JPH07140655A - Water-developable photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain the composition which is hardly swollen by water and highly developable, without the strength being lowered and with the dimensional change reduced by incorporating a photopolymerizable unsaturated monomer and a photopolymerization initiator into a specified granular copolymer. CONSTITUTION:A monomer mixture contg. 10-95mol% of aliphatic conjugate diene monomer, 0.1-30mol% of alpha,beta-ethylenic saturated carboxylic acid, 0.1-20mol% of a compd. having at least two addition-polymerizable compd., 0.1-30mol% of a monovinyl monomer having amino group and 0-30mol% of another copolymerizable monomer amounting to 100mol% is emulsion- polymerized or suspension-polymerized to obtain a granular copolymer. 5-1000 pts.wt. of the monomer mixture and 0.1-20 pts.wt. of polymerization initiator are incorporated into 100 pts.wt. of the coploymer. When the content of another copolymerizable monomer exceeds 30mol% in the monomer mixture, the water developability of the resin composition may be insufficient.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition that can be developed with water even though it swells less with water and has less strength reduction and dimensional change.

[0002]

2. Description of the Related Art Conventionally, various photosensitive resin compositions have been widely used in the fields of photoresists, printing inks, plate materials and the like. As the photosensitive resin composition, a composition containing a cyclized rubber and a bisazide compound, a thermoplastic elastomer, a composition containing an acrylic monomer and a photopolymerization initiator, polyester acrylate, epoxy acrylate, polyvinyl cinnamate, chloro. Methylated polystyrene, a composition mainly composed of a photosensitive resin such as an aromatic azido group-containing resin is known, but all of these photosensitive resin compositions are water-insoluble, and an organic solvent is used during development. I'm using it. However, in recent years, in addition to safety and health problems during work, the influence of organic solvents on the environment has become a problem. As a solution to such a problem, an alkali-developable photosensitive resin composition composed of a novolac resin or a poly (vinylphenol) and a quinonediazide compound is known. However, safer and simpler development with water is possible. A water-developable photosensitive resin composition is desired.

As the water-developable photosensitive resin composition, a composition comprising a water-soluble resin such as polyvinyl alcohol, gelatin and casein and a dichromate, a diazonium salt or a bisazide compound, a water-soluble resin and a water-soluble resin has already been used. A water-soluble resin-based composition such as a composition comprising an acrylic monomer and a photopolymerization initiator has been proposed.
However, the conventional water-developable photosensitive resin composition has a too high affinity for water of the base resin, so that it swells during development to cause strength reduction, dimensional change, and the like, and as a result, for example, resist dimensions. There are problems such as deterioration of accuracy, printing durability of printing plate, and deterioration of printing quality.

In order to solve the problems of such a water-developable photosensitive resin composition, the present applicants have already (i) a monomer such as an aliphatic conjugated diene type and an α, β-ethylene type monomer. A partially cross-linked copolymer with an unsaturated carboxylic acid and a polyfunctional vinyl compound is soluble in an aqueous alkaline solution, and (ii) a photopolymerizable unsaturated monomer and (iii) are added to the copolymer. It is described that a photosensitive resin composition having water developability can be obtained by adding a photopolymerization initiator (for example, JP-A-60-179411 and JP-A-60).
-219208, JP-A-61-181811), and (i) aliphatic conjugated diene, α, β-
Partially cross-linked copolymer obtained by emulsion-polymerizing an ethylenically unsaturated carboxylic acid and a compound having at least two addition-polymerizable groups, (ii) aliphatic conjugated diene-based polymer, (ii)
A water-developable photosensitive resin composition containing i) a photopolymerizable unsaturated monomer, (iv) a basic nitrogen atom-containing compound, and (v) a photopolymerization initiator is also known (for example, JP-A-1-
300246). However, for such a water-developable photosensitive resin composition, it is desired to further improve the resin plate strength after photocuring. Furthermore, a curable composition containing reactive fine particles obtained by chemically modifying a cross-linked copolymer obtained by emulsion polymerization improves various physical properties and water resistance as a photosensitive resin composition. Are also known (for example, JP-A-62-8411).
(See Japanese Patent Publication No. 3). However, even with such a composition, it is difficult to impart required water developability and elasticity.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a novel photosensitive resin composition which is less swelled in water and has water developability in spite of less strength reduction and dimensional change. With the goal.

[0006]

According to the present invention, the above-mentioned problems are as follows: (1) an aliphatic conjugated diene monomer
95 mol%, α, β-ethylenically unsaturated carboxylic acid
0.1-30 mol%, a compound having at least two addition-polymerizable groups 0.1-20 mol%, a monovinyl monomer containing an amino group 0.1-30 mol%, and other copolymerizations Particulate copolymer (a obtained by synthesizing a monomer mixture containing 0 to 30 mol% of possible monomers (however, +++ = 100 mol%) by emulsion polymerization method or suspension polymerization method (a ) 100 parts by weight of (2) photopolymerizable unsaturated monomer 5 to 1000
And a water-developable photosensitive resin composition (hereinafter referred to as "first invention"), characterized by containing 0.1 to 20 parts by weight of (3) a photopolymerization initiator.

Secondly, the above problems are (1) (1-
1) 10 to 95 mol% of aliphatic conjugated diene monomer,
0.1 to 30 mol% of α, β-ethylenically unsaturated carboxylic acid, 0.1 to 20 mol% of a compound having at least two addition-polymerizable groups, and 0 to other copolymerizable monomers 30 mol%, containing a monomer mixture (however,
(+++ = 100 mol%), and the particulate copolymer (b) obtained by synthesizing by emulsion polymerization or suspension polymerization, and (1-2) 10 to 95 mol% of the aliphatic conjugated diene monomer. 0.1 to 20 mol% of a compound having at least two addition-polymerizable groups, 0.1 to 30 mol% of an amino group-containing monovinyl monomer, and 0 to 30 mol of another copolymerizable monomer. %, Which is a mixture with the particulate copolymer (c) obtained by synthesizing a monomer mixture containing 100% by weight (++++ = 100 mol%) by emulsion polymerization or suspension polymerization. Is (b) / (c) = 95/5 to 5/95 (weight ratio), the particulate copolymer (d) 1
(2) Photopolymerizable unsaturated monomer 5 to 100 parts by weight
1000 parts by weight, and (3) photopolymerization initiator 0.1-2
It is achieved by a water-developable photosensitive resin composition characterized in that it contains 0 part by weight (hereinafter referred to as "second invention").

The water-developable photosensitive resin composition of the present invention (hereinafter sometimes abbreviated as "resin composition") will be described in detail. 1st component The content rate of the said monomer mixture at the time of manufacturing the particulate copolymer (a) which comprises the water-developable photosensitive resin composition of 1st invention is as follows. The content of the aliphatic conjugated diene monomer is 10 to 95 mol%, preferably 30 to 90 mol%. Below 10 mol%,
The strength of the resin composition after photocuring is low. On the other hand, 95 mol%
If it exceeds, the water developability of the resin composition will be insufficient. α, β-ethylenically unsaturated carboxylic acid is 0.1 to 3
It is 0 mol%, preferably 0.5 to 20 mol%. 0.
When it is less than 1 mol%, the water developability of the resin composition becomes insufficient, and when it exceeds 30 mol%, the resin composition becomes hard and brittle, which is not preferable. The compound having at least two addition-polymerizable groups is 0.1 to 20 mol%, preferably 0.5 to 10 mol%. If it is less than 0.1 mol%, the water developability of the resin composition will be insufficient, and if it exceeds 20 mol%, the compatibility between the particulate polymer and the photopolymerizable monomer will be poor and the processability will be poor. Furthermore, the strength of the resin composition after photocuring is significantly reduced. The monovinyl monomer containing an amino group is 0.1 to
It is 30 mol%, preferably 0.5 to 20 mol%.
If it is less than 0.1 mol%, the strength of the resin composition may be lowered and the water developability may be insufficient, and if it exceeds 30 mol%, the resin composition becomes hard and brittle, which is not preferable. Other copolymerizable monomers are used in the range of 0 to 30 mol%. If it exceeds 30 mol%, the water developability of the resin composition may be insufficient.

The content of the monomer mixture in producing the particulate copolymer (b) constituting the water-developable photosensitive resin composition of the second invention is as follows. The content of the aliphatic conjugated diene monomer is 10 to 95 mol%, preferably 30 to 90 mol%. Below 10 mol%,
The strength of the resin composition after photocuring is low. On the other hand, 95 mol%
If it exceeds, the water developability of the resin composition will be insufficient. α, β-ethylenically unsaturated carboxylic acid is 0.1 to 3
It is 0 mol%, preferably 0.5 to 20 mol%. 0.
When it is less than 1 mol%, the water developability of the resin composition becomes insufficient, and when it exceeds 30 mol%, the resin composition becomes hard and brittle, which is not preferable. The compound having at least two addition-polymerizable groups is 0.1 to 20 mol%, preferably 0.5 to 10 mol%. If it is less than 0.1 mol%, the water developability of the resin composition will be insufficient, and if it exceeds 20 mol%, the compatibility between the particulate polymer and the photopolymerizable monomer will be poor and the processability will be poor. Furthermore, the strength of the resin composition after photocuring is significantly reduced. Other copolymerizable monomers are used in the range of 0 to 30 mol%. If it exceeds 30 mol%, the water developability of the resin composition will be insufficient.

The content of the monomer mixture in producing the particulate copolymer (c) constituting the water-developable photosensitive resin composition of the second invention is as follows. The content of the aliphatic conjugated diene monomer is 10 to 95 mol%, preferably 30 to 90 mol%. Below 10 mol%,
The strength of the resin composition after photocuring is low. On the other hand, 95 mol%
If it exceeds, the water developability of the resin composition will be insufficient. The compound having at least two addition-polymerizable groups is 0.1 to 20 mol%, preferably 0.5 to 10 mol%. If it is less than 0.1 mol%, the water developability of the resin composition will be insufficient, and if it exceeds 20 mol%, the compatibility between the particulate polymer and the photopolymerizable monomer will be poor and the processability will be poor. Furthermore, the strength of the resin composition after photocuring is significantly reduced. The monovinyl monomer containing an amino group is 0.1 to
It is 30 mol%, preferably 0.5 to 20 mol%.
If it is less than 0.1 mol%, the water developability of the resin composition will be insufficient, and if it exceeds 30 mol%, the resin composition will be hard and brittle, which is not preferable. Other copolymerizable monomers are used in the range of 0 to 30 mol%. If it exceeds 30 mol%, the water developability of the resin composition may be insufficient.

The first component of the second invention is a mixture of the particulate copolymers (b) and (c), the ratio of which is (b) / (c) = 95/5 to 5 / by weight ratio. 95, preferably 80
/ 20 to 20/80. If the content of the particulate polymer (b) is less than 5% by weight or exceeds 95% by weight, the strength of the resin composition may be lowered and the water developability may be insufficient, which is not preferable.

Specific examples of the monomer for producing the particulate copolymer of the first component are given below. Examples of the aliphatic conjugated diene monomer include butadiene, isoprene, dimethylbutadiene, chloroprene and the like. Examples of the α, β-ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetraconic acid, succinic acid, phthalic acid and other dicarboxylic acids and monoesters of unsaturated alcohols. Etc. Examples of the compound having at least two addition-polymerizable groups include ethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene glycol dimethacrylate, propylene glycol dimethacrylate. Acrylate, divinylbenzene, trivinylbenzene, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-heptanediol di (meth) acrylate, etc. Can be mentioned. These polyfunctional polymerizable monomers are
They can be used alone or in combination of two or more.

As the amino group-containing monovinyl monomer, for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
Examples thereof include dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide and the like. Other copolymerizable monomers include, for example, styrene,
α-methylstyrene, vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate and the like can be mentioned.

The copolymer of the first component must be in the form of particles. The average particle size is preferably 20 to 1000 nm. By making the particle surface of the particulate copolymer hydrophilic and making the inside of the particle hydrophobic, the water resistance and water developability of the resin composition are further improved. The particulate copolymer is prepared as a particulate copolymer by an emulsion polymerization method or a suspension polymerization method using a radical initiator, and the emulsion polymerization method is used because of the uniformity of particle size and particle size. Is desirable.
The total amount of each of the monomers and the polymerization agent such as the radical initiator may be added at the start of the reaction, or may be added after the start of the reaction in any desired amount. Further, like the particulate copolymer of the second invention, two or more particulate polymers having different monomer compositions may be separately polymerized and then mixed. Polymerization is 0-8
At 0 ° C. in a deoxygenated reactor,
During the reaction, operating conditions such as temperature and stirring can be arbitrarily changed. The polymerization method may be either continuous or batch. Although the polymerization conversion rate is arbitrarily determined, it is usually 7
It is 0% by weight or more, preferably 80% by weight or more, and more preferably 90 to 100% by weight.

Examples of the radical initiator include organic peroxides such as benzoin peroxide, cumene hydroperoxide, paramenthane hydroperoxide and lauroyl peroxide, diazo compounds represented by azobisisobutyronitrile, and potassium persulfate. Inorganic compounds, redox-based catalysts represented by a combination of organic compounds and iron sulfate, and the like are used.

Second component (2) Examples of the photopolymerizable unsaturated monomer include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, diisopropenylbenzene and divinylbenzene. Aromatic vinyl compounds, unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl Acrylate or methacrylate of alkyl alcohol such as acrylate, 2
-Hydroxyethyl acrylate, acrylates or methacrylates of hydroxyalkyl alcohols such as 2-hydroxypropyl acrylate or methacrylate, acrylates or methacrylates of alkoxy alcohols such as methoxyethyl acrylate, ethoxyethyl acrylate or methacrylate,

Acrylate or methacrylate of alkoxyalkylene glycol such as methoxyethylene glycol, methoxypropylene glycol, acrylate or methacrylate of fluoroalcohol such as trifluoroethyl acrylate, pentafluoropropyl acrylate or methacrylate, acrylic acid,
Α, β-ethylenically unsaturated carboxylic acids such as methacrylic acid, maleic acid, fumaric acid, maleic anhydride, crotonic acid, itaconic acid, itaconic anhydride, citraconic acid, mesaconic acid, cinnamic acid, succinic acid, phthalic acid (Mono) ester compounds of saturated polyvalent carboxylic acids such as allylic alcohol, 2-hydroxyethyl (meth) acrylate, monoesters of unsaturated polyvalent carboxylic acids such as monoethyl maleate, monoethyl fumarate, monoethyl itaconate, etc. , Dimethyl maleate, diethyl maleate,
Diesters of dibutyl maleate, dioctyl maleate, diethyl fumarate, dibutyl fumarate, dioctyl fumarate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dioctyl itaconate, etc.,

Acrylamide, methacrylamide, N,
Acrylamides or methacrylamides such as N′-methylenebisacrylamide and N, N′-hexamethylenebisacrylamide, polyalkylene glycols such as ethylene glycol (meth) acrylate and nonaethylene glycol (meth) acrylate (alkylene glycol units 2 to 23) Individual) monoacrylate or monomethacrylates, ethylene glycol diacrylate,
Or dimethacrylate, diacrylate or dimethacrylate of polyalkylene glycol (2 to 23 alkylene glycol units), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc., glycerin, pentaerythritol, trimethylolalkane , Diacrylates, triacrylates, tetraacrylates or dimethacrylates, trimethacrylates or tetramethacrylates of polyhydric alcohols such as tetramethylolalkanes (alkanes are methane, ethane, propane)
Oligoacrylates, vinyl chloride, vinyl acetate, cyanoethyl acrylate, cinnamic acid ester, crotonic acid ester dicyclopentadiene, ethylidene norbornene, N, N-dimethylaminoethyl acrylate, N,
Amino group-containing acrylates such as N-diethylaminoethyl acrylate and their methacrylates, N,
Examples thereof include amino group-containing acrylamides such as N-dimethylaminoethyl acrylamide and N, N-dimethylaminopropyl acrylamide, and methacrylamides thereof.

These (2) photopolymerizable monomers can be used alone or in admixture of two or more. In the present invention, by appropriately selecting these monomers or a combination thereof, it is possible to impart desired properties to the resin composition after photocuring. The combination of the (2) photopolymerizable monomer used in the present invention is not particularly limited, but in order to improve the balance between the water developability and the strength of the resin composition obtained, (2) the photopolymerizable monomer is used. Examples of the monomer include mono (meth) acrylates of polyalkylene glycol (2 to 23 alkylene glycol units) such as nonaethylene glycol (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth).
(Meth) acrylates of alkyl alcohol such as acrylate, ethylene glycol di (meth) acrylate, di (meth) acrylates of polyalkylene glycol (2 to 23 alkylene glycol units), pentaerythritol tri (meth) acrylate, trimethylol Pentaerythritol such as propane tri (meth) acrylate, trimethylolpropane, glycerin, tetramethylolalkane (as alkane, methane,
Di (meth) of polyhydric alcohols such as ethane and propane
Preference is given to using acrylates, tri (meth) acrylates, tetra (meth) acrylates.

Further, for the purpose of further improving the water developability of the resulting composition, N, N-dimethylaminoethyl (meth)
Acrylate, N, N-diethylaminoethyl (meth)
Amino group-containing (meth) acrylates such as acrylates, N, N-dimethylaminoethyl (meth) acrylamides, amino group-containing (meth) acrylamides such as N, N-dimethylaminopropyl (meth) acrylamides,
Α, β-ethylenically unsaturated carboxylic acids such as (meth) acrylic acid and maleic acid, monoesters of unsaturated polyvalent carboxylic acids such as monoethyl maleate, and saturated polycarboxylic acids such as succinic acid and phthalic acid A monoester compound with an unsaturated alcohol such as allyl alcohol or 2-hydroxyethyl (meth) acrylate may be further added.

(2) The photopolymerizable monomer can be used in an arbitrary ratio depending on the purpose, and the fluidity can be freely designed from a wax form to a low viscosity liquid form depending on the amount. Usually, it is 5 to 100 parts by weight of the particulate copolymer (1).
The amount is 1,000 parts by weight, preferably 10 to 500 parts by weight, more preferably 20 to 300 parts by weight. If the amount is less than 5 parts by weight, the strength of the obtained resin composition is poor, while on the other hand,
When it exceeds 0 parts by weight, the composition after photocuring is largely shrunk, it is difficult to achieve both the water resistance and the water developability of the composition, and the degree of freedom in the viscosity design of the composition is lowered, and both are preferable. Absent.

Third Component (3) The photopolymerization initiator is one which initiates or sensitizes the polymerization reaction of (1) the particulate copolymer and (2) the photopolymerizable monomer upon irradiation with light. (3) Examples of the photopolymerization initiator include α-diketone compounds such as diacetyl and benzyl, acyloins such as benzoin and pivaloin, acyloin ethers such as benzyne methyl ether, benzoin ethyl ether and benzoin propyl ether, anthraquinone, 1 , 4-naphthoquinone and other polynuclear quinones, 2,2-dimethoxyphenylacetophenone, trichloroacetophenone and other acetophenones, and benzophenone and methyl-o-benzoylbenzoate and other benzophenones.

(3) The amount of the photopolymerization initiator added is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the particulate copolymer (1). 0.1
If it is less than parts by weight, sufficient curing cannot be given to the photosensitive resin composition, and even if it is used in excess of 20 parts by weight, not all of the photopolymerization initiator is involved in the reaction, which is uneconomical. However, sometimes (2) the compatibility with the photopolymerizable unsaturated monomer is poor and the dispersion may be non-uniform.

Further, the photosensitive resin composition of the present invention comprises
If necessary, various additives can be added. Examples of the additive include a thermal addition polymerization inhibitor that acts as a storage stabilizer. The thermal addition polymerization inhibitor,
For example, hydroquinone, hydroquinone monomethyl ether, mono-t-butylhydroquinone, catechol, p-
Methoxyphenol, pt-butylcatechol, 2,
Examples thereof include hydroxyaromatic compounds such as 6-di-t-butyl-p-cresol and pyrogallol, quinones such as benzoquinone, p-toluquinone and p-xyloquinone, and amines such as phenol-α-naphthylamine. The blending amount of these thermal addition polymerization inhibitors is, for example, about 0.001 to 2 parts by weight per 100 parts by weight of the total resin composition.

If desired, an amino group-containing compound or a carboxyl group-containing compound may be added for the purpose of improving the water developability of the resulting photosensitive resin composition.
Specific examples of the amino group-containing compound include primary amines such as ethylamine and propylamine, secondary amines such as diethylamine and dibutylamine, and tertiary amines such as trimethylamine, triethylamine, tripropyiamine, ethyldimethylamine and diethylmethylamine. And trialcoholamines such as triethanolamine, triethanolamine, and tripropanolamine. Examples of the carboxyl group-containing compound include formic acid, acetic acid, propionic acid, butyric acid and the like.

A solvent may be added as an additive. The solvent can reduce the viscosity of the resin composition. Examples of the solvent include ethyl lactate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, diethylene glycol dimethyl ether, 2-ethoxyethyl acetate, 2-ethoxyethanol, ethylene glycol dimethyl ether, and the like. Considering the working environment, it is preferable to use ethyl lactate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate or the like. The amount of the solvent used is not particularly limited and may be arbitrarily selected depending on the purpose and application, but the amount of the solvent is 700 parts by weight or less, preferably 600 parts by weight or less, per 100 parts by weight of the particulate copolymer, It is particularly preferably 500 parts by weight or less.

The resin composition of the present invention contains (1) a particulate copolymer, (2) a photopolymerizable unsaturated monomer, and (3) a photopolymerization initiator, if necessary, and various additives. Along with this, it is usually obtained by sufficiently stirring and mixing with heating, for example, using a kneader, an intermixer or the like. The properties of the resin composition can be freely designed from wax-like or rubber-like without fluidity to low-viscosity liquid with excellent fluidity.

When a photosensitive resin plate is prepared from the resin composition of the present invention, various methods can be adopted depending on the degree of fluidity of the composition. For example, in the case of a resin composition having no fluidity, a spacer having an appropriate thickness is sandwiched so as to have a constant film thickness, or it is applied on an appropriate support using a coating device such as a roll coater, or compression molding, A photosensitive plate having a desired film thickness can be processed by extrusion molding, calender molding or the like.

In the case of a fluid resin composition, roll coating, calendar coating, doctor blade coating,
It can be coated on a support by an appropriate coating method such as air knife coating for plate making, and is particularly useful as a resist suitable for spin coating.

The photosensitive resin plate or resist thus prepared is exposed to chemical actinic rays such as ultraviolet rays through a negative film having a desired pattern, and the unexposed portion is washed and removed with water. By drying, a clear relief image can be formed. In this case, if necessary, re-exposure can be performed after drying.

[0031]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. Example 1 Using sodium lauryl sulfate as an emulsifier and potassium persulfate as a polymerization initiator, a simple mixture of butadiene / methacrylic acid / divinylbenzene / diethylaminoethyl methacrylate / methyl methacrylate = 82/7/1/3/7 (mol%) The monomer was reacted in an aqueous system at 60 ° C. for 5 hours to obtain a copolymer with a conversion rate of 96%. The salt was coagulated with calcium chloride, washed with water, and dried to obtain a particulate copolymer (a) having an average particle size of 720 nm.

The composition is 100 parts by weight of the copolymer (a),
(2) 10 parts by weight of nonaethylene glycol methacrylate as a photopolymerizable unsaturated monomer, 10 parts by weight of trimethylolpropane trimethacrylate, 10 parts by weight of N, N-dimethylaminopropylacrylamide, (3) 2 as a photopolymerization initiator , 2-dimethoxyphenylacetophenone (3 parts by weight) and t-butylcatechol (0.5 parts by weight) as a storage stabilizer were added, and the mixture was mixed in a kneader controlled at 50 ° C.
Stir for 0 minutes. The resin composition obtained was in the form of a transparent wax.

Measurement of Elution Required Time: The resin composition thus obtained was coated on a polyester sheet to a thickness of 0.5 mm to form a photosensitive resin layer. J manufactured by Nippon Denshi Seiki Co., Ltd.
Using the OW-A-4P developing machine, the photosensitive resin layer was brushed in warm water of 30 ° C., and the time required until the photosensitive resin layer disappeared was measured. Measurement of tensile strength: The resin composition was applied on a polyester sheet to a thickness of 0.5 mm to form a photosensitive resin composition layer. This photosensitive resin layer was exposed for 6 minutes using an exposure machine (JE-A ₃ -SS) manufactured by JEOL Ltd.
Tensile strength, elongation at break, and impact resilience were measured according to the procedure defined in IS K6301. The results are shown in Table-1.
The obtained resin composition exhibited excellent balance of elution, tensile strength (plate strength) and impact resilience.

Example 2 Particulate copolymers (b) and (c) were produced in the same manner as in Example 1 except for the monomer. The monomer used for producing the copolymer (b) is butadiene / methacrylic acid / divinylbenzene / methyl methacrylate = 79/13/1/7
(Mol%), the polymerization conversion rate is 97%, and the average particle size is 7
10 nm copolymer particles were obtained. The monomer used for producing the copolymer (c) was butadiene / divinylbenzene / diethylaminoethylmethacrylate / methylmethacrylate = 85/1/7/7 (mol%), and the average conversion was 96%. Copolymer particles having a particle size of 700 nm were obtained.
A transparent wax-like resin composition was obtained by the same formulation and mixing operation as in Example 1 for 50 parts by weight of the particulate copolymer (b) and 50 parts by weight of (c), a total of 100 parts by weight. .
Further, evaluation was performed in the same manner as in Example 1, and the results are shown in Table-1. As can be seen from the table, the resin composition obtained exhibited excellent properties in balance of elution, tensile strength (plate strength) and impact resilience.

Example 3 As a monomer component, butadiene / methacrylic acid / ethylene glycol dimethacrylate / diethylaminoethyl methacrylate / ethyl acrylate = 82/7/1 /
A particulate copolymer (a) having an average particle size of 720 nm was produced at a polymerization conversion rate of 96% in the same manner as in Example 1 except that 3/7 (mol%) was used. Further, a resin composition was produced with the same composition as in Example 1, and a photosensitive resin layer was formed and evaluated. The results are shown in Table-1. The resulting resin composition exhibited excellent balance of elution, tensile strength (plate strength) and impact resilience.

Example 4 (2) 10 parts by weight of lauryl methacrylate and 1 part of hexanediol diacrylate as a photopolymerizable unsaturated monomer
A resin blend composition was obtained in the same manner as in Example 1 except that 0 part by weight and 10 parts by weight of N, N-dimethylaminopropylacrylamide were used. Further, evaluation was performed in the same manner as in Example 1, and the results are shown in Table-1. As can be seen from the table, the resin composition obtained exhibited excellent properties in balance of elution property, tensile strength and impact resilience.

Comparative Example 1 As a monomer component, butadiene / methacrylic acid / divinylbenzene / methyl methacrylate = 80/7/1/1
A particulate copolymer having an average particle size of 730 nm was produced in the same manner as in Example 1 except that 2 (mol%) was used and the polymerization conversion rate was 97%. Further, a resin composition was produced with the same composition as in Example 1, and a photosensitive resin layer was formed and evaluated. The results are shown in Table-1. The obtained resin composition was excellent in water developability, but was inferior in tensile strength, elongation at break, and impact resilience.

Comparative Example 2 The same as Example 1 except that butadiene / ethylene glycol dimethacrylate / diethylaminoethyl methacrylate / ethyl acrylate = 85/1/7/7 (mol%) was used as the monomer component. , Polymerization conversion rate 96%
To produce a particulate copolymer having an average particle size of 700 nm.
With respect to 100 parts by weight of this particulate copolymer, (2) as a photopolymerizable unsaturated monomer, 10 parts by weight of nonaethylene glycol methacrylate, 10 parts by weight of trimethylolpropane trimethacrylate, 10 parts by weight of methacrylic acid,
(3) 2,2-dimethoxyphenylacetophenone (3 parts by weight) as a photopolymerization initiator, and t-butylcatechol (0.5 parts by weight) as a storage stabilizer were mixed, and compounding and evaluation were performed according to the same procedure as in Example 1. The results are shown in Table-1. This resin composition was excellent in water developability, but was inferior in tensile strength and impact resilience.

[0039]

INDUSTRIAL APPLICABILITY The photosensitive resin composition of the present invention is suitable for water development and has excellent tensile strength, elongation at break, impact resilience and the like of the resin plate after photocuring. Moreover, the composition of the present invention can be freely adjusted to a waxy or rubber-like state having no fluidity to a low-viscosity liquid state. Therefore, the present composition can be suitably used as a photosensitive resin composition that does not require an organic solvent for development in the fields of printing plates, photoresists, etc., as well as printing inks, photosensitive paints, and photosensitive adhesives. It is also useful as an agent and a photo-molding material.

[0040]

[Table 1]

[Table-1]

Claims (2)

[Claims] 1. (1) Aliphatic conjugated diene monomer 10
~ 95 mol%, α, β-ethylenically unsaturated carboxylic acid
0.1-30 mol%, a compound having at least two addition-polymerizable groups 0.1-20 mol%, a monovinyl monomer containing an amino group 0.1-30 mol%, and other copolymerizations Particulate copolymer (a) obtained by synthesizing a monomer mixture containing 0 to 30 mol% of possible monomers (however, ++++ = 100 mol%) by emulsion polymerization method or suspension polymerization method For 100 parts by weight,
A water-developable photosensitive resin composition comprising (2) 5 to 100 parts by weight of a photopolymerizable unsaturated monomer, and (3) 0.1 to 20 parts by weight of a photopolymerization initiator. 2. (1) (1-1) 10 to 95 mol% of an aliphatic conjugated diene monomer, 0.1 to 30 mol% of an α, β-ethylenically unsaturated carboxylic acid, and at least two addition polymerizations. A monomer mixture containing 0.1 to 20 mol% of a compound having a possible group and 0 to 30 mol% of another copolymerizable monomer (however, +++ = 100 mol%)
A particulate copolymer (b) obtained by synthesizing the above by an emulsion polymerization method or a suspension polymerization method, and (1-2) 10-95 mol% of an aliphatic conjugated diene monomer, at least two addition-polymerizable 0.1 to 20 mol% of a compound having a group, 0.1 to 30 mol% of an amino group-containing monovinyl monomer, and 0 to 30 mol% of another copolymerizable monomer,
Containing a monomer mixture (however, +++ = 10
0 mol%) and a particulate copolymer (c) obtained by synthesizing by an emulsion polymerization method or a suspension polymerization method, and the mixing ratio is (b) / (c) = 95/5 to 5 / 95 (weight ratio), the particulate copolymer (d) 1
(2) Photopolymerizable unsaturated monomer 5 to 100 parts by weight
1000 parts by weight, and (3) photopolymerization initiator 0.1-2
A water-developable photosensitive resin composition comprising 0 parts by weight.