Resins, curable resin compositions, curable films, and methods for their manufacture

Abstract

This invention provides a novel resin having heterocyclic structural units, and a cured film with excellent solvent resistance can be obtained even when the composition containing it is heated at low temperatures, such as below 150°C, to form a cured film. A resin comprises: a structural unit (Aa) having an α,β-unsaturated carbonyl group; a structural unit (Ab) having an active methylene or active methine group; a structural unit (Ac) having an acid group; and a structural unit (Ad) containing a heterocycle that may have substituents.

Description

Technical Field

[0001] This invention relates to a resin, a curable resin composition using the resin, and a curable film formed from the curable resin composition. Prior Technology

[0002] As display devices, liquid crystal displays (LCDs), plasma displays, paper-like displays, and touch panels are known. Among these, it is known that a spacer made of a photosensitive resin composition is used between the color filter and the array substrate of a display device such as a liquid crystal display or touch panel to maintain the distance between the two substrates.

[0003] In an embodiment of Patent Document 1, a photosensitive resin composition comprising a reaction product as a resin component is described, wherein the reaction product is obtained by polymerizing methyl methacrylate, ethyl methacrylate and methacrylic acid, and then reacting glycidyl methacrylate.

[0004] Patent document 2 (International Publication No. 2012 / 053377) describes a high refractive index resin composition for electronic components containing a carbazole compound. [Existing Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 3-172301 [Patent Document 2] International Publication No. 2012 / 053377 Summary of the Invention

[0006] [Problem to be Solved by the Invention] This invention was made in response to the following problem: hardened films formed by heating a composition containing a resin with a heterocyclic structural unit (such as a carbazole ring) at low temperatures exhibit poor solvent resistance. The object of this invention is to provide a novel resin, a curable resin composition containing the resin, and a hardened film formed from the resin composition, wherein the resin is a resin with a heterocyclic structural unit, and a hardened film with excellent solvent resistance can be obtained even when the composition containing it is heated at low temperatures, such as below 150°C, to form a hardened film. Furthermore, the hardened film obtained by this invention has a high refractive index and excellent developability. [Methods for solving problems]

[0007] This invention includes the following: [1] A resin comprising: a structural unit (Aa) having an α,β-unsaturated carbonyl group; a structural unit (Ab) having an active methylene or active methine group; a structural unit (Ac) having an acid group; and a structural unit (Ad) containing a heterocycle that may have substituents. [2] The resin as described in [1], wherein the structural unit (Aa) is represented by the following formula (Aax).

[0008] In formula (Aax), R21 and R22 independently represent hydrogen atoms or methyl groups. R 25 represents an alkyldiyl group with 1 to 20 carbon atoms, wherein the -CH 2- group may be substituted with -O- or -CO-. [3] The resin as described in [1] or [2], wherein the structural unit (Ad) is represented by the following formula (Ad-1).

[0009] In formula (Ad-1), R1 represents a hydrogen atom, a methyl group, or a hydroxymethyl group; R2 to R9 independently represent hydrogen atoms, halogen atoms, saturated hydrocarbon groups with 1 to 20 carbon atoms, or aryl groups with 6 to 20 carbon atoms, wherein the hydrogen atoms in the saturated hydrocarbon groups may be substituted by alkoxy or aryl groups; X represents a single bond, an alkyl diyl group having one or more carbon atoms, or a linear or branched group represented by the following formula (V);

[0010] (In formula (V), l represents an integer greater than or equal to 0; m represents an integer greater than or equal to 1) [4] A curable resin composition comprising a resin as described in any one of [1] to [3], a polymerizable compound, and a polymerization initiator. [5] A hardened film formed from a hardened resin composition as described in [4]. [6] A method for manufacturing a hardened film, comprising, in sequence: The coating step involves coating the curable resin composition as described in [4] onto the substrate; The drying step involves drying the resin composition to form a resin composition layer. The exposure step involves exposing the resin composition layer to light; and The heating step involves heating the resin composition layer. [7] The method for manufacturing a hardened film as described in [6], wherein, in the heating step, the exposed resin composition layer is heated to below 150°C. [The effects of the invention]

[0011] By using a curable resin composition containing the resin of the present invention, a curable film with excellent solvent resistance can be formed even when heated at a low temperature, such as below 150°C, to form a curable film. Simple Explanation of the Diagram

[0012] none Implementation

[0013] <Resin> The resin of the present invention (hereinafter referred to as "resin (A)") is mainly used as an adhesive resin in curable resin compositions. 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 or active methine group; a structural unit (Ac) having an acid group; and a structural unit (Ad) containing a heterocycle that may have substituents.

[0014] More specifically, resin (A) is as described below. Resin (A) comprises a structural unit having an α,β-unsaturated carbonyl group (hereinafter referred to as "structural unit (Aa)"), a structural unit having an active methylene or active methine group (Ab) (hereinafter referred to as "structural unit (Ab)"), a structural unit having an acid group (Ac) (hereinafter referred to as "structural unit (Ac)"), and a structural unit containing a heterocycle that may have substituents (Ad) (hereinafter referred to as "structural unit (Ad)"). The resin may also contain other repeating units (Ae). Additionally, the resin may contain two or more structural units (Aa), (Ab), (Ac), and (Ad). From the viewpoint that resin (A) is used as an adhesive resin in a curable resin composition, resin (A) is preferably an alkali-soluble resin. Alkali solubility refers to the property of dissolving in a developer solution that is an aqueous solution of an alkali compound. Resin (A) contains polymers with structural units (Ac), thus readily imparting alkali solubility. In this specification, "structural units derived from (meth)acrylic acid and / or its esters" are also referred to as "(meth)acrylic acid structural units". Furthermore, "(meth)acrylic acid" means "methacrylic acid and / or acrylic acid". The following is a detailed description of each structural unit.

[0015] [1] Structural unit (Aa) The structural unit (Aa) is a structural unit with α,β-unsaturated carbonyl groups.

[0016] The resin (A) has structural units (Aa) which can improve the solvent resistance of the hardened film obtained by heating at low temperature.

[0017] As a structural unit (Aa), for example, the structural unit represented by the following formula (Aax) can be listed (hereinafter, the structural unit is referred to as "structural unit (Aax)").

[0018]

[0019] In formula (Aax), R21 and R22 independently represent hydrogen atoms or methyl groups. R 25 represents an alkyldiyl group with 1 to 20 carbon atoms, wherein the -CH 2- in the alkyldiyl group may be substituted with -O- or -CO-. Examples of such alkyldiyl groups include: straight-chain alkyldiyl groups, branched alkyldiyl groups, cyclic alkyldiyl groups, and groups formed by combining these. Examples of linear alkyl diyl groups include: methylene, ethyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, and dodecane-1,12-diyl. Examples of branched alkyldiyl groups include: ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, and 2-methyloctane-1,8-diyl. Examples of cyclic alkyl diyl groups include: cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cyclooctane-1,5-diyl, and other cycloalkyl diyl groups; as well as polycyclic divalent alicyclic hydrocarbon groups such as norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl, and adamantane-2,6-diyl. Examples of groups that combine linear and cyclic alkyl groups include the following groups (where * denotes a bond in the following formulas).

[0020] R 25 is preferably an alkyldiyl with 4 to 18 carbon atoms, more preferably an alkyldiyl with 4 to 10 carbon atoms, and even more preferably an alkyldiyl with 6 to 9 carbon atoms.

[0021] A preferred example of the structural unit (Aax) is a structural unit formed by replacing the -CH 2- in the alkyl diene of R 25 with a -O-, and more specifically, examples include: the following formula (Aa-1), the following formula (Aa-21) and the following formula (Aa-22).

[0022] The structural unit (Aa) represented by formula (Aa-1) can be manufactured, for example, by referring to the method of manufacturing chemical structure (1) described in Japanese Patent Application Publication No. 2015-172117.

[0023]

[0024] In formula (Aa-1), R21 and R22 independently represent hydrogen atoms or methyl groups. R23 and R24 represent alkyldiyl groups independently of each other.

[0025] The combination of R 23 and R 24 is preferably an alkyldiyl group with 1 to 8 carbon atoms and an alkyldiyl group with 1 to 8 carbon atoms, more preferably an alkyldiyl group with 1 to 3 carbon atoms and a straight-chain alkyldiyl group with 4 to 10 carbon atoms, and even more preferably a methylene group and a straight-chain alkyldiyl group with 4 to 8 carbon atoms.

[0026] Furthermore, a preferred example of formula (Aa-1) is represented by formula (Aa-11) or formula (Aa-12). In formula (Aa-11), the structural unit represented by R23 is methylene and R24 is hexane-1,4-diyl. In formula (Aa-12), the structural unit represented by R23 is hexane-1,4-diyl and R24 is methylene.

[0027]

[0028] The structural unit (Aa) represented by formulas (Aa-21) and (Aa-22) can be manufactured, for example, by referring to the method of manufacturing the chemical structure (1) described in Japanese Patent Application Publication No. 2015-172117.

[0029]

[0030] In formulas (Aa-21) and (Aa-22), R27 and R28 independently represent hydrogen atoms or methyl groups. R 26 indicates an alkyldiyl group with 1 to 4 carbon atoms. The ring W indicates a cycloalkane dimethyl group with 5 to 7 carbon atoms.

[0031] R 26 is preferably methylene, and cycloW is preferably cyclohexanediyl, more preferably cyclohexane-1,4-diyl.

[0032] A preferred example of the formulas (Aa-21) and (Aa-22) is represented by the following formula (Aa-21a) or formula (Aa-22a).

[0033]

[0034] Typically, the structural unit (Aa) can be obtained by adding a compound having an α,β-unsaturated carbonyl group to a carboxyl-containing structural unit of the copolymer (hereinafter referred to as "structural unit (Aa')"), or by reacting (meth)acrylic acid with an epoxy-containing structural unit of the copolymer. The structural unit (Aa') is one of the structural units (Ac) described later. There are no particular limitations on the type of compound having an α,β-unsaturated carbonyl group, as long as it can react with the carboxylic acid contained in the structural unit (Aa'). Examples of compounds having an α,β-unsaturated carbonyl group include (meth)acrylates (Aa'') with an epoxy group.

[0035] (Meth)acrylates (Aa'') containing epoxy groups have aliphatic epoxy groups. Aliphatic epoxy groups are groups formed by the epoxidation of straight-chain or branched aliphatic unsaturated hydrocarbons.

[0036] The structural unit represented by formula (Aax) can be obtained 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 structural unit having an epoxy group. The structural unit (Aa) can be obtained by reacting 5-hydroxypentyl acrylate glycidyl ether or 6-hydroxyhexyl acrylate glycidyl ether with a (meth)acrylic structural unit having a carboxyl group or a (meth)acrylic structural unit having an epoxy group.

[0037] [2] Structural Unit (Ab) A structural unit (Ab) is a structural unit derived from an unsaturated compound having an active methylene or active methine. This structural unit can be obtained by using an unsaturated compound having an active methylene or active methine as a monomer to obtain a copolymer. Alternatively, it can be obtained by reacting a compound having an active methylene or active methine (Ab'') with other structural units (Ab').

[0038] As unsaturated compounds containing an active methylene group, compounds represented by formula (I) can be listed. As unsaturated compounds containing an active methine group, compounds represented by formula (II) can be listed.

[0039] In formulas (I) and (II), R11 independently represents a hydrogen atom or a hydrocarbon group containing 1 to 24 carbon atoms that may contain heteroatoms; R 12 represents a single bond or a divalent hydrocarbon group with 1 to 20 carbon atoms; R13 represents the divalent base represented by any one of equations (1-1) to (1-3); R 14 represents the basis represented by any one of equations (1-4) to (1-7);

[0040] (R 15 is a hydrocarbon group with 1 to 24 carbon atoms that may contain heteroatoms) X represents the divalent base represented by any one of equations (1-8) to (1-10).

[0041]

[0042] R 11 is preferably a hydrogen atom, methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, methoxy, ethoxy, propoxy, hexoxy, cyclohexyloxy or a group represented by formulas (1-11) to (1-13), and more preferably a hydrogen atom or methyl. R 15 is preferably methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, methoxy, ethoxy, propoxy, hexoxy, cyclohexyloxy or a group represented by formulas (1-11) to (1-13), and more preferably methyl.

[0043]

[0044] R 12 is preferably a single bond, methylene, ethyl, propyl, butyl, propyl, hexyl, cyclohexyl, octyl, decyl, or dodecyl, and more preferably a single bond, methyl, or ethyl.

[0045] Specifically, the following compounds can be listed as compounds represented by formula (I).

[0046]

[0047] Specifically, the following compounds can be listed as compounds represented by formula (II).

[0048]

[0049] Formulas (I-1) to (I-7), (I-16), (II-1), (II-2) and (II-5) are compounds having CH 3-CH 2=CH-, but compounds in which CH 3-CH 2=CH- is substituted to H-CH 2=CH- can also be listed.

[0050] As a structural unit (Ab), it is preferably represented by the enumeration formula (Ab-1).

[0051] [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.]

[0052] Examples of alkyl groups having 1 to 6 carbon atoms in R 34 include: methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, tributyl, n-pentyl, and n-hexyl. As R 34, hydrogen atoms and methyl groups are preferably listed. Compounds that serve as structural units represented by the derived formula (Ab-1) include, for example, ethyl 2-(methacryloxy)acetate [the compound represented by formula (I-1)].

[0053] [3] Structural unit (Ac) The structural unit (Ac) is a structural unit that can be derived from unsaturated compounds with acid groups. Examples of acid groups include carboxyl groups, phenolic hydroxyl groups, and sulfonic acid groups. The carboxyl group can also be anhydride-substituted.

[0054] This structural unit can be obtained by using an unsaturated compound with an acid group as a monomer to obtain a copolymer. Alternatively, it can be obtained by reacting a compound with an acid group (Ac'') with other structural units (Ac'). Unsaturated compounds with acid groups are preferably unsaturated carboxylic acids or unsaturated carboxylic anhydrides. Specific examples of unsaturated carboxylic acids or unsaturated carboxylic anhydrides include: (Meth)acrylic acid, butenoic 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; Unsaturated dicarboxylic acids such as maleic acid, trans-butenedioic acid, citraconic acid, medaconic 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-cyclohexene dicarboxylic acid, and 5,6-dicarboxylic acid-bicyclo[2.2.1]hept-2-ene; Unsaturated dicarboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxylic bicyclic [2.2.1]hept-2-en anhydride (himic anhydride). Unsaturated mono[(meth)acryloxyethyl] esters of divalent or higher polycarboxylic acids, such as succinate mono[2-(meth)acryloxyethyl] ester and phthalate mono[2-(meth)acryloxyethyl] ester; Unsaturated acrylates containing both hydroxyl and carboxyl groups in the same molecule, such as α-(hydroxymethyl)(meth)acrylic acid. Of these, (meth)acrylic acid and maleic anhydride are preferred in terms of copolymerization reactivity and solubility relative to alkaline aqueous solutions. These can be used alone or in combination.

[0055] [4] Structural Unit (Ad) A structural unit (Ad) is a structural unit derived from an unsaturated compound having a heterocycle. This heterocycle may have substituents. This structural unit can be obtained by using a heterocyclic unsaturated compound as a monomer to obtain a copolymer. Alternatively, it can be obtained by reacting a heterocyclic compound (Ad'') with other structural units (Ad'). By having structural units (Ad) in the resin (A), the refractive index of the obtained hardened film can be increased. The refractive index can be measured, for example, by ellipsometry.

[0056] Heterocyclic rings can be monocyclic or condensed rings. The heterocyclic ring is an n-valent heterocyclic ring, where n can be monovalent or divalent. Regarding n-valent heterocyclic rings, the remaining atomic group after removing n hydrogen atoms from the heterocyclic compound that are directly bonded to the carbon atoms or heteroatoms constituting the ring is defined as an n-valent heterocyclic ring; the remaining atomic group after removing 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 number of carbon atoms in the heterocyclic group does not include the number of carbon atoms in the substituents, and is typically 2 to 60, preferably 4 to 20.

[0057] As a heterocycle, it is preferably formed by removing n hydrogen atoms from an aromatic heterocyclic compound. Here, "aromatic heterocyclic compound" refers to compounds whose heterocycles themselves exhibit aromaticity, such as oxadiazole, thiadiazole, thiazolium, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzosiloxane, and dibenzophosphole; and compounds such as phenoxazine, phenoxazine, dibenzoborane, dibenzosiloxane, and benzopyran, which, even if the heterocycle itself does not exhibit aromaticity, have an aromatic ring condensed within the heterocycle.

[0058] In the structural unit (Ad), the heterocycle is preferably a nitrogen-containing heterocycle, and more preferably carbazole. The structural unit (Ad) is preferably the structural unit represented by the following formula (Ad-1).

[0059] In formula (Ad-1), R1 represents a hydrogen atom, a methyl group, or a hydroxymethyl group; R2 to R9 independently represent hydrogen atoms, halogen atoms, saturated hydrocarbon groups with 1 to 20 carbon atoms, or aryl groups with 6 to 20 carbon atoms, wherein the hydrogen atoms in the saturated hydrocarbon groups may be substituted by alkoxy or aryl groups; X represents a single bond, an alkyl diyl group having one or more carbon atoms, or a straight-chain or branched group represented by the following formula (V);

[0060] (In formula (V), l represents an integer greater than or equal to 0; m represents an integer greater than or equal to 1)

[0061] [5] Other structural units Resin (A) may have structural units other than structural units (Aa), structural units (Ab), structural units (Ac) and structural units (Ad) (hereinafter, the structural unit is referred to as "structural unit (Ae)"). Structural unit (Ae) is a structural unit different from structural units (Aa), (Ab), (Ac), and (Ad). Structural unit (Ae) can be derived from monomers that can be polymerized with monomers that derive structural units other than structural unit (Ae) (e.g., structural units (Aa), (Ab), (Ac), and (Ad)). Specific examples of this type of monomer can be listed as follows: Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, dibutyl methacrylate, tert-butyl methacrylate, and other alkyl methacrylates; alkyl acrylates such as methyl acrylate and isopropyl acrylate; Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6]decane-8-yl ester (commonly referred to as dicyclopentyl (meth)acrylate in this technical field), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, (Meth) phenyl acrylate, (Meth) benzyl acrylate, (Meth) 2-hydroxyethyl acrylate, (Meth) 2-hydroxypropyl acrylate, and other (Meth) acrylates; Diethyl maleate, diethyl fumarate, diethyl itaconic acid, and other dicarboxylic acid diesters; Hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 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-dicarboxylic acid bicyclo[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-methyl 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 - Dicarboxylic acid bicyclic [2.2.1]hept-2-ene anhydrous (Nadic anhydride), 5-tert-butoxycarbonyl bicyclic [2.2.1]hept-2-ene, 5-cyclohexyloxycarbonyl bicyclic [2.2.1]hept-2-ene, 5-phenoxycarbonyl bicyclic [2.2.1]hept-2-ene, 5,6-di(tert-butoxycarbonyl)bicyclic [2.2.1]hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclic [2.2.1]hept-2-ene, and other bicyclic unsaturated compounds; N-Phenylacetinimide, N-Cyclohexylmaleimide, N-Benzylmaleimide, N-Succinimido-3-maleimide benzoate, N-Succinimido-4-maleimide butyrate, N-Succinimido-6-maleimide hexanoate, N-Succinimido-3-maleimide propionate, N-(9-acridyl)maleimide, and other dicarbonyl nimidide derivatives; Styrene compounds such as α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene; Acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

[0062] Of these, in terms of reactivity in copolymerization or heat resistance of the copolymer, (meth)acrylates, styrene compounds and dicarbonyl acetimine compounds are preferred; in terms of reactivity in copolymerization and solubility relative to alkaline aqueous solutions, methyl (meth)acrylate, n-butyl (meth)acrylate, tricyclo[5.2.1.0 2,6]decane-8-yl (meth)acrylate, styrene, vinyltoluene, N-phenylcis-butene diacetimine, N-cyclohexylcis-butene diacetimine, N-benzylcis-butene diacetimine, bicyclo[2.2.1]hept-2-ene, alkyl acrylates, etc.

[0063] Resin (A) may also have two or more structural units (Ae).

[0064] [6] Ratio of each structural unit Resin (A) comprises a copolymer containing structural units (Aa), (Ab), (Ac), and (Ad), and may further contain structural units (Ae). The ratio of each structural unit, expressed as a mole fraction, is preferably within the following range relative to the total number of moles of the structural units constituting the copolymer. Structural unit (Aa): 1 mol% ~ 50 mol% Structural unit (Ab): 1 mol% ~ 50 mol% Structural unit (Ac): 1 mol% ~ 50 mol% Structural unit (Ad): 1 mol% ~ 90 mol% Structural unit (Ae): 0 mol%~50 mol%.

[0065] Furthermore, if the ratio of structural units is within the following range, the solvent resistance tends to be better, and therefore it is even better. Structural unit (Aa): 5 mol%~30 mol% Structural unit (Ab): 5 moles %~30 moles % Structural unit (Ac): 5 moles ~ 30 moles Structural unit (Ad): 5 mol%~8 mol% Structural unit (Ae): 0 mol%~30 mol%.

[0066] Copolymers containing each structural unit can be manufactured, for example, according to the methods described in the literature "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu, Chemical Dojin Publishing Co., Ltd., 1st edition, 1st printing, published March 1, 1972) and the references cited in that literature.

[0067] Resin (A) can be manufactured, for example, through a two-stage process. Specifically, a predetermined amount of each compound that derives structural unit (Ab), structural unit (Ac), and structural unit (Ad), as well as a compound that derives structural unit (Aa'), a polymerization initiator, and a solvent are placed in a reaction vessel. By replacing oxygen with nitrogen, the mixture is stirred, heated (e.g., 50°C to 140°C), and held at that temperature (e.g., 1 hour to 10 hours) under oxygen-free conditions to obtain a copolymer having structural units (Aa'), (Ab), (Ac), and (Ad). Then, the nitrogen in the reaction vessel is replaced with oxygen, and the epoxy-containing (meth)acrylate (Aa''), reaction catalyst, and polymerization inhibitor are placed into the reaction vessel. The mixture is stirred, heated (e.g., 60℃~130℃), and kept at that temperature (e.g., 1 hour~10 hours) to allow the epoxy-containing (meth)acrylate (Aa'') to react with the structural unit (Aa'), thereby deriving the structural unit (Aa) and obtaining a copolymer containing structural units (Aa), (Ab), (Ac), and (Ad). Regarding the obtained copolymer, the solution after the reaction can be used directly, or a concentrated or diluted solution can be used. Alternatively, the copolymer that has been removed in solid form by methods such as reprecipitation can be dissolved in a solvent for use.

[0068] In the case of manufacturing a resin (A) with more structural units (Ae), it is sufficient to simply load the compounds that derive structural units (Ab), (Ac), and (Ad), as well as the compound that derives structural unit (Aa'), together with the structural unit (Ae) in the above steps.

[0069] In the above, when the structural unit (Ac) has a carboxyl group, the structural unit (Aa) can be obtained by reacting the structural unit (Ac) with an epoxy-containing (meth)acrylate (Aa''). The polystyrene-converted average molecular weight of resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 10,000 to 50,000. Curable resin compositions containing resins (A) with a weight average molecular weight within the aforementioned range tend to have good coatability during coating, and are less prone to film reduction during development, thus having good peelability of uncured portions during development.

[0070] The dispersion of resin (A) [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. If the dispersion is within the range described above, the curable resin composition containing the resin (A) as an adhesive resin tends to have excellent developability, and is therefore preferred. The acid value of resin (A) is preferably 70 mg-KOH / g to 150 mg-KOH / g, and more preferably 75 mg-KOH / g to 135 mg-KOH / g. In this specification, the acid value is a value determined by Japanese Industrial Standards (JIS) K 2501-2003.

[0071] <Curing resin composition> The curable resin composition of the present invention comprises a resin (A), a polymerizable compound, and a polymerization initiator. The resin composition of the present invention may further comprise a solvent. Hereinafter, the polymerizable compound, polymerization initiator, and solvent in the curable resin composition of the present invention will be referred to as polymerizable compound (B), polymerization initiator (C), and solvent (D), respectively.

[0072] [1] Resin (A) The curable resin composition of the present invention contains resin (A), thus obtaining a curable film with excellent solvent resistance. Cured films formed from curable resin compositions containing resin (A) exhibit excellent solvent resistance even when the temperature of the post-exposure heating step (so-called post-baking step) during the production of the cured film is below 150°C, below 130°C, or below 100°C. The temperature of the heating step is, for example, above 80°C. In the curable resin composition of the present invention, the content of resin (A) is preferably 5% to 90% by mass, and more preferably 10% to 70% by mass, relative to the solid components in the curable resin composition. If the content of resin (A) is within the range described above, the solubility in the developer is sufficient, and it is not easy to produce developing residue. In addition, the parts that are exposed and hardened during development are less likely to have film reduction, and the parts that are not exposed and hardened have good peeling properties, which is therefore preferred. Here, solids content refers to the amount remaining after removing the solvent from the total amount of the curable resin composition. The total amount of solids and the content of each component therein can be determined by known analytical methods such as liquid chromatography or gas chromatography. Alternatively, acrylic adhesive resins commonly used in this field may also be used without compromising the scope of the invention.

[0073] [2] Polymer compounds (B) There are no particular limitations on the polymerizable compound (B), which is a compound that can be polymerized by active free radicals generated by a self-polymerization initiator (D) due to light irradiation or the like. Examples of polymerizable compounds (B) include compounds having vinyl unsaturated bonds, and examples include: monofunctional monomers containing one functional group with an vinyl unsaturated bond, difunctional monomers containing two such functional groups, and polyfunctional monomers containing three or more such functional groups. Specific examples of the monofunctional monomers mentioned above include: nonylphenyl carbitol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-vinylpyrrolidone, etc. Specific examples of the aforementioned difunctional monomers include: 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentyl glycol di(meth)acrylate, etc. Specific examples of the aforementioned multifunctional monomers include: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, the reaction product of pentaerythritol tri(meth)acrylate and acid anhydride, and the reaction product of dipentaerythritol penta(meth)acrylate and acid anhydride, etc. Among them, difunctional monomers or polyfunctional monomers can be used more effectively. These polymeric compounds (B) can be used alone or in combination of two or more. The content of polymeric compound (B), relative to the total amount of resin (A) and polymeric compound (B), is preferably 1% to 70% by mass, more preferably 5% to 60% by mass. If the content of polymeric compound (B) is within the above range, the hardened film formed by curing the curable resin composition tends to have good strength, smoothness, and solvent resistance, which is preferred.

[0074] [3] Polymerization initiator (C) If the polymerization initiator (C) is a compound that generates active free radicals, acids, etc. through the action of light or heat, and thus can initiate polymerization, there are no particular limitations, and known polymerization initiators can be used. The preferred polymerization initiators (C) are O-acyloxime compounds, benzyl ketone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds. By using polymerization initiation aids in these polymerization initiators (C), the obtained curable resin composition becomes more sensitive, thus improving the productivity of patterns when used to form patterns. Examples of O-acetylated oxime compounds include, for example, N-benzoyloxy-1-(4-phenylmercaptophenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylmercaptophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylmercaptophenyl)-3-cyclopentylpropane-1-one-2-imine, and N-acetylated oxime compounds having a diphenyl sulfide skeleton; N-acetylated oxime-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, and N-acetylated oxime-1-[9-ethyl- 6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1 O-acetylated compounds with a carbazole skeleton, such as [9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-one-2-imine; and O-acetylated compounds with a fluorene skeleton, such as 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluorene-2-yl]acetone O-acetylated oxime. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02, OXE03 (manufactured by BASF), N-1919 (manufactured by ADEKA), and DFI-091 (manufactured by Daito Chemix) can also be used. Among them, the O-acetylated oxime compound is preferably selected from N-benzoyloxy-1-(4-phenylsulfonylurea)octan-1-one-2-imine, N-acetylurea-1-(4-phenylsulfonylurea)-3-cyclohexylpropane-1-one-2-imine, and N-acetylurea-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-ethyl-4-(2,4-dimethyl-4-(2,3-dimethyl-4,4-ethyl ... The filter is at least one of the group consisting of [dioxanepentylmethyloxy)benzoyl]-9H-carbazole-3-yl]ethane-1-imine and 1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]acetone O-acetylgime, and preferably an O-acetylgime compound different from O-acetylgime compounds having a carbazole ring with a nitro group. If it is one of these O-acetylgime compounds, there is a tendency to obtain a color filter with high brightness.

[0075] Examples of such benzyl ketone compounds include: 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)benzene] [Base] propane-1-one, 1-hydroxycyclohexylphenyl ketone (Omnirad (registered trademark) 184, Irgacure (registered trademark) 184), oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, benzodiazepine dimethyl ketal (Omnirad (registered trademark) 651, Irgacure (registered trademark) 651), etc. Alternatively, commercially available products such as 2-benzyl-2-(dimethylamino)-4'-morpholinyl phenylbutanone (Omnirad (registered trademark) 369, formerly Irgacure (registered trademark) 369), (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one) (Omnirad (registered trademark) 907, formerly Irgacure (registered trademark) 907), and Irgacure (registered trademark) 379 (all manufactured by BASF) may be used.

[0076] Examples of such triazine 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-piperyl-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-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

[0077] Examples of the phosphine oxide compounds mentioned above include 2,4,6-trimethylbenzyldiphenylphosphine oxide. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can also be used.

[0078] Examples of the biimidazole compounds include, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Publication Nos. 6-75372 and 6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkyl) Biimidazole compounds with 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (e.g., see Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), and biimidazole compounds with 4,4',5,5'-phenyl groups substituted with alkoxycarbonyl groups (e.g., see Japanese Patent Publication No. 7-10913, etc.).

[0079] Examples of polymerization initiators that generate acids include: strontium salts of 4-hydroxyphenyl dimethyl p-toluenesulfonate, strontium salts of 4-hydroxyphenyl dimethyl hexafluoroantimonate, strontium salts of 4-acetoxyphenyl dimethyl p-toluenesulfonate, strontium salts of 4-acetoxyphenyl-methyl-benzyl hexafluoroantimonate, strontium salts of triphenyl p-toluenesulfonate, strontium salts of triphenyl hexafluoroantimonate, strontium salts of diphenyl p-toluenesulfonate, strontium salts of diphenyl hexafluoroantimonate, and strontium salts of diphenyl hexafluoroantimonate, as well as nitrobenzyl toluenesulfonates, benzoin toluenesulfonates, etc.

[0080] Furthermore, polymerization initiators commonly used in this field can be used as polymerization initiators, such as benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. More specifically, the following compounds can be listed, which can be used alone or in combination of two or more.

[0081] Examples of benzoin-based compounds include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0082] Examples of benzophenone compounds include: benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

[0083] Examples of the thioxanthone compounds include: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

[0084] Examples of anthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene.

[0085] In addition, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzodiazepine, 9,10-phenanthroquinone, camphorquinone, methyl phenylglyoxylate, and titanium ceramsite compounds can also be used as polymerization initiators.

[0086] As a polymerization initiator having a group capable of inducing chain transfer, the polymerization initiator described in Japanese Patent Publication No. 2002-544205 can be used. Examples of polymerization initiators having a group capable of inducing chain transfer include those represented by formulas (P5) to (P10).

[0087]

[0088] The polymerization initiator having a group capable of inducing chain transfer can also be used as a structural component (Ae) of the resin (A). Furthermore, the obtained resin (A) can be used as an adhesive resin for the curable resin composition of the present invention.

[0089] Polymerization initiators can also be used in combination with polymerization initiators. Preferably, the polymerization initiator is an amine compound or a carboxylic acid compound, with aromatic amine compounds being more preferred.

[0090] Specific examples of polymerization initiators include: aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; and aromatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone.

[0091] Examples of carboxylic acid compounds include: phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and other aromatic heteroacetic acids.

[0092] The content of polymerization initiator (C) is preferably 0.1% to 40% by mass, more preferably 1% to 30% by mass, relative to the total amount of resin (A) and polymerizable compound (B). The content of the polymerization initiator, relative to the total amount of resin (A) and polymerizable compound (B), is preferably 0.01% to 50% by mass, and more preferably 0.1% to 40% by mass. If the content of the polymerization initiator (C) is within the aforementioned range, the curable resin composition tends to have high sensitivity, and the strength or surface smoothness of the cured film formed using the curable resin composition becomes better, which is preferable. In addition, if the amount of the polymerization initiator is within the aforementioned range, the sensitivity of the obtained curable resin composition tends to be further improved, and the productivity of the patterned substrate formed using the curable resin composition tends to be improved, which is also preferable.

[0093] [4] Solvent (D) The curable resin composition of the present invention preferably includes a solvent (D). The solvent (D) can be any organic solvent used in the field of curable resin compositions for use after curing. Specific examples include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, etc., ethylene glycol monoalkyl ethers. Examples include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether, which are all diethylene glycol monoalkyl ethers. Examples include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether, which are diethylene glycol dialkyl ethers. Examples include ethylene glycol alkyl ether acetates, such as methyl cellosolve acetates and ethyl cellosolve acetates; Examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate, as well as alkyl glycol alkyl ether acetates. Examples include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether, as well as dipropylene glycol monoalkyl ethers. Examples include dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, and dipropylene glycol monopropyl ether acetate, as well as dipropylene glycol monoalkyl ether acetate. Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl pentyl ketone, methyl isobutyl ketone, and cyclohexanone; Such as alcohols like ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; Such as esters like ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Such as cyclic esters like γ-butyrolactone.

[0094] In terms of coatability and drying properties, organic solvents with a boiling point of 100°C to 200°C are preferred among the solvents mentioned above. More preferably, esters such as alkyl glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate are preferred. Even more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate are preferred.

[0095] Solvent (D) can be used alone or in combination of two or more. The content of solvent (D) relative to the curable resin composition is preferably 60% to 90% by mass, more preferably 70% to 85% by mass. If the content of solvent (D) is within this range, it is expected that the coatability will be good when coating using coating apparatus such as a spin coater, slit & spin coater, slit coater (sometimes also called a mold coater, curtain flow coater), inkjet printer, etc., thus it is preferable.

[0096] [5] Additives (F) In the curable resin composition of the present invention, additives such as colorants, fillers, other polymeric compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, chain transfer agents, acid generators, and alkali generators may also be used as needed (F). For example, the curable resin composition for color filters can be formed by adding colorants.

[0097] Examples of coloring agents include dyes and / or pigments. These can be used alone or in combination of two or more coloring agents. In this case, it can be any of the following: a combination of dyes only, a combination of pigments only, or a combination of dyes and pigments. Preferably, it includes dyes.

[0098] As dyes, examples include acid dyes, basic dyes, direct dyes, sulfur dyes, vat dyes, naphthol dyes, reactive dyes, disperse dyes, etc., and can be selected from dyes that are known to have been used as color filters in the past. For example, examples include pigments described in Japanese Patent Application Publication No. 64-90403, Japanese Patent Application Publication No. 64-91102, Japanese Patent Application Publication No. 1-94301, Japanese Patent Application Publication No. 6-11614, Japanese Patent No. 2592207, US Patent No. 4,808,501, US Patent No. 5,667,920, US Patent No. 5,059,500, Japanese Patent Application Publication No. 5-333207, Japanese Patent Application Publication No. 6-35183, Japanese Patent Application Publication No. 6-51115, and Japanese Patent Application Publication No. 6-194828. Specifically, examples include pyrazole azo, aniline azo, aryl azo, pyrazolotriazole azo, pyridone azo, triphenylmethane, anthraquinone, anthraquinone, benzylene, oxacyanine, anthocyanin, polymethimide, phenanthrene, pyrrolopyrazole azomethyl, xanthones, phthalocyanine, quinophthalone, benzopyran, indigo, dioxazine, coumarin, and squaric acid cyanine. More preferably, examples include pyrazole azo, aniline azo, pyrazolotriazole azo, pyridone azo, anthraquinone, anthraquinone, phthalocyanine, dioxazine, quinophthalone, and xanthones. Even more preferably, examples include pyrazole azo, pyridone azo, phthalocyanine, quinophthalone, and xanthones.

[0099] Specifically, examples include: Solvent Yellow (CI) 4 (hereinafter, only the numbers are listed), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189; CI 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; CI Solvent Orange: 2, 7, 11, 15, 26, 56, 77, 86; CI Solvent Violet: 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; Solvent Blue (CI) 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; CI Solvent Green dyes include CI solvent dyes 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35. CI 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, 1 57, 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; CI 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; CI Acid Orange: 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet: 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; Acid Blue (CI) 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; CI Acid Green dyes include 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, and 109. CI 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; CI 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; CI Direct Orange: 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Violet: 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI (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, 16 7, 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; CI Direct Green dyes include 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, and 82. CI Disperse Yellow: 51, 54, 76; CI Disperse Violet 26, 27; CI Disperse Blue (CI) disperse dyes such as 1, 14, 56, and 60; CI Basic Red 1, 10; CI 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; CI Basic Violet 2; CI Basic Red 9; CI Basic Green 1 and other CI basic dyes; CI Reactive Yellow: 2, 76, 116; CI Reactive Orange 16; CI reactive dyes such as Reactive Red 36; CI Mordant Yellow: 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI 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; CI Mordant Orange: 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI 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; Mordant Blue (CI) 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; CI Mordant Green includes CI mordant dyes in grades 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, and 53. CI vat green (Vat Green 1) and other CI vat dyes, etc. In addition, examples include dyes described in Japanese Patent Application Publication No. 2010-32999, Japanese Patent No. 4492760, Japanese Patent Application Publication No. 2013-50693, and Japanese Patent Application Publication No. 2013-178478. These dyes can be selected appropriately based on the spectroscopic spectrum of the desired color filter.

[0100] As pigments, examples include organic and inorganic pigments, and examples include compounds classified as pigments in the Color Index (published by the Society of Dyers and Colourists). For example, examples include: CI 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, etc. CI Pigment Orange includes orange pigments in grades 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73. CI Pigment Red includes red pigments in the following colors: 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 291, etc. CI Pigment Blue includes blue pigments in ratios of 15, 15:3, 15:4, 15:6, 16, and 60. CI pigments include purple pigments such as 1, 19, 23, 29, 32, 36, and 38. CI Pigment Green includes green pigments such as 7, 36, 58, and 59; CI Pigment Brown 23, 25, and other brown pigments; CI Pigment Black 1, 7 and other black pigments. Preferably, the pigment contains at least one pigment selected from CI pigments Yellow 138, 139, 150, CI pigments Red 177, 209, 254, CI pigments Violet 23, CI pigments Blue 15:6, and CI pigments Green 36. These pigments can be used alone or in combination of two or more.

[0101] The organic pigments in the pigments may also be subjected to rosin treatment, surface treatment using pigment derivatives or pigment dispersants with introduced acidic or basic groups, grafting treatment of the pigment surface using polymers, micronization treatment using sulfuric acid micronization, or cleaning treatment using organic solvents or water to remove impurities, or removal treatment of ionic impurities using ion exchange, etc., as needed. Pigments are preferably of uniform particle size. By using a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

[0102] Commercially available surfactants can be used as pigment dispersants. 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, examples include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethane, and polyethyleneimine. Furthermore, examples of surfactants by trade name include: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), Eftop (manufactured by Tohkem Products Co., Ltd.), Megafac (manufactured by DIC Co., Ltd.), Fluorad (manufactured by Sumitomo 3M Co., Ltd.), Asahiguard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.), PB821 (manufactured by Ajinomoto Co., Ltd.), and Disperbyk (manufactured by BYK-chemie Co., Ltd.), etc.

[0103] Fillers can be added to adjust the strength of the hardened film or to color it. Examples of fillers include glass, silicon dioxide, aluminum oxide, and pigments.

[0104] Other polymeric compounds can be added to adjust the strength of the hardened film. Specifically, these other polymeric compounds can include resins such as epoxy resin and maleimide resin, or thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

[0105] Adhesion promoters can be added to improve adhesion to the substrate or base material. Specific examples of adhesion promoters include: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

[0106] Antioxidants can be added to prevent deterioration caused by oxidation of the hardened film. Specific examples of such antioxidants include 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.

[0107] Ultraviolet absorbers can be added to prevent degradation of the hardened film caused by ultraviolet radiation. Specific examples of such ultraviolet absorbers include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone.

[0108] Chain transfer agents can be added to control the molecular weight during the hardening reaction. Examples of chain transfer agents include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

[0109] An acid-generating agent can be added as a catalyst for the curing reaction. Examples of such acid-generating agents include: aryldiazoium salts, diaryl monium salts, triaryl strontium salts, triaryl strontium oxide salts, pyridinium salts, quinolineium salts, isoquinolineium salts, sulfonates, and iron-aromatic complexes.

[0110] An alkali-generating agent can be added as a catalyst for the curing reaction. Examples of such alkali-generating agents include: 1-methyl-1-(4-biphenyl)ethylcarbamate, 1,1-dimethyl-2-cyanoethylcarbamate and other carbamate derivatives; urea or N,N-dimethyl-N'-methylurea and other urea derivatives; 1,4-dihydronicotinamide and other dihydropyridine derivatives; quaternary ammonium salts of organosilanes or organoboranes; dicyandiamide; compounds such as benzoylcyclohexylcarbamate or triphenylmethanol as described in Japanese Patent Application Publication No. 4-162040; and compounds described in Japanese Patent Application Publication No. 5-158242.

[0111] [6] Hardened membrane In addition, the hardened film formed from the hardened resin composition of the present invention is also one of the present inventions.

[0112] The curing film of the present invention can be obtained by a manufacturing method comprising the following steps: a coating step, wherein the curing resin composition is coated onto a substrate; a drying step, wherein the curing resin composition is dried to form a curing resin composition layer; an exposure step, wherein the curing resin composition layer is exposed; and a heating step, wherein the exposed curing resin composition layer is heated.

[0113] Examples of methods for producing the curing film of the present invention include: coating a curable resin composition onto a substrate, drying the coated curable resin composition to form a curable resin composition layer, and, if necessary, exposing and developing the curable resin composition layer through a photomask or the like; or manufacturing a patterned curing film (hereinafter sometimes referred to as "pattern") by coating a curable resin composition with an inkjet printer. Examples of substrates include: transparent glass plates, silicon wafers, polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamide-imide substrates, and resin substrates such as polyamide substrates. On the substrate, black matrices, other films or colored patterns, transparent patterns for adjusting film thickness, thin-film transistors (TFTs), etc., can also be formed. In this case, the film thickness is not particularly limited and can be appropriately adjusted according to the materials used and the application. For example, it can be about 0.1 μm to 30 μm, preferably about 1 μm to 20 μm, and even more preferably about 1 μm to 6 μm.

[0114] In the coating process, methods for coating the curable resin composition include: extrusion coating, direct gravure coating, reverse gravure coating, capillary (CAP) coating, and die coating. Alternatively, dip coaters, rod coaters, rotary coaters, slot and spin coaters, slot coaters (sometimes also called die coaters, curtain flow coaters, or non-rotation coaters), and roller coaters can also be used. Among these, using a rotary coater is preferred.

[0115] In the drying step, methods for drying the curable resin composition include natural drying, ventilation drying, and reduced pressure drying. Specifically, the heating temperature is suitable at around 30°C to 120°C, and preferably around 60°C to 100°C. The heating time is suitable at around 10 seconds to 60 minutes, and preferably around 30 seconds to 30 minutes. Reduced pressure drying can be performed at a pressure of around 50 Pa to 150 Pa and a temperature range of around 20°C to 25°C. When the curable resin composition of the present invention contains solvent (D), the solvent (D) can be removed by the aforementioned drying process.

[0116] The obtained hardened resin composition layer can also be irradiated with radiation through a photomask. As a photomask, a photomask with a light-shielding portion formed according to the target pattern is used. As radiation, gamma rays, i-rays, or other similar rays can be used. For example, a photomask alignment machine, a stepper, or similar device is preferred for radiation irradiation. After radiation irradiation, the curing resin composition layer is developed. The exposed curing resin composition layer can be developed using methods such as liquid coating, immersion, spraying, or splattering. Furthermore, if the curing resin composition layer is irradiated with radiation without the photomask, development is not required.

[0117] As a developing solution, an alkaline aqueous solution is typically used. This alkaline aqueous solution can be an aqueous solution of an alkaline compound, which can be either inorganic or organic. Alkaline developing solutions may contain surfactants. Basic compounds can be either inorganic or organic. 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, potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, and ammonia. Specific examples of organic basic compounds include: tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, etc. These inorganic and organic basic compounds can be used alone or in combination of two or more. The concentration of the basic compound in the alkaline developer is preferably 0.01% to 10% by mass, more preferably 0.03% to 5% by mass.

[0118] The surfactant in alkaline developing solutions can be any of the following: nonionic, anionic, or cationic surfactants. Specific examples of nonionic surfactants include: polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkylaryl ethers, other polyoxyethylene derivatives, ethylene oxide / propylene oxide block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerol fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines. Specific examples of anionic surfactants include: higher alcohol sulfates such as sodium lauryl sulfate or sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate; and alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate or sodium dodecylnaphthalene sulfonate. Specific examples of cationic surfactants include stearylamine hydrochloride or amine salts or quaternary ammonium salts such as lauryltrimethylammonium chloride. These surfactants can be used individually or in combination of two or more. The concentration of surfactant in alkaline developer is preferably in the range of 0.01% to 10% by mass, more preferably in the range of 0.05% to 8% by mass, and even more preferably in the range of 0.1% to 5% by mass.

[0119] In this invention, the heating (post-baking) temperature in the heating step is preferably below 150°C. Furthermore, it is preferable to use a temperature lower than the glass transition temperature (Tg) of the substrate on which the hardened film is formed. Additionally, when the substrate contains components such as colorants that deteriorate at temperatures exceeding a certain temperature, it is preferable to use a temperature lower than the temperature at which the component begins to deteriorate. Therefore, the post-baking temperature can be appropriately determined based on the type of substrate on which the hardened film is formed and the components contained in the curing resin composition. For example, it is preferably below 150°C, more preferably below 130°C, and even more preferably below 100°C. By using a post-baking temperature of 150°C or below, a hardened film with excellent solvent resistance can be obtained without reducing the properties of the substrate, colorants, etc. A post-baking temperature of 60°C or above is also preferred.

[0120] By using the curable resin composition of the present invention, it is no longer necessary to perform heating at temperatures exceeding 150°C, which is usually done in the past, to improve solvent resistance. Therefore, a curable film with excellent solvent resistance can be obtained without reducing the properties of the substrate, colorant, etc.

[0121] Through the steps described above, a hardened film can be formed on a substrate from the curable resin composition of the present invention. This hardened film can be effectively used as a photo spacer in a liquid crystal display device, an interlayer insulating film, a coating for adjusting the film thickness of a color pattern, etc. In the manufacture of the hardened film, if a hole-forming photomask is used when patterning the hardened resin composition layer, an interlayer insulating film with holes can be obtained. When the curable resin composition of the present invention contains a colorant, it can be effectively used as a coloring pattern in a color filter. In the manufacture of the hardened film, when exposing the curable resin composition layer, a hardened film can be formed by full-area exposure and heat curing without using a photomask, or by heat curing alone. The hardened film can be effectively used as an outer coating. By assembling the hardened film obtained as described above, display devices such as liquid crystal displays can be constructed. Such display devices exhibit excellent display quality. [Example]

[0122] The present invention will now be described in more detail by way of examples, but the present invention is not limited to these examples. In the examples, unless otherwise specified, the percentage and parts of the content or amount used are indicated on a quality basis.

[0123] (1) Preparation of resin <Resin 1> Resin 1, which contains the following structural units, is synthesized.

[0124]

[0125] 100.0 parts by weight of cyclopentanone were added to a flask containing a stirrer, reflux condenser, thermometer, and dropping funnel and heated to 90°C. Using the dropping funnel, a solution consisting of 63.1 parts by weight of vinylcarbazole, 19.9 parts by weight of 2-(acetylethoxy)ethyl methacrylate, 17.0 parts by weight of methacrylic acid, 5.0 parts by weight of azobis(isobutyronitrile), and 51.0 parts by weight of cyclopentanone was continuously added dropwise to the flask. The temperature inside the flask was maintained at 90±1°C during the dropwise addition process, and the addition was completed within 3 hours. After the addition is complete, the temperature inside the flask is set to 90±1℃ and the ripening reaction is carried out for 6 hours. After the reaction, the reaction solution was cooled to below 40°C, and 0.12 parts by mass of polymerization inhibitor, 12.4 parts by mass of 4-hydroxybutylacrylate glycidyl ether, 4.5 parts by mass of triphenylphosphine, and 15.6 parts by mass of cyclopentanone were added. The temperature inside the flask was then raised to 110°C, and an addition reaction was carried out at 110±1°C to obtain a resin 1 solution with a solid content of 40.1% by mass. The obtained resin 1 had a weight average molecular weight (Mw) of 6,800, a dispersion (Mw / Mn) of 2.7, and an acid value converted from solid content of 60 (mg-KOH / g).

[0126] <Resin 2> Resin 2, which contains the following structural units, is synthesized.

[0127]

[0128] 100.0 parts by weight of cyclopentanone were added to a flask containing a stirrer, reflux condenser, thermometer, and dropping funnel and heated to 90°C. Using the dropping funnel, a solution consisting of 63.2 parts by weight of vinylcarbazole, 19.8 parts by weight of 2-(acetylethoxy)ethyl methacrylate, 17.0 parts by weight of methacrylic acid, 5.0 parts by weight of azobis(isobutyronitrile), and 51.0 parts by weight of cyclopentanone was continuously added dropwise to the flask. The temperature inside the flask was maintained at 90±1°C during the dropwise addition process, and the addition was completed within 3 hours. After the addition is complete, the temperature inside the flask is set to 90±1℃ and the ripening reaction is carried out for 6 hours. After the reaction, the reaction solution was cooled to below 40°C, and 0.12 parts by mass of 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. The temperature inside the flask was then raised to 110°C, and an addition reaction was carried out at 110±1°C to obtain a resin 2 solution with a solid content of 38.5% by mass. The obtained resin 2 had a weight average molecular weight (Mw) of 15,800, a dispersion (Mw / Mn) of 2.4, and an acid value converted from solid content of 80 (mg-KOH / g).

[0129] <Resin 3> Resin 3, which contains the following structural units, was synthesized.

[0130]

[0131] A nitrogen atmosphere was created by purging an appropriate amount of nitrogen into a flask containing a reflux cooler, a dropping funnel, and a stirrer. 324 parts of propylene glycol monomethyl ether acetate were then added, and the mixture was heated to 85°C while stirring. Subsequently, over a period of 4 hours, a mixed solution of 60 parts methacrylic acid, 30 parts decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6]decane-9-yl acrylate (trade name "E-DCPA", manufactured by Daicel), 210 parts 9-vinylcarbazole, and 190 parts propylene glycol monomethyl ether acetate was added dropwise. Meanwhile, over a period of 5 hours, a mixed solution prepared by dissolving 31 parts 2,2-azobis(2,4-dimethylpentanones) in 155 parts propylene glycol monomethyl ether acetate was added dropwise. After the addition was completed, the solution was maintained at the stated temperature for 3 hours, and then cooled to room temperature to obtain a solution of resin 3 with a solid content of 31% by mass. The obtained resin 3 had a weight average molecular weight (Mw) of 7900, a dispersibility (Mw / Mn) of 1.99, and an acid value converted from solid content of 107 (mg-KOH / g).

[0132] <Resin 4> Resin 4, which contains the following structural units, was synthesized.

[0133]

[0134] 70 parts by weight of propylene glycol monomethyl ether were placed in a flask containing a stirrer, reflux condenser, thermometer, and dropping funnel and heated to 90°C. Using the dropping funnel, a solution consisting of 52.6 parts by weight of dicyclopentyl methacrylate, 20.7 parts by weight of 2-(acetylethoxy)ethyl methacrylate, 26.7 parts by weight of methacrylic acid, 5 parts by weight of azobis(isobutyronitrile), and 30 parts by weight of propylene glycol monomethyl ether was continuously added dropwise to the flask. The temperature inside the flask was maintained at 90±1°C during the dropwise addition process, and the addition was completed within 3 hours. After the dropwise addition was completed, the temperature inside the flask was maintained 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, and 85 parts by mass of propylene glycol monomethyl ether were added. The temperature inside the flask was then raised to 110°C, and an addition reaction was carried out at 110±1°C to obtain a solution of resin 4. The obtained resin 4 had a weight-average molecular weight (Mw) of 14,300, a dispersion of 2.4, an acid value of 103 (mg-KOH / g), and a solid content of 37.9% by mass.

[0135] <Resin 5> A resin 5 containing the following structural units was synthesized.

[0136]

[0137] 150.0 parts by weight of cyclopentanone were added to a flask containing a stirrer, reflux condenser, thermometer, and dropping funnel and heated to 90°C. Using the dropping funnel, a solution consisting of 71.4 parts by weight of vinylcarbazole, 17.1 parts by weight of 2-(acetylethoxy)ethyl methacrylate, 9.0 parts by weight of methacrylic acid, 5.0 parts by weight of azobis(isobutyronitrile), and 80.0 parts by weight of cyclopentanone was continuously added dropwise to the flask. The temperature inside the flask was maintained at 90±1°C during the dropwise addition process, and the addition was completed within 3 hours. After the addition is complete, the temperature inside the flask is set to 90±1℃ and the ripening reaction is 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, and 70 parts by mass of cyclopentanone were added. The temperature inside the flask was then raised to 110°C, and an addition reaction was carried out at 110±1°C to obtain a solution of resin 5. In this resin, the carboxylic acid portion of methacrylic acid was completely consumed due to the addition reaction. The obtained resin 5 had a weight-average molecular weight (Mw) of 6,800, a dispersion of 2.1, and a solid content of 26.3% by mass.

[0138] (2) Methods for determining molecular weight The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of resins 1 to 3 were determined using gel permeation chromatography (GPC) under the following conditions. Device: K2479 (manufactured by Shimadzu Corporation) Tube Column: Shimadzu Shim-pack GPC-80M Column temperature: 40℃ Solvent: tetrahydrofuran (THF) Flow rate: 1.0 mL / min Detector: Refractive index (RI) The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) obtained above after conversion to polystyrene is used as the dispersity (Mw / Mn).

[0139] (3) Preparation of curable resin composition The curable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 5, as shown in Table 1, were prepared as follows.

[0140] <Example 1> In a resin solution containing resin 1, 30 parts of trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) (hereinafter referred to as "polymerizable compound (B1)"), 3 parts of photopolymerization initiator (IRGACURE (registered trademark) OXE01, manufactured by BASF) (hereinafter referred to as "polymerization initiator (C1)"), and 502 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as "solvent D1") were mixed to obtain a curable resin composition with a solid content of 15%. This curable resin composition is designated as the curable resin composition of Example 1.

[0141] <Example 2> Except for replacing polymeric compound B1 with 30 parts of dipentaerythritol polyacrylate (A-9550, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) (hereinafter referred to as "polymeric compound (B2)"), the process was carried out in the same manner as in Example 1 to obtain a curable resin composition with a solid content of 15%. This curable resin composition is designated as the curable resin composition of Example 2.

[0142] <Example 3> Except for the aspect of using a resin solution containing resin 2 in 100 parts (calculated as solids) instead of a resin solution containing resin 1, the process was carried out in the same manner as in Example 1 to obtain a curable resin composition with a solids content of 15%. This curable resin composition was designated as the curable resin composition of Comparative Example 1.

[0143] <Comparative Example 1> Except for the aspect of using a resin solution containing resin 3 in 100 parts (based on solid content) instead of a resin solution containing resin 1, the process was carried out in the same manner as in Example 1 to obtain a curable resin composition with a solid content of 15%. This curable resin composition was designated as the curable resin composition of Comparative Example 1.

[0144] <Example 4> Except for setting the formulation of resin 1 as shown in Table 1, the same procedure as in Example 1 was followed to obtain a curable resin composition with a solid content of 15%. This curable resin composition was designated as the curable resin composition of Example 4.

[0145] <Example 5> Except for setting the formulation of resin 1 as shown in Table 1, the process was carried out in the same manner as in Example 2 to obtain a curable resin composition with a solid content of 15%. This curable resin composition was designated as the curable resin composition of Example 5.

[0146] <Comparative Example 2> Except for the aspect of using a resin solution containing resin 4 in 100 parts (based on solid content) instead of a resin solution containing resin 1, the process was carried out in the same manner as in Example 1 to obtain a curable resin composition with a solid content of 15%. This curable resin composition was designated as the curable resin composition of Comparative Example 2.

[0147] <Comparative Example 3> Except for the aspect of using a resin solution containing resin 5 in 100 parts (calculated as solids) instead of a resin solution containing resin 1, the process was carried out in the same manner as in Example 1 to obtain a curable resin composition with a solids content of 15%. This curable resin composition was designated as the curable resin composition of Comparative Example 3.

[0148] <Comparative Example 4> Except for the aspect of using a resin solution containing resin 4 in 100 parts (based on solid content) instead of a resin solution containing resin 1, the process was carried out in the same manner as in Example 2 to obtain a curable resin composition with a solid content of 15%. This curable resin composition was designated as the curable resin composition of Comparative Example 4.

[0149] <Comparative Example 5> Except for the aspect of using a resin solution containing resin 5 in 100 parts (based on solid content) instead of a resin solution containing resin 1, the process was carried out in the same manner as in Example 2 to obtain a curable resin composition with a solid content of 15%. This curable resin composition was designated as the curable resin composition of Comparative Example 5.

[0150] (4) Formation of the hardened film The curable resin compositions of Examples 1-5 and Comparative Examples 1-5 were coated onto different 2-inch square glass substrates (Eagle XG; manufactured by Corning) using spin coating, resulting in a film thickness of 1.5 μm after baking (coating step). Vacuum drying (ultimate pressure 66 Pa) was then performed to obtain a curable resin composition layer (drying step). The obtained curable resin composition layer was irradiated with light at atmospheric pressure using an exposure machine (TME-150RSK; manufactured by Topcon, light source: ultra-high pressure mercury lamp) at an exposure dose of 100 mJ / cm² (based on a wavelength of 365 nm). Then, the obtained curable resin composition layer was heated at 150°C for 15 minutes using a heating plate to obtain a cured film (heating step). The thickness of the hardened film was measured using a film thickness measuring device (DEKTAK; manufactured by Ulvac). The result was 1.5 μm.

[0151] (5) Evaluation Solvent resistance The obtained hardened film was immersed in propylene glycol monomethyl ether acetate (PGMEA) at 23°C for 5 minutes. The film thickness after immersion was measured using a film thickness measuring device (DEKTAK; manufactured by Ulvac). The ratio of the film thickness after immersion to the film thickness before immersion was calculated, and this value was set as the residual film rate. The results are shown in Table 1.

[0152] [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 Aggregation compound Aggregation Compound (B1) 30 30 30 30 30 30 Aggregation Compound (B2) 30 30 30 30 evaluate Residual film rate (%) 99 99 35 0 99 99 72 53 75 46

[0153] <Refractive index> The refractive index at 550 nm was measured using an ellipsometer (JA Woollam M2000) for the obtained hardened films. The results showed that resin 1 in Example 1 was 1.62, resin 2 in Example 3 was 1.62, resin 3 in Comparative Example 1 was 1.52, resin 4 in Comparative Example 2 was 1.54, and resin 5 in Comparative Example 3 was 1.64.

[0154] <Reproducibility> The curable resin compositions of Examples 1, 3, and Comparative Examples 1-3 were coated onto different 2-inch square glass substrates (Eagle XG; manufactured by Corning) using a spin-coating method, resulting in a film thickness of 1.5 μm after baking (coating step). Vacuum drying (ultimate pressure 66 Pa) was then performed 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 to confirm its solubility. The results showed that the solubility of resin 1 in Example 1, resin 2 in Example 3, resin 3 in Comparative Example 1, and resin 4 in Comparative Example 2 was ○, but the solubility of resin 5 in Comparative Example 3 was ×.

[0155] none

Claims

1. A resin comprising: a structural unit (Aa) having an α,β-unsaturated carbonyl group; a structural unit (Ab) having an active methylene or active methine group; a structural unit (Ac) having an acid group; and a structural unit (Ad) containing a heterocycle that may have substituents, wherein the structural unit (Aa) having the α,β-unsaturated carbonyl group is a structural unit represented by formula (Aa-11), formula (Aa-12), formula (Aa-21), or formula (Aa-22), and the structural unit (Ad) containing the heterocycle that may have substituents is a structural unit represented by formula (Ad-1), wherein in formulas (Aa-11) and (Aa-12), R21 represents a hydrogen atom or a methyl group; in formulas (Aa-21) and (Aa-22), R27 and R28 independently represent hydrogen atoms or methyl groups; R26 represents an alkyldiyl group having 1 to 4 carbon atoms; and ring W represents a cycloalkyldiyl group having 5 to 7 carbon atoms. In formula (Ad-1), R1 represents a hydrogen atom, a methyl group, or a hydroxymethyl group; R2 to R9 independently represent hydrogen atoms, halogen atoms, saturated hydrocarbon groups with 1 to 20 carbon atoms, or aryl groups with 6 to 20 carbon atoms, wherein the hydrogen atoms contained in the saturated hydrocarbon groups may be substituted by alkoxy or aryl groups; X represents a single bond, an alkyl diel group with 1 or more carbon atoms, or a linear or branched group represented by the following formula (V); In formula (V), l represents an integer greater than or equal to 0; m represents an integer greater than or equal to 1.

2. A curable resin composition comprising the resin as described in claim 1, a polymerizable compound, and a polymerization initiator.

3. A hardened film formed from a hardenable resin composition as described in claim 2.

4. A method for manufacturing a hardened film, comprising, in sequence: The coating step involves coating the curable resin composition as described in claim 2 onto the substrate. The process includes a drying step to form a cured resin composition layer by drying the cured resin composition; an exposure step to expose the cured resin composition layer; and a heating step to heat the cured resin composition layer.

5. The method for manufacturing the hardened film as described in claim 4, wherein, In the heating step, the exposed curable resin composition layer is heated to below 150°C.