JP2019117259A - Photosensitive resin composition, cured film and production method of the same - Google Patents

Abstract

To provide a photosensitive resin composition from which a cured film can be formed that has good resolution and has good chemical resistance, a small degassing amount and high hardness even when cured at a curing temperature of 120°C or lower.SOLUTION: The photosensitive resin composition comprises a resin (A), a polymerizable multi-branched urethane compound (B) having a dendrimer structure, inorganic fine particles (C), a photopolymerization initiator (D), and a solvent (E). The resin (A) contains a resin obtained by allowing (c) and (d) to react with a copolymer of (a) and (b); the polymerizable multi-branched urethane compound (B) is a compound represented by general formula (1); and the inorganic fine particles (C) contain inorganic fine particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photosensitive resin composition and a cured film using the same. The cured film can be suitably used for an interlayer insulating film or an overcoat film used for a touch panel, a liquid crystal display device, an organic EL device and the like.

  Capacitive touch panels, which have become mainstream at present, have adopted a large number of configurations using a transparent conductive film that is advantageous for weight reduction and processability, including the GFF method in which two ITO films are bonded to a cover glass. It is done. However, the use of a low heat resistant film requires low temperature firing.

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

  As the interlayer insulating film, there is also a manufacturing process of forming an electrode by partially etching ITO disposed on the insulating film, which has high resolution enabling formation of a fine pattern by photolithography for the trend of high definition. Resistance to chemicals used in the etching process (alkali resistance, acid resistance), low outgassing amount to not affect the upper layer formation process, high hardness when used in touch panels It is necessary to have the following characteristics.

As a low-temperature calcinable resin composition, for example, an alkali-soluble copolymer described in Patent Document 1, a polymerizable compound having an ethylenically unsaturated bond, a photo radical generator, a compound having two or more oxetanyl groups in one molecule, A radiation sensitive resin composition containing an acid generator, 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 resin composition containing a photopolymerization initiator Proposed. However, according to the study of the present inventors, these compositions have improved adhesion to glass and silicon nitride substrates, but the adhesion is insufficient on substrates that do not have Si atoms such as ITO and molybdenum. Also, the drug resistance was insufficient.
Moreover, although the composition excellent in adhesiveness is disclosed also about patent document 3 and 4, it was inadequate in the viewpoint of chemical | medical agent tolerance, the resolution in photolithography, and degassing.

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

  The object of the present invention is to provide a photosensitive resin composition capable of forming a cured film having good resolution, good chemical resistance, low degassing amount and high hardness even at a curing temperature of 120 ° C. or less. It is to be. In addition, by using the photosensitive composition, a high quality cured film, an interlayer insulating film, an overcoat film, and a method for producing the same are provided which are excellent in resolution, hardness and chemical resistance and in which the amount of degassing is small. be able to.

That is, the present invention is a photosensitive resin composition comprising a resin (A), a polymerizable hyperbranched urethane compound (B) having a dendrimer structure, inorganic fine particles (C), a photopolymerization initiator (D), and a solvent (E). And the resin (A) contains a resin obtained by reacting (c) and (d) with a copolymer of the following (a) and (b), and a polymerizable hyperbranched urethane compound (B) Is a compound represented by the following general formula (1), and the inorganic fine particles (C) is at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium The photosensitive resin composition containing the inorganic fine particle of this invention.
(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), which is different from (a) Mer (c): at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (d): succinic anhydride
(Wherein, X ₁ is a trivalent, tetravalent or hexavalent organic residue shown below,
R ₁ , R ₂ , R ₄ and R ₅ each independently represent a linear or branched alkylene group having 1 to 12 carbon atoms,
R ₃ represents a hydrogen atom or a methyl group,
m is an integer of 0, 3, 4, 6, n is an integer of 3, 4 or 6 when m is 0, and n is an integer of 2 m when m is 3, 4 or 6. )
(* In the trivalent, tetravalent or hexavalent organic residue shown above is a site to be bound to the general formula (1).)

  Furthermore, the present invention relates to the photosensitive resin composition further comprising a silane coupling agent (F) containing at least one organic group selected from the group consisting of (meth) acryloxy group, epoxy group and mercapto group.

  The present invention also relates to the photosensitive resin composition, wherein the inorganic fine particles (C) are inorganic fine particles of silicon.

  Further, the present invention relates to the photosensitive resin composition further comprising a polymerizable compound (G) other than the polymerizable hyperbranched urethane compound (B).

  Moreover, this invention relates to the said photosensitive resin composition whose content of a photoinitiator (D) is 0.5-7.0 mass% in the total solid of the photosensitive resin composition.

  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.

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

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

  The present invention also relates to a method for producing a cured film, comprising the steps of applying the photosensitive resin composition onto a substrate, exposing it through a mask, developing it, forming a pattern, and heating and firing it.

  Furthermore, this invention relates to the manufacturing method of the said cured film whose temperature of heating-baking is 120 degrees C or less.

FIG. 1 is a ¹ H-NMR spectrum of a compound (B-3).

First, the photosensitive resin composition of the present invention will be described.
In the present application, “(meth) acryloyl”, “(meth) acrylic”, “(meth) acrylic acid”, “(meth) acrylate” or “(meth) acrylamide” are particularly described. Unless there is any, respectively, "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide" It shall represent.

<Photosensitive resin composition>

The photosensitive resin composition of the present invention comprises a resin (A), a polymerizable hyperbranched urethane compound (B) having a dendrimer structure, inorganic fine particles (C), a photopolymerization initiator (D), and a solvent (E). A photosensitive resin composition, wherein the resin (A) comprises a resin obtained by reacting (c) and then (d) with a copolymer of the following (a) and (b): The compound (B) is a compound represented by the above general formula (1), and the inorganic fine particles (C) is selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium It is a photosensitive resin composition containing inorganic fine particles (C) of at least one element.
(A): a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b): an unsaturated bond copolymerizable with (a), which is different from (a) Mass (c): At least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (d): Succinic anhydride Hereinafter, the respective components of the photosensitive resin composition of the present invention will be described. .

<Resin (A)>
The photosensitive resin composition according to the present invention comprises a specific resin obtained by reacting (c) and then (d) with a copolymer of the following (a) and (b).
(A): a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b): an unsaturated bond copolymerizable with (a), which is different from (a) Adherence and resolution can be obtained by including a specific resin modified with succinic anhydride and at least one selected from the group consisting of (c): unsaturated carboxylic acid and unsaturated carboxylic anhydride (d): succinic anhydride It is possible to form a cured film having excellent resistance, low outgassing, 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 ethylenic unsaturated bond, and an unsaturated bond copolymerizable with (a) ( A copolymer with a monomer (b) different from a) is reacted with at least one member (c) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and then succinic anhydride (d) Since it has a complicated structure obtained by making it impossible to represent by a general formula (structure) or is not realistic, it will be described by the manufacturing method.

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

[(A): a monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond]
As (a), for example, a monomer having an oxiranyl group and an ethylenically unsaturated bond (a-X), a monomer having an oxetanyl group and an ethylenically unsaturated bond (a-Y), a tetrahydrofuryl group and The monomer (a-Z) etc. which have an ethylenically unsaturated bond are mentioned.

(Monomer having an oxiranyl group and an ethylenically unsaturated bond (a-X))
As (a-X), for example, a monomer (a-1) having a structure in which a chain olefin is epoxidized and an ethylenically unsaturated bond, a structure in which a cycloalkene is epoxidized, and a ethylenically unsaturated bond The monomer (a-2) which has is mentioned.
As (a-X), a monomer having an oxiranyl group and a (meth) acryloyloxy group is preferable, and (a-2) having a (meth) acryloyloxy group is more preferable.

  As (a-1), specifically, glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl Benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl 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 ( Glycidyl oxymeth B) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4, Examples thereof include 6-tris (glycidyloxymethyl) styrene and compounds described in JP-A-7-248625.

  Examples of (a-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclo Mer A400; Daicel Chemical Industries, Ltd., 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; Daicel Chemical Industries, Ltd.), a compound represented by Formula (I), Formula (II) And the like.

[In Formula (I) and Formula (II), R ₄ and R ₅ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group is substituted with a hydroxy group It may be done. X ₂ and X ₃ are independently a single bond to each _{other, -R 6 -, * - R} 6 -O -, * - R 6 -S -, * - represents the R ₆ -NH-. R ₆ represents a C 1 to C ₆ alkanediyl group. * Represents a bond with O. ]

  Specifically as a C1-C4 alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, a sec-butyl group, a tert- butyl group etc. are mentioned. As an alkyl group substituted by a hydroxy group, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1 And -methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

The R ₄ and R _5, preferably hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group, and a 2-hydroxyethyl group, more preferably a hydrogen atom, methyl group.

  As an alkanediyl group, a methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- 1,6-diyl group etc. are mentioned.

As X ₂ and X ₃ , preferably a single bond, a methylene group, an ethylene group, a * -CH ₂ -O- (* represents a bond with O) group, a * -CH ₂ CH ₂ -O- group Among them, more preferably a single bond, * - include CH ₂ CH ₂ -O- group.

  As a compound represented by Formula (I), the compound etc. which are represented by Formula (I-1)-Formula (I-15) are mentioned. Preferably, Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I-11)-Formula (I-15) The compound represented by either of is mentioned. More preferably, the compound represented by any one of Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) is mentioned.

  Examples of the compound represented by the formula (II) include compounds represented by the 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) to Formula (II-15) The compound represented by either of is mentioned. More preferably, the compound represented by any one of Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) is mentioned.

  The compound represented by Formula (I) and the compound represented by Formula (II) can be used independently, respectively. Also, they can be mixed in any ratio. When mixing, the mixing ratio is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, particularly preferably 20:80, in terms of molar ratio, in the formula (I): formula (II). -80: 20.

(Monomer having an oxetanyl group and an ethylenically unsaturated bond (a-Y))
It is preferable that it is a monomer which has an oxetanyl group and a (meth) acryloyloxy group as (aY). As (a-Y), for example, 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryloyloxyethyl Examples include oxetane, 3-ethyl-3- (meth) acryloyloxyethyl oxetane and the like.

(Monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (a-Z))
As (a-Z), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (a-Z) include tetrahydrofurfuryl acrylate (e.g., Biscoat 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)]
Examples of (b) include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate and the like Alkyl esters; (meth) acrylics such as cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate Acid cyclic alkyl esters;

Aryl or aralkyl esters of (meth) acrylic acid such as phenyl (meth) acrylate and benzyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, 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. .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 (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;

N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide and the like;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.

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

General formula (2)

General formula (3)
[In general formula (2) and (3), R < ₇ > is a C1-C20 alkyl group which may have a hydrogen atom or a benzene ring.
Also, * is a site to be bonded to a copolymerizable unsaturated bond such as an acryloyl group or a vinyl group. ]

Chemical formula (1)

Chemical formula (2)
[In the chemical formulas (1) and (2), * represents a site to be bonded to a copolymerizable unsaturated bond such as an acryloyl group or a vinyl group. ]

((B1) a compound having an aromatic ring group shown in the general formula (2) or the general formula (3))
Specific examples of the monomer (b1) having the structures of the general formulas (2) and (3) include styrene, α-methylstyrene, divinylbenzene, indene, acetyl naphthene, benzyl acrylate, benzyl methacrylate, and bisphenol A di. Monomers and oligomers such as glycidyl ether di (meth) acrylate, (meth) acrylic ester of methylolated melamine, and ethylenically unsaturated monomers represented by the general formula (5) can be mentioned.

General formula (4)
[In the general formula (4), R ₈ is a hydrogen atom or a methyl group, R ₉ is an alkylene group having 2 or 3 carbon atoms, and R ₁₀ is a carbon number which may have a benzene ring It is an alkyl group of 1-20, n is an integer of 1-15. ]

Examples of the ethylenically unsaturated monomer represented by the general formula (4) include
Dai-ichi Kogyo Seiyaku Co., Ltd. New Frontier CEA [EO modified cresol acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : methyl group, n = 1 or 2], NP-2 [n-nonyl phenoxy polyethylene] Glycol acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : n-nonyl group, n = 2], N-177 E [n-nonyl phenoxy polyethylene glycol acrylate, R ₈ : hydrogen atom, R ₉ : ethylene Group, R ₁₀ : n-nonyl group, n = 16 to 17], or PHE [phenoxyethyl acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : hydrogen atom, n = 1],

Daicel Co., IRR 169 [ethoxylated phenyl acrylate (EO 1 mol), R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : hydrogen atom, n = 1], or Ebecryl 110 [ethoxylated phenyl acrylate (EO 2 mol), R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : hydrogen atom, n = 2],

Toon Gosei Co., Ltd. Alonics M-101A (phenol EO modified (n ≒ 2) acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : hydrogen atom, n 2 2), M-102 (phenol EO modified ( n ア ク リ レ ー ト 4) Acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : hydrogen atom, n 4 4], M-110 [paracumylphenol EO modified (n 1 1) acrylate, R ₈ : hydrogen atom , R ₉ : ethylene group, R ₁₀ : paracumyl, n 1 1], M-111 [n-nonylphenol EO modified (n 1 1) acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : n- Nonyl group, n ≒ 1], M-113 [n-nonylphenol EO modified (n ≒ 4) acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : n-nonyl group, n ≒ 4], or M-117 [n-no] Le phenol PO-modified (n ≒ 2.5) acrylate, R _8: a hydrogen atom, R _9: a propylene group, R _10: n-nonyl group, n ≒ 2.5],

Kyoeisha light acrylate PO-A [phenoxyethyl acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : hydrogen atom, n = 1], P-200A [phenoxy polyethylene glycol acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : hydrogen atom, n ≒ 2], NP-4EA [nonylphenol EO adduct acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : n-nonyl group, n 4 4 Or NP-8 EA [[nonylphenol EO adduct acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : n-nonyl group, n ≒ 8], or light ester PO [phenoxyethyl methacrylate, R ₈ : Methyl group, R ₉ : propylene group, R ₁₀ : hydrogen atom, n = 1],

NOF Corporation Blenmer ANE-300 (nonyl phenoxy polyethylene glycol acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : nonyl group, n 5 5), ANP-300 (nonyl phenoxy polypropylene glycol acrylate, R _8: a hydrogen atom, R _9: a propylene group, R _10: n-nonyl group, n ≒ 5], 43ANEP-500 [nonylphenoxy - polyethylene glycol - polypropylene glycol - acrylate, R _8: a hydrogen atom, R _9: an ethylene group and propylene group, R _10: - nonyl group, n ≒ 5 + 5], 70ANEP-550 [nonylphenoxy - polyethylene glycol - polypropylene glycol - acrylate, R _8: a hydrogen atom, R _9: an ethylene group and a propylene group, R _10: n Nonyl group, n 9 9 + 3], 75A NEP-600 [nonylphenoxy - polyethylene glycol - polypropylene glycol - acrylate, R _8: a hydrogen atom, R _9: an ethylene group and a propylene group, R _10: n-nonyl group, n ≒ 5 + 2], AAE-50 [phenoxy polyethylene glycol Acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : hydrogen atom, n = 1], AAE-300 [phenoxy polyethylene glycol acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R _{8 10} : hydrogen Atom, n 5.5 5.5], PAE-50 [phenoxy polyethylene glycol methacrylate, R ₈ : methyl group, R ₉ : ethylene group, R ₁₀ : hydrogen atom, n = 1], PAE-100 [phenoxy polyethylene glycol methacrylate, R _8: a methyl group, R _9: an ethylene group, R _10: hydrogen atoms , N = 2], or 43PAPE-600B [phenoxy - polyethylene glycol - polypropylene glycol - methacrylate, R _8: a methyl group, R _9: an ethylene group and a propylene group, R _10: a hydrogen atom, n ≒ 6 + 6],

NK ESTER AMP-10G (Phenoxyethylene glycol acrylate (EO 1 mol), R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : hydrogen atom, n = 1) manufactured by Shin-Nakamura Chemical Co., Ltd. AMP-20 G (phenoxy ethylene glycol acrylate (EO 2 mol), R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : hydrogen atom, n ≒ 2], AMP-60G [phenoxyethylene glycol acrylate (EO 6 mol), R ₈ : hydrogen atom, R ₉ : ethylene group , R ₁₀ : hydrogen atom, n ≒ 6], PHE-1G [phenoxyethylene glycol methacrylate (EO 1 mol), R ₈ : methyl group, R ₉ : ethylene group, R ₁₀ : hydrogen atom, n = 1],

Osaka Organic Chemical Co., Ltd. biscoat # 192 (phenoxy ethyl acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : hydrogen atom, n = 1), or

Nippon Kayaku SR-339A [2-phenoxyethylene glycol acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : hydrogen atom, n = 1], or SR-504 (ethoxylated nonyl phenol acrylate, R ₈ : hydrogen atom, R ₉ : ethylene group, R ₁₀ : n-nonyl group], and the like, but not limited thereto, and two or more kinds can be used in combination.

In the ethylenically unsaturated monomer represented by the general formula (4), the carbon number of the alkyl group of R ₁₀ is 1 to 20, and more preferably 1 to 10. The alkyl group includes not only a linear alkyl group but also a branched alkyl group and an alkyl group having a benzene ring as a substituent. When the carbon number of the alkyl group of R ₁₀ is 1 to 10, the alkyl group becomes an obstacle to suppress the permeation of the ITO etching solution and the metal etching solution and the chemical resistance is enhanced, but when the carbon number exceeds 10, the alkyl group The steric hindrance effect is high, and it tends to interfere with adhesion to the substrate. This tendency becomes remarkable as the carbon chain length of the alkyl group of R ₁₀ becomes longer, and when the carbon number exceeds 20, the adhesion to the substrate is extremely reduced. Examples of the alkyl group having a benzene ring represented by R ₁₀ include benzyl and 2-phenyl (iso) propyl. By adding one side chain benzene ring, chemical resistance is further improved and developability is also improved.

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

  As monomers having the structures of the general formulas (2) and (3), styrene, α-methylstyrene, benzyl acrylate, benzyl are preferred from the viewpoint of copolymerizability with other monomers and from the viewpoint of drug resistance. Preferred are methacrylates or ethylenically unsaturated monomers represented by the general formula (4). These are because, by introducing a benzene ring into the side chain of the resin (A), the penetration effect of the drug is prevented by the stacking effect of the side chain benzene ring and the chemical resistance is improved.

((B2) a compound having an aliphatic ring group shown in the chemical formula (1) or the chemical formula (2))
Specifically as the monomer (b2) having the structure of the chemical formula (1) or (2), the ethylenically unsaturated monomer shown in the general formula (5) or the ethylenic character shown in the general formula (6) Unsaturated monomer etc. are mentioned.

General formula (5)

General formula (6)
[In general formula (5) and general formula (6), R ₁₁ is a hydrogen atom or a methyl group, R ₁₂ is an alkylene group having 2 or 3 carbon atoms, and m is an integer of 1 to 15 is there. ]

Examples of the ethylenically unsaturated monomer represented by the general formula (5) include
Hitachi Chemical Co., Ltd. Funcryl FA-513A [dicyclopentanyl acrylate, R ₁₁ : hydrogen atom, R ₁₂ : none, m = 0], or FA-513 M [dicyclopentanyl methacrylate, R ₁₁ : methyl, R ₁₂ Although there are none, m = 0] and the like, two or more kinds can be used in combination without limitation to these.

As the unsaturated ethylene monomer represented by the general formula (6), for example,
Hitachi Chemical Co., Ltd. Funcryl FA-511A (dicyclopentenyl acrylate, R ₁₁ : hydrogen atom, R ₁₂ : none, m = 0), FA-512A [dicyclopentenyl oxyethyl acrylate, R ₁₁ : hydrogen atom, R ₁₂ Ethylene group, m = 1], FA-512 M [dicyclopentenyl oxyethyl methacrylate, R ₁₁ : methyl group, R ₁₂ : ethylene group, m = 1], or FA-512 MT [dicyclopentenyl oxyethyl methacrylate, R ₁₁ : methyl group, R ₁₂ : ethylene group, m = 1] and the like, but not limited thereto, two or more kinds can be used in combination.

  Among them, dicyclopentanyl (meth) acrylate is preferable as (b2) from the viewpoint of chemical resistance and hardness.

[(C) at least one member 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-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic 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] Bicyclo unsaturated compounds containing a carboxy group such as hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl] ester of a polyvalent carboxylic acid having a valence of 2 or more such as mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] phthalate, etc. And 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 in view of copolymerization reactivity and alkali solubility.

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

[(D): succinic anhydride]
Good adhesion and high resolution are compatible by using succinic anhydride as (d), and even when cured at a low temperature of 120 ° C. or less, a coating film having good chemical resistance, high hardness and little degassing Can be made. As similar compounds, dibasic acid anhydrides such as maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, Polybasic acid anhydrides such as benzophenone tetracarboxylic acid anhydride and biphenyl tetracarboxylic acid anhydride can be mentioned, but in the case of succinic acid anhydride, the molecular size is small, and the carboxylic acid and double bond site generated by the ring opening reaction It is characterized by high degree of freedom compared with other similar compounds. Since the double bond with high degree of freedom shows higher reactivity, adhesion is improved and good chemical resistance is given, and it becomes possible to produce a coating film having high hardness and less degassing. On the other hand, by having a carboxylic acid with a high degree of freedom, the developability is improved, and it becomes possible to produce a coating film with high resolution.

  The addition reaction of (d) is carried out by a conventional method. The addition amount of (d) is 5 to 100%, preferably 30 to 100%, of the hydroxyl group generated upon introduction of the photosensitive group. When the amount of addition of (d) 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, the resin (A) most preferably 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, it is possible to achieve both good chemical resistance and high resolution. When the molecular weight is less than 3,000, a strong crosslinked structure can not 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 gel permeation chromatography "HLC-8120GPC" manufactured by Tosoh Corp., and sequentially using "TSK-GEL SUPER H5000" manufactured by Tosoh Corp. It is the polystyrene conversion molecular weight measured using tetrahydrofuran as a mobile phase using "H4000", "H3000", and "H2000".

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

(Thermoplastic resin)
As a thermoplastic resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin And polyester resins, alkyd resins, polystyrenes, 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 an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because it is high in heat resistance and transparency. Be

(Thermosetting resin)
The thermosetting resin may be, for example, 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 phenol compounds, and the present invention It is not limited to this. By including such a thermosetting resin, the resin reacts at the time of firing of the filter segment, the crosslink density of the coating film is increased, the heat resistance is improved, and the effect of suppressing pigment aggregation at the time of firing the filter segment is obtained. Be
Among these, epoxy resin, cardo resin or melamine resin is preferable.

(Photosensitive resin)
As the photosensitive resin, (meth) acrylic compounds having reactive substituents such as isocyanate group, aldehyde group and epoxy group on linear polymers having reactive substituents such as hydroxyl group, carboxyl group and amino group A resin is used in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting an acid. In addition, a linear polymer containing an acid anhydride such as styrene-maleic anhydride copolymer or α-olefin-maleic anhydride copolymer is treated with a hydroxyl group-containing (meth) acrylic compound such as hydroxyalkyl (meth) acrylate. A half esterified one is also used.

<Polymerizable multi-branched urethane compound (B)>
The photosensitive resin composition of the present invention contains the polymerizable hyperbranched urethane compound (B), which exhibits good adhesion to the substrate and exhibits good chemical resistance. In particular, by combining with the specific resin of the present invention, adhesion and chemical resistance are remarkably improved.
The polymerizable hyperbranched urethane compound (B) used for the photosensitive resin composition of the present invention will be described.

  The polymerizable hyperbranched urethane compound (B) is a polyfunctional polymerizable compound represented by the following general formula (1).

General formula (1)
(Wherein, X ₁ is a trivalent, tetravalent or hexavalent organic residue shown below,
R ₁ , R ₂ , R ₄ and R ₅ each independently represent a linear or branched alkylene group having 1 to 12 carbon atoms,
R ₃ represents a hydrogen atom or a methyl group,
m is an integer of 0, 3, 4, 6, n is an integer of 3, 4 or 6 when m is 0, and n is an integer of 2 m when m is 3, 4 or 6. )
(* In the trivalent, tetravalent or hexavalent organic residue shown above is a site to be bound to the general formula (1).)

Here, as the alkylene group of R ₁ , R ₂ , R ₄ and R ₅ , each independently, a linear or branched alkylene group having 1 to 12 carbon atoms can be mentioned, and a specific example is a methylene group Ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, isopropylene group, isobutylene group, sec-butylene group, tert-butylene group And the like, but not limited thereto, preferably methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, isopropylene group, isobutylene group And more preferably methylene, ethylene, propylene, butyrene. Group, pentylene group, and isopropylene group.

  In the general formula (1), m is an integer of 0, 3, 4 or 6, n is an integer of 3, 4 or 6 when m is 0, and n = when m is 3, 4 or 6. The integer is 2 m, preferably m is 0, n is 4 or m is 4 and n is 8.

[Method for producing polymerizable hyperbranched urethane compound]
The polymerizable hyperbranched urethane compound (B) is composed of a polyfunctional acrylate monomer (e) having 3, 4 or 6 acryloyl groups in the molecule, and a secondary alkanolamine having an alkylene group of 1 to 12 carbon atoms (e.g. It is produced by reacting a core compound formed by Michael addition reaction with f) with a (meth) acryloyl group-containing compound (g) having an isocyanate group capable of reacting with active hydrogen.

(Multifunctional acrylate monomer (e))
Examples of multifunctional acrylate monomers (e) include, but are not limited to, those having the following structures.

(Alkanolamine (f))
Examples of alkanolamines (f) include, but are not limited to, those having the following structures.

((Meth) Acryloyl Group-Containing Compound Having Isocyanate Group (g))
Examples of the (meth) acryloyl group-containing compound (g) having an isocyanate group include, but are not limited to, those having the following structures.

  It is preferable that content of the polymerizable hyperbranched urethane compound (B) with respect to the total solid in a photosensitive resin composition is 10-40 mass%. By setting it in the above-mentioned range, it is possible to form a fine pixel pattern with high definition without peeling when forming a fine pattern and suppressing a long extension of the tapered portion of the pattern. Furthermore, as for content of the urethane (meth) acrylate contained in a polymerizable hyperbranched urethane compound (B), 50-100 mass% is preferable. By setting it as the said range, it becomes what is excellent in the coating-film adhesiveness with respect to the board | substrate at the time of image development, and chemical | medical agent tolerance.

<Inorganic fine particles (C)>
The photosensitive resin composition of the present invention can obtain a coating film having higher hardness and excellent chemical resistance by containing the inorganic fine particles (C).
The inorganic fine particles (C) used for the photosensitive resin composition of the present invention will be described.

  The inorganic fine particles (C) are inorganic fine particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium, and preferably have excellent refractive index and transparency. In terms of inorganic fine particles of silicon and zirconium.

As the inorganic fine particles, for example, 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, Cu ₂ O), zinc oxide (ZnO), yttrium oxide (Y ₂ O ₃ ), niobium oxide (Nb ₂ O ₅ ), molybdenum oxide (MoO ₃ ), indium oxide (In ₂ O) 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. Of nitride There is. Further, a titanate such as barium titanate, a titanium / silicon composite oxide, a composite oxide composed of two or more metal elements such as yttrium-stabilized zirconia, and the like can also be used.

  Among them, silicon oxide is preferable from the viewpoint of refractive index and transparency.

As the inorganic fine particles, compounds in which metal oxides are doped with different elements can also be used. Examples of such a compound 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 complex oxide has a core-shell structure in which not only a compound or solid solution consisting of multi-component elements but also a metal oxide fine particle serving as a core is covered with a metal oxide composed of other metal elements And include those having a multi-component dispersion type structure in which a plurality of other metal oxide particles are dispersed in one metal oxide particle.
The inorganic fine particles may be used alone or in combination of two or more.

In the present invention, the inorganic fine particles may be surface-treated. The surface treatment refers to a treatment to bind a compound capable of reacting with a hydroxyl group present on the surface of the fine particle. Such surface treatment can be performed by dispersing inorganic fine particles in a solvent, mixing the surface treatment agent under heating or under acidic conditions, and causing the mixture to act.
The surface treatment agent for hydrophobizing the surface is not particularly limited, but may be an aliphatic type such as stearic acid, oleic acid or linoleic acid, a surfactant type such as aliphatic soap, the above-mentioned silane coupling agent, silicone compound or Some use a fluorine compound or the like.
Examples of the silicone compound include dimethicone, methicone, alkyl-modified silicone, silicone resin and the like.
The fluorine compound includes a fluorine-modified alkyl compound and a fluorine-modified silicone compound, and includes, for example, perfluoroalkyl phosphate and salts thereof, perfluoroalkylsilane, perfluoroalkylcarboxylic acid and the like. In addition to the fluorine compound, it may be subjected to a hydrophobization treatment in combination with an alkyl acrylate or an (alkyl acrylate / dimethicone) copolymer.

  Generally, three kinds of methods of producing inorganic fine particles are known, roughly divided into a solid phase method, a liquid phase method and a gas phase method. As a method of obtaining nano-sized particles, a liquid phase method or a gas phase method is generally used. The liquid phase method includes a sol-gel method of causing a chemical reaction in a solution to grow crystals and obtaining fine particles, and a mechanical pulverizing method of mechanically pulverizing crystals in a liquid medium using a liquid such as water as a medium. The gas phase method includes laser pyrolysis method, combustion method, plasma vaporization method, spray combustion method, gasification combustion method, instantaneous gas phase generation method, etc., causing reaction in the gas phase to synthesize inorganic fine particles Say how to do it.

  The average primary particle diameter of the inorganic fine particles is preferably 1 to 200 nm, more preferably 3 to 100 nm, and particularly preferably 5 to 30 nm. When the average primary particle diameter exceeds 1000 nm, the transparency of the cured product tends to decrease, and the surface state of the film tends to deteriorate. In addition, various surfactants and amines may be added to improve the dispersibility of the particles.

  The average primary particle size of the inorganic fine particles is measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of the primary particle of each pigment are measured, and the average is taken as the particle size of the primary particle of the inorganic fine particle. Next, with respect to 100 or more pigment particles, the volume (mass) of each particle is determined by approximating to the cube of the determined particle diameter, and the volume average particle diameter is defined as the average primary particle diameter.

  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. As such an organic solvent, for example, 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, γ-butyrolactone Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, Amides such as N-methyl pyrrolidone can be mentioned. Among them, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferable.

(Silicon)
As a commercial item marketed as an oxide fine particle dispersion of silicon used for the present invention, Nissan Chemical Industries Co., Ltd. product MA-ST-M, MA-ST-L, IPA-ST, IPA-ST-MS, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, PGM-ST, DMAC-ST, MEK-ST-40, MEK-ST-L, MEK- ST-ZL, MEK-ST-UP, MIBK-ST, MIBK-ST-L, CHO-ST-M, EAC-ST, PMA-ST, TOL-ST, NBA-ST, XBA-ST, DMAC-ST, Examples include ST-UP, ST-OUP, ST-30, ST-50, ST-C, ST-N, ST-O, ST-OL, etc., Catalysts Chemical Industries Co., Ltd. hollow silica CS60-IPA, etc. it can. As powder silica, Aerosil 130 manufactured by Nippon Aerosil Co., Ltd., Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, manufactured by Asahi Glass Co., Ltd. Sildex H31, H32, H51, H52, H52, H121, H122, Nippon Silica Industries E220A and E220 manufactured by Co., Ltd., SYLYSIA 470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.
In the present invention, a fine particle dispersion subjected to surface treatment for the purpose of improving developability can also be used. As a commercial item, 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 etc. can be mentioned.

(aluminum)
Commercially available products as aluminum oxide fine particle dispersions used in the present invention include alumina sol-100, alumina sol-200, alumina sol-520, AS-520-A, Sumitomo Osaka Cement (manufactured by Nissan Chemical Industries, Ltd.). Examples include AS-150I and AS-150T manufactured by Co., Ltd.

(Zirconia)
Commercially available products as zirconia fine particle oxide dispersions preferably used in the present invention include Nissan Chemical Industries, Ltd. ZR-40BL, ZR-30BS, ZR-30AL, ZR-30AH, ZR-20AS, etc. Sumitomo Osaka Cement Co., Ltd. product HXU-110JC can be mentioned. In addition, the oxide particle dispersion liquid of zirconia can be obtained by the method described in Japanese Patent No. 4692630.

(titanium)
Commercial products of titanium oxide fine particles which are particularly preferably used in the present invention include SA-TTO-S-4 (10%) MiBrid Powder (fine particles (30 nm) titanium oxide hydrophobized with dimethicone) Made by Kasei Co., Ltd., MT-02 (fine particles (20 nm) hydrophobized with methicone (20 nm) titanium oxide) (manufactured by Tayca Corporation), MT-01 (fine particles treated with aluminum oxide, aluminum hydroxide and stearic acid) 10 nm) Titanium oxide) (made by Tayca Corporation), MT-10 EX (fine particles (10 nm) titanium oxide hydrophobized with aluminum oxide, aluminum hydroxide and isostearic acid) (made by Tayca Corporation), MT-100 TV (aluminum oxide) Hydrophobized with aluminum hydroxide and stearic acid Fine particles (15 nm) titanium oxide) (made by Tayca Corporation), MT-100Z (fine particles treated with aluminum oxide, aluminum hydroxide and stearic acid (15 nm) titanium oxide) (made by Tayca Corporation), MT-150 EX (made by Tayca Corporation) 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, silicon oxide, silicon hydroxide and silicone oil with hydrophobicity) Fine particles (10 nm) titanium oxide treated with oxidation treatment (manufactured by Tayca Corporation), MTY-110M3S (fine particles (10 nm) titanium oxide treated with aluminum oxide, aluminum hydroxide, silicon oxide, silicon hydroxide and silicone oil) Taika Co., Ltd.), MT-5 0SAS (aluminum oxide, aluminum hydroxide, silicon oxide, silicon hydroxide and fine particles hydrophobized with silicone oil (30 nm) titanium oxide) (made by Tayca Corporation), MTY-700BS (fine particles treated with silicone oil (hydrophobic) 80 nm) Titanium oxide) (made by Tayca Corporation), STR-60C-LP (fine particles (30 × 90 nm) titanium oxide hydrophobized with alumina and organopolysiloxane) (made by Sakai Chemical Industry Co., Ltd.), STR-100C-LP (made by Takara Chemical Industry Co., Ltd.) Fine particles (20 × 100 nm) titanium oxide hydrophobized with alumina and organopolysiloxane (made by Sakai Chemical Industry Co., Ltd.), STR-100A-LP (D. silica, alumina and organopolysiloxane) In hydrophobized particles (20 × 100 nm) Titanium oxide) (manufactured by Sakai Chemical Industry Co., Ltd.), D-962 (manufactured by Sakai Chemical Industry Co., Ltd.), NanoTek (manufactured by CI Kasei Co., Ltd.), and the like. In addition, titanium oxide fine particle dispersion can be obtained by the method described in Japanese Patent No. 469 2630.

(zinc)
Commercially available products as a zinc oxide fine particle dispersion used in the present invention include fine particles (30 nm) zinc oxide hydrophobized with MZ-505S ((dimethicone / methicone) copolymer) (manufactured by Tayca Corporation), FINEX-K2-LP2 (fine particles (30 nm) zinc oxide treated with hydrophobization with (dimethicone / methicone) copolymer (manufactured by Sakai Chemical Industry Co., Ltd.), Z-COTE HP1 (fine particles treated with hydrophobized treatment with dimethicone (25 nm) zinc oxide ) (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%) (Fine particles (40 nm) zinc oxide hydrophobized with dimethicone and methicone) (Miyoshi Kasei MZY-303S (fine particles (35 nm) zinc oxide hydrophobized with silicone oil) (manufactured by Tayca Corporation), MZ-306X (fine particles (35 nm) zinc oxide hydrophobized with silicone oil) (Tayka MZY-505S (fine particles (25 nm) zinc oxide hydrophobized with silicone oil) (manufactured by Tayca Corporation), MZY-510 M3S (fine particles (25 nm) hydrophobized with silicone oil) zinc oxide) MZ-506X (fine particles (25 nm) zinc oxide hydrophobized with silicone oil) (manufactured by Tayca Corporation), MZ-510 HPSX (fine particles hydrophobized with silicon oxide, silicon hydroxide and silicone oil) 25 nm) Zinc oxide) (manufactured by Tayca Corporation), FINEX-30S-LP Fine particles (35 nm) hydrophobized with organopolysiloxane (Sho Chemical Industry Co., Ltd.), Fine particles (35 nm zinc oxide hydrophobized with D. silica and organopolysiloxane) Ltd., FINEX-50S-LP2 (fine particles (20 nm) zinc oxide treated with hydrophobization with organopolysiloxane (made by Sakai Chemical Industry Co., Ltd.), Fine particles hydrophobized with FINEX-50W-LP2 (D. silica and organopolysiloxane) (20 nm) zinc oxide (made by Sakai Chemical Industry Co., Ltd.), Nanotech (Ci Kasei Co., Ltd.) and the like.

(Antimony)
As a commercial item marketed as an oxide fine particle of antimony which is particularly preferably used in the present invention, PATOX-U and the like (30 nm; diantimony trioxide) manufactured by Nippon Concentrate Co., Ltd. can be mentioned. As a commercial item marketed as an oxide fine particle dispersion of antimony preferably used for the present invention, Sernax CX-Z330H manufactured by Nissan Chemical Industries, Ltd. can be mentioned.

(cerium)
Commercially available commercialized fine particles of cerium oxide which can be particularly preferably used in the present invention include TECNAPOW-CEO2 (10 nm; cerium dioxide) manufactured by Air Brown Co., Ltd. As commercially available products of cerium oxide fine particle dispersion preferably used in the present invention, SI01-5 Serigard SC6832 (fine particles (35 nm) cerium oxide hydrophobized with methicone) (made by Daito Kasei Kogyo Co., Ltd.), etc. Can be mentioned.

  The amount of the inorganic fine particles (C) added is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, and particularly preferably 15 to 50% by mass, in the solid content of the photosensitive resin composition. When the addition amount is less than 5% by mass, effects such as improvement in hardness and etchant resistance are hardly obtained. On the other hand, when it exceeds 80% by mass, problems such as a decrease in developability and adhesion may occur. is there.

<Photoinitiator (D)>
The photosensitive resin composition of the present invention is in the form of a solvent-developable or alkali-developable resist material by adding a polymerization initiator and the like when the composition is cured by ultraviolet irradiation and a filter segment is formed by photolithography. It can be prepared. The compounding quantity at the time of using a photoinitiator (D) is preferably 0.2-10.0 mass% in the total solid of the photosensitive resin composition, More preferably, 0.5-7. It is 0 mass%. When the content of the photopolymerizable compound is in the above range, a coating film having good degassing and resolution of the fine pattern can be obtained.

  As the photopolymerization initiator (D), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl Acetophenone compounds such as -1-]-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, or 2,4-diethyl thioxanthone Thioxanthone compounds of the formula: 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -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 2,4-trichloromethyl- Triazine compounds such as (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyl oxime) Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethyl) Phosphine-based compounds such as benzoyl) phenyl phosphine oxide or 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone; borate-based compounds; carbazole-based compounds Compound; imidazole compound; or titanocene compound etc. are used.

  These photopolymerization initiators (D) can be used alone or in combination of two or more at an arbitrary ratio as required.

<Sensitizer>
Furthermore, the resin composition of the present invention can contain a sensitizer. As sensitizers, unsaturated ketones represented by chalcone derivatives, dibenzalacetone etc., 1,2-diketone derivatives represented by benzyl and camphorquinone etc., benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, 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, Trapyrazino porphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo porphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrilium derivative, tetraphyrin derivative, anurene derivative, spiropyran derivative, spirooxazine Derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acyl phosphine oxide, methylphenyl glyoxylate, benzyl, 9, 10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone , 4,4'-diethylaminobenzophenone and the like.

  More specifically, edited by Ogawara Shin et al., "Dye Handbook" (1986, Kodansha), edited by Ogawara Shin et al., "Chemicals of functional dyes" (1981, CMC), edited by Ikemori Tadajiro et al. Specific examples thereof include, but are not limited to, the sensitizers described in “Specially functional materials” (1986, CMC). In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region can also be contained.

  Two or more types of sensitizers may be used at an arbitrary ratio as needed. It is preferable that the compounding quantity at the time of using a sensitizer is 3-60 mass% on the basis (100 mass%) of the total mass of the photoinitiator (D) contained in a resin composition, The content is more preferably 5 to 50% by mass from the viewpoint of curability and developability.

<Solvent (E)>
The solvent (E) used for the photosensitive resin composition of the present invention will be described.
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, and 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 alcohol, tripropylene, 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, Chill isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

(A solvent with a boiling point of 130 ° C or less)
Among them, in order to sufficiently exhibit coating film hardness and chemical resistance even in a manufacturing process at low temperature curing, it is preferable to contain 10 to 80% of a solvent having a boiling point of 130 ° C. or less in the whole solvent. As a solvent having a boiling point of 130 ° C. or less, 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, n-propyl Acetate, propyl acetate, n-butyl acetate, n-butyl alcohol, methyl isobutyl ketone and the like can be mentioned. In particular, propylene glycol monoethyl ether and propylene glycol monomethyl ether are preferable 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 a total of 100 parts by mass of solid content in the photosensitive resin composition.

<Silane coupling agent (F)>
The photosensitive resin composition of the present invention exhibits good adhesion to a substrate by containing a silane coupling agent in a specific range, and exhibits good chemical resistance. In particular, by combining with the specific resin of the present invention, resolution and chemical resistance are remarkably improved.
The silane coupling agent (F) used for the photosensitive resin composition of this invention is demonstrated.

  As the silane coupling agent (F), known ones may be used without particular limitation, and specifically, vinyl group, epoxy group, styryl group, (meth) acryloxy group, amino group, ureido group, mercapto group, sulfide group And silane coupling agents having 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.

Silane coupling agents having a styryl group such as p-styryl trimethoxysilane,

Silane coupling agents having (meth) acryloxy groups such as γ-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, etc.

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 With an amino group such as hydrochloride of 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, etc. Silane coupling agent,

Silane coupling agents 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

Silane coupling agents having an isocyano group such as 3-isocyanatopropyltriethoxysilane,

3-Carbamateethyl) propyltrimethoxysilane, (3-carbamateethyl) propyltripropoxysilane, (3-carbamatepropyl) propyltriethoxysilane, (3-carbamatepropyl) propyltrimethoxysilane, (3-carbamatepropyl) Propyl tripropoxysilane, (3-carbamate butyl) propyl triethoxysilane, (3-carbamate butyl) propyl trimethoxysilane, (3-carbamate butyl) propyl tripropoxysilane, (3-carbamate butyl) butyl tripropa xixe Silane, (3-Carbamate butyl) propylmethyldiethoxysilane, (3-Carbamate pentyl) propyltriethoxysilane, (3-Carbamatehexyl) propyltriethoxysilane, (3 Carbamate octyl) pentyl tributoxysilane, (3- carbamate ethyl) propyl silyl trichloride, (3- carbamate ethyl) propyl trimethylsilane, (3- carbamate ethyl) propyl dimethyl silane, (3- carbamate ethyl) propyl tributyl silane, ( Examples thereof include silane coupling agents having a carbamate group such as 3-carbamate ethyl) ethyl-p-xylene triethoxysilane and (3-carbamate ethyl) -p-phenylene triethoxysilane.

  These silane coupling agents (F) can be used alone or in combination of two or more at an arbitrary ratio as needed.

  Among these, the silane coupling agent (F) preferably contains at least one organic group selected from the group consisting of (meth) acryloxy group, epoxy group and mercapto group, and specifically, 3) 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 preferable because the adhesion becomes good.

  The silane coupling agent may be a silanol compound produced by hydrolysis of the above compound or a polyorganosiloxane compound in which they are condensed.

Content of the silane coupling agent in the photosensitive resin composition in this invention is 5 mass% or more in solid content of the photosensitive resin composition. When the content is less than 5% by mass, there arises a problem that part of the coating is peeled off when forming a high definition fine pixel pattern. More preferably, it is 7% by mass or more, particularly preferably 10% by mass or more. When the content is 7% by mass or more, not only fine pixel pattern formation, but also from the viewpoint of chemical resistance, it becomes good.
Moreover, content of a silane coupling agent is 20 mass% or less in solid content of the photosensitive resin composition. If it exceeds 20% by mass, a strong crosslinked structure can not be obtained, which causes a problem that the drug resistance is deteriorated. More preferably, it is 15% by mass or less. If it becomes 15 mass% or less, it becomes favorable from a viewpoint of resolution.

<Polymerizable compound (G)>
The polymerizable compound (G) which may be added to the photosensitive resin composition of the present invention is a polymerizable compound other than the polymerizable hyperbranched urethane compound (B), which is cured by ultraviolet light or heat to be a transparent resin. Containing monomers or oligomers that produce.

  Examples of monomers and oligomers that cure by ultraviolet light and heat to form a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 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 ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, pentaerythri 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, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylate of methylolated melamine, epoxy (meth) acrylate, urethane Various acrylic acid esters such as acrylate and methacrylic acid esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene Examples include glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like, but are not necessarily limited thereto.

  The polymerizable compound (G) may contain an acid group. For example, esterified products of free hydroxyl group-containing poly (meth) acrylates of polyhydric alcohol and (meth) acrylic acid with dicarboxylic acids; esterified products of polyvalent carboxylic acid and monohydroxyalkyl (meth) acrylates Can be mentioned. As a specific example, monohydroxy oligo acrylates or mono hydroxy oligo methacrylates such as trimethylol propane diacrylate, trimethylol propane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc. 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 And free carboxyl group-containing oligoesters with monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. However, the effects of the present invention are not limited to these.

(Urethane (meth) acrylate)
The polymerizable compound (G) in the present invention can contain a monomer having a polymerizable unsaturated bond group containing a urethane (meth) acrylate other than the polymerizable hyperbranched urethane compound (B). The inclusion of a urethane (meth) acrylate other than the polymerizable hyperbranched urethane compound (B) is preferable because it improves the coating film adhesion to a substrate during development and the chemical resistance. Usually, distortion occurs in the coating film due to light curing, but the inclusion of urethane (meth) acrylate results in a coating film in which the distortion is alleviated, leading to improvement in adhesion and chemical resistance.

  There is no restriction on the structure of the urethane (meth) acrylate other than the polymerizable hyperbranched urethane compound (B), and a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate or an alcohol is polyfunctional The urethane (meth) acrylate etc. which are obtained by making an isocyanate react, and also making the (meth) acrylate which has a hydroxyl group react can be used.

  As a (meth) acrylate having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri ( Meta) 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 Methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloyl propyl methacrylate, epoxy Reactant-containing compound and the carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

  Moreover, as polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate etc. are mentioned.

  In addition, although the structure of alcohol is not limited, it is preferable to use a polyhydric alcohol because the degree of crosslinking of the cured coating film is increased and the coating film resistance is increased. Examples of polyhydric alcohols include propylene glycol, ethylene glycol, glycerin, trimethylolpropane and pentaerythritol.

  As commercially available polyfunctional urethane (meth) acrylates, KAYARADUX-3204 made by Nippon Kayaku Co., Ltd., KAYARAD UX-4101, KAYARAD UX-6100, KAYARAD UX-6101, KAYARAD UX-7101, KAYARADUX-8101, KAYARAD UX-0937, KAYARAD UXF-4002, KAYARAD DPHA-40H, KAYARAD UX-5005, and Aonix M-1100 manufactured by Toa Gosei Co., Ltd., Aronix M-1200 Aronix U-6 LPA manufactured by Shin-Nakamura Chemical Co., Ltd., UA-1100H, U-15 HA, UA- 160TM, UA-122P, UA-7100, UA-W2A, and KS-M Corporation KUA-4I, KUA-6I, KUA-9N, KUA-10H, etc. are preferably used. Can.

  In the polymerizable compound (G) which can be used in the photosensitive resin composition of the present invention, in addition to the above-mentioned urethane (meth) acrylate, when reacting a (meth) acrylate having a hydroxyl group with polyfunctional isocyanate, alcohol In addition, it is also possible to include a component having a double bond group which can not be obtained as a polyfunctional urethane (meth) acrylate as another monomer when reacting a polyfunctional isocyanate with the above and further reacting a (meth) acrylate having a hydroxyl group. Good.

  These polymerizable compounds (G) can be used alone or in combination of two or more at an arbitrary ratio as needed.

  The content of the polymerizable compound (G) with respect to the total solid content in the photosensitive resin composition is preferably 10 to 40% by mass in combination with the polymerizable hyperbranched urethane compound (B). By setting it in the above-mentioned range, it is possible to form a fine pixel pattern with high definition without peeling when forming a fine pattern and suppressing a long extension of the tapered portion of the pattern. Furthermore, the content of the urethane (meth) acrylate contained in the polymerizable compound (G) is preferably 50 to 100% by mass in combination with the polymerizable hyperbranched urethane compound (B). By setting it as the said range, it becomes what is excellent in the coating-film adhesiveness with respect to the board | substrate at the time of image development, and chemical | medical agent tolerance.

<UV absorber>
The photosensitive resin composition of the present invention may contain an ultraviolet absorber in order to prevent exposure to light by diffracted light of the mask during exposure. The ultraviolet absorber is an organic compound having an ultraviolet absorbing function other than the photopolymerization initiator. It is preferable that content of the ultraviolet absorber with respect to the total solid in a photosensitive resin composition is 0.05-3.0 mass%. When the content of the ultraviolet absorber is smaller than the above, the effect of the ultraviolet absorber is small, the tapered portion of the photosensitive resin composition pattern is stretched long, and it becomes difficult to form a high definition fine pixel pattern. There are many residues. If the amount is more than the above, problems such as generation of insoluble matter and reduction in adhesion may occur.

(Absorbance)
It is preferable that the light absorbency in wavelength 365nm of a ultraviolet absorber is 0.4 or more. The absorbance is a measured value when an ultraviolet absorber is dissolved in a solvent having no absorption at a wavelength of 365 nm, such as chloroform, and diluted to 10 mg / L, and the measurement method will be described below. This method utilizes the relationship between solution concentration and light absorption known as Lambert-Beer's law. That is, when a solution of a certain concentration is enclosed in a transparent container with a certain thickness and irradiated with light of intensity I0 from one side and the light of intensity I coming out of the opposite side is observed, the incident light is inside the container Is absorbed by the solution and its strength weakens. And it is known that the weakening of the strength is proportional to the concentration of the solution. The relational expression representing this law is the absorbance of A,
A = −Log (I0 / I) = abc
It is expressed as Here, a is a constant of proportionality, b is the thickness of the solution, and c is the solution concentration.

  Furthermore, the ultraviolet absorber is preferably a benzotriazole organic compound, a benzophenone organic compound or a triazine organic compound, and as the benzotriazole organic compound having an absorbance of 0.4 or more at a wavelength of 365 nm, 2- (5 methyl) -2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [6- (benzotriazol-2-yl) -4-tert-octylphenol] etc. are mentioned. As a benzophenone series organic compound, 2, 2- di hydroxy 4, 4 dimethoxy benzophenone etc. are mentioned. Examples of triazine organic compounds include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine and the like. Specifically, "TINUVIN P" (absorbance 0.40), "TINUVIN 326" (absorbance 0.48), "TINUVIN 360" (absorbance 0.40), manufactured by BASF, "Seasorb 107" (abs. 0.60) "ADEKA STAB LA-F70" (absorbance 0.90) manufactured by ADEKA Corporation, etc. may be mentioned.

<Polymerization inhibitor>
The photosensitive resin composition of the present invention may also contain a polymerization inhibitor in order to prevent exposure to light by diffracted light of the mask during exposure.
As a polymerization inhibitor, catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol , 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert- Alkyl catechol compounds such as butyl catechol, 3,5-di-tert-butyl catechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresor Alkyl resorcinol compounds such as cinol, 2-n-butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, 4-tert-butyl resorcinol, methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, tert-butyl hydroquinone, Alkyl hydroquinone compounds such as 2,5-di-tert-butyl hydroquinone, phosphine compounds such as tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, tribenzyl phosphine, trioctyl phosphine oxide, triphenyl phosphine oxide and the like Phosphine oxides such as triphenyl phosphite and tris nonyl phenyl phosphite Compounds, pyrogallol, and the like phloroglucinol. 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.

<Leveling agent>
It is preferable to add a leveling agent 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 preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by BYK Chemie, and the like. As a specific example of dimethylsiloxane which has a polyester structure, BYK-310 BYK-310 grade | etc., Etc. are mentioned. The dimethylsiloxane having a polyether structure and the dimethylsiloxane having a polyester structure can also be used in combination. In general, the content of the leveling agent is preferably 0.003 to 0.5% by mass based on the total mass of the photosensitive resin composition (100% by mass).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a low solubility in water while having a hydrophilic group, and when added to a resin composition, It is characterized by low surface tension reduction ability, and in addition to low surface tension reduction ability, it is useful that the wettability to the glass plate is good, and the addition amount at which defects of the coating film due to foaming do not appear. Those which can sufficiently suppress the chargeability can be preferably used. As a leveling agent which has such a preferable characteristic, dimethylpolysiloxane which has a polyalkylene oxide unit can use it preferably. The polyalkylene oxide unit may be a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit to dimethylpolysiloxane is a pendent type in which the polyalkylene oxide unit is bonded to a repeating unit of dimethylpolysiloxane, a terminal-modified type bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane It may be any of linear block copolymer types alternately and repeatedly bonded. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2203. -2-207, but not limited thereto.

The leveling agent may be supplemented with an anionic, cationic, nonionic or amphoteric surfactant. The surfactant may be used as a mixture of two or more. Examples of anionic surfactants to be added to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Ester etc. are mentioned.

  Examples of the cationic surfactant added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. As a nonionic surfactant which is added to the leveling agent as auxiliaries, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And polyethylene glycol monolaurate and the like, and also alkylbetaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkyl imidazolines, and fluorine-based and silicone-based surfactants.

<Antioxidant>
The photosensitive resin composition of the present invention can contain an antioxidant. An antioxidant can suppress the fall of the transmittance | permeability by yellowing etc. by passing through a heating process. Therefore, yellowing at the time of a heating process can be prevented by containing an antioxidant, and the coating film with high transmittance | permeability can be obtained.

  In the present invention, the "antioxidant" may be a compound having an ultraviolet absorbing function, a radical trapping function, or a peroxide decomposing function, and specifically, hindered phenol type or hindered amine type as an antioxidant. And phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylic acid ester, and triazine compounds, and known ultraviolet light absorbers, antioxidants and the like can be used. The antioxidant of the present invention is particularly preferably a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film. Among phenol-based ones, hindered phenol-based antioxidants having high steric hindrance are particularly preferable.

(Phenolic antioxidant)
For example, 2,6-di-tert-butyl-4-ethylphenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3. 5-triazine, 2,2-thio-diethylene bis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, N, N'-hexamethylene bis (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-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-methoxyphenol, triethylene glycol Bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis {3- (3,5-di-tert-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, etc. may be mentioned, and 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, 3, 5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert- Hindered phenolic antioxidants selected from the group consisting of butyl-4-hydroxybenzyl phosphonate-diethyl ester and tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate are It is preferable from the viewpoint of photocurability.

(Phosphorus antioxidant)
As a phosphorus antioxidant, although what is marketed can be used, tris [2,4-di- (tert) -butylphenyl] phosphine tris [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) is mentioned, It is preferable that it is at least 1 sort (s) of compound selected from the group which consists of these, and 1 or 2 types can be used for these.

(Sulfur-based antioxidants)
Sulfur-based antioxidants are antioxidants that contain sulfur in the molecule. As such sulfur-containing antioxidants, commercially available ones can be used, but dioctadecyl 3,3'-thiodipropanoate, dimyristyl-3,3'-thiodipropionate, dipalmityl-3,3'- Thiodipropionate, distearyl-3,3′-thiodipropionate, 4,4′-thiobis-3-methyl-6-tert-butylphenol, thiodiethylenebis [3- (3,5-di-tert- Butyl 4-hydroxyphenyl) propionate] is preferable and it is preferable that it is at least 1 type of compound chosen from the group which consists of these, and 1 type or 2 types or more can be used for these.

  These antioxidants can be used alone or in combination of two or more at an arbitrary 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 the amount is less than 0.1% by mass, the effect of preventing yellowing is difficult to obtain because the antioxidant is insufficient. If the amount is more than 4% by mass, radicals generated at the time of ultraviolet light exposure are captured. Curing of the composition may be insufficient.

<Storage stabilizer>
The photosensitive resin composition of the present invention can 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, organics such as t-butylpyrocatechol, triethylphosphine and triphenylphosphine Phosphine, phosphite and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 5% by mass in the total 100% by mass of the photosensitive resin composition.

<Manufacturing method of photosensitive resin composition>
The photosensitive resin composition of the present invention is required to have a resin (A), a polymerizable hyperbranched urethane compound (B), inorganic fine particles (C), a photopolymerization initiator (D), and a solvent (E). It can obtain by stirring and mixing the silane coupling agent (F), the polymeric compound (G), etc. which are added according to. The photosensitive resin composition of the present invention can be 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, by means of centrifugation, sintered filter, membrane filter, etc. It is preferable to remove the mixed dust and foreign matter.

<Coating film>
The photosensitive resin composition of the present invention can form a coating film excellent in hardness, adhesion, etchant resistance, and heat and humidity resistance, and thus is suitable for a touch panel, a liquid crystal display device, an organic EL device, and the like.

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

  In the case of forming a coating film by photolithography, a photosensitive resin composition prepared as a solvent developing type or an alkali developing type is coated on a transparent substrate by spray coating, spin coating, slit coating, die coating, roll coating, etc. Apply by the method. The coating film dried if necessary is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact or non-contact with the coating film. Thereafter, it is immersed in a solvent or an alkaline developer, or the developer is sprayed by a spray or the like to remove an uncured portion, whereby a cured coating film can be obtained. Furthermore, in order to accelerate | stimulate superposition | polymerization of the photosensitive resin composition, heating can also be given as needed.

In the development, an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide or the like is used as an alkali developing solution, and an organic alkali such as tetramethylammonium hydroxide (TMAH), dimethylbenzylamine or triethanolamine can also be used. . Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the ultraviolet exposure sensitivity, after applying and drying the photosensitive resin composition, a water-soluble or alkali water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent inhibition of polymerization by oxygen. After film formation, UV exposure can also be performed.

  In addition, the photosensitive resin composition of the present embodiment may be used in any of protective film application, flat film application, insulating film application, antireflective film application, and coating film formation is also a touch panel, liquid crystal display device, It may be formed by any organic EL device, and since it has high hardness, high adhesion, and good transparency, it can be used in combination with applications of a protective film, a flat film, an insulating film, or an antireflective film.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to only the following examples. In addition, "part" and "%" in a following example represent "mass part" and "mass%", respectively. Also, "PGMEA" means propylene glycol monomethyl ether acetate.

  Prior to the examples, measurement of the weight average molecular weight of the resin and the acid value will be described.

(Weight average molecular weight of resin)
The weight average molecular weight (Mw) of the resin was measured using a TSK gel column (manufactured by Tosoh Corporation) and a GPC equipped with an RI detector (GPC manufactured by Tosoh Corporation, HLC-8120GPC) using polystyrene as the developing solvent in terms of polystyrene. It is a weight average molecular weight (Mw).

(Acid number)
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the resin solution, and the mixture is stirred and uniformly dissolved, using a 0.1 mol / L KOH aqueous solution as a titration solution, an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) ) And the acid value of the resin solution was measured. And the acid value per solid content of resin was computed from the acid value of resin solution, and solid content concentration of resin solution.

  Then, the manufacturing method of resin (A) solution, polymerizable hyperbranched urethane compound (B), and polymeric compound (G) used by the Example and the comparative example is demonstrated.

<Production of Resin (A) Solution>
(Resin solution (A-1))
Place 100 parts of PGMEA in a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirring device in a separable four-necked flask, heat at 120 ° C while injecting nitrogen gas into the vessel, and drop from the dropping pipe 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 is replaced with air, and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone are added to 17.0 parts of acrylic acid, and the reaction is continued at 120 ° C. for 5 hours. The reaction was terminated when it reached 8 mg KOH / g, and a resin solution having a weight average molecular weight of about 5,000 was obtained.
Furthermore, 20.0 parts of succinic anhydride and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 4 hours, PGMEA was added so that the nonvolatile content was 40%, and a resin solution (A-1) was prepared.

(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 composition and the blending amount (parts by mass) shown in Table 1 were changed.

<Production of Polymerizable Hyperbranched Urethane Compound (B)>
(Polymerizable multi-branched urethane compound (B-1))
In a reaction vessel equipped with a stirrer and a thermometer, 8.0 parts of trimethylolpropane triacrylate, 8.5 parts of diethanolamine, and 60 parts of tetrahydrofuran (THF) are charged, stirred at room temperature for 4 hours and then refluxed for 1 hour, ¹ The reaction was confirmed to be complete by H-NMR. The solvent was distilled off with an evaporator to obtain 16 parts of a precursor compound represented by the following chemical formula (3) as a colorless and transparent viscous liquid.

Chemical formula (3)

  In a reaction vessel equipped with a stirrer and a thermometer, 15 parts of the precursor compound represented by the chemical formula (3), 0.1 parts of di-n-butyltin dilaurate, 1.8 parts of cuperone (polymerization inhibitor), THF 50 The part was charged and stirred at room temperature. A mixture of 16 parts of isocyanatomethyl acrylate and 50 parts of THF was added dropwise over 2 hours, and the mixture was refluxed for 5 hours, and it was confirmed by FT-IR that the reaction was completed. The solvent was distilled off with an evaporator to obtain 28 parts of an acrylate dendrimer represented by the following chemical formula (4) as a dark brown high viscosity liquid compound (B-1).

Chemical formula (4)
Compound (B-1)

(Polymerizable multi-branched urethane compound (B-2))
In a reaction vessel equipped with a stirrer and a thermometer, 5.0 parts of pentaerythritol tetraacrylate, 6.0 parts of diethanolamine and 60 parts of tetrahydrofuran (THF) are charged, stirred at room temperature for 4 hours and then refluxed for 1 hour, ¹ H -NMR confirmed that the reaction was complete. The solvent was distilled off with an evaporator to obtain 9.6 parts of a precursor compound represented by the following chemical formula (5) as a colorless, transparent and viscous liquid.

  In a reaction vessel equipped with a stirrer and a thermometer, 8.0 parts of the precursor compound represented by the chemical formula (5), 0.1 parts of di-n-butyltin dilaurate, 1.8 parts of cuperone (polymerization inhibitor) Then, 30 parts of THF was charged and stirred at room temperature. A mixture of 12 parts of 2-isocyanatoethyl acrylate and 30 parts of THF was added dropwise thereto over 2 hours, refluxed for 5 hours, and it was confirmed by FT-IR that the reaction was completed. The solvent was distilled off with an evaporator to obtain 18 parts of an acrylate dendrimer represented by the following chemical formula (6) as a dark brown high viscosity liquid compound (B-2).

(Polymerizable multi-branched urethane compound (B-3))
In a reaction vessel equipped with a stirrer and a thermometer, 7.0 parts of the acrylate dendrimer represented by the chemical formula (6) obtained in Production Example (B-2), 3.1 parts of diethanolamine, and 50 parts of THF are charged. After stirring for 1 hour, the mixture was refluxed for 1 hour, and ¹ H-NMR confirmed that the reaction was completed. The solvent was distilled off with an evaporator to obtain 11 parts of a precursor compound represented by the following chemical formula (7) as a colorless, transparent and viscous liquid.

In a reaction vessel equipped with a stirrer and a thermometer, 9.0 parts of the precursor compound represented by the chemical formula (7), 0.1 parts of di-n-butyltin dilaurate, 1.0 part of cuperone (polymerization inhibitor) Then, 20 parts of THF was charged and stirred at room temperature. A mixture of 7.0 parts of 2-isocyanatoethyl acrylate and 20 parts of THF was added dropwise over 2 hours, and the mixture was refluxed for 5 hours, and it was confirmed by FT-IR that the reaction was completed. The solvent was distilled off with an evaporator to obtain 15 parts of an acrylate dendrimer represented by the following chemical formula (8) as a dark brown paste-like compound (B-3). The chart of ¹ H-NMR of compound (B-3) is shown in FIG.

(Polymerizable Hyperbranched Urethane Compound (B-4))
In a reaction vessel equipped with a stirrer and a thermometer, 7.0 parts of pentaerythritol tetraacrylate, 26 parts of dioctanolamine and 50 parts of tetrahydrofuran (THF) are charged, stirred at room temperature for 4 hours and then refluxed for 1 hour, ¹ H -NMR confirmed that the reaction was complete. The solvent was distilled off with an evaporator to obtain 32 parts of a precursor compound represented by the following chemical formula (9) as a colorless, transparent and viscous liquid.

  In a reaction vessel equipped with a stirrer and a thermometer, 30 parts of the precursor compound represented by the chemical formula (9), 0.1 parts of di-n-butyltin dilaurate, 1.8 parts of cuperone (polymerization inhibitor), THF 50 The part was charged and stirred at room temperature. Here, a mixture of 36 parts of 8-isocyanatooctyl acrylate and 50 parts of THF was added dropwise over 2 hours, refluxed for 5 hours, and it was confirmed by FT-IR that the reaction was completed. The solvent was distilled off with an evaporator to obtain 55 parts of an acrylate dendrimer represented by the following chemical formula (10) as a dark brown high viscosity liquid compound (B-4).

(Polymerizable multi-branched urethane compound (B-5))
In a reaction vessel equipped with a stirrer and a thermometer, 10 parts of the acrylate dendrimer represented by the chemical formula (10) obtained in Production Example (B-4), 4.7 parts of dibutanolamine, and 75 parts of THF are charged. After stirring for 1 hour, the mixture was refluxed for 1 hour, and ¹ H-NMR confirmed that the reaction was completed. The solvent was distilled off with an evaporator to obtain 12 parts of a precursor compound represented by the following chemical formula (11) as a colorless, transparent and viscous liquid.

  In a reaction vessel equipped with a stirrer and a thermometer, 13 parts of a precursor compound represented by the chemical formula (11), 0.1 parts of di-n-butyltin dilaurate, 0.5 parts of cuperone (polymerization inhibitor), THF 20 The part was charged and stirred at room temperature. A mixture of 10 parts of 4-isocyanatobutyl methacrylate and 20 parts of THF was added dropwise thereto over 2 hours, refluxed for 5 hours, and it was confirmed by FT-IR that the reaction was completed. The solvent was distilled off with an evaporator to obtain 19 parts of a methacrylate dendrimer represented by the following chemical formula (12) as a dark brown paste-like compound (B-5).

(Polymerizable Hyperbranched Urethane Compound (B-6))
In a reaction vessel equipped with a stirrer and a thermometer, 7.0 parts of pentaerythritol tetraacrylate, 35 parts of didodecanolamine and 50 parts of tetrahydrofuran (THF) are charged, stirred at room temperature for 4 hours and then refluxed for 1 hour, ¹ The reaction was confirmed to be complete by H-NMR. The solvent was distilled off with an evaporator to obtain 39 parts of a precursor compound represented by the following chemical formula (13) as a colorless, transparent and viscous liquid.

  In a reaction vessel equipped with a stirrer and a thermometer, 38 parts of the precursor compound represented by the chemical formula (13), 0.1 parts of di-n-butyltin dilaurate, 1.8 parts of cuperone (polymerization inhibitor), THF 50 The part was charged and stirred at room temperature. Here, a mixture of 44 parts of 12-isocyanatododecyl acrylate and 50 parts of THF was added dropwise over 2 hours, refluxed for 5 hours, and it was confirmed by FT-IR that the reaction was completed. The solvent was distilled off with an evaporator to obtain 72 parts of an acrylate dendrimer represented by the following chemical formula (14) as a dark brown high viscosity liquid compound (B-6).

(Polymerizable Hyperbranched Urethane Compound (B-7))
In a reaction vessel equipped with a stirrer and a thermometer, 10 parts of the acrylate dendrimer represented by the chemical formula (14) obtained in Production Example (B-6), 2.4 parts of diisopropanolamine, and 75 parts of THF are charged. After stirring for 1 hour, the mixture was refluxed for 1 hour, and ¹ H-NMR confirmed that the reaction was completed. The solvent was distilled off with an evaporator to obtain 11 parts of a precursor compound represented by the following chemical formula (15) as a colorless and transparent viscous liquid.

  In a reaction vessel equipped with a stirrer and a thermometer, 11 parts of a precursor compound represented by the chemical formula (15), 0.1 parts of di-n-butyltin dilaurate, 0.5 parts of cuperone (polymerization inhibitor), THF 20 The part was charged and stirred at room temperature. To this, a mixture of 5.0 parts of 3-isocyanato-2-methyl-propyl acrylate and 20 parts of THF is added dropwise over 2 hours, refluxed for 5 hours, and confirmed by FT-IR that the reaction is completed. did. The solvent was distilled off with an evaporator to obtain 13 parts of an acrylate dendrimer represented by the following chemical formula (16) as a dark brown paste-like compound (B-7).

(Polymerizable Hyperbranched Urethane Compound (B-8))
In a reaction vessel equipped with a stirrer and a thermometer, 7.0 parts of ditrimethylolpropane tetraacrylate, 5.0 parts of dimethanol amine, and 50 parts of tetrahydrofuran (THF) are charged, stirred at room temperature for 4 hours, and refluxed for 1 hour. The reaction was confirmed to be complete by ¹ H-NMR. The solvent was distilled off with an evaporator to obtain 11 parts of a precursor compound represented by the following chemical formula (17) as a colorless and transparent viscous liquid.

  In a reaction vessel equipped with a stirrer and a thermometer, 10 parts of the precursor compound represented by the chemical formula (17), 0.1 parts of di-n-butyltin dilaurate, 1.3 parts of cuperone (polymerization inhibitor), THF 40 The part was charged and stirred at room temperature. A mixture of 17 parts of 3-isocyanatopropyl acrylate and 40 parts of THF was added dropwise thereto over 2 hours, refluxed for 5 hours, and it was confirmed by FT-IR that the reaction was completed. The solvent was distilled off with an evaporator to obtain 25 parts of an acrylate dendrimer represented by the following chemical formula (18) as a dark brown high viscosity liquid compound (B-8).

(Polymerizable Hyperbranched Urethane Compound (B-9))
In a reaction vessel equipped with a stirrer and a thermometer, 10 parts of the acrylate dendrimer represented by the chemical formula (18) obtained in Production Example (B-8), 3.0 parts of dimethylamine and 70 parts of THF are charged, and After stirring for 1 hour, the mixture was refluxed for 1 hour, and ¹ H-NMR confirmed that the reaction was completed. The solvent was distilled off with an evaporator to obtain 10 parts of a precursor compound represented by the following chemical formula (19) as a colorless, transparent and viscous liquid.

  In a reaction vessel equipped with a stirrer and a thermometer, 10 parts of a precursor compound represented by the chemical formula (19), 0.1 parts of di-n-butyltin dilaurate, 1.0 parts of cuperone (polymerization inhibitor), THF 20 The part was charged and stirred at room temperature. Here, a mixture of 9.0 parts of 3-isocyanatopropyl acrylate and 20 parts of THF was added dropwise over 2 hours, refluxed for 5 hours, and it was confirmed by FT-IR that the reaction was completed. The solvent was distilled off with an evaporator to obtain 18 parts of an acrylate dendrimer represented by the following chemical formula (20) as a dark brown paste-like compound (B-9).

(Polymerizable multi-branched urethane compound (B-10))
In a reaction vessel equipped with a stirrer and a thermometer, 5.0 parts of dipentaerythritol hexaacrylate, 5.0 parts of diethanolamine, and 40 parts of tetrahydrofuran (THF) are charged, stirred at room temperature for 4 hours and then refluxed for 1 hour, ¹ The reaction was confirmed to be complete by H-NMR. The solvent was distilled off with an evaporator to obtain 9.1 parts of a precursor compound represented by the following chemical formula (31) as a colorless, transparent and viscous liquid.

  In a reaction vessel equipped with a stirrer and a thermometer, 9.0 parts of the precursor compound represented by the chemical formula (31), 0.1 parts of di-n-butyltin dilaurate, 1.0 part of cuperone (polymerization inhibitor) Then, 30 parts of THF was charged and stirred at room temperature. A mixture of 13 parts of 2-isocyanatoethyl acrylate and 30 parts of THF was added dropwise thereto over 2 hours, refluxed for 5 hours, and it was confirmed by FT-IR that the reaction was completed. The solvent was distilled off with an evaporator to obtain 20 parts of an acrylate dendrimer represented by the following chemical formula (32) as a dark brown high viscosity liquid compound (B-10).

(Polymerizable Hyperbranched Urethane Compound (B-11))
In a reaction vessel equipped with a stirrer and a thermometer, 10 parts of the acrylate dendrimer represented by the chemical formula (32) obtained in Production Example (B-10), 4.0 parts of diethanolamine, and 70 parts of THF are charged and stirred at room temperature for 4 hours The mixture was then refluxed for 1 hour, and ¹ H-NMR confirmed that the reaction was complete. The solvent was distilled off with an evaporator to obtain 13 parts of a precursor compound represented by the following chemical formula (33) as a colorless, transparent and viscous liquid.

  In a reaction vessel equipped with a stirrer and a thermometer, 11 parts of a precursor compound represented by the chemical formula (33), 0.1 parts of di-n-butyltin dilaurate, 1.0 parts of cuperone (polymerization inhibitor), THF 20 The part was charged and stirred at room temperature. A mixture of 9 parts of 2-isocyanatoethyl acrylate and 20 parts of THF was added dropwise thereto over 2 hours, refluxed for 5 hours, and it was confirmed by FT-IR that the reaction was completed. The solvent was distilled off with an evaporator to obtain 17 parts of an acrylate dendrimer represented by the following chemical formula (34) as a dark brown paste-like compound (B-11).

<Production of Polymerizable Compound (G)>
(Polymerizable compound (G-1))
In a reaction vessel equipped with a stirrer and a thermometer, 623 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Alonix M-400 (manufactured by Toagosei Co., Ltd.)) and 44 parts of hexamethylene diisocyanate are charged. The mixture was stirred for 8 hours, confirmed by FT-IR that the reaction was completed, and a product containing multifunctional urethane acrylate (1) was obtained. In the product, the proportion of the polyfunctional urethane acrylate (1) was 45% by mass, and the polymerizable compound (G-1) in which the remaining part was occupied by another photopolymerizable monomer was obtained.

(Polymerizable Compound (G-2))
In a reaction vessel equipped with a stirrer and a thermometer, 600 parts of hexamethylene diisocyanate adduct of trimethylolpropane (Coronate HL (manufactured by Tosoh Corporation)) and 950 parts of pentaerythritol triacrylate are charged, and stirred at 60 ° C. for 8 hours -The reaction was confirmed to be complete by IR to obtain a product containing a multifunctional urethane acrylate (2). In the product, the proportion of the polyfunctional urethane acrylate (2) was 80% by mass, and a polymerizable compound (G-2) in which the remaining part was occupied by another photopolymerizable monomer was obtained.

<Production of Photosensitive Resin Composition>
Example 1
(Photosensitive resin composition (R1)
The mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a filter with a pore size of 1 μm to obtain a photosensitive resin composition (R1).
Resin solution (A-1): 27.5 parts Polymerizable hyperbranched urethane compound (B-1): 2.00 parts PMA-ST: 20.0 parts (silica fine particles: solid content 42 mass% (manufactured by Nissan Chemical Industries, Ltd.) )
Irg. 907: 1.00 part (IRGACURE 907 (manufactured by BASF))
BYK-330 2% solution: 1.00 parts (PGMEA solution of dimethyl siloxane containing polyether structure (manufactured by Bick Chemie))
Propylene glycol monomethyl ether acetate: 28.6 parts Propylene glycol methyl ether: 20.0 parts

[Examples 2 to 40, Comparative Examples 1 to 5]
(Photosensitive resin composition (R2 to 45))
The mixture is uniformly stirred and mixed in the same manner as the photosensitive resin composition (R1) except that the composition and amount (parts by mass) shown in Tables 2 to 4 are changed. It filtered, and photosensitive resin composition (R2-45 was obtained.

<Evaluation of photosensitive resin composition>
The obtained photosensitive resin compositions (R1 to 45 were evaluated by the following method. The results are shown in Table 5.

(Drug resistant)
«ITO etchant resistance»
A substrate obtained by applying a photosensitive resin composition to a 100 mm × 100 mm, 0.7 mm thick ITO substrate (manufactured by Geomatec) using a spin coater so that the finished film thickness becomes 2.0 μm after heating at 100 ° C. for 60 minutes I got Next, after holding for 2 minutes on a hot plate heated to 80 ° C., ultraviolet exposure was performed at an illuminance of 20 mW / cm ² and an exposure amount of 100 mJ / cm ² using an extra-high pressure mercury lamp. The coated substrate was heated at 100 ° C. for 60 minutes and allowed to cool to prepare a substrate for evaluation. Then, it was immersed in ITO etchant; nitric acid / hydrochloric acid / water = 0.1 / 1/5 at 40 ° C. for 5 minutes, washed with pure water, and left for 24 hours. The obtained substrate was evaluated for adhesion to a substrate of the coating film by the adhesion (cross-cut method) test according to JIS K5600-5-6, and the number of peeled particles in 25 grids was counted and evaluated according to the following criteria. .
碁: The number of peeled pieces in the grid is 0 (good level)
碁: 1 or more and less than 3 pieces of peeled grids (practical level possible)
X: The number of peeled pieces in the grid is 3 or more (level not suitable for practical use)

«Mo etchant resistance»
After preparing a coating on Mo substrate (made by Toho Chemical Co., Ltd.) by the same method as evaluation of ITO etchant resistance, Mo etchant; phosphoric acid / acetic acid / nitric acid / water = 80/5/5/10 at 40 ° C. The substrate was immersed for 5 minutes, washed with pure water and allowed to stand for 24 hours. The obtained substrate was evaluated for adhesion to a substrate of the coating film by the adhesion (cross-cut method) test according to JIS K5600-5-6, and the number of peeled particles in 25 grids was counted and evaluated according to the following criteria. .
碁: The number of peeled pieces in the grid is 0 (good level)
碁: 1 or more and less than 3 pieces of peeled grids (practical level possible)
X: The number of peeled pieces in the grid is 3 or more (level not suitable for practical use)

(Pencil hardness)
The finished film thickness after heating at 100 ° C for 60 minutes on a glass substrate (Glass Eagle 2000 manufactured by Corning) 100 mm × 100 mm, 0.7 mm thick using a photosensitive resin composition is 2.0 μm The substrate applied to Next, after holding for 2 minutes on a hot plate heated to 80 ° C., ultraviolet exposure was performed at an illuminance of 20 mW / cm ² and an exposure amount of 100 mJ / cm ² using an extra-high pressure mercury lamp. 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 the 8.4.1 pencil scratching test of JIS K 5400-1990, and the evaluation was made according to the following criteria.
○: Pencil surface hardness is 2H or more (good level)
:: Pencil surface hardness is H (practical level)
X: Pencil surface hardness is F or less (a level not suitable for practical use)

(Resolution)
Obtain a substrate coated on a 100 mm x 100 mm, 0.7 mm thick glass substrate (Glass Eagle 2000 manufactured by Corning) using a spin coater so that the finished film thickness after heating at 100 ° C for 60 minutes becomes 2.0 μm. The Next, after holding for 2 minutes on a hot plate heated to 80 ° C., an exposure of 1000 J / m ² is performed at a wavelength of 365 nm using an i-line stepper exposure apparatus FPA-3000i5 + (Canon Co., Ltd.) The The exposure was performed through a photomask in which 5.0 μm square light-shielding portions and light-transmitting portions were arranged in a checkered pattern. The coated film after exposure was subjected to paddle development for 1 minute with an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.). After paddle development, the substrate was rinsed with pure water in a spin shower for 20 seconds, dried by spin drying, and then heated at 100 ° C. for 60 minutes in a clean oven. About the obtained pixel pattern, the hole pixel pattern formed of the light-shielding part was observed using the scanning electron microscope ("S-3000N" by Hitachi High-Tech company), and the following references | standards evaluated.
○: Hole size is 4.5 μm or more and less than 5.0 μm (good level)
Δ: Hole size is 4.0 μm or more and less than 4.5 μm (practical level)
X: Hole size less than 4.0 μm (level not suitable for practical use)

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

  Hereinafter, the abbreviations in Tables 2 to 5 are shown.

«Inorganic fine particles (C)»
PMA-ST: Silica fine particles (Nissan Chemical Industries, 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 Industries, solid content 20% by mass)

«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)]

«Solvent (E)»
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

«Silane coupling agent (F)»
KBM-403: 3-glycidoxypropyl trimethoxysilane (Shin-Etsu Silicone Co., Ltd.)
KBM-503: 3-methacryloxypropyl trimethoxysilane (Shin-Etsu Silicone Co., Ltd.)
KBM-5103: 3-acryloxypropyltrimethoxysilane (Shin-Etsu Silicone Co., Ltd.)
KBM-803: 3-mercaptopropyltrimethoxysilane (Shin-Etsu Silicone Co., Ltd.)

<< polymeric compound (G) >>
G-1: The above-synthesized polymerizable compound. 45 mass% of polyfunctional urethane acrylate containing G-2: The said polymeric compound synthesize | combined. Multifunctional urethane acrylate 80% by mass G-3 (M402): ARONIX M-402 (manufactured by Toagosei Co., Ltd.)
Mixture of dipentaerythritol penta and hexaacrylate

«Leveling agent»
BYK-330 2%: PGMEA solution of polyether structure-containing dimethylsiloxane (adjusted to 2% by mass of non volatile matter (manufactured by Bick Chemie)

  As shown in Table 5, the photosensitive resin composition of the present application containing a specific resin (A) using succinic anhydride, a polymerizable hyperbranched urethane compound (B), and an inorganic fine particle (C) is resistant to chemicals. The hardness, the resolution, and the degassing evaluation all satisfied practicable levels. On the other hand, the photosensitive resin composition containing the polymerizable multi-branched urethane compound (B) but not containing the inorganic fine particles (C) shown in Comparative Examples 1 and 2 is evaluated for chemical resistance, pencil hardness and resolution. The result was inferior. Moreover, the photosensitive resin composition shown in Comparative Examples 3 and 4 which contains the inorganic fine particles (C) but does not contain the polymerizable hyperbranched urethane compound (B) has any of chemical resistance, pencil hardness and degassing evaluation. It has not reached the practical level in heels. Furthermore, in Comparative Example 5 using resin (A-3) using tetrahydrophthalic anhydride instead of succinic anhydride, the chemical resistance and degassing evaluation did not reach a practical level.

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

Claims (10)

A photosensitive resin composition comprising a resin (A), a polymerizable hyperbranched urethane compound (B) having a dendrimer structure, inorganic fine particles (C), a photopolymerization initiator (D), and a solvent (E),
The resin (A) contains a resin obtained by reacting (c) and (d) with a copolymer of the following (a) and (b), and the polymerizable hyperbranched urethane compound (B) is A compound represented by formula (1),
The photosensitive resin composition in which an inorganic fine particle (C) contains the inorganic fine particle of the at least 1 element chosen from the group which consists of silicon, aluminum, a zirconium, titanium, zinc, indium, tin, antimony, and cerium.
(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), which is different from (a) Mer (c): at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (d): succinic anhydride
(Wherein, X ₁ is a trivalent, tetravalent or hexavalent organic residue shown below,
R ₁ , R ₂ , R ₄ and R ₅ each independently represent a linear or branched alkylene group having 1 to 12 carbon atoms,
R ₃ represents a hydrogen atom or a methyl group,
m is an integer of 0, 3, 4, 6, n is an integer of 3, 4 or 6 when m is 0, and n is an integer of 2 m when m is 3, 4 or 6. )
(* In the trivalent, tetravalent or hexavalent organic residue shown above is a site to be bound to the general formula (1).)
  The photosensitive resin composition according to claim 1, further comprising a silane coupling agent (F) containing at least one organic group selected from the group consisting of (meth) acryloxy group, epoxy group and mercapto group.   The photosensitive resin composition according to claim 1 or 2, wherein the inorganic fine particles (C) are inorganic fine particles of silicon.   The photosensitive resin composition according to any one of claims 1 to 3, further comprising a polymerizable compound (G) other than the polymerizable hyperbranched urethane compound (B).   The photosensitive resin composition according to any one of claims 1 to 4, 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.   The photosensitive resin composition according to any one of claims 1 to 5, wherein the solvent (E) contains a solvent having a boiling point of 130 ° C or less.   The cured film formed from the photosensitive resin composition of any one of Claims 1-6.   The cured film according to claim 7, which is an interlayer insulating film or an overcoat film.   A method for producing a cured film, comprising the steps of: applying the photosensitive resin composition according to any one of claims 1 to 6 onto a substrate, exposing it through a mask, developing it to form a pattern, and heating and baking it.   The method for producing a cured film according to claim 9, wherein the temperature of heating and firing is 120 ° C or less.