JPS63177128A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To make a drying stage unnecessary by incorporating a specified polyvinyl alcohol copolymer, a polymerizable monomer having at least two free hydroxyl groups and a photopolymn. initiator. CONSTITUTION:This photosensitive resin compsn. contains a water soluble or water dispersible polyvinyl alcohol copolymer having 50-70mol.% degree of saponification of vinyl ester units and 60-130 deg.C heat melting and flowing start temp., a polymerizable monomer having a compd. represented by formula I and at least two free hydroxyl groups and a photopolymn. initiator. The polyvinyl alcohol copolymer is obtd. by saponifying a copolymer consisting of 0.1-20mol.% in total of 0.1-20mol.% nonionic monomer radical- copolymerizable with vinyl ester and 0-10mol.% monomer having an ionic hydrophilic group and the balance vinyl ester. When the photosensitive resin compsn. is used, a drying stage is made unnecessary.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a water-developable photosensitive resin composition that is heat-melt moldable.

BACKGROUND OF THE INVENTION Water-developable photosensitive resin compositions for forming printing plates, relief plates or resist patterns are known.

Generally, these photosensitive resin compositions are obtained from a mixture of water-soluble or water-dispersible polyvinyl alcohol, a polymerizable monomer, and a photoinitiator.

When irradiated with light, this composition polymerizes to form a latent image, and the areas not exposed to light are washed away with water or the like to form a developed relief before use.

This photosensitive resin composition is usually obtained by dissolving polyvinyl alcohol in water, then adding monomers, and evaporating the sample water applied onto the substrate.

This method requires a drying step to evaporate water,
It requires large-scale equipment, space, and time. Also,
The monomer component added to the photosensitive resin composition has a low molecular weight,
Many have low boiling points, and monomers scatter during drying, causing environmental pollution problems.

Furthermore, if polyvinyl alcohol with a high degree of saponification of vinyl ester units is used, the developed relief will be hard and have drawbacks such as cracking, so it is necessary to reduce the hardness. Low hardness can be imparted by lowering the degree of saponification of the vinyl ester units of polyvinyl alcohol, but if the degree of saponification of the vinyl ester units is lowered, water solubility becomes poor and water development becomes difficult.

On the other hand, from the viewpoint of printing, low hardness is one of the properties necessary for excellent printing performance, and this cannot be neglected. Furthermore, the elasticity of the relief is also one of the properties necessary for excellent printing performance.

Therefore, it is necessary to have three properties: low hardness, rubber elasticity, and water solubility.

(Object of the invention) The present invention is a photosensitive resin composition that does not require a drying process, can be molded by hot melting, has high compatibility and water solubility,
Furthermore, it provides a certain degree of hardness and rubber elasticity upon curing.

(Structure of the Invention) That is, the present invention provides (a) a vinyl ester, a nonionic monomer (A) capable of radical copolymerization with the vinyl ester, and an ionic parent group-containing monomer capable of radical copolymerization with the vinyl ester. A copolymer of monomer (B), the amount of A monomer is 0.1 to 20 mol%, the amount of B monomer is 0 to 10 mol%,
The degree of saponification of vinyl ester units obtained by saponifying a copolymer in which the remainder is the vinyl ester and the total amount of A monomer and B monomer is 0.1 to 20 mol% is 50 to 70 mol%. , a water-soluble or water-dispersible polyvinyl alcohol copolymer having a hot melt flow initiation temperature of 60 to 130°C, formula (b): % formula % [In formula ([), OR.

I 1 Y OH, -0-C-C=CH, -OC(CIIt)pOH or -ORs % R
11R3 and R4 are the same or different, and each has a hydrogen atom or a methyl group, and R1 has a hydroxyl group and has a carbon number of 1
~5 alkylene group, R6 has hydroxyl group and carbon number l~
5 alkyl group, n is an integer of 4 to 23, l is 0 or l
, and p represent an integer of 1 to 5. A water-developable photosensitive resin composition capable of being melt-molded and containing a polymerizable monomer having at least two free hydroxyl groups, and (c) a photopolymerization initiator.

When obtaining the polyvinyl alcohol copolymer (a) used in the photosensitive composition of the present invention, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl benzoate, etc. can be used, but vinyl acetate is preferred. It is used in

In addition, there are no particular restrictions on the nonionic monomer (A) that can be radically copolymerized with the vinyl ester, but it has 2 carbon atoms.
~12 vinyl monomers are preferred.

For example, α-olefins such as ethylene, propylene, l-butene, isobutyne, methyl (meth)acrylate,
(Meth)acrylic esters such as ethyl (meth)acrylate and butyl (meth)acrylate, (meth)acrylamide, N,N-dimethylacrylamide, N-vinylpyrrolidone, allyl acetate, allyl alcohol, 2-methyl-3 Examples include nonionic monomers such as -buten-2-ol and isopropenyl acetate.

The ionic hydrophilic group-containing monomer (B) copolymerizable with the vinyl ester includes carboxyl moieties or salts thereof;
A vinyl monomer containing an anionic group such as a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, or an ionic group such as a cationic group such as an amino group or an ammonium group.

For example, (meth)acrylic acid or its salts, itaconic acid or its salts, maleic acid or its salts, fumaric acid or its salts, maleic anhydride, 2-acrylamidopropanesulfonic acid or its salts, (meth)allylsulfonic acid or Examples thereof include salts thereof and ionic hydrophilic group-containing monomers such as (meth)acrylamidopropyltrimethylammonium chloride. Ionic monomers have a large effect on improving water solubility even when introduced in small amounts.

These radically polymerizable monomers (AXB) can be used to form vinyl esters using nonionic monomers (A) alone or in combination with nonionic monomers (A) and a small amount of ionic monomers (B). These copolymerizable monomers are used in copolymerization, and these copolymerizable monomers greatly affect the water solubility of the polyvinyl alcohol copolymer (a) and the compatibility between the polymer and the polymerizable monomer. Among the above, preferred examples of nonionic monomers include (meth)acrylate, etc.
meth)acrylic acid ester, N,N-dimethylacrylamide, N-vinylpyrrolidone, allyl acetate, allyl alcohol, 2-methyl-3-buten-2-ol, and isopropenyl acetate are monomers containing ionic hydrophilic groups. (meth)acrylic acid, itaconic acid, maleic anhydride,
2-acrylamidopropanesulfonic acid and (meth)acrylicsulfonic acid are used.

Among these, a copolymer obtained by copolymerizing both a nonionic monomer and an ionic monomer containing a hydrophilic group is most preferably used.

The content of the above-mentioned co-electrable monomers in the copolymer is determined from 001 to 001 to
20 mol%, the ionic hydrophilic group-containing n monomer from 0 to 10 mol%, and the total amount of both types of monomers from 0.1 to 20 mol%. More preferably 5 to 15 nonionic monomers
It is desirable to use 0 to 3 mol% of the ionic shallow water group-containing monophosphor. If the nonionic monomer content is less than 0.1 mol%, the resulting composition will have poor meltability, and if it exceeds 20 mol%, the composition will have poor solid retention and cannot be used.

The polyvinyl alcohol copolymer (A) of the present invention is a copolymer of the above-mentioned vinyl ester and a nonionic monomer (A) that is radically copolymerizable with the vinyl ester, and a vinyl ester that is radically copolymerizable with the vinyl ester. It can be obtained by saponifying a terpolymer of a nonionic monomer (A) and an ionic parent tree group-containing monomer (B) by a conventional method. The properties required of the polyvinyl alcohol copolymer (a) of the present invention are: (1) appropriate melt viscosity of the resulting composition, (2) good compatibility with the polymerizable monomer, and (2) water solubility. and (ii) the resulting photosensitive resin plate has good dimensional stability (solid retention and heat-resistant creep properties of the composition). It is necessary that the thermal melt flow initiation temperature of the coalescence is 60°C to 130°C, and the saponification degree of the vinyl ester unit is 50 to 70 mol%, and the average degree of polymerization is too low, It is preferably 700 or less, more preferably 500 or less, and desirably 100 or more. That is, the average degree of polymerization O
A value exceeding OO is unsuitable because the melt viscosity is too high, whereas a value less than 100 is difficult to use due to poor retention of polymerizable monomers, and the degree of saponification of the vinyl ester unit is insufficient for radical copolymerization. Although it depends on the possible content of monomer units, those in the range of 50 to 70 mol% have excellent compatibility with polymerizable monomers and are easy to use, and more preferably 55 to 68 mol%.

If it exceeds 70 mol %, the hot melt flow initiation temperature becomes too high, resulting in inappropriate application, while if it is less than 50 mol %, the dimensional stability of the resin plate tends to deteriorate and cannot be used.

In addition, the hot melt flow initiation temperature of the polyvinyl alcohol copolymer (a) as referred to in the present invention is when the water content is 3% by weight.
of polyvinyl alcohol copolymer with a diameter of 1 txm
, with a flow tester equipped with a nozzle of length ltytm,
It shows the flow start temperature when melted and discharged under a load of 50 kg at a rate of 6°C/min. Also, water solubility in the present invention refers to a 25°Ct heavy nail % concentration. It refers to a state in which a polyvinyl alcohol copolymer is completely dissolved or dispersed when dissolved in water. Moreover, the average degree of polymerization (β) is calculated from the viscosity formula by measuring the intrinsic viscosity [η] of the polyvinyl alcohol copolymer in water at 30°C.

The polymerizable monomer (b) used in the present invention has the formula (1) above.
It is a compound shown in (B) and has at least two hydroxyl groups. Examples of this compound include: CIl3 C112.Cl1-COoCII 2CIICII t
O-(C1l x CHto) 5cIl zcllc
ll tOcOcH-cHtC113C113 CIl, ・C-C00CII t CH-CIl, 0
-(CIltc++, o) 9 CH, CIICI
I, 0COC=C11.

I CIl3 It may also be a (meth)acrylic acid ester derivative obtained by esterifying the terminal hydroxyl group of the above compound with acrylic acid or methacrylic acid.

Other general monomers may be added to the above-mentioned special monomers.

Specific examples of other monomers having a polymerizable double bond in the molecule include methyl acrylate, edyl acrylate, n
-propyl acrylate, β-hydroxyedyl acrylate, β-hydroxypropyl acrylate, polyethylene glycol noacrylate, polypropylene glycol monoacrylate, polyethylene glycol noacrylate, polypropylene glycol diacrylate, methoxybolyethylene glycol monoacrylate,
Ethoxypolyethylene glycol monoacrylate, glycerol diacrylate, pentaerythritolone acrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, methyl acrylate, ethyl methacrylate, n-propyl methacrylate, β-hydroxyethyl methacrylate-1.
, β-hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, methoxypolyethylene glycol monomethacrylate, ethoxypolyethylene glycol monomethacrylate, glycerol dimethacrylate, pentaerythritol dimethacrylate, trimethylol Propane trimethacrylate, tetramethylolmethanetetramethacrylate, acrylamide, N-methylolacrylamide, n-butoxymethylacrylamide, isobutoxyacrylamide, n-poudyl acrylamide,
Methylene bis(acrylamide), ethylene bis(acrylamide), propylene bis(acrylamide), methacrylamide, N-methylol methacrylamide, -
Mention may be made of n-butoxymethylmethacrylamide, isobutoxyacrylamide, nt-butylmethacrylamide, methylenebis(methacrylamide), ethylenebis(methacrylamide), propylenebis(methacrylamide), or mixtures thereof.

A specific polymerizable monomer may be selected by considering compatibility depending on the type of polymer used. If necessary, an appropriate solvent,
For example, water or a high-boiling alcohol (eg, ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, butanediol, trimethylolpropane, tetramethylolethane, glycerol, diglycerol) may be blended.

There are no particular restrictions on the photopolymerization initiator (iii), and aromatic ketones are usually used. Compounds having an aromatic ring and a carbonyl group in the molecule are used as the aromatic ketone, and specific examples thereof include benzoin, penzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, 2-
methylanthraquinone, 9-fluorenone, benzyl,
Examples include benzyl methyl ketal, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, l\nzophenone, phenyl-2-thenyl ketone, p-tsumethylaminobenzophenone, p,p'-tetramethyldiaminobenzophenone, and the like.

These compounds may optionally have substituents such as a cyano group, a nitro group, a methoxy group, a sulfonic acid group, and an ester such as phosphinic acid or a salt thereof. Examples of such are 2.6-methoxybenzoylene-diphenylphosphine oxide, 2,4.6-1-dimethylbenzoylene-phenylphosphine oxide,
Examples include ethyl ester of 2,4.6-trimethylbenzoylfuenylphosphinic acid, sodium salt of 2,4.6-trimethylbenzoylfuenylphosphinic acid, and the like.

The blending ratio of the above essential components (a), (b) and (c) is usually 0.01 to 10 parts by weight of the photoinitiator (c) to 100 parts by weight of the polymerizable monomer (b), and the polymer (i). )5
0 to 300 parts by weight, but preferably (c) is 0.0 parts by weight.
2 to 5 parts by weight, preferably 60 to 250 parts by weight of (a).

In addition to the above essential ingredients, polymerization inhibitors (e.g. 2,6-di-t-butyl-p-cresol, hydroquinone, p-methoxyphenol), dyes (e.g. rose bengal, eonne, methylene blue, malachite green), etc. may be added as necessary. May be blended.

Since the photosensitive resin composition of the present invention uses a specific polyvinyl alcohol copolymer (a), it can be processed by heat or melt molding. Hot melt molding is usually performed using an extruder. According to this method, a large-scale drying process is not required, the process is shortened, and production costs are significantly reduced. Is it okay to use a small amount of water as a plasticizer during hot melt molding?
The amount used is significantly different from conventional usage. The compositions of the present invention may be processed by conventional methods that do not involve hot melt molding.

A resin plate material can be obtained by extrusion molding the photopolymerizable resin composition obtained here onto a suitable support. Supports typically include metals (e.g. aluminum, zinc, iron), plastics (e.g. polyethylene terephthalate, polystyrene, polymethyl methacrylate, nylon, cellulose acetate, polyethylene, polypropylene, polycarbonate, polyacrylonitrile, polyvinyl chloride), glass, etc. used. If necessary, the surface of these supports may be subjected to a pretreatment such as etching, electrolytic oxidation, or corona discharge, or a thin layer such as an adhesive layer or an antihalation layer may be provided.

In order to form an image using the above-mentioned resin plate material, a conventional method may be adopted. For example, an image film (negative film or positive film) is brought into close contact with the surface of the resin plate material via an appropriate film or coating layer as required, and then exposed.

After exposure, an image can be formed by removing the unexposed portions with a suitable developer, specifically water.

For exposure, various active light sources can be used, such as medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, and ultraviolet fluorescent lamps. In addition, tungsten lamps, white fluorescent lamps, visible light lasers, etc. may be used.

(Effects of the Invention) According to the present invention, a photosensitive resin composition that can be hot-melt molded using a specific modified polyvinyl alcohol can be obtained. By using this composition, there is no need for a drying step, no large-scale drying equipment is required, and the number of steps can be reduced.

Furthermore, environmental pollution caused by evaporation of low-boiling monomers generated during the drying process can be prevented. The photosensitive resin composition of the present invention can be developed with water.

In addition, in the present invention, a special polymerizable monomer is used to impart higher water solubility to the photosensitive resin composition and to impart high rubber elasticity to the cured film obtained by exposure.

The compositions of the invention can be used in a variety of imaging materials, such as resists.

(Example) The present invention will be explained in more detail by giving examples below.

However, parts indicate parts by weight.

Reference Example 1 2,800 parts of vinyl acetate, 6,500 parts of methanol, and 10.5 parts of methyl acrylate were charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser. This reaction container was placed in a constant temperature bath, and the inside of the system was replaced with nitrogen while stirring, and then the internal temperature was raised to 60°C. 2,2° in this system
~285 parts of a methanol solution containing 5.7 parts of azobisisobutyronitrile was added to initiate polymerization. During a polymerization time of 5 hours, 900 parts of a methanol solution containing 180 parts of methyl acrylate was added in such a way that the monomer ratio of methyl acrylate and vinyl acetate in the polymerization system was kept constant according to the measured solid content concentration of the polymerization system. dripped into. The solid content concentration in the system at the time of termination of polymerization was 17.8%.

After heating while introducing methanol vapor to expel unreacted vinyl acetate monomer, a 65% methanol solution of the copolymer was obtained. It was confirmed by nuclear magnetic resonance (NMR) analysis that this copolymer contained 10 mol% of methyl acrylate units and 90 mol% of vinyl acetate units. While stirring 100 parts of a methanol solution of this copolymer at 40°C, 4.0 parts of a 2N methanol solution of sodium hydroxide was added thereto, mixed well, and saponified. The obtained white gel was pulverized using a pulverizer, thoroughly washed with methyl acetate/methanol=7/3 (weight ratio), and then dried to obtain polyvinyl alcohol copolymer a. This copolymer a
The degree of saponification of the vinyl ester unit was analyzed by NMR and found to be 63.8 mol%. Further, the degree of polymerization determined by measuring the intrinsic viscosity in an aqueous solution was 350.

Furthermore, the hot melt flow start temperature of this polyvinyl alcohol-based JI: polymer a was determined by the flow start temperature using a flow tester (hereinafter referred to as flow point) 12
It was 0°C.

Reference Example 2 2,420 parts of vinyl acetate, 5,100 parts of methanol, 9.1 parts of methyl acrylate, and 1.7 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt were charged into a reaction vessel. To this system was added 250 parts of a methanol solution containing 5.0 parts of 2°2°-azobisisobutyronitrile, and polymerization was initiated at 60°C. 128 parts of methyl acrylate and 2-acrylamide-2 during a polymerization time of 5 hours.
-720 parts containing 13 parts of sodium methylpropane sulfonate were added dropwise in accordance with the measured solid content concentration of the polymerization system. The solid content concentration in the system at the time of termination of polymerization was 16%.

After removing unreacted vinyl acetate monomer as in Reference Example 1, a 65% methanol solution of the copolymer was obtained. NMR analysis showed that this copolymer contained 10 mol% of methyl acrylate units, 0.4% of 2-acrylamido-2-methylpropanesulfonic acid sodium salt units, and 89.6 mol% of vinyl acetate units. Obtained.

While stirring 100 parts of a methanol solution of this copolymer at 40° C., 4.2 parts by volume of a 2N methanol solution of sodium hydroxide was added thereto, and the mixture was thoroughly mixed and saponified. 30
After a few minutes, the obtained white gel was pulverized using a pulverizer, thoroughly washed with methyl acetate/methanol=7/3 (weight ratio), and then dried to obtain a polyvinyl alcohol copolymer.

The degree of saponification of the vinyl ester unit of this copolymer is NM
R analysis showed that it was 61.0 mol%.

Furthermore, the flow point of this copolymer was 115°C.

Reference Example 3 1,125 parts of vinyl acetate, 150 parts of allyl acetate, and 1,570 parts of methanol were placed in a reaction vessel, the interior was sufficiently replaced with nitrogen, and the internal temperature was heated to 60°C, resulting in 2.2°-azobisisobutylene. Polymerization was started by adding 19.5 parts of lonitrile. When the concentration reached 31% after 5 hours, the polymerization was stopped by cooling. After treatment in the same manner as in Reference Example 1, vinyl acetate
Methanol solution of allyl acetate copolymer (solid content concentration 65
%) was obtained. As a result of NMR analysis, the allyl acetate content was 10
It was 2 mol%.

To 100 parts of this methanol solution, 20 parts by volume of a 2N-sodium hydroxide methanol solution was added, followed by saponification and post-treatment in the same manner as in Reference Example 1 to obtain polyvinyl alcohol copolymer C.
I got it. This copolymer C had a degree of saponification of vinyl ester units of 66.8 mol%, a flow point of 105°C, and a degree of polymerization of 450.

Reference Example 4 In a 24-kolben equipped with a stirrer, a condenser, and a temperature regulator, 370 g of xylene, a bifunctional poxy compound whose main component is the structural formula (commercially available as Evolite 400E from Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) 5269, and methacrylic 869 g of acid, 18 g of pure water, and tg of tetrabutylammonium chloride were charged, the temperature was raised while stirring, and the reflux state was maintained for 30 minutes. Thereafter, the temperature was cooled to room temperature.

The analysis results of the photopolymerizable vinyl monomer obtained were determined by NMR.
, In, it was confirmed that the monomer was the polymerizable monomer (III). Its acid value is 0.56 and viscosity is 20
It was 0 cps.

Reference Example 5 410 g of xylene, 526 g of the bifunctional poxy compound mentioned in Reference Example 4, 72 g of acrylic acid, 189 g of pure water, and tetrabutylammonium chloride! The same operation as in Reference Example 4 was carried out except that 9 was added to prepare the polymerizable monomer (
If) was obtained. Acid value is 0°59, viscosity is l 70 cp
It was s.

Reference Example 6 The polymerizable monomer (TV) was obtained by carrying out the same operation as in Reference Example 4, except that 330 g of xylene, 526 g of the bifunctional engineered poxy compound mentioned in Reference Example 4, 144 g of acrylic acid, and 1 g of tetrabutylammonium chloride were charged. Ta.

Reference Example 7 In a 2Q Kolben equipped with a stirrer, a condenser, and a temperature regulator, a polyethylene glycol monomethacrylate compound (Blenmar PE35 from Hiki Yushi Co., Ltd.) whose main component is the structural formula (%)
9649 (commercially available as 0), 48 g of glycidol (manufactured by Daicel Chemical Industries, Ltd.) and 11 g of dimethylbenzylamine, and stirred while blowing air to give +20
The temperature was raised to -140°C and maintained for 1 hour. Thereafter, the temperature was cooled to room temperature.

The analysis results of the obtained photopolymerizable vinyl monomer are N to I
It was confirmed from R and tR that it was the polymerizable monomer (■). Its acid value is 0. IO and the viscosity is 150
It was cps.

Reference Example 8 Polyethylene glycol monoacrylate compound 936
The polymerizable monomer (Vl) was obtained by carrying out the same operation as in Reference Example 7, except that 148 g of glycidol and 1 g of dimethylbenzylamine were charged. Acid value is 0.12,
The viscosity was 130 cps.

Example 1 100 parts by weight of polyvinyl alcohol copolymer a (saponification degree of vinyl ester unit 63.8%, degree of polymerization 350),
15 parts by weight of ethylene glycol and 10 parts by weight of pure water were placed in a Nigu and mixed for 30 minutes at a temperature of 80 to 85°C.

Polymerizability synthesized in Reference Example 4 using 0.1 part of p-methoxyphenol, 0.4 part of 2.6-di-t-butyl-p-cresol, and 3 parts of 2.2°-diftquine-2-phenylacetophenone. Monomer (dissolved in Oθ part). The resulting solution was added to the above mixture and kneaded at 80°C for 30 minutes, and the mixture was continuously fed, mixed, and defoamed at 80°C using a twin-screw extruder. Thickness 0, 2 coated with antihalation agent
It was discharged onto my treated iron plate to a thickness of 0.5 xtx. A cover film was then laminated.

A test negative film (150 lines, 3%, 5%, 10%, 20% halftone dots, diameters 100μ, 200μ, independent dots, widths 40μ, 60μ) was applied to the photosensitive surface of this photosensitive resin 1 plate material.
(with thin wires) are vacuum-adhered, and heated with 3 parts of high-pressure mercury lamp at 70°C.
It was irradiated from a distance of 300m.

The irradiation time was 4 seconds for pre-exposure and 26 seconds for main exposure.

This exposed plate material was developed by spraying neutral water at 40° C. from a spray developing device at a pressure of 4 kg/cm 2 for 1 minute. The unexposed portion, ie, the uncured portion, was eluted into the water and a relief was obtained.

When the relief plate thus obtained was dried at 100°C for 2 minutes, it had 3% halftone dots, diameter + ooil independent points,
No dropout of the 40 μm wide thin line was observed.

When this plate material was printed using a Bang-Tack proofing press (manufactured by Pander Cook Co., Ltd.), the f5 degree of the solid area was L2.
0 (measured with a Macbeth reflection densitometer), and a paper surface with good solid areas was obtained.

Incidentally, a photosensitive resin plate having a thickness of 2+U was produced using a flexo press using the discharged product of the twin-screw press used to produce this plate material, using a 2MM thick spacer.

The plate was exposed to 3 parts W high pressure mercury lamp for 5 minutes. 2cmf
When the hardness and elasticity were measured by cutting the pieces to fI and stacking them so that the thickness was 12 parts m, the hardness was 50° (20
), impact resilience value is 27% (JISK-6301
(measured at 20° C.).

Examples 2 to 6 and Comparative Examples 1 to 3 Photosensitive resin plates were obtained in the same manner as in Example 1 using the combinations of polyvinyl alcohol copolymers and polymerizable monomers shown in Table 1, and the same experiments were conducted.

The plate-making conditions and experimental results are shown in Table-1.

For comparison, 80 parts of the following three types of polymerizable monomers and polyvinyl alcohol copolymer 1 obtained in Reference Example 3 were used.
A similar experiment was conducted in combination with 00 parts. Display the results -
Shown in 1.

*, Polymerizable monomer of Comparative Example 1; Compound represented by formula % Formula % *, Polymerizable monomer of Comparative Example 2; Monomer obtained by reaction of polyglycerin and methacrylic acid *3 Polymerizable monomer of Comparative Example 3 -; Formula C11,= C11-Co-0-(CH2Cl, 0)
9COCII=CI.

compound with

Claims (1)

[Claims] 1. (a) a vinyl ester, a nonionic monomer (A) capable of radical copolymerization with the vinyl ester, and an ionic hydrophilic group-containing monomer (A) capable of radical copolymerization with the vinyl ester; In the copolymer B), the amount of A monomer is 0.1 to 20
mol%, the amount of B monomer is 0 to 10 mol%, the remainder is the vinyl ester, and the total amount of A monomer and B monomer is 0.
A water-soluble or water-dispersible polyvinyl alcohol having a degree of saponification of vinyl ester units obtained by saponifying 1 to 20 mol% of a copolymer and having a hot melt flow initiation temperature of 60 to 130°C. System copolymer, formula (B): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In formula (I), X: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Y: -OH, ▲ mathematical formulas There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or -OR_5 However, R_1, R_3 and R_4 are the same or different, and each is a hydrogen atom or a methyl group, and R_2 is a carbon number of 1 to 1 with a hydroxyl group. 5, R_5 is an alkyl group having 1 to 5 carbon atoms and having a hydroxyl group, n is an integer of 4 to 23, m is 0 or 1, and p is an integer of 1 to 5. ] and a polymerizable monomer having at least two free hydroxyl groups, and (c) a photopolymerization initiator. A hot melt moldable water-developable photosensitive resin composition. 2. The composition according to claim 1, wherein the vinyl ester is vinyl acetate. 3. The composition according to claim 1, wherein the nonionic monomer (A) is an acrylic acid alkyl ester. 4. The composition according to claim 1, wherein the ionic hydrophilic group-containing monomer (B) is sodium 2-acrylamido-2-methylpropanesulfonate. 5. The composition according to claim 1, wherein the degree of saponification of the vinyl ester unit of polyvinyl alcohol is 55 to 68 mol%. 6. The blending ratio of ingredients (a), (b), and (c) is (b) 1
00 parts by weight, (c) is 0.01 to 10 parts by weight, (
The composition according to claim 1, wherein a) is 50 to 300 parts by weight.