TW202330642A - Resin, curable resin composition, and cured film - Google Patents

Abstract

The present invention provides a novel resin which includes a constituent unit having a heterocycle. A composition including this resin gives cured films with excellent solvent resistance even when heated at low temperatures, e.g., 150 DEG C or lower. This resin comprises a constituent unit (Aa) having an [alpha],[beta]-unsaturated carbonyl group, a constituent unit (Ab) having an active methylene group or an active methine group, a constituent unit (Ac) having an acid group, and a constituent unit (Ad) having an optionally substituted heterocycle.

Description

Resin, curable resin composition and cured film

The present invention relates to a resin, a curable resin composition using the resin, and a cured film formed from the curable resin composition.

As a display device, a liquid crystal display, a plasma display (plasma display), a paper-like display (paper-like display), a touch panel, etc. are known. Among them, it is known to use a photosensitive resin composition to provide a spacer between a color filter constituting a display device such as a liquid crystal display or a touch panel and an array substrate to maintain a distance between the two substrates.

In the examples of Patent Document 1, a photosensitive resin composition comprising, as a resin component, a reaction product obtained by polymerizing methyl methacrylate, ethyl methacrylate, and methacrylic acid, It is then formed by reacting glycidyl methacrylate.

Patent Document 2 (International Publication No. 2012/053377) describes a high-refractive-index resin composition for electronic devices containing a carbazole compound. [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 3-172301 [Patent Document 2] International Publication No. 2012/053377

[Problems to be Solved by the Invention] The present invention is based on the realization of the following problem: the resistance of a cured film formed by heating at a low temperature using a composition containing a resin having a structural unit such as a carbazole ring-containing heterocycle. Poor solvent resistance. The object of the present invention is to provide a novel resin, a curable resin composition containing the resin, and a cured film formed from the resin composition, the resin is a resin having a structural unit containing a heterocyclic ring, and the resin is used even in, for example, Even when the composition containing this is heated at a low temperature of 150° C. or lower to form a cured film, a cured film excellent in solvent resistance can be obtained. In addition, the cured film obtained by the present invention has a high refractive index and excellent developability. [Means to solve the problem]

The present invention includes the following contents. [1] A resin comprising: 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; a structural unit (Ac) having an acid group; And a structural unit (Ad) containing a heterocyclic ring which may have a substituent. [2] The resin according to [1], wherein the structural unit (Aa) is represented by the following formula (Aax).

[In the formula (Aax), R ²¹ and R ²² independently represent a hydrogen atom or a methyl group, R ²⁵ represents an alkanediyl group with 1 to 20 carbon atoms, and the -CH ₂ - contained in the alkanediyl group can be Substituted by -O- or -CO-] [3] The resin according to [1] or [2], wherein the structural unit (Ad) is represented by the following formula (Ad-1).

[In formula (Ad-1), R ¹ represents a hydrogen atom, a methyl group, or a hydroxymethyl group; R ² to R ⁹ independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group with 1 to 20 carbons, or a saturated hydrocarbon group with 6 carbons ~20 aryl groups, the hydrogen atoms contained in the saturated hydrocarbon group can be substituted by alkoxy or aryl; X represents a single bond, an alkanediyl group with more than 1 carbon number, or a linear or branched lower The group represented by the formula (V);

(In formula (V), l represents an integer of 0 or greater; m represents an integer of 1 or greater)] [4] A curable resin composition comprising the resin according to any one of [1] to [3], A polymerizable compound, and a polymerization initiator. [5] A cured film formed of the curable resin composition according to [4]. [6] A method for producing a cured film, comprising sequentially: a coating step of coating the curable resin composition as described in [4] on a substrate; a drying step of drying the resin composition forming a resin composition layer; an exposing step, exposing the resin composition layer; and a heating step, heating the resin composition layer. [7] The method for producing a cured film according to [6], wherein in the heating step, the exposed resin composition layer is heated at 150° C. or lower. [Effect of the invention]

According to the curable resin composition containing the resin of this invention, even when it heats at low temperature of 150 degreeC or less, and forms a cured film, the cured film excellent in solvent resistance can be formed.

＜Resin＞ The resin of the present invention (hereinafter, the resin is referred to as “resin (A)”) is mainly used as a binder resin of a curable resin composition. Resin (A) is the following resin, that is, the resin has: structural unit (Aa), with α, β-unsaturated carbonyl; structural unit (Ab), with active methylene or active methine; structural unit (Ac ), having an acid group; and a structural unit (Ad), containing a heterocycle that may have a substituent.

More specifically, resin (A) is as follows. The resin (A) contains a structural unit having an α,β-unsaturated carbonyl group (hereinafter, this structural unit is referred to as a "structural unit (Aa)"), a structural unit (Ab) having an active methylene group or an active methine group (hereinafter, this structural unit is referred to as "structural unit (Ab)"), a structural unit (Ac) having an acid group (hereinafter, this structural unit is referred to as "structural unit (Ac)"), and A structural unit (Ad) of a heterocyclic ring (hereinafter, this structural unit is referred to as "structural unit (Ad)"). The resin may further comprise other repeating units (Ae). In addition, the resin may contain two or more kinds of structural units (Aa), structural units (Ab), structural units (Ac), and structural units (Ad), respectively. From the viewpoint of using the resin (A) as a binder resin of the curable resin composition, the resin (A) is preferably an alkali-soluble resin. Alkali solubility refers to the property of dissolving in a developing solution which is an aqueous solution of an alkali compound. Since the resin (A) contains a polymer containing a structural unit (Ac), it is easy to impart alkali solubility. In this specification, "a structural unit derived from (meth)acrylic acid and/or its ester" is also called a "(meth)acrylic structural unit". In addition, "(meth)acrylic acid" means "methacrylic acid and/or acrylic acid." Hereinafter, each structural unit will be described in detail.

[1] Structural unit (Aa) The structural unit (Aa) is a structural unit having an α,β-unsaturated carbonyl group.

Resin (A) can improve the solvent resistance of the cured film obtained by heating at low temperature by having a structural unit (Aa).

The structural unit (Aa) includes, for example, a structural unit represented by the following formula (Aax) (hereinafter, this structural unit is referred to as "structural unit (Aax)").

In formula (Aax), R ²¹ and R ²² independently represent a hydrogen atom or a methyl group, R ²⁵ represents an alkanediyl group with 1 to 20 carbon atoms, and the -CH ₂ - contained in the alkanediyl group can be Substitute -O- or -CO-. Examples of the alkanediyl group include linear alkanediyl groups, branched alkanediyl groups, cyclic alkanediyl groups, and combinations thereof. Examples of linear alkanediyl groups include methylene, ethylidene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane Alkane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, deca Monoalkane-1,11-diyl, dodecane-1,12-diyl, etc. Examples of the branched alkanediyl include: ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane Alkane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane Alkane-1,4-diyl, 2-methyloctane-1,8-diyl, etc. Examples of the cyclic alkanediyl group include cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cyclooctane-1, 5-diyl and other cycloalkanediyl groups; and norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl, adamantane-2,6- Polycyclic divalent alicyclic hydrocarbon groups such as diradicals. Examples of the group formed by combining a straight-chain alkanediyl group and a cyclic alkanediyl group include the following groups (in the formula below, * represents a bond).

R ²⁵ is preferably an alkanediyl group having 4 to 18 carbon atoms, more preferably an alkanediyl group having 4 to 10 carbon atoms, and still more preferably an alkanediyl group having 6 to 9 carbon atoms.

A preferred example of the structural unit (Aax) is a structural unit in which -CH ₂ - contained in the alkanediyl group of R ²⁵ is substituted with one -O-. Specifically, the following formula (Aa- 1), the following formula (Aa-21) and the following formula (Aa-22).

The structural unit (Aa) represented by the formula (Aa-1) can be produced by referring to, for example, the production method of the chemical structure (1) described in JP-A-2015-172117.

In the formula (Aa-1), R ²¹ and R ²² independently represent a hydrogen atom or a methyl group, and R ²³ and R ²⁴ independently represent an alkanediyl group.

The combination of ^R23 and ^R24 is preferably an alkanediyl group with 1 to 8 carbon atoms and an alkanediyl group with 1 to 8 carbon atoms, more preferably an alkanediyl group with 1 to 3 carbon atoms and an alkanediyl group with 4 carbon atoms. ∼10 straight-chain alkanediyl groups, more preferably methylene and straight-chain alkanediyl groups having 4-8 carbon atoms.

Furthermore, a preferable example of the formula (Aa-1) is represented by the following formula (Aa-11) or formula (Aa-12). The structural unit represented by the following formula (Aa-11) In the formula (Aa-1), R ²³ is methylene, R ²⁴ is hexane-1,4-diyl, the following formula (Aa-12) The structural unit represented is in formula (Aa-1), R ²³ is hexane-1,4-diyl, and R ²⁴ is methylene.

The structural unit (Aa) represented by the formula (Aa-21) and the formula (Aa-22) can be produced by referring to the production method of the chemical structure (1) described in Japanese Patent Application Laid-Open No. 2015-172117, for example.

In formula (Aa-21) and formula (Aa-22), R ²⁷ and R ²⁸ independently represent a hydrogen atom or a methyl group, R ²⁶ represents an alkanediyl group with 1 to 4 carbon atoms, and ring W represents the number of carbon atoms 5-7 cycloalkanediyl groups.

R ²⁶ is preferably a methylene group, and the ring W is preferably a cyclohexanediyl group, more preferably a cyclohexane-1,4-diyl group.

A preferable example of the formula (Aa-21) and the formula (Aa-22) is represented by the following formula (Aa-21a) or formula (Aa-22a).

Typically, the structural unit (Aa) can be obtained by adding a compound having an α,β-unsaturated carbonyl group to a structural unit having a carboxyl group in a copolymer (hereinafter, this structural unit is referred to as a "structural unit (Aa') ), or by reacting (meth)acrylic acid with a structural unit having an epoxy group in the copolymer. The structural unit (Aa') is a type of 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 contained in the structural unit (Aa′). As a compound which has an α,β-unsaturated carbonyl group, (meth)acrylate (Aa″) which has an epoxy group is mentioned.

The (meth)acrylate (Aa'') having an epoxy group has an aliphatic epoxy group. The term "aliphatic epoxy group" refers to a group obtained by epoxidizing a linear or branched aliphatic unsaturated hydrocarbon.

By reacting 4-hydroxybutyl acrylate glycidyl ether with a (meth)acrylic structural unit having a carboxyl group, or by reacting 4-hydroxybutyl acrylate glycidyl ether with a (meth)acrylic acid having an epoxy group The structural unit reaction can obtain the structural unit represented by the formula (Aax). The structural unit (Aa) can be obtained by combining 5-hydroxypentyl acrylate glycidyl ether or 6-hydroxyhexyl acrylate glycidyl ether with a carboxyl (meth)acrylic structural unit or an epoxy group ( A structural unit obtained by reacting a meth)acrylic structural unit.

〔2〕 Structural unit (Ab) The structural unit (Ab) is a structural unit derived from an unsaturated compound having an active methylene group or an active methine group. This 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 a compound (Ab'') having an active methylene group or an active methine group with another structural unit (Ab').

As an unsaturated compound which has an active methylene group, the compound represented by formula (I) is mentioned. As an unsaturated compound which has an active methine group, the compound represented by formula (II) is mentioned.

[In formula (I) and formula (II), R ¹¹ independently represents a hydrogen atom or a hydrocarbon group with 1 to 24 carbon atoms that may contain heteroatoms; R ¹² represents a single bond or a divalent group with 1 to 20 carbon atoms Hydrocarbon group; R ¹³ represents a divalent group represented by any one of formula (1-1) ~ formula (1-3); R ¹⁴ represents any one of formula (1-4) ~ formula (1-7) the basis represented by

(R ¹⁵ is a hydrocarbon group with 1 to 24 carbon atoms that may contain a heteroatom) X represents a divalent group represented by any one of formula (1-8) to formula (1-10)]

R ¹¹ is preferably a hydrogen atom, methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, methoxy, ethoxy, propoxy, hexyloxy, cyclohexyloxy or formula (1- 11) The group represented by the formula (1-13) is more preferably a hydrogen atom or a methyl group. R ¹⁵ is preferably methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, methoxy, ethoxy, propoxy, hexyloxy, cyclohexyloxy or formula (1-11)～ The group represented by the formula (1-13) is more preferably a methyl group.

^R is preferably a single bond, methylene, ethylenyl, propylenyl, butyl, propylenyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, more A single bond, a methylene group, and an ethylidene group are preferable.

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

As a compound represented by formula (II), the following compounds etc. are mentioned specifically.

Formula (I-1)～formula (I-7), formula (I-16), formula (II-1), formula (II-2) and formula (II-5) have CH ₃ -CH ₂ =CH -, but compounds in which CH ₃ -CH ₂ ═CH- is substituted by H-CH ₂ ═CH- in these formulas can also be mentioned.

As the structural unit (Ab), preferably, a structural unit represented by the formula (Ab-1) is exemplified.

[In formula (Ab-1), R ³³ represents a hydrogen atom or a methyl group, and R ³⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms]

Examples of the alkyl group having 1 to 6 carbon atoms in ^R34 include methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, third-butyl, n-pentyl, and n-hexyl Base etc. R ³⁴ preferably includes a hydrogen atom and a methyl group. Examples of compounds derived from the structural unit represented by formula (Ab-1) include ethyl 2-(methacryloxy)acetoyl acetate [compound represented by formula (I-1)].

〔3〕 Structural unit (Ac) The structural unit (Ac) is a structural unit derivable from an unsaturated compound having an acid group. As an acid group, a carboxyl group, a phenolic hydroxyl group, a sulfonic acid, etc. are mentioned. The carboxyl group can also be anhydrided.

This structural unit can be obtained by obtaining a copolymer using an unsaturated compound having an acid group as a monomer. In addition, it can also be obtained by reacting a compound (Ac'') having an acidic group with another structural unit (Ac'). The unsaturated compound having an acid group is preferably an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride. Specific examples of unsaturated carboxylic acids or unsaturated carboxylic acid anhydrides include: (Meth)acrylic acid, crotonic acid, vinylbenzoic acid, methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[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, α-(hydroxymethyl)(meth)acrylic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6- Tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid, 5,6-dicarboxybicyclo [2.2.1] Unsaturated dicarboxylic acids such as hept-2-ene; Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (nadic anhydride ( himic anhydride)) and other unsaturated dicarboxylic anhydrides; Unsaturated polycarboxylic acids with divalent or higher valences such as mono[2-(meth)acryloxyethyl]succinate and mono[2-(meth)acryloxyethyl]phthalate Mono[(meth)acryloxyalkyl]esters; Unsaturated acrylate containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)(meth)acrylic acid. Among these, (meth)acrylic acid, maleic anhydride, etc. can be used preferably from copolymerization reactivity and the solubility with respect to aqueous alkali solution. These can be used alone or in combination.

〔4〕 Structural unit (Ad) The structural unit (Ad) is a structural unit derived from an unsaturated compound having a heterocyclic ring. This heterocycle may have a substituent. This structural unit can be obtained by obtaining a copolymer using an unsaturated compound having a heterocycle as a monomer. Alternatively, it can also be obtained by reacting a compound (Ad'') having a heterocycle with another structural unit (Ad'). When the resin (A) has a structural unit (Ad), the refractive index of the obtained cured film can be raised. The refractive index can be measured by, for example, ellipsometry.

A heterocyclic ring may be a monocyclic ring or a condensed ring. The heterocycle is an n-valent heterocycle, and the n-valence is, for example, monovalent or divalent. With regard to n-valent heterocyclic rings, the remaining atomic groups after removing n hydrogen atoms directly bonded to carbon atoms or heteroatoms constituting the ring from the heterocyclic compound are referred to as n-valent heterocyclic rings. The remaining atomic group after one hydrogen atom is defined as a monovalent heterocyclic ring, and the remaining atomic group after removing two hydrogen atoms is defined as a divalent heterocyclic ring. The carbon number of the heterocyclic group does not include the carbon number of the substituent, and is usually 2-60, preferably 4-20.

The heterocyclic ring is preferably one obtained by removing n hydrogen atoms from an aromatic heterocyclic compound. Here, "aromatic heterocyclic compound" refers to oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, tris Compounds in which the heterocycle itself shows aromaticity such as oxazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzosilacyclopentadiene, and dibenzophosphorole; and phenanthoxazine , phenanthiazine, dibenzoborole, dibenzosilacyclopentadiene, benzopyran, etc. Even if the heterocycle itself does not show aromaticity, there is an aromatic ring condensed in the heterocycle compound of.

In the structural unit (Ad), the heterocycle is preferably a nitrogen-containing heterocycle, more preferably carbazole. The structural unit (Ad) is preferably a structural unit represented by the following formula (Ad-1).

[In formula (Ad-1), R ¹ represents a hydrogen atom, a methyl group, or a hydroxymethyl group; R ² to R ⁹ independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group with 1 to 20 carbon atoms, or a carbon atom An aryl group with a number of 6 to 20, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted by an alkoxy group or an aryl group; X represents a single bond, an alkanediyl group with more than 1 carbon atoms, or a linear or branched chain The group represented by the following formula (V) of the same shape;

(In formula (V), l represents an integer greater than 0; m represents an integer greater than 1)]

[5] Other structural units The resin (A) may have structural units other than the structural unit (Aa), structural unit (Ab), structural unit (Ac) and structural unit (Ad) (hereinafter, the structural unit is referred to as " Structural unit (Ae)"). The structural unit (Ae) is a structural unit different from the structural unit (Aa), structural unit (Ab), structural unit (Ac) and structural unit (Ad). Structural unit (Ae) can be derived from monomers capable of deriving structural units other than structural unit (Ae), such as structural unit (Aa), structural unit (Ab), structural unit (Ac) and structural unit (Ad) derived from polymerized monomers. Specific examples of such monomers include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth) Alkyl (meth)acrylates such as 2-butyl acrylate and 3-butyl (meth)acrylate; Alkyl acrylates such as methyl acrylate and isopropyl acrylate; Cyclohexyl (meth)acrylate, (meth)acrylate base) 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in this technical field, it is called (meth)acrylic acid Dicyclopentyl ester), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylate (meth)acrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate; dicarboxylic acids such as diethyl maleate, diethyl fumarate, diethyl itaconate, etc. Diesters; 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-carboxybicyclo[2.2.1]hept-2-ene 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 Carboxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(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-methylbicyclo[ 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 anhydrate (nadic anhydride), 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-bis(tertiary butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5 ,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N-cyclohexylmaleimide, N- Benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl Imino-6-maleimide hexanoate, N-succinimido-3-maleimide propionate, N-(9-acridyl)maleimide, etc. Dicarbonyl imide derivatives; styrene compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene; acrylonitrile, methyl Acrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3- butadiene etc.

Among these, in terms of reactivity in copolymerization or heat resistance of the copolymer, (meth)acrylates, styrene compounds, and dicarbonyl imide compounds are preferable, and in terms of reactivity in copolymerization and relative In terms of solubility in aqueous alkali solution, methyl (meth)acrylate, n-butyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (methyl) ) acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2 .1] Hept-2-ene, alkyl acrylate, etc.

The resin (A) may have two or more structural units (Ae).

〔6〕 The ratio of each structural unit Resin (A) contains a copolymer containing structural unit (Aa), structural unit (Ab), structural unit (Ac), structural unit (Ad) and may further contain structural unit (Ae), relative to the structure constituting the copolymer The total molar number of units and the ratio of each structural unit are preferably in the following ranges in terms of molar fractions. Structural unit (Aa): 1 mol% to 50 mol%, Structural unit (Ab): 1 mol% to 50 mol%, Structural unit (Ac): 1 mol% to 50 mol%, Structural unit (Ad): 1 mol% to 90 mol%, Structural unit (Ae): 0 mol% to 50 mol%.

Moreover, since solvent resistance tends to become more favorable when the ratio of a structural unit is the following range, it is more preferable. Structural unit (Aa): 5 mol% to 30 mol%, Structural unit (Ab): 5 mol% to 30 mol%, Structural unit (Ac): 5 mol% to 30 mol%, Structural unit (Ad): 5 mol% to 8 mol%, Structural unit (Ae): 0 mol% to 30 mol%.

The copolymer comprising each structural unit can be, for example, according to the method described in the document "Experimental Method for Polymer Synthesis" (by Takayuki Otsu, Chemical Doujin Publishing Co., Ltd., 1st edition, 1st printing, March 1, 1972). and the cited documents recorded in this document to manufacture.

Resin (A) can be produced through two steps, for example. Specifically, a predetermined amount of each compound deriving a structural unit (Ab), a structural unit (Ac), and a structural unit (Ad), and a compound deriving a structural unit (Aa'), a polymerization initiator, and a solvent are charged into the reaction. In the container, by replacing oxygen with nitrogen, stirring, heating (for example, 50°C to 140°C), and heat preservation (for example, 1 hour to 10 hours) are carried out in the absence of oxygen, thereby obtaining a compound having a structural unit (Aa '), a copolymer of structural units (Ab), structural units (Ac) and structural units (Ad). Then, replace the nitrogen in the reaction vessel with oxygen, put (meth)acrylate (Aa'') with epoxy group, reaction catalyst and polymerization inhibitor into the reaction vessel, stir and heat (for example 60°C～130°C), heat preservation (for example, 1 hour to 10 hours), so that the (meth)acrylate (Aa'') with epoxy group reacts with the structural unit (Aa'), thereby deriving the structural unit ( Aa), obtaining a copolymer having a structural unit (Aa), a structural unit (Ab), a structural unit (Ac) and a structural unit (Ad). Regarding the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid obtained by reprecipitation or the like may be redissolved in a solvent for use.

In the case of producing a resin (A) having a structural unit (Ae), each compound of the derived structural unit (Ab), structural unit (Ac) and structural unit (Ad) and the derived structural unit ( The compound of Aa') may be incorporated together with the structural unit (Ae).

In the above, when the structural unit (Ac) has a carboxyl group, the structural unit (Aa ). The polystyrene conversion weight average molecular weight of resin (A) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 10,000-50,000. The curable resin composition containing the resin (A) having a weight average molecular weight within the above-mentioned range tends to have good coatability at the time of coating, and is less likely to cause film reduction at the time of development, and has a tendency to be uncured at the time of development. Partial detachment tends to be good.

The degree of dispersion [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (A) is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the degree of dispersion is within the above-mentioned range, since the curable resin composition containing the resin (A) as a binder resin tends to be excellent in developability, it is preferable. The acid value of the resin (A) is preferably 70 mg-KOH/g-150 mg-KOH/g, more preferably 75 mg-KOH/g-135 mg-KOH/g. In this specification, an acid value is the value measured by Japanese Industrial Standards (Japanese Industrial Standards, JIS) K 2501-2003.

＜Curing resin composition＞ The curable resin composition of the present invention contains a resin (A), a polymerizable compound, and a polymerization initiator. The resin composition of the present 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 a polymerizable compound (B), a polymerization initiator (C), and a solvent (D), respectively.

〔1〕 Resin (A) Since the curable resin composition of the present invention contains the resin (A), a cured film excellent in solvent resistance can be obtained. Even if the temperature of the cured film formed from the curable resin composition containing the resin (A) is 150°C or less, 130° or less, or 100° or less in the heating step (so-called post-baking step) after exposure in the production of the cured film, Excellent solvent resistance can also be shown. The temperature in the heating step is, for example, 80° or higher. In the curable resin composition of the present invention, the content of the resin (A) is preferably 5% by mass to 90% by mass, more preferably 10% by mass, based on the solid content of the curable resin composition. ~70% by mass. When the content of the resin (A) is within the above range, the solubility in the developer is sufficient, and development residues are less likely to be generated. In addition, film reduction is less likely to occur in parts that are hardened by exposure during development, and are not hardened without exposure. Partial detachment tends to be good, which is preferable. Here, the solid content refers to the amount excluding the content of the solvent from the total amount of the curable resin composition. The total amount of solid content and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography (Liquid Chromatography) or gas chromatography (Gas Chromatography). Moreover, you may use together the acrylic-type binder resin normally used in this field as long as it is the range which does not impair the effect of this invention.

〔2〕 Polymeric compound (B) The polymerizable compound (B) is not particularly limited as long as it is a compound that can be polymerized by active radicals or the like 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, and include monofunctional monomers containing one functional group having an ethylenically unsaturated bond, difunctional monomers containing two such functional groups, Monomers, and other polyfunctional monomers containing three or more functional groups. Specific examples of the monofunctional monomer include: nonylphenyl carbitol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-ethylhexyl Carbitol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-vinylpyrrolidone, and the like. Specific examples of the difunctional monomer include: 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate ester, triethylene glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. Specific examples of the polyfunctional monomer include: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, base) acrylate, dipentaerythritol hexa(meth)acrylate, reactants of pentaerythritol tri(meth)acrylate and acid anhydride, reactants of dipentaerythritol penta(meth)acrylate and acid anhydride, etc. Among them, difunctional monomers or polyfunctional monomers can be 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 from 1% by mass to 70% by mass, more preferably from 5% by mass to 60% by mass, based on the total amount of the resin (A) and the polymerizable compound (B). . When the content of the polymerizable compound (B) is within the above range, the strength, smoothness, and solvent resistance of the cured film obtained by curing the curable resin composition tend to be favorable, 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. The polymerization initiator (C) is preferably an O-acyl oxime compound, a phenyl ketone compound, a triazine compound, an acyl phosphine oxide compound, and a biimidazole compound. By using these polymerization initiators (C) in combination with a polymerization initiation assistant, the obtained curable resin composition becomes more highly sensitive, so when it is used to form a pattern, the productivity of the pattern is improved, so it is preferable . As the O-acyl oxime compound, for example, N-benzoyloxy-1-(4-phenylmercaptophenyl)butane-1-one-2-imine, N-benzyl Acyloxy-1-(4-phenylmercaptophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylmercaptophenyl)-3 -Cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfonylphenyl)-3-cyclohexylpropane-1-one-2-imine O-acyl oxime compounds with a diphenylsulfide skeleton such as amines; N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- 3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4- Dioxolylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl- 6-(2-Methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl O-acyl group with carbazole skeleton such as -6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine Oxime compounds; O- Acyl oxime compounds, etc. You can also use Irgacure (registered trademark) OXE01, OXE02, OXE03 (the above are manufactured by BASF), N-1919 (manufactured by ADEKA), DFI-091 (Dadong Chemical ( Daito Chemix) Co., Ltd.) and other commercial products. Among them, the O-acyl oxime compound is preferably selected from N-benzoyloxy-1-(4-phenylsulfonylphenyl) octane-1-one-2-imine, N-ethyl Acyloxy-1-(4-phenylsulfonylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6 -{2-methyl-4-(3,3-dimethyl-2,4-dioxolanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethyl Alkane-1-imine and 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]ethanone O-acetyl oxime At least one of the group, and preferably an O-acyl oxime compound different from an O-acyl oxime compound having a carbazole ring bonded to a nitro group. These O-acyl oxime compounds tend to obtain a high-brightness color filter.

Examples of the phenylalkyl ketone compound include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1 -(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[ 4-(4-morpholinyl)phenyl]butane-1-one, 2-hydroxyl-2-methyl-1-phenylpropane-1-one, 2-hydroxyl-2-methyl-1-[ 4-(2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone (Omnirad (registered trademark) 184, former Yanjia solid (Irgacure) (registered Trademark) 184), oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, benzoyl Dimethyl ketal (Omnirad (registered trademark) 651, Irgacure (registered trademark) 651), etc. 2-benzyl-2-(dimethylamino)-4'-morpholinyl butyrophenone (Omnirad (registered trademark) 369, former Yanjia solid (Irgacure) (registered trademark) can also be used trademark) 369), (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one) (Omnirad (registered trademark) 907, Commercially available products such as Irgacure (registered trademark) 907) and Irgacure (registered trademark) 379 (the above are manufactured by BASF).

As the triazine compound, for example, 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-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2- Base) vinyl]-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.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. Commercially available items such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can also be used.

Examples of the biimidazole compound include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2, 3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5 '-Tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2 , 2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Patent Kokai No. 62-174204, etc.), biimidazole compounds in which the 4,4', 5,5'-position phenyl is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Laid-Open No. 7-10913, etc.), and the like.

Examples of polymerization initiators that generate acid include: 4-hydroxyphenyl dimethyl columium p-toluenesulfonate, 4-hydroxyphenyl dimethyl columium hexafluoroantimonate, 4-acetyloxyphenyl bismuth Methyl columbitium p-toluenesulfonate, 4-acetyloxyphenyl-methyl-benzyl columium hexafluoroantimonate, triphenyl columium p-toluenesulfonate, triphenyl columium hexafluoroantimonate, diphenyl p- Onium salts such as iodonium toluenesulfonate and iodonium diphenylhexafluoroantimonate, nitrobenzyl toluenesulfonate, benzoin toluenesulfonate, etc.

A polymerization initiator or the like generally used in this field may further be used in combination, and examples of the polymerization initiator include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, anthracene-based compounds, and the like. More specifically, the following compounds are mentioned, and these can be used individually or in combination of 2 or more types, respectively.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone-based compounds include: benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenone, Phenylsulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

Examples of the thioxanthone-based compounds include: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone , 1-chloro-4-propoxythioxanthone, etc.

Examples of the anthracene compound include: 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene etc.

In addition, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzoylquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, dioxin A titanium compound or the like is used as a polymerization initiator.

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

The polymerization initiator having a group capable of causing chain transfer can also be used as the structural component (Ae) of the resin (A). Furthermore, the obtained resin (A) can be used as a binder resin of the curable resin composition of this invention.

A polymerization start aid can also be used in combination with a polymerization initiator. As a polymerization initiation aid, an amine compound and the following carboxylic acid compound are preferable, and an aromatic amine compound is more preferable as an amine compound.

Specific examples of polymerization initiation aids include: aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; such as 4-dimethylaminobenzoic acid methyl ester, 4-dimethyl Ethylaminobenzoate, Isoamyl 4-Dimethylaminobenzoate, 2-Ethylhexyl 4-Dimethylaminobenzoate, 2-Dimethylaminoethyl Benzoate, N, Aromatic amine compounds like N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone .

Examples of the carboxylic acid compound include: phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxybenzene Thioglycolic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine Aromatic heteroacetic acids such as naphthyloxyacetic acid and naphthyloxyacetic acid.

The content of the polymerization initiator (C) is preferably 0.1% by mass to 40% by mass, more preferably 1% by mass 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 from 0.01% by mass to 50% by mass, more preferably from 0.1% by mass to 40% by mass, based on the total amount of the resin (A) and the polymerizable compound (B). When the content of the polymerization initiator (C) is within the above range, the curable resin composition becomes highly sensitive, the strength of the cured film formed using the curable resin composition, and the smoothness of the surface of the cured film are obtained. Sexual tendency to become good and thus better. In addition to the above, if the amount of the polymerization initiation auxiliary agent is within the above range, the sensitivity of the curable resin composition obtained will be further improved, and the productivity of the pattern substrate formed using the curable resin composition will be improved. tendency, which is better.

〔4〕 Solvent (D) The curable resin composition of the present invention preferably contains a solvent (D). The solvent (D) may be various organic solvents usable in the field of curable resin compositions to be cured and used. 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 ; Glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkanediol alkyl ethers such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate acid ester; 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 glycerol; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic esters such as γ-butyrolactone, etc.

Among the above-mentioned solvents, organic solvents having a boiling point of 100°C to 200°C among the above-mentioned solvents are preferable in terms of coating properties and drying properties, more preferably alkanediol alkyl ether ethers are mentioned. Esters such as esters, ketones, 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.

The solvent (D) can be used individually or in mixture of 2 or more types. The content of the solvent (D) is preferably from 60% by mass to 90% by mass, more preferably from 70% by mass to 85% by mass, based on the curable resin composition. If the content of the solvent (D) is within the above-mentioned range, it is possible to use a spin coater, a slit & spin coater, a slit coater (sometimes also called a die coater, a curtain flow coater) When coating is performed by a coating device such as a curtain flow coater (curtain flow coater) or an inkjet, it is expected that the coatability will become good, so it is preferable.

〔5〕 Additive (F) In the curable resin composition of the present invention, colorants, fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, chain transfer agents, acid generators, bases, etc. may be used in combination if necessary. Additives such as generators (F). The curable resin composition for color filters can be comprised by adding a coloring agent, for example.

As a coloring agent, a dye and/or a pigment etc. are mentioned. These may be used alone or in combination of two or more coloring agents, and in this case, any of a combination of only a dye, a combination of only a pigment, or a combination of a dye and a pigment may be used. It is especially preferred to include a dye.

Examples of dyes include acid dyes, basic dyes, direct dyes, sulfur dyes, vat dyes, naphthol dyes, reactive dyes, and disperse dyes, and can be selected from conventionally known dyes for use in color filters. For example, Japanese Patent Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. 1-94301, Japanese Patent Laid-Open No. 6-11614, Japanese Patent Teden 2592207, U.S. Patent No. 4,808,501 specification, U.S. Patent No. 5,667,920 specification, U.S. Patent No. 5,059,500 specification, Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6- Pigments described in Publication No. 51115, Japanese Patent Laid-Open Publication No. 6-194828 and the like. Specifically, pyrazole azo series, anilino azo series, arylazo series, pyrazolotriazole azo series, pyridone azo series, triphenylmethane series, anthraquinone series, anthracene Pyridone-based, benzylidene-based, oxonol-based, cyanine-based, polymethine-based, phenthiazine-based, pyrrolopyrazole-azomethine-based, xanthene-based, phthalocyanine-based, quinophthalone Benzopyran-based, indigo-based, dioxazine-based, coumarin-based, squarylium-based, preferably pyrazole azo-based, anilino-based azo-based, pyrazolotriazole-based azo-based , pyridone azo series, anthraquinone series, anthrapyridone series, phthalocyanine series, dioxazine series, quinophthalone series, xanthene series, more preferably pyrazole azo series, pyridone azo series, Phthalocyanine series, quinophthalone series, xanthene series, etc.

Specifically, examples include: C.I. Solvent Yellow (Solvent Yellow) 4 (hereinafter, the description of C.I. Solvent Yellow is omitted and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98 , 99, 117, 162, 163, 167, 189; C.I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245 , 247; C.I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86; C.I. Solvent Violet (Solvent Violet) 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94 , 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; C.I. Solvent Green (Solvent Green) 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and other C.I. solvent dyes; C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99 ,111,112,113,114,116,119,123,128,134,135,138,139,140,144,150,155,157,160,161,163,168,169,172,177,178 ,179,184,190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251 ; C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66 ,73,76,80,87,88,91,92,94,95,97,98,103,106,111,114,129,133,134,138,143,145,150,151,155,158 ,160,172,176,182,183,195,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,268,270,274,277 , 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; C.I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; C.I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42 , 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93 ,93:1,96,99,100,102,103,104,108,109,110,112,113,117,119,120,123,126,127,129,130,131,138,140,142 ,143,147,150,151,154,158,161,166,167,168,170,171,175,182,183,184,187,192,199,203,204,205,210,213,229 , 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; C.I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50: 1, 58, 63 , 65, 80, 104, 105, 106, 109 and other C.I. acid dyes; C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108 , 109, 129, 136, 138, 141; C.I. Direct Red (Direct Red) 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204 , 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Direct Violet (Direct Violet) 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; C.I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80 ,81,84,85,86,90,93,94,95,97,98,99,100,101,106,107,108,109,113,114,115,117,119,120,137,149 ,150,153,155,156,158,159,160,161,162,163,164,165,166,167,168,170,171,172,173,188,189,190,192,193,194 ,195,196,198,199,200,201,202,203,207,209,210,212,213,214,222,225,226,228,229,236,237,238,242,243,244 , 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; C.I. Direct Green (Direct Green) 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other C.I. direct dyes; C.I. Disperse Yellow 51, 54, 76; C.I. Disperse Violet 26, 27; C.I. Disperse Blue (Disperse Blue) 1, 14, 56, 60 and other C.I. disperse dyes; C.I. Basic Red (Basic Red) 1, 10; C.I. Basic Blue (Basic Blue) 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; C.I. Basic Violet 2; C.I. Basic Red (Basic Red) 9; C.I. basic dyes such as C.I. Basic Green (Basic Green) 1; C.I. Reactive Yellow 2, 76, 116; C.I. Reactive Orange 16; C.I. reactive dyes such as C.I. reactive red (Reactive Red) 36; C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; C.I. Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36 , 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; C.I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 ; C.I. Mordant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24 , 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; C.I. Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40 , 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; C.I. Mordant Green (Mordant Green) 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and other C.I. mordant dyes; C.I. Vat Green (Vat Green) 1, etc. C.I. Vat dyes, etc. In addition, dyes described in JP-A-2010-32999 , JP-A 4492760 , JP-A 2013-50693 , and JP-A-2013-178478 may be mentioned. What is necessary is just to select these dyes suitably according to the spectral spectrum of a desired color filter.

Examples of the pigment include organic pigments and inorganic pigments, and examples include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists). Examples include: C.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, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; C.I. Pigment Orange (Pigment Orange) 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. Pigment Red (Pigment Red) 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 , 291 and other red pigments; C.I. Pigment Blue (Pigment Blue) 15, 15:3, 15:4, 15:6, 16, 60 and other blue pigments; C.I. Pigment Violet (Pigment Violet) 1, 19, 23, 29, 32, 36, 38 and other purple pigments; C.I. Pigment Green (Pigment Green) 7, 36, 58, 59 and other green pigments; C.I. Pigment Brown (Pigment Brown) 23, 25 and other brown pigments; C.I. Pigment Black (Pigment Black) 1, 7 and other black pigments. Among them, it is preferable to contain at least one pigment selected from C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 209, 254, C.I. Pigment Violet 23, C.I. Pigment Blue 15:6, and C.I. Pigment Green 36. These pigments may be used alone or in combination of two or more.

The organic pigments in the above-mentioned pigments may be subjected to rosin treatment, surface treatment using pigment derivatives or pigment dispersants introduced with acidic groups or basic groups, etc., or grafting treatment on the surface of pigments with polymer compounds, etc., if necessary. , micronization treatment by sulfuric acid micronization method, etc., cleaning treatment by organic solvent or water to remove impurities, removal treatment of ionic impurities by ion exchange method, etc., etc. The pigment preferably has a uniform particle size. By carrying out the dispersion treatment with a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

As the pigment dispersant, a commercially available surfactant can be used. Examples of such surfactants include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants. These can be used alone or in combination of two or more. Specifically, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyesters, Urethane, polyethyleneimine, etc. Furthermore, examples of the surfactant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), Eftop (manufactured by Tetsu Chemical Co., Ltd.) Tohkem Products (manufactured by Tohkem Products), Megafac (manufactured by Di Aisheng (DIC) (stock)), Fluorad (manufactured by Sumitomo 3M (stock)), Asahiguard, Sand Surflon (above, manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (EFKA CHEMICALS) company), PB821 (manufactured by Ajinomoto Co., Ltd.), Disperbyk (manufactured by BYK-chemie), etc.

Fillers can be added to adjust the strength of the hardened film or for coloring. Specific examples of the filler include glass, silica, alumina, pigments, and the like.

Other polymer compounds can be added to adjust the strength of the hardened film. As another polymer compound, resins such as epoxy resins and maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, etc., can be specifically used. Thermoplastic resins such as polyurethane, etc.

An adhesion promoter may be added to improve the adhesion to the substrate or substrate. As the adhesion promoter, specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-amino Ethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

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

UV absorbing may be added to prevent UV-induced degradation of the hardened film. Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, etc. .

A chain transfer agent can be added to control molecular weight in the hardening reaction. Examples of the chain transfer agent include dodecylmercaptan, 2,4-diphenyl-4-methyl-1-pentene, and the like.

An acid generator may be added as a hardening reaction catalyst. Examples of the acid generator include: aryldiazonium salts, diaryliodonium salts, triaryliumium salts, triaryliumium oxide salts, pyridinium salts, quinolinium salts, isoquinolinium salts, sulfonium Esters, iron arene complexes, etc.

A base generator may be added as a hardening reaction catalyst. Examples of the base generating agent include: 1-methyl-1-(4-biphenyl)ethyl carbamate, 1,1-dimethyl-2-cyanoethyl carbamate, etc. Urethane derivatives; urea derivatives such as urea or N,N-dimethyl-N'-methylurea; dihydropyridine derivatives such as 1,4-dihydronicotinamide; organosilane or organoboron Quaternary ammonium salts of alkanes; dicyandiamide, etc.; compounds such as benzoylcyclohexylcarbamate or triphenylcarbinol recorded in Japanese Patent Laid-Open No. 4-162040; Japanese Patent Laid-Open No. 5-158242 Compounds described in .

〔6〕 Hardened film Moreover, the cured film formed from the curable resin composition of this invention is also one of this invention.

The cured film of the present invention can be obtained by a production method comprising the following steps: a coating step of applying the curable resin composition on a substrate; a drying step of forming a cured resin composition by drying the curable resin composition. The curable resin composition layer; the exposing step, exposing the curable resin composition layer; and the heating step, heating the exposed curable resin composition layer.

As a method of producing the cured film of the present invention, for example, coating a curable resin composition on a substrate, drying the coated curable resin composition to form a curable resin composition layer, and optionally A method of exposing and developing a curable resin composition layer through a photomask or the like; or manufacturing a cured film with a pattern by coating a curable resin composition with an inkjet device (hereinafter sometimes referred to as "pattern ")Methods. Here, examples of the substrate include resin substrates such as transparent glass plates, silicon wafers, polycarbonate substrates, polyester substrates, aramid substrates, polyamideimide substrates, and polyimide substrates. wait. A black matrix, other films or coloring patterns, transparent patterns for film thickness adjustment, thin film transistors (thin film transistor, TFT) and the like may also be formed on the substrate. The film thickness of the film in this case is not particularly limited, and can be appropriately adjusted according to the material used, application, etc., for example, about 0.1 μm to 30 μm, preferably about 1 μm to 20 μm, and more preferably 1 μm ~6 μm or so.

In the coating step, the coating method of the curable resin composition includes extrusion coating method, direct gravure coating method, reverse gravure coating method, capillary (capillary, CAP) coating method, die coating method, etc. . In addition, dip coater, rod coater, spin coater, slot & spin coater, slot coater (sometimes also called die coater, curtain flow coater) can also be used. , non-rotary coater), roller and other coaters for coating. Among them, coating using a spin coater is preferred.

In the drying step, as a method of drying the curable resin composition, natural drying, ventilation drying, reduced-pressure drying, and the like are exemplified. The specific heating temperature is suitably about 30°C to 120°C, preferably about 60°C to 100°C. The heating time is suitably about 10 seconds to 60 minutes, preferably about 30 seconds to 30 minutes. About drying under reduced pressure, it can illustrate performing it in the temperature range of about 20 degreeC - 25 degreeC under the pressure of about 50 Pa - 150 Pa. When the curable resin composition of the present invention contains the solvent (D), the solvent (D) can be removed by the drying.

The obtained curable resin composition layer may be irradiated with radiation through a photomask. As a photomask, the mask which formed the light shielding part according to the target pattern is used. As the radiation, rays such as g-rays and i-rays can be used. For irradiation of radiation, for example, 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. The curable resin composition layer after exposure can be developed by a flooding method, a dipping method, a spray method, or a shower method. In addition, when the curable resin composition layer is irradiated with radiation without interposing a photomask, it is not necessary to perform development.

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

The surfactant in the alkali developing solution may be any of nonionic surfactant, anionic surfactant, or cationic surfactant. Specific examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkylaryl ethers, other polyoxyethylene derivatives, oxyethylene/oxypropylene embedded segment copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl Amines etc. Specific examples of anionic surfactants include: higher alcohol sulfates such as sodium lauryl alcohol sulfate or sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate; Alkylarylsulfonates such as sodium dodecylbenzenesulfonate or sodium dodecylnaphthalenesulfonate, etc. Specific examples of cationic surfactants include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, quaternary ammonium salts, and the like. These surfactants may be used alone, respectively, or may be used in combination of two or more. The concentration of the surfactant in the alkaline developer is preferably in the range of 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 8% by mass, still more preferably 0.1% by mass to 5% by mass.

In the present invention, the temperature of the heating (post-baking) in the heating step is preferably 150° C. or lower. In addition, it is preferably lower than the glass transition temperature (Tg) of the substrate on which the cured film is formed. In addition, when a component such as a colorant that deteriorates at a temperature exceeding a specific temperature is included, it is preferably lower than the temperature at which the component begins to deteriorate. Low. Therefore, the temperature at the time of post-baking may be appropriately determined according to the type of the substrate on which the cured film is formed, the components contained in the curable resin composition, etc. Preferably it is below 100°C. When the temperature at the time of post-baking is 150 degreeC or less, the cured film which has excellent solvent resistance can be obtained without reducing the characteristic of a board|substrate, a coloring agent, etc. The temperature during the post-baking is preferably 60° C. or higher.

By using the curable resin composition of the present invention, it is no longer necessary to perform heating at a temperature exceeding 150° C. to improve solvent resistance, so that substrates, colorants, etc. having excellent solvent resistance can be obtained. The characteristics of the hardened film will not be reduced.

Through each step as described above, a cured film can be formed on a substrate from the curable resin composition of the present invention. This cured film can be effectively used as a photo spacer (photo spacer) 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. In the production of the cured film, if a photomask for hole formation is used for pattern exposure of the curable resin composition layer, an interlayer insulating film having holes can be obtained. When the curable resin composition of the present invention contains a colorant, it can be effectively used as a colored pattern in a color filter. In the production of the above-mentioned cured film, when exposing the curable resin composition layer, the cured film can be formed by full-surface exposure and heat curing without using a photomask, or only by heat curing. Effective as a top coat. Display devices, such as a liquid crystal display device, can be comprised by assembling the cured film obtained above. Such a display device has excellent display quality. [Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples. In the examples, unless otherwise specified, % and parts indicating content or usage are based on mass.

(1) Preparation of resin ＜Resin 1＞ Resin 1 comprising the following structural units was synthesized.

100.0 parts by mass of cyclopentanone were placed in a flask including a stirring blade, a reflux cooling tube, a thermometer, and a dropping funnel, and heated to 90°C. Using the dropping funnel, continuously drop 63.1 parts by mass of vinyl carbazole, 19.9 parts by mass of 2-(acetylacetyloxy) ethyl methacrylate, 17.0 parts by mass of methacrylic acid, azo A solution obtained by mixing 5.0 parts by mass of bis(isobutyronitrile) and 51.0 parts by mass of cyclopentanone. During the dropwise addition of the mixed solution, the temperature in the flask was kept at 90±1° C., and the dropwise addition was completed within 3 hours. After the dropwise addition, the temperature in the flask was kept at 90±1° C. and the aging reaction was carried out for 6 hours. After the reaction, the reaction solution was cooled to below 40°C, and 0.12 parts by mass of a polymerization inhibitor, 12.4 parts by mass of 4-hydroxybutyl acrylate glycidyl ether, 4.5 parts by mass of triphenylphosphine, and 15.6 parts by mass of cyclopentanone were added, After raising the temperature in the flask to 110° C., an addition reaction was performed at a temperature in the flask of 110±1° C., whereby a solution of resin 1 with a solid content of 40.1% by mass was obtained. The obtained resin 1 had a weight average molecular weight (Mw) of 6,800, a degree of dispersion (Mw/Mn) of 2.7, and an acid value in terms of solid content of 60 (mg-KOH/g).

＜Resin 2＞ Resin 2 comprising the following structural units was synthesized.

100.0 parts by mass of cyclopentanone were placed in a flask including a stirring blade, a reflux cooling tube, a thermometer, and a dropping funnel, and heated to 90°C. Using the dropping funnel, continuously drop 63.2 parts by mass of vinyl carbazole, 19.8 parts by mass of 2-(acetylacetyloxy) ethyl methacrylate, 17.0 parts by mass of methacrylic acid, azo A solution obtained by mixing 5.0 parts by mass of bis(isobutyronitrile) and 51.0 parts by mass of cyclopentanone. During the dropwise addition of the mixed solution, the temperature in the flask was kept at 90±1° C., and the dropwise addition was completed within 3 hours. After the dropwise addition, the temperature in the flask was kept at 90±1° C. and the aging reaction was carried out for 6 hours. After the reaction, the reaction solution was cooled to below 40°C, and 0.12 parts by mass of a polymerization inhibitor, 11.2 parts by mass of 3,4-epoxycyclohexyl methacrylate, 4.5 parts by mass of triphenylphosphine, and 14.0 parts by mass of cyclopentanone were added After raising the temperature in the flask to 110° C., an addition reaction was carried out at a temperature in the flask of 110±1° C., thereby obtaining a solution of resin 2 with a solid content of 38.5% by mass. The obtained resin 2 had a weight average molecular weight (Mw) of 15,800, a degree of dispersion (Mw/Mn) of 2.4, and an acid value in terms of solid content of 80 (mg-KOH/g).

＜Resin 3＞ Resin 3 comprising the following structural units was synthesized.

An appropriate amount of nitrogen was poured into a flask including a reflux cooler, a dropping funnel, and a stirrer to replace it with a nitrogen atmosphere, and 324 parts of propylene glycol monomethyl ether acetate was put in, and heated to 85° C. while stirring. Then, 60 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] Decane-9-yl acrylate mixture (trade name "E-DCPA", manufactured by Daicel) 30 parts, 9-vinyl carbazole 210 parts, propylene glycol monomethyl ether ethyl A mixed solution of 190 parts of esters. On the other hand, a mixed solution obtained by dissolving 31 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 155 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition, the temperature was maintained for 3 hours, and then cooled to room temperature to obtain a solution of the resin 3 having a solid content of 31% by mass. The obtained resin 3 had a weight average molecular weight (Mw) of 7900, a degree of dispersion (Mw/Mn) of 1.99, and an acid value in terms of solid content of 107 (mg-KOH/g).

＜Resin 4＞ Resin 4 comprising the following structural units was synthesized.

70 parts by mass of propylene glycol monomethyl ether was placed in a flask including a stirring blade, a reflux cooling pipe, a thermometer, and a dropping funnel, and heated to 90°C. Using the dropping funnel, continuously drop 52.6 parts by mass of dicyclopentyl methacrylate, 20.7 parts by mass of 2-(acetylacetyloxy) ethyl methacrylate, 26.7 parts by mass of methacrylic acid into the flask. A solution obtained by mixing parts by mass, 5 parts by mass of azobis(isobutyronitrile), and 30 parts by mass of propylene glycol monomethyl ether. During the dropwise addition of the mixed solution, the temperature in the flask was kept at 90±1° C., and the dropwise addition was completed within 3 hours. After the dropwise addition, the temperature inside the flask was kept at 90±1° C. for 6 hours. After the reaction, the reaction solution was cooled to below 40°C, and 0.12 parts by mass of 4-methoxyphenol, 17.6 parts by mass of 3,4-epoxycyclohexyl methacrylate, 4.7 parts by mass of triphenylphosphine, propylene glycol mono 85 parts by mass of methyl ether, after raising the temperature in the flask to 110° C., an addition reaction was performed at a temperature in the flask of 110±1° C., thereby obtaining a solution of resin 4 . The obtained resin 4 had a weight average molecular weight (Mw) of 14,300, a degree of dispersion of 2.4, an acid value of 103 (mg-KOH/g), and a solid content of 37.9% by mass.

＜Resin 5＞ Resin 5 comprising the following structural units was synthesized.

150.0 parts by mass of cyclopentanone were placed in a flask including a stirring blade, a reflux cooling tube, a thermometer, and a dropping funnel, and heated to 90°C. Using the dropping funnel, continuously drop 71.4 parts by mass of vinyl carbazole, 17.1 parts by mass of 2-(acetylacetyloxy) ethyl methacrylate, 9.0 parts by mass of methacrylic acid, azo A solution obtained by mixing 5.0 parts by mass of bis(isobutyronitrile) and 80.0 parts by mass of cyclopentanone. During the dropwise addition of the mixed solution, the temperature in the flask was kept at 90±1° C., and the dropwise addition was completed within 3 hours. After the dropwise addition, the temperature in the flask was kept at 90±1° C. and the aging reaction was carried out for 6 hours. After the reaction, the reaction solution was cooled to below 40°C, and 0.10 parts by mass of 4-methoxyphenol, 9.3 parts by mass of 3,4-epoxycyclohexyl methacrylate, 4.0 parts by mass of triphenylphosphine, cyclopentyl After raising the temperature in the flask to 110° C. with 70 parts by mass of ketone, an addition reaction was performed at a temperature in the flask of 110±1° C., thereby obtaining a solution of the resin 5 . In this resin, the carboxylic acid portion of methacrylic acid is completely consumed by addition reaction. The obtained resin 5 had a weight average molecular weight (Mw) of 6,800, a degree of dispersion of 2.1, and a solid content of 26.3% by mass.

(2) Determination method of molecular weight The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the said resin 1-resin 3 was performed on the following conditions using the gel permeation chromatography (GPC) method. Device: K2479 (manufactured by Shimadzu Corporation) Column: Shimadzu (SHIMADZU) Shim-pack GPC-80M Column temperature: 40°C Solvent: Tetrahydrofuran (THF) Flow rate: 1.0 mL/min Detector: Refractive Index (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).

(3) Preparation of curable resin composition Curable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 5 having the compositions shown in Table 1 were prepared as follows.

<Example 1> In the resin solution containing resin 1, 30 parts of trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) (hereinafter referred to as "polymerizable compound (B1)") were mixed, photopolymerized Initiator (IRGACURE (registered trademark) OXE01, manufactured by BASF) (hereinafter referred to as "polymerization initiator (C1)") 3 parts, propylene glycol monomethyl ether acetate (hereinafter , set as "solvent D1") 502 parts to obtain a curable resin composition with a solid content of 15%. This curable resin composition was referred to as the curable resin composition of Example 1.

<Example 2> Except for using 30 parts of dipentaerythritol polyacrylate (A-9550, manufactured by Shin-Nakamura Chemical Co., Ltd.) (hereinafter referred to as "polymerizable compound (B2)") instead of polymerizable compound B1, the same method as in Example 1 in the same manner to obtain a curable resin composition with a solid content of 15%. This curable resin composition was referred to as the curable resin composition of Example 2.

<Example 3> A curable resin composition having a solid content of 15% was obtained in the same manner as in Example 1, except that 100 parts of a resin solution containing resin 2 was used instead of resin solution containing resin 1 in terms of solid content. This curable resin composition was referred to as the curable resin composition of Comparative Example 1.

＜Comparative example 1＞ A curable resin composition having a solid content of 15% was obtained in the same manner as in Example 1, except that 100 parts of a resin solution containing resin 3 was used instead of resin solution containing resin 1 in terms of solid content. This curable resin composition was referred to as the curable resin composition of Comparative Example 1.

<Example 4> A curable resin composition having a solid content of 15% was obtained in the same manner as in Example 1 except that the compounded portion of the resin 1 was as shown in Table 1. This curable resin composition was referred to as the curable resin composition of Example 4.

<Example 5> A curable resin composition having a solid content of 15% was obtained in the same manner as in Example 2 except that the compounded portion of the resin 1 was set as shown in Table 1. This curable resin composition was referred to as the curable resin composition of Example 5.

＜Comparative example 2＞ A curable resin composition having a solid content of 15% was obtained in the same manner as in Example 1, except that 100 parts of a resin solution containing resin 4 was used instead of resin solution containing resin 1 in terms of solid content. This curable resin composition was referred to as the curable resin composition of Comparative Example 2.

＜Comparative example 3＞ A curable resin composition having a solid content of 15% was obtained in the same manner as in Example 1, except that 100 parts of a resin solution containing resin 5 was used instead of resin solution containing resin 1 in terms of solid content. This curable resin composition was referred to as the curable resin composition of Comparative Example 3.

＜Comparative example 4＞ A curable resin composition having a solid content of 15% was obtained in the same manner as in Example 2, except that 100 parts of a resin solution containing resin 4 was used instead of the resin solution containing resin 1 in terms of solid content. This curable resin composition was referred to as the curable resin composition of Comparative Example 4.

＜Comparative example 5＞ A curable resin composition having a solid content of 15% was obtained in the same manner as in Example 2, except that 100 parts of a resin solution containing resin 5 was used instead of resin solution containing resin 1 in terms of solid content. This curable resin composition was referred to as the curable resin composition of Comparative Example 5.

(4) Formation of cured film By the spin coating method, the curable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were respectively coated on different 2-inch square glass substrates (Yige (Eagle) XG; manufactured by Corning Corporation) so that the film thickness after post-baking becomes 1.5 μm (coating step), and then vacuum-dried (ultimate pressure 66 Pa) to obtain a curable resin composition layer (drying step). Using an exposure machine (TME-150RSK; manufactured by Topcon Co., ^Ltd. , light source: ultra-high pressure mercury lamp), the obtained The curable resin composition layer is irradiated with light. Then, the cured film was obtained by heating the obtained curable resin composition layer at 150° C. for 15 minutes using a hot plate (heating step). The film thickness of the obtained cured film was measured with a film thickness measuring device (DEKTAK 3; manufactured by Ulvac Co., Ltd.), and found to be 1.5 μm.

(5) Evaluation ＜Solvent resistance＞ The obtained cured film was immersed in propylene glycol monomethyl ether acetate (PGMEA) at a temperature of 23° C. for 5 minutes, and a film thickness measuring device (Dektek (DEKTAK 3; manufactured by Ulvac Co., Ltd.) The film thickness was measured, and the ratio to the film thickness before immersion was calculated, and this value was defined as the residual film rate. The results are shown in Table 1.

[Table 1] Example 1 Example 2 Example 3 Comparative example 1 Example 4 Example 5 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 composition resin Resin 1 100 100 70 70 Resin 2 100 Resin 3 100 Resin 4 100 100 Resin 5 100 100 polymeric compound Polymeric compound (B1) 30 30 30 30 30 30 Polymeric compound (B2) 30 30 30 30 evaluate Residual film rate (%) 99 99 35 0 99 99 72 53 75 46

＜Refractive Index＞ For the obtained cured film, the refractive index at 550 nm was measured using an ellipsometer (J.A. Woollam M2000). As a result, the resin 1 of Example 1 was 1.62, and the resin of Example 3 was 1.62. 2 was 1.62, resin 3 of comparative example 1 was 1.52, resin 4 of comparative example 2 was 1.54, and resin 5 of comparative example 3 was 1.64.

＜Development＞ By spin coating, the curable resin composition of Example 1, Example 3 and Comparative Example 1 to Comparative Example 3 were respectively coated on different 2-inch square glass substrates (Eagle XG; Corning ( Corning) so that the film thickness after post-baking becomes 1.5 μm (coating step), and then vacuum-dried (ultimate pressure 66 Pa) to obtain a curable resin composition layer (drying step). The obtained curable resin composition layer was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide at 23°C for 60 seconds, and the solubility was confirmed. As a result, the resin 1 of Example 1 and the resin of Example 3 2. The solubility of Resin 3 of Comparative Example 1 and Resin 4 of Comparative Example 2 was ○, but the solubility of Resin 5 of Comparative Example 3 was ×.

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none

Claims (7)

A resin comprising: 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; a structural unit (Ac) having an acid group; and a structural unit (Ad) contains a heterocyclic ring which may have a substituent. The resin according to claim 1, wherein the structural unit (Aa) is represented by the following formula (Aax), In formula (Aax), R ²¹ and R ²² independently represent a hydrogen atom or a methyl group, R ²⁵ represents an alkanediyl group with 1 to 20 carbon atoms, and the -CH ₂ - contained in the alkanediyl group can be Substitute -O- or -CO-. The resin according to claim 1 or 2, wherein the structural unit (Ad) is represented by the following formula (Ad-1), In formula (Ad-1), R ¹ represents a hydrogen atom, a methyl group, or a hydroxymethyl group; R ² to R ⁹ independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group with 1 to 20 carbons, or a saturated hydrocarbon group with 6 to 20 carbons. 20 aryl, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted by alkoxy or aryl; X represents a single bond, an alkanediyl group with a carbon number of 1 or more, or the following linear or branched The group represented by formula (V); In formula (V), l represents an integer of 0 or more; m represents an integer of 1 or more. A curable resin composition comprising the resin according to any one of claims 1 to 3, a polymerizable compound, and a polymerization initiator. A cured film formed of the resin composition according to claim 4. A method of manufacturing a hardened film, comprising sequentially: Coating step, coating the resin composition as described in Claim 4 on the substrate; a drying step, forming a resin composition layer by drying the resin composition; an exposing step of exposing the resin composition layer; and In the heating step, the resin composition layer is heated. The method for producing a cured film according to claim 6, wherein, in the heating step, the exposed resin composition layer is heated at 150° C. or lower.