JPH0248105B2 - KANKOSEIJUSHISOSEIBUTSU - Google Patents

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION The present invention relates to an aqueous emulsion type or water dispersion type photosensitive resin composition having excellent suitability for producing printing plates (particularly screen printing plates). Various photosensitive resin compositions are used as printing plate materials, photoresists in photoetching, or vehicles for paints and printing inks. In particular, photosensitive resin compositions used as printing plate materials require not only basic requirements such as high sensitivity and high resolution, but also printing durability that can withstand stress such as friction or compression when oil-based or water-based inks are applied. , adhesion to the base material, storage stability, etc. are also required. Photosensitive resin compositions used for such uses are broadly classified into solvent-developable, alkaline water-developable, and water-developable types. Most of them are homogeneous photosensitive compositions, and some of them are of water-developable type and some use aqueous emulsion. For example, there are photosensitive resin compositions in which a dichromate or diazo resin is used as a photocrosslinking agent in an aqueous emulsion of a polymer such as partially saponified polyvinyl acetate or polyvinyl acetate, which is widely used especially for screen printing plates. It is used. However, such conventional aqueous emulsion type photosensitive resin compositions also have problems. In other words, (a) the base polymer itself constituting the aqueous emulsion does not have sufficient solvent resistance, and (b) partial saponification in the photosensitive resin composition is necessary to keep the solvent resistance of the photosensitive resin composition intact. Water resistance and The problem is that a cured film with excellent solvent resistance and therefore printing durability cannot be obtained. On the other hand, a polymer in which a stilbazolium group is introduced into a partially saponified vinyl acetate polymer chain is known as a water-soluble, highly sensitive photosensitive polymer that itself has photo-crosslinking properties (Japanese Patent Laid-Open No. 55-23163, No. 55 −
62905), and this photocrosslinkable polymer is used instead of a photocrosslinking agent such as dichromate or diazo resin.
Also known is an aqueous emulsion type photosensitive resin composition which is prepared by adding a polymer emulsion such as polyvinyl acetate (Japanese Patent Application Laid-Open No. 55-62446). Although this type of composition has excellent properties in terms of sensitivity and storage stability, our research has shown that, in conjunction with the use of emulsion polymers as the main base polymer, Several problems were found. In other words, when a cured product obtained using polyvinyl acetate emulsion, which is the most typical polymer emulsion, is used as a printing plate, the printing plate may be contaminated with the organic solvent in the ink, resulting in insufficient oil resistance. In addition, when water is mixed into the organic solvent, erosion of the plate is promoted, resulting in insufficient water resistance. On the other hand, emulsions such as acrylic emulsions, ethylene-acrylic acid ester emulsions, SBR latex, silicone resin emulsions, vinyl chloride polymer emulsions, vinylidene chloride polymer emulsions, etc. are mixed with aqueous solutions of saponified vinyl acetate polymers with stilbazolium groups added. During the mixing process, problems such as thickening, gelation, dispersion of the emulsion, and generation of coarse particles tend to occur. Furthermore, since a relatively large amount of surfactant is used when using any emulsion,
This also impairs the solvent resistance and water resistance of the obtained cured product. SUMMARY OF THE INVENTION In view of the above-mentioned drawbacks of the prior art, the present invention provides an aqueous dispersion type or aqueous emulsion type,
The object of the present invention is to provide a photosensitive resin composition that can provide a cured product having good solvent resistance and water resistance, and also has good dispersion stability, sensitivity, and resolution. Summary That is, the photosensitive resin composition of the present invention comprises an aqueous solution of a saponified vinyl acetate polymer having a stilbazolium group added, an ionomer resin, a photopolymerizable unsaturated compound having an ethylenically unsaturated group,
It is characterized in that it consists of an aqueous dispersion containing a photopolymerization initiator. Effects According to the present invention, by dispersing an ionomer resin and a photopolymerizable unsaturated compound in an aqueous solution of a stilbazolium addition polymer that itself has highly sensitive photocrosslinking properties, almost no surfactant is used. A stable emulsion or water-dispersed photosensitive resin composition can be obtained without or even with a relatively small amount. Moreover, due to the photocuring of this composition, it has excellent water resistance and solvent resistance as a result of the combination of the three components mentioned above, as well as excellent film properties, making it extremely suitable as a printing plate material including screen printing plates. A cured product is obtained. The reason why the composition of the present invention has excellent properties that meet the above objectives is not necessarily clear, but it is thought to be a sum of the following factors. That is, a vinyl acetate polymer to which a stilbazolium group has been added (hereinafter often referred to as a "stilbazolium addition polymer" for convenience) is
This stilbazolium addition polymer is used as a matrix polymer and emulsifier because it not only has high-sensitivity photocrosslinking properties by itself, but also has an emulsifying effect on photopolymerizable compounds such as vinyl monomers. A stable aqueous emulsion can be obtained by emulsifying a photopolymerizable compound containing .
On the other hand, ionomer resins are not usually obtained by emulsion polymerization, but due to their ionic nature, they can be relatively easily made into aqueous dispersions. Therefore,
By mixing the two, a stable composition of the present invention can be obtained without using a large amount of surfactant. Therefore, the composition of the present invention exhibits high resolution and high resolution due to the presence of the stilbazolium addition polymer, and the excellent film properties such as water resistance and solvent resistance of the ionomer resin result in a good cured product. Contribute to formation. In addition, during curing, the photopolymerizable compound causes graft copolymerization using residual acetyl groups in the stilbazolium-added polymer. In this way, the cured product of the composition of the present invention has both good water resistance and solvent resistance, and also has good film properties. DETAILED DESCRIPTION OF THE INVENTION The photosensitive resin composition according to the present invention contains four essential components as described above. The details are
It is as follows. In the following description, "%" and "part" indicating composition are based on weight unless otherwise specified. Photosensitive saponified vinyl acetate polymer The continuous phase of the emulsion-type or water-dispersed photosensitive resin composition of the present invention consists of an aqueous solution of a saponified vinyl acetate polymer to which a stilbazolium group has been added (ie, a stilbazolium-added polymer). The polymer chain into which the stilbazolium groups are to be introduced consists of saponified vinyl acetate polymer. Here, the term "vinyl acetate polymer" refers to both homopolymers and copolymers of vinyl acetate, specifically, polyvinyl acetate and vinyl acetate and monomers copolymerizable with it. Copolymers and lower (C ₁ to _{C 4} ) acetals such as formalized or butyralized products of saponified polyvinyl acetate, p-benzaldehyde sulfonic acid, β-butyraldehyde sulfonic acid, o-benzaldehyde sulfonic acid, 2,4 - Contains acetalized products such as benzaldehyde sulfonic acid. Examples of monomers copolymerizable with vinyl acetate include ethylene, acrylates (methyl acrylate, methyl methacrylate, etc.), acrylamides (acrylamide, methacrylamide, N-
methylol acrylamide, N,N-dimethylacrylamide, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid,
fumaric acid, itaconic acid, etc.), cationic monomers (dimethylaminoethyl methacrylate, vinylimidazole, vinylpyridine, vinyl succimide, etc.). The degree of saponification of the saponified vinyl acetate polymer into which stilbazolium groups are to be introduced is determined in order to provide a composition that is water-developable and gives a cured product with excellent solvent resistance and water resistance after photocuring, and the necessary emulsifying effect. A range of 70 to 99 mol % is preferred in order to provide a stilbazolium addition polymer with . Here, "partially saponified vinyl acetate polymer with saponification degree of 70 to 99 mol%" means that when the raw vinyl acetate polymer is a homopolymer of vinyl acetate, the content of the vinyl alcohol moiety is 70 to 99 mol%. It means 99 mol%. Therefore, this partially saponified vinyl acetate polymer is synonymous with a vinyl alcohol polymer having a vinyl alcohol content of 70 to 99 mol%. Therefore, the amount of monomers copolymerizable with vinyl acetate that constitutes the vinyl acetate polymer should also be limited so as to provide this degree of saponification value. In addition, for the same reason as the limitation on the degree of saponification mentioned above, the degree of polymerization of vinyl acetate polymer is 300 to 3000.
Those within the range of are preferably used. The stilbazolium addition polymer used in the present invention is a saponified vinyl acetate polymer as described above.
It is obtained by adding a stilbazolium group by acetalization using the alcoholic hydroxyl group contained therein, and has a stilbazolium group represented by the following general formula (displayed including the saponified vinyl acetate polymer chain). However, R ₁ in the above formula represents a hydrogen atom, an alkyl group, or an aralkyl group, which may contain a hydroxyl group, a carbamoyl group, an ether bond, or an unsaturated bond, and R ₂ represents a hydrogen atom or a lower alkyl group. . X ^- represents a halogen ion, a phosphate ion, a p-toluenesulfonate ion, or a mixture of these anions, m is 0 or 1,
n represents an integer of 1 to 6. The above-mentioned stilbazolium addition polymers are disclosed in JP-A Nos. 55-23163, 55-62905, and 55-
No. 62405, etc., and the manufacturing method is also known as described in these publications, but just to be sure, the outline of the manufacturing method is as follows. First, m- or -p-formylbenzaldehyde is converted into m- or -p-formylbenzaldehyde with the general formula By conducting a condensation reaction with picolines represented by the general formula Obtain formylstilbazoles represented by
By N-alkylating this, the formula A stilbazolium salt having a formyl group represented by is obtained. Also, instead of the picolines in the above formula (2), the formula The above can also be achieved by using a pre-N-alkylated picolinium salt represented by and reacting it with m- or p-formylbenzaldehyde.
A stilbazolium salt having a formyl group of formula (4) is obtained. On the other hand, in the above method, instead of m- or p-formylbenzaldehyde, the formula If we use the formyl phenoxy acetal represented by the formula A stilbazolium salt with an acetal group represented by is obtained. Therefore, the stilbazolium addition polymer obtained by the above formula (1) is composed of a saponified vinyl acetate polymer and a stilbazolium salt having a formyl group of the above formula (4) (a stilbazolium addition polymer with m = 0 in the above formula (1)). ) or a stilbazolium salt having an acetal group of the above formula (7) (where m=
When obtaining the stilbazolium addition polymer of 1)
It is obtained by reacting (acetalization) with the following in the presence of an acid catalyst. In addition, in the above formulas (2) to (7), R ₁ , R ₂ , X ^- , m
and n have the same meaning as in formula (1),
R ₃ represents an alkyl group or an alkylene group. In the stilbazolium addition polymer used in the present invention, the introduction rate of stilbazolium groups is preferably 0.3 to 20 mol%, particularly preferably 0.5 to 10 mol%, per saponified vinyl acetate unit. If the introduction rate is less than 0.3 mol%, a stilbazolium addition polymer having the desired photocrosslinkability cannot be obtained, while if it is introduced in an amount exceeding 20 mol%, the water solubility will be significantly reduced. The continuous phase in the emulsion composition of the present invention consists of an aqueous solution of the stilbazolium addition polymer as described above (isolated by pouring the reaction solution after acetalization into a large amount of poor solvent such as acetone or alcohol). Since the yield of the above acetalization reaction is as high as about 80%, the reaction solution can be used as it is after adjusting the concentration appropriately. Note that an ion exchange resin can also be used as a catalyst without the acid used. Ionomer resin The ionomer resin that is understood to form the dispersed phase in the dispersion of the present invention can basically be of any type, but is preferably a copolymer of α-olefin and α,β-unsaturated carboxylic acid. An ionomer resin in which the aggregate is ionically crosslinked with metal ions is used. Suitable α-olefins include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, and 3-methylbutene-1.
Examples include 1,4-methylbutene-1. Further, suitable α,β-unsaturated carboxylic acids include acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, fumaric acid, and the like. Instead of these α,β-unsaturated carboxylic acids, their esters such as methyl acrylate,
Ethyl acrylate, methyl methacrylate, n-butyl methacrylate, dimethyl fumarate, diethyl itaconate, dimethyl maleate, and the like can also be used. The above-described α-olefin and α,β-carboxylic acid or ester thereof may be used alone or in combination of two or more. Preferred metal ions include Na ⁺ , Mg ⁺⁺ or
Examples include Zn ⁺⁺ . A particularly preferred ionomer resin is a copolymer of ethylene and acrylic acid or methacrylic acid ^.
It is obtained by ionic crosslinking with Mg ⁺⁺ or Zn ⁺⁺ . The production method of ionomer resin itself is well known, for example, Japanese Patent Publication No. 39-6810, Japanese Patent Publication No. 42
-125768, JP-A-49-31556, JP-A-49-
The methods described in each publication such as No. 121891 can be adopted. When obtaining the composition of the present invention, it is preferable to prepare the above-mentioned ionomer resin in advance as an aqueous dispersion. To obtain such an aqueous dispersion, the ionomer resin is pressurized,
Method of dispersing in heated water
62890, etc.), or a method in which finely pulverized ionomer resin is dispersed in water using a surfactant or a hydrophilic protective colloid such as polyvinyl alcohol can also be adopted. The dimensions of the ionomer resin particles in the dispersion range from 0.01 to 5μ, especially
A range of 0.05 to 1μ is preferable. For reference, such ionomer resins can also be made into photosensitive compositions by adding PVA, diazo resin, and dichromate in the conventional manner. In the present invention, the above-mentioned ionomer resin 1
It is preferable to use the above-mentioned stilbazolium addition polymer at a ratio of 0.5 to 10 parts. If the amount is less than 0.5 parts, the stilbazolium addition polymer does not function as a protective colloid and cannot be developed with water. Moreover, if it is used in excess of 10 parts, the effect of the addition of the ionomer resin will be insufficient. Photopolymerizable unsaturated compound The photopolymerizable unsaturated compound to be emulsified and dispersed in the stilbazolium addition polymer aqueous solution contains one photoactive group such as acryloyl group, methacryloyl group, allyl group, vinyl ether group, acrylamide group, methacrylamide group, etc. Of those having the above properties, those that are insoluble or poorly soluble in water are preferably used. In particular, those having two or more photoactive groups are preferred because they provide cured products with good solvent resistance. The photopolymerizable unsaturated compound includes photopolymerizable prepolymers or oligomers having a degree of polymerization of 10,000 or less, in addition to photopolymerizable compounds usually called vinyl monomers. Examples of such photopolymerizable unsaturated compounds include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and trimethylolpropane tri(meth)acrylate.
Acrylate, trimethylolethane tri(meth)acrylate, dibromneopentyl glycol di(meth)acrylate, 2,8-dibromopropyl(meth)acrylate, triallyl isocyanurate, methoxyethyl vinyl ether,
Tertiary butyl vinyl ether, lauryl (meth)acrylate, methoxyethylene glycol (meth)acrylate, 2-ethylhexyl (meth)
Acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, hexyldiglycol (meth)acrylate, ethylene glycol di(meth)acrylate, di~hexaethylene glycol di(meth)acrylate, ethylene glycol diacrylate Glycidyl ether (meth)acrylate, 2-ethyl-hexyl glycidyl ether (meth)acrylate, phenyl glycidyl ether (meth)acrylate, 2-methyloctylglycidyl ether (meth)acrylate, trimethylolpropane polyglycidyl ether poly(meth)acrylate , terephthalic acid diglycidyl ether (meth)acrylate, reaction product of tolylene diisocyanate and 2-hydroxypropyl (meth)acrylate, reaction product of phenyl isocyanurate and 2-hydroxyethyl (meth)acrylate, etc., or maleic acid. Examples include unsaturated polyesters having an ethylenically unsaturated group and a molecular weight of 10,000 or less, such as acid glycol esters. In the above, "(meth)acrylate"
means both acrylate and methacrylate. These photopolymerizable unsaturated compounds are preferably used alone or in combination of two or more in an amount of 0.3 to 20 parts per part of the ionomer resin.
If the amount of the photopolymerizable unsaturated compound is less than 0.3 parts, the water resistance will not be sufficient, and if it is used in excess of 20 parts, the unsaturated compound may separate and precipitate on the coated and dried film. Photopolymerization Initiator The photosensitive composition of the present invention contains a photopolymerization initiator in addition to the above components. As the photopolymerization initiator, almost all those used for photopolymerization of photopolymerizable unsaturated compounds as described above can be used. For example, there are substances that easily generate radicals under light irradiation, such as benzoyl alkyl ether, Michler's ketone, di-tertiary butyl peroxide, tribromoacetophenone, anthraquinone derivatives such as tertiary-butylanthraquinone, and thioxanthone derivatives such as chlorothioxanthone. used. These photopolymerization initiators are preferably used in an amount of 0.001 to 0.15 parts per part of the photopolymerizable unsaturated compound. Other Components The photosensitive resin composition of the present invention basically consists of the above-mentioned essential components, but may optionally contain additives normally included in this type of photosensitive composition. Examples of such optional additives include:
An emulsion stabilizer of 0.005 parts or less per 1 part of ionomer resin, 0.3 parts or less of an organic solvent per 1 part of the emulsion stabilizer as a solubilizing agent for photopolymerizable unsaturated compounds,
Furthermore, coloring agents such as thermal polymerization inhibitors, dyes, and pigments,
Examples include antifoaming agents. Further, although the stilbazolium addition polymer used in the present invention has photocrosslinking properties by itself, an additional photocrosslinking agent may be further included in the composition of the present invention in order to provide a stronger photocured product. You can also do it. Examples of photocrosslinking agents used for this purpose include (a) dichromates such as ammonium dichromate, potassium dichromate, and sodium dichromate, and (b) 1-diazodiphenylamine-paraformaldehyde. Anionic complex diazo resins such as sulfates of condensates, phosphates, and double salts of zinc chloride can be used. In addition to para-amino diphenylamine, examples of this type of diazo resin include 4-amino-4'-methyldiphenylamine, 4-amino-4'-ethyldiphenylamine,
4-Amino-4'-methoxydiphenylamine, 4
- Diazotized diphenylamines such as amino-4'-chlorodiphenylamine and 4-amino-4'-nitrodiphenylamine are added to paraformaldehyde, acetaldehyde, propionaldehyde,
A water-soluble diazo resin condensed with an aldehyde such as n-butyraldehyde can be used. These photocrosslinkers are stilbazolium addition polymer 1
It can be used up to about 0.20 parts per part. Preparation of Composition The following method is usually used to obtain the composition of the present invention from the above-mentioned components. That is, the stilbazolium addition polymer is dissolved in a predetermined amount of water to form an aqueous solution (as described above, the acetalization reaction solution may be used as it is). Separately, prepare an aqueous dispersion of ionomer resin. A solution obtained by dissolving a photopolymerization initiator in a photoactive unsaturated compound or a mixture of this and a small amount of an organic solvent used as necessary, and further adding components such as a thermal polymerization inhibitor, is prepared. Stir with the above stilbazolium addition polymer aqueous solution and ionomer resin aqueous dispersion using a kneader, screw type stirrer, etc. to emulsify, and optionally add optional components such as a coloring agent and an antifoaming agent and stir. Mix. lastly,
Add additional photocrosslinker dissolved in a small amount of water if necessary and mix. The amount of water in the composition of the present invention is not critical as long as a stable emulsion or aqueous dispersion is obtained, but it ranges from 0.25 to 1 part of the total amount of ionomer resin, stilbazolium addition polymer and photopolymerizable unsaturated compound. Approximately 19 copies is appropriate. Use of the composition The photosensitive resin composition of the present invention obtained as described above can be applied to metal plates such as aluminum, screen meshes, paper, wood, synthetic resin plates, semiconductor substrates, and other arbitrary materials depending on the purpose. on the base material to a dry thickness of, for example, 1 to 300 μm,
Used dry. This photosensitive material is irradiated with active light such as ultraviolet rays, for example, in the case of ultraviolet rays, the amount of irradiation energy in the wavelength range of 300 to 400 nm is 10 to 10.
After curing the irradiated area by imagewise irradiation at 5000 mJ/cm ² and removing the non-irradiated area with spray water, a relief image or image film is formed, which can be used as each printing plate, resist film, etc. used. One preferred embodiment of the use of the photosensitive resin composition of the present invention is use as a photosensitive material for screen plates. In this case, the composition of the present invention is repeatedly applied and dried on a screen mesh made of synthetic resin such as polyester, nylon, or polyethylene, or a metal vapor-deposited product such as nickel on these resins, or stainless steel. 40～
All you need to do is obtain a 400 μm screen plate. To obtain a screen plate, the composition of the present invention is applied onto a releasable film made of polyethylene, polyvinyl chloride, polyester, etc., and dried for 15 to 15 minutes.
It is also possible to obtain a coating film of 100 μm and transfer this coating film to a screen mesh coated with water or the photosensitive resin composition of the present invention. This method is a so-called direct method, and is easier to work with than the method of repeatedly applying the same photosensitive agent onto a screen mesh, and it also produces plates with excellent printing characteristics. I can do it. Since the photosensitive composition of the present invention has good storage stability even in a dry state, it is extremely suitable for use in such a direct method. Experimental Examples Example 1 4 parts of benzoin ethyl ether (initiator) and 0.01 p-methoxyphenol (thermal polymerization inhibitor)
30 parts of trimethylolmethane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., "A-TMM-3"), 30 parts of acrylate oligomer (manufactured by Toagosei Co., Ltd., "M-
8060'') and 5 parts of polyester acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., ``A-BPE-4'') to obtain a uniform photopolymerizable unsaturated compound solution. Separately, partially saponified polyvinyl acetate (polymerization degree
1700, degree of saponification 88 mol%, Nippon Gohsei Co., Ltd. "Gohsenol GH-17") by acetalization reaction
-10% of stilbazolium addition polymer obtained by adding 0.7 mol% of methyl-γ-(p-formylstyryl)pyridinium p-toluenesulfonate
260 parts of aqueous solution and 27% aqueous dispersion of ionomer resin (“CHEMIPEARL S” manufactured by Mitsui Petrochemical Industries, Ltd.)
Prepare 25 parts of ``-100''), mix them well,
Furthermore, the photopolymerizable unsaturated compound solution prepared above was added and mixed for 60 minutes using a stirring motor to obtain a pale yellow emulsion photosensitive liquid. This photosensitive solution was applied to Tetron 200 mesh (colored yellow) using a bucket and dried repeatedly to form a photosensitive film with a thickness of 10 μm. This photoresist film was exposed to light for 2 minutes at a distance of 1 m from a 4 kW ultra-high pressure mercury lamp (manufactured by Oak Seisakusho). After exposure, the photosensitive film was immersed in water for 2 minutes, and then developed by spraying with water to obtain a screen plate with a resolution of approximately 100 μm.The screen plate was further immersed in an aqueous bromophenol solution and dried to be dyed blue. A screen version was obtained. This screen plate was immersed in acetone for 24 hours, but no peeling of the film was observed, indicating that a plate with excellent solvent resistance was obtained. Example 2 Benzyl methyl ketal [“Irgacure 651”
(manufactured by Ciba Geigy)] and 0.005 parts of p-methoxyphenol (thermal polymerization inhibitor) were dissolved in 27 parts of pentaerythritol triacrylate to obtain a uniform photopolymerizable unsaturated compound solution. Separately, carboxyl-modified partially saponified polyvinyl acetate (polymerization degree
600, degree of saponification 76 mol%, manufactured by Kuraray Co., Ltd. "KL-
506'') by acetalization reaction to N-methyl-γ
260 parts of a 15% aqueous solution of a stilbazolium addition polymer obtained by adding 1.3 mol% of -(p-formylstyryl)pyridinium p-toluenesulfonate and a 40% aqueous dispersion of an ionomer resin (Asahi Dow
After mixing these, the photopolymerizable unsaturated compound solution prepared above was added and mixed for 60 minutes using a stirring motor. A pale yellow emulsion-like photosensitive solution was obtained. This photosensitive solution was applied to Tetron 300 mesh (colored red) using a bucket and dried repeatedly to form a photosensitive film with a thickness of 15 μm. This photoresist film was heated to 1.
Exposure was carried out for 2 minutes at a distance of m. A screen plate with a resolution of about 80 μm was obtained by immersing the exposed photoresist film in water for 2 minutes and spray developing it with water. This was further immersed in an aqueous bromophenol solution and dried to obtain a screen plate dyed blue. Comparative Example 1 In Example 2, the photosensitive solution obtained by removing the photopolymerizable unsaturated compound was repeatedly coated and dried on Tetron 300 mesh (colored red) using a bucket.
A photoresist film with a thickness of 15 μm was formed. This photoresist film is 4kw
It was exposed to an ultra-high pressure mercury lamp at a distance of 1 m for 3 minutes and developed by spraying with water. Comparative Example 2 A photosensitive solution obtained by removing the ionomer resin in Example 2 was repeatedly coated and dried on a Tetron 300 mesh (colored red) using a bucket to form a photosensitive film with a thickness of 15 μm. This photosensitive film is 4kw
It was exposed to an ultra-high pressure mercury lamp at a distance of 1 m for 3 minutes and developed by spraying with water. The evaluation results of the screen plates obtained in Example 2 and Comparative Examples 1 and 2 were as shown in the table below.

[Table] Example 3 7 parts of benzoin isobutyl ether (initiator) and p-methoxyphenol (thermal polymerization inhibitor)
0.01 part of acrylate oligomer (Toagosei Co., Ltd.)
60 parts of acrylate oligomer (M-600A- manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.)
A uniform photopolymerizable compound solution was obtained by dissolving 20 parts of the photopolymerizable compound. Separately, partially saponified polyvinyl acetate (polymerization degree
1700, saponification degree 78 mol% "Gohsenol KH-17" manufactured by Nippon Gosei Co., Ltd.) by acetal exchange reaction,
230 parts of a 10% aqueous solution of stilbazolium addition polymer with 1 mol% of N-methyl-4-{p-(2,2-dimethoxyethoxy)styryl}pyridinium methosulfate added and 27% of ionomer resin.
Prepare 25 parts of an aqueous dispersion (“CHEMIPEARL S-120” manufactured by Mitsui Petrochemical Industries, Ltd.),
Mix these well, add the photopolymerizable unsaturated compound prepared above, and use a stirring motor for 60 min.
Mixing for a minute resulted in a deep yellow emulsion-like sensitivity. This was further mixed with 0.1 g of a water-dispersible pigment ["Nyurachimin Color Green" (manufactured by Dainichiseika Co., Ltd.]) to make a colored photosensitive solution, which was applied and dried using a bucket on Tetron 250 mesh (yellow). The process was repeated to form a photoresist film with a thickness of 10 μm. This photoresist film was exposed for 2 minutes and 30 seconds from a 4 kW ultra-high pressure mercury lamp (manufactured by Oak Seisakusho) at a distance of 1 m. After exposure, the photoresist film was immersed in water for 2 minutes and further spray developed with water to obtain a screen plate with a resolution of about 100 μm. Example 4 8 parts of benzyl methyl ketal (Irgacure 651) and p-methoxyphenol (thermal polymerization inhibitor)
0.01 part was dissolved in 90 parts of acrylate oligomer (M-8060 manufactured by Toagosei Co., Ltd.) to obtain a uniform photopolymerizable unsaturated compound. Separately, partially saponified polyvinyl acetate (polymerization degree
1700, saponification degree 88 mol% Gohsenol GH-17 (manufactured by Nippon Gosei Co., Ltd.) was subjected to an acetal reaction to add 1 mol of N-methyl-4-{p-(2,2-dimethoxybutoxy)styryl}pyridinium p-toluenesulfonate. % addition of 200 parts of a 10% aqueous solution of stilbazolium addition polymer and ionomer resin.
40% aqueous dispersion (Copolene Latex L manufactured by Asahi Dow Co., Ltd.)
−4000) and 39 parts, and after mixing these,
Furthermore, the photopolymerizable unsaturated compound solution prepared above was added and mixed for 60 minutes using a stirring motor to obtain a yellow emulsion-like photosensitive liquid. This photosensitive solution was repeatedly coated and dried on a Tetron 250 mesh (colored yellow) using a bucket to form a photosensitive film with a thickness of 10 μm. This photoresist film was exposed for 3 minutes at a distance of 1 m from a 4 kW ultra-high pressure mercury lamp (manufactured by Oak Seisakusho). A screen plate with a resolution of about 100 μm was obtained by immersing the exposed photoresist film in water for 2 minutes and spray developing with water. Example 5 The photosensitive liquid of Example 1 was applied to a test bar coater model.
It was applied onto a polyester film with a thickness of 75 μm using No. 9 (Yoshimitsu Scientific Instruments Co., Ltd.) and dried with warm air (40° C.). The thickness of the photosensitive film after drying is
It was 23 μm. Place this film under a Tetron 270 mesh (colored yellow) with the photosensitive film facing up, and after fixing the screen frame, pour 10g of the photosensitive solution from Example 1 onto the screen, and apply it to the screen with a rubber squeegee. I squeegeeed it so that the whole thing was wet. Thereafter, the photosensitive layer was fixed on the screen by drying with warm air (40°C) for 30 minutes.
When the polyester film was gently peeled off by hand, the photosensitive layer was transferred to the screen and had a smooth, glossy surface. This photoresist film was placed at a distance of 1 m from a 4kw ultra-high pressure mercury lamp (manufactured by Oak Seisakusho).
Exposure was made for a minute. After exposure, the photoresist film was immersed in water for 2 minutes and further developed with water spray to obtain a screen plate with clear edges and a resolution of 100μ.

Claims (1)

[Claims] 1. Contains an aqueous solution of a saponified vinyl acetate polymer having a stilbazolium group added, an ionomer resin, a photopolymerizable unsaturated compound having an ethylenically unsaturated group, and a photopolymerization initiator. A photosensitive resin composition comprising an aqueous dispersion. 2 The ionomer resin is a copolymer of ethylene and an α,β-unsaturated carboxylic acid selected from acrylic acid and methacrylic acid, with Na ⁺ , Mg ⁺⁺ and
The composition according to item 1 above, which is a resin ionically crosslinked with metal ions selected from Zn ⁺⁺ . 3 A saponified vinyl acetate polymer with stilbazolium groups added has stilbazolium groups added at an addition rate of 0.5 to 20 mol% to a vinyl acetate polymer with a degree of saponification of 70 to 99 mol% and a degree of polymerization of 300 to 3000. The composition according to item 1 or 2 above, which is 4 Any one of the above items 1 to 3, wherein the saponified vinyl acetate polymer added with a stilbazolium group has a stilbazolium group represented by the following general formula including the vinyl acetate polymer chain. The composition described in Section. However, R ₁ in the above formula represents a hydrogen atom, an alkyl group, or an aralkyl group, which may contain a hydroxyl group, a carbamoyl group, an ether bond, or an unsaturated bond, and R ₂ represents a hydrogen atom or a lower alkyl group. . X ^- represents a halogen ion, a phosphate ion, a p-toluenesulfonate ion, or a mixture of these anions, m is 0 or 1,
n represents an integer of 1 to 6. 5 For 1 part by weight of ionomer resin, 0.5 to 10 parts by weight of saponified vinyl acetate polymer with added stilbazolium group, 0.3 to 20 parts by weight of photopolymerizable unsaturated compound
The composition according to any one of items 1 to 4 above, comprising parts by weight.