TWI696641B - Resin, photosensitive resin composition, resin cured film, and image display device - Google Patents

Abstract

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

Description

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

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

Conventionally, in a liquid crystal display panel, spacer particles are used to maintain a certain distance (cell gap) between two substrates. As the spacer particles, glass beads, plastic beads, etc. having a specified particle size are used. Generally, the spacer particles are randomly arranged on a transparent substrate such as a glass substrate. If there are spacer particles in the pixel formation area of the liquid crystal display panel, a ghost phenomenon of the spacer particles may occur, or the incident light may be scattered to reduce the contrast.

In order to solve this problem, dot-shaped or stripe-shaped spacers formed by photolithography and using a photosensitive resin composition are gradually used instead of spacer particles. The spacer can be formed by applying a photosensitive resin composition onto a substrate, and developing it after exposure to ultraviolet rays through a designated photomask. Therefore, the spacer system composed of the cured product of the photosensitive resin composition can be formed only at a predetermined position outside the pixel formation area in the liquid crystal display panel. Therefore, the spacer formed by the photolithography and using the photosensitive resin composition can solve the above-mentioned problem when the spacer particles are used.

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

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

[Problems to be solved by the invention]

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

The present invention is made in view of the above circumstances, and an object of the present invention is to provide a resin suitable as a material for a photosensitive resin composition, and a cured film obtained from the photosensitive resin composition has excellent developability And the colorant dispersibility and solvent resistance are good and have a high elastic recovery rate. In addition, an object of the present invention is to provide a photosensitive resin composition comprising the resin of the present invention, a cured film obtained from the photosensitive resin composition having excellent developability, and colorant dispersibility and solvent resistance It is good and has a high elastic recovery rate. Moreover, the subject of this invention is providing the cured resin film of the photosensitive resin composition of this invention, and the image display device provided with the same. [Means to solve the problem]

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

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

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

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

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

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

(式(1)中，R₁ 表示氫原子或甲基；R₂ 表示選自單鍵、亞甲基、碳數2~12的伸烷基之任一者；X₁ 表示選自環氧基、3,4-環氧基環己基、下述式(2-1)所表示之基、下述式(2-2)所表示之基之任一者；下述式(2-1)及下述式(2-2)中，＊表示X₁ 之與R₂ 之鍵結部位)。

(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 , 3,4-epoxycyclohexyl, any of the groups represented by the following formula (2-1), the groups represented by the following formula (2-2); the following formula (2-1) and In the following formula (2-2), * represents a bonding site between X ₁ and R ₂ ).

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

(式(2)中，A表示-CO-、-SO₂ -、-C(CF₃ )₂ -、-Si(CH₃ )₂ -、-CH₂ -、-C(CH₃ )₂ -、-O-、9,9-亞茀基或單鍵；B表示伸苯基或具有取代基的伸苯基，前述取代基表示選自碳數1~5的烷基、鹵素原子或苯基之任一者；X₂ 表示選自環氧基、3,4-環氧基環己基、下述式(2-1)所表示之基、下述式(2-2)所表示之基之任一者；下述式(2-1)及下述式(2-2)中，＊表示X₂ 之與亞甲基之鍵結部位)。

(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-oxynylene or single bond; B represents phenylene or phenylene having a substituent, and the aforementioned substituent represents a group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group Any one; X ₂ represents any one selected from the group consisting of epoxy group, 3,4-epoxycyclohexyl group, the group represented by the following formula (2-1), and the group represented by the following formula (2-2) One; in the following formula (2-1) and the following formula (2-2), * represents the bonding site of X ₂ and the methylene group).

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

[11]. A resin whose characteristics are Unsaturated monomer (a-1) with only one functional group that reacts with acid groups, Epoxy compound (a-2) with two or more epoxy groups and Compounds with 3 or more acid groups (a-3) Obtained by polymerization. [12]. A resin whose characteristics are Unsaturated monomer (a-1) with only one functional group that reacts with acid groups, Epoxy compound (a-2) with two or more epoxy groups, Compounds (a-3) with more than 3 acid groups and Compound with acid anhydride group (a-4) Obtained by polymerization.

[13]. A photosensitive resin composition characterized by containing: Such as the resin (A) of any one of [1]~[12], Solvent (B), Photopolymerization initiator (C) and Colorant (D). [14]. The photosensitive resin composition as described in [13], which contains: 1 to 20% by mass of the aforementioned resin (A), 50 to 94% by mass of the aforementioned solvent (B), The aforementioned photopolymerization initiator (C) 0.01 to 5 mass% and The aforementioned colorant (D) is 3 to 30% by mass. [15]. The photosensitive resin composition according to [14], which further contains 1 to 20% by mass of the reactive diluent (E).

[16]. A resin cured film of the photosensitive resin composition according to any one of [13] to [15]. [17]. An image display device characterized by having a resin cured film as described in [16]. [Effect of invention]

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

[The best form for carrying out the invention]

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

[Resin] The resin system of this embodiment will consist of an unsaturated monomer (a-1) having only one functional group that reacts with an acid group, an epoxy compound (a-2) having two or more epoxy groups, and three The above acid group compound (a-3) is obtained by reacting. The resin of this embodiment includes: a constituent 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) having two or more epoxy groups. -2) The constituent components and the constituent components derived from the compound (a-3) having three or more acid groups. The resin of this embodiment may contain constituent components derived from other arbitrary components within a range that does not impair the effects of the present invention.

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

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

Examples of the unsaturated monomer (a-1) having only one functional group that reacts with an acid group include glycidyl (meth)acrylate and 4-hydroxybutyl acrylate glycidyl ether. Epoxy-based (meth)acrylate, oxetanyl (meth)acrylate, (3-methyloxetan-3-yl)methyl (meth)acrylate, (methyl ) Acrylic acid (3-ethyloxetan-3-yl) methyl ester, (meth)acrylic acid (3-methyloxetan-3-yl) ethyl ester, (meth)acrylic acid (3 -Ethyl oxetane-3-yl) ethyl ester, (meth)acrylic acid (3-chloromethyloxetan-3-yl) methyl ester, (meth)acrylic acid (oxetane Alk-2-yl) methyl ester, (meth)acrylic acid (2-methyloxetan-2-yl) methyl ester, (meth)acrylic acid (2-ethyloxetan-2- Methyl), (1-methyl-1-oxetanyl-2-phenyl)-3-(meth)acrylate, (1-methyl-1-oxetanyl) -2-trifluoromethyl-3-(meth)acrylate, (1-methyl-1-oxetanyl)-4-trifluoromethyl-2-(meth)acrylate, etc. (Meth)acrylates containing oxetanyl; isocyanate-containing (meth)acrylates such as (meth)acrylic acid 2-isocyanatoethyl methacrylate, (( Hydroxy-containing (meth)acrylates such as 2-hydroxyethyl methacrylate.

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

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

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

The unsaturated monomer (a-1) having only one functional group that reacts with an acid group is preferably a compound represented by the following formula (1). If the unsaturated monomer (a-1) is a compound represented by the following formula (1), the addition reaction used to produce the resin of the present embodiment is easy, and thus it becomes a resin that can be easily manufactured. In addition, the unsaturated monomer (a-1) is a resin of a compound represented by the following formula (1). Since the unsaturated group of the unsaturated monomer (a-1) is a (meth)acryloyl group, the reaction Sex is good, so it is better.

(式(1)中，R₁ 表示氫原子或甲基；R₂ 表示選自單鍵、亞甲基、碳數2~12的伸烷基之任一者；X₁ 表示選自環氧基、3,4-環氧基環己基、下述式(2-1)所表示之基、下述式(2-2)所表示之基之任一者；下述式(2-1)及下述式(2-2)中，＊表示X₁ 之與R₂ 之鍵結部位)。

(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 , 3,4-epoxycyclohexyl, any of the groups represented by the following formula (2-1), the groups represented by the following formula (2-2); the following formula (2-1) and In the following formula (2-2), * represents a bonding site between X ₁ and R ₂ ).

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

<Epoxy compound having two or more epoxy groups (a-2)> Examples of the epoxy compound (a-2) having two or more epoxy groups include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and hydrogenated bisphenol A. Diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol Polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, resorcinol diglycidyl ether, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, double Compounds such as bisphenol fluorene diglycidyl ether, epihalohydrin such as epichlorohydrin, and compounds shown below are added.

Examples of the compound that forms an epoxy compound (a-2) having two or more epoxy groups by adding epoxyhalopropane include bis(4-hydroxyphenyl) ketone and bis(4 -Hydroxy-3,5-dimethylphenyl) ketone, bis(4-hydroxy-3,5-dichlorophenyl) ketone, bis(4-hydroxyphenyl) benzene, bis(4-hydroxy-3, 5-dimethylphenyl) ash, bis(4-hydroxy-3,5-dichlorophenyl) ash, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-di Methylphenyl) hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5 -Dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3, 5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromobenzene)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3 ,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane , 2,2-bis(4-hydroxy-3-chlorophenyl) propane, bis(4-hydroxyphenyl) ether, bis(4-hydroxy-3,5-dimethylphenyl) ether, bis(4 -Hydroxy-3,5-dichlorophenyl) ether, 9,9-bis(4-hydroxyphenyl) stilbene, 9,9-bis(4-hydroxy-3-methylphenyl) stilbene, 9,9 -Bis(4-hydroxy-3-chlorophenyl) stilbene, 9,9-bis(4-hydroxy-3-bromobenzene) stilbene, 9,9-bis(4-hydroxy-3-fluorophenyl) stilbene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl) stilbene, 3,3',5,5'-tetramethyl-4,4'-bis(epoxypropyloxy) -1,1'-biphenyl, 1,6-bis(2,3-epoxypropane-1-yloxo)naphthalene, etc.

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

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

(式(2)中，A表示-CO-、-SO₂ -、-C(CF₃ )₂ -、-Si(CH₃ )₂ -、-CH₂ -、-C(CH₃ )₂ -、-O-、9,9-亞茀基或單鍵；B表示伸苯基或具有取代基的伸苯基，前述取代基表示選自碳數1~5的烷基、鹵素原子或苯基之任一者；X₂ 表示選自環氧基、3,4-環氧基環己基、下述式(2-1)所表示之基、下述式(2-2)所表示之基之任一者；下述式(2-1)及下述式(2-2)中，＊表示X₂ 之與亞甲基之鍵結部位)。

(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-oxynylene or single bond; B represents phenylene or phenylene having a substituent, and the aforementioned substituent represents a group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group Any one; X ₂ represents any one selected from the group consisting of epoxy group, 3,4-epoxycyclohexyl group, the group represented by the following formula (2-1), and the group represented by the following formula (2-2) One; in the following formula (2-1) and the following formula (2-2), * represents the bonding site of X ₂ and the methylene group).

In formula (2), A represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -,- O-, 9,9-oxynylene or single bond, preferably 9,9-oxynylene. In formula (2), B represents phenylene or phenylene having a substituent, and phenylene is preferred. When B is a phenylene group having a substituent, the substituent means 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 represents a group selected from epoxy, 3,4-epoxycyclohexyl, the group represented by the above formula (2-1), and the group represented by the above formula (2-2) (the above In the formula (2-1) and the above formula (2-2), * represents any one of the bonding sites of X ₂ and the methylene group, and epoxy group is preferred.

<Compound with more than 3 acid groups (a-3)> The compound (a-3) having 3 or more acid groups has 3 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 phosphoric acid group, and a carboxyl group. A carboxyl group is preferred. If the acid group in the compound (a-3) having three or more acid groups is a carboxyl group, it will become a resin with better developability. In addition, in the addition reaction for producing the resin of the present embodiment, side reactions are less likely to occur, and the production can be easily performed. In this embodiment, the acid group in the compound (a-3) having three or more acid groups does not include an acid anhydride group.

As the compound (a-3) having 3 or more acid groups, specifically, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,3- Propane tricarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, 3-butene-1,2,3-tricarboxylic acid, polyphosphoric acid, Ethylene tetracarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic 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-butane tetracarboxylic acid, polycarboxylic acid, etc.

As the compound (a-3) having 3 or more acid groups, among the above compounds, a compound selected from 1,2,4-cyclohexane tricarboxylic acid and 1,2,3,4-butane tetracarboxylic acid is particularly used One or two of carboxylic acids are preferred. The above-mentioned compounds used as the compound (a-3) having three or more acid groups can be used alone or in combination of two or more kinds. In addition, the compound (a-3) which has 3 or more acid groups is a compound which does not have a functional group other than an acid group.

In the resin of this embodiment, 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, or The compound (a-3) having three or more acid groups and the compound (a-4) having an acid anhydride group are obtained by reacting. The resin contains: a constituent component derived from an unsaturated monomer (a-1) having only one functional group that reacts with an acid group, and an epoxy compound (a-2) derived from two or more epoxy groups Constituents derived from the compound (a-3) having three or more acid groups and constituents derived from the compound (a-4) having an acid anhydride group. If the resin of this embodiment contains a component derived from the compound (a-4) having an acid anhydride group, it will become a resin with 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.

In the resin of this embodiment, a compound having an acid having three or more acid groups (acid with more than three functions) and an acid anhydride group in one molecule, and an unsaturated monomer having only one functional group that reacts with the acid group The body (a-1) and the epoxy compound (a-2) having two or more epoxy groups are obtained by reacting. The resin contains a constituent component of a compound derived from an acid having more than three functions and having an acid anhydride group. The trifunctional or more acid compound having an acid anhydride group is a compound (a-3) having three or more acid groups and the compound (a-4) having an acid anhydride group. Therefore, in this embodiment, a resin containing a constituent component derived from a trifunctional or more acid compound having an acid anhydride group is regarded as a constituent component derived from a compound (a-3) having three or more acid groups And the component derived from the compound (a-4) having an acid anhydride group. Also, "the number of functional groups (β) bonded to the functional group that reacts with an acid group in the unsaturated monomer (a-1), and the function bonded to the epoxy group of the epoxy compound (a-2) The ratio of the total number of bases (γ) (β+γ)” to the “number of functional groups (α) of constituents of compounds derived from acids with trifunctional or more and acid anhydride groups” is considered to be derived from trifunctional or more Of the constituents of the acid and the compound having an acid anhydride group, the ratio of the constituents derived from the compound (a-3) having 3 or more acid groups (δ={(β+γ)/(α)}) . Proportion (1-δ) of constituent components derived from a compound (a-3) having three or more acid groups among constituent components derived from a trifunctional or more acid and having an acid anhydride group, It is regarded as the ratio of constituent components derived from the compound (a-4) having an acid anhydride group.

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

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

By performing the above-mentioned first step, the obtained resin precursor has an epoxy group of the epoxy compound (a-2) and an acid group of the compound (a-3) having three or more acid groups via a bond The bonded second bonding portion has an acid group derived from a compound (a-3) having three or more acid groups, which is not bonded to an epoxy group. After the first step, the second step is carried out to thereby make the functional group which reacts with the acid group included in the unsaturated monomer (a-1) and the source derived from the resin precursor have three The acid group of the above acid group compound (a-3) undergoes an addition reaction. According to this situation, the resulting resin will have a functional group that reacts with an acid group contained in the unsaturated monomer (a-1), and an acid included in the compound (a-3) having 3 or more acid groups The first bonding portion formed by bonding the base and the second bonding portion described above.

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

(II) The functional group of the unsaturated monomer (a-1) which reacts with the acid group becomes 40 to 90 with respect to 100 moles of the acid group of the compound (a-3) having 3 or more acid groups The molar ratio is preferred for the resin to be reacted, and the molar ratio is 40 to 60 for the resin to be reacted. That is, the resin of this embodiment reacts with the acid group included in the unsaturated monomer (a-1) among the number of acid groups in the compound (a-3) having three or more acid groups The ratio of the number of acid groups to which the functional groups are bonded 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. Therefore, with the above resin, a cured film having excellent curability and developability, good colorant dispersibility and solvent resistance, and high hardness and elastic recovery rate can be obtained.

(III) If the compound (a-4) having an acid anhydride group is used as the material of the resin, the number of functional groups that the compound (a-4) has and reacts with a hydroxyl group is to become a ring having two or more epoxy groups It is preferable that the oxygen compound (a-2) and the compound (a-3) having three or more acid groups react with a ratio of 10 to 70% of the amount of hydroxyl groups generated by the reaction to make the above-mentioned hydroxyl group The ratio of the amount of 20 to 60% to make the reaction resin is more preferable. When the number of functional groups which the compound (a-4) has and reacts with the hydroxyl group is within the above range, the addition reaction of the resin can be efficiently performed, and thus the resin has good productivity. In addition, when the number of functional groups that the compound (a-4) has and react with hydroxyl groups is within the above range, the number of hydroxyl groups in the resin is an appropriate amount, and thus it becomes a resin that can obtain a cured film having good coating film physical properties.

The resin of this embodiment has a weight average molecular weight obtained by gel permeation chromatography (GPC) in terms of polystyrene, preferably 1,000 to 40,000, and more preferably 3,000 to 30,000. When the weight-average molecular weight is 1000 or more, it is preferable that the photosensitive resin composition containing the resin is applied and exposed, and the pattern formed by development is less likely to be damaged. On the other hand, when the weight average molecular weight is 40,000 or less, the time required for development after applying the photosensitive resin composition containing the resin and exposing it is appropriate, and it is practical for use, which is preferable.

The acid value (JIS K6901 5.3) of the resin of the present embodiment is not limited as long as it can exert the desired effect of the present invention, and it is generally 20 to 300 KOHmg/g, preferably 30 to 200 KOHmg/g. When the acid value is 20 KOHmg/g or more, the developability of the photosensitive resin composition containing the resin is good, which is preferable. On the other hand, when the acid value is 300 KOHmg/g or less, the portion where the photosensitive resin composition containing the resin is applied and exposed to light for curing becomes difficult to dissolve in the developer, which is preferable.

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

In addition, the so-called unsaturated group equivalent refers to the mass of resin per mole of unsaturated bonds (ethylenic carbon-carbon double bonds) in the resin. The unsaturated group equivalent can be obtained 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 a resin means the theoretical value calculated from the loading amount of the raw material used for introducing an unsaturated group into a resin.

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

As a method of polymerizing the resin of this embodiment, it is preferable to use the method shown below. First, in the solvent, the epoxy compound (a-2) having 2 or more epoxy groups and the compound (a-3) having 3 or more acid groups are reacted according to the required catalyst. Synthetic resin precursor (step 1). The use amount of the epoxy compound (a-2) having 2 or more epoxy groups and the compound (a-3) having 3 or more acid groups in the first step is to have 3 or more acid groups It is preferable that the number of moles of acid groups in the compound (a-3) is greater than the number of moles of epoxy groups in the epoxy compound (a-2). Specifically, the epoxy group of the epoxy compound (a-2) has a ratio of 60 to 5 moles relative to 100 moles of the acid group of the compound (a-3) having three or more acid groups. In order to make the reaction better, the reaction rate is better in the ratio of 50 to 10 moles.

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

Next, in the solvent, an unsaturated monomer (a-1) having only one functional group that reacts with an acid group is added to the resin precursor according to the need to use a polymerization inhibitor (step 2) . In the second step, the unsaturated monomer (a-1) is included in 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 used as the raw material of the resin. The functional group that reacts with the acid group has a ratio of 40 to 90 moles to make the reaction better, and a ratio of 40 to 60 moles to make the reaction better. In the polymerization method of the resin of this embodiment, in the second step, an unsaturated monomer (a-1) having only one functional group that reacts with an acid group and a compound (a-4) having an acid anhydride group may also be used ) Reacts with the resin precursor. In this case, the number of functional groups that the compound (a-4) reacts with the hydroxyl group becomes the epoxy compound (a-2) having 2 or more epoxy groups and the compound having 3 or more acid groups (a-3) The ratio of the hydroxyl group produced by the reaction is preferably 10 to 70%, and the reaction is preferably 20 to 60% of the hydroxyl group.

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

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

The solvent used for producing the resin of the present embodiment is not particularly limited, and a well-known type can be suitably used. Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol mono-n -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol mono (Poly)extrusion of methyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. Alkyl glycol monoalkyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. (Poly)alkylene glycol monoalkyl ether acetate; other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran Ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropane Methyl acid ester, 2-hydroxy-2-methyl propionic acid ethyl ester, 3-methoxy propionic acid methyl ester, 3-methoxy propionic acid ethyl ester, 3-ethoxy propionic acid methyl ester, 3-ethyl Ethyl oxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyric acid methyl ester, 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 acetate -Pentyl ester, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, pyruvate Ester, n-propyl pyruvate, methyl acetoacetate, ethyl acetate, ethyl 2-oxobutanoate, etc.; aromatic hydrocarbon compounds such as toluene and xylene; N-methyl Carboxyamide compounds such as pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. These solvent systems can be used alone or in combination of two or more.

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

The amount of solvent used to manufacture the resin of this embodiment is not particularly limited, The loading amount (unsaturated monomer (a-1), epoxy compound (a-2), compound (a-3) with 3 or more acid groups, and compound with acid anhydride group contained as needed (Total amount of (a-4)) When set to 100 parts by mass, generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass. If the use amount of the above-mentioned solvent is 1000 parts by mass or less, the viscosity of the resin can be controlled within an appropriate range, which is preferable. On the other hand, when the use amount of the above-mentioned solvent is 30 parts by mass or more, it is possible to prevent burn-in caused during the reaction and to stably perform the synthesis reaction, which is preferable. In addition, if the amount of the above-mentioned solvent is 30 parts by mass or more, the coloring or gelation of the resin can be prevented.

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

Examples of the catalyst used in this embodiment include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzyl ammonium chloride, and phosphorus compounds such as triphenylphosphine. , Chromium chelate compounds, etc. These catalyst systems can be used alone or in combination of two or more. The amount of 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 usually 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass, preferably 0.2 to 1 part by mass.

In the second step, in order to prevent gelation of the resin, it is preferable to use a polymerization inhibitor. The polymerization inhibitor used in the second step is not particularly limited, and can be appropriately selected according to the raw material of the resin or 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 two or more kinds may be used. The use amount of the polymerization inhibitor is not particularly limited, but if the amount of the resin precursor is 100 parts by mass, it is usually 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass.

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

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

As the solvent (B), the same solvent that can be used for producing the resin (A) can be used, and it is preferable to use a glycol ether-based solvent. That is, as the solvent (B), (poly)alkylene glycol monoalkyl such as (poly)alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc. is used Ether ether acetate is preferred. As the material of the photosensitive resin composition other than the solvent (B), when a solution containing a solvent component is used, the solvent component contained in the above solution may also be used as the solvent (B).

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

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

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

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

Examples of pigments include Cigigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, Yellow pigments of 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc.; Cigigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, Orange pigments such as 59, 61, 64, 65, 71, 73, etc.; CIPigment Red9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216 , 224, 242, 254, 255, 264, 265 and other red pigments; CIPigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; CIPigment violet 1, 19, 23, 29 , 32, 36, 38 and other violet color pigments; CIPigment Green 7, 36, 58 and other green pigments; CIPigment Brown 23, 25 and other brown pigments; aniline black, perylene black, titanium black, flower blue black, lignin Black and black pigments such as organic black, internal black, RGB black, carbon black, iron oxide, etc.

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

When the pigment (D) contains a pigment, the photosensitive resin composition system may contain a well-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 according to the type of pigment used.

As the dispersant, since the dispersion stability over time is excellent, it is preferable to use a polymer dispersant. The polymer dispersant system can be arbitrarily selected, and examples thereof include polyurethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, and polyoxyethylene diester-based dispersions. Agent, sorbitan aliphatic ester dispersant, aliphatic modified ester dispersant, etc. As the polymer dispersant, EFKA (registered trademark, manufactured by BASF JAPAN), Disperbyk (registered trademark, manufactured by BYK), DISPARLON (registered trademark, manufactured by Nanben Chemical Co., Ltd.), SOLSPERSE (registered trademark, Zeneca) can be used Types of products sold at commercial places.

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

By containing the reactive diluent (E), the photosensitive resin composition makes it easy to adjust the viscosity and sensitivity of the photosensitive resin composition. In addition, when a resin cured film containing a photosensitive resin composition containing a reactive diluent (E) is used as a black matrix, color filter, or black column spacer, the strength of the resin cured film becomes good. It is better. In addition, after the photosensitive resin composition containing the reactive diluent (E) is applied to the surface of the resin cured film to be formed and exposed, the adhesion between the resin cured film formed by development and the surface to be formed Because it is good, it is better.

As the monofunctional monomer (monomer having only one ethylenically unsaturated bond) used as the reactive diluent (E), for example, (meth)acrylamide, hydroxymethyl (meth)acrylamide Amine, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl ( Meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2- (meth)acrylic acid Hydroxyethyl, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acrylic Acetyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, (methyl ) 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, semi-(meth)acrylates of phthalic acid derivatives, etc. ) Acrylate compounds; aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyl toluene; carboxylic acid esters such as vinyl acetate and vinyl propionate; These monofunctional single systems may be used alone, or two or more types may be used.

Examples of the multifunctional monomer (monomer having a plurality of ethylenically unsaturated bonds) used as the reactive diluent (E) include ethylene glycol di(meth)acrylate and diethylene glycol di(meth)acrylate. Methacrylate, 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-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate Methacrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acrylonitrile Diethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropane (Meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl di(meth)acrylate Group) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (ie, toluene diisocyanate), trimethylhexamethylene di (Meth)acrylic acid such as the reactant of isocyanate and hexamethylene diisocyanate with 2-hydroxyethyl (meth)acrylate, tri(meth)acrylate such as (hydroxyethyl)isocyanurate Ester compounds; aromatic vinyl compounds such as divinylbenzene, diallyl phthalate, diallyl phenylphosphonate; dicarboxylic acid ester compounds such as divinyl adipate; trimerization Condensate of triallyl cyanate, methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, polyol and N-methylol (meth)acrylamide. These polyfunctional mono-systems can be used alone or two or more types can be used.

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

The photosensitive resin composition of this embodiment contains resin (A) 1-20% by mass, solvent (B) 50-94% by mass, photopolymerization initiator (C) 0.01-5% by mass, and a coloring agent (D ) 3 to 30% by mass is preferred. Moreover, when the photosensitive resin composition of this 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. If the content of the resin (A) is 1% by mass or more, it will become a photosensitive resin composition having good photocurability, which is preferable. On the other hand, if the content of the resin (A) is 20% by mass or less, it will become a photosensitive resin composition having good coatability, which is preferable.

The content of the solvent (B) is preferably 50 to 94% by mass relative to the entire photosensitive resin composition, and more preferably 60 to 90% by mass. When the content of the solvent (B) is 50% by mass or more, it will become a photosensitive resin composition having good coatability, which is preferable. On the other hand, if the content of the solvent (B) is 94% by mass or less, it is preferable to apply a photosensitive resin composition to obtain a coating film having a sufficient film thickness.

The content of the photopolymerization initiator (C) is preferably 0.01 to 5% by mass relative to the entire photosensitive resin composition, and more preferably 0.1 to 2% by mass. When the content of the photopolymerization initiator (C) is 0.01% by mass or more, the photocurability of the photosensitive resin composition becomes good, which is preferable. On the other hand, if the content of the photopolymerization initiator (C) is 5% by mass or less, it is preferable that the photosensitive resin composition is exposed and developed, and residues are not easily generated.

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. When the content of the colorant (D) is 3% by mass or more, the cured resin film of the photosensitive resin composition will have light-shielding properties, which is preferable. On the other hand, when the content of the colorant (D) is 30% by mass or less, it is preferable that residues are not easily generated after the photosensitive resin composition is exposed and developed.

When the photosensitive resin composition contains a reactive diluent (E), the content of the reactive diluent (E) is preferably 1 to 20% by mass, and more preferably 2 to 10% by mass. When the content of the reactive diluent (E) is 1% by mass or more, it becomes a photosensitive resin composition having good curability, which is preferable. On the other hand, when the content of the reactive diluent (E) is 20% by mass or less, after the photosensitive resin composition is exposed and developed, residues are not likely to be generated, which is preferable.

[Manufacturing method of photosensitive resin composition] Next, a method of manufacturing the photosensitive resin composition of this embodiment will be described. The photosensitive resin composition of this embodiment can use any well-known mixing device to combine any of the resin (A), solvent (B), photopolymerization initiator (C), and colorant (D) of this embodiment. ) And a method of mixing any one or more components of the reactive diluent (E), dispersant, and additives contained as required.

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

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

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

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

[Manufacturing method of resin cured film] The resin cured film of this embodiment can be produced by, for example, the following method. First, the photosensitive resin composition is applied to the surface of the cured resin film to form a resin layer (coating film). Next, the resin layer is exposed through a photomask of a specified pattern to harden the exposed portion. Next, the unexposed portion of the resin layer is developed with a developing solution, and a resin cured film having a prescribed pattern is produced. After that, post-baking (heat treatment) of the cured resin film is performed as necessary. For the exposure of the resin layer, a halftone mask of a specified pattern can also be used. In this case, the unexposed portion and the half-exposed portion are developed with a developing solution to produce a resin cured film having a prescribed pattern.

The method of applying the photosensitive resin composition is not particularly limited, and examples thereof include a screen printing method, a roll coating method, a curtain coating method, a spray coating method, and a spin coating method. After the photosensitive resin composition is applied, the solvent (B) contained in the resin layer can be volatilized by heating using a heating means such as a circulating oven, an infrared heater, a hot plate, etc. as needed . The heating conditions after coating 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 set at 50°C to 120°C, and the heating time can be set at 30 seconds to 30 minutes.

The method of exposing the resin layer is not particularly limited, and examples thereof include a method of irradiating active energy rays such as ultraviolet rays and excimer laser light. The amount of energy rays irradiated on the resin layer may be appropriately set according to the composition of the photosensitive resin composition. For example, the amount of energy ray irradiated on the resin layer may be 30 to 2000 mJ/cm ² , but it 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, a metal halogen lamp, etc. can be arbitrarily selected and used.

As the developer used for development, in order to obtain excellent developability, it is preferable to use an alkali developer. 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, and dimethylethanolamine; Methylammonium, 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 ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and Aqueous solutions of p-phenylenediamine compounds such as sulfates, hydrochlorides, and p-toluenesulfonates. The developer may also contain defoamers, surfactants, etc. as needed.

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

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

The material of the base material forming the surface of the cured resin film is not particularly limited, and examples thereof include glass, silicon, polycarbonate, polyester, polyamide, polyamide imide, and polyimide. , Aluminum, printed wiring boards, etc., wiring pattern substrates, array substrates, etc. are formed on the surface.

The method of manufacturing the image display device of this embodiment may be any step as long as it includes the step of forming the resin cured film of this embodiment formed by the above-described manufacturing method. It is manufactured according to conventional methods.

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

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

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

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

To the resin solution after the reaction, propylene glycol monomethyl ether acetate as a solvent (B) was added and mixed to prepare a prepared solution (solid content concentration 40 mass) containing the resin (A) and the solvent (B) %). In addition, the so-called solid content refers to the meaning of the heating residual component which heats a composition at 130 degreeC for 2 hours, and the solid content of the prepared solution has 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) Dissolve 0.7 g of butylhydroxytoluene as a polymerization inhibitor in 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 (and The functional group (epoxy group) reacted by an acid group was a mole number of 0.4 moles), and this was dropped into the flask of the synthesized resin precursor from a dropping funnel over 10 minutes. After the dropwise addition, the mixture was further stirred at 120°C for 2 hours, and 10 g of succinic anhydride as the compound (a-4) having an acid anhydride group was added (the number of functional groups that reacted with hydroxyl groups in (a-4) was (a-2) and (a-3) 25% of the amount of hydroxyl groups generated by the reaction), and stirred at 110°C for 30 minutes to synthesize the resin (A) of Example 2-1.

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

<Examples 3-1, 8-1, 9-1, 11-1, 12-1, 14-1> 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 having three or more acid groups (a-3 ), the compound (a-4) having an acid anhydride group, except that the materials shown in Table 1 or Table 2 are used in the amounts shown in Table 1 or Table 2, in the same manner as in Example 2-1, thereby The resins (A) of Examples 3-1, 8-1, 9-1, 11-1, 12-1, and 14-1 were synthesized. To the resin solution after the completion of the reaction, propylene glycol monomethyl ether acetate as a solvent (B) was added and mixed in the same manner as in Example 1-1, thereby preparing a resin (A) and a solvent ( B) The prepared solution (solid content concentration 40% by 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 having three or more acid groups (a-3 ), in addition to using the materials shown in Table 1 or Table 2 in the amount shown in Table 1 or Table 2, and according to the required amount shown in Table 1 (the value in parentheses is the molar number of the functional group ) Except for using adipic acid, the resin (A) of Examples 4-1 to 7-1, 10-1, and 13-1 was synthesized in the same manner as in Example 1-1. To the resin solution after the reaction, propylene glycol monomethyl ether acetate as a solvent (B) was added and mixed, and the resin (A) and the solvent were prepared in the same manner as in Example 1-1. The prepared solution of (B) (solid content concentration 40% by mass).

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

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

<Measurement method of acid value> According to JIS K6901 5.3.2, a mixed indicator of bromothymol blue and phenol red was used for the measurement. It means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of resin (A).

<Measurement method of equivalent of unsaturated group> The mass of the polymer per mole of polymerizable unsaturated bonds (g/mol) is a calculated value calculated based on the amount of monomer used.

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

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

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

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

<Comparative Example 2-1> The 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 3 or more acid groups. To the resin solution after the completion of the reaction, propylene glycol monomethyl ether acetate as a solvent (B) was added and mixed in the same manner as in Example 1-1, thereby preparing a resin (A) and a solvent ( B) The prepared solution (solid content concentration 40% by mass).

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

<Examples 1-2 to 15-2 and Comparative Examples 1-2 and 2-2> The resin (A), the solvent (B), the photopolymerization initiator (C), and the colorant shown in Table 3 and Table 4 were mixed so as to become the content (mass %) shown in Table 3 and Table 4. D), a reactive diluent (E) and an additive (F), thereby obtaining the photosensitive resin compositions of Examples 1-2 to 15-2 and Comparative Examples 1-2 and 2-2. In addition, 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 prepared solution containing the resin (A). The amounts of the solvent and the solvent contained in the prepared solution containing the resin (A) are combined and calculated in the solvent (B) shown in Table 3 and Table 4.

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

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

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

<Evaluation of film thickness reduction rate (developing margin)> Using the same method as the optical density, a coating film with a thickness of 2.5 μm is formed on the glass substrate, and the reduction rate of the coating film thickness from the development time of 100 seconds to 150 seconds is measured using a stylus step meter T4000M made by Kosaka Research Institute. . The greater the thickness reduction rate of the coating film, the better the development margin, and the better the developability.

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

"Benchmark" ◎: The difference in absorbance is less than 5%. ○: The difference in absorbance is 5% or more but less than 20%. △: The difference in absorbance is 20% or more and less than 30%. ×: The difference in absorbance is 30% or more.

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

<Evaluation of developing residue> The photosensitive resin compositions of Examples 1-2 to 15-2 and Comparative Examples 1-2 and 2-2 were spin-coated to 10 cm×10 cm so that the thickness of the coating film became 1.5 μm On an IZO substrate (a substrate with a wiring pattern composed of IZO formed on the surface). After that, by heating the IZO substrate at 90° C. for 3 minutes, the solvent was evaporated from the coating film. Next, place a pattern mask on the coating film, and use Multi-light ML-251D/B made by USHIO Electric Co., Ltd. and the irradiation optical unit PM25C-100 to expose from above the mask (exposure amount 50mJ/cm ² ) To make it light harden. Thereafter, development was carried out with a 0.2% by mass potassium hydroxide aqueous solution for 120 seconds, and the presence or absence of residue (developing residue) was visually confirmed.

"Evaluation Criteria" ◎: No residue at all. ○: Although there is a little residue, it will disappear when the development time is extended for 30 seconds. ×: Even if the development time is extended by 30 seconds, residues remain.

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

Claims (16)

A resin characterized by including: a constituent component derived from an unsaturated monomer (a-1) having only one functional group that reacts with an acid group, and an epoxy compound having two or more epoxy groups ( The constituent components of a-2) and the constituent components derived from the compound (a-3) having three or more acid groups; the aforementioned unsaturated monomer (a-1) having only one functional group that reacts with the acid group It is an epoxy group-containing (meth)acrylate or an isocyanate group-containing (meth)acrylate, and the acid group of the compound (a-3) having three or more acid groups is a carboxyl group. A resin characterized by comprising: a constituent component derived from an unsaturated monomer (a-1) having only one functional group reactive with an acid group, and derived from an epoxy compound having two or more epoxy groups ( a-2), the component derived from the compound (a-3) having three or more acid groups, and the component derived from the compound (a-4) having an acid anhydride group; the aforementioned has only one The unsaturated monomer (a-1) of the acid group-reactive functional group is an epoxy group-containing (meth)acrylate or an isocyanate-containing (meth)acrylate, The acid group of the compound (a-3) having three or more acid groups is a carboxyl group, and the compound (a-4) of the acid anhydride group is an anhydride having a ring structure. The resin according to claim 1 or claim 2, which has a first bonding portion and a second bonding portion, the first bonding portion is reacted with an acid group in the unsaturated monomer (a-1) The functional group and the acid group of the compound (a-3) having three or more acid groups are bonded, and the second bonding part is the epoxy group of the epoxy compound (a-2) , And the acid group possessed by the compound (a-3) having three or more acid groups is bonded. The resin according to claim 1 or claim 2, 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 , 3,4-epoxycyclohexyl, any of the groups represented by the following formula (2-1), the groups represented by the following formula (2-2); the following formula (2-1) and In the following formula (2-2), * represents the bonding site of X ₁ and R ₂ )

The resin according to claim 1 or claim 2, wherein the epoxy compound (a-2) is a compound represented by the following formula (2),

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

The resin according to claim 1 or claim 2, wherein the aforementioned epoxy compound (a-2) is selected from ethylene glycol diglycidyl ether, bisphenol stilbene diglycidyl ether, 3,3',5,5' -Tetramethyl-4,4'-bis(epoxypropyloxy)-1,1'-biphenyl, 1,6-bis(2,3-epoxypropane-1-yloxo)naphthalene Or more than one kind of epoxyhalopropane adduct of bis(4-hydroxyphenyl)methane and epoxyhalopropane adduct of 2,2-bis(4-hydroxyphenyl)propane. The resin according to claim 1 or claim 2, wherein the compound (a-3) having 3 or more acid groups is 1,2,4-cyclohexanetricarboxylic acid or 1,2,3,4- Butane tetracarboxylic acid. The resin according to claim 1 or claim 2, wherein, among the number of acid groups possessed by the compound (a-3) having 3 or more acid groups, the ring of the epoxy compound (a-2) The ratio of the number of acid groups bonded by oxygen groups is 5 to 60%. A resin characterized by an unsaturated monomer (a-1) having only one functional group reactive with an acid group, an epoxy compound (a-2) having 2 or more epoxy groups, and 3 The above acid group compound (a-3) is obtained by polymerization; the unsaturated monomer (a-1) having only one functional group that reacts with the acid group is an epoxy group-containing (meth)acrylate Or (meth)acrylates containing isocyanate groups, The acid group of the compound (a-3) having three or more acid groups is a carboxyl group. A resin characterized by an unsaturated monomer (a-1) having only one functional group that reacts with an acid group, an epoxy compound (a-2) having two or more epoxy groups, and three The above acid group compound (a-3) and acid anhydride group compound (a-4) are obtained by polymerization; the aforementioned unsaturated monomer (a-1) having only one functional group that reacts with the acid group is The epoxy group-containing (meth)acrylate or isocyanate group-containing (meth)acrylate, the acid group of the compound (a-3) having 3 or more acid groups is a carboxyl group, and the aforementioned has The acid anhydride group compound (a-4) is an anhydride having a ring structure. The resin according to claim 9 or claim 10, wherein the aforementioned epoxy compound (a-2) is selected from ethylene glycol diglycidyl ether, bisphenol stilbene diglycidyl ether, 3,3',5,5' -Tetramethyl-4,4'-bis(epoxypropyloxy)-1,1'-biphenyl, 1,6-bis(2,3-epoxypropane-1-yloxo)naphthalene Or more than one kind of epoxyhalopropane adduct of bis(4-hydroxyphenyl)methane and epoxyhalopropane adduct of 2,2-bis(4-hydroxyphenyl)propane. A photosensitive resin composition characterized by containing: For example, the resin (A), solvent (B), photopolymerization initiator (C) and coloring agent (D) of claim 1 or claim 2. The photosensitive resin composition according to claim 12, which contains: 1 to 20% by mass of the resin (A), 50 to 94% by mass of the solvent (B), and 0.01 to 5% by mass of the photopolymerization initiator (C) % And the aforementioned coloring agent (D) 3 to 30% by mass. The photosensitive resin composition according to claim 13, which further contains 1 to 20% by mass of the reactive diluent (E). A resin cured film of the photosensitive resin composition according to claim 12. An image display device characterized by having a resin cured film as in claim 15.