JPH06194837A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a new photosensitive resin compsn. excellent in water developing property, showing small swelling during water development, little decrease in strength or dimensional change, and excellent strength of a resin plate after exposure, and having good breaking elongation, impact resistance, transparency, and excellent balance in characteristics. CONSTITUTION:This compsn. contains the following components (1)-(5) (1) Granular diene polymers having a crosslinking structure and containing carboxyl groups. (2) (a) Polymer having two or more photopolymerizable unsatd. groups at the end of the molecular chain and if necessary, having photopolymerizable unsatd. groups, carboxyl groups, hydroxyl groups, amino groups, or epoxy groups in side chains of the molecular chain, or (b) non-diene polymer having photopolymerizable unsatd. groups, carboxyl groups, hydroxyl groups, amino groups, or epoxy groups in side chains of the molecular chain, or straight-chain diene polymer having low mol.wt. (3) Photopolymerizable unsatd. monomers. (4) Amino group-contg. compd. (5) Photopolynan. initiator.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel photosensitive resin composition having water developability. More specifically, it has water developability, but is less likely to swell with water, resulting in a decrease in strength during development,
The present invention relates to a photosensitive resin composition having a small dimensional change and the like.

[0002]

2. Description of the Related Art Conventionally, various photosensitive resin compositions have been widely used in the fields of photoresists, plate making, printing inks and the like. 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, Compositions mainly composed of photosensitive resins such as chloromethylated polystyrene and aromatic azido group-containing resins are known, but all of these photosensitive resin compositions are water-insoluble and are exclusively organic during development. You are using a solvent. 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 the above-mentioned problems, there is known an alkali-developable photosensitive resin composition comprising a novolac resin or poly (vinylphenol) and a quinonediazide compound. However, safer and simpler development with water is possible. There is a demand for a photosensitive resin composition capable of achieving the above. The water-developable photosensitive resin composition, polyvinyl alcohol,
Based on water-soluble resin, such as composition consisting of water-soluble resin such as gelatin and casein and dichromate, diazonium salt or bisazide compound, water-soluble resin, composition consisting of water-soluble acrylic monomer and photopolymerization initiator What has been proposed is proposed. However, the conventional water-developable photosensitive resin composition has a too high affinity for water of the base resin, so that it easily swells during development to cause strength reduction and dimensional change, and as a result, for example, resist There are problems such as deterioration of dimensional 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 applicant has already proposed that conjugated diene compounds, acrylic ester compounds, α, β-ethylenically unsaturated carboxylic acids and A photosensitive resin composition was proposed in which a photopolymerizable unsaturated monomer, an amino group-containing compound, and a photopolymerization initiator were added to a copolymer of a polyfunctional vinyl compound that was soluble in an alkaline aqueous solution (for example, JP-A-60
-179411, JP-A-60-219208, JP-A-61-181811). As another water-developable photosensitive resin composition, a partially cross-linked copolymer of an aliphatic conjugated diene, an α, β-ethylenically unsaturated carboxylic acid and a polyfunctional vinyl compound, a molecular weight of 5000
A composition containing the above aliphatic conjugated diene-based polymer, a photopolymerizable unsaturated monomer, a basic nitrogen atom-containing compound and a photopolymerization initiator (see, for example, JP-A-1-300246), tertiary amino A composition containing a polymer having a group and a polymerizable unsaturated group, an α, β-ethylenically unsaturated monomer having a free acid group, a photopolymerizable unsaturated monomer and a photopolymerization initiator (for example, Japanese Patent Laid-Open No. 61-246742),
Contains a photopolymerizable unsaturated monomer, an amino group-containing compound (provided that at least a part of the photopolymerizable unsaturated monomer or the amino group-containing compound has a (meth) acryloyl group) and an aromatic ketone. However, there are also known compositions (for example, see JP-A-61-228002) which further polymerize. However, these photosensitive resin compositions are not sufficient from the viewpoint of the property balance including water developability, strength after photocuring and development, and the like.

[0005]

Therefore, the present invention is excellent in water developability, and is small in swelling during water development, resulting in little strength reduction, dimensional change, etc., excellent resin plate strength after exposure, and elongation at break. It is an object of the present invention to provide a novel photosensitive resin composition having good degree, impact resilience and transparency and an excellent balance of properties.

[0006]

According to the present invention, the above-mentioned problems are, firstly, (1) a particulate carboxyl group-containing diene polymer having a crosslinked structure, and (2-1) a terminal of a molecular chain. It is characterized by containing a polymer having two or more photopolymerizable unsaturated groups, (3) a photopolymerizable unsaturated monomer, (4) an amino group-containing compound, and (5) a photopolymerization initiator. It is achieved by a photosensitive resin composition (hereinafter referred to as "first invention").

The above-mentioned problems are, secondly, (1) a particulate carboxyl group-containing diene polymer having a crosslinked structure,
-2) It has two or more photopolymerizable unsaturated groups at the end of the molecular chain, and is selected from the group consisting of photopolymerizable unsaturated groups, carboxyl groups, hydroxyl groups, amino groups and epoxy groups on the side chains of the molecular chain. A polymer having at least one functional group,
(3) A photosensitive resin composition containing a photopolymerizable unsaturated monomer, (4) an amino group-containing compound, and (5) a photopolymerization initiator (hereinafter referred to as "second invention"). .)
Achieved by

The above-mentioned problems are, thirdly, (1) a particulate carboxyl group-containing diene polymer having a crosslinked structure,
-3) A non-diene polymer having at least one functional group selected from the group consisting of a photopolymerizable unsaturated group, a carboxyl group, a hydroxyl group, an amino group and an epoxy group in the side chain of the molecular chain, (3) light Achieved by a photosensitive resin composition containing a polymerizable unsaturated monomer, (4) an amino group-containing compound, and (5) a photopolymerization initiator (hereinafter referred to as "third invention"). To be done.

Further, the above-mentioned problems are, fourthly, (1) a particulate carboxyl group-containing diene polymer having a crosslinked structure, (2-4) a side chain of a molecular chain having a photopolymerizable unsaturated group, and a carboxyl group. Group, a hydroxyl group, an amino group and a linear diene-based polymer having a number average molecular weight of less than 5000 having at least one functional group selected from the group consisting of epoxy groups,
(3) Photopolymerizable unsaturated monomer, (4) amino group-containing compound, and (5) photopolymerization initiator-containing photosensitive resin composition (hereinafter, referred to as “fourth invention”). .)
Achieved by

The present invention will be described in detail below, which will clarify the purpose, constitution and effect of the present invention. Component (1) First, (1) a particulate carboxyl group-containing diene polymer having a crosslinked structure, which is commonly used in the first to fourth inventions (hereinafter, referred to as “component (1)”). A repeating unit composed of an aliphatic conjugated diene as an essential component and at least one kind of a particulate carboxyl group-containing diene polymer having a crosslinked structure.

The crosslinked structure in the component (1) can be introduced at the same time as the production of the carboxyl group-containing diene polymer and / or after the production of the carboxyl group-containing diene polymer. It is preferable to introduce the crosslinked structure at the same time as the production of the coalescence.

The particulate component (1) is emulsion polymerized,
It can be obtained at the same time as the production of a carboxyl group-containing diene polymer by suspension polymerization, precipitation polymerization, or the like, and the bulky carboxyl group-containing diene polymer produced in advance is made into particles, or a carboxyl group-containing diene is prepared from a polymer solution. It can also be obtained by obtaining the system polymer in the form of particles. In the present invention, the particulate component (1) is preferably produced by emulsion polymerization using a radical polymerization initiator, suspension polymerization, or a combination thereof, from the viewpoint of particle size, particle size uniformity, and the like. In particular, it is preferable to manufacture by emulsion polymerization. The average particle size of component (1) is
The thickness is preferably 20 to 1000 nm, more preferably 30 to 950 nm, and particularly preferably 40 to 900 nm.

The carboxyl group-containing diene polymer in the component (1) is, for example, (a-1) an aliphatic conjugated diene,
A method of copolymerizing a carboxyl group-containing unsaturated monomer and a monomer having at least two polymerizable unsaturated groups, optionally with other monomers, (a-2) an aliphatic conjugated diene and at least A monomer having two polymerizable unsaturated groups, optionally together with other monomers,
After copolymerization, the resulting copolymer is carboxylated,
For example, it can be produced by an addition reaction of an unsaturated carboxylic acid (anhydride) such as (anhydrous) maleic acid, and then hydrolyzed, if necessary, and the method (A-1) is particularly preferable.

Examples of the aliphatic conjugated diene include butadiene, isoprene, 1,3-pentadiene and 1,3-
Hexadiene, 2,3-dimethylbutadiene, 4,5-
Diethyl-1,3-octadiene, 3-butyl-1,3
-Octadiene, chloroprene, 2,3-dichlorobutadiene, 1,3-cyclopentadiene and the like can be mentioned.

Preferred aliphatic conjugated dienes are butadiene, isoprene and the like. These aliphatic conjugated dienes can be used alone or in admixture of two or more.

Examples of the unsaturated monomer containing a carboxyl group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid and cinnamic acid; (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid and citracone. Unsaturated polycarboxylic acid (anhydride) such as acid or mesaconic acid; free carboxyl group-containing ester such as monomethyl ester, monoethyl ester or monopropyl ester of the unsaturated polycarboxylic acid; Free carboxyl group-containing nitriles such as mononitrile; Free carboxyl group-containing amides such as unsaturated polycarboxylic acid monoamides; Mono (2-hydroxyethyl ester) and mono (2-hydroxypropyl) of the unsaturated polycarboxylic acids Free carboxyl group-containing hydroxyalkyl esters such as esters) In addition to the N-hydroxyalkyl derivatives of the amide containing a free carboxyl group of the unsaturated polycarboxylic acid, a non-polymerizable polycarboxylic acid such as succinic acid, adipic acid and phthalic acid, and an unsaturated alcohol, 2-hydroxyethyl (meth) Examples thereof include free carboxyl group-containing esters with a hydroxyl group-containing unsaturated compound such as acrylate.

Preferred carboxyl group-containing unsaturated monomers are (meth) acrylic acid, monovinyl succinate, monoesters of succinic acid and 2-hydroxyethyl (meth) acrylate, phthalic acid and 2-hydroxyethyl (meth). Examples include monoesters with acrylate. These unsaturated monomers containing a carboxyl group may be used alone or in combination with 2
A mixture of two or more species can be used.

Examples of the compound having at least two unsaturated groups include alkylene glycol di (, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. (Meth) acrylates;

Di (meth) acrylates of polyalkylene glycol (the number of alkylene glycol units is, for example, 2 to 20) such as polyethylene glycol and polypropylene glycol;

Polymeric di (meth) acrylates having hydroxyl groups at both ends of the molecular chain such as hydroxypolybutadiene at both ends, hydroxypolyisoprene at both ends, hydroxybutadiene-acrylonitrile copolymer at both ends, and hydroxypolycaprolactone at both ends;

Trivalent or higher polyvalent compounds such as glycerin, 1,2,4-butanetriol, trimethylolalkane (alkane has 1 to 3 carbon atoms) and tetramethylolalkane (alkane has 1 to 3 carbon atoms). Poly (meth) acrylates of polyhydric alcohols;

Poly (meth) acrylates of polyalkylene glycol adducts of trihydric or higher polyhydric alcohols;

1,4-cyclohexanediol, 1,4
-Di (meth) acrylates of cyclic polyols such as benzenediol;

Polyester resin (meth) acrylate,
Oligo (meth) acrylates such as epoxy resin (meth) acrylate, urethane resin (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, and spirane resin (meth) acrylate;

Bis (meth) acrylamides such as N, N'-methylenebis (meth) acrylamide, N, N'-ethylenebis (meth) acrylamide, N, N'-hexamethylenebis (meth) acrylamide;

Polyvinyl aromatic compounds such as divinylbenzene, diisopropenylbenzene and trivinylbenzene;

Poly (unsaturated alcohol ester) s of non-polymerizable polycarboxylic acid such as divinyl phthalate and diallyl phthalate;

Examples thereof include polyfunctional unsaturated ethers such as divinyl ether and diallyl ether.

Preferred compounds having at least two unsaturated groups are di (meth) acrylates of alkylene glycol such as ethylene glycol and polyvinyl aromatic compounds such as divinylbenzene. These compounds having at least two unsaturated groups can be used alone or in combination of two or more.

Further, other monomers other than those mentioned above are not particularly limited, but specific examples thereof include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,
p-t-butylstyrene, o-methoxystyrene, m-
Methoxystyrene, p-methoxystyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene,
1,1-diphenylethylene, N, N-dimethyl-p-
Aminostyrene, N, N-diethyl-p-aminostyrene, vinylpyridine, vinylpiperidine, vinylpiperazine, vinylfuran, vinylthiophene, vinylthiazole, N-vinylpyrrolidone, N-vinylcarbazole, (meth) acrylonitrile, α-chloro. Acrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, fumaric acid dinitrile, (meth) acrylamide, N-hydroxymethyl (meth ) Acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, crotonic acid amide, cinnamic acid amide, Le (meth) acrylate,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-
Butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-
Butyl (meth) acrylate, n-amyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth)
Acrylate, stearyl (meth) acrylate, methyl crotonic acid, ethyl crotonic acid, propyl crotonic acid, butyl crotonic acid, methyl cinnamate, ethyl cinnamate, propyl cinnamate, butyl cinnamate, dimethyl itaconate, itaconic acid Examples include diethyl, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, vinyl chloride, vinylidene chloride, vinyl acetate and allyl acetate.

Other preferred monomers are styrene, (meth) acrylonitrile, methyl (meth) acrylate,
Examples thereof include ethyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. These other monomers are
They can be used alone or in combination of two or more.

In the above-mentioned carboxyl group-containing diene copolymer, the content ratio of the aliphatic conjugated diene, the carboxyl group-containing unsaturated monomer and the compound having at least two unsaturated groups constitutes the copolymer. Based on the total amount of monomer components, the aliphatic conjugated diene is usually 1
0-95 mol%, preferably 30-90 mol%,
The unsaturated compound containing a carboxyl group is usually 0.1 to
30 mol%, preferably 0.2 to 20 mol%, and the compound having at least two unsaturated groups is usually 0.01 to 20 mol%, preferably 0.1 to 10 mol%. . The content of the other monomer is 70 mol% or less of the monomer component.

In this case, if the content of the aliphatic conjugated diene is less than 10 mol%, the strength of the composition after photocuring tends to be lowered, while if it exceeds 95 mol%, the water developability of the composition is increased. Tends to decline. If the content of the α, β-ethylenically unsaturated carboxylic acid is less than 0.1 mol%, the water developability of the composition tends to decrease.
If it exceeds mol%, the composition after photocuring tends to be hard and brittle. Further, if the content of the compound having at least two unsaturated groups is less than 0.01 mol%, the water developability of the composition tends to decrease, while if it exceeds 20 mol%, the component (1) or There is a tendency that the miscibility with (3) a photopolymerizable unsaturated monomer described later becomes insufficient, the processability decreases, and the strength of the composition after photocuring also decreases.

Examples of the radical polymerization initiator used in the emulsion polymerization and the like include benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, paramenthane hydroperoxide, di-t-butyl peroxide, dicumyl peroxide. Organic peroxides such as; azo compounds such as azobisisobutyronitrile, azobisisovaleronitrile, azobisisocapronitrile; inorganic peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide; Redox catalysts comprising peroxides or inorganic peroxides and reducing agents such as organic amines, ferrous sulfate, sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, L-ascorbic acid, sulfinic acid, etc. This Can.

As the emulsifier used in the emulsion polymerization, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and the like can be used, but especially anionic surfactants. Agents and nonionic surfactants are preferred. These surfactants can also be fluorosurfactants. In emulsion polymerization, the following suspension stabilizers or thickeners may be used in combination with emulsifiers in order to adjust the viscosity and particle size of the reaction system.

Examples of the suspension stabilizer used in the suspension polymerization include polyvinyl alcohol, sodium polyacrylate, methyl vinyl ether-maleic anhydride copolymer, water-soluble polyether, hydroxyethyl cellulose, carboxymethyl cellulose, starch, gelatin. , Casein, alginate and the like. In suspension polymerization, the emulsifier may be used in combination with a suspension stabilizer, if desired.

In each of the above polymerizations, the reaction components such as monomers and radical polymerization initiators may be added in a total amount before the reaction is started, or a part or all of them may be divided or continuously after the reaction is started. May be added. The polymerization reaction is
Usually, it is carried out at 0 to 60 ° C. in an atmosphere from which oxygen has been removed (for example, nitrogen), but operating conditions such as temperature and stirring speed can be appropriately changed during the reaction. The polymerization reaction can be carried out either continuously or batchwise.

In the first to fourth inventions, the component (1) can be used alone or in combination of two or more kinds.

Component (2-1) Next, a polymer having two or more photopolymerizable unsaturated groups at the end of the (2-1) molecular chain used in the first invention (hereinafter referred to as "component (2- 1) ”) is a polymer in which two or more photopolymerizable unsaturated groups are bonded to the end of the molecular chain directly and / or via an appropriate bonding group. The photopolymerizable unsaturated group can be present at one or both ends of the molecular chain, but is preferably present at both ends of the molecular chain, and in particular one at each end of the molecular chain. Is preferred. These multiple photopolymerizable unsaturated groups are present,
They may be the same or different from each other. The component (2-1) may be linear or branched morphologically, and in the case of a copolymer, may be a random copolymer, a block copolymer or a graft copolymer.

The main monomer constituting the molecular chain of the component (2-1) (hereinafter referred to as "main monomer a") is not particularly limited, and the desired component (2-1) is desired. Can be appropriately selected and used according to the characteristics of. Examples of the main monomer a include aliphatic conjugated dienes, alkenes, cycloalkenes, α, β-ethylenically unsaturated carboxylic acid esters, unsaturated ethers, vinyl aromatic compounds, unsaturated nitriles, unsaturated amides, cycloalkanes. , Cyclic ester,
Examples thereof include cyclic amide and cyclic ether. The polymerization of these main monomers a is carried out by a polymerization operation such as addition polymerization, polyaddition, polycondensation or a combination thereof (hereinafter, these polymerization operations are collectively referred to as “polymerization etc.”) depending on the respective polymerization characteristics. .), Radical polymerization, anionic polymerization,
It can be carried out by an appropriate method such as cationic polymerization or coordination polymerization.

Specific examples of the main monomer a include butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene, 4,5-diethyl-1,3-octadiene, 3 -Aliphatic conjugated dienes such as butyl-1,3-octadiene, chloroprene, 2,3-dichlorobutadiene, 1,3-cyclopentadiene;

Alkenes such as ethylene, propylene, 1-butene, isobutylene and 2-methyl-1-butene; cycloalkenes such as cyclobutene, cyclopentene, cyclohexene and bicyclonorbornene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate. , T-butyl (meth) acrylate, n-amyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, methyl crotonate, croton. Ethyl acid, propyl crotonate, butyl crotonate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, butyl cinnamate, dimethyl itaconate,
Unsaturated carboxylic acid esters such as diethyl itaconate, dimethyl maleate, diethyl maleate, dimethyl fumarate and diethyl fumarate;

Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether;

Styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, o-methoxystyrene,
m-methoxystyrene, p-methoxystyrene, divinylbenzene, diisopropenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene,
1,1-diphenylethylene, N, N-dimethyl-p-
Vinyl aromatic compounds such as aminostyrene, N, N-diethyl-p-aminostyrene and vinylpyridine;

(Meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile,
unsaturated nitriles such as α-methoxyacrylonitrile, α-ethoxyacrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, fumaric acid dinitrile;

(Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-
Unsaturated amides such as hydroxyethyl) (meth) acrylamide, crotonic acid amide, cinnamic acid amide;

Cycloalkanes such as 1,1-dimethylcyclopropane, cyclopentane, norbornene;

Propiolactone, β-butyrolactone,
Cyclic esters such as diketene; Cyclic amides such as pyrrolidone and ε-caprolactam;

Ethylene oxide, propylene oxide,
Cyclic ethers such as epichlorohydrin, trioxane, tetrahydrofuran, 3-methyltetrahydrofuran, 3-ethyltetrahydrofuran, 3-propyltetrahydrofuran and the like can be mentioned. These main monomers a can be used alone or in admixture of two or more.

The molecular chain in the component (2-1) is as follows:
A molecular chain having at least one repeating unit of an aliphatic conjugated diene, an aromatic vinyl compound and an unsaturated nitrile (hereinafter referred to as "molecular chain A"), or a repeating unit containing an ester bond, an amide bond or an ether bond. A molecular chain consisting of at least one of the above (hereinafter referred to as “molecular chain B”) is preferable.

In the molecular chain A, butadiene is particularly preferable as the aliphatic conjugated diene, styrene is particularly preferable as the aromatic vinyl compound, and (meth) acrylonitrile is particularly preferable as the unsaturated nitrile. Further, in the molecular chain B, The repeating unit is preferably a ring-opened unit of tetrahydrofuran or 3-methyltetrahydrofuran.

Examples of the photopolymerizable unsaturated group in the component (2-1) include (meth) acryloyl group, alkenyl group, cinnamoyl group, cinnamylideneacetyl group, benzalacetophenone group, styrylpyridine group, α-phenyl group. Maleimide group, phenylazide group, sulfonylazide group, carbonylazide group, diazo group, o-quinonediazide group, furylacryloyl group, coumarin group, pyrone group, anthracene group, benzophenone group, benzoin group, stilbene group, dithiocarbamate group, xanthate A group, 1,2,3-thiadiazole group, cyclopropene group, azadioxabicyclo group and the like can be adopted.

Preferred photopolymerizable unsaturated groups are (meth) acryloyl group, alkenyl group and cinnamoyl group, and (meth) acryloyl group is particularly preferred.

In the component (2-1), a method of introducing two or more photopolymerizable unsaturated groups at the terminal of the molecular chain is well known, and typical examples thereof include (A-1) After synthesizing a precursor molecular chain having a hydroxyl group at the terminal (hereinafter referred to as "precursor molecular chain a1"), it is reacted with a polyisocyanate compound having at least two isocyanate groups in the molecule to produce a polymer containing isocyanate groups at both ends. And then a hydroxyl group-containing photopolymerizable unsaturated compound (hereinafter referred to as "complementary unsaturated compound A"), for example, a hydroxyl group-containing (meth) acrylic acid derivative, preferably hydroxy. A method of urethanization with an alkyl (meth) acrylate can be mentioned.

The precursor molecular chain a1 can be obtained by the method shown in (a-2) Example 1 and (a-3) Example 2 which will be described later.
-4) A method in which the molecular chain of both terminal anions obtained using a bifunctional anionic polymerization initiator is reacted with a cyclic ether such as ethylene oxide and then hydrolyzed, (a-5) a bifunctional cationic polymerization initiator It can be formed by a method of reacting the molecular chain of the cations at both ends obtained by using it with an aqueous alkali solution or amino alcohol.

Further, the component (2-1) having two or more photopolymerizable unsaturated groups at both ends of the molecular chain is (a-6) as a precursor molecular chain, which is a carboxyl group (acid anhydride group) at both ends. The same shall apply hereinafter), those having at least one functional group other than hydroxyl group such as primary and / or secondary amino group, epoxy group, carbonyl group (hereinafter, "precursor molecular chain a2").
Say. ) Is used to react these functional groups with a compound having a complementary functional group capable of reacting with them and a photopolymerizable unsaturated group (hereinafter referred to as “complementary unsaturated compound B”). It can also be manufactured.

The precursor molecular chain a2 is (a-2) in Example 1 and (a)
-3) In the same manner as in Example 2, for example, (a-7) the main monomer a, optionally together with other monomers, a functional group required as a polymerization initiator, a chain transfer agent or a polymerization solvent is provided. The compounds can be synthesized by appropriately combining and polymerizing the compounds, and terminating both ends with the functional group. For example, (i-8) 4,4'-azobis-4-valeric acid as a polymerization initiator and dithiodiglycolic acid as a polymerization solvent are used for polymerization to synthesize a precursor molecular chain a2 having a carboxyl group at both ends. can do.

Examples of the complementary unsaturated compound B include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid; (meth) acrylic acid chloride. And the like unsaturated carboxylic acid halides; glycidyl (meth) acrylate and other unsaturated carboxylic acid epoxy group-containing esters; 2
-Hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and other unsaturated carboxylic acid hydroxyl group-containing esters; and the unsaturated carboxylic acid hydroxyl group-containing ester with diisocyanate compounds such as tolylene diisocyanate and methylene diisocyanate. Examples thereof include isocyanate group-containing esters of unsaturated carboxylic acids obtained by reacting in moles.

Specific examples of the reaction between the precursor molecular chain a2 and the complementary unsaturated compound B are as follows. That is, the (meth) acryloyl group is, for example, a method of reacting (i-9) (meth) acrylic acid with an epoxy group in the precursor molecular chain a2 to esterify, and (i-10) (meth) acrylic acid chloride A method of reacting with a carboxyl group in the precursor molecular chain a2 to form an acid anhydride, (a-11) a method of reacting (meth) acrylic acid chloride with an amino in the precursor molecular chain a2 to amidate, (a-12) ) A method of reacting glycidyl (meth) acrylate with a carboxyl group in the precursor molecular chain a2 to esterify, (a-13) reacting an isocyanate group-containing (meth) acrylic acid ester with a hydroxyl group in the precursor molecular chain a2 A method of urethanization, (a-14) a method of reacting an isocyanate group-containing (meth) acrylic acid ester with a primary and / or secondary amino group in the precursor molecular chain a2 to ureaize, (a-15 ) Isocyanate group included It can be introduced by a method of reacting a (meth) acrylic acid ester with a carboxyl group or an acid anhydride group group in the precursor molecular chain a2 to perform amidation. The photopolymerizable unsaturated group can be similarly introduced by using an unsaturated (poly) carboxylic acid or a derivative thereof other than (a-16) (meth) acrylic acid (derivative).

The introduction of the cinnamoyl group can be carried out basically by the same method as the above-mentioned introduction of the (meth) acryloyl group.

Further, the alkenyl group is, for example, (a-17)
Wittig reaction of a carbonyl group (aldehyde group, ketone group) in the precursor molecular chain a2 with an alkylidenephosphorane compound, (a-18) the hydroxyl group in the precursor molecular chain a2 having a p-hydroxystyrene unit It can be introduced by reaction with allyl bromide or the like.

The introduction of other photopolymerizable unsaturated groups can also be carried out according to a conventional method in synthetic organic chemistry. Those skilled in the art will be aware of the reaction reagents and reaction conditions used in that case.

The reaction between the precursor molecular chain a1 and the complementary unsaturated compound A or the reaction between the precursor molecular chain a2 and the complementary unsaturated compound B is carried out selectively between specific functional groups for each of them. The reaction may proceed or two or more reactions may occur simultaneously.

In the first invention, when the precursor molecular chain a1 or the precursor molecular chain a2 has a carbon-carbon unsaturated bond,
At least a part of the carbon-carbon unsaturated bond can be hydrogenated prior to introducing the photopolymerizable unsaturated group at the terminal of these molecular chains. In this case, the hydrogenation rate is usually 70% or less, preferably 50% or less, more preferably 40% or less.

The number average molecular weight of component (2-1) (hereinafter,
It is called "Mn". ) Can be appropriately selected according to the desired properties of the composition of the first invention, but generally, the larger Mn, the higher the strength of the composition after photocuring, and the smaller Mn, the more the composition. The water developability of the product tends to be improved. In applications where water developability is important, Mn is preferably less than 5,000, more preferably 4,500 to 1,000. M of component (2-1)
When n is 5,000 or more, the strength of the composition after photocuring is improved, but the elution property during water development, the transparency after water development, etc. tend to be reduced.

In the first invention, the component (2-1) can be used alone or in admixture of two or more.
The blending amount of the component (2-1) can be appropriately selected according to the purpose of use of the composition of the first invention, but the component (1) 1
The amount is preferably 0.1 to 300 parts by weight, more preferably 0.5 to 100 parts by weight, and particularly preferably 1.0 to 50 parts by weight with respect to 00 parts by weight. If the blending amount of the component (2-1) is less than 0.1 parts by weight, the strength of the composition after photocuring tends to decrease, and if it exceeds 300 parts by weight,
The water developability of the composition tends to decrease.

In the first invention, by using the component (2-1), the property balance between the water developability of the composition and the strength after photocuring becomes particularly excellent.

Component (2-2) Next, (2-2) used in the second invention has two or more photopolymerizable unsaturated groups at the ends of the molecular chain, and the side chains of the molecular chain are exposed to light. A polymer having at least one functional group selected from the group consisting of a polymerizable unsaturated group, a carboxyl group, a hydroxyl group, an amino group and an epoxy group (hereinafter, referred to as "component (2-
2) ”. ) Is a polymer in which the functional group is bonded to the end and side chain of the molecular chain directly and / or via an appropriate bonding group. In this case, the photopolymerizable unsaturated group at the end of the molecular chain can be present at one or both ends of the molecular chain, but it is preferable that it is present at both ends of the molecular chain, especially at each end of the molecular chain. It is preferable to have one each. The component (2-2) may be linear or branched morphologically, and in the case of a copolymer, may be a random copolymer, a block copolymer or a graft copolymer.

The main monomer constituting the molecular chain of the component (2-2) (hereinafter referred to as "main monomer b") is not particularly limited, and the desired monomer of the component (2-2). Can be appropriately selected and used according to the characteristics of. Examples of the main monomer b include aliphatic conjugated dienes, alkenes, cycloalkenes, α, β-ethylenically unsaturated carboxylic acid esters,
Examples thereof include unsaturated ethers, vinyl aromatic compounds, unsaturated nitriles, unsaturated amides, cycloalkanes, cyclic esters, cyclic amides, cyclic ethers and the like. Polymerization of these main monomers b can also be carried out by an appropriate method according to their polymerization characteristics.

Specific examples of the main monomer b include the same monomers as the main monomer a mentioned for the component (2-1).

The molecular chain in the component (2-2) is as follows:
A molecular chain similar to the molecular chain A or the molecular chain B described above for the component (2-1) is preferable.

Component (2-2) is, for example, (C-1) a precursor molecular chain having at least one functional group capable of introducing a photopolymerizable unsaturated group at the end and side chain of the molecular chain (hereinafter referred to as "precursor"). Molecular chain b1 ")), a method of introducing a photopolymerizable unsaturated group into the terminal and side chains, (C-2) a functional group capable of introducing two or more photopolymerizable unsaturated groups into the terminal of the molecular chain. A precursor molecular chain which has and has at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group and an epoxy group in the side chain of the molecular chain (hereinafter referred to as "precursor molecular chain b2").
A method of introducing a photopolymerizable unsaturated group at the terminal of (3) chemically (C-3) a precursor (co) polymer of the main monomer b having two or more photopolymerizable unsaturated groups at the terminal of the molecular chain It can be produced by a method such as post-treatment and introducing at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group and an epoxy group into the side chain of the molecular chain.

Specific examples of the photopolymerizable unsaturated group in the component (2-2) include the photopolymerizable unsaturated group mentioned for the component (2-1).

In the method (C-1), the precursor molecular chain
b1 is, for example, (C-4), (B-2) to (B-5), (B-
Using a method such as 7), a main monomer b and a monomer having at least one functional group capable of introducing a photopolymerizable unsaturated group (hereinafter referred to as “functional monomer b1”) are used. It can be synthesized by copolymerization and, if necessary, converting a terminal hydroxyl group and / or a side chain hydroxyl group into an isocyanate group in the same manner as in the above-mentioned (a-1).

Examples of the functional monomer b1 include monomers having at least one functional group such as carboxyl group, hydroxyl group, primary and / or secondary amino group, epoxy group and carbonyl group. You can

Examples of the functional monomer b1 having a carboxyl group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid and cinnamic acid; (anhydrous) maleic acid, fumaric acid and (anhydrous) itacone. Unsaturated polycarboxylic acids (anhydrides) such as acid, citraconic acid and mesaconic acid; free carboxyl group-containing esters such as monomethyl ester, monoethyl ester and monopropyl ester of the unsaturated polycarboxylic acid; Free carboxyl group-containing nitriles such as carboxylic acid mononitriles; Free carboxyl group-containing amides such as unsaturated polycarboxylic acid monoamides; Mono (2-hydroxyethyl ester), mono (2 -Hydroxypropyl ester) etc. Le acids; the other N- hydroxyalkyl derivatives of free carboxyl group-containing amides of unsaturated polycarboxylic acid, succinic acid, adipic acid, non-polymerizable polycarboxylic acids with unsaturated alcohols, such as phthalic acid, 2
Examples thereof include free carboxyl group-containing esters with a hydroxyl group-containing unsaturated compound such as hydroxyethyl (meth) acrylate.

The functional monomer b1 having a preferred carboxyl group is (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, monovinyl succinate, monovinyl phthalate and the like.

Examples of the functional monomer b1 having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 3
-Hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2
-Hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate (the number of polyethylene glycol units is, for example, 2 to
20), polypropylene glycol mono (meth) acrylate (the number of polypropylene glycol units is, for example, 2
20) and other (poly) alkylene glycol mono (meth) acrylates;

Glycerol mono (meth) acrylate,
Glycerol di (meth) acrylate, 1,2,4-butanetriol mono (meth) acrylate, 1,2,4
-Butanetriol di (meth) acrylate, trimethylolalkane mono (meth) acrylate (alkane has a carbon number of, for example, 1 to 3), trimethylolalkane di (meth) acrylate (alkane has a carbon number of, for example, 1 to
3), tetramethylolalkane mono (meth) acrylate (the number of carbons of the alkane is, for example, 1 to 3), tetramethylolalkane mono (meth) acrylate (the number of carbons of the alkane is, for example, 1 to 3), tetramethylolalkane di (meth) Acrylate (carbon number of alkane is, for example, 1 to
3), a free hydroxyl group-containing (meth) acrylate of a polyhydric alcohol having a valence of 3 or more, such as tetramethylolalkane tri (meth) acrylate (alkane has 1 to 3 carbon atoms);

Hydroxyalkyl esters of other unsaturated carboxylic acids such as 2-hydroxyethyl crotonic acid, 2-hydroxypropyl crotonic acid, 2-hydroxyethyl cinnamate, 2-hydroxypropyl cinnamate;

N-hydroxymethyl (meth) acrylamide, N-2-hydroxyethyl (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, crotonic acid N-hydroxymethylamide, crotonic acid N -(2-hydroxyethyl) amide,
Cinnamic acid N-hydroxymethylamide, cinnamic acid N-
Unsaturated hydroxyl group-containing amides such as (2-hydroxyethyl) amide;

O-Hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-
Hydroxyl group-containing vinyl aromatic compounds such as α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene and p-vinylbenzyl alcohol; unsaturated alcohols such as (meth) allyl alcohol Can be mentioned.

Functional monomer b1 having a preferred hydroxyl group
Is 2-hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like.

Examples of the functional monomer b1 having a primary and / or secondary amino group include vinylamine, vinylmethylamine, vinylethylamine, (meth) allylamine, (meth) allylmethylamine, ( (Meth) allylethylamine, o-aminostyrene, m-aminostyrene, p-aminostyrene, o-methylaminostyrene, m-methylaminostyrene, p-methylaminostyrene, o-amino-α-methylstyrene, m-amino -Α-methylstyrene, p-amino-α-methylstyrene, o-methylamino-α-methylstyrene, m-
Methylamino-α-methylstyrene, p-methylamino-α-methylstyrene, 2-aminoethyl (meth) acrylate, 2-methylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (Meth) acrylate, 2-methylaminopropyl (meth) acrylate, 3-methylaminopropyl (meth) acrylate, N- (2-aminoethyl)
(Meth) acrylamide, N- (2-methylaminoethyl) (meth) acrylamide, N- (3-aminopropyl) (meth) acrylamide, N- (3-methylaminopropyl) (meth) acrylamide, vinylpiperidine, vinyl Examples thereof include piperazine.

Further, a functional monomer b1 having an epoxy group
For example, glycidyl (meth) acrylate,
(Meth) allyl glycidyl ether etc. can be mentioned.

Further, examples of the functional monomer b1 having a carbonyl group include (meth) acrolein, vinyl methyl ketone, vinyl ethyl ketone and the like.

These functional monomers b can be used alone or in admixture of two or more. Further, the functional monomer b1 is a monomer other than the above, for example, vinyl chloride, vinylidene chloride, vinyl acetate, allyl acetate, vinyl furan, vinyl thiophene, vinyl thiazole, N-vinyl pyrrolidone, N, if necessary. -It can be used in combination with one or more kinds such as vinylcarbazole.

The method (C-1) can be carried out, for example, by using a precursor molecular chain.
The complementary unsaturated compound A and / or the complementary unsaturated compound B is appropriately selected according to the type of the functional group in b1, and the precursor molecular chain b1 and the complementary unsaturated compound A and / or the complementary unsaturated compound B are selected. It can be carried out by reacting with a saturated compound B to introduce two or more photopolymerizable unsaturated groups at the terminal of the molecular chain and at the same time introducing a photopolymerizable unsaturated group at the side chain of the molecular chain. In this case, the introduction of the photopolymerizable unsaturated group into the side chain of the molecular chain can be carried out simultaneously with the introduction of the photopolymerizable unsaturated group into the terminal of the molecular chain, or before or after the introduction thereof.

The reaction between the precursor molecular chain b1 and the complementary unsaturated compound A and / or the complementary unsaturated compound B may be carried out selectively between specific functional groups, or may be a reaction of two or more kinds. May occur simultaneously.

In the method (C-1), the precursor molecular chain
The reaction ratio between b1 and the complementary unsaturated compound A and / or the complementary unsaturated compound B is determined by the content of the functional group in the molecular chain, the complementary unsaturated compound A and / or the complementary unsaturated compound B. , 100 parts by weight of the precursor molecular chain b1, depending on the desired characteristics of the composition of the second invention, etc.,
The complementary unsaturated compound A and / or the complementary unsaturated compound B is usually 0.1 to 40 parts by weight, preferably 0.5.
To 30 parts by weight, particularly preferably 1.0 to 20 parts by weight. When the reaction ratio of the complementary unsaturated compound A and / or the complementary unsaturated compound B is less than 0.1 parts by weight, the photosensitivity of the composition tends to decrease, and when it exceeds 40 parts by weight, Water developability tends to decrease.

In the method (C-2), the precursor molecular chain
b2 is, for example, (C-5), (B-2) to (B-5), (B-
7) etc., a monomer having at least one functional group selected from the group consisting of a main monomer b and a carboxyl group, a hydroxyl group, an amino group and an epoxy group (hereinafter, referred to as “functional monomer”). b2 ")) and, if necessary, by converting the terminal hydroxyl group to an isocyanate group in the same manner as in the above-mentioned (a-1). Further, the precursor molecular chain b2 can also be produced by a chemical post-treatment of the (co) polymer of the main monomer b, for example, a reaction similar to (D-4) to (D-8) described later. .

A functional monomer b2 having a carboxyl group,
Examples of the functional monomer b2 having a hydroxyl group and the functional monomer b2 having an epoxy group may include the corresponding monomers described for the functional monomer b1. Further, as the functional monomer b2 having an amino group,
In addition to the monomer having a primary and / or secondary amino group mentioned for the functional monomer b1, as a monomer having a tertiary amino group, 2-dimethylaminoethyl (meth) acrylate , 2-diethylaminoethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate and the like, containing tertiary amino group-containing (meth) acrylates; N- (2-dimethylamino) Tertiary amino group-containing (meth) acrylamides such as ethyl) (meth) acrylamide, N- (2-dimethylaminopropyl) (meth) acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide; vinyldimethyl Containing tertiary amino groups such as amines, vinyldiethylamine, vinyldiphenylamine, etc. Amines; N, N-dimethylamino styrene, N, N-diethylamino styrene,
N, N-dimethylamino-α-methylstyrene, N, N
Examples thereof include tertiary amino group-containing vinyl aromatic compounds such as diethylamino-α-methylstyrene.
These functional monomers b2 can be used alone or in combination of two or more.

Further, the functional monomer b2 is, if necessary,
Monomers other than the above, such as vinyl chloride, vinylidene chloride, vinyl acetate, allyl acetate, vinyl furan, vinyl thiophene, vinyl thiazole, N-vinyl pyrrolidone,
It can be used in combination with one or more kinds of N-vinylcarbazole and the like.

In the method (c-2), the complementary unsaturated compound A and / or the complementary unsaturated compound B is appropriately selected depending on, for example, the type of the functional group in the precursor molecular chain b2. And unsaturated compound A and / or complementary to the precursor molecular chain b2
Alternatively, it can be carried out by reacting with a complementary unsaturated compound B to introduce two or more photopolymerizable unsaturated groups at the ends of the molecular chain.

In the above method (C-2), the component (2-
The content of the functional monomer b2 in 2) varies depending on the type of functional group in the monomer, desired properties of the composition of the second invention, etc., but is usually 0.1 to 30. % By weight, preferably 0.5
-25% by weight, particularly preferably 1.0-20% by weight. When the content of the functional monomer b2 is less than 0.1% by weight,
The photosensitivity of the composition tends to decrease, and also 30% by weight
If it exceeds, the water developability of the composition tends to decrease.

Further, in the method (c-3), for example, the methods (b-2) to (b-5) and (b-7) described above are used, and the main monomer b may be replaced by other (Co) polymerization with the above monomer, and if necessary, the terminal hydroxyl group is converted into an isocyanate group in the same manner as in the above (a-1), and then two or more photopolymerizations are carried out at the terminal of the resulting polymer. A synthetic unsaturated group can be introduced, and then the reaction described below can be performed to synthesize.

Examples of the reaction in the method (C-3) include (C-6) carboxylation or hydroxylation by hydrolysis of ester group, (C-7) hydrolysis of epoxy group, N- of amide group. Examples thereof include hydroxylation by methylolation and the like, and amination by aminomethylation of (C-8) aromatic group and the like. The reaction reagents, reaction conditions, etc. used in these reactions will be apparent to those skilled in the art.

The functional group content in the component (2-2) produced by the method (C-3) is also the same as the functional group content in the component (2-2) produced by the method (C-2). It is adjusted to correspond to the group content.

In the present invention, the above (C-1) or
In the method (C-2), the precursor molecular chain b1 or the precursor molecular chain b1
When 2 has a carbon-carbon unsaturated bond, at least a part of the carbon-carbon unsaturated bond can be hydrogenated prior to the introduction of the photopolymerizable unsaturated group, and
In the method of (C-3), when the precursor (co) polymer before introducing the photopolymerizable unsaturated group has a carbon-carbon unsaturated bond at the terminal of the molecular chain, the introduction of the photopolymerizable unsaturated group is introduced. Prior to, at least a part of the carbon-carbon unsaturated bond can be hydrogenated. In this case, the hydrogenation rate is usually 70% or less, preferably 50% or less, more preferably 40% or less.

The number average molecular weight of the component (2-2) (hereinafter,
It is called "Mn". ) Can be appropriately selected according to the desired characteristics of the composition of the second invention. Generally, the larger Mn, the higher the strength of the composition after photocuring, and the smaller Mn, the more the composition. The water developability of the product tends to be improved. In applications where water developability is important, Mn is 5
It is preferably less than 000, more preferably 4
It is 500 to 1000. Mn of component (2-2) is 50
If it is 00 or more, the strength of the composition after photocuring is improved, but
The elution property during water development and the transparency after water development tend to decrease.

In the second invention, the component (2-2) can be used alone or in admixture of two or more.
The blending amount of the component (2-2) can be appropriately selected according to the purpose of use of the composition of the second invention.
The amount is preferably 0.1 to 300 parts by weight, more preferably 0.5 to 100 parts by weight, and particularly preferably 1.0 to 50 parts by weight with respect to 00 parts by weight. If the blending amount of the component (2-2) is less than 0.1 parts by weight, the strength of the composition after photocuring tends to decrease, and if it exceeds 300 parts by weight,
The water developability of the composition tends to decrease.

In the second invention, by using the component (2-2), the property balance between the water developability of the composition and the strength after photocuring becomes particularly excellent.

Component (2-3) Next, the group consisting of a photopolymerizable unsaturated group, a carboxyl group, a hydroxyl group, an amino group and an epoxy group in the side chain of the (2-3) molecular chain used in the third invention. A non-diene polymer having at least one functional group selected from
It is called "ingredient (2-3)". ) Is a non-diene polymer in which the functional group is bonded to the side chain of the molecular chain directly and / or via an appropriate bonding group. The component (2-3) may be linear or branched morphologically, and in the case of a copolymer, may be a random copolymer, a block copolymer or a graft copolymer.

The main monomer constituting the molecular chain of the component (2-3) (hereinafter referred to as "main monomer c") is the component (2).
It can be appropriately selected and used according to the desired characteristics of (3). Examples of the main monomer c include alkenes, cycloalkenes, α, β-ethylenically unsaturated carboxylic acid esters, unsaturated ethers, vinyl aromatic compounds, unsaturated nitriles, unsaturated amides, cycloalkanes, cyclic esters, cyclics. Examples thereof include amides and cyclic ethers. Polymerization of these main monomers c can also be carried out by an appropriate method according to their polymerization characteristics.

As a specific example of the main monomer c, there can be mentioned a monomer obtained by removing the aliphatic conjugated diene from the main monomer a mentioned for the component (2-1).

As the molecular chain in the component (2-3),
A molecular chain similar to the molecular chain A or the molecular chain B described above for the component (2-1) is preferable.

The component (2-3) is, for example, (D-1) a monomer having a main monomer c and a functional group capable of introducing a photopolymerizable unsaturated group (hereinafter, referred to as "functional monomer c1"). The method of introducing a photopolymerizable unsaturated group into the side chain of the precursor molecular chain (hereinafter referred to as “precursor molecular chain c1”) composed of a copolymer with
(D-2) A monomer having a main monomer c and at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group and an epoxy group (hereinafter, referred to as “functional monomer c
2 ”. ) And (e-3) chemically pretreating the precursor (co) polymer of the main monomer c to form a side chain of the molecular chain from a carboxyl group, a hydroxyl group, an amino group and an epoxy group. It can be produced by a method of introducing at least one functional group selected from the group consisting of:

In the method (d-1) above, examples of the functional monomer c1 include the monomers mentioned for the functional monomer b1. These functional monomers c1
Can be used alone or in admixture of two or more.

Further, the functional monomer c1 is, if necessary,
Monomers other than the above, such as vinyl chloride, vinylidene chloride, vinyl acetate, allyl acetate, vinyl furan, vinyl thiophene, vinyl thiazole, N-vinyl pyrrolidone,
It can be used in combination with one or more kinds of N-vinylcarbazole and the like.

Specific examples of the photopolymerizable unsaturated group in the above method (d-1) include the photopolymerizable unsaturated groups mentioned for the component (2-1).

The method (d-1) can be carried out, for example, by using a precursor molecular chain.
The complementary unsaturated compound A and / or the complementary unsaturated compound B is appropriately selected according to the kind of the functional group in c1, and if necessary, the same method as in the above (a-1) is performed. After converting the hydroxyl groups to isocyanate groups, the precursor molecular chain c1
It can be carried out by reacting with a complementary unsaturated compound A and / or a complementary unsaturated compound B.

The reaction between the precursor molecular chain c1 and the complementary unsaturated compound A and / or the complementary unsaturated compound B may be carried out selectively between specific functional groups, or may be a reaction of two or more kinds. May occur simultaneously.

In the method (d-1), the precursor molecular chain
The reaction ratio between c1 and the complementary unsaturated compound A and / or the complementary unsaturated compound B is determined by the content of the functional group in the molecular chain, the complementary unsaturated compound A and / or the complementary unsaturated compound B. And the desired properties of the composition of the third invention, etc., but per 100 parts by weight of the precursor molecular chain c1,
The complementary unsaturated compound A and / or the complementary unsaturated compound B is usually 0.1 to 40 parts by weight, preferably 0.5.
To 30 parts by weight, particularly preferably 1.0 to 20 parts by weight. When the reaction ratio of the complementary unsaturated compound A and / or the complementary unsaturated compound B is less than 0.1 parts by weight, the photosensitivity of the composition tends to decrease, and when it exceeds 40 parts by weight, Water developability tends to decrease.

In the method (d-2) above, examples of the functional monomer c2 include the monomers mentioned for the functional monomer b2.

Further, the functional monomer c2 is, if necessary,
Monomers other than the above, such as vinyl chloride, vinylidene chloride, vinyl acetate, allyl acetate, vinyl furan, vinyl thiophene, vinyl thiazole, N-vinyl pyrrolidone,
It can be used in combination with one or more kinds of N-vinylcarbazole and the like.

The content of the functional monomer c2 in the copolymer produced in the method (d-2) depends on the kind of the functional group in the functional monomer c2, the desired content of the composition of the third invention. Although it depends on the characteristics, etc., it is usually 0.1 to 30% by weight, preferably 0.5.
-25% by weight, particularly preferably 1.0-20% by weight. When the content of the functional monomer c2 is less than 0.1% by weight,
The photosensitivity of the composition tends to decrease, and also 30% by weight
If it exceeds, the water developability of the composition tends to decrease.

Further, in the above method (d-3),
Appropriate addition reaction, substitution reaction, reduction reaction and the like can be adopted depending on the type of the main monomer c and the introduced functional group. Examples of these reactions include (D-4) functional monomer
c2 addition reaction, (E-5) carboxylation or hydroxylation by hydrolysis of ester group, (E-6) hydrolysis of epoxy group, N-methylolation of amide group, hydroxylation by reduction of carbonyl group, etc., (D-7) Reduction of nitrile group or amide group, amination of aromatic group by aminomethylation, etc. (d-8) Epoxidation of carbon-carbon unsaturated bond of side chain of molecular chain . The reaction reagents, reaction conditions, etc. used in these reactions will be apparent to those skilled in the art.

In the method (d-4), the reaction ratio of the functional monomer c2 varies depending on the kind of the functional group in the monomer, desired properties of the composition of the third invention, and the like. Main monomer c
The functional monomer c2 is usually 0.1 to 40 parts by weight, preferably 0.5 to 100 parts by weight of the precursor (co) polymer of
To 30 parts by weight, particularly preferably 1.0 to 20 parts by weight. In this case, if the reaction ratio of the functional comonomer c2 is less than 0.1 parts by weight, the photosensitivity of the composition tends to decrease,
When it exceeds 40 parts by weight, the water developability of the composition tends to be lowered. Furthermore, the content of each functional group in the component (2-3) produced by the above-mentioned methods (D-5) to (D-8) is the same as the component (2-) produced by the method (D-4). 3)
It is adjusted so as to correspond to the content of the functional group therein.

In the third invention, when the component (2-3) has a carbon-carbon unsaturated group, it can be used as a hydrogenated product. However, in the above method (D-1), hydrogenation is carried out before introducing the photopolymerizable unsaturated group into the side chain. The hydrogenation rate in this case is usually 70% or less,
It is preferably 50% or less, more preferably 40% or less.

The Mn of the component (2-3) can be appropriately selected according to the desired characteristics of the composition of the third invention.
Generally, the larger Mn, the greater the strength of the composition after photocuring, and the smaller Mn, the more the water developability of the composition tends to improve. In applications where importance is attached to water developability, Mn is preferably less than 5000, more preferably 4500 to 1000. Ingredient (2-
When Mn of 3) is 5000 or more, the strength of the composition after photocuring is improved, but the elution property during water development, the transparency after water development, etc. tend to be reduced.

In the third invention, the component (2-3) can be used alone or in admixture of two or more.
The blending amount of the component (2-3) can be appropriately selected according to the purpose of use of the composition of the third invention, but the component (1) 1
The amount is preferably 0.1 to 300 parts by weight, more preferably 0.5 to 100 parts by weight, and particularly preferably 1.0 to 50 parts by weight with respect to 00 parts by weight. When the compounding amount of the component (2-3) is less than 0.1 part by weight, the strength of the composition after photocuring tends to decrease, and when it exceeds 300 parts by weight, the water developability of the composition decreases. Tend to do.

In the third invention, by using the component (2-3), the property balance between the water developability of the composition and the strength after photocuring becomes particularly excellent.

Component (2-4) Further, the side chain of the (2-4) molecular chain used in the fourth invention is a photopolymerizable unsaturated group, a carboxyl group, a hydroxyl group,
The linear diene-based polymer having at least one functional group selected from the group consisting of an amino group and an epoxy group and having an Mn of less than 5000 (hereinafter, referred to as “component (2-4)”) is as described above. It is a linear diene polymer having a functional group directly and / or bonded to a side chain of a molecular chain through an appropriate bonding group.Component (2-3) is a random copolymer in the case of a copolymer. Alternatively, it may be a block copolymer.

The main monomer constituting the molecular chain of the component (2-4) (hereinafter referred to as "main monomer d") has an aliphatic conjugated diene as an essential component, but the component (2-
Depending on the desired properties of 4), other monomers such as alkenes, cycloalkenes, α, β-ethylenically unsaturated carboxylic acid esters, unsaturated ethers, vinyl aromatic compounds,
It may also contain unsaturated nitriles, unsaturated amides and the like. Polymerization of these main monomers d can also be performed by an appropriate method according to their polymerization characteristics.

Specific examples of the main monomer d include the same monomers as the main monomer a mentioned for the component (2-1).

The main monomer d is a monomer other than the above, for example, vinyl chloride, vinylidene chloride, vinyl acetate, allyl acetate, vinyl furan, vinyl thiophene, vinyl thiazole, N-vinyl pyrrolidone, if necessary. , N-vinylcarbazole and the like.

The molecular chain in component (2-4) is as follows:
A molecular chain having a repeating unit composed of an aliphatic conjugated diene and, if necessary, at least one repeating unit of an aromatic vinyl compound, preferably styrene, unsaturated nitrile, preferably (meth) acrylonitrile is preferable. .

Component (2-4) is, for example, (o-1) a monomer having a main monomer d and a functional group capable of introducing a photopolymerizable unsaturated group (hereinafter referred to as "functional monomer d1"). The method of introducing a photopolymerizable unsaturated group into a side chain of a precursor molecular chain (hereinafter referred to as “precursor molecular chain d1”) composed of a copolymer with
(E-2) A monomer having a main monomer d and at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group and an epoxy group (hereinafter, referred to as “functional monomer d
2 ”. ) And (e-3) chemically post-treating the precursor (co) polymer of the main monomer d to form a side chain of the molecular chain from a carboxyl group, a hydroxyl group, an amino group and an epoxy group. It can be produced by a method of introducing at least one functional group selected from the group consisting of:

In the method (e-1), examples of the functional monomer d1 include the monomers mentioned for the functional monomer b1. These functional monomers d1
Can be used alone or in admixture of two or more.

Further, the functional monomer d1 is, if necessary,
Monomers other than the above, such as vinyl chloride, vinylidene chloride, vinyl acetate, allyl acetate, vinyl furan, vinyl thiophene, vinyl thiazole, N-vinyl pyrrolidone,
It can be used in combination with one or more kinds of N-vinylcarbazole and the like.

Specific examples of the photopolymerizable unsaturated group in the method (e-1) include the photopolymerizable unsaturated group mentioned for the component (2-1).

The method (o-1) can be carried out, for example, by using a precursor molecular chain.
The complementary unsaturated compound A and / or the complementary unsaturated compound B is appropriately selected according to the kind of the functional group in d1, and if necessary, the same method as in the above (a-1) is performed. After converting the hydroxyl groups to isocyanate groups, the precursor molecular chain d1
It can be carried out by reacting with a complementary unsaturated compound A and / or a complementary unsaturated compound B.

The reaction between the precursor molecular chain d1 and the complementary unsaturated compound A and / or the complementary unsaturated compound B may be carried out selectively between specific functional groups, or may be a reaction of two or more kinds. May occur simultaneously.

In the method (o-1), the precursor molecular chain
The reaction ratio between d1 and the complementary unsaturated compound A and / or the complementary unsaturated compound B is determined by the content of the functional group in the molecular chain, the complementary unsaturated compound A and / or the complementary unsaturated compound B. Of the precursor molecular chain d1 per 100 parts by weight of the precursor molecular chain d1,
The complementary unsaturated compound A and / or the complementary unsaturated compound B is usually 0.1 to 40 parts by weight, preferably 0.5.
To 30 parts by weight, particularly preferably 1.0 to 20 parts by weight. When the reaction ratio of the complementary unsaturated compound A and / or the complementary unsaturated compound B is less than 0.1 parts by weight, the photosensitivity of the composition tends to decrease, and when it exceeds 40 parts by weight, Water developability tends to decrease.

In addition, in the method (e-2), the functional monomer d2 may be, for example, the monomer described for the functional monomer b2.

Further, the functional monomer d2 is, if necessary,
Monomers other than the above, such as vinyl chloride, vinylidene chloride, vinyl acetate, allyl acetate, vinyl furan, vinyl thiophene, vinyl thiazole, N-vinyl pyrrolidone,
It can be used in combination with one or more kinds of N-vinylcarbazole and the like.

The content of the functional monomer d2 in the copolymer produced in the method (e-2) depends on the type of the functional group in the functional monomer d2, the desired composition of the fourth invention. Although it depends on the characteristics, etc., it is usually 0.1 to 30% by weight, preferably 0.5.
-25% by weight, particularly preferably 1.0-20% by weight. When the content of the functional monomer d2 is less than 0.1% by weight,
The photosensitivity of the composition tends to decrease, and also 30% by weight
If it exceeds, the water developability of the composition tends to decrease.

Furthermore, in the above method (e-3),
Depending on the type of the main monomer d and the introduced functional group, etc.,
The same reactions as (d-4) to (d-8) can be adopted.

In the method (e-3), when the addition reaction of the functional monomer d2 to the precursor (co) copolymer (e-4) is carried out, the reaction ratio of the monomer is Depending on the type of functional group in the monomer, desired properties of the composition of the fourth invention, etc., the functional monomer d2 is added to 100 parts by weight of the precursor (co) polymer of the main monomer d. , Usually 0.1 to 40 parts by weight, preferably 0.5 to 30 parts by weight, particularly preferably 1.0 to
20 parts by weight. In this case, if the reaction ratio of the functional comonomer d2 is less than 0.1 parts by weight, the photosensitivity of the composition tends to decrease, and if it exceeds 40 parts by weight, the water developability of the composition decreases. Tend to do. Furthermore, in the method of (o-3), (o-5) carboxylation of the precursor (co) copolymer, (o-6) hydroxylation of the precursor (co) copolymer,
Content of each functional group in component (2-4) produced by amination of (o-7) precursor (co) copolymer, epoxidation of (o-8) precursor (co) copolymer, etc. Is adjusted so as to correspond to the functional group content in the component (2-4) produced by the method (e-4).

In the fourth invention, when the component (2-4) has a carbon-carbon unsaturated group, it can be used as a hydrogenated product. However, in the method (e-1), hydrogenation is carried out before introducing the photo-polymerizable unsaturated group into the side chain. In this case, the hydrogenation rate is usually 70% or less, preferably 50% or less, more preferably 40% or less.

The Mn of component (2-4) is less than 5,000, preferably 4500 to 500, and particularly preferably 4
It is 000 to 1000. Mn of component (2-4) is 50
When it is 00 or more, the strength of the composition after photocuring is improved to some extent, but the elution property during water development, the transparency after water development and the like are insufficient, which is not suitable.

In the fourth invention, the component (2-4) can be used alone or in admixture of two or more.
The blending amount of the component (2-4) can be appropriately selected according to the purpose of use of the composition of the fourth invention, but the component (1) 1
The amount is preferably 0.1 to 300 parts by weight, more preferably 0.5 to 100 parts by weight, and particularly preferably 1.0 to 50 parts by weight with respect to 00 parts by weight. If the amount of component (2-4) is less than 0.1 part by weight, the strength of the composition after photocuring tends to decrease, and if it exceeds 300 parts by weight, the water developability of the composition decreases. Tend to do.

In the fourth invention, by using the component (2-4), the property balance between the water developability of the composition and the strength after photocuring becomes particularly excellent.

Component (3) Next, the photopolymerizable unsaturated monomer (3) (hereinafter referred to as “component (3)”) commonly used in the first to fourth inventions will be described later. (5) A compound having an unsaturated bond that can be polymerized by irradiation with light in the presence of a photopolymerization initiator.

Examples of the component (3) include styrene, α-methylstyrene, o-methylstyrene,
m-methylstyrene, p-methylstyrene, pt-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, divinylbenzene, diisopropenylbenzene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 1,1-diphenylethylene, N, N-dimethyl-p-aminostyrene,
Vinyl aromatic compounds such as N, N-diethyl-p-aminostyrene and vinyl pyridine;

(Meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile,
unsaturated nitriles such as α-methoxyacrylonitrile, α-ethoxyacrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, fumaric acid dinitrile;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate. , T-butyl (meth) acrylate, n-amyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Acrylates, methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate,
Methyl cinnamate, ethyl cinnamate, propyl cinnamate,
Unsaturated monocarboxylic acid esters such as butyl cinnamate;

Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate and heptafluorobutyl (meth) acrylate;

Mono- or di- of alkylene glycols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol.
(Meth) acrylates;

Mono- or di- (meth) acrylates of polyalkylene glycol (the number of alkylene glycol units is, for example, 2 to 23) such as polyethylene glycol and polypropylene glycol;

2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3- Ethoxypropyl (meth)
Alkoxyalkyl (meth) acrylates such as acrylates;

(Meth) acrylates of alkoxy polyalkylene glycol (the number of alkylene glycol units is, for example, 2 to 23) such as methoxy polyethylene glycol, ethoxy polyethylene glycol, methoxy polypropylene glycol, ethoxy polypropylene glycol;

2-phenoxyethyl (meth) acrylate, 2-phenoxypropyl (meth) acrylate, 3
-Aryloxyalkyl (meth) acrylates such as phenoxypropyl (meth) acrylate;

Mono (meth) acrylates of aryloxypolyalkylene glycols such as phenoxypolyethylene glycol and phenoxypolypropylene glycol;

Cyanoalkyl (meth) acrylates such as cyanoethyl (meth) acrylate and cyanopropyl (meth) acrylate;

Trivalent or higher polyvalent compounds such as glycerin, 1,2,4-butanetriol, trimethylolalkane (alkane has 1 to 3 carbon atoms) and tetramethylolalkane (alkane has 1 to 3 carbon atoms). Mono- or oligo- (meth) acrylates of polyhydric alcohols;

Mono- or oligo- (meth) acrylates of a polyalkylene glycol adduct of a trihydric or higher polyhydric alcohol;

1,4-cyclohexanediol, 1,4
-Mono- or di- (meth) acrylates of cyclic polyols such as benzenediol, 1,4-dihydroxyethylbenzene;

Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid and cinnamic acid, and unsaturated compounds such as itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid, citraconic acid and mesaconic acid. Polycarboxylic acids;

Monomethyl ester, monoethyl ester, monopropyl ester of the unsaturated polycarboxylic acid,
Free carboxyl group-containing esters such as monobutyl ester, monohexyl ester and monooctyl ester;

Polyesters such as dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, dihexyl ester and dioctyl ester of the unsaturated polycarboxylic acid;

(Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-)
Hydroxyethyl) (meth) acrylamide, N, N '
-Unsaturated amides such as methylenebis (meth) acrylamide, N, N'-ethylenebis (meth) acrylamide, N, N'-hexamethylenebis (meth) acrylamide, crotonic acid amide, cinnamic acid amide, etc. You can

These components (3) can be used alone or in admixture of two or more. In the first to fourth inventions, by appropriately selecting the component (3) or a combination thereof, it is possible to impart desired properties to the composition after photocuring.

The fluidity of the compositions of the first to third inventions can be freely selected from waxy or rubbery to low viscosity liquid depending on the blending amount of the component (3). The blending amount of 3) can be appropriately selected according to the purpose of use of these compositions, but the component (1) 10
0 to 5 parts by weight, preferably 5 to 1,000 parts by weight,
More preferably, it is 10 to 500 parts by weight. When the compounding amount of the component (3) is less than 5 parts by weight, the strength of the composition after photocuring tends to decrease, and when it exceeds 1,000 parts by weight, the composition after photocuring has a large shrinkage, It may be difficult to achieve both the water developability of the composition and the water resistance after photocuring, and the degree of freedom in designing the viscosity of the composition tends to be small.

Component (4) Next, the (4) amino group-containing compound (hereinafter referred to as “component (4)”) commonly used in the compositions of the first invention to the fourth invention is the first compound. It comprises at least one compound containing at least one primary to tertiary amino group.

Examples of the component (4) include primary amines such as methylamine, ethylamine, propylamine, butylamine, cyclohexylamine and aniline;

Dimethylamine, methylethylamine, diethylamine, methylpropylamine, ethylpropylamine, dipropylamine, methylbutylamine, ethylbutylamine, propylbutylamine, dibutylamine, pyrrole, pyrrolidine, piperidine, piperazine,
Secondary amines such as indole, indoline, carbazole;

As tertiary amines, trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine, dimethylpropylamine, methylethylpropylamine, diethylpropylamine, methyldipropylamine, ethyldipropylamine, tripropylamine, dimethylbutylamine, Trialkylamines such as methyldibutylamine, methylethylbutylamine, diethylbutylamine, ethyldibutylamine, methylpropylbutylamine, ethylpropylbutylamine, dipropylbutylamine, propyldibutylamine and tributylamine;

Alkylalkanol tertiary amines such as dimethylethanolamine, methyldiethanolamine, diethylethanolamine and ethyldiethanolamine; trialkanolamines such as triethanolamine, diethanolpropanolamine, ethanoldipropanolamine and tripropanolamine; N , N-
N, N-dialkylaminoalkoxyalkanols such as dimethylaminoethoxyethanol, N, N-diethylaminoethoxyethanol, N, N-dimethylaminoethoxypropanol, N, N-diethylaminoethoxypropanol and the like;

Aromatic tertiary amines such as pyridine, 1,3,5-triazine and quinoline;

2-Dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dipropylaminoethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-dimethylaminopropyl (meth) ) Acrylate, 2-diethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, 2-dipropylaminopropyl (meth) acrylate, 3-dipropylaminopropyl (meth) acrylate and other dialkylaminoalkyl (meth) Acrylates;

Dialkylaminoalkoxyalkyl (meth) acrylates such as 2-dimethylaminoethoxyethyl (meth) acrylate and 2-diethylaminoethoxyethyl (meth) acrylate;

N- (2-dimethylaminoethyl) (meth) acrylamide, N- (2-diethylaminoethyl) (meth) acrylamide, N- (2-dimethylaminopropyl) (meth) acrylamide, N- (3-dimethyl Aminopropyl) (meth) acrylamide, N-
Tertiary amino group-containing (meth) acrylamides such as (2-diethylaminopropyl) (meth) acrylamide, N- (3-diethylaminopropyl) (meth) acrylamide;

N, N-dimethylaminoethyl-N'-
Examples thereof include tertiary amino group-containing carbamates such as (meth) acryloyl carbamate and N, N-diethylaminoethyl-N ′-(meth) acryloyl carbamate. These components (4) can be used alone or in combination of two or more.

As the component (4), a tertiary amine having good water developability is preferable, and from the viewpoint of strength of the composition after photocuring, tertiary amino group-containing (meth) acrylates, tertiary A compound having an α, β-ethylenically unsaturated group such as a primary amino group-containing (meth) acrylamide is preferred.

The blending amount of the component (4) can be appropriately selected according to the purpose of use of the composition of the first to fourth inventions.
The content of the amino group is preferably 0.1 mol or more, more preferably 0.4 mol or more, per 1 mol of the carboxyl group in the component (1). When the content of the amino group in the component (4) is 0.1 mol or less, the water developability tends to decrease. However, even if the content of amino groups exceeds 5 mol, the water developability is not particularly improved, which is uneconomical.

In the present invention, the component (3) and the component (4) may be the same compound. In that case, the compounding amount of the compound with respect to the component (1) is the component (1). It is adjusted so as to satisfy both the above preferable ranges as 3) and component (4).

Component (5) Furthermore, (5) a photopolymerization initiator commonly used in the first to fourth inventions (hereinafter referred to as "component 5").
Is the polymerization of the component (3) upon irradiation with light, and in a preferred embodiment of the present invention, α of the component (4),
Polymerization of a compound having a β-ethylenically unsaturated group is also a component that initiates or sensitizes.

Examples of the component (5) include α-diketone compounds such as diacetyl, methylbenzoylformate and benzyl; acyloins such as benzoin and pivaloine; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like. Acyloin ethers of
Anthraquinone, 2-ethylanthraquinone, 2-t-
Polynuclear quinones such as butylanthraquinone and 1,4-naphthoquinone;

Acetophenones such as acetophenone, 2-hydroxy-2-methyl-propiophenone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxyphenylacetophenone, 2,2-diethoxyacetophenone and trichloroacetophenone;

Benzophenones such as benzophenone, methyl-o-benzoylbenzoate and Michler's ketone; and xanthones such as xanthone, thioxanthone and 2-chlorothioxanthone.

The blending amount of the component (5) is 100 parts of the component (1).
It is usually 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on parts by weight. If the blending amount of the component (5) is less than 0.1 parts by weight, the photocuring of the composition tends to be insufficient, and even if it exceeds 20 parts by weight, all of the blended component (5) is light. Not only is it uneconomical because it is not involved in curing, but sometimes it is component (3) or component (4)
It may not be able to disperse uniformly because of poor compatibility with.

Further, various additives can be added to the compositions of the first to fourth inventions, if necessary. Examples of the additive include a thermal addition polymerization inhibitor that acts as a storage stabilizer. Examples of the thermal addition polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, mono-t-butylhydroquinone, catechol, pt-butylcatechol, p-methoxyphenol, pt-butylcatechol, 2,6-di- t-butyl-p-cresol, 2,6-di-t-butyl-m-
Hydroxy aromatic compounds such as cresol, pyrogallol and β-naphthol; quinones such as benzoquinone, 2,5-diphenyl-p-benzoquinone, p-toluquinone and p-xyloquinone;

Nitrobenzene, m-dinitrobenzene,
2-methyl-2-nitrosopropane, α-phenyl-t
-Butylnitrone, 5,5-dimethyl-1-pyrroline-
A nitro compound such as 1-oxide or a nitrone compound;
Chloranyl-amine-based, diphenylamine, diphenylpicrylhydrazine, phenol-α-naphthylamine, pyridine, phenothiazine and other amines; dithiobenzoyl sulfide, dibenzyl tetrasulfide and other sulfides; 1,1-diphenylethylene, α-methylthioacrylonitrile Unsaturated compounds such as;

Thiazine dyes such as thionine blue, toluidine blue and methylene blue; 1,1-diphenyl-2
-Picrylhydrazyl, 1,3,5-triphenylferdazyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 2,6-di-t-butyl-α- ( 3,5-di-t-butyl) -4-oxo-
Examples thereof include stable radicals such as 2,5-cyclohexadiene-1-ylidene-p-trioxyl. These thermal addition polymerization inhibitors may be used alone or in admixture of two or more.

The blending amount of the thermal addition polymerization inhibitor is usually
0.001 of the entire photosensitive resin composition of the first invention to the fourth invention
It is about 2.0% by weight.

Further, other additives include antioxidants, surfactants, fillers, reinforcing materials, plasticizers, antihalation agents, adhesion aids and the like.

The compositions of the first to fourth inventions require the component (1), the components (2-1) to (2-4), the component (3), the component (4) and the component (5). With various additives blended by, usually under heating, for example, a kneader,
It can be obtained by sufficiently mixing with an intermixer or the like. The composition obtained can be freely adjusted from a waxy or rubber-like composition having no fluidity to a low-viscosity liquid having good fluidity. The degree of fluidity depends on the purpose of use of the composition. It is selected as appropriate. When a composition having a low viscosity is particularly preferable, an appropriate amount of solvent can be added to the composition.

When the photosensitive resin plate is processed from the compositions of the first to fourth inventions, various methods can be adopted depending on the degree of fluidity of the composition. For example, in the case of a composition having no fluidity or low fluidity, it is passed through a spacer having an appropriate interval, coated on a suitable support using a coating device such as a roll coater, or extrusion molded. A desired film thickness can be processed by a molding method such as calender molding or pressure molding.

The composition having good fluidity can be coated on the support by an appropriate coating method such as roll coating, calendar coating, doctor blade coating and air knife coating, and a resist particularly suitable for spin coating. Is useful as

These photosensitive resin plates or resists are exposed to chemical actinic rays such as ultraviolet rays through a negative film having a desired pattern, and the unexposed area is washed and removed with water, and then dried. A clear relief image can be formed. In this case, if necessary, re-exposure can be performed after drying. The compositions of the first to fourth inventions have essentially water developability, but if desired, they can be developed using an aqueous alkaline solution.

[0193]

EXAMPLES 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. Here, parts are based on weight. Example 1 Component (1) Butadiene / methacrylic acid / ethylene glycol dimethacrylate / ethyl acrylate = 84.1 / 2.2 /
A monomer mixture having a composition of 1.2 / 12.5 (mol%),
Using sodium lauryl sulfate as an emulsifier and 2,2′-azobisisobutyronitrile as a polymerization initiator, 65
Polymerization was carried out at 0 ° C for 10 hours. The polymerization conversion rate was 95%.
After the polymerization, the produced emulsion is salted out and coagulated with calcium chloride, washed with water, and dried to obtain particles (average particle size 710
nm) component (1) was prepared.

Component (2-1) Using hydrogen peroxide as a polymerization initiator and isopropanol as a polymerization solvent, butadiene was polymerized to obtain a polybutadiene polymer (Mn = 4000) having hydroxyl groups at both ends. The polybutadiene polymer is reacted with tolylene diisocyanate to produce a polymer having isocyanate groups at both ends, and then 2-hydroxyethyl methacrylate is reacted while being careful not to shine light in the reaction process, A component (2-1) having a methacryloyl group at both ends of the molecular chain via a urethane bond was produced.

Photosensitive resin composition: 10 parts of nonaethylene glycol monomethacrylate and 10 parts of trimethylolpropane trimethacrylate as the component (3), relative to 100 parts of the component (1) and 10 parts of the component (2-1), 10 parts of N- (3-dimethylaminopropyl) acrylamide as (4), 3 parts of 2,2-dimethoxyphenylacetophenone as component (5), and 0.5 parts of pt-butylcatechol as a storage stabilizer were added. The photosensitive resin composition was prepared by stirring for 30 minutes in a kneader whose temperature was adjusted to 50 ° C.
The composition obtained was in the form of a transparent wax.

Evaluation A photosensitive resin plate was prepared by forming a resin layer having a thickness of 0.5 mm on a polyester sheet using the photosensitive resin composition prepared as described above. The resin layer of the resin plate,
By using a developing machine (JOW-A-4P) manufactured by JEOL Seiki Co., Ltd., the time required for the resin layer to be completely eluted by brushing in warm water at 30 ° C. (hereinafter, “elution required time”) Was measured to evaluate the water developability of the photosensitive resin composition. The resin plate was exposed for 6 minutes using an exposure machine (JE-A-SS) manufactured by JEOL Ltd., and then tensile strength, elongation at break and impact resilience were measured according to JIS K6301. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 1.

Example 2 Component (1) In the same manner as in Example 1, butadiene / methacrylic acid / divinylbenzene / methyl methacrylate = 84.1 /
A monomer mixture having a composition of 2.2 / 1.2 / 12.5 (mol%) was polymerized to produce a particulate (average particle size 700 nm) component (1). Polyether diol (Mn = 2000) obtained by polymerizing component (2-1) tetrahydrofuran in the presence of a polymerization initiator consisting of perchloric acid-acetic anhydride, neutralizing and hydrolyzing it, and purifying it.
Tolylene diisocyanate (TDI) and 2-hydroxyethyl methacrylate (2-HEM) are sequentially reacted with each other to give a component (2-1) consisting of a polymer having a methacryloyl group at both ends of a molecular chain through a urethane bond. ) Manufactured. Preparation and Evaluation of Photosensitive Resin Composition A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the components (1) and (2) were used. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 1.

Example 3 Component (1) and component (2-) were prepared in the same manner as in Example 2 except that a mixture of tetrahydrofuran and 3-methyltetrahydrofuran was used as a constituent monomer of component (2-1). 1) (Mn = 2100) was manufactured, and a photosensitive resin composition was prepared and evaluated. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 1.

Example 4 Component (1) and component (1) were prepared in the same manner as in Example 1 except that the monomer composition of component (1) and the blending amount of component (2-1) were as shown in Table 1. (2-1) (Mn = 400
0) was prepared, and a photosensitive resin composition was prepared and evaluated. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 1.

Example 5 Component (1) and component (2-1) (Mn =) were prepared in the same manner as in Example 1 except that the monomer composition of component (2-1) was changed as shown in Table 1. 4200), and a photosensitive resin composition was prepared and evaluated. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 1.

Example 6 Photosensitization was performed in the same manner as in Example 1 except that 15 parts of 2-diethylaminoethyl methacrylate was used as the component (4) instead of 10 parts of N- (3-dimethylaminopropyl) acrylamide. The resin composition was prepared and evaluated. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 1.

Example 7 A photosensitive resin was prepared in the same manner as in Example 1 except that 10 parts of triethanolamine was used as the component (4) instead of 10 parts of N- (3-dimethylaminopropyl) acrylamide. The composition was prepared and evaluated. as a result,
Both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, the transparency of the resin plate was good, and the composition had an excellent property balance.
The above results are shown in Table 1.

Example 8 Photosensitivity was the same as in Example 1 except that 10 parts by weight of component (2-2) produced as described below and 10 parts by weight of triethanolamine as component (4) were used. The resin composition was prepared and evaluated. Component (2-2) 4 parts by weight of maleic anhydride was added to 100 parts by weight of the solid content of the toluene solution of the component (2-1) obtained in the same manner as in Example 1 and reacted at 100 ° C. A component (2-2) having a photopolymerizable unsaturated group at the terminal and side chain of the molecular chain was produced. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 2.

Example 9 Component (1) Butadiene / methacrylic acid / ethylene glycol dimethacrylate / methyl methacrylate = 80.0 / 6.5
A monomer mixture having a composition of /1.0/12.5 (mol%) was polymerized at 65 ° C. for 10 hours using sodium lauryl sulfate as an emulsifier and potassium persulfate as a polymerization initiator. The polymerization conversion rate was 96%. After polymerization, the produced emulsion is salted out and coagulated with calcium chloride, washed with water,
Dried and particulate (average particle size 720 nm) component (1)
Was manufactured.

Component (2-3) butyl acrylate / methacrylic acid / 2-HEM = 7
Polymerization of a monomer mixture having a composition of 0.0 / 20.0 / 10.0 (mol%) with benzoyl peroxide as a polymerization initiator and toluene as a polymerization solvent at 70 ° C. for 6 hours to give a hydroxyl group. A containing copolymer (Mn = 3700) was obtained. The polymerization conversion rate was 94%. Separately, an equimolar amount of cinnamyl alcohol (CMA) was reacted with TDI while being careful not to shine light in the reaction process to synthesize an isocyanate group-containing cinnamic acid ester (CMA / TDI adduct). Based on 100 parts by weight of the hydroxyl group-containing copolymer, C
4.4 parts by weight of MA / TDI adduct was added and reacted in the presence of a catalytic amount of di-n-butyltin dilaurate to give a component (2) having a cinnamoyl group on the side chain of the molecular chain via a urethane bond. -3) was produced.

Photosensitive resin composition and evaluation 100 parts by weight of component (1) and component (2-3) 10
10 parts by weight of nonaethylene glycol monomethacrylate and 10 parts by weight of trimethylolpropane trimethacrylate as the component (3), 10 parts by weight of N- (3-dimethylaminopropyl) acrylamide as the component (4), and 5) 2 parts by weight of 2,2-dimethoxyphenylacetophenone, and 0.5 parts by weight of pt-butylcatechol as a storage stabilizer were added.
A photosensitive resin composition was prepared by stirring for 30 minutes in a kneader whose temperature was adjusted to ° C. The composition obtained was in the form of a transparent wax.

Evaluation Using the photosensitive resin composition prepared as described above,
A photosensitive resin plate was prepared in the same manner as in Example 1, and the time required for elution, tensile strength, elongation at break and impact resilience were measured. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 2.

Example 10 A photosensitive resin was prepared in the same manner as in Example 9 except that the component (2-3) produced as described below was used and 2-diethylaminoethyl methacrylate was used as the component (4). The composition was prepared and evaluated. Isocyanate group-containing methacrylic acid ester (2-HEM / TDI adduct) obtained by reacting component (2-3) with equimolar amounts of 2-HEM and TDI while being careful not to shine light in the reaction process. 0.8 parts by weight to 100 parts by weight of the hydroxyl group-containing copolymer (Mn = 3700) obtained in Example 9,
By reacting in the presence of a catalytic amount of di-n-butyltin dilaurate, a component (2-3) having a methacryloyl group in the side chain of the molecular chain via a urethane bond was produced. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 2.

Example 11 A photosensitive resin composition was prepared and evaluated in the same manner as in Example 9 except that the component (2-3) produced as described below was used. Component (2-3), a monomer mixture having a composition of butyl acrylate / methacrylic acid = 80/20 (mol%), using 2,2′-azobisisobutyronitrile as a polymerization initiator and toluene as a polymerization solvent. Polymerization at 65 ° C. for 8 hours, and a component (2-3) having a carboxyl group on the side chain of the molecular chain (Mn = 380)
0) was produced. The polymerization conversion rate was 97%. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 3.

Example 12 A photosensitive resin composition was prepared and evaluated in the same manner as in Example 9 except that the component (2-3) produced as described below was used. Component (2-3) ethyl acrylate / acrylonitrile / acrylic acid =
70/20/10 (mol%) composition of the monomer mixture,
Using 2,2′-azobisisobutyronitrile as a polymerization initiator and toluene as a polymerization solvent, polymerization is carried out at 65 ° C. for 8 hours to obtain a component (2-3) (having a carboxyl group in the side chain of the molecular chain) ( Mn = 4000) was produced. The polymerization conversion rate was 97%. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 3.

Example 13 Example 13 was repeated except that the component (2-3) produced as described below was used and 10 parts by weight of trimethylolpropane trimethacrylate and 10 parts by weight of acrylic acid were used as the component (3). In the same manner as in Example 9, the photosensitive resin composition was prepared and evaluated. Component (2-3) ethyl acrylate / acrylonitrile / 2-diethylaminoethyl methacrylate = 75/10/15 (mol%), a monomer mixture, and 2,2′-azobisisobutyronitrile as a polymerization initiator. Then, using toluene as a polymerization solvent, polymerization was carried out at 65 ° C. for 8 hours to produce a component (2-3) (Mn = 3600) having an amino group in the side chain of the molecular chain. The polymerization conversion rate was 95%. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 3.

Example 14 A photosensitive resin composition was prepared and evaluated in the same manner as in Example 9 except that the component (2-3) produced as described below was used. Component (2-3) butyl acrylate / glycidyl methacrylate / 2-
Polymerization of a monomer mixture having a composition of HEM = 70/20/10 (mol%) for 8 hours at 65 ° C. using 2,2′-azobisisobutyronitrile as a polymerization initiator and toluene as a polymerization solvent. Then, a component (2-3) (Mn = 3800) having an epoxy group and a hydroxyl group on the side chain of the molecular chain was produced. The polymerization conversion rate was 97%. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 3.

Example 15 Component (1) Butadiene / methacrylic acid / divinylbenzene / methylmethacrylate = 80.0 / 6.5 / 1.0 / 12.5
The monomer mixture having a composition of (mol%) was polymerized at 65 ° C. for 10 hours using sodium lauryl sulfate as an emulsifier and potassium persulfate as a polymerization initiator. Polymerization conversion rate is 94
%Met. After the polymerization, the produced emulsion was salted out and coagulated with calcium chloride, washed with water, and dried to produce a particulate component (average particle diameter 700 nm) of component (1).

Component (2-4) A monomer mixture having a composition of butadiene / methacrylic acid = 90.0 / 10.0 (mol%), using benzoyl peroxide as a polymerization initiator, and toluene as a polymerization solvent, Polymerization was carried out at 70 ° C. for 6 hours to give a carboxyl group-containing copolymer (Mn =
3500) was obtained. The polymerization conversion rate was 97%. To 100 parts by weight of this copolymer, 2 parts by weight of glycidyl methacrylate was added and reacted in the presence of a catalytic amount of tetra-n-butylammonium bromide to form a side chain of a molecular chain through an ester bond. A component having a methacryloyl group (2
-4) was produced.

Photosensitive resin composition 100 parts by weight of component (1) and component (2-4) 10
10 parts by weight of nonaethylene glycol monomethacrylate and 10 parts by weight of trimethylolpropane trimethacrylate as the component (3), 10 parts by weight of N- (3-dimethylaminopropyl) acrylamide as the component (4), and 5) 2 parts by weight of 2,2-dimethoxyphenylacetophenone, and 0.5 parts by weight of pt-butylcatechol as a storage stabilizer were added.
A photosensitive resin composition was prepared by stirring for 30 minutes in a kneader whose temperature was adjusted to ° C. The composition obtained was in the form of a transparent wax.

Evaluation Using the photosensitive resin composition prepared as described above,
A photosensitive resin plate was prepared in the same manner as in Example 1, and the time required for elution, tensile strength, elongation at break and impact resilience were measured. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 4.

Example 16 Component (1) was prepared in the same manner as in Example 15 except that the copolymer having the monomer composition shown in Table 3 was used as the carboxyl group-containing copolymer in component (2-4). ) And component (2-4) (Mn = 3500), and a photosensitive resin composition was prepared and evaluated. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 4.

Example 17 Component (1) As the component (1), the particulate form (average particle size 7) obtained in Example 9 was used.
20 nm) of component (1) was used.

Component (2-4) butadiene / acrylonitrile / methacrylic acid / 2-H
A monomer mixture having a composition of EM = 58.0 / 30.0 / 10.0 / 2.0 (mol%) was polymerized in the same manner as in Example 15 to give a hydroxyl group-containing copolymer (Mn = 3600). ) Got. Separately, an equimolar amount of 2-HEM and TDI are allowed to react with each other while being careful not to expose them to light during the reaction process to give an isocyanate group-containing methacrylic acid ester (2-HEM /
TDI adduct) was synthesized. The hydroxyl group-containing copolymer 1
2-HEM / TDI adduct 4.4 for 100 parts by weight
Parts by weight were added, and the components were reacted in the presence of a catalytic amount of di-n-butyltin dilaurate to prepare a component (2-4) having a methacryloyl group in the side chain of the molecular chain via a urethane bond.

Photosensitive Resin Composition and Evaluation A photosensitive resin composition was prepared and evaluated in the same manner as in Example 15 except that the components (1) and (2-4) were used. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 4.

Example 18 A photosensitive resin composition was prepared and evaluated in the same manner as in Example 15 except that the following component (2-4) was used. Component (2-4) unsaturated group-containing esterified product of an addition product of 1 mol of polybutadiene (Mn = 1000) and 1.6 mol of maleic anhydride (trade name: MM1000-80, manufactured by Nippon Petrochemical Co., Ltd.) . As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 4.

Example 19 A photosensitive resin composition was prepared and evaluated in the same manner as in Example 15 except that the component (2-4) produced as described below was used. Component (2-4) butadiene / acrylonitrile / methacrylic acid = 60.
A monomer mixture having a composition of 0 / 30.0 / 10.0 (mol%) was polymerized at 70 ° C. for 7 hours to obtain a component (2-4) (Mn.
= 3500) was produced. The polymerization conversion rate was 95%. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 4.

Example 20 A photosensitive resin composition was prepared and evaluated in the same manner as in Example 15 except that the following component (2-4) was used. Component (2-4) Addition product of 1 mol of polybutadiene (Mn = 1000) and 1.6 mol of maleic anhydride (trade name: M1000-
80, manufactured by Nippon Petrochemical Co., Ltd.). As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 5.

Examples 21 to 23 Components (2-
A photosensitive resin composition was prepared and evaluated in the same manner as in Example 15 except that 4) was used. As a result, both the water developability and the resin plate strength of the composition were excellent, the elongation at break and the impact resilience were good, and the transparency of the resin plate was also good, having an excellent property balance. The above results are shown in Table 5.

Comparative Example 1 A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the component (2-1) was not added. As a result, the water developability of the composition was good, but the resin plate strength, elongation at break, and impact resilience were all insufficient. The above results are shown in Table 6.

Comparative Example 2 Instead of the component (2-1), a styrene-butadiene-styrene block copolymer (Mn = 70000, trade name:
30 JSR TR2000 manufactured by Japan Synthetic Rubber Co., Ltd.
A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1 except that the parts by weight were used. As a result, the water developability of the composition was significantly reduced. The above results are shown in Table 6.

Comparative Example 3 Instead of the component (2-4), a butadiene-acrylonitrile copolymer (butadiene / acrylonitrile = 83.0 / 17.0) having carboxyl groups at both ends of its molecular chain.
(Mol%), Mn = 3500, trade name: Hycar C
TBN1300 × 8, BFGoodrich Co. Ltd. 10
A photosensitive resin composition was prepared and evaluated in the same manner as in Example 10 except that the parts by weight were used. As a result, the water developability of the composition was good, but the resin plate strength, elongation at break, and impact resilience were all insufficient. The above results are shown in Table 6.

[0228]

[Table 1]

[0229]

[Table 2]

[0230]

[Table 3]

[0231]

[Table 4]

[0232]

[Table 5]

[0233]

[Table 6]

[0234]

The photosensitive resin composition of the present invention is
Both the water developability and the strength of the resin plate after exposure are excellent, the elongation at break and the impact resilience are good, and the transparency of the resin plate is good, and it has an excellent property balance. In addition, these compositions can be freely adjusted to waxy or rubber-like properties having no fluidity to low-viscosity liquid properties and have good processability. Therefore, the photosensitive resin composition of the present invention can be used very suitably as a photosensitive resin plate in the field of photoresists, plate making, etc., and also can be used as a photosensitive ink, a photosensitive coating, a photosensitive adhesive, and It is also useful as a molding material and the like.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C09J 4/00 JBT 7921-4J 113/00 JDW 7211-4J G03F 7/028 H01L 21/027 // C08F 2 / 48 MDK 7442-4J 299/00 MRM 7442-4J (72) Inventor Hozumi Sato 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Japan Synthetic Rubber Co., Ltd. (72) Noboru Oshima No. 2 Tsukiji, Chuo-ku, Tokyo No. 11-24 Japan Synthetic Rubber Co., Ltd.

Claims (4)

[Claims] 1. (1) A particulate carboxyl group-containing diene polymer having a crosslinked structure, (2-1) a polymer having two or more photopolymerizable unsaturated groups at the end of a molecular chain, (3) A photosensitive resin composition comprising a photopolymerizable unsaturated monomer, (4) an amino group-containing compound, and (5) a photopolymerization initiator. 2. (1) A particulate carboxyl group-containing diene polymer having a crosslinked structure, (2-2) having at least two photopolymerizable unsaturated groups at the end of the molecular chain, and having a molecular chain of A polymer having at least one functional group selected from the group consisting of a photopolymerizable unsaturated group, a carboxyl group, a hydroxyl group, an amino group and an epoxy group in its side chain, (3) a photopolymerizable unsaturated monomer, ( A photosensitive resin composition comprising 4) an amino group-containing compound and (5) a photopolymerization initiator. 3. (1) A particulate carboxyl group-containing diene polymer having a crosslinked structure, (2-3) a photopolymerizable unsaturated group, a carboxyl group, a hydroxyl group, an amino group and an epoxy group on a side chain of a molecular chain. A non-diene polymer having at least one functional group selected from the group consisting of groups, (3) a photopolymerizable unsaturated monomer, (4) an amino group-containing compound, and (5) a photopolymerization initiator A photosensitive resin composition comprising: 4. (1) A particulate carboxyl group-containing diene polymer having a crosslinked structure, (2-4) a photopolymerizable unsaturated group, a carboxyl group, a hydroxyl group, an amino group and an epoxy group on the side chain of a molecular chain. A linear diene polymer having at least one functional group selected from the group consisting of groups and having a number average molecular weight of less than 5000, (3) a photopolymerizable unsaturated monomer, (4) an amino group A photosensitive resin composition comprising a contained compound and (5) a photopolymerization initiator.