EP0466648B1 - Procédé pour la fixation de colorants - Google Patents

Procédé pour la fixation de colorants Download PDF

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Publication number
EP0466648B1
EP0466648B1 EP91810520A EP91810520A EP0466648B1 EP 0466648 B1 EP0466648 B1 EP 0466648B1 EP 91810520 A EP91810520 A EP 91810520A EP 91810520 A EP91810520 A EP 91810520A EP 0466648 B1 EP0466648 B1 EP 0466648B1
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EP
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Prior art keywords
process according
acrylate
diacrylate
dyes
polymerisable
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EP91810520A
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German (de)
English (en)
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EP0466648A1 (fr
Inventor
Katharina Dr. Fritzsche
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BASF Schweiz AG
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Ciba Geigy AG
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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 fiber materials by fixing the goods printed or dyed with dyes which contain polymerizable double bonds or polymerizable ring systems together with at least one colorless compound which contains at least one polymerizable double bond with ionizing radiation.
  • dyes which contain activated unsaturated groups can be fixed on the 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.
  • polymerizable compounds were added to the dye liquor and the dry goods were irradiated for fixation. An increase in the fixation yield could not be determined.
  • the object of the present invention is to find an improved method for fixing, which also has the advantages of fixing by radiation.
  • the present invention relates to a method for fixing dyes on fiber materials, which is characterized in that dyes which contain at least one polymerizable double bond and / or at least one polymerizable ring system, together with at least one colorless compound which contains at least one polymerizable double bond, with the exception of N-C1-C4-alkylolacrylamide and N, N-di- (C1-C4-alkylol) - acrylamide, fixed to moist fiber material with ionizing radiation.
  • the process according to the invention is characterized in that dye and colorless compound can be applied together, so that only a single dyebath or only a single dyebath is necessary, and that the moist goods are fixed with ionizing radiation without intermediate drying, a significantly higher degree of fixation is achieved than in the known processes without a colorless polymerizable compound.
  • moist fiber material is to be understood in particular as fiber material which has a residual moisture greater than 30%, preferably 40-60%, 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 does not need to be washed out, but only rinsing and drying of the dyed or printed fiber material is required.
  • the method of fixation is that a fiber material to be dyed, e.g. textile fiber material, after treatment with a dye which contains at least one polymerizable double bond and / or a polymerizable ring system, and in the presence of at least one colorless compound which contains at least one polymerizable double bond is irradiated with ionizing radiation in the moist 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.
  • 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 by impact, or of uncharged, indirectly ionizing particles or photons, which are in matter generate directly ionizing charged secondary particles, such as the secondary electrons of X-rays or ⁇ -rays 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. Lightly charged particles, for example electrons, are of particular importance for the process according to the invention. 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. Corresponding 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 ( ⁇ 200 nm) should also 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 such as that also come as radiation sources for electron beams 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 e.g. the vinyl, halovinyl, styryl, acrylic or methacrylic group.
  • an activated unsaturated group in particular an unsaturated aliphatic group, such as e.g. the vinyl, halovinyl, styryl, acrylic or methacrylic group.
  • unsaturated groups containing halogen atoms such as halogen maleic acid and halogen propiolic acid residues, the ⁇ - or ⁇ -bromo or chloroacrylic groups, halogenated vinyl acetyl groups, halogen crotonyl or halogen methacrylic groups.
  • groups are also suitable that easily, e.g. by splitting off hydrogen halide into halogen-containing unsaturated groups, e.g.
  • 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, Pyrenchinone 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 ⁇ 4alkanoyl or benzoyl; wherein (R13) 0 ⁇ 3 represents 0 to 3 substituents from the group C1 ⁇ 4 alkyl, C1 ⁇ 4 al
  • 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. They are monomeric, oligomeric or polymeric organic compounds or a mixture thereof, which can be polymerized or crosslinked when exposed to ionizing radiation.
  • Possible monomeric colorless compounds are those with a molecular weight of up to approximately 1000 and which contain at least one polymerizable group.
  • the monomeric colorless compound can be used both directly and as a mixture with other monomers, oligomers and / or polymers.
  • Suitable oligomeric colorless compounds are those having a molecular weight between 1000 and 10000 and containing one or more polymerizable groups. If liquid, the oligomeric colorless compound can itself be used directly or as a solution in water or organic solvents or as a mixture with other monomers, oligomers and / or polymers.
  • Suitable polymeric colorless compounds are those having a molecular weight> 10,000 which contain one or more polymerizable groups.
  • the polymeric colorless compound if liquid, can itself be used directly or as a solution in water or organic solvents or as a mixture with other monomers, oligomers and / or polymers.
  • Colorless compounds which can be used are ethylenically unsaturated monomeric, oligomeric and polymeric compounds.
  • Esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers with ethylenically unsaturated groups in the chain or in side groups e.g. unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers with (meth) acrylic groups in side chains, and also mixtures of one or more such polymers.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid and unsaturated fatty acids such as linolenic acid or oleic acid.
  • Acrylic and methacrylic acid are preferred.
  • Aliphatic and cycloaliphatic polyols are suitable as polyols.
  • polyepoxides are those based on the polyols and epichlorohydrin.
  • polymers or copolymers which contain hydroxyl groups in the polymer chain or in side groups contain, such as polyvinyl alcohol and copolymers thereof or polymethacrylic acid hydroxyalkyl esters or copolymers thereof, 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, 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, Dipentaerytlrrittriacrylat, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Tripentaerythritoctacrylat, pentaerythritol dimethacrylate, pentaerythritol dipentaerythritol dimethacrylate, Dip
  • 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-pentylene diamine, 1,6-hexylene diamine, octylene diamine, dodecylene diamine, 1,4-diaminocyclohexane, isophorone diamine, phenylene diamine, bisphenylene diamine, di- ⁇ -aminoethyl ether, diethylene triamine, triethylene tetramine, di- ( ⁇ -aminoethoxy) - or di- ( ⁇ -aminopropoxy) ethane.
  • Other suitable polyamines are polymers and copolymers with amino groups in the side chain and oligoamides with amino end
  • 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-ethoxyethyl acrylate, ethylene glycol acrylate, butanediol acrylate, tetraethylene glycol glycolate Triethylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol diacrylate, bromoacrylamide, methylene bisdi (bromoacrylamide), methylene bisdiacrylamide, N-alkoxyacrylamide, tetraethylene glycol diacrylate, soybean oil ethacrylate, methacrylate acrylate, methacrylate methacrylate, 2-ethoxyethoxy) ethyl acrylate, ste
  • the method according to the invention can be applied to a wide variety of fibers, such as fibers of animal origin such as wool, silk, hair (for example as felt) or semi-synthetic Chemical 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, such as linen, hemp, jute, ramie and in particular cotton, as well as 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® or also inorganic fibers such as glass fibers.
  • fibers of animal origin such as wool, silk, hair (for example as felt) or semi-
  • 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.
  • the method according to the invention is carried out in such a way that e.g. textile goods treated with a dye solution and a solution of a colorless compound are passed through the fanned-out beam of an electron accelerator at room temperature in a moist 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 25 Mrad, the radiation dose advantageously being between 1 and 10 Mrad. With a dose of less than 1 Mrad, the degree of fixation is generally too low; with a dose of more than 25 Mrad, damage to the fiber material and the dye often occurs.
  • the specific embodiment depends primarily on the type of ionizing to be used Rays and their 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, 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. In general, however, such a measure is not necessary.
  • 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 the dyeing or printing take place continuously.
  • the fiber material used in the processes according to the invention is preferably wool, silk, hair, alginate fibers, polyvinyl, polyacrylonitrile, polyester, polyamide, polypropylene or polyurethane fibers, cellulose-containing fibers or glass fibers.
  • Dyed or printed cellulose fibers and polyester / cellulose blended fabrics are particularly preferably used.
  • 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) under a protective gas atmosphere. Prints are irradiated on one side, dyeings in two passes on both sides. After the irradiation, the dyeings or prints are washed out as is customary 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 mixed 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 100 ° C treated.
  • the two extracts are combined and the degrees of fixation are determined via the absorbance (at ⁇ max ).
  • Example 1 A cotton satin fabric is washed with an aqueous solution containing 30 g / kg of the dye of the formula Contains 50 g / kg of an oligoethylene glycol diacrylate of molecular weight 508 and 100 g / kg urea, padded (liquor absorption 67%). The wet tissue is 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 83%.
  • Example 2 A woolen garbadine fabric is washed with an aqueous solution containing 30 g / kg of the dye of the formula Contains 50 g / kg of an oligoethylene glycol diacrylate of molecular weight 508 and 100 g / kg urea, padded (liquor pickup 76%). The tissue is then irradiated as indicated in Example 1. A red dyeing of high fastness is obtained with a degree of fixation of 77%.
  • Example 3 A silk crepe fabric is made with an aqueous solution as in Example 2 indicated, padded (liquor absorption 110%) and irradiated with accelerated electrons, as indicated in Example 1. A red dyeing of high fastness is obtained with a degree of fixation of 78%.
  • Example 4 A gas fiber fabric is padded as described in Example 2 (liquor pick-up 21%) and irradiated with accelerated electrons as indicated in Example 1. A dyeing of high fastness is obtained with a degree of fixation of 86%.
  • Example 5 A cell wool fabric is padded as described in Example 2 (liquor absorption 86%) and irradiated with accelerated electrons, as indicated in Example 1. A red dyeing of high fastness is obtained with a degree of fixation of 88%.
  • Example 6 A cotton-satin fabric is made with a printing paste containing 30 g / kg of the dye of the formula (102), 100 g / kg of urea, 50 g / kg of an oligoethylene glycol diacrylate with a molecular weight of 508 and 30 g / kg Contains sodium alginate, printed and irradiated on the top with accelerated electrons at a dose of 4 Mrad. A red-colored print of high fastness and a degree of fixation of 65% is obtained.
  • Example 7 A cotton satin fabric is made with 30 g / kg of the dye of the formula 50 g / kg of the oligoethylene glycol diacrylate given in Example 1 and 100 g / kg urea padded (liquor pickup 70%) and irradiated with accelerated electrons, as given in Example 1. A blue dyeing of high fastness is obtained with a degree of fixation of 54%.
  • Example 8 A cotton-satin fabric is padded with 30 g / kg of the dye given in Example 2, 50 g / kg N-vinylpyrrolidone and 100 g / kg urea as given in Example 1 (liquor absorption 71%) and such indicated in Example 1 irradiated with accelerated electrons. A red color of high fastness is obtained a degree of fixation of 69%.
  • Example 9 A cotton satin fabric is padded with an aqueous solution which contains 30 g / kg of the dye specified in Example 2 and 50 g / kg methylene bisacrylamide (liquor absorption 68%) and with accelerated electrons, as indicated in Example 1 , irradiated. A red dyeing of high fastness is obtained with a degree of fixation of 83%.
  • Example 10 A cotton wool fabric is washed with an aqueous solution containing 30 g / kg of the dye of the formula Contains 50 g / kg of an oligoethylene glycol diacrylate with a molecular weight of 508 and 100 g / kg of urea, padded (liquor absorption 88%) and irradiated with accelerated electrons, as indicated in Example 1. A blue dyeing of high fastness is obtained with a degree of fixation of 76%.
  • Example 11 A cotton satin fabric is washed with an aqueous solution containing 30 g / kg of the dye of the formula Contains 50 g / kg of an oligoethylene glycol diacrylate, 50 g / kg of a polyester acrylate and 100 g / kg of urea, padded (liquor absorption approx. 70%). The wet tissue is irradiated on both sides with accelerated electrons at a dose of 4 Mrad per side. A dyeing of high fastness is obtained with a degree of fixation of 90%.
  • Example 12 A cotton satin fabric is washed with an aqueous solution containing 30 g / kg of the dye described in Example 11, 50 g / kg of an oligoethylene glycol diacrylate, 50 g / kg of methylene bisacrylamide and 100 g / kg of urea, as in Example 11 described fouled and irradiated. A dyeing of high fastness is obtained with a degree of fixation of 95%.
  • Example 13 A cotton satin fabric is made with an aqueous solution which contains 30 g / kg of the dyestuff described in Example 11, 50 g / kg of an oligoethylene glycol diacrylate, 50 g / kg of an oligoether triacrylate and 100 g / kg of urea fouled and irradiated as described in Example 11. A dyeing of high fastness is obtained with a degree of fixation of 90%.
  • Example 14 A cotton satin fabric is washed with an aqueous solution containing 30 g / kg of the dye described in Example 11, 50 g / kg of an oligoethylene glycol diacrylate, 50 g / kg of 2-ethyl- (2-hydroxymethyl) -1 3-propanediol triacrylate and 100 g / kg of urea contains, as described in Example 11, fouled and irradiated. A deep red dyeing of high fastness is obtained with a degree of fixation of 85%.

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Claims (23)

  1. Procédé de fixage de colorants sur des matières fibreuses, caractérisé par le fait qu'on fixe, par rayonnement ionisant, des colorants renfermant au moins une double liaison polymérisable et/ou au moins un système de noyau polymérisable, avec au moins un composé incolore renfermant au moins une double liaison polymérisable, à l'exception du N-(alkyl en C₁-C₄)-acrylamide et du N,N-di-(alkylol en C₁-C₄)-acrylamide, les matières fibreuses soumises au rayonnement ionisant contenant une humidité résiduelle supérieure à 30 %, calculée sur la matière fibreuse avant l'action du rayonnement.
  2. Procédé selon la revendication 1, caractérisé par le fait qu'on utilise comme composé incolore des composés organiques monomères, oligomères ou polymères, renfermant au moins une double liaison polymérisable, ou bien leurs mélanges.
  3. Procédé selon la revendication 1 ou 2, caractérisé par le fait qu'on utilise comme composés incolores des acrylates, diacrylates ou l'acide acrylique.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé par le fait qu'on utilise des mélanges de composés organiques incolores, monomères et oligomères.
  5. Procédé selon l'une des revendications 2 à 4, caractérisé par le fait qu'on utilise comme composés incolores monomères ceux ayant une masse moléculaire inférieure à 1000.
  6. Procédé selon l'une des revendications 2 à 4, caractérisé par le fait qu'on utilise comme composés incolores oligomères ceux ayant une masse moléculaire comprise entre 1000 et 10000.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé par le fait qu'on utilise comme composés incolores des composés renfermant comme groupe polymérisable un reste acrylique.
  8. Procédé selon la revendication 7, caractérisé par le fait qu'on utilise des oligomères d'acrylate de polyéther, d'acrylate de polyuréthanne ou d'acrylate de polyester.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé par le fait qu'on utilise comme composés incolores les suivants : la N-vinylpyrrolidone, l'acide acrylique, l'acrylate de butyle, l'acrylate de 2-éthylhexyle, l'acrylate de 2-hydroxyéthyle, l'acrylate d'hydroxypropyle, le monoacrylate de butanediol, l'acrylate de 2-éthoxyéthyle, l'acrylate d'éthylèneglycol, le bisacrylate de polyéthylèneglycol ayant une masse moléculaire comprise entre 200 et 1500, le diacrylate de butanediol, le diacrylate de tétraéthylèneglycol, le diacrylate de 1,6-hexanediol, le diacrylate de diéthylèneglycol, le diacrylate de dipropylèneglycol, le diacrylate de triéthylèneglycol, le diacrylate de tripropylèneglycol, le triacrylate de triméthylolpropane, le triacrylate de pentaérythritol, le bromoacrylamide, le mèthylènebisdi(bromoacrylamide), le méthylène-bisdiacrylamide, le N-alcoxyacrylamide, le diacrylate de tétraéthylèneglycol, l'acrylate d'huile de soja, l'acrylate de polybutadiène, le diméthacrylate de diéthylèneglycol, le diméthacrylate de 1,6-hexanediol, l'acrylate de 2-(2-éthoxyethoxy)-éthyle, l'acrylate de stéaryle, l'acrylate de tétrahydrofurfuryle, le tétraacrylate de pentaérythritol, l'acrylate de lauryle, l'acrylate de 2-phénoxyéthyle, le diacrylate de bisphénol éthoxylé, le tétraacrylate de ditriméthylolpropane, le triacrylate de tris(2-hydroxyéthyl)-iso-cyanurate, l'acrylate d'isodécyle, le pentaacrylate de dipentaérythritol, le triacrylate de triméthylolpropane éthoxylé, l'acrylate d'isobornyle, le diacrylate de tétrabromobisphénol éthoxylé, le diacrylate de néopentylglycol propoxylé, le triacrylate de glycéryle propoxylé.
  10. Procédé selon la revendication 9, caractérisé par le fait qu'on utilise comme composés incolores la N-vinylpyrrolidone, le méthylènebisacrylamide ou le bisacrylate de polyéthylèneglycol d'une masse moléculaire de 200 à 1500.
  11. Procédé selon l'une des revendications 1 à 10, caractérisé par le fait qu'on utilise comme colorant un colorant de formule



            D-(X)m   (1),



    dans laquelle D représente le reste d'un colorant organique monoazoïque ou polyazoïque, d'un colorant azoïque à complexe métallique, d'un colorant anthraquinonique, d'un colorant de phtalocyanine, d'un colorant formazanique, d'un colorant azométhinique, d'un colorant nitroarylique, d'un colorant dioxazinique, d'un colorant phénazinique, d'un colorant stilbénique, d'un colorant de triphénylméthane, d'un colorant xanthénique, d'un colorant thioxanthonique, d'un colorant naphtoquinonique, d'un colorant pyrènequinonique ou d'un colorant de la série pérylènetétracarbimide ; X représente une double liaison polymérisable ou un système de noyau polymérisable ; et m représente le nombre 1, 2, 3, 4, 5 ou 6.
  12. Procédé selon l'une des revendications 1 à 11, caractérisé par le fait qu'on utilise des colorants qui renferment en tant que double liaison polymérisable ou en tant que système de noyau polymérisable un reste acryloyle, α-bromoacryloyle, α-chloroacryloyle, vinylsulfonyle ou un reste époxydyle.
  13. Procédé selon la revendication 12, caractérisé par le fait qu'on utilise des colorants renfermant comme double liaison polymérisable ou comme système de noyau polymérisable un reste acryloyle, un reste α-bromoacryloyle ou un reste vinylsulfonyle.
  14. Procédé selon l'une des revendications 1 à 13, caractérisé par le fait qu'on utilise comme rayonnement ionisant un rayonnement d'électrons produit par un rayonnement corpusculaire et en particulier des rayons β ou des rayons γ.
  15. Procédé selon l'une des revendications 1 à 14, caractérisé par le fait que le traitement des matières fibreuses avec les colorants s'effectue par teinture ou par impression.
  16. Procédé selon l'une des revendications 1 à 15, caractérisé par le fait qu'on choisit une dose de rayonnement comprise entre 0,1 et 25 Mrad.
  17. Procédé selon l'une des revendications 1 à 16, caractérisé par le fait qu'on réalise le rayonnement sous une atmosphère protectrice et en particulier sous atmosphère d'azote.
  18. Procédé selon l'une des revendications 1 à 17, caractérisé par le fait qu'on réalise le fixage en continu.
  19. Procédé selon l'une des revendications 1 à 18, caractérisé par le fait qu'aussi bien le fixage de la matière fibreuse avec des colorants correspondants que la teinture et l'impression s'effectuent en continu.
  20. Procédé selon l'une des revendications 1 à 19, caractérisé par le fait qu'on utilise comme matière fibreuse la laine, la soie, les cheveux, des fibres d'alginate, des fibres de polyvinyle, des fibres de polyacrylonitrile, des fibres de polyester, des fibres de polyamide, des fibres de polypropylène, des fibres de polyuréthanne, des fibres cellulosiques ou des fibres de verre.
  21. Procédé selon la revendication 20, caractérisé par le fait qu'on utilise des fibres cellulosiques ou des fibres renfermant de la cellulose, teintes ou imprimées.
  22. Procédé selon la revendication 20, caractérisé par le fait qu'on utilise des fibres mixtes de polyester et de cellulose.
  23. Matière fibreuse teinte ou imprimée, fixée par le procédé selon la revendication 1.
EP91810520A 1990-07-12 1991-07-03 Procédé pour la fixation de colorants Expired - Lifetime EP0466648B1 (fr)

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CH2325/90 1990-07-12
CH232590 1990-07-12

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EP0466648B1 true EP0466648B1 (fr) 1995-09-13

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EP (1) EP0466648B1 (fr)
JP (1) JPH04241179A (fr)
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ES (1) ES2077209T3 (fr)

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US5416440A (en) * 1990-08-17 1995-05-16 Raychem Corporation Transmission window for particle accelerator
US5410016A (en) * 1990-10-15 1995-04-25 Board Of Regents, The University Of Texas System Photopolymerizable biodegradable hydrogels as tissue contacting materials and controlled-release carriers
US5626863A (en) * 1992-02-28 1997-05-06 Board Of Regents, The University Of Texas System Photopolymerizable biodegradable hydrogels as tissue contacting materials and controlled-release carriers
ES2081082T3 (es) * 1991-07-17 1996-02-16 Ciba Geigy Ag Procedimiento para la fijacion de colorantes.
DE59202603D1 (de) * 1991-09-13 1995-07-27 Ciba Geigy Ag Verfahren zum Fixieren von Farbstoffen mit UV-Licht.
KR100266912B1 (ko) 1992-02-28 2000-12-01 파라비 레이 조직접촉물질이며 방출조절운반체인 광중합성 생분해성 하이드로겔
EP0643784A1 (fr) * 1992-06-04 1995-03-22 Ciba-Geigy Ag Procede de fixation de colorants ayant au moins une double liaison polymerisable, au moyen de lumiere uv
CZ286487B6 (en) * 1992-06-04 2000-04-12 Ciba Sc Holding Ag Dyeing and printing process of organic material
US5882356A (en) * 1992-10-21 1999-03-16 Courtaulds Fibres (Holdings) Limited Fibre treatment
BR9405819A (pt) * 1993-02-01 1995-12-26 Ciba Geigy Ag Fixação de corantes induzidas por radiação
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US5725604A (en) * 1993-09-16 1998-03-10 Ciba Specialty Chemicals Corporation Thermofixing of dyes in presence of polymerizable compound and an initiator
GB9407496D0 (en) * 1994-04-15 1994-06-08 Courtaulds Fibres Holdings Ltd Fibre treatment
GB9408742D0 (en) * 1994-05-03 1994-06-22 Courtaulds Fibres Holdings Ltd Fabric treatment
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EP0144093B1 (fr) * 1983-12-08 1989-04-19 Ciba-Geigy Ag Pâtes d'impression, stables au stockage, et leur utilisation

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DE59106464D1 (de) 1995-10-19
ES2077209T3 (es) 1995-11-16
JPH04241179A (ja) 1992-08-28
US5238465A (en) 1993-08-24

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