JP2023042560A - Curable resin composition, cured film and display device - Google Patents

Abstract

To provide a curable resin composition capable of forming a favorable-shape pattern.SOLUTION: A curable resin composition including a curable resin (A) having a weight average molecular weight of 3,000 to 100,000 and a polymerization initiator (B), when an amount based on a solid content of the curable resin composition of the curable resin (A) is WA mass%, a double bond equivalent of the curable resin (A) is DAg/eq, an amount based on a solid content of a curable resin composition of a compound (C) optionally included in the curable resin composition and having two or more polymerizable unsaturated bonds is WC mass%, and a double bond equivalent of the compound (C) is DCg/eq, the amount of double bond in the solid content 100 g of the curable resin composition calculated by an expression: double bond amount=WA/DA+WC/DC is 0.09 eq or less.SELECTED DRAWING: Figure 1

Description

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

A color filter substrate, which is a member included in a liquid crystal display device, has a black matrix layer and, for example, red (R), green (G), and blue (B) color filters for forming pixels on a transparent substrate. It has a structure in which a protective film is laminated on the upper layer in some cases. Furthermore, a patterned transparent pixel electrode is formed on the upper layer. Columnar or striped spacers are formed on the color filter substrate to maintain a constant distance from the opposing TFT substrate.

The color filters, protective film and spacers contained in the above color filter substrate can all be formed from a curable resin composition. As such a curable resin composition, Patent Document 1 describes a curable resin composition containing a specific colorant, a photopolymerizable compound, and an oxime ester compound as a photopolymerization initiator. . A patterned cured product such as a color filter is formed from such a curable resin composition by, for example, a photolithographic method.

JP 2020-3614 A

When producing a patterned cured film, a development step is performed in which the curable resin composition is exposed and cured in a desired pattern, and the unexposed portion is dissolved in a developer and removed. When using the conventionally known curable resin composition, the pattern shape may deteriorate (for example, the insertion amount may increase) in the developing step.

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

The present inventors 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.
[1] A curable resin composition containing a curable resin (A) having a weight average molecular weight of 3,000 to 100,000 and a polymerization initiator (B),
The amount based on the solid content of the curable resin composition of the curable resin (A) is _WA mass%, the double bond equivalent of the curable resin (A) is _DA g / eq, and the curable resin composition The amount based on the solid content of the curable resin composition of the compound (C) having two or more polymerizable unsaturated bonds, which is optionally included, is _WC mass%, and the double bond equivalent of the compound (C) is D. When _C g/eq, the formula:
Amount of double bonds = W _A /D _A +W _C /D _C
A curable resin composition having a double bond content of 0.09 eq or less in 100 g of the solid content of the curable resin composition calculated by
[2] The curable resin composition according to [1], wherein the amount of the curable resin (A) based on the solid content of the curable resin composition (W _A mass%) is 20% by mass to 80% by mass. .
[3] The amount (W _C mass%) based on the solid content of the curable resin composition of the compound (C) having two or more polymerizable unsaturated bonds is 0 to 20 mass%, [1] or The curable resin composition according to [2].
[4] The curable resin composition according to any one of [1] to [3], wherein the amount of double bonds in 100 g of solid content of the curable resin composition is 0.03 eq or more.
[5] The curable resin composition according to any one of [1] to [4], wherein the polymerization initiator (B) is an O-acyloxime compound.
[6] The curable resin composition according to any one of [1] to [5], further containing a coloring agent.
[7] A cured film of the curable resin composition according to any one of [1] to [6].
[8] The cured film of [7], which is a color filter, spacer and/or protective layer contained in a color filter substrate.
[9] A display device comprising the cured film according to [7] or [8].

ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which can form a favorable shape pattern can be provided.

It is a schematic diagram for demonstrating insertion amount.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the gist of the present invention. In addition, when a plurality of upper and lower limits are described for a specific parameter, any upper and lower limits of these upper and lower limits can be combined to form a suitable numerical range.

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

Formula: Double bond amount = W _A /D _A +W _C /D _C
[In the formula, _WA represents the amount (% by mass) based on the solid content of the curable resin composition of the curable resin (A), and _DA represents the double bond equivalent of the curable resin (A) (g / eq), and W _C is the amount based on the solid content of the curable resin composition of the compound (C) having two or more polymerizable unsaturated bonds optionally contained in the curable resin composition (% by mass ), and D _C represents the double bond equivalent (g/eq) of the compound (C)]
The amount of double bonds calculated by is contained in 100 g of the solid content of the curable resin composition, the two derived from the curable resin (A) and the compound (C) having two or more polymerizable unsaturated bonds It represents the amount of double bonds. If the amount of double bonds exceeds 0.09 eq, a good pattern shape cannot be obtained in forming a patterned cured product such as a color filter. Here, the curable resin (A) is a resin having a weight-average molecular weight, which will be described later, and is an essential component of the curable resin composition of the present invention. The compound (C) having two or more polymerizable unsaturated bonds is a compound having two or more polymerizable unsaturated bonds, for example a compound having two or more ethylenically unsaturated bonds, and the compound is cured. However, it is not an essential component for the flexible resin composition. In addition, in this specification, a compound means a compound having a molecular weight of 2000 or less. In addition, the compound (C) having two or more polymerizable unsaturated bonds may or may not be contained in the curable resin composition, and when the compound (C) is not contained, Since W _C =0, the amount of double bonds is calculated by W _A /D _A.

The amount of double bonds calculated by the formula: amount of double bonds = W _A /D _A +W _C /D _C is 0.09 eq or less, and preferably 0.085 eq or less from the viewpoint of easily improving the pattern shape. , more preferably 0.08 eq or less. Further, from the viewpoint of easily improving the curability of the curable resin composition, it is preferably 0.03 eq or more, more preferably 0.04 eq or more, still more preferably 0.05 eq or more, and still more preferably 0.06 eq or more. be. As a method for adjusting the amount of double bonds within the above range, the amount W _A (% by mass) based on the solid content of the curable resin composition of the curable resin (A) in the above formula, two or more polymerizable When the amount W _C (% by mass) based on the solid content of the curable resin composition of the compound (C) having an unsaturated bond is small, and the double bond equivalent D _A (g/ _eq ) and the double bond equivalent D _C (g/eq) of _the compound (C) increases, the double bond equivalent decreases. Each of _C and D _C should be adjusted. W _A and W _C may be calculated from the charge ratio of each component contained in the curable resin composition, or the content may be calculated by analysis. Further, D _A and D _C may be calculated by analyzing the structure, molecular weight, etc. of each component contained in the curable resin composition, or may be measured by an infrared absorption method or a nuclear magnetic resonance method. .

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

(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 it is preferably an alkali-soluble resin. The curable resin composition of the present invention may contain one type of curable resin (A), or may contain two or more types of curable resins (A). A curable resin is a resin having one or more polymerizable unsaturated bonds, such as ethylenically unsaturated bonds.

Examples of the curable resin (A) include the following resins [K1] to [K6].
Resin [K1]: a structural unit derived from at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as "(a)"); A copolymer having a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure and an ethylenically unsaturated bond of to 4;
Resin [K2]; a structural unit derived from (a), a structural unit derived from (b), and a monomer (c) copolymerizable with (a) (where (a) and (b) are different.) (hereinafter sometimes referred to as "(c)") and a copolymer having a structural unit derived from;
Resin [K3]; a copolymer having a structural unit derived from (a) and a structural unit derived from (c);
Resin [K4]; a copolymer having a structural unit 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 structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a polyvalent carboxylic acid and/or a carboxylic acid anhydride, and a structural unit derived from (c); A copolymer with
The curable resin (A) preferably contains a resin having another double bond in addition to the polymerizable unsaturated bond, and at least one selected from the group consisting of resins [K4] to [K6]. More preferably, it contains a resin.

Specifically, as (a), for example,
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;
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, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclounsaturated compounds containing a carboxy group;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;
Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate kind;
Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid.
Among these, acrylic acid, methacrylic acid, and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an alkaline aqueous solution.

(b) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. say. (b) is preferably a monomer having a cyclic ether structure with 2 to 4 carbon atoms and a (meth)acryloyloxy group.
In this specification, "(meth)acrylic acid" represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond, a monomer (b2) (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc. mentioned.

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

(b1-1) includes 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.

(b1-2) includes vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cychromer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cychromer M100; manufactured by Daicel Corporation), 3,4-epoxytricyclo [5.2.1. 0 ^2,6 ]decyl (meth)acrylate, compounds represented by formula (BI), compounds represented by formula (BII), and the like.

［式（ＢＩ）及び式（ＢＩＩ）中、Ｒ^e及びＲ^fは、水素原子、又は炭素数１～４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
Ｘ^e及びＸ^fは、単結合、＊－Ｒ^g－、＊－Ｒ^g－Ｏ－、＊－Ｒ^g－Ｓ－又は＊－Ｒ^g－ＮＨ－を表す。
Ｒ^gは、炭素数１～６のアルカンジイル基を表す。
＊は、Ｏとの結合手を表す。］

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

Examples of alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.
Alkyl groups in which hydrogen atoms are substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.
R ^e and R ^f are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

The alkanediyl group includes methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane- A 1,6-diyl group and the like can be mentioned.
X ^e and X ^f are preferably a single bond, a methylene group, an ethylene group, *--CH ₂ --O-- and *--CH ₂ CH ₂ --O--, more preferably a single bond and *--CH ₂ CH ₂ --O-- (* represents a bond with O).

(b2) is more preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. (b2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane , 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane and the like.

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

In the case of resin [K1] or resin [K2], (b) is (b1) in that the reliability of the resulting cured film, such as heat resistance and chemical resistance, can be increased. preferable.

(c) includes, for example, 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[5.2.1.02 ,6] Decane-8-yl (meth)acrylate (in the technical field, it is commonly referred to as “dicyclopentanyl (meth)acrylate”. It is also sometimes referred to as “tricyclodecyl (meth)acrylate” ), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate (in the art, it is commonly called “dicyclopentenyl (meth)acrylate”), di Cyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate (meth)acrylic acid esters such as acrylates;
Hydroxy group-containing (meth)acrylic acid esters 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-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2′-hydroxyethyl)bicyclo[2.2. 1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy -5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2 .2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyl oxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 - dicarbonylimide derivatives such as maleimidopropionate, N-(9-acridinyl)maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , isoprene, 2,3-dimethyl-1,3-butadiene, and the like.
Among these, (meth)acrylates are preferred.

In the resin [K1], the ratio of the structural units derived from each of the total structural units constituting the resin [K1] is
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (b); 40 to 98 mol%
is preferably
Structural unit derived from (a); 10 to 50 mol%
Structural unit derived from (b); 50 to 90 mol%
is more preferable.
When the ratio of the structural units of the resin [K1] is within the above range, it is easy to adjust the double bond content of the curable composition of the present invention to a preferred range, and the storage stability of the curable resin composition and the pattern and the resulting cured film tends to be excellent in solvent resistance.

The resin [K1] is, for example, the method described in the document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin, 1st edition, 1st edition, published on March 1, 1972) and the literature It can be manufactured with reference to the cited document described in .

Specifically, predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and, for example, by replacing oxygen with nitrogen, a deoxygenated atmosphere is created, and while stirring, A method of heating and keeping warm can be mentioned. The polymerization initiator, solvent, and the like used here are not particularly limited, and those commonly used in the relevant field can be used. For example, polymerization initiators include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, t -Butyl peroxy-2-ethylhexanoate, etc.), and the solvent may be one that dissolves each monomer, and the solvent (F) that can be contained in the curable resin composition of the present invention will be described later. and the like.

The obtained copolymer may be used as a solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. You can use things. In particular, by using the solvent contained in the curable resin composition of the present invention as the solvent for this polymerization, the solution after the reaction can be used as it is for the preparation of the curable resin composition of the present invention. Therefore, the manufacturing 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 the total structural units constituting the resin [K2] is
Structural unit derived from (a); 2 to 45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
is preferably
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
is more preferable.
When the ratio of the structural units of the resin [K2] is within the above range, it is easy to adjust the double bond content of the curable composition of the present invention to a preferable range, and the storage stability of the curable resin composition and the pattern and the resulting cured film tends to be excellent in solvent resistance, heat resistance and mechanical strength.

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

In the resin [K3], the ratio of the structural units derived from each is, from the viewpoint of facilitating adjustment of the double bond content of the curable composition of the present invention to a preferred range, among all the structural units constituting the resin [K3],
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (c); 40 to 98 mol%
is preferably
Structural unit derived from (a); 10 to 50 mol%
Structural unit derived from (c); 50 to 90 mol%
is more preferable.
Resin [K3] can be produced, for example, in the same manner as the method for producing resin [K1].

Resin [K4] is a carboxylic acid and/or carboxylic acid anhydride obtained by obtaining a copolymer of (a) and (c), and having (a) a cyclic ether having 2 to 4 carbon atoms possessed by (b). It can be produced by adding to
First, a copolymer of (a) and (c) is produced in the same manner as the method for producing resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same ratio as mentioned for the resin [K3].

Next, part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms of (b).
Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst (e.g., tris ( Dimethylaminomethyl)phenol, triphenylphosphine, etc.) and a polymerization inhibitor (e.g., hydroquinone, metoquinone, etc.) are placed in a flask and reacted at, for example, 60 to 130 ° C. for 1 to 10 hours to obtain a resin [K4 ] can be manufactured.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting this range, the storage stability of the curable resin composition, the developability when forming a pattern, the pattern shape, the curability at a low temperature, and the solvent resistance, heat resistance, mechanical There tends to be a good balance of strength and sensitivity. Since the cyclic ether has high reactivity and unreacted (b) hardly remains, (b1) is preferable as the (b) used in the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by weight per 100 parts by weight of the total amount of (a), (b) and (c).
Reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. As with the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

For resin [K5], as the first step, a copolymer of (b) and (c) is obtained in the same manner as in the method for producing resin [K1] described above. In the same manner as described above, the obtained copolymer may be used as a solution after the reaction as it is, may be used as a concentrated or diluted solution, or may be converted into a solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer is, respectively,
Structural unit derived from (b); 5 to 95 mol%
Structural unit derived from (c); 5 to 95 mol%
is preferably
Structural unit derived from (b); 10 to 90 mol%
Structural unit derived from (c); 10 to 90 mol%
is more preferable.
When the ratio of the structural units of the resin [K5] is within the above range, it is easy to adjust the double bond content of the curable composition of the present invention to a preferable range, and the storage stability of the curable resin composition and the pattern Developability, pattern shape, curability at low temperature, solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting cured film tend to be well balanced.

Furthermore, under the same conditions as in the method for producing resin [K4], the cyclic ether derived from (b) in the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic anhydride of (a). Resin [K5] can be obtained by reacting substances.
The amount of (a) to be reacted with the copolymer is preferably 5 to 100 mol per 100 mol of (b). Since the cyclic ether has high reactivity and unreacted (b) does not easily remain, (b1) is preferable as (b) used in resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by reacting resin [K5] with a polyvalent carboxylic acid and/or a carboxylic acid anhydride. The hydroxy group generated by the reaction of the cyclic ether derived from (b) and the carboxylic acid or carboxylic anhydride derived from (a) is further reacted with a polyvalent carboxylic acid and/or a carboxylic anhydride.
Polyvalent carboxylic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, tricarbanilic acid and the like. Carboxylic anhydrides include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, and 3,4,5,6-tetrahydrophthalic acid. anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and the like. The amount of polyvalent carboxylic acid and/or carboxylic acid anhydride used is preferably 0.05 to 1 mol, more preferably 0.1 to 0.5 mol, per 1 mol of (a) used.

As the curable resin (A), a resin (resin [K4] or resin [K5]) having a structural unit having an ethylenically unsaturated bond in the side chain is preferable, and a structure containing a (meth)acryloyl group in the side chain. Resins having units are more preferred.
Examples of resins having a structural unit containing a (meth)acryloyl group in the side chain include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 3-methyl-3-methacrylloyl as (b). Resin [K4] using a monomer having a (meth)acryloyl group such as oxymethyloxetane and tetrahydrofurfuryl acrylate, and (a) acrylic acid, methacrylic acid, and mono[2-(meth)acryloyloxyethyl succinate] ] and the like are preferable.
In Resin [K4] and Resin [K5], (c) is preferably dicarbonylimide derivatives and vinyltoluene.

The curable resin (A) has a polystyrene equivalent weight average molecular weight of 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 hardness of the cured film used as, for example, color filters, spacers, protective films, etc. is improved, the residual film rate is high, and the unexposed area has good solubility in a developer. , the pattern shape tends to be improved and the pattern resolution tends to be improved.

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

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

The amount ( _WA mass%) of the curable resin (A) based on the solid content of the curable resin composition is preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more. be. Also, the amount is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, even 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, pattern formation tends to be easy, and pattern resolution and residual film ratio tend to improve. Moreover, the solvent resistance of the resulting cured film is further improved. In this specification, the term "total amount of solid content" refers to the total amount of the curable resin composition minus the content of the solvent. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

(Polymerization initiator B)
The polymerization initiator (B) is a compound capable of initiating polymerization by generating active radicals, acids, etc. by the action of light or heat. The polymerization initiator (B) is not particularly limited, but includes O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds and acylphosphine oxide compounds. Among them, O-acyloxime compounds are preferred. The polymerization initiator (B) preferably has a maximum absorption wavelength in the range of 365 to 390 nm, more preferably 370 to 390 nm, from the viewpoint of easily improving the curability of the curable resin composition. have a wavelength. The curable resin composition of the present invention may contain one type of polymerization initiator (B), or may contain two or more types of polymerization initiators (B).

O-acyloxime compounds are preferred as the polymerization initiator (B). Moreover, the polymerization initiator (B) is preferably a compound having a carbazole skeleton, and is also preferably a compound having a nitro group.

で表される構造を有する化合物である。以下、＊は結合手を表す。 The O-acyl oxime compound has the formula (c1):

is a compound having a structure represented by Below, * represents a bond.

で表される構造を有する化合物である。 A compound having a carbazole skeleton has the formula (c2):

is a compound having a structure represented by

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

［式（ｃ３）及び（ｃ４）中、
Ｒ^ａは、置換基を有していてもよい炭素数６～１８の芳香族炭化水素基又は置換基を有していてもよい炭素数１～１５の脂肪族炭化水素基を表し、前記脂肪族炭化水素基に含まれるメチレン基（－ＣＨ₂－）は、－Ｏ－、－ＣＯ－又は－Ｓ－に置き換わっていてもよく、前記脂肪族炭化水素基に含まれるメチン基（－ＣＨ＜）は、－ＰＯ₃＜に置き換わっていてもよく、前記脂肪族炭化水素基に含まれる水素原子はＯＨ基で置換されていてもよい。
なお、本明細書において、メチレン基（－ＣＨ₂－）等が、－Ｏ－、－ＣＯ－又は－Ｓ－等に置き換わる場合、炭素数は、置き換わる前の炭素数を意味する。
Ｒ^ｂは、置換基を有していてもよい炭素数６～１８の芳香族炭化水素基、置換基を有していてもよい炭素数３～３６の複素環基、置換基を有していてもよい炭素数１～１５のアルキル基、又は芳香族炭化水素基と該アルキル基から導かれるアルカンジイル基とを組み合わせた、置換基を有していてもよい基を表し、前記アルキル基に含まれるメチレン基（－ＣＨ₂－）は、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ₂－又は－ＮＲ^ｈ－に置き換わっていてもよい。Ｒ^ｈは、炭素数６～１８の芳香族炭化水素基、炭素数３～３６の複素環基又は炭素数１～１０のアルキル基を表す。
Ｒ^ｃは、置換基を有していてもよい炭素数６～１８の芳香族炭化水素基、炭素数３～３６の複素環基又は炭素数１～１０のアルキル基を表す。
Ｒ^ｄは、置換基を有していてもよい炭素数６～１８の芳香族炭化水素基又は置換基を有していてもよい炭素数３～３６の複素環基を表す。
ｐは１～４の整数、好ましくは１又は２の整数、より好ましくは１を表す。 The polymerization initiator (B) is more preferably an O-acyloxime compound having a carbazole skeleton. Such compounds include, for example, a compound represented by formula (c3) (hereinafter sometimes referred to as compound (c3)), and a compound represented by formula (c4) (hereinafter sometimes referred to as compound (c4) There is at least one selected from the group consisting of

[In formulas (c3) and (c4),
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, The methylene group (—CH ₂ —) contained in the aliphatic hydrocarbon group may be replaced with —O—, —CO— or —S—, and the methine group (—CH< ) may be replaced with —PO ₃ <, and hydrogen atoms contained in the aliphatic hydrocarbon group may be replaced with OH groups.
In this specification, when a methylene group ( _--CH.sub.2-- ) or the like is replaced with --O--, --CO--, --S-- or the like, the number of carbon atoms means the number of carbon atoms before the replacement.
R ^b is an optionally substituted C 6-18 aromatic hydrocarbon group, an optionally substituted C 3-36 heterocyclic group, a substituted represents an optionally substituted alkyl group having 1 to 15 carbon atoms, or a combination of an aromatic hydrocarbon group and an alkanediyl group derived from the alkyl group; The methylene group (--CH ₂ --) contained may be replaced with --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 C 6-18 aromatic hydrocarbon group or an optionally substituted C 3-36 heterocyclic group.
p represents an integer of 1 to 4, preferably an integer of 1 or 2, more preferably 1;

The number of carbon atoms in the aromatic hydrocarbon group represented by R ^a is preferably 6-15, more preferably 6-12, still more preferably 6-10. Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group and terphenyl group, with phenyl group and naphthyl group being more preferred, and phenyl group being even more preferred.
Also, the aromatic hydrocarbon group represented by R ^a may have one or more substituents. Examples of the substituent include the same substituents that the aromatic hydrocarbon group of R ^b described later may have.

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

Examples of the optionally substituted aliphatic hydrocarbon group represented by R ^a include groups represented by the following formulae. In the formula, * represents a bond.

R ^a is preferably an optionally substituted chain aliphatic hydrocarbon group, more preferably an unsubstituted chain alkyl group, still more preferably an unsubstituted linear A chain or branched alkyl group.

The number of carbon atoms in the aromatic hydrocarbon group represented by R ^b is preferably 6-15, more preferably 6-12, still more preferably 6-10. Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group, terphenyl group and the like, with phenyl group and naphthyl group being more preferred, and phenyl group being particularly preferred.
In addition, the aromatic hydrocarbon group represented by ^Rb may have one 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 methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group and pentadecyl group. alkyl groups having 1 to 15 carbon atoms such as; halogen atoms such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom;
The number of carbon atoms in the alkyl group as the substituent is preferably 1-10, more preferably 1-7. The alkyl group as the substituent may be linear, branched, or cyclic, or may be a combination of a chain group and a cyclic group. A methylene group ( _--CH.sub.2-- ) contained in the alkyl group as the substituent may be replaced with --O-- or --S--. Further, the hydrogen atom contained in the alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom, and is preferably substituted with a fluorine atom.

Examples of the alkyl group as a substituent of the aromatic hydrocarbon group represented by ^Rb include groups represented by the following formulae. In the formula, * represents a bond.

Examples of the optionally substituted aromatic hydrocarbon group represented by R ^b include groups represented by the following formulae. In the formula, * represents a bond.

［式中、Ｒ^ｉは、それぞれ独立に、ハロゲン原子で置換されていてもよい炭素数１～１０のアルキル基を表し、Ｒ^ｉに含まれるメチレン基（－ＣＨ₂－）は、－Ｏ－又は－Ｓ－に置き換えられていてもよく、Ｒ^ｊは、それぞれ独立にハロゲン原子で置換されていてもよい炭素数１～１０のアルキル基を表し、ｑは１～５の整数を表し、ｒは０～４の整数を表す。但し、ｑ＋ｒの合計は５以下である。］ As the optionally substituted aromatic hydrocarbon group represented by ^Rb , groups represented by the following formulas are preferable.

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

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

The heterocyclic group represented by R ^b 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 pyrrolyl group, furyl group, thienyl group, indolyl group, benzofuryl group and carbazolyl group.
Moreover, the heterocyclic group represented by ^Rb may have one or more substituents. Examples of the substituent include the same groups as those exemplified as the substituent that the aromatic hydrocarbon group represented by R ^b may have.

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

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

Specific examples of the optionally substituted alkyl group represented by R ^b include groups represented by the following formulae. * represents a bond.

Furthermore, the number of carbon atoms in the group represented by R ^b , which is a combination of the aromatic hydrocarbon group and the alkanediyl group derived from the alkyl group represented by R ^b , is preferably 7 to 33, and more It is preferably 7-18, more preferably 7-12. The combined group may have one or more substituents, and the substituents are the same as the groups exemplified as the substituents that the aromatic hydrocarbon group and the alkyl group may have. group. Examples of the group represented by R ^b in which an aromatic hydrocarbon group and an alkanediyl group derived from an alkyl group represented by R ^b are combined include an aralkyl group. A group represented by can be mentioned. In the formula, * represents a bond.

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

The aromatic hydrocarbon group represented by R ^c preferably has 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group and terphenyl group.
The heterocyclic group represented by R ^c 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 pyrrolyl group, furyl group, thienyl group, indolyl group, benzofuryl group and carbazolyl group.
The number of carbon atoms in the alkyl group represented by R ^c is preferably 1-7, more preferably 1-5, still more preferably 1-3. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. The alkyl group may be linear, branched, or cyclic, or may be a combination of a chain group and a cyclic group.

R ^c 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 is preferably a methyl group. Especially preferred.

The number of carbon atoms in the aromatic hydrocarbon group represented by R ^d is preferably 6-15, more preferably 6-12, still more preferably 6-10. Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group and terphenyl group, with phenyl group and naphthyl group being more preferred.
In addition, the aromatic hydrocarbon group represented by ^Rd may have one 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 methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and nonyl. Alkyl groups having 1 to 15 carbon atoms such as groups and decyl groups; Alkenyl groups having 1 to 15 carbon atoms such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl and decenyl groups; is mentioned.
The number of carbon atoms in the aliphatic hydrocarbon group which may be possessed by the aromatic hydrocarbon group represented by R ^d is more preferably 1 to 7, and the aliphatic hydrocarbon group may be linear or branched. It may be branched or cyclic, and may be a group in which a chain group and a cyclic group are combined. In addition, the methylene group (-CH ₂ -) contained in the aliphatic hydrocarbon group may be replaced with -O-, -CO- or -S-, and the methine group (-CH<) may be replaced with -N < may be replaced.

Examples of the aliphatic hydrocarbon group which the aromatic hydrocarbon group represented by R ^d may have include groups represented by the following formulae. In the formula, * represents a bond.

Examples of the optionally substituted aromatic hydrocarbon group represented by R ^d include groups represented by the following formulae. In the formula, * represents a bond.

The heterocyclic group represented by R ^d 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 pyrrolyl group, furyl group, thienyl group, indolyl group, benzofuryl group and carbazolyl group.
In addition, the heterocyclic group represented by R ^d may have one or more substituents, and the substituents include the aromatic hydrocarbon group represented by R ^b . The same groups as the groups exemplified as good substituents can be mentioned.

Among them, R ^d is 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). The number of groups is preferably 2 or more and 5 or less.

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

［式中、Ｒ^ｊは炭素数１～３のアルキル基であり、Ｒ^ｉは式＊－Ｒ^ｊ１－Ｏ－Ｒ^ｊ２で表される基であり〔ここで、Ｒ^ｊ１は、炭素数１～４の直鎖状又は分枝状の、ハロゲン原子で置換されていてもよい脂肪族炭化水素基を表し、Ｒ^ｊ２は、炭素数１～４の直鎖状又は分枝状の、ハロゲン原子で置換されていてもよいアルキル基を表す〕
、Ｒ^ｉ及びＲ^ｊに含まれる水素原子はハロゲン原子に置換されていてもよい。ｑ及びｒは１である。］
で表される基であり、Ｒ^ｃが炭素数１～４のアルキル基であり、かつｐが１である化合物である。
化合物（ｃ３）の市販品としては、ＮＣＩ－８３１（ＡＤＥＫＡ社製）が挙げられる。 In the compound (c3), preferably R ^a is an optionally substituted alkyl group having 1 to 15 carbon atoms, and R ^b is an optionally substituted C 6 to 18 aromatic group. is a group hydrocarbon group, R ^c 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, and R ^b is the following formula:

[In the formula, R ^j is an alkyl group having 1 to 3 carbon atoms, and R ⁱ is a group represented by the formula *-R ^j1 -OR ^j2 [here, R ^j1 has 1 to 3 carbon atoms; 4 represents a linear or branched aliphatic hydrocarbon group optionally substituted with a halogen atom, and R ^j2 is a linear or branched halogen atom having 1 to 4 carbon atoms; represents an optionally substituted alkyl group]
, R ⁱ and R ^j may be substituted with a halogen atom. q and r are 1; ]
is a group represented by, R ^c is an alkyl group having 1 to 4 carbon atoms, and p is 1.
Commercially available products of compound (c3) include NCI-831 (manufactured by ADEKA).

In the compound (c4), preferably R ^a is an optionally substituted alkyl group having 1 to 10 carbon atoms, and R ^b is an optionally substituted C 6 to 10 aromatic group. is a group hydrocarbon group, R ^c is an alkyl group having 1 to 4 carbon atoms, and R ^d is an aromatic hydrocarbon group which may have a substituent.
Commercially available products of compound (c4) include Irgacure OXE03 (manufactured by BASF).

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

Examples of compounds having a structure represented by formula (d4) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl )-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like be done. Commercially available products such as Irgacure 369, 907 and 379 (manufactured by BASF) may also be used.
Compounds having a structure represented by formula (d5) 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,α-diethoxyacetophenone, benzyl dimethyl ketal and the like.
From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (d4).

Biimidazole compounds 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, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4', 5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis (2-chlorophenyl)-4,4′,5,5′-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), 4,4 Examples include biimidazole compounds in which the phenyl groups at the ',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913). Among them, compounds represented by the following formulas and mixtures thereof are preferable.

Triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 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)ethenyl]-1,3,5-triazine, 2,4-bis( trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methyl phenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine and the like. .

Acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

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

(Compound (C) having two or more polymerizable unsaturated bonds)
The curable resin composition of the present invention may or may not contain a compound (C) having two or more polymerizable unsaturated bonds. From the viewpoint of easily adjusting the amount of double bonds in the curable resin composition to the above preferable range, the amount of the compound (C) having two or more polymerizable unsaturated bonds based on the solid content of the curable resin composition W _C (% by mass) is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. The lower limit of W _C may be 0% by mass or more. Examples of the compound (C) include compounds having two or more polymerizable ethylenically unsaturated bonds, such as (meth)acrylic acid ester compounds.

Examples of such compound (C) include, but are not limited to, trimethylolpropane tri(meth)acrylate, pentaerythritol 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 one polymerizable unsaturated bond)
The curable resin composition of the present invention may contain a compound (J) having one polymerizable unsaturated bond. When containing a compound (J) having one polymerizable unsaturated bond, the content of the compound (J) based on the solid content of the curable resin composition is from the viewpoint of improving the solvent resistance of the resulting cured film. Therefore, it is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, still more preferably 0.2% by mass or less, and even more preferably 0.1% by mass or less. The lower limit of the content of compound (J) may be 0% by mass or more.

(Colorant D)
The curable resin composition of the present invention may further contain at least one coloring agent (D). When the curable resin composition of the present invention contains at least one colorant (D), the composition can be suitably used as a colored curable resin composition for forming a resist layer in a color filter. . Moreover, the curable resin composition of the present invention having the above composition can be darkened when used as a color resist composition, and a desired color can be easily achieved. The coloring agent may be either a dye or a pigment, but preferably contains a pigment. As the pigment, known pigments can be used, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

Specifically, C.I. 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, yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214;
C. I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
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, red pigments such as 269, 273, 291;
C. I. Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 16, 60;
C. I. Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Pigment Green 7, 36, 58, 59 green pigments;
C. I. Brown pigments such as Pigment Brown 23 and 25;
C. I. Black pigments such as Pigment Black 1 and 7 are included.

If necessary, the pigment is subjected to rosin treatment, surface treatment using a pigment derivative into which an acidic group or basic group is introduced, graft treatment to the pigment surface with a polymer compound, etc., atomization by a sulfuric acid atomization method, etc. Treatment, washing treatment with an organic solvent, water, or the like for removing impurities, removal treatment by an ion exchange method or the like for ionic impurities, or the like may be performed.
The pigment preferably has a uniform 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, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. As pigment dispersants, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Lubrizol), EFKA (manufactured by CIBA), Ajisper (Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie), and the like.

When the pigment dispersant (F) is used, the amount used is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less, relative to the total amount of the pigment. When the amount of the pigment dispersant used is within the above range, there is a tendency to obtain a uniformly dispersed pigment dispersion.

The content of the pigment in the coloring agent (D) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more. % by mass.

The coloring agent (D) may contain a dye. The dye is not particularly limited, and known dyes can be used, including solvent dyes, acid dyes, direct dyes, mordant dyes, and the like. Dyes include, for example, compounds classified as having hues other than pigments in the Color Index (published by The Society of Dyers and Colorists), and known dyes described in Dye Note (Shikisensha). be done. Also, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin Dyes, quinoline dyes, nitro dyes, and the like. Among these, organic solvent-soluble dyes are preferred.

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

The content of the dye in the coloring agent (D) is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less. % 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 solid content of the curable resin composition. be. When the content of the coloring agent (D) is within the above range, the color density of the color filter is sufficient and the required amount of the curable resin (A) can be contained in the composition. , a pattern with sufficient mechanical strength can be formed.

Especially in the curable resin composition that is required to be darkened, the content of the colorant (D) is preferably 15 to 60% by mass, based on the total solid content of the curable resin composition, and more It is preferably 20 to 55% by mass, more preferably 23 to 50% by mass. When the content of the coloring agent (D) is within the above range, a particularly high color density can be achieved when used as a color filter, and the necessary amount of the curable resin (A) is included in the composition. Therefore, a pattern with sufficient mechanical strength can be formed.

(Polymerization initiation aid E)
The curable resin composition of the present invention may further contain at least one polymerization initiation aid (E). A polymerization initiation aid is a compound or a sensitizer used to accelerate the polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator. When the polymerization initiation aid (E) is included, 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), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, and 2,4-diethylthioxanthone. , N-phenylglycine and the like.

When using these polymerization initiation aids (E), the content thereof is preferably 0.1 with respect to 100 parts by mass of the total amount of the curable resin (A) and optionally the polymerizable compound (C). to 30 parts by mass, more preferably 0.5 to 20 parts by mass. When the amount of the polymerization initiation aid (E) is within this range, the pattern can be formed with higher sensitivity, and the productivity of color filters and the like tends to be improved.

(Solvent H)
The curable resin composition of the present invention may further contain at least one solvent (H). The solvent is not particularly limited, and solvents commonly used in the field can be used. For example, ester solvent (solvent containing -COO- in the molecule but not containing -O-), ether solvent (solvent containing -O- in the molecule but not containing -COO-), ether ester solvent (solvent containing -COO- in the molecule solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-, - solvents containing no CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and 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, phenetol, methylanisole and the like.

Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy ethyl propionate, 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, diethylene glycol monobutyl ether acetate and the like.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, di Acetone alcohol, isophorone, and the like.

Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.

Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

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

The content of the solvent (H) is preferably 30-80% by mass, more preferably 35-75% by mass, relative to 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 20-70 mass %, more preferably 25-65 mass %. When the content of the solvent (H) is within the above range, the smoothness at the time of coating is improved, and for example, when a coloring agent is contained, the color density is not insufficient when forming a color filter. display characteristics tend to be good.

(Leveling agent G)
The curable resin composition of the present invention may further contain at least one leveling agent. Examples of the leveling agent (G) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.

Examples of silicone-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray SH7PA, Toray DC11PA, Toray SH21PA, Toray SH28PA, Toray SH29PA, Toray SH30PA, Toray SH8400 (trade name: Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC), etc. .

Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, Florard FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Florado F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Examples include S382, SC101, SC105 (manufactured by AGC Co., Ltd. (former Asahi Glass Co., Ltd.)) and E5844 (manufactured by Daikin Fine Chemicals Laboratory Co., Ltd.).

Examples of the fluorine atom-containing silicone-based surfactants include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, F477 and F443 (manufactured by DIC Corporation) and the like can be mentioned.

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

(other ingredients)
The curable resin composition of the present invention may optionally contain fillers, other polymer compounds, adhesion promoters, and antioxidants such as 2,2'-methylenebis(4-methyl-6-t-butylphenol). , light stabilizers, chain transfer agents such as n-dodecyl mercaptan, and other additives known in the art.

<Method for producing curable resin composition>
The curable resin composition of the present invention includes, for example, a curable resin (A), a polymerization initiator (B), and optionally a coloring agent (D), a polymerization initiation aid (E), a leveling agent ( It can be prepared by mixing G), solvent (H), compound (C) and other ingredients.
Colorant (D) may be prepared using the pigment dispersion described above. The desired curable resin composition can be prepared by mixing the pigment dispersion with the remaining components to a predetermined concentration. The curable resin composition after mixing is preferably filtered through a filter having a pore size of about 0.01 to 10 μm.

<Method for producing cured film>
Examples of methods for producing a patterned cured film from the curable resin composition of the present invention include a photolithography method, an inkjet method, and a printing method. Among them, the photolithographic method is preferred. The photolithographic method is a method in which the resin composition is applied to a substrate, dried to form a composition layer, exposed through a photomask, and developed. A non-patterned cured film can be formed by a photolithographic method without using a photomask during exposure and/or without developing. Both the patterned cured film and the non-patterned cured film thus formed are the cured film of the present invention.
The thickness of the cured film to be produced is not particularly limited, and can be appropriately adjusted according to the purpose and application. ˜6 μm.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass whose surface is coated with silica; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; A thin film of aluminum, silver, silver/copper/palladium alloy, etc., is formed on the substrate. Another cured film (for example, another color filter or the like), a resin layer, a transistor, a circuit, or the like may be formed on these substrates.

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

Next, the resin composition layer is exposed through a photomask to form a desired pattern. The pattern on the photomask is not particularly limited, and a pattern suitable for the intended use is used.
The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You can Specifically, light sources include mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, and the like. Further, the exposure dose based on a wavelength of 365 nm is preferably 50 to 300 J/cm ² , more preferably 60 to 200 J/cm ² , and even more preferably 65 to 180 J/cm ² . .
Exposure equipment such as a mask aligner and a stepper can be used because it is possible to uniformly irradiate the entire exposure surface with parallel light rays and to perform accurate alignment between the photomask and the substrate on which the resin composition layer is formed. is preferred.

A pattern is formed on the substrate by developing the exposed resin composition layer in contact with a developer. By development, the unexposed portion of the resin composition layer is dissolved in the developer and removed. As the developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate and tetramethylammonium hydroxide are preferred. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant.
The developing method may be any of a puddle method, a dipping method, a spray method, and the like. Furthermore, the substrate may be tilted at any angle during development.
It is preferable to wash with water after development.

Furthermore, it is preferable to post-bake the obtained pattern. The post-baking temperature may be 200° C. or lower, preferably 170° C. or lower, and more preferably 150° C. or lower in order to form a cured film such as a color filter used in an organic EL display device. be. In the present invention, post-baking is preferably performed at a lower temperature, for example, 130° C. or less. The lower limit of the post-baking temperature is preferably 70°C or higher, more preferably 75°C or higher. Post-baking time is preferably 1 to 120 minutes, more preferably 5 to 60 minutes. In recent years, in order to improve production efficiency and reduce the influence on other members constituting color filters and the like, it is also required that curable resin compositions can be sufficiently cured at low temperatures. When the baking temperature is low, for example, about 150° C. or lower, it is difficult to expect the pattern shape to be improved by the heat of post-baking. . According to the curable resin composition of the present invention, a good pattern shape can be obtained, so even if the post-baking temperature is low, a cured film with a good pattern shape can be obtained.

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

In addition to color filters, protective films, spacers, and the like can also 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 color filters, spacers and/or protective films.

The present invention also provides a cured product (preferably a cured film) of the curable resin composition of the present invention. Moreover, according to this invention, the display apparatus containing this hardened|cured material can also be provided. The cured product of the present invention is useful as a colored layer, spacer and/or protective layer. The display device of the present invention containing the cured product of the present invention as at least one member is useful as a display device with few display defects. Furthermore, according to the curable resin composition of the present invention, since it is possible to form a good pattern shape, the cured product is a composition that constitutes, for example, a color filter, a protective film, a spacer, etc. contained in a color filter substrate. and is particularly suitable as a color filter for an organic EL display device.

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples, percentages and parts representing contents or usage amounts are based on mass unless otherwise specified.

<Weight average molecular weight>
The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using the GPC method under the following conditions. The ratio (Mw/Mn) of the polystyrene equivalent weight average molecular weight (Mw) to the number average molecular weight (Mn) obtained under the following conditions was defined as the molecular weight distribution.
Apparatus; HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature; 40°C
Solvent; Tetrahydrofuran [THF]
Flow rate; 1.0 mL/min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Standard material for calibration; 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)
C. I. Pigment Green 59 5.9 parts C.I. I. Pigment Yellow 150 4.1 parts C.I. I. Pigment Yellow 139 1.4 parts C.I. I. Pigment Blue 15:4 1.0 parts (dispersant F)
Acrylic pigment dispersant 3.6 parts (solvent)
Propylene glycol monomethyl ether acetate 84 parts The above amounts of colorant, dispersant and solvent were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion.

<Synthesis Example 2: Preparation of curable resin (A1)>
277 parts of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas inlet tube, stirred while replacing with nitrogen, and heated to 120°C.
To a monomer mixture consisting of 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate and 12.3 parts of dicyclopentanyl methacrylate was then added 35.3 parts of t-butylperoxy-2-ethylhexano The ate addition was dripped into the flask from the dropping funnel over 2 hours. After completion of dropping, the mixture was further stirred at 120° C. for 30 minutes to carry out a copolymerization reaction to produce an addition copolymer.
After that, the inside of the flask was replaced with air, and 93.7 parts of acrylic acid, 1.5 parts of triphenylphosphine and 0.8 parts of methoquinone were put into the above addition copolymer solution and reacted at 110°C for 10 hours. followed by the reaction between the epoxy group derived from glycidyl methacrylate and acrylic acid to cleave the epoxy group and simultaneously introduce a polymerizable unsaturated bond into the side chain of the polymer. Next, 24.2 parts of succinic anhydride was added to the reaction system, and the reaction was continued at 110°C for 1 hour to react the hydroxy groups generated by the cleavage of the epoxy groups with the succinic anhydride to introduce carboxy groups into the side chains. , and a weight-average molecular weight of 6400, a curable resin (A1) (double bond equivalent: 350 g/eq) was obtained. The double bond equivalent of the curable resin (A1) was calculated by analyzing the structure, molecular weight, etc. 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 added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas inlet tube, stirred while replacing with nitrogen, and heated to 120°C.
To a monomer mixture consisting of 140.5 parts of 2-ethylhexyl acrylate, 125.3 parts of glycidyl methacrylate and 11.2 parts of dicyclopentanyl methacrylate was then added 37.4 parts of t-butylperoxy-2-ethylhexano. The ate addition was dripped into the flask from the dropping funnel over 2 hours. After completion of dropping, the mixture was further stirred at 120° C. for 30 minutes to carry out a copolymerization reaction to produce an addition copolymer.
After that, the inside of the flask was replaced with air, 63.5 parts of acrylic acid, 1.4 parts of triphenylphosphine and 1.4 parts of methoquinone were put into the above addition copolymer solution and reacted at 120°C for 10 hours. followed by the reaction between the epoxy group derived from glycidyl methacrylate and acrylic acid to cleave the epoxy group and simultaneously introduce a polymerizable unsaturated bond into the side chain of the polymer. Next, 22.1 parts of succinic anhydride was added to the reaction system, and the reaction was continued for an additional 15 minutes. A curable resin (A2) having an average molecular weight of 6400 (double bond equivalent: 470 g/eq) was obtained. The double bond equivalent of the curable resin (A2) was calculated by analyzing the structure, molecular weight, etc. 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 added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and the mixture was stirred while being replaced with nitrogen and heated to 100°C.
Then, 47.1 parts of dimethyl 2,2'-azobis(2-methyl propionate) was added dropwise into the flask from the dropping funnel over a period of 2 hours. 10 after finishing dripping
The mixture was further stirred at 0° C. for 30 minutes to carry out a copolymerization reaction to form an addition copolymer.
Thereafter, the inside of the flask is replaced with air, 43.8 parts of acrylic acid, 1.0 part of triphenylphosphine and 1.0 part of dibutylhydroxytoluene are introduced into the above addition copolymer solution, and the mixture is heated at 120° C. for 10 hours. The reaction was continued over a period of time, and the reaction between the epoxy group derived from glycidyl methacrylate and acrylic acid cleaved the epoxy group and at the same time introduced a polymerizable unsaturated bond into the side chain of the polymer. Next, 22.1 parts of succinic anhydride was added to the reaction system, and the reaction was continued for an additional 1.5 hours to allow the hydroxy groups produced by the cleavage of the epoxy groups to react with the succinic anhydride to introduce carboxy groups into the side chains. A curable resin (A3) (double bond equivalent: 670 g/eq) having a weight average molecular weight of 6,500 was obtained. The double bond equivalent of the curable resin (A3) was calculated by analyzing the structure, molecular weight, etc. of each structural unit constituting the curable resin.

<Synthesis Example 5: Preparation of curable resin (A4)>
A 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer is filled with an appropriate amount of nitrogen to create a nitrogen atmosphere, 371 parts by mass of 1-methoxy-2-propyl acetate is added, and the flask is heated to 85° C. while stirring. bottom. Then, 54 parts by mass of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ² A mixed solution of 225 parts by mass of a mixture of ^,6 ]decane-9-yl acrylate, 81 parts by mass of vinyltoluene (isomer mixture) and 80 parts by mass of 1-methoxy-2-propyl acetate was added dropwise over 4 hours. On the other hand, a solution prepared by dissolving 30 parts by mass of 2,2-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator in 160 parts by mass of 1-methoxy-2-propyl acetate was added dropwise over 5 hours. After dropping the initiator solution, the temperature was kept 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>
Each component shown in Table 1 was mixed so as to have the compounding amount (solid content) shown in Table 1 to obtain a colored curable resin composition. Colorant D and dispersant F in Table 1 are components derived from the pigment dispersion liquid obtained in Synthesis Example 1 and contained. Moreover, in preparing the curable resin composition, propylene glycol monomethyl ether acetate was mixed so that the solid content of the curable resin composition was 14% by mass. The unit of the compounding amount of each component in Table 1 is "mass part", and colorant (D), curable resin (A), polymerization initiator (B), polymerizable compound (C), leveling agent (G). and the dispersing agent (F) are in terms of solid content.

重合開始剤（Ｂ２）：下記式で表される化合物

重合開始剤（Ｂ３）：ＮＣＩ－７３０（株式会社ＡＤＥＫＡ製；Ｏ－アシルオキシム化合物）
レベリング剤（Ｇ）：ポリエーテル変性シリコーンオイル（東レ・ダウコーニング（株）製の商品名「トーレシリコーンＳＨ８４００」）。 The polymerization initiator (B), polymerizable compound (C) and leveling agent (G) are as follows.
Polymerizable compound (C): Aronix (registered trademark) M-930 (manufactured by Toagosei Co., Ltd.; glycerin triacrylate (double bond equivalent: 85 g / eq)
Polymerization initiator (B1): a compound represented by the following formula

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

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

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

<Evaluation of patterning property>
A curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; Corning Incorporated) by spin coating, and then prebaked at 100° C. for 3 minutes to form a composition layer. After cooling, the distance between the substrate on which the composition layer was formed and the quartz glass photomask was set to 50 μm, and exposure was performed at 100 mJ/cm ² in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). (365 nm standard). A photomask having a 100 μm line-and-space pattern was used. The colored composition layer after light irradiation is immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 24 ° C. for 60 seconds, and washed with water to obtain a pattern. rice field.
The shape of the resulting pattern was observed using a scanning electron microscope (S-4000; manufactured by Hitachi High-Technologies Corporation). Table 2 shows the result of the insertion amount at the pattern end shown in FIG. The smaller the amount of insertion, the closer the shape is to vertical, and the tendency is that peeling from the base is less likely to occur.

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

Claims (9)

A curable resin composition comprising a curable resin (A) having a weight average molecular weight of 3,000 to 100,000 and a polymerization initiator (B),
The amount based on the solid content of the curable resin composition of the curable resin (A) is _WA mass%, the double bond equivalent of the curable resin (A) is _DA g / eq, and the curable resin composition The amount based on the solid content of the curable resin composition of the compound (C) having two or more polymerizable unsaturated bonds, which is optionally included, is _WC mass%, and the double bond equivalent of the compound (C) is D. When _C g/eq, the formula:
Amount of double bonds = W _A /D _A +W _C /D _C
A curable resin composition having a double bond content of 0.09 eq or less in 100 g of the solid content of the curable resin composition calculated by The curable resin composition according to claim 1, wherein the amount of the curable resin (A) based on the solid content of the curable resin composition (W _A mass%) is 20% by mass to 80% by mass. The amount (W _C mass%) based on the solid content of the curable resin composition of the compound (C) having two or more polymerizable unsaturated bonds is 0 to 20 mass%, curing according to claim 1 elastic resin composition. 2. The curable resin composition according to claim 1, wherein the amount of double bonds in 100 g of solid content of the curable resin composition is 0.03 eq or more. 2. The curable resin composition according to claim 1, wherein the polymerization initiator (B) is an O-acyloxime compound. The curable resin composition according to claim 1, further comprising a colorant. 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 color filters, spacers and/or protective layers contained in a color filter substrate. A display device comprising the cured film according to claim 7 .

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