TW201927847A - Resin, photosensitive resin composition, resin cured film, and image display device - Google Patents

Abstract

The present invention provides a resin including a structural component derived from an unsaturated monomer (a-1) having only a functional group which reacts with an acid radical, a structural component derived from an epoxy compound (a-2) having at least two epoxy functions, and a structural component derived from a compound (a-3) having at least three acid radicals.

Description

Resin, photosensitive resin composition, resin cured film, and image display device

The present invention relates to a resin, a photosensitive resin composition, a resin cured film, and an image display device.
This application claims priority based on Japanese Patent Application No. 2017-197128 filed in Japan on October 10, 2017, and incorporates this content in this application.

Conventionally, in a liquid crystal display panel, spacer particles have been used in order to maintain a certain distance (cell gap) between two substrates. As the spacer particles, glass beads, plastic beads, and the like having a predetermined particle diameter are used. Generally, the spacer particles are randomly arranged on a transparent substrate such as a glass substrate. When spacer particles are present in the pixel formation area of the liquid crystal display panel, problems such as the ghost phenomenon of the spacer particles or the problem that the incident light is scattered and the contrast is reduced may occur.

In order to solve this problem, a dot-like or stripe-shaped spacer formed by a photolithography and using a photosensitive resin composition is gradually used instead of the spacer particles. This spacer can be formed by applying a photosensitive resin composition to a substrate, and developing it after ultraviolet exposure through a predetermined photomask. Therefore, the spacer composed of the cured product of the photosensitive resin composition can be formed only at a predetermined position other than the pixel formation region in the liquid crystal display panel. Therefore, with the spacer formed by the photolithography and the use of the photosensitive resin composition, the problems described above when using spacer particles can be solved.

As a material of the spacer included in the liquid crystal display panel, as a photosensitive resin composition to be used, for example, there is a radiation-sensitive resin composition described in Patent Document 1.
Further, Patent Document 2 describes a photosensitive composition, which is preferably used as a resist for forming a color filter, and particularly preferably used as a resist for forming a black matrix. The photosensitive composition described in Patent Document 2 can also be used as a resist for a black column spacer.
In addition, Patent Document 3 describes a photosensitive resin composition for a black columnar spacer, which contains an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a light-shielding agent.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-302712
[Patent Document 2] Japanese Patent Application Laid-Open No. 2011-170075
[Patent Document 3] Japanese Patent Laid-Open No. 2013-134263

[Problems to be Solved by the Invention]

Recently, stricter dimensional accuracy has been demanded for liquid crystal display elements and various members forming the liquid crystal display elements. Therefore, a photosensitive resin composition used as a material of a black matrix, a color filter, and a black columnar spacer is required to have more excellent developability. In addition, in order to improve the display characteristics of a liquid crystal display element, a cured film obtained by curing the photosensitive resin composition used in the above-mentioned applications must have good dispersibility of a coloring agent. Furthermore, in order to prevent deterioration of a liquid crystal display element, a cured film obtained by curing a photosensitive resin composition used in the above-mentioned applications is required to have good solvent resistance and high elastic recovery.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin suitable as a material for a photosensitive resin composition. The cured film system obtained from the photosensitive resin composition has excellent developability. In addition, the colorant has good dispersibility and solvent resistance and has a high elastic recovery rate.
Another object of the present invention is to provide a photosensitive resin composition including the resin of the present invention, and the cured film system obtained from the photosensitive resin composition has excellent developability, colorant dispersibility, and solvent resistance. Is good and has a high elastic recovery rate.
Moreover, the subject of this invention is providing the resin hardened film of the photosensitive resin composition of this invention, and the image display device provided with the same.

[Means for solving problems]

The constitution of the present invention for solving the above problems is as follows.

[1]. A resin, characterized in that:
A component derived from an unsaturated monomer (a-1) having only one functional group that reacts with an acid group,
A component derived from an epoxy compound (a-2) having two or more epoxy groups and a component derived from a compound (a-3) having three or more acid groups.

[2]. A resin, the characteristics of which include:
A component derived from an unsaturated monomer (a-1) having only one functional group that reacts with an acid group,
A component derived from an epoxy compound (a-2) having two or more epoxy groups,
A component derived from the compound (a-3) having three or more acid groups and a component derived from the compound (a-4) having an acid anhydride group.

[3]. The resin according to [1] or [2], which has a first bonding portion and a second bonding portion,
The first bonding portion is a functional group that reacts with an acid group in the unsaturated monomer (a-1) and an acid group via the acid group in the compound (a-3) having three or more acid groups. To form,
The second bonding portion is formed by bonding an epoxy group of the epoxy compound (a-2) and an acid group of the compound (a-3) having three or more acid groups.

[4]. The resin according to any one of [1] to [3], wherein the acid group contained in the compound (a-3) having three or more acid groups is a carboxyl group.

[5]. The resin according to any one of [1] to [4], wherein the unsaturated monomer (a-1) is a compound represented by the following formula (1).

(In formula (1), R ₁ represents a hydrogen atom or a methyl group; R ₂ represents any one selected from a single bond, a methylene group, and an alkylene group having 2 to 12 carbon atoms; X ₁ represents an epoxy group selected , 3,4-epoxycyclohexyl, any one of the group represented by the following formula (2-1) and the group represented by the following formula (2-2); the following formula (2-1) and In the following formula (2-2), * represents a bonding site between X ₁ and R ₂ ).

[6]. The resin according to any one of [1] to [5], wherein the functional group that reacts with the acid group of the unsaturated monomer (a-1) is an epoxy group.

[7]. The resin according to any one of [1] to [6], wherein the epoxy compound (a-2) is a compound represented by the following formula (2).

(In formula (2), A represents -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9,9-fluorenylene or a single bond; B represents a phenylene group or a phenylene group having a substituent, and the aforementioned substituent group is selected from an alkyl group, a halogen atom or a phenyl group having 1 to 5 carbon atoms Either; X ₂ represents any one selected from an epoxy group, a 3,4-epoxy cyclohexyl group, a group represented by the following formula (2-1), and a group represented by the following formula (2-2) In one of the following formulae (2-1) and (2-2), * represents a bonding site between X ₂ and a methylene group).

[8]. The resin according to any one of [1] to [7], wherein the compound (a-3) having three or more acid groups is 1,2,4-cyclohexanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid.
[9]. The resin according to any one of [1] to [8], wherein among the number of acid groups contained in the compound (a-3) having three or more acid groups, and the epoxy resin The proportion of the number of the epoxy group-bonded acid groups of the compound (a-2) is 5 to 60%.
[10]. The resin according to any one of [2] to [9], wherein the compound (a-4) having an acid anhydride group is an anhydride having a ring structure.

[11]. A resin characterized by an unsaturated monomer (a-1) having only one functional group that reacts with an acid group,
Epoxy compound (a-2) having two or more epoxy groups and compound (a-3) having three or more acid groups
Obtained by polymerization.
[12]. A resin characterized by an unsaturated monomer (a-1) having only one functional group that reacts with an acid group,
Epoxy compound (a-2) having two or more epoxy groups,
Compound (a-3) having three or more acid groups and compound (a-4) having an acid anhydride group
Obtained by polymerization.

[13]. A photosensitive resin composition comprising:
Resin (A) such as any of [1] ~ [12],
Solvent (B),
Photopolymerization initiator (C) and coloring agent (D).
[14]. The photosensitive resin composition according to [13], which contains:
1-20% by mass of the resin (A),
The aforementioned solvent (B) is 50 to 94% by mass,
The photopolymerization initiator (C) is 0.01 to 5% by mass and the colorant (D) is 3 to 30% by mass.
[15]. The photosensitive resin composition according to [14], further comprising a reactive diluent (E) in an amount of 1 to 20% by mass.

[16]. A resin cured film of the photosensitive resin composition according to any one of [13] to [15].
[17]. An image display device comprising a resin hardened film as described in [16].

[Effect of the invention]

The resin system of the present invention can be suitably used as a material of a photosensitive resin composition. The cured film system obtained from the photosensitive resin composition has excellent developability, has good colorant dispersibility and solvent resistance, and has high Flexible response rate.
Since the photosensitive resin composition system of this invention contains the resin of this invention, the hardened film which has the outstanding developability, the colorant dispersibility, and solvent resistance is favorable, and has a high elastic recovery rate can be obtained. Therefore, the photosensitive resin composition of the present invention can be suitably used as a material for a black matrix, a color filter, and a black columnar spacer.
The resin hardened film system of the present invention can be suitably used as a black matrix, a color filter, and a black columnar spacer of a member of an image display device.

[Best Mode for Implementing Invention]

Hereinafter, embodiments of the resin, the photosensitive resin composition, the resin cured film, and the image display device of the present invention will be described in detail. However, the present invention is not limited to the embodiments shown below.

[Resin]
The resin system of this embodiment includes an unsaturated monomer (a-1) having only one functional group that reacts with an acid group, an epoxy compound (a-2) having two or more epoxy groups, and three The above-mentioned acid-based compound (a-3) is obtained by a reaction. The resin according to this embodiment includes a constituent component derived from an unsaturated monomer (a-1) having only one functional group which reacts with an acid group, and an epoxy compound (a derived from an epoxy group having two or more epoxy groups. -2) A constituent component and a constituent component derived from a compound (a-3) having three or more acid groups. The resin according to this embodiment may contain a constituent component derived from another arbitrary component within a range that does not impair the effect of the present invention.

It is estimated that the resin of this embodiment has an epoxy compound (a-) having a functional group of an unsaturated monomer (a-1) having only one functional group that reacts with an acid group, and an epoxy group having two or more epoxy groups. 2) A three-dimensional structure formed by reacting an epoxy group and an acid group of a compound (a-3) having three or more acid groups. From this, it is estimated that the photosensitive resin composition system including the resin of this embodiment can obtain a cured film having excellent developability, good colorant dispersibility and solvent resistance, and high elastic recovery.

<Unsaturated monomer (a-1) having only one functional group that reacts with an acid group>
The functional group that reacts with an acid group in the unsaturated monomer (a-1) having only one functional group that reacts with an acid group is not particularly limited, and examples thereof include an epoxy group and an oxetanyl group. , Isocyanato group, hydroxyl group, etc., since the raw materials are inexpensive and the reaction for producing the resin of this embodiment is easy and the reaction rate is high, an epoxy group is particularly preferred.

Specific examples of the unsaturated monomer (a-1) having only one functional group that reacts with an acid group include glycidyl (meth) acrylate, glycidyl ether of 4-hydroxybutyl acrylate, and the like. Epoxy (meth) acrylate, oxetanyl (meth) acrylate, (3-methyloxetan-3-yl) methyl (meth) acrylate, (methyl ) (3-ethyloxetane-3-yl) acrylate, (3-methyloxetane-3-yl) ethyl (meth) acrylate, (3) -Ethyloxetane-3-yl) ethyl ester, (3-chloromethyloxetane-3-yl) methyl (meth) acrylate, (oxetane (meth) acrylate Alkyl-2-yl) methyl ester, (2-methyloxetane-2-yl) methyl (meth) acrylate, (2-ethyloxetane-2- (meth) acrylate) ) Methyl ester, (1-methyl-1-oxetan-2-phenyl) -3- (meth) acrylate, (1-methyl-1-oxetanyl) 2-trifluoromethyl-3- (meth) acrylate, (1-methyl-1-oxetanyl) -4-trifluoromethyl-2- (meth) acrylate, etc. (Meth) acrylic acid esters containing oxetanyl group; 2-isocyanate group of (meth) acrylic acid (Meth) acrylate ester containing isocyanate group (2-isocyanatoethyl methacrylate) and the like, (meth) acrylate, 2-hydroxy ethyl (meth) acrylate containing a hydroxyl group.

In this specification, "(meth) acrylate" means "acrylate" or "methacrylate" or both.

As the unsaturated monomer (a-1) having only one functional group that reacts with an acid group, among the above, a monomer selected from glycidyl methacrylate and 2-isocyanatoethyl methacrylate is particularly used. One or two of them are preferable.
The above-mentioned compounds used as the unsaturated monomer (a-1) having only one functional group that reacts with an acid group may be used alone or in combination of two or more kinds.

Examples of the unsaturated monomer (a-1) having only one functional group that reacts with an acid group include a (meth) acrylate having only one functional group that reacts with an acid group.

The unsaturated monomer (a-1) having only one functional group that reacts with an acid group is preferably a compound represented by the following formula (1). When the unsaturated monomer (a-1) is a compound represented by the following formula (1), the addition reaction for producing the resin of this embodiment is easy, and therefore it is a resin that can be easily produced. The unsaturated monomer (a-1) is a resin of a compound represented by the following formula (1). Since the unsaturated group of the unsaturated monomer (a-1) is a (meth) acrylfluorenyl group, the reaction proceeds. Good properties are preferred.

(In formula (1), R ₁ represents a hydrogen atom or a methyl group; R ₂ represents any one selected from a single bond, a methylene group, and an alkylene group having 2 to 12 carbon atoms; X ₁ represents an epoxy group selected , 3,4-epoxycyclohexyl, any one of the group represented by the following formula (2-1) and the group represented by the following formula (2-2); the following formula (2-1) and In the following formula (2-2), * represents a bonding site between X ₁ and R ₂ ).

In formula (1), R ₁ represents a hydrogen atom or a methyl group.
In the formula (1), R ₂ represents any one selected from a single bond, a methylene group, and an alkylene group having 2 to 12 carbon atoms, and any one selected from the group consisting of a methylene group and an alkylene group having 2 to 7 carbon atoms. One is better.
In the formula (1), X ₁ represents a group selected from the group consisting of an epoxy group, a 3,4-epoxycyclohexyl group, the group represented by the above formula (2-1), and the group represented by the above formula (2-2) (above In the formula (2-1) and the above formula (2-2), * represents any one of the bonding site of X ₁ and R ₂ ), and an epoxy group is preferred.

<Epoxy compound (a-2) having two or more epoxy groups>
Specific examples of the epoxy compound (a-2) having two or more epoxy groups include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and hydrogenated bisphenol A. Diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol Polyglycidyl ether, Diglycerol polyglycidyl ether, Sorbitol polyglycidyl ether, Resorcinol diglycidyl ether, Diglycidyl terephthalate, Diglycidyl phthalate, Di A bisphenol fluorene diglycidyl ether or a compound obtained by adding epihalohydrin such as epichlorohydrin to a compound shown below.

Examples of a compound that forms an epoxy compound (a-2) having two or more epoxy groups by addition of an epoxy halopropane include bis (4-hydroxyphenyl) ketone and bis (4) -Hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) fluorene, bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, bis (4-hydroxy-3,5-dichlorophenyl) fluorene, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-di (Methylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5 -Dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromobenzene) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3 , 5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane , 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4 -Hydroxy-3,5-dichlorophenyl) ether, 9, 9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9 , 9-bis (4-hydroxy-3-bromobenzene) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylformaldehyde) Phenyl) fluorene, 3,3 ', 5,5'-tetramethyl-4,4'-bis (glycidyloxy) -1,1'-biphenyl, 1,6-bis (2 , 3-epoxypropane-1-yloxo) naphthalene and the like.

As the epoxy compound (a-2) having two or more epoxy groups, among the above compounds, a compound selected from the group consisting of ethylene glycol diglycidyl ether and bisphenol diglycidyl ether, 3,3 ', 5,5'-tetramethyl-4,4'-bis (glycidyloxy) -1,1'-biphenyl, 1,6-bis (2,3-epoxypropane-1-yl One or two of the oxo) naphthalenes are preferred.
The above-mentioned compounds used as the epoxy compound (a-2) having two or more epoxy groups may be used alone or in combination of two or more kinds.

The epoxy compound (a-2) having two or more epoxy groups is preferably a compound represented by the following formula (2).

(In formula (2), A represents -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9,9-fluorenylene or a single bond; B represents a phenylene group or a phenylene group having a substituent, and the aforementioned substituent group is selected from an alkyl group, a halogen atom or a phenyl group having 1 to 5 carbon atoms Either; X ₂ represents any one selected from an epoxy group, a 3,4-epoxy cyclohexyl group, a group represented by the following formula (2-1), and a group represented by the following formula (2-2) In one of the following formulae (2-1) and (2-2), * represents a bonding site between X ₂ and a methylene group).

In formula (2), A represents -CO-, -SO _2- , -C (CF ₃ ) _2- ,
-Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9,9-fluorenylene or a single bond, and 9,9-fluorenylene is more preferable.
In the formula (2), B represents a phenylene group or a phenylene group having a substituent, and the phenylene group is preferred. When B is a phenylene group having a substituent, the substituent represents any one selected from an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group.
In the formula (2), X ₂ represents a group selected from the group consisting of an epoxy group, a 3,4-epoxycyclohexyl group, the group represented by the above formula (2-1), and the group represented by the above formula (2-2) (above In the formula (2-1) and the formula (2-2), * represents any one of the bonding site of X ₂ and a methylene group), and an epoxy group is preferred.

<Compound (a-3) having three or more acid groups>
The compound (a-3) having three or more acid groups has three or more acid groups in one molecule. The acid group in the compound (a-3) having three or more acid groups is not particularly limited, and examples thereof include a sulfo group, a phosphate group, and a carboxyl group, and a carboxyl group is preferred. When the acid group in the compound (a-3) having three or more acid groups is a carboxyl group, a resin having better developability will be obtained. In addition, in the addition reaction for producing the resin of this embodiment, side reactions are less likely to occur, and the resin can be easily produced.
In this embodiment, the acid group in the compound (a-3) having three or more acid groups does not include an acid anhydride group.

Specific examples of the compound (a-3) having three or more acid groups include 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,3- Propane tricarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, 3-butene-1,2,3-tricarboxylic acid, polyphosphoric acid, Ethylene tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3,4,4-biphenyltetracarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid, 1, 1'-Bicyclohexane-3,3 ', 4,4'-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, polycarboxylic acid, and the like.

As the compound (a-3) having three or more acid groups, among the above compounds, a compound selected from 1,2,4-cyclohexanetricarboxylic acid and 1,2,3,4-butanete One or two of the carboxylic acids are preferred.
The above-mentioned compounds used as the compound (a-3) having three or more acid groups may be used alone or as a mixture of two or more kinds.
The compound (a-3) having three or more acid groups is a compound having no functional group other than an acid group.

The resin of this embodiment may include an unsaturated monomer (a-1) having only one functional group that reacts with an acid group, an epoxy compound (a-2) having two or more epoxy groups, and The compound (a-3) having three or more acid groups and the compound (a-4) having an acid anhydride group are obtained by reaction. This resin includes a constituent component derived from an unsaturated monomer (a-1) having only one functional group that reacts with an acid group, and an epoxy compound (a-2) derived from two or more epoxy groups. A constituent component derived from the compound (a-3) having three or more acid groups, and a constituent component derived from the compound (a-4) having an acid anhydride group.
When the resin of this embodiment contains the component derived from the compound (a-4) which has an acid anhydride group, it will become resin with more favorable developability.

As the compound (a-4) having an acid anhydride group, an anhydride having a ring structure is preferably used. Specifically, examples of the anhydride having a ring structure include carboxylic anhydrides such as tetrahydrophthalic anhydride and succinic anhydride.

The resin of this embodiment may be an unsaturated monomer having an acid (a trifunctional or higher acid) compound having three or more acid groups and an acid anhydride group in one molecule, and an unsaturated monomer having only one functional group that reacts with an acid group. The compound (a-1) is obtained by reacting an epoxy compound (a-2) having two or more epoxy groups. This resin contains a constituent component of a compound derived from a trifunctional or higher acid and having an acid anhydride group. The compound having a trifunctional or higher acid and having an acid anhydride group is a compound (a-3) having three or more acid groups and a compound (a-4) having an acid anhydride group.
Therefore, in this embodiment, a resin containing a constituent component derived from a tri- or more-functional acid and having a compound having an acid anhydride group is considered to contain a constituent component derived from a compound (a-3) having three or more acid groups. And a component derived from the compound (a-4) having an acid anhydride group.
In addition, "the number of functional groups (β) bonded to the functional group that reacts with the acid group in the unsaturated monomer (a-1), and the function of the epoxy group (a-2) to the The ratio of the total number of bases (γ) (β + γ) to "the number of functional groups (α) of the constituents of the compound derived from an acid having a trifunctional or higher function and having an acid anhydride group" is regarded as being derived from a trifunctional or higher function Of the constituents of the acid-containing compound having an acid anhydride group, the ratio of the constituent components derived from the compound (a-3) having three or more acid groups (δ = {(β + γ) / (α)}) . The ratio (1-δ) of the constituent components derived from the compound (a-3) having three or more acid groups among the constituent components derived from the trifunctional or more acid-containing compound having an acid anhydride group, The ratio of the component derived from the compound (a-4) which has an acid anhydride group is considered.

The resin of this embodiment preferably has a first bonding portion and a second bonding portion, and the first bonding portion is a functional group that reacts with an acid group in the unsaturated monomer (a-1) and has 3 The acid group of the compound (a-3) having more than one acid group is bonded, and the second bonding portion is an epoxy group of the epoxy compound (a-2) and an acid having 3 or more The acid group of the base compound (a-3) is bonded. By having the first bonding portion and the second bonding portion, it is possible to obtain hardening having excellent hardenability and developability, good colorant dispersibility and solvent resistance, and high hardness and elastic recovery. membrane.

Such a resin can be obtained, for example, by performing the first step and the second step. The first step is an epoxy compound (a-2) and a compound (a-3) having three or more acid groups. The compound (a-3) having three or more acid groups is formed in a state where the number of moles of the acid group is greater than the number of moles of the epoxy group of the epoxy compound (a-2). A resin precursor is obtained; in the second step, the unsaturated monomer (a-1) and the resin precursor are reacted.

By performing the first step, the obtained resin precursor has an epoxy group of the epoxy compound (a-2) and an acid group via a bond of the compound (a-3) having three or more acid groups. The second bonded portion formed has an acid group derived from the compound (a-3) having three or more acid groups which is not bonded to the epoxy group.
The second step is performed after the first step, whereby three functional groups that react with the acid group contained in the unsaturated monomer (a-1) and the remaining residues in the resin precursor have three The acid group of the compound (a-3) of the above acid group undergoes an addition reaction. In this case, the obtained resin will have a functional group that reacts with an acid group contained in the unsaturated monomer (a-1) and an acid that the compound (a-3) has three or more acid groups. The first bonding portion bonded to the base and the second bonding portion described above.

The preferable constituent unit ratio of the resin in this embodiment is as shown in the following (I) to (III).
(I) The ratio of the epoxy group of the epoxy compound (a-2) to 60 to 5 moles relative to 100 moles of the acid group of the compound (a-3) having three or more acid groups. The resin to be reacted is more preferable, and the resin to be reacted at a ratio of 50 to 10 mol is more preferable. That is, the resin of this embodiment has an acid group bonded to the epoxy group of the epoxy compound (a-2) among the number of acid groups of the compound (a-3) having three or more acid groups. The proportion of the amount is preferably 5 to 60%, and more preferably 10 to 50%. Such a resin system sufficiently contains an epoxy group of the epoxy compound (a-2) and a second bond formed by bonding an acid group of the compound (a-3) having three or more acid groups. Knot. The 2nd bonding part system contributes to the hardness improvement of a hardened film. Therefore, with the above resin, a cured film having excellent curability and developability, good colorant dispersibility and solvent resistance, and high hardness and elastic recovery can be obtained.

(II) The functional group that reacts with the acid group of the unsaturated monomer (a-1) is 40 to 90 with respect to 100 mol of the acid group of the compound (a-3) having three or more acid groups. It is more preferable that the resin is reacted in a molar ratio, and the resin is reacted in a ratio of 40 to 60 molar. That is, the resin of this embodiment reacts with the acid group contained in the unsaturated monomer (a-1) among the number of acid groups contained in the compound (a-3) having three or more acid groups. The ratio of the number of acid groups bonded to the functional group is preferably 40 to 90%, and more preferably 40 to 60%. In such a resin, the unsaturated monomer (a-1) which is bonded to the acid group of the compound (a-3) having three or more acid groups contributes to improvement of the hardenability of the cured film. Therefore, with the above resin, a cured film having excellent curability and developability, good colorant dispersibility and solvent resistance, and high hardness and elastic recovery can be obtained.

(III) When the compound (a-4) having an acid anhydride group is used as the material of the resin, the number of functional groups that the compound (a-4) has to react with the hydroxyl group is to form a ring having two or more epoxy groups. Oxygen compound (a-2) and compound (a-3) having 3 or more acid groups are reacted in a ratio of 10 to 70% of the amount of hydroxyl groups generated by the reaction, and the resin is preferably made to become the above-mentioned hydroxyl group. A resin with a ratio of 20 to 60% of the amount is more preferable. When the number of functional groups that react with a hydroxyl group in the compound (a-4) is within the above range, the addition reaction of the resin can be effectively performed, and thus the resin has good productivity. When the number of functional groups that react with a hydroxyl group in the compound (a-4) is within the above range, the number of hydroxyl groups in the resin is an appropriate amount, and therefore it is a resin that can obtain a cured film having good coating film physical properties.

The weight average molecular weight of the resin of this embodiment obtained by polystyrene conversion by gel permeation chromatography (GPC) is preferably 1,000 to 40,000, and more preferably 3,000 to 30,000. If the weight-average molecular weight is 1,000 or more, it is preferred that the pattern formed by development is less likely to be damaged after the photosensitive resin composition containing the resin is applied and exposed. On the other hand, when the weight-average molecular weight is 40,000 or less, the time required for the development of the photosensitive resin composition containing the resin after application and exposure is moderate, and it is practical for use, so it is preferable.

The acid value (JIS K6901 5.3) of the resin in this embodiment is not limited as long as it can exhibit the desired effect of the present invention, and is generally 20 to 300 KOHmg / g, and preferably 30 to 200 KOHmg / g. When the acid value is 20 KOHmg / g or more, the developability of the photosensitive resin composition containing the resin is good, so it is preferable. On the other hand, if the acid value is 300 KOHmg / g or less, the photosensitive resin composition containing the resin is applied and exposed to light-harden the part, so that it is difficult to dissolve the developer, so it is preferable.

The unsaturated group equivalent of the resin in this embodiment is not limited as long as it can exert the desired effect of the present invention, and is generally 100 to 4000 g / mole, preferably 200 to 2000 g / mole, and more preferably 300 ~ 500g / mole. When the unsaturated group equivalent is 100 g / mole or more, the developability of the photosensitive resin composition containing the resin is good. Therefore, a resin-cured film that photocures a photosensitive resin composition containing the resin has better characteristics when used as a black matrix, a color filter, and a black columnar spacer. On the other hand, if the unsaturated group equivalent is 4000 g / mole or less, the sensitivity of the photosensitive resin composition containing the resin becomes higher, and a finer pattern can be formed, which is preferable.

The term "unsaturated group equivalent" refers to the mass of the resin per mole of unsaturated bonds (ethylene-carbon-carbon double bonds) in the resin. The unsaturated group equivalent is obtained by dividing the mass of the resin by the number of unsaturated groups in the resin (g / mole). In this specification, the equivalent of an unsaturated group of a resin refers to a theoretical value calculated from the amount of a raw material used to introduce an unsaturated group into a resin.

[Manufacturing method of resin]
Next, a method for manufacturing the resin of this embodiment will be described.
The resin of this embodiment can use an arbitrary polymerization method to convert an unsaturated monomer (a-1) having only one functional group that reacts with an acid group, and an epoxy compound having two or more epoxy groups. (a-2), a compound (a-3) having three or more acid groups, and a method of polymerizing the compound (a-4) having an acid anhydride group to be used as required.

As a method of polymerizing the resin of this embodiment, it is preferable to use the method shown below.
First, in a solvent, a catalyst is used as required, and an epoxy compound (a-2) having two or more epoxy groups and a compound (a-3) having three or more acid groups are reacted. Synthetic resin precursor (first step). The amount of the epoxy compound (a-2) having two or more epoxy groups and the compound (a-3) having three or more acid groups is used in the first step so that The compound (a-3) is preferably performed such that the number of moles of the acid group is larger than the number of moles of the epoxy group of the epoxy compound (a-2). Specifically, the ratio of the epoxy group of the epoxy compound (a-2) to 60 to 5 mol is 100 mol of the acid group of the compound (a-3) having three or more acid groups. It is better to make it react, and it is more preferable to make it react at a ratio of 50 to 10 mol.

The reaction conditions in the first step can be appropriately set according to a conventional method.
For example, the reaction temperature in the first step is preferably 50 to 150 ° C, and more preferably 60 to 140 ° C. The reaction time in the first step can be, for example, 1 to 6 hours.

Next, in the solvent, an unsaturated monomer (a-1) having only one functional group that reacts with an acid group is added to the resin precursor using a polymerization inhibitor as needed (step 2). . In the second step, the unsaturated monomer (a-1) is included in the unsaturated monomer (a-1) with respect to 100 mol of the acid group of the compound (a-3) having three or more acid groups used as a raw material of the resin. The functional group that reacts with an acid group is preferably 40 to 90 moles for the reaction, and it is more preferable to be 40 to 60 moles for the reaction.
In the method for polymerizing a resin of this embodiment, in the second step, an unsaturated monomer (a-1) having only one functional group that reacts with an acid group and a compound (a-4 having an acid anhydride group) ) The reaction is performed on the resin precursor. In this case, the number of functional groups that the compound (a-4) has to react with the hydroxyl group is to form an epoxy compound (a-2) having two or more epoxy groups and a compound having three or more acid groups. (a-3) The ratio of 10 to 70% of the amount of hydroxyl groups generated by the reaction is preferably made to react, and the ratio of 20 to 60% of the amount of the hydroxyl group is preferably made to react.

The reaction conditions in the second step can be appropriately set according to a conventional method.
For example, the reaction temperature in the second step is preferably 50 to 150 ° C, and more preferably 60 to 140 ° C. The reaction time in the second step can be, for example, 1 to 6 hours.

The solvent used in the second step may include the solvent used in the first step. That is, without removing the solvent remaining in the reaction system after the completion of the first step, the second step can be continuously performed after the first step.

The solvent used for producing the resin of the present embodiment is not particularly limited, and a known type can be suitably used. Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol mono-n. -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol mono (Poly) extensions of methyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether Alkyl glycol monoalkyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. (Poly) alkylene glycol monoalkyl ether acetate; other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran ; Ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionate Methyl ester, ethyl 2-hydroxy-2-methylpropionate, 3-methoxy Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy- Methyl 3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-butyl acetate , N-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, butyl N-propyl acid, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, 2 -Ester compounds such as ethyl oxobutyrate; aromatic hydrocarbon compounds such as toluene and xylene; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylethyl Carboxamide compounds such as amidine and the like. These solvents can be used alone or in combination of two or more.

Among the above solvents, a glycol ether-based solvent is preferred. That is, as the solvent, (poly) alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether and (poly) alkylene glycol monoalkyl ether acetic acid such as propylene glycol monomethyl ether acetate are used. Esters are preferred.

The amount of the solvent used for producing the resin of this embodiment is not particularly limited.
Loading amount (unsaturated monomer (a-1), epoxy compound (a-2), compound (a-3) having three or more acid groups, and compound having acid anhydride group as required When the total amount of (a-4) is 100 parts by mass, it is generally 30 to 1,000 parts by mass, and preferably 50 to 800 parts by mass. When the amount of the above-mentioned solvent is 1000 parts by mass or less, the viscosity of the resin can be controlled within an appropriate range, which is preferable. On the other hand, if the amount of the solvent used is 30 parts by mass or more, it is preferable to prevent burn-in caused during the reaction and to stably proceed the synthesis reaction. In addition, when the amount of the solvent used is 30 parts by mass or more, the coloring or gelation of the resin can be prevented.

In this embodiment, in order to promote the reaction between the epoxy compound (a-2) having two or more epoxy groups and the compound (a-3) having three or more acid groups, it is preferable to use a catalyst. The catalyst used in this embodiment is not particularly limited, and can be appropriately selected depending on the raw material of the resin and the like.

Examples of the catalyst used in this embodiment include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzyl ammonium chloride, and phosphorus compounds such as triphenylphosphine. , Chelates of chromium, etc. These catalysts can be used alone or in combination of two or more.
The amount of the catalyst used in this embodiment is not particularly limited, but if the resin precursor synthesized in the first step is 100 parts by mass, it is usually 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass.

In the second step, in order to prevent gelation of the resin, it is preferable to use a polymerization inhibitor. The polymerization inhibitor used in the second step is not particularly limited, and can be appropriately selected depending on the raw material of the resin and the like.

Examples of the polymerization inhibitor used in the second step include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and butylhydroxytoluene. These polymerization inhibitors may be used alone or in combination of two or more.
The amount of the polymerization inhibitor is not particularly limited, but when the amount of the resin precursor is 100 parts by mass, it is usually 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass.

[Photosensitive resin composition]
The photosensitive resin composition according to this embodiment contains the resin (A), the solvent (B), the photopolymerization initiator (C), and the coloring agent (D) according to any one of the embodiments.

<Solvent (B)>
The solvent (B) is not particularly limited as long as it is an inert solvent that can dissolve the resin (A) and does not react with the resin (A), and can be arbitrarily selected according to the type of the resin (A) and the like. The solvent (B) is preferably compatible with a reactive diluent to be described later.

As the solvent (B), the same solvent as that used when the resin (A) can be used may be used, and a glycol ether solvent is preferably used. That is, as the solvent (B), (poly) alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and (poly) alkylene glycol monoalkanes such as propylene glycol monomethyl ether acetate are used. Ether ether acetate is preferred.
When a solution containing a solvent component is used as a material of the photosensitive resin composition other than the solvent (B), the solvent component contained in the solution may be used as the solvent (B).

<Photopolymerization initiator (C)>
The photopolymerization initiator (C) is not particularly limited, and examples thereof include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; phenethyl Ketone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1-t-butyldioxy-1-methylethyl) benzene Ethyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-propane-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinylphenyl) acetophenone compounds such as butanone-1; anthracenes such as 2-methylanthraquinone, 2-pentylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone Quinone compounds; xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and other xanthone compounds; acetophenone Ketal compounds such as dimethyl ketal, benzyl dimethyl ketal; benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3 , 3 ', 4,4'-(t-butyldioxycarbonyl) benzophenone compounds such as benzophenone; fluorenyl phosphine oxide compounds, 1,2-octanedione, 1- [4 -(Phenylthio)-, 2- (O-benzidine oxime)] and the like. These photopolymerization initiators (C) may be used alone or in combination of two or more.

<Colorant (D)>
The colorant (D) is not particularly limited as long as it can be dissolved or dispersed in the solvent (B). Examples of the colorant (D) include dyes and pigments. As the colorant (D), only a dye or a pigment may be used, or a dye and a pigment may be used in combination. When the resin-cured film of the photosensitive resin composition of this embodiment is used as any one of a black matrix, a color filter, and a black columnar spacer, the purpose of the member formed from the resin-cured film, etc., is considered as described above. The colorant (D) can be used alone or in combination of two or more. For example, when a black type is used as the colorant (D), the resin cured film system of the photosensitive resin composition can be suitably used as a black matrix and a black columnar spacer.

Examples of dyes include acid alizarin violet N; acidblack1,2,24,48; acid blue1,7,9,25,29,40,45,62,70,74,80,83,90,92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acidgreen1, 3, 5, 25, 27, 50; acid orange6, 7, 8, 10, 12, 50, 51, 52, 56, 63 , 74, 95; acid red1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72 , 73, 76, 79, 98, 99, 111, 112, 114, 116; foodyellow3 and their derivatives.

Among these dyes, azo-based, xanthene-based, anthraquinone-based, or phthalocyanine-based acid dyes are preferably used.
These dye systems can be used alone or in combination of two or more.

Examples of pigments include CIPigment Yellow1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CIPigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, Orange pigments of 59, 61, 64, 65, 71, 73, etc .; CIPigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216 , 224, 242, 254, 255, 264, 265 and other red pigments; CIPigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; CIPigment violet 1, 19, 23, 29 , 32, 36, 38 and other violet pigments; CIPigment Green 7, 36, 58 and other green pigments; CIPigment Brown 23 and 25 and other brown pigments; aniline black, black, titanium black, flower blue black, lignin Black, black pigments such as organic amine organic black, RGB black, carbon black, iron oxide, etc.

These pigments can be used alone or in combination of two or more.
From the viewpoint of the optical density of an image display device including a resin cured film of the photosensitive resin composition of this embodiment, it is preferable to use an inorganic black pigment and an organic black pigment together as a black pigment, and to use a combination of carbon black and Lactamamine organic black is more preferred.

When a pigment is contained as a coloring agent (D), the photosensitive resin composition system can contain a well-known dispersing agent from a viewpoint of improving the dispersibility of the pigment in a photosensitive resin composition. The content of the dispersant can be appropriately set according to the type of pigment and the like to be used.

As a dispersant, since the dispersion stability over time is excellent, it is preferable to use a polymer dispersant. The polymer dispersant system can be arbitrarily selected, and examples thereof include a polyurethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, and a polyoxyethylene glycol diester-based dispersion. Agents, sorbitan fatty ester-based dispersants, aliphatic modified ester-based dispersants, and the like. As the polymer dispersant, EFKA (registered trademark, manufactured by BASF JAPAN), Disperbyk (registered trademark, manufactured by BYK), DISPARLON (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), and SOLSPERSE (registered trademark, Zeneca) can be used. Types) and other commercially available types.

<Reactive Diluent (E)>
The photosensitive resin composition of this embodiment may contain a reactive diluent (E) in addition to the resin (A), the solvent (B), the photopolymerization initiator (C), and the coloring agent (D).
The reactive diluent (E) is a compound having at least one ethylenically unsaturated group in the molecule, and a compound having a plurality of ethylenically unsaturated groups is preferred.

The photosensitive resin composition contains a reactive diluent (E), which makes it easy to adjust the viscosity and sensitivity of the photosensitive resin composition. When a resin cured film of a photosensitive resin composition containing a reactive diluent (E) is used as a black matrix, a color filter, and a black columnar spacer, the strength of the resin cured film becomes good. It is better. In addition, after the photosensitive resin composition containing the reactive diluent (E) is applied to the formed surface of the resin cured film and exposed, the adhesion between the formed resin cured film and the formed surface is developed. For good, it is better.

Examples of the monofunctional monomer (monomer having only one ethylenically unsaturated bond) used as the reactive diluent (E) include (meth) acrylamide, hydroxymethyl (meth) acrylamine Amine, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl ( (Meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2- (meth) acrylate 2- Hydroxyethyl ester, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) propylene Ethoxy-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, (methyl ) (Methyl) such as 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, semi- (meth) acrylate of phthalic acid derivatives, etc. ) Acrylate compounds; styrene, α-methylstyrene, α-chloromethylstyrene, vinyl toluene Aromatic vinyl compounds; vinyl acetate, vinyl propionate and the like carboxylic acid ester. These monofunctional monosystems can be used alone, or two or more kinds can be used.

Examples of the polyfunctional monomer (a monomer having a plurality of ethylenically unsaturated bonds) used as the reactive diluent (E) include ethylene glycol di (meth) acrylate and diethylene glycol di ( (Meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acrylic acid) Didiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloxypropane (Meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl bis (methyl) Base) acrylate, Oil triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., toluene diisocyanate), trimethylhexamethylene diisocyanate, and hexamethylene (Meth) acrylic acid ester compounds such as reactants with 2-hydroxyethyl (meth) acrylate and the like, and (meth) acrylic acid compounds such as tris (meth) acrylate of ginsyl (hydroxyethyl) isocyanurate; Aromatic vinyl compounds such as benzene, diallyl phthalate, diallyl phenylphosphonate, etc .; dicarboxylic acid compounds such as divinyl adipate; triallyl cyanurate Ester, methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, polycondensate of polyhydric alcohol and N-methylol (meth) acrylamide. These polyfunctional monosystems can be used alone or in combination of two or more.

Furthermore, the photosensitive resin composition of this embodiment may contain well-known additives, such as a coupling agent, a leveling agent, and a thermal polymerization inhibitor, in the range which does not impair the effect of this invention. Examples of the coupling agent include KBM-403 (3-glycidoxypropyltriethoxysilane, manufactured by Shinetsu Silicone) and the like. The content of these additives is not particularly limited as long as it is within a range that does not impair the effect of the present invention.

The photosensitive resin composition of this embodiment contains 1 to 20% by mass of the resin (A), 50 to 94% by mass of the solvent (B), 0.01 to 5% by mass of the photopolymerization initiator (C), and a coloring agent (D ) 3 to 30% by mass is preferred.
When the photosensitive resin composition of the present embodiment contains a reactive diluent (E), the content of the reactive diluent (E) is preferably 1 to 20% by mass.

The content of the resin (A) is preferably 1 to 20% by mass, and more preferably 5 to 15% by mass with respect to the entire photosensitive resin composition. When the content of the resin (A) is 1% by mass or more, a photosensitive resin composition having good photocurability is preferable, and therefore it is preferable. On the other hand, when the content of the resin (A) is 20% by mass or less, a photosensitive resin composition having good coatability is preferable, and therefore, it is preferable.

The content of the solvent (B) is preferably 50 to 94% by mass, and more preferably 60 to 90% by mass with respect to the entire photosensitive resin composition. When the content of the solvent (B) is 50% by mass or more, a photosensitive resin composition having good coatability is preferable, and therefore it is preferable. On the other hand, when the content of the solvent (B) is 94% by mass or less, a coating film having a sufficient film thickness can be obtained by applying the photosensitive resin composition, and therefore, it is preferable.

The content of the photopolymerization initiator (C) is preferably 0.01 to 5% by mass with respect to the entire photosensitive resin composition, and still more preferably 0.1 to 2% by mass. When the content of the photopolymerization initiator (C) is 0.01% by mass or more, the photocurability of the photosensitive resin composition is improved, and therefore it is preferable. On the other hand, if the content of the photopolymerization initiator (C) is 5% by mass or less, it is preferred that residues are unlikely to occur after the photosensitive resin composition is exposed and developed.

The content of the colorant (D) is preferably 3 to 30% by mass, and more preferably 5 to 20% by mass with respect to the entire photosensitive resin composition. When the content of the colorant (D) is 3% by mass or more, the resin cured film of the photosensitive resin composition is preferred to have light-shielding properties. On the other hand, when the content of the colorant (D) is 30% by mass or less, it is preferred that residues are unlikely to occur after the photosensitive resin composition is exposed and developed.

When the photosensitive resin composition contains a reactive diluent (E), the content of the reactive diluent (E) is preferably 1 to 20% by mass, and more preferably 2 to 10% by mass. When the content of the reactive diluent (E) is 1% by mass or more, a photosensitive resin composition having good curability is preferable, and therefore it is preferable. On the other hand, when the content of the reactive diluent (E) is 20% by mass or less, it is preferred that residues are unlikely to occur after the photosensitive resin composition is exposed and developed.

[Manufacturing method of photosensitive resin composition]
Next, the method of manufacturing the photosensitive resin composition of this embodiment is demonstrated.
The photosensitive resin composition of this embodiment can use any of the resin (A), the solvent (B), the photopolymerization initiator (C), and the colorant (D) in this embodiment by using a well-known mixing device. ) And a method in which any one or more components of the reactive diluent (E), dispersant, and additive contained are mixed as required.

The photosensitive resin composition of this embodiment can also be prepared in advance by a composition containing a resin (A) and a solvent (B), and then a photopolymerization initiator (C) and coloring can be added to the above composition. The agent (D) and any one or more components of a reactive diluent (E), a dispersant, and an additive are produced by a method of mixing.

The composition containing the resin (A) and the solvent (B) can be produced, for example, by a method in which the resin (A) is isolated from the resin solution after the reaction for synthesizing the resin (A), and the resin (A) The solvent (B) is added and mixed.
In this embodiment, it is not always necessary to isolate the target resin (A) from the resin solution after the reaction for synthesizing the resin (A). Therefore, as the composition containing the resin (A) and the solvent (B), it is not necessary to separate the solvent contained in the resin solution from the resin solution at the time point when the reaction for synthesizing the resin (A) is completed, and the reaction can be used directly. After the resin solution. In addition, as the composition containing the resin (A) and the solvent (B), another solvent may be added to the resin solution after the reaction and mixed.

Since the photosensitive resin composition of this embodiment contains the resin (A) of this embodiment, a cured film having excellent developability, good colorant dispersibility and solvent resistance, and high elastic recovery can be obtained. Therefore, the photosensitive resin composition of this embodiment is suitable as a material for a black matrix, a color filter, and a black columnar spacer.
In addition, the photosensitive resin composition of this embodiment can satisfactorily satisfy general characteristics such as developability even if it has a good toner dispersibility and sufficiently contains a black toner (D). A resin cured film having good adhesion to the surface to be formed is formed. Therefore, the photosensitive resin composition according to this embodiment can form a black pattern with good adhesion to the surface to be formed and sufficient light-shielding properties.

[Resin hardened film]
The resin-cured film of this embodiment is a resin-cured film that photocures the photosensitive resin composition of this embodiment.
Since the resin cured film of this embodiment has good colorant dispersibility, solvent resistance, and elastic recovery, it is suitable as a black matrix, a color filter, and a black columnar spacer as a member of an image display device.

[Manufacturing method of resin hardened film]
The resin cured film system of this embodiment can be manufactured by the method shown below, for example.
First, a photosensitive resin composition is applied to a formation surface of a resin cured film, and a resin layer (coating film) is formed. Next, the resin layer is exposed through a photomask of a predetermined pattern to harden the exposed portion. Next, the unexposed portion of the resin layer is developed using a developing solution, and a resin hardened film having a predetermined pattern is formed. After that, post-baking (heat treatment) of the resin cured film is performed as necessary.
When exposing the resin layer, a halftone mask with a specified pattern can also be used. In this case, the unexposed portion and the semi-exposed portion are developed with a developing solution to produce a resin-hardened film having a predetermined pattern.

The method for applying the photosensitive resin composition is not particularly limited, and examples thereof include a screen printing method, a roll coating method, a curtain coating method, a spray coating method, and a spin coating method.
After coating the photosensitive resin composition, if necessary, heating is performed by using a heating means such as a circulating baking oven, an infrared heater, or a hot plate, and the solvent (B) contained in the resin layer may be volatilized. . The heating conditions after coating are not particularly limited, and may be appropriately set in accordance with the composition of the photosensitive resin composition. For example, the heating temperature after coating can be set from 50 ° C to 120 ° C, and the heating time can be set from 30 seconds to 30 minutes.

The method of exposing the resin layer is not particularly limited, and examples thereof include a method of irradiating active energy rays such as ultraviolet rays and excimer laser light.
The amount of energy rays irradiated onto the resin layer may be appropriately set in accordance with the composition of the photosensitive resin composition. For example, the amount of energy rays irradiated onto the resin layer may be 30 to 2000 mJ / cm ² , but it is not limited to this range.
The light source used for the exposure is not particularly limited, and a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be arbitrarily selected for use.

As a developing solution used for development, in order to obtain excellent developability, it is preferable to use an alkali developing solution. Examples of the alkaline developer include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; aqueous solutions of amine-based compounds such as ethylamine, diethylamine, and dimethylethanolamine; four Methylammonium, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl Methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and An aqueous solution of such a p-phenylenediamine-based compound such as a sulfate, a hydrochloride, or a p-toluenesulfonate.
According to need, the developing solution may also include a defoaming agent, a surfactant, and the like.

After developing with a developing solution, it is preferable that the resin cured film having a predetermined pattern is washed with water and dried.
In addition, after developing with a developing solution, post-baking (heat treatment) of a resin-hardened film having a predetermined pattern is preferably performed. By performing the post-baking, the curing of the resin cured film can be further improved. The conditions for the post-baking are not particularly limited, and can be arbitrarily selected, and may be appropriately set in accordance with the composition of the photosensitive resin composition. For example, the post-baking heating temperature can be set to 130 ° C to 250 ° C. The post-baking heating time is preferably 10 minutes to 4 hours, and more preferably 20 minutes to 2 hours.

[Image display device]
The image display device of this embodiment includes the resin cured film of this embodiment. Specific examples of the image display device include a liquid crystal display device and an organic EL display device.
As the image display device, for example, one or more members selected from the group consisting of a black matrix, a color filter, and a black columnar spacer are preferably formed by using the resin cured film of this embodiment.

The material of the base material forming the formed surface of the resin cured film is not particularly limited, and examples thereof include glass, silicon, polycarbonate, polyester, polyimide, polyimide, and polyimide. A wiring pattern substrate, an array substrate, and the like are formed on the surface of aluminum, printed wiring substrate, and the like.

The method of manufacturing the image display device of this embodiment may be any process as long as it includes a step of the resin cured film of this embodiment formed by the above-mentioned manufacturing method, and members other than those formed by the resin cured film may be used. It is manufactured according to a conventional method.

The resin cured film system for curing the photosensitive resin composition of the present embodiment has excellent developability, has good colorant dispersibility and solvent resistance, and has a high elastic recovery rate. Therefore, it is suitable as a material of a black matrix, a color filter, and a black columnar spacer included in an image display device.

[Example]

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited by the examples.

<Example 1-1>
(Step 1)
In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 98 g of propylene glycol monomethyl ether acetate as a solvent and an epoxy compound having two or more epoxy groups ( a-2) 100 g of bisphenol diglycidyl ether (BPFG) (mole number of epoxy group 0.38 mol), 1, 2, 4 as compound (a-3) having three or more acid groups -72 g of cyclohexane tricarboxylic acid (CHTC) (mole number of acid group 1 mol) and 0.7 g of triphenylphosphine as a catalyst, agitate the inside of the flask while blowing air to raise the temperature to It reacted at 120 degreeC for 2 hours, and the resin precursor was synthesize | combined.

(Step 2)
Next, 0.7 g of butylhydroxytoluene as a polymerization inhibitor was dissolved in glycidyl methacrylate (GMA) 56.8 as an unsaturated monomer (a-1) having only one functional group that reacts with an acid group. g (the functional group (epoxy group) that reacts with an acid group is 0.4 moles), and this is dropped into the flask of the synthesized resin precursor from the dropping funnel over 10 minutes. After completion of the dropwise addition, the resin (A) of Example 1-1 was synthesized by stirring at 120 ° C for 2 hours.

To the resin solution after the reaction, propylene glycol monomethyl ether acetate as a solvent (B) was added and mixed to prepare a prepared solution (solid content concentration: 40 mass) containing the resin (A) and the solvent (B). %). The solid content refers to the meaning of the heating residual component that is heated at 130 ° C for 2 hours, and the solid content of the preparation solution is based on the resin (A) as the main component.

<Example 2-1>
The first step was performed in the same manner as in Example 1-1 to synthesize a resin precursor.

(Step 2)
0.76.8 g of butylhydroxytoluene as a polymerization inhibitor was dissolved in 56.8 g of glycidyl methacrylate (GMA) as an unsaturated monomer (a-1) having only one functional group that reacts with an acid group. The functional group (epoxy group) of the acid group reaction was 0.4 mol), and this was dropped into the flask of the synthesized resin precursor from the dropping funnel over 10 minutes. After the completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours, and 10 g of succinic anhydride (a), which is an acid anhydride group-containing compound (in (a-4), the number of functional groups that react with the hydroxyl group are (a-2) (a-3) 25% of the amount of hydroxyl groups produced by the reaction), and stirred at 110 ° C for 30 minutes to synthesize the resin (A) of Example 2-1.

To the resin solution after the reaction, propylene glycol monomethyl ether acetate as a solvent (B) was added and mixed, and the resin (A) and the solvent (A) were prepared in the same manner as in Example 1-1. B) Prepared solution (solid content concentration: 40% by mass).

<Examples 3-1, 8-1, 9-1, 11-1, 12-1, 14-1>
Unsaturated monomer (a-1) having only one functional group, epoxy compound (a-2) having two or more epoxy groups, and compound (a-3) having three or more acid groups ). The compound (a-4) having an acid anhydride group is the same as that used in Example 2-1, except that the materials shown in Table 1 or Table 2 are used in the amounts shown in Table 1 or Table 2. The resins (A) of Examples 3-1, 8-1, 9-1, 11-1, 12-1, and 14-1 were synthesized.
To the resin solution after the reaction, propylene glycol monomethyl ether acetate as a solvent (B) was added and mixed, and the resin (A) and the solvent (A) were prepared in the same manner as in Example 1-1. B) Prepared solution (solid content concentration: 40% by mass).

<Examples 4-1 to 7-1, 10-1, and 13-1>
Unsaturated monomer (a-1) having only one functional group, epoxy compound (a-2) having two or more epoxy groups, and compound (a-3) having three or more acid groups ), Except that the materials shown in Table 1 or Table 2 are used in the amount shown in Table 1 or Table 2, and the amount shown in Table 1 is used as required (the values in parentheses are the mole numbers of functional groups ) The resin (A) of Examples 4-1 to 7-1, 10-1, and 13-1 was synthesized in the same manner as in Example 1-1 except that adipic acid was used.
To the resin solution after the reaction, propylene glycol monomethyl ether acetate as a solvent (B) was added and mixed, and the resin (A) and the solvent were prepared in the same manner as in Example 1-1. (B) A prepared solution (solid content concentration: 40% by mass).

Tables 1 and 2 describe unsaturated monomers (a-1) having only one functional group and epoxy resins having two or more epoxy groups used in Examples 1-1 to 14-1. Materials and amounts of the compound (a-2) and the compound (a-3) having three or more acid groups. In addition, Tables 1 and 2 describe compounds (a) having an acid anhydride group used in Examples 2-1, 3-1, 8-1, 9-1, 11-1, 12-1, and 14-1. -4) materials and usage.
In Tables 1 and 2, the numerical values in parentheses in the fields of (a-1) to (a-3) are the mole numbers of the functional groups of (a-1) to (a-3).
In addition, the numerical value in parentheses in the field of (a-4) refers to "the number of functional groups that react with a hydroxyl group in (a-4)" versus "(a-2) and (a-3) the hydroxyl group formed by the reaction Value.

Regarding the resin (A) synthesized in Examples 1-1 to 14-1, the acid value, weight average molecular weight, and unsaturated group equivalent of the solid content were measured according to the measurement methods shown below. The results are shown in Tables 1 and 2.

<Measurement method of acid value>
The measurement was performed according to JIS K6901 5.3.2 using a mixed indicator of bromothymol blue and phenol red. It means the meaning of mg of potassium hydroxide required when neutralizing the acid component contained in 1g of resin (A).

<Method for measuring unsaturated group equivalents>
The mass (g / mole) of the polymer per mole of polymerizable unsaturated bonds is a calculated value based on the amount of monomer used.

<Method for measuring weight average molecular weight (Mw)>
The standard polystyrene conversion was measured using gel permeation chromatography (GPC) under the following conditions.
Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Corporation)
Column temperature: 40 ℃
Sample: 0.2% tetrahydrofuran solution of copolymer Development solvent: tetrahydrofuran Detector: Differential refractometer (Shodex (registered trademark) RI-71S) (manufactured by Showa Denko Corporation)
Flow rate: 1mL / min

<Comparative Example 1-1>
In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 58 g of propylene glycol monomethyl ether acetate as a solvent, 89 g of bisphenol hydrazone, 25 g of acrylic acid, and triphenyl as a catalyst were added. 0.7 g of phosphine and 0.7 g of butylhydroxytoluene as a polymerization inhibitor were stirred in the flask while blowing air, and the temperature was raised to 120 ° C. and the reaction was carried out for two hours.

Next, in the same flask, put 22.2 g of 1,1'-bicyclohexane-3,3 ', 4,4'-tetracarboxylic acid-3,4: 3', 4'-dianhydride, and It stirred at 120 degreeC for 2 hours. Furthermore, 25 g of tetrahydrophthalic anhydride was added to the flask, and it stirred at 110 degreeC for 30 minutes, and the resin (A) of the comparative example 1-1 was synthesized.
To the resin solution after the reaction, propylene glycol monomethyl ether acetate as a solvent (B) was added and mixed, and the resin (A) and the solvent (A) were prepared in the same manner as in Example 1-1. B) Prepared solution (solid content concentration: 40% by mass).

Regarding the resin (A) synthesized in Comparative Example 1-1, the acid value, weight average molecular weight, and unsaturated group equivalent of the solid content were measured in the same manner as in Example 1-1. As a result, the resin (A) synthesized in Comparative Example 1-1 had an acid value of 40 KOHmg / g, a weight average molecular weight (Mw) of 5000, and an unsaturated group equivalent weight of 440.

〈Comparative example 2-1〉
A resin (A) of Comparative Example 2-1 was synthesized in the same manner as in Example 1-1 except that adipic acid was used instead of the compound (a-3) having three or more acid groups.
To the resin solution after the reaction, propylene glycol monomethyl ether acetate as a solvent (B) was added and mixed, and the resin (A) and the solvent ( B) Prepared solution (solid content concentration: 40% by mass).

Regarding the resin (A) synthesized in Comparative Example 2-1, the acid value, weight average molecular weight, and unsaturated group equivalent of the solid content were measured in the same manner as in Example 1-1. The results are shown in Table 1.

<Examples 1-2 to 15-2 and Comparative Examples 1-2 and 2-2>
The resin (A), the solvent (B), the photopolymerization initiator (C), and the coloring agent (C) shown in Tables 3 and 4 are mixed so that the content (% by mass) shown in Tables 3 and 4 becomes. D), a reactive diluent (E) and an additive (F) to obtain the photosensitive resin compositions of Examples 1-2 to 15-2 and Comparative Examples 1-2 and 2-2.
The content of the resin (A) shown in Tables 3 and 4 does not include the content of the solvent and solvent contained in the prepared solution (solid content concentration: 40% by mass) containing the resin (A). The content of the resin (A) shown in Tables 3 and 4 includes only the solid content in the preparation solution containing the resin (A). The amounts of the solvent and the solvent contained in the resin (A) -containing preparation solution are combined and calculated in the solvents (B) shown in Tables 3 and 4.

For the photosensitive resin compositions of Examples 1-2 to 15-2 and Comparative Examples 1-2 and 2-2, the optical density (colorant dispersibility) and film thickness reduction rate (development margin) were evaluated according to the following methods, respectively. ), Solvent resistance, elastic recovery rate, development residue. The results are shown in Tables 5 to 7.

<Evaluation of optical density (colorant dispersibility)>
The photosensitive resin compositions of Examples 1-2 to 15-2 and Comparative Examples 1-2 and 2-2 were spin-coated to a 10 cm × 10 cm IZO (In ₂ O) so that the thickness of the coating film became 1.5 μm. _3- ZnO) substrate (a substrate having a wiring pattern pattern made of IZO formed on the surface). Thereafter, the IZO substrate was heated at 90 ° C. for 3 minutes to evaporate the solvent in the coating film. Next, the entire surface of the coating film was exposed by using Multi-light ML-251D / B made by USHIO Electric Co., Ltd. and an irradiation optical unit PM25C-100 (exposure amount: 50 mJ / cm ² ) to harden the light. Thereafter, development was performed using a 0.2% by mass potassium hydroxide aqueous solution for 120 seconds, and further post-baking at 230 ° C. for 30 minutes to obtain a target resin cured film.

The optical density (Optical Density: OD) of the resin cured film having a thickness of 1.0 μm was measured by using a transmission densitometer (361T, X-lite).
The higher the optical density, the better the colorant dispersibility.

<Evaluation of film thickness reduction rate (development margin)>
Using the same method as the optical density, a 2.5 μm-thick coating film was produced on a glass substrate, and a stylus step meter T4000M manufactured by Kosaka Research Institute was used to measure the reduction rate of the coating film thickness from 100 seconds to 150 seconds of development . The larger the thickness reduction rate of the coating film, the more excellent the development margin, and the better the development property.

＜ Evaluation of solvent resistance ＞
Using the same method as the evaluation of optical density, a resin cured film was produced on a glass substrate, cut into a size of 1 cm × 1 cm, and a UV spectrometer (UV-1650PC, manufactured by Shimadzu Corporation) was used to measure the resin cured film. Absorbance at maximum absorption wavelength. After that, a resin-hardened film having a size of 1 cm × 1 cm was put and immersed in a glass bottle containing 5 mL of N-methylpyrrolidone. After that, the cured resin film was taken out from the N-methylpyrrolidone, wiped with a clean wiping paper or cloth, and left in a 100 ° C baking oven for 15 minutes. Thereafter, the absorbance at the maximum absorption wavelength of the resin cured film was measured in the same manner as before immersion in N-methylpyrrolidone. In addition, based on the following criteria, the discoloration of the resin cured film was evaluated from the difference in absorbance before and after immersion in N-methylpyrrolidone. The smaller the difference in absorbance is, the less discoloration is. Therefore, it can be said that the more excellent the solvent resistance is.

"Benchmark"
：: The difference in absorbance is less than 5%.
：: The difference in absorbance is 5% or more and less than 20%.
Δ: The difference in absorbance is 20% or more and less than 30%.
×: The difference in absorbance is 30% or more.

＜ Evaluation of elastic response rate ＞
The resin cured film used for the evaluation of the optical density was used to measure the elastic recovery rate at 25 ° C using an elasticity measuring device (DUH-W201S, manufactured by Shimadzu Corporation) under the following measurement conditions.
As the pressing body for pressing the resin cured film, a flat pressing body having a diameter of 50 μm was used. In order to obtain a recognizable result between the comparison groups, the elastic recovery rate was measured by using a test with a load of 300 mN. A load speed of 3 gf / second and a holding time of 3 seconds were maintained constant. Regarding the elastic recovery rate, the elastic recovery rate of the resin cured film before and after the load was measured using a three-dimensional thickness measuring device by removing a load after a constant load was applied to a flat pressing body for 3 seconds. The elastic recovery rate refers to the ratio of the distance returned (recovery distance) to the distance compressed (compression displacement) when a certain force is applied after the recovery time of 10 minutes elapses, which is expressed by the following formula.
Elastic recovery rate (%) = (recovery distance / compression displacement) × 100

＜ Evaluation of development residues ＞
The photosensitive resin compositions of Examples 1-2 to 15-2 and Comparative Examples 1-2 and 2-2 were spin-coated on a 10 cm × 10 cm IZO substrate (on the surface so that the thickness of the coating film became 1.5 μm). A substrate having a wiring pattern made of IZO is formed. Thereafter, the IZO substrate was heated at 90 ° C. for 3 minutes to evaporate the solvent from the coating film. Next, a patterned photomask was placed on the coating film, and exposure was performed from above the photomask using the Multi-light ML-251D / B made by USHIO Electric Co., Ltd. and the irradiation optical unit PM25C-100 (exposure amount 50mJ / cm ² ) To light harden. After that, development was performed with a 0.2% by mass potassium hydroxide aqueous solution for 120 seconds, and the presence or absence of a residue (development residue) was visually confirmed.

"Evaluation benchmark"
：: No residue at all.
○: Although there is a little residue, it disappears when the development time is extended by 30 seconds.
×: Even if the development time is extended by 30 seconds, a residue remains.

As shown in Tables 5 to 7, the photosensitive resin compositions of Examples 1-2 to 15-2 had a reduction in the optical density (colorant dispersibility), film thickness reduction (development margin), and elasticity of the resin cured film. Since the recovery rate was high, the evaluation of the solvent resistance and the development residue was good.
On the other hand, compared with Examples 1-2 to 15-2, the evaluation of the solvent resistance and development residue of the resin cured film of the photosensitive resin composition of Comparative Example 1-2 was inferior. This is presumably because the resin contained in the photosensitive resin composition of Comparative Example 1-2 does not have a three-dimensional structure, and therefore has a linear structure.
In addition, when the resin cured film of the photosensitive resin composition of Comparative Example 2-2 was compared with Examples 1-2 to 15-2, the optical density (colorant dispersibility) and film thickness reduction rate of the resin cured film ( Development margin) and elastic recovery rate were low, so the evaluation of solvent resistance and development residue was poor. This is presumably because the resin contained in the photosensitive resin composition of Comparative Example 2-2 does not contain a constituent component derived from the compound (a-3) having three or more acid groups, and thus cannot be made to have three times. Meta structure, and therefore has a linear structure.

Claims (17)

A resin characterized by: A component derived from an unsaturated monomer (a-1) having only one functional group that reacts with an acid group, Components derived from an epoxy compound (a-2) having two or more epoxy groups, and A component derived from the compound (a-3) having three or more acid groups. A resin characterized by: A component derived from an unsaturated monomer (a-1) having only one functional group that reacts with an acid group, A component derived from an epoxy compound (a-2) having two or more epoxy groups, Components derived from the compound (a-3) having three or more acid groups, and The component derived from the compound (a-4) which has an acid anhydride group. For example, the resin of claim 1 or claim 2, which has a first bonding portion and a second bonding portion, The first bonding portion is a functional group that reacts with an acid group in the unsaturated monomer (a-1) and an acid group via the acid group in the compound (a-3) having three or more acid groups. To form, The second bonding portion is formed by bonding an epoxy group of the epoxy compound (a-2) and an acid group of the compound (a-3) having three or more acid groups. The resin according to any one of claim 1 to claim 3, wherein the acid group of the compound (a-3) having three or more acid groups is a carboxyl group. The resin according to any one of claim 1 to claim 4, wherein the unsaturated monomer (a-1) is a compound represented by the following formula (1), (In the formula (1), R ₁ represents a hydrogen atom or a methyl group; R ₂ represents any one selected from a single bond, a methylene group, and an alkylene group having 2 to 12 carbon atoms; X ₁ represents a group selected from an epoxy group , 3,4-epoxycyclohexyl, any one of the group represented by the following formula (2-1) and the group represented by the following formula (2-2); the following formula (2-1) and In the following formula (2-2), * represents a bonding site between X ₁ and R ₂ ) . The resin according to any one of claim 1 to claim 5, wherein the functional group that reacts with the acid group of the unsaturated monomer (a-1) is an epoxy group. The resin according to any one of claim 1 to claim 6, wherein the epoxy compound (a-2) is a compound represented by the following formula (2), (In formula (2), A represents -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9,9-fluorenylene or a single bond; B represents a phenylene group or a phenylene group having a substituent, and the aforementioned substituent group is selected from an alkyl group, a halogen atom, or a phenyl group having 1 to 5 carbon atoms. Either: X ₂ represents any one selected from an epoxy group, a 3,4-epoxy cyclohexyl group, a group represented by the following formula (2-1), and a group represented by the following formula (2-2) One of the following formulae (2-1) and (2-2), * represents a bonding site between X ₂ and a methylene group) . The resin according to any one of claim 1 to claim 7, wherein the compound (a-3) having three or more acid groups is 1,2,4-cyclohexanetricarboxylic acid or 1,2, 3,4-butanetetracarboxylic acid. The resin according to any one of claim 1 to claim 8, wherein among the number of acid groups contained in the compound (a-3) having three or more acid groups, and the epoxy compound (a- 2) The ratio of the number of the epoxy group-bonded acid groups is 5 to 60%. The resin according to any one of claim 2 to claim 9, wherein the compound (a-4) having an acid anhydride group is an anhydride having a ring structure. A resin characterized by An unsaturated monomer (a-1) having only one functional group that reacts with an acid group, Epoxy compound (a-2) having two or more epoxy groups and Compound (a-3) having 3 or more acid groups Obtained by polymerization. A resin characterized by An unsaturated monomer (a-1) having only one functional group that reacts with an acid group, Epoxy compound (a-2) having two or more epoxy groups, Compound (a-3) having three or more acid groups, and Compound (a-4) with acid anhydride group Obtained by polymerization. A photosensitive resin composition comprising: For example, the resin (A) of any one of claim 1 to 12, Solvent (B), Photopolymerization initiator (C) and Colorant (D). The photosensitive resin composition according to claim 13, which contains: 1-20% by mass of the resin (A), The aforementioned solvent (B) is 50 to 94% by mass, The aforementioned photopolymerization initiator (C) is 0.01 to 5% by mass and The colorant (D) is 3 to 30% by mass. The photosensitive resin composition according to claim 14, further comprising a reactive diluent (E) in an amount of 1 to 20% by mass. The resin hardened film of the photosensitive resin composition as described in any one of Claims 13-15. An image display device includes a resin cured film as claimed in claim 16.