DE3227913A1 - Photopolymerisable mixture, and photopolymerisable copying material produced therefrom - Google Patents

Abstract

A radiation-polymerisable mixture is described which contains a polymeric binder, a radiation-activatable polymerisation initiator and a polymerisable compound of one of the formulae I and II <IMAGE> in which R1 is a phenylene or biphenyldiyl group or a group formed from two phenylene radicals linked via a bridge, where the bridge is an oxygen or sulphur atom, a sulphone group, an optionally substituted alkylene or cycloalkylene group or a group of the formula (O-alkylene)nO where n is 1-3, R2 is an oxygen atom or the CH2-CH2-CO group, R3 is a hydrogen atom or a methyl radical, and R4 is a hydrogen atom or the <IMAGE> radical. The mixture is used for the production of photopolymerisable printing plates and for the production of photoresists and is distinguished by insensitivity towards oxygen.

Description

Photopolymerizable mixture and one produced therewith

Photopolymerizable Copy Material The invention relates to a photopolymerizable copy material Mixture, the essential constituents (a) a free-radically polymerizable Compound with terminal ethylenically unsaturated groups, (b) a polymeric Binder and (c) a radiation activatable polymerization initiator contains.

Such photopolymerizable mixtures are, for. B.

known from US-A-2,760,863, 3,060,023 and 3,149,975. As polymerizable ethylenically unsaturated compounds are there low molecular weight and high molecular weight Compounds with terminal or pendent vinyl or vinylidene groups, in particular acrylic and methacrylic acid esters of low or high molecular weight Polyhydroxy compounds. In practice so far have almost exclusively photopolymerizable materials based on such esters as polymerizable Connections enforced. Of these, it is especially the low molecular weight ones Representatives who are preferred in technology.

When processing photopolymerizable materials of the specified It is necessary to determine the influence of atmospheric oxygen on the radical genus Polymerization off or suppress as much as possible. This is mostly done by that the photopolymerizable layer with a strippable oxygen-impermeable Cover sheet (US-A 3 060 026) or with an oxygen-impermeable cover layer which is soluble in the developer (US-A 3,458,311). This prevents that during the light-induced polymerization oxygen diffuses into the layer and there leads to chain termination reactions, which result in incomplete polymerization and thus lower photosensitivity.

The disadvantage of the known materials is the additional work step, which is required for the application of the cover film or cover layer. Farther the image resolution when using self-supporting cover foils, which is usually have a thickness of around 20 µm, deteriorated in contact copying. Top layers that are soluble in the developer have a more rapid consumption of the same and an additional one Wastewater pollution result. Attempts have therefore been made to use photopolymerizable materials to produce that have sufficient photosensitivity even without a top layer show the image-wise polymerization.

In DE-A 28 30 143 such a material is described which certain polymerizable compounds of higher molecular weight and certain Contains initiator systems and therefore has a low sensitivity to oxygen. As polymerizable compounds are the acrylic or methacrylic acid ester used by reacting acrylic or r-ethacrylic acid with bis-epoxy compounds can be obtained.

Similar materials are described in BE-A 838 135 which are preferably used for the production of photoresist images.

The known.PIaterialien have a number of advantages Disadvantage that they can only be used to set certain desired properties. So it is z.

B. desired that photopolymerizable layers without oxygen inhibitors Top layer to be used, non-sticky, but flexible and none Show a tendency to crystallize. It is generally not possible to do this To achieve combination of properties without the addition of other monomers, whereby in turn, other advantageous properties are impaired.

The invention is based on the object of radiation-polymerizable To formulate mixtures that are characterized by high radiation sensitivity, which cannot be crystallized and still have layers with a non-sticky surface allow to produce, especially if on an oxygen-shielding top layer is waived.

The invention is based on a mixture that polymerizes by radiation can be and as essential components a) a radically polymerizable Compound with terminal acrylic or methacrylic acid ester groups, b) a polymer Binder.

c) contains a polymerization initiator which can be activated by radiation.

The mixture according to the invention is characterized in that it contains, as polymerizable compound (a), a compound of one of the general formulas contains where R1 is a phenylene, biphenyldiyl group or a group formed from two phenylene radicals linked by a bridge, the bridge being an oxygen or sulfur atom, a sulfonic group, an optionally substituted alkylene or cycloalkylene group or a group of the formula (O-alkylene ) nO with n = 1-3, R2 is an oxygen atom or the group CH2-CH2-CO, R3 is a hydrogen atom or a methyl radical and R4 is a hydrogen atom or the radical is.

Examples of groups R1 are phen-1,4-ylene, phen-1,3-ylene, biphenyl-4,4'-diyl, Tol-2,4-ylene, 1,3-xyl-4,6-ylene and l, l, l-triphenyl-ethan-4,4'-ylene. To be favoured Groups in which two phenyl groups are replaced by an oxygen or sulfur atom or by a substituted alkylene group, in particular by an oxygen atom or an alkylene group substituted by a carboxylic acid ester group.

The polymerizable ones contained in the mixture according to the invention Connections can be made by known methods. So z. B. valuable Phenols HO-R1-OH by reaction with phosgene (such as from H. Schnell and L. Bottenbruch in iilakromolekulare Chenie 57, 1 (1962)) in the corresponding bis (chlorocarbonic acid aryl ester) are converted. By subsequent Reaction with ß-hydroxyethyl methacrylate or with 1,3-bis (methacryloyl) glycerine compounds of the general formula I with R2 = oxygen are obtained.

By acylating aromatic compounds with chloroacetyl chloride under the conditions of the Friedel-Crafts reaction (e.g. according to A. Dechamp, J.P. Tortei and E. + larechal, Bull. Soc. chim. France 1972, 3234) chloroacetyl aromatics formed which, with acrylic or methacrylic acid, form polymerizable compounds of the general formula II can be used as acylation component in the Friedel-Crafts reaction succinic anhydride is used, so are W -carboxylpropiophenonderivate obtained whose esterification with hydroxyalkyl acrylate or methacrylate polymerizable Compounds of the general formula I with R2 = CH2CH2CO provides.

The photopolymerizable mixtures according to the invention also contain polymeric binders. A large number of soluble organic polymers can be used Find use.

Examples include: polyamides, polyvinyl esters, polyvinylacetaie, Polyvinyl ether, polyacrylic acid ester, Polymethacrylic acid ester, polyester, Alkyd resins, polyacrylamide, polyvinyl alcohol, polyethylene oxide, polydimethylacrylamide, Polyvinylmethylformamide, polyvinylmethylacetamide and copolymers of the monomers, which form the homopolymers listed.

Natural substances or converted natural substances are also used as binders into consideration, e.g. B. gelatin or cellulose ether.

With advantage, binders are used that are in aqueous alkaline Solutions are soluble or at least swellable, as there are layers with such binders develop with the preferred aqueous alkaline developers. Such Binders can e.g. B. contain the following groups: -COOH, -P03H2, -S03H, -S02NH2, -S02-NH-CO-. Examples include: maleinate resins, polymers from N- (p-tolylsulfonyl) carbamic acid (ß-methacryloyloxyethyl) ester and copolymers this and similar monomers with other ionomers, also methyl methacrylate-methacrylic acid copolymers or copolymers of methacrylic acid, alkyl methacrylates and methyl methacrylate and or styrene, acrylonitrile, etc.

However, styrene-maleic anhydride or styrene-maleic acid ester-fish polymers are preferred used.

A large number of substances can be used as photoinitiators Find. Examples are benzoin, benzoin ether, core quinones, z. B. 2-ethyl-anthraquinone, acridine derivatives, e.g. B. 9-phenyl-acridine, 9-p-ethoxyphenylacridine, 9-acetylamino-acridine, benz (a) acridine; Phenazine derivatives, e.g. B. 9,10-dimethyl-benz (a) phenazine, 9-methylbenz (a) phenazine, 10-methoxy-benz (a) phenazine, quinoxaline derivatives, e.g. B. 6.4 ' , 4 "-Triinethoxy-2,3-diphenyl-quinoxaline, 4 ', 4" -Dimethoxy-2,3-diphenyl-5-aza-quinoxaline- or quinazoline derivatives.

The mixtures according to the invention can, in addition to monomers, binders and photoinitiators contain a number of other common additives, e.g. B. Inhibitors to prevent the thermal polymerization of the monomers, hydrogen donors, sensitometric regulators, dyes, colored pigments and uncolored pigments.

These components are expediently selected so that they are in the as far as possible not the actinic radiation range that is important for the initiation process absorb too much.

Actinic radiation is to be understood as meaning any radiation whose Energy at least corresponds to that of short-wave visible light. Suitable is in particular long-wave UV radiation, but also electron, X-ray and laser radiation.

The mixtures according to the invention produce photopolymerizable layers with high photosensitivity. This is also the case when on oxygen shielding Top layer is dispensed with. The layers show Even without a top layer there is no tendency to stick and are stable when exposed against alkaline developers and acidic alcoholic wipers.

The manufacture of photosensitive materials using the mixture according to the invention is carried out in a known manner. So you can do this in absorb a solvent and the solution or dispersion by pouring, spraying, Apply immersion or application with rollers to the intended support as a film and then dry.

The copy layers are exposed and developed in a known manner. Aqueous, preferably aqueous-alkaline solutions, e.g. B. from Alkali phosphates or alkali silicates, suitable, where appropriate, small amounts of miscible organic solvents and wetting agents can be added. If desired, organic solvents or mixtures thereof can also be used as developers be used.

The mixtures according to the invention are particularly suitable in the form of a presensitized copying material on a suitable support, e.g. B. aluminum or zinc, for the photomechanical production of offset printing plates. they are also for the production of dry resist films, relief images, screen printing stencils and color proofing films are suitable, and use as a photoresist solution is also suitable possible.

The following first describes the production of the polymerizable compounds described. The following examples explain individual embodiments of the mixture according to the invention. The quantities of the layer components used are given in parts by weight (pbw). Percentages and proportions are, unless otherwise stated, to be understood in units of weight.

Examples of the preparation of compounds of the general formula I with R2 = oxygen atom A. Chlorocarboxylation of phenols of the formula HO-R1-OH a) In a solution of 75.3 g (0.25 mol) of 2,2-bis (4-hydroxyphenyl) butyl acetate 85 g (0.86 mol) of phosgene are introduced into 250 ml of toluene below 5 "C. is cooled to -10 "C and 60.5 g (0.5 mol) of dimethylaniline, dissolved in 60 ml of toluene, are added dropwise. After a reaction time of 15 hours at room temperature, the excess becomes Phosgene driven off by introducing a stream of nitrogen. After diluting with 250 ml of toluene is washed several times with water and the solvent is distilled off in vacuo. 66 g (0.15 mol; 62%) of 2,2-bis (4-chlorocarbonyloxyphenyl) -ess remain butyl acetate.

b) According to a) 47.5 g (0.15 mol) of 1,1,1-trichloro-2,2-bis- (4-hydroxyphenyl) ethane are obtained in 200 ml of toluene with 53 g (0.53 mol) of phosgene in the presence of 36.3 g (0.3 mol) of dimethylaniline implemented, 61 g (0.138 mol; 92%) of l, 1, l-trichloro-2,2-bis (4-chlorocarbonyloxyphenyl) ethane obtain.

B. Implementation of chlorocarbonyloxy aromatic compounds with hydroxyethyl methacrylates a) 17.7 g (50 mmol) of 2,2-bis (4-chlorocarbonyloxyphenyl) propane and 0.5 g of hydroquinone are dissolved in 100 ml of toluene, and at 20-25 "C are first 28.6 g (220 mmol) Hydroxyethyl methacrylate, then 12 g (120 mmol) of triethylamine were added dropwise. After 5 hours a further 100 ml of toluene are added and the reaction mixture is washed with water.

After concentrating the organic phase, 20 g (37 mmol; 74 %) 2,2-bis (4-methacryloyloxyethyloxycarbonyloxy-phenyl) propane (Compound 1).

b) 19.1 g (50 mmol) of 2,2-bis (4-chlorocarbonyloxyphenyl) acetic acid methyl ester are dissolved in 100 ml of toluene and treated with 0.5 g of hydroquinone. It will be 28.6 g (220 mmol) of hydroxyethyl methacrylate were added and 32 ml of triethylamine were added while cooling with ice added dropwise so that the temperature does not exceed 20 "C. After 5 hours, with Water added. The organic phase will ah separated, the watery one extracted with toluene and the combined organic phases repeated with Water washed. After the solvent has been distilled off, 22 g (38.6 anol; 77%) 2,2-bis (4-methacryloyloxyethyloxycarbonyloxyphenyl) acetic acid methyl ester (Compound 5).

c) To a solution of 9.6 g (25 mmol) of 2,2-bis (4-chlorocarbonyloxyphenyl) acetic acid methyl ester and 0.5 g of hydroquinone in 100 ml of toluene are 25 g (110 mmol) at room temperature L, 3-bis-methacryloylglycerol was added and 17 ml of triethylamine were added dropwise at 10 ° C. After 15 hours, work-up is carried out as under b). This results in 18 g (23.5 inmol; 94%) of compound 6.

d) 16.3 g (50 mmol) of 4,4'-bis-chlorocarbonyloxydiphenyl ether and 0.5 g of hydroquinone in 100 ml of toluene are mixed with 28.6 g (0.25 mol) of hydroxyethyl methacrylate at room temperature added, and then 33 ml of triethylamine are added dropwise with ice cooling. After 15 hours, it is diluted with toluene, washed well with water and the solvent distilled off in vacuo. There remain 18 g (35 mmcl; 70%) of 4,4'-bis (methacryloyloxyethyloxycarbonyloxy) ) diphenyl ether (compound 8).

e) 21.5 g (50 mmol) 1,1-8is- (4-chlorocarbonyloxyphenyl) -l-phenyl-ethane and 0.5 g of hydroquinone monomethyl ether are dissolved in 100 ml of toluene, 28.6 g (220 mmol) of hydroxyethyl methacrylate were added and 32 ml of triethylamine reacted at approx. 10 ° C.

After working up as under b), 26.4 g (44 mmol; 88 %) of compound 14.

f) 10.8 g (25 mmol) of l, l-bis (4-chlorocarbonyloxyphenyl) -1-phenyl-ethane are obtained and 12.5 g (55 mmol) of 1,3-bis-methacryloyl-glycerol in 100 ml of toluene in the presence of 0.3 g of hydroquinone reacted by adding 17 ml of triethylamine and worked up as described above, leaving 19.5 g (24.4 mmol; 98%) of the Connection 15.

g) 19.25 g (50 mmol) 1,1-bis (4-chlorocarbonyloxyphenyl) cyclohexane and 0.5 g of hydroquinone monomethyl ether in 100 ml of toluene are mixed with 28.6 g (220 mmol) Hydroxyethyl methacrylate is added and 34 ml of triethylamine are added dropwise with ice cooling.

After 20 hours, double the amount of toluene is added, repeated Washed out with water and the solvent was distilled off in vacuo. It remains 23.2 g (40 mmol; 80%) 1,1-bis (4-methacryloyloxyethoxycarbonyloxy-phenyl) -cyclohexane (Compound 17).

h) 9.6 9 (25 mmol) l, l-bis (4-chlorocarbonyloxyphenyl) cyclohexane and 0.2 g of hydroquinone are dissolved in 100 ml of toluene, and 14 g of 1,3-bis-meth- acryloyl glycerin are admitted. When 17 ml of triethylamine are added dropwise, the temperature rises to approx. 45 ° C., after 15 hours of post-reaction at room temperature, the work-up follows as described under g). The yield of compound 18 is 17 g (22 mmol; 88 %).

Table I Examples of compounds of the general formula I with R2 = oxygen and R3 = CH3 Ver bin- R1 R4 you-ng No. 1Ci CH3 2 2 to t1 1) CH3 Ver bin- R1 R4 manure No. 3 <H 4th > Pl 3 M¼2c4H9 H 4 --- M C02C4Hg 1 C ° 2CH3 6 MM M C ° 2CH3 H 7mm H. Ccl Ver R1 am- manure - No. 8th 9 r 10 S02 H 11 to H 12 G CH2 to H 13 bCH2 <fl R1 R4 am- manure No. CH7, 14> H I. CH3 15th 16 MM H CH i2 CH2 COOH H O 17 H. 18 to to M Ver R1 am- manure No. CH3 19 {2H CH2 - COOCH3 CH3 20 <IMM CH2-COOCH3

1) M is the rest Examples of the preparation of compounds of the general formula II A. Preparation of chloroacetyl compounds a) To a suspension of 200 g of aluminum chloride in 500 ml of dry methylene chloride, 81 ml (1.02 ml) of chloroacetyl chloride, dissolved in 200 ml of methylene chloride and after one hour 85 g (0.5 mol) of diphenyl ether, also dissolved in 200 ml of methylene chloride, added dropwise. It is refluxed for 10 to 15 hours, poured onto ice, acidified with conc. Acidified hydrochloric acid and extracted with methylene chloride.

After the organic phase has been concentrated, the remaining 4,4'-bis-chloroacetyl-diphenyl ether becomes recrystallized twice from toluene / hexane. Melting point 108 "C (Lit. 102" C) b) As under a) 84 g (0.5 mol) of diphenylmethane are reacted, with 50 g (31%) of 4,4'-bis-chloroacetyldiphenylmethane with a melting point of 122-124 "C.

c) To a mixture of 188 g of phenol, 60 ml of water and 120 g of caustic soda 180 g of 2,2'-dibromodiethyl ether are added dropwise at 100.degree. C. After 16 hours, in Poured ice water, suction filtered and recrystallized from ethyl acetate. 158 is obtained g (80%) 2,2'-bis (phenoxy) diethyl ether of melting point 60 "C.

80 g of aluminum chloride are suspended in 200 ml of methylene chloride, and 46 g of chloroacetyl chloride are added dropwise. After one hour, 52 g of bis (2-phenoxJ-ethyl) ether, dissolved in 80 ml of 'lethylene chloride, added dropwise, and the mixture is 15 hours for Heated to reflux. It is carefully poured onto ice, with 200 ml of conc. hydrochloric acid acidified, extracted with vlethylene chloride, the organic phase washed with water, concentrated and the product recrystallized from toluene / hexane. The result is 55 g (32%) 2,2'-bis- (4-chloroacetyl-phenoxy) -diethyl ether of melting point 134 C.

d) To a mixture of 94 g of phenol, 30 ml of water and 60 g of sodium hydroxide 160 g of 2-bromo-ethylphenyl ether are added at 100.degree. After a reaction time of 16 hours is poured into water, filtered off with suction and the product is recrystallized from ethyl acetate. 90 g (53 7>) 1,2-diphenoxyethane with a melting point of 95 ° C. are obtained.

120 g of aluminum chloride are suspended in 300 ml of ethylene chloride, and 70 g of chloroacetyl chloride, dissolved in 120 ml of methylene chloride, are added dropwise. After one hour, a solution of 64 g of 1,2-diphenoxyethane is added dropwise and that The reaction mixture was heated to reflux for 15 hours. It is poured on ice and how worked up under c). There are 45 g (41 t) of 1,2-bis (4-chloroacetylphenoxy) ethane obtained from melting point 165 r.

B. Reaction of chloroacetyl compounds with (ileth) acrylic acid a) 70 g of 4,4'-bis-chloroacetyl diphenyl ether, 60 g of methacrylic acid and 0.2 g of hydroquinone are dissolved in 350 ml of acetone, treated with 100 g of triethylamine and 5 hours for Heated to reflux. The precipitated ammonium salt is filtered off with suction, concentrated in vacuo, taken up in ethylene chloride, the organic phase with 2N HC1, 2N NaOH and with Water washed. After concentration, it is recrystallized from ethyl acetate, whereby 49 g (50%) of the compound 21 with a melting point of 103-105 "C result.

b) 25 g of 4,4'-bis-chloroacetyl-diphenyl sulfide, 19 g of thiethacrylic acid and 0.2 g of hydroquinone are dissolved in 350 ml of acetone, 38 g of triethylamine are added dropwise, and the mixture is refluxed for 5 hours. It is worked up as under a) and recrystallized from ethanol to give 21 g (66 g) of compound 23 of melting point 99 "C can be obtained.

c) 15.4 g of 4,4'-bis-chloroacetyl-biphenyl, 0.2 g of hydroquinone and 11 g of acrylic acid are dissolved in 300 ml of acetone, and 45 g of triethylamine are added dropwise. The reaction mixture is refluxed for 5 hours and as described under a) worked up. There are 13.6 g (72%) of the compound 26 with a melting point of approx. 190 "C obtained.

d) 16 g of 4,41-bis-chloroacetyl-diphenylmethane and 11 g of acrylic acid dissolved in 300 ml of acetone and stabilized with 0.1 g of hydroquinone. After adding 26 g of triethylamine is refluxed for 4 hours and, as described under a), worked up. After recrystallization from ethyl acetate 10 g (51%) of compound 28, melting point 118 "C.

e) 20.6 g of 2,2'-bis (4-chloroacetylphenoxy) diethyl ether and 13 g of methacrylic acid are as described under c), implemented, with 14.6 g (57%) of the compound 29 with a melting point of 138 "C can be obtained.

f) Is used in the reaction described under e) instead of 21ethacrylic acid the equivalent amount of acrylic acid is used, 18.5 g (77%) of the compound are used 30 received.

g) 18.4 g of 1,2-bis (4-chloroacety-l-phenoxy) ethane are in 300 ml Acetone reacted with 13 g of methacrylic acid under the action of 45 g of triethylamine. The reaction product is recrystallized from ethyl acetate 7, -2 g (36 %) of compound 31 with a melting point of 142-146 "C.

h) 6 g of 1,3-bis (4-chloroacetylphenoxy) propane and 0.1 g of hydroquinone are dissolved in 200 ml of acetone. After adding 4.1 g of methacrylic acid, 14.2 g of triethylamine are added dropwise, and the reaction mixture is refluxed for 6 hours heated. It is concentrated, in methyl Lene chloride added and washed with 2N hydrochloric acid, 2N sodium hydroxide solution and water. After distilling off the The solvent is taken up in ethyl acetate and the insoluble residue is filtered off. The yield of compound 33 is 3.6 g (48%).

Table II Examples of compounds of the general formula II Ver bin- R1 R3 manure No. 210-- CH3 22 b 4 H 23 -Q- S - <CH3 CH3 24 w Szu H 25 to CH3 Rl legr ~ R1 R3 manure No. 1 26 H. 27 tCH2 <CH3 28 eCH2 29 eo O ° to S CH3 30Q- H | - Ver R1 am- R'z manure No. 31 5 O to CH3 32 H. 33 o O <O5 CH3 Examples of the preparation of compounds of the general formula I with R2 = CH2CH2CO and R3 = H.

a) 22 g of bis [4- (3-carboxy-propionyl) phenyl] ether and 0.3 g of hydroquinone are dissolved in 350 ml of toluene and treated with 2 ml of concentrated sulfuric acid. The reaction mixture is heated to reflux on a water separator, and there are slowly added dropwise 23.5 g of hydroxyethyl methacrylate. After about 3 ml of an aqueous Phase separated, the toluene phase is washed with 2N NaOH and concentrated, whereby 32 g (90%) of compound 34 are obtained.

b) 18.5 g of bis [4- (3-carboxy-propionyl) phenyl] ether, 0.2 g of hydroquinone and 1.5 ml of concentrated sulfuric acid are refluxed in 350 ml of toluene. When 34 g of 1,3-bis (methacryloyl) -glycerol are added dropwise, 2.5 ml of water are separated away. The organic phase is filtered off from the polymeric residue formed washed with water and concentrated, 31 g (81%) of compound 35 remaining.

c) 3S, 6 g of bis [4- (3-carboxy-propionyl) phenyl] sulfide, 3 ml concentrated Sulfuric acid, 0.4 g of hydroquinone and 0.4 g of copper (I) oxide are dissolved in 350 ml of toluene heated to reflux, and 27 g of hydroxyethyl methacrylate are added dropwise. After this 4 ml of an aqueous phase have separated out and are washed with 2N sodium hydroxide solution and constricted. The A '~ si.Deu Wt?; 5 VrIndua is 56 g (92%).

d) 18.4 g of bis [4- (3-carboxy-propionyl) phenyl} methane with 1.5 ml. concentrated sulfuric acid, 0.2 g hydroquinone and 19.4 g hydroxyethyl methacrylate heated to reflux in 300 ml of toluene until 2.3 ml of water have separated out. It is then washed with 2N NaOH and water and concentrated in vacuo. It remains 20 g (55%) of compound 37.

e) 17.7 g of 4,4'-bis (3-carboxy-propionyl) biphenyl are as below d) described implemented, whereby 26.5 g (92%) of the compound 38 are obtained.

Table III Examples of compounds of the general formula I with R2 = CH2CH2CO and R3 = H. Ver R1 am- manure No. 34 e ° 5 H. 35 e ° t 1) 36 ffff H 37 oCH2 o H 38 H. EXAMPLE 1 The substrate used for printing plates was electrochemically roughened and anodized aluminum with an oxide layer of 3 g / m 2, which had been pretreated with an aqueous solution of polyvinylphosphonic acid.

A solution of: 2 pbw of a styrene-maleic anhydride copolymer was obtained with an average molecular weight of 20,000 and an acid number of 180-200 (Scripset 540 from Monsanto), 2 pbw of compound 4, 0.125 pbw of 9-phenyl-acridine and 0.06 pbw of des Azo dye from 2,4-dinitro-6-chlorobenzene diazonium salt and 2-methoxy-5-acetylamino-N-cyanoethyl-N-hydroxyethyl-aniline in 26 pbw of butanone and 14 pbw of butyl acetate on the carrier described above in the Centrifuged in a manner that a dry weight of 3.7-4 g / m2 was obtained. then the plate was dried for 2 minutes at 100 ° C. in a circulating air drying cabinet.

The printing plate obtained was produced by means of a 5 klff Iletal I.halonenid lamp at a distance of 110 cm between the lamp and the vacuum frame under a 13-step Exposure wedge exposed with density increments of 0.15 for 40 seconds.

Then the plate was manually made with a developer as follows Composition developed: 3.0 pbw sodium metasilicate x 9 water, Q, 03 pbw non-ionic Wetting agent (coconut fatty alcohol polyoxyethylene ether with approx. 8 oxyethylene units), 0.003 pbw of antifoam agent, 96.967 pbw of fully demineralized water.

5 fully crosslinked wedge steps were obtained.

Example 2 The coating solution given in Example 1 were used 0.04 g amorphous, highly porous silica, mean particle size 8 μm, (Syloid Al 1) was added, and the dispersion was spun onto the substrate in such a way that that a layer weight of 3.5 g / m2 was obtained.

The plate was processed in the same way as in Example 1.

5 fully crosslinked wedge steps were obtained.

The printing plate reached one print run in the conventional dampening system of 180,000 sheets, in the alcohol dampening unit one of 90,000 sheets.

Example 3 The coated plate from Example 2 was dried with a 15% aqueous solution of polyvinyl alcohol (12% residual acetyl groups, K value 4) coated.

After drying, a top layer was made with a weight of 5 g / m² obtain.

Parts of the plate were then measured using a metal halide lamp 5, 10, 20 or 40 seconds under a 13-step exposure wedge with density increments exposed by 0.15 and then with the developer solution described in Example 1 developed.

In a further experiment, the plate was 5 seconds after exposure heated at 100 ° C in a circulating air drying cabinet and then developed.

The following table shows that the layer works strictly reciprocally and that the post-heating step results in a significant increase in the number of fully crosslinked wedge steps: Exposure time (seconds) 5 5 10 20 40 Wedge steps without 7 heating 3 5 7 9 Wedge steps with 11 heating 8 9 11 13 Layers with other monomers (e.g. trimethylolethane triacrylate) crosslink under the influence of oxygen (ie without a top layer) much less than with a top layer (3 wedge steps without a top layer, 9 wedge steps with a top layer at 40 seconds exposure time).

Example 4 A coating solution was obtained from 1 part by weight of a methyl methacrylate / methacrylic acid copolymer with a molecular weight of 30,000 and an acid number of 117.1 pbw of that given in Example 1 Styrene-maleic anhydride copolymer, 2 pbw of compound 3, 0.125 pbw 9-phenyl-acridine, 0.07 pbw of the blue dye described in Example 1 and 0.04 pbw of that in Example 2 specified silica in 21 pbw butanone and 11 pbw butyl acetate produced and spun onto the aluminum carrier described in Example 1 so that a Layer weight of 5 g / m² was obtained.

Exposure, development and evaluation were carried out as in Example 1.

4 fully crosslinked wedge steps were obtained.

Example 5 On the support given in Example 1 were Solutions of the following composition are centrifuged so that a layer weight of 3.5 g / m2 was obtained: 2 pbw of the copolymer specified in Example 1, 1.8 Gt one of the compounds listed in Table IV, 0.5 Gt 9-phenyl-acridine and 0.05 pbw of the azo dye from Example 1 in 23 pbw butanone, 12 pbw butyl acetate and 12 pbw of ethylene glycol monomethyl ether.

The plates were exposed for 40 seconds and with that in Example 1 specified developer solution.

The following number of fully cross-linked wedge steps was obtained: Tabel IV connection no. Wedge steps connection no. Wedge steps 1 2 20 4 2 1 - 2 21 4 3 3 - 4 22 4 4 4 23 1 2 5 5 24 2 6 3 25 2 7 2 26 1 - 2 8 4 27 3 9 4 28 2 - 3 10 3 29 2 11 3 30 1 - 2 12 4 31 2 13 2 - 3 32 3 14 3 33 2 - 3 15 2 - 3 34 4 16 3 35 3 - 4 17 2 36 2 18 3 37 3 19 5 38 2 - 3 Example 6 6.5 pbw of a terpolymer from n-hexyl methacrylate, methacrylic acid and styrene (60: 30: 10 by weight) with an average Molecular weight of approx.

35,000, 5.6 pbw of the monomer described in Example 1, 0.2 pbw 9-phenyl-acridine, 0.03 pbw of the blue azo dye from Example 1 in 25 pbw of butanone, 2 pbw of ethanol and 1 pbw of butyl acetate were biaxially drawn and heat-set Polyethylene terephthalate film with a thickness of 25 / um spin-coated so that after drying a layer weight of 35 g / m2 was obtained at 100 ° C.

The dry resist film produced in this way was coated with a commercially available Laminating device at 1200C on a copper foil laminated with 35 µm thick Phenolic laminate laminated and 20 seconds with a commercially available Exposure device exposed. A line template with line widths served as a template and distances down to 80 / µm.

After the exposure, the polyester film was peeled off and the layer with the developer solution described in Example 1 in a spray developer Developed for 90 seconds.

The plate was then rinsed with tap water for 30 seconds, 30 seconds Etched in a 15 dough ammonium peroxydlsulfate solution and then one after the other Galvanized in the following electrolyte baths: 1) 30 rinsing in a copper electrolyte bath from Schlötter, Geislingen / Steige, type "shiny copper bath", current density: 2.5 A / dm2 Metal build-up: approx. 14 / around 2) 10 minutes in a "Norma" type nickel bath from the company Schlötter, Geislingen / Steige Current density: 4 A / dm2 metal structure: 9 / um The plate showed no infiltration or damage.

The plate could then be stripped in 5% KOH solution at 50.degree and the exposed pluckers are etched away in the usual etching media.

Example 7 The photoresist solution described in Example 6 was made as described there on a laminated phenoplastic laminate board with a 35 μm thick copper foil centrifuged and dried (30 g / m2).

Analogously to Example 6, the plate was exposed, developed and electroplated, instead of nickel plating, the following procedure was used: 15 minutes in a lead-tin bath LA from Schlötter, Geislingen / Steige Current density: 1 A / qdm Metal structure: 15 / um This plate also showed no infiltration or damage and left remove the coating with KOH solution and etch with common etchants.

Table V Connection no. Wedge steps 4 4 5 5 19 5 21 4 example 8 A solution of the following composition was applied to the support given in Example 1 centrifuged in such a way that a layer weight of 3.5 g / m² was obtained: 2.6 pbw Compound 19, 6.5 pbw of a styrene-maleic ester copolymer with a Acid number of 145 - 160 and a softening point of 140 - 1600C, 70 pbw of ethylene glycol monomethyl ether, 0.1 pbw of 9-phenyl-acridine, 0.035 pbw of the azo dye indicated in Example 1 and 1.0 pbw of the reaction product from 1 mol of 2,2,4-trimethylhexamethylene diisocyanate and 2 moles of 2-hydroxy-ethyl methacrylate.

The coated plate was then 2 minutes at 100 "C im The circulating air drying cabinet was dried and provided with a top layer as in Example 3. On a Laserite (R) device 150 R from Eocom Corp., which works with an argon-ion laser was equipped, the plate was irradiated with 200 mW and 1200 L / 2.54 cm (5.3 mJ / cm2). The image contrast after irradiation was good.

The plate was then developed with the developer of Example 1. The number of fully crosslinked wedge steps of a halftone step wedge was on exposure and immediately following development 3.

If the same plate was processed in the same way, however between exposure and development in one Heating device 7 seconds was heated to 80 ° C, wedge steps were obtained.

The proof and edition printing were done in a Heidelberg offset printing machine GTO carried out with Dahlgren dampening system and totaled 100,000 sheets. In the case of the reheated Plate, the print run increased to 150,000 sheets.

Claims (5)

Radiation-polymerizable mixture which is used as a essential components a) a polymerizable compound with terminal acrylic or methacrylic ester groups, b) a polymeric binder. c) contains a polymerization initiator which can be activated by radiation, characterized in that it is a compound of one of the formulas as polymerizable compound (a) contains, where R1 is a phenylene, biphenyldiyl group or a group formed from two phenylene radicals linked by a bridge, the bridge being an oxygen or sulfur atom, a sulfonic group, an optionally substituted alkylene or cycloalkylene group or a group of the formula (O-alkylene ) nO with n = 1-3, R2 is an oxygen atom or the group CH2-CH2-C0, R3 is a hydrogen atom or a methyl radical and R4 is a hydrogen atom or the radical is. 2. Mixture according to claim 1, characterized in that it is a compound of a of formulas I or II, in which R3 is a methyl group. 3. Mixture according to claim 1, characterized in that there is a compound contains one of the formulas I or II in which R1 is a diphenyl ether group. 4. Mixture according to claim 1, characterized in that there is a compound one of the formulas I or II contains, serine R1 is a diphenylalkanoic acid ester group is. 5. Mixture according to claim 1, characterized in that it is a polymer Contains binder that is soluble or at least swellable in aqueous alkaline solution is.