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    • 专利摘要:
    polymeric dye, composition, and method of dyeing organic material the present invention discloses polymeric dyes of formula (1a), (1b), or (1c), where a and b, independently of each other,. represents the polymer backbone; x1 and x2, independently of one another are a linking group selected from -s-, -ss-, -n, -n=-, -n(rj-, -s(o)-, -so2-, - ( ch2,ch2,-o)]-5-, -(ch2,ch2,ch2,-o)1-5-, -c(o-, -c(o)o-, -hollow-, formula ii, - con(r1-, -c(nr1r2)2-, -(r1)nc(o)-, -c(s)r1-;which can be interrupted and/or terminated at one or both ends by one or more of a -c1-c30alkylene- or -c2-c12-alkenylene; or a fused or unfused, saturated or unsaturated, optionally substituted divalent aromatic or non-aromatic (heterocyclic) radical, optionally substituted, optionally comprising at least one heteroatom; a divalent aromatic or non-aromatic radical fused or unfused, saturated or unsaturated aromatics comprising at least one heteroatom, which is optionally substituted by c1-c30alkyl, c1-c30alkoxy, c2-c12 alkenyl, c5-c10aryl, c5-c10cycloalkyl, c1-c10alkylac5-c10arylene) hydroxy or halogen; r1 and r2 independently of each other are hydrogen; substituted or unsubstituted, straight-chain or branched, monocyclic or polycyclic, interrupted or uninterrupted c1-c4alkyl; c2-c14alkenyl; c6-c10 aryl; c1-c10aryl-c1-c10alkyl, or c5-c10alkyl(c5-c10aryl); y] and y2 independently of each other are a residue of an organic dye selected from hydrazone dyes of the formula where z1, z2 and z3, independently of each other are -cr8- or -nr9"-, and at least one of z1, z2 and z3 is -nr9+-; wherein at least one of y1 and y2 is a residue of an organic dye; r, r3, r4, r5, r6, r7, r8 and r9 independently of one another are hydrogen; hydroxy; c1 -c5alkyl; hydroxy-c1-c5alkyl; -c1-c5alkoxy; -no2; -c1,-br, -cooh, -so3h; -cn; nh2, or ch3, -co-nh-; an1, an2 and an3 independently of each other are an anion; a and b independent of each other are a number from 1 to 3; m is a number from 0 to 5000; n is a number from 0 to 5000; and p is a number from 1 to 5000; where the sum of m+n+p>3 dyes are distinguished by their color depth and their properties of good wash stability, such as light fastness, washability and friction.
    公开号:BR112012000793B1
    申请号:R112012000793-9
    申请日:2010-07-15
    公开日:2021-06-22
    发明作者:Christian Cremer；Oliver Becherer；Beate Fröhling
    申请人:Basf Se；
    IPC主号:
    专利说明:

    [1] The present invention relates to new polymeric dyes and compositions comprising these compounds, a process for their preparation and their use for dyeing organic materials, such as keratin, which contain fibers, leather, silk, cellulose or polyamides, natural and synthetic fibers such as wool or polyacrylonitrile, paper or wood.
    [2] They can also be used in the form of printing inks, printing inks or coating compositions.
    [3] Cationic compounds are known to have a good affinity for negatively charged hair. These characteristics have been used for contact with hair with small molecules, but also with polymers.
    [4] Numerous polymeric cationic dyes have been disclosed for use as a dye for human hair, for example in US 4,228,259, US 4,182,612 or FR 2 456 764. These references teach that the polymer portion has the cationic charge.
    [5] Surprisingly, it has been found that very good dye results are obtained with polymeric hair dyes where the cationic charge is located on the dye portion.
    [6] Therefore, the present invention relates to polymeric dyes of the formula (1a)

    to An 1 -
    or (1c) where A and B independently of one another represent the polymer backbone; X1 and X2 independently of each other are a linking group selected from -S-, -SS-, -N, -N=-, -N(R5)-, -S(O)-, -SO2-, - (CH2CH2-O)1-5-, -(CH2CH2CH2-O)1-5-, -C(O -, -C(O)O-,
    -C(S)R1-;which may be interrupted and/or terminated at one or both ends by one or more of a C1-C30-alkylene or -C2-C12-alkenylene; or an optionally substituted, saturated or unsaturated aromatic fused or unfused or non-aromatic (heterocyclic) divalent radical optionally comprising at least one heteroatom; a saturated or unsaturated aromatic, fused or unfused, or divalent non-aromatic radical comprising at least one heteroatom, which is optionally substituted by C1-C30alkyl, C1-C30alkoxy, C2-C12 alkenyl, C5-C10aryl, C5-C10cycloalkyl, C1- C10(C5-C10alkylarylene) hydroxy or halogen; R 1 and R 2 independently of each other are hydrogen; substituted or unsubstituted, straight-chain or branched, monocyclic or polycyclic, interrupted or uninterrupted C1-C4alkyl; C2-C14alkenyl; C6-C10 aryl; C1-C10aryl-C1-C10alkyl, or C5-C10alkyl(C5-C10aryl); Y1 and Y2 independently of each other are a residue of an organic dye selected from hydrazone dyes of formula
    Z1, Z2 and Z3, independently of one another are -CR8- or -NR9+-, and at least one of Z1, Z2 and Z3 is -NR9+-; wherein at least one of Y1 and Y2 is a residue of an organic dye; R, R3, R4, R5, R6, R7, R8 and R9 independently of one another are hydrogen; hydroxy; C1-C5alkyl; hydroxy-C1-C5alkyl; -C1-C5alkoxy; - NO2; -Cl,-Br,-COOH,-SO3H;-CN; NH2 or CH3 -CO-NH-; An1, An2 and An3, independently of each other are an anion; a and b independent of each other are a number from 1 to 3; m is a number from 0 to 5000; n is a number from 0 to 5000; ep is a number from 1 to 5000; where the sum of m + n + p> 3.
    [7] C1-C14alkyl is, for example, methyl, ethyl, propyl, isopropyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2'-n-hexyl, n- octyl,
    [8] C1-C14alkenyl is, for example allyl, metalyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct- 2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-dodec-2-enyl or n-octadec-4-enyl.
    [9] C6-C10aryl is for example phenyl or naphthyl.
    [10] C1-C30alkylene is for example methylene, ethylene, propylene isopropylene, n-tetramethylene-, sec-tetramethylene, tert-tetramethylene, n-pentamethylene, 2-pentamethylene 3-pentamethylene, 2,2'dimethylpropylene, cyclopentamethylene, cyclohexamethylene, n-hexamethylene, n-octamethylene, 1,1',3,3'-tetramethyltetramethylene, 2-ethylhexamethylene, nonamethylene, decamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene or eicosamethylene.
    [11] Preferred are dyes of formula (1a), (1b) or (1c), where Y1 and Y2 correspond to the formula
    where Z1, Z2 and Z3, R, R3, R4, R5, R6, R7, R3 and R9 are as defined in (1a), (1b) or (1c).
    [12] Most preferred are dyes of formulas (1a), (1b) and (1c), where Y1 and Y2 correspond to the formula

    [13] More preferably Y1 and Y2 have the same meaning.
    [14] Preferably X1 and X2 independently of one another are a linking group selected from -SO2- and -C(O)-.
    [15] Preferably in formulas (1a), (1b) and (1c) A and B independently of one another are selected from polyethylenimine, polypropyleneimine, polyvinylamine, polyvinilimine; polysiloxane; polystyrene, polyvinylimidazole, polyvinylpyridine, vinylimidazole copolymers or vinylpyridine and vinylpyrrolidone, DADMAC/DAA copolymers, polyetheramines, polyvinyl alcohol, polyacrylate, polymethacrylate, polyurethanes derived from hydroxyl terminated polyethers, polyesters or polybutadienes on the other side aliphatic or polyisoromatics , as well as their precursors; polyamides and copolyamides derived from diamines and dicarboxylic acids and/or aminocarboxylic acids or the corresponding lactams; polysaccharide, starch, cellulose, lignin, and copolymers and mixtures of the mentioned polymers.
    [16] Especially preferred are polyethyleneimine, polyvinylamine, polyetheramines.
    [17] Polyethyleneimines can be prepared by known processes as described in Rompps Chemie Lexikon, 8. Aufl. 1992, S. 3532-3533 or in Ullmanns Enzyklopadie der Technischen Chemie, 4. Auf. 1974, Bd. 8, S. 212-213. They have a molecular weight in the range of 200 to 1,000,000 g/mol. Trade names are eg Lupasol® from BASF SE or Epomin from Nippon Shokubai.
    [18] Also preferred are polyamidoamines or polyvinylamines grafted with ethylenimine.
    [19] Homopolymers and copolymers mentioned above can have any stereostructure including syndiotactic, isotactic, hemiisotactic or atactic, where atactic polymers are preferred. Stereoblock polymers are also included.
    [20] Examples of halogen-containing polymers are polychloroprene, chlorinated rubbers, chlorinated and brominated isobutylene-isoprene copolymer (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, homo- and copolymers of e-epichlorohydrin, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride as well as copolymers thereof such as vinyl chloride/vinylidene chloride copolymers, vinyl chloride/vinylidene acetate or vinylidene chloride/vinyl acetate.
    [21] Examples of polymers derived from α,β-unsaturated acids and derivatives thereof are polyacrylates and polymethyacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
    [22] Examples of copolymers of the above-mentioned monomers with each other or with other unsaturated monomers are acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl acrylonitrile copolymers or acrylatetrile halide copolymers /alkyl methacrylate/butadiene.
    [23] Examples of polymers derived from unsaturated alcohols and amines or acyl derivatives or acetals thereof are, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, phthalate of polyallyl or polyallyl melamine, as well as their copolymers with olefins mentioned above.
    [24] Examples of homopolymers and copolymers of cyclic ethers are polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
    [25] Examples of polyacetals are polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
    [26] Examples of polyamides and copolyamides derived from diamines and dicarboxylic acids and/or aminocarboxylic acids or the corresponding lactams are polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/ 6, 12/12, polyamide 11, polyamide 12, aromatic polyamides from m-xylene diamine and adipic acid, polyamides prepared from hexamethylenediamine and isophthalic and/or terephthalic acid and with or without an elastomer as a modifier, eg poly- 2, 4,4-trimethylhaxamethylene terephthalamide or poly-m-phenylene isophthalamide, and also block copolymers of polyamides with the aforementioned polyolefins, olefin copolymers, grafted or chemically bonded ionomers or elastomers, or with polyethers, for example with polyethylene glycol , polypropylene glycol or polytetramethylene glycol, as well as polyamides or copolyamides modified with EPDM or ABS and polyamides condensed during processing (RIM polyamide systems).
    [27] Examples of natural polymers are cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, eg cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methylcellulose as well as rosin and its derivatives.
    [28] Preferably both the polymer backbone (A and B) and residue of an organic dye (Y1 and Y2) have a functional group selected from the electrophilic group selected from halide, tosylate, mesylate, methoxy, hydrochloric acid, sulfonyl chloride , epoxides, anhydride, or a nucleophilic group selected from amine, hydroxyl and thiol.
    [29] Preferably the molecular weight of the polymeric dye is 400 to 50000.
    [30] "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 C1-C8alkyl sulfate , especially methyl sulfate or ethyl sulfate; anion also denotes lactate, formate, acetate, propionate, or a complex anion such as the double salt of zinc chloride.
    [31] Most preferred are dyes of the formula
    A and B independently of each other represent the polymer backbone; X1 and X2, independently of one another, are a linking group selected from -SO2- and -C(O)-; Y1 and Y2 independently of each other are a radical of formula (1f); a and b independent of each other are a number from 1 to 3; m is a number from 0 to 5000; n is a number from 0 to 5000; and where the sum of m + n>2.
    [32] A further embodiment of the present invention relates to processes for preparing the dyes of formula (1a), (1b) and (1c).
    [33] Generally, the process comprises a) first synthesizing a hydrazone dye of formula (1d) and then reacting with a polymer comprising at least one nucleophilic functionality or b) first reacting the building block of phenyl of the hydrazone dye with a polymer comprising at least one nucleophilic functionality and then preparing the hydrazone dye in the phenyl moiety attached to the polymer.
    [34] For both routes a) or b) the phenyl portion of the hydrazone chromophores contains at least one electrophilic functionality, to react with a polymer comprising at least one nucleophilic functionality, which may be selected from acetate, brosylate, mesylate, nosylate , tosylate, trifluoroacetate, trifluorosulfonate, chlorine, bromine or iodine, sulfate esters, vinylsulfones, carboxylic acids, their acid esters or chlorides, epoxides or halohydrin ethers.
    [35] Synthetic procedures for the preparation of the hydrazone chromophore are described, for example, in the Ullmann Encyclopedia of Industrial Chemistry, chapter on Metine Dyes and Pigments, 6.2.2.
    [36] Reactions are usually initiated by contacting for example by mixing starting compounds or by adding drops of one starting compound to another.
    [37] Usually, the temperature is in the range of 0 to 150°C, preferably it is in the range of 17 to 27°C during mixing of the starting compounds.
    [38] The reaction time is generally dependent on the reactivity of the starting compounds, the chosen reaction temperature, and the desired conversion. The chosen duration of reaction is usually in the range of one hour to three days.
    [39] The reaction temperature for the reaction of the compounds is advisable to select in the range of 0 to 150°C, especially in the range of 0 to 62°C.
    [40] The reaction pressure chosen is generally in the range of 70 kPa to 10 MPa, especially from 90 kPa to 5 MPa, and more especially atmospheric pressure.
    [41] It may be desirable to conduct the reaction of compounds in the presence of a catalyst.
    [42] The molar ratio of the compound of formula (1a) to the catalyst is generally selected in the range of 10:1 to 1:5, especially in the range of 10:1 to 1:1.
    [43] Suitable catalysts are, for example an alkali metal C1-C6alkyloxide, such as sodium, potassium, lithium C1-C6alkyloxide, preferably sodium methoxide, potassium methoxide or lithium methoxide, or sodium ethoxide, lithium ethoxide. potassium or, lithium ethoxide, or tertiary amines, for example, as quinuclidine, N-methylpiperidine, pyridine, trimethylamine, triethylamine, trioctylamine, 1,4-diazabicyclo[2.2.2]octane, quinuclidine, N-methylpiperidine; or alkali metal acetate, for example such as sodium acetate, potassium acetate or lithium acetate.
    [44] Preferred are potassium acetate, sodium methoxide, pyridine, and 1,4-diaza-bicyclo [2.2.2] octane.
    [45] Furthermore, reactions can be carried out with or without a solvent, but are preferably carried out in the presence of a solvent.
    [46] Solvents are organic solvents and water, or a mixture of organic solvents or a mixture of organic solvents and water.
    [47] Organic solvents are, for example, polar protic or aprotic organic solvents such as alcohols, for example methanol, ethanol, butanol n-propanol, isopropanol, butanol or glycols, especially isopropanol, or nitrile, such as acetonitrile or propionitrile, or amide, such as dimethylformamide, dimethylacetamide, or N-methylpyridine, N-methylpyrrolidone, or sulfoxide, such as dimethylsulfoxide, or mixtures thereof.
    [48] The product prepared according to the process of the present invention can be advantageously worked and isolated and, if desired, be purified.
    [49] Typically, work starts by lowering the temperature of the reaction mixture in the range of 7 to 27°C, especially in the range of 17 to 27°C.
    [50] It may be beneficial to lower the temperature slowly over a period of several hours.
    [51] For isolation it may also be advantageous to add organic or inorganic acids such as hydrochloric acid, methanesulfonic acid, acetic acid or formic acid to the reaction mixture.
    [52] In general, the reaction product is usually filtered and then washed with water or a saline solution and then dried.
    [53] Filtration is normally carried out in standard filtration equipment, eg Büchner funnels, press filters, suction filters under pressure, preferably vacuum.
    [54] The temperature for drying depends on the pressure applied. Drying is normally carried out in a vacuum at 5-20 mbar.
    [55] Drying is normally carried out at a temperature in the range of 40 to 70 °C, especially 50 to 70 °C, and more especially in the range of 45 to 65 °C.
    [56] Advantageously the product is purified by recrystallization after isolation.
    [57] Organic solvents and solvent mixtures are suitable for recrystallization, preferably alcohols, for example methanol, ethanol, 2-propanol or butanol, especially 2-propanol.
    [58] The hydrazone compounds of the formula (1a), (1b), (1c) are used in particular as dyes for dyeing and printing textiles, paper and leather and for preparing dyes.
    [59] Suitable textile materials are natural and synthetic materials that can be dyed by cationic processes. The new hydrazone compounds are preferably used for dyeing and printing paper, cardboard and thin cardboard on the pulp and surface, and also textile materials which, for example, advantageously consist of homopolymers or copolymers of acrylonitrile or of synthetic polyamides or polyesters modified with acid groups. These textile materials are preferably dyed in an aqueous, neutral or acidic medium by the exhaust method, if applicable, under pressure, or by the continuous method. In this sense, the textile material can be in a wide variety of different forms, for example, as fibers, filaments, fabrics, knits, piece items and ready-made items such as shirts or pullovers.
    [60] The dyes according to the invention make it possible to produce level dyeings or prints which are distinguished by very good general strength properties, at a certain very high degree of exhaustion and good water stability properties.
    [61] In addition, the new hydrazone compounds of the formula (1a), (1b), (1c) can also be used to dye and print natural and regenerated cellulose materials, in particular cotton and viscose, deep colored dyes are also being obtained.
    [62] On these textile materials, the new hydrazone compounds of the formula (1a), (1b), (1c) have a good substantially good degree of exhaustion, and the dyeings obtained show very good fastness properties, in particular fastness. wet processing.
    [63] A preferred use of the new hydrazone compounds of the formula (1a), (1b), (1c) is their use for dyeing paper of all types, in particular bleached, uncalibrated and sized, paper free from lignin, it being possible to use bleached or raw pulp as the starting material and to use short fiber pulp or long fiber pulp, such as birch and/or pine sulphite and/or sulphate pulp. These compounds are very particularly suitable for dyeing uncalibrated papers (eg table napkins, tablecloths and toiletries) as a result of their high affinity for this substrate.
    [64] The new hydrazone compounds of formula (1a), (1b), (1c) are strongly adsorbed onto these substrates, the effluents remaining practically colorless. Dyeings in yellow, green-yellow or orange tones are obtained.
    [65] The dyeings obtained are distinguished by good general strength properties, such as good light fastness and, at the same time, having a high clarity and color depth and fastness to wet processing, that is, they do not have a tendency to bleed. when dyed paper is brought into contact under wet conditions with damp white paper. Furthermore, they exhibit good stability to alum, acids and alkalis. Wet processing strength is related not only to water, but also to milk, fruit juices and sweetened mineral water; due to their good stability to alcohol, the colorants also have fastness to alcoholic beverages. This property is particularly desirable, for example, for table napkins and tablecloths, in which case the dyed paper can be expected to come into contact in a wet state (eg impregnated with water, alcohol, surfactant solution, etc.) with external surfaces such as textiles, paper and the like, which must be protected from dirt.
    [66] The high affinity for paper and the high exhaust rate of new dyestuffs is a great advantage for continuous dyeing of paper.
    [67] Hair dyes are distinguished by their shade depth and good wash fastness properties, such as light fastness, wash fastness and rub fastness.
    [68] Generally, hair dyeing agents in a synthetic base can be classified into three groups: - temporary dyeing agents - semi-permanent dyeing agents, and - permanent dyeing agents.
    [69] The multiplicity of shades of dyes can be increased by combining with other dyes.
    [70] Therefore, the dyes of formula (1a), (1b) and (1c) of the present invention can be combined with dyes of the same or other classes of dyes, especially with direct dyes, oxidation dyes; dye precursor combinations of a coupler compound, as well as a diazotized compound, or a diazotized capped compound; and/or reactive cationic dyes.
    [71] Especially preferred is the combination of the dyes of formula (1a), (1b) and (1c) with other polymeric dyes as described in GB 2440219, WO 09/090121, WO 09/090122, WO 09/090124 or WO 09 /090125.
    [72] Direct dyes are of natural origin or can be prepared synthetically. They are uncharged, cationic or anionic, such as acidic dyes.
    [73] The dyes of formula (1a), (1b) and (1c) can be used in combination with at least one single direct dye other than the dyes of formula (1a), (1b) and (1c).
    [74] The inventive polymeric hair dyes do not require any addition of an oxidizing agent to develop their dyeing effect. This fact could reduce hair damage. Furthermore, many of the perceived or documented disadvantages of current oxidative hair dyes such as their skin irritation, skin sensitization and allergenic properties can be prevented by using the inventive hair dyes. Furthermore, inventive hair dyes are easier to apply and use in formulations than oxidative hair dyes as no chemical reaction occurs upon application to the head. Especially advantageous is the fact that the dyeing time is significantly shorter (ca. 5-10 min) than dyeing using oxidative dyes.
    [75] Examples of direct dyes are described in "Dermatology", edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basel, 1986, vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, p. 248-250, and in "Europaisches Inventar der Kosmetikrohstoffe", 1996, published by the European Commission, obtained on diskette from the Bundesverband der deutschen Industrie- und Handelsunternehmen für Arzneimittel, Reformwaren und Korperpflegemittel eV, Mannheim.
    [76] Most preferred direct dyes that are useful for combination with at least one single dye of the formula (1a), (1b) and (1c), especially for semi-permanent dyeing, are: 2-amino-3-nitrophenol, sulfate of 2-amino-4-hydroxyethylamino-anisole, 2-amino-6-chloro-4-nitrophenol, 2-chloro-5-nitro-N-hydroxyethylene-p-phenylenediamine, 2-hydroxyethyl picramic acid, 2,6-diamino -3-((pyridine-3yl)-azo)pyridine, 2-nitro-5-glyceryl-methylanyl., 3-methyl-amino-4-nitro-phenoxyethanol, 4-amino-2-nitrodiphenyleneamine-2'-carboxylic acid , 6-nitro-1,2,3,4,-tetrahydroquinoxal, 4-N-ethyl-1,4-bis(2'-hydroxyethylamino-2-nitrobenzene, 1-methyl-3-nitro-4-(hydrochloride) 2'-hydroxyethyl)-aminobenzene, 3-nitro-p-hydroxyethylaminophenol, 4-amino-3-nitrophenol, 4-hydroxypropylamine-3-nitrophenol, hydroxyanthryl-aminopropylmethyl morpholino 4-nitrophenyl-aminoethylurea metasulfate, 6-nitro-p- toluidine, Acid Blue 62, Acid Blue 9, Acid Red 35, Acid Red 87 (Eosin), Acid Violet 43, Acid Yellow 1, Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 12, Basic Blue 26, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Red 2, Basic Red 22, Basic Red 76, Basic Violet 14, Basic Yellow 57 , Basic Yellow 9, Disperse Blue 3, Disperse Orange 3, Disperse Red 17, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Fast Green FCF, HC Blue 2, HC Blue 7, HC Blue 8, HC Blue 12, HC Orange 1, HC Orange 2, HC Red 1, HC Red 10-11, HC Red 13, HC Red 16, HC Red 3, HC Red BN, HC Red 7, HC Violet 1, HC Violet 2, HC Yellow 2, HC Yellow 5, HC Yellow 5, HC Yellow 6, HC Yellow 7, HC Yellow 9, HC Yellow 12, HC Red 8, hydroxyethyl-2-nitro-p-toluidine, N,N-Bis-(2-hydroxyethyl)-2 -nitro-p-phenylenediamine, HC Violet BS, picramic acid, Solvent Green 7.
    [77] Furthermore, the dyes of formula (1a), (1b) and (1c) can be combined with at least one cationic azo dye, for example the compounds disclosed in GB-A-2 319 776 as well as the dyes of oxazine described in DE-A-299 12 327 and mixtures thereof with the other direct dyes mentioned therein, and even more preferred with cationic dyes such as Basic Yellow 87, Basic Orange 31 or Basic Red 51, or with cationic dyes as described in WO 01/66646, especially example 4, or with cationic dyes as described in WO 02/31056, especially example 6, the compound of formula 106, or the cationic dye of formula (3), as described in EP -A-714, 954, or with a yellow cationic formula dye.
    [78] The dyes of formula (1a), (1b) and (1c) can also be combined with acid dyes, eg those dyes that are known from the international names (Color Index), or trade names. Preferred acid dyes which are useful for combination with a dye of formula (1a), (1b) and (1c) are described in US Patent 6,248,314. They include Red Color No. 120, Yellow Color No. 4, Yellow Color No. 5, Red Color No. 201, Red Color No. 227, Orange Color No. 205, Brown Color No. 201, Red Color No. 502, Red Color No. 503, Red Color No. 504, Red Color No. 506, Orange Color No. 402, Yellow Color No. 402, Yellow Color No. 406, Yellow Color No. 407, Red Color No. 213, Red Color No. 214, Red Color No. 3, Red Color No. 104, Red Color No. 105(1), Red Color No. 106, Green Color No. 2, Green Color No. 3, Orange Color No. 207, Yellow Color No. 202(1), Yellow Color No. 202(2), Blue Color No. 202, Blue Color No. 203, Blue Color No. 205, Blue Color No. 2, Yellow Color No. 203, Blue Color No. 201, Green Color No. 201, Blue Color NO. 1, Red Color No. 230(1), Red Color No. 231, Red Color No. 232, Green Color No. 204, Green Color No. 205, Red Color No. 401, Yellow Color No. 403(1), Green Color No. 401, Green Color No. 402, Black Color No. 401 and Purple Color No. 401, especially Black Color No. 401, Purple Color 401, Orange Color No. 205.
    [79] These acid dyes can be used either as a single component or in any combination thereof.
    [80] The dyes of formula (1a), (1b) and (1c) can also be combined with uncharged dyes.
    [81] In addition, dyes of formula (1a), (1b) and (1c) can also be used in combination with oxidation dye systems.
    [82] Oxidation dyes, which, in the initial state, are not dyes but dye precursors are classified according to their chemical properties into developer compounds and couplers.
    [83] Suitable oxidation dyes are described for example in - DE 19 959 479, especially in col. 2, I.6 to col. 3, I.11; - "Dermatology", edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basel, 1986, vol. 7Ch. Zviak, The Science of Hair Care, Chapter 8, at p. 264-267 (oxidation dyes).
    [84] Preferred developer compounds are for example primary aromatic amines, which are substituted in the para- or ortho- position with a substituted or unsubstituted hydroxy or amino residue, or diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives, derivatives of 2,4,5,6-tetraaminopyrimidine, or unsaturated aldehydes as described in DE 19 717 224, especially p. 2, I.50 to I.66 and on p. 3 I. 8 to I. 12, or developing cationic compounds as described in WO 00/43367, especially p. 2 I. 27 to p. 8, I. 24, in particular, p. 9, I. 22 to p. 1, I.6.
    [85] In addition, developing compounds in their physiologically compatible acid addition salt form such as hydrochloride or sulfate can be used. Developer compounds, which have aromatic OH radicals are also indicated in their salt form, along with a base, such as alkali metal phenolates.
    [86] Developer preferred compounds are disclosed in DE 19959479, p. 2, I. 8-29.
    [87] Most preferred developer compounds are p-phenylenediamine, p-tolylendiamine, p-, m-, o-aminophenol, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine sulfate, 2-amino-sulfate 4-hydroxy-ethylaminoanisole, hydroxyethyl-3,4-methylenedioxianyl, 1-(2'-hydroxyethyl)-2,5-diaminobenzene, 2,6-dimethoxy-3,5-diamino-pyridine, hydroxypropyl-bis-(hydrochloride) N-hydroxyethyl-p-phenylenediamine), hydroxyethyl-p-phenylenediamine sulfate, 4-amino-3-methylphenol, 4-methylaminophenol sulfate, 2-aminomethyl-4-aminophenol, 4,5-diamino-1-(2- hydroxyethyl)-1H-pyrazole, 4-amino-m-cresol, 6-amino-m-cresol, 5-amino-6-chloro-cresol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4 sulfate ,5,6-triaminopyrimidine or 4-hydroxy-2,5,6-triaminopyrimidine.
    [88] Preferred coupler compounds are m-phenylenediamine derivatives, naphthol, resorcine and resorcine derivatives, pyrazolone and m-aminophenol derivatives, and more preferably coupler compounds disclosed in DE 19959479, p.1,I. 33 to p.3, I.11.
    [89] The dyes of formula (1a), (1b) and (1c) can also be used together with unsaturated aldehydes as disclosed in DE 19 717 224 (p. 2, I. 50 to I. 66 and p. 3. I.8 to I.12) which can be used as direct dyes or, alternatively, together with oxidation dye precursors.
    [90] Most preferred for a combination with a dye of formula (1a), (1b) and (1c) are the following oxidation dye precursors: - the developer/coupler combination 2,4,5,6-tetraaminopyrimidine and 2 -methylresorcin to assess red tones; - p-toluenediamine and 4-amino-2-hydroxytoluene for the evaluation of blue-violet tones; - p-toluenediamine and 2-amino-4-hydroxyethylaminoanisole for the evaluation of blue tones; - p-toluenediamine and 2,4-diamino-phenoxyetinol for the evaluation of blue tones; - methyl-4-aminophenol and 4-amino-2-hydroxytoluene to evaluate orange tones; - p-toluenediamine and resorcin for the evaluation of brown-green tones; - p-toluenediamine and 1-naphthol for the evaluation of blue-violet tones, or - p-toluenediamine and 2-methylresorcine for the evaluation of golden-brown tones.
    [91] Furthermore, the autooxidizing compounds can be used in combination with the dyes of the formula (1a), (1b) and (1c).
    [92] The dyes of formula (1a), (1b) and (1c) can also be used in combination with natural dyes.
    [93] In addition, dyes of formula (1a), (1b) and (1c) can also be used in combination with diazotized capped compounds.
    [94] Suitable diazotized compounds are, for example the compounds of formulas (1) - (4) in WO 2004/019897 (linking model 1 and 2) and the corresponding water-soluble coupling components (I) - (IV) as disclosed in the same reference on p. 3-5.
    [95] Furthermore, the dyes of the present invention can also be combined with dyes that are prepared by the reaction of a reactive carbonyl compound and a CH-acid compound, as described in DE 10 2006 062 435 A1, WO 00038638, DE 10241076 and WO 05120445; - with thiadiazole dyes as described in DE 10 2006 0368 98 and DE 10 2005 0554 96, - with stilbenic sulfur fluorescent dyes as described in, for example, WO 07110532, WO 07110542, - with tetraazapentamethine dyes as described in WO 07071684 and WO 07071686, with cationic dimeric dyes as described in FR 2879195, FR 2879127, FR 2879190, FR 2879196, FR 2879197, FR 2879198, FR 2879199, FR 2879200, FR 2879928, FR 2879929, WO 06063869, - with azo dyes in EP 0850636, - with anionic polymeric dyes as described in FR 2882929, - with disulfide dyes as described in WO 0597051, EP 1647580, WO 06136617, - with thiol dyes as described in WO 07025889, WO 07039527, and - with polymers conductors as described in US 20050050650, US 7217295
    [96] The present invention also relates to formulations, which are used for dyeing organic materials, preferably fibers containing keratin, and more preferably human hair, comprising at least one dye of the formula (1a), (1b) and ( 1c).
    [97] Preferably, the dyes of formula (1a), (1b) and (1c) are incorporated into the composition for the treatment of organic material, preferably for dyeing in amounts of 0.001 - 5% by weight (hereinafter only indicated by "%"), particularly 0.005-4%, more particularly 0.1-3%, based on the total weight of the composition.
    [98] The dye compositions of the present invention are applied to hair in a temperature range of 10 to 200, preferably 18 to 80, and more preferably 20 to 40°C.
    [99] The formulations can be applied to fibers containing keratin, preferably human hair, in different technical ways.
    [100] Technical forms of formulations are, for example, a solution, especially a thickened aqueous or alcoholic aqueous solution, a cream, foam, shampoo, powder, gel or emulsion.
    [101] Typically dyeing compositions are applied to the keratin-containing fiber in an amount of 50 to 100 g.
    [102] Preferred forms of formulations are ready-to-use compositions or multi-compartment dyeing devices or 'kits' or any of the multi-compartment packaging systems with compartments as described, for example, in US 6,190.421, col 2 , I. 1631.
    [103] The pH value of ready-to-use dye compositions is generally 2 to 11, preferably 5 to 10.
    [104] Cosmetic formulations suitable for hair care are hair care preparations, eg hair washing preparations in the form of shampoos and conditioners, hair care preparations, eg pretreatment preparations or no-rinse products such as sprays, creams, gels, lotions, mousses and oils, hair tonics, styling creams, styling gels, ointments, hair washes, treatment packs, intensive hair treatments, hair structuring preparations, eg hair styling preparations curl hair for permanent waves (heat waves, light waves, cold waves), hair straightening preparations, liquid hair setting preparations, hair foams, hair spray, lightening preparations, eg peroxide solutions of hydrogen, illuminating shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, hair dyes, semi-permanent or permanent, temporary river, preparations containing auto-oxidizing dyes or natural hair dyes such as henna or chamomile.
    [105] For use on human hair, the dye compositions of the present invention can generally be incorporated into an aqueous cosmetic vehicle. Suitable aqueous cosmetic carriers include, for example W/O, O/W, O/W/O, W/O/W or PIT emulsions and all types of microemulsions, creams, sprays, emulsions, gels, powders and also solutions of foaming containing surfactant, for example shampoos or other preparations, which are suitable for use on fibers containing keratin.
    [106] Such usage forms are described in detail in Research Disclosure 42448 (August 1999). If necessary, it is also possible to incorporate the dyeing compositions in dry vehicles, as described, for example, in US 3 369 970, 1 especially, col. 1, I. 70 to col. 3, 1. 55. The dyeing compositions according to the invention are also excellently suited for the dyeing method described in DE-A-3 829 870 using a dyeing comb or brush.
    [107] The components of the aqueous vehicle are present in the dyeing compositions of the present invention in usual amounts, for example emulsifiers may be present in the dyeing compositions in concentrations from 0.5 to 30% by weight and thickeners in concentrations from 0.1 to 25% by weight of the total dye composition.
    [108] Additional vehicles for dye compositions are, for example, described in "Dermatology", edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basel, 1986, vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, p. 248-250, especially on p. 243, I. 1 to p. 244, 1. 12.
    [109] If the dyes of formula (1a), (1b) and (1c) are used together with oxidation dyes and/or addition salts thereof with an acid, they can be stored separately or together. Preferably oxidation dyes and direct dyes which are not stable to reduction or base are stored separately.
    [110] The dyes of formula (1a), (1b) and (1c) can be stored in a paste-like liquid (aqueous or non-aqueous) or as a dry powder.
    [111] When colorants are stored separately, the reactive components are intimately mixed with one another directly before use. In the case of dry storage, a defined amount of hot water (from 50 to 80°C) is usually added and a homogeneous mixture prepared before use.
    [112] Dyeing compositions according to the invention may comprise any known active ingredients, additives or adjuvants for such preparations, such as surfactants, solvents, bases, acids, perfumes, polymeric adjuvants, thickeners and light stabilizers.
    [113] The following adjuvants are preferably used in the hair dye compositions of the present invention: nonionic polymers, cationic polymers, acrylamide/dimethyldiallylammonium chloride copolymers, dimethylaminoethyl/vinyl pyrrolidone diethylsulfate-quaternised methacrylate copolymer, vinylpyrrolidone copolymers /imidazolinium methchloride; quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers, anionic polymers, thickeners, structuring agents, hair conditioning compounds, protein hydrolysates, perfume oils, dimethyl isosorbitol and cyclodextrins, solubilizers, anti-dandruff active ingredients, substances to adjust the pH value , panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and salts thereof, plant extracts and vitamins, cholesterol, light stabilizers and UV absorbers, consistency regulators, fats and waxes, fatty alkanolamides, polyethylene glycol and polypropylene glycol having a weight molecular 150 to 50,000, complexing agents, penetration and swelling substances, opacifiers, pearlizing agents, propellants, antioxidants, polymers containing sugar, quaternary ammonium salts and bacterial inhibiting agents.
    [114] Dyeing compositions according to the present invention generally comprise at least one surfactant. Suitable surfactants are zwitterionic or ampholytic, or more preferably anionic, nonionic and/or cationic surfactants.
    [115] A further embodiment of the present invention relates to dyeing keratin containing fibers.
    [116] The process comprises (a) treating keratin fibers containing at least one dye of the formula (1a), (1b) and (1c) and (b) letting the fiber remain and then rinsing the fiber.
    [117] The dyes of formula (1a), (1b) and (c) are suitable for the complete dyeing of hair, ie when dyeing the hair on a first occasion, and also for re-dyeing later, or dyeing curls or parts of hair.
    [118] The dyes of formula (1a), (1b) and (1c) are applied to the hair for example by hand massage, a comb, a brush, or a bottle, which is combined with a comb or a nozzle.
    [119] In dyeing processes according to the invention, whether or not dyeing should be carried out in the presence of an additional dye will depend on the shade of color to be obtained.
    [120] Most preferred is a process for dyeing keratin containing fibers which comprises treating keratin containing fibers with at least one dye of the formula (1a), (1b) and (1c), a base and an oxidizing agent.
    [121] The preferred modality for dyeing keratin containing fibers, in particular human hair, with a dye of the formula (1a), (1b) and (1c) and an oxidizing agent, comprises a1) treating the keratin containing fibers with the oxidizing agent, which optionally contains at least one dye of the formula (1a), (1b) and (1c), b1) treating the keratin-containing fibers with an oxidizing agent-free composition, which optionally contains at least one dye of the formula ( 1a), (1b) and (1c), or alternatively, a2) treating the keratin-containing fibers with an oxidizing agent-free composition, which optionally contains at least one dye of the formula (1a), (1b) and (1c); b2) treating the keratin-containing fibers with the oxidizing agent, which optionally contains at least one dye of the formula (1a), (1b) and (1c), with the proviso that at least one of the process steps a1), a2 ), b1) or b2) a dye of formula (1a), (1b) and (1c) is present.
    [122] In general, the composition containing the oxidizing agent is left on fiber for 0 to 45 minutes, in particular for 15 to 30 minutes at 15-45°C.
    [123] The oxidizing agent-free composition generally comprises usual adjuvants and additives. Preferred are those, which are described in the German patent application, at col. 3, I. 17 to I. 41.
    [124] In general, the dye of formula (1a), (1b) and (1c) and the composition free of oxidizing agent are left on the fiber for 5 to 45 minutes, in particular for 10 to 25 minutes to 15 to 50°C.
    [125] A preferred modality of the process is to wash the hair after dyeing it with a shampoo and/or a weak acid such as citric acid or tartaric acid.
    [126] Dyes of formula (1a), (1b) and (1c) that are stable to reduction can be stored together with the oxidizing agent-free compositions and can be applied as a single composition.
    [127] Advantageously compositions comprising a dye of formula (1a), (1b) and (1c) which are not stable to reduction are prepared with the composition free of oxidizing agent shortly before the dyeing process.
    [128] In a further embodiment, the dye of formula (1a), (1b) and (1c) and the oxidizing agent-free composition can be applied simultaneously or in succession.
    [129] Typically, the oxidizing agent-free composition is uniformly applied in a sufficient amount related to the amount of hair, usually in amounts of 30 to 200 g.
    [130] Oxidizing agents are for example persulfate or dilute hydrogen peroxide solutions, hydrogen peroxide emulsions or hydrogen peroxide gels, alkaline earth metal peroxides, organic peroxides such as urea peroxides, melamine peroxides, or Alkali metal bromate fixations are equally applicable if a semi-permanent direct hair dye based shade powder is used.
    [131] Most preferred oxidizing agents are - oxidizing agents to achieve lighter coloration, as described in WO 97/20545, especially p. 9, I. 5-9, - oxidizing agents in the form of permanent wave fixation solution, as described in DE-A-19 713 698, especially p. 4, 1. 52-55, and I. 60 and 61 or EP-A-1062940, especially p. 6, I. 41-47 (and in the equivalent WO 99/40895).
    [132] Most preferred oxidizing agent is hydrogen peroxide, preferably used in a concentration of about 2 to 30%, more preferably about 3 to 20%, and most preferably 6 to 12% by weight of the corresponding composition.
    [133] Oxidizing agents may be present in the dyeing compositions according to the invention preferably in an amount of from 0.01% to 6%, especially from 0.01% to 3%, based on the total dye composition.
    [134] In general, dyeing with an oxidizing agent is carried out in the presence of a base, for example ammonia, alkali metal carbonates, earth metal carbonates (potassium or lithium), alkanol amines such as mono-, di- or triethanolamine, alkali metal hydroxides (sodium), earth metal hydroxides or compounds of the formula
    7 L is a propylene residue, which may be substituted with OH or C1-C4 alkyl, and R5, R6, R7 and R8 independently or independently of one another are hydrogen; C1-C4alkyl, or hydroxy-(C1-C4)alkyl.
    [135] The pH value of the oxidizing agent-containing composition is generally about 2 to 7, and in particular about 2 to 5.
    [136] A preferred method of applying formulations comprising the dyes of formula (1a), (1b) and (1c) onto keratin-containing fibers, preferably the hair, is using a multi-compartment dyeing device or "kit" or any other multi-compartment packaging system as described, for example, in WO 97/20545 at p. 4, I.19 to I.27.
    [137] The hair is usually rinsed after treatment with the dye solution and/or permanent wave solution.
    [138] A more preferred embodiment of the present invention relates to a method of dyeing hair with oxidizing dyes, comprising a. mixing at least one dye of formula (1a), (1b) and (1c) and optionally composed of at least one coupler compound and at least one developer compound and an oxidizing agent, which optionally contains at least one additional dye, and B. contacting the keratin containing fibers with the mixture as prepared in step a.
    [139] To adjust the pH value of organic or inorganic acids, as for example described in DE 199 59 479, col. 3, I. 46 to I. 53 are suitable.
    [140] Furthermore, the present invention relates to a process for dyeing keratin containing fibers of the dyes of formula (1a), (1b) and (1c) with autooxidizing compounds and optionally additional dyes.
    [141] The process comprises a. mixing at least one auto-oxidizing compound and at least one developer compound and at least one dye of the formula (1a), (1b) and (1c) and optionally further dyes, and b. treating the keratin containing fibers with the mixture prepared in step a.
    [142] Furthermore, the present invention relates to a process for dyeing keratin containing fibers with the dyes of formula (1a), (1b) and (1c) and diazotized capped compounds, which comprises, a. treating the keratin containing fibers under alkaline conditions with at least one diazotized capped compound and a coupler compound, and optionally a developer compound and optionally an oxidizing agent, and optionally in the presence of an additional dye and optionally with at least a dye of formula (1a), (1b) and (1c), and b. adjust the pH in the range of 6 to 2 by treatment with an acid, optionally in the presence of an additional dye and optionally at least one dye of formula (1a), (1b) and (1c), with the proviso that at least less in step a. or b. at least one dye of formula (1a), (1b) and (1c) is present.
    [143] The diazotized capped compound and coupling compound and, optionally, the oxidizing agent and developer compound can be applied in any desired order successively or simultaneously.
    [144] Preferably, the diazotized capped compound and the coupling compound are applied simultaneously, in a single composition.
    [145] "Alkaline conditions" denotes a pH in the range of 8 to 10, preferably 9 to 10, especially 9.5 to 10, which is achieved by the addition of bases, eg sodium carbonate, ammonia, or sodium hydroxide.
    [146] Bases can be added to the hair, for dye precursors, diazotized capped compound and/or water-soluble coupling component, or for dye compositions comprising dye precursors.
    [147] Acids are, for example, tartaric acid or citric acid, a citric acid gel, a suitable buffer solution with optionally an acid dye.
    [148] The ratio of the amount of the alkaline dyeing composition applied in the first stage to that of the acidic dyeing composition applied in the second stage is preferably about from 1:3 to 3:1, especially about 1:1.
    [149] Alkaline dyeing compositions of step a. and the acidic dyeing compositions of step b. are left on the fiber for 5 to 60 minutes at 15 to 45°C, in particular for 5 to 45 minutes at 20 to 30°C.
    [150] Furthermore, the present invention relates to a process for dyeing fibers containing keratin with the dyes of formula (1a), (1b) and (1c) and at least one acid dye.
    [151] The following examples serve to illustrate the dyeing processes without limiting the respective processes. Unless otherwise stated, parts and percentages refer to weight. The amounts of dye specified are relative to the material being dyed. Preparation examples Example A1: Step 1: Condensation
    [152] To a suspension of 76 g of 4-hydrazino-benzoic acid in 1 l of isopropanol 54 g of 4-pyridine aldehyde are added slowly.
    [153] The reaction mixture is stirred for 1/2h at room temperature and 2h at 60°C.
    [154] After cooling to room temperature the product is isolated by filtration, washed with isopropanol and water and finally dried under vacuum at 60°C, to obtain 119 g of a yellow powder corresponding to the formula

    [155] LC-MS: m/z = 242, /-x = 413 nm, 13 C NMR (DMSO-d 6 ): δ [pm] 167.130, 148.946, 147.971, 143.478, 135.532, 131.143, 121.599, 120.202, 111.862. Step 2: Alkylation
    [156] The product obtained in step 1 is suspended in 70 ml of water, the pH is adjusted to > 12 and the reaction mixture is cooled to 15-18°C.
    [157] Next, 153g of dimethyl sulfate is added slowly, while the pH is maintained at 12-12.5. The reaction mass is stirred for 18h at room temperature. During this time the pH is kept at 12-12.5.
    [158] The reaction mass is then stirred at 45°C.
    [159] After 2 h, the product is precipitated by the addition of hydrochloric acid, filtered and washed with a dilute sodium chloride solution.
    [160] obtained.
    [161] [pm] 166.865, 150.600, 149,246, 145.045, 130.683, 128.845, 124.499, 122.347, 115.665, 46.810, 34.102.
    Step 3: Chlorination
    [162] At room temperature 30.7g of the product from step 2 is carefully added to 275ml of thionyl chloride.
    [163] The reaction mass is stirred for 1 h at room temperature and 1 h at 50°C.
    [164] Then thionyl chloride is removed under reduced pressure to obtain 36 g of a yellow residue of formula (101 c).

    [165] Examples A2 - A15 were prepared by reacting the product from step 3 of example A1 with the polymers in Table 1. Table 1:
    Example A2:
    [166] A solution of 0.29g of Polymer 1 in 30ml of water was cooled to 0-5 °C and the pH was adjusted to 11.2. Then, 1 g of the compound (101c) was added stepwise, while the pH value was kept at 11 by the addition of 0.5 M NaOH.
    [167] When the addition was complete, the reaction mixture was allowed to return to room temperature.
    [168] Then the reaction mixture was neutralized with hydrochloric acid, the solvent was evaporated under vacuum and the residue dissolved in methanol.
    [169] After filtration the solvent was evaporated and the residue dissolved in water at pH 5. This solution was purified by dialysis (MWCO 1000) to remove low molecular weight impurities. Finally, the solvent was evaporated to obtain 0.2 g of a yellow powder. Example A3:
    [170] A dispersion of 0.6 g of compound (101c) in 15 ml of MEK was added over 4h in small steps at room temperature to a solution of 0.8 g of Polymer 1 in 50 ml of isopropanol.
    [171] The mixture was stirred for 1 h.
    [172] Then 2.7ml conc. have been added.
    [173] The resulting suspension was filtered and the filter cake was dried to obtain 1.6 g of a yellow powder. Examples A4 - A15 were prepared following the same procedure as for ex. A3, using the conditions given in Table 2.
    Example A16:
    [174] A solution of 2.34 g of Polymer 7 in 40 ml of water was adjusted to pH 11.8 with sodium hydroxide. At 0-5 °C 1 g of the dye (101c) was added slowly as a solid while the pH was kept constant. After the addition was complete the temperature was raised to room temperature and stirred overnight. The obtained polymer solution was purified by dialysis. Finally, water was evaporated from the polymer-containing fraction under reduced pressure to obtain 1.62g of a yellow powder. Analytics:
    [175] Examples A2 - A15 have the following 1H NMR signals (MeOH-d4 ): δ [pm] 8.7 (br), 8.1 (br), 7.7 (br), 7.5 ( br), 4.3 (br), 3.8 (vbr), 3.6 (br). 8. Application examples: Hair samples
    [176] For the application examples the following hair types were used: - 1 blonde hair braid (VIRGIN white hair from IMHAIR Ltd., via G. Verga 8, 90134 Palermo (Italy)), - 1 hair braid of medium blond (UNA-Europ. natural hair, medium blond color from Fischbach & Miller, PO Box 1163, 88461 Laupheim, Germany), - 1 bleached hair braid (UNA-Europ. natural hair, medium bleached blond color Fischbach & Miller , PO Box 1163, 88461 Laupheim, Germany). - 1 85-90% gray hair braid (International Hair Importers &Products Inc., 251-71 JerichoTurnpike, Bellerose, NY 11426, USA) 1 Coloring solution:
    [177] 0.1% w/w of one of the dyes described in examples A2 to A11 (0.2% w/w of dyes A12 to A15) is dissolved in a Plantaren solution (10% w/w Plantacare 200UP (ID : 185971.5) in water, pH adjusted to 9.5 with 50% citric acid solution or monoethanolamine solution). Dyeing procedure:
    [178] Hair braids are dyed according to the following procedure:
    [179] The coloring solution is applied directly to dry hair, incubated for 20min. at room temperature, and then rinsed under running water (water temperature: 37°C +/- 1°C, water flow rate: 5-6 l/min).
    [180] The braids are then pressed out with a paper towel and dried overnight at room temperature on a glass plate. Wash fastness
    [181] For determination of wash fastness two sets of hair braids are dyed under the same conditions.
    [182] A set of dyed braids is washed with a commercial shampoo (Goldwell definition Color & Highlights) using approx. 0.5g of shampoo for each braid under tap water (water temperature: 37°C +/- 1°C; flow rate 5-6 l/min).
    [183] Finally, the braids are washed in tap water, pressed with a paper towel, combed and dried with a hair dryer or at room temperature.
    [184] This procedure is repeated 10 times.
    [185] The color position of colored hair braids in the CIELAB color coordinate system can be determined spectrophotometrically by giving the rectangular coordinates L* (Luminosity), a* and b* or, alternatively, the polar coordinates L*, C* (chroma ) eh (hue) [W. Herbst & K. Hunger in Industrial Organic Pigments, VCH Verlagsgesellschaft, 2nd ed. 1997, page 50 and references therein.
    [186] Another reference would be M. - Bohnert et al, Rechtsmedizin (1998) 8, 207-211].
    [187] Colorimetric reflectance measurements are performed with the following spectrophotometer: "Datacolor Spectraflash SF 450" equipped with a D65-filtered xenon light source with a diffuse illumination measurement geometry and 8° of view.
    [188] Measurements of hair braids are conducted directly on the measured head using the plate with an opening (hole) of 6.6 mm.
    [189] Measurements are conducted eight times and mean values used.
    [190] Prior to measurements, the spectrophotometer was calibrated with a black and white standard supplied by Datacolor.
    [191] Next, the color loss of the washed braid set relative to the unwashed braid set is assessed using the Gray Scale according to: Industrial Organic Pigments by Herbst & Hunger, 2nd ed, p. 61, No. 10: DIN 54 001-8-1982, “Herstellung und Bewertung der Ànderung der Farbe”, ISO 105-A02-1993.
    Mixtures of polymeric dyes (Ex. B16 - B28) Example B16:
    [192] A 0.1% w/w solution of yellow A 9, a 2% w/w solution of red A7 in GB2440219 and a solution of blue A9 in PCT/EP2009/066421 are mixed at a ratio of 3 .5, 0.7 and 2.5. The brown solution is applied to human hair.
    Example B17:
    [193] A 0.2% w/w solution of yellow A 9, and a 0.2% w/w solution of red A7 in GB2440219 are mixed in a ratio of 1:1. The orange solution is applied to the human hair.

    [194] The dye emulsion, pH = 10.5
    is mixed with 1.5% by weight of a 9% hydrogen peroxide solution, and the mixture is immediately applied to a braid of brown hair.
    [195] After 30 minutes the braid is rinsed, washed, rinsed and dried.
    [196] The color of the dyed braids is given in Tables 4 and 5. Table 4: Polymeric dye mixtures.
    1)S = black, B = brown 2) Polymeric dyes described in patent application No. EP2007/056945. 3) Polymeric dyes described in patent application No. WO09/090124 Table 5: Mixtures of polymeric dyes and direct dyes

    1) Sc. = Black, B = brown, V = violet, G = green
    [197] In the examples below the abbreviation RKN is a grade designation and indicates the purity of the cellulose; the acronym SR (Chope-Riegler) indicates refining. Example 31:
    [198] 50 parts of chemically bleached beech sulfite are mixed with 50 parts of bleached RKN 15 (22 degrees SR refining) and two parts of the colorant according to Example A4 in water (pH 6, water hardness 10 German hardness degrees, temperature 20 degrees and liquor ratio 40:1). After stirring for 15 minutes, sheets of paper are produced in a Frank sheet former.
    [199] The paper was dyed a very intense yellow tone. The effluent is completely colorless. A degree of exhaustion of nearly 100 percent is achieved. The light fastness and wet processing properties are excellent. Example 32:
    [200] A sheet of paper composed of bleached beech sulfite pulp (22 grades SR) is produced on a continuous-running laboratory papermaking machine. An aqueous solution of the dye according to Example A7 is continuously metered into the low density pulp 10 seconds upstream of the headbox, with vigorous turbulence (0.5 percent dyeing, liquor ratio 400:1, hardness of the water 10 degrees German hardness, pH 6, temperature 20 degrees).
    [201] A medium intensity deep yellow coloration is formed on the sheet of paper. The effluent is completely colorless. Example 33:
    [202] 10 pieces of cotton fabric (mercerized, bleached cotton) are dyed in a laboratory beam dyeing machine in 200 parts of a liquor (water hardness 10 degrees German hardness, pH 4, dye liquor circulated three times per minute) containing 0.05 part of the dye according to Example A4. The temperature is raised over 60 minutes from 20 to 100 degrees and is then held constant for 15 minutes.
    [203] The dye liquor is completely depleted. A deep yellow coloration distinguished by good fastness to light fastness and very good stability to wet processing is formed on the cotton fabric. A tissue composed of regenerated (viscose) is dyed by the same procedure. Deep yellow dye which has good fastness to light fastness and very good stability to wet processing is also obtained from this material by means of the dye of Example A4. Example 34 of a wood paint containing simply solvent:
    [204] 3.0 parts by weight of hydrazone dye A15
    [205] 40.0 parts by weight of ethyl alcohol,
    [206] 40.0 parts by weight of a methoxy-2-propanol and
    [207] 17.0 parts by weight of isopropanol Example 35 of an aqueous paint for wood:
    [208] 3.0 parts by weight of hydrazone dye A7 are dissolved in 100.0 ml of water containing
    [209] 0.05 percent by weight of Invadin LU (a wetting agent).
    [210] The wood paints obtained according to the above examples are applied by means of a brush to a 10.times.5.5 cm piece of colored wood. The colored piece of wood is air-dried for 12 hours.
    权利要求:
    Claims (16)
    [0001]
    1. Polymeric dye, characterized by having the formula
    [0002]
    2. Dyestuff according to claim 1, characterized in that Y1 and Y2 correspond to the formula
    [0003]
    3. Dyestuff according to claim 1, characterized in that Y1 and Y2 correspond to the formula
    [0004]
    4. Dyestuff according to claim 1, characterized in that Y1 and Y2 have the same meaning.
    [0005]
    5. Dyestuff according to claim 1, characterized in that X1 and X2, independently of one another, are a linking group selected from -SO2- and -C(O)-.
    [0006]
    6. Dyestuff according to claim 1, characterized in that A and B, independently of each other, are selected from polyethylenimine, polypropyleneimine, polyvinylamine, polyvinilimine; polysiloxane; polystyrene, polyvinylimidazole, polyvinylpyridine, vinylimidazole copolymers or vinylpyridine and vinylpyrrolidone, DADMAC/DAA copolymers, polyetheramines, polyvinyl alcohol, polyacrylate, polymethacrylate, polyurethanes derived from hydroxyl terminated polyethers, polyesters or polybutadienes on the other side aliphatic or polyisoromatics , as well as their precursors; polyamides and copolyamides derived from diamines and dicarboxylic acids and/or aminocarboxylic acids or the corresponding lactams; polysaccharide, starch, cellulose, lignin, and copolymers and mixtures of the mentioned polymers.
    [0007]
    7. Dye according to any one of claims 1 to 6, characterized in that the molecular weight of the polymeric dye is 400 to 50000.
    [0008]
    8. Dyestuff according to any one of claims 1 to 7, characterized in that the dyes correspond to the formula
    [0009]
    9. Composition, characterized in that it comprises at least one dye of the formula (1a), (1b) or (1c) as defined in claim 1.
    [0010]
    10. Composition according to claim 9, characterized in that it further comprises at least a single additional direct dye and/or an oxidizing agent.
    [0011]
    11. Composition according to claim 9, characterized in that it comprises being in the form of a shampoo, a conditioner, a gel or an emulsion.
    [0012]
    12. Method of dyeing organic material, characterized in that it comprises treating the organic material with at least one dye of the formula (1a), (1b) or (1c) as defined in claim 1, or with a composition as defined in any one of claims 9 to 11.
    [0013]
    13. Method according to claim 12, characterized in that it comprises treating the organic material with at least one dye of the formula (1a), (1b) or (1c) as defined in claim 1 and an oxidizing agent and optionally , an additional direct dye.
    [0014]
    14. Method according to claim 12 or 13, characterized in that it comprises treating the organic material with at least one compound of formula (1a), (1b) or (1c) as defined in claim 1 and at least one single dye oxidative, or treating the organic material with a dye of formula (1a), (1b) or (1c) as defined in claim 1 and at least a single oxidative dye and an oxidizing agent.
    [0015]
    15. Method according to any one of claims 12 to 14, characterized by the fact that the organic material is human hair.
    [0016]
    16. Method according to any one of claims 12 to 14, characterized in that the organic material is wool, leather, textiles, paper or wood.
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    同族专利:
    公开号 | 公开日
    CN102471596A|2012-05-23|
    EP2454328A2|2012-05-23|
    TW201116595A|2011-05-16|
    US20120110750A1|2012-05-10|
    EP2454328B1|2013-10-16|
    US8337569B2|2012-12-25|
    JP2012532976A|2012-12-20|
    MX2012000557A|2012-03-07|
    BR112012000793A2|2016-02-23|
    ES2436469T3|2014-01-02|
    WO2011006946A2|2011-01-20|
    CN102471596B|2015-09-09|
    KR20120046255A|2012-05-09|
    WO2011006946A3|2011-03-31|
    JP5536208B2|2014-07-02|
    KR101526037B1|2015-07-06|
    WO2011006946A9|2012-03-29|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-02-05| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-07-16| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-10-20| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-04-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-22| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/07/2010, OBSERVADAS AS CONDICOES LEGAIS. PATENTE CONCEDIDA CONFORME ADI 5.529/DF, , QUE DETERMINA A ALTERACAO DO PRAZO DE CONCESSAO. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP09165528|2009-07-15|
    EP09165528.2|2009-07-15|
    PCT/EP2010/060175|WO2011006946A2|2009-07-15|2010-07-15|Polymeric hair dyes|
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