JPH06230568A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To provide a photosensitive resin compsn. excellent in both stability of the photosensitive liq. and water resistance after exposure, especially a photosensitive resin compsn. fit for a relief printing plate or a screen printing plate. CONSTITUTION:This photosensitive resin compsn. consists of an emulsion (A) of a hydrophobic resin having >=45 deg.C glass transition temp. such as polymethyl methacrylate, polyvinyl chloride or polystyrene, polyvinyl alcohol resin (B), a polymerizable monomer (C) such as methyl methacrylate or methyl acrylate and a photopolymn. initiator (D). The amt. of the hydrophobic resin in the emulsion A is 10-30wt.% and the amt. of the resin B is 10-30wt.% of the total amt. of the resin B and the monomer C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition having excellent storage stability of a photosensitive solution and excellent water resistance after exposure.

[0002]

2. Description of the Related Art Among photosensitive resin plate resin compositions, a system comprising a mixture of a water-soluble polymer and a polymerizable monomer can be subjected to development treatment with water, and therefore other photosensitive resin plate resin compositions can be used. It has the advantage that it is easier to handle.

For example, Japanese Patent Publication No. 46-39401 discloses a water-soluble photosensitive resin composition containing a water-soluble monomer containing hydroxy (meth) acrylate as an essential component.
(x), a water-developable photosensitive polymer composition for relief convex plates, which comprises a water-soluble polymer compound represented by polyvinyl alcohol (y) and a uranyl salt-based photopolymerization initiator (z) is shown. , In that example, a water-soluble monomer
About 28 to 38% by weight of the water-soluble polymer compound (y) is used with respect to the total amount of (x) and the water-soluble polymer compound (y).

In Japanese Patent Publication No. 46-42450, a photosensitive polymer plate made of a composition comprising a water-soluble acrylic monomer and a water-soluble polymer is used as a support through both an adhesive layer and an antihalation layer. A method for obtaining a relief relief photopolymer plate by adhering to According to the production example, the ratio of the water-soluble polymer to the total amount of the water-soluble acrylic monomer and the water-soluble polymer is 2
It is 8.7% by weight.

JP-B-45-9614 discloses that a polyvinyl alcohol resin is used as a trunk polymer, and a vinyl monomer composed of an acrylic ester or / and acrylonitrile is graft-polymerized in an aqueous system to have a hydroxyl group in the molecule. There is disclosed a photoresist photosensitive solution in which an emulsion of a polymer and an organic photosensitive agent selected from a tetrazonium salt, a diazide compound or a diazo resin are mixed with a uranyl salt as a sensitizer.
Due to the nature of the photosensitive film, the amount of the polyvinyl alcohol resin used in the photosensitive solution must be 70% by weight or more based on the total solid content.

Japanese Patent Application Laid-Open No. 63-12 filed by the present applicant
2702 (Japanese Patent Application No. 61-270391) discloses a polymerizable vinyl compound, a polyvinyl alcohol-based resin having a saponification degree of 65 to 90 mol%, a polyvinyl alcohol-based resin having a saponification degree of 65 mol% or less, and a polymerization. A curable resin composition comprising an initiator is shown. The amount of the polymerizable vinyl compound used is 20 to 80% by weight based on the total amount of the two polyvinyl alcohol-based resins.

The Japanese Patent Publication No.
15936 (JP-A-57-108688)
Discloses a photosensitive resin composition obtained by adding a photoreaction accelerator to an aqueous synthetic resin dispersion containing an acetoacetylated polyvinyl alcohol-based resin or an allylated polyvinyl alcohol-based resin.

In the invention of this publication, there are three cases as a method for preparing an aqueous synthetic resin dispersion containing the above-mentioned specific polyvinyl alcohol resin. The first case is a method of emulsion-polymerizing or suspension-polymerizing a monomer using the polyvinyl alcohol resin as an emulsifier or a protective colloid. The second case is a method of post-emulsifying or post-suspending a solution or a melt of a synthetic resin with this polyvinyl alcohol resin. The third case is a method of adding the polyvinyl alcohol resin to a synthetic resin emulsion or suspension obtained by an arbitrary method.

In the case of the third of these cases, the styrene / butadiene polymer, cis-1,4
-Polyisoprene polymer, chloroprene polymer, acrylonitrile / butadiene polymer, vinyl pyridine polymer, methyl methacrylate / butadiene polymer, polyurethane, acrylic ester polymer, vinyl acetate polymer, ethylene-vinyl acetate polymer, The above polyvinyl alcohol resin is added to an emulsion or suspension of a vinyl chloride polymer, polystyrene, polyethylene, silicone, polybutene, thiochol, or the like. The addition amount is 5 to 500% by weight based on the solid content of the emulsion or suspension.

[0010]

[Problems to be Solved by the Invention] Japanese Patent Publication No. 46-3940
The photosensitive polymer compositions of JP-A No. 1 and JP-B-46-42450 are typical water-developable photosensitive resin compositions of a water-soluble acrylic monomer / polyvinyl alcohol system. It is necessary to add at least 28% by weight of the total amount of water-soluble acrylic monomer and polyvinyl alcohol, and since hydrophilic monomer is used in addition, the water resistance of the plate after exposure is naturally limited. was there. The curable resin composition of JP-A-63-122702 also had the same problem in terms of water resistance.

The photoresist photosensitive solution disclosed in Japanese Patent Publication No. 45-9614 is unavoidable in that the water resistance is insufficient because the blending amount of polyvinyl alcohol accounts for 70% by weight or more of the total solid content.

Insufficient water resistance of the plate after exposure means that the plate softens when the water-based ink is used as the ink, and the bare strips lose their shape, which impairs printability.

One method for improving the water resistance is to reduce the content of the polyvinyl alcohol resin as much as possible, but this will impair the stability of the photosensitive solution.

Among the documents cited above, Japanese Patent Publication No. 4-
15936 (JP-A-57-108688)
The photosensitive resin composition described in (1) is prepared by adding a photoreaction accelerator to an aqueous dispersion of a synthetic resin containing an acetoacetylated polyvinyl alcohol resin or an allylated polyvinyl alcohol resin. The agent is for causing the acetoacetyl group or the allyl group of the polyvinyl alcohol resin to undergo a crosslinking reaction. This method
Japanese Patent Publication No. 46-39401 and Japanese Patent Publication No. 46-4
The system is different from the system of 2450 and Japanese Patent Publication No. 45-9614, and there is still room for improvement in respect of leaving stability and improvement of image contrast.

Under such a background, the present invention provides a photosensitive resin composition having excellent stability of a photosensitive solution and water resistance after exposure (especially, a photosensitive resin composition suitable for relief relief printing or screen printing printing). It is intended to provide a resin composition).

[0016]

The photosensitive resin composition of the present invention comprises a hydrophobic resin emulsion (A) having a glass transition point of 45 ° C. or higher, a polyvinyl alcohol resin (B), a polymerizable monomer (C) and Consisting of photopolymerization initiator (D), hydrophobic resin in emulsion (A), polyvinyl alcohol resin
The ratio of the polyvinyl alcohol resin (B) to the total amount of (B) and the polymerizable monomer (C) is 10 to 30% by weight.

The present invention will be described in detail below.

As the emulsion (A) of the hydrophobic resin,
An emulsion of a hydrophobic resin having a glass transition temperature of 45 ° C. or higher, preferably 60 ° C. or higher is used. Examples of the hydrophobic resin include polyvinyl chloride, polystyrene, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, polyacrylonitrile, styrene-acrylonitrile copolymer and the like. Emulsion
The concentration of the hydrophobic resin in (A) is often about 20 to 65% by weight.

The type of polyvinyl alcohol resin (B) is not particularly limited, but general-purpose polyvinyl alcohol having a saponification degree of about 80 to 96 mol% and a polymerization degree of about 500 to 1800 is often used.

The polyvinyl alcohol resin (B) is
In addition to polyvinyl alcohol, which is a saponification product of vinyl acetate homopolymer, vinyl acetate and other comonomers (α-
Olefin, ethylenically unsaturated carboxylic acid or its salt, anhydride, ester, nitrile, amide, etc., ethylenically unsaturated sulfonic acid or its salt, vinyl ester other than vinyl acetate, alkyl vinyl ether, vinyl chloride,
Vinylidene chloride, N-acrylamidomethyltrimethylammonium chloride, dimethyldiallyl vinyl ketone, N-vinylpyrrolidone, etc.) is a saponified product of "copolymer modified polyvinyl alcohol, or polyvinyl alcohol or copolymer modified polyvinyl alcohol thereof". It may be a “post-modified” polyvinyl alcohol obtained by post-modifying by means such as urethanization, acetalization, etherification, sulfonation, cationization.

As the polymerizable monomer (C), for example,
Examples include monofunctional acrylic monomers, polyfunctional acrylic monomers, and styrene monomers. In this case, if too much water-soluble monomer is used as the polymerizable monomer (C), water resistance may be impaired. Therefore, the proportion of the water-soluble monomer in the polymerizable monomer (C) is 70% or less, especially 60% or less. It is better to stay at

Among the above-mentioned monofunctional acrylic monomers, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meta)
Acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2 Examples include-(meth) acryloyloxyethyl acid phosphate, half (meth) acrylate of phthalic acid derivative, N-methylol (meth) acrylamide, (meth) acrylamide, diacetone acrylamide, and (meth) acrylonitrile.

Examples of polyfunctional acrylic monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate. , Neopentyl glycol di (meta)
Acrylate, 1,6-hexane glycol di (meth)
Acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxy Phenyl)
Propane, 2-hydroxy-3- (meth) acryloyloxypropyl acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, 1,6-hexamethyldiglycidyl ether di (meth) Acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate,
Examples thereof include glycerin polyglycidyl ether poly (meth) acrylate.

The mixing ratio of each component is such that the total amount of the hydrophobic resin, the polyvinyl alcohol resin (B) and the polymerizable monomer (C) in the emulsion (A) is 10 to 10 parts by weight of the polyvinyl alcohol resin (B). Set within the range of 30% by weight,
About 30 to 70% by weight of hydrophobic resin, polymerizable monomer
It is desirable that (C) be 15 to 40% by weight. When the proportion of the polyvinyl alcohol resin (B) is less than 10% by weight, water developability is impaired, and when it exceeds 30% by weight, water resistance is impaired. Hydrophobic resin, polymerizable monomer
When the ratio of (C) is out of the above range, the balance of mechanical properties of the coating film tends to be impaired, but some deviation from the above range is acceptable.

As the photopolymerization initiator (C), p, p'-diethylaminobenzophenone, benzyl dimethyl ketal, hexaaryl imidazole dimer, benzoin,
Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-
Butyl ether, benzoin phenyl ether, benzyl diphenyl disulfide, dibenzyl, diacetyl,
Anthraquinone, naphthoquinone, 3,3'-dimethyl-
4-methoxybenzophenone, benzophenone, p,
p'-bis (dimethylamino) benzophenone, 4,
4′-bis (diethylamino) benzophenone, pivaloin ethyl ether, 1,1-dichloroacetophenone, p-t-butyldichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4
-Diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibesoparone, 1- ( 4-isopropylphenyl) -2-hydroxy-2-methyl-1-propanone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, tribromophenyl sulfone, tribromomethylphenyl sulfone, N-phenylglycine, urazyl salt, tetrazonium salt, diazide compound and the like are used. Photopolymerization initiator
The blending ratio of (C) is 0.01 to 1 with respect to the polymerizable monomer (C).
It is often about 0% by weight.

If necessary, the photosensitive resin composition comprising the above components may include a surfactant, a thermal polymerization inhibitor, an antioxidant, an adhesion promoter, a plasticizer, a solvent, a surface tension modifier, and a stabilizer. It is also possible to add additives such as a chain transfer inhibitor, an antifoaming agent, a flame retardant, a filler, a coloring agent, an antibacterial agent, an emulsion having a glass transition point of less than 45 ° C., and other water-soluble polymers.

The photosensitive resin composition of the present invention is particularly useful as a composition for relief relief printing plate or screen printing plate, but can be used for various other purposes. In the production of the plate, a photosensitive solution comprising this composition was applied to a substrate and dried to form a coating film, or a film formed by an extrusion method or previously applied to a support and dried to form a film. Attach the membrane to the substrate. Then, a pattern mask is brought into close contact with the coating film or the adhered film and exposed. The exposure is usually carried out by ultraviolet irradiation, and as the light source at that time, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp and the like are used. The development is carried out with water, but it can also be carried out using a dilute aqueous alkali solution. After the development, a heat treatment may be performed if necessary.

[0028]

In the present invention, a system comprising a polyvinyl alcohol resin (B) and a polymerizable monomer (C) is provided with a hydrophobic resin emulsion (A) having a high glass transition point, which alone cannot form a homogeneous film. By containing it, the storage stability of the photosensitive solution is ensured, it has water developability, and good water resistance and mechanical property balance are obtained.

[0029]

EXAMPLES The present invention will be further described with reference to examples. Hereinafter, "parts" and "%" are expressed by weight unless otherwise specified.

Example 1 Methyl methacrylate-methacrylic acid copolymer (copolymerization ratio 95: as an example of hydrophobic resin emulsion (A))
5 (weight ratio), glass transition point 120 ° C.) 100 parts of emulsion (solid content 45%, particle size 0.1 μm) in 100 parts of polyvinyl alcohol resin (B) saponification degree 88 as an example
Polyvinyl alcohol powder 1 with mol% and degree of polymerization 1700
5 parts were added and stirred at 50 ° C. for 1 hour to obtain a viscous paste.

After cooling this to room temperature, 0.2 parts of sodium polyoxyethylene nonylphenyl ether sulfate as a surfactant and 0.1 part of benzoin methyl ether as an example of the photopolymerization initiator (D) were added. , Methyl methacrylate 1 as an example of polymerizable monomer (C)
5 parts were added and mixed with stirring to form a uniform paste. A photosensitive solution was obtained by filtering and defoaming this paste.

The blending amount of each component is 45 parts by weight of the hydrophobic resin in the emulsion (A) and polyvinyl alcohol resin (B).
Is 15 parts and the polymerizable monomer (C) is 15 parts, the ratio of each component to the total amount of these is 6 for the hydrophobic resin.
0%, polyvinyl alcohol resin (B) is 20%, and polymerizable monomer (C) is 20%.

Next, this photosensitive solution was applied onto an aluminum plate and dried at 60 ° C. to prepare a photopolymer plate.
The coating film of the obtained photopolymer plate was hard, and its hardness was 75 in Shore D.

After a line drawing or a halftone dot negative was brought into close contact with the coating film of the photopolymer plate thus produced, 6
Ultraviolet irradiation was performed for 5 minutes from a distance of 0 cm with a high pressure mercury lamp of 3 KW. When this was water-developed, a good relief image for relief having a thickness of 500 μm was obtained. Therefore, heat treatment was carried out at 150 ° C. for 1 minute in order to enhance the water resistance of the relief image.

Further, the above photosensitive solution was coated on a polyester film and dried at 60 ° C. to prepare a photopolymer plate. This photopolymer plate did not lose its shape even after peeling after drying. This photopolymer plate was exposed to ultraviolet rays for 5 minutes from a distance of 60 cm with a high pressure mercury lamp of 3 KW without any negative exposure for total exposure, and then heat-treated at 150 ° C. for 1 minute.

The exposed photosensitive layer (thickness: 500 μm) was peeled off from the polyester film and cut into 4 cm squares to obtain 6
When a water resistance test was carried out by immersing it in pure water at 0 ° C. for 1 hour, the swelling degree (%) = 100 × ((weight after test / absolute dry weight after test) −1) showed a swelling degree of 0.5. % Or less, it had water resistance that can be practically used even when it is used such as polishing the plate or using water in the printing process that requires water resistance. Moreover, the test piece after the water resistance test was not deformed or softened.

Example 2 Example 1 was repeated except that the following ingredients were used: -Emulsion of hydrophobic resin (A): 100 parts Emulsion of polyvinyl chloride (glass transition temperature 100 ° C) (solid content 45%)-Polyvinyl alcohol resin (B): 15 parts Saponification degree 80 mol%, degree of polymerization 500 polyvinyl alcohol powder-Polymerizable monomer (C): 15 parts Methyl acrylate The mixing ratio of each component is 60% of hydrophobic resin, 20% of polyvinyl alcohol resin (B), and 20% of polymerizable monomer (C).
Becomes

Example 3 Example 1 was repeated except that the following ingredients were used: -Emulsion of hydrophobic resin (A): 100 parts Polystyrene (glass transition point 100 ° C) emulsion (solid content 40%)-Polyvinyl alcohol resin (B): 30 parts Saponification degree of 92 mol%, polymerization degree of 1700 Polyvinyl alcohol powder-Polymerizable monomer (C): 30 parts Methyl methacrylate The mixing ratio of each component is 40% hydrophobic resin, 30% polyvinyl alcohol resin (B), 30% polymerizable monomer (C).
Becomes

Example 4 Example 1 was repeated except that the following ingredients were used and the relief thickness was 100 μm. -Emulsion of hydrophobic resin (A): 100 parts Emulsion of polymethylmethacrylate (glass transition point 105 ° C) (solid content 50%)-Polyvinyl alcohol resin (B): 25 parts Degree of saponification 88 mol%, degree of polymerization 1700 polyvinyl alcohol powder-Polymerizable monomer (C): 25 parts Mixture of methyl methacrylate and 2-hydroxyethyl methacrylate in a weight ratio of 1: 1 The mixing ratio of each component is 50% hydrophobic resin, polyvinyl alcohol-based Resin (B) 25%, Polymerizable monomer (C) 25%
Becomes

Comparative Example 1 Without using the hydrophobic resin emulsion (A), the weight ratio of methyl methacrylate and 2-hydroxyethyl methacrylate as an example of the polymerizable monomer (C) was 1:
As an example of the polyvinyl alcohol-based resin (B), the saponification degree of 88 mol% and the polymerization degree of 17
After adding 40 parts of polyvinyl alcohol powder of No. 00 and 0.1 part of benzoin methyl ether as an example of the photopolymerization initiator (D), the mixture was stirred and mixed to form a paste. A photosensitive solution was obtained by filtering and defoaming this paste, and Example 1 was repeated below.

Comparative Example 2 Example 1 was repeated except that the following components were used. -Emulsion of hydrophobic resin: 100 parts Emulsion of polyvinyl acetate (glass transition point 35 ° C) (solid content 45%)-Polyvinyl alcohol resin (B): 15 parts Polyvinyl with a saponification degree of 88 mol% and a polymerization degree of 1700 Alcohol powder-Polymerizable monomer (C): 15 parts Mixture of methyl acrylate and 2-hydroxyethyl methacrylate at a weight ratio of 1: 1 The mixing ratio of each component is 60% hydrophobic resin, polyvinyl alcohol resin (B ) 20%, polymerizable monomer (C) 20%
Becomes

Comparative Example 3 The following components were used without using the polymerizable monomer (C), 2.5 parts of a condensation resin of diphenylamine-4-diazonium chloride and formalin was used as the photopolymerization initiator (D), and a relief was used. Example 1 was repeated except that the thickness was 100 μm. -Emulsion of hydrophobic resin: 100 parts Emulsion of polyvinyl acetate (glass transition point 35 ° C) (solid content 50%)-Polyvinyl alcohol resin (B): 19 parts Polyvinyl with a saponification degree of 88 mol% and a polymerization degree of 1700 Alcohol powder

<Results> The above Examples 1 to 4 and Comparative Example 1
The results of ~ 3 are shown in Table 1. No item is provided for storage stability, but it is good in all cases. Example 1
The formulations of to 3 are suitable for relief relief printing, and the formulation of Example 4 is suitable for screen printing printing plates.

[0044]

[Table 1] Relief thickness State after water resistance test Swelling degree Example 1 500 μm No change 0.5% or less Example 2 500 μm No change 0.5% or less Example 3 500 μm No change 0.5% or less Example 4 100 μm No change 0.5% or less Comparative example 1 500 μm Slightly soft 5.0% Comparative example 2 500 μm Slightly soft 4.0% Comparative example 3 100 μm Shape collapse 10.0%

[0045]

The photosensitive resin composition of the present invention has properties such as storage stability of the photosensitive solution, water developability, water resistance of the exposed film, mechanical property balance of the exposed film, and printing durability. ,
It is useful for various applications including relief relief printing and screen printing printing.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location G03F 7/033

Claims (2)

[Claims] 1. An emulsion (A) comprising a hydrophobic resin emulsion (A) having a glass transition point of 45 ° C. or higher, a polyvinyl alcohol resin (B), a polymerizable monomer (C) and a photopolymerization initiator (D). A photosensitive resin composition in which the proportion of the polyvinyl alcohol resin (B) in the total amount of the hydrophobic resin, polyvinyl alcohol resin (B) and polymerizable monomer (C) is 10 to 30% by weight. 2. The photosensitive resin composition according to claim 1, which is a composition for relief relief printing or screen printing printing.