JP6783605B2 - Resin composition - Google Patents

Description

The present invention relates to resin compositions. More specifically, it relates to a resin composition containing an alkali-soluble resin.

The alkali-soluble resin is a compound used in various fields from civil engineering and building materials to electronic information materials. For example, an alkali-developable resist composition (also referred to as a photosensitive resin composition) used for forming a color filter or the like. It is preferably used as a material such as (referred to as). The photosensitive resin composition includes, for example, a photopolymerizable acrylic resin obtained by subjecting a polymer having an acid group (for example, a carboxyl group) to an addition reaction of a compound having an epoxy group and a (meth) acryloyl group. A photosensitive resin composition containing the same is known (Patent Document 1). The photosensitivity of this photosensitive resin composition is improved by adding the compound. However, in the above-mentioned photosensitive resin composition, an OH group is generated by adding the compound, and the polymer becomes hydrophilic. As a result, there is a problem that the developability, solvent resistance, adhesion to the substrate, and the like of the cured product (for example, a color filter) formed from the photosensitive resin composition are lowered.

Japanese Unexamined Patent Publication No. 9-114095

By adding a vinyl ether compound to the acid group of the polymer having an acid group (for example, a carboxyl group), it becomes possible to introduce a photosensitive group without generating an OH group, and the above problem is improved. I found that a certain effect can be obtained. On the other hand, the resin composition containing the alkali-soluble resin to which the vinyl ether compound is added has poor storage stability, and the acid value and molecular weight of the alkali-soluble resin significantly decrease with time, especially in the presence of an alcohol solvent. There is a problem of doing.

The present invention has been made to solve the above problems, and an object of the present invention is a resin composition containing an alkali-soluble resin to which a vinyl ether compound is added, which is excellent in storage stability. It is to provide things.

式（Ａ）中、Ｒ_１は、水素原子またはメチル基を表し、Ｒ_２は、炭素数２〜１８の直鎖状、分岐状もしくは環状のアルキレン基、炭素数２〜２０のアルコキシアルキレン基、炭素数２〜８のハロゲン化アルキレン基、末端水酸基を除くポリエチレングリコール骨格、末端水酸基を除くポリプロピレングリコール骨格、末端水酸基を除くポリブチレングリコール骨格またはアリール基を表し、Ｒ_３は、水素原子、炭素数１〜１０の直鎖状、分岐状もしくは環状のアルキル基、または炭素数６〜１１の置換基を有する芳香族基である。
１つの実施形態においては、上記ビニルエーテル系化合物が、(メタ)アクリル酸２−（２−ビニロキシエトキシ）エチルである。
１つの実施形態においては、上記塩基性化合物が、３級アミン基またはニトロキシラジカルを有する。 The resin composition of the present invention is a resin composition containing an alkali-soluble resin having a structure derived from a vinyl ether compound and a basic compound, and the content ratio of the basic compound in the resin composition. It is 0.01 part by weight or more with respect to 100 parts by weight of the alkali-soluble resin.
In one embodiment, the alkali-soluble resin has a carboxyl group.
In one embodiment, the vinyl ether compound is represented by the following formula (A);

In the formula (A), R ₁ represents a hydrogen atom or a methyl group, and R ₂ is a linear, branched or cyclic alkylene group having 2 to 18 carbon atoms, an alkoxyalkylene group having 2 to 20 carbon atoms, and the like. Represents an alkylene group halide having 2 to 8 carbon atoms, a polyethylene glycol skeleton excluding a terminal hydroxyl group, a polypropylene glycol skeleton excluding a terminal hydroxyl group, a polybutylene glycol skeleton excluding a terminal hydroxyl group, or an aryl group, and R ₃ is a hydrogen atom and a carbon number. It is an aromatic group having 1 to 10 linear, branched or cyclic alkyl groups, or substituents having 6 to 11 carbon atoms.
In one embodiment, the vinyl ether compound is 2- (2-vinyloxyethoxy) ethyl (meth) acrylate.
In one embodiment, the basic compound has a tertiary amine group or a nitroxy radical.

According to the present invention, it is possible to provide a resin composition containing an alkali-soluble resin to which a vinyl ether compound is added and having excellent storage stability.

The resin composition of the present invention contains an alkali-soluble resin having a structure derived from a vinyl ether compound and a basic compound. The content ratio of the basic compound is 0.01 part by weight or more with respect to 100 parts by weight of the alkali-soluble resin in the resin composition. In the present invention, it is possible to provide a resin composition having excellent storage stability by containing a predetermined amount or more of a basic compound. It is considered that this is because the protons existing in the resin composition are trapped by the basic compound, and the structural portion derived from the vinyl ether compound is difficult to be desorbed from the alkali-soluble resin. In addition, in this specification, a basic compound means a compound which can accept a proton. In one embodiment, the resin composition of the present invention is used as a photosensitive resin composition. In one embodiment, the resin composition of the present invention further comprises a polyfunctional monomer, a photopolymerization initiator. The solid content concentration of the resin composition is preferably 90% by weight or less, more preferably 80% by weight or less, and further preferably 70% by weight or less.

A. Alkali-soluble resin A-1. Composition of Alkali-Soluble Resin The alkali-soluble resin has a structure derived from a vinyl ether compound as described above. Such an alkali-soluble resin can be obtained by adding a vinyl ether compound to the acid group of the acid group-containing polymer. In the present invention, by adding a vinyl ether compound, it is possible to introduce a photosensitive group without generating an OH group, and as a result, it is excellent in photosensitivity and has developability, solvent resistance and resistance. It is possible to obtain a resin composition capable of forming a cured product having excellent adhesion to a substrate.

The alkali-soluble resin preferably has an acid group. Examples of the acid group include functional groups that neutralize with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group, and have only one of these. It may have two or more kinds. Of these, a carboxyl group and / or a carboxylic acid anhydride group is preferable, and a carboxyl group is more preferable.

式（１）中、Ｒ_１は水素原子または炭素数１〜３のアルキル基を表す。Ｘは、酸性基を表す。酸性基としては、例えば、カルボキシル基、スルホン酸基、フェノール性水酸基、カルボン酸無水物基、リン酸基等が挙げられる。なかでも好ましくはカルボキシル基である。 In one embodiment, the alkali-soluble resin has a structural unit (a-1) represented by the following formula (1) and a structural unit (a-2) represented by the following formula (2).

In formula (1), R ₁ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X represents an acidic group. Examples of the acidic group include a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group and the like. Of these, a carboxyl group is preferable.

式（２）中、Ｒ_１は前記（１）中のＲ_１と同様である。Ｒ_２は水素原子、炭素数２〜１８の直鎖状、分岐状もしくは環状のアルキル基、炭素数２〜２０のアルコキシアルキル基、炭素数２〜８のハロゲン化アルキル基、末端に水酸基または（メタ）アクリレート基を有するポリエチレングリコール骨格、末端に水酸基または（メタ）アクリレート基を有するポリプロピレングリコール骨格、末端に水酸基または（メタ）アクリレート基を有するポリブチレングリコール骨格、置換基を有しても良い芳香環基、置換基を有しても良い脂肪族環基、置換基を有しても良いヘテロ環基またはアリル基を表す。Ｙは、炭素数２〜１８の直鎖状、分岐状もしくは環状のアルキル基、炭素数２〜２０のアルコキシアルキル基、炭素数２〜８のハロゲン化アルキル基、末端に水酸基または（メタ）アクリレート基を有するポリエチレングリコール骨格、末端に水酸基または（メタ）アクリレート基を有するポリプロピレングリコール骨格、末端に水酸基または（メタ）アクリレート基を有するポリブチレングリコール骨格、置換基を有しても良い芳香環基、置換基を有しても良い脂肪族環基、置換基を有しても良いヘテロ環基またはアリル基を表す。好ましくは、Ｙは、（メタ）アクリロイル基を有する官能基である。

In formula (2), _{R 1} is the same as _{R 1} in the (1). R ₂ is a hydrogen atom, a linear, branched or cyclic alkyl group having 2 to 18 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an alkyl halide group having 2 to 8 carbon atoms, a hydroxyl group at the terminal or ( Polyethylene glycol skeleton having a meta) acrylate group, polypropylene glycol skeleton having a hydroxyl group or (meth) acrylate group at the end, polybutylene glycol skeleton having a hydroxyl group or (meth) acrylate group at the end, fragrance which may have a substituent. Represents a ring group, an aliphatic ring group which may have a substituent, a heterocyclic group which may have a substituent, or an allyl group. Y is a linear, branched or cyclic alkyl group having 2 to 18 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an alkyl halide group having 2 to 8 carbon atoms, and a hydroxyl group or (meth) acrylate at the terminal. Polyethylene glycol skeleton having a group, polypropylene glycol skeleton having a hydroxyl group or (meth) acrylate group at the end, polybutylene glycol skeleton having a hydroxyl group or (meth) acrylate group at the end, aromatic ring group which may have a substituent, Represents an aliphatic ring group which may have a substituent, a heterocyclic group which may have a substituent, or an allyl group. Preferably, Y is a functional group having a (meth) acryloyl group.

The acid value (solid acid value) of the alkali-soluble resin is preferably 20 mgKOH / g to 300 mgKOH / g, more preferably 30 mgKOH / g to 250 mgKOH / g, and further preferably 30 mgKOH / g to 200 mgKOH / g. Yes, more preferably 30 mgKOH / g to 150 mgKOH / g. Within such a range, it is possible to obtain a resin composition capable of forming a cured product having excellent curability and excellent developability and solvent resistance.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 to 300,000, more preferably 8,000 to 250,000, and even more preferably 8,000 to 100,000. Within such a range, a resin composition capable of forming a cured product having excellent heat resistance, mechanical strength and the like can be obtained. The method for measuring the weight average molecular weight (Mw) will be described later.

In one embodiment, the alkali-soluble resin has a ring structure in the main chain. By having a ring structure in the main chain, it is possible to obtain a resin composition capable of forming a cured product having excellent heat resistance, surface hardness, and adhesion to a substrate.

The glass transition temperature (Tg) of the alkali-soluble resin is preferably 100 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 0 ° C. or lower. Within such a range, a resin composition capable of forming a cured product having a high crosslink density can be obtained.

A-2. Production of Alkali-Soluble Resin The alkali-soluble resin can be obtained by adding a vinyl ether compound to an acid group-containing polymer.

A-2-1. Polymerization of Acid Group-Containing Polymer The acid group-containing polymer can be obtained, for example, by polymerizing a monomer composition containing a monomer having an acid group. The above-mentioned monomer composition may further contain other monomers. Further, in one embodiment, the monomer composition may further contain a monomer capable of introducing a ring structure into the main chain skeleton of the polymer.

(Monomer having an acid group)
The monomer having an acid group is a compound having an acid group and a polymerizable double bond in the molecule. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group and the like. Of these, a carboxyl group is preferable. Examples of the monomer having an acid group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, silicic acid, and vinyl benzoic acid; maleic anhydride, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Unsaturated polyvalent carboxylic acids such as; unsaturated monos such as monosuccinate (2-acryloyloxyethyl) and monosuccinate (2-methacryloyloxyethyl) in which the chain is extended between the unsaturated group and the carboxyl group. Examples thereof include carboxylic acids; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; and phosphoric acid group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.). Among these, it is preferable to use carboxylic acid-based monomers (unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids, unsaturated acid anhydrides) from the viewpoint of versatility, availability, and the like. More preferably, it is an unsaturated monocarboxylic acid in terms of reactivity, alkali solubility, etc., and more preferably (meth) acrylic acid (that is, acrylic acid and / or methacrylic acid).

The blending ratio of the monomer having an acid group is preferably 5 parts by weight or more, more preferably 5 parts by weight to 90 parts by weight, based on 100 parts by weight of all the monomers in the monomer composition. It is more preferably 10 parts by weight to 80 parts by weight, and particularly preferably 15 parts by weight to 70 parts by weight. Within such a range, it is possible to obtain a resin composition capable of forming a cured product having excellent solubility in alkali and excellent appearance, adhesion and the like.

(Other monomers)
As the other monomer, any suitable monomer can be used. Examples of other monomers include cyclic structure-containing (meth) acrylic acid ester-based monomers; cyclic structure-free (meth) acrylic acid ester-based monomers; aromatic vinyl compounds; butadiene such as butadiene and isoprene. Alternatively, substituted butadiene compounds; ethylene such as ethylene, propylene, vinyl chloride, acrylonitrile, or substituted ethylene compounds; vinyl esters such as vinyl acetate, etc. may be mentioned (however, those corresponding to "monomers having an acid group" are excluded. ).

Examples of the cyclic structure-containing (meth) acrylate-based monomer include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, and (. Dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, biphenyl (meth) acrylate, o-biphenyloxyethyl (meth) acrylate, o-biphenyloxyethoxy Ethyl (meth) acrylate, m-biphenyloxyethyl acrylate, p-biphenyloxyethyl (meth) acrylate, o-biphenyloxy-2-hydroxypropyl (meth) acrylate, p-biphenyloxy-2-hydroxypropyl (meth) acrylate , M-biphenyloxy-2-hydroxypropyl (meth) acrylate, N- (meth) acryloyloxyethyl-o-biphenyl = carbamate, N- (meth) acryloyloxyethyl-p-biphenyl = carbamate, N- (meth) Examples thereof include biphenyl group-containing monomers such as acryloyloxyethyl-m-biphenyl = carbamate and o-phenylphenol glycidyl ether acrylate, terphenyl (meth) acrylate, and o-terphenyloxyethyl (meth) acrylate.

Examples of the cyclic structure-free (meth) acrylic acid ester-based monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. Examples thereof include n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Of these, methyl (meth) acrylate is preferable in terms of copolymerizability.

Examples of the aromatic vinyl compound include styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene and the like.

Among the other monomers described above, a cyclic structure-containing (meth) acrylic acid ester-based monomer and an aromatic vinyl compound are preferable because they have good transparency and do not easily impair heat resistance. More preferably, cyclohexyl (meth) acrylate and benzyl (meth) acrylate.

The blending ratio of the other monomers is preferably 0 parts by weight to 70 parts by weight, more preferably 1 part by weight to 50 parts by weight, based on 100 parts by weight of all the monomers in the monomer composition. It is a department.

(A monomer that can introduce a ring structure into the main chain skeleton of a polymer)
Examples of the monomer capable of introducing a ring structure into the main chain skeleton of the polymer include a monomer having a double bond-containing ring structure in the molecule and a weight having a ring structure in the main chain by cyclization polymerization. Examples thereof include monomers forming a coalescence. As such a monomer, at least one selected from the group consisting of an N-substituted maleimide-based monomer, an acrylic ether-based monomer, and an α- (unsaturated alkoxyalkyl) acrylate-based monomer can be used. ..

Examples of the N-substituted maleimide-based monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, N-dodecylmaleimide, and N. -Benzylmaleimide, N-naphthylmaleimide, p-methylbenzylmaleimide, p-butylbenzylmaleimide, p-hydroxybenzylmaleimide, o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide, p-dichlorobenzylmaleimide and the like, among others. From the viewpoint of transparency, N-phenylmaleimide and N-benzylmaleimide are preferable, and N-benzylmaleimide is particularly preferable. Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; o-chlorobenzylmaleimide, Examples thereof include halogen-substituted benzyl maleimides such as o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide;

式（３）中、Ｒ_１およびＲ_２はそれぞれ独立して、水素原子、または置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。炭化水素基としては、例えば、直鎖状又は分岐状のアルキル基；アリール基；脂環式基；アルコキシで置換されたアルキル基；アリール基で置換されたアルキル基；等が挙げられる。中でも、メチル、エチル、シクロヘキシル、ベンジル等のような、酸や熱で脱離しにくい１級又は２級炭素の炭化水素基が耐熱性の点で好ましい。 Examples of the acrylic ether dimer include compounds represented by the following general formula (3).

In the formula (3), R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. Examples of the hydrocarbon group include a linear or branched alkyl group; an aryl group; an alicyclic group; an alkyl group substituted with an alkoxy; an alkyl group substituted with an aryl group; and the like. Of these, hydrocarbon groups of primary or secondary carbons such as methyl, ethyl, cyclohexyl, and benzyl that are difficult to be desorbed by acid or heat are preferable in terms of heat resistance.

Among the acrylic ether dimers, dialkyl-2,2'-(oxydimethylene) diacrylate-based monomers are preferable. Specifically, for example, dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-propyl). ) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2, 2'-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2,2'-[ Oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (stearyl) -2,2'-[oxybis (methylene) ] Bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2'-[oxybis (methylene)] bis-2 -Propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxyethyl) -2,2'-[oxybis (methylene)] bis-2 -Propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'-[oxybis (Methylene)] bis-2-propenoate, di (t-butylcyclohexyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[ Oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] )] Bis-2-propenoate, diadamantyl-2,2'-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] Bis-2-propenoate and the like can be mentioned.

Examples of the α- (unsaturated alkoxyalkyl) acrylate-based monomer include alkyl- (α-metharyloxymethyl) acrylate and α- (allyloxymethyl) acrylate. Of these, α- (allyloxymethyl) acrylate is preferable.

The content ratio of the monomer capable of introducing the ring structure into the main chain skeleton of the polymer is preferably 1 part by weight to 40 parts by weight or more with respect to 100 parts by weight of all the monomers in the monomer composition. It is more preferably 2 parts by weight to 30 parts by weight.

Any suitable polymerization method can be adopted as the method for polymerizing the above-mentioned monomer component. For example, bulk polymerization, solution polymerization, emulsion polymerization and the like can be mentioned. Above all, solution polymerization is preferable because it is industrially advantageous and structural adjustment such as molecular weight is easy.

The above-mentioned polymerization step may be carried out in the absence of a solvent or in the presence of a solvent, but it is preferable to carry out the polymerization in the presence of a solvent, that is, to carry out the polymerization by a solution polymerization method. As the solvent, it is preferable to use a compound inert to the polymerization and addition steps, for example, benzene, toluene, N, N-dimethylformamide, dimethyl sulfoxide, acetone, 2-butanone (methyl ethyl ketone), methyl isobutyl ketone, methyl amyl. Ketone, 1,4-dioxane, chloroform, carbon tetrachloride, tetrahydrofuran, ethyl acetate, trifluoromethylbenzene, 1-methoxy-2-propyl acetate, propylene glycol monomethyl ether acetate, ethyl cellosolve, butyl cellosolve, 1-methoxy-2- Examples thereof include organic solvents such as benzene and diacetone alcohol.

A-2-2. Addition of Vinyl Ether Compounds Examples of the vinyl ether compounds include methyl vinyl ethers, ethyl vinyl ethers, n-propyl vinyl ethers, n-butyl vinyl ethers, hexyl vinyl ethers, octyl vinyl ethers, decyl vinyl ethers, ethylhexyl vinyl ethers, methoxyethyl vinyl ethers, and ethoxyethyl vinyl ethers. Chlorethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether Alkyl vinyl ethers such as: vinyl phenyl ethers, vinyl trill ethers, vinyl chlorophenyl ethers, vinyl-2,4-dichlorophenyl ethers, vinyl naphthyl ethers, vinyl anthranyl ethers and the like; cyclohexyl vinyl ethers, cyclohexanedimethanol monovinyl ethers Vinyl ethers containing alicyclic compounds such as, and allyl group-containing vinyl ethers such as allyl vinyl ethers.

In one embodiment, a compound having a (meth) acryloyl group is used as the vinyl ether compound. By using such a compound, it becomes possible to introduce a photosensitive group into the side chain of the acid group-containing polymer. As the compound having a (meth) acryloyl group and a vinyl ether group, (meth) acrylic acid esters represented by the following general formula (A) are preferably used.

式（Ａ）中、Ｒ_１は、水素原子またはメチル基を表す。
式（Ａ）中、Ｒ_２は、炭素数２〜１８の直鎖状、分岐状もしくは環状のアルキレン基、炭素数２〜２０のアルコキシアルキレン基、炭素数２〜８のハロゲン化アルキレン基、末端水酸基を除くポリエチレングリコール骨格、末端水酸基を除くポリプロピレングリコール骨格、末端水酸基を除くポリブチレングリコール骨格またはアリール基を表す。Ｒ_２は、好ましくは、重合度が２〜１００００のポリエチレングリコールから末端の水酸基を除く骨格、重合度が２〜１００００のポリプロピレングリコールから末端の水酸基を除く骨格、重合度が２〜１００００のポリブチレングリコールから末端の水酸基を除く骨格または炭素数２〜４のアルキレン基であり、より好ましくは、重合度が２〜１００のポリエチレングリコールから末端の水酸基を除く骨格、重合度が２〜１００のポリプロピレングリコールから末端の水酸基を除く骨格、重合度が２〜１００のポリブチレングリコールから末端の水酸基を除く骨格、炭素数２のアルキレン基（−ＣＨ_２ＣＨ_２−）、炭素数３のアルキレン基（−ＣＨ_２ＣＨ_２ＣＨ_２−）または炭素数４のアルキレン基（−ＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２−）であり、さらに好ましくは、重合度が２〜１５のポリエチレングリコールから末端の水酸基を除く骨格、重合度が２〜１５のポリプロピレングリコールから末端の水酸基を除く骨格、重合度が２〜１５のポリブチレングリコールから末端の水酸基を除く骨格、炭素数２のアルキレン基（−ＣＨ_２ＣＨ_２−）、炭素数３のアルキレン基（−ＣＨ_２ＣＨ_２ＣＨ_２−）または炭素数４のアルキレン基（−ＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２−）である。
式（Ａ）中、Ｒ_３は、水素原子、炭素数１〜１０の直鎖状、分岐状もしくは環状のアルキル基、または炭素数６〜１１の置換基を有する芳香族基である。Ｒ_３は、好ましくは、水素原子、炭素数１〜２のアルキル基または炭素数６〜８の芳香族基である。

In formula (A), R ₁ represents a hydrogen atom or a methyl group.
In the formula (A), R ₂ is a linear, branched or cyclic alkylene group having 2 to 18 carbon atoms, an alkoxyalkylene group having 2 to 20 carbon atoms, a halogenated alkylene group having 2 to 8 carbon atoms, and a terminal. It represents a polyethylene glycol skeleton excluding a hydroxyl group, a polypropylene glycol skeleton excluding a terminal hydroxyl group, a polybutylene glycol skeleton excluding a terminal hydroxyl group, or an aryl group. R2 is preferably a skeleton of polyethylene glycol having a degree of polymerization of ₂ to 10000 excluding the terminal hydroxyl group, a skeleton of polypropylene glycol having a degree of polymerization of 2 to 10000 excluding the terminal hydroxyl group, and polybutylene having a degree of polymerization of 2 to 10000. A skeleton excluding the terminal hydroxyl group from the glycol or an alkylene group having 2 to 4 carbon atoms, more preferably a skeleton excluding the terminal hydroxyl group from a polyethylene glycol having a degree of polymerization of 2 to 100, and a polypropylene glycol having a degree of polymerization of 2 to 100. A skeleton excluding the terminal hydroxyl group from, a skeleton excluding the terminal hydroxyl group from polybutylene glycol having a degree of polymerization of 2 to 100, an alkylene group having 2 carbon atoms (-CH ₂ CH _2- ), an alkylene group having 3 carbon atoms (-CH). _A skeleton of ₂ CH ₂ CH ₂ −) or an alkylene group having 4 carbon atoms (−CH ₂ CH ₂ CH ₂ CH ₂ −), more preferably a polyethylene glycol having a degree of polymerization of 2 to 15 excluding the terminal hydroxyl group. A skeleton of polypropylene glycol having a degree of polymerization of 2 to 15 excluding the terminal hydroxyl group, a skeleton of polybutylene glycol having a degree of polymerization of 2 to 15 excluding the terminal hydroxyl group, an alkylene group having 2 carbon atoms (-CH ₂ CH _2- ), It is an alkylene group having 3 carbon atoms (−CH ₂ CH ₂ CH ₂ −) or an alkylene group having 4 carbon atoms (−CH ₂ CH ₂ CH ₂ CH ₂ −).
In formula (A), R ₃ is an aromatic group having a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a substituent having 6 to 11 carbon atoms. R ₃ is preferably a hydrogen atom, an alkyl group having 1 to 2 carbon atoms or an aromatic group having 6 to 8 carbon atoms.

In one embodiment, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate is used as the vinyl ether compound. By using 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, a resin composition having excellent photosensitivity can be obtained.

The reaction temperature during the addition step is preferably 0 ° C. to 150 ° C., more preferably 20 ° C. to 100 ° C. The polymerization time is preferably 1 minute to 100 hours, more preferably 0.1 to 30 hours.

Any suitable method can be adopted as a method for adding the vinyl ether compound to the acid group-containing polymer. The acid group polymer and the vinyl ether compound may be charged in a batch at the initial stage of the reaction, or either or both may be continuously or intermittently added to the reaction system. In the above addition reaction, the reaction can be carried out without a catalyst, but a catalyst can also be used in combination. Examples of the catalyst that can be used in the present invention include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, trichloroacetic acid, dichloroacetic acid, pyruvate, and glycolic acid; oxalic acid, maleic acid, and oxaloacetate. , Malonic acid, fumaric acid, tartaric acid, citric acid and other aliphatic polyvalent carboxylic acids; benzoic acid, terephthalic acid and other aromatic carboxylic acids; benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium salt, Aromatic sulfonic acid such as p-toluene sulfonic acid quinolinium salt or a salt thereof; sulfate such as sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, nickel sulfate, copper sulfate, zirconium sulfate; sodium hydrogen sulfate, potassium hydrogen sulfate, etc. Hydrogen sulfate; mineral acids such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, polyphosphoric acid; heteropolyacids such as limvanadido molybdic acid, lintangsto molybdic acid, keitangsto molybdic acid; acidic zeolite The base resin is a phenolic resin or a styrene resin, exhibits either a gel type, a porous type, or a macroporous type, and is at least one selected from the group consisting of a sulfonic acid group and an alkyl sulfonic acid group. Examples thereof include an acidic ion exchange resin having an ion exchange group. These may be used alone or in combination of two or more. The amount of the catalyst used can be any appropriate amount depending on the type of the acid group-containing polymer and the vinyl ether compound.

A-2-3. Dehydration treatment In one embodiment, a dehydration treatment is performed after the acid group-containing polymer is polymerized and before the addition of the vinyl ether compound. In the dehydration treatment, water (for example, water contained in the raw material and remaining in the composition, water existing due to moisture absorption in the polymerization step, etc.) is added from the reaction system from the acid group-containing polymer composition obtained by the above polymerization. It is a process to eliminate. As the dehydration treatment, a method using an azeotropic solvent can be adopted.

The amount of the azeotropic solvent added is preferably 10 parts by weight to 500 parts by weight, more preferably 20 parts by weight to 400 parts by weight, and further preferably 30 parts by weight with respect to 100 parts by weight of the acid group-containing polymer. Parts to 300 parts by weight.

The boiling point of the azeotropic solvent is preferably 150 ° C. or lower, more preferably 60 ° C. to 90 ° C.

Examples of the azeotropic solvent include cyclohexane, methyl ethyl ketone, tetrahydrofuran, 1,2-dimethoxyethane, ethyl acetate, diisopropyl ether, acetonitrile, dioxane, benzene, hexane, heptane and the like.

In one embodiment, a hydrophobic solvent is used as the azeotropic solvent. Examples of the hydrophobic solvent include cyclohexane, 1,2-dimethoxyethane, diisopropyl ether, heptane and the like. In the present specification, the hydrophobic solvent means a solvent having an SP value of less than 8.5 (cal / cm ³ ) ^1/2 . The SP value is a solubility parameter calculated by Small's formula.

In one embodiment, a mixed solvent of a hydrophilic solvent and a hydrophobic solvent is used as the azeotropic solvent. By using such a mixed solvent, dehydration can be efficiently performed and white turbidity of the resin composition in the dehydration treatment can be prevented. Further, if the acid group-containing polymer obtained through the dehydration treatment using the above mixed solvent is subjected to the addition step of the next step, the addition reaction rate of the vinyl ether compound to the acid group-containing polymer is remarkably improved. be able to. As a result, it is possible to obtain a resin composition capable of forming a cured product having excellent photosensitivity and excellent developability, solvent resistance and adhesion to a base. In the present specification, the hydrophilic solvent means a solvent having an SP value of 8.5 (cal / cm ³ ) ^1/2 or more.

In the above mixed solvent, the weight ratio of the hydrophilic solvent to the hydrophobic solvent (hydrophilic solvent / hydrophobic solvent) is preferably 10/90 to 90/10, more preferably 20/80 to 80/20. , More preferably 30/70 to 70/30.

The SP value of the mixed solvent is preferably 7.5 (cal / cm ³ ) ^{1/2 to} 11.5 (cal / cm ³ ) ^1/2 , and more preferably 8.0 (cal / cm ³ ). ^{It is 1/2 to} 11.0 (cal / cm ³ ) ^1/2 , more preferably 8.5 (cal / cm ³ ) ^{1/2 to} 10.5 (cal / cm ³ ) ^1/2 . Within such a range, the addition reaction rate of the vinyl ether compound to the acid group-containing polymer can be remarkably improved. The SP value of the mixed solvent can be calculated based on the mole fraction of each solvent constituting the mixed solvent.

In the above mixed solvent, the difference between the SP value of the hydrophilic solvent and the SP value of the hydrophobic solvent is preferably 0.2 (cal / cm ³ ) ^{1/2 to} 5 (cal / cm ³ ) ^1/2 . , More preferably 0.3 (cal / cm ³ ) ^{1/2 to} 3.0 (cal / cm ³ ) ^1/2 , and even more preferably 0.4 (cal / cm ³ ) ^1/2 to 2. It is 5 (cal / cm ³ ) ^1/2 . Within such a range, the amount of the vinyl ether compound added to the acid group-containing polymer can be remarkably improved.

After the dehydration treatment, it is preferable to remove the azeotropic solvent from the reaction system.

B. Basic compound As the basic compound, any suitable basic compound can be used as long as the effects of the present invention can be obtained. Preferably, as the basic compound, a compound having a tertiary amine group or a nitroxy radical is used.

Examples of the basic compound having a tertiary amine group include N, N-dimethylbenzylamine, trimethylamine, triethylamine, tributylamine, N, N-dimethylethylamine, N, N-diethylmethylamine and N-butyldimethylamine. , N, N-diisopropylethylamine, N, N-dimethylisopropylamine, N, N, N', N'-tetramethylethylenediamine, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylallylamine , Trisdimethylaminomethane, 1,1,4,7,10,10-hexamethyltriethylenetetramine, N, N, N ″, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, Examples thereof include N', -tetramethyl-1,3-diaminopropane, tetramethylurea and pyridine. Of these, N, N-dimethylbenzylamine, triethylamine, pyridine, N, N-diisopropylethylamine, N, N, N', N'-tetramethylethylenediamine, N, N-dimethylformamide, N, N-dimethyl are preferable. It is acetamide.

Examples of the basic compound having a nitroxy radical include 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidin 1-oxyl and 4-cyano. -2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxylbenzoate, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-oxo-2 , 2,6,6-tetramethylpiperidin1-oxyl, 2,2,6,6-tetramethyl4- (2-propiniroxy) piperidin1-oxyl and the like. Of these, 2,2,6,6-tetramethylpiperidin1-oxyl is preferable.

The content ratio of the basic compound is 0.01 part by weight or more with respect to 100 parts by weight of the alkali-soluble resin in the resin composition. Within such a range, a resin composition can be obtained in which the acid value is unlikely to increase and the molecular weight of the alkali-soluble resin is unlikely to decrease even with time. The content ratio of the basic compound is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, still more preferably 0, based on 100 parts by weight of the alkali-soluble resin in the resin composition. .2 parts by weight or more. The upper limit of the content ratio of the basic compound is preferably 10 parts by weight or less, more preferably 8 parts by weight or less, based on 100 parts by weight of the alkali-soluble resin in the resin composition. Within such a range, a resin composition capable of forming a cured product having excellent developability and adhesion to a substrate can be obtained.

C. Polyfunctional Monomer In one embodiment, the resin composition comprises a polyfunctional monomer.

Examples of the polyfunctional monomer include polyfunctional aromatic vinyl-based monomers such as divinylbenzene, diallythritolate, and diallythritol phosphonate; (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and trimethyl propanedi. (Meta) acrylate, trimethritol propanthritol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol Tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol di (meth) acrylate, tripentaerythritol tri (meth) acrylate , Tryentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tris (hydroxyethyl) ) Polyfunctional (meth) acrylates such as tri (meth) acrylate of isocyanurate; polyfunctional monomers obtained by modifying these monomers with caprolactone or alkylene oxide. Of these, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, Tri (meth) acrylate of tris (hydroxyethyl) isocyanurate is preferable. When these polyfunctional monomers are used, a cured product having a high crosslink density can be obtained because the number of functional groups is large.

The content ratio of the polyfunctional monomer is preferably 5 parts by weight to 200 parts by weight, more preferably 10 parts by weight to 150 parts by weight, and further, with respect to 100 parts by weight of the alkali-soluble resin in the resin composition. It is preferably 30 parts by weight to 120 parts by weight, and particularly preferably 35 parts by weight to 100 parts by weight.

D. Photopolymerization Initiator The resin composition of the present invention may contain any suitable photopolymerization initiator. Examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether and benzoin ethyl ether and their alkyl ethers; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone. Anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butyl anthraquinone and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; benzophenone and other benzophenones; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one, 2-benzyl-2-dimethyl Α-Aminoketones such as amino-1- (4-morpholinophenyl) -butanone-1; 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl}- Α-Hydroxyketones such as 2-methyl-propane-1-one; acylphosphine oxides, xanthones and the like can be mentioned. These photopolymerization initiators may be used alone or in combination of two or more.

The content ratio of the photopolymerization initiator is preferably 0.1 parts by weight to 50 parts by weight, more preferably 0.5 parts by weight, based on 100 parts by weight of the total weight of the alkali-soluble resin and the polyfunctional monomer. ~ 30 parts by weight.

Further, a photopolymerization initiator may be used in combination with the photopolymerization initiator. A plurality of combinations of photopolymerization initiators can also be used. Specific examples of the photopolymerization initiator include 1,3,5-tris (3-mercaptopropionyloxyethyl) -isocyanurate and 1,3,5-tris (3-mercaptobutyloxyethyl) -isocyanurate (Showa). Trifunctional thiol compounds such as Karenz MT (registered trademark) NR1) and trimethylol propanthris (3-mercaptopropionate) manufactured by Denkosha; pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto). Butyrate) (manufactured by Showa Denko Co., Ltd., Karenz MT (registered trademark) PE1) and other tetrafunctional thiol compounds;

E. Solvents The resin compositions of the present invention may contain any suitable solvent. Examples of the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 3-methoxy. Esters such as butyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, ethylbenzene; chloroform, dimethyl sulfoxide, etc. Can be mentioned. The amount of solvent can be set to any suitable amount depending on the desired viscosity of the resin composition.

F. Additives The resin compositions of the present invention may optionally contain any suitable additive. Additives include, for example, fillers such as aluminum hydroxide, talc, clay, barium sulfate, dyes, pigments, defoaming agents, coupling agents, leveling agents, sensitizers, mold release agents, lubricants, plasticizers, etc. Antioxidants, UV absorbers, flame retardants, polymerization inhibitors, thickeners, dispersants, organic fine particles, inorganic fine particles (zinc oxide, silicon oxide, talconia, titanium), porous fine particles such as silica, Examples include hollow fine particles such as silica. In one embodiment, the resin composition of the present invention comprises a UV absorber.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. The evaluation method in the examples is as follows.

(1) Acid Value A mixed solution is prepared by mixing 1.5 g of a copolymer solution containing the alkali-soluble resin obtained in Examples and Comparative Examples, 90 g of acetone, and 10 g of water, and the mixed solution is 0. The acid value of the solution was measured by titrating with a 1 N aqueous solution of KOH. Titration was performed using an automatic titration device (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.). Moreover, the solid acid value per 1 g of the polymer was determined from the solid content concentration of the copolymer solution (mgKOH / g).
(2) Weight average molecular weight: Mw
It was measured by GPC (trade name: HLC-8220 GPC, manufactured by Tosoh Corporation) using tetrahydrofuran (THF) as an eluent and TSKgel SuperHZM-N (manufactured by Tosoh Corporation) on the column, and calculated in terms of standard polystyrene.

[Manufacturing Example 1]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 10 parts by weight of N-benzylmaleimide (BzMI), 40 parts by weight of acrylic acid (AA) and 50 parts by weight of cyclohexyl acrylate (CHA) were charged into the monomer dropping tank as the monomer composition. Further, in the monomer dropping tank, 2 parts by weight of t-butylperoxy-2-ethylhexanoate (trade name: Perbutyl (registered trademark) O, manufactured by Nippon Yushi Co., Ltd., hereinafter also referred to as PBO), propylene glycol monomethyl ether. 7 parts by weight of acetate (PGMEA) and 3 parts by weight of diethylene glycol ethyl methyl ether (EMDG) were added and mixed by stirring. Further, 4 parts by weight of n-dodecyl mercaptan (n-DM) as a chain transfer agent solution, 20 parts by weight of PGMEA and 8 parts by weight of EMDG were put into the chain transfer agent dropping tank and mixed by stirring.
103 parts by weight of PGMEA and 44 parts by weight of EMDG were charged into the reaction vessel, and after nitrogen substitution, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring.
After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. After aging at 90 ° C. for 30 minutes, 0.5 parts by weight of PBO was added. After another 30 minutes, the temperature of the tank was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 0.3 parts by weight of Antage W-400 (manufactured by Kawaguchi Chemical Industry Co., Ltd.) and 78 parts by weight of 2- (vinyloxyethoxy) ethyl acrylate (VEEA: manufactured by Nippon Shokubai Co., Ltd.) were charged into the reaction vessel as a polymerization inhibitor. , 40 ° C. for 3 hours to obtain a copolymer solution I containing an alkali-soluble resin.
The solution acid value of the copolymer solution I was 21.8 mgKOH / g, and the solid content concentration was 49.1% by weight. The solid acid value of the alkali-soluble resin was 42.8 mgKOH / g, and the weight average molecular weight was 10816.

[Manufacturing Example 2]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 10 parts by weight of N-benzylmaleimide (BzMI), 40 parts by weight of methacrylic acid (MAA) and 50 parts by weight of benzylmethacrylate (BzMA) were charged into the monomer dropping tank as the monomer composition. Further, in the monomer dropping tank, 2 parts by weight of t-butylperoxy-2-ethylhexanoate (trade name: Perbutyl (registered trademark) O, manufactured by Nippon Yushi Co., Ltd., hereinafter also referred to as PBO), diethylene glycol ethylmethyl ether 10 parts by weight of (EMDG) was added, and the mixture was stirred and mixed. Further, 3 parts by weight of n-dodecyl mercaptan (n-DM) as a chain transfer agent solution and 29 parts by weight of EMDG were put into the chain transfer agent dropping tank and mixed by stirring.
147 parts by weight of EMDG was charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C.
After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. After aging at 90 ° C. for 30 minutes, 0.5 parts by weight of PBO was added. After another 30 minutes, the temperature of the tank was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 0.3 parts by weight of Antage W-400 (manufactured by Kawaguchi Chemical Industry Co., Ltd.) and 87 parts by weight of 2- (vinyloxyethoxy) ethyl acrylate (VEEA: manufactured by Nippon Shokubai Co., Ltd.) were charged into the reaction vessel as a polymerization inhibitor. , 40 ° C. for 3 hours to obtain a copolymer solution II containing an alkali-soluble resin.
The solution acid value of the copolymer solution II was 2.7 mgKOH / g, and the solid content concentration was 49.2% by weight. The solid acid value of the alkali-soluble resin was 5.4 mgKOH / g, and the weight average molecular weight was 14413.

[Manufacturing Example 3]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, in the monomer dropping tank, as the monomer composition, 10 parts by weight of N-benzylmaleimide (BzMI), 42.8 parts by weight of methacrylic acid (MAA), 45.2 parts by weight of benzyl methacrylate (BzMA), and methyl methacrylate ( MMA) 2 parts by weight was charged. Further, in the monomer dropping tank, 2 parts by weight of t-butylperoxy-2-ethylhexanoate (trade name: Perbutyl (registered trademark) O, manufactured by Nippon Yushi Co., Ltd., hereinafter also referred to as PBO), diethylene glycol ethylmethyl ether 10 parts by weight of (EMDG) was added, and the mixture was stirred and mixed. Further, 5 parts by weight of n-dodecyl mercaptan (n-DM) as a chain transfer agent solution and 8.5 parts by weight of EMDG were put into the chain transfer agent dropping tank and mixed by stirring.
167 parts by weight of EMDG was charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C.
After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90 ° C. After aging at 90 ° C. for 30 minutes, 0.5 parts by weight of PBO was added. After another 30 minutes, the temperature of the tank was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started.
Next, 0.2 parts by weight of Antage W-400 (manufactured by Kawaguchi Chemical Industry Co., Ltd.) and 43 parts by weight of 2- (vinyloxyethoxy) ethyl acrylate (VEEA: manufactured by Nippon Shokubai Co., Ltd.) were charged into the reaction vessel as a polymerization inhibitor. , 40 ° C. for 3 hours to obtain a copolymer solution III containing an alkali-soluble resin.
The solution acid value of the copolymer solution III was 45.6 mgKOH / g, and the solid content concentration was 41.4% by weight. The solid acid value of the alkali-soluble resin was 110 mgKOH / g, and the weight average molecular weight was 9231.

[Examples 1 to 19, Comparative Examples 1 to 6]
A resin composition was prepared by mixing copolymer solutions I to III containing an alkali-soluble resin, a solvent, a basic compound, and a polymerization inhibitor. The resin composition was stored at 40 ° C. for a predetermined period (Examples 1 to 14 and 16 to 19 and Comparative Examples 1 to 6 for 3 days and Example 15 for 1 month), and after the predetermined period had elapsed. The molecular weight and solution acid value of the alkali-soluble resin were measured. The results are shown in Table 1.
The types and amounts of the copolymer solutions, solvents, basic compounds and polymerization inhibitors used in each Example and Comparative Example are as shown in Table 1.
The abbreviations in Table 1 mean the following substances.
IPA: Isopropyl alcohol PGME: Propylene glycol monomethyl ether DMBA: N, N-dimethylbenzylamine TEA: Triethylamine DIEA: N, N-diisopropylethylamine TEMPO: 2,2,6,6-tetramethylpiperidin 1-oxyl W-400: 2,2'-Methylenebis (4-methyl-6-t-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd., trade name "Antage W-400")

As shown in Comparative Examples 1 to 5 in Table 1, the alkali-soluble resin having a structure derived from a vinyl ether compound (VEEA) shows a decrease in molecular weight and an increase in acid value with time. On the other hand, as is clear from Table 1, the resin composition of the present invention is suppressed from being deteriorated over time by adding a specific amount of the basic compound.

Claims (6)

A resin composition containing an alkali-soluble resin having a structure derived from a vinyl ether compound and a basic compound.
Content of the basic compound is, relative to 100 parts by weight of the alkali-soluble resin in the resin composition state, and are less than 0.01 part by weight,
The alkali-soluble resin has a ring structure in the main chain and has a ring structure.
The weight average molecular weight (Mw) of the alkali-soluble resin is 9231 to 300,000.
Resin composition. The resin composition according to claim 1, further comprising a photopolymerization initiator. The resin composition according to claim 1 or 2 , wherein the alkali-soluble resin has a carboxyl group. The resin composition according to any one of claims 1 to 3, wherein the vinyl ether compound is represented by the following formula (A);

In the formula (A), R ₁ represents a hydrogen atom or a methyl group, and R ₂ is a linear, branched or cyclic alkylene group having 2 to 18 carbon atoms, an alkoxyalkylene group having 2 to 20 carbon atoms, and the like. Represents an alkylene group halide having 2 to 8 carbon atoms, a polyethylene glycol skeleton excluding a terminal hydroxyl group, a polypropylene glycol skeleton excluding a terminal hydroxyl group, a polybutylene glycol skeleton excluding a terminal hydroxyl group, or an aryl group, and R ₃ is a hydrogen atom and a carbon number. It is an aromatic group having 1 to 10 linear, branched or cyclic alkyl groups, or substituents having 6 to 11 carbon atoms. The resin composition according to any one of claims 1 to 4 , wherein the vinyl ether compound is 2- (2-vinyloxyethoxy) ethyl (meth) acrylate. The resin composition according to any one of claims 1 to 5 , wherein the basic compound has a tertiary amine group or a nitroxy radical.