JP2021031625A - Thiol resin and photosensitive resin composition comprising thiol resin - Google Patents

Abstract

To provide a thiol resin (A) capable of achieving developability, dispersibility of a colorant, solvent resistance of a cured film, and a high elastic recovery rate, and a photosensitive resin composition.SOLUTION: The thiol resin (A) contains a mercapto group and a carboxy group and is obtained by adding a polybasic acid anhydride (a-3) to an addition reaction product (M) of a polyfunctional thiol compound (a-1) including at least three mercapto groups and a polyfunctional compound (a-2) having at least two reactive groups (RG) having reactivity with a mercapto group. The addition reaction product (M) is an addition reaction product of the mercapto group of the polyfunctional thiol compound (a-1) and the reactive group (RG) of the polyfunctional compound (a-2). The ratio of the total molar number of the reaction groups (RG) in the compound (a-2) with respect to the total molar number of the mercapto groups in the compound (a-1) is 0.20 to 0.60.SELECTED DRAWING: None

Description

The present invention relates to a thiol resin and a photosensitive resin composition containing a thiol resin.

Conventionally, in a liquid crystal display panel, a spacer is used in order to keep the distance (cell gap) between two substrates constant.
In Patent Document 1, as a material capable of forming a spacer by photolithography, a 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. A resin characterized by containing a constituent component derived from (a-2) and a constituent component derived from a compound (a-3) having three or more acid groups is disclosed.

International Publication No. 2019/073806

In recent years, in liquid crystal display elements and each member (black matrix, color filter, spacer, black column spacer, flattening film, interlayer insulating film, etc.) forming the liquid crystal display element, better developability and colorant dispersibility have been achieved. Further improvement of various properties such as solvent resistance of the cured film and high elastic recovery rate is required.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a thiol resin capable of realizing developability, colorant dispersibility, solvent resistance of a cured film, and high elastic recovery rate. And.
Further, the present invention provides a photosensitive resin composition capable of obtaining a cured film having solvent resistance and a high elastic recovery rate, a resin cured film obtained by curing the photosensitive resin composition, and an image display device including the same. The purpose is to do.

（式（１）中、Ｒは、水素原子、置換基を有していてもよい合計炭素数１〜１０の炭化水素基、または−Ｘ^４−Ｙ^４−Ｚ^４−（ＣＲ^９Ｒ^１０）−ＳＨを表す。Ｘ^４およびＺ^４は、それぞれ独立に、置換基を有していてもよい２価の合計炭素数１〜１０の脂肪族炭化水素基を表し、Ｙ^４は、−ＣＨ_２−、−ＯＣ（Ｏ）−、−Ｃ（Ｏ）Ｏ−、−ＮＨＣ（Ｏ）−、−Ｃ（Ｏ）ＮＨ−、−ＳＣ（Ｏ）−及び−Ｃ（Ｏ）Ｓ−から選択される２価の基を表す。Ｒ^９およびＲ^１０は、それぞれ独立して水素原子または炭素原子数１〜１０のアルキル基である。
式（１）及び式（２）中、Ｘ^１、Ｘ^２、Ｘ^３、Ｚ^１、Ｚ^２およびＺ^３は、それぞれ独立に、置換基を有していてもよい２価の合計炭素数１〜１０の脂肪族炭化水素基を表し、Ｙ^１、Ｙ^２、及びＹ^３は、−ＣＨ_２−、−ＯＣ（Ｏ）−、−Ｃ（Ｏ）Ｏ−、−ＮＨＣ（Ｏ）−、−Ｃ（Ｏ）ＮＨ−、−ＳＣ（Ｏ）−及び−Ｃ（Ｏ）Ｓ−から選択される２価の基を表す。Ｒ^３〜Ｒ^８は、それぞれ独立して水素原子または炭素原子数１〜１０のアルキル基である。）
［９］ 前記多官能チオール化合物（ａ−１）が式（１）及び（２）からなる群から選択される少なくとも１種の化合物である、［１］〜［８］のいずれかに記載のチオール樹脂。

［１０］ 前記多官能化合物（ａ−２）が下記式（２）で表される化合物である、［１］〜［９］のいずれかに記載のチオール樹脂。

（式（５）中、Ａは、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｓｉ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、９,９−フルオレニリデン、または単結合を示す。Ｂは、フェニレン基または置換基を有するフェニレン基を示し、前記置換基は、炭素数１〜５のアルキル基、ハロゲン原子またはフェニル基から選ばれるいずれかを示す。Ｘ_２はエポキシ基、３，４−エポキシシクロヘキシル基、下記式（５−１）で表される基、下記式（５−２）で示される基から選ばれるいずれかを示す。下記式（５−１）および下記式（５−２）中、＊はＤと式（５）中のメチレン基との結合部位を示す。）

［１１］ 前記多官能化合物（ａ−２）が２個のイソシアナト基を有する化合物である、［１］〜［９］のいずれかに記載のチオール樹脂。
［１２］ ［１］〜［１１］のいずれかに記載のチオール樹脂（「チオール樹脂（Ａ）」という）と、
エチレン性不飽和基含有化合物（Ｂ）と、
溶剤（Ｃ）と、
光重合開始剤（Ｄ）と、
を含有することを特徴とする感光性樹脂組成物。
［１３］ 更に着色剤（Ｅ）を含有する［１２］に記載の感光性樹脂組成物。
［１４］ 前記チオール樹脂（Ａ）を１〜２０質量％含有し、
前記エチレン性不飽和基含有化合物（Ｂ）を１〜２０質量％含有し、
前記溶剤（Ｃ）を５０〜９４質量％含有し、
前記光重合開始剤（Ｄ）を０．０１〜５質量％含有し、
前記着色剤（Ｅ）を３〜３０質量％含有する［１２］に記載の感光性樹脂組成物。
［１５］ ［１２］〜［１４］のいずれか１項に記載の感光性樹脂組成物を硬化させてなる樹脂硬化膜。
［１６］ ［１５］に記載の樹脂硬化膜を備える画像表示装置。 The present invention includes the following aspects.
[1] A thiol resin containing a mercapto group and a carboxy group.
The thiol resin is obtained by adding a polybasic acid anhydride (a-3) to an addition reaction product (M) of a polyfunctional thiol compound (a-1) and a polyfunctional compound (a-2). ,
The polyfunctional thiol compound (a-1) has three or more mercapto groups and has three or more mercapto groups.
The polyfunctional compound (a-2) has two or more reactive groups (RG) that are reactive with the mercapto group.
The addition reaction product (M) is an addition reaction product of the mercapto group of the polyfunctional thiol compound (a-1) and the reactive group (RG) of the polyfunctional compound (a-2).
The ratio of the total number of moles of the reactive group (RG) of the compound (a-2) to the total number of moles of the mercapto group of the compound (a-1) is 0.20 to 0.60.
A thiol resin characterized by that.
[2] The thiol resin according to [1], wherein the reactive group (RG) of the polyfunctional compound (a-2) is at least one selected from the group consisting of an epoxy group and an isocyanato group.
[3] The total number of binding portions of the addition reaction product (M) due to the addition reaction between the mercapto group of the polyfunctional thiol compound (a-1) and the reactive group (RG) of the polyfunctional compound (a-2). The thiol according to [1] or [2], wherein the ratio of the total number of moles of the acid anhydride group of the polybasic acid anhydride (a-3) to the number of moles is 0.3 to 0.7. resin.
[4] The thiol resin according to any one of [1] to [3], wherein the mercapto group equivalent is 200 to 2000 g / mol.
[5] The thiol resin according to any one of [1] to [4], which has an acid value of 10 to 100 mgKOH / g.
[6] The thiol resin according to any one of [1] to [5], which has a mass average molecular weight of 3000 to 20000.
[7] The thiol resin according to [1] to [6], which has an average of 3 or more mercapto groups per molecule.
[8] The thiol resin according to any one of [1] to [7], wherein the polyfunctional thiol compound (a-1) is a compound represented by the following general formula (1) or (2).

(In the formula (1), R represents a hydrogen atom, the sum may have a substituent hydrocarbon group having 1 to 10 carbon atoms or ^{-X 4 -Y 4 -Z 4, -} (CR 9 R 10) -SH is represented. X ⁴ and Z ⁴ each independently represent a divalent aliphatic hydrocarbon group having a total carbon number of 1 to 10 which may have a substituent, and Y ⁴ is -CH _2. -, -OC (O)-, -C (O) O-, -NHC (O)-, -C (O) NH-, -SC (O)-and -C (O) S- Representing a divalent group. R ⁹ and R ¹⁰ are independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms.
In formulas (1) and (2), X ¹ , X ² , X ³ , Z ¹ , Z ² and Z ³ each independently have a divalent total carbon number of 1 which may have a substituent. Representing 10 to 10 aliphatic hydrocarbon groups, Y ¹ , Y ² and Y ³ are -CH _2- , -OC (O)-, -C (O) O-, -NHC (O)-,-. Represents a divalent group selected from C (O) NH-, -SC (O)- and -C (O) S-. R ^{3 to} R ⁸ are independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms. )
[9] The above-described in any of [1] to [8], wherein the polyfunctional thiol compound (a-1) is at least one compound selected from the group consisting of the formulas (1) and (2). Thiol resin.

[10] The thiol resin according to any one of [1] to [9], wherein the polyfunctional compound (a-2) is a compound represented by the following formula (2).

(In the formula (5), 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. Indicates any of the groups selected. X ₂ is selected from an epoxy group, a 3,4-epoxycyclohexyl group, a group represented by the following formula (5-1), and a group represented by the following formula (5-2). In the following formula (5-1) and the following formula (5-2), * indicates the bonding site between D and the methylene group in the formula (5).)

[11] The thiol resin according to any one of [1] to [9], wherein the polyfunctional compound (a-2) is a compound having two isocyanato groups.
[12] The thiol resin according to any one of [1] to [11] (referred to as "thiol resin (A)") and
Ethylene unsaturated group-containing compound (B) and
Solvent (C) and
Photopolymerization initiator (D) and
A photosensitive resin composition comprising.
[13] The photosensitive resin composition according to [12], which further contains a colorant (E).
[14] The thiol resin (A) is contained in an amount of 1 to 20% by mass.
The ethylenically unsaturated group-containing compound (B) is contained in an amount of 1 to 20% by mass.
The solvent (C) is contained in an amount of 50 to 94% by mass, and the solvent (C) is contained in an amount of 50 to 94% by mass.
The photopolymerization initiator (D) is contained in an amount of 0.01 to 5% by mass.
The photosensitive resin composition according to [12], which contains the colorant (E) in an amount of 3 to 30% by mass.
[15] A resin cured film obtained by curing the photosensitive resin composition according to any one of [12] to [14].
[16] An image display device including the resin cured film according to [15].

According to the present invention, it is possible to provide a thiol resin (hereinafter referred to as "thiol resin (A)") capable of realizing developability, colorant dispersibility, solvent resistance of a cured film, and high elastic recovery rate. Further, it is possible to provide a photosensitive resin composition capable of obtaining a cured film having solvent resistance and a high elastic recovery rate, a resin cured film obtained by curing the photosensitive resin composition, and an image display device including the same. ..

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments shown below.

[Thiol resin (A)]
The thiol resin (A) of the present embodiment contains a mercapto group and a carboxy group. In the thiol resin (A), a polybasic acid anhydride (a-3) is added to an addition reaction product (M) of the polyfunctional thiol compound (a-1) and the polyfunctional compound (a-2). It is a resin made of thiol. The polyfunctional thiol compound (a-1) has three or more mercapto groups. The polyfunctional compound (a-2) has two or more reactive groups (RG) that are reactive with the mercapto group. The addition reaction product (M) is an addition reaction product of the mercapto group of the polyfunctional thiol compound (a-1) and the reactive group (RG) of the polyfunctional compound (a-2). The ratio of the total number of moles of the reactive group (RG) of the compound (a-2) to the total number of moles of the mercapto group of the compound (a-1) is 0.20 to 0.60.
The thiol resin (A) of the present embodiment preferably contains 3 or more mercapto groups, more preferably 8 or more, and further preferably 10 or more in one molecule.
The thiol resin (A) of the present embodiment has a complicated structure in which the polyfunctional thiol compound (a-1) having three or more mercapto groups is three-dimensionally added to the polyfunctional compound (a-2). And the molecule contains unreacted mercapto groups at random. Therefore, it is impossible and impractical to limit the thiol resin (A) only by its structure.

The ratio of the total number of moles of the reactive group (RG) of the compound (a-2) to the total number of moles of the mercapto group of the compound (a-1) is 0.20 to 0.60. The thiol resin (A) contains an unreacted mercapto group derived from the polyfunctional thiol compound (a-1) and substantially does not contain the reactive group (RG) derived from the compound (a-2). By using such a thiol resin (A) in combination with an ethylenically unsaturated group-containing compound as a photosensitive resin composition, excellent photosensitivity due to the chain transfer action of the mercapto group can be imparted. Further, by advancing the Michael addition reaction and the thiol-ene reaction with the ethylenically unsaturated group-containing compound (B) and incorporating the thiol resin (A) into the cured product, excellent solvent resistance and elastic recovery rate are imparted. can do.

Further, the acid anhydride of the polybasic acid anhydride (a-3) is relative to the addition reaction product (M) of the polyfunctional thiol compound (a-1) and the polyfunctional compound (a-2). Since the group is added, the thiol resin (A) has a carboxy group introduced into the thiol resin (A). As a result, the photosensitive resin composition using the thiol resin (A) has excellent developability.
For example, when the reactive group (RG) of the polyfunctional compound (a-2) is an epoxy group, the addition of the polyfunctional thiol compound (a-1) opens the epoxy group to generate a hydroxy group. .. Therefore, the acid anhydride group of the polybasic acid anhydride (a-3) is an unreacted mercapto group derived from the polyfunctional thiol compound (a-1) or an epoxy derived from the polyfunctional compound (a-2). The group is added to the hydroxy group formed by opening the ring.
Similarly, when the reactive group (RG) of the polyfunctional compound (a-2) is an isocyanato group, the addition of the polyfunctional thiol compound (a-1) produces a thiourethane bond. Therefore, the acid anhydride group of the polybasic acid anhydride (a-3) is added to the unreacted mercapto group derived from the polyfunctional thiol compound (a-1) or the nitrogen atom of the thiourethane bond.

<Polyfunctional thiol compound (a-1)>
The polyfunctional thiol compound (a-1) is a compound having three or more mercapto groups. The number of mercapto groups in the polyfunctional thiol compound (a-1) is preferably 3 to 10, more preferably 3 to 6. When the number of mercapto groups is 3 or more, the compound (a-2) is three-dimensionally crosslinked with the reactive group (RG) by an addition reaction, and is not reacted in the product thiol resin (A). It is possible to leave the mercapto group.

As the mercapto group-containing group, the group represented by the following general formula (6) is preferable.

In the above general formula (6), R ¹¹ and R ¹² are independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, respectively. The alkyl group having 1 to 10 carbon atoms represented by R ¹¹ and R ¹² is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. From the viewpoint of controlling the reaction rate when synthesizing the thiol resin (A) and from the viewpoint of storage stability as a photosensitive resin composition, ^{at least one of R 11} and R ¹² is preferably an alkyl group. ..

The alkyl group having 1 to 10 carbon atoms represented by R ¹¹ and R ¹² may be linear or branched, and may be, for example, a methyl group, an ethyl group, an n-propyl group or an iso-propyl group. , N-butyl group, iso-butyl group, tert-butyl group, n-hexyl group, n-octyl group and the like. Of these, a methyl group or an ethyl group is preferable.
m is an integer of 0 to 2, preferably 0 or 1.

As the polyfunctional thiol compound (a-1), a compound having a carboxylic acid derivative structure represented by the following general formula (7) is more preferable.

The polyfunctional thiol compound (a-1) is more preferably an ester of a mercapto group-containing carboxylic acid represented by the following general formula (8) and alcohols having a trivalent or higher valence.

^{The definitions of R 11} , R ¹² and m in the general formula (7) and the general formula (8) are the same as these definitions in the general formula (6).

The trihydric or higher alcohols are not particularly limited as long as they are polyfunctional alcohols having three or more hydroxy groups. By using a polyfunctional alcohol, the compound after the esterification reaction can be made into a branched polyfunctional thiol compound.
Examples of the polyfunctional alcohol include trimethylolpropane, pentaerythritol, dipentaerythritol, 1,3,5-triazine-1,3,5 (2H, 4H, 6H) -tris (ethanol) and the like. Of these, trimethylolpropane, pentaerythritol, and 1,3,5-triazine-1,3,5 (2H, 4H, 6H) -tris (ethanol) are preferable from the viewpoint of reactivity for obtaining the thiol resin (A). ..

Examples of the mercapto group-containing carboxylic acid in the general formula (8) include 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, 2-mercaptoisobutyric acid, and 3-mercapto-3-phenylpropionic acid. , 3-Mercaptobutyric acid, 2-Mercaptoisobutyric acid, 3-Mercaptoisobutyric acid, 2-Mercapto-3-methylbutyric acid, 3-Mercapto-3-methylbutyric acid, 3-Mercaptovaleric acid, 3-Mercapto-4-methylyoshi Examples include herric acid.

Examples of the compound having three or more mercapto group-containing groups represented by the above general formula (6) include trimethylpropanthris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), and dipentaerythritol. Hexakis (3-mercaptobutyrate), trimetylolpropanthris (3-mercaptopropionate), trimetylolpropanthris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), dipenta Ellisritol Hexakis (2-mercaptopropionate), Trimethylolpropanthris (3-mercaptoisobutyrate), Trimethylolpropanthris (2-mercaptoisobutyrate), Trimethylolpropanthris (4-mercaptovalerate), Trimethylolpropanthris (3-mercaptovalerate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione And so on.

Among these, from the viewpoint of viscosity and reactivity, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), 1, At least one selected from the group consisting of 3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred.

The polyfunctional thiol compound (a-1) may be, for example, a compound represented by the following general formula (1) or (2).

In the formula (1), R represents a hydrogen atom, the sum may have a substituent hydrocarbon group having 1 to 10 carbon atoms or ^{-X 4 -Y 4 -Z 4, -} (CR 9 R 10) - Represents SH. X ⁴ and Z ⁴ each independently represent a hydrocarbon group having a total divalent aliphatic carbon number of 1 to 10 which may have a substituent, and Y ⁴ is -CH _2- , -OC (. A divalent group selected from O)-, -C (O) O-, -NHC (O)-, -C (O) NH-, -SC (O)-and -C (O) S- Represent. R ⁹ and R ¹⁰ are independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms. The ^{divalent aliphatic hydrocarbon group represented by X 4} and Z ⁴ having a total carbon number of 1 to 10 is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 2 carbon atoms. ..
In formulas (1) and (2), X ¹ , X ² , X ³ , Z ¹ , Z ² and Z ³ each independently have a divalent total carbon number of 1 which may have a substituent. Representing 10 to 10 aliphatic hydrocarbon groups, Y ¹ , Y ² and Y ³ are -CH _2- , -OC (O)-, -C (O) O-, -NHC (O)-,-. Represents a divalent group selected from C (O) NH-, -SC (O)- and -C (O) S-. The divalent aliphatic hydrocarbon group having a total carbon number of 1 to 10 represented by ^{X 1} , X ² , X ³ , Z ¹ , Z ² and Z ^{3 is preferably an alkylene group having 1 to 6 carbon atoms, and more.} It is preferably an alkylene group having 1 to 2 carbon atoms.
R ^{3 to} R ⁸ are independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms represented by R ¹ and R ² is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. From the viewpoint of controlling the reaction rate when synthesizing the thiol resin (A) and from the viewpoint of storage stability as a photosensitive resin composition, ^{at least one of R 3} and R ⁴ is an alkyl group, and R ⁵ And R ⁶ are preferably alkyl groups and at least one of R ⁷ and R ^{8 is preferably an alkyl group.}

Specific examples of the polyfunctional thiol compound (a-1) include compounds represented by the following formulas (3) and (4).

<Polyfunctional compound (a-2)>
The polyfunctional compound (a-2) is not particularly limited as long as it is a compound having two or more reactive groups (RG) reactive with the mercapto group. Examples of the reactive group (RG) having reactivity with the mercapto group include an epoxy group, an isocyanato group, an aldehyde group, an acetal group, a ketone group and the like. Of these, an epoxy group and an isocyanato group are preferable from the viewpoint of easiness of reaction for obtaining a thiol resin.

Specific examples of the compound having two or more epoxy groups include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, and diethylene glycol diglycidyl. Ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, resordinol diglycidyl ether, diglycidyl terephthalate, di Examples thereof include glycidyl orthophthalate, bisphenol full orange glycidyl ether, and compounds in which epihalohydrin such as epichlorohydrin is added to the following compounds.

Examples of the compound that forms a compound having two or more epoxy groups by adding epihalohydrin include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, and bis (4-hydroxyphenyl) ketone. 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-hydroxy-3,5-dichlorophenyl) 4-Hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethyl Sulfone, 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-3-3) 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-3-3) 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 and the like can be mentioned.

Among the above compounds, epoxy compounds having two or more epoxy groups include ethylene glycol diglycidyl ether, bisphenol full orange glycidyl ether, 3,3', 5,5'-tetramethyl-4,4'-bis. It is preferable to use one or two selected from (glycidyloxy) -1,1'-biphenyl and 1,6-bis (2,3-epoxypropane-1-yloxy) naphthalene.

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

The epoxy compound having two or more epoxy groups is more preferably a compound represented by the following formula (5).

(In the formula (5), 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. Indicates any of the groups selected. X ₂ is selected from an epoxy group, a 3,4-epoxycyclohexyl group, a group represented by the following formula (5-1), and a group represented by the following formula (5-2). In the following formula (5-1) and the following formula (5-2), * indicates the bonding site between D and the methylene group in the formula (5).)

In formula (5), A is preferably -CO-, -CH _2- , -C (CH ₃ ) _2- , -O-, or a single bond, and more preferably -CH _2- , -C. (CH ₃ ) _2- .
In formula (5), B is preferably a phenylene group.
In formula (5), D is preferably an epoxy group.

Specific examples of the compound having two or more epoxy groups include a compound represented by the following formula (9).

Examples of the compound having two or more isocyanato groups include low molecular weight polyisocyanates such as aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, and aromatic polyisocyanates, prepolymers, isocyanurates, and triones. , And derivatives and modified products of these polyisocyanates.

Examples of the aliphatic polyisocyanate include diisocyanates (for example, trimethylene diisocyanate, 1,2-propylene diisocyanate, tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylylene diisocyanate, hexamethylene diisocyanate). , Pentamethylene diisocyanate, C2-16 alcandiisocyanate such as 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.), Polyisocyanate (eg, lysine ester) Triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2 , 5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, etc. C6-20 alcantriisocyanate, etc.) and the like.

Examples of the alicyclic polyisocyanate include diisocyanates (for example, 1,3-cyclopentanediisocyanate, 1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (for example, 1,3-cyclopentanediisocyanate). Common name: isophorone diisocyanate), 4,4'-methylenebis (cyclohexylisocyanate), methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) ) Cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, norbornandiisocyanate, etc.), polyisocyanate (for example, 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2- (3-Isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl)- Bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2.5-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-Isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanato) Propyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) -heptane, 6- (2-Isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) triisocyanate such as heptane) can be mentioned.

As the aromatic aliphatic polyisocyanate, diisocyanate (for example, 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω, ω'-diisocyanato-1,4-diethylbenzene, 1,3- or 1,4- Bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof, etc.), polyisocyanate (for example, triisocyanate such as 1,3,5-triisocyanatomethylbenzene, etc.) Can be mentioned.
Examples of the aromatic polyisocyanate include diisocyanates (for example, m-phenylenediocyanate, p-phenylenediocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalenediocyanate, 2,4'-or 4,4'-diphenylmethane diisocyanate or The mixture, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, etc.), polyisocyanate (for example, triphenylmethane-4,4' , 4''-Triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanate toluene and other triisocyanates, such as 4,4'-diphenylmethane-2,2', 5,5' − Tetraisocyanate such as tetraisocyanate).
Examples of the polyisocyanate derivative include 2,4,6- obtained by reacting the dimer, trimer (isocyanurate ring-containing polyisocyanate), biuret, allophanate, carbon dioxide gas of the polyisocyanate with the polyisocyanate monomer. Examples thereof include polyisocyanate having an oxadiazine trione ring, carbodiimide, uretdione, polymethylene polyphenyl polyisocyanate (crude MDI, polypeptide MDI) and crude TDI.

Examples of the modified polyisocyanate include the polyisocyanate or a derivative of the polyisocyanate and a low molecular weight polyol or a low molecular weight polyamine described later, and the isocyanato group of the polyisocyanate is a hydroxyl group or a low molecular weight polyamine of the low molecular weight polyol. Examples thereof include a polyol-modified product and a polyamine-modified product obtained by reacting with an equivalent ratio that is excessive to that of the amino group.

As the compound having two or more isocyanato groups, a compound having two or three isocyanato groups is preferable, and a compound having two isocyanato groups is more preferable, because the thiol resin (A) can be easily synthesized. Particularly preferable specific examples include diphenylmethane diisocyanate and hexamethylene diisocyanate because of their price and availability.

<Polybasic acid anhydride (a-3)>
Examples of the polybasic acid anhydride (a-3) include maleic anhydride, itaconic anhydride, citraconic anhydride, succinic anhydride and the like. Of these, succinic anhydride is preferable from the viewpoint of reactivity for obtaining the thiol resin (A). By adding the polybasic acid anhydride (a-3) to the addition reaction product (M) of the polyfunctional thiol compound (a-1) and the polyfunctional compound (a-2), the polyfunctional acid anhydride (a-3) is added to the thiol resin (A). A carboxy group can be introduced to impart developability to an alkaline aqueous solution.

In the thiol resin (A) of the present embodiment, the total number of moles of the reactive group (RG) derived from the compound (a-2) is relative to the total number of moles of the mercapto group derived from the polyfunctional thiol compound (a-1). The ratio of is 0.25 to 0.60, preferably 0.25 to 0.50, and more preferably 0.30 to 0.45. When the ratio of the total number of moles of the reactive groups (RG) is 0.20 or more, the thiol resin (A) having a desired molecular weight and mercapto group equivalent can be obtained. When the ratio of the total number of moles of the reactive group (RG) is 0.60 or less, the total number of moles of the mercapto group derived from the polyfunctional thiol compound (a-1) becomes sufficiently excessive, and the unreacted reactive group (unreacted reactive group (RG)) RG) does not remain substantially.

The total number of moles of the binding portion of the addition reaction product (M) due to the addition reaction between the mercapto group of the polyfunctional thiol compound (a-1) and the reactive group (RG) of the polyfunctional compound (a-2). On the other hand, the ratio of the total number of moles of the acid anhydride groups of the polybasic acid anhydride (a-3) is preferably 0.3 to 0.7, more preferably 0.4 to 0.6. When the ratio of the total number of moles of the acid anhydride groups of the polybasic acid anhydride (a-3) is 0.3 or more, a sufficient amount of carboxy groups are introduced into the thiol resin (A), and the photosensitive resin Good developability can be obtained when used as a composition. When the ratio of the total number of moles of the acid anhydride group of the polybasic acid anhydride (a-3) is 0.7 or less, the increase in molecular weight due to the side reaction can be suppressed, which is preferable.

Specific examples of the polybasic acid anhydride (a-3) include a compound represented by the following formula (10).

[Evaluation of thiol resin (A)]
<Mass average molecular weight>
The mass average molecular weight of the thiol resin (A) of the present embodiment is preferably 3000 to 20000, more preferably 4000 to 15000, and even more preferably 4500 to 12000. When the mass average molecular weight is 3000 or more, the developability of the photosensitive resin composition is good, and the solvent resistance of the cured resin film is improved. When the mass average molecular weight is 20000 or less, the storage stability and developability of the photosensitive resin composition are good. The mass average molecular weight is a value 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 KK)
Column temperature: 40 ° C
Sample: 0.2% tetrahydrofuran solution of thiol resin (A) Developing solvent: tetrahydrofuran Detector: Differential refractometer (SHODEX (registered trademark) RI-71S) (manufactured by Showa Denko KK)
Flow velocity: 1 mL / min

<Mercapt group equivalent>
The mercapto group equivalent of the thiol resin (A) of the present embodiment is preferably 200 to 2000 g / mol, more preferably 300 to 1500 g / mol, and even more preferably 400 to 1000 g / mol. When the mercapto group equivalent is 200 g / mol or more, the molecular weight of the thiol resin (A) becomes sufficiently large, and the sensitivity of the photosensitive resin composition and the solvent resistance of the cured resin film are improved. When the mercapto group equivalent is 2000 or less, the sensitivity of the photosensitive resin composition and the solvent resistance of the cured resin film are improved. The mercapto group equivalent is the mass of the thiol resin (A) per mole of the mercapto group, and is measured by the iodine titration method. Specifically, 0.2 g of the thiol resin (A) is dissolved in 20 ml of chloroform, 10 ml of isopropanol, 20 ml of water, and 1 ml of a starch indicator are added, and then titrated with an iodine solution for measurement.
By using the thiol resin (A) having the mass average molecular weight and the mercapto group equivalent in the above range, it can be estimated that the thiol resin (A) has 3 to 20 mercapto groups per molecule. For example, the average number of mercapto groups per molecule of the thiol resin (A) is preferably 3 or more, more preferably 5 to 30, and even more preferably 8 to 20.

<Average number of mercapto groups per molecule of thiol resin (A)>
Since it is equal to the number of moles of mercapto groups per 1 mol of molecule, the value is obtained by dividing the mass average molecular weight by the mercapto group equivalent.

<Acid value>
The acid value of the thiol resin (A) of the present embodiment is preferably 10 to 100 mgKOH / g, more preferably 20 to 80 mgKOH / g, and even more preferably 30 to 70 mgKOH / g. When the acid value is 10 mgKOH / g or more, the thiol resin (A) contains a sufficient amount of carboxy groups, so that the developability of the photosensitive resin composition is improved. When the acid value is 100 mgKOH / g or less, the sensitivity does not decrease due to pattern scraping during development. The acid value means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the thiol resin (A), and bromothymol blue and phenol according to JIS K6901 5.3.2. It is a value measured using a red mixed indicator.

[Manufacturing method of thiol resin (A)]
Next, a method for producing the thiol resin (A) of the present embodiment will be described.
The thiol resin (A) of the present embodiment comprises the polyfunctional thiol compound (a-1), the compound (a-2), and the polybasic acid anhydride (a-3) by any method. It can be produced by reacting.

As the method for producing the thiol resin (A) of the present embodiment, it is preferable to use the method shown below.
First, a thiol resin (A) precursor is synthesized by subjecting the polyfunctional thiol compound (a-1) and the compound (a-2) to a double addition reaction in a solvent, if necessary, using a catalyst (first). Process). The amount of the polyfunctional thiol compound (a-1) and the compound (a-2) used in the first step is the reaction in which the total number of moles of the mercapto groups of the polyfunctional thiol compound (a-1) is the compound (a-2). It is preferable that the number of groups (RG) is larger than the total number of moles. Specifically, the ratio of the total number of moles of the reactive group (RG) of the compound (a-2) to the total number of moles of the mercapto group is preferably 0.20 to 0.60, preferably 0.30. More preferably, it is ~ 0.45.

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

Next, the polybasic acid anhydride (a-3) is subjected to an addition reaction to the thiol resin (A) precursor using a polymerization inhibitor in a solvent as needed (second step). In the second step, the binding portion of the addition reaction product (M) due to the addition reaction between the mercapto group of the polyfunctional thiol compound (a-1) and the reactive group (RG) of the polyfunctional compound (a-2). The ratio of the total number of moles of the acid anhydride group of the polybasic acid anhydride (a-3) to the total number of moles of the polybasic acid anhydride (a-3) is preferably 0.3 to 0.7, more preferably 0.4 to 0.6. ..

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, the second step may be continuously performed after the first step without removing the solvent remaining in the reaction system after the first step is completed.

The solvent used for producing the thiol resin (A) of the present embodiment is not particularly limited, and known solvents can be appropriately used. Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, and dipropylene. (Poly) alkylene glycol monoalkyl ethers such as glycol monoethyl ether and tripropylene glycol monomethyl ether; (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and propylene glycol monomethyl ether acetate. 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, 2-hydroxypropionic acid Ethyl, methyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyric acid Methyl, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-acetate Amil, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate, etc. Ester compounds; aromatic hydrocarbon compounds such as toluene and xylene; 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 the above solvents, glycol ether solvents are preferable. 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.

The amount of the solvent used for producing the thiol resin (A) of the present embodiment is not particularly limited, but the amount charged (polyfunctional thiol compound (a-1) and compound (a-2) is large. When the total amount of the basic acid anhydride (a-3) is 100 parts by mass, it 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 thiol resin (A) can be controlled within an appropriate range, which is preferable. On the other hand, when the amount of the solvent used is 30 parts by mass or more, seizure can be prevented during the reaction and the synthesis reaction can be stably carried out, which is preferable. Further, when the amount of the above solvent used is 30 parts by mass or more, coloring or gelation of the thiol resin (A) can be prevented.

In the present embodiment, an addition reaction between the polyfunctional thiol compound (a-1) and the compound (a-2), and an addition reaction between the thiol resin (A) precursor and the polybasic acid anhydride (a-3). It is preferable to use a catalyst to promote the above. The catalyst used in the present embodiment is not particularly limited, and is appropriately selected depending on the raw material of the thiol resin (A) and the like.

Examples of the catalyst used in the present embodiment include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chromium chelate compounds. .. 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 it is 100 parts by mass of the raw materials (polyfunctional thiol compound (a-1) and compound (a-2)) used in the first step. Generally, it is 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. After the completion of the first step, the polybasic acid anhydride (a-3) can be subsequently added to carry out the second step. At that time, the catalyst used in the first step can be used as it is in the second step, and a catalyst may be further added in the second step.

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 used is not particularly limited, but when the amount of the thiol resin (A) precursor is 100 parts by mass, it is generally 0.01 to 5 parts by mass, preferably 0. It is 1 to 2 parts by mass, more preferably 0.2 to 1 part by mass.

[Photosensitive resin composition]
The photosensitive resin composition of the present embodiment contains a thiol resin (A), an ethylenically unsaturated group-containing compound (B), a solvent (C), and a photopolymerization initiator (D). If necessary, the colorant (E) may be further contained.

<Ethylene unsaturated group-containing compound (B)>
The ethylenically unsaturated group-containing compound (B) is a compound having at least one ethylenically unsaturated group in the molecule, and is preferably a compound having a plurality of ethylenically unsaturated groups.

The inclusion of the ethylenically unsaturated group-containing compound (B) facilitates adjustment of the viscosity and sensitivity of the photosensitive resin composition. Further, the Michael addition reaction with the mercapto group contained in the thiol resin (A) and the thiol-ene reaction proceed to obtain a cured resin film having good solvent resistance and elastic recovery rate.

Examples of the monofunctional monomer (monomer having only one ethylenically unsaturated bond) used as the ethylenically unsaturated group-containing compound (B) include (meth) acrylamide, methylol (meth) acrylamide, and 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-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy- 2-Hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetra (Meta) acrylate compounds such as fluoropropyl (meth) acrylate and half (meth) acrylate of phthalic acid derivatives; aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene; vinyl acetate, propion Examples thereof include carboxylic acid esters such as vinyl acid acid. These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer (monomer having a plurality of ethylenically unsaturated bonds) used as the ethylenically unsaturated group-containing compound (B) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and 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, Trimethylol Propanetri (meth) Acrylate, Glycerindi (Meta) Acrylate, Pentaerythritol Di (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Dipentaerythritol Penta (Meta) Acrylate, Dipentaerythritol Hexa (Meta) Acrylate, 2,2-bis (4- (meth) acryloxidiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxipolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyl Oxypropyl (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 (that is, tolylene diisocyanate), trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, etc. and 2-vidroxyethyl (meth) acrylate, tri (meth) (Meta) acrylate compounds such as acrylates; Aromatic vinyl compounds such as divinylbenzene, diallylphthalate and diallylbenzenephosphonate; Dicarboxylic acid ester compounds such as divinyl adipate; Triallyl cyanurate, methylenebis (meth) acrylamide, (meth) acrylamide Examples thereof include methylene ether, a condensate of polyhydric alcohol and N-methylol (meth) acrylamide. These polyfunctional monomers may be used alone or in combination of two or more. Among these, a (meth) acrylate compound is preferable from the viewpoint of the elastic recovery rate of the cured resin film, and a (meth) acrylate compound having 3 to 6 functions is more preferable. Particularly preferable specific examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.

<Solvent (C)>
The solvent (C) is not particularly limited as long as it is an inert solvent capable of dissolving the thiol resin (A) and the ethylenically unsaturated group-containing compound (B) and not reacting with each of the above components. It can be arbitrarily selected according to the type of the thiol resin (A) and the like.

As the solvent (C), the same solvent as that can be used when producing the thiol 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 (C).

<Photopolymerization initiator (D)>
The photopolymerization initiator (D) is not particularly limited, and is, for example, a benzoin compound such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1. -Dichloroacetophenone, 4- (1-t-butyldioxy-1-methylethyl) acetphenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2 Acetphenone compounds such as −dimethylamino-1- (4-morpholinophenyl) butanone-1; anthraquinone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; xanthone, thioxanthone, Xantone compounds such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4- (1-t-butyldioxy-1-methylethyl) ) Benzophenone compounds such as benzophenone, 3,3', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone; acylphosphine oxide compounds, 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and the like. These photopolymerization initiators (D) may be used alone or in combination of two or more.

<Colorant (E)>
The colorant (E) may be any as long as it dissolves or disperses in the solvent (C), and is not particularly limited. Examples of the colorant (E) include dyes and pigments. As the colorant (E), only the dye may be used, only the pigment may be used, or the dye and the pigment may be used in combination. When the cured resin film of the photosensitive resin composition of the present embodiment is used as any of a black matrix, a color filter, and a black column spacer, the above-mentioned colorant (E) is used for the purpose of a member formed of the cured resin film. Depending on the situation, it can be used alone or in combination of two or more. For example, when a black colorant (E) is used, the cured resin film of the photosensitive resin composition is suitable as a black matrix and a black column spacer.

Examples of dyes include, for example, acid alizarin violet N; acid black1, 2, 24, 48; acid chrome 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; acidgreen 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63 , 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 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 chrome1,3,9,11,17,23,25,29,34,36,42,54,72 , 73, 76, 79, 98, 99, 111, 112, 114, 116; chromeello3 and derivatives thereof and the like.

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

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

As the black pigment, it is preferable to use an inorganic black pigment and an organic black pigment in combination from the viewpoint of the optical density of the image display device including the resin cured film of the photosensitive resin composition of the present embodiment, and carbon black and lactam are used. It is more preferable to use it in combination with organic black.

When the colorant (E) contains a pigment, the photosensitive resin composition may contain a known dispersant from the viewpoint of improving the dispersibility of the pigment in the photosensitive resin composition. The content of the dispersant can be appropriately set according to the type of pigment or the like used.

As the dispersant, it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time. The polymer dispersant can be arbitrarily selected, and for example, a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, and a sorbitan aliphatic ester dispersant. , Aliphatic modified ester dispersant and the like. Polymer dispersants such as EFKA (registered trademark, manufactured by BASF Japan), Disperbyk (registered trademark, manufactured by Big Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Zeneca), etc. Those commercially available under the trade name may be used.

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

The photosensitive resin composition of the present embodiment contains 1 to 20% by mass of the thiol resin (A), 1 to 20% by mass of the ethylenically unsaturated group-containing compound (B), and 50 to 94% by mass of the solvent (C). , The photopolymerization initiator (D) is preferably contained in an amount of 0.01 to 5% by mass.
When the photosensitive resin composition of the present embodiment contains the colorant (E), the content of the colorant (E) is preferably 3 to 30% by mass.

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

The content of the ethylenically unsaturated group-containing compound (B) in the photosensitive resin composition is preferably 1 to 20% by mass, more preferably 2 to 15% by mass. When the content of the ethylenically unsaturated group-containing compound (B) is 1% by mass or more, a photosensitive resin composition having good curability is obtained, which is preferable. On the other hand, when the content of the ethylenically unsaturated group-containing compound (B) is 20% by mass or less, a residue is unlikely to be generated after the photosensitive resin composition is exposed and developed, which is preferable.

The content of the solvent (C) with respect to the photosensitive resin composition is preferably 50 to 94% by mass, more preferably 60 to 87% by mass. When the content of the solvent (C) is 50% by mass or more, the photosensitive resin composition having good coatability is obtained, which is preferable. On the other hand, when the content of the solvent (C) is 94% by mass or less, a coating film having a sufficient film thickness can be obtained by applying the photosensitive resin composition, which is preferable.

The content of the photopolymerization initiator (D) in the photosensitive resin composition is preferably 0.01 to 5% by mass, more preferably 0.1 to 2% by mass. When the content of the photopolymerization initiator (D) is 0.01% by mass or more, the photocurability of the photosensitive resin composition becomes good, which is preferable. On the other hand, when the content of the photopolymerization initiator (D) is 5% by mass or less, a residue is unlikely to be generated after the photosensitive resin composition is exposed and developed, which is preferable.

When the photosensitive resin composition contains the colorant (E), the content of the colorant (E) is preferably 3 to 30% by mass, more preferably 5 to 20% by mass. When the content of the colorant (E) is 3% by mass or more, the color reproducibility of the cured resin film of the photosensitive resin composition is good, which is preferable. Further, when (E) is black, the cured resin film has sufficient light-shielding properties, which is preferable. On the other hand, when the content of the colorant (E) is 30% by mass or less, a residue is unlikely to be generated after the photosensitive resin composition is exposed and developed, which is preferable.

[Manufacturing method of photosensitive resin composition]
Next, a method for producing the photosensitive resin composition of the present embodiment will be described.
The photosensitive resin composition of the present embodiment comprises any of the thiol resins (A) of the present embodiment, an ethylenically unsaturated group-containing compound (B), a solvent (C), and a photopolymerization initiator (D). And, if necessary, one or more components of any one or more of the colorant (E), the dispersant, and the additive can be produced by a method of mixing using a known mixing device.

For the photosensitive resin composition of the present embodiment, a composition containing a thiol resin (A) and a solvent (C) is prepared in advance, and then the above composition is combined with the ethylenically unsaturated group-containing compound (B). , The photopolymerization initiator (D) and one or more components of any one or more of an optional colorant (E), a dispersant, and an additive may be further added and mixed.

The composition containing the thiol resin (A) and the solvent (C) is prepared, for example, by adding the solvent (C) to the thiol resin (A) isolated from the resin solution that has completed the reaction for synthesizing the thiol resin (A). ) Can be added and mixed.

In the present embodiment, if the solvent (C) is used as the reaction solvent for synthesizing the thiol resin (A), it is not always necessary to isolate the target thiol resin (A) from the resin solution after the reaction. Absent. Therefore, as a composition containing the thiol resin (A) and the solvent (C), the solvent contained in the resin solution at the time when the reaction for synthesizing the thiol resin (A) is completed is separated from the resin solution. The resin solution after completion of the reaction may be used as it is without separating. Further, as the composition containing the thiol resin (A) and the solvent (C), a composition obtained by adding another solvent to the resin solution after completion of the reaction and mixing the mixture may be used.

Since the photosensitive resin composition of the present embodiment contains the thiol resin (A) of the present embodiment, it has excellent developability, good colorant dispersibility and solvent resistance, and a high elastic recovery rate. A cured film is obtained. Therefore, the photosensitive resin composition of the present embodiment is suitable as a material for a transparent film, a protective film, an insulating film, an overcoat, a photo spacer, a black matrix, a black column spacer, and a color filter.

Further, the photosensitive resin composition of the present embodiment has good colorant dispersibility, and even if it sufficiently contains the black colorant (E), it sufficiently satisfies general properties such as developability. It is possible to form a cured resin film having good adhesion to the surface to be formed. Therefore, according to the photosensitive resin composition of the present embodiment, it is possible to form a black pattern having good adhesion to the surface to be formed and having sufficient light-shielding properties.

[Resin cured film]
The resin-cured film of the present embodiment is a resin-cured film obtained by photo-curing the photosensitive resin composition of the present embodiment.
Since the cured resin film of the present embodiment has good solvent resistance and elastic recovery rate, it is suitable as a transparent film, a protective film, an insulating film, an overcoat, and a photo spacer, which are members of an image display device. Further, since the colorant dispersibility is good, it is suitable as a black matrix, a color filter, and a black column spacer, which are members of an image display device.

[Manufacturing method of resin cured film]
The cured resin film of the present embodiment can be produced, for example, by the method shown below.
First, the photosensitive resin composition is applied onto 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 having a predetermined pattern, and the exposed portion is photocured. Next, the unexposed portion of the resin layer is developed with a developing solution to obtain a cured resin film having a predetermined pattern. Then, if necessary, host baking (heat treatment) of the cured resin film is performed.
When exposing the resin layer, a halftone mask having a predetermined pattern may be used. In this case, the unexposed portion and the semi-exposed portion are developed with a developing solution to obtain a resin cured film having a predetermined pattern.

The method for applying the photosensitive resin composition is not particularly limited, and examples thereof include a screen printing method, a roll coating method, a curtain coating method, a spray coating method, and a spin coating method.
After applying the photosensitive resin composition, the solvent (B) contained in the resin layer is volatilized by heating using a heating means such as a circulation oven, an infrared heater, or a hot plate, if necessary. May be good. 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 50 ° C. to 120 ° C., and the heating time can be 30 seconds to 30 minutes.

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

As the developing solution used for development, it is preferable to use an alkaline developing solution because excellent developability can be obtained. Examples of the alkaline developing solution 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; tetramethylammonium and 3-methyl. -4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfone Amidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and aqueous solutions of p-phenylenediamine compounds such as sulfates, hydrochlorides or p-toluenesulfonates thereof Can be mentioned.
The developing solution may contain an antifoaming agent, a surfactant and the like, if necessary.

After developing with a developing solution, it is preferable to wash the cured resin film having a predetermined pattern with water and dry it.
Further, after developing with a developing solution, it is preferable to perform post-baking (heat treatment) of a resin cured film having a predetermined pattern. By performing post-baking, the curing of the resin cured film can be further promoted. The post-baking conditions 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 the postbake can be 130 ° C to 250 ° C. The heating time of the post-bake is preferably 10 minutes to 4 hours, more preferably 20 minutes to 2 hours. The atmospheric gas may be either air or nitrogen.

[Image display device]
The image display device of the present embodiment includes the resin cured film of the present 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 transparent film, a protective film, an insulating film, an overcoat, a photo spacer, a black matrix, a color filter, and a black column spacer are formed of the cured resin film of the present embodiment. It is preferable that it is.

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

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

The cured resin film obtained by curing the photosensitive resin composition of the present embodiment has excellent developability, good colorant dispersibility and solvent resistance, and a high elastic recovery rate. Therefore, it is suitable as a material for a transparent film, a protective film, an insulating film, an overcoat, a photo spacer, a black matrix, a color filter, and a black column spacer provided in an image display device.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

(Example 1)
<First step>
A bisphenol A type epoxy compound (a-2) which is an epoxy compound (a-2) having 100 g of propylene glycol monomethyl ether acetate as a solvent and two or more epoxy groups in a flask equipped with a stirrer, a condenser, a thermometer and a gas introduction tube ( Trimethylolpropanetris (3-mercaptopro), which is a compound (a-1) having 75.2 g (0.4 mol of epoxy groups) and three or more mercapto groups, manufactured by Mitsui Chemicals, Inc., product name Epomic R140P). 133 g of pionate (TMMP) (1 mol of mercapto group) and 0.7 g of the catalyst triphenylphosphine were added, and the inside of the flask was stirred while blowing air, and the temperature was raised to 120 ° C. for 2 hours. The reaction was carried out to synthesize a resin precursor as an addition reaction product (M) of compound (a-1) and compound (a-2).

<Second step>
Next, 20 g (0.2 mol) of succinic anhydride (SA), which is a polybasic acid anhydride (a-3), was put into a flask in which the resin precursor was synthesized. After completion of the dropping, the mixture was further stirred at 120 ° C. for 2 hours to synthesize the thiol resin (A1) of Example 1.
The thiol resin (A1) was not isolated, and propylene glycol monomethyl ether acetate was further added to the reaction solution of the thiol resin (A1) to prepare a thiol resin (A1) solution having a solid content concentration of 40% by mass.
The solid content is a residue obtained by removing the residual monomer and the solvent component from the thiol resin (A1) solution, and the solid content concentration is a value calculated by the following method.

<Calculation of solid content concentration>
Weigh 0.5 g of a thiol resin (A1) solution in a weighed aluminum cup and spread it thinly. This was left in an oven at 140 ° C. for 1 hour, the mass of the residue of the thiol resin (A1) solution was measured again, and the solid content concentration was calculated.

(Example 2)
<First step>
A bisphenol A type epoxy compound (a-2) which is an epoxy compound (a-2) having 100 g of propylene glycol monomethyl ether acetate as a solvent and two or more epoxy groups in a flask equipped with a stirrer, a condenser, a thermometer and a gas introduction tube ( Mitsui Chemicals, Inc., product name Epomic R140P) 75.2 g (0.4 mol of epoxy group) and 1,3,5-Tris (3), which is a compound (a-3) having three or more mercapto groups. -Mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione) (NR-1) 189 g (1 mol of mercapto group) and catalyst 0.7 g of a certain triphenylphosphine was added, the inside of the flask was stirred while blowing air, the temperature was raised to 120 ° C., and the reaction was carried out for 2 hours to synthesize a resin precursor.

<Second step>
Next, 20 g (0.2 mol) of succinic anhydride (SA), which is a polybasic acid anhydride (a-3), and 0.23 g of lithium naphthenate were put into a flask in which the resin precursor was synthesized. After completion of the dropping, the mixture was further stirred at 120 ° C. for 2 hours to synthesize the thiol resin (A2) of Example 2.
In the same manner as in Example 1, a solvent was added to the reaction solution to prepare a thiol resin (A2) solution having a solid content concentration of 40%.

(Example 3)
In the first step, the same reaction as in Example 1 was carried out except that diphenylmethane diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd., reagent, number of moles of isocyanato group was 0.4 mol) was used instead of the bisphenol A type epoxy compound. .. The thiol resin (A3) of Example 3 was synthesized.
In the same manner as in Example 1, a solvent was added to the reaction solution to prepare a thiol resin (A3) solution having a solid content concentration of 40%.

(Example 4)
In the first step, the same reaction as in Example 2 was carried out except that diphenylmethane diisocyanate (0.4 mol of isocyanato group) was used instead of the bisphenol A type epoxy compound. The thiol resin (A4) of Example 4 was synthesized.
In the same manner as in Example 1, a solvent was added to the reaction solution to prepare a thiol resin (A4) solution having a solid content concentration of 40%.

(Comparative Example 1)
Using the same equipment as in Example 1, synthesis was carried out without separating the first step and the second step. That is, all the raw materials used in Example 1 were put into the flask, the inside of the flask was stirred while blowing air, and the temperature was raised to 120 ° C. to carry out the reaction. Gelation occurred 1 hour after charging.

(Comparative Example 2)
In the first step, the reaction was the same as in Example 1 except that 131.6 g of the bisphenol A type epoxy compound (0.7 mol of epoxy group) was used with respect to 133 g of TMMP (1 mol of mercapto group). Was done. After raising the temperature to 120 ° C. in the first step, gelation occurred in 30 minutes.

(Synthesis Example 1)
<Synthesis of acrylic resin (P1)>
140 g of propylene glycol monomethyl ether acetate was added as a solvent to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, and the inside of the flask was stirred while being replaced with nitrogen gas to raise the temperature to 120 ° C.
Next, 7.3 g of t was added to a monomer mixture consisting of 66.0 g (0.3 mol) of tricyclodecanyl methacrylate, 31.2 g (0.3 mol) of styrene, and 56.8 g (0.4 mol) of glycidyl methacrylate. -Butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nichiyu Co., Ltd., perbutyl (registered trademark) O) was added and prepared separately. The monomer / polymerization initiator mixture was added dropwise into the flask over 2 hours from the dropping funnel. After completion of the dropping, the copolymer was further stirred at 120 ° C. for 2 hours to carry out a copolymerization reaction to produce a copolymer (precursor of a curable polymer). Then, the inside of the flask was replaced with air, and 28.8 g (0.4 mol) of acrylic acid, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of BHT (polymerization inhibitor) were added to the above copolymer. It was put into a solution. Then, the reaction was continued at 110 ° C. for 10 hours to react the epoxy group in the polymer with acrylic acid to introduce a polymerizable unsaturated bond. Next, 38.0 g (0.25 mol) of tetrahydrophthalic anhydride was added to the reaction system, and the reaction was continued at 110 ° C. for 3 hours to make the hydroxy group and tetrahydrophthalic anhydride anhydrous generated by the cleavage of the epoxy group. The physical group was reacted to introduce a carboxy group into the side chain. The acid value of this polymer was 65 MgKOH / g, and the mass average molecular weight was 9,400. In the same manner as in Example 1, a solvent was added to the reaction solution to prepare an acrylic resin (P1) solution having a solid content concentration of 40%.

(Evaluation of thiol resin (A) and acrylic resin (P1))
Regarding the thiol resin (A) synthesized in Examples 1 to 4 and the acrylic resin (P1) synthesized in Synthesis Example 1, the acid value, mass average molecular weight, mercapto group equivalent, and mercapto group per molecule were obtained by the methods shown below. The average number of was measured or calculated. The results are shown in Table 1.

<Measurement method of acid value>
Measurements were made according to JIS K6901 5.3.2 using a mixed indicator of bromothymol blue and phenol let. It means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the thiol resin (A).

<Mercapt group equivalent>
It was the mass of the thiol resin (A) per the number of moles of the mercapto group, and was measured by the following iodine titration method. 0.2 g of the thiol resin (A) was dissolved in 20 ml of chloroform, 10 ml of isopropanol, 20 ml of water and 1 ml of a starch indicator were further added, and then titrated with an iodine solution.

<Average number of mercapto groups per molecule of thiol resin (A)>
It was calculated by the following formula from the mercapto group equivalent of the obtained thiol resin (A) and the mass average molecular weight (Mw) of the obtained thiol resin (A) below.
Average number of mercapto groups per molecule = mass average molecular weight (Mw) / mercapto group equivalent

<Measurement method of mass average molecular weight (Mw)>
It was 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 KK)
Column temperature: 40 ° C
Sample: 0.2% tetrahydrofuran solution of thiol resin (A) or acrylic resin (P1) Developing solvent: tetrahydrofuran Detector: Differential refractometer (SHODEX (registered trademark) RI-71S) (manufactured by Showa Denko KK)
Flow velocity: 1 mL / min

(Examples 5 to 12, Comparative Examples 3 to 5)
<Preparation of photosensitive resin composition>
Using the thiol resins (A1) to (A4) obtained in Examples 1 to 4 or the acrylic resin (P1) obtained in Synthesis Example 1, according to the compounding ratio (parts by mass) shown in Table 2, Examples The black photosensitive resin compositions of 5 to 12 and Comparative Examples 3 to 5 were prepared.
The values of the thiol resin (A) and the acrylic resin (P1) in Table 2 are the values of the solid content, and the solvent contained in the resin solution obtained in the examples is that of the solvent (C) in Table 2. It is added up in the column.

ＰＥＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＯＸＥ−０２：イルガキュアＯＸＥ０２（光重合開始剤、ＢＡＳＦジャパン社製）
ＤＰＨＡ：ジペンタエリスリトールヘキサアクリレート、新中村工業株式会社製Ａ−ＤＰＨ
ＮＲ−１：１，３，５−トリス（３−メルカプトブチリルオキシエチル）−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン）
ＫＢＭ−４０３：３−グリシドキシプロピルトリエトキシシラン、信越シリコーン製ＫＢＭ−４０３（カップリング剤）
ミルベース：以下の「ミルベースの調整」方法により用意した。

PEGMEA: Propylene glycol monomethyl ether acetate OXE-02: Irgacure OXE02 (photopolymerization initiator, manufactured by BASF Japan Ltd.)
DPHA: Dipentaerythritol hexaacrylate, A-DPH manufactured by Shin-Nakamura Kogyo Co., Ltd.
NR-1: 1,3,5-Tris (3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione)
KBM-403: 3-glycidoxypropyltriethoxysilane, Shinetsu Silicone KBM-403 (coupling agent)
Mill base: Prepared by the following "mill base adjustment" method.

<Mill base adjustment>
Carbon black 0.6g, lactam black (BASF, Irgaphor Black S0100CF) 3.6g, azisper PB822 7.5g as dispersant, acrylic resin 2.5g, PGMEA 15g in a metal can with zirconia beads, paint shaker A mill base was prepared by shaking with.

<Evaluation of photosensitive resin composition>
For the photosensitive resin compositions of Examples 5 to 12 and Comparative Examples 3 to 5, the optical density (colorant dispersibility), residual film ratio (development margin), solvent resistance, elastic recovery rate, respectively, were obtained by the following methods. The fine line adhesion was evaluated. The results are shown in Table 3.

<Evaluation of optical density (colorant dispersibility)>
The thickness of the coating film after solvent volatilization is applied on a glass substrate (a substrate having a wiring pattern made of IZO formed on the surface) of 10 cm × 10 cm by applying the photosensitive resin compositions of Examples 5 to 12 and Comparative Examples 3 to 5. It was spin-coated so that the size was 2.5 μm. Then, the solvent in the coating film was volatilized by heating the glass 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 was developed with a 0.2 mass% potassium hydroxide aqueous solution for 120 seconds, and further post-baked at 230 ° C. for 30 minutes to obtain a desired resin cured film.

The optical density (OD) of the 2.5 μm-thick resin cured film was measured by using a transmission densitometer (361T, X-lite).
It can be said that the higher the optical density, the better the colorant dispersibility.

<Evaluation of residual film ratio (development margin)>
A coating film with a thickness of 2.5 μm after solvent volatilization was prepared on a glass substrate by the same method as the optical density, and the residual film ratio of the coating film thickness between 100 seconds and 150 seconds of development time was investigated by Kosaka Research. The measurement was performed using a stylus type step meter T4000M manufactured by the company. It can be said that the larger the residual film ratio of the coating film, the better the development margin and the better the developability.

<Evaluation of solvent resistance>
It was produced on a glass substrate by the same method as the evaluation of optical density. The cured resin film was cut into a size of 1 cm × 1 cm, and the absorbance at the maximum absorption wavelength of the cured resin film was measured using a UV spectrum meter UV-1650PC manufactured by SIMAZU. Then, a resin cured film having a size of 1 cm × 1 cm was placed in a glass bottle containing 5 mL of N-methylpyrrolidone, and left in an oven at 100 ° C. for 15 minutes. Then, the removed coating film was wiped with a cloth and the absorbance at the maximum absorption wavelength of the cured resin film was measured in the same manner as before immersion in N-methylpyrrolidone. Then, the rate of change in absorbance before and after immersion in N-methylpyrrolidone was calculated. It can be said that the smaller the rate of change in absorbance, the less color loss and the better the solvent resistance.

<Evaluation of elastic recovery rate>
With respect to the resin cured film used for the evaluation of the optical density, the elastic recovery rate at 25 ° C. was measured using an elastic measuring device (DUH-W201S, Shimadzu Corporation) according to the following measurement conditions.
As the pressing body for pressing the resin cured film, a flat pressing body having a diameter of 50 μm was used. After starting the load at a load rate of 3 gf / sec, hold it at a load of 300 mN for 3 seconds, and then unload it, and use a stylus type step meter (fully automatic fine shape measuring machine) ET400M to measure the thickness of the resin cured film before and after the load. Was measured. The elastic recovery rate means the ratio of the distance recovered after the lapse of the recovery time of 10 minutes (recovery distance) to the distance compressed by the resin cured film under load (compressive displacement), and is expressed by the following equation.
Elastic recovery rate (%) = (recovery distance / compression displacement) x 100

<Adhesion to fine lines>
The photosensitive resin compositions of Examples 5 to 12 and Comparative Examples 3 to 5 were spin-coated on a 10 cm × 10 cm glass substrate so that the thickness of the coating film was 2.5 μm. After that, the solvent was volatilized by heating the glass substrate at 90 ° C. for 3 minutes. Next, a pattern mask of dots having a diameter of 1 μm from 20 to 3 μm was placed on the coating film, and a multi-light ML-251D / B manufactured by Ushio Denki Co., Ltd. and an irradiation optical unit PM25C-100 were used on the mask. A fixed amount (40 ^{mJ / cm 2} or 10 mJ / cm ² ) was exposed and photocured. Then, it was developed with a 0.2 mass% potassium hydroxide aqueous solution for 60 seconds, and the fine line adhesion was evaluated by confirming the minimum diameter of the developed pattern.

As shown in Table 3, the photosensitive resin compositions of Examples 5 to 12 have high optical density (colorant dispersibility), residual film ratio (development margin) and elastic recovery rate of the cured resin film, and are solvent resistant. And the evaluation of fine line adhesion at low exposure was good.
On the other hand, the cured resin films of the photosensitive resin compositions of Comparative Examples 3 to 5 have lower residual film ratio (development margin) and elastic recovery rate of the cured resin film as compared with Examples 5 to 12, and have solvent resistance. Alternatively, the fine line adhesion at low exposure was inferior. This is because the resin contained in the photosensitive resin compositions of Comparative Examples 3 to 5 does not contain the constituent components derived from the compound (a-1) having three or more mercapto groups, so that the resin does not have a three-dimensional structure. It can be presumed that it has a linear structure.

According to the present invention, there is provided a resin capable of achieving developability, colorant dispersibility, solvent resistance of a cured film, and a high elastic recovery rate. Further, a photosensitive resin composition capable of obtaining a cured film having solvent resistance and a high elastic recovery rate, a resin cured film obtained by curing the photosensitive resin composition, and an image display device including the same are provided. The photosensitive resin composition can be preferably used as a transparent film, a protective film, an insulating film, an overcoat, a photo spacer, a black matrix, a black column spacer, and a resist for a color filter.

Claims (16)

A thiol resin having a mercapto group and a carboxy group.
The thiol resin is obtained by adding a polybasic acid anhydride (a-3) to an addition reaction product (M) of a polyfunctional thiol compound (a-1) and a polyfunctional compound (a-2). ,
The polyfunctional thiol compound (a-1) has three or more mercapto groups and has three or more mercapto groups.
The polyfunctional compound (a-2) has two or more reactive groups (RG) that are reactive with the mercapto group.
The addition reaction product (M) is an addition reaction product of the mercapto group of the polyfunctional thiol compound (a-1) and the reactive group (RG) of the polyfunctional compound (a-2).
The ratio of the total number of moles of the reactive group (RG) of the compound (a-2) to the total number of moles of the mercapto group of the compound (a-1) is 0.20 to 0.60.
A thiol resin characterized by that. The thiol resin according to claim 1, wherein the reactive group (RG) of the polyfunctional compound (a-2) is at least one selected from the group consisting of an epoxy group and an isocyanato group. The total number of moles of the binding portion of the addition reaction product (M) due to the addition reaction between the mercapto group of the polyfunctional thiol compound (a-1) and the reactive group (RG) of the polyfunctional compound (a-2). On the other hand, the ratio of the total number of moles of the acid anhydride groups of the polybasic acid anhydride (a-3) is 0.3 to 0.7.
The thiol resin according to claim 1 or 2. The thiol resin according to any one of claims 1 to 3, wherein the mercapto group equivalent is 200 to 2000 g / mol. The thiol resin according to any one of claims 1 to 4, which has an acid value of 10 to 100 mgKOH / g. The thiol resin according to any one of claims 1 to 5, wherein the mass average molecular weight is 3000 to 20000. The thiol resin according to any one of claims 1 to 6, which has an average of 3 or more mercapto groups per molecule. The thiol resin according to any one of claims 1 to 7, wherein the polyfunctional thiol compound (a-1) is a compound represented by the following general formula (1) or (2).

(In the formula (1), R represents a hydrogen atom, the sum may have a substituent hydrocarbon group having 1 to 10 carbon atoms or ^{-X 4 -Y 4 -Z 4, -} (CR 9 R 10) -SH is represented. X ⁴ and Z ⁴ each independently represent a hydrocarbon group having a total divalent aliphatic carbon number of 1 to 10 which may have a substituent, and Y ⁴ is -CH _2. -, -OC (O)-, -C (O) O-, -NHC (O)-, -C (O) NH-, -SC (O)-and -C (O) S- Representing a divalent group. R ⁹ and R ¹⁰ are independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms.
In formulas (1) and (2), X ¹ , X ² , X ³ , Z ¹ , Z ² and Z ³ each independently have a divalent total carbon number of 1 which may have a substituent. Representing 10 to 10 aliphatic hydrocarbon groups, Y ¹ , Y ² and Y ³ are -CH _2- , -OC (O)-, -C (O) O-, -NHC (O)-,-. Represents a divalent group selected from C (O) NH-, -SC (O)- and -C (O) S-. R ^{3 to} R ⁸ are independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms. ) The thiol resin according to any one of claims 1 to 8, wherein the polyfunctional thiol compound (a-1) is at least one compound selected from the group consisting of the formulas (3) and (4).

The thiol resin according to any one of claims 1 to 9, wherein the polyfunctional compound (a-2) is a compound represented by the following formula (5).

(In the formula (5), 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. Indicates any of the groups selected from the groups. D is an epoxy group, a 3,4-epoxycyclohexyl group, a group represented by the following formula (5-1), or any of the groups represented by the following formula (5-2). In the following formula (5-1) and the following formula (5-2), * indicates the bond site between D and the methylene group in the formula (5).)

The thiol resin according to any one of claims 1 to 9, wherein the polyfunctional compound (a-2) is a compound having two isocyanato groups. The thiol resin according to any one of claims 1 to 11 (referred to as "thiol resin (A)") and
Ethylene unsaturated group-containing compound (B) and
Solvent (C) and
Photopolymerization initiator (D) and
A photosensitive resin composition comprising. The photosensitive resin composition according to claim 12, further containing a colorant (E). The thiol resin (A) is contained in an amount of 1 to 20% by mass.
The ethylenically unsaturated group-containing compound (B) is contained in an amount of 1 to 20% by mass.
The solvent (C) is contained in an amount of 50 to 94% by mass and contains.
The photopolymerization initiator (D) is contained in an amount of 0.01 to 5% by mass.
The photosensitive resin composition according to claim 12, which contains 3 to 30% by mass of the colorant (E). A resin cured film obtained by curing the photosensitive resin composition according to any one of claims 12 to 14. An image display device including the resin cured film according to claim 15.