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CN111566560B - Photosensitive resin composition, partition wall, organic electroluminescent element, image display device and lighting - Google Patents

Photosensitive resin composition, partition wall, organic electroluminescent element, image display device and lighting Download PDF

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Publication number
CN111566560B
CN111566560B CN201980007829.5A CN201980007829A CN111566560B CN 111566560 B CN111566560 B CN 111566560B CN 201980007829 A CN201980007829 A CN 201980007829A CN 111566560 B CN111566560 B CN 111566560B
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mass
resin composition
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CN111566560A (en
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木村明日香
中谷和裕
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/122—Pixel-defining structures or layers, e.g. banks

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electroluminescent Light Sources (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

本发明提供一种能够形成在UV清洗处理后拒墨性也良好的间隔壁的感光性树脂组合物。本发明的感光性树脂组合物是含有(A)拒液剂、(B)碱可溶性树脂、(C)光聚合性化合物、及(D)光聚合引发剂的感光性树脂组合物，其中，所述(A)拒液剂包含具有多环式饱和烃骨架及烯属双键的丙烯酸类树脂(a)，所述感光性树脂组合物还包含(E)链转移剂。The present invention provides a photosensitive resin composition capable of forming partition walls having good ink repellency even after UV cleaning treatment. The photosensitive resin composition of the present invention is a photosensitive resin composition containing (A) a liquid repellent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator, wherein the (A) liquid repellent comprises an acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and olefinic double bonds, and the photosensitive resin composition further comprises (E) a chain transfer agent.

Description

Photosensitive resin composition, partition wall, organic electroluminescent element, image display device, and illumination
Technical Field
The present invention relates to a photosensitive resin composition, a partition wall composed of the photosensitive resin composition, an organic electroluminescent element having the partition wall, and an image display device and an illumination including the organic electroluminescent element.
The entire contents of the specification, claims and abstract of japanese patent application publication No. 2018-011087, the entire contents of which are filed in the japanese patent office at 1/26 of 2018, and the entire contents of the documents cited in the specification and the like are incorporated as the contents of the present specification.
Background
Conventionally, organic electroluminescent devices included in organic electroluminescent displays, organic electroluminescent lights, and the like are manufactured by forming barrier ribs (banks) on a substrate, and then laminating various functional layers in regions surrounded by the barrier ribs. As a method for easily forming such a partition wall, a method of forming by photolithography using a photosensitive resin composition is known.
As a method of stacking various functional layers in a region surrounded by a partition wall, a method of first preparing ink containing a material constituting the functional layers and then injecting the prepared ink into the region surrounded by the partition wall is known. In this method, since a given amount of ink is easily injected accurately into a given area, an inkjet method is often used.
Further, in the case of forming a functional layer using ink, it is sometimes required to impart ink repellency (liquid repellency) to the partition wall for the purpose of preventing adhesion of ink to the partition wall, preventing mixing of ink injected between adjacent regions, and the like. As a method for imparting ink repellency to the partition wall, for example, a method in which a fluorine compound is contained in the partition wall is known (see patent documents 1 and 2).
Patent document 3 describes that a cured product having high ink repellency can be formed by using a specific fluororesin.
Prior art literature
Patent literature
Patent document 1: international publication No. 2013/161829
Patent document 2: japanese patent application laid-open No. 2015-179257
Patent document 3: japanese patent application laid-open No. 2012-092308
Disclosure of Invention
Problems to be solved by the invention
When the partition wall is formed using the photosensitive resin composition, when residues of the composition are generated in the pixel region surrounded by the partition wall, a part of the pixel portion may not emit light. Therefore, UV cleaning treatment may be performed for the purpose of removing residues or the like after formation of the partition walls, but the following problems are involved: although the residue is removed, the ink repellency of the partition wall is lowered.
The present inventors have studied and found that the photosensitive resin composition described in patent document 1 is insufficient in ink repellency after UV cleaning treatment.
It is also known that the photosensitive resin compositions described in patent documents 2 and 3 have insufficient ink repellency.
Accordingly, an object of the present invention is to provide a photosensitive resin composition capable of forming a partition wall having good ink repellency even after UV cleaning treatment.
The present invention also provides a partition wall comprising the photosensitive resin composition, an organic electroluminescent element provided with the partition wall, and an image display device and an illumination device comprising the organic electroluminescent element.
Means for solving the problems
As a result of intensive studies, the present inventors have found that the above problems can be solved by using a specific structure of a liquid repellent and a chain transfer agent in a photosensitive resin composition containing a liquid repellent, an alkali-soluble resin, a photopolymerizable compound and a photopolymerization initiator, and have completed the present invention.
Namely, the gist of the present invention is as follows.
[1] A photosensitive resin composition comprising: (A) a liquid repellent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator, wherein,
The liquid repellent agent (A) comprises an acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an olefinic double bond,
The photosensitive resin composition further comprises (E) a chain transfer agent.
[2] The photosensitive resin composition according to the above [1], wherein the acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an olefinic double bond has a crosslinked portion containing a poly (perfluoroalkylene ether) chain.
[3] The photosensitive resin composition according to the above [1], wherein the acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an olefinic double bond comprises a partial structure represented by the following general formula (1).
[ Chemical formula 1]
(In the formula (1), R 1 each independently represents a hydrogen atom or a methyl group, X 1 represents a perfluoroalkylene group, a plurality of X 1 contained in the formula (1) are optionally the same or different, and when a plurality of X 1 are different from each other, they are optionally present in a random or block form, X 2 each independently represents a direct bond or an optional 2-valent linking group, n is an integer of 1 or more, and X represents a bonding position.)
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the polycyclic saturated hydrocarbon skeleton is an adamantane skeleton.
[5] The photosensitive resin composition according to any one of the above [1] to [4], wherein the acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an olefinic double bond comprises a partial structure represented by the following general formula (2).
[ Chemical formula 2]
(In the formula (2), R 2 and R 3 each independently represent a hydrogen atom or a methyl group, X 3 represents a 2-valent polycyclic saturated hydrocarbon group optionally having a substituent, X 4 represents a urethane bond or an ester bond, X 5 represents a 2-valent hydrocarbon group optionally having a substituent, and X represents a bonding position.)
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the alkali-soluble resin (B) comprises an epoxy (meth) acrylate resin (B1) and/or an acrylic copolymer resin (B2).
[7] The photosensitive resin composition according to the above [6], wherein the epoxy (meth) acrylate resin (b 1) is at least one selected from the group consisting of an epoxy (meth) acrylate resin (b 1-1) having a partial structure represented by the following general formula (i), an epoxy (meth) acrylate resin (b 1-2) having a partial structure represented by the following general formula (ii), and an epoxy (meth) acrylate resin (b 1-3) having a partial structure represented by the following general formula (iii).
[ Chemical formula 3]
(In the formula (i), R a represents a hydrogen atom or a methyl group, R b represents a 2-valent hydrocarbon group optionally having a substituent, the benzene ring in the formula (i) is optionally further substituted with an optional substituent,/represents a bonding position.)
[ Chemical formula 4]
(In the formula (ii), R c each independently represents a hydrogen atom or a methyl group, R d represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain, & ltCHEM & gt represents a bonding position.)
[ Chemical formula 5]
(In the formula (iii), R e represents a hydrogen atom or a methyl group, gamma represents a single bond, -CO-, alkylene group optionally having a substituent, or cyclic hydrocarbon group of 2 valence optionally having a substituent, and the benzene ring in the formula (iii) is optionally further substituted with an optional substituent: -represents a bonding position.)
[8] The photosensitive resin composition according to the above [6] or [7], wherein the acrylic copolymer resin (b 2) is an acrylic copolymer resin (b 2-1) comprising a partial structure represented by the following general formula (I).
[ Chemical formula 6]
(In the formula (I), R A and R B each independently represent a hydrogen atom or a methyl group, and each represents a bonding position.)
[9] The photosensitive resin composition according to any one of [1] to [8], wherein the (D) photopolymerization initiator contains at least one selected from the group consisting of a hexaarylbiimidazole-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, and an acetophenone-based photopolymerization initiator.
[10] The photosensitive resin composition according to any one of [1] to [9], which further contains an ultraviolet absorber.
[11] The photosensitive resin composition according to any one of [1] to [10], which further contains a polymerization inhibitor.
[12] The photosensitive resin composition according to any one of [1] to [11], which is used for forming a partition wall.
[13] A partition wall comprising the photosensitive resin composition according to any one of the above [1] to [12 ].
[14] An organic electroluminescent device comprising the partition wall according to [13 ].
[15] An image display device comprising the organic electroluminescent element described in [14 ].
[16] An illumination comprising the organic electroluminescent element as described in [14 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a photosensitive resin composition capable of forming a partition wall having good ink repellency even after UV cleaning treatment can be provided.
Detailed Description
The present invention will be described in detail below. The following description is an example of the embodiment of the present invention, and the present invention is not limited to these examples within a range not exceeding the gist of the present invention.
In the present invention, "meth" acrylic acid "means" acrylic acid and/or methacrylic acid ", and" all solid components "means all components except the solvent in the photosensitive resin composition. In the present invention, the numerical range indicated by "to" indicates a range including the numerical values described before and after "to" as the lower limit value and the upper limit value. In addition, "a and/or B" means one or both of a and B, specifically A, B, or a and B.
In the present invention, "co-polymer" means both a single polymer (homopolymer) and a copolymer (copolymer), and "polybasic acid (anhydride)" means "polybasic acid and/or polybasic acid anhydride".
In the present invention, the weight average molecular weight refers to a polystyrene-equivalent weight average molecular weight (Mw) based on GPC (gel permeation chromatography).
In the present invention, the acid value means an acid value converted into an effective solid component, and can be calculated by neutralization titration.
In the present invention, the partition wall material means a dam material, a wall material, and similarly, the partition wall means a dam, a wall, and a wall.
In the present invention, the light emitting portion (pixel portion) refers to a portion that emits light when electric energy is applied thereto.
[1] Photosensitive resin composition
The photosensitive resin composition of the present invention comprises (A) a liquid repellent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator, and is characterized in that the liquid repellent (A) comprises an acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an olefinic double bond, and the photosensitive resin composition of the present invention further comprises (E) a chain transfer agent. Other components may be contained as needed, and for example, an ultraviolet absorber and a polymerization inhibitor may be contained.
In the present invention, the partition wall is, for example, a portion for dividing the functional layer (organic layer, light emitting portion) in the active-driving type organic electroluminescent element, and is used for forming a pixel or the like including the functional layer and the partition wall by ejecting ink as a material for constituting the functional layer to the divided region (pixel region) and drying the ink.
[1-1] Ingredients and compositions of photosensitive resin composition
The components and the compositions constituting the photosensitive resin composition of the present invention will be described.
The photosensitive resin composition of the present invention contains (A) a liquid repellent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator, and further contains (E) a chain transfer agent, and usually contains a solvent.
[1-1-1] (A) component: liquid repellent agent
The photosensitive resin composition of the present invention contains (A) a liquid repellent. Since the liquid repellent (a) is contained, the surface of the obtained partition wall can be imparted with ink repellency (liquid repellency), it is considered that adhesion of ink to the partition wall can be prevented and mixing of ink injected between adjacent regions can be prevented when the organic electroluminescent element is produced by the inkjet method.
[ Acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an olefinic double bond ]
The liquid repellent (a) in the photosensitive resin composition of the present invention includes an acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an olefinic double bond (hereinafter, may be simply referred to as "acrylic resin (a)").
It is considered that, by making the acrylic resin (a) have an olefinic double bond, the acrylic resin (a) is fixed to the surface thereof when the coating film is exposed, and therefore, the acrylic resin (a) is less likely to flow out in the development treatment, and as a result, the ink repellency of the obtained partition wall can be improved.
The acrylic resin (a) has a polycyclic saturated hydrocarbon skeleton, and by having a polycyclic saturated hydrocarbon skeleton, the film surface after UV irradiation is improved in ink repellency, which is thought to be obtained by the following action.
It is considered that the surface layer temperature of the cured product tends to rise due to heat release caused by UV absorption of the resin or the like in the cured product by UV irradiation, and the acrylic resin (a) segregated on the surface layer is susceptible to the heat release.
It is considered that the heat resistance is high because the linear structure is decomposed by cutting at 1 part, but the cyclic structure is not decomposed by cutting at a plurality of parts, and the heat resistance is improved because the linear structure is less likely to be decomposed particularly when forming a polycyclic type. It is also considered that the saturated cyclic hydrocarbon skeleton has no bond as a reaction starting point, compared with the unsaturated cyclic hydrocarbon skeleton, and has an advantage of low reactivity of the ring itself.
Further, it is considered that the main chain of the acrylic resin (a) is not easily cut by having a polycyclic hydrocarbon skeleton, which itself becomes a steric hindrance, and the heat resistance is further improved.
Further, it is considered that since the acrylic resin (a) has an acryl structure, compatibility with the (B) alkali-soluble resin and the (C) photopolymerizable compound can be improved, and the preservability of the photosensitive resin composition can be improved, and the generation of residue in the pixel portion can be suppressed, thereby improving the wetting expansibility.
The polycyclic saturated hydrocarbon skeleton may be a 1-valent group or a 2-valent or more group. Further, the compound may be unsubstituted or substituted.
The number of carbon atoms of the polycyclic saturated hydrocarbon skeleton is not particularly limited, but is usually 6 or more, preferably 8 or more, more preferably 9 or more, still more preferably 10 or more, and is preferably 20 or less, more preferably 15 or less, still more preferably 12 or less. When the lower limit value is not less than the upper limit value, the ink repellency after the UV cleaning treatment tends to be good, and when the upper limit value is not more than the upper limit value, the compatibility in the photosensitive resin composition tends to be good. The number of carbon atoms of the polycyclic saturated hydrocarbon skeleton is, for example, 6 to 20, preferably 8 to 20, more preferably 9 to 15, and still more preferably 10 to 12.
The number of rings in the polycyclic saturated hydrocarbon skeleton is not particularly limited, but is preferably 3 or more, more preferably 5 or less, and still more preferably 4 or less. When the lower limit value is not less than the upper limit value, the ink repellency after the UV cleaning treatment tends to be good, and when the upper limit value is not more than the upper limit value, the compatibility in the photosensitive resin composition tends to be good. The number of rings in the polycyclic saturated hydrocarbon skeleton is, for example, 2 to 5, preferably 3 to 4.
Specific examples of the polycyclic saturated hydrocarbon skeleton include: adamantane skeleton, tricyclodecane skeleton, norbornane skeleton, decalin skeleton and the like are preferable from the viewpoint of ink repellency after UV cleaning treatment.
The polycyclic saturated hydrocarbon skeleton may be present at any part of the chemical structure of the acrylic resin (a), and may be present in the main chain of the acrylic resin or in a side chain, for example. From the viewpoint of easy synthesis, it is preferably present in a side chain.
The content of the polycyclic saturated hydrocarbon skeleton in the acrylic resin (a) is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, particularly preferably 30% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less. When the lower limit value is not less than the upper limit value, the ink repellency after the UV cleaning treatment tends to be good, and when the upper limit value is not more than the upper limit value, the compatibility in the photosensitive resin composition tends to be good. The content of the polycyclic saturated hydrocarbon skeleton in the acrylic resin (a) is, for example, 10 to 50% by mass, preferably 20 to 40% by mass, more preferably 25 to 35% by mass, and still more preferably 30 to 35% by mass.
The acrylic resin (a) preferably has a crosslinking unit containing a poly (perfluoroalkylene ether) chain. In the case of having a crosslinking unit containing a poly (perfluoroalkylene ether) chain, since the crosslinking unit is bonded to 2 or more main chains, the poly (perfluoroalkylene ether) chain is not easily detached from the acrylic resin (a) even by UV cleaning, and a sufficient amount of fluorine atoms can be present on the surface of the partition wall, and as a result, it is considered that the ink repellency is good even after UV cleaning treatment.
The chemical structure of the acrylic resin (a) is not particularly limited, and from the viewpoint of exhibiting sufficient ink repellency even after UV cleaning, the partial structure having a crosslinked portion including a poly (perfluoroalkylene ether) chain is preferably one including a partial structure represented by the following general formula (1).
[ Chemical formula 7]
In formula (1), R 1 each independently represents a hydrogen atom or a methyl group, X 1 represents a perfluoroalkylene group, and a plurality of X 1 groups contained in formula (1) may be the same or different, and when a plurality of X 1 groups are different from each other, they may exist in a random form or in a block form, X 2 each independently represents a direct bond or an arbitrary 2-valent linking group, n is an integer of 1 or more, and X represents a bonding position.
(X1)
In the above formula (1), X 1 represents a perfluoroalkylene group.
The number of carbon atoms of the perfluoroalkylene group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the upper limit value, sufficient ink repellency tends to be exhibited, and when the lower limit value is not more than the upper limit value, compatibility with other materials tends to be good.
Specific examples of the perfluoroalkylene group include groups represented by the following general formulae (1-a) to (1-e).
[ Chemical formula 8]
*-CF2-* (1-a)
*-CF2CF2-* (1-b)
*-CF2CF2CF2-* (1-c)
In the formulae (1-a) to (1-e), the bonding position is represented.
In the formulae (1-a) to (1-e), the group represented by the formula (1-a) and the group represented by the formula (1-b) are preferable from the viewpoint of obtaining high ink repellency.
Further, from the viewpoint of ink repellency, it is more preferable to include both the group represented by the above formula (1-a) and the group represented by the above formula (1-b) in the formula (1). The molar ratio of the group represented by the formula (1-a) to the group represented by the formula (1-b) contained in the formula (1) is not particularly limited, but is preferably 1:10 to 10:1, more preferably 1:4 to 4:1, and still more preferably 1:2 to 2:1 from the viewpoint of ink repellency.
(X2)
In the above formula (1), X 2 represents a direct bond or an optional 2-valent linking group.
Examples of the optional 2-valent linking group include: -O-, -CO-NH-, -O-CO-NH-, optionally substituted 2-valent hydrocarbon radical. The portion-CH 2 -contained in the hydrocarbon group may be replaced with at least one selected from the group consisting of-O-, -CO-NH-, and-O-CO-NH-.
Examples of the 2-valent hydrocarbon group include a 2-valent aliphatic group and a 2-valent aromatic ring group.
Examples of the 2-valent aliphatic group include: a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkenylene group.
The number of carbon atoms of the 2-valent aliphatic group is not particularly limited, but is usually 1 or more, and is preferably 5 or less, more preferably 3 or less, and further preferably 2 or less. When the ink repellency is lower than the upper limit, the ink repellency tends to be improved.
Specific examples of the 2-valent aliphatic group include: methylene, ethylene, vinylene, propylene, butylene, etc.
Examples of the substituent optionally contained in the 2-valent aliphatic group include a hydroxyl group and an alkoxy group.
Examples of the 2-valent aromatic ring group include a 2-valent aromatic hydrocarbon ring group and a 2-valent aromatic heterocyclic group.
The number of carbon atoms of the 2-valent aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, more preferably 6 or more, and is preferably 30 or less, more preferably 20 or less, more preferably 15 or less. When the lower limit value is not less than the upper limit value, compatibility with other materials tends to be good, and when the upper limit value is not more than the upper limit value, ink repellency tends to be improved.
Examples of the 2-valent aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,A group having 2 free valencies such as a ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
Examples of the 2-valent aromatic heterocyclic group include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring,Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisotropic ringAn azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring,A group having 2 free valencies such as a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, and the like.
Examples of the substituent optionally contained in the 2-valent aromatic ring group include a hydroxyl group, an alkyl group, and an alkoxy group.
Specific examples of X 2 include the following groups.
[ Chemical formula 9]
*-CH2-*
*-CH2CH2-*
Among these, from the viewpoint of ensuring ink repellency and suppressing the residual liquid repellency in the pixel portion at the time of development, a 2-valent aliphatic group is preferable, a methylene group and an ethylene group are more preferable, and a methylene group is further preferable.
(n)
In the above formula (1), n is an integer of 1 or more, preferably an integer of 3 to 40, more preferably an integer of 6 to 30, and still more preferably an integer of 10 to 20, from the viewpoint of ink repellency.
The acrylic resin (a) has a polycyclic saturated hydrocarbon skeleton and an olefinic double bond, and preferably contains a partial structure represented by the following general formula (2) as a partial structure containing the polycyclic saturated hydrocarbon skeleton and the olefinic double bond from the viewpoints of ink repellency and sensitivity after UV cleaning.
[ Chemical formula 10]
In the formula (2), R 2 and R 3 each independently represent a hydrogen atom or a methyl group, X 3 represents a 2-valent polycyclic saturated hydrocarbon group optionally having a substituent, X 4 represents a urethane bond or an ester bond, X 5 represents a 2-valent hydrocarbon group optionally having a substituent, and X represents a bonding position.
(X3)
In the above formula (2), X 3 represents a 2-valent polycyclic saturated hydrocarbon group optionally having a substituent.
The number of carbon atoms of the 2-valent polycyclic saturated hydrocarbon group is not particularly limited, but is usually 6 or more, preferably 8 or more, more preferably 9 or more, still more preferably 10 or more, and is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. When the lower limit value is not less than the upper limit value, the ink repellency after the UV cleaning treatment tends to be suppressed, and when the upper limit value is not more than the upper limit value, the ink repellency tends to be improved.
Specific examples of the 2-valent polycyclic saturated hydrocarbon group include: among these, adamantylene, dicyclopentadienylene, norbornylene, naphthylene, and the like, adamantylene is preferable from the viewpoint of ink repellency after UV cleaning treatment.
Examples of the substituent optionally contained in the 2-valent polycyclic saturated hydrocarbon group include an alkoxy group, a halogen atom, and a hydroxyl group.
(X4)
In the above-mentioned formula (2), X 4 represents a urethane bond (-O-CO-NH-) or an ester bond (-O-CO-). Among these, urethane bonds are preferable from the viewpoint of suppressing the decrease in ink repellency after UV cleaning treatment.
(X5)
In the above formula (2), X 5 represents a 2-valent hydrocarbon group optionally having a substituent.
Examples of the 2-valent hydrocarbon group include a 2-valent aliphatic group and a 2-valent aromatic ring group.
Examples of the 2-valent aliphatic group include: a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkenylene group.
The number of carbon atoms of the 2-valent aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is preferably 10 or less, more preferably 8 or less, still more preferably 5 or less, and particularly preferably 3 or less. When the lower limit value is not less than the upper limit value, the ink repellency after the UV cleaning treatment tends to be suppressed from decreasing, and when the upper limit value is not more than the upper limit value, the ink repellency tends to be improved.
Specific examples of the 2-valent aliphatic group include: methylene, ethylene, vinylene, propylene, butylene, cyclohexylene, adamantylene, and the like.
Examples of the substituent optionally contained in the 2-valent aliphatic group include a hydroxyl group, an alkoxy group, and a halogen atom.
Examples of the 2-valent aromatic ring group include a 2-valent aromatic hydrocarbon ring group and a 2-valent aromatic heterocyclic group.
The number of carbon atoms of the 2-valent aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, more preferably 6 or more, and is preferably 30 or less, more preferably 20 or less, more preferably 15 or less. When the lower limit value is not less than the upper limit value, the ink repellency after the UV cleaning treatment tends to be suppressed, and when the upper limit value is not more than the upper limit value, the ink repellency tends to be improved.
Examples of the 2-valent aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,A group having 2 free valencies such as a ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
Examples of the 2-valent aromatic heterocyclic group include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring,Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisotropic ringAn azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring,A group having 2 free valencies such as a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, and the like.
Examples of the substituent optionally contained in the 2-valent aromatic ring group include a hydroxyl group, an alkyl group, an alkoxy group, and a halogen atom.
Among these, from the viewpoint of ensuring ink repellency and suppressing the residual liquid repellent in the pixel portion at the time of development, a 2-valent aliphatic group is preferable, a methylene group and an ethylene group are more preferable, and an ethylene group is further preferable.
The acrylic resin (a) may further contain another partial structure, and from the viewpoint of reducing the residue of the light-emitting portion, the other partial structure preferably contains a partial structure represented by the following general formula (3).
[ Chemical formula 11]
In the formula (3), R 4 represents a hydrogen atom or a methyl group, X 6 represents a 1-valent hydrocarbon group optionally having a substituent, and X represents a bonding position.
(X6)
In the above formula (3), X 6 represents a 1-valent hydrocarbon group optionally having a substituent.
Examples of the 1-valent hydrocarbon group include a 1-valent aliphatic group and a 1-valent aromatic ring group.
Examples of the 1-valent aliphatic group include: a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkenyl group.
The number of carbon atoms of the 1-valent aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, particularly preferably 8 or more, and is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. When the lower limit value is not less than the upper limit value, the ink repellency after the UV cleaning treatment tends to be suppressed, and when the upper limit value is not more than the upper limit value, the ink repellency tends to be improved.
Specific examples of the 1-valent aliphatic group include: methyl, ethyl, vinyl, propyl, propenyl, butyl, butenyl, cyclohexyl, gold alkyl, and the like.
Examples of the substituent optionally contained in the 1-valent aliphatic group include a hydroxyl group, an alkoxy group, and a halogen atom.
Examples of the 1-valent aromatic ring group include a 1-valent aromatic hydrocarbon ring group and a 1-valent aromatic heterocyclic group.
The number of carbon atoms of the 1-valent aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, more preferably 6 or more, and is preferably 30 or less, more preferably 20 or less, more preferably 15 or less. When the lower limit value is not less than the upper limit value, the ink repellency after the UV cleaning treatment tends to be suppressed, and when the upper limit value is not more than the upper limit value, the ink repellency tends to be improved.
Examples of the 1-valent aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,A group having 1 free valence such as a ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
Examples of the 1-valent aromatic heterocyclic group include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring,Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisotropic ringAn azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring,A group having 1 free valence of a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, or the like.
Examples of the substituent optionally contained in the 1-valent aromatic ring group include a hydroxyl group, an alkyl group, and an alkoxy group.
Among these, from the viewpoint of ink repellency, a 1-valent aliphatic group optionally having a substituent is more preferable, an ethyl group optionally having a substituent is more preferable, and a gold alkyl group optionally having a substituent is still more preferable.
When the acrylic resin (a) has a partial structure represented by the above general formula (1), the content thereof is not limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 3 mol% or more, still more preferably 5 mol% or more, particularly preferably 7 mol% or more, and further preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 13 mol% or less, particularly preferably 10 mol% or less. When the lower limit value is not less than the upper limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the compatibility with other materials tends to be good. When the acrylic resin (a) has a partial structure represented by the above general formula (1), the content thereof is, for example, 1 to 20 mol%, preferably 2to 20 mol%, more preferably 3 to 15 mol%, still more preferably 5 to 15 mol%, and still more preferably 7 to 10 mol%.
On the other hand, in the case where the acrylic resin (a) has a partial structure represented by the above general formula (2), the content thereof is not limited, but is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, further preferably 60 mol% or more, particularly preferably 70 mol% or more, and further preferably 95 mol% or less, further preferably 90 mol% or less. When the content is equal to or higher than the lower limit, the outflow of the liquid repellent during development is suppressed, and the ink repellency tends to be improved, and when the content is equal to or lower than the upper limit, the content of fluorine atoms in the liquid repellent tends to be relatively improved. When the acrylic resin (a) has a partial structure represented by the above general formula (2), the content thereof is, for example, 30 to 95 mol%, preferably 40 to 95 mol%, more preferably 50 to 90 mol%, still more preferably 60 to 90 mol%, and still more preferably 70 to 90 mol%.
On the other hand, in the case where the acrylic resin (a) has a partial structure represented by the above general formula (3), the content thereof is not limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 3 mol% or more, particularly preferably 5 mol% or more, and further preferably 60 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less, further more preferably 30 mol% or less, particularly preferably 20 mol% or less. When the lower limit value is not less than the upper limit value, the residue of the light-emitting portion tends to be reduced, and when the lower limit value is not more than the upper limit value, the ink repellency tends to be improved. When the acrylic resin (a) has a partial structure represented by the above general formula (3), the content thereof is, for example, 1 to 60 mol%, preferably 2 to 50 mol%, more preferably 3 to 40 mol%, still more preferably 5 to 30 mol%, still more preferably 5 to 20 mol%.
In the case where the acrylic resin (a) contains two or more partial structures selected from the above general formulae (1) to (3), the acrylic resin (a) may be a random copolymer or a block copolymer, and in the case of a block copolymer, an AB block copolymer containing an a block having a partial structure represented by the above general formula (1) and a B block having a partial structure represented by the above general formula (2) and/or a partial structure represented by the above general formula (3) is preferable from the viewpoint of ink repellency.
The weight average molecular weight of the acrylic resin (a) is not particularly limited, and may be a low molecular weight compound or a high molecular weight compound. The weight average molecular weight of the acrylic resin (a) is preferably 1000 or more, more preferably 5000 or more, more preferably 8000 or more, more preferably 10000 or more, and is preferably 100000 or less, more preferably 50000 or less, more preferably 30000 or less, and particularly preferably 20000 or less. When the amount is within the above range, the fluidity of the liquid repellent due to post baking is suppressed, and the outflow of the liquid repellent from the partition wall tends to be suppressed. The weight average molecular weight of the acrylic resin (a) is, for example, 1000 to 100000, preferably 5000 to 50000, more preferably 8000 to 30000, and still more preferably 10000 to 20000.
When the acrylic resin (a) contains a fluorine atom, the content is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, and further preferably 50% by mass or less, more preferably 25% by mass or less. When the lower limit value is not less than the upper limit value, the acrylic resin (a) tends to be inhibited from remaining in the light-emitting portion. When the acrylic resin (a) contains a fluorine atom, the content thereof is, for example, 1 to 50% by mass, preferably 5 to 25% by mass, and more preferably 8 to 25% by mass.
The content ratio of the liquid repellent (a) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, still more preferably 0.2 mass% or more, particularly preferably 0.4 mass% or more, and is preferably 1 mass% or less, more preferably 0.7 mass% or less, still more preferably 0.5 mass% or less, of the total solid content of the photosensitive resin composition. When the lower limit value is not less than the upper limit value, the ink repellency tends to be high, and when the upper limit value is not more than the upper limit value, the outflow of the liquid repellent to the pixel portion tends to be suppressed. The content of the liquid repellent (a) in the total solid content of the photosensitive resin composition is, for example, 0.01 to 1% by mass, preferably 0.1 to 0.7% by mass, more preferably 0.2 to 0.7% by mass, and still more preferably 0.4 to 0.5% by mass.
The content of the acrylic resin (a) in the photosensitive resin composition of the present invention is not particularly limited, and is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, still more preferably 0.2 mass% or more, particularly preferably 0.4 mass% or more, and is preferably 1 mass% or less, more preferably 0.7 mass% or less, still more preferably 0.5 mass% or less, of the total solid content of the photosensitive resin composition. When the lower limit value is not less than the upper limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the outflow of the acrylic resin (a) into the pixel portion tends to be suppressed. The content of the acrylic resin (a) in the total solid content of the photosensitive resin composition is, for example, 0.01 to 1% by mass, preferably 0.1 to 0.7% by mass, more preferably 0.2 to 0.7% by mass, and still more preferably 0.4 to 0.5% by mass.
The (a) liquid repellent in the photosensitive resin composition of the present invention may contain other liquid repellent than the acrylic resin (a).
Specific examples of the other liquid repellent include, for example: organic compounds containing fluorine atoms such as perfluoroalkyl sulfonic acid, perfluoroalkyl carboxylic acid, perfluoroalkyl alkylene oxide adduct, perfluoroalkyl trialkylammonium salt, perfluoroalkyl ester, perfluoroalkyl phosphate ester, oligomer containing perfluoroalkyl group, oligomer containing perfluoroalkylene group, and the like.
As commercial products of these fluorine-containing organic compounds, those commercially available under the trade names "Megafac (registered trademark, hereinafter the same )F116"、"Megafac F120"、"Megafac F142D"、"Megafac F144D"、"Megafac F150"、"Megafac F160"、"Megafac F171"、"Megafac F172"、"Megafac F173"、"Megafac F177"、"Megafac F178A"、"Megafac F178K"、"Megafac F179"、"Megafac F183"、"Megafac F184"、"Megafac F191"、"Megafac F812"、"Megafac F815"、"Megafac F824"、"Megafac F833"、"Megafac RS101"、"Megafac RS102"、"Megafac RS105"、"Megafac RS201"、"Megafac RS202"、"Megafac RS301"、"Megafac RS303"、"Megafac RS304"、"Megafac RS401"、"Megafac RS402"、"Megafac RS501"、"Megafac RS502"、"Megafac RS-56"、"Megafac RS-72-K"、"DEFENSA( registered trademark), MCF300", "DEFENSA MCF310", "DEFENSA MCF", "DEFENSA MCF323", 3M Japan, fluorad FC-430"," Fluorad FC-431"," FC-4430"," FC-4432", AGC," Asahi Guard (registered trademark) AG-710", AGC SEIMI CHEMICAL," Surfron (registered trademark, hereinafter the same )S-382"、"Surfron SC-101"、"Surfron SC-102"、"Surfron SC-103"、"Surfron SC-104"、"Surfron SC-105"、"Surfron SC-106"、 Dai Kagaku Kogyo "Optool (registered trademark) DAC-HP" are used.
(A) The content of the acrylic resin (a) in the liquid repellent is not particularly limited, and is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and is usually 100% by mass or less. When the lower limit value is not less than the above, the decrease in ink repellency after UV cleaning treatment tends to be suppressed. The content of the acrylic resin (a) in the liquid repellent (a) is, for example, 50 to 100% by mass, preferably 80 to 100% by mass, and more preferably 90 to 100% by mass.
(A) In the case where the liquid repellent agent contains another liquid repellent agent, the content ratio of the other liquid repellent agent in the liquid repellent agent (a) is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less. When the lower limit value is not less than the upper limit value, the residue of the pixel portion tends to be suppressed, and when the upper limit value is not more than the upper limit value, the ink repellency after the UV cleaning treatment tends to be suppressed. (A) When the liquid repellent agent contains another liquid repellent agent, the content of the other liquid repellent agent in the liquid repellent agent (a) is, for example, 10 to 50% by mass, preferably 15 to 40% by mass, and more preferably 20 to 30% by mass.
[1-1-2] (B) component: alkali-soluble resin
The photosensitive resin composition of the present invention contains (B) an alkali-soluble resin. The alkali-soluble resin is not particularly limited as long as it can be developed in an alkali developer. Examples of the alkali-soluble resin include various resins containing a carboxyl group and/or a hydroxyl group. Among them, the carboxyl group-containing resin is preferable from the viewpoints that a partition wall having a moderate taper angle can be obtained, outflow of a liquid repellent agent due to thermal fusion of the partition wall surface during post baking is suppressed, and ink repellency can be maintained.
[ Alkali-soluble resin (b) having an olefinic double bond ]
In the photosensitive resin composition of the present invention, (B) the alkali-soluble resin preferably contains an alkali-soluble resin (B) having an olefinic double bond (hereinafter, sometimes simply referred to as "alkali-soluble resin (B)"). By including the alkali-soluble resin (b) having an olefinic double bond, sensitivity tends to be improved, and ink repellency of the partition wall obtained by suppressing outflow of a liquid repellent agent at the time of development tends to be improved.
The specific structure of the alkali-soluble resin (b) having an olefinic double bond is not particularly limited, but the epoxy (meth) acrylate resin (b 1) and/or the acrylic copolymer resin (b 2) are preferable from the viewpoint of developing solubility, and the epoxy (meth) acrylate resin (b 1) is more preferable from the viewpoint of reducing degassing.
The epoxy (meth) acrylate resin (b 1) will be described in detail below.
[ Epoxy (meth) acrylate resin (b 1) ]
The epoxy (meth) acrylate resin (b 1) is a resin obtained by adding an acid or ester compound having an ethylenically unsaturated bond (an ethylenic double bond) to an epoxy resin, and further adding a polybasic acid or an acid anhydride thereof. For example, a resin obtained by ring-opening addition of a carboxyl group of an acid having an ethylenically unsaturated bond to an epoxy group of an epoxy resin, thereby adding an ethylenically unsaturated bond to the epoxy resin via an ester bond (-COO-) and simultaneously adding a hydroxyl group formed at this time to one carboxyl group of a polybasic acid anhydride can be cited. In addition, a resin obtained by adding a polyhydric alcohol at the same time as adding a polyhydric acid anhydride can be mentioned. Further, the epoxy (meth) acrylate resin (b 1) is also a resin obtained by further reacting the carboxyl group of the resin obtained in the above reaction with a compound having a reactive functional group.
As described above, the epoxy (meth) acrylate resin has substantially no epoxy group in chemical structure and is not limited to "(meth) acrylate", but is named according to the conventional practice because an epoxy compound (epoxy resin) is a raw material and "(meth) acrylate" is a typical example.
The term "epoxy resin" as used herein also includes a raw material compound before forming a resin by heat curing, and as the epoxy resin, a known epoxy resin may be appropriately selected and used. The epoxy resin may be a compound obtained by reacting a phenolic compound with epichlorohydrin. The phenolic compound is preferably a compound having a phenolic hydroxyl group of 2 or more members, and may be a monomer or a polymer.
Specific examples include: bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, triphenol epoxy resin, epoxy of a polymer of phenol and dicyclopentadiene, dihydroxyfluorene type epoxy resin, dihydroxyalkylene oxyfluorene type epoxy resin, diglycidyl etherate of 9, 9-bis (4 '-hydroxyphenyl) fluorene, diglycidyl etherate of 1, 1-bis (4' -hydroxyphenyl) adamantane, and the like, and a compound having an aromatic ring in the main chain as such can be preferably used.
Among them, bisphenol a type epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, epoxides of polymers of phenol and dicyclopentadiene, diglycidyl etherate of 9, 9-bis (4' -hydroxyphenyl) fluorene, and the like are preferable, and bisphenol a type epoxy resins are more preferable, from the viewpoint of high strength of the cured film.
Examples of the acid having an ethylenically unsaturated bond include: (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, and the like, pentaerythritol tri (meth) acrylate succinic anhydride adduct, pentaerythritol tri (meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride adduct, reaction products of (meth) acrylic acid and epsilon-caprolactone, and the like. Among them, (meth) acrylic acid is preferable from the viewpoint of sensitivity.
Examples of the polybasic acid (anhydride) include: succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, anhydrides thereof, and the like. These polybasic acids (anhydrides) may be used singly or in combination of two or more. Among these, succinic anhydride, maleic anhydride, and itaconic anhydride are preferable, and succinic anhydride is more preferable, from the viewpoint of reducing residues in the pixel portion after development.
By using a polyol, the molecular weight of the epoxy (meth) acrylate resin (b 1) tends to be increased, and branching is introduced into the molecule, so that the balance between the molecular weight and the viscosity tends to be obtained. In addition, the rate of introduction of an acid group into a molecule tends to be increased, and a balance of sensitivity, adhesion, and the like tends to be easily obtained.
The polyhydric alcohol is preferably one or two or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2, 3-glycerol, for example.
The acid value of the epoxy (meth) acrylate resin (b 1) is not particularly limited, but is preferably 10mg-KOH/g or more, more preferably 20mg-KOH/g or more, still more preferably 40mg-KOH/g or more, still more preferably 60mg-KOH/g or more, and is preferably 200mg-KOH/g or less, more preferably 180mg-KOH/g or less, still more preferably 150mg-KOH/g or less, still more preferably 120mg-KOH/g or less, and particularly preferably 100mg-KOH/g or less. When the lower limit value is equal to or higher than the lower limit value, the residue tends to be reduced and the taper angle tends to be increased, and when the upper limit value is equal to or lower than the upper limit value, the outgassing during element light emission tends to be reduced. The acid value of the epoxy (meth) acrylate resin (b 1) is, for example, 10 to 200mg-KOH/g, preferably 10 to 180mg-KOH/g, more preferably 20 to 150mg-KOH/g, still more preferably 40 to 120mg-KOH/g, and still more preferably 60 to 100mg-KOH/g.
The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (b 1) is not particularly limited, and is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, more preferably 4000 or more, more preferably 5000 or more, particularly preferably 6000 or more, most preferably 7000 or more, and is usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, more preferably 10000 or less. When the lower limit value is equal to or higher than the upper limit value, the outgassing tends to be reduced when the element emits light, and when the lower limit value is equal to or lower than the upper limit value, the residue tends to be reduced. The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (b 1) is, for example, 1000 to 30000, preferably 2000 to 20000, more preferably 3000 to 20000, still more preferably 4000 to 15000, still more preferably 5000 to 15000, particularly preferably 6000 to 10000, and most preferably 7000 to 10000.
(B) When the alkali-soluble resin contains the epoxy (meth) acrylate resin (B1), the content of the epoxy (meth) acrylate resin (B1) contained in the alkali-soluble resin is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and further, usually 100% by mass or less. When the lower limit value is not less than the above, the degassing tends to be reduced. (B) When the alkali-soluble resin contains the epoxy (meth) acrylate resin (B1), the content of the epoxy (meth) acrylate resin (B1) contained in the alkali-soluble resin (B) is, for example, 30 to 100% by mass, preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass.
The epoxy (meth) acrylate resin (b 1) can be synthesized by a conventionally known method. Specifically, the following method may be employed: the epoxy resin is dissolved in an organic solvent, and the acid or ester compound having an ethylenically unsaturated bond is added in the presence of a catalyst and a thermal polymerization inhibitor to carry out an addition reaction, and a polybasic acid or an acid anhydride thereof is further added to continue the reaction.
Here, as the organic solvent used for the reaction, there may be mentioned: one or more organic solvents selected from methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, and the like. In addition, as the above-mentioned catalyst, there may be mentioned: one or more of tertiary amines such as triethylamine, benzyl dimethylamine and tribenzyl amine, quaternary ammonium salts such as tetramethyl ammonium chloride, methyl triethyl ammonium chloride, tetraethyl ammonium chloride, tetrabutyl ammonium chloride and trimethyl benzyl ammonium chloride, phosphorus compounds such as triphenylphosphine and antimony such as triphenylantimony. The thermal polymerization inhibitor may be one or more of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, and the like.
The acid or ester compound having an ethylenically unsaturated bond may be used in an amount of usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, relative to the chemical equivalent of the epoxy group 1 of the epoxy resin. The temperature at the time of the addition reaction may be generally 60 to 150℃and preferably 80 to 120 ℃. The amount of the polybasic acid (anhydride) to be used may be generally 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents, relative to the chemical equivalent of the hydroxyl group 1 generated in the addition reaction.
From the viewpoint of degassing when the element emits light, the epoxy (meth) acrylate resin (b 1) preferably contains at least one selected from the group consisting of: an epoxy (meth) acrylate resin (b 1-1) containing a partial structure represented by the following general formula (i) (hereinafter, sometimes simply referred to as "epoxy (meth) acrylate resin (b 1-1)"), an epoxy (meth) acrylate resin (b 1-2) containing a partial structure represented by the following general formula (ii) (hereinafter, sometimes referred to as "epoxy (meth) acrylate resin (b 1-2)"), and an epoxy (meth) acrylate resin (b 1-3) containing a partial structure represented by the following general formula (iii) (hereinafter, sometimes simply referred to as "epoxy (meth) acrylate resin (b 1-3)").
Among the above epoxy (meth) acrylate resins (b 1), the epoxy (meth) acrylate resin (b 1-1) having a partial structure represented by the following general formula (i) is preferable from the viewpoint of reducing outgassing at the time of light emission of the element. One of the reasons is that the main skeleton is rigid, and therefore decomposition or the like is unlikely to occur with respect to heat.
[ Chemical formula 12]
In the formula (i), R a represents a hydrogen atom or a methyl group, R b represents a 2-valent hydrocarbon group optionally having a substituent, and the benzene ring in the formula (i) is optionally further substituted with an optional substituent.
(Rb)
In the above formula (i), R b represents a 2-valent hydrocarbon group optionally having a substituent.
Examples of the 2-valent hydrocarbon group include: a 2-valent aliphatic group, a 2-valent aromatic ring group, and a group formed by linking 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic ring groups.
Examples of the 2-valent aliphatic group include linear, branched, and cyclic groups. Of these, a linear group is preferable from the viewpoint of developing solubility, and a cyclic 2-valent aliphatic group is preferable from the viewpoint of reducing penetration of the developing solution into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, more preferably 10 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-hexylene, n-heptylene, and the like. Among these, methylene is preferable from the viewpoint of reducing residues.
Specific examples of the 2-valent branched aliphatic group include: the above-mentioned 2-valent linear aliphatic group has a structure such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like as a side chain.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less. When the film residue ratio is equal to or higher than the lower limit, the film residue ratio tends to be increased, and when the film residue ratio is equal to or lower than the upper limit, the film residue ratio tends to be reduced. Specific examples of the 2-valent cyclic aliphatic group include: a group obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornyl ring, or an adamantane ring. Among these groups, a group in which 2 hydrogen atoms are removed from the adamantane ring is preferable from the viewpoint of development adhesion.
Examples of the substituent optionally contained in the 2-valent aliphatic group include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, no substitution is preferable.
The 2-valent aromatic ring group includes a 2-valent aromatic hydrocarbon ring group and a 2-valent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, more preferably 10 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the 2-valent aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,A group having 2 free valencies such as a ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocycle in the 2-valent aromatic heterocycle group may be a single ring or a condensed ring. Examples of the 2-valent aromatic heterocyclic group include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring,Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisotropic ringAn azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring,A group having 2 free valencies such as a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, and the like. Among these, benzene rings or naphthalene rings having 2 free valences are preferable from the standpoint of photocurability, and benzene rings having 2 free valences are more preferable.
Examples of the substituent optionally contained in the 2-valent aromatic ring group include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, and a glycidyl ether group. Among these, from the viewpoint of curability, unsubstituted ones are preferable.
Examples of the group formed by linking 1 or more aliphatic groups having 2 valences to 1 or more aromatic groups having 2 valences include groups formed by linking 1 or more aliphatic groups having 2 valences to 1 or more aromatic groups having 2 valences.
The number of the 2-valent aliphatic groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
The number of the 2-valent aromatic ring groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the group formed by linking 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic ring groups include: and groups represented by the following formulas (i-A) to (i-F). Among these groups, from the viewpoints of rigidity of the skeleton and hydrophobization of the film, the group represented by the following formula (i-a) is preferable. The chemical formula indicates the bonding position.
[ Chemical formula 13]
As described above, the benzene ring in formula (i) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of substituents is not particularly limited, and may be 1 or 2 or more.
Among these, from the viewpoint of curability, unsubstituted ones are preferable.
From the viewpoint of developing solubility, the partial structure represented by the above formula (i) is preferably a partial structure represented by the following formula (i-1).
[ Chemical formula 14]
In the formula (i-1), R a and R b are synonymous with R a and R b in the formula (i), R 1 represents a 2-valent hydrocarbon group having 1 to 4 carbon atoms and optionally having a substituent, and represents a bonding position. The benzene ring in the formula (i-1) is optionally further substituted with an optional substituent.
(R1)
In the above general formula (i-1), R 1 represents a C1-4 2-valent hydrocarbon group optionally having a substituent. Examples of the 2-valent hydrocarbon group include an alkylene group and an alkenylene group.
The alkylene group may be linear or branched, and is preferably linear from the viewpoint of developing solubility. The number of carbon atoms is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 4 or less, preferably 3 or less. When the lower limit value is not less than the upper limit value, the residual film ratio tends to be increased, and when the upper limit value is not more than the upper limit value, the outgas amount tends to be reduced at the time of element light emission.
Specific examples of the alkylene group include methylene, ethylene, propylene and butylene, and from the viewpoint of reducing degassing, methylene and ethylene are preferable, and ethylene is more preferable.
The alkenylene group may be linear or branched, and is preferably linear from the viewpoint of developing solubility. The number of carbon atoms is not particularly limited, but is usually not less than 2, and is usually not more than 4, preferably not more than 3. When the lower limit value is not less than the upper limit value, the residual film ratio tends to be increased, and when the upper limit value is not more than the upper limit value, the outgas amount tends to be reduced at the time of element light emission.
Specific examples of the alkenylene group include a vinylene group, a propenylene group, and a butenylene group, and from the viewpoint of degassing, a vinylene group is preferable.
The substituent optionally contained in the 2-valent hydrocarbon group having 1 to 4 carbon atoms is not particularly limited, and examples thereof include: halogen atoms, alkoxy groups, benzoyl groups, hydroxyl groups, and the like are preferably unsubstituted from the viewpoint of ease of synthesis.
Among these, R 1 is preferably a 2-valent alkylene group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylene group, and even more preferably an ethylene group, from the viewpoint of reducing degassing.
The partial structure represented by the above formula (i-1) contained in the 1-molecule epoxy (meth) acrylate resin (b 1-1) may be one kind or two or more kinds.
The number of the partial structures represented by the above formula (i) contained in the 1-molecule epoxy (meth) acrylate resin (b 1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and is preferably 10 or less, more preferably 8 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
The number of the partial structures represented by the above formula (i-1) contained in the 1-molecule epoxy (meth) acrylate resin (b 1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and further preferably 10 or less, more preferably 8 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the epoxy (meth) acrylate resin (b 1-1) are listed below.
[ Chemical formula 15]
[ Chemical formula 16]
[ Chemical formula 17]
[ Chemical formula 18]
[ Chemical formula 19]
[ Chemical formula 20]
[ Chemical formula 21]
On the other hand, from the viewpoint of development adhesion, the epoxy (meth) acrylate resin (b 1) is preferably an epoxy (meth) acrylate resin (b 1-2) containing a partial structure represented by the following formula (ii).
[ Chemical formula 22]
In the formula (ii), R c each independently represents a hydrogen atom or a methyl group, R d represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and represents a bonding position.
(Rd)
In the above formula (ii), R d represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.
The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more carbon atoms, and is preferably 40 or less, more preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less carbon atoms. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornyl ring, adamantane ring, and the like. Among these, an adamantane ring is preferable from the viewpoints of film strength and development adhesion.
On the other hand, the number of rings in the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less, more preferably 4 or less. When the lower limit value is equal to or higher than the upper limit value, the residue tends to be reduced, and when the upper limit value is equal to or lower than the upper limit value, the development adhesion tends to be improved.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, and is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, particularly preferably 15 or less. When the lower limit value is equal to or higher than the upper limit value, the residue tends to be reduced, and when the upper limit value is equal to or lower than the upper limit value, the development adhesion tends to be improved.
Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,Ring, benzophenanthrene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc. Among these, a fluorene ring is preferable from the viewpoint of patterning characteristics.
The 2-valent hydrocarbon group of the 2-valent hydrocarbon groups having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include: a 2-valent aliphatic group, a 2-valent aromatic ring group, and a group formed by linking 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic ring groups.
Examples of the 2-valent aliphatic group include linear, branched, and cyclic groups. Of these, a linear 2-valent aliphatic group is preferable from the viewpoint of developing solubility, and a cyclic 2-valent aliphatic group is preferable from the viewpoint of reducing penetration of the developing solution into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and is preferably 25 or less, more preferably 20 or less, more preferably 15 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-hexylene, n-heptylene, and the like. Among these, methylene is preferable from the viewpoint of residue.
Specific examples of the 2-valent branched aliphatic group include: the above-mentioned 2-valent linear aliphatic group has a structure such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like as a side chain.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced. Specific examples of the 2-valent cyclic aliphatic group include: a group obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornyl ring, or an adamantane ring. Among these, a group in which 2 hydrogen atoms are removed from the adamantane ring is preferable from the viewpoint of development adhesion.
Examples of the substituent optionally contained in the 2-valent aliphatic group include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, no substitution is preferable.
The 2-valent aromatic ring group includes a 2-valent aromatic hydrocarbon ring group and a 2-valent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and is preferably 30 or less, more preferably 20 or less, more preferably 15 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the 2-valent aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,A group having 2 free valencies such as a ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocycle of the 2-valent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the 2-valent aromatic heterocyclic group include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring,Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisotropic ringAn azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring,A group having 2 free valencies such as a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, and the like. Among these, from the standpoint of photocurability, a benzene ring or naphthalene ring having 2 free valences is preferable, and a benzene ring having 2 free valences is more preferable.
Examples of the substituent optionally contained in the 2-valent aromatic ring group include: hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. Among these, from the viewpoint of curability, unsubstituted ones are preferable.
Examples of the group formed by linking 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic ring groups include: and a group in which 1 or more of the above-described 2-valent aliphatic groups and 1 or more of the above-described 2-valent aromatic ring groups are linked.
The number of the 2-valent aliphatic groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
The number of the 2-valent aromatic ring groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the group formed by linking 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic ring groups include: groups represented by the above-mentioned formulas (i-A) to (i-F), and the like. Among these groups, the groups represented by the above formula (i-C) are preferable from the viewpoint of reducing residues.
The bonding form of the cyclic hydrocarbon group as the side chain with respect to these 2-valent hydrocarbon groups is not particularly limited, and examples thereof include: the form of the side chain is a form in which 1 hydrogen atom of the aliphatic group or the aromatic ring group is substituted with the side chain, or a form in which a cyclic hydrocarbon group as a side chain is constituted by including 1 carbon atom of the aliphatic group.
From the viewpoint of development adhesion, the partial structure represented by the above formula (ii) is preferably a partial structure represented by the following formula (ii-1).
[ Chemical formula 23]
In the formula (ii-1), R c is synonymous with the formula (ii), R α represents a 1-valent cyclic hydrocarbon group optionally having a substituent, n is an integer of 1 or more, and the benzene ring in the formula (ii-1) is optionally further substituted with an optional substituent.
(Rα)
In the above formula (ii-1), R α represents a cyclic hydrocarbon group having a valence of 1, which may have a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.
The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 6 or less, preferably 4 or less, more preferably 3 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more carbon atoms, and is preferably 40 or less, more preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less carbon atoms. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornyl ring, adamantane ring, and the like. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.
On the other hand, the number of rings in the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and is preferably 30 or less, more preferably 20 or less, more preferably 15 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, and the like. Among these, a fluorene ring is preferable from the viewpoint of development adhesion.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group and the like; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxy, nitro; cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, no substitution is preferable.
N represents an integer of 1 or more, preferably 2 or more, and further preferably 3 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Among these, R α is preferably an aliphatic cyclic group of 1 valence, more preferably an adamantyl group, from the viewpoint of firm film curability and electrical characteristics.
As described above, the benzene ring in formula (ii-1) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of substituents is not particularly limited, and may be 1 or 2 or more. Among these, from the viewpoint of curability, unsubstituted ones are preferable.
Specific examples of the partial structure represented by the above formula (ii-1) are given below.
[ Chemical formula 24]
[ Chemical formula 25]
[ Chemical formula 26]
[ Chemical formula 27]
[ Chemical formula 28]
From the viewpoint of development adhesion, the partial structure represented by the above formula (ii) is preferably a partial structure represented by the following formula (ii-2).
[ Chemical formula 29]
In the formula (ii-2), R c is synonymous with the formula (ii) above, R β represents a 2-valent cyclic hydrocarbon group optionally having a substituent, and the benzene ring in the formula (ii-2) is optionally further substituted with an optional substituent.
(Rβ)
In the above formula (ii-2), R β represents a cyclic hydrocarbon group having a valence of 2, which may have a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.
The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more carbon atoms, and preferably 40 or less, more preferably 35 or less, more preferably 30 or less carbon atoms. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornyl ring, adamantane ring, and the like. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.
On the other hand, the number of rings in the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, and is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, and the like. Among these, a fluorene ring is preferable from the viewpoint of development adhesion.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group and the like; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, no substitution is preferable.
Among these, from the viewpoint of curability, R β is preferably a 2-valent aliphatic cyclic group, more preferably a 2-valent adamantyl cyclic group.
On the other hand, from the viewpoint of development adhesion, R β is preferably a 2-valent aromatic ring group, more preferably a 2-valent fluorene ring group.
As described above, the benzene ring in formula (ii-2) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of substituents is not particularly limited, and may be 1 or 2 or more. Among these, from the viewpoint of curability, unsubstituted ones are preferable.
Specific examples of the partial structure represented by the above formula (ii-2) are given below.
[ Chemical formula 30]
[ Chemical formula 31]
[ Chemical formula 32]
[ Chemical formula 33]
On the other hand, from the viewpoint of curability, the partial structure represented by the above formula (ii) is preferably a partial structure represented by the following formula (ii-3).
[ Chemical formula 34]
In formula (ii-3), R c and R d are synonymous with formula (ii) above, and R 1 is synonymous with formula (i-1) above, and represents a bonding position.
The partial structure represented by the above formula (ii-3) contained in the 1-molecule epoxy (meth) acrylate resin (b 1-2) may be one kind or two or more kinds.
The number of the partial structures represented by the above formula (ii) contained in the 1-molecule epoxy (meth) acrylate resin (b 1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
On the other hand, from the viewpoint of reducing outgassing at the time of element light emission, the epoxy (meth) acrylate resin (b 1) is preferably an epoxy (meth) acrylate resin (b 1-3) containing a partial structure represented by the following general formula (iii).
[ Chemical formula 35]
In formula (iii), R e represents a hydrogen atom or a methyl group, γ represents a single bond, -CO-, an alkylene group optionally having a substituent, or a 2-valent cyclic hydrocarbon group optionally having a substituent, and the benzene ring in formula (iii) is optionally further substituted with an optional substituent.
(γ)
In the above formula (iii), γ represents a single bond, -CO-, an alkylene group optionally having a substituent, or a 2-valent cyclic hydrocarbon group optionally having a substituent.
The alkylene group may be linear or branched, and is preferably linear from the viewpoint of developing solubility, and is preferably branched from the viewpoint of developing adhesion. The number of carbon atoms is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 6 or less, preferably 4 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the alkylene group include: the methylene group, ethylene group, propylene group, butylene group, hexylene group, and heptylene group are preferably methylene group, ethylene group, or propylene group, and more preferably dimethylmethylene group, from the viewpoint of both of development adhesion and development solubility.
Examples of the substituent optionally contained in the alkylene group include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; cyano group; carboxyl groups, and the like. Among these, from the viewpoint of both development adhesion and development solubility, no substitution is preferred.
Examples of the 2-valent cyclic hydrocarbon group include a 2-valent aliphatic cyclic group and a 2-valent aromatic cyclic group.
The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more carbon atoms, and preferably 40 or less, more preferably 35 or less, more preferably 30 or less carbon atoms. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornyl ring, adamantane ring, and the like. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.
On the other hand, the number of rings in the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, and is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, and the like. Among these, a fluorene ring is preferable from the viewpoint of development adhesion.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group and the like; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, no substitution is preferable.
Among these, γ is preferably an alkylene group optionally having a substituent, and more preferably a dimethylmethylene group, from the viewpoint of reducing residue.
As described above, the benzene ring in formula (iii) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of substituents is not particularly limited, and may be 1 or 2 or more. Among these, from the viewpoint of curability, unsubstituted ones are preferable.
On the other hand, from the viewpoint of developing solubility, the partial structure represented by the above formula (iii) is preferably a partial structure represented by the following formula (iii-1).
[ Chemical formula 36]
In formula (iii-1), R e and γ are synonymous with those in formula (iii) above, R 1 is synonymous with R 1 in formula (i-1) above, and represents a bonding position. The benzene ring in formula (iii-1) is optionally further substituted with an optional substituent.
The number of the partial structures represented by the above formula (iii) contained in the 1-molecule epoxy (meth) acrylate resin (b 1-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, further preferably 10 or more, and is preferably 18 or less, further preferably 15 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
The number of the partial structures represented by the above formula (iii-1) contained in the 1-molecule epoxy (meth) acrylate resin (b 1-3) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and is preferably 18 or less, further preferably 15 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the epoxy (meth) acrylate resin (b 1-3) are given below.
[ Chemical formula 37]
[ Chemical formula 38]
[ Chemical formula 39]
[ Acrylic copolymer resin (b 2) ]
Next, the acrylic copolymer resin (b 2) will be described in detail. From the viewpoint of curability, the acrylic copolymer resin (b 2) is preferably an acrylic copolymer resin having an olefinic double bond in a side chain.
Among the acrylic copolymer resin (b 2), the acrylic copolymer resin (b 2-1) containing a partial structure represented by the following general formula (I) is preferable from the viewpoint of developing solubility.
[ Chemical formula 40]
In formula (I), R A and R B each independently represent a hydrogen atom or a methyl group, and represent a bonding position.
From the viewpoint of developability, the partial structure represented by the above formula (I) is preferably a partial structure represented by the following general formula (I-1).
[ Chemical formula 41]
In formula (I-1), R A and R B are synonymous with those in formula (I) above, and R 1 is synonymous with those in formula (I-1) above.
From the viewpoint of sensitivity, the partial structure represented by the above formula (I) is preferably a partial structure represented by the following formula (I-2).
[ Chemical formula 42]
In the formula (I-2), R A and R B are synonymous with those in the above formula (I).
When the acrylic copolymer resin (b 2-1) contains a partial structure represented by the above general formula (I), the content of the partial structure represented by the above general formula (I) in the acrylic copolymer resin (b 2-1) is not particularly limited, but is preferably 5 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 50 mol% or more, particularly preferably 70 mol% or more, most preferably 80 mol% or more, and further preferably 99 mol% or less, more preferably 97 mol% or less, still more preferably 95 mol% or less. When the lower limit value is equal to or higher than the upper limit value, the residue tends to be reduced, and when the upper limit value is equal to or lower than the upper limit value, the development adhesion tends to be improved. When the acrylic copolymer resin (b 2-1) contains a partial structure represented by the above general formula (I), the content of the partial structure represented by the above general formula (I) contained in the acrylic copolymer resin (b 2-1) is, for example, 5 to 99 mol%, preferably 20 to 99 mol%, more preferably 30 to 97 mol%, still more preferably 50 to 97 mol%, still more preferably 70 to 95 mol%, and particularly preferably 80 to 95 mol%.
When the acrylic copolymer resin (b 2-1) contains a partial structure represented by the above general formula (I-1), the content of the partial structure represented by the above general formula (I-1) in the acrylic copolymer resin (b 2-1) is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% or more, still more preferably 10 mol% or more, and is preferably 99 mol% or less, still more preferably 60 mol% or less, still more preferably 40 mol% or less, still more preferably 30 mol% or less, and particularly preferably 20 mol% or less. When the lower limit value is not less than the upper limit value, the sensitivity tends to be improved and the residue tends to be reduced, and when the lower limit value is not more than the upper limit value, the development adhesion tends to be improved. When the acrylic copolymer resin (b 2-1) contains a partial structure represented by the above general formula (I-1), the content of the partial structure represented by the above general formula (I-1) in the acrylic copolymer resin (b 2-1) is, for example, 1 to 99 mol%, preferably 5 to 60 mol%, more preferably 5 to 40 mol%, still more preferably 8 to 40 mol%, and still more preferably 10 to 20 mol%.
When the acrylic copolymer resin (b 2-1) contains a partial structure represented by the above general formula (I-2), the content of the partial structure represented by the above general formula (I-2) in the acrylic copolymer resin (b 2-1) is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 70 mol% or more, and further preferably 99 mol% or less, more preferably 95 mol% or less, still more preferably 90 mol% or less, and particularly preferably 85 mol% or less. When the sensitivity is set to be equal to or higher than the lower limit, the sensitivity tends to be improved, and when the sensitivity is set to be equal to or lower than the upper limit, the developability tends to be improved. When the acrylic copolymer resin (b 2-1) contains a partial structure represented by the above general formula (I-2), the content of the partial structure represented by the above general formula (I-2) in the acrylic copolymer resin (b 2-1) is, for example, 10 to 99 mol%, preferably 30 to 95 mol%, more preferably 50 to 90 mol%, still more preferably 70 to 90 mol%, and still more preferably 70 to 85 mol%.
When the acrylic copolymer resin (b 2-1) contains a partial structure represented by the above general formula (I), the partial structure that may be additionally contained is not particularly limited, and from the viewpoint of development adhesion, the partial structure represented by the following general formula (I') is preferably contained.
[ Chemical formula 43]
In the above formula (I'), R D represents a hydrogen atom or a methyl group, and R E represents an optionally substituted alkyl group, an optionally substituted aryl group (aromatic ring group), or an optionally substituted alkenyl group.
(RE)
In the above formula (I'), R E represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkenyl group.
Examples of the alkyl group in R E include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and further preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. When the lower limit value is not less than the upper limit value, the film strength tends to be improved and the development adhesion tends to be improved, and when the lower limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the alkyl group include: methyl, ethyl, cyclohexyl, dicyclopentyl, dodecyl, and the like. Among these groups, dicyclopentyl or dodecyl is preferable, and dicyclopentyl is more preferable from the viewpoint of film strength.
Examples of the substituent optionally included in the alkyl group include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryl, methacryl, etc., and from the viewpoint of developability, hydroxy, oligoethylene glycol are preferred.
Examples of the aryl group (aromatic ring group) in R E include a 1-valent aromatic hydrocarbon ring group and a 1-valent aromatic heterocyclic group. The number of carbon atoms is preferably 4 or more, more preferably 6 or more, and further preferably 24 or less, more preferably 22 or less, further preferably 20 or less, particularly preferably 18 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, and examples thereof include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,Ring, benzophenanthrene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc.
The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring, and examples thereof include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring,Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisotropic ringAn azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring,A pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, and the like. Among these, from the viewpoint of curability, a benzene ring group or a naphthalene ring group is preferable, and a benzene ring group is more preferable.
Examples of the substituent optionally included in the aryl group include: methyl, ethyl, propyl, methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, and the like, with hydroxy and oligoethylene glycol groups being preferred from the viewpoint of developability.
Examples of the alkenyl group in R E include linear, branched or cyclic alkenyl groups. The number of carbon atoms is preferably not less than 2, more preferably not more than 22, still more preferably not more than 20, still more preferably not more than 18, still more preferably not more than 16, particularly preferably not more than 14. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the alkenyl group include: ethenyl, propenyl, butenyl, cyclohexenyl, and the like. Of these, vinyl or propenyl is preferable, and vinyl is more preferable from the viewpoint of curability.
Examples of the substituent optionally contained in the alkenyl group include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, and the like, with hydroxy, oligoethylene glycol being preferred from the standpoint of developability.
As described above, R E represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkenyl group, and among these groups, from the viewpoint of developability, an alkyl group or an alkenyl group is preferable, an alkyl group is more preferable, and a dicyclopentyl group is further preferable.
When the acrylic copolymer resin (b 2-1) contains a partial structure represented by the above general formula (I '), the content of the partial structure represented by the above general formula (I') contained in the acrylic copolymer resin (b 2-1) is not particularly limited, but is preferably 0.5 mol% or more, more preferably 1 mol% or more, still more preferably 1.5 mol% or more, particularly preferably 2 mol% or more, and is preferably 90 mol% or less, more preferably 70 mol% or less, still more preferably 50 mol% or less, still more preferably 30 mol% or less, and particularly preferably 10 mol% or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced. When the acrylic copolymer resin (b 2-1) contains a partial structure represented by the above general formula (I '), the content of the partial structure represented by the above general formula (I') contained in the acrylic copolymer resin (b 2-1) is, for example, 0.5 to 90 mol%, preferably 1 to 70 mol%, more preferably 1.5 to 50 mol%, still more preferably 1.5 to 30 mol%, and still more preferably 2 to 10 mol%.
When the acrylic copolymer resin (b 2-1) contains a partial structure represented by the above general formula (I), it is preferable to further contain a partial structure represented by the following general formula (I ") from the viewpoints of heat resistance and film strength.
[ Chemical formula 44]
In the above formula (I "), R F represents a hydrogen atom or a methyl group, R G represents an optionally substituted alkyl group, an optionally substituted alkenyl group, a hydroxyl group, a carboxyl group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylthio group, and t represents an integer of 0 to 5.
(RG)
In the above formula (I "), R G represents an optionally substituted alkyl group, an optionally substituted alkenyl group, a hydroxyl group, a carboxyl group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylthio group.
Examples of the alkyl group in R G include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and further preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the alkyl group include: methyl, ethyl, cyclohexyl, dicyclopentyl, dodecyl, and the like. Among these groups, dicyclopentyl or dodecyl is preferable, and dicyclopentyl is more preferable from the viewpoint of development adhesion.
Examples of the substituent optionally included in the alkyl group include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryl, methacryl, etc., and from the viewpoint of developability, hydroxy, oligoethylene glycol are preferred.
Examples of the alkenyl group in R G include linear, branched or cyclic alkenyl groups. The number of carbon atoms is preferably not less than 2, more preferably not more than 22, still more preferably not more than 20, still more preferably not more than 18, still more preferably not more than 16, particularly preferably not more than 14. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the alkenyl group include: ethenyl, propenyl, butenyl, cyclohexenyl, and the like. Of these, vinyl or propenyl is preferable, and vinyl is more preferable from the viewpoint of curability.
Examples of the substituent optionally contained in the alkenyl group include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, and the like, with hydroxy, oligoethylene glycol being preferred from the standpoint of developability.
The halogen atom in R G includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom is preferable from the viewpoint of ink repellency.
The alkoxy group in R G may be a linear, branched or cyclic alkoxy group. The number of carbon atoms is preferably 1 or more, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Examples of the substituent optionally contained in the alkoxy group include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryl, methacryl, etc., and from the viewpoint of developability, hydroxy, oligoethylene glycol are preferred.
Examples of the alkylthio group in R G include linear, branched or cyclic alkylthio groups. The number of carbon atoms is preferably 1 or more, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced.
Specific examples of the alkylthio group include: methylthio, ethylthio, propylthio, butylthio, and the like. Among these, methylthio or ethylthio is preferable from the viewpoint of developability.
Examples of the substituent optionally contained in the alkyl group in the alkylthio group include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryl, methacryl, etc., and from the viewpoint of developability, hydroxy, oligoethylene glycol are preferred.
As such, R G represents an optionally substituted alkyl group, an optionally substituted alkenyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an optionally substituted alkylthio group, and among these groups, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable from the viewpoint of developability.
(t)
In the above formula (I "), t represents an integer of 0 to 5, and is preferably 2 or less, more preferably 1 or less, and still more preferably 0 from the viewpoint of developability.
When the acrylic copolymer resin (b 2-1) contains a partial structure represented by the above general formula (I "), the content of the partial structure represented by the above general formula (I") in the acrylic copolymer resin (b 2-1) is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 3 mol% or more, particularly preferably 5 mol% or more, and is preferably 90 mol% or less, more preferably 70 mol% or less, still more preferably 50 mol% or less, still more preferably 30 mol% or less, particularly preferably 20 mol% or less, and most preferably 10 mol% or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced. When the acrylic copolymer resin (b 2-1) contains a partial structure represented by the above general formula (I "), the content of the partial structure represented by the above general formula (I") contained in the acrylic copolymer resin (b 2-1) is, for example, 1 to 90 mol%, preferably 2 to 70 mol%, more preferably 2 to 50 mol%, still more preferably 3 to 30 mol%, still more preferably 3 to 20 mol%, and particularly preferably 5 to 10 mol%.
When the acrylic copolymer resin (b 2-1) contains a partial structure represented by the above general formula (I), it is preferable to further contain a partial structure represented by the following general formula (I' ") from the viewpoint of developability.
[ Chemical formula 45]
In the above formula (I'), R H represents a hydrogen atom or a methyl group.
When the acrylic copolymer resin (b 2-1) contains a partial structure represented by the general formula (I '"), the content of the partial structure represented by the general formula (I'") in the acrylic copolymer resin (b 2-1) is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 30 mol% or more, and is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly preferably 50 mol% or less. When the lower limit value is equal to or higher than the upper limit value, the residue tends to be reduced, and when the upper limit value is equal to or lower than the upper limit value, the development adhesion tends to be improved. When the acrylic copolymer resin (b 2-1) contains a partial structure represented by the above general formula (I '"), the content of the partial structure represented by the above general formula (I'") contained in the acrylic copolymer resin (b 2-1) is, for example, 5 to 90 mol%, preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and even more preferably 30 to 50 mol%. On the other hand, from the viewpoint of degassing, it is preferably 0 mol%, that is, it does not contain a partial structure represented by the above general formula (I' ").
The acid value of the acrylic copolymer resin (b 2) is not particularly limited, but is preferably 5mg-KOH/g or more, more preferably 10mg-KOH/g or more, still more preferably 20mg-KOH/g or more, still more preferably 25mg-KOH/g or more, and is preferably 100mg-KOH/g or less, more preferably 80mg-KOH/g or less, still more preferably 60mg-KOH/g or less, still more preferably 40mg-KOH/g or less. When the lower limit value is equal to or higher than the upper limit value, the residue tends to be reduced, and when the upper limit value is equal to or lower than the upper limit value, the development adhesion tends to be improved. The acid value of the acrylic copolymer resin (b 2) is, for example, 5 to 100mg-KOH/g, preferably 10 to 80mg-KOH/g, more preferably 20 to 60mg-KOH/g, and still more preferably 25 to 40mg-KOH/g.
The weight average molecular weight (Mw) of the acrylic copolymer resin (b 2) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, more preferably 3000 or more, more preferably 4000 or more, particularly preferably 5000 or more, and is usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, more preferably 10000 or less, particularly preferably 8000 or less. When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the residue tends to be reduced. The weight average molecular weight (Mw) of the acrylic copolymer resin (b 2) is, for example, 1000 to 30000, preferably 2000 to 20000, more preferably 3000 to 15000, still more preferably 4000 to 10000, still more preferably 5000 to 8000.
(B) When the alkali-soluble resin contains the acrylic copolymer resin (B2), the content of the acrylic copolymer resin (B2) contained in the alkali-soluble resin is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, and further, is usually 100% by mass or less, preferably 80% by mass or less, further preferably 50% by mass or less. When the ratio is equal to or higher than the lower limit, the developing solubility tends to be good, and when the ratio is equal to or lower than the upper limit, the taper angle tends to be high. (B) When the alkali-soluble resin contains the acrylic copolymer resin (B2), the content of the acrylic copolymer resin (B2) contained in the alkali-soluble resin (B) is, for example, 5 to 100% by mass, preferably 10 to 100% by mass, more preferably 15 to 80% by mass, and still more preferably 20 to 50% by mass.
(B) The alkali-soluble resin may contain either one of the epoxy (meth) acrylate resin (b 1) and the acrylic copolymer resin (b 2) alone or both of them. Further, the alkali-soluble resin (B) may contain an alkali-soluble resin other than the alkali-soluble resin (B).
The content ratio of the alkali-soluble resin (B) in the photosensitive resin composition of the present invention is as follows: the total solid content is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, and further usually 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, particularly preferably 50% by mass or less. When the lower limit value is equal to or higher than the upper limit value, the developability tends to be improved, and when the upper limit value is equal to or lower than the upper limit value, the outgassing during light emission of the element tends to be reduced. The content of the alkali-soluble resin (B) in the total solid content of the photosensitive resin composition is, for example, 10 to 90% by mass, preferably 20 to 70% by mass, more preferably 30 to 60% by mass, and still more preferably 40 to 50% by mass.
In the case where the photosensitive resin composition of the present invention contains the epoxy (meth) acrylate resin (b 1), the content of the epoxy (meth) acrylate resin (b 1) is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, and is usually 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, particularly preferably 50% by mass or less, of the total solid content. When the lower limit value is equal to or higher than the upper limit value, the developability tends to be improved, and when the upper limit value is equal to or lower than the upper limit value, the outgassing during light emission of the element tends to be reduced. When the photosensitive resin composition of the present invention contains the epoxy (meth) acrylate resin (b 1), the content of the epoxy (meth) acrylate resin (b 1) in the total solid content is, for example, 5 to 90% by mass, preferably 10 to 70% by mass, more preferably 20 to 60% by mass, still more preferably 30 to 50% by mass, and still more preferably 40 to 50% by mass.
In the case where the photosensitive resin composition of the present invention contains the epoxy acrylic copolymer resin (b 2), the content of the acrylic copolymer resin (b 2) is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, and is usually 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, particularly preferably 50% by mass or less, of the total solid content. When the lower limit value is equal to or higher than the upper limit value, the developability tends to be improved, and when the upper limit value is equal to or lower than the upper limit value, the outgassing during light emission of the element tends to be reduced. When the photosensitive resin composition of the present invention contains the epoxy acrylic copolymer resin (b 2), the content of the acrylic copolymer resin (b 2) in the total solid content is, for example, 5 to 90 mass%, preferably 10 to 70 mass%, more preferably 20 to 60 mass%, still more preferably 30 to 50 mass%, still more preferably 40 to 50 mass%.
The total content of the alkali-soluble resin (B) and the photopolymerizable compound (C) in the total solid content is usually 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, still more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and further usually 99% by mass or less, preferably 97% by mass or less, more preferably 95% by mass or less. When the lower limit value is equal to or higher than the upper limit value, the curability tends to be improved, and when the upper limit value is equal to or lower than the upper limit value, the outgassing tends to be reduced when the element emits light. The total content of the alkali-soluble resin (B) and the photopolymerizable compound (C) in the total solid content is, for example, 5 to 99% by mass, preferably 10 to 99% by mass, more preferably 30 to 99% by mass, still more preferably 50 to 97% by mass, still more preferably 70 to 97% by mass, particularly preferably 80 to 95% by mass, and most preferably 90 to 95% by mass.
The blending ratio of the alkali-soluble resin (B) to the photopolymerizable compound (C) in the photosensitive resin composition is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, still more preferably 70 parts by mass or more, particularly preferably 80 parts by mass or more, and further preferably 400 parts by mass or less, more preferably 300 parts by mass or less, still more preferably 200 parts by mass or less, particularly preferably 100 parts by mass or less, based on 100 parts by mass of the photopolymerizable compound (C). When the lower limit value is not less than the upper limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the upper limit value, the curability tends to be improved. The blending ratio of the alkali-soluble resin (B) to 100 parts by mass of the photopolymerizable compound (C) in the photosensitive resin composition is, for example, 50 to 400 parts by mass, preferably 60 to 300 parts by mass, more preferably 70 to 200 parts by mass, and still more preferably 80 to 100 parts by mass.
[1-1-3] (C) component: photopolymerizable compound
The photosensitive resin composition of the present invention contains (C) a photopolymerizable compound. The inclusion of the photopolymerizable compound (C) is considered to be highly sensitive.
The photopolymerizable compound used herein means a compound having 1 or more ethylenic unsaturated bonds (ethylenic double bonds) in the molecule, and is preferably a compound having 2 or more ethylenic unsaturated bonds in the molecule, and is preferably a (meth) acrylate compound which is a compound having an (meth) acryloyloxy group, in view of polymerizability, crosslinkability, and a difference in solubility of a developer in an exposed portion and a non-exposed portion which can be increased in accordance with the polymerizability, crosslinkability, and the like.
In the photosensitive resin composition of the present invention, it is particularly preferable to use a polyfunctional olefinic monomer having 2 or more ethylenically unsaturated bonds in 1 molecule. The number of the ethylenically unsaturated groups included in the polyfunctional olefinic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more, and is preferably 15 or less, more preferably 10 or less, further preferably 8 or less, particularly preferably 7 or less. When the ratio is equal to or higher than the lower limit, the polymerization property tends to be improved and the sensitivity tends to be high, and when the ratio is equal to or lower than the upper limit, the developability tends to be further improved. The number of the ethylenically unsaturated groups contained in the polyfunctional olefinic monomer is, for example, 2 to 15, preferably 3 to 10, more preferably 4 to 8, still more preferably 5 to 7.
Specific examples of the photopolymerizable compound include: esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; and esters obtained by esterification of polyhydric hydroxyl compounds such as aliphatic polyhydric compounds and aromatic polyhydric compounds with unsaturated carboxylic acids and polycarboxylic acids.
Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include: aliphatic polyhydroxy compound acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, methacrylates obtained by substituting the acrylates of the above-mentioned exemplary compounds with methacrylates, itaconic esters substituted with itaconic esters, crotonates substituted with crotonates, and maleates substituted with maleates, and the like.
Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include: and acrylates and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate and pyrogallol triacrylate.
The ester obtained by esterification of a polyhydric hydroxyl compound such as an aliphatic polyhydric compound or an aromatic polyhydric compound with an unsaturated carboxylic acid or a polycarboxylic acid is not necessarily a single product, and typical specific examples thereof include: condensation products of acrylic acid, phthalic acid and ethylene glycol, condensation products of acrylic acid, maleic acid and diethylene glycol, condensation products of methacrylic acid, terephthalic acid and pentaerythritol, condensation products of acrylic acid, adipic acid, butanediol and glycerol, and the like.
As examples of the photopolymerizable compound used in the photosensitive resin composition of the present invention, urethane (meth) acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or reacting a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth) acrylate; epoxy acrylates such as addition reactants of a polyvalent epoxy compound and a hydroxyl group-containing (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate are useful.
Examples of the urethane (meth) acrylates include: DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kagaku Co., ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Nippon Kagaku chemical Co., ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kogyo Rong She Co., ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV B (manufactured by Nippon synthetic chemical Co., ltd.), and the like.
Among these, from the viewpoint of proper taper angle and sensitivity, ester (meth) acrylates or urethane (meth) acrylates are preferably used as the (C) photopolymerizable compound, and dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2-tri (meth) acryloxymethyl ethyl phthalate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dibasic acid anhydride adduct of dipentaerythritol penta (meth) acrylate, dibasic acid anhydride adduct of pentaerythritol tri (meth) acrylate, and the like are more preferably used.
These compounds may be used singly or in combination of two or more.
In the photosensitive resin composition of the present invention, the molecular weight of the photopolymerizable compound (C) is not particularly limited, but is preferably 100 or more, more preferably 150 or more, still more preferably 200 or more, still more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, and preferably 1000 or less, still more preferably 700 or less from the viewpoints of sensitivity, ink repellency and taper angle. The molecular weight of the photopolymerizable compound (C) is, for example, 100 to 1000, preferably 150 to 700, more preferably 200 to 700, still more preferably 300 to 700, still more preferably 400 to 700, and particularly preferably 500 to 700.
The number of carbon atoms of the photopolymerizable compound (C) is not particularly limited, but is preferably 7 or more, more preferably 10 or more, still more preferably 15 or more, still more preferably 20 or more, particularly preferably 25 or more, and is preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, particularly preferably 30 or less, from the viewpoints of sensitivity, ink repellency, and taper angle. The number of carbon atoms of the photopolymerizable compound (C) is, for example, 7 to 50, preferably 10 to 40, more preferably 15 to 35, still more preferably 20 to 30, still more preferably 25 to 30.
Among them, from the viewpoints of sensitivity, ink repellency, and taper angle, ester (meth) acrylates, epoxy (meth) acrylates, and urethane (meth) acrylates are preferable, and from the viewpoints of sensitivity, ink repellency, and taper angle, acid anhydride adducts of 3-functional or more ester (meth) acrylates such as pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate, and acid anhydride adducts of 3-functional or more ester (meth) acrylates such as 2, 2-tri (meth) acryloxymethyl ethyl phthalate, and dipentaerythritol penta (meth) acrylate are more preferable.
The content of the photopolymerizable compound (C) in the photosensitive resin composition of the present invention is usually 5 mass% or more, preferably 10 mass% or more, more preferably 20 mass% or more, still more preferably 30 mass% or more, particularly preferably 40 mass% or more, and is usually 80 mass% or less, preferably 70 mass% or less, more preferably 60 mass% or less, still more preferably 55 mass% or less, particularly preferably 50 mass% or less, based on the total solid content. When the lower limit value is not less than the upper limit value, sensitivity and taper angle at the time of exposure tend to be good, and when the upper limit value is not more than the upper limit value, development tends to be good. The content of the photopolymerizable compound (C) in the total solid content of the photosensitive resin composition is, for example, 10 to 80 mass%, preferably 20 to 70 mass%, more preferably 30 to 60 mass%, still more preferably 40 to 55 mass%, and still more preferably 40 to 50 mass%.
In the photosensitive resin composition of the present invention, the content of the photopolymerizable compound (C) is usually 15 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, further preferably 80 parts by mass or more, particularly preferably 90 parts by mass or more, and usually 150 parts by mass or less, preferably 130 parts by mass or less, more preferably 120 parts by mass or less, further preferably 110 parts by mass or less, based on 100 parts by mass of the alkali-soluble resin (B). When the lower limit value is not less than the upper limit value, the sensitivity at the time of exposure tends to be good, and the taper angle tends to be good, and when the upper limit value is not more than the upper limit value, the development tends to be good. The content of the photopolymerizable compound (C) in the photosensitive resin composition is, for example, 15 to 150 parts by mass, preferably 30 to 130 parts by mass, more preferably 50 to 120 parts by mass, still more preferably 80 to 120 parts by mass, and still more preferably 90 to 110 parts by mass, based on 100 parts by mass of the alkali-soluble resin (B).
[1-1-4] (D) component: photopolymerization initiator
The photosensitive resin composition of the present invention contains (D) a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize the ethylenically unsaturated bond of the photopolymerizable compound (C) by active light, and a known photopolymerization initiator can be used.
In the photosensitive resin composition of the present invention, as the photopolymerization initiator (D), a photopolymerization initiator generally used in this field can be used. Examples of such photopolymerization initiators include: a hexaarylbiimidazole photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, an oxime ester photopolymerization initiator, a triazine photopolymerization initiator, an acetophenone photopolymerization initiator, and a benzophenone photopolymerization initiator.
As the hexaarylbiimidazole-based photopolymerization initiator, hexaarylbiimidazole-based compounds represented by the following general formula (1-1) and/or the following general formula (1-2) are preferable from the viewpoints of absorbance and sensitivity and matching with the absorption wavelength of the ultraviolet absorber.
[ Chemical formula 46]
In the above formula, R 11～R13 each independently represents an optionally substituted C1-4 alkyl group, an optionally substituted C1-4 alkoxy group, or a halogen atom, and m, n, and l each independently represent an integer of 0 to 5.
The number of carbon atoms of the alkyl group of R 11～R13 is not particularly limited as long as it is within a range of 1 to 4, and is preferably 3 or less, more preferably 2 or less, from the viewpoint of sensitivity. The alkyl group may be chain-shaped or cyclic. Specific examples of the alkyl group include methyl, ethyl, propyl and isopropyl, and among them, methyl and ethyl are preferable. As the substituent optionally contained in the alkyl group having 1 to 4 carbon atoms of R 11～R13, a group having a 1-valent nonmetallic atom other than hydrogen can be used, and as a preferable example, a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, an alkoxy group can be cited.
The number of carbon atoms of the alkoxy group of R 11～R13 is not particularly limited as long as it is within the range of 1 to 4, and is preferably 3 or less, more preferably 2 or less, from the viewpoint of sensitivity. The alkyl portion of the alkoxy group may be chain or cyclic. Specific examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, and butoxy groups, and among them, methoxy and ethoxy groups are preferable. The substituent optionally contained in the alkoxy group having 1 to 4 carbon atoms of R 11～R13 may be an alkyl group or an alkoxy group, and is preferably an alkyl group.
Examples of the halogen atom of R 11～R13 include a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom, and among them, a chlorine atom or a fluorine atom is preferable, and a chlorine atom is more preferable from the viewpoint of ease of synthesis.
Among these, R 11～R13 is independently preferably a halogen atom, more preferably a chlorine atom, from the viewpoints of sensitivity and ease of synthesis.
M, n and l each independently represent an integer of 0 to 5, and from the viewpoint of ease of synthesis, at least 1 of m, n and l is preferably an integer of 1 or more, more preferably any 1 of m, n and l is 1 and the remaining 2 are 0.
Examples of the hexaarylbisimidazoles represented by the general formula (1-1) and/or the general formula (1-2) include: 2,2 '-bis (o-chlorophenyl) -4,5,4',5 '-tetraphenyl-biimidazole, 2' -bis (o-methylphenyl) -4,5,4',5' -tetraphenyl-biimidazole, 2 '-bis (o-chlorophenyl) -4,4',5 '-tetra (o, p-dichlorophenyl) biimidazole, 2' -bis (o, p-dichlorophenyl) -4,4', 5' -tetrakis (o, p-dichlorophenyl) biimidazole, 2 '-bis (o-chlorophenyl) -4,4',5,5 '-tetrakis (p-fluorophenyl) biimidazole, 2' -bis (o-chlorophenyl) -4,4', 5' -tetrakis (o, p-dibromophenyl) biimidazole, 2 '-bis (o-bromophenyl) -4,4',5,5 '-tetrakis (o, p-dichlorophenyl) biimidazole, 2' -bis (o-chlorophenyl) -4,4', 5' -tetrakis (p-chloronaphthyl) biimidazole, and the like. Among them, hexaphenylbisimidazole compounds are preferable, and compounds in which the ortho position of the benzene ring bonded to the 2,2' -position on the imidazole ring is substituted with a methyl group, a methoxy group or a halogen atom are more preferable, and compounds in which the benzene ring bonded to the 4,4', 5' -position on the imidazole ring is unsubstituted or substituted with a halogen atom or a methoxy group are preferable.
As the photopolymerization initiator (D), either one of the hexaarylbiimidazole compound represented by the general formula (1-1) and the hexaarylbiimidazole compound represented by the general formula (1-2) may be used, or both may be used in combination. In the case of using the combination, the ratio thereof is not particularly limited.
Further, as the acylphosphine oxide-based photopolymerization initiator, preferable examples are: 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, and the like.
As the oxime ester photopolymerization initiator, an oxime ester compound having a carbazole skeleton and a diphenyl sulfide skeleton is preferably contained, and an oxime ester compound having a diphenyl sulfide skeleton is more preferable. It is considered that the inclusion of the oxime ester compound having a diphenyl sulfide skeleton enhances the light absorption at a short wavelength and the surface curability, and therefore, the outflow of the liquid repellent at the time of development can be suppressed, and the ink repellency can be improved.
The chemical structure of the oxime ester compound having a diphenyl sulfide skeleton is not particularly limited, and from the viewpoint of sensitivity, an oxime ester compound represented by the following general formula (D-I) is preferably used.
[ Chemical formula 47]
In the above general formula (D-I), R 23 represents an optionally substituted alkyl group or an optionally substituted aromatic ring group;
R 24 represents an optionally substituted alkyl group or an optionally substituted aromatic ring group;
r 25 represents a hydroxyl group, a carboxyl group or a group represented by the following general formula (D-II), and h represents an integer of 0 to 5.
The benzene ring represented by the formula (D-I) may further have a substituent.
[ Chemical formula 48]
R25c-R25b-R25a-* (D-II)
In the formula (D-II), R 25a represents-O-, -S-; -OCO-or-COO-;
R 25b represents an alkylene group optionally having a substituent;
The alkylene portion of R 25b may be substituted by-O-, -S-, -COO-or-OCO-is interrupted 1-5 times, the alkylene portion of R 25b may have a branched side chain or may be a cycloalkylene group;
r 25c represents a hydroxyl group or a carboxyl group.
The number of carbon atoms of the alkyl group in R 23 is not particularly limited, but is preferably 1 or more from the viewpoint of solubility in a solvent, and is preferably 20 or less, more preferably 10 or less, further preferably 8 or less, further preferably 5 or less, particularly preferably 3 or less from the viewpoint of developability.
Specific examples of the alkyl group include methyl, hexyl, and cyclopentylmethyl, and among these, methyl or hexyl is preferable, and methyl is more preferable from the viewpoint of developability.
Examples of the substituent optionally contained in the alkyl group include: the aromatic ring group, hydroxyl group, carboxyl group, halogen atom, amino group, amide group, etc., are preferably hydroxyl group, carboxyl group, more preferably carboxyl group, from the viewpoint of alkali developability. In addition, from the viewpoint of ease of synthesis, it is preferably unsubstituted.
Examples of the aromatic ring group in R 23 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in a solvent, and is preferably 30 or less, more preferably 20 or less, and further preferably 12 or less from the viewpoint of developability.
Specific examples of the aromatic ring group include: phenyl, naphthyl, pyridyl, furyl, etc., among these, phenyl or naphthyl is preferred, and phenyl is more preferred from the viewpoint of developability.
Examples of the substituent optionally contained in the aromatic ring group include: hydroxyl group, carboxyl group, halogen atom, amino group, amide group, alkyl group, etc., and from the viewpoint of developability, hydroxyl group and carboxyl group are preferable, and carboxyl group is more preferable.
Among these, from the viewpoint of developability, R 23 is preferably an alkyl group optionally having a substituent, more preferably an unsubstituted alkyl group, and further preferably a methyl group.
The number of carbon atoms of the alkyl group in R 24 is not particularly limited, but is preferably 1 or more from the viewpoint of sensitivity, and is preferably 20 or less, more preferably 10 or less, further preferably 5 or less, particularly preferably 3 or less from the viewpoint of sensitivity.
Specific examples of the alkyl group include: methyl, ethyl, propyl, and the like, among which methyl or ethyl is preferred from the viewpoint of sensitivity, and methyl is more preferred.
Examples of the substituent optionally contained in the alkyl group include: halogen atoms, hydroxyl groups, carboxyl groups, amino groups, amide groups, and the like are preferable from the viewpoint of alkali developability, hydroxyl groups and carboxyl groups are more preferable, and on the other hand, unsubstituted is preferable from the viewpoint of ease of synthesis.
Examples of the aromatic ring group in R 24 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is preferably 30 or less, more preferably 12 or less, and is usually 4 or more, preferably 6 or more. When the upper limit value is not more than the lower limit value, the sensitivity tends to be high, and when the lower limit value is not less than the lower limit value, the sublimation tends to be low.
The aromatic hydrocarbon ring group may be a single ring or a condensed ring, and examples thereof include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,A group having 1 free valence such as a ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocyclic group may be a single ring or a condensed ring, and examples thereof include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring,Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisotropic ringAn azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring,A group having 1 free valence of a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, or the like.
Examples of the substituent optionally contained in the aromatic ring group include: alkyl, halogen, hydroxy, carboxyl, etc.
Among these, from the viewpoint of sensitivity, R 24 is preferably an alkyl group optionally having a substituent, more preferably an unsubstituted alkyl group, and further preferably a methyl group.
On the other hand, from the viewpoint of platemaking, R 24 is preferably an aromatic ring group optionally having a substituent, more preferably an aromatic hydrocarbon group optionally having a substituent, further preferably an unsubstituted aromatic hydrocarbon group, and particularly preferably a phenyl group.
R 25 is a hydroxyl group, a carboxyl group or a group represented by the above general formula (D-II), and among these, a group represented by the above general formula (D-II) is preferable from the viewpoints of sensitivity and developability.
In the above general formula (D-II), as described above, R 25a represents-O-, -S-; -OCO-or-COO-, among these, from the viewpoints of sensitivity and developability, preferably-O-or-OCO-, more preferably-O-.
As previously described, R 25b represents an alkylene group optionally having a substituent.
The number of carbon atoms of the alkylene group in R 25b is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 20 or less, more preferably 10 or less, more preferably 5 or less, and particularly preferably 3 or less, from the viewpoint of solubility in the photosensitive resin composition.
The alkylene group may be linear or branched, and may contain an aliphatic ring. Of these, a linear chain is preferable from the viewpoint of solubility in the photosensitive resin composition.
Specific examples of the alkylene group include: among these, ethylene, propylene, and the like are more preferable from the viewpoint of solubility in the photosensitive resin composition.
As previously described, R 25c is hydroxy or carboxy. From the viewpoint of development adhesion, R 25c is preferably a hydroxyl group.
In the above general formula (D-I), h represents an integer of 0 to 5. In particular, h is preferably 1 or more, and is preferably 4 or less, more preferably 3 or less, further preferably 2 or less, and most preferably 1 from the viewpoint of developability.
On the other hand, from the viewpoint of ease of synthesis, h is preferably 0.
As the triazine-based photopolymerization initiator, halomethylated s-triazine derivatives are exemplified, and examples thereof include: 2,4, 6-tris (monochloromethyl) s-triazine, 2,4, 6-tris (dichloromethyl) s-triazine, 2,4, 6-tris (trichloromethyl) s-triazine, 2-methyl-4, 6-bis (trichloromethyl) s-triazine, 2-n-propyl-4, 6-bis (trichloromethyl) s-triazine, 2- (. Alpha.,. Beta. -trichloroethyl) -4, 6-bis (trichloromethyl) s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (3, 4-epoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-chlorophenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- [ 1- (p-methoxyphenyl) -2, 4-butadienyl ] -4, 6-bis (trichloromethyl) s-triazine, 2-styryl-4, 6-bis (trichloromethyl) s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-chlorophenyl) -4, 6-bis (trichloromethyl) s-triazine, p-trichloromethyl) s-3, 6-bis (trichloromethyl) s-triazine, halomethylated s-triazine derivatives such as 2- (p-methoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-ethoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-ethoxycarbonylnaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2-phenylthio-4, 6-bis (trichloromethyl) s-triazine, 2,4, 6-tris (dibromomethyl) s-triazine, 2,4, 6-tris (tribromomethyl) s-triazine, 2-methyl-4, 6-bis (tribromomethyl) s-triazine, 2-methoxy-4, 6-bis (tribromomethyl) s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, and among them, bis (trihalomethyl) s-triazine are preferable from the viewpoint of sensitivity.
Examples of the acetophenone photopolymerization initiator include: 2, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 1-hydroxy-1-methylethyl (p-isopropylphenyl) ketone, 1-trichloromethyl (p-butylphenyl) ketone, α -hydroxy-2-methylphenylacetone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, ethyl 4-dimethylaminobenzoate, isoamyl 4-diethylaminoacetophenone, 4-dimethylaminophenylacetone, 2-ethylhexyl 1, 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 4- (diethylamino) chalcone, and the like.
Examples of the benzophenone photopolymerization initiator include: benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, mi ketone, and the like.
These photopolymerization initiators may be contained in the photosensitive resin composition singly or in combination of two or more. Among these photopolymerization initiators, at least one type selected from the group consisting of hexaarylbiimidazole photopolymerization initiators, oxime ester photopolymerization initiators, and acetophenone photopolymerization initiators is preferably contained. The hexaarylbiimidazole compound is particularly preferable in that it has high absorbance, high surface curability, high ink repellency, and high cone angle. In addition, oxime ester compounds are particularly preferred in that they have high sensitivity and impart ink repellency even at low exposure. In addition, acetophenone photopolymerization initiators are particularly preferred in that they have high internal curability and can provide high ink repellency and high taper angle.
The content of the photopolymerization initiator (D) in the photosensitive resin composition of the present invention is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1.5% by mass or more, particularly preferably 2% by mass or more, most preferably 2.5% by mass or more, and usually 25% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less, and particularly preferably 3% by mass or less, based on the total solid content of the photosensitive resin composition. When the lower limit value is not less than the upper limit value, there is a tendency that a coating film is formed without causing film reduction during development and sufficient ink repellency is generated, and when the upper limit value is not more than the upper limit value, a desired pattern shape tends to be easily formed. The content of the photopolymerization initiator (D) in the total solid content of the photosensitive resin composition is, for example, 0.01 to 25% by mass, preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and still more preferably 1 to 5% by mass. In one embodiment, the content is preferably 1.5 to 3% by mass, in another embodiment, 2 to 3% by mass, and in yet another embodiment, 2.5 to 5% by mass.
In the photosensitive resin composition, the mixing ratio of the (D) photopolymerization initiator to the (C) photopolymerizable compound is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, and further preferably 200 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 50 parts by mass or less, still more preferably 20 parts by mass or less, particularly preferably 10 parts by mass or less, and most preferably 5 parts by mass or less, based on 100 parts by mass of the (C) photopolymerizable compound. When the lower limit value is equal to or higher than the upper limit value, the sensitivity tends to be suitable, and when the upper limit value is equal to or lower than the upper limit value, the desired pattern shape tends to be easily formed. The mixing ratio of the photopolymerization initiator (D) to 100 parts by mass of the photopolymerizable compound (C) in the photosensitive resin composition is, for example, 1 to 200 parts by mass, preferably 1 to 100 parts by mass, more preferably 2 to 50 parts by mass, still more preferably 2 to 20 parts by mass, still more preferably 3 to 10 parts by mass, and particularly preferably 3 to 5 parts by mass.
In addition, a sensitizer may be used in combination with the photopolymerization initiator. By increasing the sensitivity by the sensitizer and reducing the transmittance into the photosensitive resin composition, the taper angle tends to be large.
As the sensitizer, a sensitizer commonly used in the art can be used. The sensitizer has a feature of transferring the energy obtained by absorption to the photopolymerization initiator or generating transfer of electrons with the photopolymerization initiator, thereby effectively promoting radical polymerization. Examples of such sensitizer include: unsaturated ketones such as chalcone derivatives and dibenzylidene acetone, 1, 2-diketones such as benzil and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, and combinations thereof xanthones, thioxanthones, coumarins, xanthenes, thioxanthones, thio coumarin compounds, cyanine compounds polymethine dye such as merocyanine compound and oxonol derivative, acridine compound, azine compound, thiazine compound, and the like,Oxazine compound, indoline compound, azulene compound and azuleneClass compound, squarylium class compound, porphyrin class compound, tetraphenylporphyrin class compound, triarylmethane class compound, tetrabenzoporphyrin class compound, tetrapyrazino tetrazaporphyrin class compound, phthalocyanine class compound, tetrazaporphyrin class compound, tetraquinoxalino tetrazaporphyrin class compound, naphthalocyanine class compound, subphthalocyanine class compound, pyran class compoundClass of compounds, thiopyransClass compound, tetraporphyrin class compound, rotaene class compound, spiropyran class compound, spiroOxazine compounds, thiospiropyran compounds, metal aromatic complexes, organic ruthenium complexes, benzophenone compounds, and the like.
These sensitizers may be used singly or in combination of two or more.
Among these, thioxanthone compounds and benzophenone compounds are preferable from the viewpoints of improving sensitivity and increasing cone angle.
Examples of thioxanthones include: thioxanthone, 2-methyl thioxanthone, 4-methyl thioxanthone, 2, 4-dimethyl thioxanthone, 2-ethyl thioxanthone, 4-ethyl thioxanthone, 2, 4-diethyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4-diisopropyl thioxanthone, 2-chloro thioxanthone, 4-chloro thioxanthone, 2, 4-dichloro thioxanthone and the like. Among these compounds, 2, 4-diethylthioxanthone is preferable from the viewpoints of improving sensitivity and increasing cone angle.
Examples of the benzophenone compound include: benzophenone, 4' -bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4' -bis (ethylmethylamino) benzophenone, and the like. Among these compounds, 4' -bis (diethylamino) benzophenone is preferable from the viewpoints of improvement of sensitivity and increase of cone angle.
When the photosensitive resin composition contains a sensitizer, the content of the sensitizer in the photosensitive resin composition is usually 0.1 mass% or more, preferably 0.3 mass% or more, more preferably 0.5 mass% or more, still more preferably 0.8 mass% or more, still more preferably 1 mass% or more, particularly preferably 1.2 mass% or more, and further is usually 10 mass% or less, preferably 7 mass% or less, still more preferably 5 mass% or less, and still more preferably 3 mass% or less, based on the total solid content of the photosensitive resin composition. When the lower limit value is not less than the upper limit value, the sensitivity and the taper angle tend to be improved, and when the upper limit value is not more than the upper limit value, a desired pattern tends to be formed easily. When the photosensitive resin composition contains a sensitizer, the content of the sensitizer in the total solid content of the photosensitive resin composition is, for example, 0.1 to 10% by mass, preferably 0.3 to 10% by mass, more preferably 0.5 to 7% by mass, still more preferably 0.8 to 7% by mass, still more preferably 1 to 5% by mass, and particularly preferably 1.2 to 3% by mass.
[1-1-5] (E) chain transfer agent
The photosensitive resin composition of the present invention contains (E) a chain transfer agent. By containing the chain transfer agent, radical deactivation in the vicinity of the surface due to oxygen inhibition or the like is improved, and the surface curability is improved, so that the taper angle tends to be large. Further, by improving the surface curability, outflow of the liquid repellent can be suppressed, and the liquid repellent tends to be easily fixed near the surface of the partition wall, and the contact angle tends to be high.
Examples of the chain transfer agent include mercapto compounds and carbon tetrachloride, and the use of mercapto compounds is more preferable because of the tendency of high chain transfer effect. The thiol-group-containing compound tends to have a low S-H bond energy, which leads to easy bond cleavage and easy chain transfer reaction, and thus can improve surface curability.
Among the chain transfer agents, a mercapto compound having an aromatic ring and an aliphatic mercapto compound are preferable from the viewpoints of taper angle and surface curability.
As the mercapto group-containing compound having an aromatic ring, a compound represented by the following general formula (E-1) is preferably used from the viewpoint of the taper angle.
[ Chemical formula 49]
In the formula (E-1), the amino acid sequence, Z represents-O- -S-or-NH-, R 61、R62、R63 and R 64 each independently represent a hydrogen atom or a 1-valent substituent.
Of these, from the viewpoint of the taper angle, Z is preferably-S-or-NH-; more preferably-NH-.
From the viewpoint of the taper angle, R 61、R62、R63 and R 64 are each independently preferably a hydrogen atom, a C1-4 alkyl group, or a C1-4 alkoxy group, and more preferably a hydrogen atom.
Specific examples thereof include: 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazoleMercapto compounds having an aromatic ring such as oxazole, 3-mercapto-1, 2, 4-triazole, 2-mercapto-4 (3H) -quinazoline, β -mercapto naphthalene, 1, 4-dimethylmercapto benzene and the like are preferably 2-mercaptobenzothiazole or 2-mercaptobenzimidazole from the viewpoint of taper angle.
On the other hand, as the aliphatic thiol-group-containing compound, from the viewpoint of surface curability, hexanedithiol, decanedithiol, or a compound represented by the following general formula (E-2) can be preferably used.
[ Chemical formula 50]
In the formula (E-2), m represents an integer of 0 to 4, n represents an integer of 2 to 4, R 71 and R 72 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents an n-valent group.
In the above general formula (E-2), m is preferably 1 or 2 from the viewpoint of ease of synthesis. From the viewpoint of surface curability, n is preferably 3 or 4.
The alkyl groups of R 71 and R 72 are preferably alkyl groups having 1 to 3 carbon atoms from the viewpoint of surface curability. From the viewpoint of surface curability, at least one of R 71 and R 72, for example, R 72 is preferably a hydrogen atom, and in this case, R 71 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
When n is 2, X is preferably an alkylene group having 1 to 6 carbon atoms which optionally has an ether bond and/or a branching portion, from the viewpoint of surface curability. Among them, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 4 carbon atoms is further preferable from the viewpoints of surface curability and ease of synthesis.
When n is 3, X is preferably a structure represented by the following general formula (E-2-1) or (E-2-2) from the viewpoints of surface curability and ease of synthesis.
[ Chemical formula 51]
In the formula (E-2-1), R 73 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxymethyl group. In R 73, ethyl is preferable from the viewpoint of taper angle.
[ Chemical formula 52]
In the formula (E-2-2), R 74 represents an alkylene group having 1 to 4 carbon atoms. In R 74, ethylene is preferable from the viewpoint of taper angle.
On the other hand, when n is 4, X is preferably a structure represented by the following general formula (E-2-3).
[ Chemical formula 53]
Specific examples thereof include: butanediol bis (3-mercaptopropionate), butanediol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (mercaptoacetate), trishydroxyethyl tris (mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butanediol bis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, and the like.
Among them, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione are preferable, and pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are more preferable.
Of these, one of the various compounds may be used alone, or two or more of them may be used in combination.
Among these, from the viewpoint of improving ink repellency, it is preferable to select from 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoOne or more kinds of azoles are used in combination with a photopolymerization initiator as a photopolymerization initiator system. For example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and a combination of 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used.
From the viewpoint of surface curability, one or more selected from pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are preferably used.
The content of the chain transfer agent in the photosensitive resin composition of the present invention is usually 0.01% by mass or more, preferably 0.025% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, particularly preferably 1% by mass or more, and usually 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less, based on the total solid content of the photosensitive resin composition. When the ratio is equal to or higher than the lower limit, the taper angle tends to be high, the surface curability tends to be high, and the ink repellency tends to be high, and when the ratio is equal to or lower than the upper limit, a desired pattern tends to be easily formed. The content of the chain transfer agent in the total solid content of the photosensitive resin composition is, for example, 0.01 to 5% by mass, preferably 0.025 to 4% by mass, more preferably 0.05 to 4% by mass, still more preferably 0.1 to 3% by mass, and still more preferably 1 to 3% by mass.
In addition, when the mercapto compound having an aromatic ring and the aliphatic mercapto compound are used as the chain transfer agent in combination, the content of the mercapto compound having an aliphatic ring is usually 10 parts by mass or more, preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and is usually 400 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, still more preferably 150 parts by mass or less, based on 100 parts by mass of the mercapto compound having an aromatic ring. When the ink repellency is higher than the lower limit, the sensitivity tends to be higher than the upper limit. When a mercapto compound having an aromatic ring and an aliphatic mercapto compound are used as a chain transfer agent in combination, the content thereof is, for example, 10 to 400 parts by mass, preferably 50 to 300 parts by mass, more preferably 80 to 200 parts by mass, and even more preferably 80 to 150 parts by mass, relative to 100 parts by mass of the mercapto compound having an aromatic ring.
The mixing ratio of the chain transfer agent to the photopolymerization initiator (D) in the photosensitive resin composition is preferably 10 parts by mass or more, more preferably 25 parts by mass or more, still more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, and further preferably 500 parts by mass or less, more preferably 400 parts by mass or less, still more preferably 300 parts by mass or less, still more preferably 200 parts by mass or less, particularly preferably 150 parts by mass or less, based on 100 parts by mass of the photopolymerization initiator (D). When the ratio is equal to or higher than the lower limit, the taper angle tends to be high, the surface curability tends to be high, and the ink repellency tends to be high, and when the ratio is equal to or lower than the upper limit, a desired pattern tends to be easily formed. The mixing ratio of the chain transfer agent to 100 parts by mass of the photopolymerization initiator (D) in the photosensitive resin composition is, for example, 10 to 500 parts by mass, preferably 25 to 400 parts by mass, more preferably 50 to 300 parts by mass, still more preferably 80 to 200 parts by mass, and still more preferably 80 to 150 parts by mass.
[1-1-6] Ultraviolet absorber
The photosensitive resin composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is added for the following purposes: the light curing distribution is controlled by absorbing a specific wavelength of a light source for exposure with an ultraviolet absorber. By adding the ultraviolet absorber, effects such as improving the taper angle shape after development, and eliminating residues remaining in the non-exposed portion after development can be obtained. As the ultraviolet absorber, a compound having a maximum absorption at a wavelength of 250nm to 400nm, for example, can be used from the viewpoint of blocking light absorption of the photopolymerization initiator.
Examples of the ultraviolet absorber include: benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthyl compounds, phenanthroline compounds, dyes, etc.
These ultraviolet absorbers may be used singly or in combination of two or more.
Among these, benzotriazole compounds and/or hydroxyphenyl triazine compounds are preferable from the viewpoint of increasing the taper angle, and benzotriazole compounds are particularly preferable.
Among the benzotriazole-based compounds, benzotriazole compounds represented by the following general formula (Z1) are preferable from the viewpoint of taper shape.
[ Chemical formula 54]
In the above formula (Z1), R 1e and R 2e each independently represent a hydrogen atom, an alkyl group optionally having a substituent, a group represented by the following general formula (Z2), or a group represented by the following general formula (Z3). R 3e represents a hydrogen atom or a halogen atom.
[ Chemical formula 55]
In the above formula (Z2), R 4e represents an alkylene group optionally having a substituent, and R 5e represents an alkyl group optionally having a substituent.
[ Chemical formula 56]
In the above formula (Z3), R 6e represents an alkylene group optionally having a substituent, and R 7e represents a hydrogen atom or a methyl group.
(R 1e and R 2e)
In the above formula (Z1), R 1e and R 2e each independently represent a hydrogen atom, an alkyl group optionally having a substituent, a group represented by the general formula (Z2), or a group represented by the general formula (Z3).
Examples of the alkyl group include a linear, branched or cyclic alkyl group. The number of carbon atoms is preferably 1 or more, more preferably 2 or more, still more preferably 4 or more, and further preferably 10 or less, more preferably 6 or less, still more preferably 4 or less.
Specific examples of the alkyl group include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like. Of these alkyl groups, tert-butyl is preferred.
Examples of the substituent optionally included in the alkyl group include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryl, methacryl, and the like.
(R3e)
In the above formula (Z1), R 3e represents a hydrogen atom or a halogen atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Among these, from the viewpoint of synthesis, R 3e is preferably a hydrogen atom.
(R4e)
In the above formula (Z2), R 4e represents an alkylene group optionally having a substituent.
Examples of the alkylene group include linear, branched or cyclic alkylene groups. The number of carbon atoms is usually 1 or more, preferably 2 or more, and further preferably 6 or less, more preferably 4 or less, and further preferably 3 or less.
Specific examples of the alkylene group include: methylene, ethylene, propylene, butylene, and the like. Of these, ethylene is preferable.
Further, as the substituent optionally contained in the alkylene group, there may be mentioned: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryl, methacryl, and the like.
Of these, R 4e is preferably ethylene.
(R5e)
In the above formula (Z2), R 5e represents an optionally substituted alkyl group.
Examples of the alkyl group include a linear, branched or cyclic alkyl group. The number of carbon atoms is preferably 4 or more, more preferably 5 or more, still more preferably 7 or more, and further preferably 15 or less, more preferably 10 or less, still more preferably 9 or less.
Specific examples of the alkyl group include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and the like.
Examples of the substituent optionally included in the alkyl group include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryl, methacryl, and the like.
Among these, R 5e is preferably heptyl, octyl or nonyl from the viewpoint of taper.
(R6e)
In the above formula (Z3), R 6e represents an alkylene group optionally having a substituent.
Examples of the alkylene group include linear, branched or cyclic alkylene groups. The number of carbon atoms is usually 1 or more, preferably 2 or more, and further preferably 6 or less, more preferably 4 or less, and further preferably 3 or less.
Specific examples of the alkylene group include: methylene, ethylene, propylene, butylene, and the like. Of these, ethylene is preferable.
Further, as the substituent optionally contained in the alkylene group, there may be mentioned: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryl, methacryl, and the like.
Among these, from the viewpoint of taper, a compound in which R 1e is a tert-butyl group, R 2e is a group represented by the above formula (Z2) (wherein R 4e is an ethylene group, R 5e is an alkyl group having 7 to 9 carbon atoms), R 3e is a hydrogen atom, or a compound in which R 1e is a hydrogen atom, R 2e is a group represented by the above formula (Z3) (wherein R 6e is an ethylene group, and R 7e is a methyl group), R 3e is a hydrogen atom is preferable, and a compound in which R 1e is a tert-butyl group, R 2e is a group represented by the above formula (Z2) (wherein R 4e is an ethylene group, and R 5e is an alkyl group having 7 to 9 carbon atoms), and R 3e is a hydrogen atom is more preferable.
Specific examples of the benzotriazole-based compounds include: 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate in combination with 2-ethylhexyl-3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate, 2- [ 2-hydroxy-3, 5-bis (. Alpha.,. Alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, phenylpropionic acid, 3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxy, C7-alkyl-9-side-esters, linear 2H-benzotriazol, 2- (3, 5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-octyl-2-phenyl) benzotriazole, 2- (2-hydroxy-3-hydroxy-phenyl) benzotriazole, and linear chain esters thereof, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1, 3-tetramethylbutyl) phenol. Among these, 3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester compounds are preferred from the viewpoints of taper angle and exposure sensitivity.
Examples of commercially available benzotriazole compounds include: SUMISORB (registered trademark, the same applies hereinafter) 200, SUMISORB, SUMISORB, SUMISORB, SUMISORB (manufactured by Sumitomo Chemical Co., ltd.), JF77, JF78, JF79, JF80, JF83 (manufactured by North Chemical Co., ltd.), TINUVIN (registered trademark, the same applies hereinafter) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN 326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF Corporation )、EVERSORB70、EVERSORB71、EVERSORB72、EVERSORB73、EVERSORB74、EVERSORB75、EVERSORB76、EVERSORB234、EVERSORB77、EVERSORB78、EVERSORB80、EVERSORB81(, the same applies hereinafter) 100, tomisorb (manufactured by API Corporation), SEESORB (registered trademark, the same applies hereinafter) 701, SEESORB, 702, 703, SEESORB, SEESORB706, SEESORB707, SEESORB (manufactured by Chemical Co., ltd.), RUVA-93 (Otsuka), etc.
As the triazine compound, there can be mentioned: 2- [4, 6-bis (2, 4-xylyl) -1,3, 5-triazin-2-yl ] -5-octyloxyphenol, 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl ] -5- [3- (dodecyloxy) -2-hydroxypropoxy ] phenol, the reaction product of 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine with glycidic acid (2-ethylhexyl) ester, 2, 4-bis [ 2-hydroxy-4-butoxyphenyl ] -6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine, and the like. Among these, the hydroxyphenyl triazine compound is preferable from the viewpoints of taper angle and exposure sensitivity.
Examples of the commercially available triazine compound include: TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479 (manufactured by BASF corporation), and the like.
Examples of the other ultraviolet absorbers include: SUMISORB 130 (manufactured by Sumitomo chemical Co., ltd.), EVERSORB10, EVERSORB, EVERSORB (manufactured by Taiwan Yongchuang chemical Co., ltd.), tomisorb 800 (manufactured by API Corporation, manufactured by )、SEESORB100、SEESORB101、SEESORB101S、SEESORB102、SEESORB103、SEESORB105、SEESORB106、SEESORB107、SEESORB151(SHIPRO KASEI), and the like; SUMISORB 400 (manufactured by Sumitomo chemical Co., ltd.), phenyl salicylate, and other benzoate compounds; cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethylhexyl p-methoxycinnamate, isopropyl methoxycinnamate, and isoamyl methoxycinnamate; naphthalene derivatives such as α -naphthol, β -naphthol, α -naphthol methyl ether, α -naphthol ethyl ether, 1, 2-dihydroxynaphthalene, 1, 3-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, and 2, 7-dihydroxynaphthalene; anthracene such as anthracene and 9, 10-dihydroxyanthracene, and derivatives thereof; azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, para-aminobenzoic acid dyes, and the like; etc. Among these, from the viewpoint of exposure sensitivity, cinnamic acid derivatives and naphthalene derivatives are preferably used, and cinnamic acid derivatives are particularly preferably used.
When the ultraviolet absorber is contained in the photosensitive resin composition of the present invention, the content of the ultraviolet absorber in the photosensitive resin composition is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and is usually 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, based on the total solid content. When the lower limit value is equal to or higher than the upper limit value, the taper angle tends to be increased, and when the upper limit value is equal to or lower than the upper limit value, the sensitivity tends to be high. When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber in the total solid content of the photosensitive resin composition is, for example, 0.01 to 15% by mass, preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, still more preferably 0.5 to 3% by mass, and still more preferably 1 to 3% by mass.
In the case where the photosensitive resin composition of the present invention contains an ultraviolet absorber, the amount of the ultraviolet absorber to be blended with respect to 100 parts by mass of the photopolymerization initiator (D) is usually 1 part by mass or more, preferably 10 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, and usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and still more preferably 150 parts by mass or less. When the lower limit value is equal to or higher than the upper limit value, the taper angle tends to be increased, and when the upper limit value is equal to or lower than the upper limit value, the sensitivity tends to be high. When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the mixing ratio of the ultraviolet absorber to 100 parts by mass of the photopolymerization initiator (D) is, for example, 1 to 500 parts by mass, preferably 10 to 300 parts by mass, more preferably 30 to 200 parts by mass, still more preferably 50 to 150 parts by mass, and still more preferably 80 to 150 parts by mass.
[1-1-7] Polymerization inhibitor
The photosensitive resin composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, it is considered that the taper angle of the resulting partition wall can be increased because it inhibits radical polymerization.
Examples of the polymerization inhibitor include: hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, 2, 6-di-tert-butyl-4-methylphenol (BHT), and the like. Among these polymerization inhibitors, methyl hydroquinone or methoxyphenol is preferable, and methyl hydroquinone is more preferable from the viewpoint of polymerization inhibition ability.
The polymerization inhibitor preferably contains one or two or more kinds. In general, in the production of the alkali-soluble resin (B), a polymerization inhibitor may be contained in the resin, and the resin may be used as the polymerization inhibitor of the present invention, or in addition to the polymerization inhibitor in the resin, the same or different polymerization inhibitor may be added in the production of the photosensitive resin composition.
When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor in the photosensitive resin composition is usually 0.0005 mass% or more, preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and is usually 0.3 mass% or less, preferably 0.2 mass% or less, more preferably 0.1 mass% or less, based on the total solid content of the photosensitive resin composition. When the lower limit value is equal to or higher than the upper limit value, the taper angle tends to be increased, and when the upper limit value is equal to or lower than the lower limit value, the sensitivity tends to be maintained. When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor in the total solid content of the photosensitive resin composition is, for example, 0.0005 to 0.3 mass%, preferably 0.001 to 0.2 mass%, and more preferably 0.01 to 0.1 mass%.
[1-1-8] Amino compounds
The photosensitive resin composition of the present invention may contain an amino compound in order to promote thermosetting.
When the photosensitive resin composition of the present invention contains an amino compound, the content of the amino compound in the photosensitive resin composition is usually 40 mass% or less, preferably 30 mass% or less, and is usually 0.5 mass% or more, preferably 1 mass% or more, based on the total solid content of the photosensitive resin composition. When the upper limit value is not more than the lower limit value, the storage stability tends to be maintained, and when the lower limit value is not less than the upper limit value, sufficient thermosetting properties tend to be ensured. When the photosensitive resin composition of the present invention contains an amino compound, the content of the amino compound in the total solid content in the photosensitive resin composition is, for example, 0.5 to 40% by mass, preferably 1 to 30% by mass.
Examples of the amino compound include: an amino compound having, as a functional group, at least 2 of hydroxymethyl groups and alkoxymethyl groups obtained by subjecting hydroxymethyl groups to alcohol condensation modification of 1 to 8 carbon atoms. Specific examples include: a melamine resin obtained by polycondensing melamine with formaldehyde; benzoguanamine resin obtained by polycondensing benzoguanamine with formaldehyde; a glycoluril resin obtained by polycondensing glycoluril with formaldehyde; urea resin obtained by polycondensing urea with formaldehyde; a resin obtained by copolycondensation of formaldehyde with two or more kinds of melamine, benzoguanamine, glycoluril, urea, and the like; and modified resins obtained by alcohol condensation modification of the methylol groups of the above resins. These amino compounds may be used singly or in combination of two or more. Among these amino compounds, melamine resins and modified resins thereof are preferable, and modified resins having a hydroxymethyl group modification ratio of 70% or more are more preferable, and modified resins having 80% or more are particularly preferable.
Specific examples of the amino compound include melamine resins and modified resins thereof, for example: examples of the benzoguanamine resin and modified resins thereof include Cymel 1123, 1125, 1128, etc. manufactured by SaiTech, and examples of the glycoluril resin and modified resins thereof include Cymel 1170, 1171, 1174, 1172, nicarac MX-270, etc. manufactured by SaiTech, and examples of the urea resin and modified resins thereof include "UFR" (registered trademark, the same shall apply hereinafter) 65, 300, and Nicarac MX-290, etc. manufactured by SaiTech, etc. manufactured by SANWA CHEMICAL.
[1-1-9] Colorant
The photosensitive resin composition of the present invention may contain a colorant for the purpose of coloring the partition wall. As the colorant, known colorants such as pigments and dyes can be used. In addition, for example, when a pigment is used, a known dispersant or dispersion aid may be used in combination so that the pigment can be stably present in the photosensitive resin composition without aggregation or the like. In particular, coloring the ink-repellent partition wall black has an effect of enabling clear pixel display. As the black colorant, in addition to a black dye or a black pigment, carbon black, titanium black, or the like, mixing an organic pigment to color to black is also effective in obtaining an effect of low conductivity. The content of the colorant is usually 60 mass% or less, preferably 40 mass% or less, based on the total solid content of the photosensitive resin composition, from the viewpoints of platemaking and color properties.
On the other hand, in the case of reducing the degassing from the partition wall, it is preferable to make the partition wall transparent, and in this case, the content of the colorant is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 0% by mass relative to the total solid content of the photosensitive resin composition.
[1-1-10] Coatability improving agent and development improving agent
The photosensitive resin composition of the present invention may contain a coating property improving agent and a development improving agent in order to improve the coating property and development solubility. As the coating property improving agent or the development improving agent, for example, known cationic, anionic, nonionic, fluorine-based, silicone-based surfactants can be used. The surfactant may be used for the purpose of improving the coatability of the coating liquid as the photosensitive resin composition, the developability of the coating film, and the like, and among them, a fluorine-based or silicone-based surfactant is preferable.
In particular, since the composition has a function of removing residues of the photosensitive resin composition from the unexposed portions during development and has a function of exhibiting wettability, the composition is preferably a silicone surfactant, and more preferably a polyether-modified silicone surfactant.
The fluorine-based surfactant is preferably a compound having a fluoroalkyl group or a fluoroalkylene group at least at any one of the terminal, main chain and side chain. Specific examples thereof include: 1, 2-tetrafluorooctyl (1, 2-tetrafluoropropyl) ether 1, 2-tetrafluorooctyl hexyl ether octaethylene glycol di (1, 2-tetrafluorobutyl) ether, hexaethylene glycol di (1, 2, 3-hexafluoropentyl) ether octapropylene glycol bis (1, 2-tetrafluorobutyl) ether, hexapropylene glycol bis (1, 2, 3-hexafluoropentyl) ether sodium perfluorododecyl sulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,2, 3-hexafluorodecane, etc. Examples of the commercial products include: "BM-1000", "BM-1100", made by BM Chemie, made by DIC, made by Megafac F "," Megafac F475", made by 3M Japan, made by FC430", made by Neos, made by DFX-18", etc.
In addition, as the organosilicon surfactant, examples include: commercial products such as "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Additive", "SH8400", and "BYK (registered trademark, the same shall apply hereinafter)" 323 "and" BYK330 "manufactured by Dow Corning Toray.
The surfactant may contain a surfactant other than a fluorine-based surfactant and a silicone-based surfactant, and examples of the other surfactant include nonionic, anionic, cationic, and amphoteric surfactants.
Examples of the nonionic surfactant include: polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, and the like. Examples of the commercial products include: polyoxyethylene surfactants such as "EMULGEN 104P" and "EMULGEN A60" manufactured by Kao corporation.
In addition, as the above anionic surfactant, examples include: alkyl sulfonates, alkylbenzenesulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, higher alcohol sulfates, fatty alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, specialty polymeric surfactants, and the like. Among them, a specific polymer surfactant is preferable, and a specific polycarboxylic acid type polymer surfactant is more preferable. As such anionic surfactants, commercially available ones can be used, and examples thereof include "Emal (registered trademark) 10" made by Kao corporation, etc., alkyl naphthalene sulfonates such as "Perex (registered trademark) NB-L" made by Kao corporation, and specific polymer surfactants such as "Homogenol (registered trademark, the same applies hereinafter), L-18", "Homogenol L-100" made by Kao corporation.
Further, examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, alkylamine salts, and the like, and examples of the amphoteric surfactant include betaine compounds and imidazolesSalts, imidazolines, amino acids, and the like. Of these, quaternary ammonium salts are preferable, and stearyl trimethylammonium salts are more preferable. As the commercially available product, for example, alkylamine salts may be mentioned "Acetamin (registered trademark) 24" manufactured by Kao corporation, and quaternary ammonium salts may be mentioned "KOTAMIN (registered trademark, the same applies hereinafter) 24P", "KOTAMIN W" manufactured by Kao corporation, and the like.
The surfactant may be used in combination of two or more kinds, and examples thereof include: and combinations of silicone surfactants/fluorine surfactants, silicone surfactants/specific polymer surfactants, fluorine surfactants/specific polymer surfactants, and the like. Among them, a combination of a silicone surfactant and a fluorine surfactant is preferable. The combination of the silicone surfactant and the fluorine surfactant includes, for example: "DFX-18" by Neos, "BYK-300" by BYK Chemie, or "S-393" by BYK-330"/AGC SEIMI CHEMICAL, or" KP340 "/F-478" by Shin-Etsu Silicone, or "F-475" by DIC, or "SH7PA"/Daikin corporation "DS-401" by Dow Corning Toray, or "L-77"/FC 4430 "by NUC, etc.
As the development improving agent, a known development improving agent such as an organic carboxylic acid or an acid anhydride thereof may be used.
In the case where the photosensitive resin composition of the present invention contains the coating upward agent and the development improving agent, the content ratio of the coating upward agent and the development improving agent is usually 20% by mass or less, preferably 10% by mass or less, respectively, of the total solid components of the photosensitive resin composition from the viewpoint of sensitivity.
[1-1-11] Silane coupling agent
In order to improve adhesion to a substrate, a silane coupling agent is preferably added to the photosensitive resin composition of the present invention. As the type of the silane coupling agent, various silane coupling agents such as epoxy, methacrylic, amino, imidazole and the like can be used, and epoxy and imidazole silane coupling agents are particularly preferable from the viewpoint of improving adhesion.
When the photosensitive resin composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is usually 20 mass% or less, preferably 15 mass% or less, of the total solid components of the photosensitive resin composition from the viewpoint of adhesion.
[1-1-12] Phosphoric acid-based adhesion improving agent
In order to improve adhesion to a substrate, a phosphoric acid-based adhesion improving agent is preferably added to the photosensitive resin composition of the present invention. The phosphoric acid adhesion improving agent is preferably a phosphoric acid ester containing a (meth) acryloyloxy group, and among these, phosphoric acid adhesion improving agents represented by the following general formulae (Va), (Vb) and (Vc) are preferable.
[ Chemical formula 57]
In the general formulae (Va), (Vb) and (Vc), R 8 represents a hydrogen atom or a methyl group, R and R' are integers of 1 to 10, and s is 1,2 or 3.
When the photosensitive resin composition of the present invention contains the phosphoric acid-based adhesion improving agent, the content thereof is not particularly limited, but is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, still more preferably 0.5 mass% or more, and further preferably 5 mass% or less, more preferably 3 mass% or less, still more preferably 1 mass% or less, of the total solid content. When the lower limit value is not less than the upper limit value, adhesion to the substrate tends to be improved, and when the upper limit value is not more than the upper limit value, surface curability tends to be improved. When the photosensitive resin composition of the present invention contains the phosphoric acid-based adhesion improving agent, the content of the phosphoric acid-based adhesion improving agent in the total solid content is, for example, 0.1 to 5% by mass, preferably 0.3 to 3% by mass, and more preferably 0.5 to 1% by mass.
[1-1-13] Inorganic filler
In order to improve the strength of the cured product and to improve the excellent flatness and taper angle of the coating film due to appropriate interaction with the alkali-soluble resin (formation of matrix structure), the photosensitive resin composition of the present invention may further contain an inorganic filler. Examples of such inorganic fillers include: talc, silica, alumina, barium sulfate, magnesium oxide, or a substance obtained by subjecting them to surface treatment with various silane coupling agents.
The average particle diameter of these inorganic fillers is usually 0.005 to 20. Mu.m, preferably 0.01 to 10. Mu.m. The average particle diameter in this embodiment is a value measured by a laser diffraction/scattering particle size distribution measuring apparatus manufactured by Beckman Coulter, or the like. Among these inorganic fillers, silica sol and silica sol modified products in particular tend to have excellent dispersion stability and excellent cone angle improving effect, and therefore, blending is preferable.
When the photosensitive resin composition of the present invention contains an inorganic filler, the content thereof is usually 5 mass% or more, preferably 10 mass% or more, and usually 80 mass% or less, preferably 70 mass% or less, of the total solid content from the viewpoint of sensitivity. When the photosensitive resin composition of the present invention contains an inorganic filler, the content of the inorganic filler in the entire solid content is, for example, 5 to 80% by mass, preferably 10 to 70% by mass.
[1-1-14] Solvent
The photosensitive resin composition of the present invention generally contains a solvent, and can be used in a state where the aforementioned components are dissolved or dispersed in the solvent (hereinafter, the photosensitive resin composition containing the solvent is also referred to as a "photosensitive resin composition solution"). The solvent is not particularly limited, and examples thereof include the organic solvents described below.
Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxypentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether; glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-1-butyl acetate and other glycol alkyl ether acetates; Glycol diacetates such as ethylene glycol diacetate, 1, 3-butanediol diacetate and 1, 6-hexanediol diacetate; alkyl acetates such as cyclohexanol acetate; ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethylisobutyl ether, and dihexyl ether; ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone; monohydric or polyhydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol; Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexyl; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; chain or cyclic esters such as amyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and gamma-butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxy methyl pentanone; nitriles such as acetonitrile and benzonitrile; tetrahydrofuran such as tetrahydrofuran, dimethyltetrahydrofuran and dimethoxytetrahydrofuran, and the like.
The commercial solvents corresponding to the above are: MINERAL SPIRIT, valsol #2, apco #18Solvent, apco Thinner, socal Solvent No.1 and No.2, solvesso #150, shell TS Solvent 28, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names), and the like.
The solvent is a solvent capable of dissolving or dispersing the components in the photosensitive resin composition, and may be selected according to the method of using the photosensitive resin composition of the present invention, but from the viewpoint of coatability, it is preferable to select a solvent having a boiling point in the range of 60 to 280 ℃ at atmospheric pressure (1013.25 hPa). More preferably a solvent having a boiling point of 70 to 260 ℃, preferably for example: propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate.
These solvents may be used singly or in combination of two or more. The solvent is preferably used so that the content of all solid components in the photosensitive resin composition is usually 10% by mass or more, preferably 15% by mass or more, more preferably 18% by mass or more, and usually 90% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. When the lower limit value is not less than the upper limit value, a coating film tends to be obtained even at a high film thickness, and when the upper limit value is not more than the upper limit value, a proper coating uniformity tends to be obtained. For example, the solvent may be used so that the content of the total solid content in the photosensitive resin composition is 10 to 90% by mass, preferably 10 to 50% by mass, more preferably 15 to 40% by mass, and still more preferably 18 to 30% by mass.
[1-2] Physical Properties of photosensitive resin composition
The physical properties of the photosensitive resin composition of the present invention include, for example, an acid value.
The acid value of the photosensitive resin composition is not particularly limited, but is preferably 20mg to KOH/g, more preferably 22mg to KOH/g, still more preferably 24mg to KOH/g, still more preferably 26mg to KOH/g, particularly preferably 28mg to KOH/g, and is usually 60mg to KOH/g, preferably 55mg to KOH/g, still more preferably 50mg to KOH/g, still more preferably 40mg to KOH/g, particularly preferably 35mg to KOH/g. When the ratio is equal to or higher than the lower limit, the solubility in the developer is high, and the unexposed portion can be sufficiently dissolved and removed, so that the taper angle tends to be large, and when the ratio is equal to or lower than the upper limit, the development adhesion tends to be good. The acid value of the photosensitive resin composition is, for example, 20 to 60mg-KOH/g, preferably 22 to 55mg-KOH/g, more preferably 24 to 50mg-KOH/g, still more preferably 26 to 40mg-KOH/g, and still more preferably 28 to 35mg-KOH/g, relative to the total solid content of the photosensitive resin composition.
[1-3] Process for producing photosensitive resin composition
The photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned components by a stirrer. The photosensitive resin composition may be filtered using a membrane filter or the like in order to homogenize the prepared photosensitive resin composition.
[2] Partition wall and method for forming partition wall
The photosensitive resin composition of the present invention can be used for forming a partition wall, particularly a partition wall for dividing an organic layer (light-emitting section) of an organic electroluminescent element. The partition wall of the present invention is formed of the photosensitive resin composition of the present invention.
The method for forming the partition wall using the photosensitive resin composition described above is not particularly limited, and a conventionally known method can be employed. Examples of the method for forming the partition wall include a coating step of forming a photosensitive resin composition layer by coating the photosensitive resin composition on a substrate, and an exposure step of exposing the photosensitive resin composition layer to light. Specific examples of such a method for forming the barrier rib include photolithography.
In the photolithography method, a photosensitive resin composition layer is formed by applying the photosensitive resin composition to the entire surface of a region of a substrate where a partition wall is to be formed. After exposing the formed photosensitive resin composition layer to light corresponding to the pattern of the given partition wall, the exposed photosensitive resin composition layer is developed to form the partition wall on the substrate.
In the coating step of coating a substrate with a photosensitive resin composition in photolithography, a photosensitive resin composition layer is formed by applying the photosensitive resin composition on a substrate on which a partition wall is to be formed using a contact transfer type coating apparatus such as a roll coater, a reverse coater, a bar coater, or a non-contact type coating apparatus such as a spin coater (spin coater) or a curtain coater, and drying the composition as necessary to remove a solvent.
Next, in the exposure step, the photosensitive resin composition is irradiated with active energy rays such as ultraviolet rays and excimer lasers using a negative mask, so that the photosensitive resin composition layer is partially exposed in accordance with the pattern of the partition wall. As the exposure, a light source emitting ultraviolet rays such as a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc lamp, or the like can be used. The exposure amount also varies depending on the composition of the photosensitive resin composition, but is preferably, for example, about 10 to 400mJ/cm 2.
Next, in the developing step, the exposed photosensitive resin composition layer corresponding to the pattern of the partition wall is developed in a developing solution to form the partition wall. The developing method is not particularly limited, and dipping method, spraying method, and the like can be used. Specific examples of the developer include: organic developer such as dimethylbenzylamine, monoethanolamine, diethanolamine and triethanolamine, or aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salt. In addition, a defoaming agent and a surfactant may be added to the developer.
Thereafter, the developed spacers are subjected to post baking to be heat-cured. The post-baking is preferably carried out at 150 to 250℃for 15 to 60 minutes.
After forming the barrier ribs, a cleaning process for cleaning the unexposed portions may be performed. The cleaning method is not particularly limited, and plasma irradiation, excimer light irradiation, and UV irradiation may be mentioned. In the excimer light irradiation and the UV light irradiation, the active oxygen can decompose and remove the organic substances attached to the pixel portion by the light irradiation.
The substrate used for forming the barrier ribs is not particularly limited, and may be appropriately selected according to the type of organic electroluminescent element to be manufactured using the substrate on which the barrier ribs are formed. Preferred substrate materials include glass and various resin materials. Specific examples of the resin material include: polyesters such as polyethylene terephthalate; polyolefin such as polyethylene and polypropylene; a polycarbonate; a poly (meth) acrylic resin; polysulfone; polyimide. Among these substrate materials, glass and polyimide are preferable because they are excellent in heat resistance. In addition, a transparent electrode layer such as ITO or ZnO may be provided in advance on the surface of the substrate on which the barrier ribs are to be formed, depending on the type of the organic electroluminescent element to be manufactured.
[3] Organic electroluminescent device
The organic electroluminescent element of the present invention is provided with the partition wall of the present invention.
Various organic electroluminescent elements can be manufactured using the substrate provided with the partition wall pattern manufactured by the method described above. The method of forming the organic electroluminescent element is not particularly limited, but it is preferable to manufacture the organic electroluminescent element by forming an organic layer such as a pixel by injecting ink into a region surrounded by the barrier ribs on the substrate after forming the pattern of the barrier ribs on the substrate by the above method.
The type of the organic electroluminescent element includes a bottom emission type and a top emission type.
In the bottom emission type, for example, a partition wall is formed on a glass substrate on which a transparent electrode is laminated, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated on an opening surrounded by the partition wall. On the other hand, in the top emission type, for example, a spacer is formed on a glass substrate on which a metal electrode layer is laminated, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are laminated on an opening surrounded by the spacer.
The light-emitting layer may be an organic electroluminescent layer as described in japanese patent application laid-open No. 2009-146691 and japanese patent No. 5734681. Further, quantum dots as described in japanese patent No. 5653387 and japanese patent No. 5653101 may be used.
As the solvent used in forming the ink for forming an organic layer, water, an organic solvent, and a mixed solvent thereof can be used. The organic solvent is not particularly limited as long as it can be removed from the formed coating film after the ink is injected. Specific examples of the organic solvent include: toluene, xylene, anisole, mesitylene, tetrahydronaphthalene, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, 3-phenoxytoluene, and the like. In addition, a surfactant, an antioxidant, a viscosity regulator, an ultraviolet absorber, and the like may be added to the ink.
As a method of injecting ink into the region surrounded by the partition wall, an inkjet method is preferable because a small amount of ink can be easily injected into a given site. The ink used for forming the organic layer may be appropriately selected according to the kind of the organic electroluminescent element to be manufactured. In the case of injecting the ink by the inkjet method, the viscosity of the ink is not particularly limited as long as the ink can be satisfactorily ejected from the inkjet head, but is preferably 4 to 20mpa·s, more preferably 5 to 10mpa·s. The viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity regulator, and the like.
[4] Image display device
The image display device of the present invention includes the organic electroluminescent element of the present invention. The type and structure of the image display device are not particularly limited as long as the organic electroluminescent element of the present invention is included, and for example, the organic electroluminescent element of an active driving type may be used for assembly according to a conventional method. For example, the image display device of the present invention can be formed by a method described in "organic EL display" (OHM corporation, release of the display at 8 months and 20 days of the year of the flat formation, time Ren Jingshi, the ampere kilowave vector, and the village Tian Yingxing). For example, an organic electroluminescent element that emits white light may be combined with a color filter to display an image, or an organic electroluminescent element that emits light of different colors such as RGB may be combined to display an image.
[5] Lighting device
The illumination of the present invention comprises the organic electroluminescent element of the present invention. The type and structure thereof are not particularly limited, and the organic electroluminescent element of the present invention may be used for assembly according to a conventional method. The organic electroluminescent element may be driven by a simple matrix or an active matrix.
In order to cause the illumination of the present invention to emit white light, an organic electroluminescent element that emits white light may be used. The organic electroluminescent elements having different emission colors may be combined to mix the colors into white, or the color mixing ratio may be adjusted to provide a color mixing function.
Examples
The photosensitive resin composition of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples within a range not exceeding the gist thereof.
The components of the photosensitive resin compositions used in the following examples and comparative examples are as follows.
A-1: acrylic resin (liquid repellent) synthesized in the following manner
55 Parts by mass of propylene glycol monomethyl ether acetate as a solvent was charged into a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropwise adding device, and the mixture was heated to 105℃under stirring under a nitrogen gas flow. Next, 3 kinds of dropping solutions including 20 parts by mass of a compound (aa-1) having a poly (perfluoroalkylene ether) chain having a chemical structure shown below, a monomer solution in which 84.6 parts by mass of propylene glycol monomethyl ether acetate had 3-hydroxy-1-adamantyl methacrylate dissolved therein and a polymerization initiator solution in which 10.6 parts by mass of propylene glycol monomethyl ether acetate had tert-butylperoxy-2-ethylhexanoate dissolved therein as a polymerization initiator were respectively set in respective dropping devices, and these were dropped for 2 hours while maintaining the inside of the glass flask at 105 ℃. After the completion of the dropwise addition, stirring was carried out for 5 hours at 105℃and then 103.5 parts by mass of the solvent was distilled off under reduced pressure, whereby a polymer (aa-2) solution was obtained.
[ Chemical formula 58]
(In the formula (aa-1), X is a perfluoromethylene group or a perfluoroethylene group, an average of 7 perfluoromethylene groups and 8 perfluoroethylene groups are present per 1 molecule, and the number of fluorine atoms is 46 on average.)
Next, to the polymer (aa-2) solution obtained above, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 part by mass of tin octoate as a urethane formation catalyst were added, and stirring was started under an air flow, and 29.9 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining at 60 ℃. After completion of the dropwise addition, the mixture was stirred at 60℃for 2 hours, then heated to 80℃and stirred for 10 hours, and the disappearance of the isocyanate group was confirmed by IR spectrum measurement, and 53.3 parts by mass of propylene glycol monomethyl ether acetate was added to obtain a propylene glycol monomethyl ether acetate solution containing 50% by mass of an acrylic resin (a-1) having an adamantane skeleton, a crosslinking moiety containing a poly (perfluoroalkylene ether) chain, and an olefinic double bond. The weight average molecular weight (Mw) of the obtained acrylic resin (a-1) was 10000 in terms of polystyrene as measured by GPC.
A-2: acrylic resin (liquid repellent) synthesized in the following manner
35 Parts by mass of propylene glycol monomethyl ether acetate as a solvent was charged into a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropwise addition device, and the mixture was heated to 105℃under stirring under a nitrogen gas flow. Next, 3 kinds of dropping solutions, namely 20 parts by mass of the above-mentioned compound (aa-1), a monomer solution in which 46.1 parts by mass of 2-hydroxyethyl methacrylate was dissolved in 84.6 parts by mass of propylene glycol monomethyl ether acetate, and a polymerization initiator solution in which 10.6 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator was dissolved in 10.6 parts by mass of propylene glycol monomethyl ether acetate, were respectively set in respective dropping apparatuses, and these were dropped for 2 hours while keeping the inside of the glass flask at 105 ℃. After completion of the dropwise addition, the mixture was stirred for 5 hours at 105℃and then 83.5 parts by mass of the solvent was distilled off under reduced pressure, whereby a polymer (ab-2) solution was obtained.
Next, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 part by mass of tin octoate as a urethane-forming catalyst were added to the polymer (ab-2) solution obtained above, stirring was started under an air flow, and 33.3 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining at 60 ℃. After completion of the dropwise addition, the mixture was stirred at 60℃for 2 hours, then heated to 80℃and stirred for 10 hours, and the disappearance of the isocyanate group was confirmed by IR spectrum measurement, and 50.0 parts by mass of propylene glycol monomethyl ether acetate was added to obtain a propylene glycol monomethyl ether acetate solution containing 50% by mass of an acrylic resin (a-2) having a crosslinking unit containing a poly (perfluoroalkylene ether) chain and an olefinic double bond. The weight average molecular weight (Mw) of the obtained acrylic resin (a-2) was 12000 as measured by GPC in terms of polystyrene.
B-1: an alkali-soluble resin (corresponding to the epoxy (meth) acrylate resin (b 1-3)) obtained by synthesis in the following manner
100 Parts by mass of a bisphenol A type epoxy compound represented by the following formula (186 g/eq, a mixture of compounds having m and n of 1 to 20 in the formula), 40 parts by mass of acrylic acid, 0.06 part by mass of p-methoxyphenol, 2.4 parts by mass of triphenylphosphine, and 126 parts by mass of propylene glycol monomethyl ether acetate were charged into a reaction vessel, and stirred at 95℃until the acid value became 5mg-KOH/g or less. Then, to 80 parts by mass of the reaction solution obtained by the above reaction, 12 parts by mass of propylene glycol monomethyl ether acetate was added, succinic anhydride was added, and the mixture was reacted at 95℃for 3 hours to obtain an alkali-soluble resin (b-1) solution having a solid content acid value of 60mg-KOH/g and a polystyrene-equivalent weight-average molecular weight (Mw) of 8,000 as measured by GPC.
[ Chemical formula 59]
(G represents glycidyl)
B-2: the following acrylic copolymer resin (corresponding to acrylic copolymer resin (b 2-1))
An alkali-soluble acrylic copolymer resin (b-2) obtained by adding acrylic acid to a copolymer resin comprising dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio 0.02/0.05/0.93) as a constituent monomer in such a manner that the copolymer resin undergoes an equivalent addition reaction with glycidyl methacrylate, and further adding tetrahydrophthalic anhydride to the copolymer resin in such a manner that the molar ratio of the copolymer resin to 1 mol reaches 0.1. The weight average molecular weight (Mw) in terms of polystyrene as measured by GPC was 7700, and the solid content acid value was 28.5mg-KOH/g.
C-1: dipentaerythritol hexaacrylate (DPHA, manufactured by Japanese Kagaku Co., ltd.)
D-1:2,2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenyl-1, 2' -bisimidazole (manufactured by Baotu chemical Co., ltd.)
D-2: irgacure 369 (Compound having the following chemical structure, manufactured by BASF corporation)
[ Chemical formula 60]
E-1: 2-mercaptobenzimidazole (Tokyo chemical Co., ltd.)
E-2: pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Takara Shuzo Co., ltd.)
F-1: TINUVIN 384-2 (ultraviolet absorber manufactured by BASF corporation)
G-1: KAYAMER PM-21 (manufactured by Japanese Kai-drug Co., ltd.)
H-1: methyl hydroquinone (a compound having the following chemical structure, manufactured by Seikovia chemical Co., ltd.)
[ Chemical formula 61]
[1] Preparation and evaluation of photosensitive resin composition
The respective components were used in the blending ratios shown in table 1, and propylene glycol monomethyl ether acetate was used so that the total solid content became 19 mass%, and the components were stirred until the respective components became uniform, whereby photosensitive resin compositions of examples 1 to 5 and comparative examples 1 to 2 were produced. The blending ratio (mass%) of each component in table 1 is a value of the solid content of each component in all the solid contents.
TABLE 1
The properties of the photosensitive resin compositions of examples 1 to 5 and comparative examples 1 to 2 were evaluated by the methods described below.
(Measurement of contact Angle)
Each photosensitive resin composition was applied to a glass substrate by a spin coater so as to have a thickness of 1.7 μm after heat curing. Then, the resultant coating film was dried by heating on a hot plate at 95℃for 2 minutes, and the entire surface of the coating film was exposed to light at an exposure of 120mJ/cm 2 using an exposure machine MA-1100 manufactured by Dain scientific Co., ltd without using a mask. The intensity at 365nm was 40mW/cm 2. Then, after spray development was performed for 60 seconds using a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 24 ℃, the film was washed with pure water for 10 seconds. The substrate was cured by heating at 230℃for 30 minutes in an oven to obtain a substrate for measuring a contact angle with a cured product.
The contact angle was measured by using a Drop Master 500 contact angle measuring apparatus manufactured by Kyowa Kagaku Co., ltd.) at a temperature of 23℃and a humidity of 50%. Propylene glycol methyl ether acetate (0.7. Mu.L) was added dropwise to the cured product of the contact angle measurement substrate, and the contact angle after 1 second was measured. The measurement results are shown in Table 1. A large contact angle indicates high ink repellency.
(Evaluation of UV resistance (contact angle))
Ultraviolet (UV) light was irradiated to the above contact angle measurement substrate for 3 minutes using a drying processor VUM-3073 manufactured by Oak Corporation. The intensity at the wavelength of 254nm at this time was 9mW/cm 2.
The contact angle of the substrate after UV irradiation was measured as described above. The results were evaluated from the following 2 viewpoints, and the measurement results and evaluation results are shown in table 1.
[ Contact Angle evaluation-1 ]
The contact angle after UV irradiation was evaluated according to the following criteria.
A: the contact angle after UV irradiation was shown to be 30 ° or more.
B: the contact angle after UV irradiation is shown to be 15 ° or more and less than 30 °.
C: the contact angle after UV irradiation was shown to be less than 15 °.
A is the ideal property.
[ Contact Angle evaluation-2 ]
The decrease rate of the contact angle was derived from the following equation, and evaluated according to the following criteria. Here, the decrease rate of the contact angle was not calculated as NA (Not Available) for the contact angle less than 30 ° at the time before UV irradiation.
Decrease rate of contact angle (%) =100- { (contact angle after UV irradiation)/(contact angle before UV irradiation) } ×100
A: the contact angle before UV irradiation was 30 ° or more, and the decrease rate of the contact angle after UV irradiation was less than 20%.
B: the contact angle before UV irradiation is 30 ° or more, and the decrease rate of the contact angle after UV irradiation is 20% or more and less than 30%.
C: the contact angle before UV irradiation was 30 ° or more, and the decrease rate of the contact angle after UV irradiation was 30% or more.
D: the contact angle before UV irradiation did not show more than 30 °.
A is the ideal property.
[2] Formation and evaluation of partition wall
Using the photosensitive resin compositions of examples 1 to 5, formation of partition walls and performance evaluation were performed according to the methods described below.
(Formation of partition walls)
Each photosensitive resin composition was applied to the ITO film of the glass substrate having the ITO film formed on the surface thereof by using a spin coater so as to reach a thickness of 1.7 μm after heat curing. Then, the resulting coating film was dried by heating on a hot plate at 95℃for 2 minutes, and then exposed to light using a photomask (a mask having a plurality of coating portions of 80 μm X280 μm at 40 μm intervals) with an exposure gap of 16. Mu.m, using an exposure machine MA-1100 manufactured by Dain scientific Co., ltd. At this time, the irradiation was performed in air at a wavelength of 365nm and an intensity of 40mW/cm 2 and an exposure of 120mJ/cm 2. Then, after development was performed for 60 seconds Zhong Penlin using a 2.38 mass% aqueous solution of TMAH (tetramethylammonium hydroxide) at 24 ℃, the film was washed with pure water for 1 minute. The substrate from which unnecessary portions were removed by these operations and the patterned was cured by heating at 230 ℃ for 30 minutes in an oven to obtain a substrate having lattice-like partition walls.
(Evaluation of UV resistance (suitability for inkjet coating of partition walls))
Ultraviolet (UV) was irradiated to the above substrate having the lattice-shaped partition walls for 3 minutes using a drying processor VUM-3073 manufactured by Oak Corporation. The intensity at the wavelength of 254nm at this time was 9mW/cm 2.
The pixel portion surrounded by the grid-like partition walls of the substrate after UV irradiation was inkjet-coated with DMP-2831 manufactured by Fuji Film co. As an ink, 480pL of the solvent (isoamyl benzoate) was used alone to apply the ink for each 1 pixel, and the presence or absence of a break (a phenomenon in which the ink was mixed into an adjacent pixel portion across a partition wall) was evaluated according to the following criteria.
The higher the ink repellency of the partition wall, the more the collapse tends to be suppressed. In examples 1 to 5, the wettability in the partition wall after inkjet coating was excellent, and the evaluation for breaking (inkjet coating suitability) shown below was a.
[ Evaluation of collapsibility (inkjet coating suitability) ]
A: the ink can be applied to the inside of the pixel without overflowing outside of the partition wall.
B: ink overflows from the inside of the pixel to the entire upper surface of the partition wall, and is mixed into the adjacent pixel portion (break).
A is the ideal property.
The coated substrates using the photosensitive resin compositions of examples 1 to 5 were found to have high contact angles after UV irradiation and good inkjet coating suitability after UV irradiation. It is considered that the inclusion of the chain transfer agent suppresses the decrease in curability of the film surface due to oxygen inhibition, suppresses the dissolution of the liquid repellent in the developing step, fixes a sufficient amount of the liquid repellent on the film surface, and improves the contact angle. Further, since a liquid repellent having a rigid polycyclic saturated hydrocarbon skeleton which is not easily decomposed by UV irradiation is used as the liquid repellent, it is considered that the decomposition reaction of the liquid repellent is suppressed at the time of UV irradiation, and the presence amount of fluorine atoms on the film surface after UV irradiation can be sufficiently ensured.
In contrast, the coated substrate using the photosensitive resin composition of comparative example 1 did not exhibit sufficient ink repellency from before UV irradiation. This is considered to be because the surface curability is low and the liquid repellent flows out during development because the chain transfer agent is not contained.
Further, the coated substrate using the photosensitive resin composition of comparative example 2 gave a low contact angle after UV irradiation. This is considered to be because the liquid repellent (a-2) used does not have a polycyclic saturated hydrocarbon skeleton, and therefore, the amount of fluorine atoms present in the film surface becomes small due to decomposition of the liquid repellent by UV irradiation, and thus ink repellency is not sufficiently exhibited.
[3] Preparation and evaluation of photosensitive resin composition, preparation and evaluation of partition wall
The photosensitive resin composition of example 6 was prepared by using propylene glycol monomethyl ether acetate and stirring the mixture so that the solid content of each component in the total solid content became equal to the following blend ratio (parts by mass) and so that the content of the total solid content became 19% by mass.
(Measurement of contact Angle)
The photosensitive resin composition of example 6 was applied to a glass substrate using a spin coater so as to have a thickness of 1.7 μm after heat curing. Then, the resultant coating film was dried by heating on a hot plate at 95℃for 2 minutes, and the entire surface of the coating film was exposed to light at an exposure of 200mJ/cm 2 using an exposure machine MA-1100 manufactured by Dain scientific Co., ltd without using a mask. The intensity at 365nm was 40mW/cm 2. Then, after spray development was performed for 60 seconds using a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 24 ℃, the film was washed with pure water for 10 seconds. The substrate was cured by heating at 230℃for 30 minutes in an oven to obtain a substrate for measuring a contact angle with a cured product.
The contact angle measurement and UV resistance evaluation (inkjet coating suitability of the barrier ribs) were performed in the same manner as described above, and the following results were obtained.
(Formation of partition walls)
The photosensitive resin composition of example 6 was applied to the ITO film of the glass substrate having the ITO film formed on the surface thereof by using a spin coater so as to reach a thickness of 1.7 μm after heat curing. Then, the resulting coating film was dried by heating on a hot plate at 95℃for 2 minutes, and then exposed to light using a photomask (a mask having a plurality of coating portions of 80 μm X280 μm at 40 μm intervals) with an exposure gap of 16. Mu.m, using an exposure machine MA-1100 manufactured by Dain scientific Co., ltd. At this time, the irradiation was performed in air at a wavelength of 365nm at an intensity of 40mW/cm 2 and an exposure of 200mJ/cm 2. Then, after development was performed for 60 seconds Zhong Penlin using a 2.38 mass% aqueous solution of TMAH (tetramethylammonium hydroxide) at 24 ℃, the film was washed with pure water for 1 minute. The substrate from which unnecessary portions were removed by these operations and the patterned was cured by heating at 230 ℃ for 30 minutes in an oven to obtain a substrate having lattice-like partition walls.
The UV resistance (suitability for inkjet coating of the barrier ribs) was evaluated in the same manner as described above, and the following results were obtained.
Inkjet coating suitability (after UV irradiation): a

Claims (19)

1.一种感光性树脂组合物，其含有：(A)拒液剂、(B)碱可溶性树脂、(C)光聚合性化合物、及(D)光聚合引发剂，其中，1. A photosensitive resin composition comprising: (A) a liquid repellent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator, wherein: 所述(A)拒液剂包含具有多环式饱和烃骨架及烯属双键的丙烯酸类树脂(a)，The liquid repellent (A) comprises an acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and olefinic double bonds, 所述具有多环式饱和烃骨架及烯属双键的丙烯酸类树脂(a)具有包含聚(全氟亚烷基醚)链的交联部，The acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and olefinic double bonds has a crosslinking portion including a poly(perfluoroalkylene ether) chain, 所述感光性树脂组合物还包含(E)链转移剂。The photosensitive resin composition further includes (E) a chain transfer agent. 2.根据权利要求1所述的感光性树脂组合物，其中，所述具有多环式饱和烃骨架及烯属双键的丙烯酸类树脂(a)包含下述通式(1)所示的部分结构，2. The photosensitive resin composition according to claim 1, wherein the acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and olefinic double bonds comprises a partial structure represented by the following general formula (1): 式(1)中，R1各自独立地表示氢原子或甲基，X1表示全氟亚烷基，式(1)中所含的多个X1任选相同或不同，在多个X1不同的情况下，它们任选以无规状或嵌段状存在，X2各自独立地表示直接键或任意的2价连结基团，n为1以上的整数，*表示键合位置。In formula (1), R1 each independently represents a hydrogen atom or a methyl group, X1 represents a perfluoroalkylene group, multiple X1 contained in formula (1) are optionally the same or different, and when multiple X1 are different, they are optionally present in a random or block form, X2 each independently represents a direct bond or an arbitrary divalent linking group, n is an integer greater than 1, and * represents a bonding position. 3.一种感光性树脂组合物，其含有：(A)拒液剂、(B)碱可溶性树脂、(C)光聚合性化合物、及(D)光聚合引发剂，其中，3. A photosensitive resin composition comprising: (A) a liquid repellent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator, wherein: 所述(A)拒液剂包含具有多环式饱和烃骨架及烯属双键的丙烯酸类树脂(a)，The liquid repellent (A) comprises an acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and olefinic double bonds, 所述多环式饱和烃骨架为金刚烷骨架，The polycyclic saturated hydrocarbon skeleton is an adamantane skeleton, 所述感光性树脂组合物还包含(E)链转移剂。The photosensitive resin composition further includes (E) a chain transfer agent. 4.根据权利要求3所述的感光性树脂组合物，其中，所述具有多环式饱和烃骨架及烯属双键的丙烯酸类树脂(a)具有包含聚(全氟亚烷基醚)链的交联部。4 . The photosensitive resin composition according to claim 3 , wherein the acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and ethylenic double bonds has a crosslinking portion including a poly(perfluoroalkylene ether) chain. 5.一种感光性树脂组合物，其含有：(A)拒液剂、(B)碱可溶性树脂、(C)光聚合性化合物、及(D)光聚合引发剂，其中，5. A photosensitive resin composition comprising: (A) a liquid repellent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator, wherein: 所述(A)拒液剂包含具有多环式饱和烃骨架及烯属双键的丙烯酸类树脂(a)，The liquid repellent (A) comprises an acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and olefinic double bonds, 所述具有多环式饱和烃骨架及烯属双键的丙烯酸类树脂(a)包含下述通式(2)所示的部分结构，The acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and olefinic double bonds comprises a partial structure represented by the following general formula (2): 式(2)中，R2及R3各自独立地表示氢原子或甲基，X3表示任选具有取代基的2价的多环式饱和烃基，X4表示氨基甲酸酯键或酯键，X5表示任选具有取代基的2价烃基，*表示键合位置，In formula (2), R2 and R3 each independently represent a hydrogen atom or a methyl group, X3 represents a divalent polycyclic saturated hydrocarbon group which may have a substituent, X4 represents a carbamate bond or an ester bond, X5 represents a divalent hydrocarbon group which may have a substituent, * represents a bonding position, 所述感光性树脂组合物还包含(E)链转移剂。The photosensitive resin composition further includes (E) a chain transfer agent. 6.根据权利要求5所述的感光性树脂组合物，其中，所述具有多环式饱和烃骨架及烯属双键的丙烯酸类树脂(a)具有包含聚(全氟亚烷基醚)链的交联部。6 . The photosensitive resin composition according to claim 5 , wherein the acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and ethylenic double bonds has a crosslinking portion including a poly(perfluoroalkylene ether) chain. 7.根据权利要求5所述的感光性树脂组合物，其中，所述多环式饱和烃骨架为金刚烷骨架。7 . The photosensitive resin composition according to claim 5 , wherein the polycyclic saturated hydrocarbon skeleton is an adamantane skeleton. 8.根据权利要求6所述的感光性树脂组合物，其中，所述多环式饱和烃骨架为金刚烷骨架。8 . The photosensitive resin composition according to claim 6 , wherein the polycyclic saturated hydrocarbon skeleton is an adamantane skeleton. 9.根据权利要求1～8中任一项所述的感光性树脂组合物，其中，所述(B)碱可溶性树脂包含环氧(甲基)丙烯酸酯树脂(b1)和/或丙烯酸类共聚树脂(b2)。9 . The photosensitive resin composition according to claim 1 , wherein the (B) alkali-soluble resin comprises an epoxy (meth)acrylate resin (b1) and/or an acrylic copolymer resin (b2). 10.根据权利要求9所述的感光性树脂组合物，其中，所述环氧(甲基)丙烯酸酯树脂(b1)为选自包含下述通式(i)所示的部分结构的环氧(甲基)丙烯酸酯树脂(b1-1)、包含下述通式(ii)所示的部分结构的环氧(甲基)丙烯酸酯树脂(b1-2)、及包含下述通式(iii)所示的部分结构的环氧(甲基)丙烯酸酯树脂(b1-3)中的至少一种，10. The photosensitive resin composition according to claim 9, wherein the epoxy (meth) acrylate resin (b1) is at least one selected from an epoxy (meth) acrylate resin (b1-1) comprising a partial structure represented by the following general formula (i), an epoxy (meth) acrylate resin (b1-2) comprising a partial structure represented by the following general formula (ii), and an epoxy (meth) acrylate resin (b1-3) comprising a partial structure represented by the following general formula (iii), 式(i)中，Ra表示氢原子或甲基，Rb表示任选具有取代基的2价烃基，式(i)中的苯环任选进一步被任意的取代基取代，*表示键合位置，In formula (i), Ra represents a hydrogen atom or a methyl group, Rb represents a divalent hydrocarbon group which may have a substituent, the benzene ring in formula (i) may be further substituted with an arbitrary substituent, * represents a bonding position, 式(ii)中，Rc各自独立地表示氢原子或甲基，Rd表示具有环状烃基作为侧链的2价烃基，*表示键合位置，In formula (ii), R c each independently represents a hydrogen atom or a methyl group, R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, * represents a bonding position, 式(iii)中，Re表示氢原子或甲基，γ表示单键、-CO-、任选具有取代基的亚烷基、或任选具有取代基的2价的环状烃基，式(iii)中的苯环任选进一步被任意的取代基取代，*表示键合位置。In formula (iii), Re represents a hydrogen atom or a methyl group, γ represents a single bond, -CO-, an alkylene group optionally having a substituent, or a divalent cyclic hydrocarbon group optionally having a substituent, the benzene ring in formula (iii) may be further substituted with any substituent, and * represents a bonding position. 11.根据权利要求9所述的感光性树脂组合物，其中，所述丙烯酸类共聚树脂(b2)为包含下述通式(I)所示的部分结构的丙烯酸类共聚树脂(b2-1)，11. The photosensitive resin composition according to claim 9, wherein the acrylic copolymer resin (b2) is an acrylic copolymer resin (b2-1) comprising a partial structure represented by the following general formula (I): 式(I)中，RA及RB各自独立地表示氢原子或甲基，*表示键合位置。In formula (I), RA and RB each independently represent a hydrogen atom or a methyl group, and * represents a bonding position. 12.根据权利要求1～8中任一项所述的感光性树脂组合物，其中，所述(D)光聚合引发剂含有选自六芳基联咪唑类光聚合引发剂、肟酯类光聚合引发剂及苯乙酮类光聚合引发剂中的至少一种。12 . The photosensitive resin composition according to claim 1 , wherein the (D) photopolymerization initiator comprises at least one selected from the group consisting of a hexaarylbiimidazole-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, and an acetophenone-based photopolymerization initiator. 13.根据权利要求1～8中任一项所述的感光性树脂组合物，其进一步含有紫外线吸收剂。13 . The photosensitive resin composition according to claim 1 , further comprising an ultraviolet absorber. 14.根据权利要求1～8中任一项所述的感光性树脂组合物，其进一步含有阻聚剂。14 . The photosensitive resin composition according to claim 1 , further comprising a polymerization inhibitor. 15.根据权利要求1～8中任一项所述的感光性树脂组合物，其用于形成间隔壁。15 . The photosensitive resin composition according to claim 1 , which is used for forming partition walls. 16.一种间隔壁，其由权利要求1～8中任一项所述的感光性树脂组合物构成。16 . A partition wall composed of the photosensitive resin composition according to claim 1 . 17.一种有机场致发光元件，其具备权利要求16所述的间隔壁。17. An organic electroluminescent element comprising the partition wall according to claim 16. 18.一种图像显示装置，其包含权利要求17所述的有机场致发光元件。18. An image display device comprising the organic electroluminescent element according to claim 17. 19.一种照明，其包含权利要求17所述的有机场致发光元件。19. A lighting device comprising the organic electroluminescent element according to claim 17.
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