JPH0242212B2 - - 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, in addition to basic requirements such as high sensitivity and high resolution, photosensitive resin compositions used as printing plate materials have
Printing durability that can withstand stress such as friction or compression when oil-based or water-based ink is applied, adhesion to the substrate,
Storage stability is also required. Photosensitive resin compositions used for such purposes 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 that use a dichromate or diazo resin as a photocrosslinking agent in an aqueous emulsion of a polymer such as partially saponified polyvinyl acetate, and these are widely used especially for screen printing plates. . However, such conventional aqueous emulsion type photosensitive resin compositions also have problems. In other words, (a) the solvent resistance of the base polymer itself constituting the aqueous emulsion is not sufficient, and (b) partial saponification in the photosensitive resin composition in order to avoid deterioration of the solvent resistance of the photosensitive resin composition. (c) Water resistance decreases as the amount of polyvinyl acetate increases.
Due to the use of a relatively large amount of surfactant as an emulsifier in polymer emulsion, it has been recognized that a cured film with excellent water resistance and solvent resistance, and hence printing durability, cannot be obtained. It will be done. On the other hand, a polymer in which a styrylpyridinium 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 (JP-A-55-23163, JP-A-55-23163;
62905), and an aqueous emulsion type photosensitive resin composition in which this photocrosslinkable polymer is added to a polymer emulsion of polyvinyl acetate instead of a photocrosslinking agent such as dichromate or diazo resin is also known. (Japanese Unexamined Patent Publication No. 1983-62446). This type of composition has excellent properties in terms of sensitivity and storage stability, but according to the research of the present inventors, in connection with the use of an emulsion polymer as the main base polymer, the following Some problems were found, such as: 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 plate may be exposed to organic solvents in the ink, resulting in oil resistance. Furthermore, water resistance is also insufficient, as erosion of the plate is promoted when water is mixed in the organic solvent. On the other hand, emulsions such as acrylic ester resin emulsion, ethylene-acrylic ester resin emulsion, SBR latex, silicone resin emulsion, vinyl chloride resin emulsion, vinylidene chloride resin emulsion,
In the process of mixing with an aqueous solution of a saponified vinyl acetate polymer to which a styrylpyridinium group or a styrylpyridinium group has been added, 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, the solvent resistance and water resistance of the obtained cured product are
This is also an obstacle. SUMMARY OF THE INVENTION In view of the above-mentioned drawbacks of the prior art, the present invention is a water dispersion type or aqueous emulsion type.
It is possible to provide a cured product with good solvent resistance, water resistance, and abrasion resistance, as well as dispersion stability and
The object of the present invention is to provide a photosensitive resin composition with good sensitivity and resolution. In other words, the photosensitive resin composition according to the present invention is
It is characterized in that it consists of an aqueous dispersion containing the following essential components (1) to (4). (1) Water-soluble saponified vinyl acetate polymer with added styrylpyridinium or styrylquinolinium groups, (2) Water-dispersible polymer, (3) Photopolymerizable unsaturated compound having an ethylenically unsaturated group, and (4) a photopolymerization initiator (if component (1) is a water-soluble saponified product of vinyl acetate polymer with added styrylpyridinium groups, component (2) is an ionomer resin alone) (No) Effects According to the present invention, a water-dispersible polymer and a photopolymerizable unsaturated compound are dispersed in an aqueous solution of a styrylpyridinium group- or styrylquinolinium-added polymer that itself has highly sensitive photocrosslinkability. As a result, a stable aqueous emulsion or water-dispersed photosensitive resin composition can be obtained using little or a relatively small amount of surfactant. Moreover, by photo-curing this composition, as a result of the combination of the three components mentioned above, it has excellent water resistance and solvent resistance, as well as excellent film properties, making it extremely suitable for printing plate materials such as screen printing plates. You can get things. 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 styrylpyridinium group or a styrylquinolinium group has been added (hereinafter often referred to as a "water-soluble photodimerizable polymer" for convenience) is emulsified with a photopolymerizable compound such as a vinyl monomer. Therefore, if this water-soluble photodimerizable polymer is used as a matrix and emulsifier to emulsify a photopolymerizable compound containing a photoinitiator, a safe aqueous emulsion can be obtained. Even if the photopolymerization initiator and photopolymerizable compound are sparingly soluble or insoluble in water, the emulsifying power of the water-soluble photodimerizable polymer provides a water-developable photosensitive material. On the other hand, a water-dispersible polymer itself has water-dispersibility. Therefore, by mixing the above components, a stable composition of the present invention can be obtained without using large amounts of surfactants. However,
The composition of the present invention exhibits high sensitivity and high resolution due to the presence of the water-soluble photodimerizable polymer, and it also has excellent film properties such as water resistance and solvent resistance of the water-dispersible polymer, resulting in good curing. Contributes to the formation of things. In addition, the photopolymerizable compound causes graft copolymerization using residual acetyl groups and the like in the water-soluble photodimerizable polymer upon curing. 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 Photosensitive Resin Composition The photosensitive resin composition according to the present invention contains the four essential components as described above. The details are as follows. In the following description, "%" and "part" representing composition are based on weight unless otherwise specified. Photosensitive saponified vinyl acetate polymer (component (1)) The continuous phase of the aqueous emulsion type or water dispersion type photosensitive resin composition of the present invention is component 1, that is,
It consists of an aqueous solution of a saponified vinyl acetate polymer (ie, a water-soluble photodimerizable polymer) to which a styrylpyridinium group or a styrylquinolinium group has been added. This polymer can generally be obtained by saponifying a vinyl acetate polymer and adding styrylpyridinium or quinolinium groups, preferably in this order. The polymer chains which contain styrylpyridinium or quinolinium groups or into which these groups are to be introduced in the preferred order mentioned above consist of saponified vinyl acetate polymers. Here, "vinyl acetate polymer" means:
Refers to both homopolymers and copolymers of vinyl acetate, specifically polyvinyl acetate, copolymers of vinyl acetate and monomers copolymerizable with vinyl acetate, and formal saponified polyvinyl acetate. lower (C ₁ - _{C 4} ) acetals such as oxidation or butyralization, and acetals formed by p-benzaldehyde sulfonate, β-butyraldehyde sulfonate, o-benzaldehyde sulfonate, 2,4-benzaldehyde sulfonate, etc. It contains chemical substances. When the vinyl acetate polymer is a copolymer, monomers copolymerizable with vinyl acetate include, for example, ethylene, acrylates (methyl acrylate, methyl methacrylate, etc.), acrylamides (acrylamide, methacrylamide, N-
methylol acrylamide, N,N-dimethylacrylamide, etc.), unsaturated carboxylic acids or their salts (acrylic acid, methacrylic acid, crotonic acid,
fumaric acid, itaconic acid, maleic acid, or salts thereof), cationic monomers (dimethylaminoethyl methacrylate, vinylimidazole, vinylpyridine, vinyl succinimide, etc.), and the like. The degree of saponification of the saponified vinyl acetate polymer into which styrylpyridinium or quinolinium groups are to be introduced is set to 70% in order to obtain a composition that is water-developable and gives a cured product with excellent solvent resistance and water resistance after photocuring. It is preferably in the range of ~99 mol%. 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%. In other words, 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 saponification degree value. Further, for the same reason as the above-mentioned limitation on the degree of saponification, a vinyl acetate polymer having a degree of polymerization in the range of 300 to 3000 is preferably used. The styryl pyridinium group or styryl quinolinium group addition polymer used in the present invention is prepared by applying an appropriate method to the above-mentioned saponified vinyl acetate polymer, preferably utilizing the alcoholic hydroxyl groups contained therein. It is obtained by adding a styrylpyridinium group or a styrylquinolinium group by acetalization.
The styrylpyridinium or quinolinium group obtained by this preferred method is typically represented by the following formula. [In the formula, m represents 0 or 1, and n represents an integer of 1 to 6. A is

[expression] or

[Formula] is shown. However, R ₁ 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). _R2 is
Indicates a hydrogen atom or a lower alkyl group. X ^- represents a halogen ion, a phosphate ion, a p-toluenesulfonate ion, a methylsulfate ion, an ethylsulfate ion, or a mixture of these anions]. This component (1) is thought to dimerize with styryl groups by light energy, and the introduction rate of styrylpyridinium or quinolinium groups is preferably 0.3 to 20 mol%, particularly 0.5 to 10% by mole per saponified vinyl acetate unit. The ratio in mol% is preferred. If the introduction rate is less than 0.3 mol %, a water-soluble photopolymerizable polymer having the desired photocrosslinkability cannot be obtained, while if it is introduced in excess of 20 mol %, the water solubility of the product will decrease significantly. Methods for producing such polymers with added styrylpyridinium or quinolinium groups are disclosed in JP-A-55-23163 and JP-A-55-62905.
No., JP-A-55-62405, and JP-A-58-49365. The continuous phase in the emulsion composition of the present invention is a water-soluble photodimerizable polymer as described above (this polymer itself can be prepared by adding the reaction solution after acetalization to a large amount of a poor solvent such as acetone or alcohol). The yield of the acetalization reaction is as high as about 80%, so the reaction solution can be used as it is after adjusting the concentration appropriately.
In addition, an ion exchange resin can be used without the acid used as a desolator. The polymer of component 1 may be used in combination. Water-dispersible polymer (component (2)) Component (2) of the composition of the present invention is a water-dispersible polymer that is understood to form a dispersed phase in the dispersion of the composition. Here, the term "water-dispersible polymer" means that a hydrophilic group is bonded to the base polymer, and that group allows it to be used without the use of an emulsifier (or in a small amount compared to the emulsification of hydrophobic polymers). means a polymer capable of forming an aqueous emulsion (by the use of an emulsifier). Even if the hydrophilic group is present in the polymer chain of the base polymer,
It may also be pendant from the polymer chain. The hydrophilic group is
It may be cationic, anionic, nonionic, or a combination thereof, and specifically includes quaternary ammonium groups, carboxylate groups, phosphonium groups, sulfonium groups, sulfonate groups, phosphonate groups, polyethylene oxide groups,
There are others. Preferred among these are anionic groups, particularly carboxylate groups and sulfonate groups. Specific examples of such water-dispersible polymers include those in which the base polymer is a polyurethane resin;
In particular, there are aqueous dispersions thereof. Many methods for producing aqueous dispersions of polyurethane resins have already been disclosed, such as a method in which polyurethane is dispersed in water under high shear in the presence of an emulsifier (U.S. Pat. No. 3,294,724). There are aqueous dispersions available, but they have the drawbacks that the dispersion state is insufficient and the resulting films have weak resistance to water. These drawbacks can be improved by water-dispersible high molecular weight polyurethane resins in which a small amount of hydrophilic groups are bonded to high molecular weight polyurethane resins. Dispersions of water-dispersible high molecular weight polyurethane resins in water are semi-permanently stable, and the films formed therefrom exhibit high elasticity, high tensile strength and high resistance to hydrolysis. In the present invention, as one of the water-dispersible polymers forming the dispersed phase, one that is imparted with water-dispersibility by a hydrophilic group bonded to a high molecular weight polyurethane resin can be used without using an emulsifier. The method for manufacturing these polyurethane dispersions is described in Japanese Patent Publication No. 43-9076.
There are those described in Japanese Patent Publication No. 44-27904, Japanese Patent Publication No. 45-26312, Japanese Patent Publication No. 50-2794, and Japanese Patent Publication No. 40-27349. West German Publication Nos. 2141805 and 2141807 disclose polyurethanes that have amino groups in their main chains and are dispersible in water.
Appl. Polym. Sci., 9 , 2451 (1965), etc. are known. Similar products that can be used in the present invention include a polyurethane dispersion modified with a vinyl polymer (JP-A-50-3159) and an aqueous emulsifier-free dispersion of polyurethane amide (JP-A-50-3159). Publication No. 13495). Another specific example of a water-dispersible polymer that is understood to form the dispersed phase in the dispersion of the present invention is a dispersion of polyester resin. For example, U.S. Pat.
No. 4052368, No. 3779993, No. 3639352 and No.
These include sulfonated polyesters such as those listed in No. 3853820. Yet another specific example of a water-dispersible polymer is an ionomer resin. Ionomer resins are generally copolymers of α-olefins and α,β-unsaturated carboxylic acids that are ionically crosslinked with metal ions, particularly Na ⁺ , K ⁺ or Z ⁺⁺ , and are produced by is Special Publication No. 39-6810, Special Publication No. 125768-1977,
This method is known from Japanese Patent Application Laid-open No. 49-31556 and Japanese Patent Application Laid-Open No. 49-121891. In order to obtain the composition of the present invention, it is preferable to prepare the water-dispersible polymer in advance as an aqueous dispersion. Water-dispersible polymers (polyurethane,
Polyester, ionomer, etc.) particle size is 0.01
A range of ~5μ is preferred. In the present invention, the above water-dispersible polymer 1
water-soluble photodimerizable polymer per part of
Preferably it is used in a proportion of 10 parts. If the amount is less than 0.2 part, the water-soluble photodimerizable polymer will not function as a protective colloid, resulting in poor uniform dispersibility and water developability. Furthermore, if the amount exceeds 10 parts, the effect of adding the water-dispersible polymer will be insufficient. Multiple types of the polymers of component 2 can also be used in combination. In the present invention, when component (1) is a water-soluble saponified product of vinyl acetate polymer to which a styrylpyridinium group has been added, an ionomer resin is not used alone as component (2). Photopolymerizable unsaturated compound (component (3)) Component 3 is a photopolymerizable unsaturated compound. The photopolymerizable unsaturated compound to be emulsified and dispersed in the aqueous solution of the styrylpyridinium- or styrylquinolinium-added polymer includes photoactive groups such as acryloyl group, methacryloyl group, allyl group, vinyl ether group, acrylamide group, and methacrylamide group. Those having one or more of the following and are insoluble or poorly soluble in water are preferably used. especially,
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-dipromopropyl(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 may be used alone or in combination of two or more to form a compound with respect to 1 part of the water-dispersible polymer.
It is preferable to use it in a range of 0.1 to 15 parts. When a plurality of water-dispersible polymers are used together, the total solid content is 1 part. If the amount of the photopolymerizable unsaturated compound is less than 0.1 part, the water resistance will not be sufficient, and if it is used in excess of 15 parts, there is a risk that the unsaturated compound will separate and precipitate on the coated and dried film. . Photopolymerization initiator (component (4)) The photosensitive composition of the present invention contains a photopolymerization initiator (component (4)) in addition to the above-mentioned components. As the photopolymerization initiator, almost all those used for photopolymerization of photopolymerizable unsaturated compounds as described above can be used. For example, substances that easily generate radicals under light irradiation are used, such as benzoin alkyl ether, Michler's ketone, di-tertiary butyl peroxide, tribromoacetophenone, or anthraquinone derivatives such as tertiary-butylanthraquinone, and thioxanthone derivatives such as chlorothioxanthone. . These photopolymerization initiators are
Use in the range of 0.001 to 0.15 parts (single use or combined use)
It is preferable to do so. Optional Components The photosensitive resin composition of the present invention basically consists of the above-mentioned components, but additives that are normally included in this type of photosensitive composition can be optionally added. Examples of such optional additives include, for example, emulsion stabilizers of 0.005 parts or less per 1 part of the water-dispersible polymer, and 0.3 parts or less of emulsion stabilizers per 1 part of photopolymerizable unsaturated compounds as solubilizers. Examples include organic solvents, thermal polymerization inhibitors, colorants such as dyes and pigments, antifoaming agents, and plasticizers. 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 water-soluble photoduplexable polymer (component (1)) 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 a water-dispersible polymer (component (2)).
Furthermore, a photopolymerization initiator (component (4)) is dissolved in a photoactive unsaturated compound (component (3)) or a mixture of this and a small amount of an organic solvent (especially a water-soluble one) used as necessary. Further, a solution obtained by adding components such as a thermal polymerization inhibitor is prepared, and this is mixed with the above-mentioned aqueous solution of the water-soluble photodimerizable polymer and aqueous dispersion of the water-dispersible polymer in a kneader, screw type stirrer, etc. The mixture is stirred to emulsify the mixture, and optional components such as a coloring agent and an antifoaming agent are added as necessary, and the mixture is stirred and mixed. Finally, optionally add additional photocrosslinker dissolved in a small amount of water and mix. The amount of water in the composition of the invention is not critical as long as a stable emulsion or aqueous dispersion is obtained, but the total amount of water-dispersible polymer, water-soluble photodimerizable polymer and photopolymerizable unsaturated compound is 1 Approximately 0.25 to 19 parts per part 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. It is applied onto a substrate to a dry thickness of, for example, 1 to 300 μm, dried, and used. 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 mm is 10 to 400 mm.
After curing the irradiated area by imagewise irradiation at 5000 mJ/cm ² , a relief image or image film is formed by removing the non-irradiated area with spray water, etc.
Used as various printing plates, resist films, etc. 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 get a 400μm screen version. To obtain a screen plate, the composition of the present invention is coated on a removable film such as 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 called the direct method, and it is easier to work with than the method of repeatedly applying the same photosensitive agent onto a screen mesh, and it also allows the production of plates with excellent printing properties. can. Since the photosensitive composition of the present invention has good storage stability even in a dry state, it has excellent suitability for use in such a direct method. As described above, according to the present invention, by dispersing a water-dispersible polymer and a photopolymerizable unsaturated compound in an aqueous solution of a water-soluble photodimerizable polymer that itself has highly sensitive photocrosslinkability, A stable emulsion or water-dispersed photosensitive resin composition can be obtained using little or even a relatively small amount of surfactant. Furthermore, by photo-curing this composition, as a result of the combination of the three components mentioned above, it has excellent water resistance and solvent resistance, as well as excellent film properties, making it extremely suitable as a printing plate material including screen printing plates. A cured product is obtained. Examples Examples 1 to 6 Ingredients used PVA manufactured by Kuraray Co., Ltd. (trade name "KL-506", degree of polymerization 600, degree of saponification 76 mol%) as a saponified product of vinyl acetate polymer to which styrylpyridinium groups have been added.
N-methyl-γ-(p
A 15% aqueous solution (hereinafter referred to as "Liquid A-1") of a polymer to which 1.3 mol % of -formylstyryl) pyridinium and p-toluenesulfonate is added is prepared. As photopolymerization components, 3 parts by weight of benzyl methyl ketal ("Irgacure651" manufactured by Ciba Geigy) and p-methoxyphenol (thermal polymerization inhibitor)
0.01 part by weight was added to 30 parts by weight of tetramethylolmethane triacrylate (photopolymerizable unsaturated compound "A-TMM-3" manufactured by Shin Nakamura Chemical Co., Ltd.), acrylate oligomer ("M-8060" manufactured by Toagosei Co., Ltd.) 15 parts by weight,
Polyester acrylate (2,2-bis(4
-acryloxydiethoxyphenyl)propane)
(Photopolymerizable unsaturated compound “A” manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
-BPE-4'') mixed with 5 parts by weight (hereinafter referred to as ``BPE-4'').
-1 solution). Examples of water-dispersible polymers include commercially available “Desmocol KA-8100” and “Desmocol KA-8100”.
8066” (polyurethane emulsion manufactured by Sumitomo Bayer Urethane Co., Ltd.), “Hydran HW-100”, “Hydran HW-140”, “Hydran HW-111” (polyurethane emulsion manufactured by Dainippon Ink and Chemicals Co., Ltd.), "Finetex ES-675" (polyester emulsion manufactured by Dainippon Ink & Chemicals Co., Ltd.) is used and mixed at the weight ratio shown in Table 1. Experimental method When mixed at the composition ratio of Example 1, a highly viscous suspension is obtained. Add methyl cellosolve or methanol to adjust the viscosity so that the viscosity is 2,500 to 5,000 cps/20°C. The photosensitive solution is passed through a Tetron 300 mesh screen, and the Tetron 300 mesh screen is fixed to an aluminum frame, and then the photosensitive solution is applied using a stainless steel bucket and dried. This process was repeated to form a photoresist film with a thickness of 15 μm. A positive film is attached to this photosensitive film,
Exposure was carried out for 2 minutes at a distance of 1 m from a 4KW ultra-high pressure mercury lamp. A screen plate with a resolution of approximately 100 μm was obtained by immersing it in water for 2 minutes and spray developing it with water. Similar experiments were conducted using the compositions of Examples 2 to 6, and screens with a resolution of 100μ were also obtained. Comparative example PVA (“GH”) manufactured by Nippon Gosei Co., Ltd. was
12% aqueous solution of a polymer in which 1.0 mol% of N-methyl-γ-(p-formylstyryl)pyridinium p-toluenesulfonate was added by acetalization reaction to ``-17'', polymerization degree 1700, saponification degree 88 mol%) Make 260 polymerization parts, add 62.4 parts by weight of vinyl acetate polymer emulsion to this, mix well, and prepare a photosensitive solution. This photosensitive solution was applied onto a 300 Tetron mesh screen fixed to an aluminum frame in the same manner as in Examples 1 to 6 to form a photosensitive film with a thickness of 15 μm. A positive film was applied to this, exposed for 3 minutes, and developed with water. A screen version with a resolution of about 150μ was obtained. When the plates of Examples 1 to 6 and the plates of Comparative Example were wiped with a rag using acetone, Examples 1 to 6 were
Although the photoresist film did not become sticky or the image was damaged in the case of the comparative example, it became sticky and the halftone dots were broken.

【table】

[Table] * ◎ Excellent ○ Good △ Bad Examples 7 to 12 The above "Liquid A-1" was used as the saponified product of the vinyl acetate polymer to which styrylpyridinium groups were added, and the above "B-1" was used as the photopolymerization system component. 1 liquid" was used, and water-dispersible polymers were mixed and used as shown in Table 2. The experiment is carried out in the same manner as in Examples 1-6. Table 2 shows the composition and evaluation.

[Table] The photosensitive solutions prepared in Examples 1 to 12 were uniformly dispersed and could be stored for one year without any problem. Examples 13 to 18 PVA manufactured by Nippon Gosei Co., Ltd. was used as a saponified product of vinyl acetate polymer with added styrylpyridinium groups.
(GL-05, degree of polymerization 500, degree of saponification 88 mol%) was subjected to acetalization reaction to N-methyl-γ-(p-
A 15% aqueous solution (hereinafter referred to as "Liquid A-2") of a polymer to which 1.3 mol % of (formylstyryl) pyridinium p-toluenesulfonate and 1 mol % of sodium o-benzaldehyde sulfonate were added was prepared. "Liquid B-1" was used as a photopolymerization system component, and as water-dispersible polymers, in addition to those used in Examples 1 to 12, commercially available ones were used, such as "Corpolene Latex L6000", “Same L-4000”, “Same L-
6004” (ionomer dispersion manufactured by Asahi Dow Co., Ltd.), “Chemipearl S-100”, “Chemipearl S-120” (Mitsui Petrochemical Co., Ltd.)
ionomer dispersion), “Surlyn 2”, “Surlyn S2”
(Ionomer dispersion manufactured by Dupont Co., Ltd.) was used,
Mix at the weight ratio shown in Table 3. The experiment was conducted in the same manner as in Examples 1 to 12,
Get the screen version. The results are shown in Table 3. Examples 19-22 PVA manufactured by Nippon Gosei Co., Ltd. was used as a saponified product of vinyl acetate polymer added with styrylpyridinium groups.
("GH-17", degree of polymerization 1700, degree of saponification 88 mol%)
N-methyl-γ-(p
-Formylstyryl) A 12% aqueous solution (hereinafter referred to as "Liquid A-3") of a polymer to which 1.3 mol% of pyridinium p-toluenesulfonate and 0.5 mol% of sodium o-benzaldehyde sulfonate are added is prepared. The photopolymerization system components include 2 parts by weight of benzyl dimethyl ketal (Irgacure651), 1 part by weight of RTX (thioxanthone photoinitiator manufactured by Nippon Kayaku Co., Ltd.), and DMBI (photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd.). A liquid (hereinafter referred to as "B- 2 liquid). The water-dispersible polymers shown in Table 4 are used. The experiment is carried out in the same manner as in Examples 1 to 18 to obtain screen plates. The results are shown in Table 4.

【table】

【table】

[Table] Examples 23 to 26 PVA manufactured by Nippon Gosei Co., Ltd. as a saponified product of vinyl acetate polymer with added styrylquinolinium groups
(“GM-11”, degree of polymerization 1100) N-methyl-γ-(p-formylstyryl) was formed by acetalization reaction.
A 12% aqueous solution of a polymer to which 1.0 mol% of quinolinium p-toluenesulfonate has been added (hereinafter referred to as “A-
Make 4 liquids). "Liquid B-2" is used as a photopolymerization system component, and those shown in Table 5 are used as water-dispersible polymers. The experiment was carried out in the same manner as in Examples 1 to 22,
Get the screen version. The results are shown in Table 5.

[Table] Application example 1 A polyester base made of matte photosensitive liquid prepared in Example 3 (product name "DIAMAT", Kimoto Co., Ltd.)
Co., Ltd.) to a thickness of 15 μm, dried, covered with positive film, and exposed to a 4KW ultra-high pressure mercury lamp at a distance of 1 m for 2 minutes. I lightly sprinkled the entire surface with tap water and developed it with spray water. Thereafter, when it was stained with a staining solution (bromophenol blue solution or "Dr. Martens" (trade name)), a negative visible image was formed on the polyester film compared to the positive film. Negative visible images were obtained using the compositions obtained in Examples 1 and 2 and Examples 4 to 26 in a similar manner. Application Example 2 The photosensitive solution of Example 13 was applied to a polyester film with a smooth surface and a thickness of 75 μm using a test bar coater, and dried with warm air (40° C.). The thickness of the photoresist film after drying was 25μ. next,
Fix the Tetron 300 mesh net to the screen frame,
The screen was washed, and the photoresist surface of the above film and the wet screen were gently pasted together.
Thereafter, the screen plate with the photosensitive film and polyester film was placed on a flat table, and pressed from the side of the screen using a rubber roller or squeegee so that the screen and the photosensitive film were in good contact.
After drying this with warm air (40°C) for 30 minutes, the polyester film was gently peeled off, and the photoresist film was transferred to the screen, leaving a smooth film on the warm polyester surface. In this state, I left it in a dark place for a month, covered it with positive film, and put it under a 1m 4KW ultra-high pressure mercury lamp.
The film was exposed to light for 2 minutes at a distance of 2 minutes, and developed with water to obtain a screen plate with a 100μ resolution and clear edges. Reference example Apply a photosensitive liquid to a polyester film in the same way as above, dry it, place it on a table with the photosensitive film side facing up, and place Tetron 270 on top of it.
Place a mesh (colored screen) and keep it on the stand. A small amount of the photosensitive solution of Example 13 was placed thereon and a bar coater was used to wet the screen and photosensitive film. After drying using a hairdryer, remove the adhesive to form a photoresist film fixed to the screen. In addition, by applying a resin treatment to the screen to reduce its elasticity and coating it with photosensitive liquid and drying it, a screen plate in which the screen and photosensitive film are integrated can be made. Application example 3 Tetron 130 mesh mesh is treated with resin to reduce screen expansion and contraction, and the photosensitive liquid of Example 13 is coated with a coating machine to increase the screen thickness.
I got a 15μ photosensitive resin processed screen. This screen was cut into 20cm x 30cm pieces and stored in a black plastic bag for 6 months at room temperature. Thereafter, it was taken out and plate-made using a positive film with a one-point mark for T-shirts. When this plate was attached to a wooden frame and printed on a T-shirt using water-based ink, a beautiful one-point mark was printed. Application example 4 The photosensitive solution of Example 13 was applied to a 75μ polyester film.
The film was applied twice using a coating machine to create a 30μ direct film. This direct method film was poured onto a Tetron 270 mesh orange-dyed screen, and after drying, the same photosensitive solution was applied back and forth from the screen side using a bucket and dried. The resulting version was stored as a PS version in a plastic bag for one year. Later, I took it out and made a plate for pattern printing (line width 100μ) for printed circuit boards, and printed 3000 sheets with UV ink, but the plate was not damaged. Application example 5 The photosensitive solution of Example 13 was applied to a 75μ polyester film.
A 20 μm direct film was created by applying the film using a coating machine. 300 polyester mesh red dyed screen aluminum frame 950mm x 950
It was applied evenly to mm. After applying the above film to a degreased and cleaned screen and drying it thoroughly,
I removed the film base. A 150-line halftone positive film was vacuum-adhered to this surface for plate making. When I printed on paper using this version, I was able to get a clear print that I had never experienced before with screen printing. For reference, when using diazo photosensitive liquid, the limit is 120 lines.

Claims (1)

[Scope of Claims] 1. A photosensitive resin composition comprising an aqueous dispersion containing the following essential components (1) to (4). (1) Water-soluble saponified vinyl acetate polymer with added styrylpyridinium or styrylquinolinium groups, (2) Water-dispersible polymer, (3) Photopolymerizable unsaturated compound having an ethylenically unsaturated group, and (4) a photopolymerization initiator (if component (1) is a water-soluble saponified product of vinyl acetate polymer with added styrylpyridinium groups, component (2) is an ionomer resin alone) (No) 2. A patent in which the water-dispersible polymer is a polyurethane resin or polyester resin imparted with water-dispersibility by a quaternary ammonium group, a carboxylate group, a phosphonium group, a sulfonium group, a sulfonate group, a phosphonate group, or a polyethylene oxide group. A composition according to claim 1. 3 Component (1) has a degree of saponification of 70 to 99 mol% and a degree of polymerization
300 to 3000 vinyl acetate polymer with a styrylpyridinium group or styrylquinolinium group added at an addition rate of 0.3 to 20 mol%, the composition according to claim 1 or 2. . 4. Any one of claims 1 to 3, wherein component (1) has a styrylpyridinium group or a styrylquinolinium group represented by the following general formula including a vinyl acetate polymer chain. 1
The composition described in Section. [In the formula, m represents 0 or 1, and n represents an integer of 1 to 6. A is [Formula] or [Formula] (wherein R ₁ represents a hydrogen atom, an alkyl group, or an aralkyl group (these may contain a hydroxyl group, a carbamoyl group, an ether bond, or an unsaturated bond). R ₂ represents a hydrogen atom ^or a lower alkyl group. A patent claim containing 0.2 to 10 parts by weight of a saponified vinyl acetate polymer to which a styrylpyridinium group or a styrylquinolinium group has been added and 0.1 to 15 parts of a photopolymerizable unsaturated compound per 1 part by weight of the polyester polymer. The composition according to any one of the ranges 1 to 4.