JP5350208B2 - Curable resin composition for flattening film, flattening film and display device - Google Patents

Abstract

PURPOSE: A cured membrane is provided to prevent generation of defect caused by solvent bumping and to ensure high penetration rate. CONSTITUTION: A cured membrane is obtained from a resin composition. The resin composition contains resin, surfactant, and solvent. The content of surfactant is 0.005-0.5 mass%. The surfactant contains at least one atom selected from a group consisting of silicon atom and fluorine atom.

Description

  The present invention relates to a curable resin composition for a planarization film, a planarization film, and a display device.

In recent liquid crystal display panels and the like, the size of the substrate has been increased. Usually, the substrate surface on which color pixels, semiconductor elements, and the like are formed is filled with unevenness on the surface to flatten the substrate surface. Further, the curable resin composition is formed by spin coating, slit & spin, or the like.
On the other hand, from the viewpoints of improving productivity and dealing with large screens, a method for forming a high-quality uniform coating film while reducing the liquid content of the curable resin composition solution has been studied.

  As a method for forming a high-quality uniform cured film, for example, a method for forming a film using 3-methoxy-1-butanol and 3-methoxybutyl acetate as a solvent for a specific resin has been proposed. (For example, Patent Document 1).

JP 2006-193718 A

However, when the resin composition using the solvent described above is applied to a slit die (also referred to as spinless) coating method or the like, which is a typical coating method, fine bubbles contained in the resin composition at the time of evaporation of the solvent. May cause bumping. Such bumping causes bubbles to appear on the surface of the coating film, resulting in crater-like defects.
The present invention has been made in view of the above problems, and does not generate defects due to bumping of a solvent, and can form a coating film having excellent flatness over the entire coating film. It is an object to provide an object, a planarizing film, a display device using the same, and the like.

［式（Ｉ）及び式（ＩＩ）中、
Ｒ_１及びＲ_２は、それぞれ独立に、水素原子又はヒドロキシ基が置換されていてもよい炭素数１〜４のアルキル基を表す。
Ｘ_１及びＸ_２は、それぞれ独立に、単結合、炭素数１〜６のアルキレン基又は−（ＣＨ_２）_ｓ−Ｘ'−（ＣＨ_２）_ｔ−を表す。
Ｘ'は、−Ｓ−、−Ｏ−又は−ＮＨ−を表す。
ｓ及びｔは、それぞれ独立に、０〜６の整数、ただしｓ＋ｔ＝６を表す。］
[７]溶剤（Ｃ）が、ジエチレングリコールブチルエーテルアセテートを含む溶剤である[１]〜[６]のいずれかの平坦化膜用硬化性樹脂組成物。
[８]溶剤（Ｃ）が、溶剤全量に対するジエチレングリコールブチルエーテルアセテートの含有量が１〜４０質量％である溶剤である[７]の平坦化膜用硬化性樹脂組成物。 The present invention includes the following inventions [1] to [10].
[1] Containing resin (A), surfactant (B) and solvent (C), substantially free of polymerizable monomer and colorant, and the content of surfactant (B) is based on the solid content A curable resin composition for a planarizing film, which is 0.005% by mass to 0.5% by mass.
[2] The planarizing film curable resin composition according to [1], wherein the surfactant (B) is a surfactant containing at least one atom selected from the group consisting of a silicon atom and a fluorine atom.
[3] A monomer in which the resin (A) has at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (A1) and a cyclic ether bond having 2 to 4 carbon atoms. The curable resin composition for a flattened film according to [1] or [2], which is a copolymer obtained by polymerizing (A2).
[4] The curable resin composition for a flattened film according to [3], wherein the monomer (A2) having a cyclic ether bond having 2 to 4 carbon atoms is a monomer having an oxiranyl group.
[5] The flattening film curability according to [3] or [4], wherein the monomer (A2) having a cyclic ether bond having 2 to 4 carbon atoms is a monomer having an aliphatic polycyclic epoxy group Resin composition.
[6] The monomer (A2) having a cyclic ether bond having 2 to 4 carbon atoms is at least one selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II) The curable resin composition for a flattened film according to any one of [3] to [5], which is a compound of

[In Formula (I) and Formula (II),
R ₁ and R ₂ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxy group.
X ₁ and X ₂ each independently represent a single bond, an alkylene group having 1 to 6 carbon atoms, or — (CH ₂ ) _s —X ′ — (CH ₂ ) _t —.
X ′ represents —S—, —O— or —NH—.
s and t each independently represent an integer of 0 to 6, provided that s + t = 6. ]
[7] The curable resin composition for a flattened film according to any one of [1] to [6], wherein the solvent (C) is a solvent containing diethylene glycol butyl ether acetate.
[8] The curable resin composition for a flattened film according to [7], wherein the solvent (C) is a solvent in which the content of diethylene glycol butyl ether acetate is 1 to 40% by mass relative to the total amount of the solvent.

[9] A planarization film formed using the curable resin composition for a planarization film according to any one of [1] to [8].
[10] A display device including the planarizing film of [9] described above.

According to the curable resin composition for a flattened film of the present invention, it is possible to form a coating film having excellent flatness over the entire coating film without causing defects or the like due to bumping of the solvent.
Moreover, a high quality display device can be obtained by using such a resin composition.

  The planarizing film curable resin composition of the present invention (hereinafter sometimes simply referred to as “resin composition”) mainly comprises a resin (A), a surfactant (B), and a solvent (C). .

  Although resin (A) used for the resin composition of this invention is not specifically limited, What shows the reactivity by the effect | action of at least any one of light and a heat | fever is preferable.

Examples of such a resin (A) include the following copolymers [K1] to [K4].
[K1] Unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (A1) (hereinafter sometimes simply referred to as “(A1)”) and a monomer having a C2-C4 cyclic ether bond A copolymer obtained by polymerizing (A2) (hereinafter sometimes simply referred to as “(A2)”).
[K2] A copolymer obtained by polymerizing (A1), (A2) and the monomer (A3). Here, the monomer (A3) (hereinafter sometimes simply referred to as “(A3)”) is a monomer copolymerizable with (A1) and / or (A2), and (A1) And / or a monomer that is not (A2).
[K3] In the copolymer of (A1) and (A3), by reacting a part of the carboxy group derived from (A1) with a C2-C4 cyclic ether bond derived from (A2). The resulting copolymer.
[K4] A copolymer of (A1) and (A3).
Especially, it is preferable that it is a copolymer formed by polymerizing at least (A1) and (A2).

Examples of the unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (A1) include aliphatic unsaturated carboxylic acid and / or aliphatic unsaturated carboxylic acid anhydride. In particular,
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; and anhydrides of these unsaturated dicarboxylic acids;
Unsaturated mono [(meth) acryloyloxyalkyl] of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;
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] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (highmic acid anhydride), etc. A carboxy group or a carboxylic anhydride-containing bicyclo [2.2.1] hept-2-ene;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and alkali solubility.
In the present specification, unless otherwise specified, the exemplified compounds, components, agents and the like can be used alone or in combination of two or more.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  The monomer (A2) having a cyclic ether bond having 2 to 4 carbon atoms is, for example, at least selected from the group consisting of a cyclic ether bond having 2 to 4 carbon atoms (for example, an oxiranyl group, an oxetanyl group, and a tetrahydrofuryl group). What is necessary is just to have 1 type of group, and also it is preferable that it is a monomer which has an unsaturated bond.

  Examples of (A2) include a monomer having an oxiranyl group, a monomer having an oxetanyl group, and a monomer having a tetrahydrofuryl group.

The monomer having an oxiranyl group refers to, for example, a polymerizable compound having at least one group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group.
The monomer having an oxiranyl group is preferably a compound having at least one group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group and having an unsaturated bond.

（式（III)中、Ｒ^１１〜Ｒ^１３は、それぞれ独立に水素原子又は炭素原子数１〜１０のアルキル基であり、ｍは１〜５の整数である。）。 The aliphatic epoxy group refers to a group having a structure obtained by epoxidizing a chain olefin.
Specific examples of the compound having an aliphatic epoxy group include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and JP-A-7-248625. Examples thereof include compounds represented by the following formula (III).

(In formula (III), R ^{11 to} R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m is an integer of 1 to 5).

Here, examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, 1-methyl-n-propyl group, 2-methyl- n-propyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n- Examples thereof include a propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group and the like.
In any chemical structural formula, although it varies depending on the number of carbons, unless otherwise specified, examples of substituents and the like can be similarly applied throughout the present specification. Moreover, the thing which can take both a linear or branched includes both.

  Examples of the compound represented by the formula (III) include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl. -M-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2 , 6-Diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5 -Triglycidyloxymethylstyrene 2,4,6-triglycidyloxymethylstyrene and the like.

An alicyclic epoxy group means a group having a structure obtained by epoxidizing a cyclic olefin.
Examples of the monomer having an alicyclic epoxy group include a monomer having an aliphatic monocyclic epoxy group, a monomer having an aliphatic polycyclic epoxy group, and the like. The monomer having an aliphatic monocyclic epoxy group refers to a polymerizable compound having a group having a structure obtained by epoxidizing a monocyclic cyclic olefin. The monomer having an aliphatic polycyclic epoxy group refers to a polymerizable compound having a group having a structure obtained by epoxidizing a polycyclic cyclic olefin. The monomer having an epoxy group is a compound having at least one selected from the group consisting of an aliphatic monocyclic epoxy group and an aliphatic polycyclic epoxy group and having an unsaturated bond. A compound having at least one selected from the group consisting of an aliphatic monocyclic epoxy group and an aliphatic polycyclic epoxy group and having a (meth) acryloyloxy group is more preferable.

Examples of the monocyclic olefin include cyclopentene, cyclohexene, cycloheptene, and cyclooctene. Especially, a C5-C7 compound is preferable.
Specific examples of the monomer having an aliphatic monocyclic epoxy group include vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3 , 4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), and the like. It is done.

  Examples of the polycyclic cyclic olefin include dicyclopentene, tricyclodecene, norbornene, isonorbornene, bicyclooctene, bicyclononane, bicycloundecene, tricycloundecene, bicyclododecene, and tricyclododecene. Can be mentioned. Especially, a C8-C12 compound is preferable.

式（Ｉ）及び式（II）において、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又はヒドロキシ基で置換されていてもよい炭素数１〜４のアルキル基を表す。
Ｘ_１及びＸ_２は、それぞれ独立に、単結合、炭素数１〜６のアルキレン基又は−（ＣＨ_２）_ｓ−Ｘ'−（ＣＨ_２）_ｔ−を表す。
Ｘ'は−Ｓ−、−Ｏ−又は−ＮＨ−を表す。
ｓ及びｔは、それぞれ独立に、０〜６の整数、ただしｓ＋ｔ＝６を表す。 Examples of the monomer having an aliphatic polycyclic epoxy group include 3,4-epoxynorbornyl acrylate, 3,4-epoxynorbornyl methacrylate, compounds represented by the formula (I), and the formula And at least one compound selected from the group consisting of compounds represented by (II).

In Formula (I) and Formula (II), R ¹ and R ² each independently represent a C 1-4 alkyl group which may be substituted with a hydrogen atom or a hydroxy group.
X ₁ and X ₂ each independently represent a single bond, an alkylene group having 1 to 6 carbon atoms, or — (CH ₂ ) _s —X ′ — (CH ₂ ) _t —.
X ′ represents —S—, —O— or —NH—.
s and t each independently represent an integer of 0 to 6, provided that s + t = 6.

Specific examples of R ¹ and R ² include a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group;
Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxymethylethyl group, 1-hydroxy-1-methylethyl group , 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and other hydroxy group-substituted alkyl groups.
Of these, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are preferable. More preferably, they are a hydrogen atom and a methyl group.

Specific examples of X ¹ and X ² include a single bond; an alkylene group such as a methylene group, an ethylene group, and a propylene group;
Examples include heteroatom-containing alkylene groups such as a thioalkylene group, an oxyalkylene group, and an iminoalkylene group. Specific examples include an oxymethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group, an iminomethylene group, an iminoethylene group, and an iminopropylene group.
Of these, a single bond, a methylene group, an ethylene group, an oxymethylene group, and an oxyethylene group are preferable. More preferably, they are a single bond and an oxyethylene group.

式（Ｉ’）及び式（II’）において、Ｒ^１’及びＲ^２’は、それぞれ前記Ｒ^１及びＲ^２と同義である。 At least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II) is a compound represented by the following formula (I ′) and formula (II ′): It is preferable that it is at least 1 type of compound chosen from the group which consists of a compound represented by these.

In Formula (I ′) and Formula (II ′), R ¹ ′ and R ² ′ have the same meanings as R ¹ and R ² , respectively.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I-11) to Formula (I-15) It is. More preferred are formula (I-1), formula (I-7), formula (I-9) and formula (I-15).

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9), Formula (II-11) to Formula (II-15) It is. More preferred are formula (II-1), formula (II-7), formula (II-9), and formula (II-15).

  At least one compound selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (II) can be used alone. Moreover, it can mix in arbitrary ratios. In the case of mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 to Formula (I): Formula (II). 80:20.

The monomer having an oxetanyl group refers to a polymerizable compound having an oxetanyl group, for example. The monomer having an oxetanyl group is preferably a compound having an oxetanyl group and an unsaturated bond, and preferably a compound having an oxetanyl group and a (meth) acryloyloxy group.
Specific examples of the monomer having an oxetanyl group include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3- Ethyl-3-acryloxymethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane or 3-ethyl-3-acryloxy And ethyl oxetane.

The monomer having a tetrahydrofuryl group refers to a polymerizable compound having at least one group selected from the group consisting of tetrahydrofuryl groups, for example. The monomer having a tetrahydrofuryl group is preferably a compound having a tetrahydrofuryl group and an unsaturated bond, and having a tetrahydrofuryl group and a (meth) acryloyloxy group. Is preferred.
Specific examples of the monomer having a tetrahydrofuryl group include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As the copolymerizable monomer (A3), for example,
(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, dicyclopenta (Meth) acrylate cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and the like;
(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
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-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-di (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Chlorounsaturated compounds;
N-alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide;
N-cycloalkylmaleimides such as N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cyclooctylmaleimide;
N-bridged carbocyclic group-substituted maleimides such as N-adamantyl maleimide, N-norbornyl maleimide;
N-arylmaleimides such as N-phenylmaleimide;
N-aralkylmaleimides such as N-benzylmaleimide;
N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide, etc. Dicarbonylimide derivatives of
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.

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

  Such resin (A) is, for example, a method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972). And it can manufacture with reference to the cited reference described in the said literature.

  Specifically, monomers (A1) and (A2) constituting the copolymer, optionally a predetermined amount of (A3), a polymerization initiator and a solvent are charged into a reaction vessel, and oxygen is substituted with nitrogen. In the absence of oxygen, the polymer is obtained by stirring, heating, and keeping the temperature. Polymerization conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of production equipment, the amount of heat generated by polymerization, and the like.

As the polymerization initiator and the solvent used here, any of those usually used in the art can be used. For example, a polymerization initiator and a solvent (C) described later can be used.
In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used.
In particular, by using a solvent (C) described later as a solvent during the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

In copolymer [K1], the ratio of each monomer is preferably in the following range with respect to the total number of moles of monomers constituting copolymer [K1].
(A1) 5 to 95 mol%, more preferably 10 to 90 mol%
(A2) 5 to 95 mol%, more preferably 10 to 90 mol%.
When the molar fraction is within this range, the storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be good.

Moreover, it is preferable that copolymer [K2] has the ratio of each monomer in the following ranges with respect to the total mole number of the monomer which comprises copolymer [K2].
(A1) 2 to 40 mol%, more preferably 5 to 35 mol%
(A2) 2 to 95 mol%, more preferably 5 to 80 mol%
(A3) 1 to 65 mol%, more preferably 1 to 60 mol%.
When the molar fraction is within this range, the storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be good.

The copolymer [K3] can be produced through a two-step process.
First, (A1) and (A3) are copolymerized in the same manner as described above to obtain a copolymer.
In this case, the ratio of each monomer is preferably in the following range with respect to the total number of moles of monomers constituting the resin.
(A1) 5 to 50 mol%, preferably 10 to 45 mol%
(A3) 50 to 95 mol%, preferably 55 to 90 mol%.

Next, a part of the carboxylic acid and / or carboxylic anhydride of (A1) derived from the copolymer of (A1) and (A3) is converted to an epoxy group, oxetanyl group or tetrahydrofuryl group derived from (A2). React.
For that purpose, the atmosphere in the flask is subsequently replaced with nitrogen to air, (A2), a reaction catalyst, a polymerization inhibitor and the like are placed in the flask, and the reaction is continued at 60 to 130 ° C. for 1 to 10 hours, for example. The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization.
In this case, the number of moles of (A2) is suitably from 5 to 80 mole%, preferably from 10 to 75 mole%, more preferably from 15 to 70 mole%, based on the number of moles of (A1). is there.
When the ratio of each monomer is within this range, the balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tends to be good.

As the reaction catalyst, for example, those used as a reaction catalyst between a carboxy group and an epoxy group, oxetanyl group or tetrahydrofuryl group are suitable. Specific examples include trisdimethylaminomethylphenol.
As for the usage-amount of a reaction catalyst, about 0.001-5 mass% is illustrated with respect to the total amount of (A1)-(A3), for example.
Examples of the polymerization inhibitor include hydroquinone.
As for the usage-amount of a polymerization inhibitor, about 0.001-5 mass% is illustrated with respect to the total amount of (A1)-(A3), for example.

In copolymer [K4], the ratio of each monomer is preferably in the following range with respect to the total number of moles of monomers constituting copolymer [K4].
(A1) 2 to 40 mol%, more preferably 5 to 35 mol%
(A2) 60 to 98 mol%, more preferably 65 to 95 mol%.
When the molar fraction is within this range, the storage stability, solvent resistance, heat resistance and mechanical strength tend to be good.

The weight average molecular weight in terms of polystyrene of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (A) is in this range, the coatability tends to be good.
The dispersity (molecular weight distribution) of resin (A), [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.1 to 6.0, more preferably 1.2 to 4. 0. When the degree of dispersion is within this range, the coatability tends to be excellent.

  Content of resin (A) which can be used for the resin composition of this invention becomes like this. Preferably it is 5-99 mass% with respect to solid content in a resin composition, More preferably, it is 10-70 mass%. When content of resin (A) exists in this range, it exists in the tendency for solvent resistance, heat resistance, and mechanical strength to become favorable.

  The surfactant (B) in the resin composition of the present invention is not particularly limited, and examples thereof include surfactants containing at least one atom selected from the group consisting of silicon atoms and fluorine atoms. The Specific examples include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. Of these, a silicone-based surfactant having a fluorine atom is preferred. By using such a surfactant (B), generation of fine bubbles contained in the composition can be prevented in combination with other components in the resin composition and the content thereof. As a result, bumping at the time of solvent evaporation can be effectively suppressed.

Examples of the silicone surfactant include surfactants having a siloxane bond.
Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: Torresilicone; 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, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials) Japan GK) and the like.

Examples of the fluorosurfactant include surfactants having a fluorocarbon chain.
Specifically, Florinart (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, R30, F489 (Manufactured by DIC Corporation), F-Top (registered trademark) EF301, EF303, EF351, EF352, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (all trade names: manufactured by BM Chemie), and the like.

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned. Preferably, MegaFac (registered trademark) F475 is used.

  The surfactant (B) is 0.005% by mass to 0.5% by mass and preferably 0.01% by mass to 0.1% by mass with respect to the solid content of the resin composition of the present invention. . By containing the surfactant in this range, the flatness can be improved, and bumping can be effectively prevented as described above.

The resin composition of the present invention contains a solvent (C). Examples of the solvent (C) include various organic solvents used in the field of resin compositions.
Specific examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol 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, 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 Propylene glycol alkyl ether propionates such as propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate;

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, 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, hydroxyethyl acetate, 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 acetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, propoxy Ethyl acetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2- Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxy Propyl propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3- Methyl toxipropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxy Esters such as butyl propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate;
Cyclic ether groups such as tetrahydrofuran and pyran;
and cyclic esters such as γ-butyrolactone.

In particular, the solvent (C) is preferably a solvent containing diethylene glycol butyl ether acetate.
Further, from the viewpoints of coating properties, drying properties and bumping prevention, alkylene glycol alkyl ether acetates; alcohols such as methoxybutanol and ethoxybutanol; ketones such as cyclohexanone; ethyl 3-ethoxypropionate and methyl 3-methoxypropionate It is preferable to contain esters such as methyl 3-methoxyacetate, ethyl 3-ethoxyacetate, butyl 3-methoxyacetate and butyl 3-ethoxyacetate.

Content of the solvent (C) in the resin composition of this invention becomes like this. Preferably it is 60-90 mass% with respect to a resin composition, More preferably, it is 65-85 mass%. If the content of the solvent (C) is within this range, there is a possibility that the coatability will be good when applied by various coating apparatuses described later.
In particular, the content of diethylene glycol butyl ether acetate is preferably 1 to 40% by mass and more preferably 5 to 25% by mass with respect to the solvent.

The resin composition of the present invention contains substantially no polymerizable monomer. That is, in the resin composition of the present invention, the content of the polymerizable monomer with respect to the entire composition is, for example, less than 1% by mass, preferably less than 0.5% by mass. Examples of the polymerizable monomer include a monofunctional monomer having an unsaturated bond, a bifunctional monomer, or a trifunctional or higher polyfunctional monomer.
Monofunctional monomers include nonylphenyl carbitol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, lauryl (meth) ) Acrylate, stearyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propoxylated nonylphenol (meth) ) Acrylate or N-vinyl pyrrolidone.

  Bifunctional monomers include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, 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, bis (acryloyloxyethyl) ether of bisphenol A, Ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate or 3-methylpenta Diol di (meth) acrylate.

  The trifunctional or higher polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) ) Acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tri Pentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate Rate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, tripentaerythritol hepta (meta ) Acrylate and anhydride caprolactone modified trimethylolpropane tri (meth) 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) Chryrate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate, caprolactone-modified tripenta Erythritol octa (meth) acrylate, reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride, or caprolactone-modified tripentaerythritol A reaction product of hepta (meth) acrylate and an acid anhydride.

  The resin composition of the present invention does not substantially contain colorants such as pigments and dyes. That is, in the resin composition of the present invention, the content of the colorant with respect to the entire composition is, for example, less than 1% by mass, preferably less than 0.5% by mass.

  The resin composition of the present invention may contain at least one compound selected from the group consisting of a carboxylic acid anhydride and a compound having at least two carboxy groups. Examples of the compound having two carboxy groups include polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids.

  As the carboxylic acid anhydride, an epoxy resin curing agent made of a commercially available colorless acid anhydride can also be suitably used. Specifically, ADEKA HARDNA-EH-700 (trade name (hereinafter the same), manufactured by Asahi Denka Kogyo Co., Ltd.), Rikacid-HH, MH-700 (manufactured by Shin Nippon Rika Co., Ltd.), Epikinia 126, YH -306, DX-126 (manufactured by Yuka Shell Epoxy Co., Ltd.) and the like.

As the polyvalent carboxylic acid anhydride, for example,
Aliphatic dicarboxylic acids such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, norbornene dicarboxylic acid, and hymic anhydride Anhydride;
Aliphatic polycarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride;
Aromatic polycarboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride;
And ester group-containing acid anhydrides such as ethylene glycol bistrimellitate and glycerin tristrimellitate.
Of these, phthalic anhydride and trimellitic anhydride are preferred from the viewpoint of high transparency in the visible light region.

Examples of the polyvalent carboxylic acid include
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, itaconic acid;
Alicyclic polycarboxylic acids such as hexahydrophthalic acid, 1,2-cyclohexanecarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid;
Examples include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, aromatic polyvalent carboxylic acids such as 1,4,5,8-naphthalene tetracarboxylic acid, benzophenone tetracarboxylic acid, and the like.
Of these, phthalic acid and trimellitic acid are preferred from the viewpoint of high transparency in the visible light region.

  The content of at least one compound selected from the group consisting of a carboxylic acid anhydride and a compound having at least two carboxy groups in the resin composition of the present invention is preferably relative to the total amount of the resin (A). It is 0.1-20 mass%, More preferably, it is 1-15 mass%. When this compound is in this range, the reliability of the coating film can be improved.

The resin composition of the present invention may contain a cationic polymerization initiator.
As the cationic polymerization initiator, those composed of an onium cation and an anion derived from a Lewis acid can also be used.

  Specific examples of the onium cation include diphenyliodonium, bis (p-tolyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, bis ( p-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (p-octadecyloxyphenyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, triphenylsulfonium, tris (p-tolyl) ) Sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (p-tert-butylphenyl) sulfonium, tris (p-cyano) Eniru) sulfonium, tris (p- chlorophenyl) sulfonium, or dimethyl (tris (trichloromethyl) methyl) sulfonium, and the like.

  Preferred onium cations include bis (p-tolyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium or tris (p-tert-butylphenyl). ) Sulfonium and the like.

Specific examples of the Lewis acid-derived anion include hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, and tetrakis (pentafluorophenyl) borate. Preferred anions derived from Lewis acid include hexafluoroantimonate or tetrakis (pentafluorophenyl) borate.
These onium cations and Lewis acid-derived anions can be arbitrarily combined.

  Specific examples of the cationic polymerization initiator include diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-octylphenyl) iodonium hexa Fluorophosphate, bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium Hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophos , Methyl naphthyl iodonium hexafluorophosphate, ethyl naphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexafluorophosphate, tris (2, 6-dimethylphenyl) sulfonium hexafluorophosphate, tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium Hexafluorophosphate, diethylnaphthyls Phosphonium hexafluorophosphate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluorophosphate;

  Diphenyliodonium hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, bis (p-octylphenyl) iodonium hexafluoroarsenate, bis (p -Octadecylphenyl) iodonium hexafluoroarsenate, bis (p-octyloxyphenyl) iodonium hexafluoroarsenate, bis (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarsenate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, methylnaphthyl iodonium Oxafluoroarsenate, ethyl naphthyl iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (p-tolyl) sulfonium hexafluoroarsenate, tris (p-isopropylphenyl) sulfonium hexafluoroarsenate, tris (2, 6-dimethylphenyl) sulfonium hexafluoroarsenate, tris (p-tert-butylphenyl) sulfonium hexafluoroarsenate, tris (p-cyanophenyl) sulfonium hexafluoroarsenate, tris (p-chlorophenyl) sulfonium hexafluoroarsenate , Dimethylnaphthylsulfonium hexafluoroarsenate, diethylnaphthylsulfonium hexafluoroarsenate Dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroarsenate;

  Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, bis (p-octylphenyl) iodonium hexafluoroantimonate, bis (p -Octadecylphenyl) iodonium hexafluoroantimonate, bis (p-octyloxyphenyl) iodonium hexafluoroantimonate, bis (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroantimonate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, methyl naphthalate Tyl iodonium hexafluoroantimonate, ethyl naphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate, tris (p-isopropylphenyl) sulfonium hexafluoroantimonate, tris ( 2,6-dimethylphenyl) sulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium hexafluoroantimonate, tris (p-chlorophenyl) sulfonium hexafluoro Antimonate, dimethyl naphthylsulfonium hexafluoroantimonate, diethyl naphthyl Sulfo hexafluoroantimonate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroantimonate;

  Diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (p-tolyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-octylphenyl) Iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) Iodonium tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis Pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, methylnaphthyliodonium tetrakis (pentafluorophenyl) borate, ethylnaphthyliodonium tetrakis (pentafluorophenyl) borate, triphenyl Sulfonium tetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-isopropylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (2,6-dimethylphenyl) sulfonium Tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium teto Kiss (pentafluorophenyl) borate, tris (p-cyanophenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, Examples thereof include diethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate and dimethyl (tris (trichloromethyl) methyl) sulfonium tetrakis (pentafluorophenyl) borate.

  Preferably, bis (p-tolyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate , Tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsenate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, bis (p-tert- Butylphenyl) iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (pt-butylphenyl) sulfonate Muhexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, Triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium Tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentafluorophenyl) Yl) borate, tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, and the like.

  More preferably, bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenyl Sulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis ( Pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium Tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, and the like.

The content of the cationic polymerization initiator is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, based on the solid content of the resin composition.
When the total amount of the cationic polymerization initiator is within this range, the curing time tends to be shortened.

  In the resin composition of the present invention, a filler, a polymer compound other than the resin (A), an adhesion promoter, an antioxidant, an ultraviolet absorber, a light stabilizer, an anti-aggregation agent, and a chain transfer agent are included as necessary. Such additives may be used in combination.

Examples of the filler include glass, silica, and alumina.
Examples of the polymer compound other than the resin (A) include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Can be mentioned.

  As the adhesion promoter, a silane compound is preferable. Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane , 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

  Antioxidants include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5 -Di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4 , 8,10-Tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 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 ( -Tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2 , 2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropioate , Pentaerythrityltetrakis (3-laurylthiopropionate), 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-A1 ′, a ″-( Citylene-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 the like.

  Examples of ultraviolet absorbers include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H- Benzotriazol-2-yl) phenyl] propionate, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl) Phenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-bis-butyloxyphenyl) -1,3 5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2- (2H-benzo Triazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl)- Examples include 4- (1,1,3,3-tetramethylbutyl) phenol, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like.

  As a light stabilizer, a polymer composed of succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl) ethanol, N, N ′, N ″, N ′ ″ − Tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazin-2-yl) -4,7-diazadecane-1,10- Reaction product of diamine, decandioic acid, bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester and 1,1-dimethylethyl hydroperoxide, bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, 2,4-bis [N-Bu Ru-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine, bis (1, 2,2,6,6-pentamethyl-4-piperidinyl) sebacate or methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate.

Examples of the aggregation inhibitor include sodium polyacrylate.
Examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

The resin composition of the present invention suitably has a solid content of about 10 to 30% by mass, more preferably 12 to 28% by mass, and still more preferably 15 to 25% by mass. By setting it as this range, a flat coating film can be formed, without generating a defect etc. also by various coating methods, especially the slit method.
In addition, 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 a measurement wavelength of 400 to 700 nm using a spectrophotometer, the average transmittance is 70%. Or more, preferably 80% or more.

  When the resin composition of the present invention is used as a coating film, the average transmittance of the coating film is preferably 90% or more, and 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 coating film having a thickness of 3 μm after heat curing (for example, 100 to 250 ° C., 5 minutes to 3 hours). It is an average value when measured by. Thereby, the coating film excellent in transparency in the visible light region can be provided.

  The resin composition of the present invention is applied onto, for example, a substrate such as a substrate such as glass, metal, or plastic, a color filter, various insulating or conductive films, or a drive circuit as described later. By doing so, a planarizing film can be obtained. The planarizing film is preferably dried and cured. Further, the planarizing film or the like may be formed as a part of a component such as a display device.

First, the resin composition of this invention is apply | coated on the layer which consists of solid content of the base material or the resin composition formed previously.
The coating method is not particularly limited. For example, a coating apparatus such as a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater, a curtain flow coater, or a spinless coater), an inkjet, a roll coater, a dip coater, or the like. Can be used. Among these, from the viewpoint of solubility, prevention of drying, prevention of the generation of foreign substances, etc., it is preferable to use a slit coating method, that is, use a slit & spin coater, a slit coater or the like.

Then, it is suitable to remove volatile components such as a solvent by drying or prebaking. Thereby, a smooth uncured coating film can be obtained. In particular, it is suitable to perform vacuum drying. The reduced-pressure drying here is exemplified to be performed in a temperature range of about 20 to 25 ° C. under a pressure of about 50 to 150 Pa.
The film thickness of the coating film in this case is not particularly limited and can be appropriately adjusted depending on the material used, application, etc. For example, about 0.1 to 30 μm, preferably about 1 to 20 μm, more preferably 1 to 6 μm. The degree is illustrated.

  After drying, post bake is performed. The post-bake is suitable for a temperature range of 150 to 230 ° C. and 10 to 180 minutes, for example.

  In particular, the resin composition of the present invention is flattened by applying the resin composition of the present invention on a substrate using a slit coater to form a film, and drying the film formed on the substrate under reduced pressure. It is preferably used for producing a membrane.

  The resin composition of the present invention can be suitably used for forming a material for forming a planarizing film, for example, a transparent film, particularly a transparent film constituting a part of a color filter or an array substrate. . In addition, these transparent films are used as a flattening film, and a color filter, an array substrate, and the like provided with a flattening film as a part of their constituent parts, and further, these flattening films, color filters, and / or array substrates, etc. Can be used for a display device such as a liquid crystal display device or an organic EL device, and a display device including a high-quality planarization film can be manufactured with a high yield.

  EXAMPLES Hereinafter, although the resin composition of this invention is demonstrated in detail by an Example, this invention is not limited by these Examples. Moreover, in the following Examples and Comparative Examples,% and part representing the content or amount used are based on mass unless otherwise specified.

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３６質量部を３−メトキシ−１−ブタノール１０１質量部及び３−メトキシブチルアセテート１３９質量部に溶解した溶液を、別の滴下ポンプを用いて５時間かけてフラスコ内に滴下した。
重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、固形分４２．５質量％、酸価５６ｍｇ−ＫＯＨ／ｇの共重合体（樹脂Ａａ）の溶液を得た。得られた樹脂Ａａの重量平均分子量（Ｍｗ）は７．６×１０^３、分散度は２．０１であった。 Synthesis of Resin Aa In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, 59 parts by mass of 3-methoxy-1-butanol and 3-methoxybutyl acetate 81 parts by mass was added and heated to 70 ° C. with stirring.
Subsequently, 40 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) 360 parts by weight of the compound to be mixed in a 50:50 molar ratio) was dissolved in 80 parts by weight of 3-methoxy-1-butanol and 110 parts by weight of 3-methoxybutyl acetate to prepare a solution. This solution was dropped into a flask kept at 70 ° C. over 4 hours using a dropping pump.

On the other hand, a solution prepared by dissolving 36 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 101 parts by mass of 3-methoxy-1-butanol and 139 parts by mass of 3-methoxybutyl acetate, Was dropped into the flask over 5 hours using a dropping pump.
After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature, and a copolymer (resin Aa) having a solid content of 42.5 mass% and an acid value of 56 mg-KOH / g ) Was obtained. The obtained resin Aa had a weight average molecular weight (Mw) of 7.6 × 10 ³ and a dispersity of 2.01.

Synthesis of Resin Ab In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, and 56 parts by mass of 3-methoxy-1-butanol and 3-methoxybutyl acetate 84 parts by mass was added and heated to 70 ° C. with stirring.
Next, 40 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.12.02.6] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) 360 parts by mass of a compound having a molar ratio of 50:50) was dissolved in 76 parts by mass of 3-methoxy-1-butanol and 114 parts by mass of 3-methoxybutyl acetate to prepare a solution. This solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel.
On the other hand, a solution obtained by dissolving 14 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 96 parts by mass of 3-methoxy-1-butanol and 144 parts by mass of 3-methoxybutyl acetate, Was added dropwise into the flask over 4 hours using a dropping funnel. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature, so that both the solid content was 42.3% by mass and the acid value was 57 mg-KOH / g (solid content conversion). A polymer (resin Ab) solution was obtained. The obtained resin Ab had a weight average molecular weight Mw of 1.9 × 10 ⁴ and a dispersity of 2.65.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin described above were measured under the following conditions using the GPC method.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
The ratio of the weight-average molecular weight and number-average molecular weight obtained above in terms of polystyrene was defined as the degree of dispersion (Mw / Mn).

Example 1
235 parts of resin solution (A) containing the obtained resin Aa (100 parts in terms of solid content), Megafac F489 (manufactured by DIC Corporation) (B) as a fluorosurfactant (B), 0.01 part of Irganox 3114 (Ciba) -Japan Co., Ltd.) 0.8 parts and a solvent (diethylene glycol butyl ether acetate, 3-methoxybutyl acetate and 3-methoxy-1-butanol weight ratio 10:45:45) are mixed, solid content concentration is 19 3% by mass of the resin composition 1 was obtained.

Example 2
235 parts of resin solution (A) containing the obtained resin Aa (100 parts in terms of solid content), Megafac F489 (manufactured by DIC Corporation) (B) 0.05 part, Irganox 3114 (manufactured by Ciba Japan Co., Ltd.) 0.8 parts and a solvent (diethylene glycol butyl ether acetate, 3-methoxybutyl acetate and 3-methoxy-1-butanol in a weight ratio of 10:45:45) are mixed, and a resin composition having a solid content concentration of 19.3 mass% Product 2 was obtained.

Example 3
236 parts of resin solution (A) containing the obtained resin Ab (100 parts in terms of solid content), Megafac F489 (manufactured by DIC Corporation) (B) 0.01 part, Irganox 3114 (manufactured by Ciba Japan Co., Ltd.) 0.8 parts and a solvent (diethylene glycol butyl ether acetate, 3-methoxybutyl acetate and 3-methoxy-1-butanol in a weight ratio of 20:40:40) are mixed, and a resin composition having a solid content concentration of 19.3 mass% Product 3 was obtained.

Example 4
236 parts of resin solution (A) containing resin Ab (100 parts in terms of solid content), MegaFuck F489 (manufactured by DIC Corporation) (B) 0.05 part, Irganox 3114 (manufactured by Ciba Japan Co., Ltd.) 0.8 Parts and a solvent (diethylene glycol butyl ether acetate, 3-methoxybutyl acetate and 3-methoxy-1-butanol in a weight ratio of 10:45:45) are mixed, and a resin composition 4 having a solid content concentration of 19.3 mass% is obtained. Obtained.

Example 5
236 parts of resin solution (A) containing the obtained resin Ab (100 parts in terms of solid content), Megafac F489 (manufactured by DIC Corporation) (B) 0.05 part, Irganox 3114 (manufactured by Ciba Japan Co., Ltd.) 0.8 parts and a solvent (diethylene glycol butyl ether acetate, 3-methoxybutyl acetate and 3-methoxy-1-butanol in a weight ratio of 20:40:40) are mixed, and a resin composition having a solid content concentration of 19.3 mass% Product 5 was obtained.

Example 6
236 parts of resin solution (A) containing the obtained resin Ab (100 parts in terms of solid content), SH8400 (B) manufactured by Toray Dow Corning Co., Ltd., Irganox 3114 (Ciba) -Japan Co., Ltd.) 0.8 parts and a solvent (diethylene glycol butyl ether acetate, 3-methoxybutyl acetate and 3-methoxy-1-butanol weight ratio 10:45:45) are mixed, solid content concentration is 19 3% by mass of a resin composition 6 was obtained.

Example 7
236 parts of resin solution (A) containing the obtained resin Ab (100 parts in terms of solid content), Megafac F489 (manufactured by DIC Corporation) (B) 0.05 part, SH8400 (manufactured by Toray Dow Corning Corporation) (B) 0.05 part, 0.8 part of Irganox 3114 (manufactured by Ciba Japan) and solvent (diethylene glycol butyl ether acetate, 3-methoxybutyl acetate and 3-methoxy-1-butanol have a weight ratio of 10:45: 45) was mixed to obtain a resin composition 7 having a solid content concentration of 19.3 mass%.

Example 8
235 parts of resin solution (A) containing the obtained resin Aa (100 parts in terms of solid content), Megafac F489 (manufactured by DIC Corporation) (B) 0.01 part, Irganox 3114 (manufactured by Ciba Japan Co., Ltd.) 0.8 parts and a solvent (diethylene glycol butyl ether acetate, 3-methoxybutyl acetate and 3-methoxy-1-butanol in a weight ratio of 1: 49.5: 49.5) were mixed to obtain a resin composition 8.

Example 9
235 parts of resin solution (A) containing the obtained resin Aa (100 parts in terms of solid content), Megafac F489 (manufactured by DIC Corporation) (B) 0.01 part, Irganox 3114 (manufactured by Ciba Japan Co., Ltd.) 0.8 parts and a solvent (diethylene glycol butyl ether acetate, 3-methoxybutyl acetate and 3-methoxy-1-butanol in a weight ratio of 40:30:30) were mixed to obtain a resin composition 9.

Comparative Example 1
235 parts of resin solution (A) containing resin Aa (100 parts in terms of solid content), 0.8 part of Irganox 3114 (manufactured by Ciba Japan Co., Ltd.), and solvents (diethylene glycol butyl ether acetate, 3-methoxybutyl acetate and 3-methoxy) The weight ratio of -1-butanol was 10:45:45), and a resin composition 10 having a solid content concentration of 19.3% by mass was obtained.

The following evaluations were performed for each of the resin compositions obtained in Examples 1 to 9 and Comparative Example 1.
<Sudden boiling evaluation>
A 5 cm × 5 cm glass substrate (Corning Eagle 2000) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, the resin compositions of Examples 1 to 9 and Comparative Example 1 were applied at 600 rpm for 10 seconds using a spin coater. Thereafter, the pressure was reduced to 130 Pa with a vacuum dryer (VCD Microtech Co., Ltd.), and the product was dried. After cooling, the coating film surface was observed with a reflective optical microscope. The results are shown in Table 2.
The case where bumping did not occur was marked as ◯, and the case where bumping occurred was marked as x.
In addition, about what generate | occur | produced bumping, since a smooth coating film was not obtained, level | step difference evaluation was stopped.

５ｃｍ×５ｃｍのガラス基板（コーニング社製Ｅａｇｌｅ２０００）を、中性洗剤、水及びアルコールで順次洗浄してから乾燥した。このガラス基板上に、着色樹脂組成物１をスピンコートにより塗布した。次いで、クリーンオーブン中、９０℃で３分間プリベークした。冷却後、この着色樹脂組成物１を塗布した基板と石英ガラス製フォトマスクとの間隔を１００μｍとし、露光機（ＴＭＥ−１５０ＲＳＫ；トプコン（株）製、光源；超高圧水銀灯）を用いて、大気雰囲気下、１００ｍＪ／ｃｍ^２の露光量（３６５ｎｍ基準）で光照射した。なお、このときの着色樹脂組成物への照射は、超高圧水銀灯からの放射光を、光学フィルタ（ＵＶ−３５；旭テクノグラス（株）製）を通過させ使用した。また、フォトマスクとして、パターン（透光部と遮光部がそれぞれ１００μｍのライン状パターン交互に有する）が同一平面上に形成されたフォトマスクを用いた。
光照射後、非イオン系界面活性剤０．１２％と水酸化カリウム０．０４％とを含む水系現像液に上記塗膜を２３℃で８０秒間浸漬して現像し、水洗後、オーブン中、２２０℃で２０分間ポストベークを行い、１００μｍの着色ライン部と１００μｍのスペース部を交互に有する評価用基板を作成した。着色樹脂組成物の膜厚は、１．３６μｍであった。
この評価用基板に、実施例１〜９の樹脂組成物を、スピンコーターを用いて６００ｒｐｍで１０秒間の条件で塗布した。その後、減圧乾燥機（マイクロテック（株）製）で１．０torrまで減圧し乾燥させた後、９５℃設定のホットプレート上に載せ、その上で２分間プレベークして塗膜を形成した。さらに、２３０℃で２０分加熱し硬化させた。冷却後、触針式膜厚計（Ｖｅｅｃｏ社製ＤＥＫＴＡＫ ６Ｍ）を用いて、最大膜厚と最小膜厚を測定し、段差（＝最大膜厚−最小膜厚）を算出した。その結果を表２に示す。
下地の膜厚よりも段差が小さければ、良好である。 <Step evaluation>
Each component was mixed in the ratio shown in Table 1 to obtain a colored resin composition 1.

A 5 cm × 5 cm glass substrate (Corning Eagle 2000) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, the colored resin composition 1 was applied by spin coating. Subsequently, it prebaked for 3 minutes at 90 degreeC in clean oven. After cooling, the distance between the substrate coated with the colored resin composition 1 and the quartz glass photomask is set to 100 μm, and the exposure apparatus (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp) is used to form the atmosphere. Light was irradiated in an atmosphere with an exposure amount of 100 mJ / cm ² (based on 365 nm). In addition, irradiation to the colored resin composition at this time used the radiated light from an ultrahigh pressure mercury lamp through an optical filter (UV-35; manufactured by Asahi Techno Glass Co., Ltd.). In addition, a photomask in which patterns (translucent portions and light-shielding portions alternately have 100 μm line-shaped patterns) were formed on the same plane was used as the photomask.
After light irradiation, the coating film was developed by immersing in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23 ° C. for 80 seconds, washed with water, Post-baking was performed at 220 ° C. for 20 minutes to prepare an evaluation substrate having 100 μm colored line portions and 100 μm space portions alternately. The film thickness of the colored resin composition was 1.36 μm.
The resin compositions of Examples 1 to 9 were applied to this evaluation substrate using a spin coater at 600 rpm for 10 seconds. Thereafter, the pressure was reduced to 1.0 torr with a vacuum dryer (manufactured by Microtech Co., Ltd.) and dried, then placed on a hot plate set at 95 ° C. and prebaked for 2 minutes to form a coating film. Furthermore, it was cured by heating at 230 ° C. for 20 minutes. After cooling, the maximum film thickness and the minimum film thickness were measured using a stylus type film thickness meter (DEKTAK 6M manufactured by Veeco), and the level difference (= maximum film thickness-minimum film thickness) was calculated. The results are shown in Table 2.
It is good if the step is smaller than the film thickness of the base.

<Membrane average transmittance>
Using each resin composition, a cured film was produced as follows so that the film thickness after curing was 3 μm. The resin composition was diluted with diethylene glycol n-butyl ether acetate to a solid content of 20% by mass. The film was applied by spin coating so that the film thickness was 3 μm, prebaked at 100 ° C. for 10 minutes, and then heat-cured at 220 ° C. for 20 minutes.
About each obtained cured film, the average transmittance | permeability (%) in 400-700 nm was measured using the microspectrophotometer (OSP-SP200; product made by OLYMPUS).
Higher transmittance means less absorption.

In Table 2, the content (mass%) of the surfactant is the content (mass%) relative to the solid content of the surfactant, and the content (mass%) of the diethylene glycol butyl ether acetate is diethylene glycol butyl ether acetate relative to the total amount of the solvent. Content (mass%).
The average transmittance (%) is an average transmittance (%) at a wavelength of 400 to 700 nm at a film thickness of 3 μm.

  The curable resin composition for a flattened film of the present invention can form a flat coating film over the entire surface of a large area, and does not cause defects due to bumping of the solvent. Moreover, it is possible to form a coating film with high transmittance. Therefore, it can be suitably used for forming a planarization film used in a display device or the like, such as an overcoat, an insulating film, a coat layer for adjusting the thickness of a colored pattern, or the like.

Claims (9)

A curable resin composition for a planarization film containing a resin (A), a surfactant (B), and a solvent (C), and substantially free of a polymerizable monomer and a colorant ,
The monomer (A2) in which the resin (A) has at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (A1) and a cyclic ether bond having 2 to 4 carbon atoms And a copolymer obtained by polymerizing
Content of the said surfactant (B) is 0.005 mass%-0.5 mass% with respect to solid content ,
A curable resin composition for a planarizing film , wherein the content of the polymerizable monomer and the colorant is less than 1% by mass with respect to the entire composition.   2. The curable resin composition for a planarizing film according to claim 1, wherein the surfactant (B) is a surfactant containing at least one atom selected from the group consisting of a silicon atom and a fluorine atom. The curable resin composition for a planarizing film according to claim 1 or 2 , wherein the monomer (A2) having a cyclic ether bond having 2 to 4 carbon atoms is a monomer having an oxiranyl group. The curable resin composition for a flattened film according to claim 1 or 2 , wherein the monomer (A2) having a cyclic ether bond having 2 to 4 carbon atoms is a monomer having an aliphatic polycyclic epoxy group. The monomer (A2) having a cyclic ether bond having 2 to 4 carbon atoms is at least one compound selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II). The curable resin composition for a planarization film according to any one of claims 1 to 4 .

[In Formula (I) and Formula (II),
R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxy group.
X ¹ and X ² each independently represent a single bond, an alkylene group having 1 to 6 carbon atoms, or — (CH ₂ ) _s —X ′ — (CH ₂ ) _t —.
X ′ represents —S—, —O— or —NH—.
s and t each independently represent an integer of 0 to 6, provided that s + t = 6. ] The curable resin composition for a planarizing film according to any one of claims 1 to 5 , wherein the solvent (C) is a solvent containing diethylene glycol butyl ether acetate. Solvent (C) is a planarizing film curable resin composition according to any one of claims 1 to 5 in pairs in a solvent the total amount is a solvent containing diethylene glycol butyl ether acetate at a content of 1 to 40 wt%. Planarization film formed using a planarizing film curable resin composition according to any of claims 1-7. A display device comprising the planarizing film according to claim 8 .