CN115808843A - Curable resin composition, cured film thereof, and display device - Google Patents

Abstract

The invention relates to a curable resin composition, a cured film thereof, and a display device. The present invention addresses the problem of providing a curable resin composition capable of forming a pattern having a good shape. The solution of the present invention is 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 amount of the curable resin (A) based on the amount of solid components of the curable resin composition is represented by W _A Mass%, the double bond equivalent of the curable resin (A) is represented by D _A g/eq, 2 or more units of a polymerizable group optionally contained in the curable resin compositionW represents the amount of the compound (C) having a polymerizable unsaturated bond based on the amount of the solid component of the curable resin composition _C Mass%, the double bond equivalent of the compound (C) is defined as D _C g/eq, according to the formula: double bond quantity = W _A /D _A +W _C /D _C The calculated amount of double bonds in 100g of the solid content of the curable resin composition was 0.09eq or less.

Description

Curable resin composition, cured film thereof, and display device

Technical Field

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

Background

The color filter substrate, which is a member included in the liquid crystal display device, has the following structure: a black matrix layer and color filters for forming pixels, for example, red (R), green (G), and blue (B) are formed on a transparent substrate, and a protective film is laminated thereon as the case may be. A patterned transparent pixel electrode is further formed on the upper layer. Spacers (spacers) in a columnar shape, a stripe shape, or the like are formed on the color filter substrate so as to maintain a constant interval between the color filter substrate and the TFT substrate facing each other.

The color filter, the protective film, and the spacer included in the color filter substrate may be formed using a curable resin composition. As such a curable resin composition, patent document 1 describes a curable resin composition containing a specific coloring material, a photopolymerizable compound, and an oxime ester compound as a photopolymerization initiator. A patterned cured product such as a color filter can be formed from the curable resin composition by, for example, photolithography.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2020-3614

Disclosure of Invention

Problems to be solved by the invention

In the production of the patterned cured film, the curable resin composition is exposed to light and cured in a desired pattern, and a developing step is performed in which the unexposed portion is dissolved in a developer and removed. When the above-mentioned curable resin composition known in the related art is used, the pattern shape may be deteriorated (for example, the amount of embedding may be increased) in the developing step.

Accordingly, an object of the present invention is to provide a curable resin composition capable of forming a pattern having a good shape.

Means for solving the problems

The inventors of the present invention have found that the above object can be achieved by the curable resin composition of the present invention described below. That is, the present invention includes the following aspects.

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,

a solid state of a curable resin (A) based on a curable resin compositionThe amount of the component is W _A Mass%, the double bond equivalent of the curable resin (A) is represented by D _A g/eq is W which is the amount of the compound (C) having 2 or more polymerizable unsaturated bonds contained in the curable resin composition as the case may be, based on the amount of the solid components of the curable resin composition _C Mass%, the double bond equivalent of the compound (C) is defined as D _C g/eq, according to the formula: double bond quantity = W _A /D _A +W _C /D _C The calculated amount of double bonds in 100g of the solid content of the curable resin composition was 0.09eq or less.

[ 2] the curable resin composition according to [ 1], wherein the amount (W) of the curable resin (A) is based on the amount of solid components in the curable resin composition _A Mass%) is 20 to 80 mass%.

[ 3] the curable resin composition according to [ 1] or [ 2], wherein the amount (W) of the compound (C) having 2 or more polymerizable unsaturated bonds based on the amount of the solid component of the curable resin composition _C Mass%) is 0 to 20 mass%.

The curable resin composition according to any one of [ 1] to [ 3], wherein the amount of double bonds in 100g of the solid content of the curable resin composition is 0.03eq or more.

The curable resin composition according to any one of [ 1] to [ 4], wherein the polymerization initiator (B) is an O-acyloxime compound.

The curable resin composition according to any one of [ 1] to [ 5], further comprising a colorant.

A cured film of the curable resin composition according to any one of [ 7] [ 1] to [ 6 ].

[ 8] the cured film according to [ 7], which is a color filter, a spacer and/or a protective layer included in a color filter substrate.

[ 9] A display device comprising the cured film according to [ 7] or [ 8 ].

Effects of the invention

According to the present invention, a curable resin composition capable of forming a pattern having a good shape can be provided.

Drawings

Fig. 1 is a schematic diagram for explaining the embedding amount.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the scope of the present invention. When a plurality of upper and lower limits are described for a specific parameter, any of these upper and lower limits may be combined with the lower limit to form a preferred range.

< curable resin composition >

The curable resin composition of the present invention is a curable resin composition comprising at least a curable resin (a) having a weight average molecular weight of 3,000 to 100,000, and a polymerization initiator (B), wherein the amount of the curable resin (a) based on the amount of solid components of the curable resin composition is represented by W _A Mass%, the double bond equivalent of the curable resin (A) is represented by D _A g/eq is W which is the amount of the compound (C) having 2 or more polymerizable unsaturated bonds contained in the curable resin composition as the case may be, based on the amount of the solid components of the curable resin composition _C Mass%, the double bond equivalent of the compound (C) is defined as D _C g/eq, according to the formula: double bond quantity = W _A /D _A +W _C /D _C The calculated amount of double bonds in 100g of the solid content of the curable resin composition was 0.09eq or less.

By the formula: double bond quantity = W _A /D _A +W _C /D _C The calculated amount of double bonds represents the amount of double bonds derived from the curable resin (a) and the compound (C) having 2 or more polymerizable unsaturated bonds contained in 100g of the solid content of the curable resin composition.

[ in the formula, W _A Represents the amount (% by mass) of the curable resin (A) based on the amount of the solid components of the curable resin composition, D _A Represents the double bond equivalent of the curable resin (A)(g/eq)，W _C Represents the amount (% by mass) of the compound (C) having 2 or more polymerizable unsaturated bonds contained as the case may be in the curable resin composition based on the amount of the solid components of the curable resin composition, D _C Double bond equivalent (g/eq) ]of the compound (C)

When the amount of double bonds is more than 0.09eq, a satisfactory pattern shape cannot be obtained in the formation of a patterned cured product such as a color filter. Here, the curable resin (a) is a resin having a weight average molecular weight described later, and is an essential component of the curable resin composition of the present invention. The compound (C) having 2 or more polymerizable unsaturated bonds is a compound having 2 or more polymerizable unsaturated bonds, for example, a compound having 2 or more ethylenically unsaturated bonds, and is not an essential component of the curable resin composition. In the present specification, the compound refers to a compound having a molecular weight of 2000 or less. Further, the compound (C) having 2 or more polymerizable unsaturated bonds may or may not be contained in the curable resin composition, and in the case where the compound (C) is not contained, W is _C =0, so the double bond amount can be represented by W _A /D _A And (6) calculating.

By the formula: double bond quantity = W _A /D _A +W _C /D _C The calculated amount of double bonds is 0.09eq or less, and is preferably 0.085eq or less, more preferably 0.08eq or less, from the viewpoint of facilitating the improvement of the pattern shape. In addition, from the viewpoint of easily improving the curability of the curable resin composition, it is preferably 0.03eq or more, more preferably 0.04eq or more, still more preferably 0.05eq or more, and still more preferably 0.06eq or more. As a method for making the amount of double bonds within the above range, the amount W of the curable resin (A) in the above formula based on the amount of solid components of the curable resin composition _A (mass%), amount W of Compound (C) having 2 or more polymerizable unsaturated bonds based on the amount of solid component of curable resin composition _C (mass%) is small, and the double bond equivalent D of the curable resin (A) _A (g/eq) and double bond equivalent D of Compound (C) _C (g/eq) becomes largeSince the double bond equivalent becomes small, W is adjusted to fall within the above-mentioned range _A 、D _A 、W _C 、D _C And (4) finishing. In addition, W is _A And W _C The content may be calculated from the charge ratio of each component contained in the curable resin composition or may be calculated by analysis. In addition, D _A And D _C The molecular weight of each component contained in the curable resin composition can be calculated by analyzing the structure, molecular weight, and the like, or can be measured by an infrared absorption method or a nuclear magnetic resonance method.

When the curable resin composition contains 2 or more curable resins (a) and/or 2 or more compounds (C), W can be calculated for each curable resin (a) and each compound (C) _A /D _A And W _C /D _C And calculating the double bond quantity. Therefore, the above formula can also be written as:

double bond = Σ (W) _Ai /D _Ai )+Σ(W _Ci /D _Ci )

In the formula (I), the compound is represented by,

W _Ai : the amount (% by mass) of each curable resin (a) based on the amount of solid components of the curable resin composition

D _Ai : double bond equivalent (g/eq) of each curable resin (A)

W _Ci : the amount (mass%) of each compound (C) based on the amount of solid components of the curable resin composition

D _Ci : equivalent of double bond (g/eq) of each compound (C).

For example, when the curable resin composition contains 3 types of curable resins (A1) to (A3), and 2 types of compounds (C1) and (C2), the amount of double bonds can be represented by the formula: w _A1 /D _A1 +W _A2 /D _A2 +W _A3 /D _A3 +W _C1 /D _C1 +W _C2 /D _C2 And (6) calculating.

(curable 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 the present invention may contain 1 curable resin (a), or may contain 2 or more curable resins (a). The curable resin is a resin having 1 or more than 1 polymerizable unsaturated bond, for example, an ethylenically unsaturated bond.

Examples of the curable resin (a) include the following resins [ K1] to [ K6 ].

Resin [ K1]: a copolymer having a structural unit derived from at least 1 kind (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;

resin [ K2]: a copolymer having a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter, may be referred to as "(c)");

resin [ K3]: a copolymer having a structural unit from (a) and a structural unit from (c);

resin [ K4]: a copolymer having a structural unit obtained by adding (b) to a structural unit derived from (a) and a structural unit derived from (c);

resin [ K5]: a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and a structural unit derived from (c);

resin [ K6]: a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a polycarboxylic acid and/or a carboxylic acid anhydride, and a structural unit derived from (c).

The curable resin (a) preferably contains a resin having a double bond other than a polymerizable unsaturated bond, and more preferably contains at least 1 resin selected from the group consisting of resins [ K4] to [ K6 ].

Specific examples of (a) include:

unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5, 6-tetrahydrophthalic acid, 1,2,3, 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1, 4-cyclohexenedicarboxylic acid;

carboxyl group-containing bicyclic unsaturated compounds such as methyl-5-norbornene-2, 3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

unsaturated dicarboxylic acid anhydrides such as 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, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

unsaturated mono [ (meth) acryloyloxyalkyl ] esters of 2-or more-membered polycarboxylic acids such as succinic acid mono [ 2- (meth) acryloyloxyethyl ] ester and phthalic acid mono [ 2- (meth) acryloyloxyethyl ] ester;

unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α - (hydroxymethyl) acrylic acid.

Among them, acrylic acid, methacrylic acid and the like are preferable from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an aqueous alkaline solution.

(b) For example, the polymerizable compound has a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) Preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In the present specification, "(meth) acrylic acid" means at least 1 selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth) acryloyl group" and "(meth) acrylate" and the like have the same meanings.

Examples of the (b) include a monomer (b 1) (hereinafter, sometimes referred to as "(b 1)") having an oxiranyl group and an ethylenically unsaturated bond, a monomer (b 2) (hereinafter, sometimes referred to as "(b 2)") having an oxetanyl group and an ethylenically unsaturated bond, and a monomer (b 3) (hereinafter, sometimes referred to as "(b 3)") having a tetrahydrofuranyl group and an ethylenically unsaturated bond.

Examples of (b 1) include a monomer (b 1-1) (hereinafter, sometimes referred to as "(b 1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and a monomer (b 1-2) (hereinafter, sometimes referred to as "(b 1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

Examples of (b 1-1) 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-m-vinylbenzyl 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 (glycidyloxymethyl) styrene, 2,4, 6-tris (glycidyloxymethyl) styrene, and the like.

Examples of (b 1-2) include vinylcyclohexene monoxide, 1, 2-epoxy-4-vinylcyclohexane (e.g., celloxide 2000 (manufactured by Daicel Co., ltd.), 3, 4-epoxycyclohexylmethyl (meth) acrylate (e.g., cyclomer A400 (manufactured by Daicel Co., ltd.)), 3, 4-epoxycyclohexylmethyl (meth) acrylate (e.g., cyclomer M100 (manufactured by Daicel Co., ltd.)), and 3, 4-epoxytricyclo [5.2.1.0 ] meth) acrylate ^2,6 ]Decyl esterThe compound represented by the formula (BI) and the compound represented by the formula (BII).

[ chemical formula 1]

[ formula (BI) and formula (BII) wherein R ^e And R ^f Represents 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 Represents a single bond, or-R ^g -、＊-R ^g -O-、＊-R ^g -S-or-R ^g -NH-。

R ^g Represents an alkanediyl group having 1 to 6 carbon atoms.

Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group, and the like.

As R ^e And R ^f Preferred examples thereof include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferred examples thereof include a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1, 2-diyl group, a propane-1, 3-diyl group, a butane-1, 4-diyl group, a pentane-1, 5-diyl group, and a hexane-1, 6-diyl group.

As X ^e And X ^f Preferred examples thereof include a single bond, methylene, ethylene and perylene-CH ₂ -O-and-CH ₂ CH ₂ -O-is more preferably a single bond or O-CH ₂ CH ₂ -O- (. Indicates a bond to O).

As (b 2), monomers having an oxetanyl group and a (meth) acryloyloxy group are more preferable. Examples of (b 2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyleneoxetane, 3-ethyl-3-methacryloyloxyethyloxetane, and 3-ethyl-3-acryloyloxyethyleneoxetane.

As (b 3), monomers having a tetrahydrofuranyl group and a (meth) acryloyloxy group are more preferable. Specific examples of (b 3) include tetrahydrofurfuryl acrylate (for example, viscoat V #150, manufactured by Osaka organic chemical industry Co., ltd.), tetrahydrofurfuryl methacrylate, and the like.

In the case of the resin [ K1] or the resin [ K2], (b 1) is preferable in terms of further improving the reliability of the cured film obtained, such as heat resistance and chemical resistance.

Examples of (c) include:

methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 (meth) acrylate ^2,6 ]Decan-8-yl ester (which is known by a common name in the art as "dicyclopentyl (meth) acrylate". Alternatively, tricyclodecanyl (meth) acrylate "may be mentioned) and tricyclo (meth) acrylate [5.2.1.0 ] ^2,6 ]Decen-8-yl ester (commonly known in the art by the name "dicyclopentenyl" (meth) acrylate "), (dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and propylmeth) acrylate(meth) acrylates such as benzyl enoate;

hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [2.2.1] hept-2-ene dicyclic rings such as 5, 6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5, 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like Unsaturated compounds;

dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

styrene, alpha-methylstyrene, meta-methylstyrene, para-methylstyrene, vinyltoluene, para-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene and the like.

Among them, (meth) acrylates are preferable.

In the resin [ K1], the ratio of the structural units derived from each of all the structural units constituting the resin [ K1] is preferably:

structural unit from (a): 2 to 60 mol%

Structural units from (b): 40 to 98 mol percent of the total weight of the mixture,

more preferably:

structural unit from (a): 10 to 50 mol%

Structural units from (b): 50 to 90 mol%.

When the ratio of the structural units of the resin [ K1] is within the above range, the amount of double bonds in the curable composition of the present invention can be easily adjusted to a preferred range, and the curable resin composition tends to have excellent storage stability, developability during pattern formation, and solvent resistance of the resulting cured film.

The resin [ K1] can be produced, for example, by referring to the method described in "experimental procedure for polymer synthesis" (experimental procedure for polymer synthesis) (published, published by seikagaku (strain) 1, printed 1972, 3/month, and 1/day), and the literature cited therein.

Specifically, the following methods are mentioned: the predetermined amounts of (a) and (b), the polymerization initiator, the solvent and the like are charged into a reaction vessel, oxygen is replaced with, for example, nitrogen to prepare a deoxygenated atmosphere, and heating and heat-maintaining are carried out while stirring. The polymerization initiator and the solvent used herein are not particularly limited, and those generally used in the art can be used. Examples of the polymerization initiator include azo compounds (2, 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), etc.), organic peroxides (benzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, etc.), solvents that can be used as long as the monomers are dissolved, and solvents that can be included in the curable resin composition of the present invention and are described later.

The copolymer obtained may be used as it is, as a solution after the reaction, as a concentrated or diluted solution, or as a solid (powder) taken out by a method such as reprecipitation. In particular, by using the solvent contained in the curable resin composition of the present invention as a solvent in the polymerization, the solution after the reaction can be directly used for the preparation of the curable resin composition of the present invention, and therefore, the production process of the curable resin composition of the present invention can be simplified.

In the resin [ K2], the ratio of the structural units derived from each of all the structural units constituting the resin [ K2] is preferably:

structural unit from (a): 2 to 45 mol%

Structural units from (b): 2 to 95 mol%

Structural units from (c): 1 to 65 mol percent of the total amount of the catalyst,

more preferably:

structural unit from (a): 5 to 40 mol%

Structural units from (b): 5 to 80 mol%

Structural units from (c): 5 to 60 mol%.

When the ratio of the structural units of the resin [ K2] is within the above range, the amount of double bonds in the curable composition of the present invention can be easily adjusted to a preferred range, and the curable resin composition tends to have excellent storage stability, developability during patterning, and solvent resistance, heat resistance, and mechanical strength of the resulting cured film.

The resin [ K2] can be produced, for example, in the same manner as the method described as the method for producing the resin [ K1 ].

In the resin [ K3], from the viewpoint of easily adjusting the amount of double bonds in the curable composition of the present invention to a preferred range, the ratio of the structural units derived from each among all the structural units constituting the resin [ K3] is preferably:

structural unit from (a): 2 to 60 mol%

Structural units from (c): 40 to 98 mol percent of the total weight of the mixture,

more preferably:

structural unit from (a): 10 to 50 mol%

Structural units from (c): 50 to 90 mol%.

The resin [ K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [ K1 ].

The resin [ K4] can be produced by: a copolymer of (a) and (c) is obtained, and a cyclic ether having 2 to 4 carbon atoms of (b) is added to the carboxylic acid and/or carboxylic acid anhydride of (a).

First, a copolymer of (a) and (c) was produced in the same manner as the method described as the method for producing the resin [ K1 ]. In this case, the ratio of the structural units derived from each is preferably the same as the ratio recited in resin [ K3 ].

Then, the cyclic ether having 2 to 4 carbon atoms of (b) is reacted with a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the copolymer.

After the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and (b), a reaction catalyst for a carboxylic acid or a carboxylic anhydride and a cyclic ether (for example, tris (dimethylaminomethyl) phenol, triphenylphosphine, etc.), a polymerization inhibitor (for example, hydroquinone, p-hydroxyanisole, etc.), etc. are charged into the flask and reacted at 60 to 130 ℃ for 1 to 10 hours, for example, to produce resin [ K4].

The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, based on 100 moles of (a). By setting the content within this range, the storage stability of the curable resin composition, the developability during patterning, the pattern shape, the curability at low temperatures, and the balance among solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained cured film tend to be good. The (b) used for the resin [ K4] is preferably (b 1), and more preferably (b 1-1) in view of high reactivity of the cyclic ether and difficulty in leaving unreacted (b).

The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c).

The reaction conditions such as the charging method, the reaction temperature and time may be appropriately adjusted in consideration of the production facility, the amount of heat generated by polymerization, and the like. The charging method and the reaction temperature can be appropriately adjusted in consideration of the production facility, the amount of heat generated by polymerization, and the like, as in the case of the polymerization conditions.

As for the resin [ K5], a copolymer of (b) and (c) is obtained as the first stage in the same manner as in the above-described method for producing the resin [ K1 ]. As in the above, the copolymer obtained may be used as it is, as a solution after the reaction, as a concentrated or diluted solution, or as a substance taken out as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) to the total number of moles of all the structural units constituting the copolymer is preferably:

structural units from (b): 5 to 95 mol%

Structural units from (c): 5 to 95 mol percent of the total weight of the mixture,

more preferably:

structural units from (b): 10 to 90 mol%

Structural units from (c): 10 to 90 mol%.

When the ratio of the structural units of the resin [ K5] is within the above range, the amount of double bonds in the curable composition of the present invention can be easily adjusted to a preferred range, and the balance among the storage stability of the curable resin composition, the developability during patterning, the pattern shape, the curability at low temperatures, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting cured film tends to be good.

Further, the resin [ K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride contained in (a) with the cyclic ether derived from (b) contained in the copolymer of (b) and (c) under the same conditions as the process for producing the resin [ K4].

The amount of (a) to be reacted with the copolymer is preferably 5 to 100 moles per 100 moles of (b). The (b) used in the resin [ K5] is preferably (b 1), and more preferably (b 1-1), from the viewpoint that the cyclic ether has high reactivity and unreacted (b) is less likely to remain.

The resin [ K6] is a resin obtained by further reacting a polycarboxylic acid and/or a carboxylic acid anhydride with the resin [ K5]. The hydroxyl group produced by the reaction of the cyclic ether derived from (b) with the carboxylic acid or carboxylic anhydride derived from (a) is further reacted with a polycarboxylic acid and/or carboxylic anhydride.

Examples of the polycarboxylic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, tricarballylic acid (japanese: 124881252212459\\125231249112523. Examples of the carboxylic anhydride 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, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride. The amount of the polycarboxylic acid and/or carboxylic acid anhydride to be used is preferably 0.05 to 1 mol, more preferably 0.1 to 0.5 mol, based on 1 mol of the amount of (a).

The curable resin (a) is preferably a resin having a structural unit containing an ethylenically unsaturated bond in a side chain (resin [ K4] or resin [ K5 ]), and more preferably a resin having a structural unit containing a (meth) acryloyl group in a side chain.

As the resin having a structural unit containing a (meth) acryloyl group in a side chain, for example, a resin [ K4] using a monomer having a (meth) acryloyl group such as glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3-methyl-3-methacryloyloxymethyloxetane, and tetrahydrofurfuryl acrylate as (b), and a resin [ K5] using a monomer having a (meth) acryloyl group such as acrylic acid, methacrylic acid, and succinic acid mono [ 2- (meth) acryloyloxyethyl ] ester as (a) are preferable.

In the resin [ K4] and the resin [ K5], (c) is preferably a dicarbonylimide derivative or vinyltoluene.

The weight average molecular weight of the curable resin (a) in terms of polystyrene is 3,000 to 100,000, preferably 5,000 to 40,000, and more preferably 6,000 to 30,000. When the weight average molecular weight is within the above range, the following tendency is present: for example, a cured film used as a color filter, a spacer, a protective film, or the like has increased hardness, a high residual film ratio, good solubility of an unexposed portion in a developer, an improved pattern shape, and improved pattern resolution.

The dispersity [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the curable resin (a) is preferably 1.1 to 6, and more preferably 1.2 to 4.

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

Amount (W) of the curable resin (A) based on the amount of solid components of the curable resin composition _A Mass%) is preferably 20 mass% or more, more preferably 25 mass% or more, and further preferably 30 mass% or more. The amount is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, further more preferably 65% by mass or less, and particularly preferably 60% by mass or less. When the content of the curable resin (a) is within the above range, the pattern formation is facilitated, and the pattern resolution and the residual film ratio tend to be improved. In addition, the solvent resistance of the cured film obtained is further improved. In the present specification, the "total amount of solid components" refers to an amount obtained by removing the solvent content from the total amount of the curable resin composition. The total amount of solid components and the content of each component relative thereto can be measured by a known analytical means such as liquid chromatography or gas chromatography.

(polymerization initiator B)

The polymerization initiator (B) is a compound capable of generating an active radical, an acid, or the like under the action of light or heat to initiate polymerization. The polymerization initiator (B) is not particularly limited, and examples thereof include an O-acyloxime compound, an alkylphenone compound, a bisimidazole compound, a triazine compound, and an acylphosphine oxide compound. Among them, O-acyloxime compounds are preferable. From the viewpoint of facilitating further improvement in curability of the curable resin composition, the polymerization initiator (B) preferably has a maximum absorption wavelength in the range of 365 to 390nm, and more preferably has a maximum absorption wavelength in the range of 370 to 390 nm. The curable resin composition of the present invention may contain 1 polymerization initiator (B), or may contain 2 or more polymerization initiators (B).

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

The O-acyloxime compound is a compound having a structure represented by formula (c 1). Hereinafter, the symbol denotes a bond.

[ chemical formula 2]

The compound having a carbazole skeleton is a compound having a structure represented by formula (c 2).

[ chemical formula 3]

Having nitro (-N) ₂ The compound of O) is preferably a compound having at least 1 nitro group bonded to the aromatic ring, and more preferably a compound having at least 1 nitro group bonded to the aromatic ring contained in the carbazole skeleton.

The polymerization initiator (B) is more preferably an O-acyloxime compound having a carbazole skeleton. Examples of such a compound include at least 1 selected from the group consisting of a compound represented by formula (c 3) (hereinafter, sometimes referred to as compound (c 3)) and a compound represented by formula (c 4) (hereinafter, sometimes referred to as compound (c 4)).

[ chemical formula 4]

[ in the formulae (c 3) and (c 4),

R ^a represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms, and a methylene group (-CH) contained in the aliphatic hydrocarbon group ₂ -) may be replaced by-O-, -CO-or-S-, the methine group (-CH <) contained in the above aliphatic hydrocarbon group may be replaced with-PO ₃ <, the hydrogen atom contained in the above aliphatic hydrocarbon group may be substituted with an OH group.

In the present specification, methylene group (-CH) ₂ -) etc. are replaced with-O-, in the case of-CO-or-S-, etc., the number of carbon atoms means the number of carbon atoms before substitution.

R ^b Represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, an optionally substituted heterocyclic group having 3 to 36 carbon atoms, an optionally substituted alkyl group having 1 to 15 carbon atoms, or an optionally substituted group which is a combination of an aromatic hydrocarbon group and an alkanediyl group derived from the alkyl group, wherein the aromatic hydrocarbon group contains a methylene group (-CH) ₂ -) may be replaced by-O-, -CO-, -S-, -SO ₂ -or-NR ^h -。R ^h Represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms or an alkyl group having 1 to 10 carbon atoms.

R ^c Represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms or an alkyl group having 1 to 10 carbon atoms.

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 1 or 2, more preferably 1.

R ^a The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. The aromatic hydrocarbon group includes a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group, and the like, more preferably a phenyl group and a naphthyl group, and still more preferably a phenyl group.

In addition, R ^a The aromatic hydrocarbon group represented may have 1 or 2 or more substituents. Examples of the substituent include R described later ^b The aromatic hydrocarbon group in (2) may have the same substituent.

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

As R ^a Examples of the aliphatic hydrocarbon group which may have a substituent include groups represented by the following formulae. Wherein, represents a connecting bond.

[ chemical formula 5]

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

R ^b The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group,Terphenyl group and the like, more preferably phenyl group and naphthyl group, and particularly preferably phenyl group.

In addition, R ^b The aromatic hydrocarbon group represented may have 1 or 2 or more substituents. The substituent is preferably substituted at the ortho-position or para-position of the aromatic hydrocarbon group. Examples of the substituent include alkyl groups having 1 to 15 carbon atoms such as 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, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group; a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, a bromine atom, etc.; and so on.

The alkyl group as the substituent preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms. The alkyl group as the substituent may be any of linear, branched, and cyclic, and may be a combination of a chain group and a cyclic group. Methylene group (-CH) contained in alkyl group as the substituent ₂ -) may be replaced with-O-or-S-. The hydrogen atom contained in the alkyl group may be substituted with a halogen atom such as a fluorine atom, chlorine atom, iodine atom, or bromine atom, and is preferably substituted with a fluorine atom.

With respect to as R ^b Examples of the alkyl group as a substituent of the aromatic hydrocarbon group include groups represented by the following formulae. Wherein, represents a connecting bond.

[ chemical formula 6]

[ chemical formula 7]

As R ^b The aromatic hydrocarbon group which may have a substituent(s) is represented by, for example, the following formula. Wherein, represents a connecting bond.

[ chemical formula 8]

[ chemical formula 9]

As R ^b The aromatic hydrocarbon group which may have a substituent(s) is preferably a group represented by the following formula.

[ chemical formula 10]

[ in the formula, R ⁱ Each independently represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, R ⁱ Methylene group (-CH) contained in (1) ₂ -) may be replaced by-O-or-S-, R ^j Each independently represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, q represents an integer of 1 to 5, and r represents an integer of 0 to 4. Wherein the sum of q + r is 5 or less.]

As R ⁱ And R ^j The alkyl group represented by the formula (I) may be mentioned as R ^b Examples of the substituent of the aromatic hydrocarbon group include the same ones as those of the alkyl group. R ⁱ The number of carbon atoms of (3) is preferably 2 to 8, more preferably 2 to 6. In addition, R ^j The alkyl group represented may be linear, branched, or cyclic, and is preferably linear. R ⁱ Preferably of the formula < CHEM > -R ^j1 -O-R ^j2 The group represented. Here, R ^j2 Represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom. As R ^j2 The alkyl group is preferably a linear alkyl group having 1 to 3 carbon atoms. R is ^j1 Represents an alkylene group having 1 to 10 carbon atoms which may be substituted with a halogen atom. As R ^j1 The alkylene group is preferably a linear alkylene group having 1 to 3 carbon atoms.

As R ⁱ And R ^j Examples of the halogen atom in (b) include a fluorine atom, a chlorine atom, an iodine atom and a bromine atom, and a fluorine atom is particularly preferable.

In addition, R ⁱ When a halogen atom is contained, the number thereof is preferably 2 or more and 10 or less, and more preferably 3 or more and 6 or less. R ⁱ The substitution position of the O-group is preferably ortho-or para-position. R is ^j The substitution position of the-group is preferably the ortho-position or the para-position, particularly preferably the ortho-position.

Further, q is preferably 1 to 2, and particularly preferably 1.r is preferably 0 to 2, particularly preferably 0 or 1.

R ^b The heterocyclic group represented by (a) preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and still more preferably 3 to 5 carbon atoms. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.

In addition, R ^b The heterocyclic group represented may have 1 or 2 or more substituents. The substituent includes R ^b The aromatic hydrocarbon group represented may have the same substituents as those exemplified above.

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

R ^h Represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear (linear or branched), may be cyclic, may be linear, branched or cyclic, or may be a combination of a linear group and a cyclic group. In addition, R ^h In the alkyl group of (1), methylene (-CH) ₂ -) can be replaced by-O-or-CO-.

As R ^b Specific examples of the alkyl group which may have a substituent include groups represented by the following formulae. It represents a connecting bond.

[ chemical formula 11]

Furthermore, R ^b Represented by the formula (I) wherein R is an alkyl group ^b The number of carbon atoms of the group formed by combining alkanediyl groups derived from alkyl groups represented by (a) is preferably 7 to 33, more preferably 7 to 18, and still more preferably 7 to 12. The combined group may have 1 or 2 or more substituents, and examples of the substituents include the same substituents as exemplified as the substituents which the aromatic hydrocarbon group and the alkyl group may have. As the R ^b Represented by the formula (I) wherein R is an alkyl group ^b Examples of the group formed by combining alkanediyl groups derived from the alkyl groups include aralkyl groups, and specifically, groups represented by the following formulae. Wherein, represents a connecting bond.

[ chemical formula 12]

Wherein, as R ^b The alkyl group may be substituted or may be substituted, and the alkyl group may be substituted.

R ^c The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group.

R ^c The heterocyclic group represented by (a) preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and still more preferably 3 to 5 carbon atoms. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.

R ^c The alkyl group represented by (a) preferably has 1 to 7 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms. Examples of the alkyl group include 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, and a decyl group. The alkyl group may be linear, branched, or cyclic, or may be a combination of a chain group and a cyclic group.

As R ^c The alkyl group is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, still more preferably a chain alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

R ^d The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group, and a phenyl group and a naphthyl group are more preferable.

In addition, R ^d The aromatic hydrocarbon group represented may have 1 or 2 or more substituents. The substituent is preferably substituted at the ortho-position or para-position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, and specific examples thereof include alkyl groups having 1 to 15 carbon atoms such as 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, and a decyl group; alkenyl groups having 1 to 15 carbon atoms such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl, and decenyl; and so on.

R ^d The number of carbon atoms of the aliphatic hydrocarbon group that the aromatic hydrocarbon group represented may have is more preferably 1 to 7, and the aliphatic hydrocarbon group may be any of linear, branched, and cyclic, or may be a combination of a chain group and a cyclic group. In addition, the aliphatic hydrocarbon group contains methylene (-CH) ₂ -) may be replaced by-O-, -CO-or-S-, the methine group (-CH <) can be replaced by-N <.

As R ^d Examples of the aliphatic hydrocarbon group which may be contained in the aromatic hydrocarbon group include those represented by the following formulae. Wherein, represents a connecting bond.

[ chemical formula 13]

As R ^d The aromatic hydrocarbon group which may have a substituent(s) is represented by the following formula. Wherein, represents a connecting bond.

[ chemical formula 14]

R ^d The number of carbon atoms of the heterocyclic group represented by (i) is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.

In addition, R ^d The heterocyclic group represented by (A) may have 1 or 2 or more substituents, and examples of the substituent include R ^b The aromatic hydrocarbon group may have the same substituents as those exemplified above.

Wherein R is ^d Preferably an aromatic hydrocarbon group having a substituent, and the substituent is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms), and the number of the substituents is preferably 2 or more and 5 or less.

The compound (c 3) and the compound (c 4) can be produced by the production method described in japanese patent application laid-open No. 2014-500852 or international publication No. 2008-078678.

Compound (c 3) is preferably R ^a Is an optionally substituted alkyl group having 1 to 15 carbon atoms, R ^b Is an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, R ^c A compound which is an alkyl group having 1 to 10 carbon atoms and p is 1 or 2,

more preferably R ^a Is an optionally substituted alkyl group having 1 to 4 carbon atoms, R ^b Is a group represented by the formula R ^c A compound which is an alkyl group having 1 to 4 carbon atoms and p is 1.

[ chemical formula 15]

[ in the formula, R ^j Is an alkyl group of 1 to 3 carbon atoms, R ⁱ Is of the formula ^j1 -O-R ^j2 A group [ here, R ] ^j1 Represents a linear or branched aliphatic hydrocarbon group having 1 to 4 carbon atoms which may be substituted by a halogen atom, R ^j2 Represents a linear or branched alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom ],

R ⁱ and R ^j The hydrogen atom contained in (b) may be substituted with a halogen atom. q and r are 1.]

As a commercially available product of the compound (c 3), NCI-831 (manufactured by ADEKA) can be mentioned.

Compound (c 4) is preferably R ^a Is an alkyl group having 1 to 10 carbon atoms which may have a substituent, R ^b Is an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, R ^c Is an alkyl group having 1 to 4 carbon atoms and R ^d A compound which represents an optionally substituted aromatic hydrocarbon group.

As a commercially available product of the compound (c 4), irgacure OXE03 (manufactured by BASF) can be mentioned.

The alkylphenone compound has a partial structure represented by the formula (d 4) or a partial structure represented by the formula (d 5). In these partial structures, the benzene ring may have a substituent.

[ chemical formula 16]

Examples of the compound having a structure represented by the formula (d 4) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] butan-1-one. Commercially available products such as Irgacure 369, 907, and 379 (manufactured by BASF corporation, supra) can be used.

Examples of the compound having the structure represented by the formula (d 5) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, benzildimethylketal, and the like.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d 4).

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 (see, for example, japanese patent application laid-open No. 6-75372, japanese patent application laid-open No. 6-75373, etc.), 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (alkoxyphenyl) biimidazole, 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (dialkoxyphenyl) biimidazole, 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetrakis (trialkoxyphenyl) biimidazole (see, for example, japanese patent publication No. 48-38403, japanese patent application laid-open No. 62-174204, etc.), biimidazole compounds in which the phenyl group at the 4,4',5,5' -position is substituted with an alkoxycarbonyl group (see, for example, japanese patent application laid-open No. 7-10913, etc.). Among them, compounds represented by the following formula and mixtures thereof are preferable.

[ chemical formula 17]

Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (furan-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1,3, 5-triazine, and the like.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

The content of the polymerization initiator (B) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 12 parts by mass, based on 100 parts by mass of the total amount of the curable resin (a) and the compound (C) included in some cases in the curable resin composition. When the content of the polymerization initiator (B) is within the above range, a pattern having a good shape can be easily formed by exposure and development, and curability at low temperature can be easily improved. In addition, since the exposure time tends to be shortened while achieving high sensitivity, productivity of color filters and the like is improved.

(Compound (C) having 2 or more polymerizable unsaturated bonds)

The curable resin composition of the present invention may contain the compound (C) having 2 or more polymerizable unsaturated bonds, or may not contain the compound (C) having 2 or more polymerizable unsaturated bonds. The amount W of the compound (C) having 2 or more polymerizable unsaturated bonds based on the amount of the solid component of the curable resin composition is an amount W from the viewpoint of easily adjusting the amount of double bonds in the curable resin composition to the above-described preferred range _C (mass%) is preferably 20 mass% or less, more preferably 15 mass% or less, and further preferably 10 mass% or less. W _C The lower limit of (b) may be 0% by mass or more. Examples of the compound (C) include compounds having 2 or more polymerizable ethylenically unsaturated bonds, such as (meth) acrylate compounds.

Examples of such a compound (C) include, but are not particularly limited to, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl 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, and 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 1 polymerizable unsaturated bond. In the case where the compound (J) having 1 polymerizable unsaturated bond is contained, the content of the compound (J) based on the solid content of the curable resin composition is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, further preferably 0.2% by mass or less, and further more preferably 0.1% by mass or less, from the viewpoint of improving the solvent resistance of the resulting cured film. The lower limit of the content of the compound (J) may be 0% by mass or more.

(colorant D)

The curable resin composition of the present invention may further contain at least 1 kind of colorant (D). When the curable resin composition of the present invention contains at least 1 kind of colorant (D), the composition can be suitably used as a colored curable resin composition for forming a resist layer in a color filter. The curable resin composition of the present invention having the above composition can realize a deep color when used as a color resist composition, and can easily achieve a desired color. The colorant may be any of a dye and a pigment, but preferably contains a pigment. As The Pigment, known pigments can be used, and for example, pigments classified as pigments (Pigment) in The color index (published by The Society of Dyers and Colourists) can be cited.

Specifically, there may be mentioned:

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 the like;

orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

red pigments such as 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 the like;

c.i. pigment blue 15, 15: 3. 15: 4. 15: 6. 16, 60, and the like blue pigments;

c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment;

green pigment of c.i. pigment green 7, 36, 58, 59;

c.i. brown pigments such as pigment brown 23, 25;

and black pigments such as c.i. pigment black 1 and 7.

The pigment may be subjected to rosin treatment, surface treatment using a pigment derivative or the like into which an acidic group or a basic group is introduced, grafting treatment to the surface of the pigment using a polymer compound or the like, micronization treatment using a sulfuric acid micronization method or the like, cleaning treatment for removing impurities using an organic solvent, water or the like, removal treatment of ionic impurities using an ion exchange method or the like, as required.

The pigment is preferably uniform in particle size. Further, by adding the pigment dispersant (F) and performing dispersion treatment, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant (F) include cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, and other surfactants. These pigment dispersants may be used alone, or 2 or more kinds may be used in combination. Examples of the pigment dispersant include KP (manufactured by shin-Etsu chemical Co., ltd.), FLOREN (manufactured by Kyoho chemical Co., ltd.), solsperse (manufactured by Lubrizol Corporation), EFKA (manufactured by CIBA Co., ltd.), AJISPER (manufactured by FINETECHNO Co., ltd.), disperbyk (manufactured by BYK-Chemie Co., ltd.), and the like according to their trade names.

When the pigment dispersant (F) is used, the amount thereof to be used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less, with respect to the total amount of the pigment. When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

The content of the pigment in the colorant (D) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, particularly preferably 95% by mass or more, and may be 100% by mass.

The colorant (D) may contain a dye. Known dyes can be used without particular limitation, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of The dye include compounds classified as substances having a hue other than pigments in The dye index (published by The Society of Dyers and Colourists), and known dyes described in dyeing guidelines (chromo). Further, depending on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and the like can be given. Among them, organic solvent-soluble dyes are preferable.

Specifically, there may be mentioned:

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: 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 dyes such as c.i. solvent green 1,3, 4,5, 7, 28, 29, 32, 33, 34, 35,

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, 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: 1. 91, 92, 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: 1. 58, 63, 65, 80, 104, 105, 106, 109 and the like,

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, 244, 246, 247, 245, 250, 251, 252, 257, 275, 268, 293, 268, 248;

c.i. direct dyes such as c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82,

c.i. disperse yellow 51, 54, 76;

c.i. disperse violet 26, 27;

c.i. disperse dyes such as c.i. disperse blue 1, 14, 56, 60, etc.,

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. media yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

c.i. medium 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. medium 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. intermediate 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. medium 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 dyes such as c.i. mordant green 1,3, 4,5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53,

c.i. vat dyes such as c.i. vat green 1, and the like.

The dye content in the colorant (D) is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass or less, particularly preferably 5% by mass or less, and may be 0% by mass.

The content of the colorant (D) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and still more preferably 10 to 50% by mass, based on the total amount of solid components in the curable resin composition. When the content of the colorant (D) is within the above range, the color density in the formation of a color filter is sufficient, and a pattern having sufficient mechanical strength can be formed because the curable resin (a) can be contained in a necessary amount in the composition.

In particular, in the curable resin composition requiring a rich coloration, the content of the colorant (D) is preferably 15 to 60% by mass, more preferably 20 to 55% by mass, and still more preferably 23 to 50% by mass, based on the total amount of the solid components in the curable resin composition. When the content of the colorant (D) is within the above range, a particularly high color density can be achieved in the production of a color filter, and a pattern having sufficient mechanical strength can be formed because a necessary amount of the curable resin (a) can be contained in the composition.

(polymerization initiation assistant E)

The curable resin composition of the present invention may further contain at least 1 polymerization initiation aid (E). The polymerization initiation aid is a compound for promoting polymerization of a polymerizable compound whose polymerization is initiated by a polymerization initiator, or a sensitizer. When the polymerization initiator (E) is contained, it is usually used in combination with the polymerization initiator (B).

Examples of the polymerization initiation aid (E) include 4,4' -bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4' -bis (diethylamino) benzophenone, 9, 10-dimethoxyanthracene, 2, 4-diethylthioxanthone, and N-phenylglycine.

When these polymerization initiation aids (E) are used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the total amount of the curable resin (a) and the polymerizable compound (C) included in some cases. When the amount of the polymerization initiation aid (E) is within this range, a pattern can be formed with higher sensitivity, and the productivity of a color filter or the like tends to be improved.

(solvent H)

The curable resin composition of the present invention may further contain at least 1 kind of solvent (H). The solvent is not particularly limited, and a solvent generally used in this field can be used. <xnotran> , ( -COO-, -O- ), ( -O-, -COO- ), ( -COO- -O- ), ( -CO-, -COO- ), ( OH, -O-, -CO- -COO- ), , , . </xnotran>

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ -butyrolactone.

Examples of the ether solvent 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 ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methyl anisole.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 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.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, diacetone alcohol, and isophorone.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, and the like.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, and the like.

Examples of the amide solvent include N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.

The solvent (H) preferably contains 1 or more selected from the group consisting of an ether solvent, an ether ester solvent, and a ketone solvent, more preferably contains an ether solvent and an ether ester solvent, and still more preferably contains propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

The content of the solvent (H) is preferably 30 to 80% by mass, more preferably 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 20 to 70% by mass, and more preferably 25 to 65% by mass. When the content of the solvent (H) is within the above range, the following tendency is present: the flatness at the time of coating is good, and, for example, in the case of containing a colorant, the color density is not insufficient at the time of forming a color filter, and therefore, the display characteristics are good.

(leveling agent G)

The curable resin composition of the present invention may further contain at least 1 leveling agent. Examples of the leveling agent (G) include a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, examples thereof include TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH8400 (trade name, manufactured by Toray-Corning corporation), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu chemical industry Co., ltd.), TSF400, TSF401, F410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Nippon Megaku Co., ltd.).

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, examples thereof include FLOURAD (registered trademark) FC430, FLOURAD FC431 (manufactured by Sumitomo 3M Co., ltd.), MEGAFACE F142D, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F177, MEGAFACE F183, MEGAFACE F554, MEGAFACE R30, MEGAFACE RS-718-K (manufactured by DIC (Co., ltd.), EFTOP EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (manufactured by Mitsubishi Synthesis materials, inc.), SURFON (registered trademark) S381, SURFON S382, EFON SC101, SURFON SC105 (manufactured by AGC (SURFLON NITRIN CO., LTD.), and E5844 (manufactured by Seikagan chemical research institute).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, MEGAFACE (registered trademark) R08, MEGAFACE BL20, MEGAFACE F475, MEGAFACE F477, and MEGAFACE F443 (available from DIC, inc.) can be mentioned.

When the leveling agent (G) is contained, the content of the leveling agent (G) is preferably 0.0005 to 0.2% by mass, more preferably 0.0008 to 0.1% by mass, based on the total amount of the curable resin composition. The content does not include the content of the pigment dispersant. When the content of the leveling agent (G) is within the above range, the cured film of the curable resin composition of the present invention used as a color filter or the like can be made excellent in flatness.

(other Components)

The curable resin composition of the present invention may contain, as required, additives known in the art, such as a filler, another polymer compound, an adhesion promoter, an antioxidant such as 2,2' -methylenebis (4-methyl-6-tert-butylphenol), a light stabilizer, and a chain transfer agent such as n-dodecylmercaptan.

< method for producing curable resin composition >

The curable resin composition of the present invention can be prepared by, for example, mixing the curable resin (a), the polymerization initiator (B), and, if necessary, the colorant (D), the polymerization initiation aid (E), the leveling agent (G), the solvent (H), the compound (C), and other components.

The colorant (D) can also be prepared using the above-described pigment dispersion liquid. The target curable resin composition can be prepared by mixing the remaining components into the pigment dispersion so as to have a predetermined concentration. The mixed curable resin composition is preferably filtered through a filter having a pore diameter of about 0.01 to 10 μm.

< method for producing cured film >

Examples of the method for producing a patterned cured film from the curable resin composition of the present invention include photolithography, an inkjet method, a printing method, and the like. Among them, photolithography is preferable. The photolithography method is as follows: the resin composition is applied to a substrate, dried to form a composition layer, and the composition layer is exposed to light through a photomask and developed. The non-patterned cured film can be formed as a cured film of the composition layer by a photolithography method without using a photomask and/or without developing it at the time of exposure. The patterned cured film and the unpatterned cured film thus formed are the cured films of the present invention.

The thickness of the cured film to be produced is not particularly limited, and may be suitably adjusted depending on the purpose, use, and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, there can be used: glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda-lime glass coated with silica on the surface; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon; a substrate such as an aluminum, silver/copper/palladium alloy thin film is formed on the substrate. Other cured films (for example, other color filters), resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of the cured film (for example, each color pixel) by the photolithography can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.

First, a resin composition is applied onto a substrate, and is dried by removing volatile components such as a solvent by heat drying (prebaking) and/or drying under reduced pressure, thereby obtaining a smooth resin composition layer.

Examples of the coating method include spin coating, slit and spin coating.

The temperature for the heat drying is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

When the drying is performed under reduced pressure, the drying is preferably performed under a pressure of 50 to 150Pa and at a temperature of 20 to 25 ℃.

The thickness of the resin composition layer is not particularly limited, and may be appropriately selected depending on the thickness of the intended cured film.

Next, the resin composition layer is exposed to light through a photomask for forming a target pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use may be used.

The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, a filter that cuts off this wavelength region may be used for light less than 350nmTo cut off; alternatively, band pass filters (band pass filters) for extracting these wavelength regions may be used for light around 436nm, 408nm, or 365 nm. Specifically, the light source includes a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, and the like. The exposure dose based on the 365nm wavelength is preferably 50 to 300J/cm ² More preferably 60 to 200J/cm ² More preferably 65 to 180J/cm ² 。

In order to uniformly irradiate the entire exposure surface with parallel light beams or to accurately align the photomask with the substrate on which the resin composition layer is formed, an exposure apparatus such as a mask aligner or a stepper is preferably used.

The exposed resin composition layer is brought into contact with a developer to develop the resin composition layer, thereby forming a pattern on the substrate. By the development, the unexposed portion of the resin composition layer is dissolved in a developing solution and removed. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.

The developing method may be any of spin coating immersion, spraying, and the like. In addition, the substrate may be tilted at an arbitrary angle during development.

After development, washing with water is preferred.

Further, the obtained pattern is preferably subjected to post baking. The post-baking temperature may be 200 ℃ or lower, preferably 170 ℃ or lower, and more preferably 150 ℃ or lower, for forming a cured film such as a color filter used in an organic EL display device. In the present invention, the post-baking is preferably performed at a lower temperature, for example, 130 ℃. The lower limit of the post-baking temperature is preferably 70 ℃ or higher, and more preferably 75 ℃ or higher. The post-baking time is preferably 1 to 120 minutes, more preferably 5 to 60 minutes. In recent years, in order to improve the production efficiency and reduce the influence on other members constituting a color filter or the like, it is also required that a curable resin composition can be sufficiently cured at a low temperature, and particularly, in the case where the post-baking temperature is low, for example, about 150 ℃. According to the curable resin composition of the present invention, a good pattern shape can be obtained, and therefore, a cured film having a good pattern shape can be provided even if the post-baking temperature is low.

The thickness of the cured film after post-baking is, for example, preferably 3 μm or less, and more preferably 2.5 μm or less. The lower limit of the thickness of the cured film is not particularly limited, but 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, and the like can be produced by curing the curable resin composition of the present invention in the same manner as described above. Therefore, the curable resin composition of the present invention is preferably a composition for forming a color filter, a spacer and/or a protective film.

The present invention also provides a cured product (preferably a cured film) of the curable resin composition of the present invention. Further, the present invention can provide a display device comprising the cured product. 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 comprising the cured product of the present invention as at least 1 member is useful as a display device with few display defects. Further, since the curable resin composition of the present invention can form a good pattern shape, a cured product thereof can be used as a composition for forming, for example, a color filter, a protective film, a spacer, and the like included in a color filter substrate, and is particularly suitable as a color filter of an organic EL display device.

Examples

The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples, unless otherwise specified,% and part indicating the content or amount used are based on mass.

< weight average molecular weight >

The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by GPC under the following conditions. The ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in terms of polystyrene obtained under the following conditions was taken as the molecular weight distribution.

The device comprises the following steps: HLC-8120GPC (manufactured by TOSOH Co., ltd.)

Column: TSK-GELG2000HXL

Column temperature: 40 deg.C

Solvent: tetrahydrofuran [ THF ]

Flow rate: 1.0mL/min

Concentration of solid component in test solution: 0.001 to 0.01 mass%

Injection amount: 50 μ L

A detector: RI (Ri)

Calibration standard substance: TSK STANDARD POLYSTYRENE

F-40、F-4、F-288、A-2500、A-500

(manufactured by TOSOH corporation)

< Synthesis example 1: preparation of pigment Dispersion

(colorant D)

The colorant, the dispersant, and the solvent in the above amounts are mixed, and the pigment is sufficiently dispersed using a bead mill, thereby obtaining a pigment dispersion liquid.

< Synthesis example 2: preparation of curable resin (A1)

277 parts of propylene glycol monomethyl ether acetate was charged into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while being replaced with nitrogen, and the temperature was raised to 120 ℃.

Subsequently, 35.3 parts of t-butyl peroxy-2-ethylhexanoate was added to a monomer mixture comprising 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate and 12.3 parts of dicyclopentyl methacrylate, and the mixture was dropped from a dropping funnel into the flask over 2 hours. After the completion of the dropwise addition, the mixture was further stirred at 120 ℃ for 30 minutes to effect a copolymerization reaction to produce an addition copolymer.

Thereafter, the flask was purged with air, and 93.7 parts of acrylic acid, 1.5 parts of triphenylphosphine and 0.8 part of p-hydroxyanisole were added to the above addition copolymer solution, and the reaction was continued at 110 ℃ for 10 hours, whereby epoxy groups were cleaved by the reaction between epoxy groups derived from glycidyl methacrylate and acrylic acid, and polymerizable unsaturated bonds were introduced into the side chains of the polymer. Subsequently, 24.2 parts of succinic anhydride was added to the reaction system, and the reaction was continued at 110 ℃ for 1 hour to introduce carboxyl groups into the side chains by reacting hydroxyl groups generated by cleavage of the epoxy groups with succinic anhydride, thereby obtaining a curable resin (A1) (double bond equivalent: 350 g/eq) having a weight average molecular weight of 6400. The double bond equivalent of the curable resin (A1) is calculated by analyzing the structure, molecular weight, and the like of each structural unit constituting the curable resin.

< Synthesis example 3: preparation of curable resin (A2)

185 parts of propylene glycol monomethyl ether acetate was charged into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the temperature was raised to 120 ℃ while stirring was performed with nitrogen substitution.

Subsequently, 37.4 parts of tert-butyl peroxy-2-ethylhexanoate was added to a monomer mixture comprising 140.5 parts of 2-ethylhexyl acrylate, 125.3 parts of glycidyl methacrylate and 11.2 parts of dicyclopentanyl methacrylate, and the mixture was added dropwise from a dropping funnel to the flask over 2 hours. After the completion of the dropwise addition, the mixture was further stirred at 120 ℃ for 30 minutes to effect a copolymerization reaction to produce an addition copolymer.

Thereafter, the flask was purged with air, 63.5 parts of acrylic acid, 1.4 parts of triphenylphosphine and 1.4 parts of p-hydroxyanisole were added to the above addition copolymer solution, and the reaction was continued at 120 ℃ for 10 hours, whereby epoxy groups were cleaved by the reaction between epoxy groups derived from glycidyl methacrylate and acrylic acid, and polymerizable unsaturated bonds were introduced into the side chains of the polymer. Then, 22.1 parts of succinic anhydride was added to the reaction system, and the reaction was continued for 15 minutes to introduce carboxyl groups into the side chains by reacting hydroxyl groups generated by cleavage of epoxy groups with succinic anhydride, thereby obtaining a curable resin (A2) (double bond equivalent: 470 g/eq) having a weight average molecular weight of 6400. The double bond equivalent of the curable resin (A2) is calculated by analyzing the structure, molecular weight, and the like of each structural unit constituting the curable resin.

< Synthesis example 4: preparation of curable resin (A3)

178 parts of propylene glycol monomethyl ether acetate was charged into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while being purged with nitrogen, and the temperature was raised to 100 ℃.

Subsequently, 47.1 parts of dimethyl 2,2' -azobis (2-methylpropionate) was added to a monomer mixture comprising 249.0 parts of 2-ethylhexyl acrylate, 86.0 parts of glycidyl methacrylate and 13.3 parts of dicyclopentanyl methacrylate, and the mixture was added dropwise from the dropping funnel to the flask over 2 hours. After the completion of the dropwise addition, the mixture was further stirred at 100 ℃ for 30 minutes to effect a copolymerization reaction, thereby producing an addition copolymer.

Thereafter, the flask was charged with air, 43.8 parts of acrylic acid, 1.0 part of triphenylphosphine and 1.0 part of dibutylhydroxytoluene were put into the addition copolymer solution, and the reaction was continued at 120 ℃ for 10 hours, whereby epoxy groups derived from glycidyl methacrylate were cleaved by the reaction between the epoxy groups and acrylic acid, and polymerizable unsaturated bonds were introduced into the side chains 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 a hydroxyl group generated by cleavage of an epoxy group was reacted with succinic anhydride to introduce a carboxyl group into the side chain, thereby obtaining a curable resin (A3) having a weight average molecular weight of 6,500 (double bond equivalent: 670 g/eq). The double bond equivalent of the curable resin (A3) is calculated by analyzing the structure, molecular weight, and the like of each structural unit constituting the curable resin.

< Synthesis example 5: preparation of curable resin (A4)

An appropriate amount of nitrogen was passed through a 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere of nitrogen, and 1-methoxy-2-propyl acetate 371 parts by mass was added thereto and heated to 85 ℃ with stirring. Subsequently, 54 parts by mass of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylate were added dropwise over 4 hours ^2,6 ]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ^2,6 ]225 parts by mass of a mixture of decane-9-yl ester, 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 prepared by dissolving 30 parts by mass of 2, 2-azobis (2, 4-dimethylvaleronitrile), a polymerization initiator, in 160 parts by mass of 1-methoxy-2-propyl acetate was added dropwise over 5 hours. After the completion of the dropwise addition of the initiator solution, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a resin (A4) having a weight-average molecular weight of 10,600.

< preparation of curable resin compositions of examples and comparative examples >

The components shown in table 1 were mixed so as to be the blending amounts (solid content) shown in table 1, to obtain a colored curable resin composition. The colorant D and the dispersant F in table 1 are components contained from the pigment dispersion liquid obtained in synthesis example 1. In addition, in the preparation of curable resin composition, in order to curable resin composition solid content to 14 mass% mixed with propylene glycol monomethyl ether acetate. The unit of the blending amount of each component in table 1 is "part by mass", and the blending amount of each of the colorant (D), the curable resin (a), the polymerization initiator (B), the polymerizable compound (C), the leveling agent (G), and the dispersant (F) is an amount converted into a solid component.

The polymerization initiator (B), the polymerizable compound (C), and the leveling agent (G) are as follows.

Polymerizable compound (C): ARONIX (registered trademark) M-930 (manufactured by Toyo Synthesis Co., ltd.; glycerol triacrylate (double bond equivalent: 85 g/eq)

Polymerization initiator (B1): a compound represented by the following formula

[ chemical formula 18]

Polymerization initiator (B2): a compound represented by the following formula

[ chemical formula 19]

Polymerization initiator (B3): NCI-730 (manufactured by ADEKA corporation; O-acyloxime compound)

Leveling agent (G): polyether-modified SILICONE oil (trade name "TORAY SILICONE SH8400" manufactured by Torilikang Co., ltd.).

[ Table 1]

< calculation of double bond quantity >

The double bond amount of each curable resin composition was calculated from the double bond equivalent (A1: 350g/eq, A2:470g/eq, A3:670 g/eq) of the curable resins A1 to A4, the double bond equivalent (85 g/eq) of the polymerizable compound C, and the contents of the respective components according to the following formulas. The obtained results are shown in table 2.

The formula: double bond = Σ (W) _Ai /D _Ai )+Σ(W _Ci /D _Ci )

In the formula (I), the compound is represented by,

W _Ai : the amount (mass%) of each curable resin (a) based on the amount of solid components of the curable resin composition

D _Ai : double bond equivalent (g/eq) of each curable resin (A)

W _Ci : the amount (mass%) of each compound (C) based on the amount of solid components of the curable resin composition

D _Ci : double bond equivalent (g/eq) ]of each compound (C)

< evaluation of Pattern formability >

A curable resin composition was applied to a 5cm square glass substrate (Eagle 2000, manufactured by corning) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a composition layer. After the substrate on which the composition layer was formed was allowed to stand and cool, the distance between the substrate and the photomask made of quartz glass was set to 50 μm, and the substrate was exposed to an exposure apparatus (TME-150RSK, TOPCON, inc.) under an atmospheric atmosphere at a rate of 100mJ/cm ² The exposure amount (365 nm basis) of (1) was irradiated with light. As the photomask, a photomask in which a line-and-space pattern (line-and-space pattern) of 100 μm is formed was used. The colored composition layer after the light irradiation was subjected to immersion development in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ℃ for 60 seconds, and then washed with water to obtain a pattern.

For the obtained pattern, the shape was observed using a scanning electron microscope (S-4000. The results of the amount of embedding at the pattern end shown in fig. 1 are shown in table 2. As the amount of insertion is smaller, the shape tends to be more vertical, and peeling from the substrate tends to be less likely to occur.

[ Table 2]

In comparative examples 1 to 3, the amount of embedding was large, and the pattern shape was poor. In contrast, the patterns obtained in examples 1 to 7 had a small amount of embedded patterns, and exhibited good pattern shapes. The cured film of the present invention having an excellent shape can be obtained by post-baking the patterned cured film at, for example, 70 to 200 ℃.

Claims (9)

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 amount of the curable resin (A) is set based on the amount of the solid component of the curable resin compositionIs W _A Mass%, the double bond equivalent of the curable resin (A) is represented by D _A g/eq, W is the amount of the compound (C) having 2 or more polymerizable unsaturated bonds contained in the curable resin composition as the case may be, based on the amount of the solid components of the curable resin composition _C Mass%, the double bond equivalent of the compound (C) is defined as D _C g/eq, according to the formula: double bond quantity = W _A /D _A +W _C /D _C The calculated amount of double bonds in 100g of the solid content of the curable resin composition was 0.09eq or less.

2. The curable resin composition according to claim 1, wherein the amount (W) of the curable resin (A) is based on the amount of solid components of the curable resin composition _A Mass%) is 20 to 80 mass%.

3. The curable resin composition according to claim 1, wherein the amount (W) of the compound (C) having 2 or more polymerizable unsaturated bonds based on the amount of the solid components of the curable resin composition _C Mass%) is 0 to 20 mass%.

4. The curable resin composition according to claim 1, wherein the amount of double bonds in 100g of the solid content of the curable resin composition is 0.03eq or more.

5. The curable resin composition according to claim 1, wherein the polymerization initiator (B) is an O-acyloxime compound.

6. The curable resin composition according to claim 1, further comprising a colorant.

7. A cured film of the curable resin composition according to any one of claims 1 to 6.

8. The cured film according to claim 7, which constitutes a color filter, a spacer and/or a protective layer included in a color filter substrate.

9. A display device comprising the cured film of claim 7.

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