Classifications

• • 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 considered which are easy, 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. 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 rest 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 ⁇
• 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 residue of a carbocyclic or heterocyclic diazo component free of water-solubilizing substituents; Y1 chlorine, methyl, methoxy, methoxyethyl, methoxyethoxy or hydrogen; R20 and R21 independently of one another are C1-C6-alkyl, C3-C6-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 remainder 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 with 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.
• D1 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.
• Suitable further substituents are 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.
• 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.
• 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-butoxymethyl metharylamide, N-isobutoxymethyl methacrylamide, 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- (Butoxymethyl) methacrylamide, N, N, -Di- (isobut
• 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 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 such as 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 that contain 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.
• the colorless compounds can be used alone or in any mixtures.
• Polyether acrylates such as and silicone acrylates into consideration, as is known, for example, from Textilpraxis lnternational (1987) pages 848-852.
• a preferred embodiment of the process according to the invention is characterized in that the colorless compounds used are those with 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, a methylene glycol methacrylate with a 2-ethoxyethyl acrylate 200 to 1500, butanediol diacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, dipropylene glycol
• 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 coloring components directly 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 usual catalysts which form free radicals can be used for the polymerization or copolymerization. Mention may be made of hydrazine derivatives, such as hydrazine hydrochloride, organometallic compounds, such as lead tetraethyl, and in particular aliphatic azo compounds, such as .alpha .-Butyl hydroperoxide, di-tert-butyl peroxide, di-tert-amyl peroxide and p-methane hydroperoxide, and also inorganic peroxide compounds, such as sodium peroxide, alkali percarbonates, alkali persulfates or alkali perborates, and especially hydrogen peroxide, which can advantageously replace the expensive benzoyl peroxide.
• the amount of catalysts to be added depends in a known manner on the desired course of the reaction or on the desired properties of the polymer. Be about advantageous 0.05 to 10 percent by weight, based on the total amount of binder or binder mixture, is added.
• 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 medium-pressure mercury 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 method according to the invention is applicable to a wide variety of fibers, such as fibers of animal origin such as wool, silk, hair (for example as felt) or semi-synthetic 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 semi-synthetic chemical fibers
• fully synthetic fibers such as poly
• 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 done in the usual way, e.g. if it is a textile fabric, by impregnation 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 are applied together with the dye 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. It is particularly advantageous for dyeings produced using the exhaust process or padding if the fabric or knitted fabric is first impregnated with the photosensitizer and then dyed with the dye 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 process 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 further 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. These agents are to be understood in particular 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.
• the degrees of fixation are determined colorimetrically via the relative color strength.
• the colored / printed, dried but not irradiated and not washed-out pattern is used as a reference with the color strength 100%.
• the relative color strength of the second pattern which was irradiated and then washed out cold and hot and then dried again, is then determined.
• a cotton satin fabric is made with a printing paste containing 30 g / kg of the dye of the formula 50 g / kg of an oligoethylene glycol diacrylate of molecular weight 508, 50 g / kg trimethylolpropane triacrylate, 100 g / l urea, 30 g / kg sodium alginate and as a photoinitiator a mixture of 2.5 g / kg benzophenone and 2.5 g / kg phenyl- (1-hydroxycyclohexyl) -contains ketone, printed.
• the print is dried and then irradiated under a high pressure mercury lamp with UV light with an energy of 436 J / cm2 per fabric side.
• the degree of fixation is 60%. A brilliant red color of high fastness is obtained.
• a cotton satin fabric is made with a printing paste containing 30 g / kg of the dye of the formula 95 g / kg of an oligoethylene glycol diacrylate of molecular weight 508, 5 g / kg trimethylolpropane triacrylate, 100 g / l urea, 30 g / kg sodium alginate and as a photoinitiator a mixture of 2.5 g / kg benzophenone and 2.5 g / kg phenyl- (1-hydroxycyclohexyl) -contains ketone, printed.
• the print is dried and then irradiated under a high pressure mercury lamp with UV light with an energy of 436 J / cm2 per fabric side. The degree of fixation is 77%. A blue color of high fastness is obtained.
• a cotton satin fabric is made with a printing paste containing 30 g / kg of the dye described in Example 1, 100 g / kg of an oligoethylene glycol diacrylate with a molecular weight of 508, 100 g / l of urea, 30 g / kg of sodium alginate and a mixture of 2.5 g as photoinitiator / kg benzophenone and 2.5 g / kg phenyl- (1-hydroxycyclohexyl) ketone contains, printed.
• the print is dried and then irradiated under a high pressure mercury lamp with UV light with an energy of 436 J / cm2 per fabric side. The degree of fixation is 50%. A red dyeing of high fastness is obtained.
• a cotton satin fabric is mixed with a printing paste containing 30 g / kg of the dye described in Example 1, 200 g / kg of a 50% aqueous N-methylolacrylamide solution, 100 g / l urea, 30 g / kg sodium alginate and as a photoinitiator of 2.5 g / kg benzophenone and 2.5 g / kg phenyl- (1-hydroxycyclohexyl) ketone contains, printed.
• the print is dried and then irradiated under a high pressure mercury lamp with UV light with an energy of 436 J / cm2 per fabric side.
• the degree of fixation is 64%.
• a red dyeing of high fastness is obtained.
• a cotton satin fabric is made with a printing paste containing 30 g / kg of the dye described in Example 1, 50 g / kg of an oligoethylene glycol diacrylate of molecular weight 508, 50 g / kg of a polyether triacrylate, 100 g / l urea, 30 g / kg Contains sodium alginate and as photoinitiator a mixture of 2.5 g / kg benzophenone and 2.5 g / kg phenyl- (1-hydroxycyclohexyl) ketone.
• the print is dried and then irradiated under a high pressure mercury lamp with UV light with an energy of 436 J / cm2 per fabric side. The degree of fixation is 52%. A red dyeing of high fastness is obtained.
• a cotton satin fabric is made with a printing paste containing 30 g / kg of the dye described in Example 1, 50 g / kg of an oligoethylene glycol diacrylate of molecular weight 508, 50 g / kg of methylene bisacrylamide, 100 g / l of urea, 30 g / kg of sodium alginate and Photoinitiator contains a mixture of 2.5 g / kg benzophenone and 2.5 g / kg phenyl (1-hydroxycyclohexyl) ketone, printed. The print is dried and then irradiated under a high pressure mercury lamp with UV light with an energy of 436 J / cm2 per fabric side. The degree of fixation is 67%. A red dyeing of high fastness is obtained.
• a cotton satin fabric is made with a printing paste containing 30 g / kg of the dye of the formula 95 g / kg of an oligoethylene glycol diacrylate of molecular weight 508, 5 g / kg trimethylolpropane triacrylate, 100 g / l urea, 30 g / kg sodium alginate and as a photoinitiator a mixture of 2.5 g / kg benzophenone and 2.5 g / kg phenyl- (1-hydroxycyclohexyl) -contains ketone, printed.
• the print is dried and then irradiated under a high pressure mercury lamp with UV light with an energy of 436 J / cm2 per fabric side. The degree of fixation is 59%. A yellow color of high fastness is obtained.
• a cotton satin fabric is made with a printing paste containing 30 g / kg of the dye of the formula 95 g / kg of an oligoethylene glycol diacrylate of molecular weight 508, 5 g / kg trimethylolpropane triacrylate, 100 g / l urea, 30 g / kg sodium alginate and as a photoinitiator a mixture of 2.5 g / kg benzophenone and 2.5 g / kg phenyl- (1-hydroxycyclohexyl) -contains ketone, printed.
• the print is dried and then irradiated under a high pressure mercury lamp with UV light with an energy of 436 J / cm2 per fabric side. The degree of fixation is 57%. A red dyeing of high fastness is obtained.
• a cotton satin fabric is made with a printing paste containing 30 g / kg of the dye of the formula 95 g / kg of an oligoethylene glycol diacrylate of molecular weight 508, 5 g / kg trimethylolpropane triacrylate, 100 g / l urea, 30 g / kg sodium alginate and as a photoinitiator a mixture of 2.5 g / l 4- (trimethylammonium-methyl) -benzophenone chloride and 2.5 g / kg of the ketone of the formula contains, printed.
• the print is dried and then irradiated with an energy of 436 J / cm2 under a high pressure mercury lamp. The degree of fixation is 74%. A red dyeing of high fastness is obtained.
• a cotton satin fabric is mixed with a solution containing 30 g / l of the dye described in Example 9, 50 g / l of an oligoethylene glycol diacrylate of molecular weight 508, 100 g / l urea and as a photoinitiator 5.0 g / l of the mixture described in Example 9 , padded (fleet absorption 67%).
• the dyeing is dried and then irradiated with an Hg high pressure lamp with UV light with an energy of 872 J / cm2. A red dyeing of high fastness is obtained.
• a cotton satin fabric is impregnated with a 1: 1 mixture of benzophenone and phenyl (1-hydroxycyclohexyl) ketone (order approx. 0.75%) and then with a solution containing 30 g / l of the dye described in Example 9, 50 g / l of an oligoethylene glycol diacrylate of molecular weight 508, 100 g / l of urea and 2.5 g / l of benzophenone and 2.5 g / l of phenyl (1- contains hydroxycyclohexyl) ketone, padded (liquor absorption 66%).
• the dyeing is dried and then irradiated under a mercury high-pressure lamp with UV light with an energy of 109 J / cm2. A red dyeing of high fastness is obtained.
• An emulsion is produced from one part of water and 4 parts of mineral spirits with the addition of one of the emulsifiers customary in emulsion printing.
• 3% of the dye described in Example 1 12% of an oligoethylene glycol diacrylate of molecular weight 508 and 0.25% of benzophenone and 0.25% of phenyl- (1-hydroxycyclohexyl) ketone as a photoinitiator are stirred into this.
• a cotton satin fabric is printed with this emulsion (order 66%), dried and then irradiated with an Hg high-pressure lamp with UV light with an energy of 436 J / cm2. A red dyeing of high fastness is obtained.
• An emulsion is prepared from one part of water and 5 parts of an alkoxylated polyether tetraacrylate with the addition of one of the emulsifiers customary in emulsion printing.
• a cotton satin fabric is printed with this emulsion (order 66%), dried and then irradiated with an Hg high-pressure lamp with UV light with an energy of 436 J / cm2.
• the degree of fixation is determined by detaching the dye with ethanol from an irradiated, non-washed out and an unirradiated sample. The samples are treated once at 40 ° C and then 30 minutes at boiling temperature. The two extracts are combined and the degrees of fixation are determined using the absorbance (at ⁇ max ). The degree of fixation is 83%. A red dyeing of high fastness is obtained.

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• Polymerisation Methods In General (AREA)
• Macromonomer-Based Addition Polymer (AREA)
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• Dental Preparations (AREA)
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• 1992
  • 1992-09-04 AT AT92810680T patent/ATE124102T1/de not_active IP Right Cessation
  • 1992-09-04 EP EP92810680A patent/EP0532467B1/fr not_active Expired - Lifetime
  • 1992-09-04 DE DE59202603T patent/DE59202603D1/de not_active Expired - Fee Related
  • 1992-09-04 ES ES92810680T patent/ES2074351T3/es not_active Expired - Lifetime
  • 1992-09-08 US US07/941,597 patent/US5409504A/en not_active Expired - Fee Related
  • 1992-09-11 JP JP26785992A patent/JP3544547B2/ja not_active Expired - Fee Related
• 2003
  • 2003-10-29 JP JP2003368473A patent/JP2004107872A/ja not_active Withdrawn

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