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
  • C09B44/00—Azo dyes containing onium groups
  • C09B44/10—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system
  • C09B44/16—1,3-Diazoles or hydrogenated 1,3-diazoles ; (Benz)imidazolium
• • 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

• the present invention relates to novel cationic direct dyes, compositions thereof, to processes for their preparation and to their use in the dyeing of organic material, such as keratin fibers, wool, leather, silk, paper, cellulose or polyamides, especially keratin-containing fibers, cotton or nylon, and preferably hair, more preferably human hair.
• organic material such as keratin fibers, wool, leather, silk, paper, cellulose or polyamides, especially keratin-containing fibers, cotton or nylon, and preferably hair, more preferably human hair.
• cationic dyes can be used to dye organic material, for example keratin, silk, cellulose or cellulose derivatives, and also synthetic fibers, for example polyamides. Cationic dyes exhibit very brilliant shades.
• a disadvantage is their unsatisfactory fastness to hydrolysis and to light, their frequently inadequate stability under reducing or oxidizing conditions, and their frequently unsatisfactory storage stability (see: John F. Corbett'The Chemistry of Hair-Care Products", JSCD August 1976, page 290).
• the actual technical problem of the present invention was to provide brilliant dyes that are distinguished by deep dying having good fastness properties with respect to washing, light, shampooing and rubbing, and that preferably exhibit satisfactory stability under reducing or oxidizing dyeing conditions, for the dyeing of organic material.
• Ri is an unsubstituted or substituted C C 1 alkyl or an aryl radical
• X " is an anion
• R 3 is an unsubstituted or substituted CrC ⁇ alkyl, aryl radical, CrC 6 alkoxy, cyanid, nitro or halide; n is 1 or 2; and if n is 1 , then R 2 is hydrogen, unsubstituted or substituted CrCi alkyl; or if n is 2, then R 2 is unsubstituted or substituted CrC ⁇ 4 alkylen.
• Preferred is a cationic dye of formula (1), wherein Ri is methyl.
• Ri is methyl, n is 1, and
• R 2 is a substituted or unsubstituted Ci-Csalkyl.
• Ri is methyl, n is 2, and
• R 2 is a substituted or unsubstituted CrC ⁇ alkylen, preferred is a substituted or unsubstituted
• CrCaalkylen and more preferred is a substituted or unsubstituted CrC 6 alkylen.
• R 3 is hydrogen
• Ri is methyl, n is 1, and
• R 2 is an unsubstituted or substituted Ci-Csalkyl.
• R 3 is hydrogen
• Ri is methyl, n is 2, and
• R 2 is a substituted or unsubstituted C C ⁇ 4 alkylen, preferred is a substituted or unsubstituted d-Csalkylen, and more preferred is a substituted or unsubstituted C C 6 alkylen.
• substituents of C C 14 alkyl or CrCaalkylen, C C ⁇ 2 alkyl or CrCaalkylen, C ⁇ -C 8 alkyl and C ⁇ -C 8 alkylen, and preferably C ⁇ -C 6 alkyl and C ⁇ -C 6 alkylen are, for example hydroxyl; Ci-Csal yl, preferably methyl; or CrC 8 alkoxy and C C 6 alkoxy; cyanide and/or halide; or NR 5 R 6 , wherein R 5 and R 6 are each independently of the other hydrogen, unsubstituted or substituted aryl radical or C ⁇ -C 6 alkyl, preferably methyl, ethyl, propyl, isopropyl or t-butyl.
• d-Cealkyl and CrCaalkylen is d-Cealkyl or d-C ⁇ alkylen, d-C 8 aIkyl and d-C 8 alkylen, and preferably d-C 6 alkyl and d-C 6 alkylen; and preferred is Ci-Csalkyl is Ci-Csalkyl, and C ⁇ -C ⁇ 4 alkylen is preferred C ⁇ -C 6 alkylen.
• C C ⁇ 4 alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2, 2'-di methyl propyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, 1 ,1',3,3'-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl or dodecyl.
• Ci-Csalkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2'-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, I.I ⁇ S'-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl or dodecyl.
• d-C 8 alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2'-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, 1 ' ⁇ S'-tetramethylbutyl or 2-ethylhexyl.
• C ⁇ -C 6 aikyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2'-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl.
• d-dalkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.
• Preferered is methyl, 2,2'-dimethylpropyl, n-hexylen
• CrCaalkylen is, for example, methylen, ethylen, propylen, isopropylen, n-butylen, sec- butylen, tert-butylen, n-pentylen, 2-pentylen, 3-pentylen, 2,2'-dimethylpropylen, cyclo- pentylen, cyclohexylen, n-hexylen, n-octylen, 2-ethylhexylen, nonylen, decylen, undecylen or dodecylen.
• C ⁇ -C ⁇ 2 alkylen is, for example, methylen, ethylen, propylen, isopropylen, n-butylen, sec- butylen, tert-butylen, n-pentylen, 2-pentylen, 3-pentylen, 2,2'-dimethylpropylen, cyclo- pentylen, cyclohexylen, n-hexylen, n-octylen, 1 ,1',3,3'-tetramethylbutylen, 2-ethylhexylen, nonylen, decylen, undecylen or dodecylen.
• C ⁇ -C 8 alkylen is, for example, methylen, ethylen, propylen, isopropylen, n-butylen, sec- butylen, tert-butylen, n-pentylen, 2-pentylen, 3-pentylen, 2,2'-dimethyIpropylen, cyclopentylen, cyclohexylen, n-hexylen, n-octylen, 1,1',3,3'-tetramethylbutylen or 2- ethylhexylen.
• C C 6 alkylen is, for example, methylen, ethylen, propylen, isopropylen, n-butylen, sec- butylen, tert-butylen, n-pentylen, 2-pentylen, 3-pentylen, 2,2'-dimethylpropylen, cyclopentylen, cyclohexylen, n-hexylen.
• d-dalkylen is, for example, methylen, ethylen, propylen, isopropylen, n-butylen, sec- butylen, tert-butylen,
• C ⁇ -C 6 alkoxy is 0-CrC 6 alkyl, preferably 0-C C alkyl.
• Aryl radical is, for example, an unsubstituted or substituted phenyl, benzyl- or tolyl
• Halide is, for example, fluoride, chloride, bromide or iodide, especially chloride and fluoride.
• Anion denotes, for example, an organic or inorganic anion, such as halide, preferably chloride and fluoride, sulfate, hydrogen sulfate, phosphate, boron tetrafluoride, carbonate, bicarbonate, oxalate or C ⁇ -C 8 alkyl sulfate, especially methyl sulfate or ethyl sulfate; anion also denotes lactate, formate, acetate, propionate or a complex anion, such as the zinc chloride double salt.
• halide preferably chloride and fluoride
• sulfate hydrogen sulfate
• phosphate phosphate
• boron tetrafluoride carbonate
• anion also denotes lactate, formate, acetate, propionate or a complex anion, such as the zinc chloride double salt.
• the anion is especially a halide, preferably chloride or fluoride, sulfate, hydrogen sulfate, methylsulfate, phosphate, formate, acetate or lactate.
• the anion is more especially chloride, methyl sulfate, formate or acetate.
• X " is an anion
• X " is an anion
• the present invention concerns in addition a cationic dye of formula (18)
• R 7 is C C 6 alkoxy or halide, preferred halides are chloride or fluoride, preferred fluoride, and
• the present invention concerns a process for the preparation of cationic dyes of formula (18) as defined above, comprising a) diazotiation of a compound of the following formula wherein
• R 3 and R 7 have the above given definitions and preferences, and b) coupling the diazotiated compound with imidazole, and c) then alkylation or arylation; preferably methylating.
• the present invention also concerns a dye of formula (21 )
• the present invention concerns a process for the preparation of cationic dyes of formula (21 ) as defined above, comprising a) diazotizing 2-fluoroanilin and b) then coupling with imidazole.
• the present invention relates also to a process for the preparation of the dyes of formula (1), preferably to a dye of formula (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16) or (17) and comprises a) bringing a compound of formula (18)
• R 7 is CrC 6 alkoxy or halide, preferred halides are chloride or fluoride, preferred fluoride, and
• the reaction is generally initiated by bringing the compound of formula (18) and the amine of formula (19) into contact; for example by mixing together the starting compounds or by drop wise addition of one starting compound to the other.
• the temperature is in the range of 290 to 300 K during the mixing of the starting compounds.
• the molar ratio of compound of formula (18) to amine of formula (19) is generally selected in the range from 5:1 to 1:5, especially in the range from 3:1 to 1:3.
• the duration of reaction is generally dependent on the reactivity of the starting compounds, on the reaction temperature chosen and on the desired conversion.
• the chosen duration of reaction is usually in the range from one hour to three days.
• the reaction temperature for the reaction of the compound of formula (18) with the amine of formula (19) is advisable to select in the range from 293 to 363K, especially in the range from 323 to 355K, more especially in the range from 333 to 355K.
• the reaction pressure chosen is generally in the range from 70 kPa to 10 MPa, especially from 90 kPa to 5 MPa, and is more especially atmospheric pressure.
• the molar ratio of compound of formula (18) to the base is generally selected in the range from 10:1 to 1 :5, especially in the range from 1:1 to 1 :3.
• Suitable bases are for example an alkali metal hydroxide, such as sodium-, potassium or lithium hydroxide, such as sodium hydroxide, or an alkali metal carbonate, such as sodium-, potassium or lithium carbonate, such as sodium carbonate, or an alkali metal hydro- carbonate, such as sodium-, potassium or lithium hydrocarbonate, such as sodium hydrocarbonate, or an alkali metal d-C 6 alkyloxide, such as sodium-, potassium or lithium C C 6 alkyloxide, preferably sodium methoxide, potassium methoxide or lithium methoxide, or sodium ethoxide, potassium ethoxide or lithium ethoxide; or tertiary amines, for example, such as pyridine, trimethylamine, triethylamine, trioctyllamine, 1 ,4-diazabicyclo[2.2.2]octan, chinuclidine, N-methylpiperidine; or alkalimetal acetate, for example such as sodium acetate
• sodium hdroxide sodium carbonate, tertiary amines, such as pyridine and 1 ,4- diazabicyclo[2.2.2]octan.
• the molar ratio of compound of formula (18) to the catalyst is generally selected in the range from 100:0.01 to 100:10, especially in the range from 100:1 to 100:10, most preferred in the range of 100:4 to 100 to 6.
• Suitable catalysts are for example an alkali metal C ⁇ -C 6 alkyloxide, such as sodium-, potassium or lithium d-C 6 alkyloxide, preferably sodium methoxide, potassium methoxide or lithium methoxide, or sodium ethoxide, potassium ethoxide or lithium ethoxide; or tertiary amines, for example, such as pyridine, trimethylamine, triethylamine, trioctyllamine, 1 ,4-diazabicyclo[2.2.2]octan, chinuclidine, N-methylpiperidine; or alkalimetal acetate, for example such as sodium acetate, potassium acetate, or lithium acetate.
• Preferred are potassium acetate, sodium me
• reaction mixture obtained be subsequently stirred in the selected temperature range from 293 to 363 K, especially in the range from 323 to 355K, more especially in the range from 333 to 355K.
• the duration chosen for the subsequent stirring is generally from 1 hour to 24 hours.
• reaction can be carried out with or without solvent, but is preferably carried out in a solvent. Preference is given to organic solvents or solvent mixtures.
• solvents are organic solvents and water, or a mixture of organic solvents or a mixture of organic solvents and water.
• Organic solvents are, for example, protic or aprotic polare organic solvents, such as alcohols, for example methanol, ethanol, n-propanol, isopropanol, butanol orglycols, especially isopropanol, or nitrile, such as acetonitrile or propionitrile, or amide, such as dimethylformamide, dimethylacetamide or N-methyl pyridine, or sulfoxide, such as dimethylsulfoxide, or mixtures thereof.
• protic or aprotic polare organic solvents such as alcohols, for example methanol, ethanol, n-propanol, isopropanol, butanol orglycols, especially isopropanol, or nitrile, such as acetonitrile or propionitrile, or amide, such as dimethylformamide, dimethylacetamide or N-methyl pyridine, or sulfoxide, such as dimethylsulfox
• the ratio by weight of compound of formula (18) to the solvent is generally in the range from 20 to 90% by weight, especially in the range from 30 to 60% by weight.
• the prepared product may be advantageously worked up and isolated, and if desired be purified.
• the work up starts by decreasing the temperature of the reaction mixture in the range from 280 to 300 K, especially in the range from 290 to 300 K. It may be of advantageous to decrease the temperature slowly, over a period of several hours.
• reaction product is usually filtered and then washed with water or a salt solution and subsequently dried.
• Filtration is normally carried out in standard filtering equipment, for example B ⁇ chner funnels, filter presses, pressurised suction filters, preferably in vacuo.
• the temperature for the drying is dependent on the pressure applied. Drying is usually carried out in vacuo at 50-200 mbar.
• the drying is usually carried out at a temperature in the range from 313 to 363 K, especially from 323 to 353 K, and more especially in the range from 328 to 348 K.
• Organic solvents and solvent mixtures are suitable for the recrystallisation. Preference is given to alcohols, for example methanol, ethanol, 2-propanol or butanol, especially 2- propanol.
• the dyes of formula (1) according to the invention are suitable for dyeing organic material, such as keratin, wool, leather, silk, paper, cellulose or polyamides, especially keratin- containing fibers, cotton or nylon, and preferably human hair.
• the multiplicity of shades of the dye which results by the method according to the present invention, can be increased by combination with other dyes.
• the present invention relates also to the coloration of hair with a dye of formula (1) according to the present invention, and at least a single further dye.
• the dye of formula (1) of the present invention can be combined with dyes of the same or different class of dyes, especially with direct dyes, oxidation dyes; dye precursor combinations of a coupler compound and a diazotized compound, or a capped diazotized compound; and/or cationic reactive dyes.
• Direct dyes are natural or synthetic; they are uncharged, cationic or anionic, such as acid dyes.
• Oxidation dye denotes also for oxidation dye precursors, which are from the group of the developer and coupler compounds. Wherein the coupler compounds denotes also to the addition salts thereof with an acid.
• the single classes of dyes comprise the dyes defined in the Color Index of the Society of Textile Chemist and Colorist.
• combinations comprising of a compound of formula (1) are compositions, formulation, methods and.
• the present invention further comprises compositions, formulation, methods or combinations comprising of a compound of formula (1).
• cationic dyes such as
• compositions comprise a compound of formula (1) and in addition at least a single further direct dye and/or an oxidative agent.
• compositions comprise a compound of formula (1) and in addition at least a single oxidative dye and/or; at least a single oxidative dye and an oxidative agent.
• composition comprising a compound of formula (1) in form of a shampoo, conditioner, gel or emulsion.
• method of dyeing organic material, especially human hair that comprises bringing into contact with the organic material at least a single a cationic dye of formula (1 ).
• More preferred is in the present invention a method for dyeing or tinting human hair.
• a further preferred embodiment of the presentinvenmtion concerns a method for dyeing human hair or strands, that comprises contacting the hair with at least a single a cationic dye of formula (1) and an oxidative agent and, optionally, a further direct dye.
• the present invention concerns a method for dyeing human hair according to any of claims 14 to 16, that comprises contacting the hair with at least a single a cationic dye of formula (1) and at least a single oxidative dye; or contacting the hair with a cationic dye of formula (1) and at least a single oxidative dye and an oxidative agent.
• the dyes according to the invention are distinguished by brilliant shades. They are suitable for dyeing organic material, such as keratin, wool, leather, silk, paper, cellulose or polyamides, especially keratin-containing fibers, cotton or nylon, and preferably human hair.
• the dyeing obtained is distinguished by their depth of shade and their good fastness to washing properties, such as, for example, fastness to light, shampooing and rubbing.
• the stability and storage stability of the dyes according to the invention are excellent. They are accordingly especially suitable for dyeing under oxidizing and reducing conditions.
• the advantage of the new dyes according to the present invention especially those of formula (4), (5), or (6), is their stability against reduction agents e. g. sodium sulfite and ascorbic acid. Therefore, they can be combined with oxidation dyes in one emulsion.
• the obtained diazo solution is dropped to a 273 K cold solution of 7.4 g imidazole in 30 ml water, whereby the pH of the solution is maintained in the range of pH 10 to 11 by adding 36% sodium hydroxide solution.
• the obtained suspension is warmed up to 295 K, the pH is adjusted to 10.5 with 36% sodium hydroxide solution. After one hour stirring at this pH and temperature, the suspension is filtrated. Then, the obtained filtercake is washed twice with 50 ml water to obtain 55 g of the humid product.
• the humid product is suspended in 500 ml water and 0.3 mole dimethylsulphate and sodium hydroxide added simoultaniously for maintaining the pH at 10-10,3 and the temperature at 25 to 30°C. The mixture is hold for one hour, to finish the hydrolysis of excess of dimethylsulphate. The the water is evaporated and about 40 g humid solid obtained, which gives 27 g dryed (0.07 mole) product with the following formula:
• Example B1 A strongly alkaline 10 % solution of a non-ionic surfactant (Plantaren 2000, Henkel) is adjusted to pH 9.5 using citric acid. 0.1 % of the dye of formula (28) as given in example A8 is dissolved therein and a strand of human hair, bleached white, is treated with the dye solution at room temperature. After only a short period of time, the strand has been dyed a bluish-red shade, which is still very intensive even shampooing ten times. The dye also has a strong affinity to undamaged hair. In that case, too, the wash fastness is very good. The light fastness on damaged and undamaged hair is excellent. The perm fastness is on un- and damaged hair very good as well.
• a non-ionic surfactant Planten 2000, Henkel
• Example B2 A 10 % solution of a non-ionic surfactant (Plantaren 2000, Henkel) is adjusted to pH 5.5 using citric acid. 0.1 % of the dye of formula (30) as given in example A10 is dissolved therein and a strand of middle blonde undamaged human hair is treated with the dye solution at room temperature. After only a short period of time, the strand has been dyed in a bluish shade, which has a good wash, perm and light fastness.
• a non-ionic surfactant Planten 2000, Henkel
• Silica 0.1 is mixed with the same weight of 6 % hydrogen peroxide solution and the mixture is immediately applied to a tress of brown hair. After 30 minutes the tress is rinsed, shampooed, rinsed and dried. The color result is a very brilliant red shade.
• 2-Amino-3-Hydroxypyridine 0.00 1 is mixed with the same weight of 6 % hydrogen peroxide solution and the mixture is immediately applied to a tress of brown hair. After 30 minutes the tress is rinsed, shampooed, rinsed and dried.
• the color result is a very brilliant violett shade.
• the advantage of the dyes of example 1, 2 and 3 is the stability against reduction agents e. g. sodium sulfite and ascorbic acid. Therefore you can combine them with oxidation dyes in one emulsion.
• a strongly alkaline 10 % solution of a non-ionic surfactant (Plantaren 2000, Henkel) is adjusted to pH 9.5 using citric acid.
• a strongly alkaline 10 % solution of a non-ionic surfactant (Plantaren 2000, Henkel) is adjusted to pH 9.5 using citric acid.
• 0.1 % of the dye of example 1 and 0.1 % of the dye formula (25) as given in example A5 are dissolved therein and a strand of dark blonde undamaged human hair is treated with the dye solution at room temperature. After 20 minutes, the strand has been dyed a intensive aubergine shade, which has a good wash, perm and light fastness.
• a non-ionic surfactant Planten 2000, Henkel
• a strand bleached blond hair is treated with a composition comprising 5 g of 6% by weight hydrogenperoxide solution and 5 g a composition comprising an oxidation base with a pH value of 9.8 as given below:
• composition comprising an oxidation base with a pH value of 9.8
• Example B8a/Second Step After 15 minutes, the pH of the hair is adjusted to pH 5 by addition of citric acid. Then, 5 g of a 12,5% citric acid gel, comprising the 0.1% by weight of dye of formula (20) of example 1 according to the present application, is applied on the hair and combed, so that the hair has a pH of 7. After 15 minutes the hair is washed with water, rinsed and dried. The strand has been dyed in an intensive shade, which has a good wash and light fastness.
• Example B8a/Second Step After 15 minutes, without rinsing, blond hair is treated with a composition comprising 5 g of 6% by weight hydrogenperoxide solution and 5 g a composition comprising an oxidation base with a pH value of 5 as given below:
• Composition comprising an oxidation base with a pH value of 5 (adjusted with citric acid)
• Example B8c/Second Step After 15 minutes the hair is treated with 5 g composition comprising an oxidation base with a pH value of 9.8 as given below:
• composition comprising an oxidation base with a pH value of 9.8
• Example B8a/Second Step After 15 minutes, the pH of the hair is adjusted to pH 5 by addition of citric acid. Then, 5 g of a 12,5% citric acid gel, comprising the 0.1% by weight of dye of formula (20) of example 1 according to the present application, is applied on the hair and combed, so that the hair has a pH of 7. After 15 minutes the hair is washed with water, rinsed and dried. The strand has been dyed in an intensive shade, which has a good wash and light fastness.
• Example B8a/Second Step After 15 minutes, without rinsing, blond hair is treated by a comb with a composition comprising 5 g of 6% by weight hydrogenperoxide solution and 5 g of a composition comprising an oxidation base with a pH value of 9.8 as given below:
• composition comprising an oxidation base with a pH value of 9.8

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