EP0532467A1 - Process for the fixation of dyes with UV-light - Google Patents
Process for the fixation of dyes with UV-light Download PDFInfo
- Publication number
- EP0532467A1 EP0532467A1 EP92810680A EP92810680A EP0532467A1 EP 0532467 A1 EP0532467 A1 EP 0532467A1 EP 92810680 A EP92810680 A EP 92810680A EP 92810680 A EP92810680 A EP 92810680A EP 0532467 A1 EP0532467 A1 EP 0532467A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acrylate
- polymerizable
- dyes
- double bond
- colorless
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CCC(C)(CC)C(*)(*)c1nc(*)nc(N(*)C(C=C*)=C(*)C=CCB**)n1 Chemical compound CCC(C)(CC)C(*)(*)c1nc(*)nc(N(*)C(C=C*)=C(*)C=CCB**)n1 0.000 description 3
- YCNUFQQLPRQJHX-ULDVOPSXSA-N C=C(C(Nc(cc1)ccc1C(Nc(cc(cc1cc2S(O)(=O)=O)S(O)(=O)=O)c1c(O)c2/N=N/c(cc(cc1)NC(C(Br)=C)=O)c1S(O)(=O)=O)=O)=O)Br Chemical compound C=C(C(Nc(cc1)ccc1C(Nc(cc(cc1cc2S(O)(=O)=O)S(O)(=O)=O)c1c(O)c2/N=N/c(cc(cc1)NC(C(Br)=C)=O)c1S(O)(=O)=O)=O)=O)Br YCNUFQQLPRQJHX-ULDVOPSXSA-N 0.000 description 1
- XPRIAGOCLOZSHV-BQYQJAHWSA-N CC(C)(C(c(cc1)ccc1O/C=C/O)=O)O Chemical compound CC(C)(C(c(cc1)ccc1O/C=C/O)=O)O XPRIAGOCLOZSHV-BQYQJAHWSA-N 0.000 description 1
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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Abstract
Description
Die Erfindung betrifft ein Verfahren zum Fixieren von Farbstoffen, welche polymerisierbare Doppelbindungen enthalten, auf organischen Materialien durch Bestrahlung mit UV-Licht in Gegenwart eines farblosen polymerisierbaren Binders und eines Photosensibilisators.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.
Gegenstand der vorliegenden Erfindung ist somit ein Verfahren zum Fixieren von Farbstoffen auf organischen Materialien, dadurch gekennzeichnet, dass man Farbstoffe, welche mindestens eine polymerisierbare Doppelbindung oder mindestens ein polymerisierbares Ringsystem enthalten, in Gegenwart mindestens eines farblosen Binders, welcher mindestens eine polymerisierbare Doppelbindung enthält, und mindestens eines Photosensibilisators, sowie gegebenenfalls weiterer Hilfsstoffe durch Bestrahlung mit UV-Licht auf dem organischen Material fixiert.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.
Geeignet sind wasserlösliche und wasserunlösliche Farbstoffe, die dadurch charakterisiert sind, dass sie polymerisierbare Doppelbindungen tragen. Diese polymerisierbaren Gruppen können auch über einen Spacer wie z.B. eine -(CH₂-CH₂-O)n-Gruppe mit dem Chromophor verbunden sein.Suitable are water-soluble and water-insoluble dyes which are characterized in that they carry polymerizable double bonds. These polymerizable groups can also be connected to the chromophore via a spacer such as a - (CH₂-CH₂-O) n group.
Unter wasserlöslichen Farbstoffen sind vor allem solche zu verstehen, die Chromophore mit Sulfogruppen enthalten. Als wasserunlösliche Farbstoffe sind Dispersfarbstoffe geeignet, die eine polymerisierbare Gruppe besitzen und im strahlenpolymerisierbaren Binder löslich sind.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.
Als polymerisierbare Doppelbindungen kommen Vinyl-, Vinylchlorid, Vinylsulfon-, Allyl-, Allylsulfon, Acrylat-, Methacrylat-, Acrylamid-, Methacrylamid-, Halogenacrylamid-, Styryl-Gruppen und Derivate der Zimtsäure in Frage.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.
Als für dieses Fixierungsverfahren geeignete Farbstoffe kommen solche in Betracht, die eine aktivierte ungesättigte Gruppe, insbesondere eine ungesättigte aliphatische Gruppe aufweisen, wie z.B. die Vinyl-, Halogenvinyl-, Styryl-, Acryl- oder Methacryl-Gruppe.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.
Als solche Gruppen seien z.B. die Halogenatome enthaltenden ungesättigten Gruppen genannt, wie Halogenmaleinsäure- und Halogenpropiolsäurereste, die α- oder β-Brom- oder Chloracrylgruppen, halogenierte Vinylacetylgruppen, Halogencrotonyl- oder Halogenmethacrylgruppen. Weiterhin kommen auch solche Gruppen in Betracht, die leicht, z.B. durch Abspaltung von Halogenwasserstoff, in halogenhaltige ungesättigte Gruppen übergehen, z.B. die Dichlor- oder Dibrompropionylgruppe. Unter Halogenatomen sind hier Fluor-, Chlor-, Brom und Jodatome als auch Pseudohalogenatome, wie z.B. die Cyangruppe zu verstehen. Gute Resultate werden nach den erfindungsgemässen Verfahren mit Farbstoffen erzielt, welche eine α-Bromacrylgruppe enthalten. Als Farbstoffe, die eine polymerisierbare Doppelbindung enthalten, kommen vorzugsweise solche in Betracht, die mindestens einen Acryloyl-, α-Bromacryloyl-, α-Chloracryloyl-, Vinyl- oder Vinylsulfonyl-Rest enthalten; ganz besonders bevorzugt jene, die mindestens einen Acryloyl-, α-Bromacryloyl- oder Vinylsulfonyl-Rest enthalten. Als Farbstoffe, die ein polymerisierbares Ringsystem enthalten, kommen vorzugsweise solche in Betracht, die mindestens einen Epoxid-Rest enthalten.As such groups, e.g. the unsaturated groups containing halogen atoms, such as halomaleic acid and halogenpropiolic acid residues, the α- or β-bromo or chloroacrylic groups, halogenated vinyl acetyl groups, halogencrotonyl or halogenomethacrylic groups. Furthermore, 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. Good results are achieved by the processes according to the invention with dyes which contain an α-bromoacrylic group. Suitable dyes which contain a polymerizable double bond are preferably those which contain at least one acryloyl, α-bromoacryloyl, α-chloroacryloyl, vinyl or vinylsulfonyl radical; very particularly preferably those which contain at least one acryloyl, α-bromoacryloyl or vinylsulfonyl radical. Suitable dyes which contain a polymerizable ring system are preferably those which contain at least one epoxy radical.
Die verwendeten chromophoren Systeme können den verschiedensten Farbstoff-Klassen angehören.The chromophoric systems used can belong to a wide variety of dye classes.
Eine bevorzugte Ausführungsform des erfindungsgemässen Verfahrens ist dadurch gekennzeichnet, dass man als Farbstoffe solche der Formel
D-(X)m (1),
worin D der Rest eines organischen Farbstoffes der Monoazo- oder Polyazo-, Metallkomplexazo-, Anthrachinon-, Phthalocyanin-, Formazan-, Azomethin-, Nitroaryl-, Dioxazin-, Phenazin-, Stilben-, Triphenylmethan-, Xanthen-, Thioxanthon-, Naphthochinon-, Pyrenchinon- oder Perylentetracarbimid-Reihe, X eine polymerisierbare Doppelbindung oder ein polymerisierbares Ringsystem, und m die Zahl 1, 2, 3, 4, 5 oder 6 ist, verwendet.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.
Eine besonders bevorzugte Ausführungsform des erfindungsgemässen Verfahrens ist dadurch gekennzeichnet, dass man wasserlösliche Farbstoffe der Formel (1) verwendet, worin
- a) D der Rest eines Formazanfarbstoffes der Formel
- b) D der Rest eines Anthrachinonfarbstoffes der Formel
- c) D der Rest eines Phthalocyaninfarbstoffes der Formel
- d) D der Rest eines Dioxazinfarbstoffes der Formel
- a) D the rest of a formazan dye of the formula
- b) D the residue of an anthraquinone dye of the formula
- c) D the rest of a phthalocyanine dye of the formula
- d) D the rest of a dioxazine dye of the formula
Ebenfalls besonders bevorzugt werden Farbstoffe der Formel (1) verwendet, worin D der Rest eines Azofarbstoffes, insbesondere ein Rest der Formeln 6 bis 17 ist:
worin (R₇)₁₋₃ für 1 bis 3 Substituenten aus der Gruppe C₁₋₄-alkyl, C₁₋₄-Alkoxy, Halogen, Carboxy und Sulfo steht;
worin (R₉)₁₋₃ für 1 bis 3 Substituenten aus der Gruppe C₁₋₄-Alkyl, C₁₋₄-Alkoxy, Halogen, Carboxy und Sulfo steht;
worin (R₁₀)₁₋₃ für 1 bis 3 Substituenten aus der Gruppe C₁₋₄-Alkyl, C₁₋₄-Alkoxy, Halogen, Carboxy und Sulfo steht;
worin R₁₁ C₂₋₄-Alkanoyl oder Benzoyl ist;
worin R₁₂ C₂₋₄-Alkanoyl oder Benzoyl ist;
worin (R₁₃)₀₋₃ für 0 bis 3 Substituenten aus der Gruppe C₁₋₄-Alkyl, C₁₋₄-Alkoxy, Halogen, Carboxy und Sulfo steht;
worin R₁₄ und R₁₅ unabhängig voneinander Wasserstoff, C₁₋₄-Alkyl oder Phenyl, und R₁₆ Wasserstoff, Cyano, Carbamoyl oder Sulfomethyl ist;
worin (R₁₇)₁₋₄ für 1 bis 4 Substituenten aus der Gruppe Wasserstoff, Halogen, Nitro, Cyan, Trifluormethyl, Sulfamoyl, Carbamoyl, C₁₋₄-Alkyl, C₁₋₄-Alkoxy, Amino, Acetylamino, Ureido, Hydroxy, Carboxy, Sulfomethyl und Sulfo, unabhängig voneinander, steht;
worin (R₁₈)₀₋₃, (R₁₈′)₀₋₂ und (R₁₈˝)₀₋₂ unabhängig voneinander 0 bis 3 bzw. 0 bis 2 Substituenten aus der Gruppe C₁₋₄-Alkyl, C₁₋₄-Alkoxy und Sulfo stehen.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 alkoxy, halogen, carboxy and sulfo;
wherein R₁₄ and R₁₅ are independently hydrogen, C₁₋₄ alkyl or phenyl, and R₁₆ is hydrogen, cyano, carbamoyl or sulfomethyl;
wherein (R₁₇) ₁₋₄ for 1 to 4 substituents from the group hydrogen, halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁₋₄-alkyl, C₁₋₄-alkoxy, amino, acetylamino, ureido, hydroxy, carboxy , Sulfomethyl and sulfo, independently of one another, is;
wherein (R₁₈) ₀₋₃, (R₁₈ ′) ₀₋₂ and (R₁₈˝) ₀₋₂ independently of one another 0 to 3 or 0 to 2 substituents from the group C₁₋₄-alkyl, C₁₋₄-alkoxy and sulfo stand.
Eine weitere bevorzugte Ausführungsform des erfindungsgemässen Verfahrens ist dadurch gekennzeichnet, dass man als wasserunlösliche oder wenig wasserlösliche Farbstoffe Azofarbstoffe der Formel
worin D₁ den Rest einer von wasserlöslichmachenden Substituenten freien, carbocyclischen oder heterocyclischen Diazokomponente;
Y₁ Chlor, Methyl, Methoxy, Methoxyethyl, Methoxyethoxy oder Wasserstoff;
R₂₀ und R₂₁ unabhängig voneinander C₁-C₆-Alkyl, C₃-C₆-Alkenyl, Phenyl oder den Rest -B₁-X₁;
R₂₂ Wasserstoff, Methyl, Methoxy, Chlor, Brom oder den Rest X₁;
X₁ einen Rest mit einer polymerisierbaren Doppelbindung;
B₁ einen gegebenenfalls substituierten Rest der Formel -(CH₂)m-(C₆H₄)n-(CH₂)o-;
worin m eine ganze Zahl von 1 bis 6
n 0 oder 1 und
o eine ganze Zahl von 0 bis 6 bedeutet;
bedeuten und mindestens einer der Reste R₂₀, R₂₁ oder R₂₂ die Bedeutung X₁ hat bzw. durch einen Rest X₁ substituiert ist;
verwendet.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 at least one of the radicals R₂₀, R₂₁ or R₂₂ has the meaning X₁ or is substituted by a radical X₁;
used.
D₁ bedeutet vorzugsweise den Rest einer homo- oder heterocyclischen Diazokomponente, z.B. aus der Reihe Thienyl, Phenylazothienyl, Thiazolyl, Isothiazolyl, 1,2,4-Thiadiazolyl, 1,3,4-Thiadiazolyl, Benzthiazolyl, Benzisothiazolyl, Pyrazolyl, 1,2,3-Triazolyl, 1,2,4-Triazolyl, Imidazolyl, oder Phenyl. Jedes dieser Systeme kann weitere Substituenten tragen wie Alkyl, Alkoxy oder Alkylthio mit je 1 bis 4 Kohlenstoffatomen, Phenyl, elektronegative Gruppen wie Halogen, besonders Chlor oder Brom, Trifluormethyl, Cyano, Nitro, Acyl, wie z.B. Acetyl oder Benzoyl, Carboalkoxy, besonders Carbomethoxy oder Carboethoxy, Alkylsulfon mit 1 bis 4 Kohlenstoffatomen, Phenylsulfon, Phenoxysulfon, Sulfonamido oder Arylazo, insbesondere Phenylazo. Je 2 benachbarte Substituenten der genannten Ringsysteme können auch zusammen weitere ankondensierte Ringe bilden, z.B. Phenylringe oder cyclische Imide.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. 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.
Besonders bevorzugt bedeutet D₁ einen Benzthiazolyl-, Benzisothiazolyl- oder Phenylrest, welcher unsubstituiert oder ein- oder zweimal durch einen der obengenannten Reste substituiert ist.D₁ particularly preferably denotes a benzothiazolyl, benzisothiazolyl or phenyl radical which is unsubstituted or substituted once or twice by one of the abovementioned radicals.
Die Alkylreste können substituiert sein, z.B. durch Hydroxy, Alkoxy mit 1 bis 4 Kohlenstoffatomen, insbesondere Methoxy, Cyano oder Phenyl. Als weitere Substituenten sind geeignet Halogen, wie Fluor, Chlor oder Brom, oder -CO-U oder -O-CO-U, worin U Alkyl mit 1 bis 6 Kohlenstoffatomen oder Phenyl ist.The 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.
Als Alkenylreste kommen solche Reste in Betracht, welche sich von den oben aufgeführten Alkylresten durch Ersatz mindestens einer Einfachbindung durch eine Doppelbindung ableiten. Geeignete Reste sind z.B. Ethenyl oder Propenyl.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.
Unter Phenylresten sind unsubstituierte oder substituierte Phenylreste zu verstehen. Als Substituenten kommen z.B. C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Brom, Chlor, Nitro oder C₁-C₄-Alkylcarbonylamino in Betracht.Phenyl radicals are to be understood as meaning unsubstituted or substituted phenyl radicals. Examples of substituents are C₁-C₄-alkyl, C₁-C₄-alkoxy, bromine, chlorine, nitro or C₁-C₄-alkylcarbonylamino into consideration.
Für den Rest X₁ kommen beispielsweise von der Acryl-, Methacryl- oder Zimtsäure abgeleitete Reste in Frage. Besonders hervorzuheben sind die Reste der Formeln -NH-CO-CH=CH₂, -NH-CO-C(CH₃)=CH₂, -NH-CO-CBr=CH₂, -NH-CO-CH=CH-C₆H₅, -O-CO-CH=CH₂, -O-CO-C(CH₃)=CH₂, -O-CO-CBr=CH₂, -O-CO-CH=CH-C₆H₅, -CH=CH₂, -CH=CH-C₆H₅ oder -C(CH₃)=CH₂.For the rest X₁, for example, residues derived from acrylic, methacrylic or cinnamic acid are suitable. Of particular note are the residues of the formulas -NH-CO-CH = CH₂, -NH-CO-C (CH₃) = CH₂, -NH-CO-CBr = CH₂, -NH-CO-CH = CH-C₆H₅, -O -CO-CH = CH₂, -O-CO-C (CH₃) = CH₂, -O-CO-CBr = CH₂, -O-CO-CH = CH-C₆H₅, -CH = CH₂, -CH = CH-C₆H₅ or -C (CH₃) = CH₂.
Besonders bevorzugt sind Farbstoffe der Formeln:
worin R₂₃ C₁-C₆-Alkyl, C₃-C₆-Alkenyl oder Phenyl;
R₂₅ Wasserstoff, Methyl, Methoxy, Chlor, Brom, -NH-CO-CH=CH₂, -NH-CO-C(CH₃)=CH₂, -NH-CO-CBr=CH₂, -NH-CO-CH=CH-C₆H₅, -O-CO-CH=CH₂, -O-CO-C(CH₃)=CH₂, -O-CO-CBr=CH₂, oder -O-CO-CH=CH-C₆H₅;
R₂₆ -NH-CO-CH=CH₂, -NH-CO-C(CH₃)=CH₂, -NH-CO-CBr=CH₂, -NH-CO-CH=CH-C₆H₅, -O-CO-CH=CH₂, -O-CO-C(CH₃)=CH₂, -O-CO-CBr=CH₂ oder -O-CO-CH=CH-C₆H₅; und
R₂₇ -NH-CO-CH=CH₂, -NH-CO-C(CH₃)=CH₂, -NH-CO-CBr=CH₂ oder -NH-CO-CH=CH-C₆H₅ bedeuten und worin B₁, D₁ und Y₁ die Bedeutungen wie unter Formel (20) angegeben haben.Dyes of the formulas are particularly preferred:
wherein R₂₃ is C₁-C₆ alkyl, C₃-C₆ alkenyl or phenyl;
R₂₅ hydrogen, methyl, methoxy, chlorine, bromine, -NH-CO-CH = CH₂, -NH-CO-C (CH₃) = CH₂, -NH-CO-CBr = CH₂, -NH-CO-CH = CH- C₆H₅, -O-CO-CH = CH₂, -O-CO-C (CH₃) = CH₂, -O-CO-CBr = CH₂, or -O-CO-CH = CH-C₆H₅;
R₂₆ -NH-CO-CH = CH₂, -NH-CO-C (CH₃) = CH₂, -NH-CO-CBr = CH₂, -NH-CO-CH = CH-C₆H₅, -O-CO-CH = CH₂ , -O-CO-C (CH₃) = CH₂, -O-CO-CBr = CH₂ or -O-CO-CH = CH-C₆H₅; and
R₂₇ -NH-CO-CH = CH₂, -NH-CO-C (CH₃) = CH₂, -NH-CO-CBr = CH₂ or -NH-CO-CH = CH-C₆H₅ and wherein B₁, D₁ and Y₁ are the Meanings as given under formula (20).
Beispiele für obige Farbstoffe sind Farbstoffe der Formeln:
Weitere bevorzugte Farbstoffe sind wenig wasserlösliche oder wasserunlösliche Farbstoffe der Anthrachinonreihe, wie z.B.
Die genannten Farbstoffe sind bekannt oder können nach bekannten Methoden hergestellt werden. Beispielsweise wird eine Lösung der zu acylierenden Substanz in wasserfreiem Aceton mit etwa einem Molequivalent eines Acrylsäurechlorids versetzt. Bei Raumtemperatur wird dann etwa 1 Molequivalent Pyridin zugegeben und das Produkt durch Zugabe von Wasser abgeschieden.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.
Bei den zuzusetzenden Bindern handelt es sich um polymerisierbare farblose beziehungsweise nahezu farblose (d.h. evt. leicht gelbliche) monomere, oligomere oder polymere Verbindungen oder um Gemische derselben; z.B. N-C₁₋₄-Alkylolacrylamid, N-Butoxymethylacrylamid, N-Isobutoxymethylacrylamid, N-C₁₋₄-Alkylolmethacrylamid, N-Butoxymethylmetharylamid, N-Isobutoxymethylmethacrylamid, N,N,Di-(C₁₋₄-Alkolol)-acrylamid, N,N,-Di-(Butoxymethyl)-acrylamid, N,N,-Di-(Isobutoxymethyl)-acrylamid, N,N,-Di-(C₁₋₄-Methylol)-methacrylamid, N,N,-Di-(Butoxymethyl)-methacrylamid, N,N,-Di-(Isobutoxymethyl)-methacrylamid.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- (isobutoxymethyl) methacrylamide.
Vorzugsweise werden in dem erfindungsgemässen Verfahren als farblose Verbindungen monomere, oligomere oder polymere organische Verbindungen oder deren Mischungen verwendet.Monomeric, oligomeric or polymeric organic compounds or mixtures thereof are preferably used as colorless compounds in the process according to the invention.
Besonders bevorzugt werden in dem erfindungsgemässen Verfahren als farblose Verbindungen Acrylate, Diacrylate, Acrylsäure oder Acrylamide verwendet.Acrylates, diacrylates, acrylic acid or acrylamides are particularly preferably used as colorless compounds in the process according to the invention.
Ganz besonders bevorzugt werden in den erfindungsgemässen Verfahren Mischungen monomerer und oligomerer farbloser organischer Verbindungen verwendet.Mixtures of monomeric and oligomeric colorless organic compounds are very particularly preferably used in the processes according to the invention.
Die farblosen organischen Verbindungen, die mindestens eine polymerisierbare Doppelbindung enthalten, sind frei von farbgebenden Resten. Es handelt sich um monomere, oligomere oder polymere organische Verbindungen oder eine Mischung derselben, die polymerisiert bzw. vernetzt werden können.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.
Als monomere farblose Verbindung kommt eine solche mit einem Molekulargewicht bis ca. 1000 in Betracht, die mindestens eine polymerisierbare Gruppe enthält.Possible monomeric colorless compounds are those with a molecular weight of up to approximately 1000 and which contain at least one polymerizable group.
Bi-, tri- und polyfunktionelle Monomere sind ebenfalls geeignet.Bi-, tri- and polyfunctional monomers are also suitable.
Die monomere farblose Verbindung kann sowohl selbst direkt als auch als Mischung mit anderen Monomeren, Oligomeren und/oder Polymeren eingesetzt werden.The monomeric colorless compound can be used both directly and as a mixture with other monomers, oligomers and / or polymers.
Als oligomere farblose Verbindung kommt eine solche mit einem Molekulargewicht zwischen 1000 und 10000 in Betracht, die eine oder mehrere polymerisierbare Gruppen enthält. Die oligomere farblose Verbindung kann, sofern flüssig, selbst direkt oder als Lösung in Wasser oder organischen Lösungsmitteln oder als Gemisch mit anderen Monomeren, Oligomeren und/oder Polymeren eingesetzt werden.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.
Als polymere farblose Verbindung kommt eine solche mit einem Molekulargewicht >10000 in Betracht, die eine oder mehrere polymerisierbare Gruppen enthält.Suitable polymeric colorless compounds are those having a molecular weight> 10,000 which contain one or more polymerizable groups.
Die polymere farblose Verbindung kann, sofern flüssig, selbst direkt oder als Lösung in Wasser oder organischen Lösungsmitteln oder als Gemisch mit anderen Monomeren, Oligomeren und/oder Polymeren eingesetzt werden.If liquid, 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.
Als farblose Verbindungen kommen ethylenisch ungesättigte monomere, oligomere und polymere Verbindungen in Frage.Colorless compounds which can be used are ethylenically unsaturated monomeric, oligomeric and polymeric compounds.
Besonders geeignet sind z.B. Ester von ethylenisch ungesättigten Carbonsäuren und Polyolen oder Polyepoxiden, und Polymere mit ethylenisch ungesättigten Gruppen in der Kette oder in Seitengruppen, wie z.B. ungesättigte Polyester, Polyamide und Polyurethane und Copolymere hiervon, Polybutadien und Butadien-Copolymere, Polyisopren und Isopren-Copolymere, Polymere und Copolymere mit (Meth)-Acrylgruppen in Seitenketten, sowie Mischungen von einem oder mehreren solcher Polymerer.For example, 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.
Beispiele für ungesättigte Carbonsäuren sind Acrylsäure, Methacrylsäure, Crotonsäure, Itaconsäure, Zimtsäure und ungesättigte Fettsäuren wie Linolensäure oder Oelsäure. Bevorzugt sind Acryl- und Methacrylsäure.Examples of 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.
Als Polyole sind aliphatische und cycloaliphatische Polyole geeignet. Beispiele für Polyepoxide sind solche auf der Basis der Polyole und Epichlorhydrin. Ferner sind auch Polymere oder Copolymere, die Hydroxylgruppen in der Polymerkette oder in Seitengruppen enthalten, wie z.B. Polyvinylalkohol und Copolymere davon oder Polymethacrylsäurehydroxyalkylester oder Copolymere davon, als Polyole geeignet. Weitere geeignete Polyole sind Oligoester mit Hydroxylendgruppen.Aliphatic and cycloaliphatic polyols are suitable as polyols. Examples of polyepoxides are those based on the polyols and epichlorohydrin. Also included are 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.
Beispiele für aliphatische und cycloaliphatische Polyole sind Alkylendiole mit bevorzugt 2 bis 12 C-Atomen, wie Ethylenglykol, 1,2- oder 1,3-Propandiol, 1,2-, 1,3- oder 1,4-Butandiol, Pentandiol, Hexandiol, Octandiol, Dodecandiol, Diethylenglykol, Triethylenglykol, Polyethylenglykole mit Molekulargewichten von bevorzugt 200 bis 1500, 1,3-Cyclopentandiol, 1,2- 1,3- oder 1,4-Cyclohexandiol, 1,4-Dihydroxymethylcyclohexan, Glycerin, Tris-(β-hydroxyethyl)amin, Trimethylolethan, Trimethylolpropan, Pentaerythrit, Dipentaerythrit und Sorbit.Examples of 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 ( β-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol.
Die Polyole können teilweise oder vollständig mit einer oder verschiedenen ungesättigten Carbonsäuren verestert sein, wobei in Teilestern die freien Hydroxylgruppen modifiziert, z.B. verestert oder mit anderen Carbonsäuren verestert sein können.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.
Beispiele für Ester sind:
Trimethylolpropantriacrylat, Trimethylolethantriacrylat, Trimethylolpropantrimethacrylat, Trimethylolethantrimethacrylat, Tetramethylenglykoldimethacrylat, Triethylenglykoldimethacrylat, Tetraethylenglykoldiacrylat, Pentaerythritdiacrylat, Pentaerythrittriacrylat, Pentaerythrittetraacrylat, Dipentaerythritdiacrylat, Dipentaerythrittriacrylat, Dipentaerythrittetraacrylat, Dipentaerythritpentaacrylat, Dipentaerythrithexaacrylat, Tripentaerythritoctaacrylat, Pentaerythritdimethacrylat, Pentaerythrittrimethacrylat, Dipentaerythritdimethacrylat, Dipentaerythrittetramethacrylat, Tripentaerythritoctamethacrylat, Pentaerythritdiitaconat, Dipentaerythrittrisitaconat, Dipentaerythritpentaitaconat, Dipentaerythrithexaitaconat, Ethylenglykoldimethacrylat, 1,3-Butandioldiacrylat, 1,3-Butandioldimethacrylat, 1,4-Butandioldiitaconat, Sorbittriacrylat, Sorbittetraacrylat, Pentaerythritmodifiziert-triacrylat, Sorbittetramethacrylat, Sorbitpentaacrylat, Sorbithexaacrylat, Oligoesteracrylate und -methacrylate, Glyzerindi- und -triacrylat, 1,4-Cyclohexandiacrylat, Bisacrylate und Bismethacrylate von Polyethylenglykol mit Molekulargewicht von 200-1500, oder Gemische davon.Examples of 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 dimethacrylate, Dipentaerythrittetramethacrylat, Tripentaerythritoctamethacrylat, pentaerythritol, Dipentaerythrittrisitaconat, dipentaerythritol, dipentaerythritol hexaitaconate, Ethylene glycol dimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol modified triacrylate, sorbitol tetramethacrylate, sorbitol pentaacrylate, olorboxy methacrylate, sorbitol methacrylate ylates, glycerol diacrylate and triacrylate, 1,4-cyclohexane diacrylate, bisacrylates and bismethacrylates of polyethylene glycol with a molecular weight of 200-1500, or mixtures thereof.
Als farblose Verbindungen sind auch die Amide gleicher oder verschiedener ungesättigter Carbonsäuren von aromatischen, cycloaliphatischen und aliphatischen Polyaminen mit bevorzugt 2 bis 6, besonders 2 bis 4 Aminogruppen geeignet. Beispiele für solche Polyamine sind Ethylendiamin, 1,2- oder 1,3-Propylendiamin, 1,2-, 1,3- oder 1,4-Butylendiamin, 1,5-Pentylendiamin, 1,6-Hexylendiamin, Octylendiamin, Dodecylendiamin, 1,4-Diaminocyclohexan, Isophorondiamin, Phenylendiamin, Bisphenylendiamin, Di-β-aminoethylether, Diethylentriamin, Triethylentetramin, Di-(β-aminoethoxy)- oder Di-(β-aminopropoxy) ethan. Weitere geeignete Polyamine sind Polymere und Copolymere mit Aminogruppen in der Seitenkette und Oligoamide mit Aminoendgruppen.Also suitable as colorless compounds are the 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. Examples of such polyamines 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-β-aminoethyl ether, diethylenetriamine, triethylenetetramine, di- (β-aminoethoxy) - or di- (β-aminopropoxy) ethane. Other suitable polyamines are polymers and copolymers with amino groups in the side chain and oligoamides with amino end groups.
Beispiele für solche ungesättigten Amide sind: Methylen-bis-acrylamid, 1,6-Hexamethylen-bis-acrylamid, Diethylentriamin-tris-methacrylamid, Bis(methacrylamidopropoxy)-ethan, β-Methacrylamidoethylmethacrylat, N[(β-Hydroxyethoxy)ethyl-acrylamid.Examples of such unsaturated amides are: methylene-bis-acrylamide, 1,6-hexamethylene-bis-acrylamide, diethylenetriamine-tris-methacrylamide, bis (methacrylamidopropoxy) ethane, β-methacrylamidoethyl methacrylate, N [(β-hydroxyethoxy) ethyl acrylamide .
Geeignete ungesättigte Polyester und Polyamide leiten sich z.B. von Maleinsäure und Diolen oder Diaminen ab. Die Maleinsäure kann teilweise durch andere Dicarbonsäuren ersetzt sein. Sie können zusammen mit ethylenisch ungesättigten Comonomeren, z.B. Styrol, eingesetzt werden. Die Polyester und Polyamide können sich auch von Dicarbonsäuren und ethylenisch ungesättigten Diolen oder Diaminen ableiten, besonders von längerkettigen mit z.B. 6 bis 20 C-Atomen. Beispiele für Polyurethane sind solche, die aus gesättigten oder ungesättigten Diisocyanaten und ungesättigten bzw. gesättigten Diolen aufgebaut sind.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. Examples of polyurethanes are those which are composed of saturated or unsaturated diisocyanates and unsaturated or saturated diols.
Polybutadien und Polyisopren und Copolymere davon sind bekannt. Geeignete Comonomere sind z.B. Olefine wie Ethylen, Propen, Buten, Hexen, (Meth)Acrylate, Acrylnitril, Styrol oder Vinylchlorid. Polymere mit (Meth)Acrylatgruppen in der Seitenkette sind ebenfalls bekannt. Es kann sich z.B. um Umsetzungsprodukte von Epoxidharzen auf Novolakbasis mit (Meth)Acrylsäure handeln, um Homo- oder Copolymere des Polyvinylalkohols oder deren Hydroxyalkylderivaten, die mit (Meth)Acrylsäure verestert sind, oder um Homo- und Copolymere von (Meth)Acrylaten, die mit Hydroxyalkyl(meth)acrylaten verestert sind.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. For example, 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.
Die farblosen Verbindungen können allein oder in beliebigen Mischungen eingesetzt werden.The colorless compounds can be used alone or in any mixtures.
Als oligomere oder polymere farblose Verbindungen kommen bevorzugt z.B. verschiedene Polyesteracrylate, wie z.B. CH₂=CH-[CO-O(CH₂)n]-CO-O-CH=CH₂, Epoxyacrylate, wie z.B. (CH₂=CH-CO-O-CH₂-CHOH-CH₂-O-C₆H₄)₂C(CH₃)₂, Urethanacrylate, wie z.B.
Polyetheracrylate, wie z.B
und Silikonacrylate in Betracht, wie z.B. aus Textilpraxis lnternational (1987) Seiten 848-852 bekannt.Polyether acrylates, such as
and silicone acrylates into consideration, as is known, for example, from Textilpraxis lnternational (1987) pages 848-852.
Eine bevorzugte Ausführungsform des erfindungsgemässen Verfahrens ist dadurch gekennzeichnet, dass man als farblose Verbindungen solche mit dem Acrylrest als polymerisierbare Gruppe verwendet, wobei oligomere Polyether-, Polyurethan- und Polyesteracrylate besonders bevorzugt werden.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.
In dem erfindungsgemässen Verfahren werden als farblose Verbindung insbesondere N-Vinylpyrrolidin, Acrylsäure, Butylacrylat, 2-Ethylhexylacrylat, 2-Hydroxyethylacrylat, Hydroxypropylacrylat, Butandiolmonoacrylat, 2-Ethoxyethylacrylat, Ethylenglykolacrylat, Butandiolacrylat, 2-Ethoxyethylacrylat, Ethylenglykolacrylat, Bisacrylate von Polyethylenglykol mit einem Molekulargewicht von 200 bis 1500, Butandioldiacrylat, Tetraethylenglykoldiacrylat, 1,6-Hexandioldiacrylat, Diethylenglykoldiacrylat, Dipropylenglykoldiacrylat, Triethylenglykoldiacrylat, Tripropylenglykoldiacrylat, Trimethylolpropantriacrylat, Pentaerythritriacrylat, Bromacrylamid, Methylenbisdi(bromacrylamid), Methylen-bisdiacrylamid, N-Alkoxyacrylamid, Tetraethylenglykol-diacrylat, Sojabohnenöl-acrylat, Polybutadien-acrylat, Diethylenglykol-dimethacrylat, 1,6-Hexandiol-dimethacrylat, 2-(2-Ethoxyethoxy)-ethylacrylat, Stearylacrylat, Tetrahydrofurfurylacrylat, Pentaerythritol-tetraacrylat, Laurylacrylat, 2-Phenoxyethylacrylat, ethoxyliertes Bisphenol-diacrylat, Ditrimethylolpropan-tetraacrylat, Tris-(2-Hydroxyethyl)-isocyanurat-triacrylat, Isodecylacrylat, Dipentaerythriol-pentaacrylat, ethoxyliertes Trimethylolpropan-triacrylat, Isobornylacrylat, ethoxyliertes Tetrabromobisphenol-diacrylat, propoxyliertes Neopentylglykol-diacrylat, propoxyliertes Glyceryltriacrylat verwendet.In the process according to the invention, 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 diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, Pentaerythritriacrylat, bromoacrylamide, Methylenbisdi (bromoacrylamide), methylenebis bisdiacrylamid, N-alkoxyacrylamide, tetraethylene glycol diacrylate, soybean oil acrylate, polybutadiene -acrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, tetrahydrofurfury acrylate, pentaerythritol tetraacrylate, lauryl acrylate, 2-phenoxyethyl acrylate , ethoxylated bisphenol diacrylate, ditrimethylolpropane tetraacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, isodecylacrylate, dipentaerythriol pentaacrylate, ethoxylated trimethylolpropane triacrylate, isobornylacrylate, ethoxylated tetrabrylolylylylolylophenyl diacrylate, diacrylate diacrylate,
Bei Verwendung ultravioletter Strahlung ist das Vorliegen eines Photosensibilisators erforderlich. Der Photosensibilsator absorbiert die Strahlung, um freie Radikale, die die Polymerisation einleiten, zu erzeugen. Beispiele für erfindungsgemäss verwendete Photosensibilisatoren beziehungsweise Photoinitiatoren sind Carbonylverbindungen wie 2,3-Hexandion. Diacetylacetophenon, Benzoin und Benzoinether wie Dimethyl-, Ethyl- und Butylderivate, z.B. 2,2-Diethoxyacetophenon und 2,2-Dimethoxyacetophenon, Benzophenon bzw. ein Benzophenon-Salz und Phenyl-(1-hydroxycyclohexyl)-keton oder ein Keton der Formel
Benzophenon in Kombination mit einem Katalysator wie Triäthylamin, N,N′-Dibenzylamin und Dimethylaminoethanol und Benzophenon plus Michlers Keton; stickstoffhaltige Verbindungen wie Diazomethan, Azo-bis-isobutyronitril, Hydrazin, Phenylhydrazin sowie Trimethylbenzylammoniumchlorid; und schwefelhaltige Verbindungen wie Benzolsulfonat, Diphenyl-disulfid sowie Tetramethylthiuramdisulfid. Derartige Photosensibilisatoren werden für sich allein oder in Kombination miteinander verwendet.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. Such photosensitizers are used alone or in combination with one another.
Der Anteil an Photosensibilisatoren in den aufgetragenen Färbekomponenten direkt vor der Bestrahlung beträgt 0,01 - 20 %, vorzugsweise 0,1 - 5 %.The proportion of photosensitizers in the applied coloring components directly before the irradiation is 0.01-20%, preferably 0.1-5%.
Sowohl wasserlösliche wie auch wasserunlösliche Photosensibilisatoren sind geeignet. Ausserdem sind copolymerisierbare Photoinitiatoren wie sie z.B. in "Polymers Paint Colour Journal, 180, S 42f (1990)" erwähnt werden von besonderem Vorteil.Both water-soluble and water-insoluble photosensitizers are suitable. In addition, copolymerizable photoinitiators such as those mentioned, for example, in "Polymers Paint Color Journal, 180 , S 42f (1990)" are particularly advantageous.
Die Druckpasten beziehungsweise Färbeflotten können neben Farbstoff und strahlenpolymerisierbaren Binder noch die üblichen Zusätze wie Verdicker, Färbemittel, Füllstoffe, Dispergatoren, Gleitmittel, Antioxidationsmittel und Polymerisationsinhibitoren enthalten Letztere sind gewöhnlich auch den strahlenpolymerisierbaren Bindern als Stabilisatoren zugesetzt.In addition to dye and radiation-polymerizable binders, 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.
Ausserdem können neben dem Photosensibilisator noch Polymerisations-Coinitiatoren wie Peroxide oder aliphatische Azoverbindungen zugesetzt werden, welche durch die bei der Bestrahlung auftretende Wärme aktiviert werden und die Polymerisation starten.In addition to the photosensitizer, 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.
Für die Polymerisation beziehungsweise Copolymerisation können die gebräuchlichen Katalysatoren, welche freie Radikale bilden, verwendet werden. Genannt seien Hydrazinderivate, wie Hydrazinhydrochlorid, organometallische Verbindungen, wie Bleitetraethyl, und insbesondere aliphatische Azoverbindungen, wie α,α′-Azoisobutyrodinitril und organische Peroxide, Chloracetylperoxid, Trichloracetylperoxid, Benzoylperoxid, Chlorbenzoylperoxid, Benzoylacetylperoxid, Propionylperoxid, Fluorchlorpropionylperoxid, Laurylperoxid, Cumenhydroperoxid, Cyclohexanonhydroperoxid, tert.-Butylhydroperoxid, Di-tert.-butylperoxid, Di-tert.-amylperoxid und p-Methanhydroperoxid, und ebenfalls anorganische Peroxidverbindungen, wie Natriumperoxid, Alkalipercarbonate, Alkalipersulfate oder Alkaliperborate, und insbesondere Wasserstoffperoxid, welcher vorteilhaft das teure Benzoylperoxid ersetzen kann. Die zuzugebende Menge an Katalysatoren richtet sich in bekannter Weise nach dem gewünschten Verlauf der Reaktion oder nach den gewünschten Eigenschaften des Polymers. Vorteilhaft werden etwa 0,05 bis 10 Gewichtsprozent, bezogen auf die gesamte Menge an Binder beziehungsweise Binder-Mischung, zugegeben.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.
Zur Unterdrückung der Sauerstoffinhibierung kann auch der Zusatz von sogenannten "Anti Blocking Agents", das sind i.a. Amine insbesondere Acrylamine, von Vorteil sein.To suppress oxygen inhibition, the addition of so-called "anti-blocking agents" can also be used. Amines, especially acrylamines, may be beneficial.
Bei dem zu verwendenden UV-Licht handelt es sich um Strahlung, deren Emission zwischen 200 und 450 nm insbesondere zwischen 210 und 350 nm liegt. Die Strahlung wird vorzugsweise künstlich mit Quecksilber-Dampf-, Xenon- oder Wolfram-Lampen, Leuchtstoffröhren oder Kohlelichtbogenlampen erzeugt.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.
Von ganz besonderem Vorteil sind Quecksilber-Hochdrucklampen. Es sind aber auch Kapillar-Quecksilber-Hochdrucklampen, Quecksilber-Niederdrucklampen oder Quecksilber-Mitteldrucklampen geeignet. Letztere können auch gepulst betrieben werden, um die Strahlung in Peaks zu konzentrieren. Auch bei Xenonlampen ist gepulster Betrieb möglich, wenn man einen höheren Anteil an längerwelligem UV-Licht benötigt.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.
Die genaue Bestrahlungszeit der Färbungen beziehungsweise Drucke wird sich nach der Leuchtstärke der UV-Quelle, dem Abstand von der Lichtquelle, Art und Menge an Photosensibilisator sowie der Durchlässigkeit der Formulierung und des textilen Substrats für UV-Licht richten.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.
Übliche Bestrahlungszeiten betragen 2 Sekunden bis 20 Minuten, vorzugsweise 5 Sekunden bis 2 Minuten. Die Fixierung kann durch Unterbrechung der Lichteinstrahlung beendet werden, so dass sie auch diskontinuierlich durchgeführt werden kann.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.
Die Bestrahlung kann unter Schutzgas durchgeführt werden, um eine Inhibierung durch Sauerstoff zu verhindern, jedoch ist diese Vorsichtsmassnahme i.a. nicht notwendig. Die Sauerstoff-Inhibierung kann auch wirksam durch Zusatz von sogenannten "Anti Blocking Agents ", das sind Amine und speziell vor allem auch Aminoacrylate, unterdrückt werden.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.
Das erfindungsgemässe Verfahren ist auf die verschiedensten Fasern anwendbar, wie z.B. Fasern tierischer Herkunft wie Wollen, Seiden, Haare (z.B. als Filz) oder halbsynthetische Chemiefasern, wie Eiweisskunstfasern oder Alginatfasern, vollsynthetische Fasern, wie Polyvinyl-, Polyacrylnitril-, Polyester-, Polyamid-, Polypropylen- oder Polyurethanfasern und vor allem cellulosehaltige Materialien, wie Bastfasern, z.B. Leinen, Hanf, Jute, Ramie und insbesondere Baumwolle, sowie Cellulosekunstfasern, wie Viscose- oder Modalfasern, Kupfer-, Nitrat- oder verseifte Acetatfaser oder Fasern aus Celluloseacetat, wie Acetatfaser, oder Fasern aus Cellulosetriacetat, wie Arnel®, Trilan®, Courpleta® oder Tricel®.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®.
Die genannten Fasem können in Formen vorliegen, wie sie insbesondere in der Textilindustrie verwendet werden, z.B. als Fäden oder Garne, bzw. als Gewebe, Gewirke oder vliesartige Stoffe, wie Filze.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.
Als Fasermaterial werden in den erfindungsgemässen Verfahren bevorzugt Wolle, Seide, Haare, Alginatfasern, Polyvinyl-, Polyacrylnitril-, Polyester-, Polyamid-, Polypropylen- oder Polyurethanfasern oder cellulosehaltige Fasern verwendet.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.
Besonders bevorzugt werden Cellulosefasern sowie Polyester-Cellulose-Mischgewebe verwendet.Cellulose fibers and polyester-cellulose blended fabrics are particularly preferably used.
Die Behandlung des zu färbenden Materials mit einem definitionsgemässen Farbstoff kann auf die übliche Weise geschehen, z.B. wenn es sich um ein Textilgewebe handelt, durch Tränken mit einer Farbstofflösung in einem Ausziehbad beziehungsweise durch Aufsprühen oder durch Foulardieren einer Klotzlösung, oder durch Bedrucken z.B. auf einer Rakeldruckmaschine oder mittels der Ink-jet-Drucktechnik.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.
Im allgmeinen werden der farblose Binder, der Photosensibilisator und die übrigen Zusätze zusammen mit dem Farbstoff auf das zu färbende Material aufgebracht. Es ist jedoch auch möglich den farblosen Binder und/oder den Photosensibilisator sowie gegebenenfalls die Polymerisations-Coinitiatoren separat z.B. in Form einer Vor- beziehungsweise Nachbehandlung zu applizieren. So ist es vor allem bei Färbungen, die im Ausziehverfahren oder durch Foulardieren hergestellt werden, von besonderem Vorteil, wenn das Gewebe oder Gewirk zuerst mit dem Photosensibilisator imprägniert und anschliessend mit der Färbeflotte, die ebenfalls Photosensibilisator enthält, gefärbt wird.In general, the colorless binder, the photosensitizer and the other additives are applied together with the dye to the material to be colored. However, it is also possible to use 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.
Vorteilhaft sind auch Emulsionsdruckverfahren, bei welchen das Gemisch der strahlenpolymerisierbaren Binder die hydrophobe Komponente ersetzt, so dass weder Lackbenzin noch Verdicker benötigt werden.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.
Das Verfahren eignet sich besonders zur Durchführung kontinuierlicher Färbe- und Fixierprozesse, jedoch kann das Verfahren oder Teilschritte desselben auch diskontinuierlich durchgeführt werden.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.
Ein weiterer Gegenstand der Erfindung sind Mittel enthaltend einen Farbstoff, welcher mindestens eine polymerisierbare Doppelbindung oder mindestens ein polymerisierbares Ringsystem enthält, mindestens einen farblosen Binder, welcher mindestens eine polymerisierbare Doppelbindung enthält, und mindestens einen Photosensibilisator. Bevorzugte Mittel enthalten diejenigen bevorzugten Einzelkomponenten wie sie bei der Beschreibung der Farbstoffe, farblosen Binder und Photosensibilisatoren erläutert sind. Diese Mittel können weitere Zusätze wie sie zum Färben bzw. Drucken üblich sind enthalten. Insbesondere sind unter diesen Mitteln Druckpasten zu verstehen, bevorzugt solche, die sich für den Emulsionsdruck eignen.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.
In den Anwendungsbeispielen wird die Bestrahlung mit zwei 50 Watt Quecksilberhochdrucklampen bei Transportgeschwindigkeiten von 10 - 20 m/min. durchgeführt. Die Muster werden auf beiden Seiten und bei hohen Dosen in mehreren Durchläufen bestrahlt. Nach der Bestrahlung werden die Färbungen beziehungsweise Drucke wie für Reaktivfarbstoffe üblich ausgewaschen.In the application examples, 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. After the irradiation, the dyeings or prints are washed out as is customary for reactive dyes.
Die Fixiergrade werden farbmetrisch über die relative Farbstärke bestimmt. Zur Fixiergradbestimmung wird das gefärbte/ bedruckte, getrocknete aber nicht bestrahlte und nicht ausgewaschene Muster als Referenz mit der Farbstärke 100% eingesetzt. Dagegen wird dann die relative Farbstärke des zweiten Musters, das bestrahlt und anschliessend kalt und heiss ausgewaschen und wieder getrocknet wurde, bestimmt.The degrees of fixation are determined colorimetrically via the relative color strength. To determine the degree of fixation, the colored / printed, dried but not irradiated and not washed-out pattern is used as a reference with the color strength 100%. In contrast, 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.
Ein Baumwollsatin-Gewebe wird mit einer Druckpaste, die 30 g/kg des Farbstoffs der Formel
50 g/kg eines Oligoethylenglykoldiacrylats der Molmasse 508, 50 g/kg Trimethylolpropantriacrylat, 100 g/l Harnstoff, 30 g/kg Natriumalginat und als Photoinitiator eine Mischung von 2.5 g/kg Benzophenon und 2.5 g/kg Phenyl-(1-Hydroxycyclohexyl)-keton enthält, bedruckt. Der Druck wird getrocknet und dann unter einer Hg-Hochdrucklampe mit UV-Licht einer Energie von 436 J/cm² pro Gewebeseite bestrahlt. Der Fixiergrad beträgt 60%. Man erhält eine brilliante rote Färbung von hoher Echtheit.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.
Ein Baumwollsatin-Gewebe wird mit einer Druckpaste, die 30 g/kg des Farbstoffs der Formel
95 g/kg eines Oligoethylenglykoldiacrylats der Molmasse 508, 5 g/kg Trimethylolpropantriacrylat, 100 g/l Harnstoff, 30 g/kg Natriumalginat und als Photoinitiator eine Mischung von 2.5 g/kg Benzophenon und 2.5 g/kg Phenyl-(1-Hydroxycyclohexyl)-keton enthält, bedruckt. Der Druck wird getrocknet und dann unter einer Hg-Hochdrucklampe mit UV-Licht einer Energie von 436 J/cm² pro Gewebeseite bestrahlt. Der Fixiergrad beträgt 77%. Man erhält eine blaue Färbung von hoher Echtheit.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.
Ein Baumwollsatin-Gewebe wird mit einer Druckpaste, die 30 g/kg des in Beispiel 1 beschriebenen Farbstoffs, 100 g/kg eines Oligoethylenglykoldiacrylats der Molmasse 508, 100 g/l Harnstoff, 30 g/kg Natriumalginat und als Photoinitiator eine Mischung von 2.5 g/kg Benzophenon und 2.5 g/kg Phenyl-(1-Hydroxycyclohexyl)-keton enthält, bedruckt. Der Druck wird getrocknet und dann unter einer Hg-Hochdrucklampe mit UV-Licht einer Energie von 436 J/cm² pro Gewebeseite bestrahlt. Der Fixiergrad beträgt 50%. Man erhält eine rote Färbung von hoher Echtheit.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.
Ein Baumwollsatin-Gewebe wird mit einer Druckpaste, die 30 g/kg des in Beispiel 1 beschriebenen Farbstoffs, 200 g/kg einer 50%igen wässrigen N-Methylolacrylamidlösung, 100 g/l Harnstoff, 30 g/kg Natriumalginat und als Photoinitiator eine Mischung von 2.5 g/kg Benzophenon und 2.5 g/kg Phenyl-(1-Hydroxycyclohexyl)-keton enthält, bedruckt. Der Druck wird getrocknet und dann unter einer Hg-Hochdrucklampe mit UV-Licht einer Energie von 436 J/cm² pro Gewebeseite bestrahlt. Der Fixiergrad beträgt 64%. Man erhält eine rote Färbung von hoher Echtheit.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.
Ein Baumwollsatin-Gewebe wird mit einer Druckpaste, die 30 g/kg des in Beispiel 1 beschriebenen Farbstoffs, 50 g/kg eines Oligoethylenglykoldiacrylats der Molmasse 508, 50 g/kg eines Polyether-Triacrylats, 100 g/l Harnstoff, 30 g/kg Natriumalginat und als Photoinitiator eine Mischung von 2.5 g/kg Benzophenon und 2.5 g/kg Phenyl-(1-Hydroxycyclohexyl)-keton enthält, bedruckt. Der Druck wird getrocknet und dann unter einer Hg-Hochdrucklampe mit UV-Licht einer Energie von 436 J/cm² pro Gewebeseite bestrahlt. Der Fixiergrad beträgt 52%. Man erhält eine rote Färbung von hoher Echtheit.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.
Ein Baumwollsatin-Gewebe wird mit einer Druckpaste, die 30 g/kg des in Beispiel 1 beschriebenen Farbstoffs, 50 g/kg eines Oligoethylenglykoldiacrylats der Molmasse 508, 50 g/kg Methylenbisacrylamid, 100 g/l Harnstoff, 30 g/kg Natriumalginat und als Photoinitiator eine Mischung von 2.5 g/kg Benzophenon und 2.5 g/kg Phenyl-(1-Hydroxycyclohexyl)-keton enthält, bedruckt. Der Druck wird getrocknet und dann unter einer Hg-Hochdrucklampe mit UV-Licht einer Energie von 436 J/cm² pro Gewebeseite bestrahlt. Der Fixiergrad beträgt 67%. Man erhält eine rote Färbung von hoher Echtheit.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.
Ein Baumwollsatin-Gewebe wird mit einer Druckpaste, die 30 g/kg des Farbstoffs der Formel
95 g/kg eines Oligoethylenglykoldiacrylats der Molmasse 508, 5 g/kg Trimethylolpropantriacrylat, 100 g/l Harnstoff, 30 g/kg Natriumalginat und als Photoinitiator eine Mischung von 2.5 g/kg Benzophenon und 2.5 g/kg Phenyl-(1-Hydroxycyclohexyl)-keton enthält, bedruckt. Der Druck wird getrocknet und dann unter einer Hg-Hochdrucklampe mit UV-Licht einer Energie von 436 J/cm² pro Gewebeseite bestrahlt. Der Fixiergrad beträgt 59%. Man erhält eine gelbe Färbung von hoher Echtheit.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.
Ein Baumwollsatin-Gewebe wird mit einer Druckpaste, die 30 g/kg des Farbstoffs der Formel
95 g/kg eines Oligoethylenglykoldiacrylats der Molmasse 508, 5 g/kg Trimethylolpropantriacrylat, 100 g/l Harnstoff, 30 g/kg Natriumalginat und als Photoinitiator eine Mischung von 2.5 g/kg Benzophenon und 2.5 g/kg Phenyl-(1-hydroxycyclohexyl)-keton enthält, bedruckt. Der Druck wird getrocknet und dann unter einer Hg-Hochdrucklampe mit UV-Licht einer Energie von 436 J/cm² pro Gewebeseite bestrahlt. Der Fixiergrad beträgt 57%. Man erhält eine rote Färbung von hoher Echtheit.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.
Ein Baumwollsatin-Gewebe wird mit einer Druckpaste, die 30 g/kg des Farbstoffs der Formel
95 g/kg eines Oligoethylenglykoldiacrylats der Molmasse 508, 5 g/kg Trimethylolpropantriacrylat, 100 g/l Harnstoff, 30 g/kg Natriumalginat und als Photoinitiator eine Mischung von 2.5 g/l 4-(Trimethylammonium-methyl)-benzophenon Chlorid und 2.5 g/kg des Ketons der Formel
enthält, bedruckt. Der Druck wird getrocknet und dann unter einer Hg-Hochdrucklampe mit UV-Licht einer Energie von 436 J/cm² bestrahlt. Der Fixiergrad beträgt 74%. Man erhält eine rote Färbung von hoher Echtheit.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.
Ein Baumwollsatin-Gewebe wird mit einer Lösung, die 30 g/l des in Beispiel 9 beschriebenen Farbstoffs, 50 g/l eines Oligoethylenglykoldiacrylats der Molmasse 508, 100 g/l Harnstoff und als Photoinitiator 5.0 g/l der in Beispiel 9 beschriebenen Mischung enthält, foulardiert (Flottenaufnahme 67%). Die Färbung wird getrocknet und dann unter einer Hg-Hochdrucklampe mit UV-Licht einer Energie von 872 J/cm² bestrahlt. Man erhält eine rote Färbung von hoher Echtheit.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.
Ein Baumwollsatin-Gewebe wird mit einem 1:1 Gemisch von Benzophenon und Phenyl-(1-hydroxycyclohexyl)-keton imprägniert (Auftrag ca. 0.75%) und anschliessend mit einer Lösung, die 30 g/l des in Beispiel 9 beschriebenen Farbstoffs, 50 g/l eines Oligoethylenglykoldiacrylats der Molmasse 508, 100 g/l Harnstoff und als Photoinitiator 2.5 g/l Benzophenon und 2.5 g/l Phenyl-(1-hydroxycyclohexyl)-keton enthält, foulardiert (Flottenaufnahme 66%). Die Färbung wird getrocknet und dann unter einer Hg-Hochdrucklampe mit UV-Licht einer Energie von 109 J/cm² bestrahlt. Man erhält eine rote Färbung von hoher Echtheit.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.
Eine wässrige Lösung von 10 g/l des in Beispiel 1 beschriebenen Farbstoffs und 41 g/l eines Oligoethylenglykoldiacrylats der Molmasse 508, mit 1.8 g/l Benzophenon und 1.8 g/l Phenyl-(1-hydroxycyclohexyl)-keton als Photoinitiator wird auf ein Baumwollsatin-Gewebe gesprüht (Auftrag 33%). Das Gewebe wird getrocknet und dann unter einer Hg-Hochdrucklampe mit UV-Licht einer Energie von 218 J/cm² bestrahlt. Man erhält eine rote Färbung von hoher Echtheit.An aqueous solution of 10 g / l of the dye described in Example 1 and 41 g / l of an oligoethylene glycol diacrylate with a molecular weight of 508, with 1.8 g / l benzophenone and 1.8 g / l phenyl- (1-hydroxycyclohexyl) ketone as photoinitiator is added to a Cotton satin fabric sprayed (order 33%). The fabric is dried and then irradiated under a high pressure mercury lamp with UV light with an energy of 218 J / cm². A red dyeing of high fastness is obtained.
Aus einem Teil Wasser und 4 Teilen Lackbenzin wird unter Zusatz eines der im Emulsionsdruck üblichen Emulgatoren eine Emulsion hergestellt. In diese werden 3% des in Beispiel 1 beschriebenen Farbstoffs, 12 % eines Oligoethylenglykoldiacrylats der Molmasse 508, sowie als Photoinitiator 0.25% Benzophenon und 0.25% Phenyl-(1-hydroxycyclohexyl)-keton eingerührt. Ein Baumwollsatin-Gewebe wird mit dieser Emulsion bedruckt (Auftrag 66%), getrocknet und dann unter einer Hg-Hochdrucklampe mit UV-Licht einer Energie von 436 J/cm² bestrahlt. Man erhält eine rote Färbung von hoher Echtheit.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.
Aus einem Teil Wasser und 5 Teilen eines alkoxylierten Polyethertetraacrylats wird unter Zusatz eines der im Emulsionsdruck üblichen Emulgatoren eine Emulsion hergestellt. In diese werden 0.5% des Farbstoffs der Formel
sowie als Photoinitiator 0.25% Benzophenon und 0.25% Phenyl-(1-hydroxycyclohexyl)-keton eingerührt. Ein Baumwollsatin-Gewebe wird mit dieser Emulsion bedruckt (Auftrag 66%), getrocknet und dann unter einer Hg-Hochdrucklampe mit UV-Licht einer Energie von 436 J/cm² bestrahlt. Der Fixiergrad wird durch Ablösen des Farbstoffs mit Ethanol von einer bestrahlten nicht ausgewaschenen und einer unbestrahlten Probe bestimmt. Die Proben werden einmal bei 40°C und anschliessend 30 Minuten bei Siedetemperatur behandelt. Die beiden Extrakte werden vereinigt und die Fixiergrade über die Extinktion (bei λmax) ermittelt. Der Fixiergrad beträgt 83%. Man erhält eine rote Färbung von hoher Echtheit.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. In this 0.5% of the dye of the formula
as well as 0.25% benzophenone and 0.25% phenyl (1-hydroxycyclohexyl) ketone as photoinitiator. 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 λ max ). The degree of fixation is 83%. A red dyeing of high fastness is obtained.
Claims (16)
D-(X)m (1),
worin D der Rest eines organischen Farbstoffes der Monoazo- oder Polyazo-, Metallkomplexazo-, Anthrachinon-, Phthalocyanin-, Formazan-, Azomethin-, Nitroaryl-, Dioxazin-, Phenazin-, Stilben-, Triphenylmethan-, Xanthen-, Thioxanthon-, Naphthochinon-, Pyrenchinon- oder Perylentetracarbimid-Reihe, X eine polymerisierbare Doppelbindung oder ein polymerisierbares Ringsystem, und m die Zahl 1, 2, 3, 4, 5 oder 6 ist, verwendet.A method according to claim 1, 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.
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CH272491 | 1991-09-13 | ||
CH2724/91 | 1991-09-13 |
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EP0532467A1 true EP0532467A1 (en) | 1993-03-17 |
EP0532467B1 EP0532467B1 (en) | 1995-06-21 |
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US (1) | US5409504A (en) |
EP (1) | EP0532467B1 (en) |
JP (2) | JP3544547B2 (en) |
AT (1) | ATE124102T1 (en) |
DE (1) | DE59202603D1 (en) |
ES (1) | ES2074351T3 (en) |
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WO1994025665A1 (en) * | 1993-05-04 | 1994-11-10 | Ciba-Geigy Ag | Radiation-induced fixation of dyes |
US5474580A (en) * | 1992-11-27 | 1995-12-12 | Zeneca Limited | Chemical compounds |
WO2007048472A1 (en) * | 2005-10-28 | 2007-05-03 | Henkel Kommanditgesellschaft Auf Aktien | Hair treatment method that provides improved hair care and agent for carrying out said method |
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DE69403319T2 (en) * | 1993-02-01 | 1997-08-28 | Ciba Geigy Ag | RADIATION-DETECTED FIXING OF DYES |
EP0719357B1 (en) * | 1993-09-16 | 1998-01-14 | Ciba SC Holding AG | Thermofixing of dyes in presence of polymerizable compound and an initiator |
US5852126A (en) * | 1994-05-02 | 1998-12-22 | Novartis Ag | Polymerisable composition and the use thereof |
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- 1992-09-04 EP EP92810680A patent/EP0532467B1/en not_active Expired - Lifetime
- 1992-09-04 DE DE59202603T patent/DE59202603D1/en not_active Expired - Fee Related
- 1992-09-04 ES ES92810680T patent/ES2074351T3/en not_active Expired - Lifetime
- 1992-09-08 US US07/941,597 patent/US5409504A/en not_active Expired - Fee Related
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5474580A (en) * | 1992-11-27 | 1995-12-12 | Zeneca Limited | Chemical compounds |
WO1994025665A1 (en) * | 1993-05-04 | 1994-11-10 | Ciba-Geigy Ag | Radiation-induced fixation of dyes |
WO2007048472A1 (en) * | 2005-10-28 | 2007-05-03 | Henkel Kommanditgesellschaft Auf Aktien | Hair treatment method that provides improved hair care and agent for carrying out said method |
Also Published As
Publication number | Publication date |
---|---|
ATE124102T1 (en) | 1995-07-15 |
DE59202603D1 (en) | 1995-07-27 |
JP2004107872A (en) | 2004-04-08 |
US5409504A (en) | 1995-04-25 |
EP0532467B1 (en) | 1995-06-21 |
ES2074351T3 (en) | 1995-09-01 |
JP3544547B2 (en) | 2004-07-21 |
JPH05214682A (en) | 1993-08-24 |
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