JP2001042520A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition superior in water developability and remarkably excellent in mechanical characteristics. SOLUTION: The photosensitive resin composition comprises (1) a copolymer comprising aliphatic conjugated diene units, and monomer units each having at least one kind of functional group selected from one polymerizable unsaturated group, carboxylic group, amino group, hydroxy group, epoxy group, sulfonic acid group, and phosphoric acid group, and monomer units each having at least 2 polymerizable unsaturated group, (2) a block copolymer comprising >=2 polymer segments different from each other in a glass transition temp. (Tg) and at least one polymer segment except the polymer segment having the lowest Tg and having the above functional group on the side chains, (3) a photopolymerizable unsaturated monomer, and (4) a photopolymerization initiator, in a (2) amount of a >=50 weight % of the total weights of the components (1) and (2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, and more particularly, to a water-developable photosensitive resin composition which has a small swelling due to water, a small decrease in physical properties and a small dimensional change.

[0002]

2. Description of the Related Art Conventionally, photosensitive resin compositions have been widely used for photoresists, inks, printing plates and the like, but most of the photoresists and printing plates use an organic solvent during development. However, in recent years, in addition to safety and health problems at the time of work, the influence of an organic solvent on the environment has become a problem.
Therefore, there is a demand for a photosensitive resin composition that can be developed with safer water. To meet such demands, for example, polyvinyl alcohol, gelatin, water developable based on a water-soluble polymer such as casein, etc. Has been proposed. However, in these conventional photosensitive resin compositions, since the affinity of the composition for water is too high, the composition swells during water development to cause a decrease in physical properties and a change in dimensions.As a result, for example, the dimensional accuracy of the resist is reduced. Decline,
Alternatively, there is a problem that the printing durability and printing quality of the printing plate are reduced. On the other hand, the present applicant has (1) an aliphatic conjugated diene unit, one polymerizable unsaturated group and a carboxyl group,
A monomer unit having at least one functional group selected from the group consisting of an amino group, a hydroxyl group, an epoxy group, a sulfonic acid group and a phosphoric acid group, and a monomer having at least two polymerizable unsaturated groups And (2) a hard segment having a glass transition temperature (Tg) of 20 ° C. or higher and a soft segment having a glass transition temperature (Tg) of 10 ° C. or lower. A block copolymer having at least one functional group selected from the group consisting of a carboxyl group, an amino group, a hydroxyl group, an epoxy group, a sulfonic acid group and a phosphoric acid group on one or both sides; (3) photopolymerizable unsaturated The photosensitive resin composition containing a monomer and (4) a photopolymerization initiator has a small swelling due to water and a small decrease in physical properties and small dimensional change. Regardless, it has revealed that it is capable of water development (see Japanese Patent Laid-Open No. 7-114184). However, the component (2) in this composition is produced by graft-polymerizing a polymerizable unsaturated monomer having a specific functional group in the presence of a block copolymer composed of a hard segment and a soft segment. However, the distribution of functional groups in the polymer molecular chain could not be properly controlled, and it was not always satisfactory in terms of the balance between water developability and mechanical properties. Further, the present applicant has made improvements in the invention of Japanese Patent Application Laid-Open No. Hei 7-114184 as (1) an aliphatic conjugated diene unit,
A monomer unit having at least two polymerizable unsaturated groups and at least one functional group selected from the group consisting of a carboxyl group, an amino group, a hydroxyl group, an epoxy group, a sulfonic acid group and a phosphoric acid group; (2) a block copolymer composed of two or more polymer segments having different glass transition temperatures (Tg). And Tg
Is attached to a side chain of at least one polymer segment other than the polymer segment having the lowest value, a carboxyl group, an amino group, a hydroxyl group, an epoxy group capable of electrically interacting with the functional group in the (1) particulate copolymer. Block copolymer having at least one functional group selected from the group consisting of a sulfonic acid group and a phosphoric acid group, (3) a photopolymerizable unsaturated monomer, and (4) a photopolymerization initiator. (JP-A-11-1584).
No. 13). However, it is desired that this composition be further improved in mechanical properties, particularly in terms of balance between rebound resilience and hardness.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to provide a composition having a specific functional group only in a specific polymer segment as a constituent polymer component of the composition. It is an object of the present invention to provide a photosensitive resin composition having excellent water developability and having extremely excellent mechanical properties by using a block copolymer as a main component.

[0004]

According to the present invention, there is provided (1) an aliphatic conjugated diene unit as a repeating unit in a copolymer.
To 95 mol%, a monomer having one polymerizable unsaturated group and at least one functional group selected from the group consisting of a carboxyl group, an amino group, a hydroxyl group, an epoxy group, a sulfonic acid group and a phosphoric acid group. A copolymer containing 0.1 to 30 mol% of a monomer unit and 0.1 to 20 mol% of a monomer unit having at least two polymerizable unsaturated groups, (2) a glass transition temperature (Tg) A block copolymer composed of two or more different polymer segments, wherein Tg
A carboxyl group, an amino group, a side chain of at least one polymer segment other than the lowest polymer segment.
A block copolymer having at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, a sulfonic acid group and a phosphoric acid group, (3) a photopolymerizable unsaturated monomer, and (4) a photopolymerization A photosensitive composition comprising an initiator, wherein the ratio of (2) the block copolymer to the total amount of (1) the copolymer and (2) the block copolymer is 50% by weight or more. A resin composition. The "carboxyl group" and "sulfonic acid group" referred to in the present invention mean a general term for a free acid group and a salt-form thereof, and a "phosphate group".
The term “-H ₂ PO ₃ group or ＨHPO ₂ group” and a salt forming body thereof mean a general term.

[0005]

Embodiments of the present invention will be described below in detail. (1) Copolymer (1) The copolymer, which is one of the constituent components of the photosensitive resin composition of the present invention, is a repeating unit in the copolymer.
10 to 95 mol% of an aliphatic conjugated diene unit, one polymerizable unsaturated group and at least one kind of functional group selected from the group consisting of a carboxyl group, an amino group, a hydroxyl group, an epoxy group, a sulfonic acid group and a phosphoric acid group And a copolymer containing 0.1 to 30 mol% of a monomer unit having a group and 0.1 to 20 mol% of a monomer unit having at least two polymerizable unsaturated groups. Such a (1) copolymer is an aliphatic conjugated diene (hereinafter, referred to as an essential component).
It is called "monomer". ) One polymerizable unsaturated group;
A monomer having at least one functional group selected from the group consisting of a carboxyl group, an amino group, a hydroxyl group, an epoxy group, a sulfonic acid group and a phosphoric acid group (hereinafter, referred to as “monomer”); It is composed of a monomer having two polymerizable unsaturated groups (hereinafter, referred to as “monomer”), and optionally includes another polymerizable unsaturated monomer described below (hereinafter, “monomer”). ) Can be produced by, for example, emulsion polymerization or suspension polymerization.

Examples of the monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, chloroprene and the like. These monomers can be used alone or in combination of two or more. (1) In the repeating unit in the copolymer, the content of the monomer unit is 10 to 95 mol%, preferably 3 to 95 mol%.
0 to 90 mol%. In this case, when the content of the monomer unit is less than 10 mol%, the strength of the obtained composition after photocuring decreases, while when it exceeds 95 mol%, the water developability of the obtained composition is poor, Neither is preferred.

Next, among the monomers, monomers having a carboxyl group include, for example, (meth) acrylic acid,
Unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, tetraconic acid, and cinnamic acid; phthalic acid, succinic acid,
Free carboxyl group-containing esters such as monoesters of non-polymerizable polycarboxylic acids such as adipic acid with hydroxyl-containing unsaturated compounds such as (meth) allyl alcohol and 2-hydroxyethyl (meth) acrylate, and salts thereof. And the like. Among them, unsaturated carboxylic acids are preferable. These monomers having a carboxyl group can be used alone or in combination of two or more.

The monomers having an amino group include:
Monomers having a tertiary amino group are preferred, and examples thereof include dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, and 2-diethylaminoethyl (meth) acrylate 2- (di-n-propylamino) ethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 2-diethylaminopropyl (meth) acrylate, 2- (di-n-propylamino) propyl (meth) Acrylate, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, 3- (di-
dialkylaminoalkyl (meth) acrylates such as n-propylamino) propyl (meth) acrylate;
N-dimethylaminomethyl (meth) acrylamide, N
-Diethylaminomethyl (meth) acrylamide, N-
(2-dimethylaminoethyl) (meth) acrylamide, N- (2-diethylaminoethyl) (meth) acrylamide, N- (2-dimethylaminopropyl) (meth) acrylamide, N- (2-diethylaminopropyl) (meth) N- such as acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide, N- (3-diethylaminopropyl) (meth) acrylamide
Dialkylaminoalkyl group-containing unsaturated amides;
N-dimethyl-p-aminostyrene, N, N-diethyl-p-aminostyrene, dimethyl (p-vinylbenzyl) amine, diethyl (p-vinylbenzyl) amine,
Dimethyl (p-vinylphenethyl) amine, diethyl (p-vinylphenethyl) amine, dimethyl (p-vinylbenzyloxymethyl) amine, dimethyl [2- (p
-Vinylbenzyloxy) ethyl] amine, diethyl (p-vinylbenzyloxymethyl) amine, diethyl [2- (p-vinylbenzyloxy) ethyl] amine,
Dimethyl (p-vinylphenethyloxymethyl) amine, dimethyl [2- (p-vinylphenethyloxy) ethyl] amine, diethyl (p-vinylphenethyloxymethyl) amine, diethyl [2- (p-vinylphenethyloxy) ethyl] Amine, 2-vinylpyridine, 3-
Examples thereof include tertiary amino group-containing vinyl aromatic compounds such as vinyl pyridine and 4-vinyl pyridine, and among them, dialkylaminoalkyl (meth) acrylates and tertiary amino group-containing vinyl aromatic compounds are preferable. These amino group-containing monomers can be used alone or in combination of two or more.

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Hydroxyalkyl (meth) such as 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate
Acrylates; polyalkylene glycols (the number of alkylene glycol units is, for example, 2 to 23) mono (meth) acrylates such as polyethylene glycol and polypropylene glycol; N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) ( Meta)
Hydroxyl group-containing unsaturated amides such as acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene And hydroxyl-containing vinyl aromatic compounds such as m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene and p-vinylbenzyl alcohol; (meth) allyl alcohol; Acrylates and hydroxyl group-containing vinyl aromatic compounds are preferred. These monomers having a hydroxyl group can be used alone or in combination of two or more.

Examples of the monomer having an epoxy group include (meth) allyl glycidyl ether, glycidyl (meth) acrylate, and 3,4-oxycyclohexyl (meth) acrylate. These monomers having an epoxy group can be used alone or in combination of two or more. Examples of the monomer having a sulfonic acid group include 2- (meth) acrylamidoethanesulfonic acid, 2- (meth) acrylamidopropanesulfonic acid, 3- (meth) acrylamidopropanesulfonic acid, and 2- (meth) (Meth) acrylamide monomers such as acrylamide-2-methylpropanesulfonic acid and 3- (meth) acrylamide-2-methylpropanesulfonic acid; ethyl 2-sulfonate (meth) acrylate, propyl 2-sulfonate (meth) ) Acrylate, propyl 3-sulfonate (meth) acrylate,
(Meth) acrylate monomers such as ethyl 1,1-dimethyl-2-sulfonate (meth) acrylate; vinyl aromatic compound monomers such as p-vinylbenzene sulfonic acid and p-isopropenyl benzene sulfonic acid And salt compounds thereof. These monomers having a sulfonic acid group can be used alone or in combination of two or more. Further, examples of the monomer having a phosphate group include ethylene phosphate (meth) acrylate, trimethylene phosphate (meth) acrylate, tetramethylene phosphate (meth) acrylate, propylene phosphate (meth) acrylate, and phosphoric acid. Bis (ethylene (meth) acrylate), bis (trimethylene (meth) acrylate) phosphate, bis (tetramethylene (meth) acrylate), diethylene glycol (meth) acrylate phosphate, triethylene glycol (meth) acrylate phosphate, Polyethylene glycol (meth) acrylate phosphate, bis (diethylene glycol (meth) acrylate), bis (triethylene glycol (meth) acrylate), bis (polyethylene glycol (meth) acrylate) These salt compounds and the like. These monomers having a phosphate group are
They can be used alone or in combination of two or more.

The above-mentioned monomer can be arbitrarily selected according to the purpose of use of the photosensitive resin composition. However, since the characteristics of the composition obtained can be easily controlled in a wide range, the monomers are It is preferable to use at least a monomer having a carboxyl group, a monomer having an amino group, or a monomer having a hydroxyl group. Further, depending on the application, carboxyl group, amino group, hydroxyl group,
Two or more of monomers having an epoxy group, a sulfonic acid group or a phosphoric acid group, preferably, a monomer having a carboxyl group, a monomer having an amino group and a monomer having a hydroxyl group And two or more of the above may be used as a monomer component. (1) In the repeating unit in the copolymer, the content of the monomer unit is 0.1 to 3
0 mol%, preferably 0.5 to 20 mol%. In this case, when the content of the monomer unit is less than 0.1 mol%,
The water developability of the obtained composition is poor, while if it exceeds 30 mol%, the obtained composition becomes hard and brittle, and both are not preferred.

Next, as the monomers, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, divinylbenzene, diisopropenylbenzene, trivinylbenzene, etc. Is mentioned. These monomers can be used alone or in combination of two or more. (1) In the repeating unit in the copolymer, the content of the monomer unit is 0.1 to 20 mol%,
Preferably it is 0.5 to 10 mol%. In this case, if the content of the monomer unit is less than 0.1 mol%, the water developability of the obtained composition is poor, while if it exceeds 20 mol%,
The compatibility between (1) the copolymer and (3) the photopolymerizable unsaturated monomer is reduced, whereby the processability of the composition is impaired, and the strength of the composition after photocuring is remarkably reduced. Is also not preferred.

The monomer is not particularly limited as long as it is a compound having one copolymerizable unsaturated group, and examples thereof include styrene, α-methylstyrene and o-vinyl. Toluene, m-vinyltoluene, p
-Vinyltoluene, (meth) acrylonitrile, vinylidene cyanide, vinyl chloride, vinylidene chloride, (meth)
Acrylamide, maleimide, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec- Butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, Phenethyl (meth) acrylate, phenyl (meth) acrylate, and the like. These monomers can be used alone or in combination of two or more.

(1) The copolymer can be produced, for example, by an emulsion polymerization method or a suspension polymerization method using a radical initiator. It is desirable to manufacture by law. Examples of the radical initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, paramenthane hydroperoxide, di-t-butyl peroxide and dicumyl peroxide; Diazo compounds represented by butyronitrile; inorganic peroxides represented by potassium persulfate; and redox catalysts represented by the combination of these peroxides and ferrous sulfate. These radical initiators can be used alone or in combination of two or more. Examples of the emulsifier used for emulsion polymerization include, for example, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like, and these surfactants are fluorine-based. You can also. These emulsifiers can be used alone or in combination of two or more. Examples of the suspension stabilizer used for suspension polymerization include, for example, polyvinyl alcohol, sodium polyacrylate, and hydroxyethyl cellulose. These suspension stabilizers can be used alone or in combination of two or more. In emulsion polymerization or suspension polymerization, the polymerization agent such as each monomer or radical initiator may be added in its entirety at the start of the reaction, or may be added continuously or stepwise after the start of the reaction. The polymerization is usually carried out at 0 to 80 ° C. in a reactor from which oxygen has been removed, but operating conditions such as temperature and stirring can be changed as needed during the reaction. The polymerization system may be either a continuous system or a batch system. (1) When the copolymer has a particle form, the water resistance and water developability of the photosensitive resin composition can be further improved by hydrophilizing the particle surface and hydrophobizing the inside of the particle. .

The (1) copolymer having a salt-form of a carboxyl group, a sulfonic acid group or a phosphate group can be obtained by reacting a basic compound on the copolymer having a free acid group. Can be. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide, sodium-t-butoxide, and potassium-t-. Alkali metal alkoxides such as butoxide; alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, n-amyl lithium, n-propyl sodium, methyl Organometallic compounds such as magnesium chloride, ethyl magnesium bromide, n-propyl magnesium iodide, diethyl magnesium, diethyl zinc, triethyl aluminum, tri-i-butyl aluminum; ammonia; , Triethylamine, tri -n- propyl amine, tri -n- butylamine, pyridine, aniline, amines such as piperazine; lithium, sodium,
Potassium, calcium, metals such as zinc and the like,
Among them, alkali metal hydroxide and ammonia are preferable,
Particularly, sodium hydroxide and potassium hydroxide are preferable.

(2) Block copolymer The block copolymer, which is one of the constituent components of the photosensitive resin composition of the present invention, has a different glass transition temperature (Tg).
A block copolymer comprising at least one polymer segment, wherein a carboxyl group, an amino group, a hydroxyl group, and an epoxy group are added to a side chain of at least one polymer segment other than the polymer segment having the lowest Tg. And a block copolymer having at least one functional group selected from the group consisting of a sulfonic acid group and a phosphoric acid group, preferably a carboxyl group and / or a sulfonic acid group.
Hereinafter, in the block copolymer, a polymer segment other than the polymer segment having the lowest Tg, and a group of a carboxyl group, an amino group, a hydroxyl group, an epoxy group, a sulfonic acid group and a phosphoric acid group on a side chain thereof. The polymer segment having at least one kind of functional group selected from the group below is referred to as “polymer segment A”, and the other polymer segments are referred to as “polymer segment B”.

The monomer component constituting the polymer segment A (hereinafter, referred to as "monomer component a") is not particularly limited, but may be a vinyl aromatic compound, (meth)
Acrylic ester compounds and other polymerizable unsaturated compounds can be appropriately selected. Examples of the vinyl aromatic compound include styrene, α-methylstyrene, o
-Vinyltoluene, m-vinyltoluene, p-vinyltoluene, pt-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o
-Acetoxystyrene, m-acetoxystyrene, p-
Acetoxystyrene, divinylbenzene, diisopropenylbenzene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 1,1-diphenylstyrene, ot-butoxycarbonyloxystyrene, m-
t-butoxycarbonyloxystyrene, pt-butoxycarbonyloxystyrene, ot-butoxycarbonyloxy-α-methylstyrene, mt-butoxycarbonyloxy-α-methylstyrene, pt-butoxycarbonyloxy- α-methylstyrene, ot-
Butoxystyrene, mt-butoxystyrene, pt
-Butoxystyrene, ot-butoxy-α-methylstyrene, mt-butoxy-α-methylstyrene, p-
t-butoxy-α-methylstyrene, o- (2-methoxyethoxy) styrene, m- (2-methoxyethoxy)
Styrene, p- (2-methoxyethoxy) styrene, o
-(2-methoxyethoxy) -α-methylstyrene, m
-(2-methoxyethoxy) -α-methylstyrene, p
-(2-methoxyethoxy) -α-methylstyrene, o
-(2-ethoxyethoxy) styrene, m- (2-ethoxyethoxy) styrene, p- (2-ethoxyethoxy) styrene, o- (2-ethoxyethoxy) -α-methylstyrene, m- (2-ethoxyethoxy) ) -Α-methylstyrene, p- (2-ethoxyethoxy) -α-methylstyrene, o- (2-n-propoxyethoxy) styrene, m- (2-n-propoxyethoxy) styrene, p- (2- n-propoxyethoxy) styrene, o
-(2-n-propoxyethoxy) -α-methylstyrene, m- (2-n-propoxyethoxy) -α-methylstyrene, p- (2-n-propoxyethoxy) -α-
Methylstyrene, o- (2-n-butoxyethoxy) styrene, m- (2-n-butoxyethoxy) styrene,
p- (2-n-butoxyethoxy) styrene, o- (2
-N-butoxyethoxy) -α-methylstyrene, m-
(2-n-butoxyethoxy) -α-methylstyrene,
p- (2-n-butoxyethoxy) -α-methylstyrene, o- (2-t-butoxyethoxy) styrene, m-
(2-t-butoxyethoxy) styrene, p- (2-t
-Butoxyethoxy) styrene, o- (2-t-butoxyethoxy) -α-methylstyrene, m- (2-t-butoxyethoxy) -α-methylstyrene, p- (2-t
-Butoxyethoxy) -α-methylstyrene,

O- (3-methoxypropoxy) styrene, m- (3-methoxypropoxy) styrene, p-
(3-methoxypropoxy) styrene, o- (3-methoxypropoxy) -α-methylstyrene, m- (3-methoxypropoxy) -α-methylstyrene, p- (3-
Methoxypropoxy) -α-methylstyrene, o- (3
-Ethoxypropoxy) styrene, m- (3-ethoxypropoxy) styrene, p- (3-ethoxypropoxy) styrene, o- (3-ethoxypropoxy) -α-
Methylstyrene, m- (3-ethoxypropoxy) -α
-Methylstyrene, p- (3-ethoxypropoxy)-
α-methylstyrene, o- (4-methoxybutoxy) styrene, m- (4-methoxybutoxy) styrene, p-
(4-methoxybutoxy) styrene, o- (4-methoxybutoxy) -α-methylstyrene, m- (4-methoxybutoxy) -α-methylstyrene, p- (4-methoxybutoxy) -α-methylstyrene, o- (4-ethoxybutoxy) styrene, m- (4-ethoxybutoxy)
Styrene, p- (4-ethoxybutoxy) styrene, o
-(4-ethoxybutoxy) -α-methylstyrene, m
-(4-ethoxybutoxy) -α-methylstyrene, p
-(4-ethoxybutoxy) -α-methylstyrene, o
-Tetrapyranyloxystyrene, m-tetrapyranyloxystyrene, p-tetrapyranyloxystyrene,
o-tetrapyranyloxy-α-methylstyrene, m-
Tetrapyranyloxy-α-methylstyrene, p-tetrapyranyloxy-α-methylstyrene, o-tetrafuranyloxystyrene, m-tetrafuranyloxystyrene, p-tetrafuranyloxystyrene, o-tetrafura Nyloxy-α-methylstyrene, m-tetrafuranyloxy-α-methylstyrene, p-tetrafuranyloxy-α-methylstyrene,

As vinyl aromatic compounds having a carboxyl group, o-vinylbenzoic acid, m-vinylbenzoic acid,
p-vinylbenzoic acid, o-isopropenylbenzoic acid, m
-Isopropenyl benzoic acid, p-isopropenyl benzoic acid and the like; as a vinyl aromatic compound having an amino group,
N, N-dimethyl-p-aminostyrene, N, N-diethyl-p-aminostyrene, dimethyl (p-vinylbenzyl) amine, diethyl (p-vinylbenzyl) amine, dimethyl (p-vinylphenethyl) amine, diethyl (P-vinylphenethyl) amine, dimethyl (p-vinylbenzyloxymethyl) amine, dimethyl [2-
(P-vinylbenzyloxy) ethyl] amine, diethyl (p-vinylbenzyloxymethyl) amine, diethyl [2- (p-vinylbenzyloxy) ethyl] amine, dimethyl (p-vinylphenethyloxymethyl) amine, dimethyl [ 2- (p-vinylphenethyloxy)
Ethyl] amine, diethyl (p-vinylphenethyloxymethyl) amine, diethyl [2- (p-vinylphenethyloxy) ethyl] amine, 2-vinylpyridine,
-Vinylpyridine, 4-vinylpyridine and the like; as a vinyl aromatic compound having a hydroxyl group, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-
Hydroxy-α-methylstyrene, p-hydroxy-α
-Methylstyrene, o-vinylbenzyl alcohol, m
-Vinyl benzyl alcohol, p-vinyl benzyl alcohol, etc .; as a vinyl aromatic compound having a sulfonic acid group, o-vinyl benzene sulfonic acid, m-vinyl benzene sulfonic acid, p-vinyl benzene sulfonic acid, o-
Examples thereof include isopropenylbenzenesulfonic acid, m-isopropenylbenzenesulfonic acid, p-isopropenylbenzenesulfonic acid, and salt compounds thereof.

Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and n-butyl ( (Meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, n-octyl (meth)
Alkyl (meth) acrylates such as acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate; 2,2,2-trifluoroethyl (meth) acrylate, 3,3,3,2,2-pentafluoropropyl ( Meth) acrylate, 4,4,4,3,3,2
Fluoroalkyl (meth) acrylates such as 2-heptafluorobutyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxypropyl (Meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-
Alkoxyalkyl (meth) acrylates such as ethoxypropyl (meth) acrylate; and alkoxypolyalkylene glycols (the number of alkylene glycol units is, for example, 2 to 23) such as methoxypolyethylene glycol, ethoxypolyethylene glycol, methoxypolypropylene glycol, and ethoxypolypropylene glycol ( (Meth) acrylates; aryloxyalkyl (meth) acrylates such as 2-phenoxyethyl (meth) acrylate, 2-phenoxypropyl (meth) acrylate, and 3-phenoxypropyl (meth) acrylate; phenoxy polyethylene glycol, phenoxy polypropylene glycol, and the like Aryloxy polyalkylene glycol (the number of alkylene glycol units is, for example, 2
To (meth) acrylates; cyanoalkyl (meth) acrylates such as 2-cyanoethyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, and 3-cyanopropyl (meth) acrylate; ethylene glycol; 2-propanediol, 1,3-propanediol, 3-chloro-1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol Di (meth) acrylates of alkylene glycols such as 1,6-hexanediol; polyalkylene glycols such as polyethylene glycol and polypropylene glycol (the number of alkylene glycol units is, for example, 2 to 2;
3) di (meth) acrylates; glycerin, 1,
2,4-butanetriol, pentaerythritol, trimethylolalkane (the carbon number of the alkane is, for example, 1 to
3) oligo (meth) acrylates of trihydric or higher polyhydric alcohols such as tetramethylolalkane (alkane has 1 to 3 carbon atoms); polyalkylene glycol adduct of trihydric or higher polyhydric alcohol ( The number of alkylene glycol units is, for example, 2 to 23) oligo (meth) acrylates; 1,4-cyclohexanediol,
Oligo (meta) of cyclic polyol such as 4-benzenediol, 1,4-di- (2-hydroxyethyl) benzene
Acrylates,

Examples of the (meth) acrylate compound having a carboxyl group include non-polymerizable polycarboxylic acids such as phthalic acid, succinic acid and adipic acid, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth). Examples of free carboxyl group-containing esters with hydroxyalkyl (meth) acrylates such as acrylate and 3-hydroxypropyl (meth) acrylate, and salts thereof; dimethylaminomethyl (amino) (meth) acrylate compounds having an amino group Meth) acrylate, diethylaminomethyl (meth) acrylate,
2-dimethylaminoethyl (meth) acrylate, 2-
Diethylaminoethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 2-diethylaminopropyl (meth) acrylate, 2- (di-n
-Propylamino) propyl (meth) acrylate, 3
-Dimethylaminopropyl (meth) acrylate, 3-
Diethylaminopropyl (meth) acrylate, 3-
Dialkylaminoalkyl (meth) acrylates such as (di-n-propylamino) propyl (meth) acrylate; 2- (2′-dimethylaminoethoxy) ethyl (meth) acrylate, 2- (2′-diethylaminoethoxy) ethyl (Dialkylaminoalkoxy) alkyl (meth) acrylates such as (meth) acrylate;
As the (meth) acrylate compound having a hydroxyl group, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 3-chloro-1,
2-propanediol, 1,2-butanediol, 1,
3-butanediol, 1,4-butanediol, 1,5
Mono (meth) acrylates of alkylene glycols such as pentanediol and 1,6-hexanediol; mono (meth) acrylates of polyalkylene glycols (the number of alkylene glycol units is, for example, 2 to 23) such as polyethylene glycol and polypropylene glycol ;
A tri- or higher-valent compound such as glycerin, 1,2,4-butanetriol, pentaerythritol, trimethylolalkane (alkane has 1 to 3 carbon atoms), tetramethylolalkane (alkane has 1 to 3 carbon atoms). (Meth) acrylates containing a free hydroxyl group of a polyhydric alcohol; (meth) acrylates containing a free hydroxyl group of a polyalkylene glycol adduct of the trihydric or higher polyhydric alcohol (the number of alkylene glycol units is, for example, 2 to 23); 1,4-cyclohexanediol, 1,4
-Free hydroxyl group-containing (meth) acrylates of cyclic polyols such as benzenediol and 1,4-di- (2-hydroxyethyl) benzene; glycidyl (meth) as a (meth) acrylate compound having an epoxy group Acrylate, 3,4-oxycyclohexyl (meth) acrylate and the like; as a (meth) acrylate compound having a sulfonic acid group, ethyl 2-sulfonate (meth) acrylate, propyl 2-sulfonate (meth) acrylate, 3- Alkyl sulfonate (meth) acrylates such as propyl sulfonate (meth) acrylate and ethyl 1,1-dimethyl-2-sulfonate (meth) acrylate, and salt compounds thereof; (meth) acrylic acid having a phosphate group Ethyl phosphate (meth) as acid ester compound Acrylate, trimethylene (meth) acrylate, tetramethylene (meth) acrylate, propylene (meth) acrylate, bis (ethylene (meth) acrylate), bis (trimethylene (meth) acrylate), phosphorus Bis (tetramethylene (meth) acrylate), diethylene glycol (meth) acrylate phosphate, triethylene glycol (meth) acrylate phosphate, polyethylene glycol (meth) acrylate phosphate, bis (diethylene glycol (meth) acrylate) phosphorous Examples include bis (triethylene glycol (meth) acrylate), bis (polyethylene glycol (meth) acrylate) phosphate, and salt compounds thereof.

Examples of other polymerizable unsaturated compounds include methyl crotonate, ethyl crotonate, n-propyl crotonate, n-butyl crotonate, methyl cinnamate, ethyl cinnamate, and cinnamic acid. Other unsaturated monocarboxylic esters such as n-propyl and n-butyl cinnamate; dimethyl maleate, diethyl maleate, di-n-propyl maleate, di-n-butyl maleate, di-maleate n-hexyl, di-n-octyl maleate, dimethyl fumarate, diethyl fumarate, di-n-propyl fumarate, di-n-butyl fumarate, di-n-hexyl fumarate, di-n-fumarate Octyl, dimethyl itaconate, diethyl itaconate, di-n-itaconate
Propyl, di-n-butyl itaconate, di-itaconate
unsaturated dicarboxylic acid diesters such as n-hexyl and di-n-octyl itaconate; (meth) acrylamide,
N, N'-methylenebis (meth) acrylamide, N,
N'-ethylenebis (meth) acrylamide, N, N '
Unsaturated amides or unsaturated imides such as hexamethylenebis (meth) acrylamide, crotonic amide, cinnamamide, and maleimide; (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile , Α-
Unsaturated nitriles such as ethoxyacrylonitrile, nitrile crotonic acid, nitrile cinnamate, dinitrile itaconate, dinitrile maleate, dinitrile fumarate,

As the polymerizable unsaturated compound having a carboxyl group, unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid and cinnamic acid, and salt compounds thereof;
(Anhydride) maleic acid, fumaric acid, (anhydride) itaconic acid,
Unsaturated polycarboxylic acids (anhydrides) such as citraconic acid and mesaconic acid, and salts thereof; monomethyl esters and monoethyl esters of the unsaturated polycarboxylic acids;
Free carboxyl group-containing esters such as mono-n-propyl ester, mono-n-butyl ester, mono-n-hexyl ester and mono-n-octyl ester, and salts thereof; Nitriles and other free carboxyl group-containing nitriles and their salt compounds; unsaturated carboxyl group-containing amides such as the unsaturated polycarboxylic acid monoamide and their salt compounds; non-carboxyl groups such as phthalic acid, succinic acid and adipic acid Free carboxyl group-containing esters of a polymerizable polycarboxylic acid and an unsaturated alcohol such as (meth) allyl alcohol, and salts thereof; N-dimethylaminomethyl (meta) as a polymerizable unsaturated compound having an amino group; ) Acrylamide, N-diethylaminomethyl) (meth) acrylamide, N- (2-di Chill aminoethyl) (meth) acrylamide, N-(2-diethylaminoethyl) (meth)
Acrylamide, N- (2-dimethylaminopropyl)
(Meth) acrylamide, N- (2-diethylaminopropyl) (meth) acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide, N- (3-
N-dialkylaminoalkyl group-containing (meth) acrylamides such as diethylaminopropyl) (meth) acrylamide and the like; 2-hydroxyethyl crotonate, 2-hydroxypropyl crotonate, and cinnamic acid as polymerizable unsaturated compounds having a hydroxyl group Hydroxyalkyl esters of unsaturated monocarboxylic acids such as 2-hydroxyethyl acid and 2-hydroxypropyl cinnamate; N-hydroxymethyl (meth) acrylamide, N-2-hydroxyethyl (meth) acrylamide, N, N- Screw (2
-Hydroxyethyl) (meth) acrylamide, crotonic acid N-hydroxymethylamide, crotonic acid N- (2
-Hydroxyethyl) amide, cinnamic acid N-hydroxymethylamide, cinnamic acid N- (2-hydroxyethyl)
N-hydroxylalkyl group-containing amides of unsaturated monocarboxylic acids such as amides; unsaturated alcohols such as (meth) allyl alcohol; and the like; polymerizable unsaturated compounds having a carboxyl group and a hydroxyl group; Free carboxyl group-containing hydroxyalkyl esters such as mono (2-hydroxyethyl ester), mono (2-hydroxypropyl ester) and mono (3-hydroxypropyl ester) of carboxylic acid, and salt compounds thereof; N-hydroxyalkyl derivatives of free carboxyl group-containing amides of carboxylic acids,
These salt compounds; as a polymerizable unsaturated compound having an epoxy group, (meth) allyl glycidyl ether, (meth) allyl-3,4-oxycyclohexyl ether and the like; as a polymerizable unsaturated compound having a sulfonic acid group,
2- (meth) acrylamidoethanesulfonic acid, 2-
(Meth) acrylamidopropanesulfonic acid, 3- (meth) acrylamidopropanesulfonic acid, 2- (meth)
Acrylamide-2-methylpropanesulfonic acid, 3-
(Meth) acrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, (meth) allylsulfonic acid,
These include salt compounds and the like.

Of these monomer components a, vinyl aromatic compounds and (meth) acrylate compounds are preferred. Examples of preferred vinyl aromatic compounds include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, pt-butylstyrene, o-methoxystyrene, and ot-butoxycarbonyl. Oxystyrene, mt-butoxycarbonyloxystyrene, pt-butoxycarbonyloxystyrene, ot-butoxycarbonyloxy-α-methylstyrene, mt-butoxycarbonyloxy-α-methylstyrene, pt -Butoxycarbonyloxy-α
-Methylstyrene, ot-butoxystyrene, mt
-Butoxystyrene, pt-butoxystyrene, o-
t-butoxy-α-methylstyrene, mt-butoxy-α-methylstyrene, pt-butoxy-α-methylstyrene, the vinyl aromatic compound having the carboxyl group, and the vinyl aromatic compound having the sulfonic acid group Dimethyl (p-vinylbenzyl) amine, diethyl (p-vinylbenzyl) amine, dimethyl (p-vinylphenethyl) amine, diethyl (p-vinylphenethyl) amine, dimethyl (p-vinylbenzyloxymethyl) Amine, dimethyl [2- (p-vinylbenzyloxy) ethyl] amine, diethyl (p-vinylbenzyloxymethyl) amine, diethyl [2- (p-vinylbenzyloxy) ethyl] amine, 2-vinylpyridine,
3-vinylpyridine, 4-vinylpyridine, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m
-Hydroxy-α-methylstyrene, p-hydroxy-
α-methylstyrene and the like.

Examples of preferred (meth) acrylate compounds include methyl (meth) acrylate,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-
Butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-
Examples thereof include butyl (meth) acrylate, the (meth) acrylate compound having a carboxyl group, and the (meth) acrylate compound having a sulfonic acid group. The monomer component a can be used alone or in combination of two or more.

Next, the monomer component constituting the polymer segment B (hereinafter, referred to as “monomer component b”) is not particularly limited, but may be a vinyl aromatic compound,
(Meth) acrylate compounds, aliphatic conjugated diene compounds, and other polymerizable unsaturated compounds can be appropriately selected. When the monomer component b contains an aliphatic conjugated diene compound, the aliphatic conjugated diene portion in the polymer segment B may be hydrogenated as the case may be.
Examples of the vinyl aromatic compound, the (meth) acrylate compound and the other polymerizable unsaturated compound in the monomer component b include the vinyl aromatic compound exemplified for the monomer component a, (meth) acrylic acid Among the ester compounds and other polymerizable unsaturated compounds, compounds having no carboxyl group, amino group, hydroxyl group, epoxy group, sulfonic acid group and phosphate group are exemplified. Examples of the aliphatic conjugated diene compound in the monomer component b include 1,3-butadiene, isoprene,
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3
-Hexadiene, 1,3-octadiene, 4,5-diethyl-1,3-octadiene, 3-n-butyl-1,3
-Octadiene, chloroprene and the like. Among these monomer components b, a vinyl aromatic compound and an aliphatic conjugated diene compound are preferable, and examples of the vinyl aromatic compound include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, and p- Vinyl toluene, p
-T-butylstyrene, o-methoxystyrene, and the like are more preferable, and as the aliphatic conjugated diene compound, 1,3-butadiene, which can be industrially used and obtains a block copolymer having excellent physical properties, Isoprene, 1,3-pentadiene and the like are more preferable, and 1,3-butadiene and isoprene are particularly preferable. The monomer component b can be used alone or in combination of two or more.

The block copolymer in the present invention is composed of two or more polymer segments having different glass transition temperatures (Tg), and has a side chain of at least one polymer segment other than the polymer segment having the lowest Tg. Has a carboxyl group, an amino group, a hydroxyl group, an epoxy group,
It has at least one type of functional group selected from the group consisting of a sulfonic acid group and a phosphoric acid group, and is composed of a polymer segment A and a polymer segment B. Each of the polymer segment A and the polymer segment B may be composed of a single polymer block, or may be divided by factors related to the structure of the polymer chain, such as the type of the monomer component and the three-dimensional structure. It may be composed of one or more polymer subsegments. As the structure of the block copolymer, an AB diblock structure, an AB
-A triblock structure, BAB triblock structure, or (A) n- (B) m random block structure (where n and m are integers indicating the number of each polymer segment).
Can be appropriately selected. As the block copolymer in the present invention, 50% by weight or more of the monomer component a is particularly preferable from the viewpoint that the resin composition can be industrially used and a photosensitive resin composition having excellent physical properties can be easily obtained. A combination of a polymer segment A comprising a vinyl aromatic compound and a polymer segment B comprising at least 50% by weight of an aliphatic conjugated diene compound of a monomer component b, or a monomer component a
Of a polymer segment A comprising 50% by weight or more of a vinyl aromatic compound and a polymer segment B comprising a hydrogenated product of a polymer segment comprising 50% or more by weight of a monomer component b comprising an aliphatic conjugated diene compound. Combinations are preferred. The polymer segment A in the block copolymer
Weight ratio of polymer and polymer segment B (polymer segment A / polymer segment B) is usually 95/5 to 5/9.
5, preferably 80/20 to 5/95, more preferably 70/30 to 5/95.

The method for producing the block copolymer is not particularly limited, and examples thereof include (a) 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO). Used, polymer segment A in the molecule
And a monomer component that provides one of the polymer segments of the polymer segment B to produce a polymerization initiator component having the polymer segment, and subsequently a monomer that provides the other polymer segment A method of polymerizing the components,
(B) post-treating a precursor block copolymer consisting of two or more polymer segments to form a carboxyl group, amino group, hydroxyl group, epoxy group, sulfonic acid group in one or more specific polymer segments; And a method of forming the polymer segment A by introducing at least one functional group selected from the group consisting of a phosphoric acid group and a phosphoric acid group.

More specifically, in the method (b), (b-1) a precursor block copolymer containing a polymer segment having a carboxylic acid ester group in a side chain is hydrolyzed in the presence of an acid. Decomposing the carboxylic acid ester group into a carboxyl group to form a polymer segment A having a carboxyl group in the side chain, (b-2) containing a vinyl aromatic compound as a constituent monomer component Aromatic ring in a precursor block copolymer containing a polymer segment to be aminated by a conventional method to form a polymer segment A having an amino group in a side chain, (b-3) as a constituent monomer component Precursor broth containing a polymer segment containing a vinyl aromatic compound having a group that can be converted to a hydroxyl group by a hydrolysis reaction such as a t-butoxy group or a t-butylcarbonyloxy group A method of hydrolyzing a copolymer in the presence of an acid to form a polymer segment A having a hydroxyl group in a side chain, (b-4) having an aliphatic carbon-carbon double bond in a side chain. A method of epoxidizing the aliphatic carbon-carbon double bond in the precursor block copolymer containing a polymer segment by a conventional method to form a polymer segment A having an epoxy group in a side chain, (b-5) A precursor block copolymer containing a polymer segment containing a vinyl aromatic compound and / or an aliphatic conjugated diene compound as a constituent monomer component, or a vinyl aromatic compound and an aliphatic conjugated diene compound as a constituent monomer component A precursor block copolymer containing a polymer segment obtained by hydrogenating the aliphatic conjugated diene moiety in the polymer segment containing the polymer segment is sulfonated by a conventional method to obtain each polymer. A method of converting a body segment into a polymer segment A having a sulfonic acid group in a side chain, (b-6) phosphoric acid esterification of a precursor block copolymer containing a polymer segment having a hydroxyl group in a side chain by a conventional method. To form a polymer segment A having a phosphoric acid group in the side chain, and (b-7) a combination of two or more of the above methods (b-1) to (b-6). .

The block copolymer in which the polymer segment A has a carboxyl group, a sulfonic acid group or a phosphoric acid salt-former is prepared by reacting a basic compound on the block copolymer having a free acid group. Can be obtained. As the basic compound, for example,
Alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide, sodium
alkali metal alkoxides such as t-butoxide and potassium-t-butoxide; alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; methyllithium, ethyllithium, n-butyllithium, sec
Organometallic compounds such as -butyllithium, n-amyllithium, n-propylsodium, methylmagnesium chloride, ethylmagnesium bromide, n-propylmagnesium iodide, diethylmagnesium, diethylzinc, triethylaluminum, tri-i-butylaluminum; Ammonia; trimethylamine, triethylamine, tri-n-propylamine, tri-n
Amines such as butylamine, pyridine, aniline and piperazine; metals such as lithium, sodium, potassium, calcium, zinc and the like, among which alkali metal hydroxides and ammonia are preferable, and sodium hydroxide, hydroxide Potassium is preferred. These basic compounds can be used alone or in combination of two or more. Further, the basic compound can be used by dissolving it in water or an inert organic solvent. Examples of the inert organic solvent include halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethanes, tetrachloroethanes, and tetrachloroethylene; nitro compounds such as nitromethane and nitrobenzene; liquid sulfur dioxide; n-propane, n-butane; aliphatic hydrocarbons such as n-pentane, n-hexane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; alcohols such as methanol, ethanol, n-propanol, i-propanol and ethylene glycol Is mentioned. These inert organic solvents can be used alone or in combination of two or more.

A carboxyl group in the block copolymer,
The content of at least one functional group selected from the group consisting of an amino group, a hydroxyl group, an epoxy group, a sulfonic acid group and a phosphoric acid group is usually 0 as a total amount of the monomer component a having these functional groups. 0.1 to 30% by weight, preferably 0.3 to 25% by weight. In this case, if the total amount of the monomer component a having a functional group is less than 0.1% by weight, the water developability of the obtained composition tends to decrease, while 3
If it exceeds 0% by weight, the resulting composition tends to be hard and brittle. In the block copolymer, the glass transition temperature (Tg) of the polymer segment A determined by a differential scanning calorimeter (DSC) is preferably 20 ° C or higher, more preferably 20 to 250 ° C. The glass transition temperature (Tg) of segment B is preferably 10
° C or lower, more preferably 0 ° C or lower, particularly preferably-
It is in the range of 100 to -5C. Also, gel permeation chromatography (GPC) of block copolymer
Weight average molecular weight (hereinafter referred to as “M
w ". ) Is usually 5,000 to 5,000,0
00, preferably 10,000-1,000,000,
More preferably, it is 20,000 to 500,000.

The amount of the block copolymer used in the photosensitive resin composition of the present invention is (2) the block copolymer with respect to the total amount of (1) the copolymer and (2) the block copolymer. Is 50% by weight or more, preferably 50% by weight.
９５95% by weight, more preferably 50-80% by weight. In this case, (2) the proportion of the block copolymer is 50
If the amount is less than% by weight, the mechanical strength of the obtained composition is reduced, which is not preferable. If the proportion of (2) the block copolymer exceeds 95% by weight, the water developability of the resulting composition tends to decrease.

(3) Photopolymerizable Unsaturated Monomer The photopolymerizable unsaturated monomer which is one of the components of the photosensitive resin composition of the present invention is not particularly limited, and examples thereof are as follows. As styrene, α-methylstyrene,
o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, pt-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene,
Divinylbenzene, diisopropenylbenzene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 1,1-diphenylethylene, N, N-dimethyl-
p-aminostyrene, N, N-diethyl-p-aminostyrene, 2-vinylpyridine, 3-vinylpyridine,
-Vinylpyridine, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, p
-Vinyl aromatic compounds such as vinylbenzyl alcohol;
Unsaturation of (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, nitrile crotonic acid, nitrile cinnamate, dinitrile itaconic acid, dinitrile maleate, dinitrile fumarate and the like. Nitriles: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (Meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, la Lil (meth) acrylates, alkyl (meth) acrylates such as stearyl (meth) acrylate; methyl crotonate, ethyl crotonate,
N-propyl crotonate, n-butyl crotonate, methyl cinnamate, ethyl cinnamate, n-propyl cinnamate,
Other unsaturated monocarboxylic esters such as n-butyl cinnamate;

Dimethyl maleate, diethyl maleate, di-n-propyl maleate, di-n-maleate
Butyl, di-n-octyl maleate, di-maleate
n-hexyl, dimethyl fumarate, diethyl fumarate,
Di-n-propyl fumarate, di-n-butyl fumarate,
Di-n-hexyl fumarate, di-n-octyl fumarate, dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, di-n-butyl itaconate, di-n-hexyl itaconate, itaconic acid Unsaturated dicarboxylic acid diesters such as di-n-octyl; 2,2,2-
Trifluoroethyl (meth) acrylate, 3,3
Fluoroalkyl (meth) acrylates such as 3,2,2-pentafluoropropyl (meth) acrylate and 4,4,4,3,3,2,2-heptafluorobutyl (meth) acrylate; ethylene glycol; Mono-alkylene glycols such as 2-propanediol, 1,3-propanediol, 3-chloro-1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol Or di- (meth) acrylates; mono-alkylene glycols such as polyethylene glycol and polypropylene glycol (the number of alkylene glycol units is, for example, 2 to 23)
Or di- (meth) acrylates; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth)
Acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, 3
-Alkoxyalkyl (meth) acrylates such as -methoxypropyl (meth) acrylate and 3-ethoxypropyl (meth) acrylate; alkoxypolyalkylene glycol (alkylene glycol) such as methoxypolyethylene glycol, ethoxypolyethylene glycol, methoxypolypropyleneglycol, and ethoxypolypropyleneglycol The number of units is, for example, 2 to 23) (meta)
Acrylates; aryloxyalkyl (meth) acrylates such as 2-phenoxyethyl (meth) acrylate, 2-phenoxypropyl (meth) acrylate and 3-phenoxypropyl (meth) acrylate; aryls such as phenoxypolyethylene glycol and phenoxypolypropylene glycol (Meth) acrylates of roxypolyalkylene glycol (the number of alkylene glycol units is, for example, 2 to 23); cyano such as 2-cyanoethyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, and 3-cyanopropyl (meth) acrylate Alkyl (meth) acrylates; glycerin, 1,
2,4-butanetriol, pentaerythritol, trimethylolalkane (the carbon number of the alkane is, for example, 1 to
3), mono- or oligo- (meth) acrylates of trihydric or higher polyhydric alcohols such as tetramethylolalkane (alkane has 1 to 3 carbon atoms); polyalkylene of trihydric or higher polyhydric alcohol Mono- or oligo- (meth) acrylates of a glycol adduct (the alkylene glycol unit number is, for example, 2 to 23);
Cyclohexanediol, 1,4-benzenediol,
Mono- or oligo- (meth) acrylates of cyclic polyols such as 1,4-di- (2-hydroxyethyl) benzene;

Others such as 2-hydroxyethyl crotonate, 2-hydroxypropyl crotonate, 3-hydroxypropyl crotonate, 2-hydroxyethyl cinnamate, 2-hydroxypropyl cinnamate, 3-hydroxypropyl cinnamate and the like N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, croton Acid N-hydroxymethylamide, crotonic acid N- (2-hydroxyethyl) amide, cinnamic acid N-hydroxymethylamide, cinnamic acid N
N-hydroxyalkyl group-containing amides of unsaturated monocarboxylic acids such as-(2-hydroxyethyl) amide; unsaturated alcohols such as (meth) allyl alcohol; (meth) acrylic acid, crotonic acid, cinnamic acid, etc. Unsaturated polycarboxylic acids (anhydrides) such as maleic acid, fumaric acid, (anhydride) itaconic acid, citraconic acid, and mesaconic acid; monomethyl esters of the unsaturated polycarboxylic acids; Monoethyl ester, mono-
Free carboxyl group-containing esters such as n-propyl ester, mono-n-butyl ester, mono-n-hexyl ester and mono-n-octyl ester; free carboxyl group-containing nitriles such as mononitrile of the unsaturated polycarboxylic acid Amides containing a free carboxyl group such as the monoamide of the unsaturated polycarboxylic acid; mono (2-hydroxyethyl ester), mono (2-hydroxypropyl ester) and mono (3-hydroxypropyl ester) of the unsaturated polycarboxylic acid Esters) and other free carboxyl group-containing hydroxyalkyl esters; N-
Hydroxyalkyl derivatives;

Non-polymerizable polycarboxylic acids such as phthalic acid, succinic acid and adipic acid and (meth) allyl alcohol,
Free carboxyl group-containing esters such as monoesters with hydroxyl group-containing unsaturated compounds such as hydroxyethyl (meth) acrylate; dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, 2-dimethylaminoethyl (meth) Acrylate, 2-diethylaminoethyl (meth) acrylate, 2- (di-n-propylamino) ethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 2-diethylaminopropyl (meth) acrylate, 2- (di -N-propylamino) propyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, 3- (di-n-propylamino) propyl (meth) acrylate Dialkylaminoalkyl (meth) acrylates such as 2- (dimethylaminoethoxy) ethyl (meth) acrylate and 2- (diethylaminoethoxy) ethyl (meth) acrylate; N-dimethyl Aminomethyl (meth) acrylamide, N-diethylaminomethyl (meth) acrylamide, N- (2-dimethylaminoethyl) (meth) acrylamide, N- (2-diethylaminoethyl) (meth)
Acrylamide, N- (2-dimethylaminopropyl)
(Meth) acrylamide, N- (2-diethylaminopropyl) (meth) acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide, N- (3-
N-dialkylaminoalkyl group-containing (meth) acrylamides such as diethylaminopropyl) (meth) acrylamide; epoxy group-containing unsaturated compounds such as allyl glycidyl ether, glycidyl (meth) acrylate, and 3,4-oxycyclohexyl (meth) acrylate ;
(Meth) acrylamide, N, N'-methylenebis (meth) acrylamide, N, N'-ethylenebis (meth)
Unsaturated amides or unsaturated imides such as acrylamide, N, N'-hexamethylenebis (meth) acrylamide, crotonic acid amide, cinnamic acid amide, maleimide, vinyl chloride, vinyl acetate, dicyclopentadiene,
Ethylidene norbornene and the like. These photopolymerizable unsaturated monomers can be used alone or in combination of two or more.

In the present invention, the physical properties of the photosensitive resin composition after photocuring can be freely designed by selecting the photopolymerizable unsaturated monomer. The photopolymerizable unsaturated monomer can be used in any ratio depending on the purpose of use of the photosensitive resin composition, and the fluidity of the composition is changed from waxy to rubbery to low-viscosity liquid depending on the amount. Can be designed freely, but the amount of photopolymerizable unsaturated monomer used is
(1) Copolymer and (2) Block copolymer in total 1
The amount is preferably 5 to 1,000 parts by weight, more preferably 10 to 500 parts by weight, based on 00 parts by weight. In this case, if the amount of the photopolymerizable unsaturated monomer used is less than 5 parts by weight, the strength of the obtained composition tends to decrease, whereas if it exceeds 1,000 parts by weight, the composition after photocuring Shrinkage of the composition tends to increase, making it difficult to achieve both water resistance and water developability of the composition, and the degree of freedom in designing the viscosity of the composition tends to decrease.

The photosensitive resin composition of the present invention has at least one component selected from the group consisting of a carboxyl group, an amino group, a hydroxyl group, an epoxy group, a sulfonic acid group and a phosphoric acid group. A copolymer having one type of functional group is used, and (2) at least one selected from the group consisting of a carboxyl group, an amino group, a hydroxyl group, an epoxy group, a sulfonic acid group and a phosphoric acid group as a block copolymer Characterized by using a block copolymer having a functional group of (3), and another component (3).
Various compounds can be used as the photopolymerizable unsaturated monomer. However, the composition of the photosensitive resin composition can be easily controlled in a wide range (1). The combination of ()) the copolymer, (2) the block copolymer, and (3) the photopolymerizable unsaturated monomer includes:
In particular, (i) (1) a copolymer having a carboxyl group and / or a hydroxyl group and a carboxyl group and / or
Or a combination of (2) a block copolymer having a sulfonic acid group and (3) a photopolymerizable unsaturated monomer having an amino group, (ii) a (1) copolymer having a carboxyl group and a hydroxyl group (1) having a copolymer having a carboxyl group and / or a sulfonic acid group (2)
(3) Combination of a block copolymer and a photopolymerizable unsaturated monomer having an amino group, (iii) a copolymer having an amino group and (1) having a carboxyl group and / or a sulfonic acid group ( 2) a combination of a block copolymer and a (3) photopolymerizable unsaturated monomer having a carboxyl group and / or a hydroxyl group; (iv) a copolymer having an amino group (1) and a carboxyl group and / or Alternatively, a combination of (2) a block copolymer having a sulfonic acid group and (3) a photopolymerizable unsaturated monomer having a carboxyl group and (3) a photopolymerizable unsaturated monomer having a hydroxyl group is used. preferable. In these cases, the molar ratio of the amino group to the total amount of the carboxyl group and / or the sulfonic acid group and the hydroxyl group is preferably 0.1 or more, more preferably 0.4 or more. In this case, when the molar ratio of the amino group is less than 0.1 mol, the water developability of the obtained composition tends to decrease.

(4) Photopolymerization Initiator The photopolymerization initiator, which is one of the components of the photosensitive resin composition of the present invention, is usually used as a photosensitizer.
For example, α-diketones such as diacetyl and benzyl; acyloins such as benzoin and pivaloin; benein methyl ether, benzoin ethyl ether and benzoin n
Acyloin ethers such as propyl ether; polynuclear quinones such as anthraquinone and 1,4 naphthoquinone;
Examples include acetophenones such as 2,2-dimethoxyphenylacetophenone and trichloroacetophenone; and benzophenones such as benzophenone and methyl-o-benzoylbenzoate. These photopolymerization initiators can be used alone or in combination of two or more.
The amount of the photopolymerization initiator to be used is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total of (1) the copolymer and (2) the block copolymer. Department. In this case, if the amount of the photopolymerization initiator used is less than 0.1 part by weight, the obtained composition may be insufficiently cured. Not only is it uneconomical because it does not participate in the reaction, but sometimes it has poor compatibility with (1) the copolymer, (2) the block copolymer, and (3) the photopolymerizable unsaturated monomer, resulting in poor dispersion. May be uniform.

Other Additives In order to improve the water developability of the photosensitive resin composition of the present invention, a carboxyl group, an amino group, a hydroxyl group, an epoxy group, a sulfonic acid group and a phosphoric acid group are added . A non-polymerizable compound having at least one functional group selected from the group can be added in a range of 20% by weight or less based on the total weight of the composition. Examples of the non-polymerizable compound include carboxylic acids such as formic acid, acetic acid, and propionic acid, and salts thereof; primary amines such as ethylamine and propylamine; diethylamine, di-n-propylamine, and di-n. Secondary amines such as -butylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, ethyldimethylamine,
Trialkylamines such as diethylmethylamine; trialkanolamines such as triethanolamine and tripropanolamine; alcohols such as methanol, ethanol, n-propanol, n-butanol, triethanol and tripropanol; Epoxy compounds such as epoxybutane and 1,2-epoxyhexane; sulfonic acids such as ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid, and their salt compounds; phosphoric acid, monomethyl phosphate, phosphorus Examples include acidic phosphoric acid compounds such as monoethyl acid, and salt compounds thereof. These non-polymerizable compounds can be used alone or in combination of two or more.

The photosensitive resin composition of the present invention may contain, if necessary, a conventional additive such as a thermal addition polymerization inhibitor in an amount of 0.001 to 2.0% by weight based on the total weight of the composition. It can be added in a range. Examples of the thermal addition polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, mono-t-butylhydroquinone, catechol, p-
Methoxyphenol, pt-butylcatechol, 2,
6-di-t-butyl-p-cresol, 2,6-di-t
Hydroxyaromatic compounds such as -butyl-m-cresol, pyrogallol, β-naphthol; benzoquinone;
5-diphenyl-p-benzoquinone, p-toluquinone,
Quinones such as p-xyloquinone; nitrobenzene, m-
Nitro compounds or nitrone compounds such as dinitrobenzene, 2-methyl-2-nitrosopropane, α-phenyl-t-butylnitrone, 5,5-dimethyl-1-pyrroline-1-oxide; chloranyl-amine, diphenylamine, diphenyl Amines such as picrylhydrazine, phenol-α-naphthylamine, pyridine and phenothiazine; sulfides such as dithiobenzoyl sulfide and dibenzyltetrasulfide; unsaturated compounds such as 1,1-diphenylethylene and α-methylthioacrylonitrile; thionin blue , Thiazine dyes such as toluidine blue and methylene blue; 1,1-diphenyl-2-picrylhydrazyl, 1,3,5-triphenylferdazyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine- 1-Oki Le, 2,6-di -t- butyl -
α- (3,5-di-t-butyl) -4-oxo-2,5
And stable radicals such as -cyclohexadiene-1-ylidene-p-trioxyl. These thermal addition polymerization inhibitors can be used alone or in combination of two or more. Further, in order to further improve the strength of the obtained composition, the photosensitive resin composition of the present invention mainly comprises a hard segment and a soft segment, if necessary, and has a hard segment of 20%.
A thermoplastic non-elastomeric polymer segment having a glass transition point (Tg) of not lower than 10 ° C., and a soft segment comprising an aliphatic conjugated diene-based elastomeric polymer segment having a glass transition point (Tg) of not higher than 10 ° C. One or more block copolymers may be blended. Further, the other block copolymer is obtained by hydrogenating the aliphatic conjugated diene portion constituting the soft segment, so that the unsaturated double bond remaining in the soft segment after hydrogenation is contained in one molecule. It can be used as 30 mol% or less. As a typical example of the other block copolymer as described above, JSRTR2 is a trade name.
000 (styrene-butadiene-based thermoplastic elastomer, manufactured by JSR Corporation), JSR SIS50
00 (styrene / isoprene thermoplastic elastomer,
JSR DYNARO), JSR DYNARO
N1320P (hydrogenated polymer, manufactured by JSR Corporation) and the like.

Preparation and Use of Photosensitive Resin Composition The photosensitive resin composition of the present invention comprises (1) a copolymer, (2)
The block copolymer, (3) the photopolymerizable unsaturated monomer, and (4) the photopolymerization initiator, together with the optional components, are added, for example, using a kneader or an intermixer while heating. It is prepared by sufficiently kneading. The photosensitive resin composition thus obtained can be freely designed from a waxy or rubbery material having no fluidity to a low-viscosity liquid having excellent fluidity. The non-flowable photosensitive resin composition is formed into a fixed film thickness with a spacer having an appropriate thickness, applied on a support with a roll coater, etc., or compressed, extruded, etc. It can be processed into a photosensitive resin plate having a thickness. The printing plate can be obtained, for example, by applying a negative film to this and exposing it, and washing the unexposed portion with water. The photosensitive resin composition having excellent fluidity can be used as a resist suitable for, for example, spin coating by adjusting the viscosity by adding an appropriate solvent as needed. This resist can be similarly exposed, and then the unexposed portion is washed away with water to form a clear resist pattern.

[0043]

The embodiments of the present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following embodiments. Example 1 (1) Preparation of copolymer Using sodium lauryl sulfate as an emulsifier and benzoyl peroxide as a polymerization initiator, butadiene / 2-diethylaminoethyl methacrylate / divinylbenzene / ethyl acrylate = 80 / 6.5 / 1/12. 5 (mol%) of the monomer mixture was emulsion-polymerized. Next, the obtained copolymer emulsion was salt-coagulated using calcium chloride and dried to prepare a copolymer. The polymerization conversion at this time was almost 100%. (2) Preparation of block copolymer 500 g of 1,2-dichloroethane was placed in a two-liter four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a nitrogen gas inlet tube, and styrene / butadiene / After dissolving 22 g of a hydrogenated styrene block copolymer (trade name: Tuftec H1052, Mw = 72,000, manufactured by Asahi Chemical Industry Co., Ltd.), a previously prepared dichloromethane solution of sulfonated acetyl (concentration: 1.0 mol / Liter) 2.4 ml and add 40 ml with stirring.
The reaction was carried out at 1.5 ° C. for 1.5 hours. Next, after adding 20 ml of i-propanol to terminate the reaction, the reaction solution was concentrated under reduced pressure at 40 ° C. Then, water was added, and the mixture was further concentrated under reduced pressure at 60 ° C. to isolate a polymer. Next, the isolated polymer was washed with water several times, filtered, and then dried in vacuo at 60 ° C. The obtained polymer had a block structure (ABA) of a styrene / sulfonated styrene copolymer segment-hydrogenated polybutadiene segment-styrene / sulfonated styrene copolymer segment.
Block copolymer). The Mw of the block copolymer was 72,000. When the quantitative analysis of SO ₃ H groups in the block copolymer was performed by the following procedure, the content of SO ₃ H groups was 0.62% by weight, and the monomer component composed of sulfonated styrene was The content was 1.2% by weight. <Procedure for Quantitative Analysis of SO ₃ H Group> A 1,2-dichloroethane solution of a block copolymer was prepared by adding methanol / water = 80.
/ 20 (weight ratio) to remove the contaminants in the solution by performing reprecipitation purification in which a block copolymer is precipitated by dropping into a mixed solvent of / 20 (weight ratio). The amount of sulfur element contained in the coalescence was determined, and this value was converted to the content of SO ₃ H groups. Preparation of photosensitive resin composition For 40 parts by weight of (1) copolymer, 60 parts by weight of (2) block copolymer and 20 parts by weight of lauryl methacrylate as a photopolymerizable unsaturated monomer Part, 1,6
10 parts by weight of hexanediol diacrylate and 10 parts by weight of acrylic acid, (4) 2,2 as a photopolymerization initiator
-1 part by weight of dimethoxyphenylacetophenone, 0.5 part by weight of t-butylcatechol as a storage stabilizer,
The mixture was stirred in a kneader controlled at 50 ° C. for 60 minutes to prepare a photosensitive resin composition of the present invention. The resulting composition was a clear wax. Evaluation After a photosensitive resin plate having a thickness of 0.5 mm was formed on a polyester sheet using the photosensitive resin composition, a JOW-A-4P type developing machine manufactured by JEOL Ltd.
The time required for the photosensitive resin layer to disappear (elution required time) was measured by brushing in warm water at 0 ° C. The photosensitive resin plate was exposed for 6 minutes using an exposure machine (JE-A3-SS) manufactured by JEOL Ltd., and then subjected to JIS K6251, 6253, and 6255.
The tensile strength, elongation at break, rebound resilience and hardness were measured in accordance with As a result, the photosensitive resin composition has excellent water developability, tensile strength, elongation at break, and rebound resilience, no increase in hardness, good transparency of the resin plate, and an excellent property balance. Was. The above results are shown in Table 1 (parts are based on weight; the same applies hereinafter).

Example 2 (1) Preparation of copolymer butadiene / methacrylic acid / 2-hydroxybutyl methacrylate / ethylene glycol dimethacrylate = 8
A copolymer was prepared in the same procedure as in Example 1, except that a monomer mixture having a ratio of 3/5/11/1 (mol%) was used. The polymerization conversion at this time was almost 100%. Preparation of Photosensitive Resin Composition With respect to (1) 30 parts by weight of the copolymer, 70 parts by weight of (2) the block copolymer of Example 1 and (3) lauryl as the photopolymerizable unsaturated monomer. 20 parts by weight of methacrylate, 10 parts by weight of 1,6-hexanediol diacrylate and 10 parts by weight of N- (3-dimethylaminopropyl) acrylamide, (4) 2,2-
1 part by weight of dimethoxyphenylacetophenone and 0.5 part by weight of t-butylcatechol as a storage stabilizer were added, and a photosensitive resin composition of the present invention was prepared in the same procedure as in Example 1. Evaluation The obtained photosensitive resin composition was evaluated in the same manner as in Example 1. As a result, the photosensitive resin composition has excellent water developability, tensile strength, elongation at break, and rebound resilience, no increase in hardness, good transparency of the resin plate, and an excellent property balance. Was. Table 1 shows the above results.

Example 3 (2) Preparation of block copolymer 500 g of cyclohexane was placed in a two-liter four-neck flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas inlet tube. After adding 1.4 ml of an ether solution of 4-dilithiobutane (concentration: 1.8 mol / l), 260 g of isoprene was added while stirring at room temperature, and then the temperature was raised to 50 ° C. and polymerization was carried out for 3 hours. . Next, the reaction solution was cooled to 5 ° C., 30 g of t-butyl methacrylate was added, polymerization was continued for 1 hour, and a small amount of methanol was added to stop the reaction. Next, p-toluenesulfonic acid was added, and hydrolysis was performed at 85 ° C. for 12 hours under a nitrogen stream. 2,6-Di-t-butyl-p-cresol was added to the obtained reaction solution, the solvent was removed by steam stripping, and the mixture was dried with a steam dryer at 90 ° C. to obtain a polymer. The obtained polymer was a block copolymer having a block structure of methacrylic acid / t-butyl methacrylate copolymer-polyisoprene-methacrylic acid / t-butyl methacrylate copolymer. The Mw of this block copolymer was 137,000. The content of methacrylic acid in the block copolymer was determined by alkali titration and found to be 9.3% by weight. Preparation of Photosensitive Resin Composition In Example 1, (1) 40 parts by weight of the copolymer, (2) 60 parts by weight of the block copolymer, and (3) lauryl methacrylate 30 as the photopolymerizable unsaturated monomer. Parts by weight, 1,6
5 parts by weight of hexanediol diacrylate and 20 parts by weight of acrylic acid, (4) 2,2-
1 part by weight of dimethoxyphenylacetophenone and 0.5 part by weight of t-butylcatechol as a storage stabilizer were added, and
The mixture was stirred in a kneader controlled at 0 ° C. for 60 minutes to prepare a photosensitive resin composition of the present invention. The resulting composition was a clear wax. Evaluation The obtained photosensitive resin composition was evaluated in the same manner as in Example 1. As a result, the photosensitive resin composition has excellent water developability, tensile strength, elongation at break, and rebound resilience, no increase in hardness, good transparency of the resin plate, and an excellent property balance. Was. Table 1 shows the above results.

Comparative Example 1 Preparation and Evaluation of Photosensitive Resin Composition In place of the block copolymer (2) of Example 2, a hydrogenated product of styrene / butadiene / styrene block copolymer (trade name: Tuftec H1052; Mw = 72,0
Example 2 except that No. 00 (manufactured by Asahi Kasei Corporation) was used.
Preparation and evaluation of a photosensitive resin composition were carried out in the same procedure as described above. As a result, this photosensitive resin composition was incapable of water development and had high hardness. Table above shows the results.
It is shown in FIG.

Comparative Example 2 Preparation and Evaluation of Photosensitive Resin Composition 70 parts by weight of the copolymer (1) of Example 2 were used, and instead of (2) the block copolymer of Example 2, styrene / Hydrogenated product of butadiene / styrene block copolymer (trade name: Tuftec H1052, Mw = 72,00
0, manufactured by Asahi Kasei Corporation), and the preparation and evaluation of the photosensitive resin composition were performed in the same manner as in Example 2 except that 30 parts by weight were used. As a result, the photosensitive resin composition was inferior in water developability, tensile strength, elongation at break and high in hardness. Table 1 shows the above results.

Comparative Example 3 A procedure was performed in the same manner as in Example 1 except that (1) 100 parts by weight of the copolymer of Example 1 and 30 parts by weight of the block copolymer of (1) were used. , A photosensitive resin composition was prepared and evaluated. As a result, this photosensitive resin composition was inferior in tensile strength, elongation at break and rebound resilience, and had high hardness. Table 1 shows the above results.

Comparative Example 4Preparation of photosensitive resin composition 100 parts by weight of the copolymer (1) of Example 1
(2) 30 parts by weight of a block copolymer, (3) photopolymerizable
30% by weight of lauryl methacrylate as an unsaturated monomer
Parts, 1,6-hexanediol diacrylate 5 parts by weight
And 20 parts by weight of acrylic acid, (4) as a photopolymerization initiator
2,2-dimethoxyphenylacetophenone 1 weight
Parts, 0.5 weight of t-butyl catechol as storage stabilizer
And stirred for 60 minutes in a kneader adjusted to 50 ° C.
Thus, a photosensitive resin composition was prepared. Evaluation About the obtained photosensitive resin composition, it carried out similarly to Example 1.
Was evaluated. As a result, this photosensitive resin composition
Was particularly inferior in rebound resilience and high in hardness. More than
The results are shown in Table 1.

[0050]

[Table 1]

[0051]

The photosensitive resin composition of the present invention has excellent water developability, low swelling in water, excellent tensile strength, elongation at break and rebound resilience, low hardness,
In addition, the transparency of the resin plate is good, and it has an excellent property balance. Moreover, the composition can be freely designed to have properties from a waxy or rubbery state having no fluidity to a low-viscosity liquid having excellent fluidity, and has good workability. Therefore, the photosensitive resin composition of the present invention can be used very suitably as a photoresist material or a photosensitive printing plate, as well as a photosensitive ink, a photosensitive paint, a photosensitive adhesive,
It is useful as a photosensitive material in a wide range of technical fields including light molding materials.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takashi Nishioka 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Tadaaki Tanaka 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR F-term in stock (reference) 2H025 AA00 AA04 AA13 AB01 AC01 AD01 BC12 BC32 BC34 BC36 BC37 CA00 CA01 CB06 CB11 CB13 CB14 CB16 CB17 CB41 CB42 CB43 CB45 CB47 CB53 CB60 FA17 2H114 BA02 DA27 DA32 DA33 AD36 AF03 BE27 EA05 EA38

Claims (1)

[Claims] (1) As a repeating unit in the copolymer,
10 to 95 mol% of an aliphatic conjugated diene unit, one polymerizable unsaturated group, and at least one kind of functional group selected from the group consisting of a carboxyl group, an amino group, a hydroxyl group, an epoxy group, a sulfonic acid group and a phosphoric acid group A copolymer containing 0.1 to 30 mol% of a monomer unit having a group and 0.1 to 20 mol% of a monomer unit having at least two polymerizable unsaturated groups, (2) glass A block copolymer composed of two or more polymer segments having different transition temperatures (Tg), wherein the side chain of at least one polymer segment other than the polymer segment having the lowest Tg is
A block copolymer having at least one functional group selected from the group consisting of a carboxyl group, an amino group, a hydroxyl group, an epoxy group, a sulfonic acid group and a phosphoric acid group;
It contains (3) a photopolymerizable unsaturated monomer and (4) a photopolymerization initiator, and (2) a block copolymer based on the total amount of (1) a copolymer and (2) a block copolymer. A photosensitive resin composition, wherein the proportion of the polymer is 50% by weight or more.