Curable resin composition, curable film, display device, and method for manufacturing the curable film.

Abstract

To address the problem of unevenness caused by external light reflection in image display devices such as organic electroluminescent (EL), this invention provides a curable resin composition capable of forming a curable film with excellent light diffusion, low-temperature curing properties, and solvent resistance. The curable resin composition comprises a resin (A), a polymerizable compound (B), a polymerization initiator (C), and scattering particles (D). The resin (A) contains structural units (Aa) having α,β-unsaturated carbonyl groups, structural units (Ab) having active methylene or active methine groups, and structural units (Ac) having acid groups. The polymerization initiator (C) comprises an oxime compound, and the scattering particles (D) have an average particle size of 100 nm or more and 5000 nm or less.

Description

[Technical Field]

[0001] This invention relates to a resin, a curable resin composition using the resin, and a curable film formed by curing the curable resin composition. [Previous Technology]

[0002] In an image display device, a hardened film with excellent solvent resistance is desired, which serves as a hardened film for color patterns and outer coatings in a color filter.

[0003] In Patent Document 1 (Japanese Patent Application Publication No. 2018-165351), a resin containing structural units having α,β-unsaturated carbonyl groups, active methylene or active methine groups, and acid groups was described as a resin capable of forming a hardened film with excellent solvent resistance. [Prior Art Documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2018-165351 [Summary of the Invention]

[0005] [Problem to be Solved by the Invention] The object of the present invention is to solve the problem of unevenness caused by external light reflection in image display devices such as organic electroluminescence (EL) by providing a curable resin composition that can form a curable film with excellent light diffusion properties, low-temperature curing properties, and solvent resistance. [Means for Solving the Problem]

[0006] The present invention comprises the following: 〔1〕 A curable resin composition comprising a resin (A), a polymerizable compound (B), a polymerization initiator (C), and scattering particles (D), wherein the resin (A) comprises a structural unit (Aa) having an α,β-unsaturated carbonyl group, a structural unit (Ab) having an active methylene or active methine group, and a structural unit (Ac) having an acid group; the polymerization initiator (C) comprises an oxime compound; and the scattering particles (D) have an average particle size of 100 nm or more and 5000 nm or less. 〔2〕 A curable film formed by curing the curable resin composition as described in 〔1〕. 〔3〕 A display device comprising the curable film as described in 〔2〕. 〔4〕 A method for manufacturing a curable film comprising: a step of coating the curable resin composition as described in 〔1〕 onto a substrate; a step of forming a curable composition layer by drying the curable composition; a step of exposing the curable composition layer; and a step of heating the exposed curable composition layer. [5] The method for manufacturing the curing film as described in [4], wherein the exposed curable composition layer is heated to a temperature of 70°C or higher and 200°C or lower. [Effects of the Invention]

[0007] The curable resin composition according to the present invention can form a curable film with excellent light diffusivity, low-temperature curing properties and solvent resistance.

Implementation Method

[0008] <Curing Resin Composition> The curing resin composition of the present invention contains a resin, a polymerizable compound, a polymerization initiator, and scattering particles. Hereinafter, the resin will be referred to as resin (A), the polymerizable compound as polymerizable compound (B), the polymerization initiator as polymerization initiator (C), and the scattering particles as scattering particles (D).

[0009] 〔1〕 Resin (A) Resin (A) is a resin containing a structural unit (Aa) having an α,β-unsaturated carbonyl group, a structural unit (Ab) having an active methylene or active methine group, and a structural unit (Ac) having an acid group.

[0010] 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)"), and a structural unit having an acid group (Ac) (hereinafter referred to as "structural unit (Ac)"). The curable resin composition of the present invention comprises resin (A), and therefore can form a curable film with excellent low-temperature curing properties and solvent resistance. Resin (A) may also further comprise other repeating units (Ad). In addition, the resin may also comprise two or more structural units (Aa), structural units (Ab), and structural units (Ac). From the viewpoint of using it as an adhesive resin in the 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) comprises a polymer containing structural unit (Ac), and therefore readily acquires alkali solubility. Structural units derived from (meth)acrylic acid and / or its esters are also referred to as "(meth)acrylic acid-based structural units." Furthermore, "(meth)acrylic acid" means "methacrylic acid and / or acrylic acid." The following provides a detailed description of each structural unit.

[0011] 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 a copolymer (hereinafter, this structural unit is referred to as "structural unit (Aa')"), or by reacting (meth)acrylic acid with an epoxy-containing structural unit of the copolymer. Furthermore, the structural unit (Aa') is one of the structural units (Ac) described later. There is no particular limitation on the 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'') having an epoxy group.

[0012] The (meth)acrylate (Aa'') having an epoxy group has at least one group selected from the group consisting of alicyclic epoxy groups and aliphatic epoxy groups. An alicyclic epoxy group is a group formed by the epoxidation of an alicyclic unsaturated hydrocarbon, and an aliphatic epoxy group is a group formed by the epoxidation of a straight-chain or branched aliphatic unsaturated hydrocarbon. Specific examples of (meth)acrylates having alicyclic epoxy groups include: methyl 3,4-epoxycyclohexyl (meth)acrylate, 5,6-epoxy-tricyclo[5.2.1.0 2,6]decane-8-yl (meth)acrylate, 5,6-epoxy-tricyclo[5.2.1.0 2,6]decane-8-yloxy (meth)acrylate, 2,3-epoxycyclopentyl (meth)acrylate, 2-hydroxy-3-(2,3-epoxycyclopentyloxy)cyclopentyl (meth)acrylate, 3-(3,4-epoxycyclohexylmethoxycarbonyl)-6-hydroxycyclohexyl (meth)acrylate, 5,6-epoxy-tricyclo[5.2.1.0 2,6]decane-8- ... Methyl methacrylates include 2,6]decane-8-yloxy(meth)acrylate, 2,3-epoxycyclopentyl(meth)acrylate, 2-hydroxy-3-(2,3-epoxycyclopentyloxy)cyclopentyl(meth)acrylate, 3-(3,4-epoxycyclohexylmethyloxycarbonyl)-6-hydroxycyclohexyl(meth)acrylate, 2-hydroxy-5-(3,4-epoxycyclohexylcarbonyloxymethyl)cyclohexyl(meth)acrylate, 3-(3,4-epoxycyclohexyl)-9-hydroxy-1,5-dioxaspirocyclo[5,5]undecane-8-yl(meth)acrylate, and 3-(3,4-epoxycyclohexyl)-9-hydroxy-2,4-dioxaspirocyclo[5,5]undecane-8-yl(meth)acrylate, etc. These can be used alone or in combination of two or more. Among these, methyl 3,4-epoxycyclohexyl (meth)acrylate may be suitably used.

[0013] When a structural unit (Aa) is obtained by reacting methyl 3,4-epoxycyclohexyl (meth)acrylate with a (meth)acrylic structural unit having a carboxyl group, the obtained structural unit (Aa) is represented by formula (Aa-1).

[0014] [Chemical 1] [In the formula, R1 and Rx independently represent hydrogen atoms or methyl groups] Specific examples of (meth)acrylates having aliphatic epoxy groups include epoxy (meth)acrylate methyl acrylate, itaconic acid glycidyl esters, etc. Among these, epoxy (meth)acrylate methyl acrylate may be suitably used.

[0015] When a structural unit (Aa) is obtained by reacting glycidyl methacrylate with a (meth)acrylic structural unit having a carboxyl group, the obtained structural unit (Aa) is represented by formula (Aa-2).

[0016] [Chemical 2] [In the formula, R5 and Ry independently represent hydrogen atoms or methyl groups] As a copolymer containing structural unit (Aa'), examples include: copolymers with unsaturated carboxylic acids as structural units, copolymers that introduce carboxyl groups by reacting an alcohol or amine with the anhydride group of a copolymer with unsaturated anhydride as structural units, and copolymers that introduce carboxyl groups by reacting an anhydride with the hydroxyl group of a copolymer with unsaturated hydroxyl compounds as structural units.

[0017] In the case where the structural unit (Ac) described later has a carboxyl group, the structural unit (Ac) can be used as a structural unit (Aa') and reacted with an epoxy group (meth)acrylate (Aa'') to obtain the structural unit (Aa).

[0018] The structural unit (Ab) is a structural unit derived from an unsaturated compound having an active methylene or active methine group. This structural unit can be obtained by using an unsaturated compound having an active methylene or active methine group as a monomer to obtain a copolymer. Alternatively, it can be obtained by reacting a compound having an active methylene or active methine group (Ab'') with other structural units (Ab').

[0019] As an unsaturated compound having an active methylene group, compounds represented by formula (I) can be listed. As an unsaturated compound having an active methine group, compounds represented by formula (II) can be listed.

[0020] [Chemical 3] In formulas (I) and (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 hydrocarbon group with 1 to 20 carbon atoms; R 13 represents a divalent group represented by any one of formulas (1-1) to (1-3); R 14 represents a group represented by any one of formulas (1-4) to (1-7);

[0021] [Chemical 4] (R 15 is a hydrocarbon group with 1 to 24 carbon atoms that may contain heteroatoms) X represents the divalent group represented by any one of formulas (1-8) to (1-10)]

[0022] [Chemical 5]

[0023] 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), more preferably a hydrogen atom or methyl. R 15 is preferably a methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, methoxy, ethoxy, propoxy, hexoxy, cyclohexyloxy, or a group represented by formulas (1-11) to (1-13), more preferably methyl.

[0024] [Chemical 6]R 12 is preferably a single bond, methylene, ethyl, propyl, butyl, propyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, and more preferably a single bond, methyl, or ethyl.

[0025] Specifically, the following compounds can be listed as compounds represented by formula (I). [Chemistry 7]

[0026] Specifically, the following compounds can be listed as compounds represented by formula (II). [Chemical 8] 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.

[0027] The structural unit (Ab) is preferably the structural unit represented by formula (Ab-1). [Chemical 9] [In formula (Ab-1), R 3 represents a hydrogen atom or a methyl group, and R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms] Compounds that are structural units represented by the derived formula (Ab-1) can be exemplified, for example, ethyl 2-(methacryloxy)acetate [a compound represented by formula (I-1)].

[0028] The structural unit (Ac) is a structural unit that can be derived from an unsaturated compound having an acid group. Examples of acid groups include: carboxyl groups, phenolic hydroxyl groups, sulfonic acids, etc. The carboxyl group can also be anhydride-substituted.

[0029] 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'). The unsaturated compound with an acid group is preferably an unsaturated carboxylic acid or an unsaturated carboxylic anhydride. Specific examples of unsaturated carboxylic acids or unsaturated carboxylic anhydrides include: unsaturated monocarboxylic acids such as (meth)acrylic acid and butenoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, zeaxanthin, and itaconic acid; anhydrides of the aforementioned unsaturated dicarboxylic acids; unsaturated mono[(meth)acrylic acid alkyl] esters of divalent or higher polycarboxylic acids such as succinate mono[2-(meth)acrylic acid ethyl] ester and phthalate mono[2-(meth)acrylic acid ethyl] ester; and unsaturated acrylates containing 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.

[0030] Resin (A) may have structural units other than structural units (Aa), structural units (Ab), and structural units (Ac) (hereinafter referred to as "structural units (Ad)"). Structural unit (Ad) is a structural unit different from structural units (Aa), structural units (Ab), and structural units (Ac). Structural unit (Ad) may be derived from monomers capable of polymerizing with monomers that derive other structural units (e.g., structural units (Aa), structural units (Ab), and structural units (Ac)). Specific examples of such monomers include: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, dibutyl methacrylate, tributyl methacrylate, and other alkyl methacrylates; methyl acrylate, isopropyl acrylate, and other alkyl acrylates; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0 2,6]decane-8-yl ester (commonly referred to as dicyclopentyl methacrylate in this technical field), dicyclopentyloxyethyl methacrylate, isobornyl methacrylate, and other cyclic alkyl methacrylates; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0 2,6]decane-8-yl ester (commonly referred to as dicyclopentyl methacrylate in this technical field), dicyclopentyloxyethyl methacrylate, isobornyl methacrylate, and other cyclic alkyl methacrylates; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0 2,6]decane-8-yl ester (commonly referred to as dicyclopentyl methacrylate in this technical field), dicyclopentyloxyethyl methacrylate, isobornyl methacrylate, and other cyclic alkyl methacrylates. [2,6] Decane-8-yl ester (commonly known in this art as dicyclopentyl methacrylate), dicyclopentoxyethyl methacrylate, isobornyl methacrylate, and other cyclic alkyl esters of methacrylate; phenyl methacrylate, benzyl methacrylate, and other aryl esters of methacrylate; phenyl acrylate, benzyl acrylate, and other aryl acrylates; diethyl maleate, diethyl fumarate, diethyl itaconic acid, and other dicarboxylic acid diesters; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and other hydroxyalkyl esters; 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 .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-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 anhydrous (Nadic anhydride (Himic 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-di(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[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 nitriles; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

[0031] Among these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene are preferred in terms of reactivity in copolymerization and solubility relative to alkaline aqueous solutions.

[0032] The resin (A) may also have two or more structural units (Ad).

[0033] The resin (A) comprises a copolymer containing structural units (Aa), structural units (Ab), structural units (Ac), and may further contain structural units (Ad). The ratio of each structural unit, in mole fraction, is preferably within the following range relative to the total number of moles constituting the copolymer: Structural unit (Aa): 5 mol% to 50 mol%; Structural unit (Ab): 5 mol% to 50 mol%; Structural unit (Ac): 5 mol% to 50 mol%; Structural unit (Ad): 0 mol% to 70 mol.

[0034] 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): 10 mol% to 40 mol% Structural unit (Ab): 10 mol% to 40 mol% Structural unit (Ac): 10 mol% to 40 mol% Structural unit (Ad): 0 mol% to 60 mol%.

[0035] The copolymer containing each structural unit can be manufactured, for example, according to the method described in the literature "Experimental Method for Polymer Synthesis" (by Takayuki Otsu, Chemical Dojin Publishing Co., Ltd., 1st edition, 1st printing, March 1, 1972) and the references described in that literature.

[0036] Resin (A) can be manufactured, for example, through a two-stage process. Specifically, a predetermined amount of each compound that derives structural unit (Ab) and structural unit (Ac), as well as a compound that derives structural unit (Aa'), a polymerization initiator, and a solvent are loaded into a reaction vessel. By replacing oxygen with nitrogen, stirring, heating (e.g., 50°C to 140°C), and holding at this temperature (e.g., 1 hour to 10 hours) are performed under oxygen-free conditions to obtain a copolymer having structural unit (Aa'), structural unit (Ab), and structural unit (Ac). Then, the nitrogen in the reaction vessel is replaced with oxygen. Epoxy-containing (meth)acrylate (Aa''), reaction catalyst, and polymerization inhibitor are added to the reaction vessel, and the mixture is stirred, heated (e.g., 60°C–130°C), and held at that temperature (e.g., 1 hour–10 hours). This allows 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), and (Ac). The obtained copolymer can be used directly from the reaction solution, or a concentrated or diluted solution can be used. Alternatively, the copolymer, which has been removed in solid form through methods such as reprecipitation, can be dissolved in a solvent for reuse.

[0037] In the case of manufacturing a resin (A) with more structural units (Ad), it is sufficient to load the compounds of the derived structural units (Ab) and (Ac) and the compounds of the derived structural units (Aa') together with the structural units (Ad) in the above steps.

[0038] In the above, when the structural unit (Ac) has a carboxyl group, the structural unit (Aa) can be obtained by reacting an epoxy-containing (meth)acrylate (Aa'') with the structural unit (Ac). The polystyrene-converted weight average molecular weight of the 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 resin (A) within the aforementioned weight average molecular weight range tend to have good coatability during coating, and are less prone to film reduction during development, thus exhibiting good peeling properties of uncured portions during development.

[0039] 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 resin (A) as an adhesive resin tends to have excellent developability, which is therefore preferred. The acid value (converted value of solids content) of resin (A) is preferably 70 mg-KOH / g to 150 mg-KOH / g, 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.

[0040] Regarding the cured film formed from the curable resin composition containing resin (A), excellent solvent resistance is exhibited even when the temperature of the heating step (so-called post-baking step) after exposure during the production of the cured film is below 200°C or 150°C. The temperature of the post-baking step is preferably above 70°C, and more preferably above 80°C. In the curable resin composition of the present invention, the content of resin (A) relative to the solid component in the curable resin composition is preferably 5% to 90% by mass, and more preferably 10% to 70% by mass. If the content of resin (A) is within the aforementioned range, its solubility in the developer is sufficient, and it is less likely to produce development residue. Furthermore, it tends to have a good tendency for film reduction in the exposed and cured portions during development, and for good peeling of the unexposed and uncured portions. Therefore, it is preferred. Here, the solid component refers to the amount after removing the solvent from the total amount of the curable resin composition. The total amount of solid components and the relative content of each component can be determined by known analytical methods such as liquid chromatography or gas chromatography. Alternatively, acrylic adhesive resins commonly used in this field can be used without impairing the scope of the invention.

[0041] 〔2〕 Polymerizable Compound (B) There is no particular limitation on the polymerizable compound (B) if it is a compound that can be polymerized by active free radicals generated by a self-polymerization initiator (C) due to light irradiation, etc. Examples of polymerizable compounds (B) include compounds having vinyl unsaturated bonds, and examples include: monofunctional monomers containing one functional group having 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 monomer 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 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-methylpentanediol di(meth)acrylate, etc. Specific examples of the polyfunctional 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, the reaction product of dipentaerythritol penta(meth)acrylate and acid anhydride, etc. Preferably, difunctional or polyfunctional monomers are used. These polymerizable compounds (B) can be used alone or in combination of two or more. The content of polymeric compound (B), in terms of mass fraction, is preferably 1% to 70% by mass, more preferably 5% to 60% by mass, relative to the total amount of resin (A) and polymeric compound (B). If the content of polymeric compound (B) is within the aforementioned range, the hardened film formed by curing the curable resin composition tends to have good strength, smoothness, and solvent resistance, which is therefore preferable.

[0042] 〔3〕Polymerization Initiator (C) The polymerization initiator (C) comprises an oxime compound. The curable resin composition of the present invention, by comprising resin (A) and such a polymerization initiator (C), can form a curable film with excellent low-temperature curing properties and solvent resistance. Regarding the curable film formed by the curable resin composition of the present invention, even when the temperature of the heating step (so-called post-baking step) after exposure during the production of the curable film is below 200°C or below, or below 150°C, it exhibits excellent solvent resistance. The temperature of the post-baking step is preferably above 70°C, and more preferably above 80°C. In addition to comprising an oxime compound, the polymerization initiator (C) may also comprise compounds that can initiate polymerization by generating active free radicals, acids, etc., through the action of light or heat. As compounds other than oxime compounds, acetophenone-based, biimidazole-based, triazine-based, acetophosphine oxide-based compounds, and organoboron salt compounds are preferred. By using polymerization initiators in conjunction with these polymerization initiators (C), the resulting curable resin composition becomes even more sensitive, thus improving the productivity of patterns when used to form patterns.

[0043] The oxime compound contained in the polymerization initiator (C) is, for example, an O-acryloxime compound. An O-acryloxime compound is a compound having the structure represented by the following formula (d). Hereinafter, * indicates a bond.

[0044] [Chemical 10]

[0045] The O-acetylated oxime compound is preferably selected from at least one of the group consisting of the compound represented by formula (d1) (hereinafter, sometimes referred to as "compound (d1)"), the compound represented by formula (d2) (hereinafter, sometimes referred to as "compound (d2)"), and the compound represented by formula (d3) (hereinafter, sometimes referred to as "compound (d3)").

[0046] [Chemical 11]

[0047] [In formulas (d1) to (d3), R d1 represents an aromatic hydrocarbon group with 6 to 18 carbon atoms that may have substituents, a heterocyclic group with 3 to 36 carbon atoms that may have substituents, an alkyl group with 1 to 15 carbon atoms that may have substituents, or a substituent group formed by combining an aromatic hydrocarbon group with an alkyl diene derived from the alkyl group, wherein the methylene (-CH 2-) contained in the alkyl group may be substituted with -O-, -CO-, -S-, -SO 2- or -NR d5-; R d2 represents an aromatic hydrocarbon group with 6 to 18 carbon atoms, a heterocyclic group with 3 to 36 carbon atoms, or an alkyl group with 1 to 10 carbon atoms; R d3 represents an aromatic hydrocarbon group with 6 to 18 carbon atoms that may have substituents or a heterocyclic group with 3 to 36 carbon atoms that may have substituents; R d4 represents an aromatic hydrocarbon group with 6 to 18 carbon atoms that may have substituents, or an aliphatic hydrocarbon group with 1 to 15 carbon atoms that may have substituents. The methylene group (-CH 2-) in the aliphatic hydrocarbon group may be substituted with -O-, -CO-, or -S-, the methine group (-CH<) in the aliphatic hydrocarbon group may be substituted with -PO 3<, and the hydrogen atom in the aliphatic hydrocarbon group may be substituted with an OH group; R d5 represents an alkyl group with 1 to 10 carbon atoms, wherein the methylene group (-CH 2-) in the alkyl group may be substituted with -O- or -CO-.

[0048] The number of carbon atoms in the aromatic hydrocarbon group represented by R d1 is preferably 6 to 15, more preferably 6 to 12, and even more preferably 6 to 10. Examples of such aromatic hydrocarbon groups include phenyl, naphthyl, anthraceneyl, phenanthryl, biphenyl, and terphenyl, with phenyl and naphthyl being more preferred, and phenyl being even more preferred.

[0049] The aromatic hydrocarbon group represented by R d1 may also have one or more substituents. The substituents are preferably substituted at the α- or γ-position of the aromatic hydrocarbon group, and more preferably at the γ-position. Examples of such substituents include: alkyl groups with 1 to 15 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl; halogen atoms such as fluorine, chlorine, iodine, and bromine.

[0050] The alkyl group used as the substituent preferably has 1 to 10 carbon atoms, more preferably 1 to 7. The alkyl group used as the substituent can be any of straight-chain, branched, and cyclic, or it can be a group formed by combining a chain group and a cyclic group. The methylene group (-CH 2-) contained in the alkyl group used as the substituent can be substituted with -O- or -S-. The hydrogen atom contained in the alkyl group can be substituted with a halogen atom such as a fluorine atom, chlorine atom, iodine atom, or bromine atom, preferably substituted with a fluorine atom.

[0051] Regarding the aromatic hydrocarbon group represented by R d1, the alkyl groups that serve as its substituents can be represented by the following formulas, etc. In the formula, * represents a bond.

[0052] [Chemical 12]

[0053] [Chemical 13]

[0054] Regarding the group represented by R d1, as an aromatic hydrocarbon group that may have substituents, groups represented by the following formulas can be listed. In the formula, * represents a bond.

[0055] [Chemical 14]

[0056] [Chemical 15]

[0057] Regarding the group represented by R d1, as an aromatic hydrocarbon group that may have substituents, it is preferably represented by the group represented by the following formula.

[0058] [Chemical 16]

[0059] (In the formula, Rd6 represents an alkyl group with 1 to 10 carbon atoms that can be substituted by halogen atoms, and the hydrogen atoms contained in Rd6 can be substituted by halogen atoms; m2 represents an integer from 1 to 5)

[0060] As the alkyl group represented by Rd6, examples may be made of the same alkyl group as the aromatic hydrocarbon group represented by Rd1 that has been exemplified as a substituent. The number of carbon atoms in Rd6 is preferably 2 to 7, more preferably 2 to 5. The alkyl group represented by Rd6 may be any of the following: straight-chain, branched, and cyclic, preferably chain-like.

[0061] Examples of halogen atoms that can substitute for hydrogen atoms contained in Rd6 include fluorine, chlorine, iodine, and bromine atoms, with fluorine being particularly preferred. It is more preferably that two or more but less than ten hydrogen atoms contained in Rd6 are substituted with halogen atoms, and even more preferably that three or more but less than six hydrogen atoms are substituted with halogen atoms. The substitution position of the Rd6O- group is preferably ortho or para, and particularly para. m2 is preferably 1 to 2, and particularly preferably 1.

[0062] The number of carbon atoms in the heterocyclic group represented by R d1 is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 5. Examples of such heterocyclic groups include: pyrrole, furanyl, thiophene, indolyl, benzofuranyl, and carbazole.

[0063] The heterocyclic group represented by R d1 may also have one or more substituents. Examples of such substituents are those exemplified as substituents for aromatic hydrocarbon groups represented by R d1.

[0064] The alkyl group represented by Rd1 preferably has 1 to 12 carbon atoms. Examples of alkyl groups represented by Rd1 include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl. These alkyl groups can be linear, branched, or cyclic, or they can be groups formed by combining a linear group and a cyclic group. In the alkyl group represented by Rd1, the methylene group (-CH2-) can be substituted with -O-, -CO-, -S-, -SO2-, or -NRd5-, and the hydrogen atom can also be substituted with an OH group or an SH group.

[0065] R d5 represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. This alkyl group can be chain-like (linear or branched), cyclic, or any of linear, branched, and cyclic forms, and can also be a group formed by combining a chain group and a cyclic group. Furthermore, in the alkyl group of R d5, the methylene group (-CH 2-) can be substituted with -O- or -CO-.

[0066] As represented by R d1, alkyl groups that may have substituents can specifically include groups represented by the following formulas. * indicates a bond.

[0067] [Chemical 17]

[0068] The number of carbon atoms in the group represented by Rd1, which is formed by combining an aromatic hydrocarbon group with an alkyl diel derived from the alkyl group, is preferably 7 to 33, more preferably 7 to 18, and even more preferably 7 to 12. This combined group may have one or more substituents, and examples of substituents are those that are the same as those that the aromatic hydrocarbon group or alkyl group may have. Examples of the group represented by Rd1, which is formed by combining an aromatic hydrocarbon group with an alkyl diel derived from the alkyl group, include aralkyl groups, and specifically, groups represented by the following formula. In the formula, * represents a bond.

[0069] [Chemical 18]

[0070] Wherein, as R d1, it is preferably an aromatic hydrocarbon group that may have substituents or an alkyl group that may have substituents, and more preferably an aromatic hydrocarbon group that may have substituents.

[0071] The aromatic hydrocarbon group represented by R d2 preferably has 6 to 15 carbon atoms, more preferably 6 to 12, and even more preferably 6 to 10. Examples of such aromatic hydrocarbon groups include: phenyl, naphthyl, anthraceneyl, phenanthryl, biphenyl, and terphenyl.

[0072] The number of carbon atoms in the heterocyclic group represented by R d2 is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 5. Examples of such heterocyclic groups include: pyrrole, furanyl, thiophene, indolyl, benzofuranyl, and carbazole.

[0073] The alkyl group represented by R d2 preferably has 1 to 7 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. The alkyl group can be any of the following: straight-chain, branched, or cyclic, or it can be a group formed by combining a chain group and a cyclic group.

[0074] As R d2, it is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, and even more preferably a chain alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

[0075] The aromatic hydrocarbon group represented by R d3 preferably has 6 to 15 carbon atoms, more preferably 6 to 12, and even more preferably 6 to 10. Examples of such aromatic hydrocarbon groups include phenyl, naphthyl, anthraceneyl, phenanthryl, biphenyl, and terphenyl, with phenyl and naphthyl being more preferred.

[0076] The aromatic hydrocarbon group represented by R d3 may have one or more substituents. The substituents are preferably substituted at the α- or γ-position of the aromatic hydrocarbon group. Preferably, the substituent is an aliphatic hydrocarbon group having 1 to 15 carbon atoms, specifically including: alkyl groups having 1 to 15 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; and alkenyl groups having 1 to 15 carbon atoms such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl, and decenyl.

[0077] The aromatic hydrocarbon group represented by R d3 may preferably have an aliphatic hydrocarbon group with 1 to 7 carbon atoms. The aliphatic hydrocarbon group may be any of the following: linear, branched, or cyclic. It may also be a group formed by combining a chain group and a cyclic group. The methylene group (-CH 2-) contained in the aliphatic hydrocarbon group may be substituted with -O-, -CO-, or -S-, and the methine group (-CH<) may be substituted with -N<.

[0078] Aliphatic hydrocarbon groups that can be present as aromatic hydrocarbon groups represented by R d3 can be listed as groups represented by the following formula. In the formula, * represents a bond.

[0079] [Chemical 19]

[0080] Regarding Rd3, as an aromatic hydrocarbon group that can have substituents, examples include groups represented by the following formula. In the formula, * represents a bond.

[0081] [Chemical 20]

[0082] The heterocyclic group represented by Rd3 preferably has 3 to 20 carbon atoms, more preferably 3 to 10, and even more preferably 3 to 5. Examples of such heterocyclic groups include pyrrole, furanyl, thiophene, indolyl, benzofuranyl, and carbazole. The heterocyclic group represented by Rd3 may have one or more substituents, and examples of such substituents include groups that have the same substituents as the aromatic hydrocarbon group in Rd1.

[0083] R d3 is preferably an aromatic hydrocarbon group with substituents, and the substituent is preferably a chain alkyl group having 1 to 7 carbons (more preferably 1 to 3 carbons), and the number of substituents is preferably two or more and five or less.

[0084] The aromatic hydrocarbon group represented by Rd4 preferably has 6 to 15 carbon atoms, more preferably 6 to 12, and even more preferably 6 to 10. Examples of this aromatic hydrocarbon group include phenyl, naphthyl, anthraceneyl, phenanthryl, biphenyl, and terphenyl, more preferably phenyl and naphthyl, and even more preferably phenyl. The aromatic hydrocarbon group represented by Rd4 may have one or more substituents. Examples of these substituents include groups that are the same as those that may be present in the aromatic hydrocarbon group of Rd1.

[0085] The aliphatic hydrocarbon group represented by Rd4 preferably has 1 to 13 carbon atoms, more preferably 2 to 10, and even more preferably 4 to 9. Examples of aliphatic hydrocarbon groups represented by Rd4 include: alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl; and alkenyl groups such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, and pentadecenyl. These aliphatic hydrocarbon groups can be chain-like (straight-chain or branched), cyclic, or a combination of chain and cyclic groups. In the aliphatic hydrocarbon group of Rd4, the methylene (-CH 2-) can be substituted with -O-, -CO- or -S-, the methine (-CH<) can be substituted with -PO 3<, and the hydrogen atom contained in the aliphatic hydrocarbon group can be substituted with an OH group.

[0086] As represented by R d4, aliphatic hydrocarbon groups that may have substituents can include groups represented by the following formulas. In the formula, * represents a bond.

[0087] [Chemical 21]

[0088] R d4 is preferably a chain aliphatic hydrocarbon group that may have substituents, more preferably a chain alkyl group that does not have substituents, and even more preferably a chain alkyl group that does not have substituents.

[0089] As a compound (d1), compounds represented by formula (d1) can be listed, and more specifically, compounds of formula (d1) having combinations of substituents described in formulas (d1-1) to (d1-67) can be listed. In Tables 1 to 7, * indicates a bond.

[0090] [Chemical 22]

[0091] [Table 1]

[0092] [Table 2]

[0093] [Table 3]

[0094] [Table 4]

[0095] [Table 5]

[0096] [Table 6]

[0097] [Table 7]

[0098] Preferably, the compounds are those having substituents described in formula (d1-3), those having substituents described in formula (d1-6), those having substituents described in formula (d1-18), those having substituents described in formula (d1-52), those having substituents described in formula (d1-55), those having substituents described in formula (d1-56), those having substituents described in formula (d1-60), and those having substituents described in formula (d1-61). More preferably, the compounds are those having substituents described in formula (d1-3), those having substituents described in formula (d1-6), those having substituents described in formula (d1-18), and those having substituents described in formula (d1-41). Preferably, the compounds are compounds having the substituents described in formula (d1-24), compounds having the substituents described in formula (d1-36), and compounds having the substituents described in formula (d1-40), and especially preferably, compounds having the substituents described in formula (d1-24).

[0099] The compound (d1) can be manufactured, for example, by the manufacturing method described in Japanese Patent Publication No. 2014-500852.

[0100] The compound (d2) is preferably a compound in which Rd1 is an alkyl group having 1 to 15 carbon atoms that may have substituents, Rd2 is an alkyl group having 1 to 10 carbon atoms, Rd3 is an aromatic hydrocarbon group having 6 to 18 carbon atoms that may have substituents, and Rd4 is an aromatic hydrocarbon group having 1 to 15 carbon atoms that may have substituents. More preferably, the compound in which Rd1 represents methyl, ethyl, or propyl, Rd2 represents methyl, ethyl, or propyl, Rd3 represents a methyl-substituted phenyl group, and Rd4 is a methyl, ethyl, or propyl group. Even more preferably, the compound in which Rd1 and Rd2 are methyl, Rd3 is o-tolyl, and Rd4 is ethyl.

[0101] The compound (d3) is preferably a compound in which Rd1 is an alkyl group having 1 to 15 carbon atoms and Rd2 is an aromatic hydrocarbon group having 6 to 18 carbon atoms, and more preferably a compound in which Rd1 is a hexyl group and Rd2 is a phenyl group.

[0102] Examples of such O-acetylated oxime compounds include: N-benzoyloxy-1-(4-phenylmercaptophenyl)butane-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, N-acetylated 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetylated... The formulations include 1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentylmethyloxy)benzoyl}-9H-carbazole-3-yl]ethane-1-imine, N-acetyoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-imine, and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-one-2-imine. Commercially available products such as Irgacure OXE01, OXE02, OXE03 (manufactured by BASF), and N-1919 (manufactured by ADEKA) can also be used. If the compounds are O-acetylgoximes, there is a tendency to obtain hardened films with excellent low-temperature curing properties and solvent resistance.

[0103] Examples of the acetophenone family of compounds include: diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyl dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butane-1-one, 2-(2-methylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)butanone, 2-(3-methylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)butanone, and 2-(3-methylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)butanone. 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-ethylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-propylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-butylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2,3-dimethylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2,4-dimethylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-chlorobenzyl) 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(4-chlorobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-methoxybenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, Oligomers of 2-(3-methoxybenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-methyl-4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-bromo-4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one, etc.

[0104] Examples of the biimidazole compounds mentioned above include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see Japanese Patent Publication Nos. 6-75372 and 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole. -Tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), biimidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with an alkoxycarbonyl group (see Japanese Patent Publication No. 7-10913, etc.), etc., preferably 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

[0105] Examples of the 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.

[0106] Examples of phosphine oxide initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0107] Examples of organoboron salt initiators include: tetramethylammonium n-butyltriphenylborate, tetraethylammonium isobutyltriphenylborate, tetra-n-butylammonium n-butyltris(4-tert-butylphenyl)borate, tetra-n-butylammonium n-butyltrinaphthylborate, tetra-n-butylammonium methyltris(4-methylnaphthyl)borate, triphenylstrontium n-butyltriphenylborate, triphenyloxonium n-butyltriphenylborate, triphenyloxonium n-butyltriphenylborate, N-methylpyridine n-butyltriphenylborate, tetraphenylphosphonium n-butyltriphenylborate, diphenylmonium n-butyltriphenylborate, etc.

[0108] As a polymerization initiator (C), it may further include polymerization initiators commonly used in this field, such as benzoin compounds, benzophenone compounds, thioxanthone compounds, anthracene compounds, etc. More specifically, the following compounds may be listed.

[0109] As the benzoin-based compounds, examples include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.

[0110] Examples of the 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.

[0111] Examples of the thioxanthone compounds include: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

[0112] Examples of the anthracene compounds include: 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc.

[0113] In addition, the polymerization initiator (C) may also include 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzodiazepine, 9,10-phenanthroquinone, camphorquinone, methyl phenylglyoxylate, titanium ceramsite, etc.

[0114] The polymerization initiator (C) may include a polymerization initiator having a group capable of inducing chain transfer, as described in Japanese Patent Publication No. 2002-544205. Examples of polymerization initiators having a group capable of inducing chain transfer include those represented by formulas (P5) to (P10). [Chemical 23]

[0115] The polymerization initiator having a group capable of inducing chain transfer can also be used as a structural component (Ad) of the resin (A). Moreover, the obtained resin (A) can be used as an adhesive resin for the curable resin composition of the present invention.

[0116] Polymerization initiators can also be used in combination with polymerization initiators. As polymerization initiators, amine compounds and the following carboxylic acid compounds are preferred, with aromatic amine compounds being more preferred.

[0117] 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, ethyl 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.

[0118] As the carboxylic acid compound, examples 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.

[0119] 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 polymerization initiator is preferably 0.01% to 50% by mass, more preferably 0.1% to 40% by mass, relative to the total amount of resin (A) and polymerizable compound (B). If the content of polymerization initiator (C) is within the above range, the curable resin composition tends to have high sensitivity, and the strength of the cured film formed using the curable resin composition or the smoothness of the surface of the cured film becomes good, which is preferable. In addition, if the amount of polymerization initiator is within the above 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 preferable.

[0120] [4] Scattering particles (D) The curable resin composition of the present invention includes scattering particles (D). The average particle size of the scattering particles (D) is 100 nm or more and 5000 nm or less, preferably 200 nm or more and 5000 nm or less, and more preferably 300 nm or more and 5000 nm or less. The curable resin composition of the present invention has light diffusing properties by containing such scattering particles (D). By having an average particle size of 100 nm or more, the desired light diffusing properties can be imparted to the curable film, and by having an average particle size of 5000 nm or less, a foreign matter-free and uniform coating film can be formed during the fabrication of the curable film.

[0121] As the scattering particle (D), particles containing inorganic compounds or particles containing organic compounds can be used.

[0122] As particles containing inorganic compounds, metal oxides can be exemplified. Metal oxides may include one or more oxides selected from the group consisting of Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Ti, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, Ce, Ta, In, and combinations thereof.

[0123] The metal oxide may include one or more of the group consisting of Al₂O₃, SiO₂, ZnO, ZrO₂, BaTiO₃, TiO₂, Ta₂O₅, Ti₃O₅, ITO, IZO, ATO, ZnO-Al, Nb₂O₃, SnO, MgO and combinations thereof, and may also use materials that have been surface-treated with compounds having unsaturated bonds, such as acrylates, as needed.

[0124] As particles containing organic compounds, examples include those synthesized by polymerizing (meth)acrylates having a polycyclic structure or alkyl chains having 4 or more but less than 24 carbon atoms with other monomers capable of copolymerization. In 100% by mass of the monomers supplied for copolymerization, the total amount of (meth)acrylates having a polycyclic structure or alkyl chains having 4 or more but less than 24 carbon atoms is preferably 1% to 50% by mass, more preferably 3% to 25% by mass, and even more preferably 5% to 15% by mass. By setting the amount of (meth)acrylates having a polycyclic structure or alkyl chains having 4 or more but less than 24 carbon atoms within the aforementioned range, the dispersion effect can be more effectively achieved, and therefore it is preferable.

[0125] Particles containing organic compounds can be obtained by various methods and can be obtained in a dispersed state. Examples include: emulsion polymerization (one of which is soap-free emulsion polymerization), dispersion polymerization, suspension polymerization, seed polymerization, etc. Among these, emulsion polymerization and dispersion polymerization have narrower particle size distributions, which helps to reduce the wavelength dependence of the present invention, and are therefore preferred. In addition, by preparing polymers containing various (meth)acrylates, steric repulsion-based dispersibility can be imparted.

[0126] In this specification, the term "average particle size" may be the number average particle size, for example, it can be determined from images obtained by observation using a field emission-scanning electron microscope (FE-SEM) or a transmission electron microscope (TEM). Specifically, multiple samples can be extracted from the observation images of FE-SEM or TEM, the diameters of these samples can be measured, and the value obtained is the arithmetic average.

[0127] In the curable resin composition, relative to 100 parts by mass of the total curable resin composition, it may contain 0.5 parts by mass and 80 parts by mass of scattering particles (D), preferably 1 part by mass and 50 parts by mass, and more preferably 1.5 parts by mass and 40 parts by mass. By including scattering particles (D) within this range, the curable film can be endowed with the desired light scattering properties, and on the other hand, the reduction of coating properties during the fabrication of the curable film can be suppressed.

[0128] [5] Solvent (E) The curable resin composition of the present invention preferably includes a solvent (E). The solvent (E) may be any organic solvent that is used in the field of curable resin compositions. Specific examples include: ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; alkyl glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; and dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether. Examples of dipropylene glycol monoalkyl ether acetates include dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, and dipropylene glycol monopropyl ether acetate; aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene; ketones include methyl ethyl ketone, acetone, methyl pentyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; esters include ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters include γ-butyrolactone.

[0129] 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.

[0130] Solvent (E) may be used alone or in combination of two or more. The content of solvent (E) 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 (E) is within the aforementioned 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., which is therefore preferable.

[0131] 〔6〕 Additives (F) In the curable resin composition of the present invention, fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, chain transfer agents, acid generators, alkali generators and other additives (F) may also be used as needed.

[0132] Fillers can be added to adjust the strength of the hardened film. Regarding high transparency, the primary particle size of the filler in this invention is less than 100 nm, preferably less than 50 nm. The primary particle size of the filler is typically 0.10 nm or more.

[0133] Other polymeric compounds may be added to adjust the strength of the hardened film. Specifically, other polymeric compounds may be hardening 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.

[0134] A bonding promoter may be added to improve the 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.

[0135] Antioxidants may 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.

[0136] 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, alkoxybenzophenone, etc.

[0137] A chain transfer agent may be added to control the molecular weight in the hardening reaction. Examples of such chain transfer agents include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

[0138] An acid-generating agent may be added as a catalyst for the curing reaction. Examples of such acid-generating agents include: aryl diazonium salts, diaryl monazine salts, triaryl strontium salts, triaryl strontium oxide salts, pyridine salts, quinoline salts, isoquinoline salts, sulfonates, iron aromatic complexes, etc.

[0139] An alkali-generating agent may 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.

[0140] [7] Cured Film Additionally, a cured film formed by curing the curable resin composition of the present invention is also part of the present invention. The haze of the cured film of the present invention is preferably 3% or more, more preferably 5% or more. By having this haze, unevenness caused by external light reflection can be suppressed when used in an image display device. The haze of the cured film of the present invention is preferably 30% or less, more preferably 25% or less. By having this haze, the reduction in brightness of the displayed image in the image display device can be suppressed. The cured film of the present invention can be made to have a haze within the aforementioned range by using a curable resin composition containing scattering particles (D).

[0141] In this specification, the so-called haze can be calculated by the following formula (1) based on the ratio of the total light transmittance (Tt), which represents the total amount of light transmitted through the hardened film, to the diffuse light transmittance (Td) that is diffused through the hardened film: Haze (%) = (Td / Tt) × 100 (1).

[0142] Total light transmittance (Tt) is the sum of the transmittance of parallel light (Tp) and diffuse light (Td) transmitted in a state coaxial with the incident light. The total light transmittance (Tt) and diffuse light transmittance (Td) are values ​​measured according to JIS K 7361.

[0143] The curing film of the present invention can be obtained by a manufacturing method including the following steps: coating the curing resin composition onto a substrate; forming a curing resin composition layer by drying the curing resin composition; exposing the curing resin composition layer; and post-baking the exposed curing resin composition layer.

[0144] Examples of methods for manufacturing 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 using a photomask or the like; or manufacturing a patterned curing film (hereinafter sometimes referred to as "pattern") by coating a curable resin composition using an inkjet printer. Examples of substrates include: transparent glass plates, silicon wafers, polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamide-imide substrates, polyimide substrates, and other resin substrates. On these substrates, black matrices, colored patterns, other curing films, transparent patterns for film thickness adjustment, thin-film transistors (TFTs), etc., may also be formed. In this case, the thickness of the hardened film is not particularly limited and can be adjusted appropriately according to the materials used and the application. For example, it can be around 0.1 μm to 30 μm, preferably around 1 μm to 20 μm, and even more preferably around 1 μm to 6 μm.

[0145] Examples of coating methods for curable resin compositions include: extrusion coating, direct gravure coating, reverse gravure coating, capillary (CAP) coating, and die coating. Alternatively, coating machines such as 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 be used. Among these, using a rotary coater is preferred.

[0146] Examples of 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. Regarding reduced pressure drying, examples include drying at a pressure of around 50 Pa to 150 Pa and a temperature range of around 20°C to 25°C. In the case where the curable resin composition of the present invention contains a solvent (E), the solvent (E) can be removed by the aforementioned drying process.

[0147] The obtained cured resin composition layer can also be irradiated with radiation through a photomask. As the photomask, a mask with a light-blocking portion formed according to the target pattern is used. As the radiation, gamma rays, i-rays, or other similar rays can be used. For example, a mask alignment machine, a stepper, or similar device is preferred for radiation irradiation. After radiation irradiation, the cured resin composition layer is developed. The exposed cured resin composition layer can be developed using methods such as liquid coating, immersion, spraying, or splattering. Furthermore, if the cured resin composition layer is irradiated with radiation without a photomask, development is not required.

[0148] As a developer, an alkaline aqueous solution can generally be used. As an alkaline aqueous solution, an aqueous solution of an alkaline compound can be used; the alkaline compound can be an inorganic alkaline compound or an organic alkaline compound. The alkaline developer may contain a surfactant. The alkaline compound can be either an inorganic alkaline compound or an organic alkaline compound. Specific examples of inorganic alkaline compounds include: sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia, etc. Specific examples of organic alkaline compounds include: tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine, etc. These inorganic alkaline compounds and organic alkaline compounds can be used alone or in combination of two or more. The concentration of alkaline compounds in the alkaline developer is preferably 0.01% to 10% by mass, and more preferably 0.03% to 5% by mass.

[0149] The surfactant in the alkaline developer can be any of the following: 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 block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerol fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, etc. Specific examples of anionic surfactants include: higher alcohol sulfate salts such as sodium lauryl sulfate or sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate; alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate or sodium dodecylnaphthalene sulfonate, etc. Specific examples of cationic surfactants include: stearylamine hydrochloride or amine salts or quaternary ammonium salts such as lauryltrimethylammonium chloride, etc. These surfactants can be used individually or in combination of two or more. The concentration of surfactants in the alkaline developer is preferably in the range of 0.01% to 10% by mass, more preferably 0.05% to 8% by mass, and even more preferably 0.1% to 5% by mass.

[0150] In this invention, the post-baking temperature is preferably 70°C or higher. Furthermore, it is preferably lower than the glass transition temperature (Tg) of the substrate on which the hardened film is formed. Additionally, when it contains components that deteriorate at temperatures exceeding 200°C, it is preferably lower than the temperature at which that 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, the components contained in the curing resin composition, etc., for example, preferably 70°C or higher and 200°C or lower, more preferably 80°C or higher and 180°C or lower. By using a post-baking temperature of 70°C or higher, a hardened film with excellent solvent resistance can be obtained. Furthermore, when using the curing resin composition of this invention, a hardened film with excellent solvent resistance can be obtained without reducing the properties of the substrate, etc.

[0151] By using the curable resin composition of the present invention, it is no longer necessary to perform the post-baking step at a temperature of more than 200°C, which is usually performed in the past, in order to improve solvent resistance. Therefore, a curable film with excellent solvent resistance and without degradation of the properties of the substrate, etc., can be obtained.

[0152] 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, interlayer insulating film, or coating for adjusting the film thickness of a color pattern in an organic EL display device or liquid crystal display device. In the manufacture of the hardened film, if a photomask for forming holes is used during patterning exposure of the curable resin composition layer, an interlayer insulating film with holes can be obtained. 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; this hardened film can be effectively used as an outer coating. By assembling the hardened film obtained as described above, a display device such as an organic EL display device or a liquid crystal display device can be constructed. Such a display device exhibits excellent display quality. [Example]

[0153] Hereinafter, examples are given to illustrate the present invention in more detail, but the present invention is not limited to the following examples. In the examples, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass". In the following synthesis examples, the compounds were identified by mass analysis (liquid chromatography (LC); Agilent 1200 type, MASS; Agilent mass selective detection (LC / MSD) type) or elemental analysis (VARIO-EL; Elementar (stock)).

[0154] <Synthesis Example 1> A resin (A-1) containing the following structural units was synthesized. 224 parts of propylene glycol monomethyl ether were charged into a flask including a stirrer, reflux condenser, thermometer, and dropping funnel and heated to 90°C. Using the dropping funnel, a solution consisting of 170.3 parts of vinyltoluene, 87.4 parts of 2-(acetylethoxy)ethyl methacrylate, 74.9 parts of methacrylic acid, 16.0 parts of azobis(isobutyronitrile), and 96.0 parts 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 after 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 0.4 parts of 4-methoxyphenol, 53.4 parts of 3,4-epoxycyclohexyl methacrylate, 15.0 parts of triphenylphosphine, and 262.5 parts 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 resin (A-1). The obtained resin (A-1) had a weight-average molecular weight (Mw) of 14,500, an acid value (converted to solids content) of 89 (mg-KOH / g), and a solids content of 38.6% by mass. Resin (A-1) has the following structural units.

[0155] [Chemical 24]

[0156] <Dispersion Example 1> 15.0 parts of titanium dioxide (average particle size 300 nm), 2.0 parts of acidic resin-type pigment dispersant, and 83 parts of propylene glycol monomethyl ether acetate were mixed, and 300 parts of 0.4 mm zirconia beads were added. The mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU Corporation). Then, the zirconia beads were removed by filtration to obtain scattering agent D-1.

[0157] 〔Examples 1 to 4, Comparative Example 1〕 〔Preparation of Curable Resin Compositions〕 The components shown in Table 1 were mixed to obtain various curable resin compositions.

[0158] [Table 8] Unit (copy) Example Comparative example 1 2 3 4 1 Scattering agent (D-1) 10.5 Scattering agent (D-2) 27.1 Scattering agent (D-3) 5.4 Scattering agent (D-4) 11.4 Resin (A-1) 129.5 129.5 129.5 129.5 129.5 Polymerizable compound (B-1) 50 50 50 50 50 Polymerization initiator (C-1) 3 3 3 3 3 Solvent (E-1) 506 513 535 569 504

[0159] Scattering agent (D-1): The scattering agent described in Dispersion Example 1. Scattering agent (D-2): Silicon dioxide particles (average particle size 1500 nm) dispersed in 20% diethylene glycol solvent (Seahostar (registered trademark) KE-E150 manufactured by Nippon Shokubai Co., Ltd.). Scattering agent (D-3): Silicon oxyalkane particles (average particle size 500 nm) (Seahostar (registered trademark) KE-P50 manufactured by Nippon Shokubai Co., Ltd.). Scattering agent (D-4): Acrylic acid particles (average particle size 2400 nm) (Epostar (registered trademark) MV-1002 manufactured by Nippon Shokubai Co., Ltd.). Resin (A-1): Resin (A-1) described in Synthesis Example 1. Solution polymerizable compound (B-1): Dipentaerythritol polyacrylate (A9550 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). Polymerization initiator (C-1): N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) Solvent (E-1): Propylene glycol monomethyl ether acetate

[0160] <Formation of Pattern (Curing Film)> On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), the curable resin composition prepared in the above examples was coated by spin coating, and then pre-baked at 60°C for 1 minute to form a curable resin composition layer. After cooling, the substrate with the curable resin composition layer formed was irradiated with light at an exposure dose of 100 mJ / cm² (365 nm reference) under atmospheric conditions using an exposure machine (TME-150RSK; manufactured by Topcon). As a photomask, one with a 100 μm line and spatial pattern was used. The irradiated curable resin composition layer was immersed in an aqueous developer containing 2.38% tetramethylammonium hydroxide at 23°C for 60 seconds, washed with water, and then post-baked in an oven at 85°C for 30 minutes to obtain a curable film. The thickness of the obtained hardened film was measured using a film thickness measuring device (DEKTAK 3; manufactured by Ulvac (stock)). The result was confirmed to be 3.0 μm.

[0161] <Haze> The haze of the obtained hardened film was measured using a haze meter (HZ-2; manufactured by Suga Testing Equipment Co., Ltd.). The results are shown in Table 9.

[0162] <Soluble Resistance> The obtained pattern was immersed in propylene glycol monomethyl ether acetate (PGMEA) at 23°C for 10 minutes. The film thickness of the immersed pattern was measured using a film thickness measuring device (DEKTAK 3; manufactured by Ulvac, Inc.), and the ratio of the film thickness to the film thickness before immersion (3.0 μm) was calculated. The results are shown in Table 9.

[0163] <Transmittance> The transmittance at a wavelength of 450 nm was measured on an ultraviolet-visible spectrophotometer (V-650; manufactured by Nippon Spectrophotometer Co., Ltd.) with an integrating sphere (ISV-922; manufactured by Nippon Spectrophotometer Co., Ltd.). The results are shown in Table 9.

[0164] [Table 9] Example 1 2 3 4 Haze 10% 5% 7% 10% Solvent resistance (condition 1) (Film thickness ratio before and after PGMEA impregnation) 99% 99% 98% 97% Transmission rate (450 nm) 85% 92% 92% 91%

[0165] Regarding Comparative Example 1, the haze was 0%. Furthermore, regarding Comparative Example 1, the solvent resistance was 100%, and the transmittance at a wavelength of 450 nm was 92%.

[0166] 〔Examples 5 to 8, Comparative Examples 2 to 5〕 In each of Examples 1 to 4, instead of polymerization initiator (C-1) (N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF)), polymerization initiator (C-2) (Adeka arkls (registered trademark) NCI-930; manufactured by ADEKA) was used as polymerization initiator (Examples 5 to 8).

[0167] [Chemistry 25]

[0168] <Formation of Pattern (Curing Film); Condition 2> On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), the curable resin composition prepared in the above examples was coated by spin coating, and then pre-baked at 85°C for 2 minutes to form a curable resin composition layer. After cooling, the substrate with the curable resin composition layer formed was irradiated with light at an exposure dose of 100 mJ / cm² (365 nm reference) under atmospheric conditions using an exposure machine (TME-150RSK; manufactured by Topcon). As a photomask, one with a 100 μm line and spatial pattern was used. The irradiated curable resin composition layer was immersed in an aqueous developer containing 2.38% tetramethylammonium hydroxide at 23°C for 60 seconds, washed with water, and then post-baked in an oven at 85°C for 30 minutes to obtain a curable film. The thickness of the obtained hardened film was measured using a film thickness measuring device (DEKTAK 3; manufactured by Ulvac (stock)). The result was confirmed to be 3.0 μm.

[0169] <Solvent Resistance> The pattern obtained under condition 2 was immersed in PGMEA or propylene glycol monomethyl ether (PGME) at 23°C for 10 minutes. The film thickness of the immersed pattern was measured using a film thickness measuring device (DEKTAK 3; manufactured by Ulvac (stock)) and the ratio of the film thickness to the film thickness before immersion (3.0 μm) was calculated. The results are shown in Table 10.

[0170] [Table 10] Example 5 6 7 8 Solvent resistance (condition 2) (Film thickness ratio before and after PGMEA impregnation) 100% 99% 100% 99% Solvent resistance (condition 2) (Film thickness ratio before and after PGME impregnation) 98% 98% 98% 99%

[0171] In addition, for each of Examples 5 to 8, instead of the polymerization initiator (C-2), the polymerization initiator (C-3) (Irgacure (registered trademark) 907) was used as the polymerization initiator (Comparative Examples 2 to 5). In this case, the formation of the pattern (hardened film) could not be carried out (condition 2).

Claims

1. A curable resin composition comprising a resin (A), a polymerizable compound (B), a polymerization initiator (C), and scattering particles (D), wherein the resin (A) contains structural units (Aa) having α,β-unsaturated carbonyl groups, structural units (Ab) having active methylene or active methine groups, and structural units (Ac) having acid groups; the polymerization initiator (C) comprises an oxime compound; the scattering particles (D) have an average particle size of 500 nm or more and 5000 nm or less; and the content of the scattering particles (D) is 0.5 parts by mass or more and 80 parts by mass or less relative to 100 parts by mass of the total curable resin composition.

2. A curing film formed by curing a curable resin composition as described in claim 1.

3. A display device comprising a hardened film as described in claim 2.

4. A method for manufacturing a hardened film, comprising: The step of coating the curable resin composition as described in claim 1 onto a substrate; A step of forming a hardened composition layer by drying the hardened composition; The step of exposing the curing composition layer; and the step of heating the exposed curing composition layer.

5. The method for manufacturing the hardened film as described in claim 4, wherein, The exposed curable composition layer is heated to a temperature above 70°C and below 200°C.