JP2021073366A - Resin composition and cured film - Google Patents

Abstract

To provide a resin composition capable of forming a cured film having high surface flatness.SOLUTION: The resin composition contains a resin (A) and a solvent. The resin (A) is a copolymer containing: a constituent unit (Aa) derived from an alkyl (meth)acrylate having a ≥2C alkyl group; a constituent unit (Ab) derived from an unsaturated compound having a 2-4C cyclic ether structure; and a constituent unit (Ac) derived from at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin composition and a cured film.

In recent liquid crystal display devices, a curable resin composition is used to form a cured film such as a photo spacer or an overcoat. In such a curable resin composition, a ^{copolymer obtained by polymerizing methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 2,6} ] decyl acrylate, and glycidyl acrylate and methyl methacrylate. It is known that each of the copolymers obtained by polymerizing the above is used as a binder resin (Patent Document 1).

JP-A-2010-106154

The curable resin composition usually forms a cured film by applying it to a substrate and heating it. Here, when the surface to be coated has irregularities, it is difficult to obtain a cured film having a high surface flatness. For example, when a cured film is formed by applying a curable resin composition to a substrate on which a colored pattern is formed and heating the substrate, and this is used as an overcoat, an overcoat having a high surface flatness can be obtained. Was difficult.

For example, it is predicted that the flatness of the surface can be improved by thickening the overcoat, but considering other characteristics of the object on which the overcoat is formed, the thickness of the overcoat is as an overcoat. There is an aspect that the thinner it is, the more preferable it is in the range in which the function of

An object of the present invention is to provide a resin composition capable of forming a cured film having a high surface flatness, and a cured film formed from the resin composition.

The present invention includes the following inventions.
[1] Contains resin (A) and solvent,
The resin (A) is derived from a structural unit (Aa) derived from a (meth) acrylic acid alkyl ester having an alkyl group having 2 or more carbon atoms and an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms. A resin composition which is a copolymer containing a structural unit (Ab) and a structural unit (Ac) derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. ..

[2] The resin composition according to [1], wherein the ratio of the constituent units (Aa) of the resin (A) is 10 mol% or more with respect to the total of the constituent units constituting the resin (A).
[3] The resin (A) according to [1] or [2], wherein the ratio of the constituent units (Aa) is 10 to 35 mol% with respect to the total of the constituent units constituting the resin (A). Resin Composition [4] The resin (A) is a resin comprising a constituent unit (Aa), a constituent unit (Ab), and a constituent unit (Ac). The resin according to any one of [1] to [3]. Composition.
[5] The resin composition according to any one of [1] to [4], wherein the resin (A) is a copolymer having a weight average molecular weight of 5000 to 20000.
[6] The resin composition according to any one of [1] to [5], wherein the alkyl group in the structural unit (Aa) has 2 to 10 carbon atoms.
[7] The resin composition according to [6], wherein the alkyl group is a linear alkyl group having 2 to 10 carbon atoms.
[8] The resin composition according to [7], wherein the alkyl group is a linear alkyl group having 2 to 6 carbon atoms.

[9] A cured film formed from the resin composition according to any one of [1] to [8].

According to the present invention, it is possible to provide a resin composition capable of forming a cured film having a high surface flatness.

It is a figure which shows the profile of the cross-sectional shape (cross-sectional shape of a coloring pattern, the cross-sectional shape of a cured film and the evaluation substrate) of the evaluation sample of Example 1. It is a figure which shows the profile of the cross-sectional shape (cross-sectional shape of a coloring pattern, the cross-sectional shape of a cured film and the evaluation substrate) of the evaluation sample of Example 2. It is a figure which shows the profile of the cross-sectional shape (cross-sectional shape of a colored pattern, the cross-sectional shape of a cured film and the evaluation substrate) of the evaluation sample of Comparative Example 1. It is a figure which shows the profile of the cross-sectional shape (cross-sectional shape of a colored pattern, the cross-sectional shape of a cured film and the evaluation substrate) of the evaluation sample of Comparative Example 2.

In the present specification, the compounds exemplified as each component may be used alone or in combination of a plurality of types unless otherwise specified.

The resin composition of the present invention contains a resin (A) and a solvent (E), and the resin (A) is a (meth) acrylic acid alkyl ester (Aa) having an alkyl group having 2 or more carbon atoms (hereinafter, "(). A structural unit derived from (sometimes referred to as "Aa)" (hereinafter, sometimes referred to as "constituent unit (Aa)") and an unsaturated compound (Ab) having a cyclic ether structure having 2 to 4 carbon atoms (hereinafter, referred to as "Aa") At least selected from the group consisting of a structural unit derived from (sometimes referred to as "(Ab)") (hereinafter, sometimes referred to as "constituent unit (Ab)") and an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. It is a copolymer containing a structural unit (hereinafter, may be referred to as "constituent unit (Ac)") derived from one compound (Ac) (hereinafter, may be referred to as "(Ac)"). In addition, in this specification, "(meth) acrylic acid" represents at least one compound selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.

Further, the resin composition of the present invention comprises at least one compound selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin (hereinafter, may be referred to as "epoxy resin (C)") and reactivity. It preferably contains at least one component selected from the group consisting of the monomer (B), the antioxidant (F), and the surfactant (H). Examples of the reactive monomer (B) include a compound having a (meth) acryloyl group (hereinafter, may be referred to as “(meth) acrylic compound (B1)”), a compound (B2) represented by the formula (1), and the like. included.

[In the formula (1), R ^{1 to} R ³ represent a group represented by the formula (a) or a group represented by the formula (b) independently of each other, except that at least 1 of ^{R 1 to} R ^{3 is represented.} Represents a group represented by the formula (b). ]

［式（ａ）及び式（ｂ）中、Ｒ^４及びＲ^５は、互いに独立に、水素原子又は炭素数１〜８のアルキル基を表す。］

[In formulas (a) and (b), R ⁴ and R ⁵ represent hydrogen atoms or alkyl groups having 1 to 8 carbon atoms independently of each other. ]

Further, the resin composition of the present invention is at least one selected from the group consisting of a polymerization initiator (D), a polymerization initiator (D1), a thiol compound (T), a polyvalent carboxylic acid anhydride and a polyvalent carboxylic acid. It may contain at least one component selected from the group consisting of a species compound (hereinafter sometimes referred to as "polyvalent carboxylic acid (G)") and an imidazole compound (J).

<Resin (A)>
The resin (A) is a curable resin, preferably a thermosetting resin, more preferably a resin that cures with heat of 60 ° C. or higher, and has an alkyl group having 2 or more carbon atoms ((A). An unsaturated compound (Ab) having a structural unit derived from a meta) acrylic acid alkyl ester (Aa) (hereinafter, may be abbreviated as compound (Aa)) and a cyclic ether structure having 2 to 4 carbon atoms (hereinafter, referred to as compound (Aa)). A structural unit derived from the compound (Ab)), and a structural unit derived from at least one compound (Ac) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. It is a copolymer containing. The copolymer is further copolymerizable with compound (Aa), compound (Ab) or compound (Ac), and is a compound (Ad) other than compound (Aa), compound (Ab) and compound (Ac). ) May have a structural unit derived from).

(1) Structural Unit Derived from Compound (Aa) In the present invention, the resin (A) contains a structural unit derived from a (meth) acrylic acid alkyl ester (Aa) having an alkyl group having 2 or more carbon atoms. By being a polymer, the flatness of the film obtained by applying the resin composition can be improved.

Examples of the (meth) acrylic acid alkyl ester (Aa) having an alkyl group having 2 or more carbon atoms include ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth). Meta) acrylate, dodecyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl Examples include (meth) acrylate. Since peeling of the film obtained by applying the resin composition on the substrate under high temperature and high humidity can be suppressed, the number of carbon atoms of the alkyl group of the (meth) acrylic acid alkyl ester (Aa) is preferably set. It is 10 or less, more preferably 8 or less, still more preferably 6 or less. The alkyl group of the (meth) acrylic acid alkyl ester (Aa) may be linear or branched, but is preferably linear.

(2) Constituent Unit Derived from Compound (Ab) Compound (Ab) is, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring). Refers to an unsaturated compound having. The compound (Ab) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

Examples of the compound (Ab) include a compound (Ab1) having an oxylanyl group and an ethylenically unsaturated bond (hereinafter, may be referred to as “(Ab1)”), and a compound having an oxetanyl group and an ethylenically unsaturated bond. Examples thereof include (Ab2) (hereinafter, may be referred to as “(Ab2)”) and a compound (Ab3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter, may be referred to as “(Ab3)”).

(Ab1) may be, for example, a compound (Ab1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter, may be referred to as “(Ab1-1)”). ), And a compound (Ab1-2) in which an unsaturated alicyclic hydrocarbon has an epoxidized structure (hereinafter, may be referred to as “(Ab1-2)”).

Examples of (Ab1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p. -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene , 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene , 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (Glysidyloxymethyl) styrene and the like can be mentioned.

Examples of (Ab1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, celloxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), and 3,4-epoxycyclohexylmethyl (meth) acrylate. For example, Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd., 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industry Co., Ltd.), represented by the formula (I). Examples thereof include a compound and a compound represented by the formula (II).

[In formulas (I) and (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. You may.
X ^b1 and ^{X b2} represents a single ^{bond, -R b3 -, * - R} b3 -O -, * - R b3 -S- or ^* -R b3 represents a -NH-.
R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms. * Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like. Alkyl groups in which the hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxy. Examples thereof include -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.
^Examples of R b1 and R ^b2 include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

The alkanediyl group includes a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-. Examples include 1,6-diyl group.
The X ^b1 and ^{X b2,} preferably a single bond, a methylene group, an ethylene _{group, * - CH 2 -O -,} * - CH 2 CH 2 -O- and the like, more preferably a single bond, * - CH ₂ CH _2- O- can be mentioned. * Represents a bond with O.

Examples of the compound represented by the formula (I) include compounds represented by any of the formulas (I-1) to (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15). The compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the compound represented by the formula (I-15) is more preferable.

Examples of the compound represented by the formula (II) include compounds represented by any of the formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15). The compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the compound represented by the formula (II-15) is more preferable.

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or mixed in an arbitrary ratio. When used in combination, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is based on a molar basis, preferably 5:95 to 95: 5, and more preferably 10:90 to. It is 90:10, more preferably 20:80 to 80:20. For example, a mixture containing a compound represented by the formula (I-1) and a compound represented by the formula (II-1) at a ratio of 50:50 (commercially available, trade name "E-DCPA" (Co., Ltd.) (Made by Daicel) is available).

As (Ab2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (Ab2) include 3-methyl-3-methacrylloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 3-ethyl-3-acryloyloxymethyloxetane. , 3-Methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane and the like.

As (Ab3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is preferable. Examples of (Ab3) include tetrahydrofurfuryl acrylate (for example, Viscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.

The compound (Ab) is preferably (Ab1) in that the reliability of the obtained cured film such as heat resistance and chemical resistance can be further increased. Further, (Ab1-2) is more preferable in that the storage stability of the resin composition is excellent.

(3) Structural Unit Derived from Compound (Ac) As at least one compound (Ac) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, for example, acrylic acid, methacrylic acid, and crotonic acid. , O-, m-, p-vinylbenzoic acid and other unsaturated monocarboxylic acids;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexendicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] Bicyclounsaturated compounds containing a carboxy group such as hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride; monosuccinate [2-( Meta) acryloyloxyethyl], mono [2- (meth) acryloyloxyethyl] and other unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylate.

Of these, (meth) acrylic acid, maleic anhydride and the like are preferable, and (meth) acrylic acid is more preferable, in terms of copolymerization reactivity and solubility in an alkaline aqueous solution.

(4) Structural Unit Derived from Compound (Ad) Examples of the compound (Ad) include methyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (In the technical field, it is commonly referred to as "dicyclopentanyl (meth) acrylate".
In addition, it may be referred to as "tricyclodecyl (meth) acrylate". ), Tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (in the art, it is commonly referred to as "dicyclopentenyl (meth) acrylate"), di. Cyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) (Meta) acrylic acid esters such as acrylates;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2] .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] Hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2. 1] Hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy -5-Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2] .2.1] Hept-2-ene, 5-
tert-Butyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept -2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept- Bicyclounsaturated compounds such as 2-ene;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3 -Butadiene, isoprene and 2,3-dimethyl-1,3-butadiene and the like can be mentioned.

Of these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferable from the viewpoint of copolymerization reactivity and heat resistance. ..

(5) Ratio of each structural unit The resin (A) is the following resin [K1] or [K2].
Resin [K1]: Compound (Aa), compound (Ab) and copolymer of compound (Ac);
Resin [K2]: A copolymer of compound (Aa), compound (Ab), compound (Ac) and compound (Ad).

In the resin [K1], the ratio of each structural unit is relative to all the structural units constituting the resin [K1].
Constituent units derived from compound (Aa); 5-40 mol%,
Constituent units derived from compound (Ab); 5-90 mol%,
Constituent units derived from compound (Ac); preferably 5-40 mol%.
Constituent units derived from compound (Aa); 10-35 mol%,
Constituent units derived from compound (Ab); 10-80 mol%,
The structural unit derived from the compound (Ac); more preferably 10 to 35 mol%.

When the ratio of the structural units constituting the resin [K1] is within the above range, the resin composition tends to be excellent in storage stability, chemical resistance of the obtained cured film, heat resistance and mechanical strength.

The resin [K1] is, for example, the method described in the document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, Publisher: Kagaku Dojin Co., Ltd., 1st Edition, 1st Print, published on March 1, 1972). It can be manufactured with reference to the cited references described in the literature.

Specifically, a predetermined amount of compound (Aa), compound (Ab) and compound (Ac), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and oxygen is deoxidized by, for example, substituting oxygen with nitrogen. Examples thereof include a method of heating and keeping warm while creating an atmosphere and stirring. The polymerization initiator, solvent, and the like used here are not particularly limited, and those usually used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). The solvent may be any solvent that dissolves each monomer, and examples thereof include the solvents described below used in the resin composition.

As the resin obtained by the above method, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or the resin is taken out as a solid (powder) by a method such as reprecipitation. You may use the one. In particular, by using the solvent used in the resin composition of the present invention as the polymerization solvent, the solution after the reaction can be used as it is in the production of the resin composition, which simplifies the production process of the resin composition. be able to.

In the resin [K2], the ratio of each structural unit is a structural unit derived from the compound (Aa) in all the structural units constituting the resin [K2]; 5 to 40 mol%,
Constituent units derived from compound (Ab); 5-90 mol%,
Constituent units derived from compound (Ac); 5-40 mol%,
Constituent units derived from compound (Ad); preferably 1-40 mol%.
Constituent units derived from compound (Aa); 10-35 mol%,
Constituent units derived from compound (Ab); 10-80 mol%,
Constituent units derived from compound (Ac); 10-35 mol%,
A structural unit derived from compound (Ad); more preferably 5 to 35 mol%.

When the ratio of the constituent units of the resin [K2] is within the above range, the resin composition tends to be excellent in storage stability, chemical resistance of the obtained cured film, heat resistance and mechanical strength. The resin [K2] can be produced by the same method as the resin [K1].

Specific examples of the resin [K1] include ethyl (meth) acrylate / formula (I-1) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (I-2) / (meth) acrylic. Acid copolymer, ethyl (meth) acrylate / formula (I-3) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (I-4) / (meth) acrylic acid copolymer Combined, ethyl (meth) acrylate / copolymer of formula (I-5) / (meth) acrylic acid, ethyl (meth) acrylate / copolymer of formula (I-6) / (meth) acrylic acid, ethyl ( Meta) acrylate / formula (I-7) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (I-8) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / Copolymer of formula (I-9) / (meth) acrylic acid, ethyl (meth) acrylate / copolymer of formula (I-10) / (meth) acrylic acid, ethyl (meth) acrylate / formula (I-) 11) / (Meta) acrylic acid copolymer, ethyl (meth) acrylate / formula (I-12) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (I-13) / ( Copolymer of meta) acrylic acid, ethyl (meth) acrylate / copolymer of formula (I-14) / (meth) acrylic acid, ethyl (meth) acrylate / formula (I-15) / (meth) acrylic acid Copolymer, ethyl (meth) acrylate / formula (II-1) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (II-2) / (meth) acrylic acid copolymer , Ethyl (meth) acrylate / formula (II-3) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (II-4) / (meth) acrylic acid copolymer, ethyl (meth) ) Acrylate / formula (II-5) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (II-6) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (II-7) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (II-8) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (II-9) ) / (Meta) acrylic acid copolymer, ethyl (meth) acrylate / formula (II-10) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (II-11) / (meth) ) Acrylate copolymer, ethyl (meth) acrylate / formula (II-12) / (meth) acrylic A copolymer of acid, a copolymer of ethyl (meth) acrylate / formula (II-13) / (meth) acrylic acid, a copolymer of ethyl (meth) acrylate / formula (II-14) / (meth) acrylic acid Polymer, ethyl (meth) acrylate / formula (II-15) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (I-1) / formula (II-1) / (meth) acrylic Acid copolymer, butyl (meth) acrylate / formula (I-1) / (meth) acrylic acid copolymer, butyl (meth) acrylate / formula (II-1) / (meth) acrylic acid copolymer Combined, butyl (meth) acrylate / formula (I-1) / formula (II-2) / (meth) acrylic acid copolymer, butyl (meth) acrylate / formula (I-1) / crotonic acid co-weight Combined, butyl (meth) acrylate / formula (I-1) / maleic acid copolymer, butyl (meth) acrylate / formula (I-1) / (meth) acrylic acid / maleic acid anhydride copolymer, Ethyl (meth) acrylate / butyl (meth) acrylate / copolymer of formula (I-1) / (meth) acrylic acid, butyl (meth) acrylate / copolymer of formula (II-1) / crotonic acid, butyl (Meta) acrylate / formula (II-1) / maleic acid copolymer, butyl (meth) acrylate / formula (II-1) / (meth) acrylic acid / maleic acid anhydride copolymer, propyl (meth) ) Acrylate / formula (I-1) / (meth) acrylic acid copolymer, propyl (meth) acrylate / formula (II-1) / (meth) acrylic acid copolymer, propyl (meth) acrylate / formula (I-1) / formula (II-2) / (meth) acrylic acid copolymer, propyl (meth) acrylate / formula (I-1) / crotonic acid copolymer, propyl (meth) acrylate / formula (I-1) / maleic acid copolymer, propyl (meth) acrylate / formula (I-1) / (meth) acrylic acid / maleic acid anhydride copolymer, ethyl (meth) acrylate / propyl (meth) ) Acrylate / formula (I-1) / (meth) acrylic acid copolymer, propyl (meth) acrylate / formula (II-1) / crotonic acid copolymer, propyl (meth) acrylate / formula (II-) 1) / Maleic acid copolymer, propyl (meth) acrylate / formula (II-1) / (meth) acrylic acid / maleic acid anhydride copolymer, hexyl (meth) acrylate / formula (I-1) / (Meta) acrylic acid copolymer, hexyl (meth) acrylic Rate / formula (II-1) / (meth) acrylic acid copolymer, hexyl (meth) acrylate / formula (I-1) / formula (II-2) / (meth) acrylic acid copolymer, hexyl (Meta) acrylate / formula (I-1) / crotonic acid copolymer, hexyl (meth) acrylate / formula (I-1) / maleic acid copolymer, hexyl (meth) acrylate / formula (I-1) ) / (Meta) acrylic acid / maleic anhydride copolymer, hexyl (meth) acrylate / butyl (meth) acrylate / formula (I-1) / (meth) acrylic acid copolymer, hexyl (meth) Acrylate / formula (II-1) / crotonic acid copolymer, hexyl (meth) acrylate / formula (II-1) / maleic acid copolymer, hexyl (meth) acrylate / formula (II-1) / ( Copolymer of meta) acrylic acid / maleic acid anhydride, 2-ethylhexyl (meth) acrylate / copolymer of formula (I-1) / (meth) acrylic acid, 2-ethylhexyl (meth) acrylate / formula (II) -1) / (Meta) acrylic acid copolymer, 2-ethylhexyl (meth) acrylate / formula (I-1) / formula (II-2) / (meth) acrylic acid copolymer, 2-ethylhexyl (2-1) Meta) acrylate / formula (I-1) / crotonic acid copolymer, 2-ethylhexyl (meth) acrylate / formula (I-1) / maleic acid copolymer, 2-ethylhexyl (meth) acrylate / formula ( Copolymer of I-1) / (meth) acrylic acid / maleic acid anhydride, copolymer of 2-ethylhexyl (meth) acrylate / butyl (meth) acrylate / formula (I-1) / (meth) acrylic acid , 2-Ethylhexyl (meth) acrylate / formula (II-1) / crotonic acid copolymer, 2-ethylhexyl (meth) acrylate / formula (II-1) / maleic acid copolymer, 2-ethylhexyl (meth) ) Acrylate / formula (II-1) / (meth) acrylic acid / maleic acid anhydride copolymer and the like.

Examples of the resin [K2] include those in which the above-exemplified resin [K1] further contains a structural unit derived from the compound (Ad).

The polystyrene-equivalent weight average molecular weight (Mw) of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 20,000, and particularly preferably 5,000 to 10,000. When the weight average molecular weight (Mw) of the resin (A) is within the above range, the coatability of the resin composition tends to be good.
The dispersity [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the degree of dispersion is within the above range, the obtained cured film tends to have excellent chemical resistance.

The acid value of the resin (A) is preferably 30 mg-KOH / g or more and 180 mg-KOH / g or less, more preferably 40 mg-KOH / g or more and 150 mg-KOH / g or less, and further preferably 50 mg-KOH / g or more and 135 mg. -KOH / g or less. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined by titrating with an aqueous potassium hydroxide solution. When the acid value of the resin (A) is within the above range, the obtained cured film tends to have excellent adhesion to the substrate.

The ratio of the constituent unit (Aa) of the resin (A) is preferably 10 mol% or more, more preferably 10 to 35 mol%, based on the total amount of the constituent units constituting the resin (A). Some copolymers are mentioned. The resin (A) may be a resin [K1] or a resin [K2], but the resin [K1] is composed of a constituent unit (Aa), a constituent unit (Ab), and a constituent unit (Ac). ] Is preferable. The resin (A) preferably includes a copolymer having an alkyl group having 2 to 10 carbon atoms in the structural unit (Aa), and more preferably a linear alkyl group having 2 to 10 carbon atoms as the alkyl group. , And more preferably, a copolymer in which the alkyl group is a linear alkyl group having 2 to 6 carbon atoms.
The content of the resin (A) is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, and further preferably 40 to 70% by mass with respect to the solid content of the resin composition of the present invention. When the content of the resin (A) is within the above range, the obtained cured film tends to have excellent heat resistance, adhesion to the substrate, and chemical resistance. Here, the solid content of the resin composition means an amount obtained by subtracting the content of the solvent (E) from the total amount of the resin composition of the present invention.

<Reactive monomer (B)>
The reactive monomer (B) is a monomer that reacts by the action of heat or the polymerization initiator (D), and examples of the monomer include a compound having an ethylenically unsaturated bond, and a (meth) acrylic compound is preferable. (B1) is mentioned, and more preferably, a compound having at least one group selected from the group consisting of an acrylic group and a methacryloyl group can be mentioned.

Examples of the (meth) acrylic compound having one (meth) acryloyl group include (meth) acrylic acid alkyl ester, (meth) acrylic acid phenoxylated polyethylene glycol ester, (meth) acrylic acid alkoxylated polyethylene glycol ester, and isobornyl. (Meta) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc. Can be mentioned.

Examples of the (meth) acrylic compound having two (meth) acryloyl groups include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,6-hexanediol di (meth). Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, bisphenol A bis (acryloyloxyethyl) ether, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, 3-methylpentanediol di ( Meta) Acrylate and the like can be mentioned.

Examples of the (meth) acrylic compound having three or more (meth) acryloyl groups include trimethylpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and the like. Trimethylol ethoxylated propantri (meth) acrylate, propoxylated trimethylol propanthry (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripenta Elythritol tetra (meth) acrylate, tripenta erythritol penta (meth) acrylate, tripenta erythritol hexa (meth) acrylate, tripenta erythritol hepta (meth) acrylate, tripenta erythritol octa (meth) acrylate, pentaerythritol tri (meth) acrylate Reaction product of and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, reaction product of tripentaerythritol hepta (meth) acrylate and acid anhydride, caprolactone-modified trimethylpropantri ( Meta) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) Acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripenta Erislitol hepta (meth) acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride reaction product, caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride Reaction with caprolactone-modified tripentaerythritol hepta (meth) acrylate and acid anhydride Things etc. can be mentioned.

As the (meth) acrylic compound (B1), a (meth) acrylic compound having three or more (meth) acrylic loyl groups is preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.

When the resin composition of the present invention contains the (meth) acrylic compound (B1), the content thereof is preferably 20 to 100 parts by mass, more preferably 25 parts by mass with respect to 100 parts by mass of the content of the resin (A). ~ 70 parts by mass. When the content of the (meth) acrylic compound (B1) is within the above range, the chemical resistance and mechanical strength of the obtained cured film can be improved.

As a preferable example of the reactive monomer (B), a compound represented by the formula (1) (hereinafter, the compound may be abbreviated as "compound (B2)"" can be mentioned.

[In the formula (1), R ^{1 to} R ³ represent a group represented by the formula (a) or a group represented by the formula (b) independently of each other, and at least one of ^{R 1 to} R ^{3 is} Represents a group represented by the formula (b). ]

［式（ａ）及び式（ｂ）中、Ｒ^４及びＲ^５は、互いに独立に、水素原子又は炭素数１〜８のアルキル基を表す。］

[In formulas (a) and (b), R ⁴ and R ⁵ represent hydrogen atoms or alkyl groups having 1 to 8 carbon atoms independently of each other. ]

Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, an octyl group and the like.
The R ^4, preferably include a hydrogen atom or a methyl group, or more preferably a hydrogen atom.
The R ^5, a hydrogen atom or a methyl group is preferable.

It is preferable that at least one of R ^{1 to} R ³ is a group represented by the formula (a).

Examples of the compound (B2) include compounds represented by formulas (1-1) to (1-6), and preferably compounds represented by formulas (1-1) to (1-4). Compounds include.

When the resin composition of the present invention contains the compound (B2), the content thereof is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the content of the resin (A). Is. When the content of the compound (B2) is within the above range, the heat resistance of the obtained cured film can be improved.

<Epoxy resin (C)>
The epoxy resin (C) has an oxylanyl group (however, it is different from the resin (A) and the reactive monomer (B)). Examples of the epoxy resin (C) include a glycidyl ether type epoxy resin and a glycidyl ester type epoxy. Included are at least one compound selected from the group consisting of resins.

The glycidyl ether type epoxy resin is an epoxy resin having a glycidyl ether structure, and can be synthesized by reacting phenols, polyhydric alcohols and the like with epichlorohydrin. Examples of the glycidyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, and trishydroxyphenylmethane type epoxy resin. Be done.

The glycidyl ester type epoxy resin is an epoxy resin having a glycidyl ester structure, and is synthesized by reacting a carbonyl group such as a phthalic acid derivative or a fatty acid with epichlorohydrin. Examples of the glycidyl ester type epoxy resin include glycidyl ester type epoxy resins derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid and terephthalic acid.

The epoxy resin (C) is preferably a glycidyl ether type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, and polyphenol type epoxy resin. Of these, bisphenol A type epoxy resin is particularly preferable.

The glycidyl ether type epoxy resin as described above can be synthesized by condensing the corresponding phenols and epichlorohydrin in the presence of a strong alkali using a conventionally known method. Such a reaction can be carried out by a method conventionally known to those skilled in the art.
A commercially available product may be used as the glycidyl ether type epoxy resin. Examples of commercially available bisphenol A type epoxy resins include jER157S70, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, and Epicoat 828 (manufactured by Mitsubishi Chemical Corporation). Examples of commercially available bisphenol F type epoxy resins include Epicoat 807 (manufactured by Mitsubishi Chemical Corporation) and YDF-170 (manufactured by Toto Kasei Co., Ltd.). Commercially available phenol novolac type epoxy resins include Epicoat 152, Epicoat 154 (manufactured by Mitsubishi Chemical Corporation), EPPN-201, PPN-202 (manufactured by Nippon Kayaku Co., Ltd.), and DEN-438 (manufactured by Dow Chemical Corporation). ) Etc. can be mentioned. Examples of commercially available o-cresol novolac type epoxy resins include EOCN-125S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.). Examples of commercially available polyphenol type epoxy resins include Epicoat 1032H60 and Epicoat YX-4000 (manufactured by Mitsubishi Chemical Corporation).

The epoxy equivalent of the epoxy resin (C) is preferably 100 to 500 g / eq, more preferably 150 to 400 g / eq. Here, the epoxy equivalent is defined by the molecular weight of the epoxy resin per epoxy group. The epoxy equivalent is, for example, JIS K723.
It can be measured by the method specified in 6.

The acid value of the epoxy resin (C) is usually less than 30 mg-KOH / g, preferably 10 mg-KOH / g or less. The weight average molecular weight of the epoxy resin (C) is preferably 300 to 10,000, more preferably 400 to 6,000, and even more preferably 500 to 4,800.

When the resin composition of the present invention contains the epoxy resin (C), the content thereof is preferably 1 to 60 parts by mass with respect to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). Parts, more preferably 5 to 50 parts by mass. When the content of the epoxy resin (C) is within the above range, the obtained cured film tends to have excellent adhesion to the substrate.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids, etc. by the action of light or heat and initiating the polymerization of the reactive monomer (B), and is known for polymerization. Initiators can be used. As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound and a biimidazole compound is preferable, and an O-acyloxy compound is preferable. A polymerization initiator containing a compound compound is more preferable. These polymerization initiators tend to have high sensitivity and high transmittance in the visible light region.

The O-acyloxime compound is a compound having a structure represented by the formula (d1).
Hereinafter, * represents a bond.

Examples of the O-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-. 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4) −Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-Il] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane-1 −On-2-imine can be mentioned. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), and N-1919 (manufactured by ADEKA Corporation) may be used.

The alkylphenone compound is a compound having a structure represented by the formula (d2) or a structure represented by the formula (d3). In these structures, the benzene ring may have a substituent.

Examples of the compound having a structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-). Morphorinophenyl) -2-benzyl butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one Can be mentioned. Commercially available products such as Irgacure® 369, 907 and 379 (all manufactured by BASF) may be used. Further, a polymerization initiator having a group capable of causing chain transfer, which is described in JP-A-2002-544205, may be used. Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2). -Hydroxyethoxy) phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxy Examples thereof include acetophenone and benzyl dimethyl ketal. In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d2).

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxy). Naftyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) )-1,3,5-Triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) −Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine. Be done.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure 819 (manufactured by BASF Japan Ltd.) may be used.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4. , 4', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4, 4', 5,5'-Tetraphenyl biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) 2-Chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxy) Phenyl) Biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), the phenyl group at the 4,4'5,5'-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (see, for example, Japanese Patent Application Laid-Open No. 7-10913).

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl- Benzoin compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrene quinone, Kinone compounds such as 2-ethylanthraquinone and camphorquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycoxylate, titanosen compounds and the like. These are preferably used in combination with the polymerization initiation aid (D1) (particularly amines) described later.

An acid generator can also be used as the polymerization initiator (D). Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyltosylates, etc. Examples include benzointosylates.

When the resin composition of the present invention contains a polymerization initiator (D), the content thereof is preferably 0.1 with respect to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). It is ~ 30 parts by mass, more preferably 0.5 to 15 parts by mass, still more preferably 1 to 8 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity is improved and the visible light transmittance of the obtained pattern tends to be high. There is.

<Polymerization initiation aid (D1)>
The polymerization initiator (D1) is used together with the polymerization initiator (D) to promote the polymerization of a polymerizable compound (for example, (meth) acrylic compound (B)) whose polymerization has been initiated by the polymerization initiator (D). It is a compound or a sensitizer used for the purpose.

Examples of the polymerization initiation aid (D1) include thiazolin compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the thiazolin compound include compounds represented by formulas (III-1) to (III-3), compounds described in JP-A-2008-65319, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and the like.
2-Ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'- Examples thereof include bis (ethylmethylamino) benzophenone, and among them, 4,4'-bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene and the like can be mentioned.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

When the resin composition of the present invention contains a polymerization initiation aid (D1), the content thereof is preferably 0, based on 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). It is 1 to 30 parts by mass, more preferably 0.2 to 10 parts by mass. When the amount of the polymerization initiation aid (D1) is within the above range, the sensitivity tends to be higher when forming the pattern.

<Thiol compound (T)>
The thiol compound (T) is a compound having a sulfanil group (-SH) in the molecule. Among them, a compound having two or more sulfanil groups is preferable, and a compound having two or more sulfanil groups bonded to a carbon atom having an aliphatic hydrocarbon structure is more preferable. The thiol compound (T) is preferably used together with the polymerization initiator (D).

Examples of the thiol compound (T) include hexanedithiol, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanyl propionate), butanediol bis (3-sulfanyl acetate), and ethylene. Glycolbis (3-sulfanyl acetate), trimethylolpropanthris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylolpropanthris (3-sulfanylpropionate), trimethylolpropanthris (3-sulfanylpropionate) 3-Sulfanyl Acetate), Pentaerythritol Tetrakis (3-Sulfanyl Propionate), Pentaerythritol Tetrakis (3-Sulfanyl Acetate), Trishydroxyethyl Tris (3-Sulfanyl Propionate), Pentaerythritol Tetrakis (3-Sulfanyl Butyrate) ), 1,4-Bis (3-sulfanylbutyloxy) butane.

When the resin composition of the present invention contains the thiol compound (T) together with the polymerization initiator (D), the content thereof is preferably 10 to 90 parts by mass with respect to 100 parts by mass of the content of the polymerization initiator (D). Parts, more preferably 15 to 70 parts by mass. When the content of the thiol compound (T) is within the above range, the sensitivity tends to be high and the developability tends to be good.

<Antioxidant (F)>
Examples of the antioxidant (F) include phenolic antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. Among them, a phenolic antioxidant is preferable because the cured film is less colored.

Examples of the phenolic antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate and 2- [1- (2-hydroxy). -3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis (6-tert-butyl-4-methyl) Phenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2,2'-thiobis (6-) tert-Butyl-4-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3', 3 ", 5,5', 5" -hexa-tert-butyl-a, a', a "-(mesitylen-2,4,6-triyl) tri- p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and 6- [3-( 3-tert-Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosfepine As the phenol-based antioxidant, a commercially available product may be used. Examples of the commercially available phenol-based antioxidant include Sumilyzer (registered trademark) BHT, GM, GS, GP (all of the above). Examples thereof include Sumitomo Chemical Co., Ltd., and Irganox (registered trademark) 1010, 1076, 1330, and 3114 (all manufactured by BASF).

Examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, disstearyl 3,3'-thiodipropionate, and pentaerythrityl tetrakis (3). -Laurylthiopropionate). As the sulfur-based antioxidant, a commercially available product may be used. Examples of commercially available sulfur-based antioxidants include Sumilyzer (registered trademark) TPL-R and TP-D (all manufactured by Sumitomo Chemical Co., Ltd.).

Phosphorus-based antioxidants include, for example, trioctylphosphite, trilaurylphosphite, tridecylphosphite, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra (tridecyl) -1,1, Examples thereof include 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite. As the phosphorus-based antioxidant, a commercially available product may be used. Examples of commercially available phosphorus-based antioxidants include Irgaphos (registered trademark) 168, 12, 38 (all manufactured by BASF), ADEKA STAB 329K, and ADEKA STAB PEP36 (all manufactured by ADEKA Corporation). Be done.

Examples of amine-based antioxidants include N, N'-di-sec-butyl-p-phenylenediamine, N, N'-di-isopropyl-p-phenylenediamine, and N, N'-dicyclohexyl-p-phenylene. Examples thereof include diamine, N, N'-diphenyl-p-phenylenediamine and N, N'-bis (2-naphthyl) -p-phenylenediamine. As the amine-based antioxidant, a commercially available product may be used. Examples of commercially available amine-based antioxidants include Sumilyzer (registered trademark) BPA, BPA-M1, and 4ML (all manufactured by Sumitomo Chemical Co., Ltd.).

When the resin composition of the present invention contains an antioxidant (F), the content thereof is preferably 0.1 with respect to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). It is 5 parts by mass or more, more preferably 0.5 parts by mass or more and 3 parts by mass or less. When the content of the antioxidant (F) is within the above range, the obtained cured film tends to be excellent in heat resistance and pencil hardness.

<Surfactant (H)>
Examples of the surfactant (H) include a silicone-based surfactant (which does not have a fluorine atom), a fluorine-based surfactant (which does not have a siloxane bond), and a silicone-based surfactant having a fluorine atom.

Examples of the silicone-based surfactant include a surfactant having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322. , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK) And so on.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Fluorinert (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), MegaFvck (registered trademark) F142D, F171, F172, F173, F177, F183, F552, F552. F553, F554, F555, F556, F558, F559, R30 (manufactured by DIC Co., Ltd.), Ftop (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Materials Electronics Co., Ltd.) ), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.) and the like.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples thereof include MegaFvck (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation). Preferably, Mega Fvck® F475 is mentioned.

When the resin composition of the present invention contains a surfactant (H), the content thereof is usually 0.001% by mass or more and 0.2% by mass or less, preferably 0.001% by mass or more, preferably 0.2% by mass or less, based on the total amount of the resin composition of the present invention. Is 0.002% by mass or more and 0.1% by mass or less, more preferably 0.01% by mass or more and 0.05% by mass or less. When the content of the surfactant (H) is within the above range, the flatness of the cured film can be improved.

<Polyvalent carboxylic acid (G)>
The polyvalent carboxylic acid (G) is at least one compound selected from the group consisting of polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids. The polyvalent carboxylic acid is a compound having two or more carboxy groups, and the polyvalent carboxylic acid anhydride is an anhydride of the polyvalent carboxylic acid. The polyvalent carboxylic acid (G) can be distinguished from the reactive monomer (B) in that it does not have a polymerizable substituent such as a carbon-carbon double bond.
The molecular weight of the polyvalent carboxylic acid (G) is preferably 3000 or less, more preferably 1000.
It is as follows.

Examples of the polyvalent carboxylic acid anhydride include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic acid anhydride, 2-dodecylsuccinic anhydride, 2- (2-octa-). 3-Enyl) succinic anhydride, 2- (2,4,6-trimethylnona-3-enyl) succinic anhydride, tricarbaryl anhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride Chain polyvalent carboxylic acid anhydrides such as those; 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrophthalate Acid anhydride, 4-methylhexahydrophthalic anhydride, norbornene dicarboxylic acid anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2.2.1] heptane- 2,3-Dicarboxylic acid anhydride, bicyclo [2.2.1] hepta-5-en-2,3-dicarboxylic acid anhydride, methylbicyclo [2.2.1] hepta-5-en-2,3 -Alicyclic polyvalent carboxylic acid anhydrides such as dicarboxylic acid anhydrides and cyclopentanetetracarboxylic acid dianhydrides; phthalic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, pyromellitic anhydride, Trimellitic anhydride, benzophenone tetracarboxylic acid anhydride, 3,3'4,4'-diphenylsulfone tetracarboxylic acid anhydride, ethylene glycol bis (anhydrotrimeritate), glycerintris (anhydrotrimerite) Tate), glycerinbis (anhydrotrimericate) monoacetate, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2- c] Aromatic polyvalent carboxylic acid anhydrides such as furan-1,3-dione; Adeka Hardener-EH-700 (trade name (same below), manufactured by ADEKA Corporation), Ricacid-HH, same-TH, same-MH, same MH-700 (made by New Japan Chemical Co., Ltd.), Epikinia 126, same Commercially available products such as YH-306 and DX-126 (manufactured by Yuka Shell Epoxy Co., Ltd.) may be used.

Examples of the polyvalent carboxylic acid include chain polyvalent carboxylic acids such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and polyvalent carboxylic acids that lead to chain polyvalent carboxylic acid anhydrides. Acids; alicyclic polyvalent carboxylic acids such as cyclohexanedicarboxylic acids, polyvalent carboxylic acids that lead to alicyclic polyvalent carboxylic acid anhydrides; isophthalic acid, terephthalic acid, 1,4,5,8-
Examples thereof include aromatic polyvalent carboxylic acids such as naphthalenetetracarboxylic acid and polyvalent carboxylic acid that lead to aromatic polyvalent carboxylic acid anhydride.

Among them, chain carboxylic acid anhydrides and alicyclic polyvalent carboxylic acid anhydrides are preferable, and alicyclic polyvalent carboxylic acids are preferable because the cured film has excellent heat resistance and the transparency in the visible light region is unlikely to decrease. Acid anhydrides are more preferred.

When the resin composition of the present invention contains a polyvalent carboxylic acid (G), the content thereof is preferably 1 to 1 with respect to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). It is 30 parts by mass, more preferably 2 to 20 parts by mass, and even more preferably 2 to 15 parts by mass. When the content of the polyvalent carboxylic acid (G) is within the above range, the heat resistance and adhesion of the cured film are excellent.

<Imidazole compound (J)>
The imidazole compound (J) is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include a compound known as an epoxy curing agent. Of these, the compound represented by the formula (2) is preferable.

[In the formula (2), R ¹¹ represents an alkyl group having 1 to 20 carbon atoms, a phenyl group, a benzyl group or a cyanoalkyl group having 2 to 5 carbon atoms.
R ^{12 to} R ¹⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group, or an acyl group having 1 to 20 carbon atoms, and the alkyl group and the phenyl group. The hydrogen atom contained in may be substituted with a hydroxy group. ]

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and a heptadecyl group. , Undecyl group is mentioned.
Examples of the cyanoalkyl group having 2 to 5 carbon atoms include a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, a cyanobutyl group and a cyanopentyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the acyl group having 1 to 20 carbon atoms include a formyl group, an acetyl group, a propionyl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group, a lauroyl group, a myristolyl group and a stearoyl group.

Examples of the imidazole compound (J) include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl-4-methylimidazole, and 2-ethylimidazole. , 2-Undecylimidazole, 2-Heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-hydroxymethyl-2-phenylimidazole, 2-phenylimidazole, 2-phenyl-2- Hydroxymethylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-phenylimidazole, 1-benzyl-5-hydroxymethylimidazole, 2- (p-hydroxyphenyl) imidazole , 1-Cyanomethyl-2-methylimidazole, 1- (2-cyanoethyl) -2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2-ethyl-4 -Methylimidazole, 1-cyanomethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole can be mentioned. Of these, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole are preferable.

When the resin composition of the present invention contains the imidazole compound (J), the content thereof is preferably 0.1% by mass with respect to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). More than 25 parts by mass, more preferably 0.2 parts by mass or more and 15 parts by mass or less, still more preferably 0.5 parts by mass or more and 5 parts by mass or less. When the content of the imidazole compound (J) is in the above range, the obtained cured film tends to have excellent transparency in the visible light region.

<Solvent (E)>
The resin composition of the present invention contains a solvent (E). Examples of the solvent (E) include various organic solvents used in the field of resin compositions, and specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol. Ethylene glycol monoalkyl ethers such as monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate;
Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether propylene glycol propyl methyl ether, propylene glycol ethyl propyl ether propylene glycol methyl ether propionate, propylene glycol ethyl ether Propionates, propylene glycol alkyl ether propionates such as propylene glycol propyl ether propionates, propylene glycol butyl ether propionates;
Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol, butoxybutyl alcohol;
Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate;
Butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate;
Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol methyl ethyl ether;
Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin;
Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxy Butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methylbutane Methyl acid, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate , Methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2-ethoxypropionate Methyl, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate , Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, Butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3 -Esters such as propyl butoxypropionate and butyl 3-butoxypropionate;
Cyclic ether groups such as tetrahydrofuran and pyran;
Cyclic esters such as γ-butyrolactone can be mentioned.

Among the above solvents, an organic solvent having a boiling point of 100 to 200 ° C. is preferable from the viewpoint of coatability and drying property. Specific examples of the organic solvent having a boiling point of 100 to 200 ° C. include alkylene glycol alkyl ether acetates, alcohols such as methoxybutanol and ethoxybutanol, and ketones such as cyclohexanone.
Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate are mentioned, and more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutanol, methoxybutyl acetate, 3-ethoxypropion. Examples thereof include ethyl acid acid and methyl 3-methoxypropionate. These solvents (E) can be used alone or in combination of two or more.

The content of the solvent (E) in the resin composition of the present invention is preferably 60 to 95% by mass, more preferably 70 to 95% by mass, based on the total amount of the resin composition. In other words, the solid content of the resin composition of the present invention is preferably 5 to 40% by mass, more preferably 5 to 30% by mass. When the content of the solvent (E) is in the above range, the flatness of the film obtained by applying the resin composition tends to be high.

<Other ingredients>
If necessary, the resin composition of the present invention contains additives known in the art such as fillers, other polymer compounds, thermal radical generators, ultraviolet absorbers, chain transfer agents, adhesion promoters, and the like. It may be contained.

Examples of the filler include glass, silica, alumina and the like. Examples of other polymer compounds include thermosetting resins such as maleimide resin and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and polyurethane. Examples of the thermal radical generator include 2,2'-azobis (2-methylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and the like. Examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like. Examples of the chain transfer agent include dodecanethiol, 2,4-diphenyl-4-methyl-1-pentene and the like.

Adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxyxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy. Propylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(
3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltri Methoxysilane, 3-isopropylpropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl Examples thereof include -3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxysilane.

It is preferable that the resin composition of the present invention does not substantially contain a colorant such as a pigment and a dye. That is, in the resin composition of the present invention, the content of the colorant in the entire composition is usually less than 1% by mass, preferably less than 0.5% by mass.

When the resin composition of the present invention is filled in a quartz cell having an optical path length of 1 cm and the transmittance is measured under the condition of a measurement wavelength of 400 to 700 nm using a spectrophotometer, the average transmittance is preferably It is 70% or more, more preferably 80% or more.

When the resin composition of the present invention is used as a cured film, the average transmittance of the cured film is preferably 90% or more, more preferably 95% or more. This average transmittance is measured under the conditions of a measurement wavelength of 400 to 700 nm using a spectrophotometer for a cured film having a thickness of 2 μm after heat curing (100 to 250 ° C., 5 minutes to 3 hours). It is the average value when Thereby, it is possible to provide a cured film having excellent transparency in the visible light region.

<Manufacturing method of resin composition>
The resin composition of the present invention comprises a resin (A) and a solvent (E), as well as a (meth) acrylic compound (B), an epoxy resin (C), a polymerization initiator (D), and a polymerization initiator used as needed. It is produced by mixing an auxiliary agent (D1), an antioxidant (F), a surfactant (H), a polyvalent carboxylic acid (G), an imidazole compound (J) and other components by a known method. Can be done. After mixing, it is preferable to filter with a filter having a pore size of about 0.05 to 1.0 μm.

<Manufacturing method of cured film>
The cured film can be produced by applying the resin composition of the present invention on a substrate, drying the film, and then curing the film by heat. More specifically, the method for producing a cured film of the present invention includes the following steps (1) to (3).
Step (1): Step of applying the resin composition of the present invention to the substrate Step (2): Step of drying the coated resin composition under reduced pressure to form a composition layer (3): Forming the composition layer Heating process

When the resin composition of the present invention contains the polymerization initiator (D), a cured film having a pattern can be produced by performing the following steps.
Step (1): Step of applying the resin composition of the present invention to the substrate Step (2): Step of drying the coated resin composition under reduced pressure to form a composition layer Step (2a): Forming the composition layer , Step of exposing through a photo mask (2b): Step of developing the composition layer after exposure Step (3a): Step of heating the composition layer after development

Step (1) is a step of applying the resin composition of the present invention to a substrate. Examples of the substrate include glass, metal, plastic, etc., and a color filter, an insulating film, a conductive film, and /
Alternatively, a drive circuit or the like may be formed. The coating on the substrate is preferably performed using a coating device such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, or a dip coater.

The step (2) is a step of forming the composition layer by drying the resin composition after coating under reduced pressure. By performing this step, volatile components such as a solvent in the resin composition are removed. The vacuum drying is preferably carried out under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C. Heat drying (pre-baking) may be performed before or after vacuum drying. Heat drying is usually performed using a heating device such as an oven or a hot plate. The heat-drying temperature is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

The step (3) is a step (post-baking) of heating the composition layer. By heating, the composition layer is cured to form a cured film. Heating is usually performed using a heating device such as an oven or a hot plate. The heating temperature is preferably 130 to 270 ° C, more preferably 150 to 260 ° C, and even more preferably 200 to 250 ° C. When the heating temperature is 200 to 250 ° C., it is possible to prevent unnecessary solvent from remaining on the cured film. The heating time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

The step (2a) is a step of exposing the composition layer formed by the step (2) through a photomask. As the photomask, a photomask having a light-shielding portion formed corresponding to a portion of the composition layer to be removed is used. The shape of the light-shielding portion is not particularly limited and can be selected according to the intended use. As the light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is selectively extracted by using a bandpass filter that extracts these wavelength ranges. You may do it. Examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp and the like. It is preferable to use an exposure device such as a mask aligner or a stepper because it is possible to uniformly irradiate the entire exposed surface with parallel light rays and accurately align the photomask and the composition layer.

Step (2b) is a step of developing the composition layer after exposure. By bringing the exposed composition layer into contact with a developing solution for development, the unexposed portion of the composition layer is dissolved in the developing solution and removed to form a composition layer having a pattern on the substrate. As the developing solution, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant. The developing method may be any of a paddle method, a dipping method, a spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.

The step (3a) is a step of heating the composition layer after development. By heating in the same manner as in the above step (3), the composition layer having a pattern is cured, and a cured film having a pattern is formed on the substrate.

Since the cured film thus obtained is excellent in surface flatness, it is useful as a protective film or overcoat for, for example, a liquid crystal display device, an organic EL display device, a color filter substrate used for electronic paper, and a touch panel. ..
The resin composition of the present invention makes it possible to manufacture a display device provided with a high-quality cured film. Even in a color filter substrate having irregularities of a coloring pattern on the surface, the flatness of the surface can be improved by forming an overcoat with the resin composition of the present invention. The film thickness of the overcoat layer (the film thickness from the surface of the convex portion when the surface to be coated has irregularities) is preferably 0.5 μm or more and 5 μm or less, and more preferably 0.5 μm or more and 3 μm or less. When the surface to be coated has irregularities, the film thickness of the overcoat layer is preferably 30% or more of the height difference of the irregularities on the surface to be coated. According to the present invention, the flatness of the surface can be improved even by the overcoat layer having such a thin film thickness. By forming the overcoat layer with the resin composition of the present invention, the height difference of the unevenness on the surface of the overcoat layer can be set to 50% or less of the height difference of the unevenness of the surface to be coated.

Hereinafter, the present invention will be described in more detail by way of examples. Unless otherwise specified, "%" and "part" in the example are mass% and parts by mass.

[Examples 1 and 2 and Comparative Examples 1 and 2]
<Preparation of resin composition>
The resin (A) shown in Table 1 is mixed with propylene glycol monomethyl ether acetate as the solvent (E) at the ratio shown in Table 1, and further as a surfactant (H), Megafuck (registered trademark) F554 (registered trademark). A resin composition was obtained by adding 0.1 part by mass with respect to 100 parts by mass of the resin (A) manufactured by DIC Corporation.

(Synthesis Example 1: Resin (A1))
Nitrogen was flowed at 0.02 L / min into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 140 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 70 ° C. with stirring. Then 25 parts of methacrylic acid; a mixture of a monomer of formula (I-1) and a monomer of formula (II-1) {a monomer of formula (I-1) and a simple compound of formula (II-1). A solution was prepared by dissolving 145 parts of the molar ratio with the monomer = 50:50}; and 75 parts of ethyl methacrylate in 190 parts of propylene glycol monomethyl ether acetate, and this solution was applied over 4 hours using a dropping pump. Then, the solution was dropped into a flask kept at 70 ° C.

On the other hand, a solution prepared by dissolving 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of propylene glycol monomethyl ether acetate was placed in a flask over 5 hours using another dropping pump. Dropped in. After the dropping of the polymerization initiator solution was completed, the mixture was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (A1)) having a solid content of 30%. The weight average molecular weight (Mw) of the obtained resin A1 was 9600, the dispersity (Mw / Mn) was 1.9, and the acid value in terms of solid content was 60 mg-KOH / g. The resin (A1) has the following structural units.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained resin were measured by using the GPC method under the following conditions.
Equipment: K2479 (manufactured by Shimadzu Corporation)
Column: SHIMADZU Sim-pack GPC-80M
Column temperature: 40 ° C
Solvent: tetrahydrofuran (THF)
Flow velocity: 1.0 mL / min
Detector: RI
Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was defined as the degree of dispersion.

(Synthesis Example 2: Resin (A2))
Nitrogen was flowed at 0.02 L / min into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 140 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 70 ° C. with stirring. Then 25 parts of methacrylic acid; a mixture of a monomer of formula (I-1) and a monomer of formula (II-1) {a single amount of the monomer of formula (I-1) and the monomer of formula (II-1). A solution prepared by dissolving 145 parts of the molar ratio with the body = 50:50}; and 75 parts of butyl methacrylate in 190 parts of propylene glycol monomethyl ether acetate was prepared, and this solution was applied over 4 hours using a dropping pump. , Dropped into a flask kept warm at 70 ° C.

On the other hand, a solution prepared by dissolving 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of propylene glycol monomethyl ether acetate was placed in a flask over 5 hours using another dropping pump. Dropped in. After the dropping of the polymerization initiator solution was completed, the mixture was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (A2)) having a solid content of 30%. The weight average molecular weight (Mw) of the obtained resin A1 was 9000, the dispersity (Mw / Mn) was 1.9, and the acid value in terms of solid content was 61 mg-KOH / g. The resin (A2) has the following structural units.

(Synthesis Example 3: Resin (A3))
Nitrogen was flowed at 0.02 L / min into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 140 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 70 ° C. with stirring. Then 25 parts of methacrylic acid; a mixture of a monomer of formula (I-1) and a monomer of formula (II-1) {a single amount of the monomer of formula (I-1) and the monomer of formula (II-1). A solution prepared by dissolving 145 parts of the molar ratio with the body = 50:50}; and 75 parts of methyl methacrylate in 190 parts of propylene glycol monomethyl ether acetate was prepared, and this solution was applied over 4 hours using a dropping pump. , Dropped into a flask kept warm at 70 ° C.

On the other hand, a solution prepared by dissolving 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of propylene glycol monomethyl ether acetate was placed in a flask over 5 hours using another dropping pump. Dropped in. After the dropping of the polymerization initiator solution was completed, the mixture was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (A3)) having a solid content of 30%. The weight average molecular weight (Mw) of the obtained resin A1 was 9200, the dispersity (Mw / Mn) was 1.9, and the acid value in terms of solid content was 61 mg-KOH / g. The resin (A3) has the following structural units.

(Synthesis Example 4: Resin (A4))
Nitrogen was flowed at 0.02 L / min into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 140 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 70 ° C. with stirring. Then 40 parts of methacrylic acid; and a mixture of the monomer of formula (I-1) and the monomer of formula (II-1) {the monomer of formula (I-1) and the simple compound of formula (II-1). A solution prepared by dissolving 360 parts of the molar ratio with the monomer = 50:50} in 190 parts of propylene glycol monomethyl ether acetate was prepared, and this solution was kept at 70 ° C. for 4 hours using a dropping pump. Dropped into the flask.

On the other hand, a solution prepared by dissolving 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of propylene glycol monomethyl ether acetate was placed in a flask over 5 hours using another dropping pump. Dropped in. After the dropping of the polymerization initiator solution was completed, the mixture was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (A4)) having a solid content of 42.3%. The weight average molecular weight (Mw) of the obtained resin Aa was 8000, the dispersity (Mw / Mn) was 1.91, and the acid value in terms of solid content was 60 mg-KOH / g. The resin (A4) has the following structural units.

<Creation of evaluation board>
A 2-inch square glass substrate (Eagle XG; manufactured by Corning Inc.) was washed successively with a neutral detergent, water and isopropanol, and then dried. Each of the colored photosensitive resin compositions shown in Table 1 was spin-coated on this substrate so that the film thickness after post-baking was 2.0 μm. Next, a colored composition layer was formed by prebaking at 100 ° C. for 3 minutes in a clean oven. After allowing to cool, the distance between the colored composition layer on the substrate and the quartz glass photomask is set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd., light source; ultra-high pressure mercury lamp) is used in an atmospheric atmosphere. , 100 mJ / cm ² exposure (based on 365 nm). This light irradiation was performed by passing the synchrotron radiation from the ultra-high pressure mercury lamp through an optical filter (UV-31; manufactured by Asahi Techno Glass Co., Ltd.). As the photomask, a photomask for forming a line-and-space pattern having a line width of 30 μm was used. The colored composition layer after light irradiation is developed by immersing it in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 60 seconds, washed with water, and then in an oven. In the middle, post-baking was performed at 230 ° C. for 30 minutes to prepare an evaluation substrate on which a line-and-space coloring pattern having a line width of 30 μm was formed.

The film thickness of the formed colored pattern was measured using a contact-type film thickness measuring device (DEKTAK6M; manufactured by ULVAC Co., Ltd.) under the conditions of a measuring width of 500 μm and a measuring speed of 10 seconds, and a profile of the cross-sectional shape of the colored pattern. Got In addition, the average value of the film thickness of the coloring pattern was calculated from the profile. The average value of the film thickness was 2.0 μm.

<Preparation of cured film and evaluation of flatness>
The resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were applied to the evaluation substrate by spin coating under the condition that the film thickness after post-baking (the film thickness from the surface of the colored pattern) was 1.0 μm. I applied the thing. After that, it is dried under reduced pressure with a vacuum dryer (manufactured by VCD Microtech Co., Ltd.) at a rotary pump rotation speed of 1000 rpm, a booster pump rotation speed of 700 rpm, and a room temperature of 25 ° C. , Prebaked at a temperature of 100 ° C. for 3 minutes. After allowing to cool, a cured film was formed by post-baking at a temperature of 230 ° C. for 30 minutes. The film thickness of the cured film on the evaluation substrate was measured using a contact-type film thickness measuring device (DEKTAK6M; manufactured by ULVAC Co., Ltd.) under the conditions of a measuring width of 500 μm and a measuring speed of 10 seconds, and the cross-sectional shape of the cured film was measured. Profile was obtained. Further, when the average value of the film thickness of the cured film was calculated from the profile, the average value of the film thickness from the surface of the colored pattern was 1.0 μm.

1 to 4 show the cross-sectional shapes of the cured films obtained from the compositions of Examples 1 and 2 and Comparative Examples 1 and 2, respectively. The horizontal axis represents the position in the plane direction, and the vertical axis represents the position in the height direction. One convex portion in the cross-sectional shape of the colored pattern corresponds to one colored cell. In addition, the average height difference of the uneven pattern on the surface of the cured film was calculated from the profile of the outer surface shape of the obtained cured film. The results are shown in Table 1. When the height difference is 1.0 μm or less, preferably 0.8 μm or less, more preferably 0.5 μm or less, the flatness of the cured film is good, and it can be said that it is particularly useful as a protective film for a color filter.

According to the present invention, it is possible to provide a resin composition capable of forming a cured film having a high surface flatness. Since the cured film obtained from the curable resin composition has excellent flatness, it can be suitably used for display devices and the like.

Claims (9)

Contains resin (A) and solvent
The resin (A) is derived from a structural unit (Aa) derived from a (meth) acrylic acid alkyl ester having an alkyl group having 2 or more carbon atoms and an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms. A resin composition which is a copolymer containing a structural unit (Ab) and a structural unit (Ac) derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. .. The resin composition according to claim 1, wherein the resin (A) has a ratio of the constituent units (Aa) of 10 mol% or more with respect to the total of the constituent units constituting the resin (A). The resin composition according to claim 1 or 2, wherein the resin (A) has a ratio of the constituent units (Aa) of 10 to 35 mol% with respect to the total of the constituent units constituting the resin (A). The resin composition according to any one of claims 1 to 3, wherein the resin (A) is a copolymer composed of a constituent unit (Aa), a constituent unit (Ab), and a constituent unit (Ac). The resin composition according to any one of claims 1 to 4, wherein the resin (A) is a copolymer having a weight average molecular weight of 5000 to 20000. The resin composition according to any one of claims 1 to 5, wherein the alkyl group in the structural unit (Aa) has 2 to 10 carbon atoms. The resin composition according to claim 6, wherein the alkyl group is a linear alkyl group having 2 to 10 carbon atoms. The resin composition according to claim 7, wherein the alkyl group is a linear alkyl group having 2 to 6 carbon atoms. A cured film formed from the resin composition according to any one of claims 1 to 8.

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