EP0532467B1 - Procédé de fixation de colorants à l'aide des rayonnements UV - Google Patents

Procédé de fixation de colorants à l'aide des rayonnements UV Download PDF

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Publication number
EP0532467B1
EP0532467B1 EP92810680A EP92810680A EP0532467B1 EP 0532467 B1 EP0532467 B1 EP 0532467B1 EP 92810680 A EP92810680 A EP 92810680A EP 92810680 A EP92810680 A EP 92810680A EP 0532467 B1 EP0532467 B1 EP 0532467B1
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Prior art keywords
acrylate
process according
polymerizable
diacrylate
double bond
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German (de)
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EP0532467A1 (fr
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Katharina Dr. Fritzsche
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BASF Schweiz AG
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Ciba Geigy AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
    • D06P1/5257—(Meth)acrylic acid
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65112—Compounds containing aldehyde or ketone groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65118—Compounds containing hydroxyl groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
    • D06P5/2005—Treatments with alpha, beta, gamma or other rays, e.g. stimulated rays
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/02—Vinyl sulfones and precursors thereof

Definitions

  • the invention relates to a method for fixing dyes, which contain polymerizable double bonds, on organic materials by irradiation with UV light in the presence of a colorless polymerizable binder and a photosensitizer.
  • the present invention thus relates to a process for fixing dyes to organic materials, characterized in that dyes which contain at least one polymerizable double bond or at least one polymerizable ring system are present in the presence of at least one colorless binder which contains at least one polymerizable double bond at least one photosensitizer, and optionally other auxiliaries fixed on the organic material by irradiation with UV light.
  • Water-soluble dyes are primarily to be understood as those which contain chromophores with sulfo groups. Disperse dyes which have a polymerizable group and are soluble in the radiation-polymerizable binder are suitable as water-insoluble dyes.
  • Suitable polymerizable double bonds are vinyl, vinyl chloride, vinyl sulfone, allyl, allyl sulfone, acrylate, methacrylate, acrylamide, methacrylamide, haloacrylamide, styryl groups and derivatives of cinnamic acid.
  • Suitable dyes for this fixing process are those which have an activated unsaturated group, in particular an unsaturated aliphatic group, such as the vinyl, halovinyl, styryl, acrylic or methacrylic group.
  • groups e.g. the unsaturated groups containing halogen atoms, such as halomaleic acid and halogenpropiolic acid residues, the ⁇ - or ⁇ -bromo or chloroacrylic groups, halogenated vinyl acetyl groups, halogencrotonyl or halogenomethacrylic groups.
  • groups are also suitable that easily, e.g. by splitting off hydrogen halide into halogen-containing unsaturated groups, e.g. the dichloro or dibromopropionyl group.
  • Halogen atoms here include fluorine, chlorine, bromine and iodine atoms as well as pseudohalogen atoms, e.g. to understand the cyano group.
  • Suitable dyes which contain a polymerizable double bond are preferably those which contain at least one acryloyl, ⁇ -bromoacryloyl, ⁇ -chloroacryloyl, vinyl or vinylsulfonyl radical; very particularly preferably those which contain at least one acryloyl, ⁇ -bromoacryloyl or vinylsulfonyl radical.
  • Suitable dyes which contain a polymerizable ring system are preferably those which contain at least one epoxy radical.
  • the chromophoric systems used can belong to a wide variety of dye classes.
  • a preferred embodiment of the process according to the invention is characterized in that the dyes are those of the formula D- (X) m (1), wherein D is the residue of an organic dye of monoazo or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, nitroaryl, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, Naphthoquinone, pyrenequinone or perylene tetracarbimide series, X is a polymerizable double bond or a polymerizable ring system, and m is the number 1, 2, 3, 4, 5 or 6.
  • Dyes of the formula (1) are likewise particularly preferably used, in which D is the residue of an azo dye, in particular a residue of the formulas 6 to 17: wherein (R7) 1 ⁇ 3 represents 1 to 3 substituents from the group C1 ⁇ 4 alkyl, C1 ⁇ 4 alkoxy, halogen, carboxy and sulfo; wherein (R9) 1 ⁇ 3 represents 1 to 3 substituents from the group C1 ⁇ 4 alkyl, C1 ⁇ 4 alkoxy, halogen, carboxy and sulfo; wherein (R10) 1 ⁇ 3 represents 1 to 3 substituents from the group C1 ⁇ 4 alkyl, C1 ⁇ 4 alkoxy, halogen, carboxy and sulfo; wherein R11 is C2 ⁇ 4 alkanoyl or benzoyl; wherein R12 is C2 ⁇ 4 alkanoyl or benzoyl; wherein (R13) 0 ⁇ 3 represents 0 to 3 substituents from the group C1 ⁇ 4 alkyl, C1 ⁇ 4 al
  • a further preferred embodiment of the process according to the invention is characterized in that azo dyes of the formula are used as the water-insoluble or slightly water-soluble dyes wherein D1 is the balance of a carbocyclic or heterocyclic diazo component free from water-solubilizing substituents; Y1 chlorine, methyl, methoxy, methoxyethyl, methoxyethoxy or hydrogen; R20 and R21 independently of one another are C1-C6-alkyl, C3-C Al-alkenyl, phenyl or the rest -B1-X1; R22 is hydrogen, methyl, methoxy, chlorine, bromine or the radical X1; X1 is a residue with a polymerizable double bond; B1 is an optionally substituted radical of the formula - (CH2) m - (C6H4) n - (CH2) o -; where m is an integer from 1 to 6 n 0 or 1 and o represents an integer from 0 to 6; mean and
  • D1 is preferably the residue of a homo- or heterocyclic diazo component, e.g. from the series thienyl, phenylazothienyl, thiazolyl, isothiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, benzthiazolyl, benzisothiazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, imidazolyl , or phenyl.
  • a homo- or heterocyclic diazo component e.g. from the series thienyl, phenylazothienyl, thiazolyl, isothiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, benzthiazolyl, benzisothiazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, imidazolyl , or phenyl.
  • Each of these systems can carry further substituents such as alkyl, alkoxy or alkylthio each having 1 to 4 carbon atoms, phenyl, electronegative groups such as halogen, especially chlorine or bromine, trifluoromethyl, cyano, nitro, acyl, such as e.g. Acetyl or benzoyl, carboalkoxy, especially carbomethoxy or carboethoxy, alkyl sulfone with 1 to 4 carbon atoms, phenyl sulfone, phenoxysulfone, sulfonamido or arylazo, especially phenylazo.
  • Two adjacent substituents of the ring systems mentioned can also together form further fused rings, e.g. Phenyl rings or cyclic imides.
  • D 1 particularly preferably denotes a benzothiazolyl, benzisothiazolyl or phenyl radical which is unsubstituted or substituted once or twice by one of the abovementioned radicals.
  • alkyl radicals can be substituted, e.g. by hydroxy, alkoxy with 1 to 4 carbon atoms, especially methoxy, cyano or phenyl.
  • Halogen such as fluorine, chlorine or bromine, or -CO-U or -O-CO-U, where U is alkyl having 1 to 6 carbon atoms or phenyl, are suitable as further substituents.
  • Suitable alkenyl radicals are those radicals which are derived from the alkyl radicals listed above by replacing at least one single bond with a double bond.
  • Suitable residues are e.g. Ethenyl or propenyl.
  • Phenyl radicals are to be understood as meaning unsubstituted or substituted phenyl radicals.
  • substituents are C1-C4-alkyl, C1-C4-alkoxy, bromine, chlorine, nitro or C1-C4-alkylcarbonylamino into consideration.
  • residues derived from acrylic, methacrylic or cinnamic acid are suitable.
  • dyes of the formulas are dyes of the formulas:
  • Other preferred dyes are sparingly water-soluble or water-insoluble dyes of the anthraquinone series, such as The dyes mentioned are known or can be prepared by known methods. For example, about a mole equivalent of an acrylic acid chloride is added to a solution of the substance to be acylated in anhydrous acetone. About 1 mole equivalent of pyridine is then added at room temperature and the product is separated off by adding water.
  • the binders to be added are polymerizable colorless or almost colorless (ie possibly slightly yellowish) monomeric, oligomeric or polymeric compounds or mixtures thereof; e.g. N-C1 ⁇ 4-alkylolacrylamide, N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-C1 ⁇ 4-alkylolmethacrylamide, N-butoxymethylmetharylamide, N-isobutoxymethylmethacrylamide, N, N, di- (C1 ⁇ 4-alkolol) acrylamide, N, N, -Di- (butoxymethyl) acrylamide, N, N, Di- (isobutoxymethyl) acrylamide, N, N, Di- (C1 ⁇ 4-methylol) methacrylamide, N, N, Di- (butoxymethyl) -methacrylamide, N, N, -Di- (isobutoxymethyl) methacrylamide.
  • N-C1 ⁇ 4-alkylolacrylamide N-but
  • Monomeric, oligomeric or polymeric organic compounds or mixtures thereof are preferably used as colorless compounds in the process according to the invention.
  • Acrylates, diacrylates, acrylic acid or acrylamides are particularly preferably used as colorless compounds in the process according to the invention.
  • Mixtures of monomeric and oligomeric colorless organic compounds are very particularly preferably used in the processes according to the invention.
  • the colorless organic compounds which contain at least one polymerizable double bond are free from coloring residues. These are monomeric, oligomeric or polymeric organic compounds or a mixture thereof, which can be polymerized or crosslinked.
  • Possible monomeric colorless compounds are those with a molecular weight of up to approximately 1000 and which contain at least one polymerizable group.
  • the monomeric colorless compound can be used both directly and as a mixture with other monomers, oligomers and / or polymers.
  • Suitable oligomeric colorless compounds are those having a molecular weight between 1000 and 10000 and containing one or more polymerizable groups. If liquid, the oligomeric colorless compound can itself be used directly or as a solution in water or organic solvents or as a mixture with other monomers, oligomers and / or polymers.
  • Suitable polymeric colorless compounds are those having a molecular weight> 10,000 which contain one or more polymerizable groups.
  • the polymeric colorless compound if liquid, can itself be used directly or as a solution in water or organic solvents or as a mixture with other monomers, oligomers and / or polymers.
  • Colorless compounds which can be used are ethylenically unsaturated monomeric, oligomeric and polymeric compounds.
  • Esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers with ethylenically unsaturated groups in the chain or in side groups e.g. unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers with (meth) acrylic groups in side chains, and also mixtures of one or more such polymers.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid and unsaturated fatty acids such as linolenic acid or oleic acid.
  • Acrylic and methacrylic acid are preferred.
  • Aliphatic and cycloaliphatic polyols are suitable as polyols.
  • polyepoxides are those based on the polyols and epichlorohydrin.
  • polymers or copolymers containing hydroxyl groups in the polymer chain or in side groups e.g. Polyvinyl alcohol and copolymers thereof or polymethacrylic acid hydroxyalkyl esters or copolymers thereof, are suitable as polyols.
  • Other suitable polyols are oligoesters with hydroxyl end groups.
  • aliphatic and cycloaliphatic polyols are alkylene diols with preferably 2 to 12 carbon atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol , Octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols with molecular weights of preferably 200 to 1500, 1,3-cyclopentanediol, 1,2- 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris ( ⁇ -hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol.
  • the polyols can be partially or completely esterified with one or different unsaturated carboxylic acids, the free hydroxyl groups in partial esters being modified, for example esterified or esterified with other carboxylic acids.
  • esters are: Trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Tripentaerythritoctaacrylat, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol
  • amides of identical or different unsaturated carboxylic acids of aromatic, cycloaliphatic and aliphatic polyamines with preferably 2 to 6, particularly 2 to 4, amino groups are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di- ⁇ -aminoethyl ether, diethylenetriamine, triethylenetetramine, di- ( ⁇ -aminoethoxy) - or di- ( ⁇ -aminopropoxy) ethane.
  • Other suitable polyamines are polymers and copolymers with amino groups in the side chain and oligoamide
  • Examples of such unsaturated amides are: methylene-bis-acrylamide, 1,6-hexamethylene-bis-acrylamide, diethylenetriamine-tris-methacrylamide, bis (methacrylamidopropoxy) ethane, ⁇ -methacrylamidoethyl methacrylate, N [( ⁇ -hydroxyethoxy) ethyl] - acrylamide.
  • Suitable unsaturated polyesters and polyamides are derived, for example, from maleic acid and diols or diamines.
  • Maleic acid can be partially replaced by other dicarboxylic acids. They can be used together with ethylenically unsaturated comonomers, for example styrene.
  • the polyesters and polyamides can also differ from dicarboxylic acids and derive ethylenically unsaturated diols or diamines, especially from longer-chain ones with, for example, 6 to 20 carbon atoms.
  • polyurethanes are those which are composed of saturated or unsaturated diisocyanates and unsaturated or saturated diols.
  • Polybutadiene and polyisoprene and copolymers thereof are known.
  • Suitable comonomers are e.g. Olefins such as ethylene, propene, butene, hexene, (meth) acrylates, acrylonitrile, styrene or vinyl chloride.
  • Polymers with (meth) acrylate groups in the side chain are also known. are reaction products of novolak-based epoxy resins with (meth) acrylic acid, homo- or copolymers of polyvinyl alcohol or their hydroxyalkyl derivatives which are esterified with (meth) acrylic acid, or homo- and copolymers of (meth) acrylates with hydroxyalkyl (meth ) acrylates are esterified.
  • the colorless compounds can be used alone or in any mixtures.
  • a preferred embodiment of the process according to the invention is characterized in that the colorless compounds used are those having the acrylic radical as a polymerizable group, oligomeric polyether, polyurethane and Polyester acrylates are particularly preferred.
  • the colorless compound used is, in particular, N-vinylpyrrolidine, acrylic acid, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, butanediol monoacrylate, 2-ethoxyethyl acrylate, ethylene glycol acrylate, butanediol acrylate, 2-ethoxyethylglycol acrylate, a methylene glycol methacrylate, a methylene glycol methacrylate, a methylene glycol methacrylate, with a ethylene glycol ethoxylate 200 to 1500, butanediol diacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, trimethylol
  • photosensitizer When using ultraviolet radiation, the presence of a photosensitizer is required.
  • the photosensitizer absorbs the radiation to generate free radicals that initiate the polymerization.
  • Examples of photosensitizers or photoinitiators used according to the invention are carbonyl compounds such as 2,3-hexanedione.
  • Diacetylacetophenone, benzoin and benzoin ethers such as dimethyl, ethyl and butyl derivatives, for example 2,2-diethoxyacetophenone and 2,2-dimethoxyacetophenone, benzophenone or a benzophenone salt and phenyl (1-hydroxycyclohexyl) ketone or a ketone of the formula Benzophenone in combination with a catalyst such as triethylamine, N, N'-dibenzylamine and dimethylaminoethanol and Benzophenone plus Michler's ketone; nitrogen-containing compounds such as diazomethane, azo-bis-isobutyronitrile, hydrazine, phenylhydrazine and trimethylbenzylammonium chloride; and sulfur-containing compounds such as benzenesulfonate, diphenyl disulfide and tetramethylthiuram disulfide.
  • photosensitizers are used alone or in combination
  • the proportion of photosensitizers in the applied color components immediately before the irradiation is 0.01-20%, preferably 0.1-5%.
  • the printing pastes or dyeing liquors can also contain the usual additives such as thickeners, colorants, fillers, dispersants, lubricants, antioxidants and polymerization inhibitors.
  • the latter are usually also added to the radiation-polymerizable binders as stabilizers.
  • polymerization coinitiators such as peroxides or aliphatic azo compounds can also be added, which are activated by the heat occurring during the irradiation and start the polymerization.
  • the customary catalysts which form free radicals can be used for the polymerization or copolymerization.
  • anti-blocking agents can also be used.
  • the UV light to be used is radiation whose emission is between 200 and 450 nm, in particular between 210 and 350 nm.
  • the radiation is preferably generated artificially with mercury vapor, xenon or tungsten lamps, fluorescent tubes or carbon arc lamps.
  • High-pressure mercury lamps are particularly advantageous.
  • Capillary mercury high-pressure lamps, mercury low-pressure lamps or mercury medium-pressure lamps are also suitable.
  • the latter can also be operated in a pulsed manner in order to concentrate the radiation in peaks. Pulsed operation is also possible with xenon lamps if a higher proportion of longer-wave UV light is required.
  • the exact irradiation time of the dyeings or prints will depend on the luminosity of the UV source, the distance from the light source, the type and amount of photosensitizer and the permeability of the formulation and the textile substrate to UV light.
  • Usual irradiation times are 2 seconds to 20 minutes, preferably 5 seconds to 2 minutes.
  • the fixation can be ended by interrupting the light so that it can also be carried out discontinuously.
  • the irradiation can be carried out under protective gas to prevent inhibition by oxygen, but this precaution is generally unnecessary. Oxygen inhibition can also be effectively suppressed by the addition of so-called "anti-blocking agents", which are amines and especially also aminoacrylates.
  • the process according to the invention can be applied to a wide variety of fibers, such as fibers of animal origin such as wool, silk, hair (for example as felt) or semisynthetic chemical fibers such as protein synthetic fibers or alginate fibers, fully synthetic fibers such as polyvinyl, polyacrylonitrile, polyester, polyamide , Polypropylene or polyurethane fibers and especially cellulose-containing materials, such as bast fibers, such as linen, hemp, jute, ramie and in particular cotton, and also cellulose synthetic fibers, such as viscose or modal fibers, copper, nitrate or saponified acetate fibers or fibers made of cellulose acetate, such as acetate fibers, or fibers made of cellulose triacetate, such as Arnel®, Trilan®, Courpleta® or Tricel®.
  • fibers of animal origin such as wool, silk, hair (for example as felt) or semisynthetic chemical fibers such as protein synthetic fibers or alginate
  • the fibers mentioned can be in forms as are used in particular in the textile industry, e.g. as threads or yarns, or as woven, knitted or non-woven materials, such as felts.
  • Wool, silk, hair, alginate fibers, polyvinyl, polyacrylonitrile, polyester, polyamide, polypropylene or polyurethane fibers or cellulose-containing fibers are preferably used as fiber material in the processes according to the invention.
  • Cellulose fibers and polyester-cellulose blended fabrics are particularly preferably used.
  • the treatment of the material to be colored with a dye according to the definition can be carried out in the usual way, e.g. if it is a textile fabric, by drinking with a dye solution in a pull-out bath or by spraying or by padding a block solution, or by printing e.g. on a squeegee printing machine or using inkjet printing technology.
  • the colorless binder, the photosensitizer and the other additives together with the dye are applied to the material to be colored.
  • the colorless binder and / or the photosensitizer and, if appropriate, the polymerization coinitiators separately, e.g. to apply in the form of a pretreatment or aftertreatment. So it is particularly advantageous for dyeings that are produced in, exhaust processes or by padding if the fabric or knitted fabric is first impregnated with the photosensitizer and then dyed with the dyeing liquor, which also contains photosensitizer.
  • Emulsion printing processes in which the mixture of radiation-polymerizable binders replaces the hydrophobic component are also advantageous, so that neither mineral spirits nor thickeners are required.
  • the method is particularly suitable for carrying out continuous dyeing and Fixing processes, however, the process or sub-steps thereof can also be carried out discontinuously.
  • the invention furthermore relates to compositions comprising a dye which contains at least one polymerizable double bond or at least one polymerizable ring system, at least one colorless binder which contains at least one polymerizable double bond and at least one photosensitizer.
  • Preferred agents contain those preferred individual components as explained in the description of the dyes, colorless binders and photosensitizers. These agents can contain further additives as are customary for dyeing or printing. In particular, these means are to be understood as printing pastes, preferably those which are suitable for emulsion printing.
  • the irradiation with two 50 watt high-pressure mercury lamps at transport speeds of 10-20 m / min. carried out.
  • the samples are irradiated on both sides and at high doses in several passes.
  • the dyeings or prints are washed out as is customary for reactive dyes.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coloring (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Dental Preparations (AREA)
  • Photometry And Measurement Of Optical Pulse Characteristics (AREA)

Claims (16)

  1. Procédé de fixage de colorants sur des matières organiques, en particulier sur des matières fibreuses, caractérisé en ce qu'on fixe sur la matière organique des colorants dont la molécule comporte au moins une double liaison permettant une polymérisation ou au moins un système cyclique permettant une polymérisation, en présence d'au moins un liant incolore dont la molécule comporte au moins une double liaison permettant une polymérisation, et d'au moins un photo-sensibilisateur, ainsi que d'autre éventuels adjuvants, par irradiation avec de la lumière UV.
  2. Procédé conforme à la revendication 1, caractérisé en ce qu'on utilise, comme colorants, des composés de formule :



            D-(X)m   (1),



    dans laquelle D représente le reste d'un colorant organique de la série des colorants monoazoïques, polyazoïques, complexes métalliques de colorant azoïque, anthraquinoniques, phtalocyanines, formazans, azométhiniques, nitroaryliques, dioxazines, phénazines, stilbéniques, de triphénylméthane, de xanthène, de thioxanthone, naphtoquinoniques, pyrènequinoniques ou de pérylènetétracarbimide, X représente un sytème comportant un cycle ou une double liaison permettant une polymérisation, et m représente le nombre 1, 2, 3, 4, 5 ou 6.
  3. Procédé conforme à l'une des revendications 1 et 2, caractérisé en ce qu'on utilise des colorants dont la molécule comporte, en tant que double liaison permettant une polymérisation ou en tant que système cyclique permettant une polymérisation, un groupe acryloyle, α-bromoacryloyle, α-chloroacryloyle, vinylsulfonyle, vinyle ou époxydyle.
  4. Procédé conforme à la revendication 3, caractérisé en ce qu'on utilise des colorants dont la molécule comporte, en tant que double liaison permettant une polymérisation ou en tant que système cyclique permettant une polymérisation, un groupe acryloyle, α-bromoacryloyle ou vinylsulfonyle.
  5. Procédé conforme à l'une des revendications 1 à 4, caractérisé en ce qu'on utilise, en tant que composés incolores, des composés dont la molécule comporte un reste acrylique en tant que groupe permettant une polymérisation.
  6. Procédé conforme à la revendication 5, caractérisé en ce qu'on utilise, en tant que composés incolores, un acrylaté, un diacrylate, de l'acide acrylique ou de l'acrylamide.
  7. Procédé conforme à l'une des revendications 1 à 6, caractérisé en ce qu'on utilise un mélange de composés organiques incolores, monomères et oligomères.
  8. Procédé conforme à la revendication 7, caractérisé en ce qu'on utilise des oligomères de type acrylate de polyéther, acrylate de polyuréthane ou acrylate de polyester.
  9. Procédé conforme à l'une des revendications 1 à 8, caractérisé en ce qu'on utilise, en tant que composé incolore, la N-vinylpyrrolidine, l'acide acrylique, l'acrylate de butyle, l'acrylate de 2-éthythexyle, l'acrylate de 2-hydroxyéthyle, l'acrylate d'hydroxypropyle, le monoacrylate de butanediol, l'acrylate de 2-éthoxyéthyle, l'acrylate d'éthylèneglycol, les bisacrylates de polyéthylèneglycol dont la masse moléculaire vaut de 200 à 1500, le diacrylate de butanediol, le diacrylate de tétra-éthylèneglycol, le diacrylate de 1,6-hexanediol, le diacrylate de di-éthylèneglycol, le diacrylate de dipropylèneglycol, le diacrylate de triéthylèneglycol, le diacrylate de tripropylèneglycol, le triacrylate de triméthylolpropane, le triacrylate de pentaérythritol, le bromo-acrylamide, le méthylène-bis(bromoacrylamide), le méthylène-bis (acrylamide), les N-alcoxyacrylamides, l'acrylate d'huile de soja, l'acrylate de polybutadiène, le diméthacrylate de diéthylèneglycol, le diméthacrylate de 1,6-hexanediol, l'acrylate de 2-(2-éthoxyéthoxy)-éthyle, l'acrylate de stéaryle, l'acrylate de tétrahydrofurfuryle, le tétraacrylate de pentaérythrytol, l'acrylate de lauryle, l'acrylate de 2-phénoxyéthyle, le diacrylate de bisphénol éthoxylé, le tétraacrylate de ditriméthylolpropane, le triacrylate de tris-(2-hydroxyéthyl)-isocyanurate, l'acrylate d'isodécyle, le pentaacrylate de dipentaérythritol, le triacrylate de triméthylolpropane éthoxylé, l'acrylate d'isobornyle, le diacrylate de tétrabromobisphénol éthoxylé, le diacrylate de néopentylglycol propoxylé et le triacrylate de glycérol propoxylé.
  10. Procédé conforme à l'une des revendications 1 à 9, caractérisé en ce qu'on utilise, en tant que photosensibilisateurs, des composés carbonylés comme la 2,3-hexanedione, la diacétylacétophénone, la benzoïne et les éthers de benzoïne comme ses dérivés diméthylés, éthylés ou butylés, par exemple la 2,2-diéthoxyacétophénone et la 2,2-diméthoxyacétophénone, la benzophénone ou un sel de benzophénone, la phényl-(1-hydroxycyclohexyl)-cétone ou une cétone de formule :
    Figure imgb0034
     de la benzophénone combinée avec un catalyseur comme la triéthylamine, la N,N'-dibenzylamine et le diméthylaminoéthanol, et la benzophénone associée à la cétone de Michler, des composés azotés, comme le diazométhane, l'azo-bis-isobutyronitrile, l'hydrazine, la phénylhydrazine, et le chlorure de triméthylbenzylammonium, ainsi que des composés soufrés, comme les benzènesulfonates, le disulfure de diphényle et le disulfure de tétraméthylthiurame, ou des photosensibilisateurs copolymérisables.
  11. Procédé conforme à la revendication 1, caractérisé en ce qu'on utilise comme colorants des composés dont la molécule comporte, en tant que double liaison permettant une polymérisation ou en tant que système cyclique permettant une polymérisation, un groupe α-bromoacryloyle ou un résidu de l'acide cinamique, en ce qu'on utilise comme liant un diacrylate d'oligoéthylèneglycol, du N-hydroxyméthylacrylamide, du triacrylate de triméthylolpropane, un triacrylate de polyéther, du méthylène-bis(acrylamide) ou un tétraacrylate de polyéther alcoxylé, et en ce qu'on utilise en tant que photosensibilisateur un mélange constitué de benzophénone ou d'un sel de benzophénone et de phényl-(1-hydroxycyclohexyl)-cétone ou d'une cétone de formule :
    Figure imgb0035
  12. Procédé conforme à l'une des revendications 1 à 11, caractérisé en ce qu'on utilise, comme matière fibreuse, de la laine, de la soie, des poils, des fibres d'alginate, des fibres polyvinyliques, des fibres de polyacrylonitrile, des fibres de polyester, des fibres de polyamide, des fibres de polypropylène, des fibres de polyuréthane ou des fibres cellulosiques.
  13. Procédé conforme à l'une des revendications 1 à 12, caractérisé en ce qu'on effectue le traitement de la matière fibreuse avec le colorant, le liant incolore et le photosensibilisateur par imprégnation, pulvérisation, foulardage ou impression, y compris l'impression au jet d'encre.
  14. Procédé conforme à la revendication 13, caractérisé en ce qu'on effectue le traitement de la matière fibreuse avec le photosensibilisateur avant de réaliser la teinture.
  15. Agent de teinture que l'on peut fixer à l'aide d'une lumière UV, et qui contient un colorant dont la molécule comporte au moins une double liaison permettant une polymérisation ou au moins un système cyclique permettant une polymérisation, ainsi qu'au moins un liant incolore dont la molécule comporte au moins une double liaison permettant une polymérisation, et au moins un agent photosensibilisateur.
  16. Matière fibreuse teinte ou imprimée, ayant subi un fixage selon le procédé conforme à la revendication 1.
EP92810680A 1991-09-13 1992-09-04 Procédé de fixation de colorants à l'aide des rayonnements UV Expired - Lifetime EP0532467B1 (fr)

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CH2724/91 1991-09-13
CH272491 1991-09-13

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EP0681623B1 (fr) * 1993-02-01 1997-05-21 Ciba SC Holding AG Fixation de teinture induite par irradiation
AU6647394A (en) * 1993-05-04 1994-11-21 Ciba-Geigy Ag Radiation-induced fixation of dyes
WO1995008018A1 (fr) * 1993-09-16 1995-03-23 Ciba-Geigy Ag Thermofixage des colorants en presence d'un compose polymerisable et d'un initiateur
US5852126A (en) * 1994-05-02 1998-12-22 Novartis Ag Polymerisable composition and the use thereof
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ES2074351T3 (es) 1995-09-01
DE59202603D1 (de) 1995-07-27
EP0532467A1 (fr) 1993-03-17
JPH05214682A (ja) 1993-08-24
JP2004107872A (ja) 2004-04-08
JP3544547B2 (ja) 2004-07-21
ATE124102T1 (de) 1995-07-15

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