EP0466648A1 - Process for the fixation of dyes - Google Patents

Abstract

The 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 are excluded together with at least one colorless compound which contains at least one polymerizable double bond N-C1-C4-alkylolacrylamide and N, N-di- (C1-C4-alkylol) -acrylamide, fixed with ionizing radiation on moist fiber material.

Description

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.

It is known that dyes which contain activated unsaturated groups can be fixed on the fiber material by the action of ionizing radiation. Compared to the conventional methods for fixing dyes, in particular reactive dyes, radiation fixation is characterized by the fact that e.g. Fixing baths and fixatives can be completely avoided. Another advantage has been the simultaneous application and fixing of dye and textile finishing agents, e.g. viewed to improve antistatic properties, crease resistance and reduce dirt retention. Furthermore, to improve the crosslinking of the dye and the fiber, 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 practice of dyeing, especially with reactive dyes, has recently led to increased demands on the quality of the dyeing and the economy of the dyeing process. The fixing of reactive dyes with ionizing radiation no longer meets today's requirements with regard to the degree of fixation to be achieved. As a result, the object of the present invention is to find an improved method for fixing, which also has the advantages of fixing by radiation.

It has been shown that the new process fulfills the task.

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 on damp 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 in 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.

In the context of this invention, 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 γ-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 (β, γ) 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 α 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. Correspondingly, natural or artificial radioactive substances and especially nuclear reactors come into consideration as radiation sources. The radioactive fission products resulting from 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 as well as 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.

Β-emitters such as that also come as radiation sources for electron beams Strontium-90 into consideration.

The γ-rays, which are easy to produce, in particular with cesium-137 or cobalt-60 isotope sources, may also be mentioned as technically advantageously applicable 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. 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 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.

The chromophoric systems used can belong to a wide variety of dye classes.

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 $${\text{D- (X)}}_{\text{m}}$$

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.

• a) D der Rest eines Formazanfarbstoffes der Formel
  
  ist, worin die Benzolkerne weiterhin durch Alkyl mit 1 bis 4 C-Atomen, Alkoxy mit 1 bis 4 C-Atomen, Alkylsulfonyl mit 1 bis 4 C-Atomen, Halogen oder Carboxy substituiert sein können,
• b) D der Rest eines Anthrachinonfarbstoffes der Formel
  
  ist, worin G ein Phenylen-, Cyclohexylen- oder C₂-C₆-Alkylenrest ist; wobei der Anthrachinonkern durch eine weitere Sulfogruppe, und G als Phenylrest durch Alkyl mit 1 bis 4 C-Atomen, Alkoxy mit 1 bis 4 C-Atomen, Halogen, Carboxy oder Sulfo substituiert sein kann, und der Farbstoff vorzugsweise mindestens 2 stark wasserlöslichmachende Gruppen enthält.
• c) D der Rest eines Phthalocyaninfarbstoffes der Formel
  
  worin Pc der Rest eines Kupfer- oder Nickelphthalocyanins; W -OH und/oder -NR₅R₆; R₅ und R₆ unabhängig voneinander Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen, das durch Hydroxy oder Sulfo substituiert sein kann; R₄ Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen; E ein Phenylenrest, der durch Alkyl mit 1 bis 4 C-Atomen, Halogen, Carboxy oder Sulfo substituiert sein kann; oder ein Alkylenrest mit 2 bis 6 C-Atomen, vorzugsweise ein Sulfophenylen- oder Aethylenrest; und k = 1, 2 oder 3 ist.
• d) D der Rest eines Dioxazinfarbstoffes der Formel

ist, worin E ein Phenylenrest, der durch Alkyl mit 1 bis 4 C-Atomen, Halogen, Carboxy oder Sulfo substituiert sein kann; oder ein Alkylenrest mit 2 bis 6 C-Atomen ist; und die äusseren Benzolringe in den Formeln (5a) und (5b) durch Alkyl mit 1 bis 4 C-Atomen, Alkoxy mit 1 bis 4 C-Atomen, Acetylamino, Nitro, Halogen, Carboxy oder Sulfo weitersubstituiert sein können.A particularly preferred embodiment of the process according to the invention is characterized in that dyes of the formula (1) are used in which

• a) D the rest of a formazan dye of the formula
  
  is in which the benzene nuclei can further be substituted by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylsulfonyl having 1 to 4 carbon atoms, halogen or carboxy,
• b) D the residue of an anthraquinone dye of the formula
  
  is where G is a phenylene, cyclohexylene or C₂-C₆ alkylene radical; where the anthraquinone nucleus can be substituted by a further sulfo group, and G as a phenyl radical by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogen, carboxy or sulfo, and the dye preferably contains at least 2 highly water-solubilizing groups .
• c) D the rest of a phthalocyanine dye of the formula
  
  wherein Pc is the balance of a copper or nickel phthalocyanine; W -OH and / or -NR₅R₆; R₅ and R₆ independently of one another are hydrogen or alkyl having 1 to 4 carbon atoms, which may be substituted by hydroxy or sulfo; R₄ is hydrogen or alkyl of 1 to 4 carbon atoms; E is a phenylene radical which can be substituted by alkyl having 1 to 4 carbon atoms, halogen, carboxy or sulfo; or an alkylene radical having 2 to 6 carbon atoms, preferably a sulfophenylene or ethylene radical; and k = 1, 2 or 3.
• d) D the rest of a dioxazine dye of the formula

E is a phenylene radical which can be substituted by alkyl having 1 to 4 carbon atoms, halogen, carboxy or sulfo; or is an alkylene radical having 2 to 6 carbon atoms; and the outer benzene rings in the formulas (5a) and (5b) can be further substituted by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, acetylamino, nitro, halogen, carboxy or sulfo.

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, C₁₄-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')₀₋₂und (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, C₁₄ 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 ') ₀₋₂und (R₁₈ ") ₀₋₂ independently of one another have 0 to 3 or 0 to 2 substituents from the group C₁₋₄-alkyl, C₁₋₄-alkoxy and sulfo .

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 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.

Bi-, tri- and polyfunctional monomers are also suitable.

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.

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.

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.

Aliphatic and cycloaliphatic polyols are suitable as polyols. Examples of polyepoxides are those based on the polyols and epichlorohydrin. Furthermore, there are also 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.

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.

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.

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 and 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.

Also suitable as colorless compounds are the amides of the same 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-pentylene diamine, 1,6-hexylene diamine, octylene diamine, dodecylene diamine, 1,4-diaminocyclohexane, isophorone diamine, phenylene diamine, bisphenylene diamine, di-β-aminoethyl ether, diethylene triamine, triethylene tetramine, 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.

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.

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 longer-chain ones with e.g. 6 to 20 carbon atoms. Examples of 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. 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.

The colorless compounds can be used alone or in any mixtures.

und Silikonacrylate in Betracht, wie z.B. aus Textilpraxis International (1987) Seiten 848-852 bekannt.Preferred oligomeric or polymeric colorless compounds are, for example, various polyester acrylates, such as, for example, CH₂ = CH- [CO-O (CH₂) _n ] -CO-O-CH = CH₂, epoxyacrylates, such as (CH₂ = CH-CO-O-CH₂ -CHOH-CH₂-O-C₆H₆) ₂C (CH₃) ₂, urethane acrylates, such as

and silicone acrylates into consideration, as known, for example, from Textilpraxis International (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 being particularly preferred.

In the processes according to the invention, 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, pentaerythritriacrylate, bromacrylamide, methylenebisdi (bromacrylamide), methylene bisdiacrylamide, N-alkoxyacrylamide, tetraethylene glycol diacrylate, soybean oil methacrylate, methacrylate acrylate, methacrylate methacrylate, 2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, pentaerythritol tetraacrylate, lauryl acrylate, 2-phenoxyethyl acrylate, ethoxylated bisphenol diacrylate, ditrimethylolpropane tetraacrylate, tris (2-hydroxyuryl) tri-acrylate, tri-2-hydroxyethyl iso-acrylate , Dipentaerythriol pentaacrylate, ethoxylated trimethylolpropane triacrylate, isobornyl acrylate, ethoxylated tetrabromobisphenol diacrylate, propoxylated neopentylglycol diacrylate, propoxylated glyceryl triacrylate.

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 or polyurethane fibers, polypropylene and, above all, cellulose-containing materials, such as bast fibers, such as linen, hemp, jute, ramie and especially 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.

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. It is advisable to squeeze a tissue soaked with dye solution and a solution of a colorless compound on a padder to a lower liquid content before irradiation and, depending on the diffusibility of the specific dye, for a time, e.g. 15 minutes to 24 hours to leave yourself. The dye concentrations of the dye solutions or printing pastes used can be the same as in conventional dyeing or Printing process can be selected, e.g. 0.01 to 10 percent by weight based on the fiber material used. After exposure to ionizing radiation, the treated material only needs to be washed and dried. The degrees of fixation that can be achieved are high, e.g. more than 75%. The process according to the invention gives dyeings with generally good properties, e.g. good fastness to washing and light.

When carrying out the method according to the invention, the respective technical requirements must of course be taken into account. So 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 γ-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.

In order to prevent oxidative destruction of the dye, it is in some cases advantageous to irradiate in the atmosphere of an inert protective gas, e.g. under nitrogen. In general, however, no such measure is 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.

Wool, silk, hair, alginate fibers, polyvinyl, polyacrylonitrile, polyester, polyamide, polypropylene or polyurethane fibers, cellulose-containing fibers or glass fibers are preferably used as fiber material in the processes according to the invention.

Dyed or printed cellulose fibers and polyester-cellulose blended fabrics are particularly preferably used.

In the following exemplary embodiments, 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 the pad-batch process and irradiated with accelerated electrons (acceleration voltage ∼ 165 kV) in 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.

The degrees of fixation are determined by detaching the dye from an irradiated, non-washed out 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 tetramethylurea 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 using the absorbance (at λ _max ).

Example 1:

50 g/kg eines Oligoethylenglykol-diacrylates der Molmasse 508 und 100 g/kg Harnstoff enthält, foulardiert (Flottenaufnahme 67 %). Das nasse Gewebe wird beidseitig mit beschleunigten Elektronen einer Dosis von 4 Mrad pro Seite bestrahlt. Man erhält eine gelbe Färbung von hoher Echtheit mit einem Fixiergrad von 83 %.A cotton satin fabric is covered 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:

50 g/kg eines Oligoethylenglykol-diacrylates der Molmasse 508 und 100 g/kg Harnstoff enthält, foulardiert (Flottenaufnahme 76 %). Das Gewebe wird dann wie in Beispiel 1 angegebenen bestrahlt. Man erhält eine rote Färbung von hoher Echtheit mit einem Fixiergrad von 77 %.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 with a molecular weight of 508 and 100 g / kg of urea, padded (liquor absorption 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 pickup 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 cellular 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 which contains 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 of 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:

50 g/kg des in Beispiel 1 angegebenen Oligoethylenglykol-diacrylates und 100 g/kg Harnstoff foulardiert (Flottenaufnahme 70 %) und mit beschleunigten Elektronen, wie in Beispiel 1 angegeben, bestrahlt. Man erhält eine blaue Färbung von hoher Echtheit mit einem Fixiergrad von 54 %.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 as in Example 1 specified 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 irradiated with accelerated electrons, as specified in Example 1. A red dyeing of high fastness is obtained with a degree of fixation of 83%.

Example 10:

50 g/kg eines Oligoethylenglykol-diacrylats mit der Molmasse 508 und 100 g/kg Harnstoff enthält, foulardiert (Flottenaufnahme 88 %) und mit beschleunigten Elektronen, wie in Beispiel 1 angegeben, bestrahlt. Man erhält eine blaue Färbung von hoher Echtheit mit einem Fixiergrad von 76 %.A cellulose tissue is covered 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%.

Comparative example:

If the procedure described in Example 10 is followed, but a solution without 50 g / kg of the oligoethylene glycol diacrylate with the molecular weight 508 is used, a blue coloration with a degree of fixation of only 39% is obtained after the irradiation.

Example 11:

50 g/kg eines Oligoethylenglykol-diacrylates, 50 g/kg eines Polyesteracrylates und 100 g/kg Harnstoff enthält, fouladiert (Flottenaufnahme ca. 70 %). Das nasse Gewebe wird beidseitig mit beschleunigten Elektronen einer Dosis von 4 Mrad pro Seite bestrahlt. Man erhält eine Färbung von hoher Echtheit mit einem Fixiergrad von 90 %.A cotton satin fabric is covered 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 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 padded 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 methylene bisacrylamide and 100 g / kg urea, as described in Example 11, and irradiated. A dyeing of high fastness is obtained with a degree of fixation of 95%.

Example 13:

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 an oligoether triacrylate 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 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%.

Claims (23)

Process for fixing dyes on fiber materials, 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, with ionizing radiation on fiber material, which has a residual moisture greater than 30%, based on the treated fiber material before the radiation, fixed. Process according to claim 1, characterized in that the colorless compounds used are monomeric, oligomeric or polymeric organic compounds which contain at least one polymerizable double bond, or mixtures thereof. Process according to one of claims 1 and 2, characterized in that acrylates, diacrylates or acrylic acid are used as colorless compounds. Method according to one of claims 1 and 3, characterized in that mixtures of monomeric and oligomeric colorless organic compounds are used. Process according to one of claims 2 to 4, characterized in that the monomeric colorless compounds used are those having a molecular weight of up to 1000. Process according to one of claims 2 to 4, characterized in that the oligomeric colorless compounds used are those having a molecular weight between 1000 and 10000. Method according to one of claims 1 to 6, characterized in that those are used as colorless compounds with the acrylic radical as a polymerizable group. A method according to claim 7, characterized in that one uses oligomeric polyether, polyurethane or polyester acrylates. Method according to one of claims 1 to 8, characterized in that as colorless compound N-vinylpyrrolidone, acrylic acid, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, butanediol monoacrylate, 2-ethoxyethylacrylate, ethylene glycol acrylate, bisacrylates of polyethylene glycol with a molecular weight of 200 to 1500, toledoldoldyl acrylate, hexane diol ethylenediyl acrylate , Dipropylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythriacrylate, bromoacrylamide, methylenebisdi (bromacrylamide), methylene-bisdiacrylamide, N-alkoxyacrylamide, tetraethylene glycol-diacrylate-acrylate, polyacrylate-diacrylate-diacrylate-diacryl-acrylate-di-acrylate-diacryl-acrylate 2- (2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, pentaerythritol tetraacrylate, lauryl acrylate, 2-phenoxyethyl acrylate, ethoxylated bisphenol diacrylate, ditrimethylolpropane tetraacrylate, tris (2-hydroxyuryl), tris (2-hydroxyuryl) Acrylate, dipentaerythriol pentaacrylate, ethoxylated trimethylolpropane triacrylate, isobornyl acrylate, ethoxylated tetrabromobisphenol diacrylate, propoxylated neopentylglycol diacrylate, propoxylated glyceryl triacrylate are used. Process according to claim 9, characterized in that the colorless compound used is N-vinylpyrrolidone, methylenebisacrylamide or bisacrylates of polyethylene glycol with a molecular weight of 200 to 1500. Method according to one of claims 1 to 10, characterized in that the dyes are those of the formula $${\text{D- (X)}}_{\text{m}}$$

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. Process according to one of claims 1 to 11, characterized in that dyes are used which contain an acryloyl, α-bromoacryloyl, α-chloroacryloyl, vinylsulfonyl or epoxidyl radical as a polymerizable double bond or as a polymerizable ring system. A method according to claim 12, characterized in that dyes are used which contain an acryloyl, α-bromoacryloyl or vinylsulfonyl radical as a polymerizable double bond or as a polymerizable ring system. Method according to one of claims 1 to 13, characterized in that electron beams generated in a particle accelerator, in particular β or γ rays, are used as ionizing radiation. Method according to one of claims 1 to 14, characterized in that the treatment of the fiber material with appropriate dyes is carried out by dyeing or printing. Method according to one of claims 1 to 15, characterized in that an irradiation dose of 0.1 to 25 Mrad is selected. Method according to one of claims 1 to 16, characterized in that the irradiation is carried out under a protective gas atmosphere, in particular under a nitrogen gas atmosphere. Method according to one of claims 1 to 17, characterized in that the fixation takes place continuously. Method according to one of claims 1 to 18, characterized in that both the fixing of the fiber material with appropriate dyes and the dyeing or printing is carried out continuously. Method according to one of claims 1 to 19, characterized in that wool, silk, hair, alginate fibers, polyvinyl, polyacrylonitrile, polyester, polyamide, polypropylene or polyurethane fibers, cellulose-containing fibers or glass fibers are used as the fiber material. A method according to claim 20, characterized in that colored or printed cellulose fibers or cellulose-containing fibers are used. A method according to claim 20, characterized in that polyester-cellulose blend used. The fixed fiber material dyed or printed by the method according to claim 1.