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
  • C09B55/00—Azomethine dyes
  • C09B55/009—Azomethine dyes, the C-atom of the group -C=N- being part of a ring (Image)
• • 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
  • A61K8/494—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
• • 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
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
  • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
• • 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
  • C09B23/164—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms only nitrogen atoms containing one nitrogen atom

Definitions

• the present invention relates to cationic azacyanine dyes containing agents for dyeing fibers, such as keratinic fibers, wool, silk or furs, and in particular human hair, as well as novel azacyanine dyes.
• Cationic substantive dyes have long been known in hair tints.
• oxidative dyeing systems which simultaneously lighten the natural hair melanin during the dyeing process, especially nitro and azo dyes are used, since most other dye types do not survive the oxidation process.
• the present application therefore provides (a) an agent for the non-oxidative dyeing of fibers, preferably keratin fibers and in particular human hair, characterized in that it contains at least one cationic azacyanine dye of the general formula (I); (B) a means for simultaneous lightening and dyeing of fibers, preferably keratin fibers and in particular human hair, which in addition to the dye of formula (I) contains an oxidizing agent and is characterized in that it comprises at least one oxidizing agent stable cationic azacyanine dye of the general Contains formula (I); and
• an oxidative dye for dyeing fibers preferably keratin fibers, and in particular human hair, based on at least one oxidation dye precursor characterized by containing at least one cationic azacyanine dye of general formula (I) which is stable to oxidants;
• A is the group required to form an aromatic carbocyclic or heterocyclic (nitrogen, oxygen or sulfur, which may contain up to two further heteroatoms in addition to the bridge nitrogen) 5- or 6-membered ring;
• R 1 ' is an unbranched or branched (C 1 -C 10) -alkyl chain which may be substituted by one or more alkoxy groups, hydroxyl groups, carboxylic acid amide groups, dialkylamino groups, alkylamino groups, carboxylic acid ester groups, carboxylic acid groups or sulfonic acid groups, an unsubstituted benzyl group, one with a or more alkyl groups, alkoxy groups, alkoxyalkyl groups, hydroxy groups, hydroxyalkyl groups, carboxamide groups, Dialkylamine groups, carboxylic acid ester groups, alkylcarboxylic acid ester groups, carboxylic acid groups, alkylcarboxylic acid groups, sulfonic acid groups or halogen atom
• R2 is hydrogen, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, a halogen atom (F, Cl, Br, J), or a six-membered or five-membered aromatic carbocyclic or heterocyclic (nitrogen, oxygen or sulfur) ring which is unsubstituted or substituted with an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxy group, a hydroxyalkyl group, an alkylcarboxylic acid amide group, a dialkylamino group, a carboxylic acid ester group, an alkylcarboxylic ester group, a carboxylic acid group, an alkylcarboxylic acid group, a sulfonic acid group, an alkylsulfonic acid group, an unsubstituted or substituted benzyl group or a halogen atom (F, Cl, Br, J) may be substituted;
• R 1 ', R 2' and B have the abovementioned meaning and R3 'is hydrogen, an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxy group, a hydroxyalkyl group, an alkylcarboxylic acid amide group, an amino group, an alkylamino group, a dialkylamino group, a carboxylic acid ester group, an alkylcarboxylic acid ester group, a carboxylic acid group, an alkylcarboxylic acid group, a sulfonic acid group , an alkylsulfonic acid group or a halogen atom (F, Cl, Br, J);
• radicals R 1 are the same as a straight or branched (C 1 -C 10) -alkyl chain which may be substituted by one or more alkoxy groups, hydroxy groups, carboxylic acid amide groups, dialkylamino groups, alkylamino groups, carboxylic acid ester groups, carboxylic acid groups or sulfonic acid groups, an unsubstituted benzyl group, a with one or more alkyl groups, alkoxy groups, alkoxyalkyl groups, hydroxy groups, hydroxyalkyl groups, carboxamide groups, dialkylamine groups, carboxylic acid ester groups, alkylcarboxylic acid ester groups, carboxylic acid groups, alkylcarboxylic acid groups, sulfonic acid groups or halogen atoms (F, Cl, Br, J) substituted benzyl group, or a six-membered or five-membered aromatic carbocyclic or heterocyclic (nitrogen, oxygen or sulfur) ring which is
• R7, R8, R1Q, R13, R14, R16, R17, R19 and R22 are each independently hydrogen, a straight or branched (C1-C10) -alkyl chain unsubstituted or having an alkoxy group, a hydroxy group, a carboxamide group , a dialkylamine group, an alkylamine group, a carboxylic acid ester group, a carboxylic acid group or a sulfonic acid group, an unsubstituted benzyl group, one having an alkyl group, an alkoxy group, an alkoxyalkyl group, a hydroxy group, a hydroxyalkyl group, a carboxylic acid amide group, a Dialkylamino group, a carboxylic acid ester group, an alkylcarboxylic acid ester group, a carboxylic acid group, an alkylcarboxylic acid group, a sulfonic acid group or a halogen atom (F,
• the symmetrical azacyanines in which the two ring systems attached to the N atom are identical can be prepared by the method of F. W. Kröck and F. Kröhnke, Chem. Ber. 104, 1645-1654 (1971). This is based on an aromatic nitrogen compound which carries in 2- position an alpha-keto alkyl chain, z.
• 2-acetylpyridine which is reacted in synthesis stage 1 under alkaline conditions with an aromatic aldehyde and then in a second stage in the presence of ammonium acetate / glacial acetic coupling with itself to the dye.
• Unsymmetrical dyes ie compounds of the formula (I) in which the two ring systems attached to the N atom are not identical, for example the following compounds of the formula (III) to (VII)
• a primary Amine without addition of an ammonium compound
• an ammonium compound with a ketone or aldehyde prepared.
• Symmetrical dyes of the invention may, for example, have the following mesomeric basic structure (II),
• X 'and X are identical and hydrogen, an alkyl group, an alkoxy group, an alkoxyalkyl group, represents a hydroxy group, a hydroxyalkyl group, an alkylcarboxylic acid amide group, a dialkylamino group, a carboxylic acid ester group, an alkylcarboxylic ester group, a carboxylic acid group, an alkylcarboxylic acid group, a sulfonic acid group, an alkylsulfonic acid group or a halogenator, and Y is a counterion selected from the group of organic or inorganic acid anions , such as As halides (chloride, bromide, iodine id), sulfates, acetates, lactates, perchlorate or hexa
• the dye (III) or (IV) is added in the second stage instead of ammonium an aromatic amine.
• the dye (III) or (IV) is added in the second stage instead of ammonium an aromatic amine.
• the radical R1 4 or R1 is preferably mixed with the aldehydes vanillin (4-hydroxy-3-methoxybenzaldehyde), isovanillin (3-hydroxy-4-methoxybenzaldehyde), 3,4-dihydroxybenzaldehyde, 4-hydroxybenzaldehyde, 3,5 Dimethoxy-4-hydroxybenzaldehyde, 4-dimethylaminobenzaldehyde, A-methyl-5-imidazole-carboxaldehyde, 4-methoxybenzaldehyde, A-dimethylamino-cinnamaldehyde,
• the self-coupling or a reaction with other ketones, amines, or aldehydes in question Preferred is the self-coupling and in particular the reaction with other ketones or amines.
• nitrogen-containing heterocycles or their organic or inorganic salts such as.
• Particularly preferred ketone coupling partners for preparing the azacyanines are methylisatin, ethylisatin and N-2-hydroxyethyl isatin.
• the dyes of the formula (I) are present in the colorant in a total amount of from 0.01 to 15 percent by weight, preferably from 0.05 to 10 percent by weight.
• the colorant according to the invention may contain, in addition to the dyes of the general formula (I), in addition further natural or synthetic non-oxidative dyes.
• natural dyes plant dyes such as henna or indigo may be mentioned, while as synthetic non-oxidative dyes azo dyes, triphenylmethane dyes, quinone dyes and in particular nitro dyes, such as 1, 4-bis [(2-hydroxyethyl) amino] -2 nitrobenzene, 1- (2-hydroxyethyl) amino-2-nitro-4- [di (2-hydroxyethyl) amino] benzene, (HC Blue No.
• anionic (“acidic”) dyes compatible with the cationic dyes used may be added in special cases, such as, for example, 6-hydroxy-5 - [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid disodium salt (CH 5985 Food Yellow No. 3, FD & C Yellow No. 6), 2,4-dinitro-1-naphthol-7-sulfonic acid disodium salt (CH 0316, Acid Yellow No. 1, Food Yellow No. 1), 2- (indan - 1, 3-dione-2-yl) quinoline-x, x-sulfonic acid (mixture of mono- and Disulfonic acid) (CI47005, D & C Yellow No.
• 6-hydroxy-5 - [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid disodium salt CH 5985 Food Yellow No. 3, FD & C Yellow No. 6
• the total content of additional natural and / or synthetic non-oxidative dyes in the colorant according to the invention is about 0.01 to 15 weight percent, in particular about 0.1 to 12 weight percent.
• oxidative dye precursors such as paraphenylenediamines, metaphenylenediamines, aminophenols or 4,5-diaminopyrazoles may also be added to the colorant of the invention.
• the additional developing agents and couplers may be included in the colorant in a total amount of about 0.01 to 20, respectively Percent by weight, preferably about 0.1 to 10 percent by weight and especially 0.1 to 5 percent by weight.
• the carriers customary in cosmetic systems can be added to increase the color intensity.
• Suitable compounds are described for example in DE-OS 196 18 595, which is incorporated herein by reference.
• Particularly suitable carriers are, for example, benzyl alcohol, vanillin and isovanillin.
• the dyes described above are applied for coloring in a suitable dye carrier mass.
• the preparation form of the colorant according to the invention can be, for example, a solution, in particular an aqueous or aqueous-alcoholic solution.
• the particularly preferred preparation forms are a cream, a gel, an emulsion or a powder or granule preparation.
• Their composition is a mixture of the dyes with the usual additives for such preparations.
• Typical additives in solutions, creams, emulsions, gels, powders or granules are, for example, solvents such as water, lower aliphatic alcohols, for example ethanol, propanol or isopropanol, glycerol or glycols such as 1, 2-propylene glycol, wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or non-ionic surface-active substances, for example fatty alcohol sulfates, ethoxylated fatty alcohol sulfates, alkyl sulfonates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid alkanolamides and ethoxylated fatty acid esters, furthermore thickeners such as higher fatty alcohols, starch, cellulose derivatives, petrolatum, par
• constituents mentioned are used in the amounts customary for such purposes, for example the wetting agents and emulsifiers in concentrations of about 0.1 to 30 percent by weight, the thickeners in an amount of about 0.1 to 30 percent by weight and the conditioners in one Concentration of about 0.1 to 5.0 percent by weight.
• the dyeing agent may contain other conventional additives, for example antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite, as well as perfume oils, penetrating agents, buffer systems, complexing agents, preservatives, wetting agents, emulsifiers, thickeners, encapsulating agents, granulation aids and conditioners.
• antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite
• perfume oils for example antioxidants such as ascorbic acid, thioglycolic acid or sodium sulfite, as well as perfume oils, penetrating agents, buffer systems, complexing agents, preservatives, wetting agents, emulsifiers, thickeners, encapsulating agents, granulation aids and conditioners.
• the ready-to-use colorant according to the invention can be used undiluted or can be prepared immediately before use by mixing the color carrier mass containing the dyes with water, a care product or with an oxidizing agent.
• the oxidizing agent are mainly hydrogen peroxide or its addition compounds of urea, melamine, sodium borate or sodium carbonate in the form of a 1- to 12prozentigen, preferably a 3- to ⁇ prozentigen, aqueous solution into consideration.
• Dye of formula (1) additionally persulfates, z.
• ammonium persulfate, potassium persulfate or sodium persulfate can be added.
• the weight ratio between dye carrier mass and oxidizing agent is in this case preferably about 5: 1 to 1: 3, in particular 1: 1 to 1: 2. Larger amounts of oxidizing agent are mainly used at higher concentrations of oxidative dye precursors in the colorant, or when at the same time a greater bleaching of the keratin fiber (especially the hair) is intended.
• the pH of the ready-to-use dyeing agent according to the invention can be adjusted so that it can be applied undiluted, or it is adjusted to a pH when mixing the dye-carrier mass with a diluent (conditioner, water, etc.) or the oxidizing agent. which is determined by the pH values of the dye carrier mass and of the diluent or of the oxidizing agent and by the mixing ratio.
• the ready-to-use agent has a pH of from 2 to 11, preferably a pH of from 5 to 11.
• the setting of an alkaline pH is preferably carried out with ammonia, but also organic amines, for example 2-amino-2-methyl-1-propanol, tris (hydroxymethyl) amino-methane, monoethanolamine and triethanolamine, or mixtures of organic amines and ammonia and inorganic bases such as sodium hydroxide and potassium hydroxide can be used.
• the pH is too high, it can be corrected with inorganic or organic acids, for example phosphoric acid, acetic acid, lactic acid, ascorbic acid, citric acid or tartaric acid.
• the dyeing treatment amount generally about 60 to 200 grams, pure or of the mixture on the keratin fiber and leaves the dyeing preparation at about 15 to 50 0 C, preferably 30 to 40 0 C, about 10 to 45 minutes long, preferably for 30 minutes, act on the keratin fiber, then rinsed the keratin fiber with water and dried.
• a shampoo and optionally rinsed with a weak organic acid such as citric acid or tartaric acid.
• the keratin fiber is dried.
• the dyeing center! with canonical azacyanine dyes of the forms! (I) allows, inter alia, a simple and gentle coloring of differently damaged hair (for example, re-dyeing already oxidatively dyed hair lots), wherein the pre-damaged hair parts (for example, the hair tips) the color carrier mass without oxidizing agent -pur or mixed with an acidic, neutral or basic aqueous diluent is applied, while on the little or no pre-damaged hair parts (for example, the young hair) mixed with the oxidizing agent color carrier mass is applied.
• the aqueous component used for dilution may contain the abovementioned customary additives for solutions, creams, emulsions or gels.
• This method allows for color matched to the hair texture, which are characterized by a hair-friendly balance between approach and tips, which is not possible with the use of conventional oxidative hair dye, since the coupling of the dye precursors always an oxidizing agent is needed.
• the colorant according to the invention is characterized by colorations with particularly high color intensity and luminosity, good color balance between damaged and undamaged hair (such as between hair tips and hair offspring), good durability, very good hair care and variable applications with and without oxidant.
• Another object of the present application are novel asymmetric cationic azacyanine dyes of the formula (I), which are to be understood as asymmetrically those compounds of formula (I) in which the seated on the nitrogen radical B is different from that also sitting on this nitrogen ring system ,
• Example 1 Synthesis of (1E) -1 - [(1-ethyl-5-hydroxy-1H-pyrazol-4-yl) imino] -3- [4- (methyloxy) phenyl] -1H-indolizinium acetate
• Step 1 Synthesis of 2- [3- (4-methoxyphenyl) -1-oxoprop-2-enyl1pyridin 7.4 g (61 mmol) of 2-acetylpyridine at 0 0 C to a solution of 8.3 g (61 mmol ) 4-Methoxybenzaldehyde in 100 ml of methanol. 100 ml of a 2 N sodium hydroxide solution are added with vigorous stirring. After stirring for 14 hours at room temperature, the yellow precipitate is filtered off, washed with 10 ml of methanol and three times with 50 ml of water and dried in vacuo. Yield: 11.4 g (78% of theory).
• Step 2 Synthesis of (1 E) -1 - [(1-ethyl-5-hydroxy-1H-pyrazol-4-yl) imino1-3-f4 (methyloxy) -phenyl-1H-indolizinium acetate
• the pH is adjusted to 10 with 25% ammonia.
• Washed shampoo rinsed with lukewarm water and then dried n.
• the pH is adjusted to 10 with 25% ammonia.
• the pH is adjusted to 10 with 25% ammonia.
• the pH is adjusted to 10 with 25% ammonia.
• the pH is adjusted to 9 with 25% ammonia.
• the pH is adjusted to 10 with 25% ammonia.
• 5 g of the above color carrier mass are mixed with 5 g of a conditioner.
• the ready-to-use hair dye is applied to bleached hair strands and spread evenly with a brush. After an exposure time of 20 minutes at 40 0 C, the hair is rinsed with lukewarm water, washed with a shampoo, rinsed again with lukewarm water and then dried. This gives an intense red streak.
• the pH is adjusted to 10 with 25% ammonia.
• 5 g of the above color carrier mass are mixed with 5 g of a 6% hydrogen peroxide solution.
• the ready-to-use hair dye is applied to light brown hair strands and spread evenly with a brush. After an exposure time of 20 minutes at 40 0 C, the hair is rinsed with lukewarm water, washed with a shampoo, rinsed again with lukewarm water and then dried. This gives a deep blue-green colored streak.
• Dye pellets prepared in the top spray method (component A) 3.86 g of 2,4-diamino-phenoxyethanol * HCl
• the spray rate and the supply air temperature are kept constant.
• the amount of air is, depending on the dye mixture to max. 10O m 3 / h increased.
• the product temperature is kept depending on the dye mixture throughout the process between 40 and 60 0 C. After applying the dye dispersion, the pellets are dried at a maximum product temperature of 60 0 C, then allowed to cool to about 30 ° C and sieved.
• Cream base (component B)

Applications Claiming Priority (2)

Publications (1)

Family

ID=35456935

Family Applications (1)

Country Status (10)

Families Citing this family (4)

Family Cites Families (6)

• 2004
  • 2004-10-20 DE DE102004051071A patent/DE102004051071A1/de not_active Withdrawn
• 2005
  • 2005-09-23 EP EP05792753A patent/EP1802375A1/de not_active Withdrawn
  • 2005-09-23 BR BRPI0517005-2A patent/BRPI0517005A/pt not_active IP Right Cessation
  • 2005-09-23 WO PCT/EP2005/010322 patent/WO2006042614A1/de active Application Filing
  • 2005-09-23 AU AU2005297546A patent/AU2005297546A1/en not_active Abandoned
  • 2005-09-23 CA CA002582868A patent/CA2582868A1/en not_active Abandoned
  • 2005-09-23 JP JP2007537138A patent/JP2008517000A/ja active Pending
  • 2005-09-23 CN CN2005800358608A patent/CN101043918B/zh not_active Expired - Fee Related
  • 2005-09-23 MX MX2007004715A patent/MX2007004715A/es active IP Right Grant
• 2007
  • 2007-04-03 US US11/732,214 patent/US7374583B2/en active Active

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events