JP2010106154A - Curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition not only exhibiting excellent storage stability but also capable of forming a coated film or a pattern having high transmittance. <P>SOLUTION: The curable resin composition contains (A) a binder resin and (B) at least one kind of compounds selected from the group consisting of a carboxylic anhydride and a compound having at least two carboxyl groups, wherein the binder resin (A) is prepared by polymerizing at least (A-a) an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, and (A-b) a monomer copolymerizable with the component (A-a) and/or (A-c) a monomer having a 2-4C cyclic ether group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a curable resin composition, a coating film, a pattern, and a display device.

  It has been proposed that a spacer (photo spacer) is formed by photolithography using a curable resin composition between a color filter constituting the display device such as a liquid crystal display device or a touch panel and the array substrate. According to this method, the spacer can be formed at an arbitrary place.

As such a curable resin composition, a resin obtained by polymerizing a monomer having a glycidyl group, at least one compound selected from a polyvalent carboxylic acid anhydride and a polyvalent carboxylic acid, and a silane coupling agent There is known a curable resin composition containing (Patent Document 1).
JP-A-60-217230

However, the storage stability of the composition is not always sufficient in the curable resin composition.
The subject of this invention is providing the curable resin composition which can form the coating film or pattern of high transmittance | permeability while showing the outstanding storage stability.

  As a result of studying to find a curable resin composition that can solve the above-mentioned problems, the present inventors have found that at least an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (Aa) and the (A A binder resin obtained by polymerizing a monomer (Ab) copolymerizable with -a) and / or a monomer having a cyclic ether group having 2 to 4 carbon atoms (Ac); It has been found that the storage stability of the composition is improved by using at least one compound selected from the group consisting of a carboxylic acid anhydride and a compound having at least two carboxyl groups, and the present invention has been achieved.

［式（Ｉ）及び式（ＩＩ）中、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表す。該アルキル基に含まれる水素原子は、水酸基で置換されていてもよい。
Ｘ_１及びＸ_２は、それぞれ独立に、単結合又はヘテロ原子を含んでもよい炭素数１〜６のアルキレン基を表す。］
［６］カルボン酸無水物及び少なくとも２個のカルボキシル基を有する化合物からなる群から選ばれる少なくとも１種の化合物（Ｂ）が、カルボン酸無水物である、前記［１］〜［５］のいずれかに記載の硬化性樹脂組成物。
［７］不飽和カルボン酸及び／又は不飽和カルボン酸無水物（Ａ−ａ）が、脂肪族不飽和カルボン酸及び／又は脂肪族不飽和カルボン酸無水物である、前記［１］〜［６］のいずれかに記載の硬化性樹脂組成物。
［８］式（Ｉ）で表される化合物及び式（ＩＩ）で表される化合物からなる群から選ばれる少なくとも１種の化合物が、式（Ｉ’）で表される化合物及び式（ＩＩ’）で表される化合物からなる群から選ばれる少なくとも１種の化合物である、前記［５］〜［７］のいずれかに記載の硬化性樹脂組成物。

［式（Ｉ’）及び式（ＩＩ’）中、Ｒ_１’及びＲ_２’は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表す。該アルキル基に含まれる水素原子は、水酸基で置換されていてもよい。］
［９］塗膜又はパターンを形成するための、前記［１］〜［８］のいずれかに記載の硬化性樹脂組成物の使用。
［１０］前記［１］〜［８］のいずれかに記載の硬化性樹脂組成物を用いて形成される塗膜。
［１１］前記［１０］に記載の塗膜を含む表示装置。 That is, the present invention provides the following [1] to [11].
[1] containing a binder resin (A) and at least one compound (B) selected from the group consisting of a carboxylic acid anhydride and a compound having at least two carboxyl groups,
The binder resin (A) comprises at least an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (Aa), a monomer (Ab) and / or copolymerizable with the (Aa). Or the curable resin composition which is a binder resin formed by superposing | polymerizing with the monomer (Ac) which has a C2-C4 cyclic ether group.
[2] The binder resin (A) is a monomer having at least an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (AA) and a cyclic ether group having 2 to 4 carbon atoms (Ac The curable resin composition according to the above [1], which is a binder resin obtained by polymerization of
[3] The curable resin composition according to the above [1] or [2], wherein the monomer having a cyclic ether group having 2 to 4 carbon atoms (Ac) is a monomer having an epoxy group. .
[4] The curable resin composition according to [3], wherein the monomer having an epoxy group is a monomer having an aliphatic polycyclic epoxy group.
[5] The monomer having an aliphatic polycyclic epoxy group is at least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II). Curable resin composition as described in said [4].

[In Formula (I) and Formula (II), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.
X ₁ and X ₂ each independently represent a C 1-6 alkylene group that may contain a single bond or a hetero atom. ]
[6] Any of [1] to [5] above, wherein at least one compound (B) selected from the group consisting of a carboxylic acid anhydride and a compound having at least two carboxyl groups is a carboxylic acid anhydride. A curable resin composition according to claim 1.
[7] The above [1] to [6], wherein the unsaturated carboxylic acid and / or the unsaturated carboxylic acid anhydride (Aa) is an aliphatic unsaturated carboxylic acid and / or an aliphatic unsaturated carboxylic acid anhydride. ] The curable resin composition in any one of.
[8] At least one compound selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (II) is a compound represented by formula (I ′) and formula (II ′). The curable resin composition according to any one of [5] to [7], which is at least one compound selected from the group consisting of compounds represented by:

[In Formula (I ′) and Formula (II ′), R ₁ ′ and R ₂ ′ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. ]
[9] Use of the curable resin composition according to any one of [1] to [8] for forming a coating film or a pattern.
[10] A coating film formed using the curable resin composition according to any one of [1] to [8].
[11] A display device including the coating film according to [10].

  According to the curable resin composition of the present invention, it is possible to form a coating film or pattern having a high transmittance even after storage for a predetermined period, as in the case before storage.

Hereinafter, the present invention will be described in detail.
The curable resin composition of the present invention contains a binder resin (A) and at least one compound (B) selected from the group consisting of a carboxylic acid anhydride and a compound having at least two carboxyl groups,
The binder resin (A) comprises at least an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (Aa), a monomer (Ab) and / or copolymerizable with the (Aa). Alternatively, it is a binder resin obtained by polymerizing a monomer (Ac) having a cyclic ether group having 2 to 4 carbon atoms.

  Examples of the binder resin (A) used in the curable resin composition of the present invention include the binder resin (A1) and the binder resin (A2). The binder resin (A1) exhibits alkali solubility, and the binder resin (A2) exhibits alkali solubility and reactivity due to the action of at least one of light and heat.

  As the binder resin (A1), at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (A-a) (hereinafter sometimes referred to as “(A-a)”), Copolymer with monomer (Ab) copolymerizable with (Aa) (excluding (Aa)) (hereinafter sometimes referred to as “(Ab)”) Is exemplified.

Examples of (Aa) include aliphatic unsaturated carboxylic acids and / or aliphatic unsaturated carboxylic acid anhydrides. Specifically, for example,
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
And anhydrides of the aforementioned unsaturated dicarboxylic acids;
Unsaturated mono [(meth) acryloyloxy of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Alkyl] esters;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid or maleic anhydride is preferably used from the viewpoint of copolymerization reactivity and alkali solubility. These may be used alone or in combination.

As (Ab),
(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, dicyclopenta Nyl (meth) acrylate), (meth) acrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate, isoboronyl (meth) acrylate;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate (commonly referred to in the art as dicyclopentanyl acrylate), dicyclo. Acrylic acid cyclic alkyl esters such as pentaoxyethyl acrylate and isobornyl acrylate;
(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-carboxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1 ] Hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5,6- Di (hydroxymethyl) bicyclo [2.2.1] hept-2-e 5,6-di (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6 -Diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2 .1] Hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6- Ethylbicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxy Carbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (tert-butoxycarbonyl) bicyclo [2.2. 1] Bicyclo unsaturated compounds such as hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;
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 maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and alkali solubility.
(Aa) and (Ab) are used alone or in combination.

In the copolymer obtained by copolymerizing (Aa) and (Ab), the ratio of the constituent components derived from each of them is 100 in terms of the total number of moles of the constituent components constituting the copolymer. It is preferable that the molar fraction is in the following range when the mol% is used.
Structural units derived from (Aa); 2 to 40 mol%
Structural units derived from (Ab); 60-98 mol%
Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (Aa); 5-35 mol%
Structural units derived from (Ab); 65-95 mol%
When the composition ratio is in the above range, storage stability, developability and solvent resistance tend to be good.

For example, the binder resin (A1) is a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document. Can be produced with reference to the cited references described in 1.
Specifically, by supplying a predetermined amount of units (Aa) and (Ab) constituting the copolymer, a polymerization initiator and a solvent into a reaction vessel, and substituting oxygen with nitrogen, A polymer is obtained by stirring, heating, and heat-retaining in the absence. In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and took out as solid (powder) by methods, such as reprecipitation. Things may be used.

The polystyrene-reduced weight average molecular weight of the binder resin (A1) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. If the weight-average molecular weight of the resin (A1) having alkali solubility is in the above range, the coating property tends to be good, the film is not easily reduced during development, and the non-pixel portion can be removed during development. Tends to be good, which is preferable.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (A1) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. The molecular weight distribution in the above range is preferable because it tends to be excellent in developability.
Content of binder resin (A1) which can be used for the curable resin composition of this invention is a mass fraction with respect to solid content in curable resin composition, Preferably it is 5-90 mass%, More preferably Is 10-70 mass%. When the content of the binder resin (A1) is in the above range, the solubility in the developer is sufficient, and development residues are not easily generated on the non-pixel portion of the substrate. This is preferable because the film loss is less likely to occur, and the non-exposed portion tends to be easily removed.

Examples of the binder resin (A2) exhibiting alkali solubility and reactivity by at least one of light and heat include (A2-1) to (A2-3).
The binder resin (A2-1) is composed of (Aa), (Ab), and a monomer having a cyclic ether group having 2 to 4 carbon atoms (Ac) (hereinafter referred to as “(Ac)”. In some cases).
In the copolymer of (Aa) and (Ab), the binder resin (A2-2) is derived from (Ac) with a part of the carboxyl group derived from (Aa). It is a copolymer obtained by reacting with a C2-C4 cyclic ether group.
The binder resin (A2-3) is a copolymer of (Aa) and (Ac).

  (Ac) refers to a polymerizable compound having at least one group selected from the group consisting of, for example, a cyclic ether group having 2 to 4 carbon atoms (for example, an epoxy group, an oxetanyl group, and a tetrahydrofuryl group). (Ac) is preferably a compound having at least one group selected from the group consisting of cyclic ether groups having 2 to 4 carbon atoms and having an unsaturated bond.

  Examples of (Ac) include a monomer having an epoxy group, a monomer having an oxetanyl group, and a monomer having a tetrahydrofuryl group.

  The monomer having an epoxy group refers to, for example, a polymerizable compound having at least one group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group. The monomer having an epoxy group is preferably a compound having at least one group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group and having an unsaturated bond.

（式中、Ｒ^１１〜Ｒ^１３は、それぞれ独立に水素原子又は炭素原子数１〜１０のアルキル基であり、ｍは１〜５の整数である。）。 Among the above-mentioned monomers having an epoxy group, specific examples of the compound having an aliphatic epoxy group include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, and β-ethylglycidyl (meth) acrylate. , Glycidyl vinyl ether, and compounds represented by the following formulas described in JP-A-7-248625.

(In formula, R < ¹¹ > -R < ¹³ > is a hydrogen atom or a C1-C10 alkyl group each independently, and m is an integer of 1-5.).

  Examples of the compound represented by the formula [I] include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl. -M-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2 , 6-Diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5 -Triglycidyloxymethylstyrene And 2,4,6 glycidyloxymethyl styrene.

  Among the monomers having an epoxy group, examples of the monomer having an alicyclic epoxy group include a monomer having an aliphatic monocyclic epoxy group and a monomer having an aliphatic polycyclic epoxy group. Examples include masses.

The monomer having an aliphatic monocyclic epoxy group refers to a polymerizable compound having an epoxy group on the ring of the aliphatic monocyclic compound. The monomer having an aliphatic monocyclic epoxy group is preferably a compound having an epoxy group on the ring of the aliphatic monocyclic compound and having an unsaturated bond.
Examples of the aliphatic monocyclic compound include cyclopentane, cyclohexane, cycloheptane, cyclooctane, and the like. Among these, compounds having 5 to 7 carbon atoms are preferable.
As the monomer having an aliphatic monocyclic epoxy group, specifically, vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), and the like. Can be mentioned.

The monomer having an aliphatic polycyclic epoxy group refers to a polymerizable compound having an epoxy group on the ring of the aliphatic polycyclic compound. The monomer having an aliphatic polycyclic epoxy group is preferably a compound having an epoxy group on the ring of the aliphatic polycyclic compound and having an unsaturated bond.
Examples of the aliphatic polycyclic compound include dicyclopentane, tricyclodecane, norbornane, isonorbornane, bicyclooctane, bicyclononane, bicycloundecane, tricycloundecane, bicyclododecane, and tricyclododecane. Compounds having 8 to 12 carbon atoms are preferred.

  Examples of the monomer having an aliphatic polycyclic epoxy group include 3,4-epoxynorbornyl acrylate, 3,4-epoxynorbornyl methacrylate, compounds represented by the formula (I), and the formula And at least one compound selected from the group consisting of compounds represented by (II).

In Formula (I) and Formula (II), R ₁ and R ₂ each independently represent a C 1-4 alkyl group that may be substituted with a hydrogen atom or a hydroxyl group.
X ₁ and X ₂ each independently represent a C 1-6 alkylene group that may contain a single bond or a hetero atom.

As R ₁ and R ₂ , specifically, a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group;
Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy-isopropyl group, And hydroxyl group-containing alkyl groups such as 2-hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group and 4-hydroxy-n-butyl group. It is done. Among these, Preferably a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group is mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

Specific examples of X ₁ and X ₂ include a single bond; an alkylene group such as a methylene group, an ethylene group, and a propylene group;
Examples thereof include heteroatom-containing alkylene groups such as oxymethylene group, oxyethylene group, oxypropylene group, thiomethylene group, thioethylene group, thiopropylene group, aminomethylene group, aminoethylene group, and aminopropylene group. Of these, a single bond, a methylene group, an ethylene group, an oxymethylene group, and an oxyethylene group are preferable, and a single bond and an oxyethylene group are more preferable.

As at least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II), a compound represented by the following formula (I ′) and formula (II ′) It is preferably at least one compound selected from the group consisting of compounds represented by

In Formula (I ′) and Formula (II ′), R ₁ ′ and R ₂ ′ have the same meanings as R ₁ and R ₂ , respectively.

  Specific examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15), and the formula (I-1) is preferable. , Formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15), and more preferably (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

  Specific examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15), and the formula (II-1) is preferable. , Formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), more preferably formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) are mentioned.

  At least one compound selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (II) can be used alone, and can be mixed in any ratio. In the case of mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, more preferably 20:80 to Formula (I) :( II). 80:20.

The monomer having an oxetanyl group refers to, for example, a polymerizable compound having at least one group selected from the group consisting of an aliphatic oxetanyl group and an alicyclic oxetanyl group. The monomer having an oxetanyl group is preferably a compound having at least one group selected from the group consisting of an aliphatic oxetanyl group and an alicyclic oxetanyl group and having an unsaturated bond.
Specific examples of the monomer having an oxetanyl group include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3 -Ethyl-3-acryloxymethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane or 3-ethyl-3-acryl Examples include roxyethyl oxetane.
These may be used alone or in combination.

The monomer having a tetrahydrofuryl group refers to a polymerizable compound having at least one group selected from the group consisting of an aliphatic tetrahydrofuryl group and an alicyclic tetrahydrofuryl group, for example. The monomer having a tetrahydrofuryl group is preferably a compound having at least one group selected from the group consisting of an aliphatic tetrahydrofuryl group and an alicyclic tetrahydrofuryl group and having an unsaturated bond. .
Specific examples of the monomer having a tetrahydrofuryl group include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.
These may be used alone or in combination.

In the binder resin (A2-1), the ratio of the component derived from each of the binder resin (A2-1) is in the following range in terms of a mole fraction with respect to the total number of moles of the component constituting the binder resin (A2-1). preferable.
Structural units derived from (Aa); 2 to 40 mol%
Structural units derived from (Ab); 1 to 65 mol%
Structural units derived from (Ac); 2 to 95 mol%
Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (Aa); 5-35 mol%
Structural units derived from (Ab); 1 to 60 mol%
Structural units derived from (Ac); 5 to 80 mol%
When the composition ratio is in the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be good.
The binder resin (A2-1) can be obtained by, for example, the method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and It can manufacture with reference to the cited reference described in the said literature.
Specifically, a predetermined amount of a compound that leads to units (Aa), (Ab), and (Ac) constituting the copolymer, a polymerization initiator, and a solvent are charged into a reaction vessel, and nitrogen is added. By substituting oxygen with the above, a polymer is obtained by stirring, heating, and keeping the temperature in the absence of oxygen. In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and took out as solid (powder) by methods, such as reprecipitation. Things may be used.

In producing the binder resin (A2-2), first, (Aa) and (Ab) are copolymerized to produce a copolymer. It is preferable that the ratio of the component derived from each is in the following range in terms of a mole fraction with respect to the total number of moles of the component constituting the copolymer.
Structural units derived from (Aa); 5-50 mol%
Structural units derived from (Ab); 50-95 mol%
Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (Aa); 10 to 45 mol%
Structural units derived from (Ab); 55 to 90 mol%

Next, in order to give reactivity by the action of light or heat, the carboxylic acid and carboxylic acid of (Aa) derived from the copolymer obtained by copolymerizing (Aa) and (Ab) A part of the acid anhydride is reacted with an epoxy group, oxetanyl group or tetrahydrofuryl group derived from (Ac).
The number of moles of (Ac) is 5 to 80 mole%, preferably 10 to 75 mole%, more preferably 15 to 70 mole%, based on the number of moles of (Aa). .
When the composition ratio is in the above range, the balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tends to be good.

The binder resin (A2-2) can be produced through a two-step process. For example, in the method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu Publishing Co., Ltd., Chemical Dojin Co., Ltd., First Edition, First Edition, issued on March 1, 1972), Japanese Patent Laid-Open No. 2001-89533 It can be produced with reference to the described method.
Specifically, the first stage process will be described first. A predetermined amount of a compound that leads to units (Aa) and (Ab) constituting a copolymer (ie, binder resin) obtained by copolymerizing (Aa) and (Ab), polymerization The binder resin is obtained by charging the initiator and the solvent into the reaction vessel and substituting oxygen with nitrogen, and stirring, heating, and keeping the temperature in the absence of oxygen. In addition, the obtained resin may use the solution after the reaction as it is, a concentrated or diluted solution, or a solid (powder) taken out by a method such as reprecipitation. May be used. The weight average molecular weight in terms of polystyrene of the resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. If the weight average molecular weight of the resin is in the above range, the coating property tends to be good, the film is less likely to be reduced during development, and the non-pixel part is liable to be easily removed during development. preferable.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. A molecular weight distribution in the above range is preferable because it tends to be excellent in coating properties and developability.

  Next, the second stage process will be described. Subsequently, the atmosphere in the flask was replaced from nitrogen to air, and 5 to 80 mol% of the component (Ac), carboxyl group and epoxy group, oxetanyl group or the number of moles of the component (Aa) As a reaction catalyst for the tetrahydrofuryl group, for example, trisdimethylaminomethylphenol is 0.001 to 5% on a mass basis with respect to the total amount of monomers (Aa) to (Ac), and as a polymerization inhibitor, for example, Put 0.001 to 5% hydroquinone in a flask on a mass basis with respect to the total amount of monomers (Aa) to (Ac), and continue the reaction at 60 to 130 ° C. for 1 to 10 hours. Thus, the resin and the constituent component (Ac) can be reacted. In addition, like 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.

In the binder resin (A2-3), the ratio of the component derived from each of the binder resin (A2-3) is in the following range in terms of a mole fraction with respect to the total number of moles of the component constituting the binder resin (A2-3). preferable.
Structural units derived from (Aa); 5-95 mol%
Structural units derived from (Ac); 5-95 mol%
Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (Aa); 10 to 90 mol%
Structural units derived from (Ac); 10 to 90 mol%
When the composition ratio is in the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be good.

The binder resin (A2-3) can be obtained by, for example, the method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and It can manufacture with reference to the cited reference described in the said literature.
Specifically, a predetermined amount of a compound that leads to the units (Aa) and (Ac) constituting the copolymer, a polymerization initiator and a solvent are charged into a reaction vessel, and oxygen is substituted with nitrogen. Thus, a polymer can be obtained by stirring, heating and heat-retaining in the absence of oxygen. In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and took out as solid (powder) by methods, such as reprecipitation. Things may be used.

  As the at least one compound (B) selected from the group consisting of a carboxylic acid anhydride and a compound having at least two carboxyl groups contained in the curable resin composition of the present invention, for example, a polyvalent carboxylic acid anhydride Products, polycarboxylic acids and the like.

Examples of the polyvalent carboxylic acid anhydride include:
Aliphatic dicarboxylic acid anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride;
Aliphatic polycarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride;
Aromatic polycarboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride;
Examples include ester group-containing acid anhydrides such as ethylene glycol bis trimellitate and glycerin tris trimellitate.
Among these, trimellitic anhydride is preferable because it has a high degree of curing and high transparency.
Moreover, as the carboxylic acid anhydride, an epoxy resin curing agent made of a commercially available colorless acid anhydride can also be suitably used. Specifically, ADEKA HARDNA-EH-700 (trade name (hereinafter the same), manufactured by Asahi Denka Kogyo Co., Ltd.), Rikacid-HH, MH-700 (manufactured by Shin Nippon Rika Co., Ltd.), Epikinia 126, YH -306, DX-126 (made by Yuka Shell Epoxy Co., Ltd.) and the like.

As the polyvalent carboxylic acid, for example,
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, itaconic acid;
Alicyclic polyvalent carboxylic acids such as hexahydrophthalic acid, 1,2-cyclohexanecarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid;
Examples thereof include aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 1,4,5,8-naphthalene tetracarboxylic acid, and benzophenone tetracarboxylic acid.
Among these, trimellitic acid is preferable because it has a high degree of curing and high transparency.

  These polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids can be used alone or in combination of two or more.

  Content of the compound (B) in the curable resin composition of this invention is a mass fraction with respect to the total amount of binder resin (A) and a compound (B), Preferably it is 3-50 mass%, More preferably It is 5-30 mass%. When content of a compound (B) is less than 3 mass%, there exists a possibility that it may become a curing defect. On the other hand, when content of a compound (B) exceeds 50 mass%, there exists a possibility that storage stability may worsen.

The curable resin composition of the present invention can contain a polymerizable compound (C) as necessary. Examples of the polymerizable compound (C) include monofunctional monomers, bifunctional monomers, and other trifunctional or higher polyfunctional monomers.
Specific examples of the monofunctional monomer include nonylphenyl carbitol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Lauryl (meth) acrylate, stearyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propoxylation Nonylphenol (meth) acrylate, N-vinylpyrrolidone, etc. are mentioned.

  Specific examples of the bifunctional monomer include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) ) Acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, bisphenol A bis (acryloyloxy) Ethyl) ether, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate or 3- Such as chill-pentanediol di (meth) acrylate.

  Specific examples of other trifunctional or higher polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated tri Methylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra ( (Meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol (Meth) acrylate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, tripenta Erythritol hepta (meth) acrylate and acid anhydride caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified Pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol Hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate, Caprolactone-modified tripentaerythritol octa (meth) acrylate, reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride, or caprolactone Examples include modified tripentaerythritol hepta (meth) acrylate and acid anhydrides.

  In the present specification, caprolactone modification means that a caprolactone ring-opening product or ring-opening polymer is introduced between the alcohol-derived site of the (meth) acrylate compound and the (meth) acryloyloxy group. means.

  In particular, bifunctional or higher polyfunctional monomers are preferably used. These polymerizable compounds (C) can be used alone or in combination of two or more.

  Content of polymeric compound (C) is a mass fraction with respect to the total amount of binder resin (A) and polymeric compound (C), Preferably it is 1-70 mass%, More preferably, it is 5-60 mass%. It is. When the content of the polymerizable compound (C) is in the above range, the sensitivity, the strength of the coating film and the pattern, the smoothness, the reliability and the mechanical strength tend to be good, which is preferable.

  The curable resin composition of the present invention can contain a polymerization initiator (D) as necessary. The polymerization initiator (D) is a compound that initiates polymerization by the action of light or heat, and is preferably a biimidazole compound, an acetophenone compound, a triazine compound, an acylphosphine oxide compound, or an oxime compound, Biimidazole compounds are particularly preferred because of their excellent sensitivity.

  The polymerization initiator (D) contained in the curable resin composition of the present invention is a compound that initiates polymerization by the action of light or heat, and is a biimidazole compound, an acetophenone compound, a triazine compound, an acylphosphine. Oxide compounds or oxime compounds are preferred, and biimidazole compounds are particularly preferred because of their excellent sensitivity.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 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'-tetraphenylbiimidazole, 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 (trialkoxy) Phenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), imidazole in which the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group Compounds (see, for example, JP-A-7-10913) and the like, and preferably 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5 ′ -Tetraphenylbiimidazole is mentioned.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl]. 2-methylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 1 -Hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one 2- (2-Methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -buta 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl)- Butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl)- Butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chloro) Ndyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-chloro Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromo Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methoxy) Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1 -(4-morpholinophenyl) -butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxybenzyl) -2- Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromo- 4-Methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer Etc.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -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-methylphenyl Ethenyl] -1,3,5-triazine, such as 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine

  Examples of the acylphosphine oxide initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the oxime compound include O-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, a compound represented by the formula (IV), a compound represented by the formula (V), and the like.

As long as the effects of the present invention are not impaired, a photopolymerization initiator or the like can be further used together. Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, and thioxanthone compounds.
More specifically, the following compounds can be mentioned, and these can be used alone or in combination of two or more.

  Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxide). Oxycarbonyl) benzophenone or 2,4,6-trimethylbenzophenone.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

  Other examples of photopolymerization initiators include 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds. .

Further, as a photopolymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in JP-T-2002-544205 can be used.
As a photoinitiator which has the group which can raise | generate the said chain transfer, the photoinitiator of following formula (5)-following formula (10) is mentioned, for example.

In addition, light and / or thermal cationic polymerization initiators can be used.
As the light and / or thermal cationic polymerization initiator, those composed of an onium cation and an anion derived from a Lewis acid can also be used.

  Specific examples of the onium cation include diphenyliodonium, bis (p-tolyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, bis (P-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (p-octadecyloxyphenyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, triphenylsulfonium, tris (p- Tolyl) sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (p-tert-butylphenyl) sulfonium, tris (p-si Nophenyl) sulfonium, tris (p-chlorophenyl) sulfonium, dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecanoxy) sulfonium, Dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromo Propoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (8-nitroo) Yloxy) sulfonium, dimethyl (18-trifluoromethyl octadecanoic oxy) sulfonium, dimethyl (2-hydroxy-isopropoxyphenyl) sulfonium, or dimethyl (tris (trichloromethyl) methyl) sulfonium and the like.

  Preferred onium cations include bis (p-tolyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium or tris (p-tert-butylphenyl). ) Sulfonium and the like.

Specific examples of the Lewis acid-derived anion include hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, and tetrakis (pentafluorophenyl) borate. Preferred anions derived from Lewis acid include hexafluoroantimonate or tetrakis (pentafluorophenyl) borate.
The onium cation and Lewis acid-derived anion can be arbitrarily combined.

Specific examples of the cationic polymerization initiator include diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-octylphenyl) iodonium hexa Fluorophosphate, bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium Hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophos , Methyl naphthyl iodonium hexafluorophosphate, ethyl naphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexafluorophosphate, tris (2, 6-dimethylphenyl) sulfonium hexafluorophosphate, tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium Hexafluorophosphate, diethylnaphthyls Honium hexafluorophosphate, dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl (ethoxy) sulfonium hexafluorophosphate, dimethyl (propoxy) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluoro Phosphate, dimethyl (octadecanoxy) sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium Hexafluorophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluorophosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, Dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluorophosphate, dimethyl (tris (trichloromethyl) methyl) Sulfonium hexafluorophosphate;
Diphenyliodonium hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, bis (p-octylphenyl) iodonium hexafluoroarsenate, bis (p -Octadecylphenyl) iodonium hexafluoroarsenate, bis (p-octyloxyphenyl) iodonium hexafluoroarsenate, bis (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarsenate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, methylnaphthyl iodonium Oxafluoroarsenate, ethyl naphthyl iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (p-tolyl) sulfonium hexafluoroarsenate, tris (p-isopropylphenyl) sulfonium hexafluoroarsenate, tris (2, 6-dimethylphenyl) sulfonium hexafluoroarsenate, tris (p-tert-butylphenyl) sulfonium hexafluoroarsenate, tris (p-cyanophenyl) sulfonium hexafluoroarsenate, tris (p-chlorophenyl) sulfonium hexafluoroarsenate , Dimethylnaphthylsulfonium hexafluoroarsenate, diethylnaphthylsulfonium hexafluoroarsenate Dimethyl (methoxy) sulfonium hexafluoroarsenate, dimethyl (ethoxy) sulfonium hexafluoroarsenate, dimethyl (propoxy) sulfonium hexafluoroarsenate, dimethyl (butoxy) sulfonium hexafluoroarsenate, dimethyl (octyloxy) sulfonium hexafluoroarsenate , Dimethyl (octadecanoxy) sulfonium hexafluoroarsenate, dimethyl (isopropoxy) sulfonium hexafluoroarsenate, dimethyl (tert-butoxy) sulfonium hexafluoroarsenate, dimethyl (cyclopentyloxy) sulfonium hexafluoroarsenate, dimethyl (cyclohexyloxy) ) Sulfonium hexafluoroarsenate, dimethyl (Fluoromethoxy) sulfonium hexafluoroarsenate, dimethyl (2-chloroethoxy) sulfonium hexafluoroarsenate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarsenate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroarsenate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroarsenate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroarsenate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroarsenate, dimethyl (tris (trichloromethyl) Methyl) sulfonium hexafluoroarsenate;
Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, bis (p-octylphenyl) iodonium hexafluoroantimonate, bis (p -Octadecylphenyl) iodonium hexafluoroantimonate, bis (p-octyloxyphenyl) iodonium hexafluoroantimonate, bis (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroantimonate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, methyl naphthalate Tyl iodonium hexafluoroantimonate, ethyl naphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate, tris (p-isopropylphenyl) sulfonium hexafluoroantimonate, tris ( 2,6-dimethylphenyl) sulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium hexafluoroantimonate, tris (p-chlorophenyl) sulfonium hexafluoro Antimonate, dimethyl naphthylsulfonium hexafluoroantimonate, diethyl naphthyl Rufonium hexafluoroantimonate, dimethyl (methoxy) sulfonium hexafluoroantimonate, dimethyl (ethoxy) sulfonium hexafluoroantimonate, dimethyl (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimonate, dimethyl (octyl) Oxy) sulfonium hexafluoroantimonate, dimethyl (octadecanoxy) sulfonium hexafluoroantimonate, dimethyl (isopropoxy) sulfonium hexafluoroantimonate, dimethyl (tert-butoxy) sulfonium hexafluoroantimonate, dimethyl (cyclopentyloxy) sulfonium hexafluoro Antimonate, dimethyl (cyclohexyl) Ruoxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium hexafluoroantimonate, dimethyl (2-chloroethoxy) sulfonium hexafluoroantimonate, dimethyl (3-bromopropoxy) sulfonium hexafluoroantimonate, dimethyl (4-cyano Butoxy) sulfonium hexafluoroantimonate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroantimonate , Dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoro Nchimoneto;
Diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (p-tolyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-octylphenyl) Iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) Iodonium tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis Pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, methylnaphthyliodonium tetrakis (pentafluorophenyl) borate, ethylnaphthyliodonium tetrakis (pentafluorophenyl) borate, triphenyl Sulfonium tetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-isopropylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (2,6-dimethylphenyl) sulfonium Tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium teto Kiss (pentafluorophenyl) borate, tris (p-cyanophenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, Diethyl naphthylsulfonium tetrakis (pentafluorophenyl) borate, dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (ethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (propoxy) sulfonium tetrakis (pentafluorophenyl) borate, Dimethyl (butoxy) sulfonium tetrakis (pentafluorophenyl) bo Dimethyl (octyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octadecanoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tert-butoxy) Sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclopentyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclohexyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (fluoromethoxy) sulfonium tetrakis (pentafluorophenyl) borate , Dimethyl (2-chloroethoxy) sulfonium tetra (Pentafluorophenyl) borate, dimethyl (3-bromopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (4-cyanobutoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) Methyl) sulfonium tetrakis (pentafluorophenyl) borate and the like, preferably bis (p-tolyl) Donium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tert- Butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsenate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarcete Nate, triphenylsulfonium hexafluoroarsenate, tris (pt-butylphenyl) sulfonium hexafluoroarsenate, Bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate Nates, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) Borate, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (pt rt-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate and the like, more preferably bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, Bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) ) Borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butyl) Phenyl) iodonium tetrakis (pentafluorophenyl) borate, triphenyl sulfonium tetrakis (pentafluorophenyl) borate, or tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate.

In addition, the polymerization initiator (D) can be used in combination with the polymerization initiation assistant (D-1) to such an extent that the effects of the present invention are not impaired, and the polymerization initiation assistant can be used in a plurality of combinations.
The polymerization initiation assistant (D-1) is represented by an amine compound, a carboxylic acid compound, a polyfunctional thiol compound, a compound represented by the formula (III), a formula (A-1) or a formula (A-2). And the like.

  Examples of the amine compounds include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4- 2-ethylhexyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name: Michler's ketone) or 4,4′-bis (diethylamino) Examples include aromatic amine compounds such as benzophenone.

  Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, Aromatic heteroacetic acids such as N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine or naphthoxyacetic acid can be mentioned.

The polyfunctional thiol compound is a compound having two or more thiol groups in the molecule. Among these, a compound having two or more aliphatic thiol groups is more preferable because the sensitivity of the curable resin composition of the present invention is increased.
Specific examples of the polyfunctional thiol compound include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and trimethylol. Propane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltris Thiopropionate, pentaerythritol tetrakis (3-mercaptobutyrate) or 1,4-bis (3-mercaptobutyryloxy) butane Etc., and the like.
Content of a polyfunctional thiol compound is a mass fraction with respect to a polymerization initiator (D), Preferably it is 0.5-20 mass%, More preferably, it is 1-15 mass%. When the content of the polyfunctional thiol compound is in the above range, the sensitivity tends to be high and the developability tends to be good, which is preferable.

  As the polymerization initiation assistant (D-1), a compound represented by the following formula (III) can also be used.

In formula (III), the dotted line represented by X represents an aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom.
Y represents an oxygen atom or a sulfur atom.
R ²¹ represents an alkyl group having 1 to 6 carbon atoms.
R ²² represents an alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom or an aryl group which may be substituted with a halogen atom.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring and a naphthalene ring.

  Examples of the aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom include a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, a hexylbenzene ring, Examples include cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring, and the like.

  Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2-methyl-n-propyl group, tert- Butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2- Examples include dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group and the like.

  Examples of the alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2- Methyl-n-propyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl- n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group, 1-chloro-n-butyl group, 2-chloro-n- A butyl group, 3-chloro-n-butyl group, etc. are mentioned.

  The aryl group which may be substituted with a halogen atom includes a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobromophenyl group, a biphenyl group, a chlorobiphenyl group, a dichlorobiphenyl group, and a bromophenyl group. , Dibromophenyl group, naphthyl group, chloronaphthyl group, dichloronaphthyl group, bromonaphthyl group, dibromonaphthyl group and the like.

As the compound represented by the formula (III), specifically,
2-benzoylmethylene-3-methyl-naphtho [2,1-d] thiazoline,
2-benzoylmethylene-3-methyl-naphtho [1,2-d] thiazoline,
2-benzoylmethylene-3-methyl-naphtho [2,3-d] thiazoline,
2- (2-naphthoylmethylene) -3-methylbenzothiazoline,
2- (1-naphthoylmethylene) -3-methylbenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-phenylbenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-fluorobenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-fluorobenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-chlorobenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-bromobenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-bromobenzothiazoline,
2- (4-biphenoylmethylene) -3-methylbenzothiazoline,
2- (4-biphenoylmethylene) -3-methyl-5-phenylbenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,
2- (4-biphenoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,
2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,
2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,
2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,
2-benzoylmethylene-3-methyl-naphtho [2,1-d] oxazoline,
2-benzoylmethylene-3-methyl-naphtho [1,2-d] oxazoline,
2-benzoylmethylene-3-methyl-naphtho [2,3-d] oxazoline,
2- (2-naphthoylmethylene) -3-methylbenzoxazoline,
2- (1-naphthoylmethylene) -3-methylbenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-phenylbenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-fluorobenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-fluorobenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-chlorobenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-bromobenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-bromobenzoxazoline,
2- (4-biphenoylmethylene) -3-methylbenzoxazoline,
2- (4-biphenoylmethylene) -3-methyl-5-phenylbenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline,
2- (4-biphenoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,
2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline,
2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,
2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline,
Etc.

Among them, 2- (2-naphthoylmethylene) -3-methylbenzothiazoline represented by the formula (III-1), 2-benzoylmethylene-3-methyl-naphtho represented by the formula (III-2) [1,2 -D] thiazoline and 2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline represented by the formula (III-3) are preferred.

  As the polymerization initiation aid (D-1), a compound represented by at least one selected from the group consisting of formula (A-1) and formula (A-2) can also be used.

[In Formula (A-1) and Formula (A-2), Ring X ³¹ and Ring X ³² each independently represent an aromatic ring having 6 to 12 carbon atoms. Y ³¹ and Y ³² represent an oxygen atom or a sulfur atom. R ³¹ and R ³² represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.
The carbon atom contained in the aromatic ring, the alkyl group or the aryl group may be substituted with an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. ]

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the aromatic ring having 6 to 12 carbon atoms include benzene ring, methylbenzene ring, dimethylbenzene ring, ethylbenzene ring, propylbenzene ring, butylbenzene ring, pentylbenzene ring, hexylbenzene ring, cyclohexylbenzene ring, chlorobenzene ring, and dichlorobenzene. Ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring, phenanthrene ring, chrysene ring, fluoranthene ring, benzo [a] pyrene ring, Examples include benzo [e] pyrene ring, perylene ring, and derivatives thereof.

  Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2-methyl-n-propyl group, tert- Butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2- Dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group, 1-chloro-n-butyl group, 2-chloro-n-butyl group, 3-chloro-n- A butyl group etc. are mentioned.

  Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, dibromophenyl group, chlorobromophenyl group, hydroxyphenyl group, alkoxyphenyl group, biphenyl group, chlorobiphenyl group, dichlorobiphenyl. Group, bromophenyl group, dibromophenyl group, naphthyl group, chloronaphthyl group, dichloronaphthyl group, bromonaphthyl group, dibromonaphthyl group, hydroxynaphthyl group and the like.

As a compound represented by Formula (A-1) or Formula (A-2), specifically,
Dialkoxynaphthalenes such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene, dibutoxynaphthalene, dimethoxyanthracene, diethoxyanthracene, dipropoxyanthracene, diisopropoxyanthracene, dibutoxyanthracene, dipentaoxyanthracene, Dihexoxyoxyanthracene, methoxyethoxyanthracene, methoxypropoxyanthracene, methoxyisopropoxyanthracene, methoxybutoxyanthracene, ethoxypropoxyanthracene, ethoxyisopropoxyanthracene, ethoxybutoxyanthracene, propoxyisopropoxyanthracene, propoxybutoxyanthracene, isopropoxybutoxyanthracene, etc. Alkoxy anthracenes dimethoxy naphthacene, diethoxy naphthacene, dipropoxy naphthacene, diisopropoxy Sina lid Sen, dibutoxyethoxyethyl Sina lid but Sen and dialkoxy naphthacene such as including but not limited to it.

Content of a polymerization initiator (D) is a mass fraction with respect to the total amount of binder resin (A) and polymeric compound (C), Preferably it is 0.1-40 mass%, More preferably, it is 1-30. % By mass.
The content of the polymerization initiation assistant (D-1) is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass, based on the same standard as described above.
The content of the compound represented by at least one selected from the group consisting of formula (A-1) and formula (A-2) is preferably relative to the content of polymerization initiation aid (D-1). It is 50 to 100%, more preferably 60 to 100%, still more preferably 65 to 100%. When the content of the compound represented by at least one selected from the group consisting of the formula (A-1) and the formula (A-2) is in the above range, it is applied using a curable resin composition containing the compound. When a film is formed, the transparency of the coating film is improved, which is preferable.
When the total amount of the polymerization initiator (D) is in the above range, the curable resin composition becomes highly sensitive, and the strength of the coating film or pattern formed using the curable resin composition, The smoothness on the surface of the film or pattern tends to be good, which is preferable. In addition to the above, when the amount of the polymerization initiating aid (D-1) is in the above range, the sensitivity of the resulting curable resin composition is further increased, and is formed using the curable resin composition. The pattern productivity tends to be improved, which is preferable.

The curable resin composition of this invention can contain a solvent (E) as needed. Examples of the solvent (E) include various organic solvents used in the field of curable resin compositions, and specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether. And ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate;
Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether, propylene glycol ethyl propyl ether, propylene glycol methyl ether propionate, propylene glycol ethyl ether Propylene glycol alkyl ether propionates such as propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate;
Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol, butoxybutyl alcohol;
Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate;
Butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate;
Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether;
Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin;
Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyethyl acetate, hydroxy Butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methylbutane Methyl acetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, propoxy Ethyl acetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2- Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxy Propyl propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3- Methyl toxipropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxy Esters such as butyl propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate;
Cyclic ether groups such as tetrahydrofuran and pyran;
and cyclic esters such as γ-butyrolactone.

Among the above solvents, an organic solvent having a boiling point of 100 to 200 ° C. is preferable among the above solvents from the viewpoints of coating properties and drying properties. As an organic solvent having a boiling point of 100 to 200 ° C., specifically, alkylene glycol alkyl ether acetates, alcohols such as methoxybutanol and ethoxybutanol, ketones such as cyclohexanone,
And esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutanol, methoxybutyl acetate, 3-ethoxypropion Examples include ethyl acid and methyl 3-methoxypropionate.
These solvents (E) can be used alone or in combination of two or more.

  Content of the solvent (E) in the curable resin composition of this invention is a mass fraction with respect to curable resin composition, Preferably it is 60-90 mass%, More preferably, it is 65-85 mass%. When the content of the solvent (E) is in the above range, a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater or a curtain flow coater), an ink jet, a roll coater, a dip coater, etc. The coating property is expected to be good when applied with a coating apparatus, which is preferable.

  The curable resin composition of the present invention does not substantially contain colorants such as pigments and dyes. That is, in the curable resin composition of the present invention, the content of the colorant relative to the entire composition is, for example, a mass fraction of less than 10% by mass, preferably less than 1% by mass.

In the curable resin composition of the present invention, a filler, other polymer compound, a leveling agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, a light stabilizer, an anti-aggregation material, chain transfer, if necessary. An additive such as an agent can also be used in combination.
Specific examples of the filler include glass, silica, and alumina.

  Specific examples of other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Can be mentioned.

  As the leveling agent, a commercially available surfactant can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, and amphoteric surfactants. Two or more kinds may be used in combination. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (manufactured by Dainippon Ink & Chemicals, Inc.) ), Florard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS), PB821 (manufactured by Ajinomoto Co., Inc.) ) And the like.

  As the adhesion promoter, silane compounds are preferable, and specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyl. Dimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

  Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy- 3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy]- 2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3,9-bis [2- {3- (3-tert-butyl-4 -Hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2′-methyle Bis (6-tert-butyl-4-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (2-tert-butyl-5-methylphenol) ), 2,2′-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′- Thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine -2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', ''-(Mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di -Tert-butyl-4-methylphenol and the like.

  Specific examples of the ultraviolet absorber include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro). -2H-benzotriazol-2-yl) phenyl] propionate, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4- Dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2, 4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-bis-butyloxyphenyl) 1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1- Phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole or alkoxybenzophenone. Can be mentioned.

  Specifically, the light stabilizer is a polymer composed of succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl) ethanol, N, N ′, N ″, N ′. '' -Tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazin-2-yl) -4,7-diazadecane-1 , 10-diamine, decandioic acid, reaction of bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester with 1,1-dimethylethyl hydroperoxide Bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, 2, 4-bis N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine, bis ( 1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate or methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate.

Examples of the aggregation preventing material include sodium polyacrylate.
Examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

  The curable resin composition of the present invention exhibits excellent storage stability. For example, the curable resin composition of the present invention does not change in viscosity even when stored at 23 ° C. for 2 weeks.

  Moreover, when the curable resin composition of the present invention is filled in a quartz cell having an optical path length of 1 cm and the transmittance is measured under a measurement wavelength of 400 to 700 nm using a spectrophotometer, the transmittance is 70. % Or more, preferably 80% or more.

  The method for applying the curable resin composition of the present invention to the substrate surface is not particularly limited. For example, a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater or a curtain flow coater), It can apply | coat with coating apparatuses, such as an inkjet, a roll coater, and a dip coater.

  The curable resin composition of the present invention has a measurement wavelength of 400 to 700 nm using a spectrophotometer for a coating having a thickness of 3 μm after heat curing (for example, 100 to 250 ° C., 5 minutes to 3 hours). When the transmittance is measured under the conditions, the transmittance is 90% or more, preferably 95% or more. Thereby, the coating film excellent in transparency can be provided.

The curable resin composition of the present invention is applied onto a substrate on which a glass substrate, a film substrate, a color filter or a drive circuit is formed, for example, as described below, and photocured and developed to form a coating film or pattern. Can be formed.
First, this curable resin composition is applied onto a substrate (usually glass) or a layer made of a solid content of a curable resin composition formed in advance, and prebaked from the applied curable resin composition layer. By removing volatile components such as a solvent, a smooth uncured coating film is obtained. The thickness of the uncured coating film at this time is approximately 1 to 6 μm. The uncured coating film thus obtained is irradiated with ultraviolet rays generated from a mercury lamp or a light emitting diode through a mask for forming a target pattern.
In the pattern formation, the line width can be appropriately controlled depending on the mask size.

  Recent exposure machines use a band-pass filter that cuts out light of less than 350 nm using a filter that cuts the wavelength range, and extracts light of wavelengths near 436 nm, 408 nm, and 365 nm. Or the like, and the parallel light beam is uniformly irradiated on the entire exposed portion. At this time, it is preferable to use a device such as a mask aligner or a stepper so that the mask and the substrate are accurately aligned. Further, after that, the coating film after the light irradiation is brought into contact with an alkaline aqueous solution to dissolve the non-exposed portion and developed, whereby a desired coating film or pattern is obtained. The developing method may be any of a liquid piling method, a dipping method, a spray method, and the like. Further, the substrate may be tilted at an arbitrary angle during development.

  The developer used for development after patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound may be either an inorganic or organic alkaline compound.
Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, Examples thereof include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate or ammonia.
Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine or ethanolamine. Etc. These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

Further, the surfactant in the alkali developer may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
Specific examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Examples thereof include oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.
Specific examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and dodecylnaphthalene. And alkylaryl sulfonates such as sodium sulfonate.
Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, or quaternary ammonium salts.
These surfactants can be used alone or in combination of two or more.
The concentration of the surfactant in the alkali developer is preferably in the range of 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.

  After development, it is washed with water, and if necessary, post-baking can be performed at 150 to 230 ° C. for 10 to 180 minutes.

  By using the curable resin composition of the present invention, a coating film or a pattern can be formed on the substrate or the color filter substrate through the above steps. This coating film or pattern is useful as a photo spacer used in a liquid crystal display device or a patternable overcoat. In addition, if a photomask for hole formation is used during patterning exposure to an uncured coating film, holes can be formed, which is useful as an interlayer insulating film. Furthermore, when exposing an uncured coating film, a transparent film can be formed only by exposure and heat curing, or only by heat curing, without using a photomask, and this transparent film is useful as an overcoat. It can also be used for touch panels.

  By incorporating the coating film or pattern thus obtained in a display device such as a liquid crystal display device, an excellent quality display device can be manufactured with a high yield.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it cannot be overemphasized that this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

[Synthesis Example 1]
Nitrogen was flowed at a rate of 0.02 L / min into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to form a nitrogen atmosphere. Subsequently, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) The compound to be mixed is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts by mass and 140 parts by mass of 3-methoxybutyl acetate, and the solution is added using a dropping funnel for 4 hours. And dropped in a flask kept at 70 ° C. On the other hand, a solution obtained by dissolving 45 parts by mass of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of 3-methoxybutyl acetate was added to a flask over another 4 hours using another dropping funnel. It was dripped in. After dropping of the solution of the polymerization initiator is completed, the copolymer is kept at 70 ° C. for 4 hours and then cooled to room temperature, and a copolymer having a solid content of 32.3% by mass and an acid value of 110 KOH / g (in terms of solid content) A resin solution was obtained. The obtained resin Aa had a weight average molecular weight Mw of 9.1 × 10 ³ and a molecular weight distribution (Mw / Mn) of 2.02.

[Synthesis Example 2]
Nitrogen was flowed at 0.02 L / min into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, 300 parts by mass of cyclohexanone was added, and the mixture was heated to 90 ° C. with stirring. Next, a solution was prepared by dissolving in 240 parts by mass of glycidyl acrylate, 60 parts by mass of methyl methacrylate, and 240 parts by mass of cyclohexanone, and the solution was kept at 90 ° C. for 3 hours using a dropping funnel. It was dripped in the flask. On the other hand, a solution prepared by dissolving 1.5 parts by mass of the polymerization initiator azobisisobutyronitryl in 60 parts by mass of cyclohexanone was dropped into the flask using another dropping funnel over 3 hours. Furthermore, after stirring at 90 ° C. for 1 hour, a solution in which 0.3 part by mass of azobisisobutyronitryl was dissolved in 60 parts by mass of cyclohexanone was added, and then the temperature was raised to 120 ° C. and stirred for 2 hours. Thereafter, the mixture was cooled to room temperature to obtain a copolymer resin solution having a solid content of 33.0%. The obtained resin Ab had a weight average molecular weight Mw of 8.0 × 10 ⁴ and a molecular weight distribution (Mw / Mn) of 2.35.

(Measurement of molecular weight)
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resins Aa and Ab were measured using the GPC method under the following conditions.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 ml / min
Detector; RI
The ratio of the weight average molecular weight and number average molecular weight obtained in the above-mentioned manner was defined as the molecular weight distribution (Mw / Mn).

[Example 1]
266 parts of resin solution (A) containing resin Aa obtained in Synthesis Example 1 (86 parts in terms of solid content), 14 parts of phthalic anhydride (B), 120 parts of diethylene glycol methyl ethyl ether, 1 part of 3-methoxybutyl acetate By mixing, a curable resin composition was obtained.

[Example 2]
A curable resin composition was obtained in the same manner as in Example 1 so that the composition shown in Table 1 was obtained.

[Comparative Example 1]
A curable resin composition was obtained in the same manner as in Example 1 so that the composition shown in Table 1 was obtained.

  The following evaluation was performed about the curable resin composition obtained as mentioned above. The results are shown in Table 1.

<Storage stability>
The viscosity of the curable resin composition obtained above was measured. Thereafter, the curable resin composition was sealed in a light-shielding container, and the container was stored in a thermostat at 23 ° C. for 2 weeks.
The viscosity of the curable resin composition after storage was measured, and the change in viscosity was determined based on the following formula.

If the change in viscosity is smaller, for example in the range of 100 to 103%, it means that the storage stability is better.
The viscosity was measured at 23 ° C. using a viscometer (VISCOMETER TV-30; manufactured by Toki Sangyo Co., Ltd.).

<Average transmittance of composition>
About each curable resin composition, the average transmittance (%) in 400-700 nm was measured using the microspectrophotometer (OSP-SP200; OLYMPUS company make).

<Membrane average transmittance>
Using each curable resin composition, a cured film was produced under the following conditions so that the film thickness after curing was 3 μm.
A 2-inch square glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. The curable resin composition 1 was spin-coated on this glass substrate, pre-baked at 90 ° C. for 3 minutes, and then post-baked at 220 ° C. for 20 minutes.
About each obtained cured film, the average transmittance | permeability (%) in 400-700 nm was measured using the microspectrophotometer (OSP-SP200; product made by OLYMPUS).
Higher transmittance means less absorption.

  From the results of Examples 1 to 3 shown in Table 1, it can be seen that the curable resin composition of the present invention containing a specific compound has a small viscosity change even after storage and is excellent in storage stability. On the other hand, the curable resin composition of Comparative Example 1 had a large viscosity change after storage and was inferior in storage stability.

  The curable resin composition of the present invention exhibits excellent storage stability and can form a coating film and a pattern with high transmittance. Therefore, it can be suitably used for forming a coating film or a pattern used in a display device such as an overcoat, a photo spacer, an insulating film, a protrusion for controlling liquid crystal alignment, and a coating layer for adjusting the film thickness of a colored pattern.

Claims (11)

Containing a binder resin (A) and at least one compound (B) selected from the group consisting of a carboxylic acid anhydride and a compound having at least two carboxyl groups,
The binder resin (A) comprises at least an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (Aa), a monomer (Ab) and / or copolymerizable with the (Aa). Or the curable resin composition which is a binder resin formed by superposing | polymerizing with the monomer (Ac) which has a C2-C4 cyclic ether group.   The binder resin (A) includes at least an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (Aa) and a monomer (Ac) having a cyclic ether group having 2 to 4 carbon atoms. The curable resin composition according to claim 1, which is a binder resin obtained by polymerization.   The curable resin composition of Claim 1 or 2 whose monomer (Ac) which has a C2-C4 cyclic ether group is a monomer which has an epoxy group.   The curable resin composition according to claim 3, wherein the monomer having an epoxy group is a monomer having an aliphatic polycyclic epoxy group. The monomer having an aliphatic polycyclic epoxy group is at least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II). The curable resin composition described in 1.

[In Formula (I) and Formula (II), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.
X ₁ and X ₂ each independently represent a C 1-6 alkylene group that may contain a single bond or a hetero atom. ]   The curability according to any one of claims 1 to 5, wherein at least one compound (B) selected from the group consisting of a carboxylic acid anhydride and a compound having at least two carboxyl groups is a carboxylic acid anhydride. Resin composition.   The unsaturated carboxylic acid and / or the unsaturated carboxylic acid anhydride (Aa) is an aliphatic unsaturated carboxylic acid and / or an aliphatic unsaturated carboxylic acid anhydride. Curable resin composition. At least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II) is represented by a compound represented by formula (I ′) and formula (II ′). The curable resin composition according to any one of claims 5 to 7, wherein the curable resin composition is at least one compound selected from the group consisting of:

[In Formula (I ′) and Formula (II ′), R ₁ ′ and R ₂ ′ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. ]   Use of the curable resin composition in any one of Claims 1-8 for forming a coating film or a pattern.   The coating film formed using the curable resin composition in any one of Claims 1-8.   The display apparatus containing the coating film of Claim 10.