CN106030407B - Photosensitive resin composition - Google Patents

Abstract

The present invention relates to a photosensitive resin composition which contains (A), (B), (C) and (D), wherein the content of (A) is 45-80% by mass relative to the total content of (A) and (C). (A) The polymer is a polymer which contains a structural unit derived from an aromatic carboxylic acid having an ethylenically unsaturated bond, a structural unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms, and does not contain a structural unit containing a perfluoroalkyl group having 4 to 6 carbon atoms, (B) a polymer containing a structural unit containing a perfluoroalkyl group having 4 to 6 carbon atoms, (C) a polymerizable compound, and (D) a polymerization initiator.

Description

Photosensitive resin composition

Technical Field

The present invention relates to a photosensitive resin composition.

Background

In recent years, display devices and the like have produced color filters, ITO electrodes for liquid crystal display elements, organic EL display elements, circuit wiring boards, and the like by an ink jet method. In addition, the inkjet method uses a partition wall formed using a photosensitive resin composition.

As the photosensitive resin composition, for example, a photosensitive resin composition containing a copolymer of methacrylic acid and 3, 4-epoxytricyclo [5.2.1.02.6] decyl acrylate as a resin is known (patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2012 and 73603

Disclosure of Invention

When ink containing an organic functional material is applied to a concave portion defined by a partition wall formed on a substrate and the substrate using an ink jet apparatus, the wettability of the substrate surface is preferably high so that the substrate surface of the concave portion is completely covered with the ink, and the wettability of the upper surface of the partition wall is preferably low (the liquid repellency is high) in order to prevent the ink from leaking out of a target region. However, the wettability of the partition wall formed using the conventionally proposed photosensitive resin composition and the substrate surface of the concave portion defined by the substrate may not be satisfactory.

The present invention provides the following [1] to [6 ].

[1] A photosensitive resin composition comprising (A), (B), (C) and (D), wherein the content of (A) is 45 to 80 mass% relative to the total content of (A) and (C), (A) a polymer comprising a structural unit derived from an aromatic carboxylic acid having an ethylenically unsaturated bond, a structural unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms, and having no structural unit containing a perfluoroalkyl group having 4 to 6 carbon atoms, (B) a polymer comprising a structural unit containing a perfluoroalkyl group having 4 to 6 carbon atoms, (C) a polymerizable compound, and (D) a polymerization initiator.

[2] The photosensitive resin composition according to [1], wherein (D) is a polymerization initiator containing at least one selected from the group consisting of a biimidazole compound, an alkylphenone compound and an O-acyloxime compound.

[3] A pattern formed from the photosensitive resin composition according to [1] or [2 ].

[4] An ink jet partition wall comprising the photosensitive resin composition according to [1] or [2 ].

[5] A display device comprising the pattern of [3 ].

[6] A display device comprising the inkjet partition wall according to [4 ].

According to the photosensitive resin composition of the present invention, a pattern having excellent wettability, that is, a pattern having high wettability of the substrate surface of the concave portion defined by the partition walls and the substrate and high liquid repellency of the upper surface of the partition walls can be obtained.

drawings

Fig. 1 is a cross-sectional view schematically showing a part of a display device 1 in an enlarged manner.

Fig. 2 is a partially enlarged schematic plan view of the display device 1 according to the embodiment of the present invention.

Detailed Description

The photosensitive resin composition of the present invention is a photosensitive resin composition containing (A), (B), (C) and (D).

(A) A polymer (hereinafter, sometimes referred to as "resin (A)") comprising a structural unit derived from an aromatic carboxylic acid having an ethylenically unsaturated bond, a structural unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms and having no structural unit containing a perfluoroalkyl group having 4 to 6 carbon atoms

(B) a polymer containing a structural unit having a C4-6 perfluoroalkyl group (hereinafter, sometimes referred to as "resin (B)")

(C) Polymerizable compound

(D) A polymerization initiator.

Further, the photosensitive resin composition of the present invention preferably contains a solvent (E).

The photosensitive resin composition of the present invention may contain at least 1 selected from the group consisting of resins other than the resin (a) and the resin (B) (hereinafter, may be referred to as "resin (a 1)"), a polymerization initiation aid (D1), a polyfunctional thiol compound (T), and a surfactant (F).

In the present specification, the compounds exemplified as the respective components may be used alone or in combination unless otherwise specified.

Examples of the resin (a) contained in the photosensitive resin composition of the present invention include:

Resin (A-1): a polymer containing a structural unit derived from an aromatic carboxylic acid (a) (hereinafter sometimes referred to as "(a)") having an ethylenically unsaturated bond and a structural unit derived from an unsaturated compound (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms,

Resin (A-2): a polymer obtained by polymerizing (a) and (b) with a monomer (c) (hereinafter sometimes referred to as "(c)") which is polymerizable with (a) and (b) and does not have a cyclic ether structure having 2 to 4 carbon atoms. Wherein each of (a), (b) and (c) has a C4-6 perfluoroalkyl group.

(a) At least one monomer selected from the group consisting of an aromatic carboxylic acid having an ethylenically unsaturated bond and an aromatic carboxylic acid anhydride having an ethylenically unsaturated bond, and specifically, aromatic carboxylic acids such as o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, 3-vinylphthalic acid, and 4-vinylphthalic acid; aromatic carboxylic acid anhydrides such as 3-vinylphthalic anhydride and 4-vinylphthalic anhydride.

(b) The monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring), preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated double bond, and more preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In the present specification, "(meth) acrylic acid" means at least 1 selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth) acryloyl group", "meth (acrylate)" and the like have the same meaning.

Examples of (b) include a monomer (b1) having an oxiranyl group (hereinafter sometimes referred to as "(b 1)"), a monomer (b2) having an oxetanyl group (hereinafter sometimes referred to as "(b 2)"), a monomer (b3) having a tetrahydrofuranyl group (hereinafter sometimes referred to as "(b 3)"), and the like.

Examples of (b1) include a monomer (b1-1) (hereinafter sometimes referred to as "(b 1-1)") having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized, and a monomer (b1-2) (hereinafter sometimes referred to as "(b 1-2)") having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized.

The (b1) is preferably a monomer having an epoxyethyl group and a (meth) acryloyloxy group, and more preferably a monomer having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized and a (meth) acryloyloxy group. These preferable monomers provide a photosensitive resin composition having excellent storage stability.

Specific examples of (b1-1) include glycidyl (meth) acrylate,. beta. -methylglycidyl (meth) acrylate,. beta. -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether,. alpha. -methyl-o-vinylbenzyl glycidyl ether,. alpha. -methyl-m-vinylbenzyl glycidyl ether,. alpha. -methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis (glycidyloxymethyl) styrene, 2, 4-bis (glycidyloxymethyl) styrene, 2, 5-bis (glycidyloxymethyl) styrene, 2, 6-bis (glycidyloxymethyl) styrene, p-vinylbenzyl glycidyl ether, 2, 4-bis (glycidyloxymethyl) styrene, 2, 5, 2, 3, 4-tris (glycidyloxymethyl) styrene, 2, 3, 5-tris (glycidyloxymethyl) styrene, 2, 3, 6-tris (glycidyloxymethyl) styrene, 3, 4, 5-tris (glycidyloxymethyl) styrene, 2, 4, 6-tris (glycidyloxymethyl) styrene, a compound described in Japanese patent application laid-open No. 7-248625, and the like.

Examples of (b1-2) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Dailuo Chemicals Co., Ltd.), 3, 4-epoxycyclohexylmethyl acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Dailuo Chemicals Co., Ltd.), 3, 4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer (registered trademark) M100; manufactured by Dailuo Chemicals Co., Ltd.), the compound represented by the formula (I), the compound represented by the formula (II), and the like.

[ in the formulae (I) and (II), R1 and R2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X1 and X2 each independently represent a single bond, -R3-, -R3-O-, -R3-S-, or-R3-NH-.

R3 represents an alkanediyl group having 1 to 6 carbon atoms.

Denotes a bond to O. ]

Examples of the alkyl group having 1 to 4 carbon atoms represented by R1 and R2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and the like.

Examples of the alkyl group substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.

R1 and R2 preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably include a hydrogen atom and a methyl group.

Examples of the alkanediyl group represented by R3 include a methylene group, an ethylene group, a propane-1, 2-diyl group, a propane-1, 3-diyl group, a butane-1, 4-diyl group, a pentane-1, 5-diyl group, and a hexane-1, 6-diyl group.

Preferred examples of X1 and X2 include a single bond, methylene, ethylene, a group of — CH2 — O- (' which is a bond to O), and a group of — CH2CH2-O-, and more preferred examples thereof include a single bond, and a group of — CH2CH 2-O-.

Examples of the compound represented by the formula (I) include compounds represented by the formulae (I-1) to (I-15). Among them, preferred are compounds represented by formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formulae (I-11) to (I-15), and more preferred are compounds represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

Examples of the compound represented by the formula (II) include compounds represented by the formulae (II-1) to (II-15). Among them, preferred are compounds represented by the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9) or the formulae (II-11) to (II-15), and more preferred are compounds represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used each alone or in combination of 2 or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio [ the compound represented by the formula (I): the compound represented by the formula (II) is preferably 5: 95 to 95: 5, more preferably 20: 80 to 80: 20 on a molar basis.

As (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is preferable. Examples of (b2) include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 3-methyl-3- (meth) acryloyloxyethyloxyoxetane, and 3-ethyl-3- (meth) acryloyloxyethyloxyoxetane.

As (b3), a monomer having a tetrahydrofuranyl group and a (meth) acryloyloxy group is preferable.

specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., VISCOATV # 150, available from Osaka organic Chemicals, Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Examples of (c) include (meth) acrylates, N-substituted maleimides, unsaturated dicarboxylic diesters, alicyclic unsaturated compounds, unsaturated carboxylic acids, unsaturated carboxylic anhydrides, styrenes, and other vinyl compounds.

Examples of the (meth) acrylates include alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate;

Cycloalkyl esters such as cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02, 6] decan-8-yl (meth) acrylate (commonly known in the art as dicyclopentanyl (meth) acrylate), dicyclopentanyloxyethyl (meth) acrylate, tricyclo [5.2.1.02, 6] decen-8-yl (meth) acrylate (commonly known in the art as "dicyclopentenyl (meth) acrylate"), isobornyl (meth) acrylate, and the like;

Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Aryl and aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate.

Examples of the N-substituted maleimide include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimidobenzoate, N-succinimide-4-maleimidobutyrate, N-succinimide-6-maleimidohexanoate, N-succinimide-3-maleimidopropionate, and N- (9-acridinyl) maleimide.

Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, and diethyl itaconate.

Examples of alicyclic unsaturated compounds include 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-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, Unsaturated bicyclo compounds such as 5, 6-dimethoxybicyclo [2.2.1] hept-2-ene, 5, 6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [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 and 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene.

Examples of the unsaturated carboxylic acids include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid;

Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, sec-conic acid (mesaconic acid), itaconic acid, 3, 4, 5, 6-tetrahydrophthalic acid, 1, 2, 3, 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1, 4-cyclohexenedicarboxylic acid; carboxyl group-containing bicyclic unsaturated compounds such as methyl-5-norbornene-2, 3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Unsaturated mono [2- (meth) acryloyloxyalkyl ] esters of 2-or more-membered polycarboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl ] ester and phthalic acid mono [2- (meth) acryloyloxyethyl ] ester;

And unsaturated (meth) acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α - (hydroxymethyl) acrylic acid.

Examples of the unsaturated carboxylic acid anhydride include unsaturated diacid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3, 4, 5, 6-tetrahydrophthalic anhydride, 1, 2, 3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride.

The styrene may, for example, be styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene or p-methoxystyrene.

Examples of the other vinyl compound include (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1, 3-butadiene, isoprene, and 2, 3-dimethyl-1, 3-butadiene.

As (c), styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of polymerization reactivity and alkali solubility.

In the resin (a-1), the ratio of the structural units derived from the respective monomers to the total mole number of the structural units constituting the resin (a-1) is preferably in the following range.

Structural unit derived from (a): 5 to 60 mol% (more preferably 10 to 50 mol%)

Structural units derived from (b): 40 to 95 mol% (more preferably 50 to 90 mol%)

When the ratio of the structural unit of the resin (A-1) is within the above range, the storage stability of the photosensitive resin composition, the developability in forming a pattern from the photosensitive resin composition, and the solvent resistance, heat resistance and mechanical strength of the resulting coating film and pattern tend to be good.

The resin (A-1) is preferably the resin (A-1) wherein (b) is (b1), more preferably the resin (A-1) wherein (b) is (b 1-2).

The resin (A-1) can be produced, for example, by referring to the method described in "Experimental methods for Polymer Synthesis" (published by Otsu Longxu Co., Ltd., 1 st edition, chemical Co., Ltd., 1972, 3/1), and the cited documents described in the above documents.

Specifically, for example, a method in which a certain amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, oxygen in the atmosphere is replaced with nitrogen, for example, to set a deoxygenated atmosphere, and heating and heat-maintaining are performed while stirring. The polymerization initiator and the solvent used herein are not particularly limited, and those generally used in the art can be used. Examples of the polymerization initiator include azo compounds (e.g., 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), etc.) and organic peroxides (e.g., benzoyl peroxide), and the solvent may be a solvent that dissolves each monomer, and the solvent (E) of the photosensitive resin composition described below may be used. In order to adjust the molecular weight of the resin obtained, a chain transfer agent may be added during the polymerization reaction. Examples of the chain transfer agent include mercaptans such as n-butanethiol, tert-butanethiol, n-dodecanethiol, 2-mercaptoethanol, ethylmercaptic acid, ethyl ethylmercaptate, 2-ethylhexyl ethylmercaptic acid, methoxybutyl ethylmercaptate, 3-mercaptopropionic acid, and mercapto group-containing silicone (KF-2001: manufactured by shin-Etsu chemical Co., Ltd.); halogen alkyl esters such as chloroform, carbon tetrachloride and carbon tetrabromide.

The polymer obtained may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a solid (powder) taken out by a method such as reprecipitation. In particular, in the polymerization, the same solvent as the solvent (E) described later is used as a solvent, and the solution after the reaction can be used as it is, whereby the production process can be simplified.

In the resin (a-2), the ratio of the structural units derived from the respective monomers to the total mole number of all the structural units constituting the resin (a-2) is preferably in the following range.

Structural unit derived from (a): 2 to 40 mol% (more preferably 5 to 35 mol%)

Structural units derived from (c): 1 to 65 mol% (more preferably 1 to 60 mol%)

Structural units derived from (b): 2 to 95 mol% (more preferably 5 to 80 mol%)

When the ratio of the structural unit of the resin (a-2) is within the above range, the storage stability of the photosensitive resin composition, the developability in forming a pattern from the photosensitive resin composition, and the solvent resistance, heat resistance, and mechanical strength of the resulting coating film and pattern tend to be good.

The resin (A-2) is preferably a resin (A-2) in which (b) is (b1), and more preferably a resin (A-2) in which (b) is (b 1-2).

The resin (A-2) can be produced by the same method as that for the resin (A-1).

The weight average molecular weight of the resin (A) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (a) is within the above range, the coating property tends to be excellent, and the film at the exposed portion is less likely to be reduced during development, and the unexposed portion is more likely to be removed during development.

The molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the resin (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the molecular weight distribution is within the above preferred range, the developability tends to be excellent.

The acid value of the resin (A) is usually 20 to 150mgKOH/g, preferably 40 to 135mgKOH/g, more preferably 50 to 135 mgKOH/g. The acid value is a value measured by the amount (mg) of potassium hydroxide required to neutralize 1g of the resin, and can be determined by titration with an aqueous potassium hydroxide solution.

The content of the resin (a) is 45 mass% to 80 mass%, preferably 48 mass% to 75 mass%, and more preferably 50 mass% to 70 mass% with respect to the total content of the resin (a) and the polymerizable compound (C).

When the content of the resin (a) exceeds 80% by mass of the total content of the resin (a) and the polymerizable compound (C), the development time during development of a coating film formed from the photosensitive resin composition tends to be long.

When the content of the resin (a) is within the above-described preferable range, the wettability of the surface of the patterned base plate in the partition wall formed of the photosensitive resin composition is good.

The photosensitive resin composition of the present invention contains a resin (B). The resin (B) is a polymer containing a structural unit derived from an unsaturated compound (d) having a perfluoroalkyl group having 4 to 6 carbon atoms (hereinafter, sometimes referred to as "(d)").

As (d), a compound represented by the formula (d-0) can be mentioned.

[ in the formula (d-0), Rf represents a C4-6 perfluoroalkyl group.

Rd represents a hydrogen atom, a halogen atom, a cyano group, a phenyl group, a benzyl group or an alkyl group having 1 to 21 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a halogen atom or a hydroxyl group.

xd represents a single bond, a 2-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a 2-valent alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a 2-valent aromatic hydrocarbon group having 6 to 12 carbon atoms, and-CH 2-contained in the aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be replaced by-O-, -CO-, -NRe-, -S-or-SO 2-. ]

Rf is a C4-C6 perfluoroalkyl group, preferably a perfluorobutyl group or a perfluorohexyl group.

examples of the alkyl group having 1 to 21 carbon atoms in Rd include straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; isopropyl group, isobutyl group, sec-butyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propylbutyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 2-propylpentyl group, 1-butylbutyl group, butyl group, methyl-pentyl group, methyl, 1-butyl-2-methylbutyl, 1-butyl-3-methylbutyl, tert-butyl, 1-dimethylpropyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 3-dimethylbutyl, 1-ethyl-2-methylpropyl, 1-dimethylpentyl, branched alkyl groups such as 1, 2-dimethylpentyl group, 1, 3-dimethylpentyl group, 1, 4-dimethylpentyl group, 2-dimethylpentyl group, 2, 3-dimethylpentyl group, 2, 4-dimethylpentyl group, 3-dimethylpentyl group, 3, 4-dimethylpentyl group, 1-ethyl-1-methylbutyl group, and 2-ethyl-3-methylbutyl group.

Rd is preferably a hydrogen atom, a halogen atom or a methyl group.

Examples of the 2-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms in Xd include alkanediyl groups such as a methylene group, an ethylene group, a propane-1, 3-diyl group, a propane-1, 2-diyl group, a butane-1, 4-diyl group, a butane-1, 3-diyl group, a butane-1, 2-diyl group, a pentane-1, 5-diyl group, a hexane-1, 6-diyl group, a heptane-1, 7-diyl group, and an octane-1, 8-diyl group.

Examples of the 2-valent alicyclic hydrocarbon group having 3 to 10 carbon atoms in Xd include cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, and cyclodecanediyl.

Examples of the 2-valent aromatic hydrocarbon group having 6 to 12 carbon atoms in Xd include a phenylene group and a naphthalenediyl group.

Examples of Xd which is obtained by substituting-CH 2-with-O-, -CO-, -NRe-, -S-, or SO2-, and which is contained in a 2-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms and a 2-valent alicyclic hydrocarbon group having 3 to 10 carbon atoms, include groups represented by the formulae (Xd-1) to (Xd-10).

Xd is preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably an ethylene group.

As (d), a compound represented by the formula (d-0') is preferred.

[ in the formula (d-0'), Rh represents a C4-6 perfluoroalkyl group.

Rg represents a hydrogen atom, a halogen atom or a methyl group. ]

Examples of the compound represented by the formula (d-0) include compounds (d-1) to (d-94). In the table, the formula numbers shown in the column Xd are those of the above exemplified groups. Further, for example, the compound (d-1) is a compound represented by the following formula (d-1).

[ Table 1]

[ Table 2]

The resin (B) is preferably a resin containing at least one member selected from the group consisting of a structural unit derived from (d), a structural unit derived from (a), and a structural unit derived from an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride (e) (which is different from (a)) (hereinafter, may be referred to as "(e)"), more preferably a resin containing a structural unit derived from (d) and a structural unit derived from (e), and still more preferably a resin containing a structural unit derived from (d), a structural unit derived from (e), and a structural unit derived from (B). By including the structural unit derived from (a) and/or (e) in the resin (B), the developing property is excellent, and therefore unevenness derived from residue or development tends to be suppressed. By including the structural unit derived from (B) in the resin (B), the solvent resistance tends to be excellent. The resin (B) may contain other structural units. Examples of the monomer (hereinafter, sometimes referred to as "(c')") having another structural unit introduced thereinto include monomers other than the unsaturated carboxylic acid and the unsaturated carboxylic acid anhydride among the monomers represented by the above (c).

When the resin (B) is a polymer of (a) and/or (e) and (d), the ratio of the structural units derived from the respective monomers is preferably in the following range with respect to the total mole number of the structural units constituting the resin (B).

Structural units derived from (a) and/or (e); 5 to 40 mass% (more preferably 10 to 30 mass%)

A structural unit derived from (d); 60 to 95 mass% (more preferably 70 to 90 mass%)

When the resin (B) is a polymer of (a) and/or (e), (B) and (d), the ratio of the structural units derived from the respective monomers to the total mole number of the structural units constituting the resin (B) is preferably in the following range.

Structural units derived from (a) and/or (e); 5 to 40 mass% (more preferably 10 to 30 mass%)

A structural unit derived from (b); 5 to 80 mass% (more preferably 10 to 70 mass%)

A structural unit derived from (d); 10 to 80 mass% (more preferably 20 to 70 mass%)

When the resin (B) is a polymer of (a) and/or (e), (B), (c') and (d), the ratio of the structural units derived from the respective monomers to the total mole number of the structural units constituting the resin (B) is preferably in the following range.

Structural units derived from (a) and/or (e); 5 to 40 mass% (more preferably 10 to 30 mass%)

A structural unit derived from (b); 5 to 70 mass% (more preferably 10 to 60 mass%)

A building block derived from (c'); 10 to 50 mass% (more preferably 20 to 40 mass%)

A structural unit derived from (d); 10 to 80 mass% (more preferably 20 to 70 mass%)

When the ratio of each constituent unit is within the above range, the liquid repellency and the developability tend to be excellent.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3000 to 20000, and more preferably 5000 to 15000. When the weight average molecular weight of the resin (B) is within the above preferred range, the coating property tends to be excellent, the film at the exposed portion is less likely to be formed during development, and the unexposed portion is more likely to be removed during development.

The acid value of the resin (B) is 20 to 200mgKOH/g, preferably 40 to 150 mgKOH/g.

The content of the resin (B) is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the total amount of the resin (a), the resin (a1) and the polymerizable compound (C). When the content of the resin (B) is within the above preferable range, the developability at the time of pattern formation is excellent, and the obtained pattern tends to be excellent in liquid repellency.

The photosensitive resin composition of the present invention may contain a resin (a 1). Examples of the resin (A1) include

Resin (A1-1): (e) a polymer obtained by polymerizing the monomer (a) and (b),

Resin (a 1-2): (e) a polymer obtained by polymerizing (b) and (c'),

Resin (a 1-3): (e) a polymer obtained by polymerization with (c'), (ii),

Resin (a 1-4): (e) a resin obtained by reacting a polymer obtained by polymerization with the (c) and the (b),

Resin (a 1-5): (b) a resin obtained by reacting (a) and/or (e) with a polymer obtained by polymerizing (c').

In the resin (A1-1), the ratio of the structural units derived from the respective monomers is preferably in the following range with respect to the total number of moles of all the structural units constituting the resin (A1-1).

A structural unit derived from (e); 5 to 60 mol% (more preferably 10 to 50 mol%)

A structural unit derived from (b); 40 to 95 mol% (more preferably 50 to 90 mol%)

When the ratio of the structural units of the resin (a1-1) is in the above range, the storage stability of the photosensitive resin composition, the developability in forming a pattern from the photosensitive resin composition, and the solvent resistance of the resulting coating film and pattern tend to be good.

In the resin (A1-2), the ratio of the structural units derived from the respective monomers is preferably in the following range relative to the total mole number of all the structural units constituting the resin (A1-2).

A structural unit derived from (e); 2 to 45 mol% (more preferably 5 to 40 mol%)

A structural unit derived from (b); 2 to 95 mol% (more preferably 5 to 80 mol%)

A building block derived from (c'); 1 to 65 mol% (more preferably 5 to 60 mol%)

When the ratio of the structural units of the resin (a1-2) is in the above range, the storage stability of the photosensitive resin composition, the developability in forming a pattern from the photosensitive resin composition, and the solvent resistance of the resulting coating film and pattern tend to be good.

In the resin (A1-3), the ratio of the structural units derived from the respective monomers is preferably in the following range with respect to the total number of moles of all the structural units constituting the resin (A1-3).

A structural unit derived from (e); 2 to 40 mol% (more preferably 5 to 35 mol%)

A building block derived from (c'); 60 to 98 mol% (more preferably 65 to 95 mol%)

When the ratio of the structural units of the resin (a1-1) is in the above range, the storage stability of the photosensitive resin composition, the developability in forming a pattern from the photosensitive resin composition, and the solvent resistance of the resulting coating film and pattern tend to be good.

The resin (A1-4) is a resin obtained by reacting the polymer of (e) and (c') with (b).

The resin (A1-4) can be produced, for example, by a two-stage process. In this case, the polymer can be produced by a method described in "Experimental methods for Polymer Synthesis" (published by Otsu Longxu institute of chemistry, 1 st edition, 1972, 3 months and 1 days), a method described in Japanese patent laid-open No. 2001-89533, and the like.

First, as a first stage, the polymers (e) and (c') were obtained in the same manner as in the above-described method for producing the resin (A-1).

In this case, the polymer obtained may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a substance taken out as a solid (powder) by a method such as reprecipitation. Further, the same polystyrene-equivalent weight average molecular weight and molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] are preferable.

However, the ratio of the structural units derived from (e) and (c') is preferably in the following range with respect to the total number of moles of all the structural units constituting the polymer.

A structural unit derived from (e); 5 to 50 mol% (more preferably 10 to 45 mol%)

A building block derived from (c'); 50 to 95 mol% (more preferably 55 to 90 mol%)

next, as a second stage, a part of the carboxylic acid and carboxylic anhydride of (e) derived from the obtained polymer is reacted with the cyclic ether of (b). Since the cyclic ether has high reactivity and unreacted (b) does not easily remain, the (b) used as the resin (A1-2) is preferably (b1) or (b2), and more preferably (b 1-1).

Specifically, resin (A1-4) can be obtained by replacing the atmosphere in the flask with nitrogen and placing into the flask a catalyst for the reaction between a carboxyl group and a cyclic ether (e.g., tris (dimethylaminomethyl) phenol) in an amount of 5 to 80 mol% relative to the mole number of (e) and a polymerization inhibitor (e.g., hydroquinone) in an amount of 0.001 to 5 mass% relative to the total amount of (a), (b), and (c), and reacting the mixture at 60 to 130 ℃ for 1 to 10 hours. In addition, as in the case of the polymerization conditions, the method of addition or the reaction temperature can be appropriately adjusted in consideration of the production facilities, the amount of heat generation due to polymerization, and the like.

In this case, the number of moles of (b) is preferably 10 to 75 mol%, more preferably 15 to 70 mol%, based on the number of moles of (e). When the content is within the above preferred range, the storage stability of the photosensitive resin composition, the developability in forming a pattern from the photosensitive resin composition, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained coating film and pattern tend to be well balanced.

As the first stage, the resin (A1-5) can be obtained as a polymer of (b) and (c') in the same manner as the above-mentioned method for producing the resin (A-1).

In this case, the polymer obtained may be used as it is, as a solution after the reaction, as a concentrated or diluted solution, or as a solid (powder) taken out by a method such as reprecipitation.

the ratio of the structural units derived from (b) and (c') is preferably in the following range with respect to the total number of moles of all the structural units constituting the polymer.

A structural unit derived from (b); 5 to 95 mol% (more preferably 10 to 90 mol%)

A building block derived from (c'); 5 to 95 mol% (more preferably 10 to 90 mol%)

Further, similarly to the method for producing the resin (a1-4), the resin can be obtained by reacting the cyclic ether derived from (b) with the carboxylic acid or carboxylic acid anhydride contained in (a) and/or (e) in the polymer of (b) and (c'). The hydroxyl group produced by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride may be further reacted with the carboxylic anhydride.

The amount of (a) and/or (e) to be used in the reaction with the polymer is preferably 5 to 80 mol% based on the mole number of (b). Since the cyclic ether has high reactivity and unreacted (b) is less likely to remain, it is preferably (b1) and more preferably (b1-1) as (b).

The weight average molecular weight of the resin (A1) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (a) is within the above preferred range, the coating property tends to be excellent, and the film reduction at exposed portions is less likely to occur during development, and further, non-exposed portions are more likely to be removed during development.

The molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the resin (A1) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the molecular weight distribution is within the above preferred range, the developability tends to be excellent.

The acid value of the resin (A1) is 20 to 150mgKOH/g, preferably 40 to 135mgKOH/g, and more preferably 50 to 135 mgKOH/g.

When the resin (A1) is contained, the content thereof is preferably 1 to 80% by mass, more preferably 1 to 50% by mass, based on the total amount of the resin (A) and the resin (A1). When the content of the resin (a1) is within the above preferable range, a pattern can be formed with high sensitivity and excellent developability can be obtained.

The polymerizable compound (C) is a compound polymerizable by an active radical generated by the polymerization initiator (D), and is, for example, a compound having an ethylenically unsaturated bond, and is preferably a (meth) acrylate compound.

Examples of the polymerizable compound (C) having 1 ethylenically unsaturated bond include the same compounds as those exemplified in the above (a), (b) and (C), and among them, (meth) acrylates are preferable.

Examples of the polymerizable compound (C) having 2 ethylenically unsaturated bonds include 1, 3-butanediol di (meth) acrylate, 1, 3-butanediol (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, bis (acryloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, and the like.

Examples of the polymerizable compound (C) having 3 or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, a reaction product of pentaerythritol tri (meth) acrylate and an acid anhydride, a polymer obtained by reacting a compound obtained by reacting a, A reactant of dipentaerythritol penta (meth) acrylate and an acid anhydride, a reactant of tripentaerythritol hepta (meth) acrylate and an acid anhydride, caprolactone-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate, caprolactone-modified tripentaerythritol octa, A reactant of caprolactone-modified pentaerythritol tri (meth) acrylate and an acid anhydride, a reactant of caprolactone-modified dipentaerythritol penta (meth) acrylate and an acid anhydride, a reactant of caprolactone-modified tripentaerythritol hepta (meth) acrylate and an acid anhydride, and the like.

Among them, the polymerizable compound (C) having 3 or more ethylenically unsaturated bonds is preferable, and dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate are more preferable.

The content of the polymerizable compound (C) is preferably 20 to 55% by mass, more preferably 30 to 45% by mass, based on the total amount of the resin (a), the resin (a1) and the polymerizable compound (C).

When the content of the polymerizable compound (C) is within the above range, the sensitivity, the strength of the pattern obtained, the smoothness, and the reliability tend to be good.

The photosensitive resin composition of the present invention contains a polymerization initiator (D). The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by the action of light or heat, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include alkylphenone compounds, bisimidazole compounds, triazine compounds, acylphosphine oxide compounds, and O-acyloxime compounds. Further, a photo-and/or thermal cationic polymerization initiator (for example, an initiator composed of an onium cation and an anion derived from a Lewis acid) described in Japanese patent application laid-open No. 2008-181087 may be used. Among them, at least 1 selected from the group consisting of a biimidazole compound, an alkylphenone compound and an O-acyloxime compound is preferable, and an alkylphenone compound is particularly preferable. A polymerization initiator containing these compounds is preferable because it tends to have particularly high sensitivity.

The O-acyloxime compound is a compound having a partial structure represented by formula (d 1). Hereinafter, is a bond.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylmercaptophenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylmercaptophenyl) octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylmercaptophenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, and N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4-imine - (3, 3-dimethyl-2, 4-dioxolanylmethyloxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine and the like. Commercially available products such as IRGACURE (registered trademark), OXE01, OXE02 (available from BASF corporation), N-1919 (available from ADEKA corporation), and the like can also be used.

The alkylphenyl ketone compound has a partial structure represented by the formula (d2) or a partial structure represented by the formula (d 3). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] butan-1-one. Commercially available products such as IRGACURE (registered trademark) 369, 907, and 379 (available from BASF corporation, supra) may also be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, benzildimethylketal, and the like.

From the viewpoint of sensitivity, the alkylphenyl ketone compound is preferably a compound having a partial structure represented by the formula (d 2).

Examples of the biimidazole compound include 2, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetraphenylbiimidazole, 2 ' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5 ' -tetraphenylbiimidazole (see, for example, japanese unexamined patent publication No. 6-75372, japanese unexamined patent publication No. 6-75373, etc.), 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetraphenylbiimidazole, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (alkoxyphenyl) biimidazole, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (dialkoxyphenyl) biimidazole, 2, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (trialkoxyphenyl) biimidazole (see, for example, Japanese patent publication No. 48-38403 and Japanese patent application laid-open No. 62-174204), and imidazole compounds in which the phenyl group at the 4, 4 ', 5, 5 ' -position is substituted with a carbonylalkoxy group (see, for example, Japanese patent application laid-open No. 7-10913). Preferred examples thereof include 2, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetraphenylbiimidazole, 2 ' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5 ' -tetraphenylbiimidazole and 2, 2 ' -bis (2, 4-dichlorophenyl) -4, 4 ', 5, 5 ' -tetraphenylbiimidazole.

Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl ] -triazine -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) vinyl ] -1, 3, 5-triazine, and the like.

Examples of the acylphosphine oxide compound include 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide and the like.

Further, examples of the polymerization initiator (D) include benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone-based compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenylsulfide, 3 ', 4, 4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2, 4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, and the like. They are preferably used in combination with a polymerization initiation aid (D1) described later.

Further, as the polymerization initiator having a group capable of causing chain transfer, the polymerization initiator described in Japanese patent application laid-open No. 2002-544205 can be used.

The polymerization initiator having a group capable of causing chain transfer can also be used as the component (c) constituting the resin (A).

In the photosensitive resin composition of the present invention, the polymerization initiator (D) and the polymerization initiation aid (D1) may be used together. The polymerization initiation aid (D1) is a compound used in combination with the polymerization initiator (D) to accelerate polymerization of the polymerizable compound whose polymerization is initiated by the polymerization initiator, or a sensitizer. Examples of the polymerization initiation aid (D1) include thioxanthone compounds, amine compounds, carboxylic acid compounds, and compounds described in jp 2008-65319 a and jp 2009-139932 a.

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

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, and aromatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone (commonly known as michelson), and 4, 4' -bis (diethylamino) benzophenone.

Examples of the carboxylic acid compound include aromatic heteroacetates such as phenylthioglycolic acid, methylphenylthioglycolic acid, ethylphenylthioglycolic acid, methylethylphenylthioglycolic acid, dimethylphenylthioglycolic acid, methoxyphenylthioglycolic acid, dimethoxyphenylthioglycolic acid, chlorophenylthioglycolic acid, dichlorophenylthioglycolic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioglycolic acid, N-naphthylglycine and naphthyloxyacetic acid.

Examples of the combination of the polymerization initiator (D) and the polymerization initiation aid (D1) include an alkylphenone compound and a thioxanthone compound, and an alkylphenone compound and an aromatic amine compound, and specific examples thereof include 2-methyl-2-morpholino-1- (4-methylmercaptophenyl) propan-1-one and 2, 4-diethylthioxanthone, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one and 2, 4-diethylthioxanthone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one and 2, 4-diethylthioxanthone, and 2-morpholino-1- (4-methylmercaptophenyl) -2-methylmercaptoxanthone Phenylpropan-1-one with 2-isopropylthioxanthone with 4-isopropylthioxanthone, 2-morpholino-1- (4-methylmercaptophenyl) -2-methylpropan-1-one with 4, 4 ' -bis (diethylamino) benzophenone, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one with 4, 4 ' -bis (diethylamino) benzophenone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one with 4, 4 ' -bis (diethylamino) benzophenone, and the like.

Among them, a combination of an alkylphenone compound and a thioxanthone compound is preferable, and 2-methyl-2-morpholino-1- (4-methylmercaptophenyl) propan-1-one and 2, 4-diethylthioxanthone, 2-methyl-2-morpholino-1- (4-methylmercaptophenyl) propan-1-one and 2-isopropylthioxanthone and 4-isopropylthioxanthone are more preferable. These combinations can provide a pattern having high sensitivity and high visible light transmittance.

The content of the polymerization initiator (D) is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total amount of the resin (a), the resin (a1), and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above-mentioned preferable range, a pattern can be obtained with high sensitivity.

The amount of the polymerization initiator aid (D1) used is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, based on 100 parts by mass of the total amount of the resin (A), the resin (A1) and the polymerizable compound (C). When the amount of the polymerization initiation aid (D1) is within the above-mentioned preferred range, a pattern can be obtained with high sensitivity, and the shape of the obtained pattern is good.

The photosensitive resin composition of the present invention may contain a solvent (E).

Examples of the solvent usable in the present invention include ester solvents (intramolecular-COO-free solvents), ether solvents (intramolecular-O-free solvents), ether ester solvents (intramolecular-COO-free solvents), ketone solvents (intramolecular-CO-free solvents), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ -butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1, 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methyl anisole.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, methyl ethyl methoxyacetate, methyl ethoxypropionate, ethyl ethoxypropionate, methyl ethoxypropionate, ethyl ethoxybutyl acetate, 3-methyl-3-methoxy, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, and the like.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, and the like.

Examples of the amide solvent include N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.

These solvents may be used alone or in combination of 2 or more.

Among the above solvents, an organic solvent having a boiling point of 1atm of 120 ℃ to 180 ℃ is preferable from the viewpoint of coatability and drying property. Among them, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, and the like are preferable. If the solvent (E) is the preferred solvent, unevenness in coating can be suppressed, and the flatness of the coating film can be improved.

The content of the solvent (E) in the photosensitive resin composition of the present invention is preferably 60 to 95% by mass, and more preferably 70 to 90% by mass, based on the total amount of the photosensitive resin composition.

In other words, the solid content of the photosensitive resin composition is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. When the content of the solvent (E) is within the above preferable range, the flatness of a film formed by applying the photosensitive resin composition tends to be improved. Here, the solid content means an amount of the solvent (E) removed from the photosensitive resin composition.

The photosensitive resin composition of the present invention may further contain a polyfunctional thiol compound (T). The polyfunctional thiol compound (T) is a compound having 2 or more mercapto groups (-SH) in the molecule. In particular, when a compound having 2 or more mercapto groups bonded to a carbon atom derived from an aliphatic hydrocarbon group is used, the sensitivity of the photosensitive resin composition of the present invention tends to be improved.

Specific examples of the polyfunctional thiol compound (T) include hexanedithiol, decanedithiol, 1, 4-bis (methylthio) benzene, butanediol bis (3-thiopropionate), butanediol bis (3-thioacetate), ethylene glycol bis (3-thioacetate), trimethylolpropane tris (3-thioacetate), butanediol bis (3-thiopropionate), trimethylolpropane tris (3-thiopropionate), trimethylolpropane tris (3-thioacetate), pentaerythritol tetrakis (3-thiopropionate), pentaerythritol tetrakis (3-thioacetate), trihydroxyethyl tris (3-thiopropionate), pentaerythritol tetrakis (3-thiobutyrate), 1, 4-bis (3-thiobutyloxy) butane, and the like.

The content of the polyfunctional thiol compound (T) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, per 100 parts by mass of the polymerization initiator (D). When the content of the polyfunctional thiol compound (T) is within the above preferable range, the sensitivity of the photosensitive resin composition is improved and the developability tends to be good, which is preferable.

The photosensitive resin composition of the present invention may contain a surfactant (F) (but is different from the resin (B)). Examples of the surfactant include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms.

Examples of the silicone surfactant include surfactants having siloxane bonds.

Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, polyether modified Silicone oil SH8400 (trade name: Tow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu chemical Co., Ltd.), TSF400, TSF401, TSF410, F4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Moive Performance Materials Japan Co., Ltd.), and the like can be cited.

Examples of the fluorine-based surfactant include surfactants having fluorocarbon chains.

Specifically, examples thereof include Fluorinert (registered trademark) FC430, Fluorinert FC431 (manufactured by sumitomo 3M corporation), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC R30 (manufactured by DIC corporation), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (manufactured by mitsubishi electro Chemical corporation), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by asahi corporation), and E5844 (manufactured by Daikin Fine corporation).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, there may be mentioned MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (available from DIC Co., Ltd.). Preferably, MEGAFAC (registered trademark) F475 is used.

The content of the surfactant (F) is 0.001 to 0.2 mass%, preferably 0.002 to 0.1 mass%, and more preferably 0.01 to 0.05 mass% with respect to the total amount of the photosensitive resin composition. By containing the surfactant in the range of 0.001 mass% to 0.2 mass%, the flatness of the coating film can be improved.

The photosensitive resin composition of the present invention may contain various additives such as a filler, another polymer compound, an adhesion promoter, an antioxidant, an ultraviolet absorber, a light stabilizer, and a chain transfer agent, as necessary.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-tert-butylaminopropylmethyldimethoxysilane, N-propylmethyldimethoxysilane, N-propyltrimethoxysilane, N-ethylmethyldimethoxysil, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, etc.

The photosensitive resin composition of the present invention does not substantially contain a colorant such as a pigment or a dye. That is, the content of the colorant in the photosensitive resin composition of the present invention is, for example, preferably less than 1% by mass, and more preferably less than 0.5% by mass, based on the total composition.

The photosensitive resin composition of the present invention has an average transmittance of preferably 70% or more, more preferably 80% or more, when the transmittance is measured using a spectrophotometer under the condition of a measurement wavelength of 400 to 700nm by filling a quartz cuvette having an optical path length of 1 cm.

When the photosensitive resin composition of the present invention is formed into a coating film, the average transmittance of the coating film is preferably 90% or more, more preferably 95% or more. The average transmittance is an average value when a coating film having a thickness of 3 μm after heat curing (for example, curing under conditions of 100 to 250 ℃ for 5 minutes to 3 hours) is measured at a measurement wavelength of 400 to 700nm using a spectrophotometer. This can provide a coating film having excellent transparency in the visible light region.

The photosensitive resin composition of the present invention can be applied to a substrate made of glass, metal, plastic, or the like, or the above-mentioned substrate having a color filter, various insulating or conductive films, a driver circuit, or the like formed thereon, and patterned into a desired shape. Further, the pattern may be used by being formed as a part of a constituent member of a display device or the like.

First, the photosensitive resin composition of the present invention is coated on a substrate.

As described above, the coating can be performed using various coating apparatuses such as a spin coater, a slit & spin coater, a slit coater, inkjet printing, a roll coater, and a dip coater.

It is preferable to dry or pre-bake the mixture, remove volatile components such as solvents, and then dry the mixture. This gives a smooth uncured coating film.

The film thickness of the coating film is not particularly limited, and may be appropriately adjusted depending on the material used, the application, and the like, and is, for example, about 1 to 6 μm.

The obtained uncured coating film is irradiated with light, such as ultraviolet light generated from a mercury lamp or a light emitting diode, through a mask for forming a desired pattern. The shape of the mask in this case is not particularly limited, and the shape or size may be selected according to the application of the pattern.

In recent years, light of less than 350nm can be cut by using a color filter for cutting the wavelength region, or light of about 436nm, about 408nm, or about 365nm can be selectively extracted by using a band-pass filter for extracting the wavelength region, and then substantially parallel light rays can be uniformly irradiated to the entire exposure surface. If a mask alignment exposure machine, a stepper or the like is used, the mask can be aligned to the substrate at the correct position.

The exposed coating film is brought into contact with a developer to dissolve a specific portion, for example, a non-exposed portion (i.e., a non-image portion), and then developed to obtain a desired pattern shape.

The developing method may be any of a liquid bath method, a dipping method, a spraying method, and the like. The substrate can be tilted at any angle during further development.

The developer used for development is preferably an aqueous solution of an alkaline compound.

The basic compound may be any of inorganic and organic basic compounds.

Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, diammonium hydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia.

Examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine.

The concentration of these inorganic and organic alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The developer may contain a surfactant.

The surfactant may be any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, ethylene oxide/propylene oxide block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene alkylamines, and the like.

Examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, and alkylaryl sulfonate salts such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.

Examples of the cationic surfactant include amine salts such as stearyl amine hydrochloride and lauryl trimethyl ammonium chloride, and quaternary ammonium salts.

The concentration of the surfactant in the alkali developing solution is preferably in the range of 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and still more preferably 0.1 to 5% by mass.

after development, the pattern can be obtained by washing with water. Further, post-exposure baking may be performed as necessary. The post-exposure baking is preferably performed at a temperature of 150 to 240 ℃ for 10 to 180 minutes, for example.

When the uncured coating film is exposed to light, the entire surface is irradiated with light and/or development is omitted without using a mask having a pattern, whereby a coating film having no pattern can be obtained.

As an example of the display device of the present invention, an organic EL (electroluminescence) display device will be described below.

Fig. 1 is a schematic enlarged cross-sectional view of a part of a display device 1 which is an example of the display device of the present invention. Fig. 2 is a schematic enlarged plan view of a part of a display device 1 as an example of the display device of the present invention. The display device 1 is mainly configured to include a support substrate 2, partition walls 3 partitioning a predetermined region on the support substrate 2, and a plurality of organic EL elements 4 provided in the region partitioned by the partition walls 3. The partition wall 3 corresponds to the partition wall for inkjet printing of the present invention.

The partition walls 3 are formed on the support substrate 2, for example, in a lattice shape or a stripe shape. In fig. 2, as one embodiment, a display device 1 provided with a lattice-shaped partition wall 3 is shown. In the figure, hatching is applied to the region where the partition wall 3 is provided.

On the support substrate 2, a plurality of recesses 5 defined by the partition walls 3 and the support substrate 2 are set. The recess 5 corresponds to a region partitioned by the partition wall 3.

The partition walls 3 in the display device 1 are arranged in a lattice shape. Therefore, the plurality of recesses 5 are arranged in a matrix when viewed from one side in the thickness direction Z of the support substrate 2 (hereinafter, may be referred to as "in plan view"). That is, the recesses 5 are arranged to be spaced apart by a specific interval in the row direction X and also spaced apart by a specific interval in the column direction Y, thereby performing alignment. The shape of each concave portion 5 in a plan view is not particularly limited. For example, the recess 5 is formed in a substantially rectangular shape, a substantially elliptical shape, an elliptical shape, or the like in a plan view. In the present embodiment, a substantially rectangular recess 5 is provided in a plan view. In this specification, the row direction X and the column direction Y are perpendicular to the thickness direction Z of the support substrate and perpendicular to each other.

In another embodiment, when the stripe-shaped partition walls are provided, the partition walls are, for example, a plurality of partition wall members extending in the row direction X and are arranged at specific intervals in the column direction Y. In this embodiment, the stripe-shaped concave portions are defined by the stripe-shaped partition walls in common with the support substrate.

The partition walls are formed to be narrower in width as they are farther from the support substrate. For example, the cross-sectional shape of the partition wall extending in the column direction Y when cut along a plane perpendicular to the extending direction (column direction Y) is formed so that the width becomes narrower as the distance from the support substrate becomes larger. In fig. 1, the partition walls are in the shape of an isosceles trapezoid, and the lower bottom is wider than the upper bottom by comparing the upper bottom with the lower bottom on the side of the supporting substrate. The cross section of the partition wall actually formed does not necessarily have to be a trapezoidal shape, and the straight line portions and corners of the trapezoidal shape may be rounded.

The partition walls 3 preferably have a liquid-repellent property on the top surface thereof. The top surface is a plane existing at a position farthest from the support substrate 2 among the surfaces of the partition walls 3. Since the top surface of the partition wall 3 is liquid-repellent, ink supplied to the region (recess 5) surrounded by the partition wall 3 is prevented from being transferred to the top surface of the partition wall 3 and overflowing to the adjacent region.

The organic EL elements 4 are provided in the regions partitioned by the partition walls 3 (i.e., the concave portions 5). When the lattice-shaped partition walls 3 are provided in the display device 1, the organic EL elements 4 are provided in the respective concave portions 5. That is, the organic EL elements 4 are arranged in a matrix like the recesses 5, and are arranged on the support substrate 2 at a specific interval in the row direction X and at a specific interval in the column direction Y, and are aligned in a column.

The shape and arrangement of the partition walls 3 are appropriately set in accordance with the specification of the display device such as the number of pixels and the resolution, the ease of manufacturing, and the like. For example, the width of the partition wall 3 in the row direction X or column direction Y is about 5 μm to 50 μm, the height of the partition wall 3 is about 0.5 μm to 5 μm, and the width of the recess 5 in the row direction X or column direction Y, which is the interval between the partition walls 3 adjacent to each other in the row direction X or column direction Y, is about 10 μm to 200 μm. The width of the 1 st electrode 6 in the row direction X or the column direction Y is about 10 μm to 200 μm, respectively.

The partition walls 3 can be formed by the photosensitive resin composition of the present invention by the above-described pattern forming method.

In another embodiment, when the stripe-shaped partition walls are provided, the organic EL elements 4 are arranged in the row direction X with a specific interval in each of the concave portions extending in the row direction X.

The display device 1 is provided with 3 kinds of organic EL elements 4. Namely, (1) a red organic EL element 4R that emits red light, (2) a green organic EL element 4G that emits green light, and (3) a blue organic EL element 4B that emits blue light are provided.

The organic EL element 4 is constituted by stacking a1 st electrode, an organic EL layer, and a 2 nd electrode in this order on the support substrate side. In this specification, one or more layers provided between the 1 st electrode 6 and the 2 nd electrode 10 are referred to as organic EL layers, respectively. The organic EL element 4 includes at least 1 light-emitting layer as an organic EL layer. In addition, the organic EL element may include an organic EL layer different from the light-emitting layer, if necessary, in addition to the 1-layer light-emitting layer. For example, a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, an electron injection layer, and the like are provided as the organic EL layer between the 1 st electrode 6 and the 2 nd electrode 10. Further, 2 or more light emitting layers may be provided between the 1 st electrode 6 and the 2 nd electrode 10.

The organic EL element 4 includes a1 st electrode 6 and a 2 nd electrode 10 as a pair of electrodes including an anode and a cathode. One of the 1 st electrode 6 and the 2 nd electrode 10 is provided as an anode, and the other is provided as a cathode. The display device 1 is configured such that a1 st electrode 6 functioning as an anode, a1 st organic EL layer 7 functioning as a hole injection layer, a 2 nd organic EL layer 9 functioning as a light-emitting layer, and a 2 nd electrode 10 functioning as a cathode are sequentially stacked on a support substrate 2.

The 1 st electrodes 6 are provided with organic EL elements 4, respectively. That is, the organic EL elements 4 and the same number of 1 st electrodes 6 are provided on the supporting substrate 2. The 1 st electrode 6 is provided corresponding to the arrangement of the organic EL elements 4, and is arranged in a matrix like the organic EL elements 4. The partition walls 3 are formed in a lattice shape mainly in the region excluding the 1 st electrode 6, but are further formed so as to cover the peripheral edge of the 1 st electrode 6 (see fig. 1).

The 1 st organic EL layer 7 corresponding to the hole injection layer is provided on the 1 st electrode 6 in the recess 5, respectively. The 1 st organic EL layer 7 is provided with a material or a film thickness different depending on the kind of the organic EL element as necessary. In addition, from the viewpoint of the ease of the step of forming the 1 st organic EL layer 7, all of the 1 st organic EL layers 7 may be formed of the same material and the same thickness.

The 1 st organic EL layer 7 is formed by the following method: ink containing a material of the 1 st organic EL layer 7 is supplied to the region (recess 5) surrounded by the partition walls 3 by an ink jet method, and then dried, heated, and/or irradiated with light to cure the ink.

The 2 nd organic EL layer 9 functioning as a light-emitting layer is provided on the 1 st organic EL layer 7 in the recess 5. The light-emitting layer as described above is provided depending on the type of the organic EL element. Therefore, the red light-emitting layer 9R is provided in the concave portion 5 where the red organic EL element 4R is provided, the green light-emitting layer 9G is provided in the concave portion 5 where the green organic EL element 4G is provided, and the blue light-emitting layer 9B is provided in the concave portion 5 where the blue organic EL element 4B is provided.

The 2 nd electrode 10 is formed over the entire surface in the display region where the organic EL element 4 is disposed. That is, the 2 nd electrode 10 is formed not only on the 2 nd organic EL layer 9 but also on the partition wall 3, and is continuously formed over a plurality of organic EL elements.

As described above, the organic EL display device can be manufactured by covering the plurality of organic EL elements 4 formed on the support substrate 2 with the sealing layer and the sealing substrate (not shown).

The pattern obtained from the photosensitive resin composition of the present invention has high wettability between the partition walls and the substrate surface of the concave portion defined by the substrate, and high liquid repellency on the upper surface of the partition walls, and therefore, is particularly useful as partition walls used for producing ITO electrodes of color filters and liquid crystal display elements, organic EL display elements, circuit wiring substrates, and the like by an ink jet method. The coating film having no pattern obtained as described above is useful as a protective film for a touch panel, for example, a photosensitive Spacer (Photo Spacer) constituting a part of a color filter substrate and/or an array plate, a patternable protective film, an interlayer insulating film, a projection for controlling liquid crystal alignment, a microlens, a coating layer for adjusting film thickness, and the like. The color filter substrate and the array substrate are suitably used for liquid crystal display devices, organic EL display devices, electronic paper, and the like.

Examples

The present invention will be described in more detail with reference to examples. In the examples, "%" and "part(s)" are% by mass and part(s) by mass unless otherwise specified.

(Synthesis example 1)

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, 166 parts of propylene glycol monomethyl ether acetate and 52 parts of methoxypropanol were added to a nitrogen atmosphere instead of flowing nitrogen in an appropriate amount, and the mixture was heated to 85 ℃ with stirring. Then, a mixed solution of 233 parts of a mixture of 3, 4-epoxytricyclo [5.2.1.02, 6] decan-8 or/and 9-yl acrylate, 77 parts of p-vinylbenzoic acid, 125 parts of propylene glycol monomethyl ether acetate and 115 parts of methoxypropanol was dropped over 4 hours. On the other hand, a mixed solution of 32 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) dissolved in 210 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition, the mixture was held at the same temperature for 3 hours and then cooled to room temperature to obtain a polymer (resin Aa) solution having a B-type viscosity (23 ℃ C.) of 46mPas, a solid content of 33.7% and a solution acid value of 83 mgKOH/g. The weight-average molecular weight Mw of the obtained resin Aa was 7.7X 103, and the molecular weight distribution was 1.90.

The resin Aa has the following structural units.

(Synthesis example 2)

Nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer at a flow rate of 0.02L/min to form a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added, and the mixture was heated to 70 ℃ with stirring. Then, 60 parts by mass of methacrylic acid and 240 parts by mass of 3, 4-epoxytricyclo [5.2.1.02.6] decyl acrylate (a compound represented by the formula (I-1) and a compound represented by the formula (II-1) are mixed at a molar ratio of 50: 50) were dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was added dropwise to a flask kept at 70 ℃ over 4 hours using a dropping funnel.

On the other hand, a solution in which 30 parts by mass of 2, 2' -azobis (2, 4-dimethylvaleronitrile), a polymerization initiator, was dissolved in 225 parts by mass of 3-methoxybutyl acetate, was added dropwise to the flask over 4 hours using another dropping funnel. After the completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained at 70 ℃ for 4 hours, and then the mixture was cooled to room temperature to obtain a polymer (resin A1a) solution having a solid content of 32.6% by mass and an acid value of 110mgKOH/g (in terms of solid content). The weight-average molecular weight Mw of the resulting resin A1a was 1.3X 104, and the molecular weight distribution was 2.50. The resin A1a has the following structural units.

(Synthesis example 3)

To a four-necked flask equipped with a reflux condenser, a nitrogen gas inlet tube, a thermometer, and a stirrer, 78 parts of α -chloroacrylic acid 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl ester, 19.5 parts of methacrylic acid, 19.5 parts of isobornyl methacrylate, 13 parts of glycidyl methacrylate, 12.7 parts of dodecanethiol, and 266 parts of propylene glycol monomethyl ether acetate were charged, heated to 70 ℃, and then stirred under a nitrogen stream for 30 minutes. To this solution, 1 part of azobisisobutyronitrile was added and the mixture was polymerized for 18 hours to obtain a polymer (resin Ba) solution having a solid content of 33% by mass and an acid value of 68mgKOH/g (in terms of solid content). The weight average molecular weight of the resin Ba obtained was 7500. The resin Ba has the following structural units.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured by GPC under the following conditions.

A device; k2479 ((manufactured by Kabushizu Shimadzu corporation))

A chromatographic column; SHIMADDZUShim-packGPC-80M

Column temperature; 40 deg.C

A solvent; THF (tetrahydrofuran)

A flow rate; 1.0mL/min

A detector; RI (Ri)

The molecular weight distribution was determined as the ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above.

(examples 1 to 4 and comparative examples 1 to 3)

< preparation of photosensitive resin composition >

The components in Table 3 were mixed to obtain a photosensitive resin composition.

[ Table 3]

The ingredients in table 3 are as follows. The parts in the columns of the resin (a) and the resin (B) represent parts by mass in terms of solid content.

A resin (A); aa: resin Aa obtained in Synthesis example 1

A resin (A1); a1 a: resin A1a obtained in Synthesis example 1

A resin (A1); a1 b: synthesis example 2 resin A1b

A resin (B); ba: resin Ba obtained in Synthesis example 3

A polymerizable compound (C); ca: trimethylolpropane triacrylate (A-TMPT; manufactured by Ningzhongcun chemical industry Co., Ltd.)

A polymerizable compound (C); cb: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemicals, Inc.)

A polymerization initiator (D); da: 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one (IRGACURE (registered trademark) 907; manufactured by BASF corporation)

A polymerization initiator (D); db: ethanone, 1- [ 9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime) (IRGACURE (registered trademark) OXE 02; manufactured by BASF Corp.)

A polymerization initiation aid (D1); 4, 4' -bis (diethylamino) benzophenone (EAB-F; manufactured by Baotu chemical industry Co., Ltd.)

A solvent (E); ea; propylene glycol monomethyl ether acetate

A solvent (E); eb; 3-Ethoxypropionic acid ethyl ester

A solvent (E); ec; 3-methoxy-1-butanol

A solvent (E); ed; 3-Methoxybutyl acetate

The solvent (E) was a mixture of the solid content of the photosensitive resin composition as "solid content (%)" in table 3, and the values of the solvent components (Ea) to (Ed) in the solvent (E) were mass ratios in the solvent (E).

< average transmittance of composition >

The average transmittance (%) at 400 to 700nm of each of the obtained photosensitive resin compositions was measured using an ultraviolet-visible near-infrared spectrophotometer (V-650; manufactured by Nippon spectral Co., Ltd.) (quartz cuvette, optical path length; 1 cm). The results are shown in Table 3.

< preparation of coating film >

A2-inch square glass substrate (EAGLEXG; manufactured by KANGNING corporation) was washed with a neutral detergent, water and alcohol in this order and then dried. The photosensitive resin compositions obtained above were each spin-coated on the glass substrate so that the film thickness after the post-exposure baking became 3.0 μm, and were dried under reduced pressure by a reduced pressure dryer (manufactured by MICROTEK) with a reduced pressure of 66kPa, and then prebaked on a hot plate at 80 ℃ for 2 minutes to dry. After condensation, the resultant was irradiated with light having an exposure of 50mJ/cm2(365nm standard) in an atmospheric environment using an exposure apparatus (TME-150 RSK; manufactured by Topukang, Ltd., light source: ultra-high pressure mercury lamp). In addition, in this case, an ultrahigh pressure mercury lamp was used for irradiation of the photosensitive resin composition. After the light irradiation, the coating film was immersed and shaken in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ℃ for 60 seconds to be brought into contact with each other, and then heated in an oven at 230 ℃ for 20 minutes (post-exposure baking), thereby obtaining a coating film.

< average transmittance of coating film >

The average transmittance (%) at 400 to 700nm of the obtained coating film was measured using a microspectrophotometer (OSP-SP 200; manufactured by OLYMPUS). The higher transmittance means that the absorption becomes smaller. The results are shown in Table 3.

< contact Angle >

the contact angle of anisole was measured on the obtained coating film by using a contact angle meter (DGDFast/60; manufactured by GBX Co.).

The higher the contact angle, the higher the lyophobicity. When the contact angle in the coating film is high, the contact angle is also high in a pattern formed using the same photosensitive resin composition. When a partition wall is formed of a photosensitive resin composition having a high contact angle and ink is printed (written) in the partition wall by an ink jet printing apparatus, the ink is easily repelled. Therefore, when a color filter is manufactured by, for example, an inkjet method, ink mixing between adjacent image areas is less likely to occur. The results are shown in Table 5.

< Pattern formation >

A2-inch square glass substrate (EAGLEXG; manufactured by KANGNING corporation) on which ITO was deposited was washed with a neutral detergent, water and 2-propanol in this order and then dried. The photosensitive resin compositions obtained above were spin-coated on the glass substrates so that the film thickness after post-baking became 1.0 μm, dried under reduced pressure by a reduced pressure dryer (manufactured by Microtech corporation) to a reduced pressure of 66kPa, and then pre-baked for 2 minutes at 90 ℃ by a hot plate.

After the condensation, the substrate coated with the photosensitive resin composition was irradiated with light at an exposure dose of 200mJ/cm2(365nm standard) in an atmospheric atmosphere using an exposure machine (TME-150 RSK; TOPCON, Inc., light source; ultra high pressure mercury lamp) with a gap of 100 μm from a quartz glass mask. A mask having a pattern formed on the same plane (the light shielding portion has a rectangular shape (oval) with four corners rounded off from a rectangle with a major axis direction of 300 μm and a minor axis direction of 100 μm) is used as the mask.

After the light irradiation, the coating film was developed while being shaken and dipped at 23 ℃ for 60 seconds in a developer prepared by diluting an aqueous tetramethylammonium hydroxide solution (TOKUYAMA, manufactured by TOKUSOSD25) with pure water to a concentration of 2.38%, and after washing with water, the coating film was post-baked in an oven at 230 ℃ for 20 minutes to obtain a pattern.

< wettability >

[ preparation of solution for wettability evaluation ]

As the solvents for evaluating the wettability of the partition wall, 2 kinds of N, N-dimethylacetamide (99.5% or more, manufactured by Wako pure chemical industries, Ltd.) and 1, 3-dimethyl-2-imidazolidinone (99.0% or more, manufactured by Tokyo chemical industries, Ltd.) were selected. Since the 2 solvents selected had low viscosity, the partition wall was filled with a liquid by an ink jet printing apparatus, and cyclohexanol (98.0% or more, manufactured by Wako pure chemical industries, Ltd.) was added as a viscosity adjusting material, and used as a mixed solvent.

Further, as for the solvent monomer, rhodamine B (manufactured by tokyo chemical industries, ltd., purity 95% or more) was used as a solute because it was difficult to observe the coating range after drying with a microscope.

The solutions were prepared into 3 kinds of the following table 4.

[ Table 4]

	Solution (1)	Solution 2	Solution 3
				N, N-dimethyl acetamide	50 portions of
1, 3-dimethyl-2-imidazoline		50 portions of	60 portions of
				Cyclohexanol	50 portions of	50 portions of	40 portions of
Rhodamine B	1％	1％	1％

[ evaluation of wettability ]

The solution described above was filled in each partition wall so that 1000 partitions were filled per 200pL using an ink jet printing apparatus (Litlex 120L manufactured by ULVAC) in the partition wall, and after drying, the diffusion of the solute in 30 partitions to the end of the partition wall was observed using a microscope (MX 61L manufactured by olaplus, lens LCPFLN20 xLCD). In all the solutions shown in Table 4, the wettability was good as O when the film extended at 30 points, and the other points were X. The results are shown in Table 5.

[ Table 5]

Example 1

Example 2

Example 3

Example 4

Comparative example 1

Comparative example 2

Comparative example 3

Contact angle

23

25

27

33

31

52

30

Wettability

○

○

○

○

×

X

×

From the results of the examples, it is understood that a coating film and a pattern having excellent wettability can be obtained from the photosensitive resin composition of the present invention while maintaining a contact angle at which color mixing of ink does not occur.

industrial applicability

According to the photosensitive resin composition of the present invention, a pattern having excellent wettability, that is, a pattern having high wettability with respect to the substrate surface of the concave portion defined by the partition walls and the substrate and high liquid repellency on the upper surface of the partition walls can be obtained.

Description of the symbols

1 display device

2 supporting substrate

3 partition wall

4 organic EL element

5 concave part

6 st electrode

7 st 1 organic EL layer (hole injection layer)

9 nd 2 nd organic EL layer (luminescent layer)

10 nd 2 nd electrode

Claims (6)

1. A photosensitive resin composition which contains (A), (B), (C) and (D) and in which the content of (A) is 45 to 80 mass% based on the total content of (A) and (C),

(A) A polymer containing a structural unit derived from an aromatic carboxylic acid having an ethylenically unsaturated bond, a structural unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms, and no structural unit containing a perfluoroalkyl group having 4 to 6 carbon atoms,

(B) A polymer containing a structural unit having a C4-6 perfluoroalkyl group,

(C) A polymerizable compound,

(D) A polymerization initiator, which is a polymerization initiator,

(C) The polymerizable compound is a (meth) acrylate compound.

2. The photosensitive resin composition according to claim 1, wherein (D) is a polymerization initiator containing at least one selected from the group consisting of a biimidazole compound, an alkylphenone compound and an O-acyloxime compound.

3. A pattern formed from the photosensitive resin composition according to claim 1 or 2.

4. An inkjet partition wall formed of the photosensitive resin composition according to claim 1 or 2.

5. A display device comprising the pattern of claim 3.

6. A display device comprising the inkjet partition wall according to claim 4.