WO2019073806A1

WO2019073806A1 - Resin, photosensitive resin composition, cured resin film, and image display device

Info

Publication number: WO2019073806A1
Application number: PCT/JP2018/035922
Authority: WO
Inventors: 正義柳; 健宏木下; 恭章川口; 司原; 拓樹倉本; 優介青木; 英理永井
Original assignee: 昭和電工株式会社
Priority date: 2017-10-10
Filing date: 2018-09-27
Publication date: 2019-04-18
Also published as: KR102344248B1; CN111032720B; TW201927847A; JPWO2019073806A1; TWI696641B; JP7342705B2; KR20200032133A; CN111032720A

Abstract

A resin which comprises: a component derived from an unsaturated monomer (a-1) having a single functional group reactive with acid groups; 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.

Description

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

The present invention relates to a resin, a photosensitive resin composition, a cured resin film, and an image display device.
Priority is claimed on Japanese Patent Application No. 2017-197128, filed Oct. 10, 2017, the content of which is incorporated herein by reference.

Heretofore, in liquid crystal display panels, spacer particles are used to keep the distance (cell gap) between two substrates constant. As the spacer particles, glass beads, plastic beads or the like having a predetermined particle diameter are used. Usually, spacer particles are randomly disposed on a transparent substrate such as a glass substrate. If the spacer particles are present in the pixel formation region of the liquid crystal display panel, problems such as reflection of the spacer particles may occur or incident light may be scattered to lower the contrast.

In order to solve this problem, in place of the spacer particles, dot-like or stripe-like spacers formed by photolithography using a photosensitive resin composition have been adopted. This spacer can be formed by a method in which a photosensitive resin composition is applied on a substrate, exposed to ultraviolet light through a predetermined mask, and then developed. Therefore, the spacer which consists of hardened | cured material of the photosensitive resin composition can be formed only in predetermined places other than the pixel formation area in a liquid crystal display panel. Therefore, the said problem in the case of using a spacer particle is solvable by forming a spacer by photolithography using a photosensitive resin composition.

As a photosensitive resin composition used as a material of the spacer with which a liquid crystal display panel is equipped, there exists a radiation sensitive resin composition of patent document 1, for example.
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 may be used as a black column spacer resist.
Further, Patent Document 3 describes a photosensitive resin composition for a black column spacer containing an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a light shielding agent.

JP 2001-302712 A JP, 2011-170075, A JP, 2013-134263, A

Recently, in liquid crystal display elements and members forming the liquid crystal display elements, stricter dimensional accuracy is required. For this reason, the photosensitive resin composition used as a material of a black matrix, a color filter, and a black column spacer is calculated | required more excellent developability. Moreover, in order to improve the display characteristic of a liquid crystal display element, the cured film which hardened the photosensitive resin composition used for the said application needs to have favorable coloring agent dispersibility. Furthermore, in order to prevent deterioration of a liquid crystal display element, it is calculated | required that the cured film which hardened the photosensitive resin composition used for the said use has favorable solvent resistance, and has a high elastic recovery factor.

The present invention has been made in view of the above-mentioned circumstances, and has a photosensitive resin composition which has excellent developability, and which can obtain a cured film having good colorant dispersibility and solvent resistance and high elastic recovery rate. An object of the present invention is to provide a resin suitable as a material of a product.
In addition, the present invention is a photosensitive resin composition which contains the resin of the present invention, has excellent developability, and is capable of obtaining a cured film having good colorant dispersibility and solvent resistance and high elastic recovery rate. The task is to provide.
Moreover, this invention makes it a subject to provide the resin cured film of the photosensitive resin composition of this invention, and an image display apparatus provided with this.

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

[1] 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 resin comprising: a component derived from a compound (a-3) having three or more acid groups.

[2] 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 a compound (a-3) having three or more acid groups,
A resin comprising: a component derived from a compound (a-4) having an acid anhydride group.

[3] A first bonding portion in which a functional group which reacts with an acid group in the unsaturated monomer (a-1) and an acid group which a compound (a-3) having three or more of the acid groups has are bonded;
[1] or [2] having a second bonding part in which the epoxy group of the epoxy compound (a-2) and the acid group of the compound (a-3) having three or more acid groups are bonded Description resin.

[4] The resin according to any one of [1] to [3], wherein the acid group possessed by the compound (a-3) having three or more acid groups is a carboxy 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, 3 Or 4-epoxycyclohexyl group, a group represented by the following formula (2-1), or any one selected from a group represented by the following formula (2-2): In 2-2), * indicates the binding site of X ₁ to 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 is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- B represents a phenylene group or a phenylene group having a substituent, and the substituent is an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group; X ₂ is selected from an epoxy group, a 3,4-epoxycyclohexyl group, a group represented by the following formula (2-1), and a group represented by the following formula (2-2) In the following formula (2-1) and the following formula (2-2), * represents a bonding site to a methylene group of X _2. )

[8] The compound (a-3) having three or more acid groups is 1,2,4-cyclohexanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid [1] to [7] The resin according to any of the above.
[9] The ratio of the number of acid groups bonded to the epoxy group of the epoxy compound (a-2) to the number of acid groups of the compound (a-3) having three or more acid groups is The resin according to any one of [1] to [8], which 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] 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,
A resin characterized by being obtained by polymerizing a compound (a-3) having three or more acid groups.
[12] 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,
A compound (a-3) having three or more acid groups,
A resin characterized by being obtained by polymerizing a compound (a-4) having an acid anhydride group.

[13] a resin (A) according to any one of [1] to [12],
A solvent (B),
The photosensitive resin composition characterized by including a photoinitiator (C) and a coloring agent (D).
[14] 1 to 20% by mass of the resin (A),
50 to 94% by mass of the solvent (B)
The photosensitive resin composition according to [13], which contains 0.01 to 5% by mass of the photopolymerization initiator (C) and 3 to 30% by mass of the colorant (D).
[15] The photosensitive resin composition as described in [14], further comprising 1 to 20% by mass of a reactive diluent (E).

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

The resin of the present invention is suitable as a material of a photosensitive resin composition from which a cured film having excellent developability, good colorant dispersibility and solvent resistance, and high elastic recovery rate can be obtained.
Since the photosensitive resin composition of the present invention contains the resin of the present invention, a cured film having excellent developability, good colorant dispersibility and solvent resistance, and high elastic recovery rate can be obtained. Therefore, the photosensitive resin composition of this invention is suitable as a material of a black matrix, a color filter, and a black column spacer.
The resin cured film of the present invention is suitable as a black matrix, a color filter, and a black column spacer, which are members of an image display device.

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

[resin]
The resin of the present embodiment includes an unsaturated monomer (a-1) having only one functional group which reacts with an acid group, an epoxy compound (a-2) having two or more epoxy groups, and three acid groups. It is obtained by reacting the compound (a-3) possessed above. The resin of this embodiment has a component derived from an unsaturated monomer (a-1) having only one functional group that reacts with an acid group, and a configuration derived from an epoxy compound (a-2) having two or more epoxy groups. The component includes a component derived from a compound (a-3) having three or more acid groups. The resin of the present embodiment may contain a component derived from other optional components, as long as the effects of the present invention are not impaired.

The resin of the present embodiment includes a functional group of unsaturated monomer (a-1) having only one functional group that reacts with an acid group, and an epoxy group of epoxy compound (a-2) having two or more epoxy groups. It is presumed to have a three-dimensional structure formed by the reaction with the acid group of the compound (a-3) having three or more acid groups. As a result, when the photosensitive resin composition containing the resin of the present embodiment has excellent developability, and a cured film having good colorant dispersion and solvent resistance and high elastic recovery rate is obtained. Presumed.

<Unsaturated Monomer (a-1) Having Only One Functional Group Reactive with Acid Group>
The functional group reactive with the acid group in the unsaturated monomer (a-1) having only one functional group reactive with the acid group is not particularly limited, and examples thereof include epoxy group, oxetanyl group, isocyanato group, hydroxyl group and the like. An epoxy group is particularly preferable because the raw materials are inexpensive, the reaction for producing the resin of the present embodiment is easy, and the reaction rate is high.

Specifically, epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and 4-hydroxybutyl acrylate glycidyl ether, as the unsaturated monomer (a-1) having only one functional group that reacts with an acid group Oxetanyl (meth) acrylate, (meth) acrylic acid (3-methyloxetan-3-yl) methyl, (meth) acrylic acid (3-ethyloxetan-3-yl) methyl, (meth) acrylic acid (3-methyloxetane -3-yl) ethyl, (meth) acrylic acid (3-ethyloxetan-3-yl) ethyl, (meth) acrylic acid (3-chloromethyloxetan-3-yl) methyl, (meth) acrylic acid (oxetane-) 2-yl) methyl, (meth) acrylic acid (2-methyloxetan-2-yl) methyl, (meth) acrylic Acid (2-ethyloxetan-2-yl) methyl, (1-methyl-1-oxetanyl-2-phenyl) -3- (meth) acrylate, (1-methyl-1-oxetanyl) -2-trifluoromethyl Oxetanyl group-containing (meth) acrylates such as -3- (meth) acrylate and (1-methyl-1-oxetanyl) -4-trifluoromethyl-2- (meth) acrylate; 2-isocyanatoethyl (meth) acrylate and the like And (iv) hydroxyl group-containing (meth) acrylates such as isocyanato group-containing (meth) acrylate and 2-hydroxyethyl (meth) acrylate.

As used herein, "(meth) acrylate" refers to "acrylate" or "methacrylate" or both.

Among the above, one or two selected from glycidyl methacrylate and 2-isocyanatoethyl methacrylate may be used as the unsaturated monomer (a-1) having only one functional group which reacts with an acid group. Is preferred.
The above 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.

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

The unsaturated monomer (a-1) having only one functional group which 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 the present embodiment is easy, so the resin can be easily produced. Further, in the resin in which the unsaturated monomer (a-1) is a compound represented by the following formula (1), since the unsaturated group of the unsaturated monomer (a-1) is a (meth) acrylic group, the reactivity is Is good and preferred.

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

<Epoxy Compound Having Two or More Epoxy Groups (a-2)>
Specific examples of the epoxy compound (a-2) having two or more epoxy groups include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 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, resordinol diglycidyl ether Glycidyl terephthalate, diglycidyl ortho phthalate, bisphenol full orange glycidyl ether , Compounds prepared by adding the epihalohydrin, such as epichlorohydrin, and the like to the compound shown below.

As a compound which forms an epoxy compound (a-2) which has two or more epoxy groups by adding an epihalohydrin, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) Ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-) Dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) 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-dibromophenyl) 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-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9- Bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 3,3 ', 5,5'-tetramethyl-4,4'-bis (glycidyloxy) -1,1'-biphenyl, 1,6- Bis (2,3-epoxypropan-1-yloxy) naphthalene and the like can be mentioned.

Among the above compounds, as the epoxy compound (a-2) having two or more epoxy groups, ethylene glycol diglycidyl ether and bisphenol fluorene glycidyl ether, 3,3 ′, 5,5′-tetramethyl-4 It is preferable to use one or two selected from 4,4'-bis (glycidyloxy) -1,1'-biphenyl and 1,6-bis (2,3-epoxypropan-1-yloxy) naphthalene. .
The above 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.

The epoxy compound (a-2) having two or more epoxy groups is more 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-fluorenylidene, or a single bond is shown, preferably 9, 9-fluorenylidene.
In Formula (2), B represents a phenylene group or a phenylene group having a substituent, and is preferably a phenylene group. When B is a phenylene group having a substituent, the substituent is 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 is an epoxy group, a 3,4-epoxycyclohexyl group, a group represented by the above formula (2-1), a group represented by the above formula (2-2) 1) and in the above formula (2-2), * represents any one selected from the bonding site to the methylene group of X ₂ ), and is preferably an epoxy group.

<Compound Having Three or More Acid Groups (a-3)>
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 carboxy group, with a carboxy group being preferable. If the acid group in the compound (a-3) having three or more acid groups is a carboxy group, a resin having a better developability is obtained. In addition, side reactions do not easily occur in the addition reaction for producing the resin of the present embodiment, and the resin can be easily produced.
In the present embodiment, the acid group in the compound (a-3) having three or more acid groups does not contain an acid anhydride group.

Specifically, as the compound (a-3) having three or more acid groups, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,3-propanetricarboxylic acid 1,2,4-cyclohexanetricarboxylic 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.

Among the above compounds, the compound (a-3) having three or more acid groups is particularly selected from 1,2,4-cyclohexanetricarboxylic acid and 1,2,3,4-butanetetracarboxylic acid It is preferable to use one or two kinds.
The above compounds used as the compound (a-3) having three or more acid groups may be used alone or in combination of two or more.
The compound (a-3) having three or more acid groups is a compound having no functional group other than the acid group.

The resin of the present embodiment includes an unsaturated monomer (a-1) having only one functional group which reacts with an acid group, an epoxy compound (a-2) having two or more epoxy groups, and three acid groups. It may be obtained by reacting the compound (a-3) having the above and the compound (a-4) having an acid anhydride group. This resin comprises a component derived from an unsaturated monomer (a-1) having only one functional group that reacts with an acid group, and a component derived from an epoxy compound (a-2) having two or more epoxy groups, A component derived from a compound (a-3) having three or more acid groups, and a component derived from a compound (a-4) having an acid anhydride group are included.
When the resin of the present embodiment contains a component derived from the compound (a-4) having an acid anhydride group, it becomes a resin having a better 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 the present embodiment is an acid having at least three acid groups in one molecule (a trifunctional or higher acid) and having a compound having an acid anhydride group, and only one functional group that reacts with the acid group. It may be obtained by reacting an unsaturated monomer (a-1) having one or more and an epoxy compound (a-2) having two or more epoxy groups. This resin contains components derived from a compound having a trifunctional or higher functional acid and having an acid anhydride group. The compound having three or more functional groups and having an acid anhydride group serves as a compound (a-3) having three or more acid groups and a compound (a-4) having an acid anhydride group.
Therefore, in the present embodiment, the resin containing a component which is a trifunctional or higher functional acid and derived from a compound having an acid anhydride group is a 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, it is a trifunctional or higher functional acid and has a functional group that reacts with an acid group in the unsaturated monomer (a-1) with respect to the functional group number (α) of the component derived from the compound having an acid anhydride group The ratio of the total (β + γ) of the number of functional groups (β) and the number of functional groups (γ) bonded to the epoxy group of epoxy compound (a-2) (β + γ) is a trifunctional or higher acid compound having an acid anhydride group It is regarded as the ratio of the component derived from the compound (a-3) having three or more acid groups among the components derived from (δ = {(β + γ) / (α)}). The ratio (1-δ) excluding the component derived from the compound (a-3) having three or more acid groups among the components derived from the compound having a trifunctional or higher acid and having an acid anhydride group And the ratio of the component derived from the compound (a-4) having an acid anhydride group.

In the resin of the present embodiment, a first bonding portion in which a functional group that reacts with an acid group in the unsaturated monomer (a-1) and an acid group of a compound (a-3) having three or more acid groups are bonded It is preferable to have a second bonding part in which the epoxy group of the epoxy compound (a-2) and the acid group of the compound (a-3) having three or more acid groups are bonded. According to a resin having a first bonding portion and a second bonding portion, a cured film having excellent curability and developability, good colorant dispersibility and solvent resistance, and high hardness and elastic recovery rate Is obtained.

Such a resin may be, for example, an epoxy compound (a-2) and a compound (a-3) having three or more acid groups, as compared to the number of moles of epoxy groups of the epoxy compound (a-2). A first step of obtaining a resin precursor by reacting in a state in which the number of moles of the acid group possessed by the compound (a-3) having three or more is large, and reacting the unsaturated monomer (a-1) with the resin precursor It is obtained by performing the second step.

The resin precursor obtained by performing the first step is a second bond in which the epoxy group of the epoxy compound (a-2) is bonded to the acid group of the compound (a-3) having three or more acid groups. It has an acid group derived from a compound (a-3) having a moiety and having three or more acid groups not bonded to an epoxy group.
By performing the second step after the first step, an unsaturated monomer (a) can be added to the acid group derived from the compound (a-3) having three or more acid groups remaining in the resin precursor. The functional group reactive with the acid group contained in -1) undergoes an addition reaction. As a result, a first bonding portion in which a functional group reactive with an acid group contained in the unsaturated monomer (a-1) is bonded to an acid group possessed by the compound (a-3) having three or more acid groups; A resin having the above-mentioned second bonding portion is obtained.

The preferable constituent unit ratio of the resin of the present embodiment is as shown in the following (I) to (III).
(I) A resin in which the epoxy group of the epoxy compound (a-2) is reacted at a ratio of 60 to 5 moles with respect to 100 moles of the acid group possessed by the compound (a-3) having three or more acid groups. It is preferable that the resin be reacted at a ratio of 50 to 10 moles. That is, in the resin of the present embodiment, among the number of acid groups possessed by the compound (a-3) having three or more acid groups, the number of acid groups bound with the epoxy group of the epoxy compound (a-2) The proportion of is preferably 5 to 60%, more preferably 10 to 50%. In such a resin, the second bonding portion in which the epoxy group of the epoxy compound (a-2) and the acid group of the compound (a-3) having three or more acid groups are bonded is sufficiently contained. The second bonding portion contributes to the improvement of the hardness of the cured film. Therefore, according to the above-mentioned resin, a cured film having excellent curability and developability, good colorant dispersibility and solvent resistance, and high hardness and elastic recovery rate can be obtained.

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

(III) When a compound (a-4) having an acid anhydride group is used as a material of a resin, an epoxy compound having two or more epoxy groups (the number of functional groups reactive with the hydroxyl group of the compound (a-4) is (a) It is preferable that the resin is reacted at a ratio of 10 to 70% of the amount of hydroxyl groups generated by reacting -2) with the compound (a-3) having three or more acid groups, and It is more preferable that the resin be reacted at a rate of 60%. When the number of functional groups that react with the hydroxyl group of the compound (a-4) is in the above range, the addition reaction of the resin proceeds efficiently, and a resin with good productivity can be obtained. In addition, when the number of functional groups that react with the hydroxyl group of the compound (a-4) is in the above range, the number of hydroxyl groups in the resin is an appropriate amount, so a resin can be obtained from the cured film having good coating film properties.

The resin of the present embodiment preferably has a weight average molecular weight in terms of polystyrene as determined by gel permeation chromatography (GPC) of 1,000 to 40,000, and more preferably 3,000 to 30,000. After the photosensitive resin composition containing this resin is apply | coated and exposed that a weight average molecular weight is 1000 or more, it is hard to produce a crack in the pattern formed and developed, and it is preferable. On the other hand, when the weight average molecular weight is 40,000 or less, the time required for development after applying and exposing a photosensitive resin composition containing this resin is appropriate, and it is preferable for practical use.

The acid value (JIS K 6901 5.3) of the resin of the present embodiment is not limited as long as the desired effects of the present invention are exhibited, but it is usually 20 to 300 KOHmg / g, preferably 30 to 200 KOHmg / g. Since the developability of the photosensitive resin composition containing this resin becomes it favorable that an acid value is 20 KOHmg / g or more becomes preferable. On the other hand, when the acid value is 300 KOHmg / g or less, the photosensitive resin composition containing this resin is applied and exposed to light, so that it is difficult to dissolve the photocured part in the developer, which is preferable.

The unsaturated group equivalent of the resin of the present embodiment is not limited as long as the desired effects of the present invention are exhibited, but it is usually 100 to 4000 g / mol, preferably 200 to 2000 g / mol, and more preferably 300 to 500 g. / Mole. The developability of the photosensitive resin composition containing this resin becomes it favorable that an unsaturated group equivalent is 100 g / mol or more. For this reason, the resin cured film which photocured the photosensitive resin composition containing this resin will have a more favorable characteristic as a black matrix, a color filter, and a black column spacer. On the other hand, when the unsaturated group equivalent is 4000 g / mol or less, the sensitivity of the photosensitive resin composition containing this resin becomes higher, and a thinner pattern can be formed, which is preferable.

The unsaturated group equivalent is the mass of resin per mole of unsaturated bond (ethylenic carbon-carbon double bond) in the resin. The unsaturated group equivalent can be determined by dividing the mass of the resin by the number of unsaturated groups in the resin (g / mol). In the present specification, the unsaturated group equivalent of the resin is a theoretical value calculated from the amount of raw materials used to introduce the unsaturated group into the resin.

[Method of producing resin]
Next, a method of manufacturing the resin of the present embodiment will be described.
The resin of the present embodiment includes an unsaturated monomer (a-1) having only one functional group which reacts with an acid group, an epoxy compound (a-2) having two or more epoxy groups, and three acid groups. It can manufacture by the method of polymerizing the compound (a-3) which has the above, and the compound (a-4) which has an acid anhydride group used as needed by the arbitrary polymerization method.

It is preferable to use the method shown below as a polymerization method of resin of this embodiment.
First, a resin precursor is prepared by reacting an epoxy compound (a-2) having two or more epoxy groups with a compound (a-3) having three or more acid groups, using a catalyst in a solvent, if necessary. Synthesize (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 in the first step is a compound having three or more acid groups (a-3) It is preferable that the number of moles of the acid group in the above be greater than the number of moles of the epoxy group of the epoxy compound (a-2). Specifically, the reaction is carried out at a ratio of 60 to 5 moles of the epoxy group of the epoxy compound (a-2) to 100 moles of the acid group of the compound (a-3) having three or more acid groups. It is preferable to react at a ratio of 50 to 10 moles.

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., more preferably 60 to 140 ° C. The reaction time in the first step can be, for example, 1 to 6 hours.

Next, an unsaturated monomer (a-1) having only one functional group capable of reacting with an acid group is addition-reacted to the resin precursor using a polymerization inhibitor, if necessary, in a solvent (the second step ). In the second step, the acid group contained in the unsaturated monomer (a-1) is reacted with 100 moles of the acid group possessed by the compound (a-3) having three or more acid groups used as a raw material of the resin The reaction is preferably carried out at a rate of 40 to 90 mol, more preferably 40 to 60 mol, of the functional group.
In the resin polymerization method of the present embodiment, in the second step, the resin precursor contains an unsaturated monomer (a-1) having only one functional group that reacts with an acid group and a compound (a) having an acid anhydride group -4) may be reacted. In this case, the epoxy compound (a-2) having two or more epoxy groups and the compound (a-3) having three or more acid groups react with each other as the number of functional groups reacting with the hydroxyl group of the compound (a-4) The reaction is preferably carried out at a rate of 10 to 70% of the amount of hydroxyl groups produced, and more preferably at a rate of 20 to 60% of the above amount of hydroxyl groups.

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

It does not specifically limit as a solvent used in order to manufacture resin of this embodiment, A well-known thing can be used suitably. Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 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 monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene Glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as ropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (poly) alkylene glycol monoalkyl Ether acetate; Other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran etc. Ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, methyl 2-hydroxypropionate, 2-hydroxypropion Ethyl acid, 2 Methyl hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxyacetic acid Ethyl, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate , I-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, Methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, aceto Ester compounds such as methyl acetate, ethyl acetoacetate and ethyl 2-oxobutyrate; aromatic hydrocarbon compounds such as toluene and xylene; carboxylic acids such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like An amide compound etc. are mentioned. These solvents may be used alone or in combination of two or more.

Among the above solvents, glycol ether solvents are preferable. That is, as the solvent, it is preferable to use (poly) alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, and (poly) alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate.

The use amount of the solvent used to produce the resin of the present embodiment is not particularly limited, but the charge amount (the unsaturated monomer (a-1), the epoxy compound (a-2), and the three acid groups are used. When the total amount of the compound (a-3) and the compound (a-4) having an acid anhydride group contained as necessary is 100 parts by mass, generally 30 to 1000 parts by mass Part, preferably 50 to 800 parts by mass. It is preferable that the amount of the solvent used is 1000 parts by mass or less because the viscosity of the resin can be controlled to an appropriate range. On the other hand, if the amount of use of the above-mentioned solvent is 30 mass parts or more, it can prevent that burning occurs at the time of reaction, and since synthetic reaction can be performed stably, it is preferable. Moreover, coloring and gelation of resin can be prevented as the usage-amount of said solvent is 30 mass parts or more.

In the present embodiment, a catalyst is preferably used to promote the reaction of the epoxy compound (a-2) having two or more epoxy groups and the compound (a-3) having three or more acid groups. It does not specifically limit as a catalyst used in this embodiment, According to the raw material of resin, etc., it selects suitably.

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

In the second step, a polymerization inhibitor is preferably used to prevent gelation of the resin. It does not specifically limit as a polymerization inhibitor used in a 2nd process, According to the raw material of resin, etc., it selects suitably.

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

[Photosensitive resin composition]
The photosensitive resin composition of the present embodiment contains the resin (A), the solvent (B), the photopolymerization initiator (C) and the colorant (D) of any of the present 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 the reactive diluent described later.

As the solvent (B), the same solvents as can be used when producing the resin (A) can be used, and it is preferable to use a glycol ether solvent. That is, it is preferable to use, as the solvent (B), (poly) alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, and (poly) alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate.
When using the solution containing a solvent component as a material of photosensitive resin compositions other than a solvent (B), you may use the solvent component contained in the said solution as a solvent (B).

<Photoinitiator (C)>
The photopolymerization initiator (C) is not particularly limited, and examples thereof include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1 -Dichloroacetophenone, 4- (1-t-butyldioxy-1-methylethyl) acetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2 Acetophenone compounds such as -dimethylamino-1- (4-morpholinophenyl) butanone-1; anthraquinone compounds such as 2-methyl anthraquinone, 2-amyl anthraquinone, 2-t-butyl anthraquinone, 1-chloroanthraquinone and the like; xanthone, thioxanthate Xanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4- (1-t-butyldioxy-1-methyl) Ethyl benzophenone, benzophenone compounds such as 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone and the like; acyl phosphine oxide compounds, 1.2-octanedione, 1- [4- (phenylthio)- , 2- (O-benzoyloxime)] 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 dissolves or disperses in the solvent (B). As a coloring agent (D), a dye and a pigment are mentioned, for example. As the colorant (D), only a dye may be used, only a pigment may be used, or a combination of a dye and a pigment may be used. When using the resin cured film of the photosensitive resin composition of this embodiment as any of a black matrix, a color filter, and a black column spacer, the above-mentioned coloring agent (D) is the purpose etc. of the member formed with a resin cured film Depending on the kind, it can use individually or in combination of 2 or more types. For example, when a black thing is used as a coloring agent (D), the resin cured film of the photosensitive resin composition becomes a thing suitable as a black matrix and a black column spacer.

Examples of the dye include, for example, acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63 , 74, 95; acid red 1, 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, 1 4, 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, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; foodyellow3 and these Derivatives of and the like.

Among these dyes, it is preferable to use an azo-based, xanthene-based, anthraquinone-based or phthalocyanine-based acid dye.
These dyes may be used alone or in combination of two or more.

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

These pigments may be used alone or in combination of two or more.
As a black pigment, it is preferable to use an inorganic black pigment and an organic black pigment in combination from the viewpoint of the optical density of the image display device provided with the resin cured film of the photosensitive resin composition of this embodiment. More preferably, it is used in combination with organic black.

When a pigment is contained as the colorant (D), the photosensitive resin composition may contain a known dispersant from the viewpoint of improving the dispersibility of the pigment in the photosensitive resin composition. The content of the dispersant can be appropriately set in accordance with the type of pigment and the like used.

As the dispersant, it is preferable to use a polymer dispersant because it is excellent in dispersion stability with time. The polymer dispersant can be selected arbitrarily, and for example, a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant And aliphatic modified ester dispersants. Examples of polymer dispersants include EFKA (registered trademark, manufactured by BASF Japan Ltd.), Disperbyk (registered trademark, manufactured by BIC Chemie Inc.), Disparon (registered trademark, manufactured by Kushimoto Kasei Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Zeneca), etc. You may use what is marketed by a brand name.

<Reactive Diluent (E)>
The photosensitive resin composition of the present embodiment contains a reactive diluent (E) in addition to the resin (A), the solvent (B), the photopolymerization initiator (C) and the colorant (D). It is also good.
The reactive diluent (E) is a compound having at least one ethylenically unsaturated group in the molecule, and is preferably a compound having a plurality of ethylenically unsaturated groups.

The photosensitive resin composition containing the reactive diluent (E) facilitates adjustment of the viscosity and sensitivity of the photosensitive resin composition. Moreover, when the resin cured film of the photosensitive resin composition containing a reactive diluent (E) is used as a black matrix, a color filter, or a black column spacer, the strength of the resin cured film becomes good, which is preferable. In addition, a photosensitive resin composition containing a reactive diluent (E) is applied onto a surface to be formed of a cured resin film, exposed to light, and developed to form a cured resin film, which adheres to the surface to be formed. The properties are good and preferred.

Examples of monofunctional monomers (monomers having only one ethylenically unsaturated bond) used as the reactive diluent (E) include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, and ethoxy. Methyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxy methoxymethyl (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acrylate Iroxy-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3 -(Meth) acrylate compounds such as tetrafluoropropyl (meth) acrylate, half (meth) acrylate of phthalic acid derivative, etc .; aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyl toluene; vinyl acetate And carboxylic acid esters such as vinyl propionate. These monofunctional monomers may be used alone or in combination of two or more.

As a polyfunctional monomer (monomer having a plurality of ethylenic unsaturated bonds) used as the reactive diluent (E), for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate ) Acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Lupenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl ) Propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) Acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), trimethylhexamethylene diisocyanate Of hexamethylene diisocyanate, etc. with 2-bihydroxyethyl (meth) acrylate, (meth) acrylate compounds such as tri (meth) acrylate of tris (hydroxyethyl) isocyanurate; divinyl benzene, diallyl phthalate, diallyl benzene phosphonate etc. Aromatic vinyl compounds; dicarboxylic acid ester compounds such as divinyl adipate; triallyl cyanurate, methylene bis (meth) acrylamide, (meth) acrylamido methylene ether, condensates of polyhydric alcohol and N-methylol (meth) acrylamide Be These polyfunctional monomers may be used alone or in combination of two or more.

Furthermore, the photosensitive resin composition of the present embodiment may contain known additives such as a coupling agent, a leveling agent, and a thermal polymerization inhibitor, as long as the effects of the present invention are not impaired. Examples of the coupling agent include KBM-403 (3-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Silicone). The content of these additives is not particularly limited as long as the effects of the present invention are not impaired.

The photosensitive resin composition of the present embodiment contains 1 to 20% by mass of resin (A), 50 to 94% by mass of solvent (B), 0.01 to 5% by mass of photopolymerization initiator (C), and coloring It is preferable to contain 3 to 30% by mass of the agent (D).
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) relative to the entire photosensitive resin composition is preferably 1 to 20% by mass, and more preferably 5 to 15% by mass. Since it will become a photosensitive resin composition which has favorable photocurability as content of resin (A) is 1 mass% or more, 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 obtained, which is preferable.

The content of the solvent (B) relative to the entire photosensitive resin composition is preferably 50 to 94% by mass, and more preferably 60 to 90% by mass. When the content of the solvent (B) is 50% by mass or more, a photosensitive resin composition having good coatability is obtained, which 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, which is preferable.

The content of the photopolymerization initiator (C) with respect to the entire photosensitive resin composition is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass. The photocurability of the photosensitive resin composition becomes favorable for content of a photoinitiator (C) to be 0.01 mass% or more, and it is preferable. On the other hand, it is preferable for the content of the photopolymerization initiator (C) to be 5% by mass or less because a residue is hardly generated after the photosensitive resin composition is exposed and developed.

The content of the colorant (D) relative to the entire photosensitive resin composition is preferably 3 to 30% by mass, and more preferably 5 to 20% by mass. It is preferable that the content of the colorant (D) is 3% by mass or more, because the resin cured film of the photosensitive resin composition has light shielding properties. On the other hand, it is preferable that the content of the coloring agent (D) is 30% by mass or less, because residues do not easily 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. preferable. When the content of the reactive diluent (E) is 1% by mass or more, a photosensitive resin composition having good curability is obtained, which is preferable. On the other hand, it is preferable for the content of the reactive diluent (E) to be 20% by mass or less because the photosensitive resin composition is exposed and developed, so that a residue is hardly generated.

[Method of producing photosensitive resin composition]
Next, a method of producing the photosensitive resin composition of the present embodiment will be described.
The photosensitive resin composition of the present embodiment includes, if necessary, the resin (A), the solvent (B), the photopolymerization initiator (C), and the colorant (D) of any of the present embodiments. It can manufacture by the method of mixing the reactive diluent (E) contained, the dispersing agent, and any one or more components of an additive using a well-known mixing apparatus.

The photosensitive resin composition of this embodiment prepares in advance a composition containing a resin (A) and a solvent (B), and then, in the above composition, a photopolymerization initiator (C) and a colorant ( You may manufacture by the method of further adding and mixing D) and the reactive diluent (E) which is an optional component, a dispersing agent, and any 1 or more components of an additive further.

The composition containing the resin (A) and the solvent (B) is prepared, for example, by adding the solvent (B) to the resin (A) isolated from the resin solution which has completed the reaction for synthesizing the resin (A). It can be manufactured by the method of mixing and mixing.
In the present embodiment, it is not necessary to isolate the target resin (A) from the resin solution after the reaction for synthesizing the resin (A). Therefore, as a composition containing resin (A) and solvent (B), the solvent contained in the resin solution when the reaction for synthesizing resin (A) is completed is not separated from the resin solution The resin solution after completion of the reaction may be used as it is. Moreover, you may use what mixed and added the other solvent to the resin solution after reaction completion as a composition containing resin (A) and a solvent (B).

Since the photosensitive resin composition of the present embodiment contains the resin (A) of the present embodiment, the photosensitive resin composition has excellent developability, and has excellent colorant dispersibility and solvent resistance, and has a high elastic recovery rate. A membrane is obtained. Therefore, the photosensitive resin composition of this embodiment is suitable as a material of a black matrix, a color filter, and a black column spacer.
In addition, the photosensitive resin composition of the present embodiment has good colorant dispersibility, and is sufficiently satisfactory in general characteristics such as developability even if it contains a black colorant (D) sufficiently. It is possible to form a cured resin film having good adhesion to the surface to be formed. For this reason, according to the photosensitive resin composition of the present embodiment, it is possible to form a black pattern having good adhesion to the surface to be formed and sufficient light shielding properties.

[Resin cured film]
The resin cured film of the present embodiment is a resin cured film obtained by photocuring the photosensitive resin composition of the present embodiment.
The cured resin film of the present embodiment is suitable as a black matrix, a color filter, and a black column spacer, which are members of an image display device, because the colorant dispersibility, the solvent resistance, and the elastic recovery rate are good.

[Method for producing cured resin film]
The cured resin film of the present embodiment can be produced, for example, by the method described below.
First, a photosensitive resin composition is applied on the formation surface of a cured resin film to form a resin layer (coating film). Next, the resin layer is exposed through a mask of a predetermined pattern to photocure the exposed portion. Next, the unexposed portion of the resin layer is developed with a developer to form a resin cured film having a predetermined pattern. Thereafter, host baking (heat treatment) of the cured resin film is performed as necessary.
When exposing the resin layer, a halftone mask of a predetermined pattern may be used. In this case, the unexposed area and the semi-exposed area are developed with a developer to form a cured resin film having a predetermined pattern.

The method for applying the photosensitive resin composition is not particularly limited, and examples thereof include screen printing, roll coating, curtain coating, spray coating, and spin coating.
After applying the photosensitive resin composition, the solvent (B) contained in the resin layer is volatilized by heating using a heating means such as a circulating oven, an infrared heater, a hot plate, etc., if necessary. It is also good. The heating conditions after application are not particularly limited, and may be appropriately set according to the composition of the photosensitive resin composition. For example, the heating temperature after coating can be 50 ° C. to 120 ° C., and the heating time can be 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 energy dose to be applied to the resin layer may be appropriately set according to the composition of the photosensitive resin composition. For example, the energy dose applied to the resin layer can be 30 to 2000 mJ / cm ² , but is not limited to this range.
The light source used for exposure is not particularly limited, but a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp and the like can be arbitrarily selected and used.

As a developing solution used for development, it is preferable to use an alkaline developing solution because excellent developability can be obtained. Examples of the alkaline developer include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide and the like; aqueous solutions of amine compounds such as ethylamine, diethylamine, dimethylethanolamine and the like; tetramethyl ammonium, 3-methyl -4-Amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfone Aqueous solutions of amidoethyl aniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethyl aniline and p-phenylenediamine compounds such as their sulfates, hydrochlorides or p-toluenesulfonates; It can be mentioned.
The developer may contain an antifoaming agent, a surfactant, and the like, as necessary.

After development with a developer, the cured resin film having a predetermined pattern is preferably washed with water and dried.
Moreover, it is preferable to perform post-baking (heat treatment) of the resin cured film which has a predetermined | prescribed pattern, after developing with a developing solution. By post-baking, curing of the cured resin film can be further advanced. The conditions for post-baking are not particularly limited and may be arbitrarily selected, and may be appropriately set according to the composition of the photosensitive resin composition. For example, the heating temperature for post-baking can be 130 ° C. to 250 ° C. The post-baking heating time is preferably 10 minutes to 4 hours, more preferably 20 minutes to 2 hours.

[Image display device]
The image display apparatus of the present embodiment includes the resin cured film of the present embodiment. As a specific example of an image display apparatus, a liquid crystal display device, an organic electroluminescence display etc. are mentioned, for example.
As the image display device, for example, it is preferable that one or more members selected from a black matrix, a color filter, and a black column spacer be formed of the resin cured film of the present embodiment.

The material of the base forming the surface on which the resin cured film is to be formed is not particularly limited, and, for example, on the surface of glass, silicon, polycarbonate, polyester, polyamide, polyamideimide, polyimide, aluminum, printed wiring board, etc. A substrate on which a wiring pattern is formed, an array substrate, and the like can be mentioned.

The method of manufacturing the image display device of the present embodiment may include the step of forming the cured resin film of the present embodiment by the above-described manufacturing method, and the members other than the members formed of the cured resin film are It can be manufactured according to a conventional method.

The cured resin film obtained by curing the photosensitive resin composition of the present embodiment has excellent developability, good colorant dispersion and solvent resistance, and a high elastic recovery rate. For this reason, it is suitable as a material of a black matrix, a color filter, and a black column spacer with which an image display device is equipped.

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

Example 1-1
(Step 1)
In a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction pipe, 98 g of propylene glycol monomethyl ether acetate as a solvent, and bisphenol fluorene as an epoxy compound (a-2) having two or more epoxy groups. 100 g of glycidyl ether (BPFG) (0.38 mol of epoxy groups) and 72 g of 1,2,4-cyclohexanetricarboxylic acid (CHTC) which is a compound (a-3) having three or more acid groups And 1 g of triphenylphosphine as a catalyst, and the inside of the flask was stirred while blowing in air, and the temperature was raised to 120 ° C. for reaction for 2 hours to synthesize a resin precursor.

(Step 2)
Next, 56.8 g of glycidyl methacrylate (GMA), which is an unsaturated monomer (a-1) having only one functional group that reacts with an acid group (the number of moles of the functional group (epoxy group) that reacts with an acid group) A solution of 0.7 g of butylhydroxytoluene, which is a polymerization inhibitor, was dropped from the dropping funnel over 10 minutes into the flask in which the resin precursor was synthesized.
After completion of the dropping, the mixture was further stirred at 120 ° C. for 2 hours to synthesize a resin (A) of Example 1-1.

Propylene glycol monomethyl ether acetate as a solvent (B) was added to the resin solution after completion of the reaction and mixed to obtain a prepared solution (solid content concentration: 40% by mass) containing the resin (A) and the solvent (B). In addition, solid content means a heating residue when a composition is heated at 130 degreeC for 2 hours, and solid content of a preparation solution becomes resin (A) as a main component.

Example 2-1
The first step was carried out in the same manner as in Example 1-1 to synthesize a resin precursor.
(Step 2)
56.8 g of glycidyl methacrylate (GMA), which is an unsaturated monomer (a-1) having only one functional group that reacts with an acid group (the number of moles of a functional group (epoxy group) that reacts with an acid group) A solution of 0.7 g of butylhydroxytoluene, which is a polymerization inhibitor, was dropped from the dropping funnel into the flask where the resin precursor was synthesized over 10 minutes. After completion of the dropwise addition, the mixture is further stirred at 120 ° C. for 2 hours, and 10 g of succinic anhydride which is a compound (a-4) having an acid anhydride group (the number of functional groups reacting with the hydroxyl group in (a-4) is (a The resin (A) of Example 2-1 was synthesized by adding 30% of the amount of hydroxyl groups formed by the reaction of -2) and (a-3) and stirring at 110 ° C. for 30 minutes.

After completion of the reaction, propylene glycol monomethyl ether acetate as a solvent (B) was added to the resin solution and mixed, and a preparation solution (solid) containing a resin (A) and a solvent (B) was prepared in the same manner as Example 1-1. Minute 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, compound (a-3) having three or more acid groups, acid anhydride group Example 3-1, in the same manner as Example 2-1, except that the materials shown in Table 1 or Table 2 were used at the amounts shown in Table 1 or Table 2 as the compound (a-4) having Resins (A) of 8-1, 9-1, 11-1, 12-1 and 14-1 were synthesized.
After completion of the reaction, propylene glycol monomethyl ether acetate as a solvent (B) was added to the resin solution and mixed, and a preparation solution (solid) containing a resin (A) and a solvent (B) was prepared in the same manner as Example 1-1. Minute concentration (40% by mass).

Examples 4-1 to 7-1, 10-1 and 13-1
Table 1 or Table as an unsaturated monomer (a-1) having only one functional group, an epoxy compound (a-2) having two or more epoxy groups, and a compound (a-3) having three or more acid groups The materials shown in 2 are used in the amounts shown in Table 1 or Table 2 and, if necessary, the adipic acid is used in the amounts shown in Table 1 (the numerical value in parentheses is the number of moles of functional groups) In the same manner as in Example 1-1, a resin (A) of Examples 4-1 to 7-1, 10-1 and 13-1 was synthesized.
After completion of the reaction, propylene glycol monomethyl ether acetate as a solvent (B) was added to the resin solution and mixed, and a preparation solution (solid) containing a resin (A) and a solvent (B) was prepared in the same manner as Example 1-1. Minute concentration (40% by mass).

In Tables 1 and 2, unsaturated monomers (a-1) having only one functional group used in Examples 1-1 to 14-1, epoxy compounds having two or more epoxy groups (a-2), The materials and amounts used of the compound (a-3) having three or more acid groups are described. In addition, 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 in Tables 1 and 2 (a) -Describe the materials and amounts used in -4).
In Tables 1 and 2, the numerical values in parentheses in the column of (a-1) to (a-3) are the number of moles of the functional group of (a-1) to (a-3).
Also, the numerical values in parentheses in the column of (a-4) indicate the number of functional groups that react with the hydroxyl group in (a-4) with respect to the amount of hydroxyl groups generated by the reaction of (a-2) and (a-3) It is.

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

<Measurement method of acid number>
It measured using the mixed indicator of bromothymol blue and a phenol let according to JISK6901 5.3.2. It means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin (A).

<Method of measuring unsaturated group equivalent>
It is the mass (g / mol) of the polymer per mole number of the polymerizable unsaturated bond, and is a calculated value calculated based on the amount of the monomer used.

<Measurement Method of Weight Average Molecular Weight (Mw)>
It measured on condition of the following using gel permeation chromatography (GPC), and standard polystyrene conversion was carried out.
Column: Showdex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko KK)
Column temperature: 40 ° C
Sample: 0.2% tetrahydrofuran solution of copolymer Developing solvent: Tetrahydrofuran Detector: Differential refractometer (Showex (registered trademark) RI-71S) (manufactured by Showa Denko KK)
Flow rate: 1 mL / min

Comparative Example 1-1
In a flask equipped with a stirrer, dropping funnel, condenser, thermometer and gas inlet tube, 58 g of propylene glycol monomethyl ether acetate as solvent, 89 g of bisphenol fluorene, 25 g of acrylic acid, 0.7 g of triphenylphosphine as catalyst And 0.7 g of butylhydroxytoluene as a polymerization inhibitor were added, and the inside of the flask was stirred while blowing in air, and the temperature was raised to 120 ° C. for reaction for 2 hours.

Then, 22.2 g of 1,1'-bicyclohexane-3,3 ', 4,4'-tetracarboxylic acid-3,4: 3', 4'-dianhydride is introduced into the same flask, and 120 Stirred for a further 2 hours at ° C. Furthermore, 25 g of tetrahydrophthalic anhydride was added to the flask and stirred at 110 ° C. for 30 minutes to synthesize a resin (A) of Comparative Example 1-1.
After completion of the reaction, propylene glycol monomethyl ether acetate as a solvent (B) was added to the resin solution and mixed, and a preparation solution (solid) containing a resin (A) and a solvent (B) was prepared in the same manner as Example 1-1. Minute concentration (40% by mass).

With respect to the resin (A) synthesized in Comparative Example 1-1, the acid value, weight average molecular weight and unsaturated group equivalent of solid content were measured in the same manner as Example 1-1. As a result, the acid value of the resin (A) synthesized in Comparative Example 1-1 was 40 KOH mg / g, the weight average molecular weight (Mw) was 5,000, and the unsaturated group equivalent was 440.

Comparative Example 2-1
A resin (A) of Comparative Example 2-1 was synthesized in the same manner as Example 1-1 except that adipic acid was used instead of the compound (a-3) having three or more acid groups.
After completion of the reaction, propylene glycol monomethyl ether acetate as a solvent (B) was added to the resin solution and mixed, and a preparation solution (solid) containing a resin (A) and a solvent (B) was prepared in the same manner as Example 1-1. Minute concentration (40% by mass).

With respect to 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 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), the colorant (D), the reactive diluent (E) and the additive (F) shown in Tables 3 and 4 are shown in Table 3 and By mixing so as to obtain the content (mass%) shown in Table 4, photosensitive resin compositions of Examples 1-2 to 15-2 and Comparative Examples 1-2 and 2-2 were obtained.
The content of the resin (A) shown in Table 3 and Table 4 does not include the content of the solvent and the solvent contained in the preparation 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 solvent and the amount of solvent contained in the preparation solution containing the resin (A) are added to the solvent (B) shown in Tables 3 and 4.

With respect to 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 the film thickness reduction rate (development margin) were respectively obtained by the following methods. , Solvent resistance, elastic recovery, and development residue were evaluated. The results are shown in Tables 5-7.

<Evaluation of optical density (colorant dispersibility)>
A 10 cm × 10 cm IZO (In ₂ O ₃ -ZnO) substrate (a wiring pattern of IZO is formed on the surface) of the photosensitive resin compositions of Examples 1-2 to 15-2 and Comparative Examples 1-2 and 2-2 On the substrate, and the coating was spin-coated to a thickness of 1.5 .mu.m. Then, the solvent in the coating was volatilized by heating the IZO substrate at 90 ° C. for 3 minutes. Next, the entire surface of the coated film was exposed (exposure amount: 50 mJ / cm ² ) using Multilight ML-251D / B manufactured by Ushio Inc. and an irradiation optical unit PM25C-100 to be photocured. Thereafter, development was carried out with a 0.2% by mass aqueous potassium hydroxide solution for 120 seconds, and post-baking was further carried out at 230 ° C. for 30 minutes to obtain a target resin cured film.

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

<Evaluation of film thickness reduction rate (development margin)>
A coating with a thickness of 2.5 μm is prepared on a glass substrate in the same manner as the optical density, and the reduction rate of the thickness of the coating between 100 seconds and 150 seconds of development time It measured using level difference meter T4000M. It can be said that the larger the thickness reduction rate of the coating film, the better the development margin and the better the developability.

<Evaluation of solvent resistance>
A cured resin film is prepared on a glass substrate by the same method as in the evaluation of optical density, cut into a size of 1 cm × 1 cm, and cured with a UV spectrometer (UV-1650PC, manufactured by Shimadzu Corporation) The absorbance at the maximum absorption wavelength of the film was measured. Thereafter, the resin cured film of 1 cm × 1 cm in size was immersed in a glass bottle containing 5 mL of N-methylpyrrolidone. Thereafter, the cured resin film was taken out of N-methylpyrrolidone, wiped with a clean wiping paper or cloth, and left in an oven at 100 ° C. for 15 minutes. Thereafter, the absorbance at the maximum absorption wavelength of the cured resin film was measured in the same manner as before immersion in N-methylpyrrolidone. Then, the color loss of the cured resin film was evaluated according to the following criteria from the difference in absorbance before and after immersion in N-methylpyrrolidone. The smaller the difference in absorbance, the smaller the color loss and the better the solvent resistance.

"Standard"
◎: 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 between 20% and 30%.
X: Difference in absorbance is 30% or more.

<Evaluation of elastic recovery rate>
The elastic recovery rate at 25 ° C. of the cured resin film used for the evaluation of the optical density was measured using an elasticity measuring apparatus (DUH-W201S, manufactured by Shimadzu Corporation) according to the following measurement conditions.
As a pressing body for pressing the resin cured film, a flat pressing body having a diameter of 50 μm was used. The elastic recovery was measured in a test with a load of 300 mN in order to obtain distinguishable results between the compared groups. The loading rate of 3 gf / sec and the holding time of 3 seconds were kept constant. The elastic recovery rate was unloaded after applying a constant load to the flat pressing body for 3 seconds, and the elastic recovery rate of the cured resin film before and after the loading was measured by using a three-dimensional thickness measuring device. The elastic recovery rate means the ratio of the distance recovered after 10 minutes of recovery time (recovery distance) to the distance compressed upon application of a constant force (compression displacement), which is expressed by the following equation .
Elastic recovery rate (%) = (recovery distance / compression displacement) x 100

<Evaluation of development residue>
The photosensitive resin compositions of Examples 1-2 to 15-2 and Comparative Examples 1-2 and 2-2 were coated on a 10 cm × 10 cm IZO substrate (a substrate having a wiring pattern of IZO formed on the surface). It spin-coated so that the thickness of a coating film might be 1.5 micrometers. After that, the solvent was evaporated from the coating film by heating the IZO substrate at 90 ° C. for 3 minutes. Next, a pattern mask is placed on the coating film, and exposure (exposure dose 50 mJ / cm ² ) is performed using Multilight ML-251 D / B manufactured by Ushio Inc. and an irradiation optical unit PM25C-100 from above the mask to perform photocuring I did. Thereafter, development was carried out with a 0.2% by mass potassium hydroxide aqueous solution for 120 seconds, and the presence or absence of a residue (developing residue) was visually confirmed.

"Evaluation criteria"
◎: There is no residue at all.
Good: Although there is a little residue, it will disappear if the development time is extended for 30 seconds.
X: Residue remains even if the development time is extended for 30 seconds.

As shown in Tables 5 to 7, in the photosensitive resin compositions of Examples 1-2 to 15-2, the optical density (colorant dispersibility), thickness reduction ratio (development margin) and elasticity of the cured resin film were obtained. The recovery rate was high, and the evaluation of solvent resistance and development residue was good.
On the other hand, the cured resin film of the photosensitive resin composition of Comparative Example 1-2 was inferior in evaluation of solvent resistance and development residue as compared with Examples 1-2 to 15-2. It can be estimated that this is because the resin contained in the photosensitive resin composition of Comparative Example 1-2 does not have a three-dimensional structure but has a linear structure.
Moreover, the resin cured film of the photosensitive resin composition of Comparative Example 2-2 has an optical density (colorant dispersion property) and a film thickness reduction ratio of the resin cured film as compared with Examples 1-2 to 15-2. (Development margin) and elastic recovery rate were low, and evaluation of solvent resistance and development residue was inferior. This is because the resin contained in the photosensitive resin composition of Comparative Example 2-2 does not have a three-dimensional structure because the component derived from the compound (a-3) having three or more acid groups is not contained. , It can be estimated that it has a linear structure.

Claims

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 resin comprising: a component derived from a compound (a-3) having three or more acid groups.
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 a compound (a-3) having three or more acid groups,
A resin comprising: a component derived from a compound (a-4) having an acid anhydride group.
A first bonding portion in which a functional group which reacts with an acid group in the unsaturated monomer (a-1) and an acid group of a compound (a-3) having three or more of the acid groups are bonded;
The second bonding portion in which the epoxy group of the epoxy compound (a-2) and the acid group of the compound (a-3) having three or more of the acid groups are bonded to each other. Description resin.
The resin according to any one of claims 1 to 3, wherein the acid group possessed by the compound (a-3) having three or more acid groups is a carboxy group.
The resin according to any one of claims 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, 3 Or 4-epoxycyclohexyl group, a group represented by the following formula (2-1), or any one selected from a group represented by the following formula (2-2): In 2-2), * indicates the binding site of X 1 to R 2 ).
The resin according to any one of claims 1 to 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 claims 1 to 6, wherein the epoxy compound (a-2) is a compound represented by the following formula (2).

(In Formula (2), A is -CO-, -SO 2- , -C (CF 3 ) 2- , -Si (CH 3 ) 2- , -CH 2- , -C (CH 3 ) 2- B represents a phenylene group or a phenylene group having a substituent, and the substituent is an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group; X 2 is selected from an epoxy group, a 3,4-epoxycyclohexyl group, a group represented by the following formula (2-1), and a group represented by the following formula (2-2) In the following formula (2-1) and the following formula (2-2), * represents a bonding site to a methylene group of X 2. )
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 one item.
The ratio of the number of acid groups bonded to the epoxy group of the epoxy compound (a-2) to the number of acid groups of the compound (a-3) having three or more acid groups is 5 to 60 The resin according to any one of claims 1 to 8, which is%.
The resin according to any one of claims 2 to 9, wherein the compound (a-4) having an acid anhydride group is an anhydride having a ring structure.
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,
A resin characterized by being obtained by polymerizing a compound (a-3) having three or more acid groups.
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,
A compound (a-3) having three or more acid groups,
A resin characterized by being obtained by polymerizing a compound (a-4) having an acid anhydride group.
The resin (A) according to any one of claims 1 to 12;
A solvent (B),
The photosensitive resin composition characterized by including a photoinitiator (C) and a coloring agent (D).
1 to 20% by mass of the resin (A),
50 to 94% by mass of the solvent (B)
The photosensitive resin composition according to claim 13, containing 0.01 to 5% by mass of the photopolymerization initiator (C) and 3 to 30% by mass of the colorant (D).
The photosensitive resin composition according to claim 14, further comprising 1 to 20% by mass of a reactive diluent (E).
A cured resin film of the photosensitive resin composition according to any one of claims 13 to 15.
An image display apparatus comprising the resin cured film according to claim 16.