl) phenyl 2,5-dimethyl benzoquinoneimine 0.003 g N-(4'-hydroxy)phenyl 2.6-dimethyl benzoquinoneimine 0.003 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 60 /1. vinyl acetate 40 7:, molecular weight 45,000 60.000) 2.0 g Ethyl alcohol. 96 titer 50 cc Triethanolamine. q.s.p. pH 6 Water. q.s.p. 100 cc This hair-setting lotion when applied to hair dyed light blond, imparts thereto ash pearl glints.
- Dye of Example 22 0.0l0 g Nitroparaphenylenediamine 0.010 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 4 60 71, vinyl acetate 4O 7:, molecular weight Ethyl alcohol. 96 titer 60 cc Triethanolamine, q.s.p. pH 9 Water. q.s.p.
- This hair-setting lotion when applied to hair dyed light brown, imparts thereto golden copper glints.
- Crotonic acid-vinyl acetate copolymer Crotonic acid l0 /t. vinyl acetate 7:.
- Rg- X and l I RN where R is hydrogen or lower alkyl having 1-4 carbon atoms; or C(R)(R")-, where R each independently have the meaning above;
- R is hydrogen or lower alkyl having l-4 carbon atoms, or R; and R when taken together with the carbon atoms to which they are attached form a benzene ring, a halogen-substituted benzene ring, a benzene ring substituted with lower alkyl having l-4 carbon atoms, a benzene ring substituted with lower alkoxy having l-4 carbon atoms, or a nitrosubstituted benzene ring; and B is a member selected from the group consisting of where R and R, together with the ears mafia nitrogen atoms to which they are attached, form a morpholine group and R is hydrogen and R is hydrogen or lower alkyl having l-4 carbon atoms, or R and R together with the carbon and nitrogen atoms to which and they are attached, form a morpholine group, and E is hydrogen and R is hydrogen, lower alkyl having 14 carbon atoms and alkanoyl having 2 to 5 carbon
- X is a halide, fluorborate, perchlorate, sulfate, di-
Abstract
Hair setting lotions, hair dye compositions and hair lacquers containing the diazamerocyanines, preferably in alcoholic solutions, are also disclosed.
Novel diazamerocyanines and salts thereof useful for dyeing keratinous fibers, particularly human hair, are disclosed. Illustrative is 3-methyl 2,3-dihydro 2:4''-azino benzothiazole 3''amino 6''-methyl 1''-oxo 1'', 4''-dihydro benzene having the formula:
Novel diazamerocyanines and salts thereof useful for dyeing keratinous fibers, particularly human hair, are disclosed. Illustrative is 3-methyl 2,3-dihydro 2:4''-azino benzothiazole 3''amino 6''-methyl 1''-oxo 1'', 4''-dihydro benzene having the formula:
Description
United States Patent Lang et al.
[451 Mar. 4, 1975 NOVEL DIAZAMEROCYANINES AND THEIR USE FOR DYEING KERATINOUS FIBERS [75] Inventors: Gerard Lang, Epinay-sur-Seine;
Andre Bugaut, Boulogne-sur-Seine, both of France [73] Assignee: Societe Anonyme dite: LOreal, Paris, France [22] Filed: June 5, 1972 [21] App]. No.: 259,689
[30] I Foreign Application Priority Data June 4, 1971 France 71.63287 Jan. 6, 1972 France 72.64565 521 vs. CI 260/2441 8/10, 8/101,
Coles et a1. 200/305 Maier et al 260/244 R 3,749,716 7/l973 Kalopissis et al. 260/244 R Primary E.\umine/'R. J. Gallagher Attorney, Agent, or I-irmCushman, Darby 8.: Cushman 57 ABSTRACT Novel diazamerocyanines and salts thereof useful for dyeing keratinous fibers, particularly human hair, are
disclosed. Illustrative is 3-methyl 2,3-dihydro 2:4- azino benzothiazole 3'-amino 6-methyl 1-oxo l, 4-
'dihydro benzene having the formula:
s CH3 Hair setting lotions, hair dye compositions and hair lacquers containing the diazamerocyanines, preferably in alcoholic solutions, are also disclosed.
2 Claims, N0 Drawings NOVEL DIAZAMEROCYANINES AND THEIR USE FOR DYEING KERATINOUS FIBERS Currently, one of the most frequently used processes in capillary dyeing includes using oxidation dyes or bases" associated with dyeing modifiers or couplers which can be aromatic metadiamines or metaaminophenols, or pyrazolones or diketones. When using this process of capillary dyeing, an oxidizing agent as hydrogen peroxide is added to the mixture of bases and couplers selected which has been previously alkalized.
It is known to use heterocyclic hydrazones associated with couplers for'dyeing hair, as described for example in French Pat. No. 1,599,968.
However, this process has the disadvantage of requiring the use of hydrogen peroxide in an alkaline medium. which has been found to cause degradation of the hair, which rapidly becomes porous and brittle. Further, the shades obtained are capable of reproduction only with great difficulty because of secondary reactions that occur along with the reaction of coupling hydrazone and coupler. An additional disadvantage is that the hydrazones are relatively aggressive compounds in regard to the skin, which often causes probwherein A is a nitrogen heterocycle of the formula R7 Rs wherein R is selected from the group consisting of lower alkyl having l4 carbon atoms and phenyl; X is selected from the group consisting of oxygen, sulfur, -NR-, wherein R is lower alkyl having 1-4 carbon atoms, CH=CH,
wherein R" is selected from the group consisting of hydrogen and lower alkylhaving l4 carbon atoms, and C(R")(R"), wherein R each independently have the meaning given above, Z is a member selected from the group consisting of CH=CH and NR', wherein R is a lower alkyl having l4 carbon atoms; R; is selected from the group consisting of hydrogen,
'lower alkyl having 1-4 carbon atoms and phenyl; R is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, or R and R,,, taken together with the carbon atoms to which they are linked, form a benzene ring, a halogen-substituted benzene ring, a benzene ring substituted with lower alkyl having 14 carbon atoms, a benzene ring substituted with lower alkoxy having 14 carbon atoms or a nitrosubstituted benzene ring; B is selected from the group consisting of (i) a nitrogen-containing heterocycle different from the nitrogen containing heterocycle of A; (ii) a cycle of the formula wherein Y is a member selected from the group consisting of oxygen and wherein R and R each independently represent a member selected from the group consisting of hydrogen, lower alkyl having 1-4 carbon atoms and phenyl; and Z is an anion derived from a member selected from the group consisting of inorganic acids and organic acids, such as halide, fluoborate, perchlorate, sulfate, bisulfate and acetate; R represents a member selected from the group consisting of hydrogen, lower alkyl, lower alkoxy and phenyl carbamyl; R and R each independently represent a member selected from the group consisting of hydrogen, lower alkyl having 1-4 carbon atoms and lower alkoxy having [-4 carbon atoms, and R,-, represents a member selected from the group consisting of hydrogen, amino, alkylated amino having l4 carbon atoms, acylated amino having 25 carbon atoms; R and R being able, together with the carbon atoms to which they are attached, to form a condensed benzene ring; (iii) a cycle having the formula wherein R and R together with the nitrogen and carbon atoms to which they are attached, form a compound selected from the group consisting of a saturated heterocycle having 5 ring atoms, an unsaturated het- 3 erocycle having ring atoms, a saturated heterocycle having 6 ring atoms, an unsaturated heterocycle having 6 ring atoms, in which case R is hydrogen and R represents a member selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms; or wherein R and R when taken together with the nitrogen and carbon atoms to which they are attached, form a compound selected from the group consisting of a saturated heterocycle having 5 ring atoms, an unsaturated heterocycle having 5 ring atoms, a saturated heterocycle having 6 ring atoms and an unsaturated heterocycle having 6 ring atoms, in which case R is hydrogen and R, is selected from the group consisting of hydrogen, lower alkyl having l4 carbon atoms and acyl having 2 to 5 carbon atoms; and a cycle having the formula where R and R are each independently hydrogen and lower alkyl having l4 carbon atoms.
The above-described hair dyeing compositions according to the present invention are aqueous solutions, to which most often have been added low molecular weight alcohols such as ethanol or isopropanol, or glycols such as propylene glycol or butylglycol, the alcohol or glycol facilitating the solution of the dye in the composition. These solutions are easily prepared by dissolving one or more compounds of Formula I in water or in a water-alcohol mixture. The proportion of alcohol used is generally between and 70% by weight, while the proportion of glycol is generally between 1 and 6% by weight.
The concentration of the dye or dyes of Formula I in the dyeing compositions according to the present invention can vary in broad limits, because of the great affinity of these compounds for keratinous fibers. This concentration is generally between about 0.001 and about 0.5% by weight and preferably between about 0.002 and about 2% by weight.
The pH of the compositions according to the present invention is generally between about 2,5 and l0 and preferably between about 3 and 8. Preferably, however, the pH is adjusted to the desired value by addition of an acid such as orthophosphoric acid, lactic acid or acetic acid or a base such as mono-, dior triethanolamine or ammonia.
The compositions according to the present invention can contain only one or more of the dyes of Formula I, in which case they make it possible to obtain on the hair shades rich in glints that go from yellow to blue, covering the light spectrum. The composition according to the invention can, however, contain other direct dyes, for example, azo or anthraquinone dyes, nitro dyes of the benzene series, indoanilines, indophenols or indamines.
The hair-dyeing compositions according to the present invention can also contain various adjuvants and ingredients customarily used in capillary cosmetics, for example, wetting agents, dispersing agents, swelling agents, penetrating agents, thickeners, softeners or perfumes. They can also be packaged under pressure in aerosol bombs or containers, together with a conventional aerosol propellant such as dichlorodifluoromethane, trichloromonofluoromethane and their mixtures. Of course, other conventional aerosol propellants can be used.
Dyeing of keratinous fibers, particularly human hair, with the dye compositions according to the invention, can be performed in the usual way, by application at ambient temperature of the composition to the fibers to be dyed, the composition being left in contact for a period varying from 3 to 30 minutes. Following this application, the fibers are rinsed and, if desired, washed. Thereafter the treated fibers are dryed.
In another embodiment of the present invention the compounds of Formula I can be employed in the production of capillary setting lotions. These lotions comprise an aqueous dilute alcohol solution, at least one cosmetic resin and at least a compound of Formula I or a salt thereof as defined above. The setting lotions according to the invention generally contain from 20 to by weight of the total hairsetting lotion composition, of a low molecular weight alkanol such as ethanol or isopropanol and from i to 3% by weight of cosmetic resin.
Representative cosmetic resins that can be employed in the hair-setting lotions of the present invention include, for instance, polyvinyl pyrrolidone having a molecular weight of 40,000-400,000, copolymer of crotonic acid and vinyl acetate, said copolymer having a molecular weight ranging from about 10,000 to 70,000, copolymer vinyl pyrrolidone and vinyl acetate, wherein the ratio of PVP to VA ranges between 50-70: 5030, said copolymer having a molecular weight ranging from about 30,000 to 200,000 and maleic anhydridebutylvinyl ether copolymers, a 1% solution of which is methylethyl ketone has a viscosity of 0.1-3.5 cps at 25C. These resins are used in a proportion of l to 3% by weight of the hair-setting lotion composition.
The pH of the hair setting lotions according to the invention is generally between 3 and 8. As stated above, it is possible to regulate the pH to the desired value by using mono or di or triethanolamine and an acidifying agents, acetic acid or lactic acid.
The setting lotions according to the invention can contain only the dyes of Formula I, in which case they constitute what is known as shading compositions. However, the hair-setting lotions of this invention can also contain other direct dyes such as anthraquinone dyes, nitro dyes of the benzene series and those mentioned above. The hair-setting lotions can also contain various ingredients usually'used in capillary cosmetics, for example, wetting agents, dispersing agents, swelling agents, penetrating agents, thickeners, softeners or perfumes, as mentioned above. The hair-setting lotions disclosed herein are used in the customary manner by applying at ambient temperature to wet hair that has been previously washed and rinsed, followed by rolling the hair up on curlers and drying of the hair.
In another embodiment of the present invention, the dyes of Formula I can also be used in the production of hair lacquers. These lacquers contain in alcohol solution at least one cosmetic resin and at least a compound of Formula I.
The alcohols suitable for the preparation of the hair lacquers according to the invention are low molecular weight alcohols, such as ethanol or isopropanol. As resin there may be used one or more of polyvinyl pyrrolidone, copolymer of crotonic acid and. vinyl acetate, copolymer of vinyl pyrrolidone and vinyl acetate, copolymer of maleic anhydride and butylvinyl ether, all as described above. The amount of dye of Formula I ranges from about 0.00l to about 0.5% by weight and the amount of cosmetic resin used is between about 1 and 3% by weight. Of course the hair lacquers of the present invention are conveniently packaged in pressurized containers or aerosol bombs of the type described above. The hair lacquers are conveniently applied directly to the hair, preferably in the form of a spray at ambient temperature.
Of the dyes of Formula I as described above, there are a certain number of novel compounds which are also part of and comprise another embodiment of the present invention.
Thus. the present invention in the composition of matter aspect thereof, includes novel diazamerocyanines and salts thereof of the formula A N N B (1') wherein A is a nitrogen heterocycle as defined above and B is a residue corresponding to one of the following formulae:
in the above formulae X" represents an anion derived from an inorganic or organic acid;
R, is selected from the group consisting of hydrogen or lower alkyl having 1-4 carbon atoms;
R is hydrogen, lower alkyl having 1-4 carbon atoms. lower alkyl having 14 carbon atoms substituted by an amine. lower alkyl having l-4 carbon atoms substituted by an amide, and
wherein W is selected from the group consisting of oxygen and sulfur. and R is selected from the group consisting of amino and lower alkyl of l-4 carbon atoms, R1, and R each independently represent a member selected from the group consisting of hydrogen and lower alkyl having 14 carbon atoms; Y represents a member selected from the group consisting of wherein R, and R each independently represent a member selected from the group consisting of hydrogen and lower alkyl having l-4 carbon atoms, and Z is an anion derived from an inorganic or organic acid. such as halide. perchlorate, fluoborate. acetate. bisullate and sulfate;
R represents a member selected from the group consisting of hydrogen and wherein W represents a member selected from the group consisting of oxygen and sulfur, and R represents a member selected from the group consisting of amino and lower alkyl having 1-4 carbon atoms, R and R each independently represent a member selected from the group consisting of hydrogen, lower alkyl having l-4 carbon atoms and methoxy, provided that R represents hydrogen when R',, R and R,-, represent hydrogen, R and R together with the carbon and nitrogen atoms to which they are attached, represent a member selected from the group consisting of a saturated heterocycle containing 5 ring atoms, an unsaturated heterocycle containing 5 ring atoms, a saturated heterocycle containing 6 ring atoms, an unsaturated heterocycle containing 6 ring atoms, in which case R represents hydrogen and R represents a member selected from the group consisting of hydrogen and lower alkyl having l-4 carbon atoms;
Or R and R together with the nitrogen atoms to which they are attached, represent a member selected from the group consisting of a saturated heterocycle containing 5 ring atoms, an unsaturated heterocycle containing 5 ring atoms, a saturated heterocycle containing 6 ring atoms, an unsaturated heterocycle containing 6 ring atoms, in which case R represents hydrogen and R represents a member selected from the group consisting of hydrogen, lower alkyl having l-4 carbon atoms and acyl having 2 to 5 carbon atoms.
These novel compounds according to the present invention are obtained by known'processes, including condensation of a hydrazone of the general formula wherein A has the signification indicated above, with a coupler corresponding to one of the following formulae:
where Y designates a residue -NHR or kaline medium or an acid medium, in case it is desired to obtain a compound with a quaternary ammonium group. The acid used can be that corresponding to the desired salt, or a different acid, in which case the condensation is followed by an addition to the reaction medium ofa salt of the acid corresponding to the desired diazamerocyanine salt that is more soluble in water than said diazamerocyanine salt, which is then isolated by filtering. This method of preparation has been generally described by S. Hunig in Angewandte Chemie, International Edition, Volume 7, pages 335-344 (1968), the disclosure of which is hereby incorporated by reference.
The following examples are intended to illustrate various aspects of the present invention. Unless otherwise indicated, all parts and percentages are by weight and all temperatures used herein are expressed in degrees centigrade.
EXAMPLE 1 I 3-methyl 2,3-dihydro 2:4-azino benzothiazole 3- amino 6'-methyl l'-oxo l,4-dihydro benzene having the formula as indicated below is prepared as follows:
EXAMPLE 2 3-methyl 2,3-dihydro 2:4'-azino benzothiazole 2',6- climethyl l'-oxo l,4-dihydr benzene having the formula below is prepared as follows:
In a manner similar to that of Example 1. but using 2,6-dimeth vl phenol for the 2-amino-6-methyl phenol, the above-indicated dye is obtained in form of a bright red solid with a melting point of236. Molecular weight was calculated in a similar manner as Example 1 and found by potentiometric determination to be 300 (theory: 297).
' EXAMPLE 3 Preparation of 3-methyl 2,3-dihydro 2:4-azino benzothiazole 3'-acetamino 6'-methyl l'-oxo l,4-dihydro benzene having the formula below is prepared as follows:
l on, Niicoom In a manner identical to that of Example 1, but using 3-acetamino-6-methyl phenol a reddish orange product is obtained with a melting point above 260. Similarly, molecular weight was calculated by potentiometric determination and found to be 350 (theory: 340).
EXAMPLE 4 Preparation of 3-methyl 2,3-dihydro 2:4-azino benzothiazole 3'-amino 2',6'-dimethyl l-oxo l,4- dihydro benzene having the formula below is prepared as follows:
In a manner identical to that of Example 1, but using 3-amino-2,6-dimethyl phenol a brown product is obtained with a melting point of 250.
Molecular weight was determined by potentiometric determination and found to be 321 (theory: 312).
EXAMPLE 5 3-phenyl 4-methyl 2,3-dihydro 2:4'-azino thiazole l,4-dihydro l'-oxo 2-naphthanilide having the formula below was prepared as described by S. Huenig in Liebigs Annalen der Chemie, Vol. 47, p. 77, the disclosure of which is hereby incorporated by reference.
A red product is obtained with a melting point of 238.
EXAMPLE 6 3,4-diphenyl 2,3-dihydro 2:4-azino thiazole l,4- dihydro l-oxo 2'-naphthanilide having the following formula:
S CONHCoHs is prepared as described in Example 5, but using 3,4-
diphenyl 2,3-dihydrothioazole.
A red product is obtained with a melting point of 240.
EXAMPLE 7 2[(l-dimethylamino-phenyl (4) azol-3 methyl benzothiazolium perchlorate having the following formula:
is prepared by the method described by S. Huenig in Liebigs Annalen der Chemie," Vol. 628, p. 88, the disclosure of which is hereby incorporated by reference.
A product with green glints is obtained with a melting point of 230.
EXAMPLE 8 l,3-dimethyl-2[( l-dimethylamino phenyl (4 azolimidazolium perchloate having the following formula:
is prepared by the method described by S. Huenig in Liebig s Annalen der Chemie, Vol. 628, p. 90, the disclosure of which is hereby incorporated by reference.
A product with green glints is obtained with a melting point of 242.
EXAMPLE 9 2[( l,3-diamino o-methyl-phenyl (4)) azo]-3 methyl benzothiazolium iodide having the below formula, is prepared as follows:
1.80 g of N-methyl benzothiazolone hydrazone are dissolved in 160 cc of normal hydrochloric acid containing 10 mg of ferrous sulfate. 1.22 g of metatoluylene diamine are added and thereafter 2.5 cc of hydrogen peroxide are added with stirring. The reaction mixture is stirred for a half hour at 30C, then 10 cc of formic acid are added. The reaction mixture is next heated to 70C, it is filtered and 2.2 g of potassium iodide are added to the filtrate. After cooling the precipitate is drained, washed with water and dried on phosphoric anhydride.
The dye is obtained in the form of a reddish violet solid with a melting point of 180 (decomposition).
EXAMPLE l0 2[l,3-diamino 2,6-dimethyl phenyl (4)) 21201-3 methyl benzothiazolium iodide having the below formula CII:
ANN-116 is prepared in a manner identical with that of Example 9, except that 1,3-diamino 2.6-dimethyl phenol is cmployed.
The dye is isolated in the form of a reddish violet solid with a melting point of 170 (decomposition).
EXAMPLE ll 3-methyl 2.3-dihydro 2:4-azino benzothiazole lphenyl 3-methyl 4-ylidene 5'-pyrazolone of the below formula is prepared asfollows:
1.80 g of N-methyl benzothiazolone hydrazone are dissolved in 200 cc of 50% methanol. A solution of 1.74 g of l-phenyl-3-methyl-S-pyrazolone in 50 cc of 50% methanol are added and then a solution of 14.5 g of potassium ferricyanide in a mixture of cc of 50% methanol and l0 cc of 25% ammonia are introduced with stirring. The reaction mixture is stirred for a half hour, then 300 cc of water are added. The precipitate that results is drained, washed with water and dried on phosphoric anhydride. The dye obtained is in the form of a reddish orange solid with a melting point of 262.
EXAMPLE l2 1,3-dimethyl 2,3-dihydro 2:4'-a2ino benzimidazole l-phenyl 3"-methyl 4-ylidene 5'-pyrazolone of the below formula:
(IJH
is prepared in a manner identical with that of Example 1 1, except that 1,3-dimethyl 2,3-dihydro benzimidazolone hydrazone is employed.
The dye is isolated in the form of a reddish orange product with a melting point of 268.
EXAMPLE l3 1,2-dimethyl 2,3-dihydro 2:4'-azino indazole l'- phenyl 3'-methyl 4-pyrazolone of the below formula ii N 01/ Jana is prepared in a manner similar to that of-Example 11. The dye is obtained in the form of a brownish orange product with a melting point of 264.
Molecular weight calculated by potentiometric determination was found to be 348 (theory: 346).
EXAMPLE l4 4-methyl 3-phenyl 2,3-dihydro 2:4-azino thiazole lphenyl 3-methyl 4'-ylidene 5-pyrazolone of the below formula is prepared in a manner as described by S. Huenig in Liebigs Annalen der Chemie,' Vol 636, p. 27, the disclosure of which is hereby incorporated by reference.
A dye is obtained in the form of a deep violet solid with a melting point of 213.
EXAMPLE l6 l-methyl l,4-dihydro 4,4-azino pyridine l,4- dihydro l'-oxo naphthalene of the below formula:
is prepared by the process as described by S. Huenig in Liebigs Annalen der Chemie," Vol. 636, p. 28. the disclosure of which is hereby incorporated by reference.
The dye is obtained in the form of a solid with green glints with a melting point of 225.
EXAMPLE I? 1,2-dimethyl 2,3-dihydro 3:7'-azino indazole 6'-oxo 6',7-dihydro benzomorpholine of the below formula. is prepared as follows:
N-CHa 2.12 g of 1,2-dimethyl 3-indaz0lone hydrazone hydrochloride are dissolved in cc ofwater. At ambient temperature a solution of 1.5] g of 6-hydroxy benzomorpholine in 80 cc of water is added, then, with stirring, in 15 minutes a solution of 4.56 g of ammonium persulfate and 12 cc of ammonia at 22Be is added. Stirring is continued for 30 minutes, followed by filtering, washing with cold water and drying of the precipitate thus obtained on phosphoric anhydride. The product obtained is a brownish red dye with a melting point of 230.
EXAMPLE l8 1,3-din1ethyl 1,2-dihydro 2:7-.azin0 benzimidazole 6-0xo 6,7-dihydro benzomorpholine of the below formula:
is prepared in a manner identical with that described in Example 17. The dye is obtained in the form ofa brown solid with green glints having a melting point of 184.
Molecular weight found: 324. Molecular weight calculated (theoretical): 323.
EXAMPLE l9 3-methyl 2,3-dihydro 2:7-aminobenzothiazole 6- oxo 6,7-dihydro benzomorpholine of the below formula:
I j: i H who.
is prepared in a manner identical with that described in Example 17. The dye is obtained in the form of a brown solid with a melting point of 195.
EXAMPLE 7-(6-hydrox y benzomorpholine) 2-azo 3-rnethyl benzothiaiolium chloride of the below formu1a, is prepared as follows:
C7z: 48.66 48.66 (49.3 theoretical) H/(: 3.87 3.99 (4.62 theoretical) v N'/: 14.35 15.51 (14.12 theoretical) Analysis:
EXAMPLE 21 7 "-(6 hydroxy benzomorpholine) 2-az o 3-methyl benzothiazolium perchlorate'is obtained by dissolving of the chloride prepared in Example 20 in a suitable quantity of acetic acid and reprecipitation by sodium perchlorate.
C /z: 42.69 4246(4240 theoretical) H71: 3.62 3.68 (3.97 theoretical) N54: 12.43 12.55 (12.37 theoretical) Analysis:
The melting point was found to be 240C (decomposition).
EXAMPLE 22 3.45 g (0.01 mole) of 4-methyl 3-phenyl thiazolone benzene sulfonylhydrazone and 1.51 g (0.01 mole) of 6-hydroxy benzomorpholine are dissolved in cc of crystallizable acetic acid. Thereafter, in 15 minutes about 2.28 g (0.01 mole) of ammonium persulfate in 10 cc of water is added and the solution takes on a violet tint. The reaction mixture is stirred for 30 minutes, then 5 cc of sodium perchlorate dissolved in 20 cc of water are added. The reaction mixture is again stirred for 1 hour, then filtered and dried under vacuum on phosphoric anhydride.
The product is purified by dissolving in a suitable quantity of dichlorethane, filtering of the insoluble material and reprecipitation by carbon tetrahydrochloride. A powder with green glints is obtained with a melting point of 230.
C7r: 45.18 44.70 (54.04 theoretical) H71: 4.07 3.94 (4.17 theoretical) N/(: 11.69 11.84 (11.68 theoretical) Analysis:
EXAMPLE 23 7-(6-hydroxy benzomorpholine) 2-azo 3,4-diphenyl' thiazolium perchlorate of the below formula, is prepared as follows:
1.33 g (0.005 mole) of 3.4-diphenyl thiazolone hydrazone and 0.75 g (0.005 mole) of 6-hydroxy benzomorpholine are dissolved in 50 cc of crystallizable acetic acid. 2.28 g (0.001 mole) of ammonium persulfate dissolved in 10 cc of water are added in 30 minutes and an intense violet coloring appears. After stirring the reaction mixture for 30 minutes. 2 g of sodium perchlorate dissolved in 10 cc of water are added. The reaction mixture is filtered, washed with water and dried under a vacuum on phosphoric anhydride.
The product is purified by dissolving in a sufficient quantity of dichlorethane and precipitation by carbon tetrachloride, there being obtained crystals with green glints with a melting point of C.
Analysis: C/z:52.57 52.60 (52.75 theoretical) H71: 438 4.10 (3.82 theoretical) N7r: 10.05 10.29 (10.7 theoretical) Determination by water (Karl Fisher): 1.5%
EXAMPLE 24 25 10 g (0.04 mole) of N,N-dimethyl benzimidazolone hydrazone dihydrochloride and 6.04 g (0.04 mole) of -hydroxy benzomorpholine are dissolved in 250 cc of acetic acid. g of sodium acetate dissolved in 100 cc of acetic acid are added and then, in about 30 minutes, 30 18.24 g (0.08 mole) of ammonium persulfate dissolved in 100 cc of water are added. The mixture is allowed to react for 30 minutes, then the inorganic salts are separated by filtering and the product is precipitated by addition of 20 g of sodium perchlorate dissolved in 300 cc of water. 9 g of the product are collected, corresponding to a yield of 70%, which is purified by extraction with methanol and concentration. The melting point was found to be 240C.
Analysis: C|1HutN502 ClO,
CV1: 48.6 (48.2 theoretical) H7r: 4.6 (4.2 theoretical) EXAMPLE 25 The following hair-setting lotion is prepared Dye of Example 8 Vinyl pyrrolidone-vinyl acetate copolymer (Vinyl pyrrolidone 7O 7:, vinyl acetate 30 "/1, molecular weight Ethyl alcohol, 96 titer Triethanolamine. q.s.pt
Water, q.s.p.
This hair-setting lotion when applied to hair dyed brown, imparts thereto a purplish brown shade.
EXAMPLE 26 The following hair-setting lotion is prepared:
Dye of Example 7 0.1 g Vinyl acetate-crotonic acid copolymer (vinyl acetate-90% crotonic acid- 10 7!, molecular weight 45,000 50,000)
Ethyl alcohol, 96' titer 50 cc Benzylidene camphor 0.2 g Triethanolamine, q.s.pt pH 7 Water, q.s.p. 100 cc This hair-setting lotion when applied to hair dyed deep blond, imparts thereto a luminous ash glint.
EXAMPLE 27 The following dyeing composition is prepared:
Dye of Example 7 Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 7:, vinyl acetate 30 7:, molecular weight Ethyl alcohol, 96 titer 200 volume hydrogen peroxide Orthophosphoric acid, q.s.p.
Water, q.s.p.
unurtu This hair-setting lotion is applied at ambient temperature to naturally light brown hair. After setting and drying, the hair is lightly brightened and imparts thereto a pearly glint,
EXAMPLE 28 The following composition is prepared:
Dye of Example 7 0.0015 g Ethyl alcohol, 96 titer 50 cc 200 volume hydrogen peroxide 5 g Orthophosphoric acid, q.s.p. pH 3 Water, q.s.p. 100 cc This composition is applied to naturally dark blond hair. After setting and drying the hair is lightlybrightened up and the lotion imparts thereto anash rose glint.
EXAMPLE 29 The following dyeing composition is prepared Dye of Example 1 0.0006 g Dye of Example 8 0.0006 g Vinyl acetate-crotonic acid copolymer (vinyl acetate /z. crotonic acid 10 7(, molecular weight 45,000 50,000) 2 g Ethyl alcohol, 96 titer 55 cc 200 volume hydrogen peroxide 5 g Orthophosphoric acid, q.s.p. pH 3 Water, q.s.p. 100 cc This lotion is applied to natural blond hair. After setting and drying, the hair is brightened and presents an ash pearly blond shade.
EXAMPLE 30 The following dyeing composition suitable for packaging in an aerosol container is prepared:
Dye of Example 4 Dye of Example 1 Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 60 vinyl acetate- 40 7:, molecular weight 45,000 60,000) 3 g Ethyl alcohol, 96 titer. q.s.p. 100 cc This composition, packaged in an aerosol container with dichlorodifluoromethane as the propellant and 20 g of water are added to 20 g of the solution thus sprayed in the form of a lacquer gives natural blond prepared. A gel is obtained which, applied at ambient hair luminous golden glints.
EXAMPLE 31 The following hair-setting lotion is prepared:
Dye of Example 1 I 0.005 g Dye of Example l 0.01 g Dye of Example 8 0.00] g Vinyl pyrrolidone-Vin l acetate copolymer (Vinyl pyrrolidone 7:, vinyl acetate 40 71, molecular weight Ethyl alcohol, 96 titer 50 cc Triethanolamine, q.s.p. pH 7 Water, q.s.p. I00 cc This hair-setting lotion when applied to freshly bleached hair, imparts thereto a light silvery shade EXAMPLE 32 The following dyeing composition is prepared:
IQ Id 00000 20 g of 20 volume hydrogen peroxide is added to 20 g of the solution thus prepared and the gel thus obtained which, applied to ambient temperatures to bleached hair for 10 minutes, imparts to the hair a beige pearly shade.
EXAMPLE 33 The following dyeing composition is prepared:
Dye of Example 17 0.2 Butylcellosolre 8 g Propylene glycol 8 g Alkylphenol polyethoxyether sold under the name "Remcopal 334" by the Gerland company 22 g Alkylphenol polyethoxyether sold under the name Remcopal 349- by the Gerland company 22 g Ammonia at 22Be 10 g Water. q.s.p. l00 g g g g 20 g of water are added to 20 g of the solution thus temperature for l0 minutes to previously bleached hair, imparts to the hair an iridescent blond shade.
EXAMPLE 35 The following hair-setting lotion is prepared:
Dye of Example 20 0.0l0 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 60 '71. vinyl acetate 40 7!, molecular weight 45,00060,000) 2.0 g Ethyl alcohol, 96 titer 50 cc Triethanolamine. q.s.p. pH 7 Water, q.s.p. 100 cc This hair-setting lotion when applied to hair dyed blond, imparts thereto a golden glint.
EXAMPLE 36 The following hair-setting composition is prepared:
Dye of Example 22 Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 60 72, vinyl acetate 40 "/1, molecular weight, 45,000 60,000) 2.0 g Ethyl alcohol, 96 titer 50 cc Triethanolamine, q.s.p. pH 7 Water, q.s.p. 100 g This hair-setting lotion when applied to bleached hair, imparts thereto a particularly luminous golden pink blond shade.
EXAMPLE 37 The following hair-setting lotion is prepared:
40 Dye of Example 24 0,0l0 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 7O 71, vinyl acetate 30 /t, molecular weight 35,000 45,000) 2.0 g Ethyl alcohol, 96 titer cc 45 Triethanolamine, q.s.p. pH 7 Water, q.s.p. 100 cc This hair-setting lotion when applied to hair dyed golden blond, imparts thereto a luminous and aesthetic 5O pearl glint.
EXAMPLE 38 The following hair-setting lotion is prepared:
prepared. A gel is obtained which, applied to brown hair at ambient temperature for 15 minutes, imparts to the hair, after rinsing, a dark auburn brown shade.
EXAMPLE 34 The following dyeing composition is prepared:
Dye of Example 8 0.050 g Butylcellosolrc 8 g Propylene glycol 8 g Alkylphenol polyethoxyether sold under the name -Remcopal 334" by the Gerland company 22 g Alkylphenol polyethoxyether sold under the name "Remcopal 349 by the Gerland company 22 g Water. q.s.p. l
Dye of Example 23 Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 70 /r, vinyl acetate 30 7:. molecular weight 35,000 45.000) Ethyl alcohol, 96 titer l't'iethanolantine. q.s.p.
Water. q.s.p.
This hair-setting lotion when applied to bleached hair, imparts thereto a very luminous light pink blond shade.
EXAMPLE 39 The following hair-setting lotion is prepared:
Dye of Example 7 0.70 g Vinyl acetate-crotonic acid copolymer (vinyl acetate 90 Ii. crotonic acid H) 'x), molecular weight. 45.000 50.000) 2.0 g Ethyl alcohol. 90" titer 50 cc Benzylidene camphor 0.2 g Triethanolamine. q.s.p. pH 7 This hair-setting lotion when applied to hair dyed dark blond, imparts thereto a luminous pearl ash glint.
EXAMPLE 40 The following hair-setting lotion is prepared:
Dye of Example 22 i 0.010 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 70 7, vinyl acetate 30 molecular weight 35,000 45.000) 2.0 g Ethyl alcohol, 96 titer 50 cc Triethanolamine. q.s.p. pH 7 N-[(4'-amino 2-methoxy 3'.5-dintethyl) phenyl] 2.5-dimethyl benzoquinoneimine 0.010 g Water. q.s.p 100 cc This hair-setting lotion, when applied to light blond hair, imparts thereto a pearl ash shade.
EXAMPLE 4) The following dyeing composition is prepared:
Dye of Example 24 0.0l2 g N-l(4'-hydroxy)phenyl] 3-aamino 6-methyl heazoquinoneimine 0.010 g N-[(4-amino 2'-methoxy 3.5'-dimethyl) phenyl] 2.6-dimethyl bcnzoquinoneimine 0.002 g Ethyl alcohol. 96 titer 50 cc Water. q.s.p. 100 cc This dye composition when applied to strongly bleached hair for 20 minutes at ambient temperature, imparts thereto after rinsing and shampooing, a golden apricot shade. 7
EXAMPLE 42 The following hair-setting composition is prepared:
Dye of Example 20 0.005 g Dye of Example 24 0.005 g N-[ 4'-h \'drox )phenylB-amino o-methyl hemoquinoneimine 0.0025 g N-[(-l-amino 2-methox v 3'.5'-dimethyl) phenyl]2.5-tlimethyl benzoquinoacimine 0.001 g Vinyl pyrrolitlone-vinyl acetate copolymer (vinyl p \'rrolidone 70 /1. vinyl acetate- 30 /1. molecular weight 35,000 45.000) 2.0 g Triethanolamine. q.s.p. pH 7 Water. q.s.p. I cc This hair-setting lotion when applied to blond hair imparts thereto a pearly glint.
EXAMPLE 43 The following setting lotion is prepared:
Dye of Example 24 0.006 g Dye of Example 22 0.004 g N-[(4' l1ydroxy)phenyl] 3-amino 6-methyl benzequinoneimine 0.001 g N-l(4'-amino 2'-methoxy '-methyl)phenyl] 3-acetylamino oanethyl benzoquinoneimine 0.005 g Vinylpyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 60 72. vinyl acetate 40 /2. molecular weight 45.000 60.000) 2.0 g Ethyl alcohol. 96 titer 50 cc '-Continued Triethanolamine. q.s.p. pH 7 Benzylidene camphor 0.2 g Water. q.s.p. 100 cc This hair-setting lotion when applied to very light natural blond hair, imparts thereto a luminous ash pearl glint.
EXAMPLE 44 The following hair-setting lotion is prepared:
Dye of Example 23 0.007 g N-(4'-amino 2-methoxy 3,5'-dimethyl) phenyl 2,5-dimethyl benzoquinoneimine 0.003 g N-(4'-hydroxy)phenyl 2.6-dimethyl benzoquinoneimine 0.003 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 60 /1. vinyl acetate 40 7:, molecular weight 45,000 60.000) 2.0 g Ethyl alcohol. 96 titer 50 cc Triethanolamine. q.s.p. pH 6 Water. q.s.p. 100 cc This hair-setting lotion when applied to hair dyed light blond, imparts thereto ash pearl glints.
EXAMPLE 45 The following hair-setting lotion isprepared:
Dye of Example 22 0.0l0 g Nitroparaphenylenediamine 0.010 g Vinyl pyrrolidone-vinyl acetate copolymer (vinyl pyrrolidone 4 60 71, vinyl acetate 4O 7:, molecular weight Ethyl alcohol. 96 titer 60 cc Triethanolamine, q.s.p. pH 9 Water. q.s.p.
This hair-setting lotion when applied to hair dyed light brown, imparts thereto golden copper glints.
EXAMPLE 46 The following dyeing composition is prepared:
Dye of Example 22 0.010 g Dye of Example 23 0.0l0 g -lanethyl di-B-hydroxyniethylamine-8t2.3-h)
morpholino phenoxazonium bromide 0.0l0 g Crotonic acid-vinyl acetate copolymer (crotonic acid l0 /t. vinyl acetate 7:.
molecular weight 45.000 50.000) 2.0 g Ethyl alcohol. 96 titer 50 cc Triethanolamine, q.s.p. pH 6 Water, q.s.p. 100 cc wherein A is a nitrogen heterocycle selected from the group consisting of It It;
Rg- X and l I RN where R is hydrogen or lower alkyl having 1-4 carbon atoms; or C(R)(R")-, where R each independently have the meaning above;
Z is --CH=CH or -NR, where R' is lower alkyl having l4 carbon atoms R; is hydrogen, lower alkyl having l-4 carbon atoms,
or phenyl;
R is hydrogen or lower alkyl having l-4 carbon atoms, or R; and R when taken together with the carbon atoms to which they are attached form a benzene ring, a halogen-substituted benzene ring, a benzene ring substituted with lower alkyl having l-4 carbon atoms, a benzene ring substituted with lower alkoxy having l-4 carbon atoms, or a nitrosubstituted benzene ring; and B is a member selected from the group consisting of where R and R, together with the ears mafia nitrogen atoms to which they are attached, form a morpholine group and R is hydrogen and R is hydrogen or lower alkyl having l-4 carbon atoms, or R and R together with the carbon and nitrogen atoms to which and they are attached, form a morpholine group, and E is hydrogen and R is hydrogen, lower alkyl having 14 carbon atoms and alkanoyl having 2 to 5 carbon atoms;
and X is a halide, fluorborate, perchlorate, sulfate, di-
sulfate or acetate anion.
2. The compound of claim 1 which is selected from benzimidazolium perchlorate.
3-melhyl UNTTED STATES PATENT OFFICE CERTIFICATE 0F CORRECTION Patent No. 3,869,454 Dated March 4, 1975 Inventor 5 Gerard LANG and Andree BUGAUT It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
In the Heading Under Foreign Application Priority Data Change "France" (both occurrences) to Luxembourg Signed and Sealed this twenty-first Day Of October 1975 [SEAL] Attest:
RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofPaIents and Trademarks UNITED STATES PATENT OFFICE CERTIFICATE 0i CORRECTION Patent No. 3, 869,454 Dated March 4, 1975 Inventor(s) Gerard LANG and Andree BUGAUT It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
In the Heading Under Foreign Application Priority Data Change "France" (both occurrences) to Luxembourg Signed and Sealed this twenty-first Day Of October 1975 smu Arrest:
RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner ofParents and Trademarks
Claims (2)
1. A DIAZAMEROCYANINE, INCLUDING THE MESOMORPHIC FORM THEREOF, HAVING THE FORMULA
2. The compound of claim 1 which is selected from the group consisting of: 1,2-dimethyl 2,3-dihydro 3:7''-azino indazole 6''-oxo 6'',7''-dihydro benzomorpholine, 1,3-dimethyl 1,2-dihydro 2:7''-azino benzimidazole 6''-oxo 6'',7''-dihydro benzomorpholine, 3-methyl 2,3-dihydro 2:7''-aminobenzothiazole 6''-oxo 6'',7''-dihydro benzomorpholine, 7''-(6''-hydroxy benzomorpholine) 2-azo 3-methyl benzothiazolium chloride, 7''-(6''-hydroxy benzomorpholine)2-azo 3-methyl benzothiazolium perchlorate, 7-(6''-hydroxy benzomorpholine) 2-azo 4-methyl 3-phenyl thiazolium perchlorate, 7-(6''-hydroxy benzomorpholine) 2-azo 3,4-diphenyl thiazolium perchlorate, and 7-(6''-hydroxy benzomorpholine) 2-azo 1,3-dimethyl benzimidazolium perchlorate.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/554,701 US3985499A (en) | 1971-06-04 | 1975-03-03 | Diazamerocyanines for dyeing keratinous fibers |
US05/707,769 US4151162A (en) | 1971-06-04 | 1976-07-22 | Diazomerocyanines and mesomeric forms thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
LU63287 | 1971-06-04 | ||
LU64565 | 1972-01-06 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/554,701 Continuation-In-Part US3985499A (en) | 1971-06-04 | 1975-03-03 | Diazamerocyanines for dyeing keratinous fibers |
Publications (1)
Publication Number | Publication Date |
---|---|
US3869454A true US3869454A (en) | 1975-03-04 |
Family
ID=26640087
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US259689A Expired - Lifetime US3869454A (en) | 1971-06-04 | 1972-06-05 | Novel diazamerocyanines and their use for dyeing keratinous fibers |
Country Status (8)
Country | Link |
---|---|
US (1) | US3869454A (en) |
BE (1) | BE784359A (en) |
CA (1) | CA1021324A (en) |
CH (1) | CH560539A5 (en) |
DE (1) | DE2227214A1 (en) |
FR (1) | FR2140205B1 (en) |
GB (1) | GB1360562A (en) |
IT (1) | IT982408B (en) |
Cited By (56)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2812287A1 (en) | 1977-03-28 | 1978-10-05 | Lilly Industries Ltd | FUNGICIDE AGENT |
US4151162A (en) * | 1971-06-04 | 1979-04-24 | L'oreal | Diazomerocyanines and mesomeric forms thereof |
US5032138A (en) * | 1989-05-23 | 1991-07-16 | Clairol Incorporated | Chlorites as oxidants in hair coloring |
US5733343A (en) * | 1993-07-05 | 1998-03-31 | Ciba Specialty Chemicals Corporation | Process for dyeing keratin-containing fibres with cationic dyes |
US5879412A (en) * | 1996-12-23 | 1999-03-09 | L'oreal | Compositions and processes for dyeing keratin fibers with an oxidation base, a coupler, a cationic direct dye, and an oxidizing agent |
US5888252A (en) * | 1993-11-30 | 1999-03-30 | Ciba Specialty Chemicals Corporation | Processes for dyeing keratin-containing fibres with cationicazo dyes |
US5919273A (en) * | 1996-12-23 | 1999-07-06 | L'oreal | Compositions and processes for dyeing keratin fibers with an oxidation base, a coupler, a cationic direct dye, and an oxidizing agent |
US5980587A (en) * | 1995-12-01 | 1999-11-09 | L'oreal | Method for dyeing keratin fibers with a dye compositions containing at least one direct dye and at least one basifying agent |
US5993490A (en) * | 1996-12-23 | 1999-11-30 | L'oreal | Composition for the oxidation dyeing of keratin fibers containing a cationic direct dye and dyeing process using this composition |
US6001135A (en) * | 1996-12-23 | 1999-12-14 | L'oreal | Compositions and processes for dyeing keratin fibers with cationic direct dyes, oxidation bases, and oxidizing agents |
US6371994B2 (en) * | 1998-05-28 | 2002-04-16 | L'oreal S.A. | Dye composition for keratin fibers, with a cationic direct dye and a polyol or polyol ether |
US6432146B1 (en) | 1999-01-19 | 2002-08-13 | L'oreal S.A. | Use of a combination of two cationic dyes for the direct dyeing of keratin fibers |
US6436153B2 (en) * | 1998-05-28 | 2002-08-20 | L'ORéAL S.A. | Composition for the direct dyeing of keratin fibres with a cationic direct dye and a polyol and/or a polyol ether |
US6530959B1 (en) | 1998-08-19 | 2003-03-11 | L'oreal S.A. | Dyeing composition for keratinous fibres with a direct cationic coloring agent and a surfactant |
WO2003042199A1 (en) * | 2001-11-14 | 2003-05-22 | Wella Aktiengesellschaft | Agent and method for coloring keratin fibers containing 2-benzothiazolinone-hydrazone and quinone derivatives |
US6592633B2 (en) * | 1998-05-25 | 2003-07-15 | L'oreal S.A. | Dye composition for keratin fibers, with a cationic direct dye and a substantive polymer |
US6613102B2 (en) | 1998-07-09 | 2003-09-02 | L'oreal S.A. | Composition for dyeing keratin fibers with a cationic direct dye and a thickening polymer |
US20050071933A1 (en) * | 1998-08-19 | 2005-04-07 | L'oreal S.A. | Composition for dyeing keratinous fibres with a cationic direct dye and a quaternary ammonium salt |
US20050086748A1 (en) * | 1998-08-26 | 2005-04-28 | L'oreal S.A. | Composition for dyeing keratinous fibres with a cationic direct dye and a silicone |
US20050235433A1 (en) * | 1998-07-09 | 2005-10-27 | L'oreal S.A. | Composition for dyeing keratin fibers with a cationic direct dye and a thickening polymer |
US20060070191A1 (en) * | 1998-08-24 | 2006-04-06 | L'oreal S.A. | Composition for dyeing keratinous fibres with a cationic direct dye and a nonionic surfactant |
US20070039107A1 (en) * | 1998-07-09 | 2007-02-22 | L'oreal S.A. | Composition for dyeing keratin fibers with a cationic direct dye and a thickening polymer |
US20080078036A1 (en) * | 1998-04-06 | 2008-04-03 | L'oreal S.A. | Dye composition for keratin fibers, with a cationic direct dye and a substantive polymer |
US7474419B2 (en) | 2005-11-01 | 2009-01-06 | Fei Company | Stage assembly, particle-optical apparatus comprising such a stage assembly, and method of treating a sample in such an apparatus |
US8403999B2 (en) | 2009-12-22 | 2013-03-26 | L'oreal | Dyeing and/or bleaching composition comprising a polycondensate of ethylene oxide and propylene oxide |
US8419807B2 (en) | 2009-10-13 | 2013-04-16 | L'oreal | Composition including a glyceride and an organophosphonic acid or one of the salts thereof, dyeing or colour-lightening method implementing same and devices |
US8551188B2 (en) | 2009-09-02 | 2013-10-08 | L'oreal | Composition comprising a hydrophobic dye, a particular organic and/or mineral alkaline agent, a particular compound (I) and a particular organic compound (II), and dyeing use thereof |
US8808401B2 (en) | 2010-12-20 | 2014-08-19 | L'oreal | Hair dyeing process using an insoluble silicate, an aromatic compound and a hydroxylated aliphatic solvent |
US8840684B2 (en) | 2010-12-15 | 2014-09-23 | L'oreal | Process for dyeing keratin fibres using a direct dye bearing a disulfide/thiol/protected thiol function and water vapour |
US9044412B2 (en) | 2011-07-05 | 2015-06-02 | L'oreal | Dye composition using a long-chain ether of an alkoxylated fatty alcohol and a cationic polymer, processes and devices using the same |
US9060944B2 (en) | 2011-07-05 | 2015-06-23 | L'oreal | Cosmetic composition rich in fatty substances comprising a polyoxyalkylenated fatty alcohol ether and a direct dye and/or an oxidation dye, the dyeing method and the device |
US9066890B2 (en) | 2011-07-05 | 2015-06-30 | L'oreal | Dye composition comprising an alkoxylated fatty alcohol ether and a fatty alcohol |
KR20150080607A (en) * | 2012-10-31 | 2015-07-09 | 로레알 | Oil-rich composition and use thereof in a lightening or non-lightening direct dyeing process |
US9265705B2 (en) | 2011-02-25 | 2016-02-23 | L'oreal | Composition for dyeing keratin fibres comprising a direct dye bearing a disulphide/thiol function, a nonionic surfactant, an amphoteric surfactant, an ethoxylated fatty alcohol, an alkaline agent and a reducing agent |
US9271915B2 (en) | 2011-02-25 | 2016-03-01 | L'oreal | Composition for dyeing keratin fibres comprising a direct dye bearing a disulphide/thiol function, a non-cellulose-based thickening polymer, an alkaline agent and a reducing agent |
US9345652B2 (en) | 2011-02-25 | 2016-05-24 | L'oreal | Composition for dyeing keratin fibres comprising a direct dye bearing a disulphide/thiol function, a sparingly or non-ethoxylated fatty alcohol, a cationic surfactant, an alkaline agent and a reducing agent |
US9408785B2 (en) | 2012-10-15 | 2016-08-09 | L'oreal | Hair styling compositions containing aqueous wax dispersions |
US9474700B2 (en) | 2012-11-09 | 2016-10-25 | L'oreal | Methods for altering the color and appearance of hair |
US9522106B2 (en) | 2011-02-25 | 2016-12-20 | L'oreal | Composition for dyeing keratinous fibres comprising a direct dye having a disulphide/thiol functional group, a thickening polymer, an ethoxylated fatty alcohol and/or a nonionic surfactant, an alkaline agent and a reducing agent |
US9566221B2 (en) | 2012-11-09 | 2017-02-14 | L'oreal | Methods for altering the color and appearance of hair |
US9565915B2 (en) | 2011-11-09 | 2017-02-14 | L'oreal | Compositions and methods for altering the appearance of hair |
US9565916B2 (en) | 2011-11-09 | 2017-02-14 | L'oreal | Compositions and methods for altering the appearance of hair |
US9827185B2 (en) | 2012-08-02 | 2017-11-28 | L'oreal | Dyeing composition comprising at least one fatty substance, at least one oxidizing agent and at least one non-ionic, anionic and amphoteric surfactant |
US10117811B2 (en) | 2013-12-23 | 2018-11-06 | L'oreal | Packaging article comprising an envelope and an anhydrous dye composition comprising an oxidation dye, use of the same and process for dyeing keratin fibres |
US10130829B2 (en) | 2013-12-23 | 2018-11-20 | L'oreal | Packaging article comprising an envelope and an anhydrous dye composition comprising a direct dye, use of the same and process for dyeing keratin fibres |
US10137063B2 (en) | 2012-08-02 | 2018-11-27 | L'oreal | Dye composition comprising nonionic guar gum or a nonionic derivative thereof, process and device for the same |
US10201483B2 (en) | 2012-08-02 | 2019-02-12 | L'oreal | Dye composition in cream form comprising at least one oil and little or no solid fatty alcohol, dyeing process and suitable device |
US10226411B2 (en) | 2012-08-02 | 2019-03-12 | L'oreal | Dyeing composition comprising a fatty substance, a non-ionic guar gum, an amphoteric surfactant and a non-ionic or anionic surfactant, and an oxidizing agent, dyeing process and suitable device |
US10413496B2 (en) | 2012-10-15 | 2019-09-17 | L'oreal | Aqueous wax dispersions |
US10561596B2 (en) | 2014-04-11 | 2020-02-18 | L'oreal | Compositions and dispersions containing particles comprising a polymer |
US10626294B2 (en) | 2012-10-15 | 2020-04-21 | L'oreal | Aqueous wax dispersions containing volatile solvents |
US10765612B2 (en) | 2016-11-28 | 2020-09-08 | L'oreal | Dye composition comprising 12-hydroxystearic acid, an organic amine and a dye |
US11096880B2 (en) | 2017-06-16 | 2021-08-24 | L'oreal | Process for dyeing keratin fibres using at least one direct dye and at least one disulfide, thiol or protected-thiol fluorescent dye |
US11278482B2 (en) | 2017-06-16 | 2022-03-22 | L'oreal | Process for dyeing keratin materials using at least one blue, purple or green dye and at least one disulfide, thiol or protected thiol fluorescent dye |
US11672747B2 (en) | 2018-12-21 | 2023-06-13 | L'oreal | Process for dyeing keratin materials using a direct dye and an aliphatic ammonium salt, and composition comprising same |
US11911636B2 (en) | 2013-12-23 | 2024-02-27 | L'oreal | Process for treating keratin fibers using a packaging article comprising an envelope and an anhydrous composition comprising an oxidizing agent |
Families Citing this family (66)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
LU75425A1 (en) * | 1976-07-21 | 1978-02-08 | ||
FR2359182A1 (en) * | 1976-07-21 | 1978-02-17 | Oreal | Liq. hair colouring compsns. contg. indoaniline and indophenol dyes - which are storage stable as solns. to provide reproducible colourations |
TW325998B (en) * | 1993-11-30 | 1998-02-01 | Ciba Sc Holding Ag | Dyeing keratin-containing fibers |
FR2779054B1 (en) | 1998-05-26 | 2001-06-29 | Oreal | KERATINIC FIBER OXIDATION DYE COMPOSITION AND DYEING METHOD USING THE SAME |
FR2780882B1 (en) * | 1998-07-09 | 2001-04-06 | Oreal | DYE COMPOSITION FOR KERATINIC FIBERS WITH CATIONIC DIRECT DYE AND THICKENER POLYMER |
FR2822062B1 (en) * | 2001-03-15 | 2005-12-02 | Oreal | NOVEL TINCTORIAL COMPOSITIONS FOR DYEING KERATIN FIBERS COMPRISING THE BASIC OXIDATION OF HYDRAZONE HETEROCYCLIC 5-CHAIN COMPOUNDS |
FR2829926B1 (en) * | 2001-09-26 | 2004-10-01 | Oreal | COMPOSITION FOR DYEING KERATINIC FIBERS COMPRISING A SPECIAL DICATION DIAZOIC DYE |
FR2925323B1 (en) | 2007-12-21 | 2009-12-18 | Oreal | COLORING PROCESS IN THE PRESENCE OF AN OXIDIZING AGENT AND A PARTICULAR ORGANIC AMINE AND DEVICE |
FR2925307B1 (en) | 2007-12-21 | 2009-12-18 | Oreal | METHOD FOR DIRECT LIGHTENING OR OXIDATION COLORING IN THE PRESENCE OF A PARTICULAR ORGANIC AMINE AND DEVICE |
FR2928085B1 (en) | 2008-02-28 | 2010-06-18 | Oreal | COMPOSITION COMPRISING A HYDROPHOBIC DYE AND AN ALKYLENE CARBONATE OR A LACTONE AND KERATINIC FIBER COLORING |
FR2940103B1 (en) | 2008-12-19 | 2011-06-10 | Oreal | METHOD FOR LIGHTENING COLORING KERATINIC MATERIALS USING AN EMULSION COMPRISING A COLORANT AND AN ALKALI AGENT AND AN OXIDIZING COMPOSITION |
EP2198843B1 (en) | 2008-12-19 | 2017-09-13 | L'Oréal | Lightening of human keratinic fibers with a anhydrous composition comprising a mixture of monoethanolamine/basic amine acid and kit |
CN101780015A (en) | 2008-12-19 | 2010-07-21 | 莱雅公司 | Coloring or lightening human keratin fiber, using anhydrous composition comprising fatty substance and surfactants, a composition comprising mono ethanolamine and basic amino acids, and composition comprising oxidizing agents |
FR2940104B1 (en) | 2008-12-19 | 2011-08-19 | Oreal | HAIR PROCESSING METHOD USING DIRECT EMULSION COMPRISING OXIDIZING AGENT AND COMPOSITION CONTAINING ALKALINE AGENT |
FR2940077B1 (en) | 2008-12-19 | 2012-07-20 | Oreal | METHOD FOR LIGHTENING COLORING KERATINIC MATERIALS USING A COLORING ANHYDROUS COMPOSITION COMPRISING AN ALKALI AGENT AND AN OXIDIZING COMPOSITION |
US7927381B2 (en) | 2008-12-19 | 2011-04-19 | L'oreal S.A. | Process for lightening or lightening direct dyeing or oxidation dyeing in the presence of an aqueous composition comprising at least one fatty substance, and device |
BRPI0907074A2 (en) | 2008-12-19 | 2013-05-07 | Oreal | keratin fiber bleaching or coloring process, anhydrous composition and multi-compartment device |
CN101822619B (en) | 2008-12-19 | 2014-03-26 | 莱雅公司 | Method of coloring or lightening color in the presence of an oxidizing agent, and kit thereof |
US7918902B2 (en) | 2008-12-19 | 2011-04-05 | L'oreal S.A. | Process for lightening or process for direct dyeing or oxidation dyeing of keratin fibers in the presence of at least one ammonium salt and device therefor |
EP2400946B1 (en) | 2009-02-27 | 2018-10-24 | L'Oréal | Composition containing a dye and 3-phenyl-1-propanol and dyeing of keratin fibres |
WO2010097558A2 (en) | 2009-02-27 | 2010-09-02 | L'oreal | Composition containing a natural or synthetic dye and an aliphatic monohydroxylated alcohol and keratin fibre dyeing method using same |
FR2942704B1 (en) | 2009-03-04 | 2011-09-02 | Oreal | DEVICE FOR DISPENSING A TINCTORIAL COMPOSITION FOR KERATIN FIBERS AND ASSOCIATED METHOD. |
JP5866137B2 (en) | 2009-04-30 | 2016-02-17 | ロレアル | Lightening and / or coloring of human keratin fibers and apparatus using a composition comprising an aminotrialkoxysilane or aminotrialkenyloxysilane compound |
JP2011001344A (en) | 2009-04-30 | 2011-01-06 | L'oreal Sa | Lightening and/or coloring human keratin fiber using aminotrialkoxy silane or aminotrialkenyloxy silane composition and device |
FR2949338B1 (en) | 2009-09-02 | 2012-12-14 | Oreal | COMPOSITION COMPRISING AN INDIGOID TYPE ACIDIC COLOR AND METHOD OF COLORING |
FR2949335B1 (en) | 2009-09-02 | 2014-08-08 | Oreal | COLORING PROCESS FOR APPLYING A METAL SALT AND A COMPOSITION COMPRISING A HYDROPHOBIC COLOR AND A PARTICULAR COMPOUND |
FR2949971B1 (en) | 2009-09-17 | 2012-08-17 | Oreal | PROCESS FOR LIGHTENING OR COLORING IN THE PRESENCE OF A PARTICULAR ANHYDROUS COMPOSITION AND DEVICE |
FR2954121B1 (en) | 2009-12-22 | 2016-03-25 | Oreal | COLORING AND / OR DECOLOURING AGENT OF TWO - PART KERATIN FIBERS, COMPRISING A PARTICULAR FOLDER AND A REDUCTONE. |
EP2515831A2 (en) | 2009-12-22 | 2012-10-31 | L'Oréal | Inverse emulsion for treating the hair comprising a particular fatty substance and an alkaline agent |
FR2954093B1 (en) | 2009-12-22 | 2012-02-24 | Oreal | AGENT FOR COLORING AND / OR DECOLORIZING KERATINIC FIBERS IN TWO OR MORE PARTS IN THE FORM OF EMULSION AND DISPERSION |
FR2954113B1 (en) | 2009-12-22 | 2013-03-08 | Oreal | AGENT FOR COLORING AND / OR DECOLOURING KERATINIC FIBERS INTO TWO OR MORE PARTS, IN THE FORM OF EMULSION. |
FR2954101B1 (en) | 2009-12-22 | 2012-05-11 | Oreal | COLORING AND / OR DECOLOURING AGENT FOR KERATINIC FIBERS INTO TWO OR MORE PARTS, COMPRISING AN ALKALINE REVERSE EMULSION. |
FR2954160B1 (en) | 2009-12-22 | 2012-03-30 | Oreal | COLORING OR LIGHTENING COMPOSITION COMPRISING A FATTY BODY AND AN AMPHOTERIC POLYMER |
FR2954127B1 (en) | 2009-12-22 | 2015-10-30 | Oreal | COLORING AND / OR DECOLOURING AGENT OF TWO-PART KERATINOUS FIBERS, COMPRISING A BODY AND A SEQUESTRING AGENT. |
WO2011076646A2 (en) | 2009-12-22 | 2011-06-30 | L'oreal | Agent for dyeing and/or bleaching keratin fibres, comprising an inverse emulsion comprising an oxidizing agent |
FR2954161B1 (en) | 2009-12-23 | 2012-03-02 | Oreal | PROCESS FOR COLORING OR LIGHTENING KERATINIC FIBERS IN THE PRESENCE OF VOLATILE LINEAR ALKANE (S) AND DEVICE |
FR2958161B1 (en) | 2010-04-02 | 2012-04-27 | Oreal | HAIR PROCESSING METHOD USING DIRECT EMULSION COMPRISING OXIDIZING AGENT AND DIRECT EMULSION CONTAINING ALKALINE AGENT |
FR2959127B1 (en) | 2010-04-22 | 2016-01-01 | Oreal | REVERSE EMULSION FOR TREATING HAIR COMPRISING A PARTICULAR SOLVENT |
FR2960773B1 (en) | 2010-06-03 | 2015-12-11 | Oreal | COSMETIC PROCESSING METHODS USING A POLYAMIDE-POLYETHER POLYMER-BASED COATING |
WO2012084820A2 (en) | 2010-12-20 | 2012-06-28 | L'oreal | Composition comprising a natural dye and/or a cationic and/or nonionic direct dye, and/or a dye precursor, an insoluble silicate and a mono- or polyglycoside |
FR2973661A1 (en) | 2011-04-08 | 2012-10-12 | Oreal | METHOD FOR TREATING HAIR |
WO2013125052A1 (en) | 2012-02-24 | 2013-08-29 | L'oreal | Process for treating keratin fibers |
US20140102467A1 (en) | 2012-10-15 | 2014-04-17 | L'oreal | Aqueous wax dispersions for altering the color of keratinous substrates |
WO2015063122A1 (en) | 2013-10-30 | 2015-05-07 | L'oreal | Expanded dyeing composition comprising an inert gas, an oxidation dye and an oxyalkylenated nonionic surfactant |
FR3024357B1 (en) | 2014-08-01 | 2017-10-27 | Oreal | COMPOSITION COMPRISING AMPS® COPOLYMER AND OXIDATION COLORING PRECURSOR AND / OR DIRECT COLORANT |
JP2016098220A (en) | 2014-11-26 | 2016-05-30 | ロレアル | Silicone oil-rich composition |
JP2016098221A (en) | 2014-11-26 | 2016-05-30 | ロレアル | Oil-rich composition |
FR3037795B1 (en) | 2015-06-25 | 2018-08-17 | L'oreal | PACKAGING ARTICLE COMPRISING AN ENVELOPE AND ANHYDROUS COLORING, COLORING OR OXIDIZING COMPOSITION COMPRISING A FIBROUS CLAY, AND A COMPOUND SELECTED FROM A COLORING AGENT AND / OR AN OXIDIZING AGENT; USE AND METHOD FOR COLORING AND / OR DECOLORIZING KERATIN FIBERS |
JP2017114767A (en) | 2015-12-04 | 2017-06-29 | ロレアル | Compositions for dyeing keratin fibers |
JP2017132691A (en) | 2015-12-04 | 2017-08-03 | ロレアル | Composition for dyeing keratin fibers |
JP2017193513A (en) | 2016-04-22 | 2017-10-26 | ロレアル | Composition for dyeing keratin fibers |
US20180072970A1 (en) * | 2016-09-13 | 2018-03-15 | The Procter & Gamble Company | Stable violet-blue to blue imidazolium compounds |
FR3060993B1 (en) | 2016-12-22 | 2020-10-02 | Oreal | PROCESS FOR COLORING KERATINIC FIBERS USING AT LEAST ONE PARTICULAR 2-AZO (BENZ) IMIDAZOLIUM COMPOUND AND AT LEAST ONE DIRECT FLUORESCENT COLORANT |
JP2019011284A (en) | 2017-06-30 | 2019-01-24 | ロレアル | Composition for dyeing keratin fiber |
JP2020018327A (en) | 2018-07-17 | 2020-02-06 | ロレアル | Microneedle sheet |
JP7292837B2 (en) | 2018-08-29 | 2023-06-19 | ロレアル | Methods and compositions for coloring keratin fibers |
JP7199936B2 (en) | 2018-11-27 | 2023-01-06 | ロレアル | Composition for keratin fibers |
JP2020169122A (en) | 2019-03-20 | 2020-10-15 | ロレアル | Method and kit for coloring keratin fibers |
FR3097761B1 (en) | 2019-06-27 | 2021-05-28 | Oreal | Composition comprising 12-hydroxystearic acid, an organic amine and a liquid fatty substance |
JP2021094146A (en) | 2019-12-16 | 2021-06-24 | ロレアル | Cosmetic method using microneedle sheet |
EP4081183A1 (en) | 2019-12-24 | 2022-11-02 | L'oreal | Cosmetic composition comprising a polymer comprising at least one cationic (meth)acrylamide unit, a particular silicone and at least one surfactant |
FR3113240B1 (en) | 2020-08-10 | 2024-01-12 | Oreal | COMPOSITION COMPRISING AT LEAST ONE SPECIFIC SILICONE, AT LEAST ONE ALKANE AND AT LEAST ONE DIRECT COLOR AND/OR AT LEAST ONE PIGMENT |
FR3137835A1 (en) | 2022-07-15 | 2024-01-19 | L'oreal | Composition for coloring keratinous fibers |
WO2023228870A1 (en) | 2022-05-25 | 2023-11-30 | L'oreal | Composition for coloring keratin fibers |
WO2024048429A1 (en) | 2022-08-30 | 2024-03-07 | L'oreal | Cosmetic process using particle with microprotrusion |
FR3140268A1 (en) | 2022-09-29 | 2024-04-05 | L'oreal | COSMETIC PROCESS USING A PARTICLE WITH MICROPROTUBERANCE |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2951847A (en) * | 1957-10-24 | 1960-09-06 | Basf Ag | Diazacyanine dyestuffs cations |
US3043828A (en) * | 1954-07-05 | 1962-07-10 | Basf Ag | Production of dyestuffs |
US3499902A (en) * | 1967-08-09 | 1970-03-10 | Minnesota Mining & Mfg | Organic hydrazone compound containing azo coupler moiety |
US3717629A (en) * | 1970-09-11 | 1973-02-20 | Boehringer Sohn Ingelheim | Nitrofuran derivatives |
US3749716A (en) * | 1969-07-17 | 1973-07-31 | G Kalopissis | N-(7-(6-hydroxy-1-oxa-4-aza-1,2,3,4-tetra-hydro)naphthyl)benzoquinonediimines |
-
1972
- 1972-06-02 BE BE784359A patent/BE784359A/xx unknown
- 1972-06-02 CA CA143,789A patent/CA1021324A/en not_active Expired
- 1972-06-02 FR FR7219934A patent/FR2140205B1/fr not_active Expired
- 1972-06-02 CH CH823472A patent/CH560539A5/xx not_active IP Right Cessation
- 1972-06-03 IT IT68758/72A patent/IT982408B/en active
- 1972-06-05 DE DE19722227214 patent/DE2227214A1/en not_active Withdrawn
- 1972-06-05 US US259689A patent/US3869454A/en not_active Expired - Lifetime
- 1972-06-05 GB GB2620472A patent/GB1360562A/en not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3043828A (en) * | 1954-07-05 | 1962-07-10 | Basf Ag | Production of dyestuffs |
US2951847A (en) * | 1957-10-24 | 1960-09-06 | Basf Ag | Diazacyanine dyestuffs cations |
US3499902A (en) * | 1967-08-09 | 1970-03-10 | Minnesota Mining & Mfg | Organic hydrazone compound containing azo coupler moiety |
US3749716A (en) * | 1969-07-17 | 1973-07-31 | G Kalopissis | N-(7-(6-hydroxy-1-oxa-4-aza-1,2,3,4-tetra-hydro)naphthyl)benzoquinonediimines |
US3717629A (en) * | 1970-09-11 | 1973-02-20 | Boehringer Sohn Ingelheim | Nitrofuran derivatives |
Cited By (71)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4151162A (en) * | 1971-06-04 | 1979-04-24 | L'oreal | Diazomerocyanines and mesomeric forms thereof |
DE2812287A1 (en) | 1977-03-28 | 1978-10-05 | Lilly Industries Ltd | FUNGICIDE AGENT |
US5032138A (en) * | 1989-05-23 | 1991-07-16 | Clairol Incorporated | Chlorites as oxidants in hair coloring |
US5733343A (en) * | 1993-07-05 | 1998-03-31 | Ciba Specialty Chemicals Corporation | Process for dyeing keratin-containing fibres with cationic dyes |
US5888252A (en) * | 1993-11-30 | 1999-03-30 | Ciba Specialty Chemicals Corporation | Processes for dyeing keratin-containing fibres with cationicazo dyes |
US5980587A (en) * | 1995-12-01 | 1999-11-09 | L'oreal | Method for dyeing keratin fibers with a dye compositions containing at least one direct dye and at least one basifying agent |
US6368360B2 (en) | 1995-12-01 | 2002-04-09 | L'oreal S.A. | Method for dyeing keratin fibres with a dye composition containing at least one direct dye and a least one basifying agent |
US5879412A (en) * | 1996-12-23 | 1999-03-09 | L'oreal | Compositions and processes for dyeing keratin fibers with an oxidation base, a coupler, a cationic direct dye, and an oxidizing agent |
US5993490A (en) * | 1996-12-23 | 1999-11-30 | L'oreal | Composition for the oxidation dyeing of keratin fibers containing a cationic direct dye and dyeing process using this composition |
US6001135A (en) * | 1996-12-23 | 1999-12-14 | L'oreal | Compositions and processes for dyeing keratin fibers with cationic direct dyes, oxidation bases, and oxidizing agents |
US5919273A (en) * | 1996-12-23 | 1999-07-06 | L'oreal | Compositions and processes for dyeing keratin fibers with an oxidation base, a coupler, a cationic direct dye, and an oxidizing agent |
US7485157B2 (en) | 1998-04-06 | 2009-02-03 | Loreal | Dye composition for keratin fibers, with a cationic direct dye and a substantive polymer |
US20080078036A1 (en) * | 1998-04-06 | 2008-04-03 | L'oreal S.A. | Dye composition for keratin fibers, with a cationic direct dye and a substantive polymer |
US20030229950A1 (en) * | 1998-05-25 | 2003-12-18 | L'oreal S.A. | Dye composition for keratin fibres, with a cationic direct dye and a substantive polymer |
US6899739B2 (en) | 1998-05-25 | 2005-05-31 | L'oreal S.A. | Dye composition for keratin fibres, with a cationic direct dye and a substantive polymer |
US6592633B2 (en) * | 1998-05-25 | 2003-07-15 | L'oreal S.A. | Dye composition for keratin fibers, with a cationic direct dye and a substantive polymer |
US6371994B2 (en) * | 1998-05-28 | 2002-04-16 | L'oreal S.A. | Dye composition for keratin fibers, with a cationic direct dye and a polyol or polyol ether |
US6436153B2 (en) * | 1998-05-28 | 2002-08-20 | L'ORéAL S.A. | Composition for the direct dyeing of keratin fibres with a cationic direct dye and a polyol and/or a polyol ether |
US7300473B2 (en) | 1998-07-09 | 2007-11-27 | L'oreal S.A. | Composition for dyeing keratin fibers with a cationic direct dye and a thickening polymer |
US6613102B2 (en) | 1998-07-09 | 2003-09-02 | L'oreal S.A. | Composition for dyeing keratin fibers with a cationic direct dye and a thickening polymer |
US20070039107A1 (en) * | 1998-07-09 | 2007-02-22 | L'oreal S.A. | Composition for dyeing keratin fibers with a cationic direct dye and a thickening polymer |
US20050235433A1 (en) * | 1998-07-09 | 2005-10-27 | L'oreal S.A. | Composition for dyeing keratin fibers with a cationic direct dye and a thickening polymer |
US20070006396A9 (en) * | 1998-07-09 | 2007-01-11 | L'oreal S.A. | Composition for dyeing keratin fibers with a cationic direct dye and a thickening polymer |
US20050071933A1 (en) * | 1998-08-19 | 2005-04-07 | L'oreal S.A. | Composition for dyeing keratinous fibres with a cationic direct dye and a quaternary ammonium salt |
US6530959B1 (en) | 1998-08-19 | 2003-03-11 | L'oreal S.A. | Dyeing composition for keratinous fibres with a direct cationic coloring agent and a surfactant |
US7198652B2 (en) | 1998-08-19 | 2007-04-03 | L'oreal S.A. | Composition for dyeing keratinous fibers with a cationic direct dye and a quaternary ammonium salt |
US7087096B2 (en) | 1998-08-19 | 2006-08-08 | L'oreal | Composition for dyeing keratinous fibers with a cationic direct dye and a quaternary ammonium salt |
US20060070191A1 (en) * | 1998-08-24 | 2006-04-06 | L'oreal S.A. | Composition for dyeing keratinous fibres with a cationic direct dye and a nonionic surfactant |
US7507260B2 (en) | 1998-08-26 | 2009-03-24 | L'oreal S.A. | Composition for dyeing keratinous fibres with a cationic direct dye and a silicone |
US20070261178A1 (en) * | 1998-08-26 | 2007-11-15 | L'oreal S.A. | Composition for dyeing keratinous fibres with a cationic direct dye and a silicone |
US20050086748A1 (en) * | 1998-08-26 | 2005-04-28 | L'oreal S.A. | Composition for dyeing keratinous fibres with a cationic direct dye and a silicone |
US6432146B1 (en) | 1999-01-19 | 2002-08-13 | L'oreal S.A. | Use of a combination of two cationic dyes for the direct dyeing of keratin fibers |
US7070625B2 (en) | 2001-11-14 | 2006-07-04 | Wella Ag | Agent and method for coloring keratin fibers containing 2-benzothiazolinone-hydrazone and quinone derivatives |
WO2003042199A1 (en) * | 2001-11-14 | 2003-05-22 | Wella Aktiengesellschaft | Agent and method for coloring keratin fibers containing 2-benzothiazolinone-hydrazone and quinone derivatives |
US20040060124A1 (en) * | 2001-11-14 | 2004-04-01 | Cecile Pasquier | Agent and method for coloring keratin fibers containing 2-benzothiazolinone-hydrazone and quinone derivatives |
US7474419B2 (en) | 2005-11-01 | 2009-01-06 | Fei Company | Stage assembly, particle-optical apparatus comprising such a stage assembly, and method of treating a sample in such an apparatus |
US8551188B2 (en) | 2009-09-02 | 2013-10-08 | L'oreal | Composition comprising a hydrophobic dye, a particular organic and/or mineral alkaline agent, a particular compound (I) and a particular organic compound (II), and dyeing use thereof |
US8419807B2 (en) | 2009-10-13 | 2013-04-16 | L'oreal | Composition including a glyceride and an organophosphonic acid or one of the salts thereof, dyeing or colour-lightening method implementing same and devices |
US8403999B2 (en) | 2009-12-22 | 2013-03-26 | L'oreal | Dyeing and/or bleaching composition comprising a polycondensate of ethylene oxide and propylene oxide |
US8840684B2 (en) | 2010-12-15 | 2014-09-23 | L'oreal | Process for dyeing keratin fibres using a direct dye bearing a disulfide/thiol/protected thiol function and water vapour |
US8808401B2 (en) | 2010-12-20 | 2014-08-19 | L'oreal | Hair dyeing process using an insoluble silicate, an aromatic compound and a hydroxylated aliphatic solvent |
US9265705B2 (en) | 2011-02-25 | 2016-02-23 | L'oreal | Composition for dyeing keratin fibres comprising a direct dye bearing a disulphide/thiol function, a nonionic surfactant, an amphoteric surfactant, an ethoxylated fatty alcohol, an alkaline agent and a reducing agent |
US9271915B2 (en) | 2011-02-25 | 2016-03-01 | L'oreal | Composition for dyeing keratin fibres comprising a direct dye bearing a disulphide/thiol function, a non-cellulose-based thickening polymer, an alkaline agent and a reducing agent |
US9345652B2 (en) | 2011-02-25 | 2016-05-24 | L'oreal | Composition for dyeing keratin fibres comprising a direct dye bearing a disulphide/thiol function, a sparingly or non-ethoxylated fatty alcohol, a cationic surfactant, an alkaline agent and a reducing agent |
US9522106B2 (en) | 2011-02-25 | 2016-12-20 | L'oreal | Composition for dyeing keratinous fibres comprising a direct dye having a disulphide/thiol functional group, a thickening polymer, an ethoxylated fatty alcohol and/or a nonionic surfactant, an alkaline agent and a reducing agent |
US9060944B2 (en) | 2011-07-05 | 2015-06-23 | L'oreal | Cosmetic composition rich in fatty substances comprising a polyoxyalkylenated fatty alcohol ether and a direct dye and/or an oxidation dye, the dyeing method and the device |
US9066890B2 (en) | 2011-07-05 | 2015-06-30 | L'oreal | Dye composition comprising an alkoxylated fatty alcohol ether and a fatty alcohol |
US9044412B2 (en) | 2011-07-05 | 2015-06-02 | L'oreal | Dye composition using a long-chain ether of an alkoxylated fatty alcohol and a cationic polymer, processes and devices using the same |
US9565915B2 (en) | 2011-11-09 | 2017-02-14 | L'oreal | Compositions and methods for altering the appearance of hair |
US9578944B2 (en) | 2011-11-09 | 2017-02-28 | L'oreal | Compositions and methods for altering the appearance of hair |
US9565916B2 (en) | 2011-11-09 | 2017-02-14 | L'oreal | Compositions and methods for altering the appearance of hair |
US10137063B2 (en) | 2012-08-02 | 2018-11-27 | L'oreal | Dye composition comprising nonionic guar gum or a nonionic derivative thereof, process and device for the same |
US9827185B2 (en) | 2012-08-02 | 2017-11-28 | L'oreal | Dyeing composition comprising at least one fatty substance, at least one oxidizing agent and at least one non-ionic, anionic and amphoteric surfactant |
US10226411B2 (en) | 2012-08-02 | 2019-03-12 | L'oreal | Dyeing composition comprising a fatty substance, a non-ionic guar gum, an amphoteric surfactant and a non-ionic or anionic surfactant, and an oxidizing agent, dyeing process and suitable device |
US10201483B2 (en) | 2012-08-02 | 2019-02-12 | L'oreal | Dye composition in cream form comprising at least one oil and little or no solid fatty alcohol, dyeing process and suitable device |
US10626294B2 (en) | 2012-10-15 | 2020-04-21 | L'oreal | Aqueous wax dispersions containing volatile solvents |
US9408785B2 (en) | 2012-10-15 | 2016-08-09 | L'oreal | Hair styling compositions containing aqueous wax dispersions |
US10888504B2 (en) | 2012-10-15 | 2021-01-12 | L'oreal | Hair styling compositions containing aqueous wax dispersions |
US10413496B2 (en) | 2012-10-15 | 2019-09-17 | L'oreal | Aqueous wax dispersions |
KR20150080607A (en) * | 2012-10-31 | 2015-07-09 | 로레알 | Oil-rich composition and use thereof in a lightening or non-lightening direct dyeing process |
US9987205B2 (en) | 2012-10-31 | 2018-06-05 | L'oreal | Oil-rich composition and use thereof in a lightening or non-lightening direct dyeing process |
US9474700B2 (en) | 2012-11-09 | 2016-10-25 | L'oreal | Methods for altering the color and appearance of hair |
US9566221B2 (en) | 2012-11-09 | 2017-02-14 | L'oreal | Methods for altering the color and appearance of hair |
US10130829B2 (en) | 2013-12-23 | 2018-11-20 | L'oreal | Packaging article comprising an envelope and an anhydrous dye composition comprising a direct dye, use of the same and process for dyeing keratin fibres |
US10117811B2 (en) | 2013-12-23 | 2018-11-06 | L'oreal | Packaging article comprising an envelope and an anhydrous dye composition comprising an oxidation dye, use of the same and process for dyeing keratin fibres |
US11911636B2 (en) | 2013-12-23 | 2024-02-27 | L'oreal | Process for treating keratin fibers using a packaging article comprising an envelope and an anhydrous composition comprising an oxidizing agent |
US10561596B2 (en) | 2014-04-11 | 2020-02-18 | L'oreal | Compositions and dispersions containing particles comprising a polymer |
US10765612B2 (en) | 2016-11-28 | 2020-09-08 | L'oreal | Dye composition comprising 12-hydroxystearic acid, an organic amine and a dye |
US11096880B2 (en) | 2017-06-16 | 2021-08-24 | L'oreal | Process for dyeing keratin fibres using at least one direct dye and at least one disulfide, thiol or protected-thiol fluorescent dye |
US11278482B2 (en) | 2017-06-16 | 2022-03-22 | L'oreal | Process for dyeing keratin materials using at least one blue, purple or green dye and at least one disulfide, thiol or protected thiol fluorescent dye |
US11672747B2 (en) | 2018-12-21 | 2023-06-13 | L'oreal | Process for dyeing keratin materials using a direct dye and an aliphatic ammonium salt, and composition comprising same |
Also Published As
Publication number | Publication date |
---|---|
BE784359A (en) | 1972-12-04 |
CA1021324A (en) | 1977-11-22 |
CH560539A5 (en) | 1975-04-15 |
FR2140205B1 (en) | 1977-12-23 |
IT982408B (en) | 1974-10-21 |
GB1360562A (en) | 1974-07-17 |
FR2140205A1 (en) | 1973-01-12 |
DE2227214A1 (en) | 1972-12-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3869454A (en) | Novel diazamerocyanines and their use for dyeing keratinous fibers | |
US3985499A (en) | Diazamerocyanines for dyeing keratinous fibers | |
EP1037586B1 (en) | Utilization of onium aldehydes and onium ketones for dying fibers containing keratin | |
US5931973A (en) | 4,5-dIiminopyrazolines, processes for their preparation, and their application in keratin fiber dyeing compositions and processes | |
KR101364872B1 (en) | Hair dyeing composition | |
KR100391696B1 (en) | Dyeing composition for keratinous fibres with direct cationic colouring agent and a quaternary ammonium salt | |
KR20030036914A (en) | Method of dyeing keratin-containing fibres | |
US3867094A (en) | Dyeing keratinous fibers with dye compositions containing indoanilines | |
JPH08501322A (en) | Method for dyeing keratin-containing fibers | |
JP4566985B2 (en) | Cationic dimer dye | |
KR100391695B1 (en) | Dyeing composition for keratinous fibres with a direct cationic colouring agent and a surfactant | |
US5096455A (en) | Process for dyeing keratinous fibres employing an indole dye and at least one para-phenylenediamine containing a secondary amino group absent an oxidant other than air | |
US5167669A (en) | Composition for dyeing keratinous fibers employing an indole dye and at least one para-phenylenediamine containing a secondary amino group and process for use | |
US3963764A (en) | Indoanilines | |
US3853464A (en) | Human hair dyeing compositions containing diphenylamines | |
US3516778A (en) | Naphthoquinone imine compositions and method for using the same | |
US4023926A (en) | Diaminobenzoquinones in hair dye compositions | |
US5089025A (en) | Hair dye compositions and certain 1,2,3,4-tetrahydronitroquinoxalines useful therein | |
AU734004B2 (en) | Colorants | |
US5752984A (en) | Use of 1,2,3,4-tetrahydroquinoxalines as oxidation dye precursors in oxidative coloring formulations | |
JP4002883B2 (en) | Composition for dyeing keratin fibers containing diheteroylarylmethane direct dye or leuco precursor of this dye and dyeing method using the same | |
US3972937A (en) | Diphenylamines for dyeing keratinous fibers | |
US3894837A (en) | Dye composition containing indophenol for keratinous fibers and method using the same | |
US3824074A (en) | Hair dye compositions containing salts of morpholino(2,3-b)phenoxazonium | |
US3749716A (en) | N-(7-(6-hydroxy-1-oxa-4-aza-1,2,3,4-tetra-hydro)naphthyl)benzoquinonediimines |