TW202313860A - Curable resin composition, cured film thereof and display device capable of forming a well-formed pattern - Google Patents

Abstract

The present invention provides a curable resin composition capable of forming a well-formed pattern. The curable resin composition of the present invention includes a curable resin (A) having a weight average molecular weight of 3,000 to 100,000, and a polymerization initiator (B), wherein when the amount based on the solid content of the curable resin composition of the curable resin (A) is set to WA mass%, the double bond equivalent of the curable resin (A) is set to DA g/eq, the amount based on the solid content of the curable resin composition of the compound (C) having two or more polymerizable unsaturated bonds, optionally included in the curable resin composition is set to WC mass %, and the double bond equivalent of compound (C) is set to DC g/eq, the curable resin composition has the amount of double bonds in 100 g of solid content, as calculated by the formula: amount of double bonds = WA/DA+WC/DC, is 0.09 eq or less.

Description

Curable resin composition, its cured film, and display device

The present invention relates to a curable resin composition, its cured film, and a display device.

A color filter substrate as a component included in a liquid crystal display device has the following structure: a black matrix layer is formed on a transparent substrate, and pixels such as red (R), green (G), and blue (B) are used to form each pixel. ) color filter, and a protective film is laminated on it as the case may be. Furthermore, a patterned transparent pixel electrode is formed on the upper layer. Columnar or strip-shaped spacers are formed on the color filter substrate to keep a certain distance between it and the opposing TFT (Thin Film Transistor, thin film transistor) substrate.

The color filters, protective films, and spacers contained in the above-mentioned color filter substrate can all be formed using a curable resin composition. As such a curable resin composition, Patent Document 1 describes a curable resin composition containing a specific color material, a photopolymerizable compound, and an oxime ester compound as a photopolymerization initiator. A patterned cured product such as a color filter is formed from such a curable resin composition, for example, by photolithography. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2020-3614

[Problem to be solved by the invention]

When manufacturing a patterned cured film, a developing step is performed: exposing and curing the curable resin composition into a desired pattern, and removing the unexposed portion by dissolving it in a developing solution. In the case of using the previously known above-mentioned curable resin composition, in the developing step, the shape of the pattern may deteriorate (for example, the amount of insertion (insertion) increases).

Therefore, an object of the present invention is to provide a curable resin composition capable of forming a pattern of a favorable shape. [Technical means to solve the problem]

The inventors of the present invention have found that the above objects can be achieved by using the curable resin composition of the present invention described below. That is, the present invention includes the following aspects. [1] A curable resin composition comprising a curable resin (A) having a weight average molecular weight of 3,000 to 100,000 and a polymerization initiator (B), wherein the curable resin (A) is The amount of the solid content of the curable resin composition is set as W _A mass %, and the double bond equivalent of the curable resin (A) is set as D _A g/eq, which will be contained in the curable resin composition as the case may have 2 The amount of the compound (C) having more than one polymerizable unsaturated bond based on the solid content of the curable resin composition is W _C mass %, and the double bond equivalent of the compound (C) is D _C g/eq In this case, the amount of double bonds in 100 g of solid content of the curable resin composition calculated by the formula: amount of double bonds = W _A / _DA + W _C /D _C is 0.09 eq or less. [2] The curable resin composition as described in [1], wherein the amount (W _A mass %) of the curable resin (A) based on the solid content of the curable resin composition is 20% by mass to 80% by mass. quality%. [3] The curable resin composition as described in [1] or [2], wherein the compound (C) having two or more polymerizable unsaturated bonds is based on the solid content of the curable resin composition The amount (W _C mass %) is 0 to 20 mass%. [4] The curable resin composition according to any one of [1] to [3], wherein the amount of double bonds in 100 g of solid content of the curable resin composition is 0.03 eq or more. [5] The curable resin composition according to any one of [1] to [4], wherein the polymerization initiator (B) is an O-acyl oxime compound. [6] The curable resin composition according to any one of [1] to [5], which further contains a colorant. [7] A cured film of the curable resin composition according to any one of [1] to [6]. [8] The cured film as described in [7], which is a color filter, a spacer, and/or a protective layer contained in a color filter substrate. [9] A display device comprising the cured film as described in [7] or [8]. [Effect of Invention]

According to the present invention, it is possible to provide a curable resin composition capable of forming a good-shaped pattern.

Hereinafter, embodiments of the present invention will be described in detail. In addition, the scope of the present invention is not limited to the embodiment described here, and various changes can be made in the range which does not deviate from the summary of the present invention. Also, when there are multiple upper limits and lower limits described for a specific parameter, an appropriate value can be set by combining any of these upper limits and lower limits. scope.

<Curable resin composition> The curable resin composition of the present invention contains at least a curable resin (A) having a weight average molecular weight of 3,000 to 100,000, and a polymerization initiator (B), and the curable resin ( The amount of A) based on the solid content of the curable resin composition is W _A mass%, and the double bond equivalent of the curable resin (A) is D _A g/eq, which will be viewed in the curable resin composition The amount of the compound (C) having two or more polymerizable unsaturated bonds included in the case based on the solid content of the curable resin composition is W _C mass %, and the double bond equivalent of the compound (C) is In the case of D _C g/eq, the amount of double bonds in 100 g of solid content of the curable resin composition calculated by the formula: Amount of double bonds = W _A / _DA + W _C /D _C is 0.09 eq or less.

By the formula: double bond amount = W _A / D _A + W _C / D _C [wherein, W _A represents the amount (mass %) of the solid content of the curable resin (A) based on the curable resin composition, D _A represents the double bond equivalent (g/eq) of the curable resin (A), and W _C represents the compound (C) having two or more polymerizable unsaturated bonds contained in the curable resin composition as the case may be. The amount (mass %) of the solid content of the curable resin composition, D _C represents the double bond equivalent (g/eq) of the compound (C)] The calculated double bond amount represents the solid content derived from the curable resin composition The amount of the double bond of the curable resin (A) contained in 100 g, and the compound (C) which has 2 or more polymerizable unsaturated bonds. When the amount of the double bond exceeds 0.09 eq, a good pattern shape cannot be obtained in the formation of a patterned cured product such as a color filter. Here, curable resin (A) is resin which has the following weight average molecular weight, and is an essential component of the curable resin composition of this invention. The compound (C) having two or more polymerizable unsaturated bonds is a compound having two or more polymerizable unsaturated bonds, such as a compound having two or more ethylenically unsaturated bonds, and the compound is not a combination of curable resins necessary ingredients. In addition, in this specification, a compound means the compound which has a molecular weight of 2000 or less. Also, the compound (C) having two or more polymerizable unsaturated bonds may or may not be contained in the curable resin composition. When the compound (C) is not contained, since W _C = 0, double The key amount can be calculated by W _A /D _A.

The amount of double bonds calculated by the formula: amount of double bonds = W _A / D _A + W _C / D _C is 0.09 eq or less. From the viewpoint of making the pattern shape better, it is preferably 0.085 eq or less, more preferably 0.08 below eq. Moreover, from the viewpoint of easily improving the curability of the curable resin composition, it is preferably at least 0.03 eq, more preferably at least 0.04 eq, still more preferably at least 0.05 eq, even more preferably at least 0.06 eq. As a method of setting the amount of double bonds within the above range, the amount W _A (mass %) of the curable resin (A) in the above formula based on the solid content of the curable resin composition has 2 or more When the amount W _C (mass %) of the compound (C) based on the solid content of the curable resin composition decreases, and the double bond equivalent D _A of the curable resin (A) (g/eq) and the double bond equivalent D _C (g/eq) of the compound (C) increase, the double bond equivalent will decrease, so as long as they are within the above range, adjust W _A and D respectively _A , W, _C , and _D can be used. In addition, _WA and _WC can be calculated from the addition ratio of each component contained in curable resin composition, and can also calculate content by analysis. In addition, _DA and D _C can be calculated by analyzing the structure and molecular weight of each component contained in the curable resin composition, and can also be measured by infrared absorption method or nuclear magnetic resonance method.

When the curable resin composition contains two or more curable resins (A) and/or two or more compounds (C), W _A can be calculated for each curable resin (A) and each compound (C) /D _A and W _C /D _C to calculate the amount of double bonds. Therefore, the above formula can also _be described as the amount of double bonds = Σ(W _Ai /D _Ai ) + Σ(W _Ci /D _Ci ) Amount of solid content (mass %) D _Ai : Double bond equivalent (g/eq) of each curable resin (A) W _Ci : % of solid content of each compound (C) based on the curable resin composition Amount (mass %) D _Ci : double bond equivalent (g/eq) of each compound (C)]. For example, when the curable resin composition contains three kinds of curable resins (A1) to (A3), and two kinds of compounds (C1) and (C2), the amount of double bonds can be calculated by the following formula: W _A1 / D _A1 +W _A2 /D _A2 +W _A3 /D _A3 +W _C1 /D _C1 +W _C2 /D _C2 .

(hardening resin A) The curable resin (A) is not particularly limited as long as it is a curable resin having a weight average molecular weight of 3,000 to 100,000, but is preferably an alkali-soluble resin. The curable resin composition of this invention may contain 1 type of curable resin (A), and may contain 2 or more types of curable resin (A). Furthermore, the curable resin is a resin having one or more polymerizable unsaturated bonds such as ethylenically unsaturated bonds.

As curable resin (A), the following resin [K1] - [K6] etc. are mentioned, for example. Resin [K1]; having a structural unit derived from (a) (hereinafter sometimes referred to as "(a)"), and a structural unit derived from monomer (b) (hereinafter sometimes referred to as "(b)") The above-mentioned (a) is at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the above-mentioned monomer (b) has a cyclic ether structure with 2 to 4 carbon atoms and an ethylenic non- saturated bond; Resin [K2]; having a structural unit derived from (a), a structural unit derived from (b), and a monomer (c) derived from (a) copolymerizable (but different from (a) and (b) ) (hereinafter sometimes referred to as "(c)"), copolymers of structural units; Resin [K3]; a copolymer having a structural unit derived from (a) and a structural unit derived from (c); Resin [K4]; a copolymer having a structural unit derived from (b) added to a structural unit derived from (a), and a structural unit derived from (c); Resin [K5]; a copolymer having a structural unit derived from (a) added to a structural unit derived from (b), and a structural unit derived from (c); Resin [K6]; having a structural unit derived from (a) added to the structural unit derived from (b), and further adding polycarboxylic acid and/or carboxylic anhydride; and copolymerization of the structural unit derived from (c) things. The curable resin (A) is preferably a resin containing a double bond other than a polymerizable unsaturated bond, and more preferably contains at least one resin selected from the group consisting of resins [K4] to [K6]. .

As (a), specifically, for example, it can be exemplified: Acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid and other unsaturated monocarboxylic acids; Maleic acid, fumaric acid, citraconic acid, methylfumaric 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 other unsaturated dicarboxylic acids Carboxylic acids; Methyl-5-norcamphene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]-2-heptene, 5,6-dicarboxybicyclo[2.2.1]-2-heptene, 5-carboxy-5-methylbicyclo[2.2.1]-2-heptene, 5-carboxy-5-ethylbicyclo[2.2.1]-2-heptene, 5-carboxy-6-methylbicyclo[ 2.2.1]-2-heptene, 5-carboxy-6-ethylbicyclo[2.2.1]-2-heptene and other carboxyl-containing bicyclic unsaturated compounds; Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, bicyclo[2.2.1]-2-heptene-5,6-dicarboxylic anhydride and other unsaturated dicarboxylic Carboxylic anhydrides; Unsaturated polycarboxylic acids with more than two valences such as mono[2-(meth)acryloxyethyl]succinate and mono[2-(meth)acryloxyethyl]phthalate Mono[(meth)acryloxyalkyl]esters; Unsaturated acrylic esters such as α-(hydroxymethyl)acrylic acid containing a hydroxyl group and a carboxyl group in the same molecule, etc. Among these, acrylic acid, methacrylic acid, and the like are preferable from the viewpoint of copolymerization reactivity or the solubility of the obtained resin in an alkaline aqueous solution.

(b) means, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring), and ethylenic Polymeric compounds with unsaturated bonds. (b) It is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloxy group. In addition, in this specification, "(meth)acrylic acid" means at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Expressions such as "(meth)acryl" and "(meth)acrylate" also have the same meaning.

As (b), for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond, Monomer (b2) with an unsaturated bond (hereinafter sometimes referred to as "(b2)"), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc. .

As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)") . A monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

Examples of (b1-1) include: glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl Ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-methylene Benzyl benzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl) Styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl) Styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxy methyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Co., Ltd.), (methyl) 3,4-epoxycyclohexylmethyl acrylate (such as Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (such as Cyclomer M100; manufactured by Daicel Corporation) ), 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate, compounds represented by formula (BI) and compounds represented by formula (BII), etc.

[式(BI)及式(BII)中，R ^e及R ^f表示氫原子、或碳數1～4之烷基，該烷基中所含之氫原子可被取代為羥基。 X ^e及X ^f表示單鍵、*-R ^g-、*-R ^g-O-、*-R ^g-S-或*-R ^g-NH-。 R ^g表示碳數1～6之烷二基。 *表示與O之鍵結鍵] [chemical 1]

[In formula (BI) and formula (BII), R ^e and R ^f represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X ^e and X ^f represent a single bond, *-R ^g -, *-R ^g -O-, *-R ^g -S- or *-R ^g -NH-. R ^g represents an alkanediyl group having 1 to 6 carbon atoms. *Denotes bond with O]

The alkyl group having 1 to 4 carbon atoms may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl or third-butyl. Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include: hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1 -Hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl and the like. As R ^e and R ^f , preferably, hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group are mentioned, more preferably, hydrogen atom and methyl group are mentioned.

Examples of the alkanediyl group include methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1, 5-diyl, hexane-1,6-diyl, etc. As X ^e and X ^f , preferably, a single bond, methylene, ethylidene, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, more preferably a single bond, *-CH ₂ CH ₂ -O- (* indicates a bond with O).

(b2) is more preferably a monomer having an oxetanyl group and a (meth)acryloxy group. As (b2), for example: 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3 -Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-methyl-3-methacryl Oxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane, 3-Ethyl-3-acryloyloxyethyloxetane, etc.

(b3) is more preferably a monomer having a tetrahydrofuryl group and a (meth)acryloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), in the case of resin [K1] or resin [K2], (b1) is preferable at the point which can further improve reliability, such as heat resistance and chemical resistance of the cured film obtained.

As (c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second-butyl (meth)acrylate, (meth)acrylic acid Tertiary butyl ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid Cyclopentyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.02,6]decane-8-yl (meth)acrylate (in this In the technical field, it is called "dicyclopentyl (meth)acrylate" as a common name. Also, it is sometimes called "tricyclodecanyl (meth)acrylate"), tricyclo[5.2 (meth)acrylate .1.0 ^2,6 ]decen-8-yl ester (in this technical field, as a common name, called "(meth)acrylate dicyclopentenyl ester"), (meth)acrylate dicyclopentyl Ethyl, iso(meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylate (meth)acrylic acid esters such as naphthyl acrylate, benzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. ) acrylates; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; bicyclo[2.2.1]-2-heptene, Methylbicyclo[2.2.1]-2-heptene, 5-ethylbicyclo[2.2.1]-2-heptene, 5-hydroxybicyclo[2.2.1]-2-heptene, 5-hydroxymethyl Bicyclo[2.2.1]-2-heptene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]-2-heptene, 5-methoxybicyclo[2.2.1]-2-heptene , 5-ethoxybicyclo[2.2.1]-2-heptene, 5,6-dihydroxybicyclo[2.2.1]-2-heptene, 5,6-bis(hydroxymethyl)bicyclo[2.2. 1]-2-heptene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]-2-heptene, 5,6-dimethoxybicyclo[2.2.1]-2- Heptene, 5,6-diethoxybicyclo[2.2.1]-2-heptene, 5-hydroxy-5-methylbicyclo[2.2.1]-2-heptene, 5-hydroxy-5-ethane Basebicyclo[2.2.1]-2-heptene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]-2-heptene, 5-tert-butoxycarbonylbicyclo[2.2.1]- 2-heptene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]-2-heptene, 5-phenoxycarbonylbicyclo[2.2.1]-2-heptene, 5,6-bis(third Butoxycarbonyl)bicyclo[2.2.1]-2-heptene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]-2-heptene and other bicyclic unsaturated compounds; N-benzene N-cyclohexylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-butadiamide-3-maleimide Aminobenzoate, N-Succimidyl-4-maleimide Butyrate, N-Succimidyl-6-Maleimide Hexanoate, N-butadiimide-3-maleimide propionate, N-(9-acridyl)maleimide and other dicarbonyl imide derivatives; Styrene , α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide , methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. Among these, (meth)acrylates are preferable.

In the resin [K1], regarding the ratio of the structural units derived from each, among all the structural units constituting the resin [K1], preferably: Structural unit derived from (a); 2-60 mol% Structural unit derived from (b); 40-98 mole%, Even better: Structural unit derived from (a); 10-50 mol% Structural unit derived from (b); 50-90 mol%. If the ratio of the structural unit of the fat [K1] is within the above range, it is easy to adjust the amount of double bonds of the curable composition of the present invention to a preferable range, and the storage stability of the curable resin composition, when forming a pattern, etc. Developability and solvent resistance of the obtained cured film tend to be excellent.

Resin [K1], for example, can refer to the method described in the document "Experimental Method of Polymer Synthesis" (Takayuki Otsu, Chemical Doujin Publishing Co., Ltd., first edition, first printing, March 1, 1972), and the Cited documents recorded in the literature to manufacture.

Specifically, the following method can be exemplified: adding specific amounts of (a) and (b), a polymerization initiator and a solvent, etc. into a reaction vessel, for example, replacing oxygen with nitrogen, thereby setting it as a deoxidizing atmosphere, and stirring One side is heated and kept warm. In addition, the polymerization initiator, solvent, etc. used here are not specifically limited, What is common in this field can be used. For example, as a polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or Organic peroxides (benzoyl peroxide, tertiary butyl peroxide 2-ethylhexanoate, etc.), as long as the solvent can dissolve each monomer, it can be exemplified below as the curable resin of the present invention The solvent etc. which can be contained in a composition are demonstrated for the solvent (F).

Furthermore, the obtained copolymer can be used directly as a solution after reaction, or as a concentrated or diluted solution, or as a solid (powder) obtained by reprecipitation or the like. Especially in this polymerization, by using the solvent contained in the curable resin composition of the present invention as a solvent, the solution after the reaction can be directly used to prepare the curable resin composition of the present invention, so the present invention can be simplified The production steps of the curable resin composition.

In the resin [K2], regarding the ratio of the structural units derived from each, among all the structural units constituting the resin [K2], preferably: Structural unit derived from (a); 2-45 mol% Structural unit derived from (b); 2-95 mol% Structural unit derived from (c); 1-65 mole%, Even better: Structural unit derived from (a); 5-40 mol% Structural unit derived from (b); 5-80 mol% Structural unit derived from (c); 5-60 mol%. If the ratio of the structural units of the resin [K2] is within the above range, it is easy to adjust the amount of double bonds of the curable composition of the present invention to a preferable range, and the storage stability of the curable resin composition, when forming a pattern, etc. Developability, and the solvent resistance, heat resistance and mechanical strength of the obtained cured film tend to be excellent.

Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

In the resin [K3], the ratio of the structural units derived from each is from the viewpoint of easily adjusting the amount of double bonds of the curable composition of the present invention to a preferable range, and in the entire structure constituting the resin [K3] In the unit, preferably: Structural unit derived from (a); 2-60 mol% Structural unit derived from (c); 40-98 mole%, Even better: Structural unit derived from (a); 10-50 mol% Structural unit derived from (c); 50-90 mol%. Resin [K3] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding a cyclic ether having 2 to 4 carbon atoms in (b) to the carboxylic acid in (a) and/or carboxylic anhydrides. First, the copolymer of (a) and (c) is manufactured similarly to the method described as the manufacturing method of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same ratio as exemplified in resin [K3].

Next, the cyclic ether having 2 to 4 carbon atoms contained in (b) is reacted with part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the above-mentioned copolymer. After producing the copolymer of (a) and (c), the atmosphere in the flask was replaced from nitrogen to air, and the reaction catalyst of (b), carboxylic acid or carboxylic acid anhydride and cyclic ether (such as tris(dimethylamine) (methyl) phenol, triphenylphosphine, etc.) and polymerization inhibitors (such as hydroquinone, p-methoxyphenol, etc.) are added to the flask, and the reaction is carried out at 60-130°C for 1-10 hours, for example, Resin [K4] can be manufactured by this. The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, based on 100 mol of (a). By setting it within this range, the storage stability of the curable resin composition, the developability when forming a pattern, the pattern shape, the curability at low temperature, and the solvent resistance, heat resistance, and mechanical strength of the obtained cured film are obtained. And the balance of sensitivity tends to be better. Since the reactivity of the cyclic ether is high and unreacted (b) does not easily remain, (b) used for resin [K4] is preferably (b1), and more preferably (b1-1). The usage-amount of the said reaction catalyst is preferably 0.001-5 mass parts with respect to 100 mass parts of total amounts of (a), (b) and (c). The usage-amount of the said polymerization inhibitor is preferably 0.001-5 mass parts with respect to 100 mass parts of total amounts of (a), (b) and (c). Reaction conditions such as addition method, reaction temperature, and time can be appropriately adjusted in consideration of production equipment, heat generation by polymerization, and the like. In addition, like the polymerization conditions, the method of addition and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

Regarding the resin [K5], as a first step, a copolymer of (b) and (c) was obtained in the same manner as the production method of the above-mentioned resin [K1]. Similar to the above, the obtained copolymer may be used as a solution after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by reprecipitation or the like. The ratios of the structural units derived from (b) and (c) are preferably respectively: Structural unit derived from (b); 5-95 mol% Structural unit derived from (c); 5-95 mol%, Even better: Structural unit derived from (b); 10-90 mol% Structural unit derived from (c); 10-90 mol%. If the ratio of the structural unit of the resin [K5] is within the above range, it is easy to adjust the amount of double bonds of the curable composition of the present invention to a preferable range, and the storage stability of the curable resin composition, when forming a pattern, etc. The developability, pattern shape, curability at low temperature, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained cured film tend to be well balanced.

Furthermore, under the same conditions as the production method of the resin [K4], the carboxylic acid or carboxyl contained in (a) and the cyclic ring derived from (b) contained in the copolymer of (b) and (c) are Ether reaction, whereby the resin [K5] can be obtained. The usage-amount of (a) reacted with the said copolymer is preferably 5-100 mol with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) is not likely to remain, as (b) used for resin [K5], (b1) is preferable, and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting polyvalent carboxylic acid and/or carboxylic acid anhydride with resin [K5]. Furthermore, the polyvalent carboxylic acid and/or carboxylic acid anhydride is reacted with the hydroxyl group produced by reaction of the cyclic ether derived from (b) with the carboxylic acid or carboxylic anhydride derived from (a). As the polyvalent carboxylic acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, triphenylamine formic acid and the like may, for example, be mentioned. Examples of carboxylic anhydrides include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5 ,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, bicyclo[2.2.1]-2-heptene- 5,6-Dicarboxylic anhydride, etc. The usage-amount of polycarboxylic acid and/or carboxylic acid anhydride is preferably 0.05-1 mole, more preferably 0.1-0.5 mole relative to 1 mole of the usage-amount of (a).

The curable resin (A) is preferably a resin (resin [K4] or resin [K5]) containing a structural unit having an ethylenically unsaturated bond in the side chain, more preferably a resin containing (methyl ) Resins with structural units of acryl groups. As a resin having a structural unit including a (meth)acryl group in the side chain, for example, resin [K4] using glycidyl (meth)acrylate, 3,4-cyclo(meth)acrylate, etc. Oxycyclohexyl methyl ester, 3-methyl-3-methacryloxymethyl oxetane, tetrahydrofurfuryl acrylate and other monomers with (meth)acryloyl groups are used as (b); and Resin [K5] using a monomer having a (meth)acryl group such as acrylic acid, methacrylic acid, and succinic acid mono[2-(meth)acryloxyethyl] ester as (a). Among resin [K4] and resin [K5], as (c), dicarbonyl imide derivatives and vinyl toluene are preferable.

The curable resin (A) has a polystyrene-equivalent weight average molecular weight of 3,000 to 100,000, preferably 5,000 to 40,000, more preferably 6,000 to 30,000. If the weight average molecular weight is within the above range, the hardness of the cured film used as a color filter, spacer, protective film, etc. will increase, the residual film rate will be high, and the solubility of the unexposed part to the developer will be good. As the shape improves, the resolution of the pattern tends to improve.

The degree of dispersion [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the curable resin (A) is preferably 1.1-6, more preferably 1.2-4.

In terms of solid content, the acid value of the curable resin (A) is preferably 10-170 mg-KOH/g, more preferably 20-150 mg-KOH/g, and still more preferably 30-135 mg-KOH /g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the curable resin (A), and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The amount (W _A mass %) of the curable resin (A) based on the solid content of the curable resin composition is preferably at least 20 mass %, more preferably at least 25 mass %, further preferably at least 30 mass % . Also, the amount is preferably at most 80% by mass, more preferably at most 75% by mass, still more preferably at most 70% by mass, still more preferably at most 65% by mass, especially preferably at most 60% by mass. When the content of the curable resin (A) is within the above range, it is easy to form a pattern, and the resolution of the pattern and the remaining film ratio tend to be improved. Moreover, the solvent resistance of the obtained cured film improves further. In addition, in this specification, "the total amount of solid content" means the amount which removed the content of the solvent from the total amount of curable resin composition. The total amount of solid content and the relative content of each component can be measured, for example, by known analysis methods such as liquid chromatography or gas chromatography.

(polymerization initiator B) The polymerization initiator (B) is a compound capable of generating active radicals, acids, etc. by the action of light or heat to initiate polymerization. Although it does not specifically limit as a polymerization initiator (B), O-acyl oxime compound, an alkyl phenone compound, a biimidazole compound, a trioxine compound, and an acyl phosphine oxide compound are mentioned, for example. Among them, O-acyl oxime compounds are preferred. From the viewpoint of improving the curability of the curable resin composition more easily, the polymerization initiator (B) preferably has a maximum absorption wavelength in the range of 365 to 390 nm, more preferably in the range of 370 to 390 nm Has a maximum absorption wavelength. The curable resin composition of this invention may contain 1 type of polymerization initiator (B), and may contain 2 or more types of polymerization initiators (B).

The polymerization initiator (B) is preferably an O-acyl oxime compound. Moreover, the polymerization initiator (B) is also preferably a compound having a carbazole skeleton, and is also preferably a compound having a nitro group.

。 以下，*表示鍵結鍵。 O-acyl oxime compound is the compound with the structure represented by formula (c1), [Chemical 2]

. Hereinafter, * represents a bonding key.

。 A compound having a carbazole skeleton is a compound having a structure represented by formula (c2), [Chemical 3]

.

The compound having a nitro group (-N ₂ O) is preferably a compound having at least one nitro group bonded to an aromatic ring, more preferably at least one nitro group bonded to an aromatic ring contained in a carbazole skeleton. A nitro compound.

[式(c3)及(c4)中， R ^a表示可具有取代基之碳數6～18之芳香族烴基或可具有取代基之碳數1～15之脂肪族烴基，上述脂肪族烴基中所含之亞甲基(-CH ₂-)可被取代為-O-、-CO-或-S-，上述脂肪族烴基中所含之次甲基(-CH＜)可被取代為-PO ₃＜，上述脂肪族烴基中所含之氫原子可被取代為OH基。 再者，於本說明書中，於亞甲基(-CH ₂-)等被取代為-O-、-CO-或-S-等之情形時，碳數意指取代前之碳數。 R ^b表示可具有取代基之碳數6～18之芳香族烴基、可具有取代基之碳數3～36之雜環基、可具有取代基之碳數1～15之烷基、或將芳香族烴基與由該烷基衍生之烷二基組合而成之可具有取代基之基，上述烷基中所含之亞甲基(-CH ₂-)可被取代為-O-、-CO-、-S-、-SO ₂-或-NR ^h-。R ^h表示碳數6～18之芳香族烴基、碳數3～36之雜環基或碳數1～10之烷基。 R ^c表示可具有取代基之碳數6～18之芳香族烴基、碳數3～36之雜環基或碳數1～10之烷基。 R ^d表示可具有取代基之碳數6～18之芳香族烴基或可具有取代基之碳數3～36之雜環基。 p表示1～4之整數，較佳為表示1或2之整數，更佳為表示1。 The polymerization initiator (B) is more preferably an O-acyl oxime compound having a carbazole skeleton. As such a compound, for example, a compound (hereinafter, sometimes referred to as compound (c3)) represented by formula (c3) and a compound represented by formula (c4) (hereinafter, sometimes referred to as compound ( At least one of the group consisting of c4)). [chemical 4]

[In formulas (c3) and (c4), R ^a represents an aromatic hydrocarbon group with 6 to 18 carbon atoms that may have a substituent or an aliphatic hydrocarbon group with 1 to 15 carbon atoms that may have a substituent, and the above-mentioned aliphatic hydrocarbon group The methylene group (-CH ₂ -) contained in it can be replaced by -O-, -CO- or -S-, and the methine group (-CH<) contained in the above aliphatic hydrocarbon group can be replaced by -PO ₃ <, the hydrogen atoms contained in the above-mentioned aliphatic hydrocarbon groups may be substituted with OH groups. In addition, in this specification, when a methylene group ( _-CH2- ) etc. is substituted with -O-, -CO-, -S- etc., a carbon number means the carbon number before substitution. R ^b represents an aromatic hydrocarbon group with 6 to 18 carbons that may have a substituent, a heterocyclic group with 3 to 36 carbons that may have a substituent, an alkyl group with 1 to 15 carbons that may have a substituent, or an aromatic A group that may have a substituent formed by a combination of an alkane group and an alkanediyl group derived from the alkyl group, and the methylene group (-CH ₂ -) contained in the above-mentioned alkyl group may be substituted by -O-, -CO- , -S-, -SO ₂ - or -NR ^h -. ^Rh represents an aromatic hydrocarbon group having 6 to 18 carbons, a heterocyclic group having 3 to 36 carbons, or an alkyl group having 1 to 10 carbons. R ^c represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbons, a heterocyclic group having 3 to 36 carbons, or an alkyl group having 1 to 10 carbons. R ^d represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted heterocyclic group having 3 to 36 carbon atoms. p represents an integer of 1 to 4, preferably represents an integer of 1 or 2, more preferably represents 1.

The carbon number of the aromatic hydrocarbon group represented by R ^a is preferably 6-15, more preferably 6-12, still more preferably 6-10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, and terphenyl, more preferably phenyl and naphthyl, and still more preferably phenyl. Also, the aromatic hydrocarbon group represented by R ^a may have one or two or more substituents. As this substituent, the same thing as the substituent which the aromatic hydrocarbon group of following R ^b may have is mentioned.

The carbon number of the aliphatic hydrocarbon group represented by R ^a is preferably 1-13, more preferably 2-10. Examples of the aliphatic hydrocarbon group represented by ^R include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, deca Alkyl, dodecyl, tridecyl, tetradecyl and pentadecyl and other alkyl groups; vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octanyl Alkenyl groups such as alkenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, heptadecenyl and pentadecenyl, etc. These aliphatic hydrocarbon groups may be chain (linear or branched), may be cyclic, and may be a combination of a chain group and a cyclic group. Also, in the aliphatic hydrocarbon group of R ^a , methylene (-CH ₂ -) can be substituted by -O-, -CO- or -S-, and methine (-CH<) can be substituted by -PO ₃ <, the hydrogen atoms contained in the above-mentioned aliphatic hydrocarbon groups may be substituted with OH groups.

As an aliphatic hydrocarbon group which may have a substituent represented by R ^a , the group represented by the following formula etc. are mentioned. In the formula, * represents a bonding bond. [chemical 5]

R ^a is preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group having no substituent, and still more preferably a linear or branched alkyl group having no substituent.

The carbon number of the aromatic hydrocarbon group represented by R ^b is preferably 6-15, more preferably 6-12, and still more preferably 6-10. The aromatic hydrocarbon group may, for example, be phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl or the like, more preferably phenyl or naphthyl, especially preferably phenyl. Also, the aromatic hydrocarbon group represented by R ^b may have one or two or more substituents. The substituent is preferably substituted at the ortho or para position of the aromatic hydrocarbon group. Examples of such substituents include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Alkyl groups having 1 to 15 carbon atoms such as alkyl groups, tetradecyl groups, and pentadecyl groups; halogen atoms such as fluorine atoms, chlorine atoms, iodine atoms, and bromine atoms; and the like. The number of carbon atoms in the alkyl group as the substituent is preferably 1-10, more preferably 1-7. The alkyl group as the substituent may be linear, branched, or cyclic, and may be a combination of a chain group and a cyclic group. The methylene group (-CH ₂ -) contained in the alkyl group as the substituent may be substituted with -O- or -S-. In addition, the hydrogen atom contained in the alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, or a bromine atom, and is preferably substituted with a fluorine atom.

As an alkyl group which is a substituent of the aromatic hydrocarbon group represented by ^Rb , the group represented by the following formula etc. are mentioned, for example. In the formula, * represents a bonding bond.

[chemical 6]

[chemical 7]

As the aromatic hydrocarbon group which may have a substituent represented by R ^b , the group represented by the following formula etc. are mentioned, for example. In the formula, * represents a bonding bond.

[chemical 8]

[chemical 9]

[式中，R ⁱ分別獨立地表示可經鹵素原子取代之碳數1～10之烷基，R ⁱ中所含之亞甲基(-CH ₂-)可被取代為-O-或-S-，R ^j分別獨立地表示可經鹵素原子取代之碳數1～10之烷基，q表示1～5之整數，r表示0～4之整數。其中，q＋r之合計為5以下] As the aromatic hydrocarbon group which may have a substituent represented by R ^b , a group represented by the following formula is preferable. [chemical 10]

[In the formula, R ⁱ each independently represent an alkyl group with 1 to 10 carbon atoms that may be substituted by a halogen atom, and the methylene group (-CH ₂ -) contained in R ⁱ may be substituted by -O- or -S - and R ^j each independently represent an alkyl group having 1 to 10 carbons which may be substituted by a halogen atom, q represents an integer of 1 to 5, and r represents an integer of 0 to 4. Among them, the total of q+r is 5 or less]

The alkyl group represented by R ⁱ and R ^j may, for example, be the same as the alkyl group exemplified as the substituent of the aromatic hydrocarbon group represented by R ^b . The carbon number of R ⁱ is preferably 2-8, more preferably 2-6. Also, the alkyl group represented by R ^j may be any of linear, branched, and cyclic, and is preferably chain. R ⁱ is preferably a group represented by the formula *-R ^j1 -OR ^j2 . Here, R ^j2 represents an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen atom. R ^j2 is preferably a linear alkyl group having 1 to 3 carbon atoms. R ^j1 represents an alkylene group having 1 to 10 carbon atoms which may be substituted by a halogen atom. R ^j1 is preferably a linear alkylene group having 1 to 3 carbon atoms. The halogen atom contained in R ⁱ and R ^j may, for example, be a fluorine atom, a chlorine atom, an iodine atom or a bromine atom, and a fluorine atom is particularly preferable. Also, when R ⁱ contains a halogen atom, the number thereof is preferably 2 or more and 10 or less, more preferably 3 or more and 6 or less. The substitution position of the R ⁱ O- group is preferably the ortho position or the para position. The substitution position of the R ^j -group is preferably the ortho position or the para position, especially preferably the ortho position. Moreover, q is preferably 1-2, especially preferably 1. r is preferably 0-2, particularly preferably 0 or 1.

The carbon number of the heterocyclic group represented by R ^b is preferably 3-20, more preferably 3-10, still more preferably 3-5. As this heterocyclic group, a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, a carbazolyl group, etc. are mentioned. Also, the heterocyclic group represented by R ^b may have one or two or more substituents. As the substituent, the same groups as those exemplified as the substituent that the aromatic hydrocarbon group represented by R ^b may have may be mentioned.

The alkyl group represented by R ^b preferably has 1-12 carbon atoms. Examples of the alkyl group represented by R ^b include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl base, tridecyl, tetradecyl and pentadecyl, etc. These alkyl groups may be linear, branched, or cyclic, and may be a combination of a chain group and a cyclic group. In addition, in the alkyl group represented by R ^b , the methylene group (-CH ₂ -) may be substituted by -O-, -CO-, -S-, -SO ₂ - or -NR ^h -, and the hydrogen atom may be replaced by Substituted by OH group or SH group.

R ^h represents an alkyl group having 1 to 10 carbons, preferably an alkyl group having 1 to 5 carbons, more preferably an alkyl group having 1 to 3 carbons. The alkyl group can be chain (straight chain or branched), also can be cyclic, can be any of straight chain, branched and cyclic, and can also be a combination of chain and ring. The base formed by the combination of bases. Also, in the alkyl group of ^Rh , methylene (-CH ₂ -) may be substituted with -O- or -CO-.

As the alkyl group which may have a substituent represented by ^Rb , the group represented by the following formula etc. are mentioned specifically,. * Indicates a bonded bond.

[chemical 11]

Furthermore, the carbon number of the group formed by combining the aromatic hydrocarbon group represented by R ^b and the alkanediyl group derived from the alkyl group represented by R ^b is preferably 7-33, more preferably 7-18, and further Preferably it is 7-12. The combined group may have one or two or more substituents, and the substituents may, for example, be the same as those exemplified as substituents that an aromatic hydrocarbon group or an alkyl group may have. As the group formed by combining the aromatic hydrocarbon group represented by R ^b and the alkanediyl group derived from the alkyl group represented by R ^b above, an aralkyl group can be mentioned, and specifically, the following formula can be exemplified: The basis of the representation. In the formula, * represents a bonding bond.

[chemical 12]

Among these, R ^b is preferably an optionally substituted aromatic hydrocarbon group or an optionally substituted alkyl group, more preferably an optionally substituted aromatic hydrocarbon group.

The carbon number of the aromatic hydrocarbon group represented by R ^c is preferably 6-15, more preferably 6-12, and still more preferably 6-10. As this aromatic hydrocarbon group, a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a biphenylyl group, a terphenyl group, etc. are mentioned. The carbon number of the heterocyclic group represented by R ^c is preferably 3-20, more preferably 3-10, and still more preferably 3-5. As this heterocyclic group, a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, a carbazolyl group, etc. are mentioned. The carbon number of the alkyl group represented by R ^c is preferably 1-7, more preferably 1-5, and still more preferably 1-3. As this alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. are mentioned. The alkyl group may be linear, branched, or cyclic, and may be a combination of a chain group and a cyclic group.

R ^c is preferably a chained alkyl group, more preferably a chained alkyl group having 1 to 5 carbons, still more preferably a chained alkyl group having 1 to 3 carbons, especially preferably a methyl group.

The carbon number of the aromatic hydrocarbon group represented by R ^d is preferably 6-15, more preferably 6-12, and still more preferably 6-10. Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, and terphenyl, and more preferably phenyl and naphthyl. Also, the aromatic hydrocarbon group represented by R ^d may have one or two or more substituents. The substituent is preferably substituted at the ortho or para position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbons, and specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl Alkyl groups with 1 to 15 carbons such as decyl and decyl; vinyls with 1 to 15 carbons such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl and decenyl alkenyl etc. The carbon number of the aliphatic hydrocarbon group that the aromatic hydrocarbon group represented by R ^d can have is more preferably 1-7, and the aliphatic hydrocarbon group can be any of linear, branched, and cyclic, and can also be A combination of a chain base and a ring base. Also, 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< .

As an aliphatic hydrocarbon group which the aromatic hydrocarbon group represented by ^Rd may have, the group represented by the following formula etc. are mentioned. In the formula, * represents a bonding bond.

[chemical 13]

As the aromatic hydrocarbon group which may have a substituent represented by ^Rd , the group represented by the following formula etc. are mentioned. In the formula, * represents a bonding bond.

[chemical 14]

The carbon number of the heterocyclic group represented by R ^d is preferably 3-20, more preferably 3-10, still more preferably 3-5. As this heterocyclic group, a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, a carbazolyl group, etc. are mentioned. In addition, the heterocyclic group represented by ^Rd may have one or more substituents, and the substituents may be the same as those exemplified as the substituents that the aromatic hydrocarbon group represented by ^Rb may have. foundation.

Among them, R ^d is preferably an aromatic hydrocarbon group with a substituent, and as the substituent, it is preferably a chain alkyl group with 1 to 7 carbons (more preferably 1 to 3 carbons), and the number of substituents is relatively small. Preferably, they are 2 or more and 5 or less.

Compound (c3) and compound (c4) can be produced by the production method described in Japanese Patent Application Publication No. 2014-500852 or International Publication No. 2008-078678.

[式中，R ^j為碳數1～3之烷基，R ⁱ為式*-R ^j1-O-R ^j2所表示之基[此處，R ^j1表示碳數1～4之直鏈狀或分枝狀之可經鹵素原子取代之脂肪族烴基，R ^j2表示碳數1～4之直鏈狀或分枝狀之可經鹵素原子取代之烷基]， R ⁱ及R ^j中所含之氫原子可經鹵素原子取代。q及r為1] 所表示之基，R ^c為碳數1～4之烷基，且p為1。 作為化合物(c3)之市售品，可例舉NCI-831(ADEKA公司製造)。 The compound (c3) is preferably the following compound, that is, R ^a is an alkyl group having 1 to 15 carbon atoms which may have a substituent, R ^b is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and R ^c is An alkyl group with 1 to 10 carbons, and p is 1 or 2, more preferably the following compound, that is, R ^a is an alkyl group with 1 to 4 carbons that may have a substituent, and R ^b is the following formula: 15]

[In the formula, R ^j is an alkyl group with 1 to 3 carbons, and R ⁱ is a group represented by the formula *-R ^j1 -OR ^j2 [Here, R ^j1 represents a linear or branched chain with 1 to 4 carbons. aliphatic hydrocarbon group that can be substituted by halogen atom, R ^j2 represents a straight-chain or branched alkyl group with 1 to 4 carbon atoms that can be substituted by halogen atom], hydrogen atoms contained in R ⁱ and R ^j It may be substituted by a halogen atom. q and r are groups represented by 1], R ^c is an alkyl group having 1 to 4 carbon atoms, and p is 1. As a commercial item of compound (c3), NCI-831 (made by ADEKA company) is mentioned.

The compound (c4) is preferably the following compound, that is, R ^a is an alkyl group having 1 to 10 carbon atoms which may have a substituent, R ^b is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and R ^c is An alkyl group having 1 to 4 carbon atoms, and R ^d represents an aromatic hydrocarbon group which may have a substituent. As a commercial item of compound (c4), Irgacure OXE03 (made by BASF Corporation) is mentioned.

The alkylphenone compound is a compound having a partial structure represented by formula (d4) or a partial structure represented by formula (d5). In these partial structures, the benzene ring may have a substituent.

[chemical 16]

As a compound having a structure represented by formula (d4), 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propane-1-one, 2-dimethyl Amino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl ]-1-[4-(4-morpholinyl)phenyl]butan-1-one, etc. Commercial items such as Irgacure 369, 907, and 379 (the above are manufactured by BASF Corporation) can be used. As a compound having a structure represented by formula (d5), 2-hydroxyl-2-methyl-1-phenylpropane-1-one, 2-hydroxyl-2-methyl-1-[4- (2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1- Ketone oligomers, α,α-diethoxyacetophenone, benzoyl dimethyl ketal, etc. In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (d4).

Examples of the biimidazole compound include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2' -bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4', 5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl) Biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), biimidazole in which the 4,4',5,5'-position phenyl is substituted by an alkoxycarbonyl group Compounds (for example, refer to Japanese Patent Application Laid-Open No. 7-10913, etc.) and the like. Among them, compounds represented by the following formulas and mixtures thereof are preferred.

[chemical 17]

Examples of trioxane compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-trimethoxyphenyl, 2,4-bis(trichloromethyl) Methyl)-6-(4-methoxynaphthyl)-1,3,5-trimethanyl, 2,4-bis(trichloromethyl)-6-helianthyl-1,3,5-trimethacin , 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three methionyl, 2,4-bis(trichloromethyl)-6-[ 2-(5-Methylfuran-2-yl)ethenyl]-1,3,5-trisulfone, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) Vinyl]-1,3,5-tris(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]- 1,3,5-trimethoxyl, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-trimethoxyphenyl wait.

The acylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzoyldiphenylphosphine oxide or the like.

The content of the polymerization initiator (B) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the total amount of the curable resin (A) contained in the curable resin composition and optionally the compound (C). parts, more preferably 0.5 to 15 parts by mass, still more preferably 1 to 12 parts by mass. When the content of the polymerization initiator (B) is within the above range, it is easy to form a pattern with a good shape by exposure and development, and it is easy to improve the curability at low temperature. In addition, as the sensitivity is increased, the exposure time tends to be shortened, so the productivity of color filters and the like is improved.

(Compound (C) having two or more polymerizable unsaturated bonds) In the curable resin composition of the present invention, the compound (C) having two or more polymerizable unsaturated bonds may or may not be contained. From the viewpoint of making it easy to adjust the amount of double bonds in the curable resin composition to the above-mentioned preferred range, the amount of solid content based on the curable resin composition of the compound (C) having two or more polymerizable unsaturated bonds The amount W _C (mass %) is preferably 20 mass % or less, more preferably 15 mass % or less, further preferably 10 mass % or less. The lower limit of W _C may be 0% by mass or more. As a compound (C), the compound which has 2 or more polymerizable ethylenically unsaturated bonds, for example, a (meth)acrylate compound is mentioned, for example.

Such compound (C) is not particularly limited, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di Pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetra Pentaerythritol nona(meth)acrylate, tris(2-(meth)acryloxyethyl)isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol Hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone Modified dipentaerythritol hexa(meth)acrylate.

(Compound J having 1 polymerizable unsaturated bond) The curable resin composition of the present invention may contain a compound (J) having one polymerizable unsaturated bond. In the case of containing a compound (J) having one polymerizable unsaturated bond, from the viewpoint of improving the solvent resistance of the obtained cured film, the amount of solid content based on the curable resin composition of the compound (J) The content thereof is preferably at most 0.5% by mass, more preferably at most 0.3% by mass, still more preferably at most 0.2% by mass, even more preferably at most 0.1% by mass. The lower limit of the content of the compound (J) may be 0% by mass or more.

(Color D) The curable resin composition of the present invention may further contain at least one colorant (D). When the curable resin composition of the present invention contains at least one colorant (D), the composition can be suitably used as a colored curable resin composition for producing a resist layer in a color filter. Moreover, when the curable resin composition of this invention which has the said composition is used as a color photoresist composition, it can be darkened, and can easily achieve a desired color. The coloring agent may be any of dyes and pigments, but preferably includes pigments. As the pigment, known pigments can be used, for example, pigments classified as pigments (Pigment) in the Dye Index (published by The Society of Dyers and Colourists).

Specifically, examples include: C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125 , 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268 , 269, 273, 291 and other red pigments; C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 16, 60 and other blue pigments; C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments; C.I. Pigment Green 7, 36, 58, 59 and other green pigments; C.I. Pigment Brown 23, 25 and other brown pigments; C.I. Pigment Black 1, 7 and other black pigments, etc.

Pigments can also be treated as follows if necessary: turpentine treatment, surface treatment using pigment derivatives with acidic or basic groups introduced, grafting treatment on the surface of pigments with polymer compounds, micronization with sulfuric acid, etc. Micronization treatment, cleaning treatment with organic solvents or water to remove impurities, treatment to remove ionic impurities by ion exchange method, etc. The pigment preferably has a uniform particle size. Moreover, by carrying out the dispersion treatment by containing the pigment dispersant (F), it is possible to obtain a pigment dispersion liquid in a state where the pigment is uniformly dispersed in the solution.

As said pigment dispersant (F), surfactants, such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, are mentioned, for example. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, in terms of trade names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Lubrizol), EFKA (manufactured by CIBA Co., Ltd.) ), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie), etc.

When the pigment dispersant (F) is used, the amount used is preferably from 1% by mass to 100% by mass, more preferably from 5% by mass to 50% by mass, based on the total amount of the pigment. When the usage-amount of a pigment dispersant exists in the said range, the pigment dispersion liquid of a uniform dispersion state tends to be obtained.

In the colorant (D), the pigment content is preferably at least 50% by mass, more preferably at least 70% by mass, further preferably at least 90% by mass, particularly preferably at least 95% by mass, and may be 100% by mass .

染料、酞菁染料、蒽醌染料、萘醌染料、醌亞胺染料、次甲基染料、甲亞胺染料、方酸鎓染料、吖啶染料、苯乙烯基染料、香豆素染料、喹啉染料及硝基染料等。該等之中，較佳為有機溶劑可溶性染料。The coloring agent (D) may contain a dye. The dye is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. As dyes, for example, compounds classified as those having a hue other than pigments in the Dye Index (published by The Society of Dyers and Colourists), or known dyes described in Dyeing Notes (Yer Dyeing Co., Ltd.). Also, depending on the chemical structure, there may be mentioned: azo dyes, cyanine dyes, triphenylmethane dyes, 𠮿

Dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, amethymine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes, etc. Among these, organic solvent-soluble dyes are preferred.

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

In the colorant (D), the content of the dye is preferably at most 50% by mass, more preferably at most 30% by mass, further preferably at most 10% by mass, especially preferably at most 5% by mass, or may be 0% by mass .

The content of the colorant (D) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, and still more preferably from 10 to 50% by mass, based on the total amount of solid content of the curable resin composition. If the content of the colorant (D) is within the above range, the color density of the color filter is sufficient, and the composition can contain a necessary amount of curable resin (A), so it can form a color filter with sufficient mechanical strength. pattern.

In particular, in curable resin compositions requiring darkening, the content of the colorant (D) is preferably 15 to 60% by mass, more preferably 20 to 55% by mass, more preferably 23 to 50% by mass. If the content of the colorant (D) is within the above range, a particularly high color density can be achieved when making a color filter, and a necessary amount of curable resin (A) can be contained in the composition, so it can be formed Pattern with sufficient mechanical strength.

、N-苯基甘胺酸等。 (Polymerization start aid E) The curable resin composition of this invention may further contain at least 1 kind of polymerization start aid (E). A polymerization initiation aid is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound whose polymerization is initiated by a polymerization initiator. In the case where the polymerization initiation aid (E) is included, it can usually be used in combination with the polymerization initiation agent (B). Examples of polymerization initiation aids (E) include: 4,4'-bis(dimethylamino)benzophenone (commonly known as Michelerone), 4,4'-bis(diethylamine) base) benzophenone, 9,10-dimethoxyanthracene, 2,4-diethyl-9-oxosulfur

, N-phenylglycine, etc.

In the case of using these polymerization initiation aids (E), the content thereof is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the total amount of the curable resin (A) and the optionally included polymerizable compound (C). parts by mass, more preferably 0.5 to 20 parts by mass. When the amount of the polymerization initiation auxiliary agent (E) is within this range, it is possible to form a pattern with a higher sensitivity, and there is a tendency for the productivity of color filters and the like to improve.

(solvent H) The curable resin composition of the present invention may further contain at least one solvent (H). The solvent is not particularly limited, and those commonly used in this field can be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -O- in the molecule and not containing -COO-), ether solvents (solvents containing Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (containing OH in the molecule and not containing -O-, -CO - and -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfide, etc.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isopentyl acetate ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetyl acetate, ethyl acetyl acetate, Cyclohexanol acetate and γ-butyrolactone, etc.

Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol , tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol Alcohol dibutyl ether, anisole, phenetole and methyl anisole, etc.

Examples of ether ester solvents include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropane Methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2 - Ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Ester, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate, etc. .

Examples of ketone solvents include: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2 -Pentanone, cyclopentanone, cyclohexanone, diacetone alcohol, isophorone, etc.

The alcohol solvent may, for example, be methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol or glycerin.

The aromatic hydrocarbon solvent may, for example, be benzene, toluene, xylene or 1,3,5-trimethylbenzene.

The amide solvent may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone.

The solvent (H) preferably contains at least one selected from the group consisting of ether solvents, ether ester solvents, and ketone solvents, more preferably includes ether solvents and ether ester solvents, and further preferably includes propylene glycol monomethyl Ether, and Propylene Glycol Monomethyl Ether Acetate.

The content of the solvent (H) is preferably from 30 to 80% by mass, more preferably from 35 to 75% by mass, based on the total amount of the curable resin composition of the present invention. In other words, the solid content of the curable resin composition is preferably from 20 to 70% by mass, more preferably from 25 to 65% by mass. If the content of the solvent (H) is within the above range, the flatness during coating becomes good, and, for example, when a colorant is contained, the color density will not be insufficient when forming a color filter, so there will be display Tendency to improve properties.

(leveling agent G) The curable resin composition of the present invention may further contain at least one leveling agent. The leveling agent (G) may, for example, be a silicone-based surfactant, a fluorine-based surfactant, or a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

As a polysiloxane-type surfactant, the thing which has a siloxane bond in a molecule|numerator, etc. are mentioned. Specifically, Toray Silicone DC3PA, same series SH7PA, same series DC11PA, same series SH21PA, same series SH28PA, same series SH29PA, same series SH30PA, same series SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd. ), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (Momentive High-Tech Materials Japan Co., Ltd. manufacturing), etc.

As said fluorine-type surfactant, what has a fluorocarbon chain in a molecule|numerator, etc. are mentioned. Specifically, examples include: Fluorad (registered trademark) FC430, same series FC431 (manufactured by Sumitomo 3M Co., Ltd.); MEGAFAC (registered trademark) F142D, same series F171, same series F172, same series F173, same series F177, Same series F183, same series F554, same series R30, same series RS-718-K (manufactured by DIC Corporation); Eftop (registered trademark) EF301, same series EF303, same series EF351, same series EF352 (Mitsubishi Materials Corporation Kasei Co., Ltd.); Surflon (registered trademark) S381, same series S382, same series SC101, same series SC105 (manufactured by AGC Co., Ltd. (formerly Asahi Glass Co., Ltd.)); and E5844 (Daikin Institute of Fine Chemicals Co., Ltd.), etc.

Examples of the polysiloxane-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, MEGAFAC (registered trademark) R08, BL20 of the same series, F475 of the same series, F477 of the same series, F443 of the same series (manufactured by DIC Co., Ltd.), etc. are mentioned.

When the leveler (G) is included, the content of the leveler (G) is preferably from 0.0005 to 0.2% by mass, more preferably from 0.0008 to 0.1% by mass, based on the total amount of the curable resin composition. In addition, the content rate of the said pigment dispersant is not included in this content rate. When the content rate of a leveling agent (G) exists in the said range, the flatness of the cured film of the curable resin composition of this invention which can be used as a color filter etc. becomes favorable.

(other ingredients) The curable resin composition of the present invention may contain fillers, other polymer compounds, adhesion promoters, antioxidants such as 2,2'-methylenebis(4-methyl-6-tert-butylphenol) as needed , light stabilizer, chain transfer agent such as n-dodecyl mercaptan and other additives known in the technical field.

<Manufacturing method of curable resin composition> The curable resin composition of the present invention can be prepared, for example, by mixing curable resin (A), polymerization initiator (B), and optionally used coloring agent (D), polymerization initiation aid (E), leveling It is prepared by mixing agent (G), solvent (H), compound (C) and other components. The colorant (D) can also be prepared using the above-mentioned pigment dispersion liquid. The intended curable resin composition can be prepared by mixing the remaining components in the pigment dispersion so as to have a specific concentration. In addition, the curable resin composition after mixing is preferably filtered through a filter having a pore diameter of about 0.01 to 10 μm.

＜Manufacturing method of cured film＞ As a method of manufacturing the patterned cured film from the curable resin composition of this invention, a photolithography method, an inkjet method, a printing method, etc. are mentioned. Among them, photolithography is preferred. Photolithography is a method in which the above-mentioned resin composition is applied to a substrate, dried to form a composition layer, and the composition layer is exposed through a photomask to be developed. Regarding the unpatterned cured film, in the photolithography method, the cured film of the above-mentioned composition layer can be formed without using a mask and/or without performing development during exposure. Either of the patterned cured film formed in this way and the unpatterned cured film is the cured film of this invention. The thickness of the produced cured film is not particularly limited, and can be appropriately adjusted according to the purpose or use, for example, 0.1-30 μm, preferably 0.1-20 μm, and more preferably 0.5-6 μm.

As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with silica on the surface; or polycarbonate, polymethylmethacrylate, polyparaffin Resin boards such as ethylene phthalate; silicon; aluminum, silver, silver/copper/palladium alloy films, etc. formed on the above substrates. Another cured film (such as another color filter, etc.), resin layer, transistor, circuit, etc. may also be formed on these substrates.

The formation of the cured film (for example, pixels of each color) using photolithography can be performed by known or commonly used devices or conditions. For example, it can be produced as follows. First, the resin composition is coated on the substrate, and the volatile components such as the solvent are removed and dried by heat drying (pre-baking) and/or reduced pressure drying to obtain a smooth resin composition layer. The coating method may, for example, be a spin coater, a slit coater, or a slit and spin coater. The temperature for heating and drying is preferably from 30 to 120°C, more preferably from 50 to 110°C. Also, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes. In the case of drying under reduced pressure, it is preferably carried out at a temperature range of 20-25°C under a pressure of 50-150 Pa. The thickness of the resin composition layer is not particularly limited, and may be appropriately selected according to the thickness of the intended cured film.

Next, the resin composition layer is exposed through a photomask for forming a target pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use can be used. As a light source used for exposure, the light source which generate|occur|produces the light of the wavelength of 250-450 nm is preferable. For example, light below 350 nm can be cut with a filter that cuts off that wavelength range, or light around 436 nm, 408 nm, or 365 nm can be cut with a bandpass filter that takes out these wavelength ranges Selectively removed. Specifically, as a light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned. Also, the exposure dose at a wavelength of 365 nm is preferably 50 to 300 J/cm ² , more preferably 60 to 200 J/cm ² , and still more preferably 65 to 180 J/cm ² . In order to uniformly irradiate the entire exposure surface with parallel light, or to accurately align the mask and the substrate on which the resin composition layer is formed, it is preferable to use exposure devices such as a mask alignment exposure machine and a stepper.

The exposed resin composition layer is developed by contacting with a developer to form a pattern on the substrate. By image development, the unexposed part of a resin composition layer melt|dissolves in a developing solution, and is removed. As a developing solution, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration in the aqueous solution of these basic compounds is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass. Furthermore, the developer may also contain a surfactant. The developing method may be any one of the liquid covering method, the dipping method, and the spraying method. Furthermore, it is also possible to incline the board|substrate at an arbitrary angle at the time of image development. After image development, it is preferable to perform water washing.

Furthermore, it is preferable to perform post-baking on the obtained pattern. In order to form cured films such as color filters used in organic EL (Electroluminescence) display devices, the post-baking temperature can also be below 200°C, but preferably below 170°C, more preferably 150°C the following. In the present invention, post-baking is preferably performed at a lower temperature, for example, a temperature below 130°C. The lower limit of the post-baking temperature is preferably above 70°C, more preferably above 75°C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 5 to 60 minutes. In recent years, in order to improve the manufacturing efficiency or reduce the influence on other members constituting the color filter, etc., it is also required that the curable resin composition can be sufficiently cured at a low temperature, especially when the post-baking temperature is set to, for example, In the case of low temperature such as below 150°C, it is not expected to improve the shape of the pattern by the heat of the post-baking, and it is also required to form a pattern with a good shape during exposure and development. According to the curable resin composition of this invention, since favorable pattern shape can be obtained, even if post-baking temperature is low temperature, the cured film of favorable pattern shape can be provided.

The thickness of the cured film after post-baking is, for example, preferably 3 μm or less, more preferably 2.5 μm or less. The lower limit of the thickness of the cured film is not particularly limited, but it is usually 0.3 μm or more, and may be 0.5 μm or more.

In addition to the color filter, a protective film, a spacer, etc. can also be manufactured by hardening the curable resin composition of this invention similarly to the above. Therefore, the curable resin composition of the present invention is preferably a composition for forming color filters, spacers and/or protective films.

Moreover, the present invention also provides a cured product (preferably a cured film) of the curable resin composition of the present invention. Furthermore, according to the present invention, a display device including the cured product can also be provided. The cured product of the present invention is useful as a colored layer, a spacer and/or a protective layer. The display device of the present invention including the cured product of the present invention as at least one member is useful as a display device with fewer display defects. Furthermore, according to the curable resin composition of the present invention, a good pattern shape can be formed, so its cured product can be used, for example, as a combination of a color filter, a protective film, a spacer, etc. included in a color filter substrate. It is especially suitable as a color filter for organic EL display devices. [Example]

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited to these examples. In the examples, unless otherwise specified, % and parts indicating content or usage amount are based on mass.

＜Weight average molecular weight＞ The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured using GPC method (Gel Permeation Chromatography, gel permeation chromatography) under the following conditions. The ratio (Mw/Mn) of the polystyrene-equivalent weight average molecular weight (Mw) obtained under the following conditions to the number average molecular weight (Mn) was made into molecular weight distribution. Device ; HLC-8120GPC (manufactured by Tosoh Co., Ltd.) Column ; TSK-GELG2000HXL Column temperature; 40°C Solvent ; Tetrahydrofuran [THF] Flow rate ; 1.0 mL/min Concentration of solid components in the tested liquid; 0.001-0.01% by mass Injection volume; 50 μL detector; RI Standard material for calibration; TSK standard polystyrene (STANDARD POLYSTYRENE) F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

<Synthesis Example 1: Preparation of Pigment Dispersion> (Color D) C.I. Pigment Green 59 5.9 parts C.I. Pigment Yellow 150 4.1 parts C.I. Pigment Yellow 139 1.4 parts C.I. Pigment Blue 15:4 1.0 parts (Dispersant F) Acrylic pigment dispersant 3.6 parts (solvent) Propylene glycol monomethyl ether acetate 84 parts The above-mentioned amount of coloring agent, dispersant, and solvent are mixed, and the pigment is fully dispersed using a bead mill to obtain a pigment dispersion.

<Synthesis Example 2: Preparation of Curable Resin (A1)> Into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 277 parts of propylene glycol monomethyl ether acetate were added, and the temperature was raised to 120° C. while stirring while replacing nitrogen. Then, in the monomer mixture containing 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate and 12.3 parts of dicyclopentanyl methacrylate, add 35.3 parts of peroxy-2-ethylhexyl The tertiary butyl ester was added dropwise from the dropping funnel into the above-mentioned flask over 2 hours. After completion of the dropwise addition, stirring was further carried out at 120° C. for 30 minutes to perform a copolymerization reaction to produce an addition copolymer. Thereafter, the inside of the flask was replaced with air, and 93.7 parts of acrylic acid, 1.5 parts of triphenylphosphine, and 0.8 parts of p-methoxyphenol were put into the above-mentioned addition copolymer solution, and the reaction was continued at 110° C. for 10 hours. The reaction between the epoxy group derived from glycidyl methacrylate and acrylic acid breaks the epoxy group and introduces a polymerizable unsaturated bond into the side chain of the polymer. Then, 24.2 parts of succinic anhydride was added to the reaction system, and the reaction was continued at 110°C for 1 hour, so that the hydroxyl group produced by the cleavage of the epoxy group reacted with succinic anhydride to introduce carboxyl groups into the side chain, and obtained a weight average molecular weight of 6400. Curable resin (A1) (double bond equivalent: 350 g/eq). In addition, the double bond equivalent of curable resin (A1) is calculated by analyzing the structure, molecular weight, etc. of each structural unit which comprises curable resin.

<Synthesis Example 3: Preparation of Curable Resin (A2)> 185 parts of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the temperature was raised to 120° C. while stirring while replacing nitrogen. Then, in the monomer mixture containing 140.5 parts of 2-ethylhexyl acrylate, 125.3 parts of glycidyl methacrylate and 11.2 parts of dicyclopentanyl methacrylate, add 37.4 parts of peroxy-2-ethylhexyl The tertiary butyl ester was added dropwise from the dropping funnel into the above-mentioned flask over 2 hours. After completion of the dropwise addition, stirring was further carried out at 120° C. for 30 minutes to perform a copolymerization reaction to produce an addition copolymer. Thereafter, the inside of the flask was replaced with air, and 63.5 parts of acrylic acid, 1.4 parts of triphenylphosphine, and 1.4 parts of p-methoxyphenol were put into the above-mentioned addition copolymer solution, and the reaction was continued at 120°C for 10 hours. The reaction between the epoxy group derived from glycidyl methacrylate and acrylic acid breaks the epoxy group and introduces a polymerizable unsaturated bond into the side chain of the polymer. Then, 22.1 parts of succinic anhydride was added to the reaction system, and the reaction was continued for 15 minutes, so that the hydroxyl group generated by the cleavage of the epoxy group reacted with succinic anhydride to introduce carboxyl groups into the side chain, and a curable resin with a weight average molecular weight of 6400 was obtained (A2) (double bond equivalent: 470 g/eq). In addition, the double bond equivalent of curable resin (A2) is calculated by analyzing the structure, molecular weight, etc. of each structural unit which comprises curable resin.

<Synthesis Example 4: Preparation of Curable Resin (A3)> 178 parts of propylene glycol monomethyl ether acetate were added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the temperature was raised to 100° C. while stirring while replacing nitrogen. Then, 47.1 parts of dimethyl 2,2'- Azobis(2-methylpropionate), the resultant was added dropwise into the above flask from the dropping funnel over 2 hours. After completion of the dropwise addition, stirring was further carried out at 100° C. for 30 minutes to perform a copolymerization reaction to produce an addition copolymer. Thereafter, the inside of the flask was replaced with air, and 43.8 parts of acrylic acid, 1.0 part of triphenylphosphine, and 1.0 part of dibutylhydroxytoluene were put into the above-mentioned addition copolymer solution, and the reaction was continued at 120°C for 10 hours. The reaction between the epoxy group derived from glycidyl methacrylate and acrylic acid breaks the epoxy group and introduces a polymerizable unsaturated bond into the side chain of the polymer. Then, 22.1 parts of succinic anhydride was added to the reaction system, and the reaction was continued for 1.5 hours, so that the hydroxyl group generated by the cleavage of the epoxy group reacted with succinic anhydride to introduce carboxyl groups into the side chain, and a curable resin with a weight average molecular weight of 6,500 was obtained (A3) (double bond equivalent: 670 g/eq). In addition, the double bond equivalent of curable resin (A3) was calculated by analyzing the structure, molecular weight, etc. of each structural unit which comprises curable resin.

<Synthesis Example 5: Preparation of Hardening Resin (A4)> Flow a proper amount of nitrogen into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, replace it with a nitrogen atmosphere, and add acetic acid 1-methoxy-2-propane 371 parts by mass of ester were heated to 85° C. while stirring. Then, 54 parts by mass of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ] A mixed solution of 225 parts by mass of a mixture of decane-9-yl esters, 81 parts by mass of vinyltoluene (isomer mixture), and 80 parts by mass of 1-methoxy-2-propyl acetate. On the other hand, a solution made by dissolving 30 parts by mass of a polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) in 1-methoxy-2 acetic acid was added dropwise over 5 hours. - Formed from 160 parts by mass of propyl ester. After dropping the starter solution, it was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a resin (A4) with a weight average molecular weight of 10,600.

<Preparation of Curable Resin Compositions of Examples and Comparative Examples> Each component described in Table 1 was mixed so that it might become the compounding quantity (solid content amount) described in Table 1, and the colored curable resin composition was obtained. Furthermore, the colorant D and dispersant F in Table 1 are derived from the pigment dispersion liquid obtained in Synthesis Example 1 and contained in it. Moreover, when preparing curable resin composition, propylene glycol monomethyl ether acetate was mixed so that the solid content of curable resin composition might become 14 mass %. The unit of the blending amount of each component in Table 1 is "parts by mass". Colorant (D), curable resin (A), polymerization initiator (B), polymerizable compound (C), leveling agent (G ) and dispersant (F) are the equivalent amounts of solid content.

聚合起始劑(B2)：下述式所表示之化合物 [化19]

聚合起始劑(B3)：NCI-730(ADEKA股份有限公司製；O-醯基肟化合物) 調平劑(G)：聚醚改性聚矽氧油(東麗道康寧股份有限公司製造之商品名「Toray Silicone SH8400」)。 The polymerization initiator (B), polymerizable compound (C) and leveling agent (G) are as follows. Polymerizable compound (C): ARONIX (registered trademark) M-930 (manufactured by Toagosei Co., Ltd.; glycerin triacrylate (double bond equivalent: 85 g/eq) Polymerization initiator (B1): represented by the following formula Compound of [Chem. 18]

Polymerization initiator (B2): a compound represented by the following formula [Chem. 19]

Polymerization initiator (B3): NCI-730 (manufactured by ADEKA Co., Ltd.; O-acyl oxime compound) Leveling agent (G): polyether-modified silicone oil (product of Toray Dow Corning Co., Ltd. name "Toray Silicone SH8400").

[Table 1] Colorant D Dispersant F hardening resin polymeric compound C polymerization initiator leveling agent G A1 A2 A3 A4 B1 B2 B3 Example 1 58 17 13 - 50 - - 2 - - 0.1 2 56 16 7 - 59 - - 2 - - 0.1 3 56 16 - 32 33 - - 2 - - 0.1 4 56 16 - - 56 - - 11 - - 0.1 5 58 17 13 - 50 - - - - 2 0.1 6 58 17 13 - 50 - 1 1 - - 0.1 7 58 17 - - 38 26 - 1 - - 0.1 comparative example 1 56 16 38 - 27 - - 2 - - 0.1 2 50 15 - - 33 - 39 - 2 - 0.1 3 42 12 4 - 32 - 47 - 3 - 0.1

<Calculation of double bond amount> From the double bond equivalent of curable resins A1 to A4 (A1: 350 g/eq, A2: 470 g/eq, A3: 670 g/eq), the double bond equivalent of polymerizable compound C ( 85 g/eq), and the content of each component, according to the formula: double bond amount = Σ(W _Ai /D _Ai ) + Σ(W _Ci /D _Ci ) [Wherein, W _Ai : the amount of each curable resin (A) Amount based on the solid content of the curable resin composition (mass %) D _Ai : Double bond equivalent (g/eq) of each curable resin (A) W _Ci : Combination of each compound (C) based on the curable resin The amount (mass %) of the solid content of the product D _Ci : the double bond equivalent (g/eq) of each compound (C)], and the double bond amount of each curable resin composition was calculated. The obtained results are shown in Table 2.

<Evaluation of Patternability> On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated), the curable resin composition was coated by spin coating, and then prebaked at 100° C. for 3 minutes. A composition layer is formed. After standing to cool, set the distance between the substrate on which the composition layer was formed and the quartz glass photomask to 50 μm, and use an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) at 100 mJ/cm Light irradiation was performed at an exposure amount of ² (based on 365 nm). A photomask formed with a 100 μm line-and-space pattern was used. In an aqueous developer solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, the colored composition layer after light irradiation was subjected to immersion development at 24°C for 60 seconds, and washed with water to obtain pattern. The shape of the obtained pattern was observed using a scanning electron microscope (S-4000; manufactured by Hitachi High-Tech Co., Ltd.). Table 2 shows the results of the insertion amount of the pattern end shown in FIG. 1 . The smaller the amount of insertion, the closer the shape is to vertical, and there is a tendency that peeling from the base is less likely to occur.

[Table 2] Double bond quantity [eq] Insertion amount [μm] Example 1 0.08 0.00 2 0.08 0.41 3 0.08 0.57 4 0.06 0.00 5 0.08 0.00 6 0.088 0.00 7 0.04 0.00 comparative example 1 0.11 2.08 2 0.36 1.45 3 0.44 1.14

In Comparative Examples 1 to 3, the insertion amount was large, and the pattern shape was poor. On the other hand, the insertion amount of the pattern obtained in Examples 1-7 was small, and it showed the favorable pattern shape. By post-baking these patterned cured films at, for example, 70 to 200° C., the cured film of the present invention having an excellent shape can be obtained.

Fig. 1 is a schematic diagram for explaining the amount of insertion.

Claims (9)

A curable resin composition comprising a curable resin (A) having a weight average molecular weight of 3,000 to 100,000 and a polymerization initiator (B), wherein the curable resin (A) is combined with the curable resin The amount of the solid content of the product is W _A mass %, the double bond equivalent of the curable resin (A) is D _A g/eq, and there are two or more The amount of the polymerizable unsaturated bond compound (C) based on the solid content of the curable resin composition is W _C mass %, and when the double bond equivalent of the compound (C) is D _C g/eq, borrow The amount of double bonds in 100 g of solid content of the curable resin composition calculated from the formula: Amount of double bonds = W _A / _DA + W _C /D _C is 0.09 eq or less. The curable resin composition according to claim 1, wherein the amount (W _A mass %) of the curable resin (A) based on the solid content of the curable resin composition is 20% by mass to 80% by mass. The curable resin composition according to claim 1, wherein the amount (W _C mass %) of the compound (C) having two or more polymerizable unsaturated bonds based on the solid content of the curable resin composition is from 0 to 20% by mass. The curable resin composition according to claim 1, wherein the amount of double bonds in 100 g of solid content of the curable resin composition is 0.03 eq or more. The curable resin composition according to claim 1, wherein the polymerization initiator (B) is an O-acyl oxime compound. The curable resin composition according to claim 1, which further contains a colorant. A cured film, which is a cured film of the curable resin composition according to any one of claims 1 to 6. The cured film according to claim 7, which constitutes a color filter, a spacer, and/or a protective layer contained in a color filter substrate. A display device comprising the cured film according to claim 7.

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