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
  • 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
  • Y10S8/916—Natural fiber dyeing
  • Y10S8/917—Wool or silk
• • 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
  • Y10S8/92—Synthetic fiber dyeing
  • Y10S8/926—Polyurethane fiber
• • 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
  • Y10S8/92—Synthetic fiber dyeing
  • Y10S8/927—Polyacrylonitrile fiber
• • 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
  • Y10S8/92—Synthetic fiber dyeing
  • Y10S8/928—Polyolefin fiber

Definitions

• the invention relates to a method for fixing dyes on organic material, characterized in that dyes which contain at least one polymerizable double bond or at least one polymerizable ring system, with the exception of water-soluble dyes with acrylamide or methacrylamide groups, together with at least one practically colorless compound , which contains at least one polymerizable double bond, is fixed with ionizing radiation on the organic material, which has a residual moisture content of less than 20% based on the treated material.
• dyes which contain activated unsaturated groups can be fixed on organic material, in particular fiber material, by the action of ionizing radiation.
• radiation fixation is characterized by the fact that e.g. Fixing baths and fixatives can be completely avoided.
• Another advantage was the simultaneous application and fixing of dye and textile finishing agents, e.g. viewed to improve antistatic properties, crease resistance and reduce dirt retention.
• the object of the present invention is to find an improved method for fixing, which also has the advantages of a fixing carried out by radiation.
• the present invention relates to a method for fixing dyes on organic material, in particular fiber material, which is characterized in that dyes which contain at least one polymerizable double bond or at least one polymerizable ring system, with the exception of water-soluble dyes with acrylamide or methacrylamide groups, together with at least one practically colorless compound which has at least one contains polymerizable double bond, fixed with ionizing radiation on the organic material, which is dried before irradiation to a residual moisture content of less than 20%, based on the treated material.
• the process according to the invention is distinguished by the fact that dye and colorless compound can be applied together, so that only a single dye bath or only a single dye liquor is necessary, a significantly higher degree of fixation being achieved than in the known processes without colorless polymerisable Connection. It is also advantageous that, in contrast to radiation in the wet state, less dye is destroyed, which leads to a high brilliance of the coloring. Another advantage of dry radiation is the possibility of fixing water-insoluble or very sparingly water-soluble dyes with the process according to the invention.
• the dry organic material is to be understood in particular as fiber material which has a residual moisture content of less than 20%, preferably 5-10%, based on the treated fiber material before the irradiation.
• the method according to the invention largely avoids a high outlay on auxiliaries and apparatus, since after the fixing process according to the invention fixing alkali need not be washed out, but only rinsing and drying of the dyed or printed fiber material is required.
• fixing alkali need not be washed out, but only rinsing and drying of the dyed or printed fiber material is required.
• the method of fixing consists in that an organic material to be colored, for example textile fiber material, after treatment with a dye which contains at least one polymerizable double bond or at least one polymerizable ring system, and in the presence of at least one colorless compound which has at least one polymerizable double bond contains, is irradiated with ionizing radiation in the dry state for a short time.
• the treatment of the fiber material to be dyed with a dye according to the definition can be done in one of the usual ways, e.g. if it is a textile fabric, by soaking in a dye solution in a pull-out bath or by spraying or by padding a block solution, or by printing e.g. on a rouleaux printing machine.
• the dye can be used in a e.g. Apply vinyl or acrylate binder dissolved by padding, spraying etc.
• There is also the possibility of such dyes in e.g. Apply vinyl or acrylate emulsion with water to the organic material by padding, spraying or printing. After application, the organic material is dried to a residual moisture of less than 20%.
• Ionizing radiation is to be understood as meaning radiation that can be detected with an ionization chamber. It consists either of electrically charged, directly ionizing particles, which generate ions in gases along their path through impact, or of uncharged, indirectly ionizing particles or photons, which generate charged secondary particles in matter, such as the secondary electrons of X-rays or ⁇ -rays, in matter or the recoil nuclei (especially protons) of fast neutrons; Indirectly ionizing particles are also slow neutrons, which can generate charged particles with high energy through nuclear reactions, partly directly, partly via photons from ( ⁇ , ⁇ ) processes. Protons, atomic nuclei or ionized atoms can be considered as heavily charged particles. Of particular importance for the process according to the invention are lightly charged particles, e.g. Electrons. Both brake radiation and characteristic radiation come into consideration as X-ray radiation. The ⁇ radiation is an important particle radiation of heavily charged particles.
• the ionizing radiation can be generated by one of the customary methods. For example, spontaneous nuclear transformations as well as nuclear reactions (forced nuclear transformations) are used for generation.
• spontaneous nuclear transformations as well as nuclear reactions (forced nuclear transformations) are used for generation.
• natural or artificial radioactive substances and especially nuclear reactors come into consideration as radiation sources.
• the radioactive fission products produced by nuclear fission in such reactors represent another important source of radiation.
• Another possible method of generating radiation is by means of an X-ray tube.
• Vacuum UV light with a wavelength of less than 200 nm and vacuum UV laser light are also to be mentioned under ionizing radiation.
• Rays consisting of particles accelerated in electrical fields are of particular importance.
• Thermal, electron impact, low-voltage arc, cold cathode and high-frequency ion sources come into consideration here as radiation sources.
• Electron beams are of particular importance for the method of the present invention. These are generated by the acceleration and bundling of electrons, which are triggered by glow, field or photoemission and by electron or ion bombardment from a cathode.
• Radiation sources are conventional electron guns and accelerators. Examples of radiation sources are known from the literature, for example the International Journal of Electron Beam & Gamma Radiation Processing, in particular 1/89 pages 11-15; Optik, 77 (1987), pages 99-104.
• ⁇ -emitters e.g. the strontium-90 into consideration.
• the ⁇ -rays which can be easily produced, in particular with cesium-137 or cobalt-60 isotope sources, may also be mentioned as technically advantageous ionizing rays.
• 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.
• unsaturated groups such as the vinyl, halovinyl, styryl, acrylic or methacrylic group.
• unsaturated groups containing halogen atoms such as halomaleic acid and halogenpropiolic acid residues, the ⁇ - or ⁇ -bromine or chloroacrylic groups, halogenated vinyl acetyl groups, halogen crotonyl or halogen methacrylic groups.
• halogen atoms such as halomaleic acid and halogenpropiolic acid residues
• chloroacrylic groups such as halomaleic acid and halogenpropiolic acid residues
• halogenated vinyl acetyl groups such as halogen crotonyl or halogen methacryl
• Halogen atoms here are understood to mean fluorine, chlorine, bromine and iodine atoms as well as pseudohalogen atoms, such as, for example, the cyano group. Good results are achieved by the processes according to the invention with dyes which contain an ⁇ -bromoacrylic group.
• Suitable dyes which contain a polymerizable double bond are preferably those which contain at least one acryloyl, ⁇ -bromoacryloyl, ⁇ -chloroacryloyl or vinylsulfonyl radical; very particularly preferably those which contain at least one acryloyl, ⁇ -bromoacryloyl or vinylsulfonyl radical.
• Suitable dyes which contain a polymerizable ring system are preferably those which contain at least one epoxy radical.
• the chromophoric systems used can belong to a wide variety of dye classes.
• a preferred embodiment of the process according to the invention is characterized in that the dyes are those of the formula D- (X) m (1), wherein D is the residue of an organic dye of monoazo or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, nitroaryl, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, Naphthoquinone, pyrenequinone or perylene tetracarbimide series, X is a polymerizable double bond or a polymerizable ring system, and m is the number 1, 2, 3, 4, 5 or 6.
• Dyes of the formula (1) are likewise particularly preferably used, in which D is the residue of an azo dye, in particular a residue of the formulas 6 to 17: wherein (R7) 1 ⁇ 3 represents 1 to 3 substituents from the group C1 ⁇ 4 alkyl, C1 ⁇ 4 alkoxy, halogen, carboxy and sulfo; wherein (R9) 1 ⁇ 3 represents 1 to 3 substituents from the group C1 ⁇ 4 alkyl, C1 ⁇ 4 alkoxy, halogen, carboxy and sulfo; wherein (R10) 1 ⁇ 3 represents 1 to 3 substituents from the group C1 ⁇ 4 alkyl, C1 ⁇ 4 alkoxy, halogen, carboxy and sulfo; wherein R11 is C2 ⁇ 4 alkanoyl or benzoyl; wherein R12 is C2 ⁇ 4 alkanoyl or benzoyl; wherein (R13) 0 ⁇ 3 represents 0 to 3 substituents from the group C1 ⁇ 4 alkyl, C1 ⁇ 4 al
• a further preferred embodiment of the process according to the invention is characterized in that the dyes are those of the formula wherein D1 is the balance of a carbocyclic or heterocyclic diazo component free from water-solubilizing substituents; Y1 chlorine, methyl, methoxy, methoxyethyl, methoxyethoxy or hydrogen; R20 and R21 independently of one another are C1-C6-alkyl, C3-C Al-alkenyl, phenyl or the rest -B1-X1; R22 is hydrogen, methyl, methoxy, chlorine, bromine or the radical X1; X1 is a residue with a polymerizable double bond; B1 is an optionally substituted radical of the formula - (CH2) m - (C6H4) n - (CH2) o -; where m is an integer from 1 to 6 n 0 or 1 and o represents an integer from 0 to 6; mean and at least one of the radicals R20, R21 or R
• D1 is preferably the residue of a homo- or heterocyclic diazo component, for example from the series thienyl, phenylazothienyl, thiazolyl, isothiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, benzothiazolyl, benzisothiazolyl, pyrazolyl, 1,2, 3-triazolyl, 1,2,4-triazolyl, imidazolyl, or phenyl.
• a homo- or heterocyclic diazo component for example from the series thienyl, phenylazothienyl, thiazolyl, isothiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, benzothiazolyl, 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 acetyl or benzoyl, carboalkoxy, especially carbomethoxy or carboethoxy, alkyl sulfone having 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, for example phenyl rings or cyclic imides.
• D 1 particularly preferably denotes a benzothiazolyl, benzisothiazolyl or phenyl radical which is unsubstituted or substituted once or twice by one of the abovementioned radicals.
• alkyl radicals can be substituted, e.g. by hydroxy, alkoxy with 1 to 4 carbon atoms, especially methoxy, cyano or phenyl.
• Halogen such as fluorine, chlorine or bromine, or -CO-U or -O-CO-U, where U is alkyl having 1 to 6 carbon atoms or phenyl, are suitable as further substituents.
• Suitable alkenyl radicals are those radicals which are derived from the alkyl radicals listed above by replacing at least one single bond with a double bond.
• Suitable residues are e.g. Ethenyl or propenyl.
• Phenyl radicals are to be understood as meaning unsubstituted or substituted phenyl radicals.
• substituents are C1-C4-alkyl, C1-C4-alkoxy, bromine, chlorine, nitro or C1-C4-alkylcarbonylamino into consideration.
• residues derived from acrylic, methacrylic or cinnamic acid are suitable.
• dyes of the formulas are dyes of the formulas:
• 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.
• colorless organic compounds which contain at least one polymerizable double bond are those which are free from coloring residues. They are monomeric, oligomeric or polymeric organic compounds or a mixture thereof, which can be polymerized or crosslinked when exposed to ionizing radiation.
• Acrylates, diacrylates, acrylic acid or acrylamides are preferably used as colorless compounds in the process according to the invention.
• Mixtures of monomeric and oligomeric colorless organic compounds are particularly preferably used in the processes according to the invention.
• 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, if liquid, itself directly or as a solution in water or organic solvents or as a mixture with other monomers. Oligomers and / or polymers are used.
• Colorless compounds which can be used are ethylenically unsaturated monomeric, oligomeric and polymeric compounds.
• Esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers with ethylenically unsaturated groups in the chain or in side groups e.g. unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers with (meth) acrylic groups in side chains, and also mixtures of one or more such polymers.
• unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid and unsaturated fatty acids such as linolenic acid or oleic acid.
• Acrylic and methacrylic acid are preferred.
• Aliphatic and cycloaliphatic polyols are suitable as polyols.
• polyepoxides are those based on the polyols and epichlorohydrin.
• polymers or copolymers containing hydroxyl groups in the polymer chain or in side groups e.g. Polyvinyl alcohol and copolymers thereof or polymethacrylic acid hydroxyalkyl esters or copolymers thereof, are suitable as polyols.
• Other suitable polyols are oligoesters with hydroxyl end groups.
• Examples of aliphatic and cycloaliphatic polyols are alkylene diols preferred 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, e.g. can be 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 e.g. on 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, e.g. Styrene.
• the polyesters and polyamides can also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially from long-chain ones with e.g. 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.
• 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 being particularly preferred.
• the colorless monomeric compound used is, in particular, N-vinylpyrrolidine, acrylic acid, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, butanediol monoacrylate, 2-ethoxyethylacrylate, ethylene glycol acrylate, butanediol acrylate, tetraethylene glycol, methylene glycol diacrylate diacrylate acrylate, , 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-hexanedi
• Oligoethylene glycol diacrylates (MW ⁇ 500) are particularly preferred for the preparation of dye solutions of sparingly or not water-soluble dyes N-vinylpyrrolidone, 2-ethyl- (2-hydroxymethyl) -1,3-propanediol triacrylate, alkoxylated oligoether polyol tetraacrylate, oligoether triacrylate, N-butoxyacrylamide, N-iso-butoxyacrylamide, their mixtures with one another, and their mixtures with methylenebisacrylamide, oligo - / polyurethane acrylate, oligo / polyester acrylate or oligo / polyether acrylate.
• Alkoxylated oligoether polyol tetraacrylate, 2-ethyl- (2-hydroxymethyl) -1,3-propanediol triacrylate, oligo- / polyurethane-acrylate, oligo are particularly preferred for the production of emulsions with water, into which sparingly or not water-soluble dyes can be introduced - / polyester acrylate, oligo- / polyether acrylate, their mixtures with one another, and their mixtures with methylene bisacrylamide, oligoethylene glycol diacrylates (MW ⁇ 500), N-vinylpyrrolidone, oligoether triacrylate, N-butoxyacrylamide or N-iso-butoxyacrylamide
• the method according to the invention is applicable to a wide variety of organic materials, such as textile material, paper, wood, leather and plastics.
• fiber materials such as fibers of animal origin such as wool, silk, hair (e.g. as felt) or semisynthetic synthetic fibers such as protein synthetic fibers or alginate fibers, fully synthetic fibers such as polyvinyl, polyacrylonitrile, polyester, polyamide or polyurethane fibers, polypropylene and above all cellulose-containing materials, such as bast fibers, for example linen, hemp, jute, ramie and in particular cotton, and 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®.
• the method can also be used for mixtures of the fibers mentioned.
• the method is very particularly preferably used for cellulosic fibers, such as cotton or rayon wool, and their mixtures with polyester, polyacrylonit
• the fibers mentioned can be in a wide variety of processing states, as are used in particular in the textile industry, e.g. as threads, yarns, fabrics, knitted fabrics or nonwovens, e.g. Felts.
• the dye and colorless compound can be applied together as a homogeneous solution, suspension, emulsion or foam by the customary processes.
• dye and colorless compound or parts of the colorless compound can also be applied separately.
• an aqueous solution of the dye can first be padded and - after the dye has dried - the colorless compound can be sprayed on, for example.
• the method according to the invention is carried out in such a way that e.g. the dyed textile fabric treated with a solution of a colorless compound is passed through the fanned beam of an electron accelerator at room temperature in the dry state. This happens at such a speed that a certain radiation dose is reached.
• the radiation doses normally to be used are between 0.1 and 15 Mrad, the radiation dose advantageously being between 0.1 and 4 Mrad. With a dose of less than 0.1 Mrad, the degree of fixation is generally too low; with a dose of more than 15 Mrad, damage to the fiber material and the dye often occurs.
• the dye concentrations of the dye solutions or printing pastes used can be selected as in conventional dyeing or printing processes, e.g.
• the special embodiment depends primarily on the type of ionizing radiation to be used and its mode of production. If, for example, a spool of yarn soaked with dye solution and the solution of the colorless compound is to be irradiated with ⁇ -rays, then this is enclosed in a cell and exposed to the radiation. If higher radiation doses are desired with low radiation intensity, the material to be irradiated can be exposed to the radiation in several passes.
• an inert protective gas e.g. under nitrogen.
• a preferred embodiment of the method according to the invention is characterized in that both the fixing of the fiber material with appropriate Dyes and dyeing or printing are carried out continuously.
• the radiation doses are usually expressed in Mrad (megarad), where 1 rad corresponds to an absorption of 10 ⁇ 2 J / kg (Joule / kg).
• the fabric specified in the examples below is printed on one side or dyed in a pad-batch process and irradiated with accelerated electrons (acceleration voltage ⁇ 165 kV) in a protective gas atmosphere. Prints are irradiated on one side, dyeings are irradiated on both sides in two runs. After the irradiation, the dyeings or prints are washed out as usual for reactive dyes.
• accelerated electrons acceleration voltage ⁇ 165 kV
• the degrees of fixation are determined by detaching the dye from an irradiated, unwashed and an unirradiated sample.
• the samples are treated once with 50 ml of a solution of 600 ml / l phosphate buffer (pH 7) and 40 ml / l tetramethyl urea in deionized water at 40 ° C and then with 50 ml of this solution for 30 minutes at 100 ° C.
• the two extracts are combined and the degrees of fixation are determined via the extinction (at ⁇ max ). In Examples 6 and 7, the extraction is carried out in the same way with dimethylformamide.
• Example A The isomer mixture of 5,6- and 6,7-dichloro-2-aminobenzothiazole is diazotized in the usual way and coupled to N-ethyl-N-hydroxyethylaniline.
• the dye of the formula is obtained 4 g of this dye are dissolved in 50 ml of anhydrous acetone. After adding 1 g of acrylic chloride, 0.8 g of anhydrous pyridine is added dropwise at room temperature. The mixture is stirred for one hour and then 500 ml of water are added to the solution. After filtering off, a black, slightly sticky product of the formula is obtained
• Example 1 A cotton satin fabric is washed with an aqueous solution containing 30 g / l of the dye of the formula Contains 100 g / l of an oligoethylene glycol diacrylate and 100 g / l urea, padded (liquor absorption approx. 70%). The tissue is dried at approx. 60-80 ° C and then irradiated on both sides with accelerated electrons at a dose of 4 Mrad per side. A yellow color of high fastness is obtained with a degree of fixation of 71%.
• Example 2 A cotton satin fabric is washed with an aqueous solution containing 30 g / l of the dye of the formula dyed, dried and irradiated as described in Example 1. A red dyeing of high fastness is obtained with a degree of fixation of 75%.
• Example 3 A cotton satin fabric is washed with an aqueous solution containing 30 g / l of the dye described in Example 2, 50 g / l of an oligoethylene glycol diacrylate, 50 g / l of 2-ethyl- (2-hydroxymethyl) - 1,3- propanediol triacrylate and 100 g / l urea contains, as described in Example 1, colored, dried and irradiated. A red dyeing of high fastness is obtained with a degree of fixation of 64%.
• Example 4 A cotton satin fabric is washed with an aqueous solution containing 30 g / l of the dye described in Example 2, 50 g / l of an oligoethylene glycol diacrylate, 50 g / l methylene bisacrylamide and 100 g / l urea, as described in Example 1 dyed, dried and irradiated. A red dyeing of high fastness is obtained with a degree of fixation of 67%.
• Example 5 A cotton satin fabric is washed with an aqueous solution containing 30 g / l of the dye described in Example 2, 50 g / l of an oligoethylene glycol diacrylate, 50 g / l of an oligoether triacrylate and 100 g / l of urea, as in Example 1 described colored, dried and irradiated. A red dyeing of high fastness is obtained with a degree of fixation of 63%.
• Example 6 A cotton satin fabric is padded with a mixture containing 30 g / l of the dye described in Example 2, 75 g / l of an oligourethane diacrylate, 50 g / l of methylene bisacrylamide and 100 g / l of urea (liquor absorption approx. 70 %). The tissue is dried and then irradiated on both sides with accelerated electrons at a dose of 4 Mrad / side. A red color is obtained with a degree of fixation of 73%.
• Example 7 A cotton satin fabric is padded with a mixture which contains 30 g / l of the dye described in Example 2, 75 g / l of an oligourethane diacrylate, 100 g / l of an oligoethylene glycol diacrylate and 100 g / l of urea (liquor absorption approx. 70%). The tissue is dried and then irradiated on both sides with accelerated electrons at a dose of 4 Mrad / side each. A red color is obtained with a degree of fixation of 77%.
• Example 8 A cotton satin fabric is padded with an aqueous solution which contains 30 g / l of the dye described in Example 2 and 100 g / l of urea (liquor absorption approx. 70%) and dried. Then padding with a solution in ethanol of 10 g / kg of 1,6-hexanediol diacrylate, 90 g / kg of an oligomeric aliphatic urethane diacrylate and 100 g / kg of an oligoethylene glycol diacrylate (liquor absorption approx. 40%). The tissue is dried and then irradiated on both sides with accelerated electrons at a dose of 4 Mrad / side each. A red color is obtained with a degree of fixation of 72%.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Coloring (AREA)
• Dental Preparations (AREA)
• Polymerisation Methods In General (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

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• 1992
  • 1992-07-08 AT AT92810523T patent/ATE130642T1/de not_active IP Right Cessation
  • 1992-07-08 EP EP92810523A patent/EP0524144B1/de not_active Expired - Lifetime
  • 1992-07-08 ES ES92810523T patent/ES2081082T3/es not_active Expired - Lifetime
  • 1992-07-08 DE DE59204404T patent/DE59204404D1/de not_active Expired - Fee Related
  • 1992-07-14 US US07/914,157 patent/US5389108A/en not_active Expired - Fee Related
  • 1992-07-17 JP JP4212383A patent/JPH05209382A/ja active Pending

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