US3787174A - Diphenylamines for dyeing keratinous fibers - Google Patents

Diphenylamines for dyeing keratinous fibers Download PDF

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Publication number
US3787174A
US3787174A US00270650A US3787174DA US3787174A US 3787174 A US3787174 A US 3787174A US 00270650 A US00270650 A US 00270650A US 3787174D A US3787174D A US 3787174DA US 3787174 A US3787174 A US 3787174A
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hair
diphenylamine
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water
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G Kalopissis
A Bugaut
F Estradier
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LOreal SA
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LOreal SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/40—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
    • 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
    • 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

  • diphenylamines are usefully employed in cosmetic compositions for the hair including hair dye compositions and hair setting lotion compositions.
  • This invention relates to novel leuco derivatives of indoanilines, a process for preparing the same and to novel cosmetic compositions containing these leuco derivatives for dyeing keratinic fibers such as human hair.
  • the leuco derivatives of indoanilines of this invention are colorless compounds which when applied in an aqueous solution to the fibers to be dyed, oxidize in the air or in the presence of another oxidizing agent thereby giving the corresponding indoanilines, which on the other hand are colored compounds directly responsible for dyeing of the fiber.
  • the dyes thus obtained present qualities of fastness and intensity of dyeing superior to those dyeings obtained by' direct application of indoanilines, because of the better solubility of the leucoderivatives of these compounds.
  • the present invention relates to a compound of the formula:
  • R. and R each independently represent a member selected from the group consisting of hydrogen, halogen, and lower alkyl containing one to four carbon atoms, with the proviso that at least one of R.
  • R R and R is other than hydrogen;
  • R R and R each independently are selected from the group consisting of hydrogen, methozy, lower alkyl containing one to four carbon atoms and lower alkyl containing one to four carbon atoms and substituted with a member selected from the group consisting of hydroxy, carbamyl, piperidinyl and acylamino;
  • R is selected from the group consisting of hydrogen, lower alkyl containing one to four carbon atoms, lower alkyl containing one to four carbon atoms and substituted with a member selected from the group consisting of hydroxy, carbamyl, piperidinyl and acylamino, and together with R and the nitrogen atom to which R is attached form a heterocycle selected from the group consisting of dihy-j drooxazine and pyrroline;
  • R is selected from the group consisting of hydrogen, lower alkyl containing one to four carbon atoms, lower alkyl containing one to four carbon atoms and
  • novel diphenylamines according to the invention can be obtained by two different processes.
  • the first process comprises reducing the corresponding indoanilines of the formula whaehfiift oliiand Z have the meaning indicated :above, said reduction being performed either in an iaqueous alkaline medium with a reducing agent such as isodium hydrosulfite or ammonium sulfide, or in a solvent such as an alcohol, for instance, ethanol, by catalytic hydrogenation at ambient pressure in the presence, for example, of palladium on barium sulfate on on carbon.
  • a reducing agent such as isodium hydrosulfite or ammonium sulfide
  • a solvent such as an alcohol, for instance, ethanol
  • the pH of said medium ranges generally between about 9-12, said pH having been attained generally by the inclusion therein of an alkalinizing agent such as sodium hydroxide or the like.
  • an alkalinizing agent such as sodium hydroxide or the like.
  • the amount of reducing agent employed can vary but generally it will be present in amounts such that the mole ratio of indoaniline being reduced to reducing agent ranges between l:l.5 to 1:3. This reducing reaction is generally carried out at ambient pressure and at a temperature ranging from about 25 to 50C.
  • the reduction of the above indoaniline can be carried out in a solvent selected from the group consisting of ethanol and ethylacetate by catalytic hydrogenation at the ordinary pressure and a temperature of 20 to 50 in the presence of catalytic amounts of palladium on a substrate selected from the group consisting of barium sulfate and carbon.
  • a solvent selected from the group consisting of ethanol and ethylacetate
  • the amount of the catalyst, i.e., the palladium on said substrate ranges between about 10 to 25 percent by weight of the indoaniline being reduced.
  • the second process which makes it possible to obtain the diphenylamines of formula (I) wherein radicals R and R both designate a hydrogen atom, and Z in NH comprises condensing a dinitro derivative of the formula:
  • the reduction of the resulting dinitrodiphenylamine can, as stated above, be carried out in an aqueous alkaline medium having a pH ranging from about 9 to 12, the pH having been attained generally by the inclusion therein of an alkalinizing agent such as sodium hydroxide or the like.
  • This reducing reaction is generally carried out at ambient pressure and at a temperature ranging from about 30 to 60 C.
  • the reduction of the above dinitrodiphenylamine can be carried out in a solvent such as ethanol by catalytic hydrogenation at the ordinary pressure and a temperature of 20 to 50 in the presence of catalytic amounts of palladium on a substrate selected from the group consisting of barium sulfate and carbon.
  • a substrate selected from the group consisting of barium sulfate and carbon.
  • the amount of the catalyst, i.e., the palladium on said substrate ranges between about 10 to 25 percent by weight of the dinitrodiphenylamine being reduced.
  • the diphenylamines of the present invention are usefully employed to dye keratinous fibers, particularly human hair.-When applied to human hair, these compounds, in an aqueous or dilute alcohol solution having a pH ranging from 4 to l l, and in extremely slight concentrations because of their good affinity for keratinous fibers and the power of the dyes obtained after oxidation either in the air or by another oxidizing agent such as hydrogen peroxide, provide an extremely rich range of shades ranging from very luminous violets to ash or silver grays passing through blues, greens, reds, pinks and golden, copper or ash blonds.
  • the dyeings thus obtained are always characterized by their richness in glints and the pearly appearance they impart to the hair.
  • the present invention also relates to a dyeing composition for keratinous fibers, particularly human hair, comprising an aqueous or dilute alcohol solution of at least one compound of formula (I) ofa salt ofsuch a compound.
  • the dyeing compositions according to the invention can contain only the compounds of formula (I). However, they can also contain other known leuco derivatives of indoanilines, indamines or indophenols, or again oxidation dyes, such as oor pphenylenediamines or 0- or p-aminophenols or again direct dyes.
  • the concentration of the compounds of formula (I) in the dyeing composition according to the present invention can vary between 0.002 and 2 percent and generally between 0.005 and 0.5 percent by weight.
  • the pH of the dye compositions according to the present invention can vary between 4 and l I.
  • the alkalizing agent ammonia, mono-, dior triethanolamine, and as an acidifying agent phosphoric acid, acetic acid or lactic acid.
  • the dye composition according to the present invention is generally in the form of an aqueous solution, to which most often a low molecular weight alcohol, such an ethanol or isopropanol, has been added in a proportion of to 70 percent by weight.
  • a low molecular weight alcohol such as ethanol or isopropanol
  • a glycol such as propyleneglycol or butylglycol, can be employed in amounts of about 1 to 6 percent by weight.
  • the alcohol or the glycol facilitate putting the diphenylamines into solution.
  • Dyeing of the keratinous fibers, and particularly human hair, with the dye compositions of the present invention is performed in the usual way by applying said composition to the fibers to be dyed, said composition being left in contact with the fibers for a time varying from 10 to 30 minutes. Following this application the fibers can be rinsed and if desired, washed. Thereafter, the thus treated fibers are dried. If a simultaneous bleaching of the fiber is desired, there can be added to the composition, before its application, either hydrogen peroxide in amounts of 20 to 60 percent in weight of hydrogen peroxide of 20V that is to say 4 to 12 percent in weight of O H or an equivalent quantity of another oxidizing agent of said composition.
  • the novel diphenylamines can also be employed in the production of capillary hair-setting lotions.
  • These lotions comprise an aqueous alcohol solution, at least one diphenylamine of Formula I or a salt thereof and at least one cosmetic resin.
  • the amount of diphenylamine or its salt, as defined above, present in the hair-setting lotion according to this invention can be extremely slight. Such an amount generally varies between 0.002 and 1 percent by weight and preferably between 0.002 and 0.5 percent by weight of the total hair-setting lotion composition, the pH of which generally lies between 5-8.
  • Representative cosmetic resins that can be employed in the hair-setting lotions of the present invention in clude, 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 of vinyl pyrrolidone and vinyl acetate wherein the ratio of PVP to VA ranges between 50-70:50-30, said copolymer having a molecular weight ranging from about 30,000 to 200,000 and maleic anhydride-butylvinyl ether copolymer, a 1 percent solution of which in methylethyl ketone has a viscosity of 0.1-3.5 cps at 25C. These resins are used in a proportion of about 1 to 3 percent by weight of the hairsetting lotion composition.
  • the alcohols suitable for the preparation of the hairblue or pink are characterized by a pearly appearance and a great richness of glints and by their regularity or evenness even in the case of application to irregularly bleached hair.
  • the hair-setting lotions according to the invention are usually employed by application to wet hair, previously washed and rinsed, followed by rolling the hair up on curlers and drying the hair.
  • Second phase Preparation of 4-hydroxy 3-ch1oro 24diamino diphenylamine 0.07 mole (20 g) of sodium hydrosulfite of percent purity is dissolved in cc of normal soda solution. To this solution there is added gradually, with good stirring, while keeping the temperature in the vicinity of 35C, 0.009 mole (2.79 g) of the dinitro derivative previously obtained in the first phase above. When the addition is completed and the reaction mixture colorless, it is neutralized with acetic acid thereby precipitating the above diphenylamine.
  • 5-tetramethyl 2, 4'-diamino diphenylamine already described in Examples 6 and 7 is as follows: 0.00372 mole (l g) of N-[(2', 4-diamino 3', 5'-dimethyl) phenyl] 2,6-dimethyl benzoquinoneimine is dissolved in cc of absolute ethyl alcohol. Then palladium or barium sulfate (5 percent Pd/SO, Ba Englehard Industries) is added as the catalyst and the product is reduced in the usual way by hydrogen at ambient pressure. After 15 minutes, the alcohol solution has become completely colorless. This solution is then filtered to recover the catalyst and it is concentrated under vacuum and nitrogen up to 15 cc.
  • palladium or barium sulfate 5 percent Pd/SO, Ba Englehard Industries
  • First phase A PrepzFatioF of 4 hydr o xy 3,? trimethyl 2', 4-dinitro diphenylamine lnto 300 cc of absolute ethanol there are introduced, on the one hand, 0.04 mole (10.44 g) of 2,4 -dinitro 5- bromo toluene, and, on the other hand, 0.04 mole (5.48 g) of 2,5-dimethyl 4-amino phenol and 4.1 g of molten sodium acetate. The resulting mixture is heated to reflux for 5 hours with stirring and filtered hot to eliminate the inorganic salts.
  • Second phase Preparation of 4-hydroxy 3,6,5- trimethyl 2, 4'-diamino diphenylamine 0.0714 mole (20 g) of sodium hydrosulfite of 75 percent purity is dissolved in 300 cc of a normal soda solution. To this resulting solution there is added gradually, 5 with good stirring, while keeping the temperature in the vicinity of 55, 0.01 mole (3.2 g) of the dinitro derivative obtained in the first phase, as described above. When the addition is completed and the reaction mixture is colorless, it is cooled and then neutralized with acetic acid to precipitate the above diphenylamine. After filtering, washing with water and drying under vacuum at 80 for 5 hours, the product melts at 214.
  • dimethyl 5'-methoxy 2, 4'-diamino diphenylamine 0.003 mole (l g) of the above dinitro derivative obtained in the first phase is dissolved in cc of ethyl acetate.
  • 0.2 g of palladium on carbon (10% Pd on C 65 of Englehard Industries) is added and the product is reduced by hydrogen at ambient pressure.
  • the solution troleum ether, 4-hydroxy 2,3-dimethyl 5'-methoxy 2', 4-diamino diphenylamine crystallizes, which is then filtered and dried under vacuum for several days. This product melts at 195.
  • the following hair dye composition is prepared:
  • Dye of Example 1 0.1 g Ethyl alcohol, 96 titer 20 g Water, g.s.p. 100 g Ammonia at 22 Be... q.s.p. pH 10 This hair dye composition when applied for 20 minutes to percent naturally white hair, imparts thereto an intense violine shade after rinsing and shampooing.
  • Dye of Example 10 0.1 g Ethyl alcohol, 96 titer 20 g Water, q.s.p. 100 g Ammonia at 22Be., q.s.p. pH 10 This hair dye composition when applied for 20 minutes to bleached hair, imparts thereto, after rinsing and shampooing, a very luminous intense parme shade.
  • the pH of the solution is 8 This hair dye composition when applied for IS minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, an intense purple violet shade.
  • Dye of Example 6 Ethyl alcohol, 96 titer Water, q.s.p. 100 g Ammonia at 22Be., q.s.p. pH l0 This hair dye composition when applied for 20 minutes to bleached hair, imparts thereto, after rinsing and shampooing, a very intense purple violet shade.
  • Example 8 in dihydrochloride form 0.l65 g Ethyl alcohol, 96 titer 30 g Water. q.s.p. I00 8 Ammonia at 22' Be.. q,s.p. pH 9
  • This hair dye composition when applied for minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a very luminous mauve shade with pink glints.
  • This hair dye composition when applied for minutes to bleached hair, imparts thereto, after rinsing and shampooing, a silvery turquoise blue shade.
  • Example 36 The solution of Example 35 is applied for 20 minutes to 95 percent naturally white hair. After rinsing and shmpooing, a very luminous silver gray is obtained.
  • This hair dye composition when applied for 20 minutes to bleached hair, imparts thereto, after rinsing and shampooing, a very strong violet shade.
  • Dye of Example 9 0
  • EXAMPLE 40 The following hair dye composition is prepared:
  • This hair dye composition when applied for 20 minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a pearly glycine shade.
  • Dye of Example 13 0.15 g Ethyl alcohol, 96 titer 50 g Water, q.s.p. I00 g l7r lactic acid solution, q.s.p, pH 7 This hair dye composition when applied for 20 minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, an iridescent violet pink shade.
  • Dye of Example I6 0.03 g Ethyl alcohol, 96 titer 30 g Water. q.s.p. I00 g 1% lactic acid solution. q.s.p. pH 6 This hair dye composition when applied for 30 minutes to bleached hair, imparts thereto, after rinsing and shampooing, a cyclamen coloring.
  • This hair dye composition when applied for min utes to bleached hair, imparts thereto, after rinsing and shampooing, a bright pink shade with golden glints.
  • This hair dye composition when applied for minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a pearly rose shade.
  • Dye of Example 17 H g Butylglycol 5 g Lauryl alcohol oxyethylenated with l0.5 moles of 5 g ethylene oxide Water, q.s.p I00 g Ammonia at 22 80.. q.s.p. pH 9
  • This hair dye composition when applied for 20 minutes to bleached hair, imparts thereto, after rinsing and shampooing, a golden blond shade with pink glints.
  • EXAMPLE 46 The following hair dye composition is prepared:
  • Dye of Example 22 0.09 g Ethyl alcohol, 96 titer 30 g Water, q.s.p. I00 g l7r lactic acid solution. q.s.p. pH 5.5
  • This hair dye composition when applied for 20 minutes to bleached, hair, imparts thereto, after rinsing and shampooing, a pale blue green shade with golden glints.
  • EXAMPLE 48 The following hair dye composition is prepared:
  • This hair-setting lotion when applied to bleached hair imparts thereto a golden blond shade with pink glints.
  • EXAMPLE 50 The following hair-setting lotion composition is prepared:
  • This hair-setting lotion when applied to bleached hair, imparts thereto a light golden bronze shade.
  • EXAMPLE 51 The following hair-setting lotion composition is prepared:
  • EXAMPLE 52 The following hair-setting lotion composition is prepared:
  • EXAMPLE 53 The following hair-setting lotion composition is prepared:
  • This hair setting lotion when applied to bleached hair, imparts thereto a pearly ash blond shade.
  • EXAMPLE 54 The following hair-setting lotion composition is prepared:
  • This hair-setting lotion when applied to bleached hair, imparts thereto a pearly pink shade.
  • EXAMPLE 55 The following hair-setting lotion composition is prepared:
  • Triethanolamine q.s.p. pH 7.5
  • This hair-setting lotion composition when applied to bleached hair, imparts thereto a very intense mauve shade.
  • EXAMPLE 56 The following hair-setting lotion composition is prepared:
  • Dyc of Example 13 0.08 g Vinyl acetatc-crotonic acid copolymer (90% vinyl 2 g acetate. 10'71 crotonic acid. average molecular weight Ethyl alcohol, 96 titer 50 g Water, q.s.p. I00 g Ammonia at 22 Be., q.s.pv pH 6 This hair-setting lotion when applied to bleached hair imparts thereto a pale pink shade with golden glints.
  • EXAMPLE 60 The following hair-setting lotion composition is prepared:
  • Example 4 0.005 g Vinyl acetate-crotonic acid copolymer (vinyl acetate 2 g 90%, crotonic acid molecular weight 45,000 to 50,000 Ethyl alcohol, 96 titer 50 g 10 Water, q.s.p. l00 g Ammonia at 22Be., q.s.p. pH 8.5
  • This hair-setting lotion when applied to bleached hair imparts thereto a golden blond shade with pink glints.
  • EXAMPLE 64 The following hair-setting lotion composition is prepared:
  • EXAMPLE 65 The following hair dye composition is prepared:
  • Dye of Example 18 0.1 g 2.6-diamino 4-N,N-diethylamino-2 phenol 0.03 g trihydrochloride Ethyl alcohol. 96 titer 20 g Water. q.s.p. I00 g Ammonia at 2'2Be.. q.s.p. pH 9 This hair dye composition when applied for 20 minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a dark copper blonde shade.
  • Dye of Example 8 0.] g Z-amino 4-methoxy phenol hydrochloride 0.02 g 4.4-dihydroxy 3,5-dimethyl diphenylamine 0.06 g Ethyl alcohol, 96 titer 20 g Water, q.s.p. I00 g Ammonia at 22Be., q.s.p. pH 9 This hair dye composition when applied for 20 minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a slightly mauve silvery gray shade.
  • Dye of Example 2 0.12 g Ethyl alcohol, 96 titer 30 g 20 volume hydrogen peroxide 50 g Water, q.s.p. 100 g Ammonia at 22Be., q.s.p. pH 9
  • This hair dye composition when applied for 20 minutes to 95 percent naturally white hair, imparts thereto, after rinsing and shampooing, a silvery blue gray shade.
  • EXAMPLE 70 The following hair dye composition is prepared:
  • Dye of Example 26 0.08 g Ethyl alcohol. 96 titer 30 g Water, q.s.p. I00 g The pH of this composition is 8 This hair dye composition when applied for 20 minutes to bleached hair, imparts thereto, after rinsing and shampooing, an intense cyclamen shade.
  • This hair dye composition when applied for 20 minutes to percent naturally white hair, imparts thereto, after rinsing and shampooing, a very luminous bronze green shade.
  • EXAMPLE 72 The following hair dye composition is prepared:
  • R. and R each independently represent a member selected from the group consisting of hydrogen, halogen and lower alkyl with the proviso that at least one of R, and R is other than hydrogen;
  • R R, and R each independently are selected from the group consisting of hydrogen, lower alkyl containing one to four carbon atoms, hydroxy lower alkyl containing one to four carbon atoms and methoxy
  • R is selected from the group consisting of hydrogen, lower alkyl containing one to four carbon atoms and hydroxy lower alkyl containing one to four carbon atoms;
  • R, is selected from the group consisting of hydrogen, lower alkyl containing one to four carbon atoms and hydroxy lower alkyl containing one to four carbon atoms;
  • Z is selected from the group consisting of amino, acylamino and hydroxy;
  • composition of claim 1 wherein said diphenylamine is 4-hydroxy-3,5,3',5'-tetramethyl-2, 4'-diamino diphenylamine.
  • composition of claim 1 having a pH between 4 and ll.
  • composition of claim 1 which also includes a dyevselected from the group consisting of orthoand para-phenylenediamines, orthoand paraaminophenols, other leuco derivatives of indoanilines, indamines or indophenols, and direct dyes.
  • composition of claim 1 wherein said alcohol is a glycol in amounts of l to 6 percent by weight.
  • composition of claim 6 wherein said glycol is selected from the group consisting of propyleneglycol and butylglycol.
  • composition of claim 1 wherein said alcohol is a low molecular weight alcohol in amounts of 20 to percent by weight.
  • composition of claim 8 wherein said low molecular weight alcohol is selected from the group consisting of ethanol and isopropanol.
  • composition of claim 1 wherein said solvent is an aqueous alcohol solution and which also includes a cosmetic resin.
  • composition of claim 10 wherein said cosmetic resin is selected from the group consisting of polyvinylpyrrolidone, copolymer of crotonic acid-vinyl acetate, copolymer of vinylpyrrolidone and vinyl acetate and copolymer of maleic anhydride and butylvinyl ether.
  • a process of dyeing keratinous fibers comprising impregnating said fibers with the composition of claim 1, permitting said composition to remain in contact with said fibers for a time ranging from about 10 to 30 minutes, rinsing said fibers and drying said fibers.
  • a process for treating human hair comprising applying to hair previously washed and rinsed, a composition defined in claim 10, rolling said hair up on curlers and drying said hair.
  • Patent No. 3,7B7p174 .5 UNITED STATES PATENT OFFICE v CERTIFICATE OF CORRECTION -Dated J anuarL 22, 1974 s; Andree Bugaut Grego ire Ka Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

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US00270650A 1969-08-11 1972-07-11 Diphenylamines for dyeing keratinous fibers Expired - Lifetime US3787174A (en)

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AT (1) AT306244B (de)
BE (1) BE754649A (de)
CA (1) CA1007247A (de)
CH (2) CH533986A (de)
DE (2) DE2039358C3 (de)
ES (1) ES382641A1 (de)
FR (1) FR2056799A5 (de)
GB (1) GB1276771A (de)
IT (1) IT986777B (de)
LU (1) LU59265A1 (de)
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929403A (en) * 1969-06-11 1975-12-30 Oreal Process for producing indoanilines and keratin fiber dye composition containing the same
US3950127A (en) * 1972-12-26 1976-04-13 Clairol Incorporated Hair dye compositions containing nitrodiphenylamine dyes and method for dyeing hair therewith
US3972937A (en) * 1969-08-11 1976-08-03 L'oreal Diphenylamines for dyeing keratinous fibers
US3981676A (en) * 1970-03-03 1976-09-21 L'oreal Lyophilized dyes and the use thereof to color keratinic fibers
US3981678A (en) * 1970-03-03 1976-09-21 L'oreal Lyophilized dyes and the use thereof to color keratinic fibers
US4092102A (en) * 1973-10-15 1978-05-30 Clairol Incorporated Dyeing keratin fibers with 2-substituted m-toluenediamines
US4112229A (en) * 1969-08-11 1978-09-05 L'oreal Diphenylamines for dyeing keratinous fibers
US4170452A (en) * 1976-01-19 1979-10-09 L'oreal Dye composition containing diphenylamine and polyhydroxybenzene
US4288622A (en) * 1974-02-22 1981-09-08 L'oreal N,N-Dialkylamino diphenylamines and the use thereof in compositions for dyeing keratinic fibers
US5026730A (en) * 1987-08-21 1991-06-25 Ciba-Geigy Corporation Anilinophenylthioureas, compositions containing them, and the use thereof in pest control
US9226883B2 (en) 2011-12-13 2016-01-05 L'oreal Particular azomethine direct dyes, dye composition comprising at least one such compound, implementation process therefore and use thereof
US9233057B2 (en) 2011-12-13 2016-01-12 L'oreal Particular quinone direct dyes, dye composition comprising at least one such dye, implementation process therefor and use thereof
US9439844B2 (en) 2011-12-13 2016-09-13 L'oreal Tri-aromatic azomethine direct dyes comprising at least one unit derived from resorcinol, dyeing composition, method and use
US9554977B2 (en) 2011-12-13 2017-01-31 L'oreal Triaromatic azomethine direct dyes, dye composition comprising at least one such dye, method of implementation and use

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE786219A (de) * 1971-07-14 1973-01-15 Oreal
FR2421606A1 (fr) * 1978-04-06 1979-11-02 Oreal Procede de teinture de fibres keratiniques en deux temps
DE3119385A1 (de) 1981-05-15 1982-12-09 Basf Ag Ethoxylierte diphenylamine als lichtschutzmittel
FR3006179B1 (fr) 2013-05-29 2015-05-15 Oreal Colorants directs quinoniques a groupe aniline encombre, composition tinctoriale comprenant au moins un tel colorant, procede de mise en œuvre et utilisation
FR3060331B1 (fr) 2016-12-16 2020-06-19 L'oreal Nouveaux colorants direct azomethiniques symetriques, composition cosmetique comprenant au moins un tel colorant, procede de mise en œuvre et utilisation
FR3060562B1 (fr) 2016-12-16 2019-05-24 L'oreal Nouveaux colorants directs azomethiniques presentant au moins une charge cationique, composition cosmetique comprenant au moins un tel colorant, procede de mise en oeuvre et utilisation
FR3060308B1 (fr) 2016-12-16 2020-06-19 L'oreal Nouveaux colorants directs azomethiniques dissymetriques, composition cosmetique comprenant au moins un tel colorant, procede de mise en oeuvre et utilisation

Citations (3)

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US2075359A (en) * 1930-10-16 1937-03-30 Du Pont Insecticide
US3563684A (en) * 1964-03-02 1971-02-16 Oreal Dyeing keratinic fibers and human hair with para-diamines and couplers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1915334A (en) * 1930-10-16 1933-06-27 Du Pont Fluosilicate of organic heterocyclic bases and process of making it
US2075359A (en) * 1930-10-16 1937-03-30 Du Pont Insecticide
US3563684A (en) * 1964-03-02 1971-02-16 Oreal Dyeing keratinic fibers and human hair with para-diamines and couplers

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929403A (en) * 1969-06-11 1975-12-30 Oreal Process for producing indoanilines and keratin fiber dye composition containing the same
US4112229A (en) * 1969-08-11 1978-09-05 L'oreal Diphenylamines for dyeing keratinous fibers
US3972937A (en) * 1969-08-11 1976-08-03 L'oreal Diphenylamines for dyeing keratinous fibers
US3981676A (en) * 1970-03-03 1976-09-21 L'oreal Lyophilized dyes and the use thereof to color keratinic fibers
US3981678A (en) * 1970-03-03 1976-09-21 L'oreal Lyophilized dyes and the use thereof to color keratinic fibers
US3950127A (en) * 1972-12-26 1976-04-13 Clairol Incorporated Hair dye compositions containing nitrodiphenylamine dyes and method for dyeing hair therewith
US4092102A (en) * 1973-10-15 1978-05-30 Clairol Incorporated Dyeing keratin fibers with 2-substituted m-toluenediamines
US4288622A (en) * 1974-02-22 1981-09-08 L'oreal N,N-Dialkylamino diphenylamines and the use thereof in compositions for dyeing keratinic fibers
US4170452A (en) * 1976-01-19 1979-10-09 L'oreal Dye composition containing diphenylamine and polyhydroxybenzene
US5026730A (en) * 1987-08-21 1991-06-25 Ciba-Geigy Corporation Anilinophenylthioureas, compositions containing them, and the use thereof in pest control
US9226883B2 (en) 2011-12-13 2016-01-05 L'oreal Particular azomethine direct dyes, dye composition comprising at least one such compound, implementation process therefore and use thereof
US9233057B2 (en) 2011-12-13 2016-01-12 L'oreal Particular quinone direct dyes, dye composition comprising at least one such dye, implementation process therefor and use thereof
US9439844B2 (en) 2011-12-13 2016-09-13 L'oreal Tri-aromatic azomethine direct dyes comprising at least one unit derived from resorcinol, dyeing composition, method and use
US9554977B2 (en) 2011-12-13 2017-01-31 L'oreal Triaromatic azomethine direct dyes, dye composition comprising at least one such dye, method of implementation and use

Also Published As

Publication number Publication date
GB1276771A (en) 1972-06-07
NL161490C (nl) 1980-02-15
DE2066053B1 (de) 1979-11-22
IT986777B (it) 1975-01-30
DE2039358B2 (de) 1980-03-13
SE375522B (de) 1975-04-21
NL7011768A (de) 1971-02-15
CA1007247A (en) 1977-03-22
DE2039358A1 (de) 1971-04-01
NL161490B (nl) 1979-09-17
ES382641A1 (es) 1974-11-01
FR2056799A5 (de) 1971-05-14
BE754649A (de) 1971-02-10
DE2039358C3 (de) 1980-11-06
LU59265A1 (de) 1971-06-21
CH550235A (fr) 1974-06-14
AT306244B (de) 1973-03-26
DE2066053C2 (de) 1980-07-31
CH533986A (fr) 1973-02-28

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