JPS5933893B2 - Photosensitive reproduction compositions containing synergistic photoinitiator systems - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The invention can be used industrially in the form of a solid layer or as a liquid compound and in fact contains at least one
The present invention relates to novel photosensitive reproduction compositions comprising a photoinitiator system consisting of a polymeric binder, at least one ethylenically unsaturated polymerizable compound, and at least two photoinitiators.

The term "polymerizable ethylenically unsaturated compound" according to the present invention means an addition polymerizable low-molecular polyfunctional monomer as well as a large number of photocrosslinkable unsaturated polymer compounds.

Many of these compounds have been described as photoinitiators for the photopolymerization of unsaturated compounds.

That is, for example, chalcones, aromatic ketones or diketones, polynuclear quinones of the anthraquinone series or phenanthrenequinone series, benzanthrone derivatives or azabenzaanthrone derivatives, aromatic nitro compounds, hexerocyclic six-membered compounds such as acridine, phenazine, Quinoxalines, quinazolines, pyrylium and thiapyrylium compounds, heterocyclic five-membered compounds such as benzothiazoles, benzoxazoles or benzimidazoles, and organic dyes such as eosin, methylene blue or fuchsin are known to be used as photoinitiators.

Due to the structure of these molecules, these photoinitiators can almost only be used as a special layer and do not actually exert their effects when used in the form of other polymerizable compositions. lose.

In order to obtain a high degree of crosslinking, it is often necessary to use large amounts of initiator, where the initiator charge is limited by its solubility in the photosensitive reproduction composition.

This lack of compatibility is observed when the reproduction composition is exposed to various temperatures in practice under unfavorable conditions of storage or transportation.

Under these conditions, the photoinitiator leaches out and/or crystallizes, resulting in impaired photosensitivity and, in some cases, significantly reducing the adhesion of the photosensitive layer and actually shortening the life of the copying composition. reduce The use of unsaturated ketones of the formula as photoinitiators in reproduction compositions containing monomers having vinyl or vinylidene groups is disclosed in German Patent Application No. 2060
It is known from the publication No. 575.

The photosensitivity of layers containing only compounds of this type is not sufficient even when used in relatively large amounts, and West German Patent No. 113
7625, when used in combination with special compounds known to be suitable photoconductors, such as moderately substituted polynuclear heterocyclic compounds containing groups exhibiting electron donor action. Nor do they satisfy the requirements for high photosensitivity combined with a high degree of crosslinking in the photoresist material, which must be corrosion resistant to electroplating baths. The object of the present invention is to obtain a highly effective photoinitiator system which has good compatibility with all other components of the copying composition, and which is particularly suitable for low molecular weight monomeric acrylates and alkyl acrylates. They are suitable for photopolymerization and provide the reproduction compositions according to the invention with very good photosensitivity under special conditions combined with a high degree of crosslinking. By the way, the photosensitivity of a copying composition containing a compound corresponding to general formula (I) (described below) as a photoinitiator in addition to the binder and the monomer acrylate or alkyl acrylate is due to the fact that the carbonyl group is directly attached to the p-dialkylaminoaryl group. Alternatively, it has been found that it can be synergistically increased by adding a second photoinitiator of the type of compound represented by the formula (below) which is bonded via a vinyl group.

The present invention relates to a photosensitive reproduction composition comprising at least one polymeric binder, at least one ethylenically unsaturated compound having at least two addition-polymerizable double bonds, and a photoinitiator system, which composition The photoinitiator to be used consists of at least two components a and b, wherein component a has the general formula I: [wherein R.

is 0. Represents S or NRl, R1 is hydrogen, number of carbon atoms is 1
~6 saturated or unsaturated unsubstituted hydrocarbon groups, 1 carbon atom
~6 saturated or unsaturated hydrocarbon groups (which are substituted by hydroxynole groups, alkoxy groups, alkoxycarbonyl groups, acyl groups, acyloxy groups and/or halogen atoms), aralkyl having 7 to 10 carbon atoms basis,
or an acyl group having 2 to 18 carbon atoms or a polyalkylene oxide group of the general formula: or (in the formula, a-2 to 4, and n = 1 to 10), R2 is hydrogen, an alkoxy group, or a polyalkylene oxide group having 1 carbon atom ~6 alkyl group or halogen atom]
Component b is at least one compound of the general formula: [In the formula, R3 represents an alkyl group having 1 to 6 carbon atoms, and R
4 represents an alkyl group having 1 to 6 carbon atoms; R5 is hydrogen; an alkyl group having 1 to 6 carbon atoms; an alkoxy group (the alkyl group has 1 to 4 carbon atoms); 12 aryl group or dialkylaminostyryl group, and X represents O or 1.

6-oxoanthra(1,9-Cd)pyrazole-2
Compounds corresponding to the (6H) type (formula 1: RO-NRl) include hydrogen at the 21-position (-R1), an unsubstituted lower alkyl group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, hydroxy ole, alkoxy, alkoxycarbonyl, preferably ethoxycarbonyl, acyl, acyloxy or substituted by halogen, preferably chlorine or bromine, or having 1 to 6 carbon atoms, preferably It may be substituted with 2 to 4 substituted alkyl groups (1 to 6 indicating the number of carbon atoms are linearly arranged in the substituted alkyl group).

Other suitable substituents in position 21 are allyl, aralkyl having 7 to 10 carbon atoms, preferably benzyl or tolyl, or acyl having 2 to 18 carbon atoms.

Among the acyl groups, from acetyl to stearyl, benzoyl, methoxybenzoyl, ethoxybenzoyl, methylbenzoyl, benzosulfonyl or tosyl are preferred.
Anthracene basic structure (Formula 1: RO=0,.S,NRl
) The substituent R2 in the 6-membered ring is 71, 8-91 or 1
It may be in the 0-1 position, preferably in the 10-1 position, and may be hydrogen, halogen, preferably chlorine or bromine, or an alkoxy group, preferably a methoxy or ethoxy group, or a carbon atom number of 1 to 1.
The alkyl group of 6 may advantageously be a methyl or ethyl group.

Suitable substituents for R3 and R4 in compounds of formula type are unsubstituted lower alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, which may be arranged in a straight or branched chain. and R3 and R4 may be the same or different. R
The substituent in 5 is hydrogen, a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, an alkoxy group, preferably a methoxy group, an ethquin group, an isoproboxy group, a propoxy group or a butoxy group, a carbon atom number. 6 to 12 aryl groups,
It may advantageously be a phenyl group, or a substituted aryl group, preferably a tolyl, dialkylaminophenyl or anisyl group, or a dialkylaminostyryl group.

X is O or 1, preferably O. Compounds corresponding to formula 1 (RO is N-R1) may contain any of the following groups as substituents in the 2-position: The following compounds are commonly used as compounds of the formula I type: Will be:
The mechanism of cooperation is still unknown.

However, it has surprisingly been found according to the invention that by combining a compound corresponding to formula 1 with a compound of the formula, in some cases by one or more of the grades depicted, it is possible, for example, to completely regenerate a step wedge. It has been found that the number of stages used provides significantly increased photosensitivity over the individual sum of each component used. Although all compounds of the formula contain a p-dialkylaminophenyl group, the presence of this group alone is not sufficient to predict synergy for compounds of this type. This means that, for example, compound 118 may be compound A. This is evidenced by the fact that when combined with B or C no photoinitiators with synergistic action result.

The effect of compound 118 is not increased by these compounds (A.B), or even decreased in the case of compound (C). It is therefore further unpredictable that the photoinitiator action of compounds of formula 1 would be significantly increased when combined with compounds of formula.

Synergy is clearly obtained at all mixing ratios, as is evident from Example 4 below.

The weight ratio of the compound of formula 1 to the compound of formula used in the present invention can vary within a wide range from 2:98 to 98:2.
Preference is given to ratios of 80:20 and 20:80; within this range, mention may be made of ratios of 40:60 to 60:40.

The reproduction compositions according to the invention consist as basic components of a binder, a liquid and/or solid polymerizable organic compound, and a photoinitiator mixture of the above-mentioned type corresponding to formula 1.

Suitable monomers are ethylenically unsaturated compounds, such as commercially available acrylic and methacrylic esters such as diethylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycol;
and those of trimethylolethane and trimethylolpropane, as well as diglycerol diacrylate, guaiacol glycerol ether diacrylate, neopentyl glycol diacrylate, 2,2-dimethylolbutanol mono(3)-diacrylate, U.S. Pat. No. 326
1686, reaction products of trimethylolpropane, alkylene oxides and acrylic or methacrylic acid according to U.S. Pat. No. 3,380,831, and acrylates and methacrylates of polyesters containing hydroxyl groups. It is.

Compounds and other monomers suitable for use in photopolymer layers according to the invention are described, for example, in US Pat. No. 2,760,863 and US Pat. No. 3,060,023. Urethane group-containing monomers known from German Patent Application No. 2064079 and German Patent Application No. 23
The biuret group-containing monomers known from JP 61041 can likewise be used.

As is clear from this list of compounds, the present invention is not limited to the use of certain specific polymerizable monomers, but it is clear that the monomers have at least two sites of ethylenically unsaturation and are polymerizable by addition polymerization. It needs to be possible.

When polyunsaturated polymeric compounds are used, they must be photocrosslinkable or addition-polymerizable with low molecular weight monomers. For example, the unsaturated compounds listed below are suitable for use in photosensitive reproduction compositions. Prepolymers of polyvinyl cinnamate and unsaturated esters, such as diallyl isophthalate, or allylimides of the polymers described in German Patent Application No. 2,203,732 and US Pat. No. 2,902,710
If commercially available or preferably artificial monomers are used, polyvinylidene acetate containing linear vinylidene groups according to the specification
These usually contain small amounts (approximately 50-100 ppm) of initiator to prevent thermally induced polymerization.

In order that the reproduction composition according to the invention does not deteriorate even under extreme storage conditions, the amount of initiator can be increased by 1% relative to the weight of monomer used.

The following compounds can be used as thermal initiators:
p-Methoxyphenol, hydroquinone, alkyl- or aryl-substituted quinones and hydroquinone, tertiary butylcatechol, pyrogallol, copper resinate, naphthylamine, β-naphthol, copper(1) chloride, 2,6-di-tert-butyl -p-cresol, phenothiazine,
Pyridine, nitrobenzene and dinitrobenzene, p-
Tolquinone, chloroanyl, and thiazine dyes, such as thionipple-GO, are further added to the photopolymerizable copying composition in a known manner with one or more binders, such as solvent-soluble polyamides, polyvinyl acetate, polymethyl (meth)-acrylate, polyvinyl butyral. , cellulose ethers or cellulose esters, polyalkylene ethers, condensation polymers of glycols and dibasic acids, copolymers of styrene and maleic anhydride, which are soluble in alkaline solutions or at least swellable or copolymers of ethylene and maleic anhydride or alkyl methacrylates and methacrylic acid according to German Patent Application No. 2064080, German Patent Application No. 23
Terpolymers of styrene, alkyl methacrylate and methacrylic acid according to German Patent No. 63806, and terpolymers of methyl methacrylate and N-(p-toluene-sulfonyl) monocarbamic acid-(β-methacryloxy) monoethyl ester according to German Patent Application No. 2027466 Consisting of copolymers, as well as maleic acid resins, terpene phenolic resins and others.

Since aqueous alkaline developers are often used in the development process, binders that are alkali soluble or softenable in aqueous alkaline solutions are advantageous.

Examples of binders of this type are copolymers of styrene and maleic anhydride and copolymers of alkyl methacrylates and methacrylic acid, terpolymers of styrene, alkyl methacrylates and methacrylic acid, maleic acid resins, and German patent application no. This is a copolymer described in Japanese Patent No. 2205046. Furthermore, plasticizers, adhesion promoters, hydrogen donors, oxygen absorbers, dyes, pigments, color formers, UV-absorbing substances and sensitivity modifiers can also be added to the copying compositions according to the invention.

The type and amount of these additives are determined by the field of application for which the reprographic composition is intended.

Furthermore, care must be taken to ensure that the added substances do not absorb too much of the actinic radiation required for the initiation process and thus do not reduce the actual photosensitivity of the reproduction composition. Suitable plasticizers are, for example, dibutyl phthalate, diisooctyl adipate, nitrate esters, alkyl and aryl phosphate esters, chlorinated paraffins, glycols and aliphatic polyols.

In order to ensure good storage properties at high atmospheric humidity, it is preferred to use water-insoluble plasticizers. Adhesion promoters are added in all cases where the photosensitive reproduction composition is to be overexposed, for example when it is to be used as a photoresist material.

The following adhesion promoters have been found to be advantageous: monomeric or polymeric organosilanes, nitrogen-containing xerocyclic compounds, such as U.S. Pat. No. 3,645,722, U.S. Pat.
No. 234 and No. 3827908, as well as West German Patent Application No. 2028773
Heterocyclic mercaptans according to German Patent Application No. 2448821, mercaptoalkanoic acid anilides according to German Patent Application No. 2448821 and German Patent Application No. 244885
Mercaptoalkanoic acid ester according to Publication No. 0.

Suitable hydrogen donors which can be used in known processes are, for example, substances containing aliphatic ether groups or cyclic β-dicarbonyl compounds.

If appropriate, it is also possible for a binder or a polymerizable substance to have this effect, provided that this substance contains unstable hydrogen atoms. Furthermore, the photopolymerizable copying composition according to the invention may contain dyes and/or pigments, which can be added to increase contrast or to solidify the layer.

Suitable dyes are described, for example, in US Pat. No. 3,218,167 and US Pat. No. 3,884,693. The photosensitive copying composition according to the invention may further contain UV-absorbers which act as anti-rayon filters.

Suitable colorless substances are described, for example, in West German Patent Application No. 22
It is described in Publication No. 43182. Within the scope of the present invention, the basic components of the photosensitive reproduction composition are preferably in the following proportions, where the percentages are by weight and are calculated with respect to the total solids content of the composition.

For industrial use, the photosensitive copying compositions according to the invention can be used in the form of solutions or dispersions, for example as so-called photoresist compositions, which can be applied by the user himself to special supports. is a process customary for example in chemical milling, in the preparation of printed circuits or stencils or in the production of plates, screen printing stencils and the like, followed by drying, exposure and image-wise development.

In this case, each component of the photosensitive copying composition is dissolved in a suitable solvent. Suitable solvents are alcohols, ketones, esters, ethers, amides, hydrocarbons and the like. Partial ethers of glycols or ketoalcohols have been found to be particularly useful solvents. However, the choice of solvent is actually determined by the binder selected. Furthermore, the photosensitive copying composition according to the invention can be sold in the form of a solid photopolymerizable layer disposed on a base material, which can be used in printing plates, relief images, corrosion protection, stencils, matrices, screens, etc. Used to make printing plates, single copies and the like. A particularly important field of use is the use as storable presensitized printing plates for lithography, relief printing or intaglio printing. The base material is coated with the composition according to the invention from a suitable organic solvent or solvent mixture by casting, spraying or dipping methods.

Suitable support materials are, for example, magnesium, zinc, copper, mechanically, chemically or electrochemically roughened aluminum,
Anodized aluminum, steel and polyester or acetate film, PerlOn
The material may be gauze or the like, and its surface can be pretreated if necessary.

The base material can be provided as the final support material or as an intermediate support material to which the photosensitive reproduction composition is transferred to the workpiece by a lamination process. If thick photopolymer layers are to be processed, for example with a thickness in the order of 10, the copying composition according to the invention is kneaded without melting, for example in a three-roll mill, and then at a pressure of 30,000 to 50,000 kp and a temperature of 90 DEG C. This can be done by pressing on the support material for 1 minute. When crosslinking is carried out solely by polymerization of ethylenically unsaturated monomers, it is generally preferred that the photosensitive copying composition according to the invention be protected from the action of atmospheric oxygen during exposure, since oxygen This is because they tend to form radicals within the layer and inactivate them.

This type of oxygen exclusion was demonstrated, for example, in West German patent application No. 1.
This can be easily achieved by providing an oxygen-impermeable barrier layer as described in Japanese Patent Nos. 572153 and 2036585. When the photosensitive copying composition contains a polymer compound capable of photochemical crosslinking reaction,
With low-molecular-weight acrylates or alkyl acrylates, crosslinking occurs very little or less, and such a barrier layer is not necessary, since in this case photocrosslinking occurs even in the presence of oxygen between exposed and unexposed areas. This is because the desired difference occurs at the exposed location.

The recording material obtained with the photosensitive copying composition according to the invention is
It can be used to produce images on suitable supports or in receiver sheets, and can also be used to produce relief images which can be used as printing plates, screens, photoresists and the like.

Furthermore, the photosensitive copying composition according to the invention is suitable for producing UV-cured lacquers which can be used for surface protection, or for cross-linking with oxygen without physical drying or chemical cross-linking. It can be used to produce UV-cured printing inks. Drying is carried out by photochemical treatment and is therefore robust and biologically safe.
Printing plates, screens, anticorrosive materials and the like can be prepared in the conventional manner from suitable copying materials according to the invention, for example by removing the image-free areas which retain their soluble parts after exposure under a suitable original, in a suitable solvent. For example, it can be manufactured by removing it by treatment with an aqueous alkaline solution. Other methods of development utilize physical differences between areas where a cured image exists and areas where an uncured image does not exist, such as differences in melting point, difference in degree of fixation, difference in degree of adhesion, difference in optical transparency, etc. It can be implemented by

Next, the present invention will be explained in detail based on examples. All amounts are by weight unless otherwise noted. The relationship between parts by weight and parts by volume is the same as the relationship between 7 and ml. Example 1 is dissolved in 1400.0 parts by weight of ethylene glycol monoethyl ether.

A series of solutions of the above composition were prepared, each containing 7.
0% by weight or a mixture consisting of 3.5 parts by weight of an initiator corresponding to formula 1 and 3.5% by weight of an initiator corresponding to formula 1 is added.

The solution is filtered and then spun onto electrochemically roughened aluminum foil at 100 revolutions per minute and dried.

After drying, 2.0 parts by weight of carboxymethylcellulose and 1 part by weight of cansyo sugar were added to this sample plate in 267.0 parts by weight of water.
．． 0 parts by weight, 1.0 parts by weight of saponin and 0.0 parts by weight of zorpic acid.
An aqueous solution containing 12 parts by weight was added to a dry layer of about 0.
Coat to have a weight of 6y.

Each sample was then passed through a 21-step halftone wedge (Kodatsu:
6Ph0t0graphicStepTab1e゛應2
) for 2 minutes. The light source used was 8000W
[XenOkOp] spot arc lamp (spacing: 72CrfL). To remove areas where no image was present, the plate was treated with 1.5 parts by weight of sodium metasilicate nonahydrate, 0.3 parts by weight of polyethylene glycol 60,000, 0.06 parts by weight of levulinic acid and strontium hydroxide in 100 parts by weight of water. PHll. consisting of 0.03 parts by weight of octahydrate. Rub with developer No. 9 for 30 seconds and rinse with water.

When the copy layer is treated in this manner, the fully regenerated steps of the Kodak step wedge are a measure of the initial activity of the initiator or initiator mixture tested. That is, the greater the number of reproduced stages, the higher the actual photosensitivity. The following table lists the number of fully regenerated steps of the step wedge for each of the initiator compositions tested.

In this case, adjacent partially colored transition stages are excluded. The photosensitivity of two adjacent steps of the step wedge differ by J orders. Step 0 of the step wedge corresponds to an optical density of 0.05 (specific absorption of the film material). Example 2 This example shows the influence of different compounds of the formula on a special compound of formula 1 (compound no. 118).

ethylene glycol monoethyl ether 1400.0
Dissolve in weight parts.

A series of solutions is prepared and to each is added 5.0 parts by weight of an initiator, or 2.5 parts by weight of an initiator corresponding to formula 118 and 2.5 parts by weight of one of the initiators corresponding to formula.

The solution is filtered and spun onto electrochemically roughened and anodized aluminum foil at 100 revolutions per minute.

The dried sample is coated with a solution of about 16 cp viscosity consisting of 3.5 parts by weight polyvinyl alcohol and 1.0 parts by weight sodium lauryl-ether sulfate in 96.5 parts by weight water and then dried.

Further processing as described in Example 1. The table shows the relative photosensitivity of the samples obtained. Example 3 This example demonstrates the influence of an initiator compound of formula H on different initiator compounds of formula 1.

The test was conducted in the same manner as in Example 2. Several compounds were used as initiators corresponding to formula 1; the initiator of formula 1 was compound 1. The results are shown in Table V below: Example 4 This example shows the range within which the mixing ratio of the two components of the initiator system can be varied without losing their synergistic effect.

A series of solutions of this type was prepared with either initiator 11 or initiator 15.0.
parts by weight, or a mixture of these two initiators.

The test compares the tests described in Examples 2 and 3 with Exact Example 5. In this example, compounds corresponding to formula I with different substitutions in the 10-position are compared.

ethylene glycol monoethyl ether 1400.0
Dissolve in weight parts.

This series of solutions is mixed with 5.0 parts by weight of initiator or 2.5 parts by weight of each of the two initiators.

Each sample was evaluated as in Example 1 and the results are summarized in the following table.

Example 6 This example shows that the synergy of the initiator system according to the invention is fully effective even in photosensitive reproduction compositions containing a large number of unsaturated polymeric compounds.

A series of solutions were mixed with 2-methyl-2-methoxypentanone-
It is prepared from 360.0 parts by weight of diallyl isophthalate prepolymer and 90.0 parts by weight of pentaerythritol triacrylate in 42900.0 parts by weight.

Each of these solutions is mixed with a mixture consisting of 16.0 parts by weight of a single initiator or 8.0 parts by weight each of two initiators of formula and formula, and the solution is then mixed until the solid material is completely dissolved. Stir until combined.

The solution is filtered and spun onto mechanically roughened aluminum foil at 100 revolutions per minute. The coated aluminum foil was dried at 50°C for 15 minutes and then heated in a vacuum flame for 2
One step halftone stair wedge (manufactured by Kodatsu: ゛PhOt)
7) using an 8000W xenon spot arc lamp below the waterfall 2).
Expose at intervals of 2 cm. After exposure, the sample was
Dip in 1-trichloroethane for 60 seconds, then spray with finishing solvent.

The plate was then coated with gum arabic (14 Be) 80.
0 parts by volume, 12.0 parts by volume of phosphoric acid (85%), 0.2 parts by volume of hydrofluoric acid (50%), 0.5 parts by volume of H2O2 (30%) and 7.3 parts by volume of water, West Germany. It is treated with a cotton pad for 45 seconds using the corrosive solution described in Japanese Patent Application Publication No. 1940280. The image areas are then colored with oil-based ink.

The relative photosensitivity is compared in the same manner as described in Example 1. The evaluation results are summarized in the table below. Example 7 140.0 parts by weight of a copolymer of 85 parts by weight of methyl methacrylate and 15 parts by weight of methacrylic acid in 1400.0 parts by weight of ethylene glycol monoethyl ether
Parts by weight, trimethylolethane triacrylate 140
．． 0 parts by weight, 1.5 parts by weight of the blue dye described in Example 2,
The solution described in Test 32 (Table), consisting of 1182.5 parts by weight of compound 1182.5 parts by weight of compound and 142.5 parts by weight of compound, was filtered and applied to an electrochemically roughened and anodized aluminum foil at 100 revolutions per minute. Rotate and apply.

The coated plates are dried in a circulating air dryer and then again coated with the aqueous solution of polyvinyl alcohol and sodium lauryl-ether sulfate as described in Example 2 and dried.

72? in the 8KW xenon exposure unit below the negative original. After exposure at intervals of
0.0, developed with a cotton pad using the alkaline developer described in Example 1 containing levulinic acid and strontium hydroxide.

After rubbing with a 1% phosphoric acid solution, the image areas of the plate are colored with oil-based ink.

The lithographic printing plates thus obtained can be used to print tens of thousands of complete prints on an offset machine.

Example 8 140.0 parts by weight of a copolymer (molecular weight approximately 43,000) of 85 parts by weight of methyl methacrylate and 15 parts by weight of methacrylic acid in 1400.0 parts by weight of ethylene glycol monoethyl ether, 140.0 parts by weight of trimethylolethane triacrylate. A solution of 1.6 parts by weight of the blue dye used in Example 2, 192.5 parts by weight of the compound and 22.5 parts by weight of the compound was filtered and placed on the chrome surface of a brass plate with a thin chrome plating layer using a centrifuge. The plate is then dried.

The plate is then coated with an aqueous solution of polyvinyl alcohol and sodium lauryl ether sulfate as described in Example 2 and dried again.

After a 2 minute exposure under the positive original in a copy form (using an 8KW xenon spot arc lamp,
(from a distance of 72 cm), the plate is developed using the alkaline developer used in Example 1 by rubbing with a cotton pad.

The plate was then treated with 42.4% CaCl2, ZnCl2
9.8%, HCLIO. Etching with a commercially available chromium etchant consisting of 8% and 37% H2O etches away the chromium layer within 2 minutes.

After rinsing with water, the copy layer was removed by dipping the plate in acetone, the image was rinsed again, and 1% dilute H
Rub with 3PO4 and finally color with cloudy ink. A complete multilayer printing plate for lithographic printing is obtained, from which a very large number of prints are possible. Example 9 Example 12 of West German Patent Application No. 2203732
describes the preparation of photocrosslinkable compounds obtained from poly(methyl vinyl ether/maleic anhydride) and allylamine.

600.0 parts by weight of this polymer, 100.0 parts by weight of trimethylolethane triacrylate, 118 parts by weight of the compound and 18.0 parts by weight of the compound were added to 14 parts by weight of methyl ethyl ketone.
00.0 parts by weight, and the solution was applied to a nylon cloth (1 cm
Approximately 80 mesh per layer) and dry. coated fabric,
8KW xenon lamp 72? Image-wise exposure is carried out for 4 minutes under the positive original using intervals of .times.1 and the resulting image is developed in acetone. A useful silk screen is thus obtained. Example 10 A coating solution was prepared using 400.0 parts by weight of styrene/maleic anhydride copolymer in 2000.0 parts by weight of methyl ethyl ketone and 200.0 parts by weight of ethylene glycol monoethyl ether.
0 parts by weight, α-methylstyrene/vinyltoluene copolymer 200.0 parts by weight, average molecular weight 30,000 to 3,500
It is prepared from 25.0 parts by weight of polyvinyl butaryl of 0.0, 500.0 parts by weight of trimethylolpropane triacrylate, 111.0 parts by weight of the compound and 14.0 parts by weight of the compound, and filtered.

Thickness 35 laminated on base of phenolic paper
Apply this solution to a μm copper foil.

After drying, this layer is coated with a layer of polyvinyl alcohol having a thickness of 1 to 2 μm. The coated copper plate is exposed for 2 minutes using an 8KW xenon lamp under the negative original showing the circuit diagram.

It is then developed using the aqueous alkaline developer used in Example 1 and etched at 50 DEG C. with an aqueous FeCl3 solution. The copper corrodes in exposed locations, yielding printed circuits of the type used in the electrical industry.

Example 11 is dissolved in 2500.0 parts by weight of methyl ethyl ketone and 200.0 parts by weight of ethyl alcohol.

Filter the solution onto a polyethylene terephthalate support.
It is applied so that the resulting dry layer has a weight of 32y/y.

Using commercially available lamination equipment, the coated film is laminated to the copper surface of a composite material consisting of copper and cardboard layers.

Claims (1)

[Scope of Claims] 1. Used in a photosensitive copying composition comprising at least one polymeric binder, at least one ethylenically unsaturated compound having at least two addition-polymerizable double bonds, and a photoinitiator system. A photoinitiator system consists of at least two components a and b, where component a has the general formula I: ▲Mathematical formula, chemical formula, table, etc.▼ I [wherein R_0 represents O, S or NR_1; R_1 is hydrogen, a saturated or unsaturated unsubstituted hydrocarbon group having 1 to 6 carbon atoms, a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms (this is a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, (substituted with an acyloxy group and/or a halogen atom), an aralkyl group having 7 to 10 carbon atoms, an acyl group having 2 to 18 carbon atoms, or the general formula: -(C_aH_2_a-O)_n-C_aH_2_
a-OH or -(C_aH_2_a-O)_n-C_a
H_2_a-OCH_3 (in the formula a = 2 to 4, and n = 1
~10) represents a polyalkylene oxide group, R_2
represents hydrogen, an alkoxy group, an alkyl group having 1 to 6 carbon atoms, or a halogen atom], and component b is the general formula II: ▲There are mathematical formulas, chemical formulas, tables, etc.▼II [ In the formula, R_3 represents an alkyl group having 1 to 6 carbon atoms,
R_4 represents an alkyl group having 1 to 6 carbon atoms, R_5
represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group (the alkyl group has 1 to 4 carbon atoms), an aryl group having 6 to 12 carbon atoms, or a dialkylaminostyryl group; 1. A photosensitive reproduction composition comprising a synergistic photoinitiator system characterized in that the photoinitiator system is at least one compound of the formula: 0 or 1. 2 The weight ratio of the compound of formula I to the compound of formula II is 2:9
Claim 1 which is variable within the range of 8 to 98:2
The photosensitive copying composition described in . 3. A photosensitive copying composition according to claim 1 or 2, which is present in the form of a photosensitive layer treated on a support. 4. A photosensitive copying composition according to claim 1 or 2, which is present in the form of a solution in a solvent.