SE423286B - APPLICATION OF A CHLORMYLETRATED S-TRIAZIN AS A RADIO SENSITIVE COMPOUND IN A COPYING MATERIAL - Google Patents

Description

Admittedly, a number of undesirable properties are overcome with some of the chromophor-substituted vinyl halomethyl-s-triazines mentioned in DE-OS 22 43 621 and.DE-OS 23 06 248; however, their relatively complicated preparation has a detrimental effect. Thus, for example, 2-methyl-4,6-bis-trichloromethyl-s-triazine must first be recovered by co-trimerization of acetonitrile and trichloroacetonitrile and this highly reactive compound to nucleophilic compounds is then condensed under the conditions of the Knoevenagel reaction. with aldehydes, which due to their partially complicated structure are cumbersome to synthesize. The vinylene group thus formed connects the triazine unit and a chromophore and forms part of the entire chromophoric system, which is responsible for the desired long-wave UV / VIS absorption.

The object of the invention was to provide easily manufacturable, actinic radiation-sensitive organohalogen compounds with good sensitivity in the ultraviolet and short-wave visible spectral range for use in radiation-sensitive masses.

The object of the invention is the use of an s-triazine of the formula I in a radiation-sensitive copying material. Said s-triazine has the formula I. cHnc13_n cHmc13_m 1 which _ m and n denote the numbers Q - 3, where m + n is not greater than 5.

The pulp according to the invention is characterized in that in this compound f represents R an optionally substituted bi- or tri-nucleic aromatic or heterocyclic aromatic, optionally partially hydrogenated group bonded via an unsaturated ring-C atom. The group R is preferably bonded via an aromatic C atom.

Within the framework of this description, actinic radiation refers to any radiation whose energy at least corresponds to the energy of the short-wave visible light. Particularly suitable for long-wave UV radiation, but also electron and laser radiation and the like.

In the above general formula I, the symbols preferably have the following meaning: R is a di- or tri-nucleus fused aryl group or a corresponding heterocyclic aromatic group having 0, S or N as heteroatoms and may be partially hydrogenated. It may also be a diphenylyl group. The nuclei of the group R may bear one or more substituents. n and m are preferably 0.

Examples of suitable bi- and tri-core aromatic groups are: naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, benzofuran, benzopyran, dibenzofuran, benzothiophene, dibenzothiophene, acenaphthene, benzoxazole, fluorene, tetrahydrophenanthrene and dihydrophthalene, especially.

As substituents there may be mentioned, for example: Chlorine, lower, optionally substituted alkyl groups having preferably 1 to 3 carbon atoms, optionally glycutomeric aryl groups, nitro-, sulfonyl-, alkylmercapto-, phenylmercapto-, acyl-, aryloxy-, hydroxy- and preferably alkoxy groups, in particular (C1-C8) -alkoxy groups, which in turn may be substituted by halogen, phenyl or phenoxy and in which individual methylene groups may be replaced by O- or S-bridges, and phenoxy-, cycloalkoxy- and alkenyloxy- groups.

Particularly preferred are s-triazines of formula I, in which R represents a group of formula II R1, II, R2 in which R1 'represents hydrogen or -OR3, preferably -OR3, R2 H, Cl, a lower alkyl, alkenyl, aryl, an optionally substituted (C 1 -C 4) alkoxy group; preferably hydrogen, a (C 1 -C 3) -alkyl or QQ 1 -C 3) -alkoxy group and R 3 a (C 1 -C 8) -alkyl group, which may be substituted by halogen, preferably chlorine, aryl or aryloxy groups and in which individual methylene groups may be replaced by Q- or S-bridges, a cycloalkyl, alkenyl or aryl group, in particular a (C1-C4) -alkyl or alkoxylalkyl group Z or R1 and R1 together denote an alkylene group, which is preferably connected with the naphthalene nucleus to form a single or 6-membered ring and N = m = 0.

Also preferred are compounds in which the triethylinyl group and an alkoxy group are arranged in the 1,4- or 2,6-position of the naphthalene nucleus of formula II.

Since the photochemical activity of the initiators through the carbon number of the alkoxy groups is only insignificantly affected, the restriction to 8 carbon atoms in -OR 3 is not to be considered as a rigid limit but can possibly be broken through, for example with nonyloxy, dodecyloxy or octadecyl groups. Organohalogen compounds are mentioned: 2- (naphth-1-yl) -4,6-bis-trichloromethyl-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-triazine, 2 - (4-ethoxy-naphth-ethyl) -4,6-bis-trichloromethyl-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [A4 (2-methoxyethyl) naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis- trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphthalyl) -4,6 -bis-trichloromethyl-s-triazine, 2- [6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, .2- (e-meth <> xi-naphth -2-yl) -4,4-bis-trichloromethyl-s-thiazine, 2- (S-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4.7 -dimethoxy-naphtha- 1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-yl} -4,6-bis-trichloromethyl-s-triazine, 2- (4,5 -dimethoxy-naphth-1-yl) ~ 4,6-bis-trichloromethyl-s-triazine and 2- (acenaphth-5-yl) -4,6-bis-trichloromethyl-s-triazine and also ~ with slightly weakened activity 2- (naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine. In addition, suitable halogen compounds from groups not to be described by formula II are: 2- (phenanthr-9-yl) -, 2- (dibenzothien-2-yl) -, 2- (benzopyran-3-yl ) - and 2- (4-alkoxyanthrac-1-yl) -4,6-bis-trichloromethyl-s-triazines. The absorption of the latter compound class extends beyond 500 nm. The aryl halomethyl triazines of the invention are most easily prepared by co-trimerization of the aryl carboxylic acid nitriles with haloacetonitriles in the presence of hydrogen chloride and Friedel-Crafts catalysts such as AlCl 3, AlBr 3, TiCl 4 and boron trifluoride with bullet ether. Chem.Soc.Jap. go, 2924 (1969) described approach. Other synthetic possibilities consist in the reaction of arylamidines with polychloraza-alkenes corresponding to that in Angew.Chem. 982 (1966) published the method or for example in the reaction of carboxylic acid chlorides or anhydrides with n- (aminoacyl) -trichloroacetamidines, by which also 2-aryl-4-methyl-6-trichloromethyl-s-triazines are easily available, as described in GB Patent Specification 912 112.

Methods for subsequent chlorination and bromination of alkyl substituents in s-triazines to haloalkyl-s-triazines, exchange reactions to replace bromine atoms in tribromomethyl groups with hydrogen and of trihalomethyl groups in s-triazines against amino and alkoxy groups can be found in J.org.

Chem. gg, 1527 (1964). The nitriles used for co-trimerization are partly commercial products or can be synthesized in a simple manner, e.g. by dehydration of carbonic acid amides or oximes or by reacting bromine aromatics with copper (I) cyanide.

The reaction of carboxylic acids or activated aromatics with chlorosulfonyl isocyanate (CSI) and then with dimethylformamide is often very advantageous in a working step which, via intermediate carboxylic acid amide -N- -sulfochlorides, leads to the nitriles, as described in Chem. Ber.

Egg, 2719 (1967).

In addition to the nitriles on which the bis-trichloromethyl-s -triazines mentioned in the examples are based, the following are also suitable, for example, as starting materials: 4-chloro-1-, 5-chloro-1-, 4-bromo-1-, 5 -bromo-1-, 2,6-dimethoxy-1-, 2,7-dimethoxy-1-, -nitro-1-, 3,6-dichloro-1-, 1-chloro-3-, 5-chloro- 2-, 6-bromo-2-, 4-methyl-1-, 5-methyl-1-, 2-ethyl-1-, 3,4-dimethyl-1-, 3,6-dimethyl-2-, 4 -isopropyloxy-1-, 7804588-7 4-bromo-3-methoxy-2-, 4- (2-chloropropyl) -1-, 4-allyloxy-1-, 4-cyclohexyloxy-1-, 4-n-octyloxy -1-, 4-phenoxy-1-, 4-p-tolyloxy-1-, 4-benzyloxy-1-, 4- (2-ethylmercaptoethyl) -1- and 4-phenyl-1-naphthonitrile and also 4- acetyl-1-, 4-acetoxy-1-, V4-hydroxy-1- and 4-methylmercapto-1-naphthonitrile; 2-chloro-, 4'-nitro-, 4'-bromo-, 3-bromo-biphenyl-4-carbonitrile, benzothiophene-2-carbonitrile, -5-carbonitrile and -7-carbonitrile, aibenzotymphene-α-carbonitrile, i benzofuran-2- and -3-carbonitrile, dibenzofuran-1-carbonitrile, -2-carbonitrile and -3-carbonitrile, anthracene-1-carbonitrile and -2-carbonylx11, 4-methyl-anthracephi-1-carbonitrile, s-clef anthracene-1-carbonitrile, phenanthrene-1-carbonitrile and -2-carbonitrile and 3-chloro-phenanthrene-9-carbonitrile, acridine-2-carbonitrile, fluoren-2-carbonitrile and -4-carbonitrile, quinoline-4-carbonitrile , isoquinoline-5-carbonitrile, benzoxazole-2-carbonitrile, xanthene-4-carbonitrile, acenaphthene-5-carbonitrile, 2,3-dihydrophenalen-6-carbonitrile and 1,2,3,4-tetrahydro-phenanthrene-9-carbonitrile .

With the exception of the unsubstituted 2-naphth-1-yl and 2-naphth-2-yl--4,6-bis-trichloromethyl-s-triazines, which, however, are also not yet known as photoinitiators, aryl-halomethyl- The s-triazines not known from the literature The new photoinitiators exhibit a wide range of uses. Thus, for example, they are useful as high activity initiators for photopolymerization reactions triggered by free radicals.

Suitable monomers, which are included in the corresponding polyadditions, are, for example, mono-, bis-, tris- and tetraacrylate and methacrylate of mono- and. multifunctional alcohols or phenols, acrylic and methacrylic acid amides, derived from mono- and multifunctional amines, vinyl esters and vinylamides. Such polymerizable pulps may additionally contain fillers, binders, polymerization inhibitors, dyes, dye diluents, plasticizers, adhesives or oxygen scavengers in various amounts. If these masses are applied in layer form to any chemically pretreated carriers, ie. for example on metal foils of steel, chrome, copper, brass, plastic or paper, on glass, wood or ceramics or on laminate materials of two or more of these substances, the photosensitive layer may also be provided with a cover layer, which prevents access of oxygen. 78045 88-7 The photoinitiators are already active in concentrations of around 0.5% of the whole solid of the pulp, an increase above 10% is generally inappropriate. Preferably concentrations of 0.4 - 7% are used.

Furthermore, the photoinitiators according to the invention are also to be used in such radiation-sensitive masses, the property change of which is initiated by acid catalysts, which are formed during photolysis of the initiator. Mention may be made of the cationic polymerization of systems containing vinyl ethers, N-vinyl compounds such as N-vinylcarbazole or special acid-labile lactones, in which case it is not excluded that radical precursors are also involved in some of these systems. As acid-curable pulps, there can also be mentioned aminoplasts such as urea / formaldehyde resins, melamine / formaldehyde resins and other N-methylol compounds as well as phenol / formaldehyde resins. Although the curing of epoxy resins generally takes place by Lewis acids resp. those whose anions exhibit a smaller nucleophilia than chloride and bromide, thus the anions of the halohydric acids formed on photolysis of the new photoinitiators, however, cures layers easily, which consist of epoxy resins and novolaks, in the presence of aryl-halomethyl-s- triazines. ß A further advantageous feature of the new photoinitiators is their ability to produce color covers in colored systems during photolysis; of color compounds, e.g. leuko compounds, induce color formation or cause batochrome color shifts and depressions in mixtures containing cyanine, merocyanine or styryl fiber bases. Also, e.g. in the mixtures described in DE-OS 1 572 080, which contain dye base, N-vinylcarbazole and a halogenated hydrocarbon, the halogen compound tetrabromethane is replaced by a fraction, ie, about 1/40, of its amount of aryl-bis-trichloromethyl-s triazine.

Color change is also desirable in the art, e.g. in the production of printing forms in order to be able to assess the copying result after the exposure even before the development. Instead of the acid sensor mentioned in DE-OS 2 331 377 and DE-OS 2 641 100, the present photoinitiators can be used to advantage.

Particularly preferred pulps according to the invention are, however, those which, in addition to aryl-halomethyl-s-triazines, contain as essential component a compound with at least one acid-cleavable C-O-C bond.

As acid-cleavable compounds may be mentioned in the first place: A) those with at least one orthocarboxylic acid ester and / or carboxylic acid? 8 amide acetal grouping, the compounds also having a polymeric character and the said groupings can appear as connecting elements in the main chain or as side substituents and 4 e 5 B) polymer compounds with recurring acetal and / or ketal groupings, in which both The aC atoms_of the alcohols required to make up these groups are aiifetic. Acid-cleavable compounds of type A as components in radiation-sensitive copying compositions have been described in detail in DE-05 26 10 842; copying materials¿ containing type B compounds are the subject of co-pending application 7804587-9.

As further acid-cleavable compounds, e.g. in addition, mention is made of the special aryl-alkyl acetals and aminals according to DE-AS 23 06 248, which are likewise degraded by the photolysis products of the aryl-halomethyl-s-trianines.

Such masses in which, by the action of actinic radiation, directly or immediately molecules, the presence of which significantly affects the chemical and / or physical properties of the mass, are transformed into, to a lesser extent, generally have an increased solubility, tack or volatility at the irradiated sites. . These portions can be removed by appropriate measures, such as ejaculation with a developer.

In the case of copying masses, in these cases we are talking about a positive working system; The novolac condensation resins, which have proved suitable for many positive-copying compositions, have proved to be particularly useful and advantageous as additives also in the copying compositions according to the invention with acid-cleavable compounds. They promote the strong differentiation between the exposed and unexposed layer portions upon development, especially the higher condensed resins with substituted phenols as formaldehyde condensation partners. The nature and amount of novolak resins may vary according to the purpose of use; Novolack shares of the total solid are preferred between 30 and 90, in particular 55-85% by weight. In addition, numerous other resins can be used simultaneously, preferably vinyl polymers such as polyvinyl acetate, polyacrylate, polyvinyl ethers and polyvinylpyrrolidones, which themselves may be modified by comonomers. The most favorable proportion of these resins complies with the technical requirements and the influence on the developing conditions and generally does not constitute more than 20% of the novolak. In small quantities, the photosensitive pulp for special requirements such as flexibility, adhesion, gloss, etc. may also contain substances such as polyglycols, cellulose derivatives such as ethylcellulose, wetting agents, dyes and finely divided pigments and, if necessary, UV absorbers.

It is preferred to develop with aqueous-alkaline developers customary in the art, which may also contain small proportions of organic solvents.

The carriers already specified in connection with the photopolymerizable pulps are also in question for positive-working copying pulps, in addition to the silicon and silica surfaces customary in microelectronics.

The amount of photoinitiator can also be very different in the positively working copy masses depending on the substance and layer. Favorable results are obtained between about 0.05 and about 10%, calculated on the total solid, preferably 0.1 - 5%. For layers with thicknesses above 10'pm, it is advisable to use a relatively small amount of acid sensors.

In principle, electromagnetic radiation with wavelengths up to about 600 nm is suitable for triggering reactions of the type described in the masses according to the invention. The preferred wavelength range is from 300 to 500 nm.

The variety of aryl-halomethyl-s-triazines, whose absorption maxima are partly to be found far within the visible part of the spectrum and whose absorption range extends over 500 nm, makes it possible to adapt the photoinitiator optimally to the light source used. In principle, however, sensitization is not excluded either. Examples of light sources are: Tube lamps, xenon impulse lamps, metal halide-doped mercury vapor high-pressure lamps and carbon arc lamps. In addition, in the case of the light-sensitive copying compositions according to the invention, exposure in conventional projection and magnification papers under the light from metal wire lamps and contact exposure with ordinary light bulbs is possible. The exposure can also be done with coherent light from a laser. Suitable for the purposes of the present invention are shortwave lasers of suitable power, for example argon laser, krypton ion laser, dye laser and helium-cadmium laser, which emit between 300 and 600 nm. The laser beam 7804588-7 is controlled by a predetermined programmed stroke and / or raster motion.

Irradiation with electron beams is an additional possibility of differentiation. Electron beams can thoroughly decompose and crosslink the acid-cleavable compounds containing the copying compositions according to the invention as well as many other organic materials, so that a negative image is generated if the unirradiated parts are removed by solvent or exposure without model and development. At lower intensity and / or higher writing speed of the electron beam, on the other hand, the electron beam achieves a differentiation in the direction of higher solubility, ie, the irradiated layer portions can be removed from the developer. The most favorable conditions can be easily determined by preliminary experiments.

It is preferred to use the radiation-sensitive compositions according to the invention in the production of molds, ie. in particular offset, autotypical gravure and serigraphic forms, in copy varnishes and in so-called dry resistance layer.

The following examples serve to further explain the invention. The preparation of a number of new aryl carbonic acid nitriles is first described, which serve as starting materials for the production of the photoinitiators.

Next, the preparation of some halomethyl-substituted s-triazines, which have been tested in copying compositions according to the invention, are described as acid-cleaving compounds. They were numbered as compounds 1 to 20 and are repeated under this designation in the use examples.

In the examples, the weight part and the volume part are in the ratio as g to ml. Percentage and quantity ratios refer to units of weight, unless otherwise stated.

Preparation of arylcarboxylic acid nitriles The following hitherto unknown arylcarbonic acid nitriles R-CN were synthesized analogously to those in Chem. Ber. Egg, 2719 (1967) left the regulations from the corresponding carboxylic acids R-COOH or directly from. alkoxyaryl compounds R-H by reaction with chlorosulfonyl isocyanate and subsequently with dimethylformamide: 780458S ~ 7 11 Table 1 Nitriles R ~ CN Nitrile R Melting point Starting nf 'W compound' 1 4- (2-Ethoxy-ethoxy) naphth-1-yl Oil; dest. in R-H ball tubes; air bath 130-140% s - 10'4 torr 2 4,7-Dimethoxy-naphth-1-yl 109-110 RH 3 4,5-Dimethoxy-naphth-1-yl 120.5-121.5 RH 4 5-Methyl-6-methoxy-naphth-2-yl 74-85 +) R ~ H 4-Methoxy-anthrac-1-yl 143-145 RH 6 '5-Merox: -naphth-1-yl-89-91 R -coon +) Raw product; purification on rose aryl-s-triazine.

The starting compound for nitrile No. 1,1- (2-ethoxy-ethoxy) -naphthalene, b.p. 91-95% / 0.002 torr, was prepared by alkylation of 1-naphthol with ethylene glycol monoethyl ether / p-toluenesulfonic acid chloride according to that in the monthly booklet Chem. âš, 588 (1951).

Preparation of bis-trichloromethyl-s-triazines In a stirred solution of 29.1 g of 1-ethoxy-naphthalene, 100 g of trichloroacetonitrile and 1.65 g of aluminum tribromide, hydrogen chloride gas is introduced at 0 ~ 5%.

After about 2 hours, the flask contents have stabilized; the gas supply is interrupted and the cooling is removed. When warming to room temperature, the reaction mixture partially returns to liquid form, it is cooled to 0% and hydrogen chloride gas is introduced again for 2 hours. After repeated self-heating, cooling to 0 - 5% and another two hours of introduction of hydrogen chloride, the now stabilized mixture is allowed to stand at room temperature overnight, dissolved in methylene chloride and shaken with some water. After drying the solution over sodium sulphate and removing the solvent in vacuo, the crude product obtained is freed by distillation in a carbon tube apparatus (air bath 110 - 130% / 0.1 torr) from unreacted starting material and simultaneously formed tris-trichloromethyl-s-triazine . The residue of 24.1 g consists of almost pure 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, which after crystallization from diethyl ether has a melting point of 154.5-1S6.5 ¶. 7804588-7 Table 2 12 Correspondingly, the aryl-bis-trichloromethyl-s-triazines listed in Table 2 are prepared, the crude product in some cases also being purified directly by crystallization, in other cases by additional filtration over silica gel with methylene chloride. as solvents and eluents.

Aryl-bis-trichloromethyl-s-triazines of formula I with n = m = 0 Photo- R I Melt- Long-wave absorption max. initi- f * point g _ (mm) ator Nr. (W) .Å max log É 1 +) Naphth-1-yl 128-129 363 4.05 2 2-Methoxy-naphth-1-yl 162-165 368 3.59 3 '4-Methoxy-naphth-1-yl 181.5 -183 388 4.33 4 5-Methoxy-naphth-1-yl 154-156 399 3.87 4-Atoxy-naphth-1-yl 154.5-156.5 7 388 4.34 6 4,5-Dimethoxy-naphth-1-yl 165-167 416 4.16 7 4,7-Dimethoxy-naphth-1-yl 136-137 404 4.27 8 '4- (2-EtOxy-etOXi) - 103-105 388 4.34 -naphth-1-yl _ 9 ++) Naphth-2-yl 7 210-211.5 367 3.52 I 1-Methoxy-naphth-2-yl 132-134.5 371 3.71 11 3 ~ Methoxy-naphth-2-yl 173-175 322 4.29 7 ass (sh) 1 2.98 12 6-Methoxy-naphth-2-yl 191.5-192 351 4.27 374 4.28 13 5-Methyl-6-methoxy-211-214 390_ 4.20 -naphth-2-yl _ 14 Quinol-3-yl1 - 201 -204 317 4.28 Zensopyran-3-yl 1ss-188.5 405 4.04 16 4-Phenyl-phenyl 149.5-151.5 332 4.49 17 Dibenzothien-3-yl 243.5-244.5 355 '4.30 18 Phenanthr- 9-yl1 4 181-184.5 l ses 4.os 19 4-Methoxy-anthrac-1-yl 221-225 '446 4.24 Acenaphth-5-yl1 204-205 _ 396 4.18 3 +)' Den i Bull. Chem. Soc. Jap. 42, 2924 (1969) mentioned melting point 216 - 219% could not be confirmed.

++) Literature: 210 - 212%. Example 1 A sheet of electrolytically roughened and anodized aluminum centrifuge is coated with a coating solution consisting of 6.7 parts by weight of trimethylene tetriacrylate, 6.5 parts by weight of copolymer of methyl methacrylate and methacrylic acid, acid number 115, 0.12 parts by weight of photoin , 64.0 parts by weight of ethylene glycol monoethyl ether, 22.7 parts by weight of butyl acetate and 0.3 parts by weight of 2,4-dinitro-6-chloro-2'-acetamido-5'-methoxy-4'- (β-hydroxyethyl-B'- cyanoethylJ-amino-azobenzene so that after drying a layer weight of 3 - 4 g / m2 is obtained.

Then the plate is provided with a 41 pm thick protective layer of polyvinyl alcohol (Mowiol 4/88, Hoechst AG), exposed under a line and grid model with a 5 kw metal halogen lamp at a distance of 110 cm for 30 seconds and developed with a 1.5 percent. sodium metasilicate solution.

A negative image of the model is obtained. A printing experiment with an offset printing plate thus produced was interrupted after 200,000 prints of still satisfactory quality.

Example 2 This example describes a negative dry resistor.

The following coating solution of 24.9 parts by weight of copolymer of 30 parts by weight of methacrylic acid, 60 parts by weight of n-hexyl methacrylate and parts by weight of styrene, 16.1 parts by weight of reaction product of 1 mole of 2,2,4-trimethylhexamethylene diisocyanate and 2 moles of hydroxyethyl methacrylate, 41 parts by weight of triethylene glycol dimethacrylate, 0.58 parts by weight of photoinitiator No. 3, 0.11 parts by weight of the dye used in Example 1 and 57.9 parts by weight of methyl ethyl ketone are centrifuged on a polyethylene terephthalate film to a dry weight of g / m 2. This material is laminated in a commercially available laminator at 120% on a support of insulating material which carries a 35 .mu.m thick copper substrate. After 60 seconds of exposure through a model, which in addition to the dash and raster motifs also contains a halftone step wedge, under the 5 kw metal halogen lamp from Example 1 and development by 0.8%. sodium carbonate solution remains a negative of dash »and 77304586-vad 14 raster motif and steps 1 - 5 of the halftone wedge as raised relief, step 6 is partially affected.

The resist layer resists etching processes, e.g. with ferric chloride, and influences from galvanic baths in the manufacture of conductor plates.

Example 3 In a crude centrifuge, a sheet of mechanically roughened aluminum is coated with a solution of the 4.3 parts by weight of phenol-formaldehyde novolac (melting range 110-120% according to DIN 53 181), 6 parts by weight of N-vinylcarbazole, 24 parts by weight of 2- (p-dimethylaminostyryl) -benstiazole, 0.25 parts by weight of photoinitiator No. 7 and 84.6 parts by weight of methyl ethyl ketone.- After drying, the photosensitive layer has a thickness of 1 - Zlpm.

The plate is pictorially exposed for 8 seconds according to Example 1, whereby the color tone of the layer on the image points changes from yellow to red-orange. Shaking the plate in the developing solution of 0.6 parts by weight of Na 2 H, 0.5 parts by weight of Na 2 SiO 3. H 2 O, 1.0 part by weight of n-butanol and 97.9 parts by weight of completely desalinated water remove in 75 seconds the unexposed layer parts, the exposed ones take on a greasy color during the treatment, so that one can print from such a plate on an offset printing machine.

Example 4 Example 3 is repeated by replacing the styryl dye base with the same amount by weight of the cyanine dye base 2- [1-cyano-3- (3-ethyl-2-benstiazolylidene) -propen-1-yl] -quinoline and photoinitiator No. 7 in the coating solution photoinitiator no. 13 in the same amount and coat a polyester foil. 16-second image exposure according to Example 1 allows the color of the image points to change from initially light red to deep violet.

By coating with the developer from example 3, the image-free places are removed. You get a negative image of the publishers.

This approach is suitable for the production of color foils. 7804-588-7 Example 5 A sheet of mechanically roughened aluminum is provided with a layer with the following composition, centrifuged from 10%. methyl ethyl ketone solution. 48.3 parts by weight of epoxy resin (of epichlorohydrin and bisphenol A, epoxy equivalent weight 182-194), 48.3 parts by weight of cresol-formaldehyde novolak (melting range 105-120% according to DIN 53 181), 2.9 parts by weight of photoinitiator no. 8 and 0.5 parts by weight of crystal violet. 60 seconds of image exposure according to Example 1 and 40 seconds of development with the developer from Example 3 produce a negative image of the publishers with haze-free image-free places.

If the epoxy resin is replaced with the same amount of the indicated novolak, a negative image will be visible for a short time during the development, but the developer resistance is so small that the entire layer is removed from the support after 30 seconds.

Example 6 The illustration of the layers, which contain the new photoinitiators and the acid-cleavable compounds, with electron beams is shown in the following: On mechanically roughened aluminum about 2 .mu.m thick-applied layers with the composition 74% novolak according to Example 5, 22% acid-cleavable compound, 3 .8% ïotoinitíatcr .0.2% dye is irradiated with 11 kV electrons. Under the conditions mentioned in Table 3, the irradiated sites are solubilized.

Develop with the developer of Example 3 or the following development solution: 5 parts by weight of sodium metasilicate. 9 H 2 O 3.4 parts by weight of trinatium phosphate. 12 H 2 O 0.4 parts by weight of monosodium phosphate, anhydrous 90.7 parts by weight of completely desalinated water. 7804588-7 16 oom Høx> Hm> fi oQ om w .mlo fl. oml fi> m uwuwH> uwE fl xocww flfl | m fi m æ fi0 x> Hm: wH> um fi uu: UO 3. m N13 1 Så ïnwu fi mco fl qoun ä. Hßwumqíom m a0x> Hmcm fi> uw fi uu: U0 3 w N13. SVA gn fi šmmcmn the .ußwumšøm m 1 Hmnëmxw A & u \ mH3onv .uz non Aumucsxmmv: Wum N fl muwcw _ K fl ß f c f U fl uwmc fl c fifi mxëmum mum fifl mxsmum UmHmuumcH mcwcwuwm umnx f w f ammuäm louom m flfi mnm f M 7804588-7 17 Example 7 For the preparation of a re magnification plate is dissolved 4.0 parts by weight of the in Example 5 of the novolak, 1.2 parts by weight of bis- (5-ethyl-5-butyl-1,3-dioxan-2-yl) ether of polyglycol 200, 0.2 parts by weight of photoinitiator No. 12 and 0.01 part by weight of crystal violet in 94.6 parts by weight of methyl ethyl ketone and centrifuged on a brushed aluminum plate.

Expose for 3 minutes with a Leitz Prado f = 85 mm 1: 2.5 projector with a 150-watt lamp through a slide at a distance of 65 cm.

By immersion in the developer indicated in Example 6, an enlarged positive copy of the black-and-white bar image on the slide is obtained within 30 seconds, which can be duplicated by printing in a small offset machine.

With similar results, one can instead of the bis-orthoester use the polymeric acetal of benzaldehyde and triethylene glycol in the same amount and also replace the photoinitiator No. 1? with initiator No. 20.

Example 8 A coating solution of 4.0 parts by weight of novolac according to Example 5, 1.2 parts by weight of the reaction product of 2,2,5,5-tetrahydroxymethyl-cyclopentanone and orthoformic acid trimethyl ester, is centrifuged on an electrolytically roughened and anodized aluminum sheet. 2 parts by weight of photoinitiator No. 1, 0.01 part by weight of crystal violet in 94.6 parts by weight of methyl ethyl ketone g - to a dry weight of 2.0 g / m 2 and is visually exposed for 40 seconds under the conditions of Example 1, after which a strong blue violet blue-green image contrast.

The plate is developed by coating with the developer according to Example 6 to a positive image of the model. Of this offset plate, 140,000 prints of satisfactory quality are obtained in a printing test.

A comparable copying result is obtained if the photoinitiator No. 1 is replaced by the same amounts by weight of the initiators No. 6, 4 or 18 or mixtures of these compounds. Example 9 A high layer thickness positive photoresist layer is prepared as follows: In 59.28 parts by weight of butan-2-one is dissolved 29.6 parts by weight of novolak according to Example 5, 8.9 parts by weight of bis- (5-ethyl-5 -butyl-1,3-dioxan-2-yl) -ether 'of 2-ethyl-2-butyl-propanediol, Å 0.12 parts by weight of photoinitiator No. 5 and 2.1 parts by weight of modified silicone glycol (commercially available paint aids ).

Using a spiral squeegee (wire bar no. 40), apply this solution to the cleaned copper surface of the laminate material of Example 2, allow the solvent to evaporate largely through twelve hours of storage at room temperature and dry the plates for 15 minutes under infrared radiation at 70%.

The imagery under a line model with 5 kwßmetal-halogen lamp from Example 1 in BO seconds exposed, 70'pm thick resist layer can be developed by spraying with 0.8-per cent. aqueous sodium hydroxide solution for 40 seconds.

Example 1OV> In a standard recipe, the new photoinitiators are tested for their acidity performance; OQS g novolac according to Example 5, 0.15 g bis-orthoester according to Example 9, 1 0.025 g photoinitiator and 0.012 g crystal violet in 12.5 ml methyl ethyl ketone 1 are centrifuged on plates with electrolytically roughened and anodised surface, so that the result is a layer thickness_of 1.5 - Zlpm, and is visually exposed for 40 seconds under the conditions specified in Example 1.

Layers, which contain the photoinitiators 2, 9, 10; 11, 15, 16, 17 and 19, are developed for 30 seconds by shaking in the developer of Example 6; the layer with the initiator 14 needs one minute with the developer from Example 3.

In all cases a positive copy of the originals is obtained.- Example 11 Aluminum sheets with electrolytically roughened and anodised surface are centrifuged with a solution of 4.7 parts by weight of novolak according to Example 5, 1.4 parts by weight of acid-splittable compound, 23 parts by weight of photoinitiator, 0.02 parts by weight of crystal violet and 93.05 parts by weight of butan-2-one, so that the result after drying is a layer thickness of about 1.7 .mu.m.

These layers are irradiated with an argon laser of 25 w light power over all spectral lines, the laser beam being focused through an optic in a spot with a diameter of 5 .mu.m. By varying the writing speeds, the sensitivity of the different combinations is determined. The exposed layer parts are triggered within 15 - 90 seconds during the treatment with the developer from example 6. By staining the unirradiated areas with bold color, the laser groove appears even clearer.

The following maximum writing speeds were obtained: Combination writing speed (m / sec) Polyacetal of propionaldehyde and 50 triethylene glycol / photoinitiator No. 12 Polyethylene of benzaldehyde and 75 1,5-pentanediol / photoinitiator No. 5 Bisortoester according to Example 9 ,. 25 'Photoinitiator No. 5.

Example 12 Aluminum sheets with electrolytically roughened and anodic, oxidized surface are coated with a solution of 2 parts by weight of novolac according to Example 5, 0.6 parts by weight of bis-orthoester according to Example 9, 0.1 parts by weight of photoinitiator and 0.016 parts by weight of crystal violet base in 50 parts by volume of methyl ethyl ketone _ in such a way that after drying a layer thickness of about 1.8 Pm is obtained. The resulting plates are exposed with the exposure apparatus given in Example 1 under a standard step wedge, the density of which is divided stepwise into 13 steps of 0.15, each, and developed for 30 seconds with the developer according to Example 6.

From the exposure times and the wedge steps depicted, the relative light sensitivities given in the following Table U are calculated, the sensitivity of the known compound 2-piperidino-6,6-bis- -tribromomethyl-s-triazine being arbitrarily assumed to be 1.

The photoinitiators used are three compounds from DE-AS 12 98 H1 fl (compounds 1, U and 5 in the table in column 2), the photoinitiators, 9 and 20 according to the invention and the additional photoinitiators 21, 22, 25 and 24 described below. column 2 of the table indicates the long-wave absorption maxima of all compounds.

Table Ä> -,, long-wave absorption- relatively light- Photoinitiator, maximum Änæx (nm) sensitivity 2-piperidino-H, 6-bis- 263 1 tribromomethyl-s-triazine_ 31Ä (sh) '2-methoxy-H, 6- bis- 26H 1,2-itribromomethyl-s-triazine 2,4,6-tris-tribromomethyl-250 (sh) H, s-triazine 24 '357 5 22 i 31114 g 13 _ 355 9 567 52 _21 341 62 23 373 69 B88 210 396 250 7894588-7 21 The photoinitiators 21, 22 and 25 were prepared as follows: a) 2- (N-ethoxy-naphth-1-yl) -N-methyl-6-trichloromethyl-s-triazine (photoinitiator 21) 1 23.6 g of U-ethoxy-1-naphthoic acid chloride and 20.4 g of N-acetimidyl-trichloroacetimidine were heated in 200 ml of toluene for 2 hours at 10,000.

The white precipitate formed was filtered off, the filtrate was diluted with 1000 ml of methylene chloride and washed successively with 2-n soda solution, 1-n hydrochloric acid and water, dried over sodium sulphate and liberated under reduced pressure from the solvent. The residue taken up in methylene chloride was filtered over silica gel and evaporated under reduced pressure. The residue was recrystallized fractionally from diisopropyl ether and then from a 1: 2 methylene chloride / methanol mixture. 5.01 g of photoinitiator 21 with a melting point of 133-135.5 ° C were obtained. b) 2- (Naphth-2-yl) -U-methyl-6-trichloromethyl-s-triazine (photoinitiator 22) U, 75 to 2-naphthoic acid chloride and 5.1 g of N-acetimidyl-trichloroacetimidine were reacted in 50 ml toluene as in a) and worked up, refraining from filtration over silica gel. Recrystallization from diisopropyl ether gave 5.17 g of photoinitiator 22, m.p. 126-12900. c) 2- (H-ethoxy-naphth-1-yl) -U, 6-bis-dichloromethyl-s-triazine (photoinitiator 23) g 2- (U-ethoxy-naphth-1-yl) -4,6- bis-trichloromethyl-s-triazine was stirred in 750 ml of glacial acetic acid for 4 hours at 7000 with H 2 g of zinc. The filtered reaction mixture was subjected to thin layer chromatography on silica gel with the solvent cyclohexane / ethyl acetate (97: 3). In addition to unreacted starting material, six pale yellow compounds were obtained, in which several chlorine atoms of the starting compound were replaced by hydrogen. The crude crude product was precipitated with water and recrystallized from toluene / ethanol mixture (1: 2). The largest part of the unreacted starting material was precipitated. The main reaction product was isolated from the mother liquor by preparative thin layer chromatography (silica gel solvent cyclohexane / ethyl acetate 97: 5) and recrystallized from methylene chloride / methanol 1: 2. Man, 1sQ4ssß-7 22 obtained photoinitiated grains 23 with melting points _113.5-115 ° c. d) 2- (H-ethoxynaphth-1-yl) -U-methyl-6-dichloromethyl-s-triazine (photoinitiator 2U) 7 g of 4-ethoxy-1-naphthoic acid chloride and crude N-acetimidyl-dichloroacetamidine, obtained from dichloroacetonitrile and acetamidinium chloride, in 70 ml of toluene was heated at reflux for 3 hours.

The reaction mixture was diluted with methylene chloride, filtered and the filtrate was washed successively with 2N soda solution, 1N H01 and water, dried over sodium sulfate and liberated under reduced pressure from the solvent.

9.1 g of residue were obtained, which contained as the main component the desired triazine. The further purification was successful by digestion of the crude product with diisopropyl ether, preparative layer chromatography (2 mm silica gel layer, solvent toluene / acetone in a volume ratio of 95: 5) and crystallization from a methylene chloride / methanol mixture (m.p. 98-100 ° C) . "'~.«

Claims (7)

LW in which R 1 represents H or OR, 7804588-7 Use of a triazine of the formula I c fl nctkn M R- <§ NI cmfäqn in which m een n tai from 0 to 3, wherein m + n is not greater than 5, and R an optionally substituted di- or polynuclear aromatic or heterocyclic aromatic, optionally partially hydrogenated group bonded via an unsaturated ring atom, as a radiation-sensitive compound in a radiation-sensitive copying material. 1 _ Use of a compound of the general formula I according to claim 1, characterized in that R represents a group of the formula II R 1 II H 2/3 R 2 represents H, Cl, an alkyl, alkenyl, aryl or alkoxy group and H 3 represents an alkyl, cycloalkyl, alkenyl or aryl group or R 1 and H 2 together represent an alkylene group Qche n and is zero. Use of a compound of the general formula I according to claim 1 in a radiation-sensitive copying material, which further contains an ethylenically unsaturated compound, which can enter into a polymerization reaction triggered by free radicals. HRS. Use of a compound of general formula I according to i7eo4sss-7. 2U according to claim 1 in a radiation-sensitive copying material, which further contains a compound whose solubility is altered by the action of acid. 5. ¿Use of a compound of general formula I according to. claim 1 in a radiation-sensitive copying material, which further contains a compound which is caused by cationic catalysts to cationic polymerization. Use of a compound of general formula I according to claim 4 in a radiation-sensitive copying material which contains a compound having at least one acid-cleavable C-O-C- bond, the solubility of which is increased by the action of acid. Use of a compound of the general formula I according to claim 6 in a radiation-sensitive copying material, which further contains a polymeric binder. REQUIRED PUBLICATIONS: Germany 1 298 414 (G03C 1/72) US 3 779 778 (96-115) Other publications: Wakabayashi, Ko et al: _ "Studies on s-Triazines", Bulletin of the Chemical Society of Japan, Vol 42 (1969) pp. 2924-2930.