KR20200032133A - Resin, photosensitive resin composition, cured resin film and image display device - Google Patents

Abstract

Constituent component derived from unsaturated monomer (a-1) having only one functional group that reacts with an acid group, component derived from epoxy compound (a-2) having two or more epoxy groups, and compound having three or more acid groups (a -3) It shall be resin containing the derived component.

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.

This application claims priority based on Japanese Patent Application No. 2017-197128 for which it applied to Japan on October 10, 2017, and uses the content here.

Conventionally, in liquid crystal display panels, spacer particles are used to maintain a constant spacing (cell gap) between two substrates. As the spacer particles, glass beads, plastic beads, and the like having a predetermined particle diameter are used. Usually, the spacer particles are randomly arranged on a transparent substrate such as a glass substrate. When the spacer particles are present in the pixel formation region of the liquid crystal display panel, there is a problem that the reflection of the spacer particles occurs, or the incident light is scattered and the contrast is lowered.

To solve this problem, instead of spacer particles, dot-shaped or stripe-shaped spacers formed by photolithography using a photosensitive resin composition have been employed. This spacer can be formed by applying a photosensitive resin composition onto a substrate, exposing ultraviolet rays through a predetermined mask, and then developing. Therefore, the spacer containing the cured product of the photosensitive resin composition can be formed only at a predetermined place other than the pixel formation region in the liquid crystal display panel. Therefore, by forming a spacer by photolithography using a photosensitive resin composition, the above problem in the case of using spacer particles can be solved.

As a photosensitive resin composition used as a material of the spacer provided in a liquid crystal display panel, the radiation sensitive resin composition of patent document 1 is mentioned, for example.

In addition, Patent Document 2 describes a photosensitive composition that 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.

In addition, Patent Document 3 discloses a photosensitive resin composition for a black column spacer containing an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a light blocking agent.

Japanese Patent Publication No. 2001-302712 Japanese Patent Publication No. 2011-170075 Japanese Patent Publication No. 2013-134263

In recent years, strict dimensional precision is demanded in each member which forms a liquid crystal display element and a liquid crystal display element. For this reason, more excellent developability is requested | required of the photosensitive resin composition used as a material of a black matrix, a color filter, and a black column spacer. Moreover, in order to improve the display characteristics of a liquid crystal display element, it is necessary for the cured film which hardened the photosensitive resin composition used for the said application to have favorable colorant dispersibility. Further, in order to prevent deterioration of the liquid crystal display device, it is required that the cured film obtained by curing the photosensitive resin composition used in the above application has good solvent resistance and a high elastic recovery rate.

The present invention has been made in view of the above circumstances, and has an object to provide a resin suitable as a material for a photosensitive resin composition having a curable film having excellent developability, good colorant dispersibility and solvent resistance, and high elastic recovery. do.

In addition, another object of the present invention is to provide a photosensitive resin composition comprising a resin of the present invention, having excellent developability, good colorant dispersibility and solvent resistance, and a cured film having a high elastic recovery rate.

Moreover, this invention makes it a subject to provide the resin cured film of the photosensitive resin composition of this invention, and the 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,

Components derived from the 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,

Components derived from the 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 resin comprising a component derived from a compound (a-4) having an acid anhydride group.

[3] A functional group that reacts with an acid group in the unsaturated monomer (a-1), and a first bonding portion in which the acid group of the compound (a-3) having three or more acid groups is bonded,

The resin according to [1] or [2], having an epoxy group of the epoxy compound (a-2) and a second bonding portion in which the acid group of the compound (a-3) having three or more acid groups is bonded.

[4] The resin according to any one of [1] to [3], wherein the acid group of 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 a single bond, a methylene group, or any one selected from alkylene groups having 2 to 12 carbon atoms. X ₁ is an epoxy group, 3,4-epoxy.) Cyclohexyl group, group represented by the following formula (2-1), and any one selected from the group represented by the following formula (2-2): In the following formula (2-1) and the following formula (2-2) , * Indicates the binding site of X ₁ with 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- , -O-, 9,9-fluorenylidene, or a single bond 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 represents any selected from epoxy groups, 3,4-epoxycyclohexyl groups, groups represented by the following formula (2-1), and groups represented by the following formula (2-2). In the following formula (2-1) and the following formula (2-2), * represents a binding site to the methylene group of X ₂ )

[8] [1] to [7] The compound (a-3) having three or more acid groups is 1,2,4-cyclohexanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid. Resin according to any one of the above.

[9] Of the number of acid groups of the compound (a-3) having three or more acid groups, the ratio of the number of acid groups bonded to the epoxy group of the epoxy compound (a-2) is 5 to 60% [ Resin according to any one of 1] to [8].

[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 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 obtained by polymerizing a compound (a-4) having an acid anhydride group.

[13] The resin (A) according to any one of [1] to [12],

Solvent (B),

Photopolymerization initiator (C) and

A photosensitive resin composition comprising a coloring agent (D).

[14] 1 to 20% by mass of the resin (A),

50 to 94% by mass of the solvent (B),

The photopolymerization initiator (C) 0.01 to 5% by mass and

The photosensitive resin composition as described in [13] containing 3-30 mass% of the said coloring agent (D).

[15] The photosensitive resin composition according to [14], further containing 1 to 20% by mass of the 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 resin cured film according to [16].

The resin of the present invention is suitable as a material for a photosensitive resin composition having a curable film having excellent developability, good colorant dispersibility and solvent resistance, and high elastic recovery.

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 is 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, color filter, and black column spacer which is a member of an image display device.

Hereinafter, embodiments of the resin of the present invention, a photosensitive resin composition, a cured resin film, and an image display device will be described in detail. In addition, this invention is not limited only to embodiment described below.

[Suzy]

The resin of this embodiment is 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 a compound having three or more acid groups (a- It was obtained by reacting 3). The resin of this embodiment is 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 an acid group Constituent component derived from compound (a-3) having three or more is included. The resin of this embodiment may contain the constituent component derived from other arbitrary components in the range which does not impair the effect of this invention.

The resin of the present embodiment has a functional group of an unsaturated monomer (a-1) having only one functional group that reacts with an acid group, an epoxy group of an epoxy compound (a-2) having two or more epoxy groups, and three or more acid groups. It is presumed to have a three-dimensional structure formed by the reaction of the acid group of compound (a-3). Thereby, it is estimated that the photosensitive resin composition containing the resin of this embodiment has excellent developability, is excellent in colorant dispersibility and solvent resistance, and has a high elastic recovery rate.

<Unsaturated monomer having only one functional group reacting with an acid group (a-1)>

The functional group that reacts with the acid group in the unsaturated monomer (a-1) having only one functional group that reacts with the acid group is not particularly limited, and examples thereof include an epoxy group, an oxetanyl group, an isocyanato group, and a hydroxyl group. Is inexpensive, and since the reaction for producing the resin of this embodiment is easy and the reaction rate is high, an epoxy group is particularly preferable.

As an unsaturated monomer (a-1) having only one functional group that reacts with an acid group, specifically, epoxy group-containing (meth) acrylics such as glycidyl (meth) acrylate and 4-hydroxybutylacrylate glycidyl ether Rate, oxetanyl (meth) acrylate, (meth) acrylic acid (3-methyloxetan-3-yl) methyl, (meth) acrylic acid (3-ethyloxetan-3-yl) methyl, (meth) acrylic acid ( 3-methyloxetan-3-yl) ethyl, (meth) acrylic acid (3-ethyloxetan-3-yl) ethyl, (meth) acrylic acid (3-chloromethyloxetan-3-yl) methyl, (meth) Acrylic acid (oxetan-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-3- (meth) acrylate, (1-methyl (Meth) acryl containing oxetanyl groups such as -1-oxetanyl) -4-trifluoromethyl-2- (meth) acrylate Rate; And isocyanato group-containing (meth) acrylates such as 2-isocyanatoethyl (meth) acrylate, hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, and the like.

"(Meth) acrylate" in this specification refers to "acrylate" or "methacrylate", or both.

As the unsaturated monomer (a-1) having only one functional group that reacts with an acid group, one or two selected from glycidyl methacrylate and 2-isocyanatoethyl methacrylate are used among the above. It is desirable to do.

The compound used as an unsaturated monomer (a-1) having only one functional group that reacts with an acid group may be used alone, or two or more of them may be used in combination.

As an unsaturated monomer (a-1) which has only one functional group which reacts with an acidic radical, (meth) acrylate which has only one functional group which reacts with an acidic radical is mentioned, for example.

It is preferable that it is a compound represented by the following formula (1) as an unsaturated monomer (a-1) which has only one functional group which reacts with an acid group. When the unsaturated monomer (a-1) is a compound represented by the following formula (1), since the addition reaction for producing the resin of the present embodiment is easy, it becomes a resin that can be easily produced. Moreover, since the unsaturated monomer (a-1) is a compound represented by the following formula (1), the unsaturation of the unsaturated monomer (a-1) is a (meth) acrylic group, and thus the reactivity is good, which is preferable.

(In formula (1), R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a single bond, a methylene group, or any one selected from alkylene groups having 2 to 12 carbon atoms. X ₁ is an epoxy group, 3,4-epoxy.) Cyclohexyl group, group represented by the following formula (2-1), any one selected from the group represented by the following formula (2-2): In the following formula (2-1) and the following formula (2-2) , * Indicates the binding site of X ₁ with R ₂ )

In Formula (1), R ₁ represents a hydrogen atom or a methyl group.

In Formula (1), R ₂ represents a single bond, a methylene group, or any one selected from an alkylene group having 2 to 12 carbon atoms, and is preferably one selected from a methylene group or an alkylene group having 2 to 7 carbon atoms.

In Formula (1), X ₁ is an epoxy group, a 3,4-epoxycyclohexyl group, a group represented by Formula (2-1), or a group represented by Formula (2-2) (Formula (2-1) ) And the formula (2-2), * represents any one selected from X ₁ represents a binding site to R ₂ ), and is preferably an epoxy group.

<Epoxy compound having two or more epoxy groups (a-2)>

As an epoxy compound (a-2) having two or more epoxy groups, specifically, 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, resorcinol diglycidyl ether, diglycidyl terephthalate, diglycidyl orthophthalate, bisphenol fluorine diglycidyl ether, as shown below And compounds in which epihalohydrin is added to the compound, such as epichlorohydrin.

As a compound forming an epoxy compound (a-2) having two or more epoxy groups by adding epihalohydrin, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethyl) Phenyl) 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-epoxypropane-1-yloxy) naphthalene, etc. are mentioned.

As the epoxy compound (a-2) having two or more epoxy groups, among the above compounds, ethylene glycol diglycidyl ether and bisphenol fluorene diglycidyl ether, 3,3 ', 5,5'-tetramethyl- Use one or two selected from 4,4'-bis (glycidyloxy) -1,1'-biphenyl, 1,6-bis (2,3-epoxy propane-1-yloxy) naphthalene It is desirable to do.

The above-mentioned compounds used as an epoxy compound (a-2) having two or more epoxy groups may be used alone or in combination of two or more.

It is more preferable that the epoxy compound (a-2) having two or more epoxy groups 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- , -O-, 9,9-fluorenylidene, or a single bond 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 represents any selected from epoxy groups, 3,4-epoxycyclohexyl groups, groups represented by the following formula (2-1), and groups represented by the following formula (2-2). In the following formula (2-1) and the following formula (2-2), * represents a binding site to the methylene group of X ₂ )

In formula (2), A is -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, and is 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 represents any one selected from an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group.

In Formula (2), X ₂ is an epoxy group, a 3,4-epoxycyclohexyl group, a group represented by Formula (2-1), or a group represented by Formula (2-2) (Formula (2-1) ) And the formula (2-2), * denotes any one selected from X ₂ represents a binding site with a methylene group, 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 sulfo groups, phosphoric acid groups, and carboxy groups, and are preferably carboxy groups. When the acid group in the compound (a-3) having three or more acid groups is a carboxy group, it becomes a more developable resin. In addition, in the addition reaction for producing the resin of the present embodiment, side reactions are unlikely to occur, and can be easily produced.

In the present embodiment, the acid anhydride group is not included in the acid group in the compound (a-3) having three or more acid groups.

As the compound (a-3) having three or more acid groups, specifically, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,3-propanetri Carboxylic 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, And 1,1'-bicyclohexane-3,3 ', 4,4'-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid and polycarboxylic acid.

As the compound (a-3) having three or more acid groups, among the above compounds, one selected from 1,2,4-cyclohexanetricarboxylic acid and 1,2,3,4-butanetetracarboxylic acid, or It is preferred to use two.

The above-mentioned compounds used as a compound (a-3) having three or more acid groups may be used alone or in combination of two or more.

Moreover, the compound (a-3) which has three or more acid groups is a compound which does not have a functional group other than an acid group.

The resin of this embodiment is 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 a compound having three or more acid groups (a- It may be obtained by reacting 3) with a compound (a-4) having an acid anhydride group. This resin is 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 three or more acid groups. It contains the structural component derived from the compound (a-3) which has, and the structural component derived from the compound (a-4) which has an acid anhydride group.

When the resin of this embodiment contains the constituent component derived from the compound (a-4) which has an acid anhydride group, it becomes a resin with more favorable developability.

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

The resin of the present embodiment is an acid having three or more acid groups in one molecule (an acid having three or more functional groups), a compound having an acid anhydride group, an unsaturated monomer (a-1) having only one functional group reacting with an acid group, and an epoxy group It may be obtained by reacting an epoxy compound (a-2) having two or more. This resin is a trifunctional or higher acid and contains a constituent component derived from a compound having an acid anhydride group. The compound having an acid anhydride group and having three or more functional groups 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 constitutional component derived from a compound having an acid anhydride group and trifunctional or higher is an acid anhydride group and a constituent component derived from a compound (a-3) having three or more acid groups. It is considered to contain the component derived from the compound (a-4) to have.

In addition, the number of functional groups (β) combined with the functional groups reacting with the acid group in the unsaturated monomer (a-1) with respect to the number of functional groups (α) possessed by the component derived from the compound having an acid anhydride group and trifunctional or higher , The ratio of the total number of functional groups (γ) combined with the epoxy group of the epoxy compound (a-2) (β + γ) is at least three acid groups among the constituents derived from the compound having an acid anhydride group and a trifunctional or higher acid It is regarded as the ratio (δ = {(β + γ) / (α)}) of the constituents derived from the compound (a-3) to have. Among the constituents derived from a compound having an acid anhydride group and having a trifunctional or higher function, the proportion (1-δ) excluding the constituent component derived from a compound (a-3) having three or more acid groups is represented by a compound having an acid anhydride group ( Consider the proportion of constituents derived from a-4).

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

Such a resin has, for example, an epoxy compound (a-2) and a compound (a-3) having three or more acid groups, a compound having three or more acid groups than the number of moles of the epoxy group of the epoxy compound (a-2) ( It is obtained by performing the first step of reacting in the state where the number of moles of the acid group of the a-3) is large, and the second step of reacting the unsaturated monomer (a-1) with the resin precursor.

The resin precursor obtained by performing the first step has a 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, and is also bonded to the epoxy group. It has an acid group derived from the compound (a-3) which has three or more acid groups not being performed.

By performing the second step after the first step, an acid group derived from the compound (a-3) having three or more acid groups remaining in the resin precursor, and an acid group contained in the unsaturated monomer (a-1) The reactive functional group reacts additionally. Thereby, it has the 1st bonding part which the functional group which reacts with the acidic radical contained in the unsaturated monomer (a-1) couple | bonded with the acidic group which the compound (a-3) which has 3 or more acid groups has, and the said 2nd bonding part Resin is obtained.

The preferable structural unit ratio of the resin of the present embodiment is as shown in the following (I) to (III).

(I) It is preferable that it is the resin which reacted at the ratio which the epoxy group of the epoxy compound (a-2) becomes 60 to 5 mol with respect to 100 mol of the acid group of the compound (a-3) which has three or more acid groups, and 50 to It is more preferable that the resin is reacted at a ratio of 10 mol. That is, in the resin of the present embodiment, the ratio of the number of acid groups 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 is 5 to It is preferable that it is 60%, and it is more preferable that it is 10-50%. 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 improving the hardness of the cured film. For this reason, according to the said resin, the cured film which has excellent hardenability and developability, and has good colorant dispersibility and solvent resistance, and has high hardness and elastic recovery rate is obtained.

(II) It is preferable that the functional group reacting with the acid group of the unsaturated monomer (a-1) at a ratio of 40 to 90 mol with respect to 100 mol of the acid group of the compound (a-3) having three or more acid groups. It is more preferable to be a resin reacted at a ratio of 40 to 60 mol. That is, the resin of the present embodiment is the number of acid groups that are bonded to a functional group that reacts with the acid group contained in the unsaturated monomer (a-1) among the number of acid groups of the compound (a-3) having three or more acid groups. The ratio of is preferably 40 to 90%, and 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. For this reason, according to the said resin, the cured film which has excellent hardenability and developability, and has good colorant dispersibility and solvent resistance, and has high hardness and elastic recovery rate is obtained.

(III) When a compound (a-4) having an acid anhydride group is used as a material for the resin, the number of functional groups reacting with the hydroxyl group of the compound (a-4) is an epoxy compound (a-2) having two or more epoxy groups. It is preferable that the compound (a-3) having three or more peracid groups reacts and reacts at a ratio of 10 to 70% of the amount of hydroxyl groups produced, and reacts at a ratio of 20 to 60% of the amount of hydroxyl groups It is more preferable that it is made resin. When the number of functional groups reacting with the hydroxyl group of the compound (a-4) is within the above range, since the addition reaction of the resin proceeds efficiently, it becomes a resin having good productivity. Moreover, since the number of hydroxyl groups in the resin is small when the number of functional groups that react with the hydroxyl group of the compound (a-4) is within the above range, it becomes a resin that can obtain a cured film having good coating film properties.

As for the resin of this embodiment, the weight average molecular weight obtained by polystyrene conversion by gel permeation chromatography (GPC) is preferably 1000 to 40000, and more preferably 3000 to 30000. When the weight average molecular weight is 1000 or more, a photosensitive resin composition containing this resin is applied and exposed, and then, a defect is unlikely to occur in the pattern formed by development, and is preferable. On the other hand, if the weight-average molecular weight is 40000 or less, the time required for the development performed after coating and exposing the photosensitive resin composition containing this resin is appropriate, and it is preferable because it is practical in use.

Although the acid value (JIS K6901 5.3) of the resin of the present embodiment is not limited as long as it exerts the desired effect of the present invention, it is usually 20 to 300 KOHmg / g, preferably 30 to 200 KOHmg / g. When the acid value is 20 KOHmg / g or more, it is preferable because the developability of the photosensitive resin composition containing this resin becomes good. On the other hand, when the acid value is 300 KOHmg / g or less, the photocured portion by coating and exposing the photosensitive resin composition containing this resin becomes difficult to dissolve in the developer, which is preferable.

The resin unsaturated group equivalent of the present embodiment is not limited as long as it exhibits the desired effect of the present invention, but is usually 100 to 4000 g / mol, preferably 200 to 2000 g / mol, and more preferably 300 to 500 g / mol to be. When the unsaturated group equivalent is 100 g / mole or more, the developability of the photosensitive resin composition containing this resin becomes good. For this reason, the resin cured film which photocured the photosensitive resin composition containing this resin is a black matrix, a color filter, and a black column spacer, and has more favorable characteristics. On the other hand, if the unsaturated group equivalent is 4000 g / mol or less, the sensitivity of the photosensitive resin composition containing this resin becomes higher, and a finer pattern can be formed, which is preferable.

In addition, the unsaturated group equivalent is the mass of the 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 this 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.

[Resin production method]

Next, a method for producing the resin of the present embodiment will be described.

The resin of this embodiment is 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 a compound having three or more acid groups (a- 3) and the compound (a-4) having an acid anhydride group used as necessary can be produced by a method of polymerization by an arbitrary polymerization method.

It is preferable to use the method shown below as a polymerization method of the resin of this embodiment.

First, a resin precursor is synthesized by reacting an epoxy compound (a-2) having two or more epoxy groups and a compound (a-3) having three or more acid groups by using a catalyst as needed in a solvent (first step). ). The amount of the epoxy compound (a-2) having two or more epoxy groups in the first step and the compound (a-3) having three or more acid groups are used in the compound (a-3) having three or more acid groups. It is preferable to make the number of moles of the acid group larger than the number of moles of the epoxy group of the epoxy compound (a-2). Specifically, it is preferable to react at a ratio of 60 to 5 moles of the epoxy group of the epoxy compound (a-2) with respect to 100 moles of the acid group of the compound (a-3) having three or more acid groups, and 50 to 10 It is more preferable to react at a molar ratio.

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.

Subsequently, an unsaturated monomer (a-1) having only one functional group that reacts with an acid group is added to the resin precursor by a polymerization inhibitor, if necessary, in a solvent (second step). In the second step, 40 to 90 moles of functional groups react with the acid groups contained in the unsaturated monomer (a-1) with respect to 100 moles of the acid groups of the compound (a-3) having three or more acid groups used as a raw material for the resin. It is preferable to react at a ratio which becomes, and it is more preferable to react at a ratio which becomes 40 to 60 mol.

In the resin polymerization method of the present embodiment, in the second step, the resin precursor may be reacted with an unsaturated monomer (a-1) having only one functional group reacting with an acid group and a compound (a-4) having an acid anhydride group. . In this case, the number of functional groups that react with the hydroxyl group of the compound (a-4) is the hydroxyl produced by 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 react at a rate of 10 to 70% of the amount of the air, and more preferably to react at a rate of 20 to 60% of the amount of the hydroxyl group.

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 include the solvent used in the first step.

That is, you may perform a 2nd process continuously after a 1st process, without removing the solvent remaining in the reaction system after a 1st process is completed.

It does not specifically limit as a solvent used for manufacturing the resin of this embodiment, A well-known thing can be used suitably. As specific examples of the solvent, 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 , (Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl 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 and 3-heptanone; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl- 3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-propionic acid Ester compounds such as butyl, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutyrate; Aromatic hydrocarbon compounds such as toluene and xylene; And carboxylic acid amide compounds such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

Among these solvents, glycol ether-based solvents are preferred. That is, it is preferable to use a (poly) alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether and a (poly) alkylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate.

The amount of the solvent used to produce the resin of the present embodiment is not particularly limited, but the input amount (unsaturated monomer (a-1), epoxy compound (a-2), and compound having three or more acid groups (a -3) and, when necessary, the total amount of the compound (a-4) having an acid anhydride group contained) is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass. When the amount of the solvent used 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 because seizure can be prevented from occurring during the reaction, and a synthetic reaction can be stably performed. Moreover, when the usage-amount of the said solvent is 30 mass parts or more, coloring and gelation of resin can be prevented.

In this embodiment, it is preferable to use a catalyst to accelerate 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. The catalyst used in the present embodiment is not particularly limited and is 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 triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chelating compounds of chromium. Can be lifted. 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 when the resin precursor synthesized in the first step is 100 parts by mass, it is generally 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass. Parts, more preferably 0.2 to 1 part by mass.

In the second step, it is preferable to use a polymerization inhibitor to prevent gelation of the resin. The polymerization inhibitor used in the second step is not particularly limited, and is 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 generally 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 of this embodiment contains any resin (A) of this embodiment, a solvent (B), a photoinitiator (C), and a coloring agent (D).

<Solvent (B)>

The solvent (B) can dissolve the resin (A) and is not particularly limited as long as it is an inert solvent that does not react with the resin (A), and can be arbitrarily selected according to the type of the resin (A) and the like. It is preferable that solvent (B) has compatibility with the reactive diluent mentioned later.

As the solvent (B), the same solvent that 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 (poly) alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether and (poly) alkylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate as the solvent (B).

When a solution containing a solvent component is used as a material for a 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)>

Although it does not specifically limit as a photoinitiator (C), For example, Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1-t-butyldioxy-1-methylethyl) acetophenone, 2-methyl-1- [ Acetophenone compounds such as 4- (methylthio) phenyl] -2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1; Anthraquinone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; Xanthone compounds such as xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone compounds such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone ; An acylphosphine oxide compound, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], and the like. These photopolymerization initiators (C) may be used alone, or two or more kinds thereof may be used.

<Colorant (D)>

The coloring agent (D) may just be dissolved or dispersed in the solvent (B), and is not particularly limited. 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 dye and a pigment may be used in combination. When the resin cured film of the photosensitive resin composition of the present embodiment is used as any one of a black matrix, a color filter, and a black column spacer, the colorant (D) may be used alone or in accordance with the purpose of the member formed of the resin cured film or the like. It can be used in combination of more than one species. For example, when a black thing is used as the colorant (D), the cured resin film of the photosensitive resin composition is suitable as a black matrix and a black column spacer.

Examples of the dye include, for example, 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 yellow1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; and foodyellow3 and derivatives thereof.

Among these dyes, it is preferable to use an azo-based, xanthene-based, anthraquinone-based or phthalocyanine-based acidic dye.

These dyes may be used alone or in combination of two or more.

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

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 together from a viewpoint of the optical density of the image display device provided with the resin cured film of the photosensitive resin composition of this embodiment, and a carbon black and a lactam organic black are used together. It is more preferable to do.

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

As the dispersant, it is preferable to use a polymer dispersant from the viewpoint of excellent dispersion stability over time. The polymer dispersant may be arbitrarily selected, but, for example, urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, aliphatic modified ester dispersants, etc. Can be mentioned. As a polymer dispersing agent, product names such as EFKA (registered trademark, manufactured by BASF Japan), Disperbyk (registered trademark, manufactured by Big Chemis), Dispalon (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Geneca) You may use what is commercially available.

<Reactive diluent (E)>

The photosensitive resin composition of this embodiment may contain the reactive diluent (E) in addition to the resin (A), the solvent (B), the photopolymerization initiator (C), and the colorant (D).

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.

When the photosensitive resin composition contains the reactive diluent (E), adjustment of the viscosity and sensitivity of the photosensitive resin composition becomes easy. In addition, when the resin cured film of the photosensitive resin composition containing the reactive diluent (E) is used as a black matrix, color filter, or black column spacer, the strength of the cured resin film is good, which is preferable. Moreover, after apply | coating and exposing the photosensitive resin composition containing a reactive diluent (E) on the surface to be formed of a resin cured film, the resin cured film developed and formed is preferable because it has good adhesiveness with the surface to be formed.

As the monofunctional monomer (monomer having only one ethylenically unsaturated bond) used as the reactive diluent (E), for example, (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, e Methoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (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-hydride Hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropylphthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylic Rate, 2,2,2-trifluoroethyl (meth (Meth) acrylate compounds such as t) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of phthalic acid derivatives; Aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, and vinyltoluene; And carboxylic acid esters such as vinyl acetate and 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 ethylenically 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, 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, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypoly on Cyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di ( Meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate), (Meth) acrylate compounds, such as a reactant of 2-hydroxyethyl (meth) acrylate, tris (hydroxyethyl) isocyanurate, and tri (meth) acrylate of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate; Aromatic vinyl compounds such as divinylbenzene, diallylphthalate and diallylbenzenephosphonate; Dicarboxylic acid ester compounds such as divinyl adipate; And triallyl cyanurate, methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, and polyhydric alcohols and condensates of N-methylol (meth) acrylamide. These polyfunctional monomers may be used alone or in combination of two or more.

Moreover, 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 Shin-Etsu Silicone), and the like. The content of these additives is not particularly limited as long as the effect of the present invention is not impaired.

In the photosensitive resin composition of this embodiment, the resin (A) is 1 to 20 mass%, the solvent (B) is 50 to 94 mass%, the photopolymerization initiator (C) is 0.01 to 5 mass%, and the colorant (D) is 3 to It is preferable to contain 30 mass%.

Moreover, when the photosensitive resin composition of this embodiment contains a reactive diluent (E), it is preferable that content of the reactive diluent (E) is 1-20 mass%.

It is preferable that content of resin (A) with respect to the whole photosensitive resin composition is 1-20 mass%, and it is more preferable that it is 5-15 mass%. When the content of the resin (A) is 1% by mass or more, it is preferable because it is a photosensitive resin composition having good photocurability. On the other hand, if the content of the resin (A) is 20% by mass or less, it is preferable because it is a photosensitive resin composition having good coatability.

It is preferable that content of the solvent (B) with respect to the whole photosensitive resin composition is 50-94 mass%, and it is more preferable that it is 60-90 mass%. When the content of the solvent (B) is 50% by mass or more, it is preferable because it is a photosensitive resin composition having good coatability. 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 a photosensitive resin composition, which is preferable.

It is preferable that content of the photoinitiator (C) with respect to the whole photosensitive resin composition is 0.01-5 mass%, and it is more preferable that it is 0.1-2 mass%. When content of a photoinitiator (C) is 0.01 mass% or more, the photocurable property of a photosensitive resin composition becomes favorable, and it is preferable. On the other hand, if the content of the photopolymerization initiator (C) is 5% by mass or less, it is preferable because residues are unlikely to occur after exposure and development of the photosensitive resin composition.

It is preferable that content of the coloring agent (D) with respect to the whole photosensitive resin composition is 3-30 mass%, and it is more preferable that it is 5-20 mass%. When the content of the colorant (D) is 3% by mass or more, the resin cured film of the photosensitive resin composition has a light-shielding property and is preferable. On the other hand, if the content of the colorant (D) is 30% by mass or less, it is preferable because residues are unlikely to occur after exposure and development of the photosensitive resin composition.

When the photosensitive resin composition contains the reactive diluent (E), the content of the reactive diluent (E) is preferably 1 to 20% by mass, more preferably 2 to 10% by mass. When the content of the reactive diluent (E) is 1% by mass or more, it is preferable because it is a photosensitive resin composition having good curability. On the other hand, if the content of the reactive diluent (E) is 20% by mass or less, it is preferable because residues are less likely to occur after exposure and development of the photosensitive resin composition.

[Method for producing photosensitive resin composition]

Next, the method of manufacturing the photosensitive resin composition of this embodiment is demonstrated.

The photosensitive resin composition of the present embodiment includes any resin (A), a solvent (B), a photopolymerization initiator (C), a colorant (D), and a reactive diluent (E) contained as necessary, Any one or more components of a dispersant and an additive can be produced by a method of mixing using a known mixing device.

In the photosensitive resin composition of the present embodiment, a composition comprising a resin (A) and a solvent (B) is prepared in advance, and thereafter, the photopolymerization initiator (C), a colorant (D), and optional components in the composition. The reactive diluent (E), a dispersing agent, and any one or more components of the additive may be further added to prepare by mixing.

The composition containing the resin (A) and the solvent (B) is mixed by adding a solvent (B) to the resin (A) isolated from the resin solution after the reaction for synthesizing the resin (A), for example. It can be manufactured by a method.

In this embodiment, it is not necessary to isolate the target resin (A) from the resin solution that has completed the reaction for synthesizing the resin (A). Therefore, as a composition comprising the resin (A) and the solvent (B), the solvent contained in the resin solution at the time when the reaction for synthesizing the resin (A) is finished is not separated from the resin solution, and after the reaction is completed. You may use the resin solution as it is. Moreover, you may use what mixed by adding another solvent to the resin solution after completion | finish of reaction 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, a cured film having excellent developability, good colorant dispersibility and solvent resistance, and high elastic recovery rate 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 sufficiently contains a black colorant (D), and can sufficiently satisfy general characteristics such as developability and adherence to the surface to be formed. This favorable resin cured film can be formed. For this reason, according to the photosensitive resin composition of this embodiment, the adhesiveness with respect to the to-be-formed surface is favorable and the black pattern which has sufficient light-shielding property can be formed.

[Resin cured film]

The resin cured film of this embodiment is the resin cured film which photocured the photosensitive resin composition of this embodiment.

Since the resin cured film of this embodiment has good colorant dispersibility, solvent resistance, and elastic recovery rate, it is suitable as a black matrix, color filter, and black column spacer which is a member of an image display device.

[Method for manufacturing resin cured film]

The cured resin film of the present embodiment can be produced, for example, by the method shown below.

First, a photosensitive resin composition is applied on the surface to be formed of the cured resin film to form a resin layer (coating film). Next, the resin layer is exposed through a mask of a predetermined pattern to photocur the exposed portion. Next, the unexposed portion of the resin layer is developed with a developer to obtain a cured resin film having a predetermined pattern. Thereafter, if necessary, post-baking (heat treatment) of the cured resin film is performed.

When exposing the resin layer, a halftone mask of a predetermined pattern may be used. In this case, the unexposed portion and the semi-exposed portion are developed with a developer solution to obtain a cured resin film having a predetermined pattern.

Although it does not specifically limit as a method of apply | coating a photosensitive resin composition, For example, the screen printing method, the roll coat method, the curtain coat method, the spray coat method, the spin coat method etc. are mentioned.

After coating the photosensitive resin composition, the solvent (B) contained in the resin layer may be volatilized by heating using a heating means such as a circulating oven, an infrared heater, or a hot plate, if necessary. The heating conditions after application are not particularly limited, and may be appropriately set depending on the composition of the photosensitive resin composition. For example, the heating temperature after application can be 50 ° C to 120 ° C, and the heating time can be 30 seconds to 30 minutes.

Although it does not specifically limit as a method of exposing a resin layer, For example, the method of irradiating active energy rays, such as ultraviolet rays and excimer laser light, is mentioned.

The energy dose irradiated to the resin layer may be appropriately set depending on the composition of the photosensitive resin composition. For example, the energy dose irradiated to the resin layer may be 30 to 2000 mJ / cm 2, but is not limited to this range.

The light source used for exposure is not particularly limited, and a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or a metal halide lamp can be arbitrarily selected and used.

As the developer used for development, it is preferable to use an alkali developer because excellent developability is obtained. Examples of the alkali developer include aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide and potassium hydroxide; Aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; Tetramethylammonium, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N -Ethyl-N-β-methanesulfonamide ethyl aniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethyl aniline and p-phenyl such as sulfate, hydrochloride or p-toluenesulfonate And an aqueous solution of the rendiamine-based compound.

An antifoaming agent, surfactant, etc. may be included in the developing solution as needed.

After developing with a developing solution, it is preferable to wash and dry the resin cured film which has a predetermined pattern.

Moreover, it is preferable to perform post-baking (heat treatment) of the cured resin film which has a predetermined pattern after developing with a developing solution. Curing of the resin cured film can be further advanced by performing post-baking. The post-baking conditions are not particularly limited and can be arbitrarily selected, and may be appropriately set depending on the composition of the photosensitive resin composition. For example, the heating temperature of the post-baking can be from 130 ° C to 250 ° C. The heating time of the post-baking is preferably 10 minutes to 4 hours, more preferably 20 minutes to 2 hours.

[Image display device]

The image display device of the present embodiment includes the resin cured film of the present embodiment. As a specific example of an image display device, a liquid crystal display device, an organic EL display device, etc. are mentioned, for example.

As the image display device, it is preferable that at least one member selected from, for example, a black matrix, a color filter, and a black column spacer is formed of the cured resin film of the present embodiment.

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

The manufacturing method of the image display device of this embodiment should just include the process of forming the resin cured film of this embodiment by the above-mentioned manufacturing method, and members other than the member formed of the resin cured film can be manufactured according to the normal method. You can.

The cured resin film obtained by curing the photosensitive resin composition of the present embodiment has excellent developability, good colorant dispersibility and solvent resistance, and high elastic recovery. For this reason, it is suitable as a material for the black matrix, color filter, and black column spacers provided in the 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 these Examples.

<Example 1-1>

(First process)

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 bisphenol fluorene diglycine as an epoxy compound (a-2) having two or more epoxy groups Diethyl ether (BPFG) 100g (0.38 moles of moles of epoxy group) and 1,2,4-cyclohexanetricarboxylic acid (CHTC) 72g (molarity of moles of acid groups) of compound (a-3) having three or more acid groups ) And 0.7 g of triphenylphosphine as a catalyst were added, the flask was stirred while blowing air, and heated to 120 ° C. to react for 2 hours to synthesize a resin precursor.

(Second process)

Next, 56.8 g of glycidyl methacrylate (GMA), which is an unsaturated monomer (a-1) having only one functional group reacting with an acid group (0.4 moles of moles of a functional group (epoxy group) reacting with an acid group), is a polymerization inhibitor. What melt | dissolved 0.7 g of butyl hydroxy toluene was dripped over 10 minutes from the dropping funnel into the flask which synthesize | combined the resin precursor.

After completion of the dropwise addition, the mixture was further stirred at 120 ° C for 2 hours to synthesize Resin (A) of Example 1-1.

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

<Example 2-1>

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

(Second process)

56.8 g of glycidyl methacrylate (GMA), an unsaturated monomer (a-1) having only one functional group that reacts with an acid group (0.4 moles of moles of a functional group (epoxy group) reacting with an acid group), butyl hydroxy, a polymerization inhibitor What melt | dissolved 0.7 g of toluene was dripped over 10 minutes from the dropping funnel into the flask which synthesize | combined the resin precursor. After completion of the dropwise addition, the mixture was further stirred at 120 ° C for 2 hours, and the number of functional groups reacting with the hydroxyl group in 10 g of succinic anhydride ((a-4)), which is a compound (a-4) having an acid anhydride group, (a-2) and (a- 3) 25% of the amount of hydroxyl groups produced by the reaction) was added and stirred at 110 ° C for 30 minutes to synthesize the resin (A) of Example 2-1.

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

<Examples 3-1, 8-1, 9-1, 11-1, 12-1, 14-1>

Unsaturated monomer having only one functional group (a-1), epoxy compound having two or more epoxy groups (a-2), compound having three or more acid groups (a-3), compound having an acid anhydride group (a-4) As in Example 2-1, except that the materials shown in Table 1 or Table 2 were used in the amounts shown in Table 1 or Table 2, Examples 3-1, 8-1, 9-1, and 11- Resins (A) of 1, 12-1 and 14-1 were synthesized.

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

<Examples 4-1 to 7-1, 10-1, 13-1>

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 Table 1 or Table 2 were used. It was carried out in the same manner as in Example 1-1, except that it was used in the amount shown in Table 1 or Table 2 and adipic acid was used in the amount shown in Table 1 (values in parentheses are moles of functional groups) as needed Resins (A) of Examples 4-1 to 7-1, 10-1 and 13-1 were synthesized.

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

In Table 1 and Table 2, unsaturated monomers (a-1) having only one functional group used in Examples 1-1 to 14-1, epoxy compounds (a-2) having two or more epoxy groups, and three or more acid groups The material and the amount of the compound (a-3) to have are described. In addition, in Table 1 and Table 2, the compound (a-4) having an acid anhydride group used in Examples 2-1, 3-1, 8-1, 9-1, 11-1, 12-1, 14-1 The material and amount of use should be described.

In Table 1 and Table 2, the numerical values in parentheses in the columns of (a-1) to (a-3) are the number of moles of the functional groups in (a-1) to (a-3).

In addition, the numerical value in the parenthesis of the column of (a-4) is the number of functional groups which react with the hydroxyl group in (a-4) with respect to the amount of hydroxyl groups produced by reaction of (a-2) and (a-3).

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

<Measurement method of acid value>

It was measured according to JIS K6901 5.3.2 using a mixed indicator of bromothymol blue and phenolic. It means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin (A).

<Measurement method of unsaturated equivalents>

It is the mass (g / mol) of the polymer per mole number of polymerizable unsaturated bonds, and is a calculated value calculated based on the amount of monomers used.

<Measurement method of weight average molecular weight (Mw)>

It measured under the following conditions using gel permeation chromatography (GPC), and converted to standard polystyrene.

Column: Showdex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Co., Ltd.)

Column temperature: 40 ° C

Sample: 0.2% tetrahydrofuran solution of copolymer

Development solvent: tetrahydrofuran

Detector: Differential refractometer (Showdex (registered trademark) RI-71S) (manufactured by Showa Denko Co., Ltd.)

Flow rate: 1 mL / 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 fluorene, 25 g of acrylic acid, 0.7 g of triphenylphosphine as a catalyst, 0.7 g of butyl hydroxytoluene, which is a polymerization inhibitor, was added, the flask was stirred while blowing air, and heated to 120 ° C. to react for 2 hours.

Next, 22.2 g of 1,1'-bicyclohexane-3,3 ', 4,4'-tetracarboxylic acid-3,4: 3', 4'-dianhydride was charged into the same flask, and 120 The mixture was further stirred at ℃ for 2 hours. Further, 25 g of tetrahydrophthalic anhydride was added to the flask and stirred at 110 ° C. for 30 minutes to synthesize Resin (A) of Comparative Example 1-1.

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

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

<Comparative Example 2-1>

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 completion of the reaction, propylene glycol monomethyl ether acetate was added as a solvent (B) and mixed, and in the same manner as in Example 1-1, a preparation solution containing a resin (A) and a solvent (B) (solid content concentration) 40 mass%).

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

<Examples 1-2 to 15-2 and Comparative Examples 1-2 and 2-2>

Contents (mass) of resins (A), solvents (B), photopolymerization initiators (C), colorants (D), reactive diluents (E) and additives (F) shown in Tables 3 and 4 are shown in Tables 3 and 4 %) To obtain a photosensitive resin composition of Examples 1-2 to 15-2 and Comparative Examples 1-2 and 2-2.

In addition, content of the solvent and solvent contained in the preparation solution (solid content concentration 40 mass%) containing resin (A) is not contained in content of resin (A) shown in Table 3 and Table 4. Content of the resin (A) shown in Table 3 and Table 4 contains only the solid content in the preparation solution containing resin (A). The amount of the solvent and the solvent contained in the preparation solution containing the resin (A) is added in 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), film thickness reduction rate (development margin), and contents were respectively determined by the following methods. Detergent, elastic recovery rate and developing residue were evaluated. 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 are 10 cm × 10 cm IZO (In ₂ O ₃ -ZnO) substrates (wiring patterns whose surface includes IZO). On the formed substrate), spin coating was performed so that the thickness of the coating film was 1.5 μm. Thereafter, the solvent in the coating film was volatilized by heating the IZO substrate at 90 ° C for 3 minutes. Next, the entire surface of the coating film was exposed (exposure amount 50 mJ / cm 2) using a multi-light ML-251D / B manufactured by Ushio Denki Co., Ltd., and an irradiation optical unit PM25C-100, and photocured. Then, it developed for 120 seconds with 0.2 mass% potassium hydroxide aqueous solution, and also post-baked at 230 degreeC for 30 minutes, and obtained the target resin cured film.

Optical density (OD) was measured for a resin cured film having a thickness of 1.0 µm by using a transmission density meter (361T, X-lite).

It can be said that the higher the optical density, the better the dispersibility of the colorant.

<Evaluation of film thickness reduction rate (development margin)>

A coating film having a thickness of 2.5 µm was prepared on the glass substrate in the same manner as the optical density, and the rate of decrease in the thickness of the coating film during the development time of 100 seconds to 150 seconds was measured using a T4000M tactile step meter manufactured by Kosaka Corporation. 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>

On a glass substrate, a cured resin film was produced in the same manner as in the evaluation of optical density, cut into 1 cm × 1 cm size, and used with a UV spectrum meter (UV-1650PC, manufactured by Shimadzu Corporation). The absorbance at the maximum absorption wavelength of the cured resin film was measured. Thereafter, a cured resin film having a size of 1 cm x 1 cm was immersed in a glass bottle containing 5 mL of N-methylpyrrolidone. Thereafter, the cured resin film was taken out from N-methylpyrrolidone, wiped with a clean wipe 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, from the difference in absorbance before and after immersion in N-methylpyrrolidone, the color loss of the cured resin film was evaluated according to the following criteria. It can be said that the smaller the difference in absorbance, the less color is missing and excellent in solvent resistance.

"standard"

?: The difference in absorbance was 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%.

X: The difference in absorbance is 30% or more.

<Evaluation of elastic recovery rate>

About the cured resin film used for evaluation of optical density, the elastic recovery rate at 25 ° C was measured using an elasticity measuring device (DUH-W201S, manufactured by Shimadzu Corporation) according to the following measurement conditions.

As a pressing body for pressing the cured resin film, a flat pressing body having a diameter of 50 µm was used. The elastic recovery rate was measured by a test that applied a load of 300 mN in order to obtain discernible results between the compared groups. The load speed of 3gf / sec and the retention time of 3 sec were kept constant. Regarding the elastic recovery rate, the flat pressing body was unloaded after a constant load was applied for 3 seconds, and the elastic recovery rate of the cured resin film before and after the load was measured by using a three-dimensional thickness measuring device. The elastic recovery rate means the ratio of the recovered distance (recovery distance) to the compressed distance (compressed displacement) when a constant force is applied after the recovery time of 10 minutes has elapsed, and is expressed by the following equation.

Elastic recovery rate (%) = (Recovery distance / compressed displacement) x 100

<Evaluation of the phenomenon residue>

The photosensitive resin compositions of Examples 1-2 to 15-2 and Comparative Examples 1-2 and 2-2 were placed on a 10 cm × 10 cm IZO substrate (substrate on which a wiring pattern including IZO is formed). Spin coating was performed so that the thickness of the coating film was 1.5 µm. Thereafter, the IZO substrate was heated at 90 ° C. for 3 minutes to volatilize the solvent from the coating film. Next, a pattern mask was put on the coating film, and photocured by exposure (50 mJ / cm 2 of exposure amount) using a multi-light ML-251D / B manufactured by Ushio Denki Co., Ltd. and the irradiation optical unit PM25C-100 from the mask. Then, it developed for 120 seconds with 0.2 mass% potassium hydroxide aqueous solution, and it was confirmed by visually checking the presence or absence of residue (developing residue).

"Evaluation standard"

◎: There is no residue at all.

(Circle): There is some residue, but it disappears when the development time is extended for 30 seconds.

X: Residue remains even if the developing time is extended for 30 seconds.

As shown in Tables 5 to 7, the photosensitive resin compositions of Examples 1-2 to 15-2 have high optical density (colorant dispersibility), film thickness reduction rate (development margin), and elastic recovery rate of the cured resin film, The evaluation of the detergent and development residue was good.

On the other hand, the resin cured film of the photosensitive resin composition of Comparative Example 1-2 was poor 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, and has a linear structure.

In addition, the resin cured film of the photosensitive resin composition of Comparative Example 2-2, compared to Examples 1-2 to 15-2, had an optical density (colorant dispersibility), film thickness reduction rate (development margin) and elastic recovery rate of the resin cured film. This was low, and evaluation of solvent resistance and development residue was poor. This does not have a three-dimensional structure because the resin contained in the photosensitive resin composition of Comparative Example 2-2 does not contain a component derived from the compound (a-3) having three or more acid groups, and has a straight chain structure. It can be presumed that it is because they have.

Claims (17)

A component derived from an unsaturated monomer (a-1) having only one functional group that reacts with an acid group,
Components derived from the 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,
Components derived from the 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 resin comprising a component derived from a compound (a-4) having an acid anhydride group. The method according to claim 1 or 2,
A functional group that reacts with an acid group in the unsaturated monomer (a-1), and a first bonding portion in which the acid group of the compound (a-3) having three or more acid groups is bonded,
A resin having an epoxy group of the epoxy compound (a-2) and a second bonding portion in which the acid group of the compound (a-3) having three or more acid groups is bonded. The method according to any one of claims 1 to 3,
The resin in which the acid group of the compound (a-3) having three or more acid groups is a carboxy group. The method according to any one of claims 1 to 4,
The resin 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 a single bond, a methylene group, or any one selected from alkylene groups having 2 to 12 carbon atoms. X ₁ is an epoxy group, 3,4-epoxy.) Cyclohexyl group, group represented by the following formula (2-1), any one selected from the group represented by the following formula (2-2): In the following formula (2-1) and the following formula (2-2) , * Indicates the binding site of X ₁ with R ₂ )

The method according to any one of claims 1 to 5,
The functional group that reacts with the acid group of the unsaturated monomer (a-1) is an epoxy group. The method according to any one of claims 1 to 6,
The epoxy compound (a-2) is a resin 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- , -O-, 9,9-fluorenylidene, or a single bond 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 represents any selected from epoxy groups, 3,4-epoxycyclohexyl groups, groups represented by the following formula (2-1), and groups represented by the following formula (2-2). In the following formula (2-1) and the following formula (2-2), * represents a binding site to the methylene group of X ₂ )

The method according to any one of claims 1 to 7,
The resin (a-3) having three or more acid groups is 1,2,4-cyclohexanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid. The method according to any one of claims 1 to 8,
The resin having a ratio of the number of acid groups bonded to the epoxy group of the epoxy compound (a-2) in the number of acid groups of the compound (a-3) having three or more acid groups is 5 to 60%. The method according to any one of claims 2 to 9,
The resin (a-4) having the 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 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 obtained by polymerizing a compound (a-4) having an acid anhydride group. The resin (A) according to any one of claims 1 to 12,
Solvent (B),
Photopolymerization initiator (C) and
A photosensitive resin composition comprising a coloring agent (D). The method of claim 13,
1 to 20% by mass of the resin (A),
50 to 94% by mass of the solvent (B),
The photopolymerization initiator (C) 0.01 to 5% by mass and
Photosensitive resin composition containing 3-30 mass% of said coloring agent (D). The method of claim 14,
Photosensitive resin composition further containing 1 to 20 mass% of reactive diluent (E). The resin cured film of the photosensitive resin composition in any one of Claims 13-15. An image display device comprising the cured resin film according to claim 16.