JPS59102232A - Photosensitive resin composition for use in screen printing plate - Google Patents

Abstract

PURPOSE:To obtain the titled compsn. superior in sensitivity, durability, etc. by adding photocross-linkable water-soluble PVA to an aq. emulsion contg. a film-forming polymer using a photocross-linkable saponified polyvinyl acetate as a protective colloid. CONSTITUTION:Photocross-linkability is given by introducing into saponified polyvinyl acetate, styryl residues represented by the formula shown in the figure in which R<1> is an aromatic heterocyclic residue contg. quternized nitrogen; R<2> is H or lower alkoxy; (n) is 1-6; and (m) is 0 or 1, or the like method. An aq. emulsion contg. a film-forming polymer, such as vinyl acetate emulsion, is prepared by emulsion polymerizing a monomer using this saponified polyvinyl acetate as a protective colloid, and 5-200pts.wt. photocross-linkable water- soluble PVA is added to this emulsion contg. 100pts.wt. polymer to obtain the titled resin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive resin composition for screen printing plates having all improved properties, and a special method for producing a screen printing plate having excellent sensitivity and stability, as well as good release properties and durability. The present invention relates to a photosensitive resin composition for printing plates.

Screen printing involves stretching an aluminum frame or wooden frame (nijiya (screen)), applying a coating to this, forming images such as letters and patterns on the rupture of the film, and passing ink through the printed areas.
This is a method of printing images by using a plate with a sealed structure to prevent ink from penetrating the non-printing areas.
Due to its many features such as good light resistance and not being particular about the shape or material of the printing material, it can be used for screen-dyed flags, banners, posters, printed wiring boards, ceramics, plastics, glass, metals, etc. The scope of its use, such as adding patterns to molded products, has expanded significantly.

By the way, the printing plate used for this screen printing is
Usually, it is manufactured by applying or transferring a photosensitive resin onto cloth, exposing it to light through an image mask to make the exposed area insoluble or solubilized, and then dissolving and removing all the soluble portion.

The most widely used photosensitive resin for this purpose was a sweet one based on ammonium dichromate salt and polyvinyl alcohol, but this was subject to limitations in the work process due to its rapid dark reaction after application. Additionally, due to the issue of hexavalent chromium emission regulations, its use is on the decline. As an alternative to this, a polyvinyl alcohol-diazo type product, such as a polyvinyl alcohol blended with a condensation product of p-diazodiphenylamine and paraformaldehyde, has been proposed, but this product is based on ammonium dichromate- Although they are not necessarily satisfactory, they have the disadvantage that they have lower sensitivity than polyvinyl alcohol-based ones, and the dark reaction progresses, albeit gradually, resulting in changes in the appropriate exposure time and a decrease in development workability. do not have.

Subsequently, stilvanolium was developed as a photosensitive resin composition that exhibits an extremely high photosensitive speed even with a small content of photosensitive groups and does not cause dark reactions like diazo resin-polyvinyl alcohol systems, which contain metals that are a source of environmental pollution. A photosensitive composition comprising a polyvinyl alcohol derivative having a group and an aqueous polymer emulsion having a film-forming ability has been proposed (Japanese Patent Application Laid-Open No. 55-62446), but this composition has low resolution and the film is not water-based. It is easily swollen by organic solvents, etc., lacks mechanical strength, and has disadvantages such as the screen film peeling off when used in humid periods. The inventors
After conducting various studies to find out the cause of this, it was found that this was caused by polyvinyl alcohol contained as a protective colloid in the polymer emulsion.

That is, in a polymer emulsion polymerized by adding a saponified polyvinyl acetate as a protective colloid, for example, a vinyl acetate emulsion, a part of the saponified material, that is, polyvinyl alcohol, is graft-copolymerized to the f11 = acid hydrogen polymer, and in this way, Polyvinyl alcohol is further adsorbed around the resulting copolymer to form a protective layer.
This allows stable emulsification and dispersion of polymers in water.

When a photosensitive composition prepared by adding photocrosslinkable water-soluble polyvinyl alcohol to such a polymer emulsion is applied onto a screen and exposed to light, the protective colloid present around the vinyl acetate polymer particles is removed. Since no chemical bond is formed between the layer and the portion insolubilized by light irradiation, the area around each vinyl acetate polymer particle is easily swollen by water or organic solvents, resulting in peeling and mechanical strength loss. bring about a decline.

Based on these findings, the present inventors conducted further research in order to find a solution to all the drawbacks, and found that by imparting photo-crosslinking properties to saponified polyvinyl acetate used as a protective colloid, The inventors have discovered that the object can be achieved, and have come up with the present invention.

That is, the non-invention is that the film-forming polymer compound 1 is added to the film-forming polymer compound-containing aqueous emulsion.
In a photosensitive resin composition in which 95 to 200 parts by weight of photocrosslinkable water-soluble polyvinyl alcohol is added per 00 parts by weight, the saponified polyvinyl acetate contained as a protective colloid in the aqueous emulsion is preliminarily injected with photocrosslinkable water-soluble polyvinyl alcohol. The present invention provides a photosensitive resin composition for screen printing plates, which is characterized in that it has been provided with the following.

Examples of the film-forming aqueous emulsion containing a polymer compound in the present invention include vinyl acetate emulsion, acrylic emulsion, ethylene-vinyl acetate emulsion, ethylene-acrylic emulsion, SDR latex, silicone resin knee r/l/john, and vinyl chloride emulsion. , chloride emulsion, etc., those obtained by emulsion polymerization using saponified polyvinyl acetate as a protective colloid are used. Such products may be commercially available as they are, or may be prepared by emulsion polymerization of specific monomers in an aqueous medium containing saponified polyvinyl acetate, a catalyst, a surfactant, etc. You can also do that. The saponified polyvinyl acetate used as the protective colloid at this time has a degree of polymerization of 300 to 300.
Partially saponified products or completely saponified products with a saponification degree of 75% or more are suitable. It is usually used at a concentration of 2 to 10% by weight in the emulsion.

The appropriate proportion of the film-forming polymer compound in the emulsion is 20 to 60% by weight.

Moreover, a plasticizer may be contained in these polymer emulsions.

In the present invention, it is necessary to impart photocrosslinkability to the saponified polyvinyl acetate present as a protective colloid in the emulsion in advance. This photo-crosslinking property can be imparted to saponified polyvinyl acetate, for example, by using the general formula (R1 in the formula is i2!), an aromatic nitrogen-containing heterocyclic residue, and R2 being a hydrogen atom or a (lower alkoxyl group). , R6 is a lower alkyl group, or two R3 are lower alkylev groups, n is an integer of 1 to 6, and m is 0 or 1). This can be carried out by introducing into the molecule a photocrosslinkable group represented by the general formula (R1, R2, n, m have the same meanings as above) into the molecule. It is sufficient if it is introduced at a ratio of 0.5 to 10 moles per monomer unit of saponified vinyl acetate, but if desired, it can be introduced into all alcohol groups in the saponified polyvinyl acetate. You can also do it.

R1 in the general formula (1) used in this case is an aromatic nitrogen-containing heterocyclic group in which at least one of the nitrogen atoms constituting the ring is quaternized, and as such, Examples include a pyridinium group, a quinolinium group, an inquinolinium group, a pyrimidinium group, a thiazolium group, a benzothiazolium group, and a benzoxacillium group. These rings may further have a substituent such as an alkyl group, an alkoxyl group, an amine group, or a carbamoyl group.

Examples of compounds of general formula (1) include 1-methyl-
2-(p-formylstyryl)pyridinium, 1-methyl-4-(p-formylstyryl)pyridinium, 1-
ethyl-2-(p-formylstyryl)pyridinium,
l-Ethyl-4-(p-formylstyryl)pyridinium, 1-allyl-4-(p-formylstyryl)pyridinium, 1-(2-hydroquinethyl)-2-(p-formylstyryl) biry/nium, 1-(2-hydroxyethyl)-4-(p-formylstyryl)pyridinium, 1-rubamoylmethyl-2-(p-formylstyryl)pyridinium, 1-rubamoylmethyl-4-(p-formylstyryl)pyridinium
-formylstyryl)pyridinium, 1-methyl-2-
(m-formylstyryl)pyridinium, 1-benzyl-2-(p-formylstyryl)pyridinium, 1-benzyl-4-(p-formylstyryl)pyridinium,
1-Methyl-4-(p-formylstyryl)-5-ethylpyridinium, 1-methyl-2-(p-formylstyryl)quinolinium, 1-ethyl-2-(p-formylstyryl)quinolinium, 1-x-thyl -4-(p-formylstyryl)quinolinium, 1-mef-2-(
Examples include p-formylstyryl)benzothiazolium, 1-ethyl-2-(p-formylstyryl)he7zothiazolium, and 1-methyl-2-(p-formylstyryl)benzoxacilium.

The compound represented by the general formula (n) is the compound represented by the general formula (1)
An acetal of a formyl compound represented by, for example, a compound having the following chemical structural formula.

n3 H3 H3 H3 Positive 3 Compounds represented by these general formulas (1) and (n) are:
It is used in the form of salts such as hydrogen halide e-salt, phosphate, sulfate, methosulfate, ethosulfate, p-toluenesulfonate, perchlorine eFA, and hydrofluoroborate.

The reaction of these compounds with the saponified polyvinyl acetate in the emulsion is advantageously carried out in the presence of an acid catalyst. As the acid catalyst, used are inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, and hydrofluoroboric acid, and organic acids such as Hensensulfonic acid and p-toluenesulfonic acid. The larger the amount used, the faster the reaction will be completed, but usually a concentration of 0.01 to 5 normality is selected. The reaction temperature is selected from room temperature to 100°C, and the reaction is usually completed in about 1 to 45 hours. If this acid catalyst remains in the aqueous emulsion, it will cause separation of the emulsion and fluctuations in the sensitivity of the resulting photosensitive resin composition. Therefore, after the reaction is complete, neutralize it with alkali hydroxide, ammonia, etc. It's good to keep it. Particularly suitable are
This is a treatment using a basic ion exchange resin.

The photocrosslinkable water-bathable polyvinyl alcohol used as the photosensitive component in the composition of the present invention is obtained by introducing a photocrosslinkable base into a completely or partially saponified product of Bo'J6 [1 vinyl]. Particularly suitable are polyvinyl alcohol derivatives having a stilbazolium group, which are described in JP-A-55-62446. Such a polyvinyl alcohol derivative can be produced, for example, by the same method as that for imparting photocrosslinking properties to the protective colloid described above. That is, the degree of polymerization is 30
A formyl steryl compound represented by the general formula (1) or fd(It) or its acetal is added to water-soluble polyvinyl alcohol with a saponification rate of 75% or more obtained by saponifying polyvinyl acetate in the range of 0 to 3000, It can be produced by reacting in an aqueous solvent in the presence of an acid catalyst. At this time, the introduction rate of the photocrosslinkable group (about 0.5 to 10 moles per unit of d monomer is desirable; if it is lower than this, sufficient photocrosslinkability cannot be obtained, and if it is higher than this, the reaction will not proceed). In fact, if the acid used as a catalyst remains in the reaction solution, the viscosity will increase during storage, and if it is mixed with an aqueous emulsion containing a film-forming polymer compound, it may cause aggregation. Since this causes undesirable results such as fluctuations in photosensitivity, it must be removed by neutralization with alkali, treatment with anion exchange resin, or non-containing agents such as acetate/alcohol, dioxane, etc.
It is preferable to use the solution after the container is heated, the photosensitive resin is precipitated, and the photosensitive resin is isolated.

The amount of photocrosslinkable water-soluble polyvinyl alcohol in the present invention is suitably in the range of 5 to 200 parts by weight, where p = 100 parts by weight of the film-forming polymer compound in the aqueous emulsion. If this amount is less than 5 parts by weight, the solvent resistance will be poor and it will not be possible to obtain a pattern with sufficient strength.
Moreover, if this amount is more than 200 parts by weight, the water resistance deteriorates and clear images cannot be obtained, making it impractical.

The photosensitive resin composition of the present invention can be prepared by coating it on a lime cloth according to a conventional method, drying it, irradiating it with light through a negative image, washing it out with water or other solvent, and developing it into a screen printing plate. can be manufactured. The printing plate thus formed has a clear image, excellent resistance to printing ink and mechanical strength, and does not swell or peel off even after long-term use.

Next, the present invention will be explained in more detail with reference to Reference Examples and Examples.

Reference Example I N-methyl 2-γ-picolinium methosulfate) 1
0.96! P and terephthalaltehyde 20.1217
' was dissolved in 40 yd of methanol while hot, piperidine 2
．． 132 was added and the mixture was refluxed for 4 hours. After removing the diolefin type compound by heating, 100 mI of ethyl acetate! was added and left overnight, and the precipitate was collected by filtration, thoroughly washed with acetone, and dried under vacuum. Yield 12. IL? TELKU-METHYL-γ
-(p-formylstyryl)pyri/nium methosulfate-1 was obtained. The melting point of this substance is 210-213℃
Met.

Reference Example 2 1-Methyl-γ-(p-formylstyryl)pyrinnium methosulfate 1.37 f obtained in Reference Example 1
and degree of polymerization 1700. Dissolve 88% saponified polyvinyl acetate 202 in distilled water 1927, and add 85%
After adding 0.42% of phosphoric acid, the mixture was heated to 45°C and stirred for 20 hours to react. It was confirmed from the ultraviolet absorption spectrum that the polyvinyl alcohol obtained by neutralizing the reaction solution with a weakly basic ion exchange resin had 0.81 mol % of styrene hathorium groups.

Reference Example 3 N-methyl-γ-(p-formylstyryl)pyridinium methosulfate 3.287 obtained in Reference Example 1 and polysaponized product 82 with a degree of polymerization of 500 and a saponification rate of 88% were dissolved in 101 rnl of distilled water, In addition to this, 85% phosphoric acid 0
．． After adding 169, add 2 at a temperature of 45℃ while stirring.
The reaction was allowed to proceed for 0 hours. It was confirmed by ultraviolet absorption spectrum that the resin obtained by neutralizing the reaction solution with a weakly basic ion exchange resin had 4.6 mol% of stilbazolium groups.

Reference Example 4 p-hydroxybenzaldehyde 12.215',! :
Potassium hydroxide 6.60? 35m7 of dimethyl sulfoxide! After heating and dissolving in chloroacetaldehyde dimethylacecool 1 after dehydration by azeotropic distillation with benzene.
Add 2.889 and heat to 147°C while stirring.
Allowed time to react. After cooling the reaction solution, toluene 100%
The mixture was washed successively with water, a dilute aqueous alkali solution, and water. This toluene solution was dried over anhydrous sodium sulfate and then vacuum distilled to obtain 17.549 p-formylphenoquine acetaldehyde dimethyl acetal having a boiling point of 123°C at a pressure of ITorr. p obtained in this way
-Formylphenoxyacetaltehyde 7Methyl acecool 21.02f and N-methyl-γ-picolinium methosulfate 21.93ji' were dissolved in 90ml of methanol, and then piperidine 4.26! i' was added and reacted under reflux for 4 hours. Add 200 ml of ethyl acetate to this reaction solution.
The precipitate was collected by filtration, thoroughly washed with acetone, and dried in vacuum. In this way the yield is 30.6
2? Thus, monomethyl-4-ip-(2,2-dimethoxyethoxy)steryl)pyridinium methosulfate was obtained. The melting point of this product was 169-170°C.

Reference Example 5 N-methyl-4-ip-(2,2dimethoxyethoxy)styryl)pyridinium methosulfate 2.52f obtained in Reference Example 4 and saponified polyvinyl acetate 202 with a degree of polymerization of 1700 and a saponification rate of 88% were distilled. Water 192Td! , and after adding 0.42% of 85% phosphoric acid to this,
The reaction was carried out at a temperature of 80° C. for 20 hours while stirring. It was confirmed from the ultraviolet absorption spectrum that 1.46 mol % of stilbazolium groups were introduced into the bilibinyl alcohol in the photosensitive solution obtained by neutralizing the reaction solution with a weakly basic ion exchange resin.

Reference Example 6 12°212 p-hydroxybenzaldehyde and 6.6 Or of potassium hydroxide were mixed with 35 m of dimethyl sulfoxide.
1. After heating and dissolving in 4-chlorobutanal dimethyl acetal and dehydrating it by azeotropic distillation with benzene, 15.26
? was added, and the mixture was reacted at a temperature of 100° C. for 20 hours while stirring. After the reaction solution was cooled, 100% of toluene was added, washed with water, washed with a dilute aqueous alkali solution, and further washed with water. This toluene solution was dried over anhydrous sodium sulfate and then vacuum distilled to give a boiling point of 14 Torr at a pressure of 1 Torr.
p-formylphenoxybutyraldehyde dimethyl acetal 21, Of at 0°C was obtained.

Thus obtained p-formylphenoxybutyraldehyde dimethyl acetal 23.83f and N-meth
Ru γ-picolinium p-toluenesulfonate 27.
94f was dissolved in 90ml of methanol, 4.269ml of piperidine was added, and the mixture was reacted under reflux for 4 hours. 200 units of ethyl acetate was added to this reaction solution and allowed to cool. The precipitate was collected by filtration, thoroughly washed with acetone, and dried in vacuum. In this way, N-methyl-4-+1) with a melting point of 169-173 °C
-(2,2-dimethoxy/butoxy/)styryl)pyridinium p-1 luenesulfonate 32.79f was obtained.

Reference Example 7 19-methyl-4-[p-(2,
2-/methoxybutkin)styryl)pyridinium I
)-toluene 100 coats 3.05 y polymerization degree 17
00, saponified polyvinyl acetate 202 with a saponification rate of 88%
was dissolved in distilled water. Add to this 85% phosphoric acid 0.
After adding 42, the reaction was carried out at a temperature of 45° C. for 20 hours under stirring conditions. The reaction solution was neutralized with a weakly basic ion exchange resin. The amount of vinyl alcohol in the photosensitive solution is 1.4
It was confirmed from the ultraviolet absorption spectrum that 6 mol% of stilbazolium groups were introduced.

Reference example 8 2-methylquinoline 28.6? and 6.72 terephthaldialdehyde with 242 acetic acid and 45 fi' of acetic anhydride.
The mixture was heated to reflux for an hour. After cooling, the precipitated crystals were dissolved in dichloromethane, washed with water, and then washed with sodium hydroxide solution to remove acetic acid. When concentrated hydrochloric acid was added to this dichloromethane solution, bulky yellow-orange crystals were immediately precipitated.

After cutting this crystal off the coast and recrystallizing it from water, approximately 300 m
The suspension was suspended in ethanol (1), neutralized with triethylamine, and heated to remove hydrochloric acid. Next, the insoluble diolefin type compound 3.91 was taken from house to house, water was added to solution E, and the mixture was left to stand to form yellow crystals of 2-(p-formylstyryl)-quinoline 35? I got it.

m, p, 1.12-113°C λmax (chloroform): 297 nm + 360 nm The thus obtained 2-(p-formils was dissolved in the solution, and 9.Of dimethyl sulfate was added to this solution for 6 hours. The mixture was heated to reflux.The precipitated crystals were collected and recrystallized from water to obtain 1.1.8S' crystals of 1-methyl-2-(p-formylstyryl)-quinolinium methosulfate.

m, p, 204-210℃ λmax (water):
245 nm + 299 nm + 366 nm
m mReference Example 1-Methyl-2-(p-formylstyryl)quinolinium methosulfate obtained in Example 8 1.96 fi
' and degree of polymerization 1700. 20 g of saponified polyvinyl acetate with a saponification rate of 88% was dissolved in 192 ml of distilled water. To this was further added 0.42 g of 85% phosphoric acid, and the mixture was allowed to react at a temperature of 45° C. for 20 hours while stirring.

It was confirmed from the ultraviolet absorption spectrum that 1.0 mol % of styrylquinolium groups had been introduced into the polyvinyl alcohol in the photosensitive solution obtained by neutralizing the reaction solution with a weakly basic ion exchange resin.

Reference example 10 1.4-dimethylquinolinium methosulfate 14.
959 and 22.35 r of terephthaldialdehyde were dissolved while hot in 40 rnl of total methanol, 0.5-piperidine was added thereto, and the mixture was heated under reflux for 10 hours.

Thereafter, when about 200 Tnl of acetone was added, a crystalline precipitate was deposited.

This was roasted, washed with acetone, and 1-methyl-4-(p
-formylstyryl) quinolinium methosulfate crude product 15.73 t was obtained. λmax (water): 2
45 nm +, 332 nm, 376 nm This crude product can be used after cutting for the production of photosensitive resins.

Reference Example 11 1-Methyl-4-(p-formylstyryl)quinolinium methosulfate obtained in Reference Example 1O 1.96 f
and degree of polymerization 1700. 2Of saponified polyvinyl acetate with a saponification rate of 88% was dissolved in 192 pieces of distilled water, and further 8
After adding 5% phosphoric acid 0.47, increase the temperature to 4 while stirring.
The reaction was carried out at 5°C for 20 hours.

The reaction solution was neutralized with a weakly basic ion exchange resin. It was confirmed from the ultraviolet absorption spectrum that the polyvinyl alcohol in the photosensitive solution had 1.0 mol % of styrylquinolinium groups.

Reference example 12 1.2-dimethylquinolinium iodide 4.28f and p
3.47 ii' of -(2,2-dimethoxyethoxy)-benzaldehyde was dissolved in 20 ml of methanol, 0.3 ml of piperidine was added to this solution, and the mixture was heated under reflux for 7 hours. This reaction solution was allowed to cool, and the precipitated crystals were collected, thoroughly washed with acetone, and 1-methyl-2-[p-C
5.039 of styrylic quinolinium iodide (2,2-dimethoxyethquine) was obtained.

m, p, 209-212℃ λmax (water):
224 hm, 255 °C m, 399 nm Reference Example 13 l-Methyl-2-[p-(2,2
-methoxyquinolinium7)-styrylquinolinium iodide 2.03 ? and degree of polymerization 1700, saponification rate 88%
Saponified polyvinyl acetate 205' was dissolved in distilled water 192-, and 0.42% of 85% phosphoric acid was added thereto, followed by reaction at a temperature of 80° C. for 20 hours with stirring. The reaction solution was neutralized with a weakly basic ion exchange resin. It was confirmed from the ultraviolet absorption spectrum that 0 mol % of styrylquinolinium groups were introduced into the polyvinyl alcohol in this photosensitive solution.

Reference Example 14 2.4.2j/p-formylphenoxyacetaldehyde dimethyl acecool obtained in Reference Example 4 and 2.911i' of 1,2-dimethylbenzothiazolium iodide were dissolved in 10 g of methanol, and Four drops of piperidine were added and the mixture was refluxed for 5 hours. When the reaction solution is cooled, crystals precipitate, so these are collected by filtration and washed with cold methanol to obtain 1-methyl-2-[p-(2,2-dimethoxyethoxy)styryl]benzothiazolium iodide 2.
．． I got 169.

Reference Example 15 l-Methyl-2-L obtained in Reference Example 14: p=(2,
2-dimethoxyethoxy)styryl]benzothiazolium iodide 2.059, degree of polymerization 1700, saponification rate 88
% of saponified polyvinyl acetate in 192ml of distilled water
After further adding 0.47 g of 85% phosphoric acid thereto, the mixture was reacted at a temperature of 80° C. for 20 hours with stirring.

The ultraviolet absorption spectrum showed that the polyvinyl alcohol in the photosensitive solution obtained by neutralizing the reaction solution with a weakly basic ion exchange resin contained 1.0 mol % of styrylbenzothiazolium groups.

Reference Example 16 10.00 ii' of the sodium salt of cunilin and 13.6 f of promoacetaltecht/ethyl acecool were added to 50 ml of dimethylacetamide and reacted by heating at a temperature of 200° C. for 3 hours. After cooling, add benzene 5 to the reaction solution.
By adding 0 ml of water, washing with water and cloth alkaline water, and distilling the organic layer under reduced pressure, a
-methoxy~4-(2,2-7ethoxy7ethyne)penzoaldehyl' 10.789 was obtained. This aldehyde is 1.729 and 1.4-methylquinolinium iodide is 1.65! i' was dissolved in 5 rnl of methanol, 5 drops of piperidine were added thereto, and the mixture was refluxed for 20 hours. By adding a mixed solvent of acetone and ethyl acetate to this and leaving it to stand, 1-methyl-4-[3'-methoxy-4'-(2,
1.04 f of 2-jethoxyethoxy)styryl]quinolinium iodide was obtained.

Reference Example 17 3-Methoxy-4-[p-(2,
2-jetoxylate 7) Styryl quinolinium iodide 2.289 and degree of polymerization 1700. 20f of saponified polyvinyl acetate with a saponification rate of 88% and 192mj of distilled water! Further, 0.41 g of 85% phosphoric acid was added thereto, and the mixture was reacted with stirring at a temperature of 80° C. for 20 hours. The reaction solution was neutralized with a weakly basic ion exchange resin. Polyvinyla/l/Co/l/K Ha1,0 in the obtained photosensitive solution
It was confirmed from the ultraviolet absorption spectrum that mol% of styrylquinolinium groups had been introduced.

Comparative Example 1 Polyvinyl acetate emulsion (
3.757 (solid content: 50%, PVA content: 4%) was thoroughly mixed. This light-sensitive emulsion was coated on a 250 mm cloth and dried to obtain a uniform film. This film is 4
60 at a distance of 1 m using a kW ultra-high pressure mercury lamp and on range 4.
The cured film was immersed in a solvent for 24 hours and the swelling ratio was measured. (The amount of membrane bundle before immersion is taken as 100%.) The results were 175% for water and 139% for acetone.

Separately, a Step Tablet & 2 (manufactured by Kodanok) was placed closely on top of this membrane, and a 4kW ultra-high pressure mercury lamp was used for 1 m.
The film was irradiated at a distance of 2/4 and developed with water using a spray can. In this method, step 1 is performed with p3o second irradiation.
Three steps were obtained with irradiation for 60 seconds. Similarly 1.
By irradiating at 2 m and at range 1, one step in 90 seconds and three steps in 150 seconds were obtained.

Example 1 0.827 of the 1-methyl-γ-(p-formylstyryl)pyridinium methosulfate obtained in Reference Example 1 was
J Vinyl acetate emulsion (50% solids).

PVA content 4%) In addition to 400f, 85% phosphoric acid 0.8? After adding, the mixture was heated to 45°C and stirred for 20 hours to react. Next, weakly basic ion exchange resin (Amberlite IRA-45) 6. After adding Oy and stirring gently to neutralize the phosphoric acid, the ion exchange resin was removed by filtration using a 400 mesh cloth.

3.75 fl of the photosensitive polyvinyl acetate emulsion thus obtained were thoroughly mixed with 107 fl of the photosensitive liquid obtained in Reference Example 2 and 2.50 fl of the photosensitive liquid obtained in Reference Example 3. This light-sensitive emulsion was applied to a 250 mesh cloth and dried to obtain a uniform film. 4. The cured film was irradiated with a kW ultra-high pressure mercury lamp at a distance of 1 m for 60 seconds under the condition of ren/4, and the swelling ratio was measured in the same manner as in Example 1.

A result of 140% water and 120% acetone was obtained.

Separately, in a curing test similar to Comparative Example 1, 3 steps of irradiation for 30 seconds at a distance of 1 m and condition of range 4,
5 steps can be obtained with 60 seconds of irradiation. Another 1.2m
Step 3 by irradiating for 90 seconds under the conditions of Range 1 at a distance of
Five steps were obtained by irradiating for 150 seconds.

Comparative Example 2 Photosensitive i12.50 obtained in Reference Example 5 and polyvinyl acetate emul/yon (solid content 50%, PVA content 4%) 3
．． 75 f was mixed well, and the prepared photosensitive emulsion was mixed with 250 f.
It was applied to Menon Utetron cloth and dried to obtain a uniform film.

According to the same curing test as in Comparative Example 1, 0 steps were obtained with irradiation for 30 seconds and 2 steps were obtained with irradiation for 60 seconds at a distance of 1 m under the conditions of Len/4.

Example 2 1-Methyl-4,-(p-(2,2-
zomethoxoethquine) styryl) pyridinium methosulfate 1.0! i' was added to the polyvinyl acetate emulsion, and 0.82% of 85% phosphoric acid was further added thereto, followed by a stirring reaction at a temperature of 80'C for 20 hours. Next, a weakly basic ion exchange resin (Amberlite RA-4 5) was added to the reaction solution.6. After adding Oy and stirring gently to neutralize the phosphoric acid, the ion exchange resin was removed by filtration using a 400 mesh cloth.

3.75 fl of the photosensitive polyvinyl acetate emulsion thus obtained and the photosensitive solution 12 and 5 obtained in Reference Example 5.
The emulsion obtained was thoroughly mixed and the resulting photosensitive emulsion was applied to a 250 mesh cloth and dried to obtain a uniform film.

In the same curing test as in Comparative Example 1, 2 steps were obtained by irradiating for 30 seconds at a distance of 1 m and 4 steps were obtained by irradiating for 60 seconds.

Comparative Example 3 Photosensitive liquid obtained in Reference Example 7 12.50! i' and polyvinyl acetate emulsion (solid content 50%, PVA content 4%)
) 3, 75f, i Mix well and add the prepared photosensitive emulsion to 2
The solution was applied to a cloth made of 50 mesostetron and dried to form a uniform film.

According to the same curing test as in Comparative Example 1, 0 steps were obtained with irradiation for 30 seconds and 2 steps were obtained with irradiation for 60 seconds at a distance of 1 m and under the condition of range 4.

Example 3 14-Methyl-4-ip-(2.2dimethoxybuty/)styryl)pyridinium p-toluenesulfone obtained in Reference Example 6 t·1.22! j′wo vinegar fil h=le x
Mulsion (solid content 50%, PVA content 4%) 40
In addition to 07, after adding 0.8f of 85% phosphoric acid,
The reaction was carried out at a temperature of 45° C. for 20 hours while stirring. Next, weakly basic ion exchange resin (An-Lye) IRA
-4 5) Add 6.07 and gently stir to neutralize the phosphoric acid, then filter and remove the ion exchange resin using a 400 meth/Utetron cloth.

Photosensitive polyvinyl acetate emul thus obtained/
Yo/3.75ii' and photosensitive liquid 12, 5 obtained in Reference Example 7
250% of the photosensitive resin composition liquid prepared by thoroughly mixing f.
A uniform film was obtained by applying it to Mesoshtetron cloth and drying it.

Curing test similar to Comparative Example 1] 1 m distance,
Under the conditions of range 4, 2 steps were obtained with irradiation for 30 seconds, and 4 steps were obtained with irradiation for 60 seconds.

Comparative Example 4 Photosensitive liquid obtained in Reference Example 9 12.59 and polyvinyl acetate emulsion (solid content 50%, PVA content 4%) 3.7
5S' was thoroughly mixed, and the resulting light-sensitive emulsion was applied to a 250 mesh cloth and dried to obtain a uniform film.

In the same curing test as in Comparative Example 1, 0 steps were obtained with irradiation for 30 seconds and 2 steps with irradiation for 60 seconds at a distance of 1 m and under the condition of range 4.

Example 4 1-methyl-2-(p-formylstyryl)-quinolinium methosulfate obtained in Reference Example 8) 0.94
f Polyvinyl acetate emulsion (solid content 50%,
PVA content 4%) In addition to 400f, 85% phosphoric acid 0.8? After adding, heat at 45℃ while stirring.
The reaction was allowed to proceed for 0 hours. Next is Amberlight (IRA-
After adding 4s) 6.0'y and stirring gently to neutralize the phosphoric acid, Amberlite RA-45 was removed by filtration using a 400 mesh Tetron cloth.

The photosensitive polyvinyl acetate emulsion 3.759 thus obtained and the photosensitive liquid i2.5 fi obtained in Reference Example 9
'Mix well. This light-sensitive emulsion was coated on a 250 mesh cloth and dried to obtain a uniform film.

In a curing test similar to Comparative Example 1, two steps were obtained with irradiation for 30 seconds and four steps were obtained with irradiation for 60 seconds under the conditions of distance range 4 of 1 m.

Comparative Example 5 A photosensitive composition emulsion obtained by mixing 12.5 r of the photosensitive liquid obtained in Reference Example 11 and 3.7 sy of polyvinyl acetate emulsion (solid content 50%, PVA content 4%) was mixed with 250 ml of photosensitive composition emulsion. It was applied to a Utetron cloth and dried to obtain a uniform film.

In the same curing test as in Comparative Example 1, one step was obtained with irradiation for 30 seconds and three steps were obtained with irradiation for 60 seconds under the conditions of distance range 4 of p and 1 m.

Example 5 ]-Methyl-4-(p-formylstyryl)quinolinium methosulfate obtained in Reference Example 10 0.94 f
l to polyvinyl acetate emulsion (solid content 50%, P
After adding 0.82% of 85% phosphoric acid to 400f (VA content 4%), stir at 45℃ for 20 minutes.
Allowed time to react. Subsequently, 6.07 g of a basic ion exchange resin (Amberlite RA-45) was added and gently stirred to neutralize the phosphoric acid, and then the ion exchange resin was filtered off using a 400 meter Utetron cloth.

The photosensitive polyvinyl acetate emulsion thus obtained was 3.757 g and the photosensitive solution obtained in Sanni Example 11 was 12.5 f.
The photosensitive resin composition emulsion obtained by thoroughly mixing t'
A uniform film was obtained by applying the solution to a cloth made from 50 Metun Utetron and drying it.

In the same curing test as in Comparative Example 1, 3 steps were obtained with irradiation for 30 seconds and 5 steps were obtained with irradiation for 60 seconds under the conditions of 1 m tUt range 4.

Comparative Example 6 12.5 f of the photosensitive solution obtained in Reference Example 13 and 3.7 sy of polyvinyl acetate emulsion (solid content 50%, PVA content 4%) were thoroughly mixed, and the resulting photosensitive emulsion was mixed with 250 ml of polyvinyl acetate emulsion. A uniform film was obtained by applying it to a cloth and drying it.

In the same curing test as in Comparative Example 1, 0 steps were obtained with irradiation for 30 seconds at a distance of 1 m and 40 conditions in the microwave, and 2 steps were obtained with irradiation for 60 seconds.

Example 6 1-Methyl-2-[p-(2,2
-dimethoxyethoquino)-styryl quinolinium iodide 1.1.6ii' in a polyvinyl acetate emulsion (
In addition to 4002 (solid content 50%, PVA content 4%),
After adding 0.82% of 85% phosphoric acid, the mixture was reacted in a trench at a temperature of 80° C. for 20 hours.

Next, basic ion exchange resin (Amberlite IRA-
45)6. After adding Of and stirring gently to neutralize the phosphoric acid, the ion exchange resin was filtered off using a 400 meth/Utetron cloth.

The photosensitive polyvinyl acetate emulsion thus obtained was 3.75 ? and 12.5f of the photosensitive liquid obtained in Reference Example 13.
The prepared photosensitive emulsion was coated on a 250 meter cloth and dried to obtain a uniform film.

According to the same curing test as in Comparative Example 1, under the conditions of 1 m distance range 4, 2 steps were obtained with irradiation for 30 seconds, and 4 steps were obtained with irradiation for 60 seconds.

Comparative Example 7 Photosensitive liquid obtained in Reference Example 15 12.59 and polyvinyl acetate emulsion (solid content 50%, PVA content 4%) 3.
The photosensitive emulsion was coated on a 250 Metsun Utetron cloth and dried to obtain a uniform film.

In the same curing test as in Comparative Example 1, at a distance of 1 m and under the condition of range 4, 0 steps were achieved with irradiation for 30 seconds, and 2 steps were achieved with irradiation for 60 seconds.

Example 7 1-Methyl-2-[p-(2,2
-dimethoxyethoxy)styryl]benzothiazolium iodide 1.17'? was added to vinyl acetate emulsion (solid content: 50%, PVA content: 4%) 4007, and 0.82% of 85% phosphoric acid was added thereto, followed by reaction at a temperature of 80° C. for 20 hours with stirring.

Next, basic ion exchange resin (Amberlite RA,
-45) 6. After adding Of and stirring gently to neutralize the phosphoric acid, the ion exchange resin was removed by filtration using a 400 meshtetron cloth.

3.75 f of the photosensitive polyvinyl acetate emulsion thus obtained and 12.57 f of the photosensitive solution obtained in Reference Example 15 were thoroughly mixed, and the resulting photosensitive resin composition emulsion was mixed with 250 m/Utetron cloth. A uniform film was obtained by coating and drying.

In the same curing test as in Example 1, two steps were obtained with irradiation for 30 seconds and four steps were obtained with irradiation for 60 seconds at a distance of 1 m and under 40 conditions in the microwave.

Comparative Example 8 Photosensitive i12.5f obtained in Reference Example 17 and polyvinyl acetate emulsion (solid content 50%, PVA content! 4%)
3.75 f/ was mixed well. 25% of this photosensitive emulsion
0 Meso/Utetron cloth was coated with 1 dried to form a uniform film.

In the same curing test as in Comparative Example 1, 0 steps were obtained with 30 seconds of irradiation and 2 steps with 60 seconds of irradiation at a distance of 1 m and the condition of microwave 4.

Example 8 1-Methyl-4-C3'-methquine obtained in Reference Example 16
4'-(2,2-jethoxyethoxy)styrylkquinolinium iodide 1.30 f' was added to polyvinyl acetate emulsion (solid content 50%, PVA content 4%) 40
(After adding 0.87 of 85% phosphoric acid in addition to
The reaction was carried out at a temperature of 80° C. for 20 hours while stirring. Next, basic ion exchange resin (Amberlite RA-4s
) 6. After adding oy and stirring gently to neutralize the phosphoric acid, the ion exchange resin was removed by filtration using a 400 meshtetron cloth.

The thus obtained photosensitive polyvinyl acetate emulsion (3.75 r) and the photosensitive solution obtained in Reference Example 17 (12.5 ml) were thoroughly mixed, and this photosensitive emulsion was applied to a 250 mm Utetron cloth and dried to form a uniform layer. A film was formed.

In the same curing test as in Comparative Example 1, two steps were obtained with irradiation for 30 seconds and four steps were obtained with irradiation for 60 seconds under the conditions of a distance of 1 m and range 4.

Proceedings IE passed away on January 17, 1981 Kazuten Wakasugi, Commissioner of the Japan Patent Office, Indication of the case, Patent Application No. 212233, filed in 1982, 2. Name of the invention, Photosensitive resin composition for screen printing plates, 3. Amendments made. Relationship with the patent applicant Makoto Ishizaka, Director of the Agency of Industrial Science and Technology, 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo (114)
4 Designated Agent 1-1-4 Higashi, Yatabe-cho, Tsukuba-gun, Ibaraki Prefecture (0034) Director, Institute of Industrial Science and Technology, Futoshi Nagaoka, Mizo Polymer Materials Research Institute
1932, sub-agent 5th floor, Tsuchiya Building, 6-4-5 Ginza, Chuo-ku, Tokyo
7. The number of inventions will increase as a result of the amendment 9. Contents of the amendment (1) The scope of the patent claims will be corrected as shown in the attached sheet.

(2) Lines 6 to 4 from the bottom of page 8 of the specification [3 is a lower alkyl group, or two R3
Remove the lower alkylene group.

(3) “Polysaponide” on page 19, lines 6-7
is corrected to "polyvinyl acetate saponified product". .

(4) Correct "pyrivinyl" in line 5 of page 21 to "polyvinyl".7.

(5) Page 23, line 6, “57yJ” as “671”
I will correct it.

(6) "Vinyl acetate" in the fifth line from the bottom of page 39 will be corrected to "1-polyvinyl acetate."

1 A photosensitive 1-resin composition prepared by adding 5 to 2.00 parts by weight of photocrosslinkable water-soluble polyvinyl alcohol per 00 parts by weight of the film-forming polymer compound into an aqueous alesion containing the film-forming polymer compound. For a screen printing plate, the polyacetic acid and nyl saponide contained in the 7J'C'1 raw emulsion as a protective colloid have been imparted with photo-crosslinking properties in advance. Photosensitivity (raw resin 1st product)

2 general formula (in the formula, R1 is a quaternized aromatic nitrogen-containing heterocyclic residue, R2 is a hydrogen atom or a lower alkoxyl group, n is an integer from j to G,
The photosensitive resin composition for screen printing plates according to claim 1, wherein a styryl residue represented by the formula (m is O or 1) is introduced to improve photocrosslinkability.

Claims (1)

[Scope of Claims] l 100 parts by weight of a film-forming polymer compound in an aqueous emulsion containing a film-forming polymer compound;
A photosensitive resin composition containing ~200 parts by weight of photocrosslinkable water-soluble polyvinyl alcohol, characterized in that the saponified polyvinyl acetate contained as a protective colloid in the aqueous emulsion is preliminarily imparted with photocrosslinkability. A photosensitive resin composition for screen printing plates. 2 General formula: 2 (In the formula, R1 is a quaternized aromatic nitrogen-containing complex complex residue, R2 is a hydrogen atom or a lower alkoxyl group, and R3 is each a lower alkyl group, or two R3 The screen printing plate according to claim 1, wherein a styryl residue represented by a lower alkylene group (i, rlj: an integer of 1 to 6, m is O or 1) is introduced to impart photocrosslinkability. Photosensitive resin composition for use.