EP0524144A1 - Process for fixing dyestuffs - Google Patents

Abstract

The invention relates to a process for fixing dyestuffs to organic material, which is characterised in that dyestuffs which contain at least one polymerisable double bond or at least one polymerisable ring system, excluding water-soluble dyestuffs having acrylamide or methacrylamide groups, are fixed to the organic material, which has a residual moisture content of less than 20 %, relative to the treated material, together with at least one virtually colourless compound which contains at least one polymerisable double bond, using ionising radiation.

Description

The invention relates to a process for fixing dyes on organic material, characterized in that dyes which contain at least one polymerizable double bond or at least one polymerizable ring system, with the exception of water-soluble dyes with acrylamide or methacrylamide groups, together with at least one practically colorless compound , which contains at least one polymerizable double bond, is fixed with ionizing radiation on the organic material, which has a residual moisture content of less than 20% based on the treated material.

It is known that dyes which contain activated unsaturated groups can be fixed on organic material, in particular 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.

The practice of dyeing, in particular with reactive dyes, but also with disperse dyes, has recently led to increased demands on the quality of the dyeing and the economy of the dyeing process. The fixation of reactive dyes using ionizing radiation alone 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 organic material, in particular fiber material, which is characterized in that dyes which contain at least one polymerizable double bond or at least one polymerizable ring system, with the exception of water-soluble dyes with acrylamide or methacrylamide groups, together with at least one practically colorless compound which has at least one contains polymerizable double bond, fixed with ionizing radiation on the organic material, which has a residual moisture content of less than 20% based on the treated material.

The process according to the invention is distinguished by the fact that dye and colorless compound can be applied together, so that only a single dye bath or only a single dyeing liquor is necessary, a significantly higher degree of fixation being achieved than in the known processes without colorless polymerizable Connection. It is also advantageous that, in contrast to radiation in the wet state, less dye is destroyed, which leads to a high brilliance of the coloring. Another advantage of dry radiation is the possibility of fixing water-insoluble or very sparingly water-soluble dyes with the process according to the invention.

In the context of this invention, the dry organic material is to be understood in particular as fiber material which has a residual moisture content of less than 20%, preferably 5-10%, based on the treated fiber material before the irradiation.

The method according to the invention largely avoids a high outlay on auxiliaries and apparatus, since after the fixing process according to the invention fixing alkali need not be washed out, but only rinsing and drying of the dyed or printed fiber material is required. By dispensing with fixing alkali, not only is the amount of wastewater limited compared to conventional processes, but also the treatment of residual wastewater is simplified.

The method of fixation is that an organic material to be colored, for example textile fiber material, after treatment with a dye which contains at least one polymerizable double bond or at least one polymerizable ring system, and in the presence of at least one colorless compound which has at least one polymerizable double bond contains, is irradiated with ionizing radiation in the dry state for a short time.

The treatment of the fiber material to be dyed with a dye according to the definition can be done in one of the usual ways, e.g. if it is a textile fabric, by soaking in a dye solution in a pull-out bath or by spraying or by padding a block solution, or by printing e.g. on a rouleaux printing machine. In the case of sparingly or not water-soluble dyes, the dye can be used in a e.g. Apply vinyl or acrylate binder dissolved by padding, spraying etc. There is also the possibility of such dyes in e.g. Apply vinyl or acrylate emulsion with water to the organic material by padding, spraying or printing. If necessary, the organic material is dried to a residual moisture of less than 20% after application.

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 generate charged secondary particles in matter, such as the secondary electrons of X-rays or γ-rays, in matter or the recoil nuclei (especially protons) of fast neutrons; Particles that are also indirectly ionizing are 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. Of particular importance for the process according to the invention are lightly charged particles, e.g. Electrons. Both brake radiation and characteristic radiation come into consideration as X-ray radiation. The 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.

Ionizing radiation also includes vacuum UV light with a wavelength of less than 200 nm and vacuum UV laser light (e.g. 193 nm).

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.

Other sources of radiation for electron beams are β-emitters, e.g. the 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 premature ionizing rays.

Suitable dyes for this fixing process are those which have an activated unsaturated group, in particular an unsaturated aliphatic group, such as the vinyl, halovinyl, styryl, acrylic or methacrylic group. Examples of such groups are the unsaturated groups containing halogen atoms, such as halomaleic acid and halogenpropiolic acid residues, the α- or β-bromine or chloroacrylic groups, halogenated vinyl acetyl groups, halogen crotonyl or halogen methacrylic groups. Also suitable are those groups which easily change, for example by splitting off hydrogen halide, into halogen-containing unsaturated groups, for example the dichloro or dibromopropionyl group. Halogen atoms here are understood to mean fluorine, chlorine, bromine and iodine atoms as well as pseudohalogen atoms, such as, for example, the cyano group. Good results are achieved by the processes according to the invention with dyes which contain an 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 ink system are preferably those which contain at least one epoxy residue.

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

A preferred embodiment of the process according to the invention is characterized in that the dyes are those of the formula

D- (X) _m (1),


wherein D is the rest of an organic dye of monoazo or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, nitroaryl, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, Naphthoquinone, pyrenequinone or perylene tetracarbimide series, X is a polymerizable double bond or a polymerizable ring system, and m is the number 1, 2, 3, 4, 5 or 6.

• a) D der Rest eines Formazanfarbstoffes der Formel
  
  oder
  
  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.
• 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

oder

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 water-soluble dyes of the formula (1) are used; eg those in which

• a) D the rest of a formazan dye of the formula
  
  or
  
  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.
• 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 can 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

or

is in which E is a phenylene radical which may 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, C₁₋₄-Alkyl oder Phenyl, und R₁₆Dyes of the formula (1) are likewise particularly preferably used, in which D is the residue of an azo dye, in particular a residue of the formulas 6 to 17:

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

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

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

wherein R₁₁ is C₂₋₄ alkanoyl or benzoyl;

wherein R₁₂ is C₂₋₄ alkanoyl or benzoyl;

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

wherein R₁₄ and R₁₅ are independently hydrogen, C₁₋₄ alkyl or phenyl, and R₁₆

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.Is hydrogen, cyano, carbamoyl or sulfomelhyl;

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

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

worin D₁ den Rest einer von wasserlöslichmachenden Substituenten freien, carbocyclischen oder heterocyclischen Diazokomponente;
Y₁ Chlor, Methyl, Methoxy, Methoxyethyl, Methoxyethoxy oder Wasserstoff;
R₂₀ und R₂₁ unabhängig voneinander C₁-C₆-Alkyl, C₃-C₆-Alkenyl, Phenyl oder den Rest -B₁-X₁;
R₂₂ Wasserstoff, Methyl, Methoxy, Chlor, Brom oder den Rest X₁;
X₁ einen Rest mit einer polymerisierbaren Doppelbindung;
B₁ einen gegebenenfalls substituierten Rest der Formel -(CH₂)_m-(C₆H₄)_n(CH₂)_o-;
   worin m eine ganze Zahl von 1 bis 6
   n 0 oder 1 und
   o eine ganze Zahl von 0 bis 6 bedeutet;
bedeuten und mindestens einer der Reste R₂₀, R₂₁ oder R₂₂ die Bedeutung X₁ hat bzw. durch einen Rest X₁ substituiert ist;
verwendet.A further preferred embodiment of the process according to the invention is characterized in that the dyes are those of the formula

wherein D₁ is the residue of a carbocyclic or heterocyclic diazo component free of water-solubilizing substituents;
Y₁ chlorine, methyl, methoxy, methoxyethyl, methoxyethoxy or hydrogen;
R₂₀ and R₂₁ independently of one another are C₁-C₆-alkyl, C₃-C₆-alkenyl, phenyl or the rest -B₁-X₁;
R₂₂ is hydrogen, methyl, methoxy, chlorine, bromine or the radical X₁;
X₁ is a residue with a polymerizable double bond;
B₁ is an optionally substituted radical of the formula - (CH₂) _m - (C₆H₄) _n (CH₂) _o -;
where m is an integer from 1 to 6
n 0 or 1 and
o represents an integer from 0 to 6;
mean and at least one of the radicals R₂₀, R₂₁ or R₂₂ has the meaning X₁ or is substituted by a radical X₁;
used.

D₁ is preferably the residue of a homo- or heterocyclic diazo component, for example from the series thienyl, phenylazothienyl, thiazolyl, isothiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, benzothiazolyl, benzisothiazolyl, pyrazolyl, 1,2, 3-triazolyl, 1,2,4-triazolyl, imidazolyl, or phenyl. Each of these systems can carry further substituents such as alkyl, alkoxy or alkylthio, each with 1 to 4 carbon atoms, phenyl, electronegative groups such as halogen, especially chlorine or bromine, trifluoromethyl, cyano, nitro, acyl, such as acetyl or benzoyl, carboalkoxy, especially carbomethoxy or carboethoxy, alkyl sulfone with 1 to 4 carbon atoms, phenyl sulfone, phenoxysulfone, sulfonamido or arylazo, especially phenylazo. Two adjacent substituents of the ring systems mentioned can also together form further fused rings, for example phenyl rings or cyclic imides.

D₁ particularly preferably denotes a benzothiazolyl, benzisothiazolyl or phenyl radical which is unsubstituted or substituted once or twice by one of the abovementioned radicals.

The alkyl radicals can be substituted, e.g. by hydroxy, alkoxy with 1 to 4 carbon atoms, especially methoxy, cyano or phenyl. Suitable further substituents are halogen, such as fluorine, chlorine or bromine, or -CO-U or -O-CO-U, where U is alkyl having 1 to 6 carbon atoms or phenyl.

Suitable alkenyl radicals are those radicals which are derived from the alkyl radicals listed above by replacing at least one single bond with a double bond. Suitable residues are e.g. Ethenyl or propenyl.

Phenyl radicals are to be understood as meaning unsubstituted or substituted phenyl radicals. Examples of substituents are C₁-C₄-alkyl, C₁-C₄-alkoxy, bromine, chlorine, nitro or C₁-C₄-alkylcarbonylamino into consideration.

For the rest X₁, for example, residues derived from acrylic, methacrylic or cinnamic acid are suitable. Of particular note are the residues of the formulas -NH-CO-CH = CH₂, -NH-CO-C (CH₃) = CH₂, -NH-CO-CBr = CH₂, -NH-CO-CH = CH-C₆H₅, -O -CO-CH = CH₂, -O-CO-C (CH₃) = CH₂, -O-CO-CBr = CH₂, -O-CO-CH = CH-C₆H₅, -CH = CH₂, -CH = CH-C₆H₅ or -C (CH₃) = CH₂.

oder

worin R₂₃ C₁-C₆-Alkyl, C₃-C₆-Alkenyl oder Phenyl;
R₂₅ Wasserstoff, Methyl, Methoxy, Chlor, Brom, -NH-CO-CH=CH₂, -NH-CO-C(CH₃)=CH₂, -NH-CO-CBr=CH₂, -NH-CO-CH=CH-C₆H₅, -O-CO-CH=CH₂, -O-CO-C(CH₃)=CH₂, -O-CO-CBr=CH₂, oder -O-CO-CH=CH-C₆H₅;
R₂₆ -NH-CO-CH=CH₂, -NH-CO-C(CH₃)=CH₂, -NH-CO-CBr=CH₂, -NH-CO-CH=CH-C₆H₅, -O-CO-CH=CH₂, -O-CO-C(CH₃)=CH₂, -O-CO-CBr=CH₂ oder -O-CO-CH=CH-C₆H₅; und
R₂₇-NH-CO-CH=CH₂, -NH-CO-C(CH₃)=CH₂, -NH-CO-CBr=CH₂ oder -NH-CO-CH=CH-C₆H₅ bedeuten und worin B₁, D₁ und Y₁ die Bedeutungen wie unter Formel (20) angegeben haben.Dyes of the formulas are particularly preferred:

or

wherein R₂₃ is C₁-C₆ alkyl, C₃-C₆ alkenyl or phenyl;
R₂₅ hydrogen, methyl, methoxy, chlorine, bromine, -NH-CO-CH = CH₂, -NH-CO-C (CH₃) = CH₂, -NH-CO-CBr = CH₂, -NH-CO-CH = CH- C₆H₅, -O-CO-CH = CH₂, -O-CO-C (CH₃) = CH₂, -O-CO-CBr = CH₂, or -O-CO-CH = CH-C₆H₅;
R₂₆ -NH-CO-CH = CH₂, -NH-CO-C (CH₃) = CH₂, -NH-CO-CBr = CH₂, -NH-CO-CH = CH-C₆H₅, -O-CO-CH = CH₂ , -O-CO-C (CH₃) = CH₂, -O-CO-CBr = CH₂ or -O-CO-CH = CH-C₆H₅; and
R₂₇-NH-CO-CH = CH₂, -NH-CO-C (CH₃) = CH₂, -NH-CO-CBr = CH₂ or -NH-CO-CH = CH-C₆H₅ and wherein B₁, D₁ and Y₁ are the Meanings as given under formula (20).

Examples of the above dyes are dyes of the formulas:

The dyes mentioned are known or can be prepared by known methods. For example, about a mole equivalent of an acrylic acid chloride is added to a solution of the substance to be acylated in anhydrous acetone. About 1 mole equivalent of pyridine is then added at room temperature and the product is separated off by adding water.

In the process according to the invention, the colorless organic compounds which contain at least one polymerizable double bond are those which 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.

Acrylates, diacrylates, acrylic acid or acrylamides are preferably used as colorless compounds in the process according to the invention.

Mixtures of monomeric and oligomeric colorless organic compounds are particularly preferably used in the processes according to the invention.

Possible monomeric colorless compounds are those with a molecular weight of up to approximately 1000 and which contain at least one polymerizable group.

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.

If liquid, the polymeric colorless compound can itself be used directly or as a solution in water or organic solvents or as a mixture with other monomers, oligomers and / or polymers.

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. Also included are polymers or copolymers that contain hydroxyl groups in the polymer chain or in side groups, e.g. Polyvinyl alcohol and copolymers thereof or polymethacrylic acid hydroxyalkyl esters or copolymers thereof, are suitable as polyols. Other suitable polyols are oligoesters with hydroxyl end groups.

Examples of aliphatic and cycloaliphatic polyols are alkylene diols preferred 2 to 12 carbon atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols with molecular weights of preferably 200 to 1500, 1,3-cyclopentanediol, 1,2-1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris (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, 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-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di-β-aminoethyl ether, diethylenetriamine, triethylenetetramine, di- (β-aminoethoxy) - or di- (β-aminopropoxy) ethane. Other suitable polyamines are polymers and copolymers with amino groups in the side chain and oligoamides with amino end groups.

Examples of such unsaturated amides are: methylene-bis-acrylamide, 1,6-hexamethylene-bis-acrylamide, diethylenetriamine-tris-methacrylamide, bis (methacrylamidopropoxy) ethane, β-methacrylamido-ethyl 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.

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, 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

Polyether acrylates are e.g. B.

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, 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-hydroxyethyl) tri-acrylyl-acrylo-acrylate t, dipentaerythriol pentaacrylate, ethoxylated trimethylolpropane triacrylate, isobornyl acrylate, ethoxylated tetrabromobisphenol diacrylate, propoxylated neopentylglycol diacrylate, propoxylated glyceryl triacrylate.

Oligoethylene glycol diacrylates (MW ∼ 500) are particularly preferred for the preparation of dye solutions of sparingly or not water-soluble dyes, N-vinylpyrrolidone, 2-ethyl- (2-hydroxymethyl) - 1,3-propanediol triacrylate, alkoxylated oligoether polyol tetraacrylate, oligoether triacrylate, N-butoxyacrylamide, N-iso-butoxyacrylamide, their mixtures with one another, and their mixtures with methylenebisacrylamide, oligo - / polyurethane acrylate, oligo / polyester acrylate or oligo / polyether acrylate.

Alkoxylated oligoether polyol tetraacrylate, 2-ethyl- (2-hydroxymethyl) -1,3-propanediol triacrylate, oligo- / polyurethane-acrylate, oligo are particularly preferred for the preparation of water-based emulsions into which sparingly or not water-soluble dyes can be introduced - / polyester acrylate, oligo- / polyether acrylate, their mixtures with one another, and their mixtures with methylenebisacrylamide, oligoethylene glycol diacrylate (MW ∼ 500), N-vinylpyrrolidone, oligoether triacrylate, N-butoxyacrylamide or N-iso-butoxyacrylamide

The method according to the invention is applicable to a wide variety of organic materials, e.g. textile material, paper, wood, leather and plastics. Fiber materials such as e.g. Fibers of animal origin such as wool, silk, hair (e.g. 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 , e.g. 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®. The method can also be used for mixtures of the fibers mentioned. The method is very particularly preferably used for cellulosic fibers, such as cotton or rayon wool, and their mixtures with polyester, polyacrylonitrile, polyamide or polypropylene fibers.

The fibers mentioned can be in a wide variety of processing states, as are used in particular in the textile industry, e.g. as threads, yarns, fabrics, knitted fabrics or nonwovens, e.g. Felts.

The dye and colorless compound can be applied together as a homogeneous solution, suspension, emulsion or foam by the customary processes. However, dye and colorless compound or parts of the colorless compound can can also be applied separately. For example, an aqueous solution of the dye can first be padded and - after the dye has dried - the colorless compound can be sprayed on, for example.

The method according to the invention is carried out in such a way that e.g. the dyed textile fabric treated with a solution of a colorless compound is passed through the fanned beam of an electron accelerator at room temperature in a dry state. This happens at such a speed that a certain radiation dose is reached. The radiation doses normally to be used are between 0.1 and 15 Mrad, the radiation dose advantageously being between 0.1 and 4 Mrad. With a dose of less than 0.1 Mrad, the degree of fixation is generally too low; with a dose of more than 15 Mrad, damage to the fiber material and the dye often occurs. The dye concentrations of the dye solutions or printing pastes used can be the same 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 special embodiment depends primarily on the type of ionizing radiation to be used and its mode of production. For example, if a spool of yarn soaked with dye solution and the solution of the colorless compound is to be irradiated with γ-rays, then this is enclosed in a cell and exposed to the radiation. If higher radiation doses are desired with low radiation intensity, the material to be irradiated can be exposed to the radiation in several passes.

To prevent oxidative destruction of the dye, it is advantageous to irradiate in the atmosphere of an inert protective gas, e.g. under nitrogen.

A preferred embodiment of the method according to the invention is characterized in that both fixing the fiber material with appropriate Dyes and dyeing or printing are carried out continuously.

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 runs 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 treated once with 50 ml of a solution of 600 ml / l phosphate buffer (pH 7) and 40 ml / l tetramethyl urea in deionized water at 40 ° C and then with 50 ml of this solution for 30 minutes at 100 ° C. The two extracts are combined and the degrees of fixation are determined via the extinction (at λ _max ). In Examples 6 and 7, the extraction is carried out in the same way with dimethylformamide.

Example A:

4 g dieses Farbstoffs werden in 50 ml waserfreiem Aceton gelöst. Nach Zugabe von 1 g Acrylchlorid werden bei Raumtemperatur 0,8 g wasserfreies Pyridin zugetropft. Man rührt eine Stunde und gibt dann 500 ml Wasser zu der Lösung. Nach dem Abfiltrieren erhält man ein schwarzes, leicht klebriges Produkt der Formel

The isomer mixture of 5,6- and 6,7-dichloro-2-aminobenzothiazole is diazotized in the usual way and coupled to N-ethyl-N-hydroxyethylaniline. The dye of the formula is obtained

4 g of this dye are dissolved in 50 ml of anhydrous acetone. After adding 1 g of acrylic chloride, 0.8 g of anhydrous pyridine is added dropwise at room temperature. The mixture is stirred for one hour and then 500 ml of water are added to the solution. After filtering off, a black, slightly sticky product of the formula is obtained

Example 1:

100 g/l eines Oligoethylenglykoldiacrylats und 100 g/l Harnstoff enthält, foulardiert (Flottenaufnahme ca. 70%). Das Gewebe wird bei ca. 60-80° C getrocknet und anschliessend beidseitig mit beschleunigten Elektronen einer Dosis von 4 Mrad pro Seite bestrahlt. Man erhält eine gelbe Färbung von hoher Echtheit mit einem Fixiergrad von 71%.A cotton satin fabric is covered with an aqueous solution containing 30 g / l of the dye of the formula

Contains 100 g / l of an oligoethylene glycol diacrylate and 100 g / l urea, padded (liquor absorption approx. 70%). The tissue is dried at approx. 60-80 ° C and then irradiated on both sides with accelerated electrons at a dose of 4 Mrad per side. A yellow color of high fastness is obtained with a degree of fixation of 71%.

Example 2:

wie in Beispiel 1 beschrieben gefärbt, getrocknet und bestrahlt. Man erhält eine rote Färbung von hoher Echtheit mit einem Fixiergrad von 75%.A cotton satin fabric is covered with an aqueous solution containing 30 g / l of the dye of the formula

dyed, dried and irradiated as described in Example 1. A red dyeing of high fastness is obtained with a degree of fixation of 75%.

Example 3 :

A cotton saline fabric is washed with an aqueous solution containing 30 g / l of the dye described in Example 2, 50 g / l of an oligoethylene glycol diacrylate, 50 g / l of 2-ethyl- (2-hydroxymethyl) -1,3-propanediol triacrylate and 100 g / l of urea contains, as described in Example 1, dried and irradiated. A red dyeing of high fastness is obtained with a degree of fixation of 64%.

Example 4:

A cotton satin fabric is dried with an aqueous solution containing 30 g / l of the dye described in Example 2, 50 g / l of an oligoethylene glycol diacrylate, 50 g / l of methylene bisacrylamide and 100 g / l of urea, dyed as described in Example 1 and irradiated. A red dyeing of high fastness is obtained with a degree of fixation of 67%.

Example 5:

A cotton satin fabric is dyed with an aqueous solution containing 30 g / l of the dye described in Example 2, 50 g / l of an oligoethylene glycol diacrylate, 50 g / l of an oligoether triacrylate and 100 g / l of urea as described in Example 1. dried and irradiated. A red dyeing of high fastness is obtained with a degree of fixation of 63%.

Example 6:

A cotton satin fabric is padded with a mixture containing 30 g / l of the dye described in Example 2, 75 g / l of an oligourethane diacrylate, 50 g / l of methylene bisacrylamide and 100 g / l of urea (liquor absorption approx. 70%). The tissue is dried and then irradiated on both sides with accelerated electrons at a dose of 4 Mrad / side. A red color is obtained with a degree of fixation of 73%.

Example 7:

A cotton satin fabric is padded with a mixture containing 30 g / l of the dye described in Example 2, 75 g / l of an oligourethane diacrylate, 100 g / l of an oligoethylene glycol diacrylate and 100 g / l of urea (liquor absorption approx. 70%) . The tissue is dried and then irradiated on both sides with accelerated electrons at a dose of 4 Mrad / side. A red color is obtained with a degree of fixation of 77%.

Example 8:

A cotton satin fabric is padded with an aqueous solution which contains 30 g / l of the dye described in Example 2 and 100 g / l of urine (liquor absorption approx. 70%) and dried. Then padding with a solution in ethanol of 10 g / kg 1,6-hexanediol diacrylate, 90 g / kg of an oligomeric aliphatic urethane diacrylate and 100 g / kg of an oligoethylene glycol diacrylate (liquor absorption approx. 40%). The tissue is dried and then irradiated on both sides with accelerated electrons at a dose of 4 Mrad / side. A red color is obtained with a degree of fixation of 72%.

Claims (25)

Process for fixing dyes on organic material, in particular fiber material, characterized in that dyes which contain at least one polymerizable double bond and / or at least one polymerizable ring system, except water-soluble dyes with acrylamide or methacrylamide groups, together with at least one practically colorless Compound which contains at least one polymerizable double bond with ionizing radiation fixed on the organic material, which has a residual moisture content of less than 20% based on the treated material before the irradiation. 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 with 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, pentaerythritriacrylate, bromoacrylamide, methylenebisdi (bromacrylamide), methylene bisdiacrylamide, N-alkoxyacrylamide, tetraethyleneglycol acrylate, methacrylate acrylate, methacrylate acrylate, methacrylate acrylate, methacrylate methacrylate, 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-hydroxy) ecyl acrylate, dipentaerythriol pentaacrylate, ethoxylated trimethylolpropane triacrylate, isobornyl acrylate, ethoxylated tetrabromobisphenol diacrylate, propoxylated neopentylglycol diacrylate, propoxylated glyceryl triacrylate. 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

D- (X) _m (1),

wherein D is the rest of an organic dye of monoazo or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, nitroaryl, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, Naphthoquinone, pyrenequinone or perylene tetracarbimide series, X is a polymerizable double bond or a polymerizable ring system, and m is the number 1, 2, 3, 4, 5 or 6. 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 the polymerizable double bond or as the 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 15 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. Dyes of the formula

wherein D₁ is the residue of a carbocyclic or heterocyclic diazo component free of water-solubilizing substituents;
Y₁ chlorine, methyl, methoxy, methoxyethyl, methoxyethoxy or hydrogen;
R₂₀ and R₂₁ independently of one another are C₁-C₆-alkyl, C₃-C₆-alkenyl, phenyl or the rest -B₁-X₁;
R₂₂ is hydrogen, methyl, methoxy, chlorine, bromine or the radical X₁;
X₁ is a residue with a polymerizable double bond;
B₁ is an optionally substituted radical of the formula - (CH₂) _m - (C₆H₄) _n - (CH₂) _o -;
where m is an integer from 1 to 6
n 0 or 1 and
o represents an integer from 0 to 6;
mean and at least one of the radicals R₂₀, R₂₁ or R₂₂ has the meaning X₁ or is substituted by a radical X₁. Dyes of the formulas

wherein R₂₃ is C₁-C₆ alkyl, C₂-C₆ alkenyl or phenyl;
R₂₅ hydrogen, methyl, methoxy, chlorine, bromine, -NH-CO-CH = CH₂, -NH-CO-C (CH₃) = CH₂, -NH-CO-CBr = CH₂, -NH-CO-CH = CH- C₆H₅, -O-CO-CH = CH₂, -O-CO-C (CH₃) = CH₂, -O-CO-CBr = CH₂, or -O-CO-CH = CH-C₆H₅;
R₂₆-NH-CO-CH = CH₂, -NH-CO-C (CH₃) = CH₂, -NH-CO-CBr = CH₂, -NH-CO-CH = CH-C₆H₅, -O-CO-CH = CH₂ , -O-CO-C (CH₃) = CH₂, -O-CO-CBr = CH₂ or -O-CO-CH = CH-C₆H₅; and
R₂₇-NH-CO-CH = CH₂, -NH-CO-C (CH₃) = CH₂, -NH-CO-CBr = CH₂ or -NH-CO-CH = CH-C₆H₅ and wherein B₁, D₁ and Y₁ are the Meanings as given under formula (20).