JP2010107755A - Photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having adequate sensitivity and capable of forming a coating film or pattern having a high transmittance. <P>SOLUTION: The photosensitive resin composition contains a binder resin (A), a photopolymerizable compound (B), a photoinitiator (C) and a solvent (D), wherein the photoinitiator (C) contains a compound (C1) having an acetophenone skeleton and a compound (C2) having at least two thiol groups. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, a coating film, a pattern, and a display device.

  It has been proposed to form a spacer (photospacer) by photolithography using a photosensitive resin composition between a color filter constituting the display device, such as a liquid crystal display device or a touch panel, and the array substrate. According to this method, the spacer can be formed at an arbitrary place.

As such a photosensitive resin composition, it contains a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), and the photopolymerization initiator (C) is acetophenone. A photosensitive resin composition that is a photopolymerization initiator containing a skeleton is known (Patent Document 1).
JP 2006-23716 A

However, the sensitivity of the photosensitive resin composition containing the photopolymerization initiator is not always sufficient.
The subject of this invention is providing the photosensitive resin composition which can form the coating film or pattern of high transmittance | permeability while having sufficient sensitivity.

  As a result of studies to find a photosensitive resin composition capable of solving the above-mentioned problems, the present inventor has found that a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a solvent (D). In the photosensitive resin composition containing a compound, a photopolymerization initiator (C) is used by combining a compound (C1) containing an acetophenone skeleton and a compound (C2) having at least two thiol groups. The present inventors have found that the sensitivity of the functional resin composition is improved and have reached the present invention.

［式（Ｉ）及び式（ＩＩ）中、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表す。該アルキル基に含まれる水素原子は、水酸基で置換されていてもよい。
Ｘ_１及びＸ_２は、それぞれ独立に、単結合又はヘテロ原子を含んでもよい炭素数１〜６のアルキレン基を表す。］
［７］不飽和カルボン酸及び／又は不飽和カルボン酸無水物（Ａ−ａ）が、脂肪族不飽和カルボン酸及び／又は脂肪族不飽和カルボン酸無水物である、前記［３］〜［６］のいずれかに記載の感光性樹脂組成物。
［８］式（Ｉ）で表される化合物及び式（ＩＩ）で表される化合物からなる群から選ばれる少なくとも１種の化合物が、式（Ｉ’）で表される化合物及び式（ＩＩ’）で表される化合物からなる群から選ばれる少なくとも１種の化合物である、前記［６］又は［７］に記載の感光性樹脂組成物。

［式（Ｉ’）及び式（ＩＩ’）中、Ｒ_１’及びＲ_２’は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表す。該アルキル基に含まれる水素原子は、水酸基で置換されていてもよい。］
［９］少なくとも２個のチオール基を有する化合物（Ｃ２）が、少なくとも２個の−Ｏ−ＣＯ−ＣＨ_２−ＣＨ_２ＳＨ基を有する化合物である、前記［１］〜［８］のいずれかに記載の感光性樹脂組成物。
［１０］少なくとも２個のチオール基を有する化合物（Ｃ２）が、少なくとも３個のチオール基を有する化合物である、前記［１］〜［９］のいずれかに記載の感光性樹脂組成物。
［１１］塗膜又はパターンを形成するための、前記［１］〜［１０］のいずれかに記載の感光性樹脂組成物の使用。
［１２］前記［１］〜［１０］のいずれかに記載の感光性樹脂組成物を用いて形成される塗膜又はパターン。
［１３］ 前記［１２］に記載の塗膜又はパターンを含む表示装置。 That is, the present invention provides the following [1] to [13].
[1] Contains a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D),
A photosensitive resin composition, wherein the photopolymerization initiator (C) is a photopolymerization initiator comprising a compound (C1) containing an acetophenone skeleton and a compound (C2) having at least two thiol groups.
[2] The photosensitive resin composition according to the above [1], wherein the compound (C1) containing an acetophenone skeleton is a compound containing an α-aminoketone skeleton.
[3] The binder resin (A) is a monomer having at least an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (Aa) and a cyclic ether group having 2 to 4 carbon atoms (Ac ) And a photosensitive resin composition according to the above [1] or [2].
[4] The photosensitive resin composition according to [3], wherein the monomer having a cyclic ether group having 2 to 4 carbon atoms is a monomer having an epoxy group.
[5] The photosensitive resin composition according to [4], wherein the monomer having an epoxy group is a monomer having an aliphatic polycyclic epoxy group.
[6] The monomer having an aliphatic polycyclic epoxy group is at least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II). The photosensitive resin composition as described in said [5].

[In Formula (I) and Formula (II), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.
X ₁ and X ₂ each independently represent a C 1-6 alkylene group that may contain a single bond or a hetero atom. ]
[7] The above [3] to [6], wherein the unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (Aa) is an aliphatic unsaturated carboxylic acid and / or an aliphatic unsaturated carboxylic acid anhydride. ] The photosensitive resin composition in any one of.
[8] At least one compound selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (II) is a compound represented by formula (I ′) and formula (II ′). The photosensitive resin composition according to [6] or [7], which is at least one compound selected from the group consisting of compounds represented by:

[In Formula (I ′) and Formula (II ′), R ₁ ′ and R ₂ ′ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. ]
[9] Any of [1] to [8] above, wherein the compound (C2) having at least two thiol groups is a compound having at least two —O—CO—CH ₂ —CH ₂ SH groups. The photosensitive resin composition as described in 2.
[10] The photosensitive resin composition according to any one of [1] to [9], wherein the compound (C2) having at least two thiol groups is a compound having at least three thiol groups.
[11] Use of the photosensitive resin composition according to any one of [1] to [10] for forming a coating film or a pattern.
[12] A coating film or pattern formed using the photosensitive resin composition according to any one of [1] to [10].
[13] A display device including the coating film or pattern according to [12].

  According to the photosensitive resin composition of the present invention, it is possible to form a coating film or pattern with high sensitivity and high transmittance.

Hereinafter, the present invention will be described in detail.
The photosensitive resin composition of the present invention contains a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a solvent (D), and the photopolymerization initiator (C) is acetophenone. The photopolymerization initiator comprises a compound containing a skeleton and a compound having at least two thiol groups.

  As binder resin (A) used for the photosensitive resin composition of this invention, binder resin (A1) and binder resin (A2) are illustrated. The binder resin (A1) exhibits alkali solubility, and the binder resin (A2) exhibits alkali solubility and reactivity due to the action of at least one of light and heat.

  As the binder resin (A1), at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (A-a) (hereinafter sometimes referred to as “(A-a)”); A copolymer with a monomer (Ab) copolymerizable with Aa) (excluding (Aa)) (hereinafter sometimes referred to as “(Ab)”); Illustrated.

Examples of (Aa) include aliphatic unsaturated carboxylic acids and / or aliphatic unsaturated carboxylic acid anhydrides. Specifically, for example,
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
And anhydrides of the aforementioned unsaturated dicarboxylic acids;
Unsaturated mono [(meth) acryloyloxy of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Alkyl] esters;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid or maleic anhydride is preferably used from the viewpoint of copolymerization reactivity and alkali solubility. These may be used alone or in combination.

As (Ab),
(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, dicyclopenta Nyl (meth) acrylate), (meth) acrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate, isoboronyl (meth) acrylate;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate (commonly referred to in the art as dicyclopentanyl acrylate), dicyclo. Acrylic acid cyclic alkyl esters such as pentaoxyethyl acrylate and isobornyl acrylate;
(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-carboxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1 ] Hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5,6- Di (hydroxymethyl) bicyclo [2.2.1] hept-2-e 5,6-di (2′-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6 -Diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2 .1] Hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6- Ethylbicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxy Carbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (tert-butoxycarbonyl) bicyclo [2.2. 1] Bicyclo unsaturated compounds such as hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and alkali solubility.
(Aa) and (Ab) are used alone or in combination.

In the copolymer obtained by copolymerizing (Aa) and (Ab), the ratio of the constituent components derived from each of them is 100 in terms of the total number of moles of the constituent components constituting the copolymer. It is preferable that the molar fraction is in the following range when the mol% is used.
Structural units derived from (Aa); 2 to 40 mol%
Structural units derived from (Ab); 60-98 mol%
Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (Aa); 5-35 mol%
Structural units derived from (Ab); 65-95 mol%
When the composition ratio is in the above range, storage stability, developability and solvent resistance tend to be good.

For example, the binder resin (A1) is a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document. Can be produced with reference to the cited references described in 1.
Specifically, by supplying a predetermined amount of units (Aa) and (Ab) constituting the copolymer, a polymerization initiator and a solvent into a reaction vessel, and substituting oxygen with nitrogen, A polymer is obtained by stirring, heating, and heat-retaining in the absence. In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and took out as solid (powder) by methods, such as reprecipitation. Things may be used.

The polystyrene-reduced weight average molecular weight of the binder resin (A1) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. If the weight-average molecular weight of the resin (A1) having alkali solubility is in the above range, the coating property tends to be good, the film is not easily reduced during development, and the non-pixel portion can be removed during development. Tends to be good, which is preferable.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (A1) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. The molecular weight distribution in the above range is preferable because it tends to be excellent in developability.
Content of binder resin (A1) which can be used for the photosensitive resin composition of this invention is a mass fraction with respect to solid content in the photosensitive resin composition, Preferably it is 5-90 mass%, More preferably Is 10-70 mass%. When the content of the binder resin (A1) is in the above range, the solubility in the developer is sufficient, and development residues are not easily generated on the non-pixel portion of the substrate. This is preferable because the film loss is less likely to occur, and the non-exposed portion tends to be easily removed.

Examples of the binder resin (A2) exhibiting alkali solubility and reactivity by at least one of light and heat include (A2-1) to (A2-3).
The binder resin (A2-1) is composed of (Aa), (Ab), and a monomer having a cyclic ether group having 2 to 4 carbon atoms (Ac) (hereinafter referred to as “(Ac)”. In some cases).
In the copolymer of (Aa) and (Ab), the binder resin (A2-2) is derived from (Ac) with a part of the carboxyl group derived from (Aa). It is a copolymer obtained by reacting with a C2-C4 cyclic ether group.
The binder resin (A2-3) is a copolymer of (Aa) and (Ac).

  (Ac) refers to a polymerizable compound having at least one group selected from the group consisting of, for example, a cyclic ether group having 2 to 4 carbon atoms (for example, an epoxy group, an oxetanyl group, and a tetrahydrofuryl group). (Ac) is preferably a compound having at least one group selected from the group consisting of cyclic ether groups having 2 to 4 carbon atoms and having an unsaturated bond.

  Examples of (Ac) include a monomer having an epoxy group, a monomer having an oxetanyl group, and a monomer having a tetrahydrofuryl group.

  The monomer having an epoxy group refers to, for example, a polymerizable compound having at least one group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group. The monomer having an epoxy group is preferably a compound having at least one group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group and having an unsaturated bond.

（式中、Ｒ^１１〜Ｒ^１３は、それぞれ独立に水素原子又は炭素原子数１〜１０のアルキル基であり、ｍは１〜５の整数である。）。 Among the above-mentioned monomers having an epoxy group, specific examples of the compound having an aliphatic epoxy group include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, and β-ethylglycidyl (meth) acrylate. , Glycidyl vinyl ether, and compounds represented by the following formulas described in JP-A-7-248625.

(In formula, R < ¹¹ > -R < ¹³ > is a hydrogen atom or a C1-C10 alkyl group each independently, and m is an integer of 1-5.).

  Examples of the compound represented by the above formula include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m- Vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6- Diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyl Oxymethylstyrene, 2 Such as 4,6-triglycidyl oxymethyl styrene.

  Among the monomers having an epoxy group, examples of the monomer having an alicyclic epoxy group include a monomer having an aliphatic monocyclic epoxy group and a monomer having an aliphatic polycyclic epoxy group. Examples include masses.

The monomer having an aliphatic monocyclic epoxy group refers to a polymerizable compound having an epoxy group on the ring of the aliphatic monocyclic compound. The monomer having an aliphatic monocyclic epoxy group is preferably a compound having an epoxy group on the ring of the aliphatic monocyclic compound and having an unsaturated bond.
Examples of the aliphatic monocyclic compound include cyclopentane, cyclohexane, cycloheptane, cyclooctane, and the like. Among these, compounds having 5 to 7 carbon atoms are preferable.
As the monomer having an aliphatic monocyclic epoxy group, specifically, vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), and the like. Can be mentioned.

The monomer having an aliphatic polycyclic epoxy group refers to a polymerizable compound having an epoxy group on the ring of the aliphatic polycyclic compound. The monomer having an aliphatic polycyclic epoxy group is preferably a compound having an epoxy group on the ring of the aliphatic polycyclic compound and having an unsaturated bond.
Examples of the aliphatic polycyclic compound include dicyclopentane, tricyclodecane, norbornane, isonorbornane, bicyclooctane, bicyclononane, bicycloundecane, tricycloundecane, bicyclododecane, and tricyclododecane. Compounds having 8 to 12 carbon atoms are preferred.

  Examples of the monomer having an aliphatic polycyclic epoxy group include 3,4-epoxynorbornyl acrylate, 3,4-epoxynorbornyl methacrylate, compounds represented by the formula (I), and the formula And at least one compound selected from the group consisting of compounds represented by (II).

In Formula (I) and Formula (II), R ₁ and R ₂ each independently represent a C 1-4 alkyl group that may be substituted with a hydrogen atom or a hydroxyl group.
X ₁ and X ₂ each independently represent a C 1-6 alkylene group that may contain a single bond or a hetero atom.

As R ₁ and R ₂ , specifically, a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group;
Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy-isopropyl group, And hydroxyl group-containing alkyl groups such as 2-hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group and 4-hydroxy-n-butyl group. It is done. Among these, Preferably a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group is mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

Specific examples of X ₁ and X ₂ include a single bond; an alkylene group such as a methylene group, an ethylene group, and a propylene group;
Examples thereof include heteroatom-containing alkylene groups such as oxymethylene group, oxyethylene group, oxypropylene group, thiomethylene group, thioethylene group, thiopropylene group, aminomethylene group, aminoethylene group, and aminopropylene group. Of these, a single bond, a methylene group, an ethylene group, an oxymethylene group, and an oxyethylene group are preferable, and a single bond and an oxyethylene group are more preferable.

As at least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II), a compound represented by the following formula (I ′) and formula (II ′) It is preferably at least one compound selected from the group consisting of compounds represented by

In Formula (I ′) and Formula (II ′), R ₁ ′ and R ₂ ′ have the same meanings as R ₁ and R ₂ , respectively.

  Specific examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15), and the formula (I-1) is preferable. , Formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15), and more preferably (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

  Specific examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15), and the formula (II-1) is preferable. , Formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), more preferably formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) are mentioned.

  At least one compound selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (II) can be used alone, and can be mixed in any ratio. In the case of mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, more preferably 20:80 to Formula (I) :( II). 80:20.

The monomer having an oxetanyl group refers to, for example, a polymerizable compound having at least one group selected from the group consisting of an aliphatic oxetanyl group and an alicyclic oxetanyl group. The monomer having an oxetanyl group is preferably a compound having at least one group selected from the group consisting of an aliphatic oxetanyl group and an alicyclic oxetanyl group and having an unsaturated bond.
Specific examples of the monomer having an oxetanyl group include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3 -Ethyl-3-acryloxymethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane or 3-ethyl-3-acryl Examples include roxyethyl oxetane.
These may be used alone or in combination.

The monomer having a tetrahydrofuryl group refers to a polymerizable compound having at least one group selected from the group consisting of an aliphatic tetrahydrofuryl group and an alicyclic tetrahydrofuryl group, for example. The monomer having a tetrahydrofuryl group is preferably a compound having at least one group selected from the group consisting of an aliphatic tetrahydrofuryl group and an alicyclic tetrahydrofuryl group and having an unsaturated bond. .
Specific examples of the monomer having a tetrahydrofuryl group include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.
These may be used alone or in combination.

In the binder resin (A2-1), the ratio of the component derived from each of the binder resin (A2-1) is in the following range in terms of a mole fraction with respect to the total number of moles of the component constituting the binder resin (A2-1). preferable.
Structural units derived from (Aa); 2 to 40 mol%
Structural units derived from (Ab); 1 to 65 mol%
Structural units derived from (Ac); 2 to 95 mol%
Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (Aa); 5-35 mol%
Structural units derived from (Ab); 1 to 60 mol%
Structural units derived from (Ac); 5 to 80 mol%
When the composition ratio is in the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be good.
The binder resin (A2-1) can be obtained by, for example, the method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and It can manufacture with reference to the cited reference described in the said literature.
Specifically, a predetermined amount of a compound that leads to units (Aa), (Ab), and (Ac) constituting the copolymer, a polymerization initiator, and a solvent are charged into a reaction vessel, and nitrogen is added. By substituting oxygen with the above, a polymer is obtained by stirring, heating, and keeping the temperature in the absence of oxygen. In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and took out as solid (powder) by methods, such as reprecipitation. Things may be used.

In producing the binder resin (A2-2), first, (Aa) and (Ab) are copolymerized to produce a copolymer. It is preferable that the ratio of the component derived from each is in the following range in terms of a mole fraction with respect to the total number of moles of the component constituting the copolymer.
Structural units derived from (Aa); 5-50 mol%
Structural units derived from (Ab); 50-95 mol%
Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (Aa); 10 to 45 mol%
Structural units derived from (Ab); 55 to 90 mol%

Next, in order to give reactivity by the action of light or heat, the carboxylic acid and carboxylic acid of (Aa) derived from the copolymer obtained by copolymerizing (Aa) and (Ab) A part of the acid anhydride is reacted with an epoxy group, oxetanyl group or tetrahydrofuryl group derived from (Ac).
The number of moles of (Ac) is 5 to 80 mole%, preferably 10 to 75 mole%, more preferably 15 to 70 mole%, based on the number of moles of (Aa). .
When the composition ratio is in the above range, the balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tends to be good.

The binder resin (A2-2) can be produced through a two-step process. For example, in the method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu Publishing Co., Ltd., Chemical Dojin Co., Ltd., First Edition, First Edition, issued on March 1, 1972), Japanese Patent Laid-Open No. 2001-89533 It can be produced with reference to the described method.
Specifically, the first stage process will be described first. A predetermined amount of a compound that leads to units (Aa) and (Ab) constituting a copolymer (ie, binder resin) obtained by copolymerizing (Aa) and (Ab), polymerization The binder resin is obtained by charging the initiator and the solvent into the reaction vessel and substituting oxygen with nitrogen, and stirring, heating, and keeping the temperature in the absence of oxygen. In addition, the obtained resin may use the solution after the reaction as it is, a concentrated or diluted solution, or a solid (powder) taken out by a method such as reprecipitation. May be used. The weight average molecular weight in terms of polystyrene of the resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. If the weight average molecular weight of the resin is in the above range, the coating property tends to be good, the film is less likely to be reduced during development, and the non-pixel part is liable to be easily removed during development. preferable.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. A molecular weight distribution in the above range is preferable because it tends to be excellent in coating properties and developability.

  Next, the second stage process will be described. Subsequently, the atmosphere in the flask was replaced from nitrogen to air, and 5 to 80 mol% of the component (Ac), carboxyl group and epoxy group, oxetanyl group or the number of moles of the component (Aa) As a reaction catalyst for the tetrahydrofuryl group, for example, trisdimethylaminomethylphenol is 0.001 to 5% on a mass basis with respect to the total amount of monomers (Aa) to (Ac), and as a polymerization inhibitor, for example, Put 0.001 to 5% hydroquinone in a flask on a mass basis with respect to the total amount of monomers (Aa) to (Ac), and continue the reaction at 60 to 130 ° C. for 1 to 10 hours. Thus, the resin and the constituent component (Ac) can be reacted. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

In the binder resin (A2-3), the ratio of the component derived from each of the binder resin (A2-3) is in the following range in terms of a mole fraction with respect to the total number of moles of the component constituting the binder resin (A2-3). preferable.
Structural units derived from (Aa); 5-95 mol%
Structural units derived from (Ac); 5-95 mol%
Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (Aa); 10 to 90 mol%
Structural units derived from (Ac); 10 to 90 mol%
When the composition ratio is in the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be good.

The binder resin (A2-3) can be obtained by, for example, the method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and It can manufacture with reference to the cited reference described in the said literature.
Specifically, a predetermined amount of a compound that leads to the units (Aa) and (Ac) constituting the copolymer, a polymerization initiator and a solvent are charged into a reaction vessel, and oxygen is substituted with nitrogen. Thus, a polymer can be obtained by stirring, heating and heat-retaining in the absence of oxygen. In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and took out as solid (powder) by methods, such as reprecipitation. Things may be used.

Examples of the photopolymerizable compound (B) contained in the photosensitive resin composition of the present invention include monofunctional monomers, bifunctional monomers, and other trifunctional or more polyfunctional monomers.
Specific examples of the monofunctional monomer include nonylphenyl carbitol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Lauryl (meth) acrylate, stearyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propoxylation Nonylphenol (meth) acrylate, N-vinylpyrrolidone, etc. are mentioned.

  Specific examples of the bifunctional monomer include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) ) Acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, bisphenol A bis (acryloyloxy) Ethyl) ether, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate or 3- Such as chill-pentanediol di (meth) acrylate.

  Specific examples of other trifunctional or higher polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated tri Methylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra ( (Meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol (Meth) acrylate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, tripenta Erythritol hepta (meth) acrylate and acid anhydride caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified Pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol Hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate, Caprolactone-modified tripentaerythritol octa (meth) acrylate, reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride, or caprolactone Examples include modified tripentaerythritol hepta (meth) acrylate and acid anhydrides.

  In the present specification, caprolactone modification means that a caprolactone ring-opening product or ring-opening polymer is introduced between the alcohol-derived site of the (meth) acrylate compound and the (meth) acryloyloxy group. means.

  In particular, bifunctional or higher polyfunctional monomers are preferably used. These photopolymerizable compounds (B) can be used alone or in combination of two or more.

  Content of a photopolymerizable compound (B) is a mass fraction with respect to the total amount of binder resin (A) and a photopolymerizable compound (B), Preferably it is 1-70 mass%, More preferably, it is 5-60. % By mass. When the content of the photopolymerizable compound (B) is in the above range, the sensitivity, the strength of the coating film and the pattern, the smoothness, the reliability and the mechanical strength tend to be good, which is preferable.

  The photopolymerization initiator (C) contained in the photosensitive resin composition of the present invention is a photopolymerization comprising a compound (C1) containing an acetophenone skeleton and a compound (C2) having at least two thiol groups. It is an initiator.

Examples of the compound (C1) containing the acetophenone skeleton include compounds containing an α-aminoketone skeleton.
Specific examples of the compound (C1) include, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2- Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane- 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) Butanone, 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl)- Butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl)- Butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2- Lorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-chloro Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromo Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methoxy) Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-dimethylamino NO-1- (4-morpholinophenyl) -butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxybenzyl) 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2 -Bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1- ON oligomers.

  The content of the compound (C1) containing an acetophenone skeleton in the photosensitive resin composition of the present invention is a mass fraction with respect to the total amount of the photopolymerization initiator (C), preferably 10 to 90% by mass, more preferably 30 to 80% by mass. It is preferable that the content of the compound (C1) containing an acetophenone skeleton is in the above range because sensitivity tends to be high and developability tends to be good.

Examples of the compound (C2) having at least two thiol groups include a compound having at least two —O—CO—CH ₂ —CH ₂ SH groups and a compound having at least three thiol groups. Can be mentioned.
Specific examples of the compound (C2) include, for example, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, Methylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl Tristhiopropionate, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane Dipentaerythritol hexakisthiopropionate, dipentaerythritol hexakis (3-mercaptobutyrate), 1,3,5-trismercaptopropionate-1,3,5-triazine-2,4,6 (1H , 3H, 5H) -trione, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like. It is done.

  The content of the compound (C2) having at least two thiol groups in the photosensitive resin composition of the present invention is a mass fraction with respect to the total amount of the photopolymerization initiator (C), preferably 5 to 80% by mass, More preferably, it is 10-70 mass%. When the content of the compound (C2) having at least two thiol groups is in the above range, the sensitivity tends to be high and the developability tends to be good, which is preferable.

  The photosensitive resin composition of the present invention may contain a photopolymerization initiator other than the compounds (C1) and (C2) to the extent that the effects of the present invention are not impaired. Such biimidazole compounds, triazine compounds, acylphosphine oxide compounds or oxime compounds are preferred, and biimidazole compounds are particularly preferred because of their excellent sensitivity.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxy) Phenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), imidazole in which the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group Compounds (see, for example, JP-A-7-10913) and the like, and preferably 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5 ′ -Tetraphenylbiimidazole is mentioned.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylphenyl Ethenyl] -1,3,5-triazine, such as 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine

  Examples of the acylphosphine oxide initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the oxime compound include O-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, a compound represented by the formula (IV), a compound represented by the formula (V), and the like.

As long as the effects of the present invention are not impaired, a photopolymerization initiator or the like can be further used together. Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, and thioxanthone compounds.
More specifically, the following compounds can be mentioned, and these can be used alone or in combination of two or more.

  Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxide). Oxycarbonyl) benzophenone or 2,4,6-trimethylbenzophenone.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

  Other examples of photopolymerization initiators include 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds. .

Further, as a photopolymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in JP-T-2002-544205 can be used.
As a photoinitiator which has the group which can raise | generate the said chain transfer, the photoinitiator of following formula (5)-following formula (10) is mentioned, for example.

In addition, light and / or thermal cationic polymerization initiators can be used.
As the light and / or thermal cationic polymerization initiator, those composed of an onium cation and an anion derived from a Lewis acid can also be used.

  Specific examples of the onium cation include diphenyliodonium, bis (p-tolyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, bis (P-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (p-octadecyloxyphenyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, triphenylsulfonium, tris (p- Tolyl) sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (p-tert-butylphenyl) sulfonium, tris (p-si Nophenyl) sulfonium, tris (p-chlorophenyl) sulfonium, dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecanoxy) sulfonium, Dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromo Propoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (8-nitroo) Yloxy) sulfonium, dimethyl (18-trifluoromethyl octadecanoic oxy) sulfonium, dimethyl (2-hydroxy-isopropoxyphenyl) sulfonium, or dimethyl (tris (trichloromethyl) methyl) sulfonium and the like.

  Preferred onium cations include bis (p-tolyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium or tris (p-tert-butylphenyl). ) Sulfonium and the like.

Specific examples of the Lewis acid-derived anion include hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, and tetrakis (pentafluorophenyl) borate. Preferred anions derived from Lewis acid include hexafluoroantimonate or tetrakis (pentafluorophenyl) borate.
The onium cation and Lewis acid-derived anion can be arbitrarily combined.

Specific examples of the cationic polymerization initiator include diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-octylphenyl) iodonium hexa Fluorophosphate, bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium Hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophos , Methyl naphthyl iodonium hexafluorophosphate, ethyl naphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexafluorophosphate, tris (2, 6-dimethylphenyl) sulfonium hexafluorophosphate, tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium Hexafluorophosphate, diethylnaphthyls Honium hexafluorophosphate, dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl (ethoxy) sulfonium hexafluorophosphate, dimethyl (propoxy) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluoro Phosphate, dimethyl (octadecanoxy) sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium Hexafluorophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluorophosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, Dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluorophosphate, dimethyl (tris (trichloromethyl) methyl) Sulfonium hexafluorophosphate;
Diphenyliodonium hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, bis (p-octylphenyl) iodonium hexafluoroarsenate, bis (p -Octadecylphenyl) iodonium hexafluoroarsenate, bis (p-octyloxyphenyl) iodonium hexafluoroarsenate, bis (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarsenate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, methylnaphthyl iodonium Oxafluoroarsenate, ethyl naphthyl iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (p-tolyl) sulfonium hexafluoroarsenate, tris (p-isopropylphenyl) sulfonium hexafluoroarsenate, tris (2, 6-dimethylphenyl) sulfonium hexafluoroarsenate, tris (p-tert-butylphenyl) sulfonium hexafluoroarsenate, tris (p-cyanophenyl) sulfonium hexafluoroarsenate, tris (p-chlorophenyl) sulfonium hexafluoroarsenate , Dimethylnaphthylsulfonium hexafluoroarsenate, diethylnaphthylsulfonium hexafluoroarsenate Dimethyl (methoxy) sulfonium hexafluoroarsenate, dimethyl (ethoxy) sulfonium hexafluoroarsenate, dimethyl (propoxy) sulfonium hexafluoroarsenate, dimethyl (butoxy) sulfonium hexafluoroarsenate, dimethyl (octyloxy) sulfonium hexafluoroarsenate , Dimethyl (octadecanoxy) sulfonium hexafluoroarsenate, dimethyl (isopropoxy) sulfonium hexafluoroarsenate, dimethyl (tert-butoxy) sulfonium hexafluoroarsenate, dimethyl (cyclopentyloxy) sulfonium hexafluoroarsenate, dimethyl (cyclohexyloxy) ) Sulfonium hexafluoroarsenate, dimethyl (Fluoromethoxy) sulfonium hexafluoroarsenate, dimethyl (2-chloroethoxy) sulfonium hexafluoroarsenate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarsenate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroarsenate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroarsenate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroarsenate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroarsenate, dimethyl (tris (trichloromethyl) Methyl) sulfonium hexafluoroarsenate;
Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, bis (p-octylphenyl) iodonium hexafluoroantimonate, bis (p -Octadecylphenyl) iodonium hexafluoroantimonate, bis (p-octyloxyphenyl) iodonium hexafluoroantimonate, bis (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroantimonate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, methyl naphthalate Tyl iodonium hexafluoroantimonate, ethyl naphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate, tris (p-isopropylphenyl) sulfonium hexafluoroantimonate, tris ( 2,6-dimethylphenyl) sulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium hexafluoroantimonate, tris (p-chlorophenyl) sulfonium hexafluoro Antimonate, dimethyl naphthylsulfonium hexafluoroantimonate, diethyl naphthyl Rufonium hexafluoroantimonate, dimethyl (methoxy) sulfonium hexafluoroantimonate, dimethyl (ethoxy) sulfonium hexafluoroantimonate, dimethyl (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimonate, dimethyl (octyl) Oxy) sulfonium hexafluoroantimonate, dimethyl (octadecanoxy) sulfonium hexafluoroantimonate, dimethyl (isopropoxy) sulfonium hexafluoroantimonate, dimethyl (tert-butoxy) sulfonium hexafluoroantimonate, dimethyl (cyclopentyloxy) sulfonium hexafluoro Antimonate, dimethyl (cyclohexyl) Ruoxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium hexafluoroantimonate, dimethyl (2-chloroethoxy) sulfonium hexafluoroantimonate, dimethyl (3-bromopropoxy) sulfonium hexafluoroantimonate, dimethyl (4-cyano Butoxy) sulfonium hexafluoroantimonate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroantimonate , Dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoro Nchimoneto;
Diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (p-tolyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-octylphenyl) Iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) Iodonium tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis Pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, methylnaphthyliodonium tetrakis (pentafluorophenyl) borate, ethylnaphthyliodonium tetrakis (pentafluorophenyl) borate, triphenyl Sulfonium tetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-isopropylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (2,6-dimethylphenyl) sulfonium Tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium teto Kiss (pentafluorophenyl) borate, tris (p-cyanophenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, Diethyl naphthylsulfonium tetrakis (pentafluorophenyl) borate, dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (ethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (propoxy) sulfonium tetrakis (pentafluorophenyl) borate, Dimethyl (butoxy) sulfonium tetrakis (pentafluorophenyl) bo Dimethyl (octyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octadecanoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tert-butoxy) Sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclopentyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclohexyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (fluoromethoxy) sulfonium tetrakis (pentafluorophenyl) borate , Dimethyl (2-chloroethoxy) sulfonium tetra (Pentafluorophenyl) borate, dimethyl (3-bromopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (4-cyanobutoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) Methyl) sulfonium tetrakis (pentafluorophenyl) borate and the like, preferably bis (p-tolyl) Donium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tert- Butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsenate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarcete Nate, triphenylsulfonium hexafluoroarsenate, tris (pt-butylphenyl) sulfonium hexafluoroarsenate, Bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate Nates, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) Borate, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (pt rt-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate and the like, more preferably bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, Bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) ) Borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butyl) Phenyl) iodonium tetrakis (pentafluorophenyl) borate, triphenyl sulfonium tetrakis (pentafluorophenyl) borate, or tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate.

Further, the photopolymerization initiator (C) can be used in combination with the photopolymerization initiator (C-1) to such an extent that the effects of the present invention are not impaired. it can.
Examples of the photopolymerization initiation assistant (C-1) include amine compounds, carboxylic acid compounds, compounds represented by the formula (III), compounds represented by the formula (A-1) or the formula (A-2), and the like. Can be mentioned.

  Examples of the amine compounds include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4- 2-ethylhexyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name: Michler's ketone) or 4,4′-bis (diethylamino) Examples include aromatic amine compounds such as benzophenone.

  Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, Aromatic heteroacetic acids such as N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine or naphthoxyacetic acid can be mentioned.

  As the photopolymerization initiation assistant (C-1), a compound represented by the following formula (III) can also be used.

In formula (III), the dotted line represented by X represents an aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom.
Y represents an oxygen atom or a sulfur atom.
R ²¹ represents an alkyl group having 1 to 6 carbon atoms.
R ²² represents an alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom or an aryl group which may be substituted with a halogen atom.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring and a naphthalene ring.

  Examples of the aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom include a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, a hexylbenzene ring, Examples include cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring, and the like.

  Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2-methyl-n-propyl group, tert- Butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2- Examples include dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group and the like.

  Examples of the alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2- Methyl-n-propyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl- n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group, 1-chloro-n-butyl group, 2-chloro-n- A butyl group, 3-chloro-n-butyl group, etc. are mentioned.

  The aryl group which may be substituted with a halogen atom includes a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobromophenyl group, a biphenyl group, a chlorobiphenyl group, a dichlorobiphenyl group, and a bromophenyl group. , Dibromophenyl group, naphthyl group, chloronaphthyl group, dichloronaphthyl group, bromonaphthyl group, dibromonaphthyl group and the like.

As the compound represented by the formula (III), specifically,
2-benzoylmethylene-3-methyl-naphtho [2,1-d] thiazoline,
2-benzoylmethylene-3-methyl-naphtho [1,2-d] thiazoline,
2-benzoylmethylene-3-methyl-naphtho [2,3-d] thiazoline,
2- (2-naphthoylmethylene) -3-methylbenzothiazoline,
2- (1-naphthoylmethylene) -3-methylbenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-phenylbenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-fluorobenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-fluorobenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-chlorobenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-bromobenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-bromobenzothiazoline,
2- (4-biphenoylmethylene) -3-methylbenzothiazoline,
2- (4-biphenoylmethylene) -3-methyl-5-phenylbenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,
2- (4-biphenoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,
2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,
2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,
2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,
2-benzoylmethylene-3-methyl-naphtho [2,1-d] oxazoline,
2-benzoylmethylene-3-methyl-naphtho [1,2-d] oxazoline,
2-benzoylmethylene-3-methyl-naphtho [2,3-d] oxazoline,
2- (2-naphthoylmethylene) -3-methylbenzoxazoline,
2- (1-naphthoylmethylene) -3-methylbenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-phenylbenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-fluorobenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-fluorobenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-chlorobenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-bromobenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-bromobenzoxazoline,
2- (4-biphenoylmethylene) -3-methylbenzoxazoline,
2- (4-biphenoylmethylene) -3-methyl-5-phenylbenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline,
2- (4-biphenoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,
2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline,
2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,
2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline,
Etc.

Among them, 2- (2-naphthoylmethylene) -3-methylbenzothiazoline represented by the formula (III-1), 2-benzoylmethylene-3-methyl-naphtho represented by the formula (III-2) [1,2 -D] thiazoline and 2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline represented by the formula (III-3) are preferred.

  As the photopolymerization initiation aid (C-1), a compound represented by at least one selected from the group consisting of formula (A-1) and formula (A-2) can also be used.

[In Formula (A-1) and Formula (A-2), Ring X ³¹ and Ring X ³² each independently represent an aromatic ring having 6 to 12 carbon atoms. Y ³¹ and Y ³² represent an oxygen atom or a sulfur atom. R ³¹ and R ³² represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.
The carbon atom contained in the aromatic ring, the alkyl group or the aryl group may be substituted with an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. ]

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the aromatic ring having 6 to 12 carbon atoms include benzene ring, methylbenzene ring, dimethylbenzene ring, ethylbenzene ring, propylbenzene ring, butylbenzene ring, pentylbenzene ring, hexylbenzene ring, cyclohexylbenzene ring, chlorobenzene ring, and dichlorobenzene. Ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring, phenanthrene ring, chrysene ring, fluoranthene ring, benzo [a] pyrene ring, Examples include benzo [e] pyrene ring, perylene ring, and derivatives thereof.

  Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2-methyl-n-propyl group, tert- Butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2- Dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group, 1-chloro-n-butyl group, 2-chloro-n-butyl group, 3-chloro-n- A butyl group etc. are mentioned.

  Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, dibromophenyl group, chlorobromophenyl group, hydroxyphenyl group, alkoxyphenyl group, biphenyl group, chlorobiphenyl group, dichlorobiphenyl. Group, bromophenyl group, dibromophenyl group, naphthyl group, chloronaphthyl group, dichloronaphthyl group, bromonaphthyl group, dibromonaphthyl group, hydroxynaphthyl group and the like.

As a compound represented by Formula (A-1) or Formula (A-2), specifically,
Dialkoxynaphthalenes such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene, dibutoxynaphthalene, dimethoxyanthracene, diethoxyanthracene, dipropoxyanthracene, diisopropoxyanthracene, dibutoxyanthracene, dipentaoxyanthracene, Dihexoxyoxyanthracene, methoxyethoxyanthracene, methoxypropoxyanthracene, methoxyisopropoxyanthracene, methoxybutoxyanthracene, ethoxypropoxyanthracene, ethoxyisopropoxyanthracene, ethoxybutoxyanthracene, propoxyisopropoxyanthracene, propoxybutoxyanthracene, isopropoxybutoxyanthracene, etc. Alkoxy anthracenes dimethoxy naphthacene, diethoxy naphthacene, dipropoxy naphthacene, diisopropoxy Sina lid Sen, dibutoxyethoxyethyl Sina lid but Sen and dialkoxy naphthacene such as including but not limited to it.

The content of the entire photopolymerization initiator (C) (including the (C1) and (C2)) in the photosensitive resin composition of the present invention is the total amount of the binder resin (A) and the photopolymerizable compound (B). The mass fraction is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass.
The content of the photopolymerization initiation assistant (C-1) is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass, based on the same standard as described above.
The content of the compound represented by at least one selected from the group consisting of formula (A-1) and formula (A-2) is preferably relative to the content of photopolymerization initiation aid (C-1). Is 50 to 100%, more preferably 60 to 100%, still more preferably 65 to 100%. When the content of the compound represented by at least one selected from the group consisting of formula (A-1) and formula (A-2) is in the above range, the photosensitive resin composition containing the compound is used for coating. When a film is formed, the transparency of the coating film is improved, which is preferable.
When the total amount of the photopolymerization initiator (C) is in the above range, the photosensitive resin composition becomes highly sensitive, the strength of the coating film or pattern formed using the photosensitive resin composition, The smoothness on the surface of the coating film or pattern tends to be good, which is preferable. In addition to the above, when the amount of the photopolymerization initiation assistant (C-1) is in the above range, the sensitivity of the obtained photosensitive resin composition is further increased, and the photosensitive resin composition is formed using the photosensitive resin composition. This is preferable because the productivity of the pattern to be improved tends to be improved.

Examples of the solvent (D) contained in the photosensitive resin composition of the present invention include various organic solvents used in the field of photosensitive resin compositions. Specific examples thereof include ethylene glycol monomethyl ether, Ethylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate;
Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether, propylene glycol ethyl propyl ether, propylene glycol methyl ether propionate, propylene glycol ethyl ether Propylene glycol alkyl ether propionates such as propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate;
Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol, butoxybutyl alcohol;
Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate;
Butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate;
Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether;
Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin;
Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyethyl acetate, hydroxy Butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methylbutane Methyl acetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, propoxy Ethyl acetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2- Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxy Propyl propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3- Methyl toxipropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxy Esters such as butyl propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate;
Cyclic ether groups such as tetrahydrofuran and pyran;
and cyclic esters such as γ-butyrolactone.

Among the above solvents, an organic solvent having a boiling point of 100 to 200 ° C. is preferable among the above solvents from the viewpoints of coating properties and drying properties. As an organic solvent having a boiling point of 100 to 200 ° C., specifically, alkylene glycol alkyl ether acetates, alcohols such as methoxybutanol and ethoxybutanol, ketones such as cyclohexanone,
And esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutanol, methoxybutyl acetate, 3-ethoxypropion Examples include ethyl acid and methyl 3-methoxypropionate.
These solvents (D) can be used alone or in combination of two or more.

Content of the solvent (D) in the photosensitive resin composition of this invention is a mass fraction with respect to the photosensitive resin composition whole quantity, Preferably it is 60-90 mass%, More preferably, it is 65-85 mass%. . When the content of the solvent (D) is in the above range, it may be called a spin coater, a slit & spin coater, or a slit coater (die coater, curtain flow coater).
), The coating property is expected to be good when applied by a coating device such as an inkjet, roll coater, dip coater, etc., which is preferable.

  The photosensitive resin composition of the present invention does not substantially contain colorants such as pigments and dyes. That is, in the photosensitive resin composition of the present invention, the content of the colorant with respect to the entire composition is, for example, a mass fraction of less than 10% by mass, preferably less than 1% by mass.

In the photosensitive resin composition of the present invention, if necessary, a filler, other polymer compound, a leveling agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, a light stabilizer, an anti-aggregation material, chain transfer An additive (F) such as an agent can also be used in combination.
Specific examples of the filler include glass, silica, and alumina.

  Specific examples of other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Can be mentioned.

  As the leveling agent, a commercially available surfactant can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, and amphoteric surfactants. Two or more kinds may be used in combination. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFac (manufactured by Dainippon Ink & Chemicals, Inc.) ), Florard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS), PB821 (manufactured by Ajinomoto Co., Inc.) ) And the like.

  As the adhesion promoter, silane compounds are preferable, and specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyl. Dimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

  Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy- 3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy]- 2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3,9-bis [2- {3- (3-tert-butyl-4 -Hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2′-methyle Bis (6-tert-butyl-4-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (2-tert-butyl-5-methylphenol) ), 2,2′-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′- Thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine -2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', ''-(Mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di -Tert-butyl-4-methylphenol and the like.

  Specific examples of the ultraviolet absorber include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro). -2H-benzotriazol-2-yl) phenyl] propionate, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4- Dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2, 4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-bis-butyloxyphenyl) 1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1- Phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole or alkoxybenzophenone. Can be mentioned.

  Specifically, the light stabilizer is a polymer composed of succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl) ethanol, N, N ′, N ″, N ′. '' -Tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazin-2-yl) -4,7-diazadecane-1 , 10-diamine, decandioic acid, reaction of bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester with 1,1-dimethylethyl hydroperoxide Bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, 2, 4-bis N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine, bis ( 1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate or methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate.

Examples of the aggregation preventing material include sodium polyacrylate.
Examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

  The photosensitive resin composition of the present invention is filled in a quartz cell having an optical path length of 1 cm, and when the transmittance is measured under a measurement wavelength of 400 to 700 nm using a spectrophotometer, the transmittance is 70% or more. Preferably, it is 80% or more.

  Moreover, the photosensitive resin composition of this invention uses a spectrophotometer about the coating film of 3 micrometers in thickness after heat-curing (for example, 100-250 degreeC, 5 minutes-3 hours), and is measured wavelength 400-. When the transmittance is measured under the condition of 700 nm, the transmittance is 90% or more, preferably 95% or more. Thereby, the coating film excellent in transparency can be provided.

The photosensitive resin composition of the present invention is applied onto a substrate on which a glass substrate, a film substrate, a color filter or a drive circuit is formed, for example, as described below, and is subjected to photocuring and development to form a coating film or pattern. Can be formed.
First, this photosensitive resin composition is applied onto a substrate (usually glass) or a layer made of a solid content of a previously formed photosensitive resin composition, and prebaked from the applied photosensitive resin composition layer. By removing volatile components such as a solvent, a smooth uncured coating film is obtained. The thickness of the uncured coating film at this time is approximately 1 to 6 μm. The uncured coating film thus obtained is irradiated with ultraviolet rays generated from a mercury lamp or a light emitting diode through a mask for forming a target pattern.
In the pattern formation, the line width can be appropriately controlled depending on the mask size.

  Recent exposure machines use a band-pass filter that cuts out light of less than 350 nm using a filter that cuts the wavelength range, and extracts light of wavelengths near 436 nm, 408 nm, and 365 nm. Or the like, and the parallel light beam is uniformly irradiated on the entire exposed portion. At this time, it is preferable to use a device such as a mask aligner or a stepper so that the mask and the substrate are accurately aligned. Further, after that, the coating film after the light irradiation is brought into contact with an alkaline aqueous solution to dissolve the non-exposed portion and developed, whereby a desired coating film or pattern is obtained. The developing method may be any of a liquid piling method, a dipping method, a spray method, and the like. Further, the substrate may be tilted at an arbitrary angle during development.

  The developer used for development after patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound may be either an inorganic or organic alkaline compound.
Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, Examples thereof include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate or ammonia.
Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine or ethanolamine. Etc. These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

Further, the surfactant in the alkali developer may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
Specific examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Examples thereof include oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.
Specific examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and dodecylnaphthalene. And alkylaryl sulfonates such as sodium sulfonate.
Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, or quaternary ammonium salts.
These surfactants can be used alone or in combination of two or more.
The concentration of the surfactant in the alkali developer is preferably in the range of 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.

  After development, it is washed with water, and if necessary, post-baking can be performed at 150 to 230 ° C. for 10 to 180 minutes.

  By using the photosensitive resin composition of the present invention, a coating film or a pattern can be formed on the substrate or the color filter substrate through the above steps. This coating film or pattern is useful as a photo spacer used in a liquid crystal display device or a patternable overcoat. In addition, if a photomask for hole formation is used during patterning exposure to an uncured coating film, holes can be formed, which is useful as an interlayer insulating film. Furthermore, when exposing an uncured coating film, a transparent film can be formed only by exposure and heat curing, or only by heat curing, without using a photomask, and this transparent film is useful as an overcoat. It can also be used for touch panels.

  By incorporating the coating film or pattern thus obtained in a display device such as a liquid crystal display device, an excellent quality display device can be manufactured with a high yield.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it cannot be overemphasized that this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

[Synthesis Example 1]
Nitrogen was flowed at a rate of 0.02 L / min into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to form a nitrogen atmosphere. Subsequently, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) The compound to be mixed is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts by mass and 140 parts by mass of 3-methoxybutyl acetate, and the solution is added using a dropping funnel for 4 hours. And dropped in a flask kept at 70 ° C. On the other hand, a solution obtained by dissolving 45 parts by mass of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of 3-methoxybutyl acetate was added to a flask over another 4 hours using another dropping funnel. It was dripped in. After completion of the dropwise addition of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours, and then cooled to room temperature, and the copolymer having a solid content of 32.3 mass% and an acid value of 35.6 mg-KOH / g A resin solution was obtained. The obtained resin Aa had a weight average molecular weight Mw of 9.1 × 10 ³ and a molecular weight distribution (Mw / Mn) of 2.02.

[Synthesis Example 2]
After introducing 402 parts by mass of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, the atmosphere in the flask was changed from air to nitrogen, the temperature was raised to 100 ° C. Thereafter, azobis was added to a mixture of 31 parts by mass of styrene, 86 parts by mass of glycidyl methacrylate, 67 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and 198 parts by mass of propylene glycol monomethyl ether acetate. A solution to which 4.1 parts by mass of isobutyronitrile was added was dropped into the flask from the dropping funnel over 2 hours, and stirring was further continued at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 52 parts by mass of methacrylic acid (100 mol% with respect to the glycidyl group of glycidyl methacrylate used in this reaction)], 1.1 parts by mass of trisdimethylaminomethylphenol and hydroquinone 0.2 parts by mass was charged into the flask, and the reaction was continued at 110 ° C. for 6 hours. When the solid content acid value reached 1 mgKOH / g, the reaction was terminated. Next, 64 parts by mass of tetrahydrophthalic anhydride and 1.0 part by mass of triethylamino were added and reacted at 120 ° C. for 3.5 hours to obtain a resin Ab having a solid content of 33.0% by mass and a solid content acid value of 91 mgKOH / g. Obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 1.8 × 10 ⁴ and the molecular weight distribution (Mw / Mn) was 2.2.

(Measurement of molecular weight)
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resins Aa and Ab were measured using the GPC method under the following conditions.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
The ratio of the weight average molecular weight and number average molecular weight obtained in the above-mentioned manner was defined as the molecular weight distribution (Mw / Mn).

[Example 1]
155 parts of resin solution (A) containing resin Aa obtained in Synthesis Example 1 (50 parts in terms of solid content), 50 parts of dipentaerythritol hexaacrylate (B), 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butan-1-one (C) 3 parts, 4,4-di (N, N-dimethylamino) -benzophenone (C) 1 part, pentaerythritol tetrakisthiopropionate (C) 3 parts, A photosensitive resin composition 1 was obtained by mixing 40 parts of 3-methoxybutyl acetate (D) and 36 parts of 3-methoxy-1-butanol (D).

[Example 2]
127 parts of resin solution (A) containing resin Ab obtained in Synthesis Example 2 (50 parts in terms of solid content), 50 parts of dipentaerythritol hexaacrylate (B), 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butan-1-one (C) 3 parts, 4,4-di (N, N-dimethylamino) -benzophenone (C) 1 part, pentaerythritol tetrakisthiopropionate (C) 3 parts, A photosensitive resin composition 2 was obtained by mixing 38 parts of propylene glycol monomethyl ether acetate (D), 24 parts of 3-ethoxyethyl propionate (D), and 5 parts of epoxy resin (ESCN-195XL).

[Comparative Example 1]
Except for the removal of pentaerythritol tetrakisthiopropionate, the same components as in Example 2 were mixed to give the photosensitive resin composition 3.

  The following evaluation was performed about the photosensitive resin compositions 1-3 obtained as mentioned above. The results are shown in Table 1.

<Average transmittance of composition>
About each photosensitive resin composition, the average transmittance (%) in 400-700 nm was measured using the microspectrophotometer (OSP-SP200; OLYMPUS company make).

<Membrane average transmittance>
Using each photosensitive resin composition, a cured film was produced under the following conditions so that the film thickness after curing was 3 μm.
A 2-inch square glass substrate (# 1737; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, the photosensitive resin composition is exposed at an exposure amount (365 nm) of 200 mJ / cm ² , spin-coated so that the film thickness after development, water washing, and post-baking becomes 3.0 μm. And prebaked at 90 ° C. for 3 minutes in a clean oven.
About each obtained cured film, the average transmittance | permeability (%) in 400-700 nm was measured using the microspectrophotometer (OSP-SP200; product made by OLYMPUS).
Higher transmittance means less absorption.

<Residual film sensitivity>
A 2-inch square glass substrate (# 1737; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, the photosensitive resin composition is exposed at an exposure amount (365 nm) of 200 mJ / cm ² , spin-coated so that the film thickness after development, water washing, and post-baking becomes 3.0 μm. And prebaked at 90 ° C. for 3 minutes in a clean oven. After cooling, the distance between the substrate coated with the photosensitive resin composition and the quartz glass photomask is set to 100 μm, and the exposure apparatus (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp) is used to form the atmosphere. In the atmosphere, light irradiation was performed at an exposure amount (based on 365 nm) of 80 mJ / cm ² and 200 mJ / cm ² . In addition, the irradiation to the photosensitive resin composition at this time used the radiated light from an ultrahigh pressure mercury lamp through the optical filter (UV-35; Asahi Techno Glass Co., Ltd.). In addition, a photomask having a pattern (having a square light-transmitting portion with one side of 10 μm and a space between the squares of 100 μm) formed on the same plane was used as the photomask.
After light irradiation, the coating film was immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23 ° C. for 80 seconds, developed, washed with water, Post-baking was carried out at 20 ° C. for 20 minutes.
The pattern height after each post-baking was measured with a three-dimensional non-contact surface shape measurement system (Micromap MM527N-PS-M100; manufactured by Ryoka Systems Inc.). Residual film sensitivity was calculated by the following equation. The results are listed in Table 1.
The larger the value of the remaining film sensitivity (%), the better the dependency of the pattern height on the exposure amount and the wider the process margin.

  From the results of Examples 1 and 2 shown in Table 1, it can be seen that the sensitivity of the photosensitive resin composition can be improved by using a specific photopolymerization initiator. On the other hand, in Comparative Example 1, the sensitivity of the photosensitive resin composition was not sufficient.

  The photosensitive resin composition of the present invention can form a coating film or pattern with high sensitivity and high transmittance. Therefore, it can be suitably used for forming a coating film or a pattern used in a display device such as an overcoat, a photo spacer, an insulating film, a protrusion for controlling liquid crystal alignment, and a coating layer for adjusting the film thickness of a colored pattern.

Claims (13)

Contains binder resin (A), photopolymerizable compound (B), photopolymerization initiator (C) and solvent (D),
A photosensitive resin composition, wherein the photopolymerization initiator (C) is a photopolymerization initiator comprising a compound (C1) containing an acetophenone skeleton and a compound (C2) having at least two thiol groups.   The photosensitive resin composition according to claim 1, wherein the compound (C1) containing an acetophenone skeleton is a compound containing an α-aminoketone skeleton.   The binder resin (A) includes at least an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (Aa) and a monomer (Ac) having a cyclic ether group having 2 to 4 carbon atoms. The photosensitive resin composition of Claim 1 or 2 which is a copolymer formed by superposition | polymerization.   The photosensitive resin composition of Claim 3 whose monomer (Ac) which has a C2-C4 cyclic ether group is a monomer which has an epoxy group.   The photosensitive resin composition of Claim 4 whose monomer which has an epoxy group is a monomer which has an aliphatic polycyclic epoxy group. 6. The monomer having an aliphatic polycyclic epoxy group is at least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II). The photosensitive resin composition as described in 2.

[In Formula (I) and Formula (II), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.
X ₁ and X ₂ each independently represent a C 1-6 alkylene group that may contain a single bond or a hetero atom. ]   The unsaturated carboxylic acid and / or the unsaturated carboxylic acid anhydride (Aa) is an aliphatic unsaturated carboxylic acid and / or an aliphatic unsaturated carboxylic acid anhydride. Photosensitive resin composition. At least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II) is represented by a compound represented by formula (I ′) and formula (II ′). The photosensitive resin composition of Claim 6 or 7 which is at least 1 sort (s) of compound chosen from the group which consists of a compound made.

[In Formula (I ′) and Formula (II ′), R ₁ ′ and R ₂ ′ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. ] Compounds having at least two thiol groups (C2) is a compound having at least two _{-O-CO-CH 2 -CH 2} SH group, the photosensitive resin according to claim 1 Composition.   The photosensitive resin composition in any one of Claims 1-9 whose compound (C2) which has an at least 2 thiol group is a compound which has an at least 3 thiol group.   Use of the photosensitive resin composition in any one of Claims 1-10 for forming a coating film or a pattern.   The coating film or pattern formed using the photosensitive resin composition in any one of Claims 1-10.   The display apparatus containing the coating film or pattern of Claim 12.