EP0466648B1 - Process for the fixation of dyes - Google Patents

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.

Printing pastes containing a water-soluble reactive dye and their use in conventional printing processes are already known from EP-A-144 093. '' Textile Chemist and Colorist, Vol. 10, No. 10, October 1978 '', describes the fixation of pigment prints using electron beams. CH-A-388 254 discloses an aftertreatment of the dyed or printed textile material with dispersions of copolymers of an N-methylolacrylamide with other polymerizable compounds and subsequent heat setting. From '' Textile Chemist and Colorist, Vol. 11, No. 5, May 1979 '' is the printing of polyester with a printing paste, which contains a pigment dispersed in 1,6-hexanediol-diacrylate, and the subsequent fixing of the Known pressure by means of electron radiation.

It is also 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, especially reactive dyes, 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. 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 increased Requirements for 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 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.

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. 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.

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

The γ-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. As such groups, e.g. the unsaturated groups containing halogen atoms, such as halogen maleic acid and halogen propiolic acid residues, the α- or β-bromo or chloroacrylic groups, halogenated vinyl acetyl groups, halogen crotonyl or halogen methacrylic groups. Furthermore, groups are also suitable that easily, 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. to 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.

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.

• 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 C₂₋₄Alkanoyl oder Benzoyl ist;

worin (R₁₃)₀₋₃ für 0 bis 3 Substituenten aus der Gruppe C₁₋₄-Alkyl, C₁₋₄-Alkoxy, Halogen, Carboxy und Sulfo steht;

worin R₁₄ und R₁₅ unabhängig voneinander Wasserstoff, C₁₋₄-Alkyl oder Phenyl, und R₁₆ Wasserstoff, Cyano, Carbamoyl oder Sulfomethyl ist,

worin (R₁₇)₁₋₄ für 1 bis 4 Substituenten aus der Gruppe Wasserstoff, Halogen, Nitro, Cyan, Trifluormethyl, Sulfamoyl, Carbamoyl, C₁₋₄-Alkyl, C₁₋₄-Alkoxy, Amino, Acetylamino, Ureido, Hydroxy, Carboxy, Sulfomethyl und Sulfo, unabhängig voneinander, steht;

worin (R₁₈)₀₋₃, (R₁₈')₀₋₂ und (R₁₈'')₀₋₂ unabhängig voneinander 0 bis 3 bzw. 0 bis 2 Substituenten aus der Gruppe C₁₋₄-Alkyl, C₁₋₄-Alkoxy und Sulfo stehen.Dyes of the formula (1) are likewise particularly preferably used, in which D is the residue of an azo dye, in particular a residue of the formulas 6 to 17:

wherein (R₇) ₁₋₃ represents 1 to 3 substituents from the group C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen, carboxy and sulfo;

wherein (R₉) ₁₋₃ represents 1 to 3 substituents from the group C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen, carboxy and sulfo;

wherein (R₁₀) ₁₋₃ represents 1 to 3 substituents from the group C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen, carboxy and sulfo;

wherein R₁₁ is C₂₋₄ alkanoyl or benzoyl;

wherein R₁₂ is C₂₋₄alkanoyl or benzoyl;

wherein (R₁₃) ₀₋₃ represents 0 to 3 substituents from the group C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen, carboxy and sulfo;

wherein R₁₄ and R₁₅ are independently hydrogen, C₁₋₄ alkyl or phenyl, and R₁yl is hydrogen, cyano, carbamoyl or sulfomethyl,

wherein (R₁₇) ₁₋₄ for 1 to 4 substituents from the group hydrogen, halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁₋₄-alkyl, C₁₋₄-alkoxy, amino, acetylamino, Ureido, hydroxy, carboxy, sulfomethyl and sulfo, independently of one another, is;

wherein (R₁₈) ₀₋₃, (R₁₈ ') ₀₋₂ and (R₁₈'') ₀₋₂ independently of one another 0 to 3 or 0 to 2 substituents from the group C₁₋₄-alkyl, C₁₋₄-alkoxy and Stand 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. 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.

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, 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, Dipentaerytlrrittriacrylat, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Tripentaerythritoctacrylat, pentaerythritol dimethacrylate, pentaerythritol 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, sorbitol hexaacrylate and olmethacrylate acrylate 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 identical or different unsaturated carboxylic acids of aromatic, cycloaliphatic and aliphatic polyamines with preferably 2 to 6, particularly 2 to 4, amino groups. Examples of such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-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 long-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.

Polyetheracrylate, sind z.B.

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 CH ₂ = CH - [CO-O (CH ₂ ) _n ] -CO-O-CH = CH ₂ , epoxy acrylates, such as (CH₂ = CH-CO- O-CH₂-CHOH-CH₂-O-C₆H₆) ₂C (CH₃) ₂, urethane acrylates, such as

Polyether acrylates are, for example

and silicone acrylates into consideration, as is 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, pentaerythritol diacrylate, bromoacrylamide, methylene bisdi (bromoacrylamide), methylene bisdiacrylamide, N-alkoxyacrylamide, tetraethylene glycol diacrylate, soybean oil ethacrylate, 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, acrylate, acrylate, tri (2-hydroxy-ethyl) tri-acrylate, Dipentaerythriol pentaacrylate, ethoxylated trimethylolpropane triacrylate, isobornyl acrylate, ethoxylated tetrabromobisphenol diacrylate, propoxylated neopentylglycol diacrylate, propoxylated glyceryl triacrylate are used.

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.

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 expedient 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, as in conventional dyeing or. Printing process can be selected, e.g. 0.001 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 wash and light fastness.

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, 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.

In the following examples, 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.

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 λ _max ).

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 %. 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%.

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 %. 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.

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 %. 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%.

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 %. 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%.

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.

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 %. 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%.

Claims (23)

1. A process for fixing dyes on fibre materials, which comprises fixing dyes which contain at least one polymerisable double bond and/or at least one polymerisable ring system on fibre material having a residual moisture content of more than 30 %, based on the treated fibre material before irradiation, using ionising radiation together with at least one colourless compound which contains at least one polymerisable double bond, but not N-C₁-C₄alklolacrylamide or N,N-di(C₁-C₄alkylol)acrylamide.
2. A process according to claim 1, wherein the colourless compounds used are monomeric, oligomeric or polymeric organic compounds which contain at least one polymerisable double bond or mixtures thereof.
3. A process according to either of claims 1 and 2, wherein the colourless compounds used are acrylates, diacrylates or acrylic acid.
4. A process according to either of claims 1 and 3, wherein mixtures of monomeric and oligomeric colourless organic compounds are used.
5. A process according to any one of claims 2 to 4, wherein the monomeric colourless compounds used are those having a molecular weight of up to 1000.
6. A process according to any one of claims 2 to 4, wherein the oligomeric colourless compounds used are those having a molecular weight between 1000 and 10,000.
7. A process according to any one of claims 1 to 6, wherein the colourless compounds used are those having an acryloyl radical as polymerisable group.
8. A process according to claim 7, wherein oligomeric polyether, polyurethane or polyester acrylates are used.
9. A process according to any one of claims 1 to 8, wherein the colourless compound used is N-vinylpyrrolidone, acrylic acid, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, butanediol monoacrylate, 2-ethoxyethyl acrylate, ethylene glycol acrylate, a bisacrylate of a polyethylene glycol having a molecular weight of from 200 to 1500, butanediol diacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, bromoacrylamide, methylenebisdi(bromoacrylamide), methylenebisdiacrylamide, N-alkoxyacrylamides, tetraethylene glycol diacrylate, soya bean oil acrylate, polybutadiene acrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, pentaerythritol tetraacrylate, lauryl acrylate, 2-phenoxyethyl acrylate, ethoxylated bisphenol diacrylate, ditrimethylolpropane tetraacrylate, tris(2-hydroxy-ethyl)isocyanurate triacrylate, isodecyl acrylate, dipentaerythritol pentaacrylate, ethoxylated trimethylolpropane triacrylate, isobornyl acrylate, ethoxylated tetrabromobisphenol diacrylate, propoxylated neopentylglycol diacrylate or propoxylated glyceryl triacylate.
10. A process according to claim 9, wherein the colourless compound used is N-vinylpyrrolidone, methylenebisacrylamide or a bisacrylate of a polyethylene glycol having a molecular weight of from 200 to 1500.
11. A process according to any one of claims 1 to 10, wherein the dyes used are those of the formula
    
    
    
            D-(X)_m   (1),
    
    
    
    where D is the radical or an organic dye of the monoazo or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, nitroaryl, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, naphthoquinone, pyrenequinone or perylenetetracarbimide series, X is a polymerisable double bond or a polymerisable ring system and m is 1, 2, 3, 4, 5 or 6.
12. A process according to any one of claims 1 to 11, wherein the dyes used contain as polymerisable double bond or as polymerisable ring system an acryloyl, α-bromoacryloyl, α-chloroacryloyl, vinylsulfonyl or epoxy radical.
13. A process according to claim 12, wherein the dyes used contain as polymerisable double bond or as polymerisable ring system an acryloyl, α-bromoacryloyl or vinylsulfonyl radical.
14. A process according to any one of claims 1 to 13, wherein the ionising radiation used comprises electron beams generated in a particle accelerator, in particular β- or γ-rays.
15. A process according to any one of claims 1 to 14, wherein the treatment of the fibre material with appropriate dyes is effected by dyeing or printing.
16. A process according to any one of claims 1 to 15, wherein an irradiation dose of from 0.1 to 25 Mrad is chosen.
17. A process according to any one of claims 1 to 16, wherein the irradiation is carried out under a protective gas atmosphere, in particular under a nitrogen gas atmosphere.
18. A process according to any one of claims 1 to 17, wherein the fixation is carried out continuously.
19. A process according to any one of claims 1 to 18, wherein not only the fixation of appropriate dyes to the fibre material but also the dyeing or printing are effected continuously.
20. A process according to any one of claims 1 to 19, wherein the fibre material used is wool, silk, hairs, alginate fibres, polyvinyl, polyacrylonitrile, polyester, polyamide, polypropylene or polyurethane fibres, cellulose-containing fibres or glass fibres.
21. A process according to claim 20, wherein dyed or printed cellulose fibres or cellulose-containing fibres are used.
22. A process according to claim 20, wherein polyester-cellulose blend fabrics are used.
23. A dyed or printed fibre material subjected to fixation by the process of claim 1.