JPS60247637A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a screen printing plate material as well as other printing plate materials superior in water and solvent resistance and film characteristics by dispersing a water-dispersible polymer and a photopolymerizable unsatd. monomer into an aq. soln. of a polymer adding styrylpyridinium or styrylquinolium group. CONSTITUTION:The continuous phase of an aq. emulsion or dispersion type resin compsn. is composed of an aq. soln. of a saponified polyvinyl acetate polymer adding styrylpyrydinium or styrylquinolium group. Such an aq. emulsion or dispersion can be prepared by dissolving a water-soluble photodimerizable polymer in a prescribed amt. of water to form an aq. soln. 1, on the other hand, preparing an aq. dispersion of a water-dispersible polymer 2, dissolving a photopolymn. initiator in a liquid mixture of a photoactivatable unsatd. compd. and a small amt. of org. solvent to be used when needed to form a soln. 3, further adding components such as heat polymn. inhibitor, to said soln. 3 to prepare a soln. 4, mixing it with the soln. 1 and the dispersion 2, and stirring the mixture in a kneader, a screw type stirrer, or the like to emulsify said mixture.

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 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 water-developable and some use aqueous emulsions. For example, there are photosensitive resin compositions that use dichromate or diazo resin as a photocrosslinking agent in an aqueous emulsion of a polymer such as partially saponified polyvinyl acetate, and 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 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 avoid deterioration of the solvent resistance of the photosensitive resin composition. Water resistance and solvent resistance are poor due to reasons such as increasing the amount of polyvinyl acetate and reducing water resistance, and (c) using a relatively large amount of surfactant as an emulsifier for polymer emulsions. The problem is that a cured film with excellent properties and therefore printing durability cannot be obtained.

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-bathable, highly sensitive photosensitive polymer that itself has photo-crosslinking properties (JP-A-55-23163, JP-A-55-23163; 62905 publications),
In addition, aqueous emulsion type photosensitive resin compositions are also known in which the photocrosslinkable polymer dichromate, diazo resin, and other photocrosslinking agents are added to polymer emulsions such as polyvinyl acetate. Publication No. 55-62446)
. This type of composition has excellent properties in terms of sensitivity and storage stability.According to the research of the present inventors, in conjunction with the use of an emulsion polymer as the main permanent 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 does not have sufficient oil resistance, as it can be contaminated by the organic solvent in the ink. In addition, when water is mixed in the organic solvent, the plate becomes more eroded and the water resistance is not sufficient. On the other hand, emulsions such as acrylic ester resin emulsions, ethylene-acrylic ester resin emulsions, SDR' latex, silicone resin emulsions, vinyl chloride resin emulsions, vinylidene chloride resin emulsions, etc., are added with styrylpyri-qunium groups or styrylpyridinium groups. In the process of mixing with an aqueous solution of a saponified vinyl acetate polymer, 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 in any emulsion, the solvent resistance and water resistance of the obtained cured product are also impaired from this point of view.

SUMMARY OF THE INVENTION In view of the above-mentioned drawbacks of the prior art, the present invention provides a cured product that has good solvent resistance, water resistance, and abrasion resistance despite being a water dispersion type or aqueous emulsion type. Another object of the present invention is to provide a photosensitive resin composition having good dispersion stability, sensitivity, and resolution.

That is, the photosensitive resin composition according to the present invention consists of an aqueous dispersion containing the following essential components (1) to (4);
It is characterized by:

(1) a water-soluble saponified vinyl acetate polymer having a styrylpyridinium or styrylquinolinium group added, (2) a water-dispersible polymer, (3) a 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 group-added polymer that itself has highly sensitive photocrosslinking properties. Accordingly, a stable aqueous emulsion or water-dispersed photosensitive resin composition can be obtained using little or even a relatively small amount of surfactant. Moreover, by photo-curing this composition, as a result of the combination of the above three components, a cured product with excellent water resistance and solvent resistance and excellent film properties is produced, which is extremely suitable for printing plate materials such as screen printing plates. can get.

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 styrylpyridinium group is added (
(hereinafter often referred to as "water-soluble photodimerizable polymer" for convenience) has an emulsifying effect on photopolymerizable compounds such as vinyl monomers, so this water-soluble photodimerizable polymer is used as a matrix and emulsifier. If a photopolymerizable compound containing a photopolymerization initiator is emulsified using this method, a safe aqueous emulsion can be obtained. Even if the photopolymerization initiator and photopolymerizable compound are poorly soluble or insoluble in 71,
The emulsifying power of the water-soluble photodimerizable polymer makes it 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 a large amount of surfactant. Therefore, the composition of the present invention exhibits high sensitivity and high resolution due to the presence of the water-soluble photodimerizable polymer. Contributes to the formation of a good cured product. In addition, during curing, the photopolymerizable compound causes graft copolymerization using residual acetyl groups in the water-soluble photodimerizable 2-rimer. 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.

The photosensitive resin composition according to the present invention has the essential 4
It contains ingredients. The details are as follows.

In addition, in the following description, "1%" and "1%" representing the composition
Units are based on weight unless otherwise specified.

Photosensitive saponified vinyl acetate polymer (component (1)) The continuous phase of the aqueous emulsion type or water thicket type photosensitive resin composition of the present invention is composed of component 1, that is, added with a styrylpyridinium group or a styrylquinolinium group. It consists of an aqueous solution of a saponified vinyl acetate polymer (i.e., a water-soluble photodimerizable polymer). 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 1
"Vinyl acetate polymer" means both homopolymers and copolymers of vinyl acetate, specifically polyvinyl acetate and copolymers of vinyl acetate and monomers copolymerizable with it. and lower (C1 to C4) acetals such as formalization or butyralization of saponified polyvinyl acetate, p-benzaldehyde sulfonate, β-butyraldehyde sulfonate, O-(nzualdehyde sulfonate, 2,4 -Contains acetalized products such as benzaldehyde sulfonate.

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-methylolacrylamide P, N, N
-dimethyl acrylamide, etc.), unsaturated carzenic acids or ionic monomers (dimethylamine ethyl methacrylate, vinyl imidazole, vinyl pyridine, vinyl succinimide, etc.).

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 provides a cured product with excellent solvent resistance and water resistance after photocuring. The range is preferably from 99 molti to 99 molti. Here, "Saponification degree 70-99
"Partially saponified vinyl acetate polymer of molti" means that the content of the vinyl alcohol moiety is 70 to 99 molti when the raw vinyl acetate polymer is a homopolymer of vinyl acetate. 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. Furthermore, for the same reason as the limitation on the degree of saponification mentioned above, the degree of polymerization of vinyl acetate polymer is 300.
-3000 is preferably used.

The styrylpyridinium group or styrylquinolinium group addition polymer used in the present invention is acetalized by a method suitable for the saponified vinyl acetate polymer as described above, preferably using the alcoholic hydroxyl group contained therein. It is obtained by adding a styrylpyridinium group or a styrylquinolinium group.

The styrylpyridinium or quinolinium group obtained by this preferred method is typically represented by the following formula.

[In the formula, m is O or 1, n is an integer from 1 to 6 r'
L, , R1 represent a hydrogen atom, an alkyl group or an aralkyl group (which may contain a hydroxyl group, a carnomoyl group, an ether bond or an unsaturated bond).

The square indicates a hydrogen atom or a lower alkyl group. r represents a halogen ion, a phosphate ion, a p-)luenesulfonate ion, a methylsulfate ion, an ethylsulfate ion, or a mixture of these anions].

It is thought that this component (1) is dimerized with styryl groups by photoene/I/key, and the introduction rate of styrylpyridinium or quinolinium groups is preferably 0.3 to 207 units per saponified vinyl acetate unit. Particularly preferred is a ratio of 0.5 to 107%. The introduction rate is 0.
If the amount is less than 3 molar, a water-soluble photopolymerizable polymer having the desired photocrosslinkability cannot be obtained, while if it is added in excess of 3 molar, the water solubility of the product is significantly reduced. Methods for producing such polymers with added styrylpyridinium or quinolinium groups are disclosed in JP-A-55-23163 and JP-A-55-55.
-62905, JP-A No. 55-62405, JP-A-Sho 5
No. 8-49365 and other publications. The continuous phase in the emulsion composition of the present invention is a water-soluble photodimerizable polymer as described above (this polymer itself is
The yield of the acetalization reaction is approximately 80%.
%, so the reaction solution can be used as it is after adjusting the concentration appropriately.

In addition, with ion exchange resin, component 1 can be used as a decomposition medium.
0 polymer 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 present composition.

Here, "water-dispersible polymer" means that a hydrophilic group is bonded to the base polymer, and because of this group, it is possible to use a small amount of emulsifier without using an emulsifier (or with a small amount of emulsifier compared to the emulsification of a hydrophobic polymer). means a polymer capable of forming an aqueous emulsion). The hydrophilic group may be present within the polymer region of the base polymer or may be pendant from the polymer chain. The hydrophilic group may be cationic, anionic, nonionic, or a combination thereof, and specifically includes quaternary ammonium groups, calxylate groups, phosphonium groups,
There are sulfonium groups, sulfonate groups, phosphonate groups, polyethyleneoxy P groups, and others. Among these, anionic groups are preferred, with carboxylate groups and sulfonate groups being particularly suitable.

A specific example of such a water-dispersible polymer is one in which the base polymer is a polyurethane resin, particularly an aqueous dispersion thereof. Many methods for producing aqueous dispersions of polyurethane resins have already been disclosed, such as a method in which polyurethane resins are dispersed in water under high shear in the presence of an emulsifier (U.S. Pat. No. 3,294,724). Although there are aqueous dispersions available, they have the disadvantage that the dispersion state is insufficient and the resulting film has low resistance to water. These drawbacks are due to the high molecular weight of 4
This is improved by using a water-dispersible high molecular weight polyurethane resin in which a small amount of hydrophilic groups are bonded to the urethane resin. 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, the method for producing a dispersion that imparts water-dispersibility by using a hydrophilic group bonded to a high molecular weight polyurethane resin without using an emulsifier is as follows: Special Publication No. 43-9076, Special Publication No. 4
4-27904, Japanese Patent Publication No. 45-26312, Japanese Patent Publication No. 50-2794, and Japanese Patent Publication No. 40-27349, which also disclose a polyurethane dispersion containing polyethylene oxide ether. West German Publication Nos. 2141805 and 2141807 also disclose water-dispersible polyurethanes having amine groups in the main chain, as disclosed by J. 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). 13495). - Another specific example of a water-dispersible polymer that is understood to form a dispersed phase in the dispersion of the present invention is a dispersion of polyester resin. For example, U.S. Pat. No. 4,052,368;
No. 779.993, No. 3,639,352 and No. 3
, 853, 820, etc.
巳 -4-し中+f+也 1 Yet another specific example of the water-dispersible polymer is an ionomer resin. Ionomer resins are generally made by ionic crosslinking of copolymers of α-olefins and α,β-unsaturated caldic acids with metal ions, particularly Na+, K'' or z++), and the manufacturing method is Kosho 39-6810
No., JP 42-125768, JP 49-315
No. 56 and Japanese Unexamined Patent Publication No. 49-121891.

In order to obtain the composition of the present invention, the water-dispersible polymer is preferably prepared in advance as an aqueous dispersion. The particle size of the water-dispersible polymer (polyurethane, polyester, ionomer, etc.) in the dispersion is preferably in the range of 0.01 to 5 μm.

In the present invention, it is preferable to use the water-soluble photodimerizable polymer in a ratio of 0.2 to 10 parts with respect to 1 part of the water-dispersible polymer described above. If the amount is less than 0.2 parts, the water-soluble photodimerizable polymer will not function as a protective colloid.
Uniform dispersibility and water developability are poor. Furthermore, if it is used in an amount exceeding 10 parts, the effect of adding the water-dispersible polymer becomes 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 vinyl acetate polymer to which styryl 2 residual dinium groups are 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 polymer having a styrylpyridinium group or styrylquinolinium group includes photoactive groups such as acryloyl group, methacryloyl group, allyl group, vinyl ether group, acrylamide group, and methacrylamide group. Those having one or more molecules and being 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 compounds include photopolymerizable preprimers or oryzamers 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, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, dibrome Neopentyl glyco-/l/di(meth)acrylate, 2,8-dibromopropyl(meth)acrylate, triallyl isocyanurate, methoxyethyl vinyl ether, tert-butyl vinyl ether, lauryl(meth)acrylate,
Methoxyethylene glycol (meth)acrylate, 2
- Ethylhexy A/(meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, hexyl diglycol (meth)acrylate, ethylene glycol di(meth)acrylate, di-hexaethylene glycol di(
meth)acrylate, ethylene glycol diglycidyl ether A/(meth)acrylate, 2-functional phenyl glycidyl ether (meth)acrylate, 2-
Methyl octyl glycidyl ether (meth)acrylate, trimethylolpropane polyglycidyl ether poly(meth)acrylate, terephthalic acid diglycidyl ether (meth)acrylate, reaction product of tolylene diincyanate and 2-hydroxypropyl (meth)acrylate, phenyl Examples include reaction products of isocyanurate and 2-hydroxyethyl JL/(meth)acrylate, and unsaturated polyesters having an ethylenically unsaturated group such as maleic acid glycol ester and having a molecular weight of 10,000 or less. 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 0.1 to 15 parts per part of the water-dispersible polymer. The water-dispersible polymer is
When multiple types are used together, the total solid wood content is 1
Department. 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. be.

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-tert-butyl peroxide, tribromoacetophenone, anthraquinone derivatives such as tert-butylanthraquinone, and thioxanthone derivatives such as chlorothioxanthone. The amount of these photopolymerization initiators ranges from 0.001 to 1 part of the photopolymerizable unsaturated compound.
It is preferable to use it (single use or in combination) in a range of 0.15 part.

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 0.005 parts or less of emulsion stabilizers per 1 part of the water-dispersible polymer, and 0.005 parts or less of emulsion stabilizers per 1 part of the water-dispersible polymer; .3 parts or less of an organic solvent, furthermore, a thermal polymerization inhibitor, coloring agents such as dyes and pigments, antifoaming agents, plasticizers and the like.

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 photodimerizable 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, an aqueous dispersion of a water-dispersible polymer (component (2)) is prepared.

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 bathable 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, a stirrer with a set of screws, etc. The mixture is stirred and emulsified, and optional components such as a coloring agent and an antifoaming agent are added as necessary and 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, and dried for use. This photosensitive material is imagewise irradiated with active light such as ultraviolet rays, for example, in the wavelength range of 300 to 400 nm, and the amount of irradiation energy is 10 to 5000 mJ/cm2 to harden the irradiated areas. After this, if the non-irradiated areas are removed by spraying water or the like, a relief image or image film is formed, which is used as each printing plate, resist film, 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, on a screen mesh made of synthetic resins such as polyester, nylon, polyethylene, or metal vapor-deposited products such as nickel on these resins, or stainless steel, etc.
By repeating application and drying of the composition of the present invention, a thickness of 4
A screen plate of 0 to 400 μm may be obtained.

To obtain a screen plate, the composition of the present invention is applied onto a releasable film of polyethylene, polyvinyl chloride, polyester, etc., dried to obtain a coating film of 15 to 100 μm, and this coating film is coated with water or Similarly, a method of transferring the photosensitive resin composition of the present invention onto a screen mesh coated thereon is also possible. This method is called the 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 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, during water leakage of a water-soluble photodimerizable polymer that itself has highly sensitive photocrosslinkability,
By dispersing a water-dispersible polymer and a photopolymerizable unsaturated compound, a stable emulsion or water-dispersible photosensitive resin composition can be created using little or a relatively small amount of surfactant. You can get things. Moreover, due to the photocuring of this composition, as a result of the combination of the three components mentioned above, it has excellent water resistance and solvent resistance, and also has excellent film properties.
Therefore, a cured product can be obtained that is extremely suitable for printing plate materials such as screen printing plates.

Experimental Examples Examples 1 to 6 Ingredients used As a saponified product of vinyl acetate polymer to which styrylpyridinium groups were added, R201M PVA (trade name "K
L-506J, degree of polymerization 600, degree of saponification 76 mol%)
A 15% aqueous solution (
(hereinafter referred to as "Liquid A-1").

As a photopolymerizable component, pendyl methyl chemer (“Ir
gacure 651 J (manufactured by Chipa Geigy) 3 parts by weight (manufactured by Shin-Nakamura Chemical Co., Ltd.) Photopolymerizable unsaturated compound [
A-TMM-3J), 15 parts by weight of acrylate oryzamer (rM-so6o J manufactured by Toagosei ■), polyester acrylate (2,2-bis(4-acryloxyjethoxyphenyl)propane) (Shin Nakamura Chemical Industry Q)
I@photopolymerizable unsaturated compound j'A-npg~4'') 5
A liquid (hereinafter referred to as 1'f-x liquid) is prepared by mixing parts by weight.

As a water-dispersible polymer, commercially available “Desmoco”
Le KA-8100J, "Desmo=y-/l/KA-
8066” (polyurethane emulsion manufactured by Sumitomo Bayer Urethane ■), [Hytran HW-100J, [Hytran HW-140J, [Hydry Hw-111J]
(polyurethane emulsion manufactured by Dainippon Ink & Chemicals) and Finetex ES-675J (polyester emulsion manufactured by Dainippon Ink & Chemicals) were mixed in the weight ratio shown in Table 1.

Experimental Method When mixed at the composition ratio of Example 1, a highly viscous suspension is obtained. Viscosity is 2,500~5,000 eps 720℃
Add methyl cellosolve or methanol to adjust the viscosity so that This photosensitive solution was filtered using a Tetron 300 mesh mesh, and the Tetron 30 mesh was placed on an aluminum frame.
A photosensitive liquid is applied onto the fixed mesh screen using a stainless steel packet and dried. This process was repeated to form a photoresist film with a thickness of 15 μm. A positive film was closely attached to this photoresist film, and exposed for 2 minutes at a distance of 1 m from a 4 KW ultra-high pressure mercury lamp. A screen plate with a resolution of about 100 μm was obtained by immersing it in water for 2 minutes and spray developing it with water. Similar experiments were conducted with the compositions of Examples 2-6, yielding the same <100μ resolution screens.

Comparative Example PVA (1'-GH-17 manufactured by Nippon Gosei) was used as a saponified product of vinyl acetate polymer to which styrylpyridinium groups were added.
J, degree of polymerization 1700, degree of saponification (mol%)) of a polymer in which 1.0 mol of N-methyl-r-(p-formylstyryl)pyridinium p-)luenesulfonate was added by a 7-cetalization reaction. Prepare 260 parts by weight of a 12% aqueous solution, and add 62.4 parts by weight of vinyl acetate polymer emulsion to this.
Add parts by weight and mix well to prepare a photosensitive liquid. This photosensitive solution was applied onto a 300-mesh Tetron 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 plate with a resolution of approximately 150μ was obtained.

When the plates of Examples 1 to 6 and the plates of Comparative Example were wiped with a rag using acetone, the photoresist film of Examples 1 to 6 did not become sticky or the image was damaged, but the comparison The one in the example has become sticky and the halftone dots are missing.

Examples 7 to 12 The above "Liquid A-1" was used as a saponified product of vinyl acetate polymer to which a styrylpyridinium group was added, and the above "Liquid B-1" was used as a photopolymerization system component. The 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.

The photosensitive solutions prepared in Examples 1 to 12 were uniformly dispersed and could be stored for -2 years without any problem.

Examples 13 to 18 PVA manufactured by Nippon Gosei (GL-05J
, polymerization degree of 500, saponification degree of 1.3 mol.
A 15% aqueous solution of a polymer to which 1 mol of sodium o-benzaldehyde sulfonate has been added (hereinafter referred to as "Liquid A-2") is prepared.

"Liquid B-1" was used as a photopolymerization system component, and as a water-dispersible polymer, in addition to those used in Examples 1 to 12, commercially available "Corpolene Latex L-
6000J, [L-4000J, [L-6004J]
(Ionomer dispersion manufactured by Asahi Dow), "Cheminoglu S-100J", "Cheminoguru S-120J (ionomer dispersion manufactured by Mitsui Petrochemicals)", "Surlyn 2", "Cheminoguru S2" (
Ionomer dispersion (manufactured by DuPont) was used and mixed at the weight ratio shown in Table 3.

Experiments are carried out in the same manner as in Examples 1-12 to obtain screen plates.

The results are shown in Table 3.

Examples 19 to 22 PVA manufactured by Nippon Gosei (“GH-17J
, degree of polymerization 1700, degree of saponification 88 mol), 1.3 mol% of N-methyl-γ-(p-formylstyryl)pyridinium p-)luenesulfonate was added by acetalization reaction, and sodium O-benzaldehyde sulfonate was 0%. ．．
A 12% aqueous solution of a polymer with 5 molar additions (hereinafter referred to as “A-
Make 3 liquids).

As a photopolymerizable component, penzyl dimethyl ketal ([
Irgacure 651 J) 2 parts by weight, RTX
(Thiogisanthone photopolymerization initiator manufactured by Nippon Kaisha ■) 1 part by weight, DMBI (Photopolymerization sensitizer manufactured by Nippon Kaisha @l) 0.
5 parts by weight, p-methoxyphenol 0.01 part by weight, acrylate oligomer (I'M-8060J) 40
Part by weight, polyester acrylate) (A-13PE
-4) Prepare a liquid (hereinafter referred to as "Liquid B-2") in which 30 parts by weight are mixed.

The water-dispersible polymers shown in Table 4 are used.

Experiments are carried out in the same manner as in Examples 1-18 to obtain screen plates.

The results are shown in Table 4.

Example n- is a saponified product of vinyl acetate polymer to which a styrylquinolinium group has been added, PVA manufactured by Nippon Gosei ("GM-11J")
, polymerization degree 1100') by acetalization reaction.
- A 12% aqueous solution (hereinafter referred to as "Liquid A-4") of a polymer to which 1.0 mol of methyl-γ-(p-formylstyryl)quinolinium p-toluenesulfonate is added is prepared. "Liquid B-2" is used as the photopolymerization component, and the water-dispersible polymer is.

Use those shown in Table 5.

Experiments are carried out in the same manner as in Examples 1-22 to obtain screen plates.

The results are shown in Table 5.

Application example 1 Polyester base made by matting the photosensitive liquid prepared in Example 3 (trade name "I" IAMAT J, manufactured by Kimoto ■)
The film was coated to a thickness of 15 μm and dried, then a positive film was applied and exposed for 2 minutes using a 4% V ultra-high pressure mercury lamp at a distance of 1 m. I lightly sprinkled the entire surface with tap water and developed it with spray water.

Thereafter, when the polyester film 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.

Example 112 and Examples 4-2 in exactly the same manner
A negative visible image was obtained using the composition obtained in 6.

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 percoater, and dried with warm air (40° C.).

The thickness of the photoresist film after drying was 5 μm. Next, a Tetron 300 mesh was firmly fixed on the screen, the screen was washed, and the photosensitive surface of the above film and the wet screen were gently pasted together.

Thereafter, the screen plate with the photoresist film and polyester film was placed on a flat table, and pressed down from the screen side using a rubber roller or squeegee so that the screen and the photoresist film were in good contact.

After drying this with warm air (40° C.) for 1 minute, the polyester film was gently peeled off, and the photosensitive film was transferred to the screen, and the polyester surface became a smooth film. In this state, it was kept in a dark place for one month, and then exposed with a positive film for 2 minutes at a distance of 1 m (7) from a 4 KW ultra-high pressure mercury lamp, and developed with water to obtain a screen plate with 1 OOμ resolution and clear etching.

Reference Example: Apply a photosensitive liquid to a polyester film in the same way as above and dry it to make a film. Place the photosensitive film side up on a stand, place a Tetron 270 mesh (colored screen) on top of it, and place it on the stand. I'll fix it. A small amount of the photosensitive solution of Example 13 was placed thereon and a percoater 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, it is possible to create a screen plate in which the screen and photosensitive film are integrated.

Application Example 3 A Tetron 130 mesh net was treated with resin to reduce screen expansion and contraction, and the photosensitive solution of Example 13 was coated with a coating machine to obtain a photosensitive resin coated screen with a screen thickness plus 15 μm. This screen at 20 am
It was cut at 30 am and placed in a black plastic bag for 6 months and stored at room temperature. Thereafter, it was taken out and plated using a positive film of a one-point mark for T-shirts.

When this plate was mounted on 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 coated twice on a 75μ polyester film using a coating machine to produce an Iμ direct and open film. This direct method film is used as Tetron 270
A screen dyed with mesh orange was filled with water, and after drying, the same photosensitive solution was coated with a packet back and forth from the screen side and dried. The resulting version was called the 28th version and was stored in a plastic bag for one year. Later, I took it out, made a plate for printing a printed circuit board pattern (line width 100μ), and exposed it to UV light.
Although 3,000 sheets were printed using ink, there was no damage to the plates.

Application Example 5 The photosensitive solution of Example 13 was coated on a 75 μm polyester film using a coating machine to prepare a direct method film with added μ. Polyester 300 mesh red dyed screen aluminum frame 950 mm x 950 rrm
It was applied evenly. The above-mentioned film was covered with water on a degreased and washed screen, thoroughly dried, and then the film base was peeled off. 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 a diazo photosensitive solution, the limit is 120 lines.

Applicant's agent Kiyoshi Inomata

Claims (1)

[Scope of Claims] 1. A photosensitive resin composition comprising an aqueous dispersion containing the following essential components (1) to (4). (1) a water-soluble saponified vinyl acetate polymer with a styrylpyridinium or styrylquinolinium group added, (2) a water-dispersible polymer, (3) a 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. The water-dispersible polymer is a polyurethane resin or polyester resin imparted with water-dispersibility by a quaternary ammonium group, a carxylate group, a phosphonium group, a sulfonium group, a sulfonate group, a phosphonate group, or a polyethylene oxide group. , the composition according to claim 1. 3. Component (1) is a vinyl acetate polymer having a degree of saponification of 70 to 99 mol and a degree of polymerization of 300 to 3000, with a styrylpyridinium group or a styryl quinolinium group added at an addition rate of 0.3 to 20 mol. The composition according to claim 1 or 2, which is 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. The composition according to item 1. α2 [In the formula, m is 0 or 1, n is an integer from 1 to 6 as R in the water formula
□ indicates a hydrogen atom, an alkyl group, or an aralkyl group (
These may contain hydroxyl groups, carbamoyl groups, ether bonds or unsaturated bonds). R2 represents a hydrogen atom or a lower alkyl group. X- represents a halogen ion, phosphate ion, p-toluenesulfonate ion, methyl sulfate ion, ethyl sulfate ion, or a mixture of these anions)] 5. Styryl per 1 part by weight of the water-dispersible polymer Claims 1 to 4 contain 0.2 to 10 parts by weight of a saponified vinyl acetate polymer to which a pyridinium group or a styrylquinolinium group has been added and 0.1 to 15 parts by weight of a photopolymerizable unsaturated compound. The composition according to any one of the above.