JP7256247B2 - Resin, curable resin composition and cured film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin, a curable resin composition using the resin, and a cured film obtained by curing the curable resin composition.

Liquid crystal displays, plasma displays, paper-like displays, touch panels and the like are known as display devices. Among them, it is known to use a photosensitive resin composition to provide a spacer between a color filter and an array substrate that constitute a display device such as a liquid crystal display or a touch panel, in order to maintain a gap between the two substrates.

Examples of Patent Document 1 describe a photosensitive resin composition containing, as a resin component, a reaction product obtained by polymerizing methyl methacrylate, ethyl methacrylate and methacrylic acid and then reacting glycidyl methacrylate.

JP-A-3-172301

The present invention provides a novel resin useful as a binder resin for a curable resin composition capable of forming a cured film having excellent solvent resistance and adhesion even when the temperature of the post-baking step is 200° C. or less. An object of the present invention is to provide a curable resin composition using the resin and a cured film obtained by curing the curable resin composition.

The present invention includes the following.
[1] A resin having a structural unit (Aa) having an α,β-unsaturated carbonyl group, a structural unit (Ab) having an active methylene group or an active methine group, and a structural unit (Ac) having an acid group.
[2] A curable resin composition comprising the resin described in [1], a polymerizable compound, and a polymerization initiator.
[3] A cured film obtained by curing the curable resin composition according to [2].
[4] A step of applying the curable resin composition described in [2] onto a substrate, a step of drying the curable resin composition to form a curable resin composition layer, and a step of forming a curable resin composition layer. A method for producing a cured film, comprising a step of exposing and a step of heating the exposed curable resin composition layer.
[5] The method for producing a cured film according to [4], wherein the exposed curable resin composition layer is heated at 150°C or higher and 200°C or lower.

According to the curable resin composition containing the resin of the present invention, a cured film having excellent solvent resistance can be formed even when the post-baking process is performed at a temperature of 200° C. or lower.

<Resin>
The resin of the present invention (hereinafter referred to as "resin (A)") is mainly used as a binder resin for curable resin compositions. The resin (A) is a resin having a structural unit (Aa) having an α,β-unsaturated carbonyl group, a structural unit (Ab) having an active methylene group or an active methine group, and a structural unit (Ac) having an acid group. be.

More specifically, the resin (A) is as follows.
The resin (A) comprises a structural unit having an α,β-unsaturated carbonyl group (the structural unit is hereinafter referred to as a “structural unit (Aa)”) and a structural unit having an active methylene group or an active methine group ( Ab) (the structural unit is hereinafter referred to as the “structural unit (Ab)”) and a structural unit (Ac) having an acid group (the structural unit is hereinafter referred to as the “structural unit (Ac)”); including.
The resin may further contain other repeating units (Ad). Moreover, the resin may contain two or more kinds of each of the structural units (Aa), the structural units (Ab), and the structural units (Ac).
From the viewpoint that the resin (A) is used as a binder resin for a curable resin composition, the resin (A) is preferably an alkali-soluble resin. Alkali solubility refers to the property of dissolving in a developer that is an aqueous solution of an alkaline compound.
Since the resin (A) contains a polymer containing the structural unit (Ac), it easily imparts alkali solubility.
A "structural unit derived from (meth)acrylic acid and/or its ester" is also referred to as a "(meth)acrylic structural unit". In addition, "(meth)acrylic acid" shall mean "methacrylic acid and/or acrylic acid." Each structural unit will be described in detail below.

The structural unit (Aa) is typically a structural unit having a carboxy group of the copolymer (hereinafter, the structural unit is referred to as "structural unit (Aa')"), and an α,β-unsaturated carbonyl It can be obtained by adding a compound having a group, or by reacting a structural unit having an epoxy group of a copolymer with (meth)acrylic acid. The structural unit (Aa') is one type of the structural unit (Ac) described later.
The compound having an α,β-unsaturated carbonyl group is not particularly limited as long as it can react with the carboxylic acid of the structural unit (Aa'). Compounds having an α,β-unsaturated carbonyl group include (meth)acrylates (Aa'') having an epoxy group.

The (meth)acrylate (Aa'') having an epoxy group has at least one group selected from the group consisting of alicyclic epoxy groups and aliphatic epoxy groups. The alicyclic epoxy group is a group obtained by epoxidizing an alicyclic unsaturated hydrocarbon, and the aliphatic epoxy group is a group obtained by epoxidizing a linear or branched unsaturated aliphatic hydrocarbon. It means the base.
Specific examples of (meth)acrylates having an alicyclic epoxy group include:
3,4-epoxycyclohexylmethyl (meth)acrylate,
5,6-epoxy-tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate,
5,6-epoxy-tricyclo[5.2.1.0 ^2,6 ]decane-8-yloxymethyl (meth)acrylate,
2,3-epoxycyclopentylmethyl (meth)acrylate,
2-hydroxy-3-(2,3-epoxycyclopentyloxy)cyclopentylmethyl (meth)acrylate,
3-(3,4-epoxycyclohexylmethyloxycarbonyl)-6-hydroxycyclohexylmethyl (meth)acrylate,
5,6-epoxy-tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate,
5,6-epoxy-tricyclo[5.2.1.0 ^2,6 ]decane-8-yloxymethyl (meth)acrylate,
2,3-epoxycyclopentylmethyl (meth)acrylate,
2-hydroxy-3-(2,3-epoxycyclopentyloxy)cyclopentylmethyl (meth)acrylate,
3-(3,4-epoxycyclohexylmethyloxycarbonyl)-6-hydroxycyclohexylmethyl (meth)acrylate,
2-hydroxy-5-(3,4-epoxycyclohexylcarbonyloxymethyl)cyclohexylmethyl (meth)acrylate,
3-(3,4-epoxycyclohexyl)-9-hydroxy-1,5-dioxaspiro[5,5]undecane-8-yl (meth)acrylate,
3-(3,4-epoxycyclohexyl)-9-hydroxy-2,4-dioxaspiro[5,5]undecane-8-yl (meth)acrylate,
etc. These can be used alone, or can be used in combination of two or more. Among these, 3,4-epoxycyclohexylmethyl (meth)acrylate is preferably used.

［式中、Ｒ^１及びＲ^ｘは、互いに独立に、水素原子又はメチル基を表す。］
脂肪族エポキシ基を有する（メタ）アクリレートの具体例としては、エポキシメチル（メタ）アクリレート、イタコン酸グリシジルエステル類等が挙げられる。これらの中でも、エポキシメチル（メタ）アクリレートが好適に用いられる。 When obtaining the structural unit (Aa) by reacting 3,4-epoxycyclohexylmethyl (meth)acrylate with a (meth)acrylic structural unit having a carboxy group, the resulting structural unit (Aa) is represented by the formula ( Aa-1).

[In the formula, R ¹ and R ^x independently represent a hydrogen atom or a methyl group. ]
Specific examples of (meth)acrylates having an aliphatic epoxy group include epoxymethyl (meth)acrylate and itaconic acid glycidyl esters. Among these, epoxymethyl (meth)acrylate is preferably used.

［式中、Ｒ^５及びＲ^ｙは、互いに独立に、水素原子又はメチル基を表す。］
構成単位（Ａａ’）を含む共重合体としては、例えば、不飽和カルボン酸を構成単位とする共重合体、不飽和酸無水物を構成単位とする共重合体の酸無水物基にアルコールやアミンを反応させてカルボキシ基を導入した共重合体、不飽和ヒドロキシル化合物を構成単位とする共重合体のヒドロキシル基に酸無水物を反応させてカルボキシ基を導入した共重合体が挙げられる。 When obtaining the structural unit (Aa) by reacting glycidyl methacrylate with a (meth)acrylic structural unit having a carboxy group, the resulting structural unit (Aa) is represented by formula (Aa-2).

[In the formula, R ⁵ and R ^y each independently represent a hydrogen atom or a methyl group. ]
Examples of the copolymer containing the structural unit (Aa′) include a copolymer having an unsaturated carboxylic acid as a structural unit, and a copolymer having an unsaturated acid anhydride as a structural unit. Examples thereof include a copolymer obtained by reacting an amine to introduce a carboxyl group, and a copolymer obtained by reacting an acid anhydride with a hydroxyl group of a copolymer having an unsaturated hydroxyl compound as a structural unit to introduce a carboxyl group.

When the later-described structural unit (Ac) has a carboxy group, the structural unit (Ac) is reacted with a (meth)acrylate (Aa'') having an epoxy group as the structural unit (Aa') to form the structural unit (Aa ) can be obtained.

A structural unit (Ab) is a structural unit derived from an unsaturated compound having an active methylene group or an active methine group.
The structural unit can be obtained by obtaining a copolymer using an unsaturated compound having an active methylene group or an active methine group as a monomer. Alternatively, it can also be obtained by reacting another structural unit (Ab') with a compound (Ab'') having an active methylene group or an active methine group.

［式（Ｉ）及び式（ＩＩ）中、Ｒ^１１は、互いに独立に、水素原子又はヘテロ原子を含有してもよい炭素数１～２４の炭化水素基を表す。
Ｒ^１２は、単結合又は炭素数１～２０の二価の炭化水素基を表す。
Ｒ^１３は、式（１－１）～式（１－３）のいずれかで表される二価の基を表す。
Ｒ^１４は、式（１－４）～式（１－７）のいずれかで表される基を表す。

（Ｒ^１５は、ヘテロ原子を含有してもよい炭素数１～２４の炭化水素基である。）Ｘは、式（１－８）～式（１－１０）のいずれかで表される二価の基を表す。］

Examples of unsaturated compounds having an active methylene group include compounds represented by formula (I). Examples of unsaturated compounds having an active methine group include compounds represented by formula (II).

[In formulas (I) and (II), R ¹¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may contain a heteroatom.
R ¹² represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms.
R ¹³ represents a divalent group represented by any one of formulas (1-1) to (1-3).
R ¹⁴ represents a group represented by any one of formulas (1-4) to (1-7).

(R ¹⁵ is a hydrocarbon group having 1 to 24 carbon atoms which may contain a heteroatom.) X is a divalent group represented by any one of formulas (1-8) to (1-10). represents a valence group. ]

Ｒ^１２は、好ましくは単結合、メチレン基、エチレン基、プロピレン基、ブチレン基、プロピレン基、へキシレン基、シクロへキシレン基、オクチレン基、デシレン基、ドデシレン基であり、より好ましくは単結合、メチレン基、エチレン基である。
R ¹¹ is preferably a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, methoxy group, ethoxy group, propoxy group, hexoxy group, cyclohexoxy group or formula (1-11) to It is a group represented by formula (1-13), more preferably a hydrogen atom or a methyl group.
R ¹⁵ is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a methoxy group, an ethoxy group, a propoxy group, a hexoxy group, a cyclohexoxy group or a group of formulas (1-11) to ( 1-13), more preferably a methyl group.

R ¹² is preferably a single bond, methylene group, ethylene group, propylene group, butylene group, propylene group, hexylene group, cyclohexylene group, octylene group, decylene group or dodecylene group, more preferably a single bond, methylene group and ethylene group.

Specific examples of the compound represented by formula (I) include the following compounds.

式（Ｉ－１）～（Ｉ－７）、（Ｉ－１６）、（ＩＩ－１）、（ＩＩ－２）及び（ＩＩ－５）は、ＣＨ_３－ＣＨ_２＝ＣＨ－を有する化合物であるが、これらの式においてＣＨ_３－ＣＨ_２＝ＣＨ－がＨ－ＣＨ_２＝ＣＨ－に置き換わった化合物も挙げることができる。 Specific examples of the compound represented by formula (II) include the following compounds.

Formulas (I-1) to (I-7), (I-16), (II-1), (II-2) and (II-5) are compounds having CH ₃ —CH ₂ ═CH— However, compounds in which CH ₃ —CH ₂ ═CH— is replaced by H—CH ₂ ═CH— in these formulas can also be mentioned.

［式（Ａｂ－１）中、Ｒ^３は水素原子又はメチル基を表し、Ｒ^４は水素原子又は炭素数１～６のアルキル基を表す。］
式（Ａｂ－１）で表される構成単位を導く化合物としては、例えば、２－（メタクリロイルオキシ）エチルアセトアセテート〔式（Ｉ－１）で表される化合物〕が挙げられる。 The structural unit (Ab) is preferably a structural unit represented by formula (Ab-1).

[In the formula (Ab-1), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]
Examples of the compound leading to the structural unit represented by formula (Ab-1) include 2-(methacryloyloxy)ethylacetoacetate [compound represented by formula (I-1)].

A structural unit (Ac) is a structural unit derived from an unsaturated compound having an acid group.
A carboxyl group, a phenolic hydroxyl group, a sulfonic acid etc. are mentioned as an acid group. The carboxyl group may be anhydrided.

The structural unit can be obtained by obtaining a copolymer using an unsaturated compound having an acid group as a monomer. It can also be obtained by reacting another structural unit (Ac') with a compound (Ac'') having an acid group.
The unsaturated compound having an acid group is preferably unsaturated carboxylic acid or unsaturated carboxylic acid anhydride. Specific examples of unsaturated carboxylic acids or unsaturated carboxylic acid anhydrides include:
Unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
anhydrides of said unsaturated dicarboxylic acids;
Unsaturated mono[(meth)acryloyloxyethyl] succinate mono[2-(meth)acryloyloxyethyl] phthalate mono[2-(meth)acryloyloxyethyl] polycarboxylic acids with a valence of 2 or more alkyl] ester;
Examples include unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)(meth)acrylic acid.
Among these, (meth)acrylic acid and maleic anhydride are preferably used because of their copolymerization reactivity and solubility in alkaline aqueous solutions. These are used singly or in combination.

The resin (A) has a structural unit other than the structural unit (Aa), the structural unit (Ab), and the structural unit (Ac) (hereinafter, the structural unit is referred to as a "structural unit (Ad)"). good.
The structural unit (Ad) is a structural unit different from the structural unit (Aa), the structural unit (Ab) and the structural unit (Ac). The structural unit (Ad) is derived from monomers polymerizable with monomers leading to other structural units (eg, structural unit (Aa), structural unit (Ab) and structural unit (Ac)).
Specific examples of such monomers include:
(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;
acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate;
cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate (in the technical field, dicyclopenta cyclic alkyl (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate and isobornyl (meth)acrylate;
Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate (commonly known in the art as dicyclopentanyl ( meth)acrylic acid (meth)acrylic acid cyclic alkyl esters such as dicyclopentoxyethyl (meth)acrylate and isobornyl (meth)acrylate;
(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 and diethyl itaconate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, 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-carboxybicyclo[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-dicarboxybicyclo[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-carboxy-5-methyl bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[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 (hymic acid anhydride), 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyl oxycarbonylbicyclo[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 and other bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 - dicarbonylimide derivatives such as maleimidopropionate, N-(9-acridinyl)maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , isoprene, 2,3-dimethyl-1,3-butadiene;
etc.

Among these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene and the like are preferred from the standpoint of reactivity in copolymerization and solubility in alkaline aqueous solution. preferable.

The resin (A) may have two or more types of structural units (Ad).

The resin (A) contains a structural unit (Aa), a structural unit (Ab), a structural unit (Ac), and further includes a copolymer that may contain a structural unit (Ad), and the ratio of each structural unit However, it is preferably in the following range in terms of mole fraction with respect to the total number of moles of structural units constituting the copolymer.
Structural unit (Aa): 5 to 50 mol%,
Structural unit (Ab): 5 to 50 mol%,
Structural unit (Ac): 5 to 50 mol%,
Structural unit (Ad): 0 to 70 mol%.

Moreover, when the ratio of the structural units is within the following range, the solvent resistance tends to be further improved, which is more preferable.
Structural unit (Aa): 10 to 40 mol%,
Structural unit (Ab): 10 to 40 mol%,
Structural unit (Ac): 10 to 40 mol%,
Structural unit (Ad): 0 to 60 mol%.

Copolymers containing each structural unit are described, for example, in the document "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu, Published by Kagaku Doujin Publishing Co., Ltd., 1st Edition, 1st Edition, March 1, 1972). It can be manufactured according to the method and the reference described in the literature.

Resin (A) can be produced, for example, through a two-stage process. Specifically, each compound leading to the structural unit (Ab) and the structural unit (Ac), and a predetermined amount of the compound leading to the structural unit (Aa′), a polymerization initiator and a solvent are charged into a reaction vessel, and nitrogen is added. By substituting oxygen, in the absence of oxygen, by stirring, heating (for example, 50 to 140 ° C.), and keeping warm (for example, 1 to 10 hours), the structural unit (Aa'), the structural unit (Ab) and the structural unit A copolymer having units (Ac) is obtained. Then, nitrogen in the reaction vessel is replaced with oxygen, (meth)acrylate (Aa'') having an epoxy group, a reaction catalyst, a polymerization inhibitor, etc. are placed in the reaction vessel, stirred and heated (for example, 60 to 130 ° C. ), and by keeping the temperature warm (for example, 1 to 10 hours), the structural unit (Aa) is introduced by reacting the structural unit (Aa′) with a (meth)acrylate (Aa'') having an epoxy group. A copolymer having (Aa), structural units (Ab) and structural units (Ac) is obtained.
The obtained copolymer may be used as a solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be taken out as a solid by a method such as reprecipitation and dissolved again in a solvent. can be used as

When the resin (A) further having the structural unit (Ad) is produced, in the above step, each compound that leads to the structural unit (Ab) and the structural unit (Ac) and the compound that leads to the structural unit (Aa'), the structural unit (Ad) should be added.

In the above, when the structural unit (Ac) has a carboxy group, the structural unit (Aa) can be obtained by reacting the structural unit (Ac) with a (meth)acrylate (Aa'') having an epoxy group. can.
The polystyrene-equivalent weight average molecular weight of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 10,000 to 50,000.
A curable resin composition containing a resin (A) having a weight-average molecular weight within the above range tends to have good coatability when applied, is less prone to film thinning during development, and is unremovable during development. It tends to be easy to remove the hardened portion.

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 curable resin composition containing this as a binder resin tends to have excellent developability, which is preferable.
The acid value of resin (A) is preferably 70-150 mg-KOH/g, more preferably 75-135 mg-KOH/g.
As used herein, the acid value is a value measured according to JIS K 2501-2003.

<Curable resin composition>
The curable resin composition of the present invention contains a resin (A), a polymerizable compound and a polymerization initiator. The curable resin composition of the invention may further contain a solvent. Hereinafter, the polymerizable compound, polymerization initiator and solvent in the curable resin composition of the present invention are referred to as polymerizable compound (B), polymerization initiator (C) and solvent (D), respectively.

[1] Resin (A)
Since the curable resin composition of the present invention contains the resin (A), it can form a cured film having excellent solvent resistance.
The cured film formed from the curable resin composition containing the resin (A) has a temperature of 200° C. or less, for example, 150° C. in the heating step after exposure (so-called post-baking step) when producing the cured film.
Even at temperatures above 200° C. and below, excellent solvent resistance can be exhibited.
In the curable resin composition of the present invention, the content of the resin (A) is preferably 5 to 90% by mass, more preferably 10 to 70% by mass relative to the solid content in the curable resin composition. % by mass.
When the content of the resin (A) is in the above range, the solubility in the developer is sufficient, the development residue is less likely to occur, and the film reduction of the exposed and cured portion during development is less likely to occur. The uncured portion tends to be easy to remove, which is preferable.
Here, the solid content refers to the amount obtained by removing the content of the solvent from the total amount of the curable resin composition. The total amount of solids and the content of each component relative thereto can be measured by known analysis means such as liquid chromatography or gas chromatography.
In addition, an acrylic binder resin that is commonly used in this field may be used in combination as long as it does not impair the effects of the present invention.

[2] Polymerizable compound (B)
The polymerizable compound (B) is not particularly limited as long as it is a compound that can be polymerized by active radicals generated from the polymerization initiator (D) by light irradiation or the like. Examples of the polymerizable compound (B) include compounds having an ethylenically unsaturated bond, monofunctional monomers having one functional group having an ethylenically unsaturated bond, and bifunctional monomers having two such functional groups. , and other polyfunctional monomers having three or more of the functional groups.
Specific examples of the monofunctional monomers include nonylphenyl carbitol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-ethylhexylcarbitol (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. , N-vinylpyrrolidone, and the like.
Specific examples of the bifunctional monomer include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bisphenol A bis(acryloyloxyethyl) ether, 3-methylpentanediol di(meth)acrylate and the like.
Specific examples of the polyfunctional monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth) ) acrylate, reaction product of pentaerythritol tri(meth)acrylate and acid anhydride, reaction product of dipentaerythritol penta(meth)acrylate and acid anhydride, and the like.
Among them, bifunctional monomers and polyfunctional monomers are preferably used.
These polymerizable compounds (B) may be used alone or in combination of two or more.
The content of the polymerizable compound (B) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, based on the total amount of the resin (A) and the polymerizable compound (B). is. When the content of the polymerizable compound (B) is within the above range, the cured film obtained by curing the curable resin composition tends to have good strength, smoothness and solvent resistance, which is preferable.

[3] Polymerization initiator (C)
The polymerization initiator (C) is not particularly limited as long as it is a compound capable of initiating polymerization by generating active radicals, acids, etc. by the action of light or heat, and known polymerization initiators can be used.
As the polymerization initiator (C), acetophenone-based, biimidazole-based, oxime-based, triazine-based, acylphosphine oxide-based polymerization initiators, and organic boron salt-based polymerization initiators are preferred.
By using these polymerization initiators (C) together with a polymerization initiation aid, the sensitivity of the curable resin composition to be obtained is further increased, and when patterns are formed using this, pattern productivity is improved. Therefore, it is preferable.

Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)butan-1-one, 2-(2-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methylbenzyl)-2-dimethylamino -1-(4-morpholinophenyl)-butanone, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-ethylbenzyl)-2-dimethylamino -1-(4-morpholinophenyl)-butanone, 2-(2-propylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-butylbenzyl)-2-dimethylamino -1-(4-morpholinophenyl)-butanone, 2-(2,3-dimethylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2,4-dimethylbenzyl)- 2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-chlorobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-bromobenzyl)- 2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-chlorobenzyl)- 2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-bromobenzyl)- 2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methoxybenzyl)- 2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-methyl-4- methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2 -(2-bromo-4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane -1-one oligomers, and the like.

Examples of the biimidazole compounds include 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2,3-dichlorophenyl)-4 ,4′,5,5′-tetraphenylbiimidazole (see JP-A-6-75372, JP-A-6-75373, etc.), 2,2′-bis(2-chlorophenyl)-4,4′ ,5,5′-tetraphenylbiimidazole, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetra(alkoxyphenyl)biimidazole, 2,2′-bis(2- chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl) Biimidazole (see JP-B-48-38403, JP-A-62-174204, etc.), imidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group ( See JP-A-7-10913, etc.), preferably 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′- and bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

Examples of the oxime compound include O-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, compounds represented by formula (P3), compounds represented by formula (P4), and the like.

Examples of the triazine-based compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4- methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxy styryl)-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-(furan-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, etc. is mentioned.

Examples of the acylphosphine oxide initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Examples of the organic boron salt initiator include tetramethylammonium n-butyltriphenylborate, tetraethylammonium isobutyltriphenylborate, tetra-n-butylammonium n-butyltri(4-tert-butylphenyl)borate, tetra-n-butylammonium n-butyltrinaphthylborate, tetra-n-butylammonium methyltri(4-methylnaphthyl)borate, triphenylsulfonium n-butyltriphenylborate, triphenyloxosulfonium n-butyltriphenylborate, triphenyloxonium n-butyl triphenylborate, N-methylpyridium n-butyltriphenylborate, tetraphenylphosphonium n-butyltriphenylborate, diphenyliodonium n-butyltriphenylborate and the like.

A polymerization initiator or the like commonly used in this field can be used in combination, and examples of the polymerization initiator include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. More specifically, the following compounds can be mentioned, and these can be used alone or in combination of two or more.

Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxy carbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

The thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

Examples of the anthracene-based compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene.

Other examples of polymerization initiators include 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds.

As the polymerization initiator having a group capable of causing chain transfer, polymerization initiators described in JP-T-2002-544205 can be used. Examples of the polymerization initiator having a group capable of causing chain transfer include polymerization initiators represented by formulas (P5) to (P10).

The polymerization initiator having a group capable of undergoing chain transfer can also be used as the constituent component (Ad) of the resin (A). Then, the obtained resin (A) can be used as a binder resin for the curable resin composition of the present invention.

A polymerization initiation aid can also be used in combination with the polymerization initiator. As the polymerization initiation aid, an amine compound and the following carboxylic acid compounds are preferred, and the amine compound is more preferably an aromatic amine compound.

Specific examples of polymerization initiation aids include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and isoamyl 4-dimethylaminobenzoate. , 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl p-toluidine, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone aromatic amine compounds such as

Examples of the carboxylic acid compounds include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, aromatic heteroacetic acids such as N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid;

The content of the polymerization initiator (C) is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, based on the total amount of the resin (A) and the polymerizable compound (B). %.
The content of the polymerization initiation aid is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass, based on the total amount of the resin (A) and the polymerizable compound (B). %.
When the total amount of the polymerization initiator (C) is within the above range, the curable resin composition becomes highly sensitive, and the strength of the cured film formed using the curable resin composition and the strength of the cured film Smoothness on the surface tends to be improved, which is preferable. In addition to the above, when the amount of the polymerization initiation aid is within the above range, the sensitivity of the resulting curable resin composition is further increased, and the productivity of patterned substrates formed using the above curable resin composition. tends to improve, which is preferable.

[4] Solvent (D)
The curable resin composition of the present invention preferably contains a solvent (D). The solvent (D) can be various organic solvents used in the field of curable resin compositions. Specific examples thereof 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 monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether and diethylene 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 and diethylene glycol dibutyl ether;
ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve 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 and methoxypentyl acetate;
dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monopropyl ether;
dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate and dipropylene glycol monopropyl ether acetate;
aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone;
alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;
Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;
Cyclic esters such as γ-butyrolactone are included.

Among the above solvents, from the viewpoint of coating properties and drying properties, the solvent preferably has a boiling point of 100
~200 ° C. organic solvents, more preferably alkylene glycol alkyl ether acetate, ketone, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate , propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate.

A solvent (D) can be used individually or in mixture of 2 or more types. The content of the solvent (D) is preferably 60 to 90% by mass, more preferably 70 to 85% by mass, based on the curable resin composition. When the content of the solvent (D) is within the above range, when applied with a coating device such as a spin coater, a slit & spin coater, a slit coater (also called a die coater or curtain flow coater), an inkjet, etc. It is expected that the coatability will be improved in this case, and is therefore preferable.

[5] Additive (F)
The curable resin composition of the present invention may optionally contain a colorant, a filler, other polymer compounds, a pigment dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber, a chain transfer agent, and an acid generator. Additives (F) such as agents and base generators can also be used in combination. A curable resin composition for a color filter can be configured by adding a coloring agent, for example.

Colorants include dyes and/or pigments. These coloring agents may be used alone or in combination of two or more. In that case, a combination of only dyes, a combination of only pigments, or a combination of dyes and pigments may be used. In particular, it preferably contains a dye.

Dyes include acid dyes, basic dyes, direct dyes, sulfur dyes, vat dyes, naphthol dyes, reactive dyes, disperse dyes, and the like, and can be selected from dyes conventionally known for use in color filters. For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-A-2592207, US Pat. No. 4,808,501 Specification, US Pat. No. 5,667,920, US Pat. and dyes described in JP-A-6-194828.
Specifically, pyrazoleazo, anilinoazo, arylazo, pyrazolotriazoleazo, pyridoneazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, cyanine, polymethine, and phenothiazine , pyrrolopyrazole azomethine series, xanthene series, phthalocyanine series, quinophthalone series, benzopyran series, indigo series, dioxazine series, coumarin series, squarylium series, preferably pyrazole azo series, anilinoazo series, pyrazolotriazole azo series and pyridone azo series. , anthraquinone, anthrapyridone, phthalocyanine, dioxazine, quinophthalone, and xanthene, more preferably pyrazole azo, pyridone azo, phthalocyanine, quinophthalone, and xanthene.

Examples of the pigment include organic pigments and inorganic pigments, and include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists).
For example, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55
, 59, 61, 64, 65, 71, 73;
C. I. red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 60;
C. I. Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as Pigment Green 7, 36;
C. I. Brown pigments such as Pigment Brown 23, 25;
C. I. black pigments such as Pigment Black 1 and 7;
Among them, C.I. I. Pigment Yellow 138, 139, 150, C.I. I. Pigment Red 177, 209, 254, C.I. I. Pigment Violet 23, C.I. I. Pigment Blue 15:6 and C.I. I. It preferably contains at least one pigment selected from Pigment Green 36. These pigments may be used alone or in combination of two or more.

Among the above pigments, organic pigments may optionally be subjected to rosin treatment, surface treatment using a pigment derivative or pigment dispersant into which an acidic group or basic group is introduced, or grafting onto the pigment surface using a polymer compound or the like. treatment, atomization treatment such as sulfuric acid atomization method, washing treatment with an organic solvent or water for removing impurities, removal treatment of ionic impurities by ion exchange method or the like may be performed.

Commercially available surfactants can be used as the pigment dispersant. Examples of such surfactants include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more. Specific examples include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid-modified polyester, tertiary amine-modified polyurethane, and polyethyleneimine. Furthermore, as the surfactant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (manufactured by Tochem Products Co., Ltd.), Megafac (manufactured by DIC Corporation), ), Florard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS), PB821 (manufactured by Ajinomoto Co., Ltd.) ), Disperbyk (manufactured by BYK-Chemie) and the like.

A filler may be added for adjusting the strength of the cured film and for coloring. Specific examples of the filler include glass, silica, alumina, and pigments.

Other polymer compounds may be added for adjusting the strength of the cured film. Specific examples of other polymer compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, and polyurethanes. can be used.

An adhesion promoter may be added to improve adhesion to the substrate or base material. Specific examples of the adhesion promoter include 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-epoxy cyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

An antioxidant may be added to prevent deterioration of the cured film due to oxidation. Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol and the like.

An ultraviolet absorber may be added to prevent deterioration of the cured film due to ultraviolet rays. Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone.

A chain transfer agent may be added for molecular weight control in the curing reaction. Examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

An acid generator may be added as a curing reaction catalyst. Examples of the acid generator include aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, triarylsulfoxonium salts, pyridinium salts, quinolinium salts, isoquinolinium salts, sulfonic acid esters, and iron arene complexes.

A base generator may be added as a curing reaction catalyst. Examples of the base generator include carbamate derivatives such as 1-methyl-1-(4-biphenylyl)ethylcarbamate and 1,1-dimethyl-2-cyanoethylcarbamate, urea and N,N-dimethyl-N'-methyl Urea derivatives such as urea, dihydropyridine derivatives such as 1,4-dihydronicotinamide, quaternary ammonium salts of organic silanes and organic boranes, dicyandiamide, benzoylcyclohexylcarbamates and triglycerides described in JP-A-4-162040. Compounds such as phenylmethanol, compounds described in JP-A-5-158242, and the like.

[6] Cured Film A cured film obtained by curing the curable resin composition of the present invention is also one aspect of the present invention.

The cured film of the present invention comprises a step of applying the curable resin composition on a substrate, a step of drying the curable resin composition to form a curable resin composition layer, and a step of forming a curable resin composition layer. It can be obtained by a manufacturing method including a step of exposing and a step of post-baking the exposed curable resin composition layer.

As a method for producing a cured film of the present invention, for example, a curable resin composition is applied on a substrate, the applied curable resin composition is dried to form a curable resin composition layer, and if necessary A cured film having a pattern (hereinafter “pattern”) is formed by a method of exposing and developing the curable resin composition layer through a photomask, or by applying a curable resin composition using an inkjet device. There is a case called.) can be mentioned.
Examples of the substrate include resin substrates such as transparent glass plates, silicon wafers, polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamideimide substrates, and polyimide substrates.
A black matrix, another cured film or colored pattern, a transparent pattern for film thickness adjustment, a TFT, and the like may be formed on the substrate. The thickness of the cured film in this case is not particularly limited, and can be appropriately adjusted depending on the material used, the application, etc. For example, it is about 0.1 to 30 μm, preferably about 1 to 20 μm, more preferably 1 to 6 μm. degree is exemplified.

The coating method of the curable resin composition includes an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, a die coating method and the like. Coating may also be performed using a dip coater, bar coater, spin coater, slit & spin coater, slit coater (also called die coater, curtain flow coater, spinless coater), roller, or the like. Especially, it is preferable to apply using a spin coater.

Methods for drying the curable resin composition include natural drying, ventilation drying, and drying under reduced pressure. As a specific heating temperature, about 30 to 120°C is suitable, and about 60 to 100°C is preferable. A suitable heating time is about 10 seconds to 60 minutes, preferably about 30 seconds to 30 minutes. The reduced pressure drying is exemplified by carrying out under a pressure of about 50 to 150 Pa and a temperature range of about 20 to 25°C. When the curable resin composition of the present invention contains the solvent (D), the solvent (D) can be removed by the drying described above.

The obtained curable resin composition layer may be irradiated with radiation through a photomask.
As a photomask, a mask in which a light shielding portion is formed according to an intended pattern is used. Rays such as g-line and i-line are used as the radiation. For irradiation with radiation, it is preferable to use devices such as a mask aligner and a stepper. After irradiation with radiation, the curable resin composition layer is developed. Development can be performed on the exposed curable resin composition layer by a puddle method, an immersion method, a spray method, a shower method, or the like. In addition, when irradiating radiation to a curable resin composition layer without passing through a photomask, development is unnecessary.

As the developer, an alkaline aqueous solution is usually used. As the alkaline aqueous solution, an aqueous solution of an alkaline compound is used, and the alkaline compound may be an inorganic alkaline compound or an organic alkaline compound. The alkaline developer may contain a surfactant.
The alkaline compound may be either inorganic or organic alkaline compounds. Specific examples of inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia and the like.
Specific examples of organic alkaline compounds include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, and the like. mentioned. These inorganic and organic alkaline compounds can be used either alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The surfactant in the alkaline developer may be any of nonionic surfactants, anionic surfactants and cationic surfactants. Specific examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, sorbitan fatty acid esters, poly oxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines and the like.
Specific examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and dodecyl and alkylarylsulfonates such as sodium naphthalenesulfonate.
Specific examples of cationic surfactants include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants can be used alone or in combination of two or more.
The concentration of the surfactant in the alkaline developer is preferably in the range of 0.01-10% by mass, more preferably 0.05-8% by mass, still more preferably 0.1-5% by mass.

In the present invention, the post-baking temperature is preferably 150° C. or higher.
In addition, it is preferably lower than the glass transition temperature (Tg) of the substrate on which the cured film is formed, and if it contains a component that deteriorates at a temperature exceeding 200 ° C. such as a coloring agent, it should be lower than the temperature at which the component starts to deteriorate. preferable.
Therefore, the temperature at the time of post-baking may be appropriately determined according to the type of substrate on which the cured film is formed, the components contained in the curable resin composition, and the like, and is preferably 150° C. or higher and 200° C. or lower. , 150° C. or higher and 180° C. or lower. A cured film having excellent solvent resistance can be obtained by setting the temperature at the time of post-baking to 150° C. or higher. Moreover, when the resin according to the present invention is used, a cured film having excellent solvent resistance can be obtained without deteriorating the properties of the substrate, colorant, and the like.

By using the curable resin composition of the present invention, in order to improve solvent resistance, the post-baking process at a temperature exceeding 200 ° C., which has been usually performed in the past, is no longer essential, so excellent solvent resistance can be obtained. It is possible to obtain a cured film that has the properties of the substrate and the colorant without deterioration.

A cured film can be formed on a substrate from the curable resin composition of the present invention through the steps described above. This cured film is useful as a photospacer used in a liquid crystal display device, an interlayer insulating film, a coating layer for adjusting the film thickness of a colored pattern, and the like.
An interlayer insulating film having holes can be obtained by using a photomask for forming holes when the curable resin composition layer is exposed for patterning in the production of the cured film.
When the curable resin composition of the present invention contains a coloring agent, it is useful as a colored pattern in a color filter.
When exposing the curable resin composition layer in the production of the cured film, the cured film can be formed only by exposure and heat curing without using a photomask, or only by heat curing. Useful as an overcoat.
A display device such as a liquid crystal display device can be configured by incorporating the cured film obtained as described above. Such a display device has excellent display quality.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In the examples, percentages and parts representing contents or usage amounts are based on mass unless otherwise specified.

攪拌翼、還流冷却管、温度計及び滴下ロートを備えたフラスコに、プロピレングリコールモノメチルエーテル７０質量部を仕込み、９０℃に加温した。ジシクロペンタニルメタクリレート５２．６質量部、２－（アセトアセトキシ）エチルメタクリレート２０．７質量部、メタクリル酸２６．７質量部、アゾビス（イソブチロニトリル）５質量部、プロピレングリコールモノメチルエーテル３０質量部を混合した溶液を滴下ロートにてフラスコ内に連続滴下を開始した。混合溶液滴下中のフラスコ内温度を９０±１℃に保ち、３時間で滴下を終了した。滴下終了後、フラスコ内温度を９０±１℃にして６時間保持した。反応後、反応液を４０℃以下になるまで冷却し、４－メトキシフェノール０．１２質量部、３，４－エポキシシクロヘキシルメチルアクリレート１７．６質量部、トリフェニルホスフィン４．７質量部、プロピレングリコールモノメチルエーテル８５質量部を投入し、フラスコ内温度を１１０℃まで昇温させた後、フラスコ内温度１１０±１℃にて付加反応を行うことにより樹脂（Ａ１）を得た。得られた樹脂（Ａ１）の重量平均分子量（Ｍｗ）は１４，３００、分散度は２．４、酸価は１０３（ｍｇ－ＫＯＨ／ｇ）、固形分は３７．９質量％であった。 <Example 1>
A resin (A1) composed of the following structural units was synthesized.

A flask equipped with a stirring blade, a reflux condenser, a thermometer and a dropping funnel was charged with 70 parts by mass of propylene glycol monomethyl ether and heated to 90°C. 52.6 parts by mass of dicyclopentanyl methacrylate, 20.7 parts by mass of 2-(acetoacetoxy)ethyl methacrylate, 26.7 parts by mass of methacrylic acid, 5 parts by mass of azobis(isobutyronitrile), 30 parts by mass of propylene glycol monomethyl ether Continuous dropping of the mixed solution into the flask was started using a dropping funnel. The temperature inside the flask was kept at 90±1° C. during the dropwise addition of the mixed solution, and the dropwise addition was completed in 3 hours. After completion of dropping, the temperature inside the flask was raised to 90±1° C. and maintained for 6 hours. After the reaction, the reaction solution is cooled to 40° C. or less and mixed with 0.12 parts by mass of 4-methoxyphenol, 17.6 parts by mass of 3,4-epoxycyclohexylmethyl acrylate, 4.7 parts by mass of triphenylphosphine, and propylene glycol. After adding 85 parts by mass of monomethyl ether and raising the temperature in the flask to 110° C., an addition reaction was carried out at the temperature in the flask of 110±1° C. to obtain a resin (A1). The obtained resin (A1) had a weight average molecular weight (Mw) of 14,300, a dispersity of 2.4, an acid value of 103 (mg-KOH/g), and a solid content of 37.9% by mass.

攪拌翼、還流冷却管、温度計及び滴下ロートを備えたフラスコに、プロピレングリコールモノメチルエーテル７０質量部を仕込み、９０℃に加温した。メチルメタクリレート４４．６質量部、２－（アセトアセトキシ）エチルメタクリレート２８．６質量部、メタクリル酸２６．８質量部、アゾビス（イソブチロニトリル）５質量部、プロピレングリコールモノメチルエーテル３０質量部を混合した溶液を滴下ロートにてフラスコ内に連続滴下
を開始した。混合溶液滴下中のフラスコ内温度を９０±１℃に保ち、３時間で滴下を終了した。滴下終了後、フラスコ内温度を９０±１℃にして６時間保持した。反応後、反応液を４０℃以下になるまで冷却し、４－メトキシフェノール０．１２質量部、３，４－エポキシシクロヘキシルメチルアクリレート２４．４質量部、トリフェニルホスフィン５質量部、プロピレングリコールモノメチルエーテル９５質量部を投入し、フラスコ内温度を１１０℃まで昇温させた後、フラスコ内温度１１０±１℃にて付加反応を行うことにより樹脂（Ａ２）を得た。得られた樹脂（Ａ２）の重量平均分子量（Ｍｗ）は１５，８００、分散度は２．４、酸価は８０（ｍｇ－ＫＯＨ／ｇ）、固形分は３８．５質量％であった。 <Example 2>
A resin (A2) composed of the following structural units was synthesized.

A flask equipped with a stirring blade, a reflux condenser, a thermometer and a dropping funnel was charged with 70 parts by mass of propylene glycol monomethyl ether and heated to 90°C. Mix 44.6 parts by mass of methyl methacrylate, 28.6 parts by mass of 2-(acetoacetoxy)ethyl methacrylate, 26.8 parts by mass of methacrylic acid, 5 parts by mass of azobis(isobutyronitrile), and 30 parts by mass of propylene glycol monomethyl ether. Continuous dropping of the obtained solution into the flask was started using a dropping funnel. The temperature inside the flask was kept at 90±1° C. during the dropwise addition of the mixed solution, and the dropwise addition was completed in 3 hours. After completion of dropping, the temperature inside the flask was raised to 90±1° C. and maintained for 6 hours. After the reaction, the reaction solution is cooled to 40° C. or less, 0.12 parts by mass of 4-methoxyphenol, 24.4 parts by mass of 3,4-epoxycyclohexylmethyl acrylate, 5 parts by mass of triphenylphosphine, and propylene glycol monomethyl ether. After adding 95 parts by mass and raising the temperature inside the flask to 110° C., an addition reaction was carried out at an inside temperature of the flask of 110±1° C. to obtain a resin (A2). The obtained resin (A2) had a weight average molecular weight (Mw) of 15,800, a dispersity of 2.4, an acid value of 80 (mg-KOH/g), and a solid content of 38.5% by mass.

撹拌装置、滴下ロート、コンデンサー、温度計、ガス導入管を備えたフラスコにプロピレングリコールモノメチルエーテルアセテート１００質量部をとり、窒素置換しながら撹拌し１２０℃に昇温した。次にメチルメタクリレート４３質量部、メタクリル酸２５質量部からなるモノマー混合物に、ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエート（パーブチルＯ；日油（株）製）をモノマー混合物１００質量部に対し１質量部を添加した。これを滴下ロートから２時間かけてフラスコに滴下し、さらに１２０℃で２時間撹拌し共重合体を得た。次にフラスコ内を空気置換し、グリシジルメタクリレート１０質量部、トリフェニルホスフィン０．４４質量部、及びメチルハイドロキノン０．０８質量部を上記共重合体の溶液中に投入し１２０℃で反応を続け、固形分の酸価が１００ＫＯＨｍｇ／ｇとなったところで反応を終了し、プロピレングリコールモノメチルエーテルアセテート５０質量部を加えることで、重量平均分子量（Ｍｗ）は３００００、分散度は２．５、酸価は１００（ｍｇ－ＫＯＨ／ｇ）、固形分が４０％である樹脂（Ａ３）を得た。 <Synthesis Example 1>
A resin (A3) composed of the following structural units was synthesized.

100 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and the mixture was stirred while being replaced with nitrogen and heated to 120°C. Next, a monomer mixture consisting of 43 parts by mass of methyl methacrylate and 25 parts by mass of methacrylic acid is added with tert-butyl peroxy-2-ethylhexanoate (Perbutyl O; manufactured by NOF Corporation) per 100 parts by mass of the monomer mixture. 1 part by weight was added. This was added dropwise from the dropping funnel to the flask over 2 hours, and stirred at 120° C. for 2 hours to obtain a copolymer. Next, the inside of the flask was replaced with air, 10 parts by mass of glycidyl methacrylate, 0.44 parts by mass of triphenylphosphine, and 0.08 parts by mass of methylhydroquinone were added to the copolymer solution, and the reaction was continued at 120°C. The reaction was terminated when the acid value of the solid content reached 100 KOH mg / g, and 50 parts by mass of propylene glycol monomethyl ether acetate was added to obtain a weight average molecular weight (Mw) of 30000, a dispersity of 2.5, and an acid value of 100 (mg-KOH/g) and a resin (A3) with a solids content of 40% was obtained.

<Method for measuring molecular weight>
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the methacrylic copolymers (A1) to (A3) were measured by GPC under the following conditions.
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 polystyrene equivalent weight average molecular weight (Mw) to the number average molecular weight (Mn) obtained above was defined as the degree of dispersion (Mw/Mn).

(2) Preparation of curable resin composition <Example 3>
132 parts of a resin solution containing the resin (A1) obtained in Example 1 and having a solid content of 37.9% (50 parts in terms of solid content) and 200 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as "solvent D1") were mixed to obtain a curable resin composition 1 having a solid content of 15%.

<Comparative Example 1>
In the same manner as in Example 3, except that 130 parts of the resin solution containing the resin (A3) and having a solid content of 40% was used instead of 132 parts of the resin solution containing the resin (A1). A resin composition 2 was obtained.

(3) Formation of cured film The curable resin composition 1 and the curable resin composition 2 are each formed on a separate 2-inch square glass substrate (Eagle XG; manufactured by Corning) to a film thickness of 1 after post-baking. 0 μm, vacuum drying (ultimate pressure 66 Pa), and pre-baking at 100° C. for 3 minutes to obtain a curable resin composition layer.
The resulting curable resin composition layer was post-baked in an oven at 150° C. for 30 minutes to obtain a cured film.
The film thickness of the obtained cured film was measured with a film thickness measuring device (DEKTAK3; manufactured by ULVAC, Inc.) and found to be 1.0 μm.

(4) Evaluation <Solvent resistance>
The obtained cured film was immersed in N-methylpyrrolidone (hereinafter sometimes abbreviated as NMP) at a temperature of 23 ° C. for 0.5 hours, and the cured film after immersion was measured by a film thickness measuring device (DEKTAK3; Ulvac) was used to measure the film thickness, and the ratio to the film thickness before immersion was calculated. Table 1 shows the results.

<Adhesion>
The resulting cured film was immersed in NMP at a temperature of 23 ° C. for 0.5 hours, and the cured film after immersion was cut into 10 × 10 squares at intervals of 1 mm using a cutter knife according to JIS K5400. A notch was made so as to form a flat surface, and cellophane tape was attached and then peeled off. Table 1 shows the results.

<Example 4>
Pentaerythritol triacrylate (A-TMM-3LM-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) ( Hereinafter referred to as "polymerizable compound (B1)") 50 parts, photopolymerization initiator (IRGACURE (registered trademark) OXE01, manufactured by BASF) (hereinafter referred to as "polymerization initiator (C1)") 3 parts, propylene 502 parts of glycol monomethyl ether acetate (hereinafter referred to as "solvent D1") was mixed to obtain a curable resin composition 3 having a solid content of 15%.

<Example 5>
In the same manner as in Example 4, except that 130 parts of a resin solution containing resin (A2) with a solid content of 38.5% was used instead of the resin solution containing resin (A1), and 504 parts of solvent D1 was mixed. A curable resin composition 4 having a solid content of 15% was obtained.

<Comparative Example 2>
In the same manner as in Example 4, except that 125 parts of a resin solution with a solid content of 40% containing resin (A3) was used instead of the resin solution containing resin (A1), and 509 parts of solvent D1 was mixed. A 15% curable resin composition 5 was obtained.

(5) Pattern formation 1
On a 2-inch square glass substrate (Eagle XG; manufactured by Corning), curable resin composition 3 to curable resin composition 5 are each spun so that the film thickness after post-baking is 1.0 μm. After coating by a coating method, vacuum drying (ultimate pressure: 66 Pa) was performed, and pre-baking was performed at 100°C for 3 minutes to obtain a curable resin composition layer. After cooling, the distance between the substrate on which the curable resin composition layer was formed and the photomask made of quartz glass was set to 80 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Corporation) was used in an air atmosphere at 100 mJ/ Light irradiation was performed with an exposure dose of cm ² (wavelength of 365 nm). A photomask having a line-and-space pattern of 50 μm was used. The curable resin composition layer after light irradiation is developed by immersing it in an aqueous solution containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 60 seconds, washed with water, and oven A pattern consisting of a cured film was obtained by performing post-baking at medium temperature and 150° C. for 30 minutes. When the film thickness of the resulting pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by ULVAC, Inc.), it was confirmed to be 1.0 μm.

(6) Evaluation <Patternability>
The resulting pattern was observed using a scanning electron microscope (S-400; manufactured by Hitachi Technologies, Ltd.) and evaluated according to the following evaluation criteria. Table 2 shows the results.

Evaluation Criteria 1: The pattern is formed in a line according to the mask.
Other than 2:1 (the line pattern is broken, there is no space part, etc.).

<Solvent resistance>
The resulting pattern was immersed in NMP at a temperature of 23° C. for 0.5 hours, and the film thickness of the pattern after immersion was measured using a film thickness measuring device (DEKTAK3; manufactured by ULVAC, Inc.). A ratio to the film thickness (1.0 μm) was calculated. Table 2 shows the results.

<Adhesion>
A cured film was obtained in the same manner as in the above pattern formation, except that the mask was not used and the development step was not performed. The resulting cured film was immersed in NMP at a temperature of 23 ° C. for 0.5 hours, and the cured film after immersion was cut into 10 × 10 squares at intervals of 1 mm using a cutter knife according to JIS K5400. A notch was made so as to form a flat surface, and cellophane tape was attached and then peeled off. Table 2 shows the results.

式（Ａ－ＩＶ）で表される化合物の同定は、下記装置を用いてＬＣ－ＭＳ分析により行った。
ＬＣ装置：アジレント社製 ＬＣ１２００シリーズ
カラム：Ｗａｋｏｓｉｌ－II ３Ｃ１８ ＨＧ（φ３．０ｍｍ＊１５０ｍｍ（Ｗ））
ＭＳ装置 ： アジレント社製 ＬＣ／ＭＳＤ６１３０
（質量分析）イオン化モード＝ＥＳＩ＋： ｍ／ｚ＝[Ｍ＋Ｈ]^＋６５９．９
Ｅｘａｃｔ Ｍａｓｓ： ６５８．９ <Example 6>
<Synthesis of Compound Represented by Formula (A-IV)>
20 parts of the compound represented by formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was heated at 110°C. Stirred for 6 hours. After the obtained reaction solution was cooled to room temperature, it was added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour to precipitate crystals. Precipitated crystals were obtained as a residue of suction filtration and dried to obtain a compound represented by formula (A-IV).

The compound represented by formula (A-IV) was identified by LC-MS analysis using the following equipment.
LC device: Agilent LC1200 series Column: Wakosil-II 3C18 HG (φ3.0mm * 150mm (W))
MS device: Agilent LC/MSD6130
(mass spectrometry) ionization mode = ESI+: m/z = [M+H] ⁺ 659.9
Exact Mass: 658.9

<Preparation of curable resin composition>
C. I. Pigment Blue 15:6 21.4 parts 7.5 parts of an acrylic pigment dispersant and 176 parts of propylene glycol monomethyl ether acetate are mixed, and the pigment is sufficiently dispersed using a bead mill.
Compound represented by formula (A-IV) (dye) 6.3 parts Resin (A1) 60 parts (solid content conversion)
Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 40 parts Polymerization initiator (NCI-930; manufactured by ADEKA Corporation; O-acyl oxime compound)
A curable resin composition 6 was obtained by mixing 16 parts of diacetone alcohol, 20 parts of propylene glycol monomethyl ether acetate, 724 parts, and 0.15 parts of a leveling agent.

<Pattern Formation 2>
A 5 cm square glass substrate (Eagle 2000; manufactured by Corning) was coated with curable resin composition 6 by spin coating, and then prebaked at 100° C. for 3 minutes to obtain a curable resin composition layer. After standing to cool, the distance between the substrate on which the curable resin composition layer was formed and the quartz glass photomask was set to 100 μm, and exposure was performed at 80 mJ under an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). /cm ² (365 nm standard). A photomask having a 1:1 line-and-space pattern of 100 μm was used as the photomask. The composition layer after light irradiation is developed by immersion in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C. for 60 seconds, washed with water, and then placed on a hot plate. A pattern was obtained by baking at 150° C. for 5 minutes. The film thickness of the pattern was 2.1 μm.
From the curable resin composition 6 of Example 6, the pattern prepared by the method of pattern formation 2 was evaluated in the same manner as above. As a result, patterning property was 1, solvent resistance was 1.0, adhesion Gender was 100/100.

From the above results, it can be seen that the curable resin composition of the present invention, which contains the resin of the present invention, provides a pattern excellent in patterning property, solvent resistance and substrate adhesion.

Claims (5)

A copolymer having a structural unit (Aa) having an α,β-unsaturated carbonyl group, a structural unit (Ab) having an active methylene group, and a structural unit (Ac) having an acid group,
5 to 50 mol% of the structural unit (Aa), 5 to 50 mol% of the structural unit (Ab), and 5 to 50 mol% of the structural unit (Ac) with respect to the total number of moles of the structural units constituting the copolymer. Including in mole % ratio,
A weight average molecular weight of 3000 to 100000,
The structural unit (Aa) having an α,β-unsaturated carbonyl group contains a structural unit represented by the following formula (Aa-1), and is β-carboxyethyl acrylate and an oil that has undergone an addition reaction with its carboxy group. It does not contain a structural unit containing a cyclic epoxy group,
A resin, wherein the structural unit (Ab) having an active methylene group includes a structural unit derived from an unsaturated compound represented by the following formula (I).

[In the formula, R ¹ and R ^x independently represent a hydrogen atom or a methyl group. ]

[In the formula, each R ¹¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may contain a heteroatom.
R ¹² represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms.
R ¹³ represents a divalent group represented by formula (1-1).
R ¹⁴ represents a group represented by formula (1-4).
X represents a divalent group represented by any one of formulas (1-8) to (1-10). ]

[In the formula, R ¹⁵ is a hydrocarbon group having 1 to 24 carbon atoms which may contain a heteroatom. ]

A curable resin composition comprising the resin according to claim 1, a polymerizable compound, and a polymerization initiator. A cured film obtained by curing the curable resin composition according to claim 2 . A step of applying the curable resin composition according to claim 2 onto a substrate;
forming a curable resin composition layer by drying the curable resin composition;
A step of exposing the curable resin composition layer, and
A method for producing a cured film, comprising the step of heating an exposed curable resin composition layer. The method for producing a cured film according to claim 4, wherein the exposed curable resin composition layer is heated at 150°C or higher and 200°C or lower.