JPH09222730A - Water-developable photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. excellent in water developability, less liable to swell at the time of water development, causing a slight reduction of strength and a slight dimensional change at the time of water development and giving a resin plate excellent in strength, breaking extension and impact resilience after photosetting. SOLUTION: This resin compsn. contains a particle-shaped copolymer obtd. by emulsion- or suspension-polymerizing a monomer mixture contg. an aliphatic conjugated diene monomer, a mono-unsatd. monomer having a carboxyl, amino, hydroxyl or epoxy group and a poly-unsatd. monomer as essential components, a block copolymer consisting of two or more polymer segments and having an O-contg. repeating units in the principal chain of at least one of the segments, a photopolymerizable unsatd. monomer and a photopolymn. initiator.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive resin composition having water developability. More specifically, the present invention relates to a water-developable photosensitive resin composition which is small in strength reduction and dimensional change during development with water and is useful for photoresists, photosensitive printing plate materials and the like.

[0002]

2. Description of the Related Art Conventionally, various photosensitive resin compositions have been widely used as photoresists, photosensitive printing plate materials, photosensitive printing inks and the like. However, most of them use organic solvents during development, and in recent years, in addition to safety and health problems during work, the influence of organic solvents on the environment has become a problem. Therefore, there is a strong demand for a photosensitive resin composition that can be developed with safer water, and in response to such a demand, for example, a water-developable water-based resin based on a water-soluble resin such as polyvinyl alcohol, gelatin, or casein is used. Photosensitive resin compositions have been proposed. However,
The conventional water-developable photosensitive resin composition has a too high affinity for water of the resin as the base, so that it easily swells during development to cause strength reduction or dimensional change, and as a result, for example, resist dimensional accuracy, There are problems such as deterioration of printing durability and printing quality of the printing plate.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art. The problem is that the swelling at the time of development with water has an excellent water developability. It is intended to provide a water-developable photosensitive resin composition having a small size and a reduced strength during development and a small dimensional change.

[0004]

According to the present invention, the above object is to provide 1 to 70 parts by weight of the following (2) block copolymer to 100 parts by weight of the following (1) particulate copolymer:
Achieved by a water-developable photosensitive resin composition comprising (3) 5 to 500 parts by weight of a photopolymerizable unsaturated monomer and (4) 0.001 to 50 parts by weight of a photopolymerization initiator. To be done. (1) 10 to 95 mol% of an aliphatic conjugated diene monomer, one polymerizable unsaturated bond and at least one functional group selected from the group consisting of a carboxyl group, an amino group, a hydroxyl group and an epoxy group. Monomers having 0.1 to 30
A particulate copolymer obtained by emulsion-polymerizing or suspension-polymerizing a monomer mixture containing 0.1 to 20 mol% of a monomer having a mol% of at least two polymerizable unsaturated bonds. 2) A block polymer composed of two or more polymer segments, and at least one of the polymer segments.
Is a block copolymer having a repeating unit containing an oxygen atom in the polymer main chain.

Hereinafter, the present invention will be described in detail. (1) Particulate Copolymer The particulate copolymer used in the water-developable photosensitive resin composition of the present invention is an aliphatic conjugated diene monomer (hereinafter abbreviated as “diene monomer”). .) A monomer having one polymerizable unsaturated bond and at least one functional group selected from the group consisting of a carboxyl group, an amino group, a hydroxyl group and an epoxy group (hereinafter, referred to as “functional monomer”). ), A monomer having at least two polymerizable unsaturated bonds (hereinafter referred to as “crosslinkable monomer”) is contained as an essential component, and in some cases, one polymerizable unsaturated bond is contained. It is obtained by emulsion polymerization or suspension polymerization of a monomer mixture containing the other copolymerizable monomer (hereinafter referred to as "other monomer").

In the present invention, examples of the diene monomer include butadiene, isoprene, 2,3-dimethylbutadiene and chloroprene. These diene-based monomers may be used alone or in admixture of two or more, and the content of the diene-based monomer in the monomer mixture is 10 to 95 mol%, preferably 30 to
90 mol%. In this case, if the content of the diene-based monomer is less than 10 mol%, the strength of the composition after photocuring is lowered, and if it exceeds 95 mol%, the water developability of the resulting composition is lowered.

Among the functional monomers, examples of the monomer having a carboxyl group include unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and tetraconic acid; Acid, adipic acid, non-polymerizable dicarboxylic acid such as phthalic acid and allyl alcohol, 2
Examples thereof include monoesters with a hydroxyl group-containing unsaturated compound such as -hydroxyethyl (meth) acrylate. These monomers having a carboxyl group can be used alone or in combination of two or more. Examples of the monomer having an amino group include dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, and 2-dimethyl. Aminopropyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 2-diethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (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) acrylamide, N-3-dimethylaminopropyl (meth) acrylamide, N- 3-diethylaminopropyl (meth) acrylamide etc. can be mentioned. These amino group-containing monomers can be used alone or in combination of two or more. Also,
Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate (alkylene glycol unit. Examples thereof include mono (meth) acrylates having a number of 2 to 12). These hydroxyl group-containing monomers can be used alone or in admixture of two or more. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether. These epoxy group-containing monomers may be used alone or in admixture of two or more. In the present invention, the functional monomer can be appropriately selected according to the application of the water-developable photosensitive resin composition, but the characteristics of the resulting water-developable photosensitive resin composition can be easily adjusted in a wide range. From the viewpoint of controllability, a monomer having a carboxyl group or a monomer having an amino group is preferably used alone or as a mixture. The content of the functional monomer in the monomer mixture is 0.1 to 30 mol%, preferably 0.5 to 20 mol%. in this case,
When the content of the functional monomer is less than 0.1 mol%, the water developability of the resulting composition is lowered, and when it exceeds 30 mol%, the composition after photocuring becomes hard and brittle , and both are Not preferable.

Next, examples of the crosslinkable monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di. (Meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, divinylbenzene, trivinylbenzene and the like. it can. These monomers can be used alone or in combination of two or more. The content of the crosslinkable monomer in the monomer mixture is 0.1 to 20.
Mol%, preferably 0.5 to 10 mol%. In this case, if the content of the crosslinkable monomer is less than 0.1 mol%, the resulting composition is likely to undergo swelling or dimensional change during water development, and if it exceeds 20 mol%, the composition may be a particulate copolymer. The compatibility with the (3) photopolymerizable unsaturated monomer described later is poor, the processability is lowered, and the strength of the composition after photocuring is significantly lowered.

Further, the other monomer optionally used is not particularly limited, but for example, styrene, α-methylstyrene, o-methylstyrene, m-
Methylstyrene, p-methylstyrene, (meth) acrylonitrile, (meth) acrylamide, methyl (meth)
Examples thereof include acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, vinyl chloride and vinylidene chloride. These other monomers can be used alone or in combination of two or more. The content of the other monomer in the monomer mixture is usually 70 mol% or less.

The particulate copolymer is produced by emulsion polymerization or suspension polymerization using a radical polymerization initiator.
From the viewpoints of particle size, particle size uniformity, and the like, it is preferable to manufacture by emulsion polymerization. Examples of the radical polymerization initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, paramenthane hydroperoxide, di-t-butyl peroxide and dicumyl peroxide; azobisisobutyrate. Examples thereof include diazo compounds typified by ronitrile; inorganic peroxides typified by potassium persulfate; and redox catalysts comprising these peroxides and a reducing agent typified by ferrous sulfate. As the emulsifier used for emulsion polymerization,
At least one kind of anionic surfactant, nonionic surfactant, cationic surfactant, amphoteric surfactant and the like can be used, but anionic surfactant and nonionic surfactant are particularly preferable. These surfactants can be fluorinated surfactants. Examples of the suspension stabilizer used in suspension polymerization include polyvinyl alcohol, sodium polyacrylate, hydroxyethyl cellulose and the like. In emulsion polymerization and suspension polymerization, each monomer, a polymerization agent such as a radical polymerization initiator, may be added in a total amount at the start of the reaction, or a part or all of them may be divided or continuously added after the start of the reaction. May be added. The polymerization reaction is usually carried out at 0 to 80 ° 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 in any of a continuous system and a batch system.
In the present invention, by making the particle surface of the particulate copolymer hydrophilic and making the inside of the particle hydrophobic, the balance between water resistance and water developability of the water-developable photosensitive resin composition is further improved. be able to. Such multi-layered copolymer particles may be prepared, for example, after the emulsion polymerization of at least a part of a hydrophilic monomer (for example, a monomer having a carboxyl group and / or an amino group), preferably in the latter half of the polymerization. And the like.

(2) Block Copolymer The block copolymer used in the water-developable photosensitive resin composition of the present invention is a block polymer composed of two or more polymer segments. At least one of the segments is a block copolymer having a repeating unit containing an oxygen atom in the polymer main chain. Hereinafter, the polymer segment having a repeating unit containing an oxygen atom in the polymer main chain is referred to as "segment A". The method for obtaining the segment A is not particularly limited, and may be a conventional method such as polycondensation of polyhydric alcohol, ring-opening polymerization of cyclic ether or cyclic ester, or polymerization of carbonyl compound. Examples of such polyhydric alcohols include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2,3-propanetriol,
1,2-butanediol, 1,3-butanediol,
1,4-butanediol, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,3,4-butanetriol, 1,2-pentanediol, 1,3-pentanediol, 1, 4-pentanediol, 1,5-
Pentanediol, 1,2-hexanediol, 1,3
-Hexanediol, 1,4-hexanediol, 1,
Examples thereof include 5-hexanediol and 1,6-hexanediol. These polyhydric alcohols can be used alone or in admixture of two or more. Examples of cyclic ethers include 3-membered ring ethers such as ethylene oxide, propylene oxide, styrene oxide, and phenylglycidyl ether, as well as 4-membered ring ethers represented by 3,3-bis (chloromethyl) oxetane and tetrahydrofuran. 5-membered ring ethers, 1,3,5-trioxane, cyclic formals and the like can be mentioned. These cyclic ethers can be used alone or in admixture of two or more. Examples of the cyclic ester include lactones represented by β-propiolactone, diketene, and cyclic ketene acetals such as 1,3-dioxepane and 2-methylene-1,3-dioxepane. . These cyclic esters can be used alone or in admixture of two or more. Examples of the carbonyl compound include formaldehyde, acetaldehyde, n-propylaldehyde, n-butyraldehyde, isobutyraldehyde, and halogenated aldehydes such as trifluoroacetaldehyde and trichloroacetaldehyde. These carbonyl compounds can be used alone or in combination of two or more. Further, any two or more of the above polyhydric alcohols, cyclic ethers, cyclic esters and carbonyl compounds may be used in combination.

The monomer constituting the other polymer segment (hereinafter referred to as "segment B") constituting the block copolymer together with the segment A is not particularly limited, and examples thereof include a vinyl aromatic compound and a conjugated diene. It can be appropriately selected from compounds, (meth) acrylic acid ester compounds, and other copolymerizable vinyl compounds. Examples of such vinyl aromatic compounds include styrene, α-methylstyrene, o-methylstyrene, m-
Methyl styrene, p-methyl styrene, pt-butyl styrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, divinyl benzene, diisopropenyl benzene, o-chloro styrene, m-chloro styrene, p- Chlorostyrene, 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, diethyl (p-vinylbenzyloxymethyl) amine, dimethyl [2- (p-vinylbenzyloxy) ethyl] amine, diethyl [2- (p-vinylbenzyloxy) ethyl ] Amine, dimethyl (p-vinylphenethyloxymethyl) amine, diethyl (p-vinylphenethyloxymethyl) amine, dimethyl [2- (p
-Vinylphenethyloxy) ethyl] amine, diethyl [2- (p-vinylphenethyloxy) ethyl) amine, vinylpyridine, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene. , M-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene,
p-vinylbenzyl alcohol and the like,
Particularly styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt
-Butyl styrene and o-methoxy styrene are preferred.

Examples of the conjugated diene compound include 1,3-butadiene, isoprene and 2,3-dimethyl-
1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene,
Examples of the block copolymer include 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, and a mixture thereof. Industrially applicable block copolymers having excellent physical properties can be used. To obtain them, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, and 1,3-butadiene and isoprene are more preferable.

Further, as the (meth) acrylic acid ester compound and the other copolymerizable vinyl compound,
For example, 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, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. Alkyl (meth) acrylates of; methyl crotonic acid, ethyl crotonic acid,
N-propyl crotonic acid, n-butyl crotonic acid, methyl cinnamate, ethyl cinnamate, n-propyl cinnamate,
Other unsaturated monocarboxylic acid esters such as n-butyl cinnamate; fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate and heptafluorobutyl (meth) acrylate Ethylene glycol, 1,
2-propanediol, 3-chloro-1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol and other alkylene glycol mono- or di-
(Meth) acrylates; mono- or di- (meth) acrylates of polyalkylene glycol (the number of alkylene glycol units is 2 to 23) such as polyethylene glycol and polypropylene glycol; 2-methoxyethyl (meth) acrylate, 2-ethoxy. Ethyl (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 glycols (alkylene glycol units such as methoxy polyethylene glycol, ethoxy polyethylene glycol, methoxy polypropylene glycol, ethoxy polypropylene glycol) 2-23) (meth) acrylates; 2-phenoxyethyl (meth) acrylate,
Aryloxyalkyl (meth) acrylates such as 2-phenoxypropyl (meth) acrylate and 3-phenoxypropyl (meth) acrylate; aryloxypolyalkylene glycols such as phenoxypolyethylene glycol and phenoxypolypropylene glycol (the number of alkylene glycol units is 2 23) mono (meth) acrylates; 2-cyanoethyl (meth) acrylate,
Cyanoalkyl (meth) acrylates such as 3-cyanopropyl (meth) acrylate; glycerin, 1,2,
Mono- or oligo- of trivalent or higher polyhydric alcohols such as 4-butanetriol, pentaerythritol, trimethylolalkane (alkane has 1 to 3 carbon atoms) and tetramethylolalkane (alkane has 1 to 3 carbon number).
(Meth) acrylates; mono- or oligo- (meth) acrylates of the polyalkylene glycol adduct of the polyhydric alcohol having a valence of 3 or more; 1,4-cyclohexanediol, 1,4-benzenediol, 1,4- Mono- or di- (meth) acrylates of cyclic diols such as dihydroxyethylbenzene;

2-hydroxyethyl crotonic acid, 2-hydroxypropyl crotonic acid, 3-hydroxypropyl crotonic acid, 2-hydroxyethyl cinnamate, 2-hydroxypropyl cinnamic acid, 3-hydroxypropyl cinnamate, etc. Of unsaturated monocarboxylic acid hydroxyalkyl esters; 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-
Hydroxyl group-containing unsaturated amides such as (2-hydroxyethyl) amide; unsaturated alcohols such as (meth) allyl alcohol; unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid; ) Unsaturated polycarboxylic acids (anhydrides) such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; monomethyl ester, monoethyl ester and mono n-propyl ester of the unsaturated polycarboxylic acid , Mono-n-hexyl ester, mono-n-octyl ester, etc., free carboxyl group-containing esters; free polycarboxylic acid-containing nitriles, such as mononitrile, etc .; unsaturated polycarboxylic acid, monoamide, etc., free Carboxyl group-containing amides; mono- (2) of the unsaturated polycarboxylic acid
-Hydroxyethyl esters), free carboxyl group-containing hydroxyalkyl esters such as mono (2-hydroxypropyl ester) and mono (3-hydroxypropyl ester); N-hydroxy of the free carboxyl group-containing amide of the unsaturated polycarboxylic acid Alkyl derivatives;
Free carboxyl group-containing esters such as monoesters of non-polymerizable polycarboxylic acids such as succinic acid, adipic acid and phthalic acid with hydroxyl group-containing unsaturated compounds such as allyl alcohol and 2-hydroxyethyl (meth) acrylate; malein; Dimethyl acid, diethyl maleate, di maleate
-Butyl, di-n-octyl maleate, diethyl fumarate, di-n-butyl fumarate, di-n-octyl fumarate,
Diesters of unsaturated dicarboxylic acids such as dimethyl itaconate, diethyl itaconate, di-n-butyl itaconate and di-n-octyl itaconate;

2-Dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 2-diethylaminopropyl (Meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, 2-di-n-propylaminopropyl (meth) acrylate, 3-di-n-propylaminopropyl (meth) Dialkylaminoalkyl (meth) acrylates such as acrylates; Dialkylaminoalkoxyalkyl (meth) acrylates such as 2-dimethylaminoethoxyethyl (meth) acrylate and 2-diethylaminoethoxyethyl (meth) acrylate Relate acids; N-(2-dimethylaminoethyl) (meth) acrylamide, N-
(2-Diethylaminoethyl) (meth) acrylamide, N- (2-dimethylaminopropyl) (meth) acrylamide, N- (2-diethylaminopropyl) (meth) acrylamide, N- (3-dimethylaminopropyl) (meth) Amino group-containing (meth) acrylamides such as acrylamide and N- (3-diethylaminopropyl) (meth) acrylamide; epoxy group-containing unsaturated compounds such as allyl glycidyl ether and glycidyl (meth) acrylate; (meth) acrylamide, N, Unsaturated amides such as N'-methylenebis (meth) acrylamide, N, N'-ethylenebis (meth) acrylamide, N, N'-hexamethylenebis (meth) acrylamide, crotonic acid amide, cinnamic acid amide; (meth) acrylonitrile , Α-chloroa Examples thereof include unsaturated nitrile compounds such as lilonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, and fumaric acid dinitrile. it can. Segment B
Can be obtained by polymerizing the above monomers alone or in combination of two or more.

In the block structure of the block copolymer, the segment A and the segment B are, for example, A-, depending on the purpose.
B diblock structure, ABA triblock structure, B-
Although it can be freely selected to take an AB triblock structure, an Am-Bn random block structure (where m and n are integers indicating the number of segments), etc., they are industrially easy to use. In addition, the Am-Bn random block structure is preferable because a block copolymer having excellent physical properties can be easily obtained. The weight ratio of segment A to segment B in the block copolymer (segment A / segment B) is usually 95/5 to 5/9.
5, preferably 80/20 to 5/95, and more preferably 70/30 to 5/95. In addition, the polystyrene reduced weight average molecular weight of the block copolymer (hereinafter referred to as “Mw”)
That. ) Is usually 5,000 to 5,000,00
It is 0, preferably 7,000 to 1,000,000. There is no particular limitation on the method for synthesizing the block copolymer, and for example, (a) a method of synthesizing one of the segment A or the segment B and then synthesizing the other,
(B) A method in which a segment A and a segment B are separately synthesized and then a coupling reaction is carried out, and (c) a segment B using a polymerization initiator having a segment A structure in the molecule.
And (d) a method of synthesizing the segment A by using a polymerization initiator having a segment B structure in the molecule. (C) Alternatively, the method (d) is preferable. The amount of the block copolymer used is (1) the particulate copolymer 10
1 to 70 parts by weight, preferably 2 to 6 parts by weight, relative to 0 parts by weight
The amount is 0 parts by weight, more preferably 3 to 50 parts by weight. In this case, when the amount of the block copolymer used is less than 1 part by weight, the water developability of the obtained composition is lowered and
When it exceeds the parts by weight, the strength of the composition after photocuring decreases,
Neither is preferred.

(3) Photopolymerizable unsaturated monomer As the photopolymerizable unsaturated monomer used in the water-developable photosensitive resin composition of the present invention, for example, 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, N, N-dimethyl-p-aminostyrene, N, N-diethyl-p-aminostyrene, 1,1-
Diphenylstyrene, dimethyl (p-vinylbenzyl)
Amine, diethyl (p-vinylbenzyl) amine, dimethyl (p-vinylphenethyl) amine, diethyl (p-
Vinylphenethyl) amine, dimethyl (p-vinylbenzyloxymethyl) amine, diethyl (p-vinylbenzyloxymethyl) amine, dimethyl [2- (p-vinylbenzyloxy) ethyl] amine, diethyl [2-
(P-Vinylbenzyloxy) ethyl] amine, dimethyl (p-vinylphenethyloxymethyl) amine, diethyl (p-vinylphenethyloxymethyl) amine, dimethyl [2- (p-vinylphenethyloxy) ethyl]
Amine, diethyl [2- (p-vinylphenethyloxy) ethyl) amine, vinylpyridine, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α- Methylstyrene, p-hydroxy-α-
Vinyl aromatic compounds such as methylstyrene and p-vinylbenzyl alcohol;

(Meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile,
Unsaturated nitrile compounds 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)
Alkyl (meth) such as acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate Acrylates; other crotonates, ethyl crotonates, n-propyl crotonates, n-butyl crotonates, methyl cinnamates, ethyl cinnamates, n-propyl cinnamates, n-butyl cinnamates, etc. Unsaturated monocarboxylic acid esters;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate and heptafluorobutyl (meth) acrylate; ethylene glycol, 1,2-propanediol, 3-chloro-1,2 Of alkylene glycols such as propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol Mono- or di- (meth) acrylates; Polyalkylene glycols such as polyethylene glycol and polypropylene glycol (the number of alkylene glycol units is 2 to 23) mono- or di- (meth) acrylates; 2-methoxyethyl (meth) Acrylate, 2 Ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate,
Alkoxyalkyl (meth) acrylates such as 2-ethoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate and 3-ethoxypropyl (meth) acrylate; methoxypolyethylene glycol, ethoxypolyethylene glycol, methoxypolypropylene glycol, ethoxypolypropylene. (Meth) acrylates of alkoxypolyalkylene glycol such as glycol (the number of alkylene glycol units is 2 to 23); 2-phenoxyethyl (meth) acrylate, 2
-Aryloxyalkyl (meth) acrylates such as phenoxypropyl (meth) acrylate and 3-phenoxypropyl (meth) acrylate; aryloxypolyalkylene glycols (the number of alkylene glycol units is 2 to 23) such as phenoxypolyethylene glycol and phenoxypolypropylene glycol. ) Mono (meth) acrylates; 2-cyanoethyl (meth) acrylate, 3
-Cyanoalkyl (meth) acrylates such as cyanopropyl (meth) acrylate; glycerin, 1,2,4
A mono- or oligo- of a polyhydric alcohol having 3 or more valences such as butanetriol, pentaerythritol, trimethylolalkane (alkane has 1 to 3 carbon atoms), tetramethylolalkane (alkane has 1 to 3 carbon number) (Meth) acrylates; mono- or oligo- (meth) acrylates of polyalkylene glycol adducts of the above-mentioned trivalent or higher polyhydric alcohols; 1,4-cyclohexanediol, 1,4-benzenediol, 1,4-dihydroxy Mono- or di- (meth) acrylates of cyclic diols such as ethylbenzene;

2-hydroxyethyl crotonic acid, 2-hydroxypropyl crotonic acid, 3-hydroxypropyl crotonic acid, 2-hydroxyethyl cinnamic acid, 2-hydroxypropyl cinnamic acid, 3-hydroxypropyl cinnamic acid, etc. Of unsaturated monocarboxylic acid hydroxyalkyl esters; 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-
Hydroxyl group-containing unsaturated amides such as (2-hydroxyethyl) amide; unsaturated alcohols such as (meth) allyl alcohol; unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid; ) Unsaturated polycarboxylic acids (anhydrides) such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; monomethyl ester, monoethyl ester and mono n-propyl ester of the unsaturated polycarboxylic acid , Mono-n-hexyl ester, mono-n-octyl ester, etc., free carboxyl group-containing esters; free polycarboxylic acid-containing nitriles, such as mononitrile, etc .; unsaturated polycarboxylic acid, monoamide, etc., free Carboxyl group-containing amides; mono- (2) of the unsaturated polycarboxylic acid
-Hydroxyethyl esters), free carboxyl group-containing hydroxyalkyl esters such as mono (2-hydroxypropyl ester) and mono (3-hydroxypropyl ester); N-hydroxy of the free carboxyl group-containing amide of the unsaturated polycarboxylic acid Alkyl derivatives;
Free carboxyl group-containing esters such as monoesters of non-polymerizable polycarboxylic acids such as succinic acid, adipic acid and phthalic acid with hydroxyl group-containing unsaturated compounds such as allyl alcohol and 2-hydroxyethyl (meth) acrylate; malein; Dimethyl acid, diethyl maleate, di maleate
-Butyl, di-n-octyl maleate, diethyl fumarate, di-n-butyl fumarate, di-n-octyl fumarate,
Diesters of unsaturated dicarboxylic acids such as dimethyl itaconate, diethyl itaconate, di-n-butyl itaconate and di-n-octyl itaconate;

2-Dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 2-diethylaminopropyl (Meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, 2-di-n-propylaminopropyl (meth) acrylate, 3-di-n-propylaminopropyl (meth) Dialkylaminoalkyl (meth) acrylates such as acrylates; Dialkylaminoalkoxyalkyl (meth) acrylates such as 2-dimethylaminoethoxyethyl (meth) acrylate and 2-diethylaminoethoxyethyl (meth) acrylate Relate acids; N-(2-dimethylaminoethyl) (meth) acrylamide, N-
(2-Diethylaminoethyl) (meth) acrylamide, N- (2-dimethylaminopropyl) (meth) acrylamide, N- (2-diethylaminopropyl) (meth) acrylamide, N- (3-dimethylaminopropyl) (meth) Amino group-containing (meth) acrylamides such as acrylamide and N- (3-diethylaminopropyl) (meth) acrylamide; epoxy group-containing unsaturated compounds such as allyl glycidyl ether and glycidyl (meth) acrylate; (meth) acrylamide, N, Unsaturated amides such as N'-methylenebis (meth) acrylamide, N, N'-ethylenebis (meth) acrylamide, N, N'-hexamethylenebis (meth) acrylamide, crotonic acid amide, cinnamic acid amide; (meth) acrylonitrile , Α-chloroa In addition to unsaturated nitrile compounds such as lilonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, and fumaric acid dinitrile, vinyl chloride , Vinyl acetate, dicyclopentadiene, ethylidene norbornene, and the like. These photopolymerizable unsaturated monomers may be used alone or in combination of two or more.

In the present invention, the physical properties of the composition after photocuring can be freely designed by appropriately selecting and combining these photopolymerizable unsaturated monomers. The amount of the photopolymerizable unsaturated monomer used is in the range of 5 to 500 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the (1) particulate copolymer. In this case, if the amount of the photopolymerizable unsaturated monomer used is less than 5 parts by weight, the strength of the composition after photocuring will decrease, and if it exceeds 500 parts by weight, shrinkage of the composition after photocuring will occur. However, both the water resistance and the water developability of the composition are difficult to achieve, and the degree of freedom in designing the viscosity of the composition is reduced. In the present invention, the photopolymerizable unsaturated monomer can be used in any ratio depending on the purpose within the above range, and the properties of the water-developable photosensitive resin composition can be changed according to the amount. It can be freely designed from waxy or rubber-like materials with no properties to low-viscosity liquid materials with good fluidity. As described above, the water-developable photosensitive resin composition of the present invention comprises (1) a particulate copolymer having a carboxyl group,
It has at least one functional group selected from the group consisting of an amino group, a hydroxyl group and an epoxy group, and (3) various monomers can be selected and used as the photopolymerizable unsaturated monomer. However, from the viewpoint that the properties of the resulting composition can be easily controlled in a wide range, at least one of (1) the particulate copolymer and (3) the photopolymerizable unsaturated monomer has a carboxyl group as a functional group. It is preferable to select such a combination that has a group and at least the other has an amino group as a functional group. The ratio of the carboxyl group to the amino group in such a water-developable photosensitive resin composition is such that the amino group is preferably 0.1 mol or more, and more preferably 0.
It is 4 to 20 mol. In this case, the ratio of amino groups is 0.
If it is less than 1 mol, the water developability of the resulting composition tends to be lowered.

(4) Photopolymerization Initiator The photopolymerization initiator used in the water-developable photosensitive resin composition of the present invention is usually used as a photosensitizer, for example, α-diketones such as diacetyl and benzyl. Acylloins such as benzoin and pivaloin; Acylloin ethers such as benzyne methyl ether, benzoin ethyl ether and benzoin propyl ether; Polynuclear quinones such as anthraquinone and 1,4-naphthoquinone; 2,2-
Examples thereof include acetophenones such as dimethoxyphenylacetophenone and trichloroacetophenone; and benzophenones such as benzophenone and methyl-o-benzoylbenzoate. The amount of photopolymerization initiator used is
(1) 0.00 based on 100 parts by weight of the particulate copolymer
It is 1 to 50 parts by weight, more preferably 0.1 to 10 parts by weight. In this case, if it is less than 0.001 part by weight, the resulting composition cannot be sufficiently photocured, and if it exceeds 50 parts by weight, all the photopolymerization initiators are not involved in the reaction, which is uneconomical. Not only that, but sometimes the compatibility with (1) the particulate copolymer, (2) the block copolymer, or (3) the photopolymerizable unsaturated monomer is poor, and the dispersion may be non-uniform.

The water-developable photosensitive resin composition of the present invention contains one or more functional groups selected from the group consisting of a carboxyl group, an amino group, a hydroxyl group and an epoxy group for the purpose of improving its water developability. The non-polymerizable compound having a group can be added in the range of 20% by weight or less of the total photosensitive resin composition. Examples of the non-polymerizable compound include carboxylic acids such as formic acid, acetic acid and propionic acid; primary amines such as ethylamine and propylamine; secondary amines such as diethylamine and dibutylamine; and trimethylamine, triethylamine and triamine as tertiary amines. Trialkylamines such as propylamine, ethyldimethylamine and diethylmethylamine; trialkanolamines such as triethanolamine and tripropanolamine; alcohols such as methanol, ethanol, propanol, butanol, triethanol and tripropanol; Examples thereof include epoxy compounds such as 1,2-epoxybutane and 1,2-epoxyhexane.

If desired, conventional additives such as thermal addition polymerization inhibitors may be added to the water-developable photosensitive resin composition of the present invention. 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,
Hydroxy aromatic compounds such as 2,6-di-t-butyl-m-cresol, pyrogallol, β-naphthol; benzoquinone, 2,5-diphenyl-p-benzoquinone, p
-Quinones such as toluquinone and p-xyloquinone; nitrobenzene, m-dinitrobenzene, 2-methyl-2-nitrosopropane, α-phenyl-t-butylnitrone,
Nitro compounds or nitrone compounds such as 5,5-dimethyl-1-pyrroline-1-oxide; amines such as chloranyl-amine compounds, diphenylamine, diphenylpicrylhydrazine, phenol-α-naphthylamine, pyridine, phenothiazine; dithiobenzoyl sulfide, Sulfides such as dibenzyl tetrasulfide;
Unsaturated compounds such as 1,1-diphenylethylene and α-methylthioacrylonitrile; 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)
Examples thereof include stable radicals such as -4-oxo-2,5-cyclohexadiene-1-ylidene-p-trioxyl. These thermal addition polymerization inhibitors can be used alone or in admixture of two or more, and the addition amount thereof is usually 0.001 to 0.001 with respect to the total photosensitive resin composition.
2.0% by weight.

In addition, the water-developable photosensitive resin composition of the present invention mainly comprises, if necessary, a hard segment and a soft segment having an aliphatic conjugated diene unit for the purpose of improving the strength of the resulting composition. A block copolymer, in which the hard segment is a thermoplastic non-elastomeric polymer segment having a glass transition point of 20 ° C. or higher, and the soft segment is an elastomeric polymer segment having a glass transition point of 10 ° C. or lower, or By hydrogenating the unsaturated bond derived from the conjugated diene unit constituting the elastomeric polymer segment in the block copolymer, the unsaturated bond derived from the conjugated diene unit constituting the soft segment after hydrogenation is 1
It is also possible to blend a block copolymer having a content of 30 mol% or less in the molecule. A typical example of such a block copolymer is JSR TR2000 (styrene-
Butadiene-based thermoplastic elastomer), JSR SIS
Examples thereof include 5000 (styrene-isoprene thermoplastic elastomer) and JSR DYNARON 1910P (hydrogenated polymer).

The water-developable photosensitive resin composition of the present invention comprises
(1) particulate copolymer, (2) block copolymer,
(3) a photopolymerizable unsaturated monomer and (4) a photopolymerization initiator, together with additives and compounding ingredients to be added as necessary,
It is prepared by sufficiently kneading with a kneader, intermixer or the like while heating. The water-developable photosensitive resin composition thus obtained can be freely designed from a waxy or rubber-like liquid having no fluidity to a low-viscosity liquid having good fluidity. The water-developable photosensitive resin composition having no fluidity is prepared by sandwiching a spacer having an appropriate thickness to a constant film thickness, applying it on a support by a roll coater, or by compression molding, extrusion molding or the like. A photosensitive resin plate can be processed by molding to a constant film thickness. A negative film is applied to this to expose it, and the unexposed portion is developed with water, whereby a photosensitive printing plate can be prepared. Further, the water-developable photosensitive resin composition having excellent fluidity can be used as a photoresist suitable for spin coating by adding an appropriate solvent as necessary to adjust the viscosity. In this case as well, a clear resist pattern can be formed by similarly developing the unexposed portion after exposure with water.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be specifically described below with reference to Examples. However, the present invention is not limited to the following Examples unless it exceeds the gist. Absent.

【Example】

Example 1 (1) Preparation of particulate copolymer Using sodium lauryl sulfate as an emulsifier and benzoyl peroxide as a polymerization initiator, butadiene / methacrylic acid / ethylene glycol dimethacrylate / ethyl acrylate (mol%) = 80/6. Emulsion polymerization of a 5 / 1.0 / 12.5 monomer mixture was carried out. The obtained copolymer emulsion is salted out and coagulated with calcium chloride,
It was dried to prepare a particulate copolymer.

(2) Preparation of Block Copolymer Under an atmosphere of nitrogen, toluene is used as a polymerization solvent, and an azo polymerization initiator having a segment A structure composed of polyethylene glycol as a polymerization initiator (trade name: MAI-0) is used.
04, 6 parts by weight of Wako Pure Chemical Industries, Ltd. and 100 parts by weight of butyl acrylate were charged, and polymerization was carried out at 60 ° C. After the polymerization conversion reached 85% by weight, the reaction solution was cooled to room temperature, then 2,6-di-t-butyl-p-cresol was added, and the solvent was removed by steam stripping. The block copolymer was prepared by drying with a dryer. The Mw of the obtained block copolymer was determined by GPC (gel permeation chromatography). Further, the nitrogen content in the block copolymer was obtained by elemental analysis, and the segment A / segment B weight ratio of the block copolymer was calculated from this value and the structure of MAI-004. as a result,
The Mw of the obtained block copolymer was 87,000, and the segment A / segment B weight ratio was 6.5 / 93.5.

Preparation of Water-Developable Photosensitive Resin Composition 30 parts by weight of the above (2) block copolymer and (3) photopolymerizable unsaturated monomer based on 100 parts by weight of the above (1) particulate copolymer. 30 parts by weight of lauryl methacrylate as a monomer,
20 parts by weight of 1,6-hexanediol diacrylate and 20 parts by weight of N- (3-dimethylaminopropyl) acrylamide, (4) 3 parts by weight of 2,2-dimethoxyphenylacetophenone as a photopolymerization initiator, and t as a storage stabilizer. -Add 0.5 parts by weight of butyl catechol and
The mixture was kneaded for 30 minutes in a kneader whose temperature was adjusted to 2, to prepare a water-developable photosensitive resin composition. The resin composition obtained was in the form of a transparent wax. Using the water-developable photosensitive resin composition thus obtained, a photosensitive resin layer having a thickness of 0.5 mm was formed on a polyester sheet to prepare a resin plate, and then JO manufactured by JEOL Ltd.
The time required for the photosensitive resin layer to disappear (elution required time) was measured by brushing in warm water of 30 ° C. using a WA-4P type developing machine. In addition, the above resin plate was used as an exposure machine (JE-A3-S) manufactured by JEOL Ltd.
S) for 6 minutes and then JIS K6301
The tensile strength, elongation at break, and impact resilience were measured in accordance with. As a result, the resulting water-developable photosensitive resin composition is excellent in both water-developability and resin plate strength, has good elongation at break and impact resilience, and hardly undergoes dimensional change during curing by exposure. , Had an excellent balance of properties. Table 1 shows the above results.

Embodiment 2(1) Preparation of particulate copolymer Following the same procedure as in Example 1, butadiene / 2-
Diethylaminoethyl methacrylate / divinylbenze
/ Ethyl acrylate (mol%) = 80 / 6.5 /
From the monomer mixture in the ratio of 1.0 / 12.5, the particle weight
A coalescence was prepared. (2) Preparation of block copolymer By the same procedure as in Example 1, Mw was 115,000,
Segment A / Segment B weight ratio = 12/88
A lock-like copolymer was prepared.Preparation and evaluation of water-developable photosensitive resin composition (1) With respect to 100 parts by weight of the particulate copolymer,
(2) 30 parts by weight of block copolymer, photopolymerizable unsaturated monomer
30 parts by weight of lauryl methacrylate as a monomer (3),
20 parts by weight of 1,6-hexanediol diacrylate
And 20 parts by weight of acrylic acid, (4) as a photopolymerization initiator
3 parts by weight of 2,2-dimethoxyphenylacetophenone,
0.5 parts by weight of t-butylcatechol as a storage stabilizer
In addition, the water-developable photosensitive resin was prepared by the same procedure as in Example 1.
The composition was prepared and evaluated. As a result
The water-developable photosensitive resin composition has high water-developability and resin plate strength.
Excellent in both degree of elongation, breaking elongation and impact resilience
Good and almost no dimensional change during curing by exposure
It had an excellent balance of properties. More than
The results are shown in Table 1-.

Example 3 The water-developable photosensitive resin composition shown in Table 1 was prepared by the same procedure as in Example 1 and evaluated. as a result,
The resulting water-developable photosensitive resin composition was excellent in both water-developability and resin plate strength, and was also excellent in elongation at break and impact resilience, and almost no dimensional change was observed during curing by exposure, which was excellent. It had a characteristic balance.
Table 1 shows the above results.

Example 4 The water-developable photosensitive resin composition shown in Table 1 was prepared by the same procedure as in Example 1 and evaluated. as a result,
The resulting water-developable photosensitive resin composition was excellent in both water-developability and resin plate strength, and was also excellent in elongation at break and impact resilience, and almost no dimensional change was observed during curing by exposure, which was excellent. It had a characteristic balance.
Table 1 shows the above results.

Comparative Example 1 Instead of the block copolymer (2) of Example 1, a styrene-isoprene-styrene block copolymer (trade name J
Using SR SIS5000, manufactured by Nippon Synthetic Rubber Co., Ltd., a photosensitive resin composition was prepared in the same procedure as in Example 1 and evaluated. As a result, the obtained photosensitive resin composition was inferior in water developability, resin plate strength, elongation at break and impact resilience. Table 1 shows the above results.

[0035]

[Table 1]

[0036]

The water-developable photosensitive resin composition of the present invention comprises:
Despite having excellent water developability, swelling during development with water is small, and dimensional change during photocuring is small,
The composition after photocuring has excellent strength, good elongation at break and good impact resilience, good transparency, and excellent property balance. Moreover, the water-developable photosensitive resin composition of the present invention can be freely designed to have a property from a waxy or rubber-like liquid having no fluidity to a low-viscosity liquid having good fluidity, and has good processability. is there. Therefore, the water-developable photosensitive resin composition of the present invention can be used very suitably as a photoresist material and a photosensitive printing plate material, and also can be used as a photosensitive ink, a photosensitive coating, a photosensitive adhesive, a photo-molding material, etc. It can be used as a photosensitive material in a wide range of fields including.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08G 81/02 NUV C08G 81/02 NUV C09D 11/00 PTE C09D 11/00 PTE 109/00 PGV 109 / 00 PGV G03F 7/00 501 G03F 7/00 501 7/027 511 7/027 511 7/028 7/028 H01L 21/027 H01L 21/30 502R

Claims (1)

[Claims] 1. To 100 parts by weight of the following (1) particulate copolymer, 1 to 70 parts by weight of the following (2) block copolymer and 5 to 500 parts by weight of (3) photopolymerizable unsaturated monomer. Parts and (4) 0.001 to 50 parts by weight of a photopolymerization initiator, a water-developable photosensitive resin composition. (1) 10 to 95 mol% of an aliphatic conjugated diene monomer, one polymerizable unsaturated bond and at least one functional group selected from the group consisting of a carboxyl group, an amino group, a hydroxyl group and an epoxy group. Monomers having 0.1 to 30
A particulate copolymer obtained by emulsion-polymerizing or suspension-polymerizing a monomer mixture containing 0.1 to 20 mol% of a monomer having a mol% of at least two polymerizable unsaturated bonds. 2) A block polymer composed of two or more polymer segments, and at least one of the polymer segments.
Is a block copolymer having a repeating unit containing an oxygen atom in the polymer main chain.