JPH0980752A - Water-developable photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure superior water developability in spite of slight swelling in water, a slight reduction of strength and a slight dimensional change by incorporating a particle-shaped copolymer of an aliphatic conjugated diene monomer, etc., a block copolymer having amino groups, a photopolymerizable unsatd. monomer and a photopolymn. initiator in a specified ratio. SOLUTION: This compsn. contains 100 pts.wt. particle-shaped copolymer produced from a monomer mixture contg. 10-95mol% aliphatic conjugated diene monomer, 0.1-30mol% monomer having one addition-polymerizable group and a functional group such as a carboxyl group and 0.1-20mol% monomer having two addition-polymerizable groups, 1-70 pts.wt. block copolymer having amino groups, consisting essentially of hard segments and soft segments and produced using a polymn. initiator having an amino group represented by the formula, 5-500 pts.wt. photopolymerizable unsatd. monomer and 0.001-50 pts.wt. photopolymn. initiator. In the formula, each of R and R<1> is 1-20C alkyl, aryl, etc., and (n) is an integer of 0-2.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water-developable photosensitive resin composition. More specifically, the present invention relates to a water-developable photosensitive resin composition that can be developed with water even though it is less swelled with water and has a lower strength and a smaller dimensional change.

[0002]

2. Description of the Related Art Conventionally, photosensitive resin compositions have been widely used in photoresists, inks, printing plates, etc., but most of the photoresists and printing plates use organic solvents during development. In recent years, in addition to safety and health problems during work, the influence of organic solvents on the environment has become a problem.
There is a need for a photosensitive resin composition that can be developed with safer water. To meet such demands, for example, a photosensitive resin composition based on a water-soluble polymer has been proposed.

[0003]

However, in the prior art, the composition has a high affinity for water, resulting in a decrease in strength and a change in size due to swelling. As a result, for example, the decrease in dimensional accuracy of the resist and the printing plate are caused. However, there are problems such as deterioration of printing durability and print quality. The present invention has been made in view of such problems, less swelling in water,
It is an object of the present invention to provide a photosensitive resin composition having water developability even though the strength is not decreased and the size is not significantly changed.

[0004]

The present invention provides (a) (a)
10 to 95 mol% of aliphatic conjugated diene monomer, (b) having one addition-polymerizable group and selected from the group of functional groups consisting of carboxyl group, amino group, hydroxyl group and epoxy group Monomers 0.1-3 containing one type of functional group
A monomer mixture containing 0 mol% and (c) 0.1 to 20 mol% of a monomer having at least two addition-polymerizable groups (provided that (a) + (b) + (c)). = 100 mol%] by an emulsion polymerization method or a suspension polymerization method (hereinafter referred to as "(a)".
(Also referred to as a "particulate copolymer"), based on 100 parts by weight of (b) a hard segment and a soft segment, one or both of the segments contains a tertiary amino group, and the hard segment has a temperature of 20 ° C or higher. A thermoplastic non-elastomeric polymer block having a glass transition point, which is an amino group-containing block copolymer composed of an elastomeric polymer block having a soft segment having a glass transition point of 10 ° C. or lower, represented by the following general formula: An amino group-containing block copolymer obtained by using the amino group-containing polymerization initiator represented by (I), an amino group-containing monomer represented by the following general formula (II) and / or (III): An amino group-containing block copolymer obtained by copolymerization, comprising an amino group-containing monomer represented by the following general formula (II) and / or (III) Amino group-containing block copolymer obtained by introducing the copolymer segment into the soft segment of the block copolymer in a tapered or random manner, and the soft segment is represented by the following general formulas (IV) to (VII). At least one selected from the group of amino group-containing block copolymers obtained by copolymerizing at least one amino group-containing monomer (hereinafter also referred to as "(b) amino group-containing block copolymer" 1 to 70 parts by weight, (c) 5 to 500 parts by weight of a photopolymerizable unsaturated monomer, and (d) 0.001 to 50 parts by weight of a photopolymerization initiator. A water-developable photosensitive resin composition is provided.

[0005]

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[In the above general formula (I), R and R'represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an alkenyl group, and u is an integer of 0 to 2. ]

[0007]

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[In the above general formula (II) or (III), R ^{1 to} R ⁶ represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an alkenyl group (provided that R ³ , R ⁶ Is a hydrogen atom), l,
m and n are integers of 0-6. ]

[0009]

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[Chemical 12]

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[In the above general formulas (IV) to (VII), R
^{1 to} R ⁸ represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an alkenyl group, and 1 to q are 0 to
6 is an integer. ]

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION (a) Particulate Copolymer The (a) particulate copolymer, which is one of the constituent components of the water-developable photosensitive resin composition of the present invention, is ) To (c), and optionally (d) another copolymerizable monomer. (A) The particulate copolymer has (a) an aliphatic conjugated diene monomer, (b) one addition-polymerizable group, and a carboxyl group, an amino group,
A polymer component of a monomer having one functional group selected from the group of functional groups consisting of a hydroxyl group and an epoxy group, and (c) a compound having at least two addition-polymerizable groups, respectively. 10-95 mol% (preferably 30-90 mol%) based on the total amount of the mixture of monomer components,
0.1-30 mol% (preferably 0.5-20 mol%), and 0.1-20 mol% (preferably 0.5-)
10 mol%). Furthermore, the component (a) is
If necessary, other copolymerizable monomers (d) other than the above-mentioned monomers (a) to (c) are copolymerized in an amount of 70 mol% or less based on the total amount of all monomer components. You may. (I)
The components are in particulate form. (A) By making the particle surface of the particulate copolymer hydrophilic and making the inside of the particle hydrophobic, the water resistance and water developability of the water-developable photosensitive resin composition are further improved. The average particle size of the particulate copolymer (a) is usually 20 to 1,000 nm, preferably 30 to 500 n.
m.

(A) Examples of the monomer (a) component constituting the particulate copolymer include, for example, 1,3-butadiene,
Examples include isoprene, dimethyl-1,3-butadiene and chloroprene. The content of the monomer (a) component is
10 to 95 mol% in the monomer mixture, preferably 30
~ 90 mol%. The content of component (a) is 10 mol%
When it is less than 1, the strength of the composition polymer after photocuring is low.
On the other hand, when it exceeds 95 mol%, the water developability of the photosensitive resin composition is poor.

Among the monomers (b) constituting the component (b), examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetraconic acid, Examples include half-esters of succinic acid, a dicarboxylic acid such as fumaric acid, and an unsaturated alcohol having an addition-polymerizable group, and examples of the amino group-containing monomer include (meth) acrylic acid dimethylaminomethyl,
Dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminomethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminomethyl (meth) acrylamide, Examples of the hydroxyl group-containing monomer include dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminomethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide. Is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene glycol mono (meth) acrylate, polyalkyle Glycols include such mono (meth) acrylate of (repeating units of 2 to 12 alkylene glycol) is, examples of the epoxy group-containing monomer, and (meth) glycidyl acrylate, allyl glycidyl ether.

As the monomer (b) component containing the above functional group, the above monomer can be arbitrarily selected according to the purpose, but the resulting water-developable photosensitive resin composition has a wide range of properties. It is preferable to use a monomer containing a carboxyl group as the kind of the component of the monomer (b) because it can be easily controlled within the range. The content of the monomer (b) component is 0.1 to 30 mol%, preferably 0.5 to 2
0 mol%. When the content of the component (b) is 0.1 mol% or less, the water-developability of the resulting photosensitive resin composition is poor, while when it exceeds 30 mol%, the resulting composition becomes hard and brittle, and both are preferable. Absent.

Examples of the monomer (c) constituting the component (a) include ethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate and propylene glycol di. (Meth) acrylate, divinylbenzene, trivinylbenzene, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) Examples thereof include acrylate. These components (c) can be used alone or in combination of two or more. The content of the monomer (c) component is 0.1 to 2
It is 0 mol%, preferably 0.5 to 10 mol%.
When the content of the component (c) is less than 0.1 mol%, the water developability of the composition is poor. On the other hand, when it exceeds 20 mol%, the compatibility between the particulate polymer and the photopolymerizable monomer is poor and the processability is deteriorated. Further, the strength of the composition polymer after photocuring is significantly reduced.

The other copolymerizable monomer (d) component is not particularly limited as long as it is a compound having one addition-polymerizable group, and specific examples are styrene, α-methylstyrene, Examples thereof include vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

The component (a) is prepared as a particulate copolymer by an emulsion polymerization method using a radical polymerization initiator or a suspension polymerization method. The emulsion polymerization method is used because of its uniform particle size and particle size. It is preferable to use. The total amount of each of the monomers and the polymerization agent such as the radical initiator may be added at the start of the reaction, or may be added after the start of the reaction in any desired amount. The polymerization is carried out in a reactor from which oxygen has been removed at 0 to 80 ° C., but operating conditions such as temperature and stirring can be arbitrarily changed during the reaction. The polymerization method is continuous,
Both batch methods are possible.

Examples of the radical initiator include organic peroxides such as benzoyl peroxide, cumene hydroperoxide, paramenthane hydroperoxide and lauroyl peroxide, diazo compounds represented by azobisisobutyronitrile, and potassium persulfate. Inorganic compounds,
A redox catalyst represented by a combination of an organic compound and iron sulfate is used.

(B) Amino Group-Containing Block Copolymer The (b) amino group-containing block copolymer, which is one of the constituent components of the water-developable photosensitive resin composition of the present invention, has a specific content in the composition. Contains a tertiary amino group as a functional group,
A thermoplastic non-elastomeric polymer block mainly composed of a hard segment and a soft segment, the hard segment having a glass transition point of 20 ° C. or higher, and the soft segment consisting of an elastomeric polymer having a glass transition point of 10 ° C. or lower. It is a block-shaped copolymer.

The method of introducing the functional group into the composition is not particularly limited, and the method of using the amino group-containing polymerization initiator represented by the general formula (I) or the general formula (I
Method of copolymerizing amino group-containing monomer represented by I) and / or (III), copolymerization of amino group-containing monomer represented by the above general formula (II) and / or (III) A method of introducing a segment into a soft segment of a block copolymer in a tapered or random manner, or copolymerizing at least one of the amino group-containing monomers represented by the above general formulas (IV) to (VII) into the soft segment. The method of doing is mentioned.

For example, as a method of introducing the functional group, a method of copolymerizing a monomer having the amino group and containing one addition-polymerizable group with another monomer component, A method for synthesizing a block copolymer satisfying the above requirements (1) using a polymerization initiator containing an amino group as a functional group such as the above general formula (I), or a block copolymer satisfying the above requirements in advance. A known method can be used, such as introducing the above-mentioned amino group into the composition by a graft reaction after passing through the required series of synthetic steps.

The amino group-containing polymerization initiator represented by the general formula (I) is, for example, JP-A-6-27951.
No. 5, Japanese Patent Publication No. 5-1298, Japanese Patent Laid-Open No. 59-3
Examples thereof include those described in Japanese Patent No. 8209, Japanese Patent Laid-Open No. 6-199923, and the like. That is, examples of the amino group-containing polymerization initiator include lithium amide compounds. Specific examples of the lithium amide compound include lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium dibutylamide, lithium dipentylamide, lithium dihexylamide, lithium dioctylamide, lithium dicyclohexylamide, lithium-N-methylbenzylamide, lithium. Examples thereof include morpholine amide and lithium piperazine amide. These lithium amide compounds are not only used alone, but one or more of the potassium compounds and organic potassium compounds disclosed in JP-A-63-297410 can be used in an amount of 0.
It is also possible to use 001 to 0.5 mol in combination. The amount of the amino group-containing polymerization initiator used depends on the Mooney viscosity of the produced polymer, but is usually 0.2 per 100 g of the monomer.
˜20 mmol, preferably 0.4 to 15 mmol, more preferably 0.5 to 10 mmol.

The hard segment constituting the component (b) is characterized by being a thermoplastic non-elastomeric polymer block having a glass transition point of 20 ° C. or higher.
A vinyl aromatic compound is mentioned as a preferable example of the monomer component which mainly comprises this polymer block. Further, if necessary, the amino group-containing monomers represented by the general formulas (II) to (III) (tertiary amino group-containing vinyl aromatic compounds) are copolymerized to give ( ) An amino group-containing block copolymer can be prepared.

Specific examples of the vinyl aromatic compound (containing a tertiary amino group) include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene and dimethyl (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)
Examples thereof include ethyl] amine, diethyl (p-vinylphenethyloxymethyl) amine, diethyl [2- (p-vinylphenethyloxy) ethyl] amine, vinylpyridine, and the like, and particularly styrene, α-methylstyrene, dimethyl (p-vinyl). Benzyl) 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 and vinylpyridine are preferred.

The hard segment constituting the component (b) may be optionally copolymerized with the vinyl aromatic compound and the amino group-containing monomer (amino group-containing vinyl aromatic compound). It can also be obtained by copolymerizing with a conjugated diene compound or another monomer component within the above-mentioned glass transition temperature range.

The soft segment constituting the component (b) is characterized by being an elastomeric polymer block having a glass transition point of 10 ° C. or lower. If necessary, the amino group-containing monomer represented by the general formulas (II) to (III) (amino group-containing vinyl aromatic compound) is copolymerized, and the amino group-containing copolymerized segment is tapered or random. In this way, the block copolymer of (b) amino group of the composition of the present invention can be prepared by introducing it into the soft segment of the block copolymer. Further, if necessary, the above general formula (IV)
The (b) amino group-containing block copolymer of the composition of the present invention can be prepared by copolymerizing the amino group-containing monomer represented by (VII). Here, examples of the amino group-containing monomer represented by the general formulas (IV) to (VII) include the following compounds.

[0027]

[Chemical 15]

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[Chemical 21]

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[Chemical formula 26]

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[Chemical 29]

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[Chemical 31]

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A conjugated diene compound is mentioned as a preferred example of the monomer component mainly constituting the soft segment. Specifically, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-
Pentadiene, 2-methyl-1,3-pentadiene,
Examples thereof include 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, and mixtures thereof, but they are industrially applicable and have excellent physical properties. To obtain the polymer block, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, and 1,3-butadiene and isoprene are more preferable.

The soft segment constituting the component (b) can be obtained by copolymerizing the conjugated diene compound with the above-mentioned amino group-containing monomer, if necessary, and the above-mentioned glass transition. It can also be obtained by copolymerizing with a vinyl aromatic compound or another monomer component within the temperature range.

The structure of the polymer block used as the component (b) constituting the composition of the present invention can be freely selected according to the purpose, but it is preferable to use the hard segment constituting the polymer block. Soft segment weight ratio is hard segment / soft segment = 9
5/5 to 5/95, more preferably 95/5 to 20/8
0, more preferably 95/5 to 30/70.

The binding content of the amino group-containing polymerization initiator and / or the amino group-containing monomer in the (b) amino group-containing block copolymer is 0.1 to 30% by weight,
Preferably 0.5 to 25% by weight, more preferably 1 to
It is 20% by weight. If it is less than 0.1% by weight, the elution time becomes short, while if it exceeds 30% by weight, the tensile strength is lowered.

The weight average molecular weight of the (b) amino group-containing block copolymer is usually 1,000 to 300,000, preferably 5,000 to 300,000 for the hard segment.
200,000, more preferably 10,000 to 10
50,000 and 10,000-5 soft segments
0,000, preferably 20,000 to 400,000
It is 0, more preferably 30,000 to 300,000. Furthermore, the total weight average molecular weight is 15,000.
~ 1,000,000, preferably 20,000-80
30,000, more preferably 30,000 to 400,
000.

The component (B) can be used in any proportion depending on the purpose, but is usually 1 to 70 parts by weight, preferably 100 parts by weight, relative to 100 parts by weight of the particulate copolymer (A). Is used in the range of 1 to 60 parts by weight, more preferably 1 to 50 parts by weight. When the amount of the component (b) used is less than 1 part by weight, the strength of the resulting composition is insufficient, and
If it exceeds the amount by weight, the water developability of the resulting composition is inferior, which is not preferable.

Examples of the (c) photopolymerizable unsaturated monomer which is one of the constituents of the present invention include the following monomers, which may be used alone or in combination.
The physical properties of the photosensitive resin composition after photocuring can be freely designed.

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

(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) acrylate. , Tert-
Butyl (meth) acrylate, n-amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
n-octyl (meth) acrylate, lauryl (meth)
Alkyl (meth) acrylates such as acrylate and stearyl (meth) acrylate;

Unsaturated monocarboxylic acid esters such as methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, butyl arsenate; trifluoroethyl (meth) Fluoroalkyl (meth) acrylates such as acrylate, pentafluoropropyl (meth) acrylate, heptafluorobutyl (meth) acrylate; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol , Mono- or di- (meth) acrylates of alkylene glycols such as 1,5-pentanediol and 1,6-hexanediol;

Mono- or di-polyalkylene glycols such as polyethylene glycol and polypropylene glycol (2 to 23 alkylene glycol units)
(Meth) acrylates; 2-methoxyethyl (meth)
Acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-
Alkoxyalkyl (meth) acrylates such as ethoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate and 3-ethoxypropyl (meth) acrylate;

Alkoxyalkylene glycols such as methoxyethylene glycol, methoxypropylene glycol, methoxypolyethylene glycol, ethoxypolyethylene glycol, methoxypolypropylene glycol, ethoxypolypropylene glycol and the like, and alkoxypolyalkylene glycols (the number of alkylene glycol units is, for example, 2 to 23) ) Acrylates; 2-
Allyloxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate, 2-phenoxypropyl (meth) acrylate, and 3-phenoxypropyl (meth) acrylate;

Mono (meth) acrylates of allyloxypolyalkylene glycols such as phenoxy polyethylene glycol and phenoxy polypropylene glycol;
Cyanoalkyl (meth) acrylates such as cyanoethyl (meth) acrylate and cyanopropyl (meth) acrylate; glycerin, 1,2,4-butanetriol, pentaerythritol, trimethylolalkane (alkane has, for example, 1 to 3 carbon atoms) , Oligo (meth) acrylates such as di (meth) acrylate, tri (meth) acrylate or tetra (me) acrylate of polyhydric alcohols such as tetramethylolalkane (the carbon number of the alkane is, for example, 1 to 3), trivalent Mono- or oligo- (meth) acrylates of the above polyalkylene glycol adducts of polyhydric alcohols;

1,4-cyclohexanediol, 1,4
-Mono- or di- (meth) of cyclic polyols such as benzenediol, 1,4-dihydroxyethylbenzene
Acrylates; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3
-Chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-
Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate;

Glycerol mono (meth) acrylate,
Mono (meth) acrylates of (poly) alkylene glycols such as polyethylene glycol mono (meth) acrylate (the number of polyethylene glycol units is, for example, 2 to 20) and polypropylene glycol mono (meth) acrylate (the number of polypropylene glycol units is, for example, 2 to 20). Kinds; Glycerol di (meth) acrylate, 1,
2,4-butanetriol mono (meth) acrylate,
1,2,4-butanetriol di (meth) acrylate, trimethylolalkane mono (meth) acrylate (alkane has 1 to 3 carbon atoms), trimethylolalkane di (meth) acrylate (alkane has 1 carbon number, for example) ~ 3), tetramethylol alkane di (meta)
Free hydroxyl group-containing (meth) acrylates of trihydric or higher polyhydric alcohols such as acrylate (alkane has 1 to 3 carbon atoms) and tetramethylolalkane tri (meth) acrylate (alkane has 1 to 3 carbon atoms). ;

Hydroxyalkyl esters of other unsaturated carboxylic acids such as 2-hydroxyethyl crotonic acid, 2-hydroxypropyl crotonic acid, 2-hydroxyethyl cinnamic acid and 2-hydroxypropyl cinnamic acid; N-
Hydroxymethyl (meth) acrylamide, N-2-hydroxyethyl (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, crotonic acid N-hydroxymethylamide, crotonic acid N-
Unsaturated amides containing hydroxyl groups such as (2-hydroxyethyl) amide, cinnamic acid N-hydroxymethylamide, cinnamic acid N- (2-hydroxyethyl) amide;

O-Hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-
Hydroxyl group-containing vinyl aromatic compounds such as α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene and p-vinylbenzyl alcohol; unsaturated alcohols such as (meth) allyl alcohol; Unsaturated (mono) carboxylic acids such as (meth) acrylic acid, crotonic acid and cinnamic acid; unsaturated polycarboxylic acids such as (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, citraconic acid and mesaconic acid ( Anhydrides);

Monomethyl ester, monoethyl ester, monopropyl ester of the above unsaturated polycarboxylic acid,
Monohexyl ester, monooctyl ester, dimethyl ester, diethyl ester, dipropyl ester,
Free carboxyl group-containing esters such as dibutyl ester; Free carboxyl group-containing nitriles such as unsaturated polycarboxylic acid mononitriles; Free carboxyl group-containing amides such as unsaturated polycarboxylic acid monoamides;

Free carboxyl group-containing hydroxyalkyl esters such as mono (2-hydroxyethyl ester) and mono (2-hydroxypropyl ester) of the above unsaturated polycarboxylic acids; Free carboxyl group-containing amides of the above unsaturated polycarboxylic acids -N-hydroxyalkyl derivatives of phthalic acid, succinic acid, adipic acid and other non-polymerizable polycarboxylic acids and allyl alcohol, 2-hydroxyethyl (meth) acrylate and the like hydroxyl group-containing unsaturated compound free monoester Carboxyl group-containing esters; dimethyl maleate, diethyl maleate,
Diesters of unsaturated dicarboxylic acids such as dibutyl maleate, dioctyl maleate, diethyl fumarate, dibutyl fumarate, dioctyl fumarate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dioctyl itaconate;

2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dipropylaminoethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-dimethylaminopropyl (meth) ) Acrylate, 2-diethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, 2-dipropylaminopropyl (meth) acrylate, 3-dipropylaminopropyl (meth) acrylate and other dialkylaminoalkyl (meth) Acrylates; 2-dimethylaminoethoxyethyl (meth) acrylate, 2-diethylaminoethoxyethyl (meth)
Dialkylaminoalkoxyalkyl (meth) acrylates such as acrylates;

N- (2-dimethylaminoethyl) (meth) acrylamide, N- (2-diethylaminoethyl) (meth) acrylamide, N- (2-dimethylaminopropyl) (meth) acrylamide, N- (3-dimethyl Aminopropyl) (meth) acrylamide, N-
Tertiary amino group-containing (meth) acrylamides such as (2-diethylaminopropyl) (meth) acrylamide and N- (3-diethylaminopropyl) (meth) acrylamide; epoxy groups such as allyl glycidyl ether and glycidyl (meth) acrylate Unsaturated compounds contained;

(Meth) acrylamide, N, N'-methylenebis (meth) acrylamide, N, N'-ethylenebis (meth) acrylamide, N, N'-hexamethylenebis (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, Unsaturated amides such as N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, crotonic acid amide, cinnamic acid amide; vinyl chloride, vinyl acetate, silica Cinnamate, crotonic acid ester, dicyclopentadiene, ethylidene norbornene.

(C) The photopolymerizable monomer can be used in an arbitrary ratio depending on the purpose, and the fluidity can be freely designed from a wax form to a low viscosity liquid form depending on the amount.
(A) Normally, 5 to 5 parts by weight of the particulate copolymer is used.
It is used in an amount of 500 parts by weight, preferably 10 to 450 parts by weight, more preferably 20 to 400 parts by weight. 5
If the amount is less than parts by weight, the strength of the resulting resin composition is poor, while if it exceeds 500 parts by weight, the composition after photocuring is largely shrunk, and it is difficult to achieve both water resistance and water developability of the composition. In addition, the degree of freedom in designing the viscosity of the composition decreases, which is not preferable.

As described above, the water-developable photosensitive resin composition of the present invention has, in the (a) particulate copolymer, a functional group consisting of a carboxyl group, an amino group, a hydroxyl group and an epoxy group. It is characterized by containing at least one kind of selected functional group and containing a specific tertiary amino group as a functional group in the component (b), and introducing any functional group into any component depending on the purpose. However, the composition can be constituted by the combination thereof. In particular, from the viewpoint that the properties of the resulting water-developable photosensitive resin composition can be easily controlled in a wide range, the component (a) constituting the composition of the present invention,
It is preferable that at least one of the components (c) contains a carboxyl group as a functional group, and at least one contains an amino group as a functional group. In that case, the ratio of the carboxyl group and the amino group in the entire composition is preferably 0.1 mole or more of the amino group to 1 mole of the carboxyl group,
More preferably, it is 0.4 mol or more. When the ratio of amino groups is less than 0.1 mol, the water developability of the resulting composition tends to be low, which is not preferable.

The (d) photopolymerization initiator used in the photosensitive resin composition of the present invention is usually used as a photosensitizer, for example, α-diketone compounds such as diacetyl and benzyl, benzoin and pivaloin. Acryloins, Benloin methyl ether, benzoin ethyl ether, benzoin propyl ether and other acyloin ethers, anthraquinone, 1,4-naphthoquinone and other polynuclear quinones, 2,2-dimethoxyphenylacetophenone, trichloroacetophenone and other acetophenones, Benzophenones such as benzophenone and methyl-o-benzoylbenzoate can be mentioned.

(D) The amount of the photopolymerization initiator added is usually 0.001 with respect to 100 parts by weight of the particulate copolymer (a) which is one of the essential components of the photosensitive resin composition of the present invention. ~
The amount is 50 parts by weight, preferably 0.1 to 20 parts by weight, and more preferably 1 to 10 parts by weight. If it is less than 0.001 part by weight, sufficient curing cannot be given to the photosensitive resin composition, while if it exceeds 50 parts by weight, all of the photopolymerization initiator does not participate in the reaction. Not only is it economical, but sometimes the compatibility with the (a) component, (b) component, and (c) component is poor, and dispersion may become uneven.

The water-developable photosensitive resin composition of the present invention is selected from the group of functional groups consisting of a carboxyl group, a hydroxyl group, an amino group and an epoxy group for the purpose of improving its water developability. The non-polymerizable compound containing one kind can be added in the range of 20% by weight or less based on the total weight of the photosensitive resin composition.

Examples of this non-polymerizable compound include primary amines such as ethylamine and propylamine, secondary amines such as diethylamine and dibutylamine, or trimethylamine, triethylamine, tripropylamine and ethyl as tertiary amines. Trialkylamines such as dimethylamine and diethylmethylamine, trialcoholamines such as triethanolamine and tripropanolamine, alcohols such as methanol, ethanol, propanol, butanol, triethanol and tripropanol, formic acid, acetic acid, propion Examples thereof include acids such as acids and epoxy compounds such as 1,2-epoxybutane and 1,2-epoxyhexane.

The photosensitive resin composition of the present invention may further contain conventional additives, if necessary, for example, 0.001 to 2.0% by weight of thermal addition polymerization based on the total weight of the photosensitive resin composition. Inhibitors can be included. Suitable inhibitors include, for example, hydroquinone, hydroquinone monomethyl ether, mono-t-butylhydroquinone, catechol, p.
-Methoxyphenol, pt-butylcatechol,
Hydroxy aromatic compounds such as 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-m-cresol, pyrogallol and β-naphthol;

Benzoquinone, 2,5-diphenyl-p-
Quinones such as benzoquinone, p-toluquinone and p-xyloquinone; nitrobenzene, m-dinitrobenzene,
2-methyl-2-nitrosopropane, α-phenyl-t
-Butylnitrone, 5,5-dimethyl-1-pyrroline-
A nitro compound such as 1-oxide or a nitrone compound; an amine such as a chloranyl-amine system, diphenylamine, diphenylpicrylhydrazine, phenol-α-naphthylamine, pyridine or phenothiazine;

Sulfides such as dithiobenzoyl sulfide and 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-
Examples thereof include stable radicals such as butyl-α- (3,5-di-t-butyl) -4-oxo-2,5-cyclohexadiene-1-ylidene-p-trioxyl. These thermal addition polymerization inhibitors can be used alone or in combination of two or more.

The resin composition of the present invention comprises, for example, (a) a particulate copolymer, (b) an amino group-containing block copolymer,
It can be obtained by sufficiently stirring the photopolymerizable unsaturated monomer (c) and the photopolymerization initiator (d) with a kneader, an intermixer or the like while heating. The photosensitive resin composition thus obtained can be freely designed from a wax-like or rubber-like state having no fluidity to a low-viscosity liquid having excellent fluidity.

The photosensitive resin composition having no fluidity has a constant film thickness with a spacer having an appropriate thickness interposed therebetween, is coated on a support by a roll coater, or is compression molded.
It can be processed into a photosensitive plate having a constant film thickness by extrusion molding or the like. A negative film is applied to this to expose it, and the unexposed portion is washed off with water to enable plate making. Further, the photosensitive resin composition having excellent fluidity can be adjusted in viscosity by adding a suitable solvent as necessary, and can be used as a resist suitable for spin coating, and similarly, the unexposed portion after exposure can be used. A clear image can be formed by rinsing with water.

[0062]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples without departing from the scope of the invention.

Example 1 Components (a) and (b) were prepared according to the procedure shown below. (A) Component Sodium lauryl sulfate as an emulsifier, benzoyl peroxide as a polymerization initiator, butadiene / methacrylic acid / ethylene glycol dimethacrylate / ethyl acrylate (mol%) = 80 / 6.5 / 1.0 / 12.5 Emulsion polymerization was carried out in proportion. This is salt-coagulated with calcium chloride and dried to (a) of the composition of the present invention.
A component, a particulate polymer, was prepared.

Component (b) The component (b) was synthesized according to the following procedure. That is, in a nitrogen atmosphere, cyclohexane was used as a solvent, and n-butyllithium was used as a polymerization initiator to first polymerize a mixture of styrene and dimethyl (p-vinylphenethyl) amine. After the conversion of polymerization reached 98%, isoprene was added to the polymerization system to carry out polymerization.
After the completion of the polymerization, methyldichlorosilane was added in an amount of ½ molar equivalent of the amount of n-butyllithium used as a polymerization initiator to carry out a coupling reaction of the block copolymer. Then, 2,6-di-t-butyl- was added to the polymer solution.
p-Cresol was added, the solvent was removed by steam stripping, and the product was dried with a steam dryer at 90 ° C. to obtain a polymer.

The obtained polymer was analyzed by GPC to determine the weight average molecular weight (hereinafter also referred to as "Mw"), and by infrared analysis, the total amount of styrene and dimethyl (p-vinylphenethyl) amine bonded in the polymer. Further, the nitrogen content in the polymer was determined by elemental analysis, and the bond content of dimethyl (p-vinylphenethyl) amine was calculated from the obtained value. As a result, the Mw of the obtained polymer was 1
The styrene bond content was 6.1% by weight, and the dimethyl (p-vinylphenethyl) amine bond content was 2.8% by weight.

Preparation of Water-Developable Photosensitive Resin Composition 30 parts by weight of the above-mentioned component (b) is added to 100 parts by weight of the above-mentioned component (a), and (c) lauryl methacrylate 30 as a photopolymerizable unsaturated monomer. Parts by weight, 20 parts by weight of 1,6-hexanediol diacrylate, 20 parts by weight of N- (3-dimethylaminopropyl) acrylamide, (d)
3 parts by weight of 2,2-dimethoxyphenylacetophenone as a photopolymerization initiator and 0.5 parts by weight of t-butylcatechol as a storage stabilizer were added, and the mixture was stirred for 30 minutes in a kneader whose temperature was controlled at 50 ° C. to obtain the photosensitive material of the present invention. A resin composition was obtained.
The resin composition obtained was in the form of a transparent wax.

Evaluation A photosensitive resin layer having a thickness of 0.5 mm was formed on a polyester sheet using the obtained photosensitive resin composition, and then a JOW-A-4P type developing machine manufactured by JEOL Ltd. And the time required for the photosensitive resin layer to disappear was measured by brushing in 30 ° C. warm water. In addition, the resin plate was manufactured by JEOL Ltd.
E-A3-SS) and then exposed for 6 minutes.
Tensile strength, elongation at break and impact resilience were measured according to K6301. As a result, the resulting water-developable photosensitive composition was excellent in both water developability and resin plate strength, and had good elongation at break and impact resilience, and had an excellent property balance. Table 1 shows the above results.

Example 2 Components (a) and (b) were prepared as follows. (B) Component Butadiene / 2-diethylaminoethyl methacrylate / divinylbenzene / ethyl acrylate (mol%) = 80 / 6.5 / 1.0 / according to the same procedure as in Example 1.
Emulsion polymerization was carried out at a ratio of 12.5 to prepare a particulate polymer which was the component (a) of the composition composition of the present invention.

(B) Component Synthesis was performed according to the same procedure as in Example 1, and Mw was 14
An amino group-containing block copolymer which is component (b) of the composition of the present invention having a styrene bond content of 7,000, a styrene bond content of 5.4% by weight, and a dimethyl (p-vinylphenethyl) amine bond content of 2.3% by weight. Prepared.

Preparation of water-developable photosensitive resin composition 30 parts by weight of the above-mentioned component (b) per 100 parts by weight of the above-mentioned component (a), and (c) lauryl methacrylate 30 as a photopolymerizable unsaturated monomer. Parts by weight, 20 parts by weight of 1,6-hexanediol diacrylate, 20 parts by weight of acrylic acid, (2) 3 parts by weight of 2,2-dimethoxyphenylacetophenone as a photopolymerization initiator, and t- as a storage stabilizer.
0.5 parts by weight of butylcatechol was added, and the water-developable photosensitive resin composition of the present invention was prepared according to the same procedure as in Example 1.

As a result, the resulting water-developable photosensitive resin composition was excellent in both water developability and resin plate strength, and had good elongation at break and impact resilience, and had an excellent property balance. . Table 1 shows the above results.

Example 3 As component (b), Mw was 104,000, the styrene bond content was 10.1% by weight, and dimethyl (p-vinylphenethyl) amine was prepared by the same procedure as in Example 1. The water-developable photosensitive resin composition of the present invention was prepared and evaluated in the same manner as in Example 1 except that the amino group-containing block copolymer having a bond content of 5.6% by weight was used. . As a result, the obtained water-developable photosensitive resin composition was excellent in both water developability and resin plate strength, and was excellent in elongation at break and impact resilience, and had an excellent property balance. Table 1 shows the above results.

Example 4 As component (b), diethyl [2- (p-vinylphenethyloxy) ethyl] amine was used as the amino group-containing monomer component, and the amino group-containing block was prepared in the same manner as in Example 1. A copolymer was prepared. The Mw of the obtained polymer was 141,000, the styrene bond content was 5.2% by weight, and the diethyl [2- (p-vinylphenethyloxy) ethyl] amine bond content was 4.1% by weight. The water-developable photosensitive resin composition of the present invention was prepared and evaluated in the same manner as in Example 1 except that the component (b) was used. As a result, the obtained water-developable photosensitive resin composition was excellent in both water developability and resin plate strength, and was excellent in elongation at break and impact resilience, and had an excellent property balance. Table 1 shows the above results.

Example 5 Instead of n-butyllithium in Example 1, lithium diethylaminoethoxide and di-n-butylamine, n-
Butyl lithium was used as a polymerization initiator, and dimethyl (p
AB of vinyl phenethyl) amine / styrene copolymer hard segment and polyisoprene soft segment
A type block copolymer was synthesized. Dimethyl (p-vinylphenethyl) amine is 5.0 in the polymer.
%, The styrene bond content was 7.1% by weight, the isoprene content was 87.9% by weight, and the weight average molecular weight of the polymer was 153,000. Using the obtained block copolymer, a photosensitive resin composition was produced and evaluated according to the same procedure as in Example 1. The results are shown in Table 1.

Example 6 A block copolymer was synthesized in the same manner as in Example 5 except that piperidine was used instead of di-n-butylamine. The weight average molecular weight of the polymer was 105,000. Dimethyl (p-vinylphenethyl) in the polymer
The amine was 5.3% by weight, the styrene bond content was 7.2% by weight, and the isoprene content was 87.5% by weight. Using the obtained block copolymer, a photosensitive resin composition was produced and evaluated according to the same procedure as in Example 1. The results are shown in Table 1.

Example 7 Example 7 was repeated except that the dimethyl (p-vinylphenethyl) amine of Example 5 was not used but isoprene and 2- (N, N-dimethylaminomethylene) -1,3-butadiene were used. A block copolymer was synthesized in the same manner as in 5. The weight average molecular weight of the polymer was 98,500. In the polymer,
Styrene bond content 13.2% by weight, isoprene content 60.5% by weight, amino group containing diene 26.3% by weight
Met. Example 1 was performed using the obtained block copolymer.
Following the same procedure as above, the photosensitive resin composition is produced,
evaluated. The results are shown in Table 1.

Comparative Example 1 As a monomer component constituting the component (b), dimethyl (p
The block copolymer and the water-developable photosensitive composition were produced according to the same procedure as in Example 1 except that -vinylphenethyl) amine was not used. As a result, when a block-shaped copolymer containing no amino group was used in place of the component (b), the resulting composition was inferior in water developability, resin plate strength, and elongation at break.
Table 1 shows the above results.

Comparative Example 2 Instead of the component (B), a styrene-isoprene-styrene block copolymer [manufactured by Nippon Synthetic Rubber Co., Ltd., JSR
SIS5000] was used to produce a photosensitive resin composition according to the same procedure as in Example 1. As a result, the obtained composition was inferior in water developability, resin plate strength, elongation at break and impact resilience. Table 1 shows the above results.

[0079]

[Table 1]

[0080]

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

 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Iwawa Iwawa 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd. No. 24 within Japan Synthetic Rubber Co., Ltd.

Claims (3)

[Claims] 1. (a) (a) an aliphatic conjugated diene monomer 1
0-95 mol%, (b) having one addition-polymerizable group, and having a carboxyl group, amino group, hydroxyl group,
0.1 to 30 mol% of a monomer containing one functional group selected from the group of functional groups consisting of epoxy groups, and (c)
Monomers having at least two addition-polymerizable groups
A monomer mixture containing 1 to 20 mol% [however,
(A) + (b) + (c) = 100 mol%] based on 100 parts by weight of the particulate copolymer obtained by copolymerizing by emulsion polymerization or suspension polymerization. A thermoplastic non-elastomeric polymer block mainly composed of a soft segment, containing a tertiary amino group in one or both of the segments, and having a hard segment having a glass transition point of 20 ° C. or higher, wherein the soft segment is 10 ° C. An amino group-containing block copolymer consisting of an elastomeric polymer block having the following glass transition point, the amino group-containing block copolymer obtained by using an amino group-containing polymerization initiator represented by the following general formula (I): Block copolymer, amino group obtained by copolymerizing amino group-containing monomer represented by the following general formula (II) and / or (III) Blocked copolymer, a copolymer segment comprising an amino group-containing monomer represented by the following general formula (II) and / or (III) is tapered or randomly formed into a soft segment of the block copolymer. The amino group-containing block copolymer obtained by introducing the amino group and the amino group obtained by copolymerizing at least one of the amino group-containing monomers represented by the following general formulas (IV) to (VII) in the soft segment 1 to 70 parts by weight of at least one kind selected from the group of contained block copolymers, (c) 5 to 500 parts by weight of a photopolymerizable unsaturated monomer, and (d) a photopolymerization initiator 0.001 The water-developable photosensitive resin composition is contained in an amount of 50 to 50 parts by weight. Embedded image [In the general formula (I), R and R'have 1 to 2 carbon atoms.
0 represents an alkyl group, a cycloalkyl group, an aryl group or an alkenyl group, and u is an integer of 0 to 2. ] [Chemical 2] Embedded image [In the above general formula (II) or (III), R ^{1 to} R ⁶
Represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, or an alkenyl group (provided that R ³ and R ⁶ are hydrogen atoms), and l, m, and n are integers of 0 to 6 Is. [Formula 4] Embedded image [Chemical 6] [Chemical 7] [In the general formulas (IV) to (VII), R ^{1 to} R ⁸ represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an alkenyl group, and 1 to q are integers from 0 to 6 is there. ] 2. The monomer component of (a) the particulate copolymer contains a carboxyl group as a functional group and (b) the soft segment of the amino group-containing block copolymer is a conjugated diene monomer. The water-developable photosensitive resin composition according to claim 1, wherein the monomer component which contains a vinyl aromatic compound containing a tertiary amino group. 3. The water-developable photosensitive resin composition according to claim 2, wherein the soft segment of the (b) amino group-containing block copolymer comprises a butadiene polymer or an isoprene polymer.