JP7210875B2 - Photosensitive resin composition, cured film and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin composition and a cured film using the same. The cured film can be suitably used for interlayer insulating films and overcoat films used in touch panels, liquid crystal display devices, organic EL devices, and the like.

Most capacitive touch panels, which are currently mainstream, use transparent conductive films, which are advantageous for weight reduction and workability, such as the GFF method, in which two sheets of ITO film are attached to a cover glass. It is However, since a film with low heat resistance is used, low-temperature firing is required.

With respect to flat panel displays such as liquid crystal display devices and organic EL display devices, there is an increasing demand for low-temperature firing of each member from the viewpoint of reducing damage to substrates and circuits in the manufacturing process and saving energy.

As an interlayer insulating film, there is also a manufacturing process that partially etches the ITO placed on the insulating film to form an electrode with high resolution that enables the formation of fine patterns by photolithography due to the trend of high definition. Chemical resistance (alkali resistance, acid resistance) to chemicals used in the etching process, low degassing amount because it does not affect the upper layer formation process, and high hardness when used in touch panels must have characteristics such as

Examples of low-temperature sinterable resin compositions include the alkali-soluble copolymer described in Patent Document 1, a polymerizable compound having an ethylenically unsaturated bond, a photoradical generator, a compound having two or more oxetanyl groups in one molecule, and A radiation-sensitive resin composition containing an acid generator, a resin composition containing a carboxyl group-containing polysiloxane described in Patent Document 2, a solvent, a compound having a double bond and/or a triple bond, and a photopolymerization initiator. Proposed. However, according to the studies of the present inventors, these compositions have improved adhesion to glass and silicon nitride substrates, but have insufficient adhesion to substrates having no Si atoms such as ITO and molybdenum. , the chemical resistance was also insufficient.
Further, although Patent Documents 3 and 4 also disclose compositions having excellent adhesion, they are insufficient in terms of chemical resistance, resolution in photolithography, and degassing.

JP 2009-003366 A JP 2008-208342 A JP 2015-030732 A JP 2011-022376 A

An object of the present invention is to provide a photosensitive resin composition that has good resolution and can form a cured film with good chemical resistance, low outgassing, and high hardness even at a curing temperature of 120° C. or less. It is to be. Further, by using the photosensitive composition, a high-quality cured film, an interlayer insulating film, an overcoat film, which is excellent in resolution, hardness and chemical resistance, and has a small amount of outgassing, and a method for producing the same are provided. be able to.

As a result of extensive studies, the present inventors have found that a photosensitive resin containing a specific resin (A), a silane coupling agent (B), a polymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) It has been found that by using a hardening resin composition, even at a curing temperature of 120° C. or less, a cured film with good chemical resistance, low outgassing, and high hardness can be formed.
<1> That is, the present invention is a photosensitive resin composition containing a resin (A), a silane coupling agent (B), a polymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), , the resin (A) contains a resin obtained by reacting a copolymer of (a) and (b) below with (c) and then (d), and the content of the silane coupling agent (B) is It relates to a photosensitive resin composition that is 5 to 20% by mass in the total solid content of the photosensitive resin composition.
(a): a monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b): a monomer having an unsaturated bond copolymerizable with (a) and different from (a) Polymer (c): at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (d): succinic anhydride

<2> The present invention also relates to the photosensitive resin composition, wherein the silane coupling agent (B) contains at least one organic group selected from the group consisting of (meth)acryloxy groups, epoxy groups and mercapto groups.

<3> In addition, the present invention further provides the photosensitive material containing inorganic fine particles (F) containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium. It relates to a resin composition.

<4> The present invention also relates to the photosensitive resin composition, wherein the inorganic fine particles (F) are inorganic fine particles containing silicon.

<5> The present invention also relates to the photosensitive resin composition, wherein the content of the photopolymerization initiator (D) is 0.5 to 7.0% by mass based on the total solid content of the photosensitive resin composition.

<6> The present invention also relates to the photosensitive resin composition, wherein the content of the silane coupling agent (B) is 7 to 15% by mass based on the total solid content of the photosensitive resin composition.

<7> The present invention further relates to the photosensitive resin composition containing an ultraviolet absorber (G).

<8> The present invention also relates to the photosensitive resin composition, wherein the polymerizable compound (C) contains urethane (meth)acrylate.

<9> The present invention also relates to the photosensitive resin composition, wherein the solvent (E) contains a solvent having a boiling point of 130°C or less.

<10> The present invention also relates to a cured film formed from the photosensitive resin composition.

<11> The present invention also relates to the cured film which is an interlayer insulating film or an overcoat film.

<12> The present invention also relates to a method for producing a cured film, which comprises coating the photosensitive resin composition on a substrate, exposing the composition to light through a mask, developing the composition to form a pattern, and heating and baking the composition.

<13> Further, the present invention relates to a method for producing the cured film, wherein the temperature for heating and baking is 120°C or less.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a photosensitive composition capable of forming a cured film having good resolution, good chemical resistance and hardness even at a curing temperature of 120° C. or less, and a small amount of outgassing. . Further, by using the photosensitive composition, a high-quality cured film, an interlayer insulating film, an overcoat film, which is excellent in resolution, hardness and chemical resistance, and has a small amount of outgassing, and a method for producing the same are provided. be able to.

First, the photosensitive resin composition of the present invention will be explained.
In the present application, when "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide""acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively, unless shall be represented.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention is a photosensitive resin composition containing a resin (A), a silane coupling agent (B), a polymerizable compound (C), a photopolymerization initiator (D) and a solvent (E). The resin (A) contains a specific resin obtained by reacting a copolymer of (a) and (b) below with (c) and then (d) succinic anhydride, and a silane coupling agent ( The content of B) is 5 to 20% by mass based on the total solid content of the photosensitive resin composition.
(a): a monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b): a monomer having an unsaturated bond copolymerizable with (a) and different from (a) Polymer (c): at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (d): succinic anhydride Various components of the photosensitive resin composition of the present invention are described below. .

<Resin (A)>
The photosensitive resin composition according to the present invention contains a specific resin obtained by reacting a copolymer of (a) and (b) below with (c) and then (d).
(a): a monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b): a monomer having an unsaturated bond copolymerizable with (a) and different from (a) Polymer (c): at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (d): succinic anhydride Adhesion and resolution by containing a specific resin modified with succinic anhydride It is possible to form a cured film with excellent chemical resistance, low outgassing properties, and good chemical resistance.

The resin (A) of the present invention has a monomer (a) having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond, and an unsaturated bond copolymerizable with (a), At least one (c) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides in a copolymer with a monomer (b) different from a)
Next, it has a complicated structure obtained by reacting succinic anhydride (d), and it is impossible or almost unrealistic to express it with a general formula (structure), so the production method will be described.

<Specific resin obtained by reacting (c) and then (d) with copolymer of (a) and (b)>
Hereinafter, the specific resin obtained by reacting the copolymer of (a) and (b) with (c) and then with (d) will be described in detail.

[(a): a monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond]
(a) includes, for example, a monomer having an oxiranyl group and an ethylenically unsaturated bond (aX), a monomer having an oxetanyl group and an ethylenically unsaturated bond (aY), a tetrahydrofuryl group and Examples thereof include monomers (aZ) having an ethylenically unsaturated bond.

(Monomer (aX) having an oxiranyl group and an ethylenically unsaturated bond)
(aX) includes, for example, a monomer (a-1) having an epoxidized chain olefin structure and an ethylenically unsaturated bond, a cycloalkene epoxidized structure and an ethylenically unsaturated bond, A monomer (a-2) having
(aX) is preferably a monomer having an oxiranyl group and a (meth)acryloyloxy group, more preferably (a-2) having a (meth)acryloyloxy group.

Specific examples of (a-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinyl benzyl 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-bis( glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris( glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2, Examples thereof include 4,6-tris(glycidyloxymethyl)styrene and compounds described in JP-A-7-248625.

(a-2) includes vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (eg, cyclo Mer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (e.g., Cychromer M100; manufactured by Daicel Chemical Industries, Ltd.), a compound represented by formula (I), formula (II) ), and the like.

[In formula (I) and formula (II), R ¹ and R ² independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. may have been X ¹ and X ² each independently represent a single bond, -R ³ -, *-R ³ -O-, *-R ³ -S-, or *-R ³ -NH-. R ³ represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond with O. ]

Specific examples of alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group. Alkyl groups substituted with hydroxy groups include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1 -methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

R ¹ and R ² are preferably hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group and 2-hydroxyethyl group, more preferably hydrogen atom and methyl group.

The alkanediyl group includes methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane- A 1,6-diyl group and the like can be mentioned.

X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, a *—CH ₂ —O— (* represents a bond with O) group, or a *—CH ₂ CH ₂ —O— group. and more preferably a single bond or *—CH ₂ CH ₂ —O— group.

Compounds represented by formula (I) include compounds represented by formulas (I-1) to (I-15). Preferably formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15) A compound represented by any one of More preferred are compounds represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

Compounds represented by formula (II) include compounds represented by formulas (II-1) to (II-15). Preferably formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11) ~ formula (II-15) A compound represented by any one of More preferred are compounds represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).

The compound represented by formula (I) and the compound represented by formula (II) can each be used alone. Also, they can be mixed in any ratio. When mixed, the mixing ratio is a molar ratio, preferably formula (I): formula (II), 5:95 to 95:5, more preferably 10:90 to 90:10, particularly preferably 20:80 ~80:20.

(Monomer (aY) having an oxetanyl group and an ethylenically unsaturated bond)
(aY) is preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. Examples of (aY) include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth)acryloyloxyethyl oxetane, 3-ethyl-3-(meth)acryloyloxyethyl oxetane and the like.

(Monomer (aZ) having a tetrahydrofuryl group and an ethylenically unsaturated bond)
(aZ) is more preferably a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group. Specific examples of (aZ) include tetrahydrofurfuryl acrylate (eg, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

[(b): a monomer having an unsaturated bond copolymerizable with (a) and different from (a)]
(b) includes, for example, (meth)acrylic acids such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate alkyl esters;
(Meth)acrylic acid cyclic alkyl esters such as cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, etc. kind;

aryl (meth)acrylates or aralkyl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; 2-hydroxyethyl (meth)acrylate, Hydroxyalkyl esters such as 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-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-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 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-hydroxymethyl-5-methylbicyclo[2 .2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyl oxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclounsaturated compounds;

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 maleimidopropionate, N-(9-acridinyl)maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, 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.

Among them, as (b), a compound (b1) having an aromatic ring group represented by general formula (1) or general formula (2), or an aliphatic ring group represented by chemical formula (3) or chemical formula (4) When at least one of the compounds (b2) is included, chemical resistance is improved and a coating film with high hardness is obtained.

General formula (1)

［一般式（１）及び（２）中、Ｒ_１は、水素原子又はベンゼン環を有していてもよい炭素数１～２０のアルキル基である。］ general formula (2)

[In general formulas (1) and (2), R ₁ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

chemical formula (3)

chemical formula (4)

((b1) a compound having an aromatic ring group represented by general formula (1) or general formula (2))
Specific examples of the monomer (b1) having the structures of general formulas (1) and (2) include styrene, α-methylstyrene, divinylbenzene, indene, acetylnaphthene, benzyl acrylate, benzyl methacrylate, bisphenol A di Examples thereof include monomers and oligomers such as glycidyl ether di(meth)acrylate, methylolated melamine (meth)acrylic acid ester, and ethylenically unsaturated monomers represented by general formula (5).

［一般式（５）中、Ｒ_６は、水素原子又はメチル基であり、Ｒ_７は、炭素数２又は３のアルキレン基であり、Ｒ_８は、ベンゼン環を有していてもよい炭素数１～２０のアルキル基であり、ｎは、１～１５の整数である。］ general formula (5)

[In the general formula (5), R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 2 or 3 carbon atoms, and R ₈ is a carbon number that may have a benzene ring. It is an alkyl group of 1-20 and n is an integer of 1-15. ]

Examples of ethylenically unsaturated monomers represented by formula (5) include:
Daiichi Kogyo Seiyaku Co., Ltd. New Frontier CEA [EO-modified cresol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : methyl group, n=1 or 2], NP-2 [n-nonylphenoxy polyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n=2], N-177E [n-nonylphenoxy polyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n=16 to 17], or PHE [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n=1],
Daicel Corporation, IRR169 [ethoxylated phenyl acrylate (EO 1 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n=1] or Ebecryl 110 [ethoxylated phenyl acrylate (EO 2 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n=2],
Aronix M-101A [phenol EO-modified (n ≈ 2) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n ≈ 2], M-102 [phenol EO-modified (n ≈ 2) acrylate manufactured by Toagosei Co., Ltd. n≈4) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈4], M-110 [paracumylphenol EO-modified (n≈1) acrylate, R ₆ : hydrogen atom , R ₇ : ethylene group, R ₈ : paracumyl, n≈1], M-111 [n-nonylphenol EO-modified (n≈1) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n- nonyl group, n≈1], M-113 [n-nonylphenol EO-modified (n≈4) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈4], or M-117 [n-nonylphenol PO-modified (n≈2.5) acrylate, R ₆ : hydrogen atom, R ₇ : propylene group, R ₈ : n-nonyl group, n≈2.5],
Kyoei Co., Ltd. Light acrylate PO-A [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n=1], P-200A [phenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈2], NP-4EA [nonylphenol EO adduct acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈4 ], or NP-8EA [[nonylphenol EO adduct acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈8], or light ester PO [phenoxyethyl methacrylate, R ₆ : methyl group, R ₇ : propylene group, R ₈ : hydrogen atom, n=1],
NOF CORPORATION BLEMMER ANE-300 [nonylphenoxy polyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : -nonyl group, n≈5], ANP-300 [nonylphenoxy polypropylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : propylene group, R ₈ : n-nonyl group, n≈5], 43ANEP-500 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group and a propylene group, R ₈ : -nonyl group, n≈5+5], 70ANEP-550 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group and propylene group, R ₈ : n -nonyl group, n≈9+3], 75ANEP-600 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group and propylene group, R ₈ : n-nonyl group, n≈5+2 ], AAE-50 [phenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n=1], AAE-300 [phenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈5.5], PAE-50 [phenoxypolyethylene glycol methacrylate, R ₆ : methyl group, R ₇ : ethylene group, R ₈ : hydrogen atom, n=1], PAE-100 [phenoxy polyethylene glycol methacrylate, R ₆ : methyl group, R ₇ : ethylene group, R ₈ : hydrogen atom, n=2], or 43PAPE-600B [phenoxy-polyethylene glycol-polypropylene glycol-methacrylate, R ₆ : methyl group, R ₇ : ethylene group and propylene group, R ₈ : hydrogen atom, n≈6+6],
NK ESTER AMP-10G [phenoxyethylene glycol acrylate (EO1 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n=1] manufactured by Shin Nakamura Chemical Co., Ltd., AMP-20G [phenoxyethylene glycol acrylate (EO 2 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈2], AMP-60G [phenoxyethylene glycol acrylate (EO 6 mol), R ₆ : hydrogen atom, R ₇ : ethylene group , R ₈ : hydrogen atom, n≈6], PHE-1G [phenoxyethylene glycol methacrylate (EO 1 mol), R ₆ : methyl group, R ₇ : ethylene group, R ₈ : hydrogen atom, n=1],
Osaka Organic Chemical Co., Ltd. Viscoat #192 [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n=1], or
Nippon Kayaku SR-339A [2-phenoxyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n=1], or SR-504 (ethoxylated nonylphenol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group], etc., but two or more types may be used in combination without being limited to these.

In the ethylenically unsaturated monomer represented by formula (5), the alkyl group of R ₈ has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Alkyl groups include not only linear alkyl groups, but also branched alkyl groups and alkyl groups having a benzene ring as a substituent. When the number of carbon atoms in the alkyl group of R ₈ is 1 to 10, the alkyl group becomes an obstacle and suppresses the penetration of ITO etchant, metal etchant, etc., and enhances chemical resistance. The steric hindrance effect becomes high, and it tends to prevent adhesion with the substrate. This tendency becomes more conspicuous as the carbon chain length of the alkyl group of _R8 becomes longer. Examples of the alkyl group having a benzene ring represented by R ₈ include a benzyl group and a 2-phenyl(iso)propyl group. By adding one side chain benzene ring, the chemical resistance is further improved, and the developability is also improved.

In the ethylenically unsaturated monomer represented by formula (5), n is preferably an integer of 1-15. If n exceeds 15, the hydrophilicity increases and the solvation effect decreases, the viscosity of the resin (A) increases, and the viscosity of the photosensitive composition using the resin (A) also increases, and fluidity is affected. may give. From the viewpoint of solvation, n is particularly preferably 1 to 4.

As monomers having structures of general formulas (1) and (2), styrene, α-methylstyrene, benzyl acrylate, benzyl Methacrylates or ethylenically unsaturated monomers represented by general formula (5) are preferred. This is because introduction of benzene rings into the side chains of the resin (A) prevents permeation of chemicals due to the stacking effect of the benzene rings on the side chains, thereby improving chemical resistance.

((b2) compound having an aliphatic ring group represented by chemical formula (3) or chemical formula (4))
As the monomer (b2) having the structure of chemical formula (3) or (4), specifically, an ethylenically unsaturated monomer represented by general formula (6) or an ethylenic monomer represented by general formula (7) Examples include unsaturated monomers.

general formula (6)

［一般式（６）、一般式（７）中、Ｒ_９は、水素原子又はメチル基であり、Ｒ_１０は、炭素数２又は３のアルキレン基であり、ｍは、１～１５の整数である。］ General formula (7):

[In general formulas (6) and (7), R ₉ is a hydrogen atom or a methyl group, R ₁₀ is an alkylene group having 2 or 3 carbon atoms, and m is an integer of 1 to 15. be. ]

Examples of ethylenically unsaturated monomers represented by the general formula (6) include:
Fancryl FA-513A [dicyclopentanyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m=0] manufactured by Hitachi Chemical Co., Ltd., or FA-513M [dicyclopentanyl methacrylate, R ₉ : methyl, R ₁₀ : none, m=0], etc., but two or more types can be used in combination without being limited to these.

Examples of unsaturated ethylene monomers represented by the general formula (7) include:
Hitachi Chemical Co., Ltd. Fancryl FA-511A [dicyclopentenyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m=0], FA-512A [dicyclopentenyloxyethyl acrylate, R ₉ : hydrogen atom, R ₁₀ : ethylene group, m = 1], FA-512M [dicyclopentenyloxyethyl methacrylate, R ₉ : methyl group, R ₁₀ : ethylene group, m = 1], or FA-512MT [dicyclopentenyloxyethyl methacrylate, R ₉ : methyl group, R ₁₀ : ethylene group, m=1], etc., but two or more types can be used in combination without being limited to these.

As (b2), dicyclopentanyl (meth)acrylate is particularly preferable from the viewpoint of chemical resistance and hardness.

[(c): at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides]
Specific examples of (c) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;
methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[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-carboxy-6-methylbicyclo [2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclounsaturated compounds containing a carboxy group;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] phthalate kind;
Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of copolymerization reactivity and alkali solubility.

The amount of (c) added is preferably 10 to 60% by mass, more preferably 30 to 40% by mass, in terms of the charged value, with respect to the copolymer obtained by copolymerizing (a) and (b). .

[(d): succinic anhydride]
By using succinic anhydride as (d), both good adhesion and high resolution are achieved, and even when cured at a low temperature of 120 ° C. or less, the coating film has good chemical resistance, high hardness, and little outgassing. can be made. Other similar compounds include dibasic acid anhydrides such as maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, Examples include polybasic acid anhydrides such as benzophenonetetracarboxylic anhydride and biphenyltetracarboxylic anhydride. In the case of succinic anhydride, the molecular size is small, and the carboxylic acid generated by the ring-opening reaction and the double bond site is characterized by a high degree of freedom compared to other similar compounds. Since double bonds with a high degree of freedom exhibit higher reactivity, adhesion is improved and good chemical resistance is imparted. On the other hand, having a carboxylic acid with a high degree of freedom improves developability, making it possible to produce a coating film with high resolution.

The addition reaction (d) is carried out by a conventional method. The amount of (d) to be added is 5 to 100%, preferably 30 to 100%, of the hydroxyl groups generated upon introduction of the photosensitive groups. If the amount of (d) added is less than 5%, the solubility in dilute alkali decreases.

The resin (A) preferably has a weight average molecular weight in the range of 3,000 to 30,000. Furthermore, it is most preferable that the resin (A) has a weight average molecular weight of 4,000 or more and 15,000 or less. When the weight average molecular weight of the resin (A) is 4,000 or more and 15,000 or less, both good chemical resistance and high resolution can be achieved. When the molecular weight is less than 3,000, a strong cross-linked structure cannot be obtained and the hardness decreases, and when the molecular weight exceeds 30,000, the resolution deteriorates.
Here, the weight-average molecular weight is obtained by connecting four separation columns in series in a gel permeation chromatography "HLC-8120GPC" manufactured by Tosoh Corporation, and using "TSK-GEL SUPER H5000" manufactured by Tosoh Corporation as a packing material. "H4000", "H3000", and "H2000" are used, and tetrahydrofuran is used as a mobile phase to measure polystyrene-equivalent molecular weights.

<Other resins>
As other resins, thermoplastic resins, thermosetting resins, photosensitive resins, and the like can be additionally used. The resin preferably has a spectral transmittance of 80% or more, more preferably 95% or more, in the entire wavelength region of 400 to 700 nm in the visible light region. When used in the form of an alkali-developable resist material, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic group. In addition, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used for the purpose of further improving photosensitivity and improving chemical resistance.

(Thermoplastic resin)
Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, and polyurethane resins. , polyester resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Among them, it is preferable to use an acrylic resin.
Among these, at least one resin selected from acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers, particularly acrylic resins having acidic groups, are preferably used because of their high heat resistance and transparency. be done.

(Thermosetting resin)
Thermosetting resins may be low-molecular-weight compounds such as epoxy compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, cardo compounds, and phenolic compounds. It is not limited to this. By containing such a thermosetting resin, the resin reacts when the filter segment is baked, increasing the crosslink density of the coating film, improving heat resistance, and suppressing pigment aggregation during baking of the filter segment. be done.
Among these, epoxy resin, cardo resin, or melamine resin is preferable.

(Photosensitive resin)
Examples of photosensitive resins include linear polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups, and (meth)acrylic compounds and cinnamon compounds having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups. A resin obtained by reacting an acid to introduce a photocrosslinkable group such as a (meth)acryloyl group or a styryl group into the linear polymer is used. In addition, linear polymers containing acid anhydrides such as styrene-maleic anhydride copolymers and α-olefin-maleic anhydride copolymers are treated with (meth)acrylic compounds having hydroxyl groups such as hydroxyalkyl (meth)acrylates. A half-esterified one is also used.

<Silane coupling agent (B)>
Since the photosensitive resin composition of the present invention contains a silane coupling agent in a specific range, it has good adhesion to substrates and exhibits good chemical resistance. In particular, by combining with the specific resin of the present application, the resolution and chemical resistance are remarkably improved.
Content of a silane coupling agent is 5 mass % or more in solid content of a photosensitive resin composition. If the content is less than 5% by mass, there arises a problem that a part of the coating film is peeled off when forming a fine pixel pattern with high definition. More preferably 7% by mass or more, particularly preferably 10% by mass or more. When it is 7% by mass or more, not only fine pixel pattern formation but also chemical resistance is improved.
Moreover, content of a silane coupling agent is 20 mass % or less in solid content of the photosensitive resin composition. If the amount exceeds 20% by mass, a strong crosslinked structure cannot be obtained, resulting in deterioration of chemical resistance. More preferably, it is 15% by mass or less. When it is 15% by mass or less, the resolution becomes favorable from the viewpoint of resolution.

As the silane coupling agent (B), known ones can be used without any particular limitation. , a carbamate group, or an isocyanate group.

Specifically as such a silane coupling agent (B),
silane coupling agents having a vinyl group such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, etc.;
β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxy silane coupling agents having an epoxy group such as propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc.;
a silane coupling agent having a styryl group such as p-styryltrimethoxysilane;
silane coupling agents having (meth)acryloxy groups such as γ-methacryloxypropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxysilane;
N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl ) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane , 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, etc. Silane coupling agent,
a silane coupling agent having a ureido group such as 3-ureidopropyltriethoxysilane;
silane coupling agents having a mercapto group such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc.;
Silane coupling agents having a sulfide group such as bis(triethoxysilylpropyl)tetrasulfide,
a silane coupling agent having an isocyano group such as 3-isocyanatopropyltriethoxysilane;
3-carbamateethyl)propyltrimethoxysilane, (3-carbamateethyl)propyltripropoxysilane, (3-carbamatepropyl)propyltriethoxysilane, (3-carbamatepropyl)propyltrimethoxysilane, (3-carbamatepropyl) Propyltripropoxysilane, (3-carbamatebutyl)propyltriethoxysilane, (3-carbamatebutyl)propyltrimethoxysilane, (3-carbamatebutyl)propyltripropoxysilane, (3-carbamatebutyl)butyltripropoxysilane Silane, (3-carbamatebutyl)propylmethyldiethoxysilane, (3-carbamatepentyl)propyltriethoxysilane, (3-carbamatehexyl)propyltriethoxysilane, (3-carbamateoctyl)pentyltributoxysilane, (3- Carbamate-ethyl)propylsilyl trichloride, (3-carbamate-ethyl) propyltrimethylsilane, (3-carbamate-ethyl) propyldimethylsilane, (3-carbamate-ethyl) propyltributylsilane, (3-carbamate-ethyl) ethyl-p-xylene trichloride Silane coupling agents having a carbamate group such as ethoxysilane, (3-carbamateethyl)-p-phenylenetriethoxysilane, and the like can be mentioned.
These silane coupling agents (B) can be used singly or as a mixture of two or more at any ratio as required.

Among these, the silane coupling agent (B) preferably contains at least one organic group selected from the group consisting of (meth)acryloxy groups, epoxy groups and mercapto groups. ) 3-methacryloxypropylmethyldimethoxysilane having an acryloxy group, 3-glycidoxypropylmethyltrimethoxysilane having an epoxy group, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- having a mercapto group Mercaptopropyltrimethoxysilane and the like are preferred because of their good adhesion.

The silane coupling agent may be a silanol compound produced by hydrolysis of the above compounds or a polyorganosiloxane compound formed by condensation thereof.

<Polymerizable compound (C)>
The polymerizable compound (C) that may be added to the photosensitive resin composition of the present invention includes monomers or oligomers that can be cured by ultraviolet light, heat, or the like to form a transparent resin.

Examples of monomers and oligomers that form transparent resins by curing with ultraviolet light or heat include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di( meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate , 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipenta Erythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate and other acrylic and methacrylic esters, ( meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile, etc.; It is not necessarily limited to these.

Moreover, the polymerizable compound may contain an acid group. For example, free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohol and (meth)acrylic acid and esters of dicarboxylic acids; esters of polyhydric carboxylic acid and monohydroxyalkyl (meth)acrylates can be mentioned. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. and free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4 - Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2- Monohydroxy monoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, or free carboxyl group-containing oligoesters with monohydroxy monomethacrylates, etc., but the effects of the present invention are limited to these. not to be

(Urethane (meth)acrylate)
The polymerizable compound (C) in the present invention can contain a monomer having a polymerizable unsaturated bond group including urethane (meth)acrylate. The inclusion of urethane (meth)acrylate is preferable because it improves the coating film adhesion to the substrate during development and chemical resistance. Normally, distortion occurs in the coating film due to photocuring, but the inclusion of urethane (meth)acrylate provides a coating film in which the distortion is relaxed, leading to improved adhesion and chemical resistance.

There are no restrictions on the structure of the urethane (meth)acrylate, and polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, or reacting a polyfunctional isocyanate with an alcohol and further having a hydroxyl group (meth ) urethane (meth)acrylate obtained by reacting acrylate, etc. can be used.

(Meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri( meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate Examples include methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy (meth)acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

Polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate and the like.

Although the structure of the alcohol is not limited, it is preferable to use a polyhydric alcohol because the degree of cross-linking of the cured coating increases and the resistance of the coating increases. Polyhydric alcohols include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like.

As commercially available polyfunctional urethane (meth) acrylates, Nippon Kayaku Co., Ltd. KAYARAD UX-3204, KAYARAD UX-4101, KAYARAD UX-6100, KAYARAD UX-6101, KAYARAD UX-7101, KAYARAD UX-8101, KAYARAD UX- 0937, KAYARAD UXF-4002, KAYARAD DPHA-40H, KAYARAD UX-5005, and Aronix M-1100 manufactured by Toagosei Co., Ltd., Aronix M-1200 and U-6LPA manufactured by Shin-Nakamura Chemical Co., Ltd., UA-1100H, U-15HA, UA-160TM, UA-122P, UA-7100, UA-W2A, and KSM KUA-4I, KUA-6I, KUA-9N, KUA-10H and the like can be preferably used.

The polymerizable compound (C) that can be used in the photosensitive resin composition of the present invention includes, in addition to the urethane (meth)acrylates described above, when reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, an alcohol When reacting with a polyfunctional isocyanate and further reacting with a (meth)acrylate having a hydroxyl group, even if it contains a component having a double bond group that was not obtained as a polyfunctional urethane (meth)acrylate as another monomer good.

These photopolymerizable monomers may be used singly or as a mixture of two or more at any ratio as required.

The content of the polymerizable compound (C) with respect to the total solid content in the photosensitive resin composition is preferably 10 to 40% by mass. By setting the thickness within the above range, it is possible to prevent peeling when forming a fine pattern, and to suppress the tapered portion of the pattern from being elongated, thereby forming a high-definition fine pixel pattern. Furthermore, the content of urethane (meth)acrylate contained in the polymerizable compound (C) is preferably 50 to 100% by mass. By setting the amount within the above range, excellent adhesion of the coating film to the substrate during development and chemical resistance can be obtained.

<Photoinitiator (D)>
When the photosensitive resin composition of the present invention is cured by ultraviolet irradiation to form a filter segment by a photolithographic method, a polymerization initiator or the like is added to form a solvent-developable or alkali-developable resist material. can be prepared. The amount when using the photopolymerization initiator (D) is preferably 0.2 to 10.0% by mass in the total solid content of the photosensitive resin composition.
and more preferably 0.5 to 7.0% by mass. When the content of the photopolymerizable compound is within the above range, a coating film having good degassing and fine pattern resolution can be obtained.

As the polymerization initiator (D), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl] -1-[4-(4-morpholinyl)phenyl]-1-butanone, or acetophenone compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin , benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide or 3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone compounds such as ,4-diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2 -(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4, 6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)- s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2, Triazine compounds such as 4-trichloromethyl-(4′-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxy shim)], or oxime ester compounds such as O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; bis(2,4,6 -trimethylbenzoyl)phenylphosphine oxide or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; borate compounds; A carbazole-based compound; an imidazole-based compound; or a titanocene-based compound or the like is used.

These photopolymerization initiators (D) can be used singly or as a mixture of two or more at any ratio as required.

<Sensitizer>
Furthermore, the resin composition of the present invention can contain a sensitizer. Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives , naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxyesters , acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3′ or 4,4′- tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone and the like.

More specifically, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al. Special Functional Materials" (CMC, 1986), but not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be included.

Two or more kinds of sensitizers may be used in an arbitrary ratio as necessary. The amount when using a sensitizer is preferably 3 to 60% by mass based on the total weight of the photopolymerization initiator (D) contained in the resin composition (100% by mass). From the viewpoint of curability and developability, it is more preferably 5 to 50% by mass.

<Solvent (E)>
Examples of the solvent (E) include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4- Dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3 -methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene , m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o- Diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether , ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene Glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene Glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl Cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like.

(Solvents with a boiling point of 130°C or less)
Above all, it is preferable that a solvent with a boiling point of 130° C. or less is contained in an amount of 10 to 80% of the total solvent so that the coating film hardness and chemical resistance can be fully exhibited even in the production process of low-temperature curing.
Solvents having a boiling point of 130° C. or less include, for example, propylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methyl-1,3-propanediol, isobutyl alcohol, isobutyl acetate, isobutyl acetate, and n-propyl. Acetate, propyl acetate, n-butyl acetate, n-butyl alcohol, methyl isobutyl ketone and the like. Propylene glycol monoethyl ether and propylene glycol monomethyl ether are particularly preferred from the viewpoint of compatibility with other compounds used in the photosensitive resin composition.

The solvent (E) can be used in an amount of 200 to 4000 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition.

<Inorganic fine particles (F)>
Since the photosensitive resin composition of the present invention contains the inorganic fine particles (F), a coating film having higher hardness and excellent chemical resistance can be obtained. Preferably, inorganic fine particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, and cerium. Inorganic fine particles of zirconium and silicon.

Examples of inorganic fine particles include zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), iron oxide (Fe ₂ O ₃ , FeO, Fe ₃ O ₄ ), copper oxide (CuO, Cu2O), zinc oxide (ZnO), yttrium oxide ( _Y2O3 ), niobium oxide _{( Nb2O5} ), molybdenum oxide _{( MoO3} ), indium oxide _{( In2O 3} , In ₂ O), tin oxide (SnO ₂ ), tantalum oxide (Ta ₂ O ₅ ), tungsten oxide (WO ₃ , W ₂ O ₅ ), lead oxide (PbO, PbO ₂ ), bismuth oxide (Bi ₂ O ₃ ), metal oxide fine particles such as cerium oxide (CeO ₂ , Ce ₂ O ₃ ), antimony oxide (Sb ₂ O ₅ , Sb ₂ O ₅ ), germanium oxide (GeO ₂ , GeO), silicon nitride, boron nitride, etc. Nitride etc. In addition, composite oxides composed of two or more metal elements, such as titanates such as barium titanate, titanium/silicon composite oxides, and yttrium-stabilized zirconia, can also be used.

Of these, silicon oxide is preferred from the viewpoint of refractive index and transparency.

A compound obtained by doping a metal oxide with a different element can also be used as the inorganic fine particles. Examples of such compounds include tantalum-doped titanium oxide and niobium-doped titanium oxide. These compounds may be used alone or in combination of two or more. Such a composite oxide is not only a compound or solid solution composed of multiple elements, but also has a core-shell structure in which the core metal oxide fine particles are coated with metal oxides composed of other metal elements. , and those having a multicomponent dispersion type structure in which a plurality of other metal oxide fine particles are dispersed in one metal oxide fine particle.
The inorganic fine particles may be used alone, or two or more of them may be mixed and used.

In the present invention, the inorganic fine particles may be surface-treated. Surface treatment refers to a treatment for binding a compound that can react with hydroxyl groups present on the surface of fine particles. Such a surface treatment can be carried out by dispersing inorganic fine particles in a solvent, mixing a surface treatment agent under heating or under acidic conditions, and allowing it to act.
The surface treatment agent for hydrophobizing the surface is not particularly limited, but stearic acid, oleic acid, aliphatics such as linoleic acid, surfactants such as aliphatic soaps, the above-mentioned silane coupling agents, silicone compounds or Some use fluorine compounds and the like.
Examples of silicone compounds include dimethicone, methicone, alkyl-modified silicones, and silicone resins.
Fluorine compounds include fluorine-modified alkyl compounds and fluorine-modified silicone compounds, and include, for example, perfluoroalkyl phosphates and salts thereof, perfluoroalkylsilanes, and perfluoroalkylcarboxylic acids. In addition, a hydrophobizing treatment may be performed in combination with an alkyl acrylate or an (alkyl acrylate/dimethicone) copolymer together with a fluorine compound.

In general, methods for producing inorganic fine particles are broadly classified into three types: a solid phase method, a liquid phase method, and a gas phase method. As a method for obtaining nano-sized fine particles, a liquid phase method or a vapor phase method is generally used. The liquid phase method includes a sol-gel method in which a chemical reaction is caused in a solution to grow crystals to obtain fine particles, and a mechanical pulverization method in which crystals are mechanically pulverized in a liquid medium such as water. Gas phase methods include laser pyrolysis, combustion, plasma vaporization, spray combustion, gasification combustion, instantaneous gas phase generation, etc. Reactions occur in the gas phase to synthesize inorganic fine particles. say how to

The average primary particle diameter of the inorganic fine particles is preferably 1 nm to 200 nm, more preferably 3 nm to 100 nm, and particularly preferably 5 nm to 30 nm. If the average primary particle size exceeds 1000 nm, the transparency of the cured product tends to be low, and the surface condition of the film tends to deteriorate. Various surfactants and amines may also be added to improve the dispersibility of the particles.

The average primary particle size of inorganic fine particles is measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the short axis diameter and long axis diameter of each primary particle of the pigment are measured, and the average is used as the particle size of the primary particles of the inorganic fine particles. Next, for 100 or more pigment particles, the volume (weight) of each particle is obtained by approximating a cube with the obtained particle size, and the volume average particle size is taken as the average primary particle size.

The inorganic fine particles are preferably used as an organic solvent dispersion. When used as an organic solvent dispersion, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate and γ-butyrolactone. , propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other esters; ethylene glycol monomethyl ether, diethylene glycol monobutyl ether and other ethers; benzene, toluene, xylene and other aromatic hydrocarbons; dimethylformamide, dimethylacetamide, Amides such as N-methylpyrrolidone can be mentioned. Among them, preferred are methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene.

(silicon)
Commercially available silicon oxide fine particle dispersions used in the present invention include PMA-ST, MA-ST-MS, IPA-ST, IPA-ST-MS, and IPA-ST manufactured by Nissan Chemical Industries, Ltd. ST-L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-L, MIBK-ST, NBA-ST, XBA-ST, DMAC- ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc. Hollow silica CS60- manufactured by Catalysts and Chemicals Industry Co., Ltd. IPA etc. can be mentioned. Examples of powdered silica include Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50 manufactured by Nippon Aerosil Co., Ltd.; E220A and E220 manufactured by Co., Ltd., SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like can be mentioned.
In the present invention, a fine particle dispersion that has undergone surface treatment for the purpose of improving developability can also be used. Commercially available products include MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Y, PGM-AC-4130Y, MIBK-AC-2140Z, MIBK-SD-L, MEK-EC -2130Y, MEK-EC-6150P, MEK-EC-7150P and the like.

(aluminum)
Commercially available aluminum oxide fine particle dispersions used in the present invention include AS-200 and AS-520-A manufactured by Nissan Chemical Industries, Ltd.

(Zirconia)
Examples of commercially available zirconia oxide fine particle dispersion liquids preferably used in the present invention include ZR-40BL, ZR-30BS, ZR-30AL and ZR-30AH manufactured by Nissan Chemical Industries, Ltd. . In addition, a zirconia oxide fine particle dispersion can be obtained by the method described in Japanese Patent No. 4,692,630.

(Titanium)
Commercially available titanium oxide fine particles that are particularly preferably used in the present invention include SA-TTO-S-4 (10%) MiBrid Powder (fine particles hydrophobized with dimethicone (30 nm) titanium oxide) (Miyoshi Kasei Co., Ltd.), MT-02 (fine particles (20 nm) titanium oxide hydrophobized with methicone) (manufactured by Tayca Co., Ltd.), MT-01 (fine particles hydrophobized with aluminum oxide, aluminum hydroxide and stearic acid ( 10 nm) titanium oxide) (manufactured by Tayca Corporation), MT-10EX (fine particles hydrophobized with aluminum oxide, aluminum hydroxide and isostearic acid (10 nm) titanium oxide) (manufactured by Tayca Corporation), MT-100TV (aluminum oxide) , Fine particles (15 nm) titanium oxide hydrophobized with aluminum hydroxide and stearic acid) (manufactured by Tayca Corporation), MT-100Z (fine particles (15 nm) titanium oxide hydrophobized with aluminum oxide, aluminum hydroxide and stearic acid ) (manufactured by Tayca Corporation), MT-150EX (fine particles (15 nm) titanium oxide hydrophobized with aluminum oxide, aluminum hydroxide and isostearic acid) (manufactured by Tayca Corporation), MTY-02 (aluminum oxide, aluminum hydroxide , fine particles (10 nm) titanium oxide hydrophobized with silicon oxide, silicon hydroxide and silicone oil) (manufactured by Tayca Corporation), MTY-110M3S (aluminum oxide, aluminum hydroxide, silicon oxide, silicon hydroxide and silicone oil Hydrophobized microparticles (10 nm) titanium oxide) (manufactured by Tayca Co., Ltd.), MT-500SAS (microparticles (30 nm) titanium oxide hydrophobized with aluminum oxide, aluminum hydroxide, silicon oxide, silicon hydroxide and silicone oil) (manufactured by Tayka Co., Ltd.), MTY-700BS (microparticles (80 nm) titanium oxide hydrophobized with silicone oil) (manufactured by Tayca Co., Ltd.), STR-60C-LP (microparticles hydrophobized with aluminum and organopolysiloxane (30× 90 nm) titanium oxide) (manufactured by Sakai Chemical Industry Co., Ltd.), STR-100C-LP (fine particles hydrophobized with aluminum and organopolysiloxane (20 × 100 nm) titanium oxide) (manufactured by Sakai Chemical Industry Co., Ltd.), STR-100A- LP (D. silica, alumina and organopolysiloxa Fine particles (20 × 100 nm) titanium oxide hydrophobized with ne (manufactured by Sakai Chemical Industry Co., Ltd.), D-962 (manufactured by Sakai Chemical Industry Co., Ltd.), Nanotech (manufactured by C.I. Kasei Co., Ltd.), and the like. In addition, a titanium oxide fine particle dispersion can be obtained by the method described in Japanese Patent No. 4,692,630.

(zinc)
Commercially available zinc oxide fine particle dispersions used in the present invention include MZ-505S (fine particles (30 nm) zinc oxide hydrophobized with (dimethicone/methicone) copolymer) (manufactured by Tayca Corporation), FINEX-K2-LP2 (fine particles (30 nm) zinc oxide hydrophobized with (dimethicone/methicone) copolymer) (manufactured by Sakai Chemical Industry Co., Ltd.), Z-COTE HP1 (fine particles (25 nm) zinc oxide hydrophobized with dimethicone ) (manufactured by BASF Japan), SAMTUFZO-450 (13%) (fine particles (40 nm) zinc oxide hydrophobized with dimethicone and myristic acid) (manufactured by Miyoshi Kasei Co., Ltd.), SAS-UFZO-450 (13%) (Microparticles (40 nm) zinc oxide hydrophobized with dimethicone and methicone) (manufactured by Miyoshi Kasei Co., Ltd.), MZY-303S (microparticles (35 nm) zinc oxide hydrophobized with silicone oil) (manufactured by Tayca Co., Ltd.), MZ -306X (microparticles (35 nm) zinc oxide hydrophobized with silicone oil) (manufactured by Tayca Co., Ltd.), MZY-505S (microparticles (25 nm) zinc oxide hydrophobized with silicone oil) (manufactured by Tayca Co., Ltd.), MZY -510M3S (microparticles (25 nm) zinc oxide hydrophobized with silicone oil) (manufactured by Tayca Co., Ltd.), MZ-506X (microparticles (25 nm) zinc oxide hydrophobized with silicone oil) (manufactured by Tayca Co., Ltd.), MZ -510HPSX (fine particles (25 nm) zinc oxide hydrophobized with silicon oxide, silicon hydroxide and silicone oil) (manufactured by Tayca Corporation), FINEX-30S-LP2 (fine particles (35 nm) zinc oxide hydrophobized with organopolysiloxane) (manufactured by Sakai Chemical Industry Co., Ltd.), FINEX-30W-LP2 (fine particles (35 nm) zinc oxide hydrophobized with D. silica and organopolysiloxane) (manufactured by Sakai Chemical Industry Co., Ltd.), FINEX-50S-LP2 (hydrophobicized with organopolysiloxane) Hydrophobized fine particles (20 nm) zinc oxide) (manufactured by Sakai Chemical Industry Co., Ltd.), FINEX-50W-LP2 (fine particles (20 nm) zinc oxide hydrophobized with D. silica and organopolysiloxane) (manufactured by Sakai Chemical Industry Co., Ltd.) , Nanotech (C.I. Kasei Co., Ltd.) and the like.

(antimony)
Commercially available antimony oxide fine particles that are particularly preferably used in the present invention include PATOX-U (30 nm; diantimony trioxide) manufactured by Nippon Seiko Co., Ltd. Commercially available antimony oxide fine particle dispersions preferably used in the present invention include CELNAX CX-Z330H manufactured by Nissan Chemical Industries, Ltd.

(cerium)
Commercially available cerium oxide fine particles that are particularly preferably used in the present invention include TECNAPOW-CEO2 (10 nm; cerium dioxide) manufactured by Air Braun Co., Ltd., and the like. Commercially available cerium oxide fine particle dispersions preferably used in the present invention include SI01-5 Cerigard SC6832 (fine particles (35 nm) cerium oxide hydrophobized with methicone) (manufactured by Daito Kasei Kogyo Co., Ltd.), etc. is mentioned.

The amount of the inorganic fine particles (F) added is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, particularly preferably 15 to 50% by mass, based on the solid content in the photosensitive resin composition. If the amount added is less than 5% by mass, it is difficult to obtain effects such as improvement in hardness and etchant resistance. be.

<Ultraviolet absorber (G)>
The photosensitive resin composition of the present invention may contain an ultraviolet absorber to prevent exposure due to diffracted light from a mask during exposure. By using an ultraviolet absorber, photocuring in the coating film becomes uniform, and the effect of suppressing swelling of the coating film when immersed in chemicals can also be obtained. An ultraviolet absorber is an organic compound other than a photopolymerization initiator that has an ultraviolet absorption function. The content of the ultraviolet absorbent with respect to the total solid content in the photosensitive resin composition is preferably 0.05 to 3.0% by mass. If the content of the ultraviolet absorber is less than the above, the effect of the ultraviolet absorber is small, the tapered portion of the photosensitive resin composition pattern is elongated, and it becomes difficult to form a high-definition fine pixel pattern. There may be a lot of residue. On the other hand, if the amount is more than the above, problems such as generation of insoluble matter and deterioration of adhesion and hardness may occur.

(absorbance)
The absorbance of the ultraviolet absorber at a wavelength of 365 nm is preferably 0.4 or more. Absorbance is a value obtained by dissolving an ultraviolet absorber in a solvent such as chloroform which does not absorb light at a wavelength of 365 nm and diluting the solution to 10 mg/L. The method of measurement will be described below.
This method utilizes the relationship between solution concentration and light absorption known as the Lambert-Beer law. In other words, when a solution of a certain concentration is enclosed in a transparent container with a certain thickness, light with an intensity of _I0 is irradiated from one side of the container, and light with an intensity of I emitted from the opposite side is observed, the light incident on the container is It is absorbed by the internal solution and its strength is weakened. It is known that the weakening of the intensity is proportional to the concentration of the solution. If A is the absorbance, the relational expression expressing this law is
A=−Log(I ₀ /I)=abc
is represented. where a is the constant of proportionality, b is the solution thickness, and c is the solution concentration.

Furthermore, the ultraviolet absorber is preferably a benzotriazole-based organic compound, a benzophenone-based organic compound, or a triazine-based organic compound. -2-hydroxyphenyl)benzotriazole, 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[6-(benzotriazol-2-yl) -4-tert-octylphenol] and the like. Benzophenone-based organic compounds include 2,2-dihydroxy-4,4-dimethoxybenzophenone and the like. Examples of triazine organic compounds include 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.
Specifically, BASF "TINUVIN P" (absorbance 0.40), "TINUVIN 326" (absorbance 0.48), "TINUVIN 360" (absorbance 0.40), Shipro Kasei "Seesorb 107" (absorbance 0.60) "ADEKA STAB LA-F70" (absorbance 0.90), etc., manufactured by ADEKA.

<Polymerization inhibitor>
The photosensitive resin composition of the present invention may contain a polymerization inhibitor in order to prevent exposure due to diffracted light from a mask during exposure.
Polymerization inhibitors include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, and 2-propylcatechol. , 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert- Alkylcatechol compounds such as butylcatechol and 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, alkylresorcinol compounds such as 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2, Alkylhydroquinone compounds such as 5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine and tribenzylphosphine, phosphines such as trioctylphosphine oxide and triphenylphosphine oxide Examples include oxide compounds, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol and phloroglucine. The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. If the content is less than the above, the effect of the polymerization inhibitor is small and the tapered portion of the photosensitive resin composition pattern is elongated, making it difficult to form a high-definition fine pixel pattern and increasing the amount of residue. Sometimes. On the other hand, if the amount is more than the above, there may occur a problem such as a decrease in adhesion.

<Leveling agent>
A leveling agent is preferably added to the photosensitive resin composition of the present invention in order to improve the leveling property of the composition on the substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK Chemie. Specific examples of dimethylsiloxane having a polyester structure include BYK-310 manufactured by BYK-Chemie. A dimethylsiloxane having a polyether structure and a dimethylsiloxane having a polyester structure can be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by mass based on the total weight of the photosensitive resin composition (100% by mass).

A particularly preferable leveling agent is a type of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule. Although it has a hydrophilic group, it has low solubility in water. It is useful that it has the characteristic of low surface tension lowering ability and good wettability to the glass plate despite the low surface tension lowering ability, and it is added in an amount that does not cause defects in the coating film due to bubbling. A substance capable of sufficiently suppressing chargeability can be preferably used. A dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used as a leveling agent having such preferred properties. Polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane is a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of dimethylpolysiloxane, a terminal modified type in which the terminal is bonded to the terminal of dimethylpolysiloxane, and a dimethylpolysiloxane. It may be of any linear block copolymer type with alternating repeating bonds. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray Co., Ltd., such as FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ -2207, but not limited to.

Anionic, cationic, nonionic, or amphoteric surfactants can be added to the leveling agent as auxiliaries. Two or more kinds of surfactants may be mixed and used.
Examples of anionic surfactants added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate and esters.

Cationic surfactants added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate. , polyethylene glycol monolaurate; alkylbetaines such as alkyldimethylaminoacetic acid betaine; amphoteric surfactants such as alkylimidazoline; and fluorine-based and silicone-based surfactants.

(Antioxidant)
The photosensitive resin composition of the present invention can contain an antioxidant. The antioxidant can suppress a decrease in transmittance due to yellowing or the like due to the heating process. Therefore, by including an antioxidant, it is possible to prevent yellowing during the heating process and obtain a coating film with high transmittance.

The "antioxidant" in the present invention may be a compound having an ultraviolet absorption function, a radical scavenging function, or a peroxide decomposition function. , phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. From the viewpoint of achieving both transmittance and sensitivity of the coating film, the antioxidant of the present invention is particularly preferably a phenol antioxidant, a phosphorus antioxidant and a sulfur antioxidant. Among phenol-based antioxidants, hindered phenol-based antioxidants with high steric hindrance are particularly preferred.

[Phenolic antioxidant]
For example, 2,6-di-t-butyl-4-ethylphenol, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3 ,5-triazine, 2,2-thio-diethylenebis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, N,N'-hexamethylenebis(3,5-di- t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris-(3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-methoxyphenol, triethylene glycol-bis{3 -(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate}, 1,6-hexanediol-bis{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, pentaerythrityl-tetrakis {3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate}, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1 , 3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenyl)benzene and the like, which may be used alone or in combination of two or more.

Among them, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N′-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t- A hindered phenolic antioxidant selected from the group consisting of butyl-4-hydroxybenzylphosphonate-diethyl ester and tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, It is preferable from the viewpoint of photocurability.

[Phosphorus antioxidant]
Commercially available phosphorus antioxidants can be used, and tris[2,4-di-(tert)-butylphenyl]phosphinetris[2-[[2,4,8,10-tetrakis( 1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11- Tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, ethyl phosphite bis(2,4-ditert-butyl-6- methylphenyl), and at least one compound selected from the group consisting of these is preferable, and one or more of these can be used.

[Sulfur-based antioxidant]
Sulfur-based antioxidants are antioxidants containing sulfur in the molecule. Commercially available sulfur-containing antioxidants can be used. thiodipropionate, distearyl-3,3'-thiodipropionate, 4,4'-thiobis-3-methyl-6-tert-butylphenol, thiodiethylenebis[3-(3,5-di-tert- Butyl-4-hydroxyphenyl)propionate], preferably at least one compound selected from the group consisting of these, one or more of which can be used.

These antioxidants can be used singly or as a mixture of two or more at any ratio as required.

The content of the antioxidant is preferably 0.1% by mass or more and 4% by mass or less in 100% by mass of the total solid content of the photosensitive resin composition. If it is less than 0.1% by mass, it is difficult to obtain an anti-yellowing effect because the antioxidant is insufficient, and if it is more than 4% by mass, the radicals generated during ultraviolet exposure are captured, so the photosensitive resin Curing of the composition may be insufficient.

(storage stabilizer)
The photosensitive resin composition of the present invention may contain a storage stabilizer. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic compounds such as t-butylpyrocatechol, triethylphosphine and triphenylphosphine. phosphine, phosphite and the like. The storage stabilizer can be used in an amount of 0.1 to 5% by mass based on the total 100% by mass of the photosensitive resin composition.

<Method for producing photosensitive resin composition>
The photosensitive resin composition of the present invention comprises a resin (A), a silane coupling agent (B), a polymerizable compound (C), a photopolymerization initiator (D), a solvent (E), and optionally It can be obtained by stirring and mixing inorganic fine particles (F), etc., which are added accordingly. The photosensitive resin composition of the present invention is filtered by means of centrifugal separation, sintered filter, membrane filter or the like to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and It is preferable to remove mixed dust and foreign matter.

<Coating film>
INDUSTRIAL APPLICABILITY The photosensitive resin composition of the present invention is suitable for touch panels, liquid crystal display devices, organic EL devices, etc., since it can form a coating film having excellent hardness, adhesion, etchant resistance, and moist heat resistance.

The photosensitive resin composition according to the present invention is coated on a glass substrate, ITO, molybdenum, other metal film, organic film, etc. by spin coating such as spin coating, casting coating such as die coating, roll coating, roll coating, and roll coating. A coating film can be formed by coating by a transfer method or the like, and can be produced by a printing method or a photolithography method. Among them, it is preferable to manufacture by photolithography.

When forming a coating film by photolithography, a photosensitive resin composition prepared as a solvent development type or an alkali development type is applied onto a transparent substrate by spray coating, spin coating, slit coating, die coating, roll coating, or the like. Apply according to method. If necessary, the dried coating film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact or non-contact with the coating film. After that, the film is immersed in a solvent or alkaline developer, or the developer is sprayed to remove the uncured portion, thereby obtaining a cured coating film. Furthermore, in order to promote polymerization of the photosensitive resin composition, heating may be applied as necessary.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide, etc. is used as an alkaline developer, and an organic alkali such as tetramethylammonium hydroxide (TMAH), dimethylbenzylamine, triethanolamine, etc. can also be used. . Moreover, an antifoaming agent or a surfactant can be added to the developer.
In order to increase the ultraviolet exposure sensitivity, after coating and drying the above photosensitive resin composition, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is coated and dried to prevent polymerization inhibition by oxygen. UV exposure can also be performed after forming the film.

In addition, the photosensitive resin composition of the present embodiment may be used for any of protective film applications, flat film applications, insulating film applications, and antireflection film applications, and the coating film formation is also possible for touch panels, liquid crystal display devices, It can be formed in any organic EL device, and has high hardness, high adhesion, and good transparency, so it can be used for both protective films, flat films, insulating films, and antireflection films.

The following examples illustrate the invention. "Parts" and "%" in the examples represent "parts by mass" and "% by mass", respectively. "PGMEA" means propylene glycol monomethyl ether acetate.

Prior to the examples, a method for measuring the weight-average molecular weight of the resin will be described.

(Weight average molecular weight of resin)
The weight average molecular weight (Mw) of the resin is measured using a TSKgel column (manufactured by Tosoh Corporation) and equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. Weight average molecular weight (Mw).

Next, methods for producing resin solutions and polymerizable compounds used in Examples and Comparative Examples will be described.

<Method for producing resin solution>
(Resin solution (A-1))
Put 100 parts of PGMEA in a reaction vessel equipped with a separable 4-necked flask, a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, heat to 120 ° C. while injecting nitrogen gas into the vessel, and drop at the same temperature. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate and 2.5 parts of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction.
Next, the inside of the flask was replaced with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120°C for 5 hours. The reaction was terminated when the molecular weight reached 0.8 to obtain a resin solution having a weight average molecular weight of about 5,000.
Further, 20.0 parts of succinic anhydride and 0.5 parts of triethylamine were added and reacted at 120° C. for 4 hours.

(Resin solution (A-2 to 3))
Resin solutions (A-2 to 3) were synthesized in the same manner as the resin solution (A-1), except that the compositions and amounts (parts by mass) shown in Table 1 were changed.

<Production of polymerizable compound>
(Polymerizable compound (C-1))
623 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Aronix M-400 (manufactured by Toagosei Co., Ltd.)) and 44 g of hexamethylene diisocyanate were charged into a 1-liter five-necked reaction vessel and heated at 60°C. After reacting for 8 hours, a product containing polyfunctional urethane acrylate (1) was obtained. A polymerizable compound (C-1) was obtained in which the polyfunctional urethane acrylate (1) accounted for 45% by mass of the product, and other photopolymerizable monomers accounted for the balance.
It was confirmed by IR analysis that no isocyanate group was present in the reaction product.

(Polymerizable compound (C-2))
600 g of hexamethylene diisocyanate adduct of trimethylolpropane (Coronate HL (manufactured by Tosoh Corporation)) and 950 g of pentaerythritol triacrylate were charged into a 1-liter five-necked reaction vessel and reacted at 60° C. for 8 hours. A product containing functional urethane acrylate (2) was obtained. A polymerizable compound (C-2) was obtained in which the polyfunctional urethane acrylate (2) accounted for 80% by mass of the product, and other photopolymerizable monomers accounted for the balance.
It was confirmed by IR analysis that no isocyanate group was present in the reaction product.

<Production of photosensitive resin composition>
[Example 1]
(Photosensitive resin composition (R1))
A mixture having the following composition was uniformly stirred and mixed, and then filtered through a 1 μm filter to obtain a photosensitive resin composition (R1).
Resin solution (A-1): 32.45 parts KBM-403: 2.00 parts (3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.))
Polymerizable compound (C-1): 4.00 parts Irg. 907: 1.00 parts (Irgacure 907 (manufactured by BASF))
BYK-330 2% solution: 1.00 parts (PGMEA solution of polyether structure-containing dimethylsiloxane (manufactured by BYK-Chemie))
Propylene glycol monomethyl ether acetate: 39.55 parts Propylene glycol methyl ether: 20.00 parts

[Examples 2 to 38, Comparative Examples 1 to 4]
(Photosensitive resin composition (R2-42))
In the same manner as the photosensitive resin composition (R1), except that the composition and the amount (parts by mass) were changed to those shown in Tables 2 to 7, the mixture was uniformly stirred and mixed, and then a 1 μm filter. to obtain photosensitive resin compositions (R2-42).

<Evaluation of photosensitive resin composition>
The obtained photosensitive resin compositions (R1 to R42) were evaluated by the following methods. The results are shown in Tables 2-7.

(Degassing)
A photosensitive resin composition is applied to a 100 mm × 100 mm, 0.7 mm glass substrate (Corning Glass Eagle 2000) using a spin coater so that the finished film thickness after heating at 100° C. for 60 minutes is 2.0 μm. A substrate was obtained. Next, after holding it on a hot plate heated to 80° C. for 2 minutes, it was exposed to ultraviolet rays using an extra-high pressure mercury lamp at an illumination intensity of 20 mW/cm ² and an exposure amount of 100 mJ/cm ² . The exposed coating film was puddle-developed for 1 minute with an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.). After puddle development, the substrate was rinsed with pure water by spin shower for 20 seconds, dried by spin drying, and then heated at 100° C. for 60 minutes in a clean oven.
5 mg of the prepared coating film was peeled off and sampled, and TG/DTA measurement was performed to measure the mass reduction rate with respect to the initial mass, and evaluated according to the following criteria. TG/DTA was measured using an EXSTAR TG/DTA6200 manufactured by Seiko Instruments Inc. under a program of increasing the temperature from room temperature to 150° C. at a rate of 5° C./min and maintaining the temperature for 20 minutes at a nitrogen flow rate of 200 mL/min.
○: Mass reduction rate is less than 1.0% (good level)
△: Mass reduction rate is 1.0% or more and less than 2.0% (practical level)
×: Mass reduction rate is 2.0% or more (level not suitable for practical use)

(Chemical resistance)
≪ITO etchant resistance≫
A photosensitive resin composition was applied to an ITO substrate (manufactured by Geomatec) of 100 mm×100 mm and 0.7 mm thickness using a spin coater so that the finished film thickness after heating at 100° C. for 60 minutes would be 2.0 μm. got Next, after holding it on a hot plate heated to 80° C. for 2 minutes, it was exposed to ultraviolet rays using an extra-high pressure mercury lamp at an illumination intensity of 20 mW/cm ² and an exposure amount of 100 mJ/cm ² . The coated substrate was heated at 100° C. for 60 minutes and allowed to cool to prepare a substrate for evaluation. After that, it was immersed in an ITO etchant; nitric acid/hydrochloric acid/water=0.1/1/1 at 40° C. for 5 minutes, washed with pure water, and left for 24 hours. Adhesion (cross-cut method) of the obtained substrate was performed according to JIS K5600-5-6 to evaluate the adhesion of the coating film to the substrate. .
○: The number of peeled cross-cuts is 0 (good level)
△: 1 or more, less than 3 pieces of peeled grid (practical level)
×: 3 or more pieces of peeled grid pattern (level unsuitable for practical use)

≪Mo etchant resistance≫
After preparing a coating film on a Mo substrate (manufactured by Toho Kaken Co., Ltd.) in the same manner as the evaluation of ITO etchant resistance, Mo etchant; phosphoric acid / acetic acid / nitric acid / water = 80/5/5/10 at 40 ° C for 5 minutes, washed with pure water, and left for 24 hours. Adhesion (cross-cut method) of the obtained substrate was performed according to JIS K5600-5-6 to evaluate the adhesion of the coating film to the substrate. .
○: The number of peeled cross-cuts is 0 (good level)
△: 1 or more, less than 3 pieces of peeled grid (practical level)
×: 3 or more pieces of peeled grid pattern (level unsuitable for practical use)

≪Swelling test≫
A photosensitive resin composition is coated on a 100 mm × 100 mm, 0.7 mm thick glass substrate (Corning Glass Eagle 2000) using a spin coater and heated at 100°C for 60 minutes to give a finished film thickness of 2.0 µm. A substrate coated in the above manner was obtained. Next, after being held on a hot plate heated to 80° C. for 2 minutes, the coating film was irradiated with ultraviolet rays of 100 mJ/cm ² using an ultra-high pressure mercury lamp through a photomask. The exposed coating film was puddle-developed for 1 minute with an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.). After puddle development, the substrate was rinsed with pure water by spin shower for 20 seconds, dried by spin drying, and then heated at 100° C. for 60 minutes in a clean oven. After measuring the film thickness of the resulting pixel pattern with a surface profiler DEKTAK150 (manufactured by ULVAC ES Co., Ltd.), it was immersed in an ITO etchant; nitric acid/hydrochloric acid/water=0.1/1/1 at 40° C. for 5 minutes, After washing with pure water, the film thickness was measured. The film thickness swelling ratio was determined by the following formula.
Film thickness swelling rate (%) = (film thickness after solvent immersion/film thickness before solvent immersion) x 100
The film thickness swelling ratio is preferably in the range of 95-105%, more preferably in the range of 97-103%.

(Resolution)
A glass substrate (Glass Eagle 2000 manufactured by Corning Incorporated) of 100 mm×100 mm and 0.7 mm thick was coated with a spin coater so that the finished film thickness after heating at 100° C. for 60 minutes was 2.0 μm to obtain a substrate. rice field. Next, after being held on a hot plate heated to 80° C. for 2 minutes, an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used to perform exposure of 1000 J/m ² at a wavelength of 365 nm. rice field. Exposure is 5.0μ
This was done through a photomask in which m-square light-shielding portions and light-transmitting portions are arranged in a checkered pattern. The exposed coating film was puddle-developed for 1 minute with an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.). After puddle development, the substrate was rinsed with pure water by spin shower for 20 seconds, dried by spin drying, and then heated at 100° C. for 60 minutes in a clean oven. With respect to the resulting pixel pattern, the hole pixel pattern formed by the light-shielding portion was observed using a scanning electron microscope (“S-3000N” manufactured by Hitachi High-Tech Co., Ltd.) and evaluated according to the following criteria.
A: Hole size of 4.8 μm or more and less than 5.0 μm (very good level)
◯: Hole size is 4.5 μm or more and less than 4.8 μm (good level)
Δ: Hole size of 4.0 μm or more and less than 4.5 μm (practical level)
×: Hole size is less than 4.0 μm (level not suitable for practical use)

(Pencil hardness)
A photosensitive resin composition was applied to a 100 mm × 100 mm, 0.7 mm thick glass substrate (Corning Glass Eagle 2000) using a spin coater so that the finished film thickness after heating at 100° C. for 60 minutes would be 2.0 μm. A substrate coated with Next, after holding it on a hot plate heated to 80° C. for 2 minutes, it was exposed to ultraviolet rays using an extra-high pressure mercury lamp at an illumination intensity of 20 mW/cm ² and an exposure amount of 100 mJ/cm ² . The coated substrate was heated at 100° C. for 60 minutes and allowed to cool. The pencil surface hardness of the protective film of this substrate was measured by JIS K-5400-1990 8.4.1 Pencil Scratch Test and evaluated according to the following criteria.
○: Pencil surface hardness is 2H or more (good level)
△: Pencil surface hardness is H (practical level)
×: Pencil surface hardness is F or less (level not suitable for practical use)

Abbreviations in Tables 2 to 7 are shown below.
<<Silane coupling agent (B)>>
KBM-403: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.) KBM-503: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.)
KBM-5103: 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.)
KBM-803: 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.)
KBM-9659: tris-(trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Silicone Co., Ltd.)
KBE-9007: 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.)
<<Polymerizable compound (C)>>
C-1: The polymerizable compound synthesized above. C-2 containing 45% by mass of polyfunctional urethane acrylate: the polymerizable compound synthesized above. C-3 containing 80% by mass of polyfunctional urethane acrylate (M402): Aronix M-402 (manufactured by Toagosei Co., Ltd.)
A mixture of dipentaerythritol penta and hexaacrylate <<photoinitiator (D)>>
Irg. 907: Irgacure 907 (manufactured by BASF)
2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one Irg. OXE-01: Irgacure OXE-01 (manufactured by BASF)
1,2-octanedione,1-[4-(phenylthio)-,2-(O-benzoyloxime)]
<<Inorganic fine particles (F)>>
PMA-ST: Silica fine particles (Nissan Chemical Co., Ltd., solid content 30% by mass)
PGM-AC-2140Y: Silica fine particles (Nissan Chemical Co., Ltd., solid content 42% by mass)
AS-520-A: Alumina fine particles (Nissan Chemical Co., Ltd., solid content 20% by mass)
ZR-20AS: zirconia fine particles (Nissan Chemical Co., Ltd., solid content 20% by mass)
<<Ultraviolet absorber (G)>>
Ultraviolet absorber (G-1): (benzotriazole compound) 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole ("TINUVIN 326" manufactured by BASF (absorbance 0. 48))
Ultraviolet absorber (G-2): (benzophenone-based organic compound) 2,2-dihydroxy-4,4-dimethoxybenzophenone (“Seesorb 107” manufactured by Shipro Kasei Co., Ltd. (absorbance 0.60))
UV absorber (G-3): (triazine-based organic compound) 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine (made by ADEKA " Adekastab LA-F70" (absorbance 0.90))
Ultraviolet absorber (G-4): (benzophenone-based organic compound) [2-hydroxy-4-(oxyloxy)phenyl](phenyl)methanone (manufactured by ADEKA "ADEKA STAB 1413" (absorbance 0.10))
≪Polymerization inhibitor≫
MH: Methylhydroquinone (“MH” manufactured by Seiko Chemical Co., Ltd.)
≪Leveling agent≫
BYK-330 2%: PGMEA solution of polyether structure-containing dimethylsiloxane (adjusted to 2% by mass of non-volatile content (manufactured by BYK-Chemie)
<<Solvent (E)>>
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

As shown in Tables 2 to 7, the specific resin (A) using succinic anhydride and the silane coupling agent (B) are contained in an amount of 5 to 20% by mass based on the total solid content of the composition. The resin composition satisfies practical levels in all of degassing, chemical resistance, resolution and hardness evaluation. On the other hand, as shown in Comparative Examples 1 to 4, Comparative Example 1 using resin (A-3) using tetrahydrophthalic anhydride instead of succinic anhydride reached a practical level in degassing and chemical resistance. not In addition, Comparative Examples 2 to 4 in which the silane coupling agent (B) is less than 5% by mass or more than 20% by mass with respect to the total solid content of the photosensitive resin composition have excellent degassing properties, chemical resistance, and resolution. None of them reached the level of practical use.

From the above results, the photosensitive resin composition of the present application has good chemical resistance even at a curing temperature of 120 ° C. or less while achieving both adhesion to the substrate and high resolution, and has a small amount of degassing. , it was possible to form a cured film with high hardness. That is, the photosensitive resin composition of the present invention can be suitably used for interlayer insulating films and overcoat films used in touch panels, liquid crystal display devices, organic EL devices, and the like.

Claims (12)

A photosensitive resin composition comprising a resin (A), a silane coupling agent (B), a polymerizable compound (C), a photopolymerization initiator (D) and a solvent (E),
Resin (A) contains a resin obtained by reacting a copolymer of (a) and (b) below with (c) and then (d),
The content of the silane coupling agent (B) is 5 to 20% by mass in the total solid content of the photosensitive resin composition ,
A photosensitive resin composition , wherein the silane coupling agent (B) is selected from 3-glycidoxypropylmethyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane .
(a): a monomer having a cyclic ether skeleton having 2 carbon atoms and an ethylenically unsaturated bond (b): a monomer having an unsaturated bond copolymerizable with (a) and different from (a) (c): at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (d): succinic anhydride 2. The photosensitive resin composition according to claim 1, further comprising inorganic fine particles (F) containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium. . 3. The photosensitive resin composition according to claim 2, wherein the inorganic fine particles (F) are inorganic fine particles containing silicon. The photosensitive resin composition according to any one of claims 1 to 3, wherein the content of the photopolymerization initiator (D) is 0.5 to 7.0% by mass in the total solid content of the photosensitive resin composition. thing. The photosensitive resin composition according to any one of claims 1 to 4, wherein the content of the silane coupling agent (B) is 7 to 15% by mass based on the total solid content of the photosensitive resin composition. 6. The photosensitive resin composition according to any one of claims 1 to 5, further comprising an ultraviolet absorber (G). The photosensitive resin composition according to any one of claims 1 to 6, wherein the polymerizable compound (C) contains urethane (meth)acrylate. The photosensitive resin composition according to any one of claims 1 to 7, wherein the solvent (E) contains a solvent having a boiling point of 130°C or less. A cured film formed from the photosensitive resin composition according to any one of claims 1 to 8. 10. The cured film according to claim 9, which is an interlayer insulating film or an overcoat film. After coating the photosensitive resin composition according to any one of claims 1 to 10 on a substrate, it is exposed through a mask, developed to form a pattern, and then heated and baked to produce a cured film. Method. 12. The method for producing a cured film according to claim 11, wherein the baking temperature is 120[deg.] C. or lower.