JP2022153270A - Curable resin composition and cured product thereof - Google Patents

Abstract

To provide a curable resin composition capable of forming a pattern having a good shape.SOLUTION: The curable resin composition contains a resin (A), a polymerizable compound (B), and a polymerization initiator (C). The polymerization initiator (C) has a maximum absorption wavelength in the range of 360-390 nm. The content of the polymerizable compound (B) is 12 mass% or more and 27 mass% or less based on the total amount of solid contents contained in the curable resin composition. The mass ratio (C/B) of the content of the polymerization initiator (C) to the content of the polymerizable compound (B) is 26% or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to a curable resin composition and its cured product.

A color filter, which is a member included in a liquid crystal display device, comprises a black matrix layer and, for example, red (R), green (G), and blue (B) color resist layers for forming pixels on a transparent substrate. , and a protective layer. In addition, a columnar or striped spacer is formed between the color filter and the electrode in order to maintain a constant distance.

All of the above color resist layer, protective layer and spacer can be formed using a curable resin composition. As such a curable resin composition, Patent Document 1 describes a photosensitive colored resin composition containing a specific colorant, a photopolymerizable compound, and an oxime ester compound as a photoinitiator. . Such a curable resin composition is obtained, for example, by coating the curable resin composition, exposing it in a desired pattern, forming a pattern consisting of an exposed portion and an unexposed portion, and exposing from the pattern. It is used as a color resist layer or the like by a method of removing only the exposed portion or only the unexposed portion.

JP 2020-3614 A

For example, the color resist layer needs to be formed in a predetermined pattern. When removing only the non-existent portion, the pattern shape may deteriorate (for example, the insertion amount may increase). A protective layer and a spacer are also produced in the same manner, and in that case, the pattern shape may deteriorate. Therefore, there is a demand for a curable resin composition that can be formed into a good shape when forming these color resist layers and the like.
In recent years, in the manufacturing process of color resist layers and the like, it has been proposed that a curable resin composition can be sufficiently cured at a low temperature in order to improve manufacturing efficiency and reduce the influence on other members constituting a color filter. is also required.
In particular, when the post-baking temperature is set to a low temperature of, for example, about 150° C. or lower, it is required to form a pattern having a good shape during exposure and development, even in that the pattern shape cannot be expected to be improved by the heat of the post-baking. ing.

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.

As a result of intensive studies by the present inventors to solve the above problems, the resin (A), a polymerizable compound (B), and a polymerization initiator (C) having a maximum absorption wavelength in the range of 360 to 390 nm. , the content of the polymerizable compound (B), and the mass ratio (C/B) of the content of the polymerization initiator (C) to the content of the polymerizable compound (B) are adjusted within a predetermined range. The inventors have found that the above problems can be solved by the composition, and have completed the present invention. That is, the present invention includes the following aspects.

[1] A curable resin composition containing a resin (A), a polymerizable compound (B), and a polymerization initiator (C),
The polymerization initiator (C) has a maximum absorption wavelength in the range of 360 to 390 nm,
The content of the polymerizable compound (B) is 12% by mass or more and 27% by mass or less with respect to the total amount of solids contained in the curable resin composition, and
A curable resin composition, wherein the mass ratio (C/B) of the content of the polymerization initiator (C) to the content of the polymerizable compound (B) is 26% or less.
[2] The curable resin composition according to [1], wherein the polymerization initiator (C) has a maximum absorption wavelength in the range of 370 to 390 nm.
[3] The curable resin composition according to [1] or [2], wherein the polymerization initiator (C) is a compound having a carbazole skeleton.
[4] The curable resin composition according to any one of [1] to [3], wherein the polymerization initiator (C) is a compound having a nitro group.
[5] The curable resin composition according to any one of [1] to [4], further containing a coloring agent (D).
[6] A cured product of the curable resin composition according to any one of [1] to [5].

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 contains at least a resin (A), a polymerizable compound (B), and a polymerization initiator (C) having a maximum absorption wavelength in the range of 360-390 nm.

(Resin A)
Although the resin (A) is not particularly limited, it is preferably an alkali-soluble resin. The curable resin composition of the present invention may contain one kind of resin (A), or may contain two or more kinds of resins (A). Examples of the 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

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 having 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.

As (b), in the case of resin [K1] or resin [K2], (b1) is preferred in that the reliability of heat resistance, chemical resistance, etc. of the resulting color filter 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)acrylic acid esters 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, the storage stability of the curable resin composition, the developability when forming a pattern, and the durability of the obtained color filter, spacer, protective film, etc. It tends to have excellent 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 described later as the organic solvent (E) of the curable resin composition of the present invention. etc.

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 in the above range, the storage stability of the curable resin composition, the developability when forming a pattern, and the resulting color filter, spacer, protective film, etc. It 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 of the total structural units constituting the resin [K3] is
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 the pattern, the pattern shape, the curability at low temperature, and the solvent resistance, heat resistance, and mechanical strength of the resulting pattern and sensitivity tend to be well-balanced. 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 in the above range, the storage stability of the curable resin composition, the developability when forming a pattern, the pattern shape, and the low temperature resistance are improved. There is a tendency that curability and the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern are 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.

The resin (A) is preferably a resin (resin [K4] or resin [K5]) having a structural unit having an ethylenically unsaturated bond in the side chain, and a structural unit containing a (meth)acryloyl group in the side chain. A resin having a
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 polystyrene equivalent weight average molecular weight of the resin (A) is preferably 3,000 to 100,000, more preferably 4,000 to 50,000, and still more preferably 5,000 to 30,000. . When the molecular weight is within the above range, the hardness of the color filter, spacer, protective film, etc. is improved, the residual film rate is high, the solubility of the unexposed area in the developing solution is good, the pattern shape is improved, and the pattern shape is improved. resolution tends to improve.

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

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

The content of the resin (A) is preferably 5 to 50% by mass, more preferably 8 to 40% by mass, still more preferably 10 to 35% by mass, based on the total solid content of the curable resin composition. % by mass. When the content of the resin (A) is within the above range, the pattern can be easily formed, and the resolution of the pattern and the residual film ratio tend to be 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.

The content of the resin (A) is preferably 10 parts by mass or more and 95 parts by mass or less, more preferably 20 parts by mass or more, relative to 100 parts by mass of the total amount of the resin (A) and the polymerizable compound (B). It is 90 parts by mass or less, more preferably 30 parts by mass or more and 85 parts by mass or less. When the content of the resin (A) is within the above range, the solvent resistance of the resulting color filter, spacer, protective film, etc. is further improved.

(Polymerizable compound B)
The polymerizable compound (B) is a compound that can be polymerized by an active radical and/or an acid generated from the polymerization initiator (C). is a (meth)acrylic acid ester compound.

Among them, the polymerizable compound (B) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include 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.
Among them, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable from the viewpoint of pattern shape.

The weight average molecular weight of the polymerizable compound (B) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less, from the viewpoint of pattern shape.

The content of the polymerizable compound (B) is 12% by mass or more and 27% by mass or less with respect to the total amount of solids contained in the curable resin composition. If the content of the polymerizable compound (B) is less than 12% by mass, the pattern tends to peel off. Further, when the content of the polymerizable compound (B) exceeds 27% by mass, the coating film of the curable resin composition is exposed to light, and when the coating film is cured, the degree of curing within the coating film varies. is likely to occur, and the hardening of deep portions of the coating film becomes insufficient, making it impossible to obtain a good pattern shape. The content of the polymerizable compound (B) is preferably 13% by mass or more, more preferably 14% by mass or more, relative to the total amount of solids contained in the curable resin composition, from the viewpoint of preventing pattern peeling. It is more preferably 15% by mass or more, and from the viewpoint of easily obtaining a good pattern shape, it is preferably 26% by mass or less, more preferably 25% by mass or less, and even more preferably 24% by mass or less.

(Polymerization initiator C)
The polymerization initiator (C) is a polymerization initiator having a maximum absorption wavelength in the range of 360-390 nm. The curable resin composition of the present invention may contain one type of polymerization initiator (C) having a maximum absorption wavelength in the range of 360 to 390 nm, or 2 having a maximum absorption wavelength in the range of 360 to 390 nm. It may contain more than one polymerization initiator (C), or one or more polymerization initiators (C) having a maximum absorption wavelength in the range of 360 to 390 nm, and a maximum absorption wavelength in the range of 360 to 390 nm. It may also contain one or two or more other polymerization initiators that do not have an absorption wavelength.

The polymerization initiator (C) is a compound capable of initiating polymerization by generating active radicals, acids, etc. by the action of light or heat. The curable resin composition contains a polymerization initiator (C) having a maximum absorption wavelength in the range of 360 to 390 nm in a predetermined mass ratio with respect to the content of the polymerizable compound (B), thereby performing exposure and development. It is believed that a pattern with a good shape can be obtained in the process. In addition, it is believed that the curable resin composition can be sufficiently cured at a low temperature. Although the reason for this is not clear, the polymerization initiator (C) having a maximum absorption wavelength in the range of 360 to 390 nm is capable of efficiently generating radicals by exposure when the coating film of the curable resin composition is exposed to light. As a result, the curing of the curable resin composition can be sufficiently advanced. The polymerization initiator (C) having a maximum absorption wavelength in the range of 360 to 390 nm means that the absorption spectrum of the polymerization initiator (C) has at least one peak having a maximum absorption wavelength in the range of 360 to 390 nm. to represent the existence of The polymerization initiator (C) has a further maximum absorption wavelength in the range of less than 360 nm or more than 390 nm as long as it has at least one peak having a maximum absorption wavelength in the range of 360 to 390 nm in the absorption spectrum. good too.

The polymerization initiator (C) is not particularly limited as long as it has a maximum absorption wavelength in the range of 360 to 390 nm. O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds and acylphosphines. Oxide compounds are mentioned. Among them, O-acyloxime compounds are preferred.
A compound having a carbazole skeleton is preferable as the polymerization initiator having a maximum absorption wavelength in the range of 360 to 390 nm.
Further, the polymerization initiator having a maximum absorption wavelength in the range of 360-390 nm is preferably a compound having a nitro group.
The polymerization initiator (C) 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.

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):

It 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):

It is a compound having a structure represented by

The compound having a nitro group (—NO ₂ ) 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. It is a compound with a nitro group.

［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 (C) having a maximum absorption wavelength in the range of 360-390 nm is 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 ^a 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 , a methylene group (-CH ₂ -) may be replaced with -O-, -CO- or -S-, and a 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 a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group having no substituents, still more preferably a linear group having no substituents. A chain or branched alkyl group.

R. ^b The number of carbon atoms in the aromatic hydrocarbon group represented by 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.
Also R ^b The aromatic hydrocarbon group represented by 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. The methylene group contained in the alkyl group as the substituent (-CH ₂ -) 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 with 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 which 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 ^Rb 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 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〕］
し、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]]
and hydrogen atoms contained in R ⁱ and R ^j may be substituted with halogen atoms. 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 optionally substituted aromatic hydrocarbon group.
Commercially available products of the 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.

Among the compounds exemplified above, a compound having a maximum absorption wavelength of 360 to 390 nm is preferably used as the polymerization initiator (C) in the curable resin composition of the present invention.

The content of the polymerization initiator (C) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, with respect to 100 parts by mass of the total amount of the resin (A) and the polymerizable compound (B). parts by mass, more preferably 1 to 12 parts by mass. When the content of the polymerization initiator (C) is within the above range, it is possible to form a pattern with a good shape by exposure and development, and it is easy to improve the curability at low temperatures. 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.

In the curable resin composition of the present invention containing the resin (A), the polymerizable compound (B) and the polymerization initiator (C) as described above, the content of the polymerization initiator (C ) content mass ratio (C/B) is 26% or less. This means that the amount of the polymerization initiator (C) is less than or equal to the predetermined ratio with respect to the amount of the polymerizable compound (B) contained in the curable resin composition. When the mass ratio (C/B) exceeds 26%, in other words, when the amount of the polymerization initiator (C) is too large relative to the amount of the polymerizable compound (B), the resolution of the pattern is lowered. From the viewpoint of easily increasing the pattern resolution, the mass ratio (C/B) of the content of the polymerization initiator (C) to the content of the polymerizable compound (B) is preferably 23% or less, more preferably 21%. 19% or less, more preferably 19% or less. In addition, from the viewpoint of easily increasing curability, the mass ratio (C/B) is preferably 3% or more, more preferably 5% or more, still more preferably 7% or more, and even more preferably 10% or more.

(Other polymerization initiators that do not have a maximum absorption wavelength in the range of 360-390 nm)
The curable resin composition of the present invention has a maximum absorption wavelength in the range of 360 to 390 nm in addition to compounds having a maximum absorption wavelength in the range of 360 to 390 nm as the polymerization initiator (C), such as the above O-acyl oxime compounds. It may further contain other polymerization initiators that do not have an absorption wavelength. Polymerization initiators that do not have a maximum absorption wavelength in the range of 360 to 390 nm include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds. Such other polymerization initiators include O-acyl oxime compounds such as Irgacure OXE01 and OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA).

(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 coloring agent (D), it can be suitably used as a colored curable resin composition for forming a resist layer in a color filter. can. 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 a pigment dispersant 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 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 a pigment dispersant 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 necessary amount of the resin (A) and the polymerizable compound (B) is contained in the composition. Therefore, 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 resin (A) and the polymerizable compound (B) are included in the composition. can be contained in a required amount, a pattern with sufficient mechanical strength can be formed.

In the curable resin composition of the present invention, the coloring agent (D) preferably contains a xanthene dye. A xanthene dye is a dye containing a compound having a xanthene skeleton in its molecule. As the xanthene dye, a dye containing a compound represented by formula (I) (hereinafter sometimes referred to as "compound (I)") is preferred.

[In formula (I), R ¹ to R ⁴ are each independently a hydrogen atom, an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a represents a monovalent aromatic hydrocarbon group having ₆ to ²⁰ carbon atoms which may be may be
R ⁵ is -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ , or - ^represents _SO2NR9R10 ^.
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5; When m is 2 or more, multiple R ⁵ may be the same or different.
a represents an integer of 0 or 1;
X represents a halogen atom.
Z ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ , or K ⁺ , and the four R ¹¹ may be the same or different.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH contained in the saturated hydrocarbon group _2- may be substituted with -O-, -CO-, -NH-, or -NR ⁸ -, and R ⁹ and R ¹⁰ are bonded together with the adjacent nitrogen atom to form a 3- to 10-membered ring It may form a heterocyclic ring.
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]

Compound (I) may be its tautomer. When compound (I) is used, the content of compound (I) in the xanthene dye is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and most preferably 100% by mass. is.

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms for R ¹ to R ⁴ include methyl group, ethyl group, propyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. , dodecyl group, hexadecyl group, icosyl group, etc.; branched chain alkyl groups, such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, cyclohexyl cycloheptyl group, cyclooctyl group, tricyclodecyl group and other alicyclic saturated hydrocarbon groups having 2 to 20 carbon atoms. The number of carbon atoms in the saturated hydrocarbon group is the number including the carbon atoms of the substituent when the saturated hydrocarbon group has a substituent. Examples of substituents that the saturated hydrocarbon group may have include halogen atoms, —OH, —OR ⁸ , —SO ₃ ^— , —SO ₃ H, —SO ₃ ^— Z ⁺ , —CO ₂ H, —CO 2R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ , -SO ₂ NR ⁹ R ₁₀ , or -Si(OR ¹² )(OR ¹³ ) ^{(OR 14 )} . R ¹² , R ¹³ , and R ¹⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, and hydrogen atoms contained in the saturated hydrocarbon group are substituted with halogen atoms; good too.

The monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms for R ¹ to R ⁴ includes a phenyl group. The monovalent aromatic hydrocarbon group having a substituent includes toluyl, xylyl, mesityl, propylphenyl, butylphenyl and the like. When the aromatic hydrocarbon group has a substituent, the number of carbon atoms in the substituent is also included. Substituents which the aromatic hydrocarbon group may have include halogen atoms, -R ⁸ , -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, —CO ₂ R ⁸ , —SR ⁸ , —SO ₂ R ⁸ , —SO ₃ R ⁸ , —SO ₂ NR ⁹ R ¹⁰ , or —Si(OR ¹² )(OR ¹³ )(OR ¹⁴ ); be done.

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms for R ⁸ to R ¹¹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and nonyl group. , decyl group, dodecyl group, hexadecyl group, icosyl group and other linear alkyl groups; isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and other branched alkyl groups; cyclopropyl group, cyclopentyl cyclohexyl group, cycloheptyl group, cyclooctyl group, tricyclodecyl group and other alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁹ and R ¹⁰ may have a substituent. The substituent includes a hydroxy group and a halogen atom.

Examples of monovalent saturated hydrocarbon groups having 1 to 4 carbon atoms for R ¹² to R ¹⁴ include linear alkyl groups such as methyl group, ethyl group, propyl group and butyl group; Alicyclic saturated hydrocarbon groups having 1 to 4 carbon atoms such as branched alkyl groups are included.

Z ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ . At least two of the four R11 in ⁺ N(R ¹¹ ) ₄ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. Further, the total carbon number of the four R ¹¹ is preferably 20-80, more preferably 20-60. When ⁺ N(R ¹¹ ) ₄ is present in compound (I), when R 11 is one of these groups, a color filter with less foreign matter can be formed from the negative resist composition of the present invention containing compound (I). .

—OR ⁸ includes, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and an icosyloxy group.

—CO ₂ R ⁸ includes, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group and an icosyloxycarbonyl group.

—SR ⁸ includes, for example, a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, an icosylsulfanyl group and the like.
—SO ₂ R ⁸ includes, for example, a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group and an icosylsulfonyl group.
—SO ₃ R ⁸ includes, for example, a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group and an icosyloxysulfonyl group.

—SO ₂ NR ⁹ R ¹⁰ includes, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-(1,1-dimethylpropyl)sulfamoyl group, N-(1,2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group, N-(3 -methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-(3,3-dimethylbutyl)sulfamoyl group, N- heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl)sulfamoyl group, N- N-1 substituted sulfamoyl groups such as (1,5-dimethyl)hexylsulfamoyl group and N-(1,1,2,2-tetramethylbutyl)sulfamoyl group;
N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group moyl group, N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group and N,N-2 substituted sulfamoyl groups such as groups.

—Si(OR ¹² )(OR ¹³ )(OR ¹⁴⁾ includes, for example, a trimethoxysilyl group, a triethoxysilyl group and the like.

R ⁵ is preferably -CO ₂ H, -CO ₂ ^- Z ⁺ , -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ ^- Z ⁺ , -SO ₃ H, or SO ₂ NHR ⁹ , SO ₃ ^- , —SO ₃ ⁻ Z ⁺ , —SO ₃ H or SO ₂ NHR ⁹ are more preferred.

m represents an integer of 0 to 5, preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

Examples of the alkyl group having 1 to 6 carbon atoms for R ⁶ and R ⁷ include those having 1 to 6 carbon atoms among the above-mentioned alkyl groups, and alkyl groups having 1 to 2 carbon atoms are preferred. More preferably, ^R6 and ^R7 are hydrogen atoms.

Examples of the aralkyl group having 7 to 10 carbon atoms for R ¹¹ include a benzyl group, a phenylethyl group and a phenylbutyl group.

a represents an integer of 0 or 1, preferably 0;

［式（Ｉａ）中、
Ｒ^ａ１及びＲ^ａ４は、それぞれ独立して、２個以下の炭素数が１～４の１価の飽和脂肪族炭化水素基を有していてもよい１価の芳香族炭化水素基である。
Ｒ^ａ２及びＲ^ａ３は、それぞれ独立して、水素原子、メチル基、又はエチル基である。
Ｒ^５～Ｒ^７、ｍ、ａ、及びＸは上記と同じ意味を表す。］ As the compound (I), a compound represented by the formula (Ia) (hereinafter "compound (Ia)" is preferably exemplified. The compound represented by the formula (Ia) is the compound (Ia) among the compounds (I) It may be used without combination with a compound other than (hereinafter sometimes referred to as "compound (Ib)"), or compound (Ia) and compound (Ib) may be used in combination. More than one species may be used in combination.

[In the formula (Ia),
R ^a1 and R ^a4 are each independently a monovalent aromatic hydrocarbon group optionally having 2 or less monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms.
R ^a2 and R ^a3 are each independently a hydrogen atom, a methyl group, or an ethyl group.
R ⁵ to R ⁷ , m, a and X have the same meanings as above. ]

R ^a1 and R ^a4 are unsubstituted monovalent aromatic hydrocarbon groups or groups having 2 or less carbon atoms of 1 to 4 among the same groups as those of R ¹ and R ⁴ above. A monovalent aromatic hydrocarbon group having a valent saturated aliphatic hydrocarbon group can be mentioned. Among these, a monovalent aromatic hydrocarbon group having a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms and having 2 or less carbon atoms is preferable.

A phenyl group is mentioned as a monovalent aromatic hydrocarbon group which does not have a substituent. Examples of the monovalent aromatic hydrocarbon group having a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms of 2 or less include a toluyl group, a xylyl group and a mesityl group. The aromatic hydrocarbon group preferably has 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, still more preferably 7 to 10 carbon atoms, and most preferably 8 carbon atoms. The number of carbon atoms in the aromatic hydrocarbon group is the number including the carbon atoms in the substituent. The aromatic hydrocarbon group preferably has no substituents other than the saturated aliphatic hydrocarbon group.

The number of saturated aliphatic hydrocarbon groups bonded to the aromatic hydrocarbon group is preferably 1 to 2, more preferably 2. The saturated aliphatic hydrocarbon group is preferably bonded at the ortho- or meta-position, more preferably at the ortho-position, with respect to the bond of the aromatic hydrocarbon group. Examples of the saturated aliphatic hydrocarbon group include saturated aliphatic hydrocarbon groups having no substituents. The saturated aliphatic hydrocarbon group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, still more preferably 1 to 2 carbon atoms, and most preferably 1 carbon atom.

R ^a2 and R ^a3 include a hydrogen atom, a methyl group, and an ethyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

［式（Ｉｂ１）中、Ｒ^ｂ１～Ｒ^ｂ４は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基、又は置換基を有していてもよい炭素数６～２０の１価の芳香族炭化水素基を表し、
Ｒ^ｂ１～Ｒ^ｂ４に含まれる少なくとも１つの飽和炭化水素基又は芳香族炭化水素基が、ハロゲン原子、－ＯＨ、－ＯＲ^８、－ＣＯ_２Ｈ、－ＣＯ_２Ｒ^８、－ＳＯ_３ ^－、－ＳＯ_３Ｈ、－ＳＯ_３ ^－Ｚ^＋、－ＳＲ^８、－ＳＯ_２Ｒ^８、－ＳＯ_３Ｒ^８、－ＳＯ_２ＮＲ^９Ｒ^１０、又は－Ｓｉ（ＯＲ^１２）（ＯＲ^１３）（ＯＲ^１４）を置換基として有するか、又はＲ^ｂ１～Ｒ^ｂ４に含まれる少なくとも１つの芳香族炭化水素基が、３個以上の炭素数が１～４の１価の飽和脂肪族炭化水素基を置換基として有し、
Ｒ^５～Ｒ^１０、Ｒ^１２～Ｒ^１４、ｍ、ａ、及びＸは上記と同じ意味を表す。］ Compound (Ib) is preferably a compound represented by formula (Ib1) (hereinafter sometimes referred to as "compound (Ib1)"). Compound formula (Ib1) is preferably used in combination with compound (Ia), but may be used without combination with compound (Ia). That is, the xanthene dye may be compound (Ia) and/or compound (Ib1), preferably compound (Ia), or compound (Ia) and compound (Ib1), and compound (Ia) It is more preferable to have

[In the formula (Ib1), R ^b1 to R ^b4 are each independently a hydrogen atom, an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a substituent represents a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may be
at least one saturated hydrocarbon group or aromatic hydrocarbon group contained in R ^b1 to R ^b4 is a halogen atom, —OH, —OR ⁸ , —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ ^— , — SO ₃ H, —SO ₃ ^— Z ⁺ , —SR ⁸ , —SO ₂ R ⁸ , —SO ₃ R ⁸ , —SO ₂ NR ⁹ R ¹⁰ , or —Si(OR ¹² ) (OR ¹³ ) (OR ¹⁴ ) as a substituent, or at least one aromatic hydrocarbon group contained in R ^b1 to R ^b4 is a monovalent saturated aliphatic hydrocarbon group having 3 or more carbon atoms of 1 to 4 as a substituent have
R ⁵ to R ¹⁰ , R ¹² to R ¹⁴ , m, a and X have the same meanings as above. ]

R ^b1 and R ^b4 are, among the same groups as those of R ¹ and R ⁴ above, a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a substituent. optionally having a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms or a monovalent saturated aliphatic hydrocarbon group with 1 to 4 carbon atoms and having 3 or more substituents An aromatic hydrocarbon group is mentioned. Among these, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms and having a substituent, or 3 An aromatic hydrocarbon group having a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms as a substituent is preferred.

The number of carbon atoms in the optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is preferably 1 to 10, more preferably 2 to 8, and even more preferably 2 to 7. The number of carbon atoms in the saturated aliphatic hydrocarbon group is the number including the carbon atoms in the substituent. Substituents include halogen atoms, -OH, -OR ⁸ , -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -SR ⁸ , -SO ₂ R ⁸ , —SO ₃ R ⁸ , —SO ₂ NR ⁹ R ¹⁰ , or —Si(OR ¹² ) (OR ¹³ ) (OR ¹⁴ ) are preferred, and —OH, —OR ⁸ , —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ ⁻ , —SO ₃ H, —SO ₃ ^— Z ⁺ , —SR ⁸ , —SO ₂ R ⁸ , —SO ₃ R ⁸ , or —Si(OR ¹² )(OR ¹³ ) (OR ¹⁴ ), more preferably —OH, —OR ⁸ , —CO ₂ H, —CO ₂ R ⁸ , or —Si(OR ¹² )(OR ¹³ )(OR ¹⁴ ), most preferably — Si(OR ¹² )(OR ¹³ )(OR ¹⁴ ). The number of substituents per saturated aliphatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, and most preferably 1.

The number of carbon atoms in the optionally substituted monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms is preferably 7 to 20, more preferably 7 to 16, still more preferably 7 to 12, Even more preferably 7-10, particularly preferably 7-8, most preferably 8. The number of carbon atoms in the aromatic hydrocarbon group is the number including the carbon atoms in the substituent. Substituents include monovalent saturated aliphatic hydrocarbon groups having 1 to 4 carbon atoms, halogen atoms, —OH, —OR ⁸ , —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ ^— , —SO ₃ H, —SO ₃ ^— Z ⁺ , —SR ⁸ , —SO ₂ R ⁸ , —SO ₃ R ⁸ , —SO ₂ NR ⁹ R ¹⁰ , or —Si(OR ¹² ) (OR ¹³ ) (OR ¹⁴ ) preferably, more preferably a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, —OH, —OR ⁸ , —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ ^— , —SO ₃ H, —SO ₃ ^— Z ⁺ , —SR ⁸ , —SO ₂ R ⁸ , —SO ₃ R ⁸ , or —SO ₂ NR ⁹ R ¹⁰ . More preferably, a monovalent saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -SR ⁸ , -SO ₂ R ⁸ , —SO ₃ R ⁸ , or —SO ₂ NR ⁹ R ¹⁰ . The number of substituents per aromatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, and most preferably 2. The substituent is preferably bonded at the ortho-position and/or the meta-position, more preferably at the ortho-position, with respect to the bond of the aromatic hydrocarbon group.

The number of carbon atoms in the aromatic hydrocarbon group having 3 or more monovalent saturated aliphatic hydrocarbon groups with 1 to 4 carbon atoms as substituents is preferably 9 to 20, more preferably 9 to 13. , more preferably 9 to 12, and most preferably 9. The number of carbon atoms in the aromatic hydrocarbon group is the number including the carbon atoms in the substituent. The aromatic hydrocarbon group preferably has no substituents other than the saturated aliphatic hydrocarbon group. The number of saturated aliphatic hydrocarbon groups is preferably 3-5, more preferably 3-4, and most preferably 3 per aromatic hydrocarbon group. The saturated aliphatic hydrocarbon group is preferably bonded at the ortho-position and/or para-position with respect to the bond of the aromatic hydrocarbon group, and is preferably bonded at the ortho-position and para-position. more preferred. The number of carbon atoms in the monovalent saturated aliphatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, most preferably 1. preferable.

R ^b2 and R ^b3 are preferably a hydrogen atom or an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms among the same groups as those of R ² and R ³ above. be done. Among them, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is more preferable, and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which has a substituent is more preferable. preferable.

The number of carbon atoms in the optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4. The number of carbon atoms in the saturated aliphatic hydrocarbon group is the number including the carbon atoms in the substituent. Substituents include halogen atoms, -OH, -OR ⁸ , -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- Z ⁺ , -SR ⁸ , -SO ₂ R ⁸ , —SO ₃ R ⁸ , —SO ₂ NR ⁹ R ¹⁰ , or —Si(OR ¹² ) (OR ¹³ ) (OR ¹⁴ ) are preferred, and —OH, —OR ⁸ and —CO ₂ are more preferred. H, —CO ₂ R ⁸ , —SO ₃ ⁻ , —SO ₃ H, —SO ₃ ^— Z ⁺ , —SR ⁸ , —SO ₂ R ⁸ , —SO ₃ R ⁸ , or —Si(OR ¹² )(OR ¹³ ) (OR ¹⁴ ), more preferably —OH, —OR ⁸ , —CO ₂ H, —CO ₂ R ⁸ , or —Si(OR ¹² ) (OR ¹³ ) (OR ¹⁴ ), most preferably is -CO ₂ H or -CO ₂ R ⁸ . The number of substituents per saturated aliphatic hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 to 2, and most preferably 1.

As the compound (Ia), compound Nos. specified by the formula (IaX) and Table 1 are used. 1 to 15 are preferred.

The symbols in the formula mean the following groups (* represents a bond below).

As the compound (Ib1), compound Nos. specified by the formula (Ibx) and Table 2 are used. 16 to 35 and compounds represented by formulas A3-1 to A3-8 are preferred.

The symbols in the formula mean the following groups (* represents a bond below).

(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 (C).
The polymerization initiation aid (E) includes 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 is preferably 0.1 to 30 parts by mass, with respect to 100 parts by mass of the total amount of the resin (A) and the polymerizable compound (B), and more It is 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 F)
The curable resin composition of the present invention may further contain at least one solvent (F). The solvent is not particularly limited, and solvents commonly used in this 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 but 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 (F) 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 (F) 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 colored resin composition is preferably 20-70% by mass, more preferably 25-65% by mass. When the content of the solvent (F) 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, Flora F172, Flora F173, Flora F177, Flora F183, Flora 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 color filter and the like can be improved.

(other ingredients)
The curable resin composition of the present invention may optionally contain fillers, other polymer compounds, adhesion promoters, 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 resin (A), a polymerizable compound (B), a polymerization initiator (C), and optionally a coloring agent (D), a polymerization initiation aid ( It can be prepared by mixing E), solvent (F), leveling agent (G) 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 remaining components with the pigment dispersion liquid so as to have 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.

<Manufacturing method of color filter>
Examples of methods for producing a colored pattern 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 colored resin composition is applied to a substrate, dried to form a colored composition layer, exposed through a photomask, and developed. In the photolithographic method, a colored coating film, which is a cured product of the colored composition layer, can be formed by not using a photomask during exposure and/or not developing. The colored pattern or colored coating film thus formed is the color filter of the present invention.
The film thickness of the color filter 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. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by the photolithographic method can be carried out using a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored resin composition is applied onto a substrate, dried by heating (pre-baking) and/or dried under reduced pressure to remove volatile components such as solvents, and dried to obtain a smooth colored 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 film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the desired film thickness of the color filter.

The colored composition layer is then exposed through a photomask to form the desired colored 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 . .
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 colored composition layer is formed. is preferred.

A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide and the like are preferable. 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 colored 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 color filter used in an organic EL display device. 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.

The film thickness of the coating 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 film thickness of the coating 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. The present invention also provides a cured product of the curable resin composition of the present invention. ADVANTAGE OF THE INVENTION According to the curable resin composition of this invention, the curable resin composition which is useful for manufacturing a color filter etc. suitable for an organic EL display device, and can form a favorable pattern shape can be provided.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited by the following examples. In the examples, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

<Synthesis Example 1: Preparation of pigment dispersion (D1)>
C. I. Pigment Red 291 8.5 parts C.I. I. Pigment Yellow 139 3.6 parts Acrylic pigment dispersant 3.9 parts Propylene glycol monomethyl ether acetate 84.0 parts are mixed, and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (D1). rice field.

<Synthesis Example 2: Preparation of pigment dispersion (D2)>
C. I. Pigment Green 59 8.2 parts C.I. I. Pigment Yellow 150 3.8 parts C.I. I. Pigment Yellow 139 0.6 parts Acrylic pigment dispersant 3.4 parts Propylene glycol monomethyl ether acetate 84.0 parts are mixed, and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (D2). rice field.

<Synthesis Example 3: Preparation of pigment dispersion (D3)>
C. I. Pigment Blue 16 9.1 parts Pink Base (manufactured by Taiyo Fine Chemical Co., Ltd.) 2.3 parts Acrylic pigment dispersant 4.6 parts Propylene glycol monomethyl ether acetate 84.0 parts were mixed, and the pigment was sufficiently dispersed using a bead mill. to obtain a pigment dispersion (D3).

<Synthesis Example 4: Preparation of Resin (A1)>
36 parts of propylene glycol monomethyl ether acetate and 14 parts of propylene glycol monomethyl ether were introduced into a separable flask equipped with a cooling tube as a reaction vessel, and after replacing with nitrogen, the temperature was raised to 90°C. On the other hand, in dropping tank 1, 4.5 parts of N-benzylmaleimide, 10 parts of acrylic acid, 0.6 parts of t-butyl peroxy-2-ethylhexanoate, 2 parts of propylene glycol monomethyl ether acetate, and 2 parts of propylene glycol monomethyl ether. The parts were mixed. Also, 15 parts of vinyl toluene and 1 part of n-dodecyl mercaptan were mixed in the dropping tank 2 .
While maintaining the reaction temperature at 90° C., the dropping tanks 1 and 2 were dropped into the reaction tank at a constant rate over 4.0 hours. After the dropwise addition was completed, the temperature was maintained at 90°C for 30 minutes, then 0.1 part of t-butylperoxy-2-ethylhexanoate was added, and the reaction was continued at 90°C for 30 minutes. After that, the reaction temperature was raised to 115° C. and the reaction was continued for 1.5 hours. After cooling to room temperature, 15 parts of glycidyl methacrylate, 0.06 parts of 2,2′-methylenebis(4-methyl-6-t-butylphenol) and 0.1 parts of triethylamine were added to adjust the oxygen concentration to 7%. While bubbling a nitrogen/air mixed gas, the temperature was raised to 110° C. and the reaction was carried out for 12 hours. Then, it was cooled to room temperature to obtain a polymer solution 1 containing resin (A1).
When various physical properties of the obtained polymer solution 1 were measured, the weight average molecular weight of the resin (A1) measured by GPC (gel permeation chromatography) using polystyrene as a standard material was 13,000 at 160°C under vacuum. The solid content concentration obtained by drying was 41%, and the acid value per solid content of resin (A1) obtained by titration was 55 mgKOH/g.

<Synthesis Example 5: Preparation of resin (A2)>
40 parts of propylene glycol monomethyl ether acetate and 16 parts of propylene glycol monomethyl ether were introduced into a separable flask equipped with a cooling tube as a reaction tank, and after replacing with nitrogen, the temperature was raised to 90°C. On the other hand, 4 parts of N-benzylmaleimide, 12 parts of acrylic acid, 0.5 parts of t-butyl peroxy-2-ethylhexanoate, 2 parts of propylene glycol monomethyl ether acetate, and 2 parts of propylene glycol monomethyl ether were added to dropping vessel 1. Mixed. Further, 10 parts of vinyl toluene and 1 part of n-dodecyl mercaptan were mixed in the dropping tank 2 .
While maintaining the reaction temperature at 90° C., the dropping tanks 1 and 2 were dropped into the reaction tank at a constant rate over 4.0 hours. After the dropwise addition was completed, the temperature was maintained at 90°C for 30 minutes, then 0.1 part of t-butylperoxy-2-ethylhexanoate was added, and the reaction was continued at 90°C for 30 minutes. After that, the reaction temperature was raised to 115° C. and the reaction was continued for 1.5 hours. After cooling to room temperature, 12.7 parts of glycidyl methacrylate, 0.06 parts of 2,2'-methylenebis(4-methyl-6-t-butylphenol) and 0.1 parts of triethylamine were added to adjust the oxygen concentration to 7%. While bubbling the adjusted nitrogen/air mixed gas, the temperature was raised to 110° C. and the reaction was carried out for 12 hours. Then, it was cooled to room temperature to obtain polymer solution 2 containing resin (A2).
When various physical properties of the obtained polymer solution 2 were measured, the weight average molecular weight of the resin (A2) measured by GPC (gel permeation chromatography) using polystyrene as a standard material was 16000, and the resin (A2) was dried at 160°C under vacuum. The solid content concentration obtained by this method was 37%, and the acid value per solid content of the resin (A2) obtained by titration was 127 mgKOH/g.

<Synthesis Example 6: Preparation of pigment dispersion (D4)>
C. I. Pigment Green 59 7.7 parts C.I. I. Pigment Yellow 150 3.8 parts C.I. I. Pigment Yellow 139 0.5 parts C.I. I. Pigment Red 177 0.6 parts Acrylic pigment dispersant 3.4 parts Propylene glycol monomethyl ether acetate 84.0 parts are mixed, and the pigment is sufficiently dispersed using a bead mill to obtain a pigment dispersion (D4). rice field.

<Synthesis Example 7: Preparation of pigment dispersion (D5)>
C. I. Pigment Blue 16 9.4 parts Pink Base (manufactured by Taiyo Fine Chemical Co., Ltd.) 2.1 parts Acrylic pigment dispersant 4.6 parts Propylene glycol monomethyl ether acetate 84.0 parts were mixed, and the pigment was sufficiently dispersed using a bead mill. to obtain a pigment dispersion (D5).

<Synthesis Example 8: Preparation of resin (A3)>
178.0 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. After completion of dropping, the mixture was further stirred at 100° C. for 30 minutes to carry out a copolymerization reaction.
After that, the inside of the flask was replaced with air, 43.8 parts of acrylic acid, 1.0 part of triphenylphosphine and 1.0 part of dibutylhydroxytoluene were added, and the reaction was continued at 120°C for 10 hours. 22.1 parts of succinic anhydride was added to the solution, and the reaction was continued for 1.5 hours to obtain a resin (A3) having a weight average molecular weight of 6,500. The acid value per solid content of resin (A3) was 42.3 mgKOH/g.

<Synthesis Example 9: Preparation of resin (A4)>
276.8 g 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 under nitrogen substitution and heated to 120°C.
Then 35.3 g of t-butyl peroxy-2-ethylhexanoate was added to a monomer mixture consisting of 92.4 g of 2-ethylhexyl acrylate, 184.9 g of glycidyl methacrylate and 12.3 g of dicyclopentanyl methacrylate. was dropped 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, 93.7 g of acrylic acid, 1.5 g of triphenylphosphine and 0.8 g of methoquinone were put into the above addition copolymer solution, and the reaction was continued at 110° C. for 10 hours. The reaction between the epoxy group derived from glycidyl methacrylate and acrylic acid cleaved the epoxy group and at the same time introduced a polymerizable unsaturated bond into the side chain of the polymer. Next, 24.2 g 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, A resin (A4) was obtained. Resin (A4) had a weight average molecular weight of 6400 and an acid value per solid content of 35.4 mgKOH/g.

<Examples 1 to 7 and Comparative Examples 1 to 2>
(1) Preparation of colored curable resin composition The components shown in Table 3 were mixed in the amounts shown in Table 3 to obtain a colored curable resin composition. In preparing the colored curable resin composition, propylene glycol monomethyl ether acetate was mixed so that the solid content of the colored curable resin composition was 15% by weight. The unit of the amount of each component in Table 3 is "parts by mass", and colorants (D1) to (D5), resins (A), polymerizable compounds (B), polymerization initiators (C), other polymerization Each compounding amount of the initiator (X) and the leveling agent (G) is in terms of solid content. Also, the content of the polymerizable compound (B) with respect to the total amount of solids contained in the curable resin composition in each composition, and the content of the polymerization initiator (C) with respect to the content of the polymerizable compound (B) Table 4 shows the mass ratio (C/B) of

重合開始剤（Ｃ２）：下記式で表される化合物（ＢＡＳＦ（株）製、商品名「イルガキュアＯＸＥ０３」）、極大吸収波長３６０ｎｍ

その他の重合開始剤（Ｘ）：下記式で表される化合物、極大吸収波長３３０ｎｍ

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 polymerizable compound (B), polymerization initiator (C), other polymerization initiator (X), and leveling agent (G) are as follows.
Polymerizable compound (B): dipentaerythritol hexaacrylate/dipentaerythritol pentaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “A-9550”)
Polymerization initiator (C1): compound represented by the following formula (NCI-831), maximum absorption wavelength 370 nm

Polymerization initiator (C2): a compound represented by the following formula (manufactured by BASF Corporation, trade name “Irgacure OXE03”), maximum absorption wavelength 360 nm

Other polymerization initiator (X): a compound represented by the following formula, maximum absorption wavelength 330 nm

Leveling agent (G): Polyether-modified silicone oil (trade name "Toray Silicone SH8400" manufactured by Dow Corning Toray Co., Ltd.)

(2) Evaluation of patterning property On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), the colored curable resin composition was applied by spin coating, and then prebaked at 100 ° C. for 3 minutes to form a colored composition. formed a layer. After standing to cool, the distance between the substrate on which the colored composition layer was formed and the quartz glass photomask was set to 50 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an air atmosphere at 100 mJ/cm. ² (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 form a colored pattern. Obtained.
The shape of the resulting colored pattern was observed using a scanning electron microscope (S-4000; manufactured by Hitachi High-Technologies Corporation). Table 4 shows the result of the insertion amount at the pattern edge 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 and 2, 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.

Claims (6)

A curable resin composition comprising a resin (A), a polymerizable compound (B), and a polymerization initiator (C),
The polymerization initiator (C) has a maximum absorption wavelength in the range of 360 to 390 nm,
The content of the polymerizable compound (B) is 12% by mass or more and 27% by mass or less with respect to the total amount of solids contained in the curable resin composition, and
A curable resin composition, wherein the mass ratio (C/B) of the content of the polymerization initiator (C) to the content of the polymerizable compound (B) is 26% or less. 2. The curable resin composition according to claim 1, wherein the polymerization initiator (C) has a maximum absorption wavelength in the range of 370-390 nm. The curable resin composition according to claim 1 or 2, wherein the polymerization initiator (C) is a compound having a carbazole skeleton. The curable resin composition according to any one of claims 1 to 3, wherein the polymerization initiator (C) is a compound having a nitro group. The curable resin composition according to any one of claims 1 to 4, further comprising a coloring agent (D). A cured product of the curable resin composition according to any one of claims 1 to 5.

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