CN111566560A - Photosensitive resin composition, partition wall, organic electroluminescent element, image display device, and illumination - Google Patents

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

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Publication number
CN111566560A
CN111566560A CN201980007829.5A CN201980007829A CN111566560A CN 111566560 A CN111566560 A CN 111566560A CN 201980007829 A CN201980007829 A CN 201980007829A CN 111566560 A CN111566560 A CN 111566560A
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木村明日香
中谷和裕
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Mitsubishi Chemical Corp
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    • 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
    • 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
    • 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

Abstract

The invention provides a photosensitive resin composition capable of forming partition walls with good ink repellency 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 liquid repellent (a) contains an acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an olefinic double bond, and the photosensitive resin composition further contains (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, an inter-partition wall formed of the photosensitive resin composition, an organic electroluminescent element provided with the inter-partition wall, an image display device including the organic electroluminescent element, and an illumination.
The entire contents of the specification, claims and abstract of Japanese patent application 2018-011097, which was filed by the patent office on the day of 2018, month 1 and day 26, and the entire contents of documents and the like cited in the specification are incorporated herein as the disclosure of the present specification.
Background
Conventionally, organic electroluminescent devices included in organic electroluminescent displays, organic electroluminescent illuminators, and the like are manufactured by forming partition walls (dams) on a substrate and then laminating various functional layers in regions surrounded by the partition walls. As a method for easily forming such partition walls, a method of forming the partition walls by photolithography using a photosensitive resin composition is known.
In addition, as a method of laminating various functional layers in the region surrounded by the partition walls, there is known a method of preparing ink including a material constituting the functional layers first and then injecting the prepared ink into the region surrounded by the partition walls. In this method, since a predetermined amount of ink can be easily and accurately injected into a predetermined portion, an ink jet method is often used.
Further, when the functional layer is formed using ink, it is sometimes required to impart ink repellency (liquid repellency) to the partition walls for the purpose of preventing adhesion of ink to the partition walls, preventing mixing of ink injected between adjacent regions, and the like. As a method for imparting ink repellency to the partition walls, for example, a method of containing a fluorine compound in the partition walls is known (see patent documents 1 and 2).
In addition, patent document 3 describes that a cured product having high ink repellency can be formed by using a specific fluororesin.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2013/161829
Patent document 2: japanese patent laid-open publication No. 2015-179257
Patent document 3: japanese laid-open patent publication No. 2012 and 092308
Disclosure of Invention
Problems to be solved by the invention
When the partition walls are formed using a photosensitive resin composition, if residue of the composition is generated in the pixel region surrounded by the partition walls, part of the pixel portion may not emit light. Therefore, the UV cleaning treatment may be performed for the purpose of removing the residue after the formation of the partition walls, but there are the following problems: although the residue is removed, the ink repellency of the partition walls is reduced.
The present inventors have conducted studies and found that the photosensitive resin composition described in patent document 1 has insufficient ink repellency after UV cleaning treatment.
Further, the photosensitive resin compositions described in patent documents 2 and 3 are known to have insufficient ink repellency.
Accordingly, an object of the present invention is to provide a photosensitive resin composition capable of forming partition walls having excellent ink repellency even after UV cleaning treatment.
It is another object of the present invention to provide a partition wall made of the photosensitive resin composition, an organic electroluminescent element provided with the partition wall, and an image display device and an illumination device including 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 liquid repellent having a specific structure and a chain transfer agent in a photosensitive resin composition containing the liquid repellent, an alkali-soluble resin, a photopolymerizable compound and a photopolymerization initiator, and have completed the present invention.
That is, 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,
the liquid repellent (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 [1], wherein the acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an olefinic double bond has a partial structure represented by the following general formula (1).
[ chemical formula 1]
Figure BDA0002576772040000031
(in the formula (1), R1Each independently represents a hydrogen atom or a methyl group, X1Represents a perfluoroalkylene group, a plurality of X's contained in the formula (1)1Optionally the same or different at a plurality of X1When they are different from each other, they are optionally present in a random or block form, X2Each 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. )
[4] The photosensitive resin composition according to any one of the above [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 includes a partial structure represented by the following general formula (2).
[ chemical formula 2]
Figure BDA0002576772040000032
(in the formula (2), R2And R3Each independently represents a hydrogen atom or a methyl group, X3Represents an optionally substituted 2-valent polycyclic saturated hydrocarbon group, X4Represents a urethane bond or an ester bond, X5Represents a 2-valent hydrocarbon group optionally having a substituent, and represents a bonding position. )
[6] The photosensitive resin composition according to any one of the above [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 [6], wherein the epoxy (meth) acrylate resin (b1) is at least one selected from the group consisting of an epoxy (meth) acrylate resin (b1-1) having a partial structure represented by the following general formula (i), an epoxy (meth) acrylate resin (b1-2) having a partial structure represented by the following general formula (ii), and an epoxy (meth) acrylate resin (b1-3) having a partial structure represented by the following general formula (iii).
[ chemical formula 3]
Figure BDA0002576772040000041
(in the formula (i), RaRepresents a hydrogen atom or a methyl group, RbRepresents a 2-valent hydrocarbon group optionally having a substituent, the benzene ring in the formula (i) is optionally further substituted with an optional substituent, and represents a bonding position. )
[ chemical formula 4]
Figure BDA0002576772040000042
(in the formula (ii), RcEach independently represents a hydrogen atom or a methyl group, RdRepresents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and represents a bonding position. )
[ chemical formula 5]
Figure BDA0002576772040000043
(in the formula (iii), ReRepresents 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 the formula (iii) is optionally further substituted with an optional substituent. )
[8] The photosensitive resin composition according to [6] or [7], wherein the acrylic copolymer resin (b2) is an acrylic copolymer resin (b2-1) containing a partial structure represented by the following general formula (I).
[ chemical formula 6]
Figure BDA0002576772040000051
(in the formula (I), RAAnd RBEach independently represents a hydrogen atom or a methyl group, and represents a bonding position. )
[9] The photosensitive resin composition according to any one of the above [1] to [8], wherein the photopolymerization initiator (D) contains at least one selected from the group consisting of hexaarylbisimidazole-based photopolymerization initiators, oxime ester-based photopolymerization initiators and acetophenone-based photopolymerization initiators.
[10] The photosensitive resin composition according to any one of the above [1] to [9], further comprising an ultraviolet absorber.
[11] The photosensitive resin composition according to any one of the above [1] to [10], further comprising a polymerization inhibitor.
[12] The photosensitive resin composition according to any one of the above [1] to [11], which is used for forming partition walls.
[13] A partition wall comprising the photosensitive resin composition according to any one of [1] to [12 ].
[14] An organic electroluminescent element comprising the partition wall according to [13 ].
[15] An image display device comprising the organic electroluminescent element according to [14 ].
[16] An illumination device comprising the organic electroluminescent element according to [14 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a photosensitive resin composition capable of forming partition walls having excellent 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 the scope not exceeding the gist thereof.
In the present invention, "(meth) acrylic acid" means "acrylic acid and/or methacrylic acid", and "total solid content" means all components except the solvent in the photosensitive resin composition. In the present invention, the numerical range represented by "to" represents a range including numerical values described before and after "to" as a lower limit value and an upper limit value. "a and/or B" means either or both of a and B, specifically A, B or a and B.
In the present invention, the term "(co) polymer" is intended to include both a single polymer (homopolymer) and a copolymer (copolymer), and the term "polybasic acid (anhydride)" is intended to mean "polybasic acid and/or polybasic acid anhydride".
In the present invention, the weight average molecular weight refers to a weight average molecular weight (Mw) in terms of polystyrene based on GPC (gel permeation chromatography).
In the present invention, the acid value is an acid value converted into an effective solid content, and can be calculated by neutralization titration.
In the present invention, the partition wall material refers to a dam material, a wall material, and similarly, the partition wall refers to a dam, a wall, and a wall.
In the present invention, the light emitting section (pixel section) is a section that emits light when electric energy is applied.
[1] Photosensitive resin composition
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 is characterized in that the liquid repellent (a) contains 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 contains (E) a chain transfer agent. Other components may be contained as required, and for example, an ultraviolet absorber and a polymerization inhibitor may be contained.
In the present invention, the partition walls are, for example, portions for partitioning the functional layer (organic layer, light emitting portion) in the active-drive-type organic electroluminescent element, and are used for forming pixels including the functional layer and the partition walls by discharging ink, which is a material for constituting the functional layer, to the partitioned areas (pixel areas) and drying the ink.
[1-1] Components and compositions of photosensitive resin compositions
The components constituting the photosensitive resin composition of the present invention and the composition thereof will be explained.
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 further contains a solvent.
[1-1-1] (A) component: liquid repellent
The photosensitive resin composition of the present invention contains (A) a liquid repellent. Since the surface of the partition walls obtained can be imparted with ink repellency (liquid repellency) by containing the liquid repellent (a), it is considered that adhesion of ink to the partition walls can be prevented and mixing of ink injected between adjacent regions can be prevented when the organic electroluminescent element is produced by an ink jet method.
[ acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and olefinic double bonds ]
The liquid repellent (a) in the photosensitive resin composition of the present invention contains 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 since the acrylic resin (a) has an ethylenic double bond and is fixed to the surface of the coating film when the coating film is exposed to light, the acrylic resin (a) is less likely to flow out during the development treatment, and as a result, the ink repellency of the obtained partition walls can be improved.
The acrylic resin (a) has a polycyclic saturated hydrocarbon skeleton, and the polycyclic saturated hydrocarbon skeleton improves the ink repellency of the film surface after UV irradiation, and this is considered to be obtained by the following action.
It is considered that the heat release by UV absorption of the resin or the like in the cured product by UV irradiation tends to increase the temperature of the surface layer of the cured product, and the acrylic resin (a) segregated in the surface layer is easily affected by the heat release.
It is considered that the linear structure is decomposed by cleavage at 1 site, and the cyclic structure is not decomposed unless the cyclic structure is cleaved at a plurality of sites, so that the heat resistance is high, and in particular, when the polycyclic structure is formed, the decomposition is further difficult, and the heat resistance is improved. Further, the saturated cyclic hydrocarbon skeleton has no bond as a reaction starting point as compared with the unsaturated cyclic hydrocarbon skeleton, and is considered to have an advantage that the reactivity of the ring itself is low.
Further, it is considered that having a polycyclic hydrocarbon skeleton itself acts as a steric hindrance, and the main chain of the acrylic resin (a) is not easily cleaved, thereby further improving heat resistance.
Further, since the acrylic resin (a) has an acryl structure, it is considered that compatibility with the alkali-soluble resin (B) and the photopolymerizable compound (C) can be improved, storage stability of the photosensitive resin composition can be improved, and generation of residue in the pixel portion can be suppressed to improve wet spreadability.
The polycyclic saturated hydrocarbon skeleton may have a valence of 1 or more and may have a valence of 2 or more. The compound may be unsubstituted or may have a substituent.
The number of carbon atoms of the polycyclic saturated hydrocarbon skeleton is not particularly limited, and is usually 6 or more, preferably 8 or more, more preferably 9 or more, and still more preferably 10 or more, and preferably 20 or less, more preferably 15 or less, and still more preferably 12 or less. When the lower limit is not less than the above-mentioned lower limit, the ink repellency after the UV cleaning treatment tends to be good, and when the upper limit is not more than the above-mentioned upper limit, the compatibility in the photosensitive resin composition tends to be good. The number of carbon atoms in 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 as long as it is 2 or more, but is preferably 3 or more, and is preferably 5 or less, and more preferably 4 or less. When the lower limit is not less than the above-mentioned lower limit, the ink repellency after the UV cleaning treatment tends to be good, and when the upper limit is not more than the above-mentioned upper limit, 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: an adamantane skeleton, tricyclodecane skeleton, norbornane skeleton, decalin skeleton, etc., and an adamantane skeleton is preferable from the viewpoint of ink repellency after UV cleaning treatment.
The polycyclic saturated hydrocarbon skeleton may be present at any position of the chemical structure of the acrylic resin (a), and may be present in, for example, the main chain or side chain of the acrylic resin. From the viewpoint of ease of synthesis, it is preferably present in the 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 is not less than the above-mentioned lower limit, the ink repellency after the UV cleaning treatment tends to be good, and when the upper limit is not more than the above-mentioned upper limit, 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.
Further, the acrylic resin (a) preferably has a crosslinked portion containing a poly (perfluoroalkylene ether) chain. In the case of having a crosslinked portion containing a poly (perfluoroalkylene ether) chain, since the crosslinked portion is bonded to 2 or more main chains, the poly (perfluoroalkylene ether) chain is less likely to be 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 repellent property after the UV cleaning treatment is good.
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, it is preferable that the acrylic resin (a) has a partial structure containing a crosslinked portion of a poly (perfluoroalkylene ether) chain, and the acrylic resin (a) preferably contains a partial structure represented by the following general formula (1).
[ chemical formula 7]
Figure BDA0002576772040000091
In the formula (1), R1Each independently represents a hydrogen atom or a methyl group, X1Represents a perfluoroalkylene group, a plurality of X's contained in the formula (1)1May be the same or different, at a plurality of X1When they are different from each other, they may be present in a random form or in a block form, and X2Each 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), X1Represents 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 preferably 5 or less, and more preferably 3 or less. When the lower limit is not less than the above-mentioned lower limit, sufficient ink repellency tends to be exhibited, and when the upper limit is not more than the above-mentioned upper limit, 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)
Figure BDA0002576772040000101
Figure BDA0002576772040000102
In the formulae (1-a) to (1-e), a symbol represents a bonding site.
Among the above 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.
From the viewpoint of ink repellency, it is more preferable that both the group represented by the formula (1-a) and the group represented by the formula (1-b) in the formula (1) are contained. 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 further preferably 1:2 to 2:1, from the viewpoint of ink repellency.
(X2)
In the above formula (1), X2Represents a direct bond or an optional linking group having a valence of 2.
As the optional linking group having a valence of 2, there may be mentioned: -O-, -CO-NH-, -O-CO-NH-,a 2-valent hydrocarbon group optionally having a substituent. A part of-CH contained in the hydrocarbon group2-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 group.
As the 2-valent aliphatic group, there may be mentioned: a linear, branched or cyclic alkylene group, or a linear, branched or cyclic alkenylene group.
The number of carbon atoms of the 2-valent aliphatic group is not particularly limited, and is usually 1 or more, and is preferably 5 or less, more preferably 3 or less, and further preferably 2 or less. When the amount is equal to or less than the upper limit, the ink repellency tends to be improved.
Specific examples of the 2-valent aliphatic group include: methylene, ethylene, vinylene, propylene, propenylene, butylene, butenylene, and the like.
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 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 preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. When the lower limit is not less than the above-mentioned lower limit, compatibility with other materials tends to be good, and when the upper limit is not more than the above-mentioned upper limit, ink repellency tends to be improved.
As the 2-valent aromatic hydrocarbon ring group, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,
Figure BDA0002576772040000111
A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, etc., having 2 free valences.
Examples of the 2-valent aromatic heterocyclic group include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrroleA ring, a pyrazole ring, an imidazole ring,
Figure BDA0002576772040000112
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring
Figure BDA0002576772040000113
An 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,
Figure BDA0002576772040000114
a group having 2 free valences such as a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, etc.
Examples of the substituent optionally having a 2-valent aromatic ring group include a hydroxyl group, an alkyl group, and an alkoxy group.
As X2Specific examples of (b) include the following groups.
[ chemical formula 9]
*-CH2-*
*-CH2CH2-*
Figure BDA0002576772040000121
Among these, from the viewpoint of ensuring ink repellency and from the viewpoint of suppressing the residue of the liquid repellent in the pixel portion during development, the 2-valent aliphatic group is preferable, the methylene group and the ethylene group are more preferable, and the methylene group is further preferable.
(n)
In the formula (1), n is an integer of 1 or more, and is preferably an integer of 3 to 40, more preferably an integer of 6 to 30, and further 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 has 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 viewpoint of ink repellency and sensitivity after UV cleaning.
[ chemical formula 10]
Figure BDA0002576772040000122
In the formula (2), R2And R3Each independently represents a hydrogen atom or a methyl group, X3Represents an optionally substituted 2-valent polycyclic saturated hydrocarbon group, X4Represents a urethane bond or an ester bond, X5Represents a 2-valent hydrocarbon group optionally having a substituent, and represents a bonding position.
(X3)
In the above formula (2), X3Represents an optionally substituted polycyclic saturated hydrocarbon group having a valence of 2.
The number of carbon atoms of the 2-valent polycyclic saturated hydrocarbon group is not particularly limited, and is usually 6 or more, preferably 8 or more, more preferably 9 or more, and still more preferably 10 or more, and is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. When the lower limit is not less than the above-described lower limit, the ink repellency after the UV cleaning treatment tends to be suppressed from decreasing, and when the upper limit is not more than the above-described upper limit, the ink repellency tends to be improved.
Specific examples of the 2-valent polycyclic saturated hydrocarbon group include: of these, adamantylene, dicyclopentenylene, norbornane, naphthylene and the like are 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 formula (2), X4Represents a urethane bond (-O-CO-NH-) or an ester bond (-O-CO-). Among these, urethane bonds are preferable from the viewpoint of suppressing a decrease in ink repellency after the UV cleaning treatment.
(X5)
In the above formula (2), X5Represents 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 group.
As the 2-valent aliphatic group, there may be mentioned: a linear, branched or cyclic alkylene group, or a linear, branched or cyclic alkenylene group.
The number of carbon atoms of the 2-valent aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 8 or less, further preferably 5 or less, and particularly preferably 3 or less. When the lower limit is not less than the above-described lower limit, the ink repellency after the UV cleaning treatment tends to be suppressed from decreasing, and when the upper limit is not more than the above-described upper limit, the ink repellency tends to be improved.
Specific examples of the 2-valent aliphatic group include: methylene, ethylene, vinylene, propylene, propenylene, butylene, butenylene, 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 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 preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. When the lower limit is not less than the above-described lower limit, the ink repellency after the UV cleaning treatment tends to be suppressed from decreasing, and when the upper limit is not more than the above-described upper limit, the ink repellency tends to be improved.
As the 2-valent aromatic hydrocarbon ring group, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,
Figure BDA0002576772040000142
Having 2 free valences, e.g. ring, benzophenanthrene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etcA group of (1).
Examples of the 2-valent aromatic heterocyclic group include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, or the like,
Figure BDA0002576772040000143
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring
Figure BDA0002576772040000144
An 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,
Figure BDA0002576772040000145
a group having 2 free valences such as a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, etc.
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 from the viewpoint of suppressing the residue of the liquid repellent in the pixel portion during development, the 2-valent aliphatic group is preferable, the methylene group and the ethylene group are more preferable, and the ethylene group is further preferable.
The acrylic resin (a) may further contain other partial structures, and among the other partial structures, a partial structure represented by the following general formula (3) is preferably contained from the viewpoint of reducing residues of a luminescent part.
[ chemical formula 11]
Figure BDA0002576772040000141
In the formula (3), R4Represents a hydrogen atom or a methyl group, X6Represents an optionally substituted 1-valent hydrocarbon group, and represents a bondAnd closing the position.
(X6)
In the above formula (3), X6Represents 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.
As the 1-valent aliphatic group, there may be mentioned: a linear, branched or cyclic alkyl group, or a linear, branched or cyclic alkenyl group.
The number of carbon atoms of the 1-valent aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 4 or more, further preferably 6 or more, particularly preferably 8 or more, and further preferably 20 or less, more preferably 15 or less, further preferably 10 or less. When the lower limit is not less than the above-described lower limit, the ink repellency after the UV cleaning treatment tends to be suppressed from decreasing, and when the upper limit is not more than the above-described upper limit, the ink repellency tends to be improved.
Specific examples of the 1-valent aliphatic group include: methyl, ethyl, vinyl, propyl, propenyl, butyl, butenyl, cyclohexyl, adamantyl, 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 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, and is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. When the lower limit is not less than the above-described lower limit, the ink repellency after the UV cleaning treatment tends to be suppressed from decreasing, and when the upper limit is not more than the above-described upper limit, the ink repellency tends to be improved.
As the 1-valent aromatic hydrocarbon ring group, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,
Figure BDA0002576772040000151
A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, etc., having 1 free valence.
Examples of the 1-valent aromatic heterocyclic group include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, or the like,
Figure BDA0002576772040000152
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring
Figure BDA0002576772040000153
An 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,
Figure BDA0002576772040000154
a group having 1 free valence of the pyridine ring, quinazoline ring, quinazolinone ring, azulene ring, etc.
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 and a adamantyl group optionally having a substituent are still more preferable, and an adamantyl 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 ratio thereof is not limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 3 mol% or more, further preferably 5 mol% or more, particularly preferably 7 mol% or more, and further preferably 20 mol% or less, more preferably 15 mol% or less, further preferably 13 mol% or less, and particularly preferably 10 mol% or less. When the lower limit is not less than the above-mentioned lower limit, the ink repellency tends to be improved, and when the upper limit is not more than the above-mentioned upper limit, the compatibility with other materials tends to be good. When the acrylic resin (a) has a partial structure represented by the general formula (1), the content thereof is, for example, 1 to 20 mol%, preferably 2 to 20 mol%, more preferably 3 to 15 mol%, further preferably 5 to 15 mol%, and further preferably 7 to 10 mol%.
On the other hand, when the acrylic resin (a) has a partial structure represented by the above general formula (2), the content ratio 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, more preferably 90 mol% or less. When the lower limit value is set to the above-mentioned lower limit value or more, the outflow of the liquid repellent during development tends to be suppressed, and the ink repellency tends to be improved. When the acrylic resin (a) has a partial structure represented by the general formula (2), the content thereof is, for example, 30 to 95 mol%, preferably 40 to 95 mol%, more preferably 50 to 90 mol%, further preferably 60 to 90 mol%, and further preferably 70 to 90 mol%.
On the other hand, when the acrylic resin (a) has a partial structure represented by the above general formula (3), the content ratio 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 is preferably 60 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less, further preferably 30 mol% or less, particularly preferably 20 mol% or less. When the lower limit value is not less than the lower limit value, the residue of the light emitting section tends to be reduced, and when the upper 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 general formula (3), the content thereof is, for example, 1 to 60 mol%, preferably 2 to 50 mol%, more preferably 3 to 40 mol%, further preferably 5 to 30 mol%, and further preferably 5 to 20 mol%.
When the acrylic resin (a) contains two or more partial structures selected from the above-mentioned general formulae (1) to (3), the acrylic resin (a) may be a random copolymer or a block copolymer, and when it is a block copolymer, an AB block copolymer containing an a block having a partial structure represented by the above-mentioned general formula (1) and a B block having a partial structure represented by the above-mentioned general formula (2) and/or a partial structure represented by the above-mentioned 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 product. The weight average molecular weight of the acrylic resin (a) is preferably 1000 or more, more preferably 5000 or more, further preferably 8000 or more, further preferably 10000 or more, and is preferably 100000 or less, more preferably 50000 or less, further 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 the post-baking is suppressed, and the liquid repellent tends to flow out of the partition wall. 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 further preferably 10000 to 20000.
When the acrylic resin (a) contains a fluorine atom, the content thereof is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and is preferably 50% by mass or less, more preferably 25% by mass or less. When the lower limit is not less than the above-mentioned lower limit, high ink repellency tends to be obtained, and when the upper limit is not more than the above-mentioned upper limit, 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 of the liquid repellent (a) in the photosensitive resin composition of the present invention is not particularly limited, and is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and particularly preferably 0.4% by mass or more, and is preferably 1% by mass or less, more preferably 0.7% by mass or less, and further preferably 0.5% by mass or less, of the total solid content of the photosensitive resin composition. When the lower limit value is not less than the lower limit value, a high ink repellency tends to be exhibited, and when the upper limit value is not more than the upper limit value, the flow of the liquid repellent to the pixel portion tends to be suppressed. The content of the liquid repellent (A) in the entire 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% by mass or more, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, particularly preferably 0.4% by mass or more, and further preferably 1% by mass or less, more preferably 0.7% by mass or less, and further preferably 0.5% by mass or less, of the total solid content of the photosensitive resin composition. When the lower limit value is not less than the lower 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) to the pixel portion tends to be suppressed. The content of the acrylic resin (a) in the entire 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 liquid repellent (a) in the photosensitive resin composition of the present invention may contain a liquid repellent other than the acrylic resin (a).
Specific examples of the other liquid repellent include: fluorine atom-containing organic compounds such as perfluoroalkyl sulfonic acid, perfluoroalkyl carboxylic acid, perfluoroalkyl oxyalkylene adduct, perfluoroalkyl trialkylammonium salt, perfluoroalkyl ester, perfluoroalkyl phosphate, perfluoroalkyl group-containing oligomer, and perfluoroalkylene group-containing oligomer.
As commercially available products of these fluorine atom-containing organic compounds, there may be used "Megafac (registered trademark, the same as hereinafter)" 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 RS301 "301 Megafac RS 301" or "Megafac RS 401" or "Megafac RS 402" Megafac RS "or" Megafac RS401 "Megafac RS" or "Megafac RS402 RS" Megafac RS "by DIC RS402, Examples of the fluorine atom-containing organic compound include those commercially available under the trade names "DEFENSA MCF 310", "DEFENSA MCF 312", "DEFENSA MCF 323", "Fluorad FC-430" manufactured by 3M Japan "," Fluorad FC-431 "," FC-4430 "," FC-4432 "," Asahi Guard (registered trademark) AG-710 "manufactured by AGC", and "Surflon (registered trademark, the same shall apply hereinafter)" S-382 "manufactured by AGC SEIMICHEMICAL", "Surflon SC-101", "Surflon SC-102", "Surflon SC-103", "Surflon SC-104", "Surflon SC-105", "Surflon SC-106", and "Optool (registered trademark) DAC-HP" manufactured by Dajin Industrial Co.
(A) The content of the acrylic resin (a) in the liquid repellent is also not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and usually 100% by mass or less. When the lower limit value is not less than the above-mentioned lower limit value, the ink repellency after the UV cleaning treatment tends to be suppressed from decreasing. 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) When the liquid repellent contains another liquid repellent, the content of the other liquid repellent in the liquid repellent (a) is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more, and is 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 above-described lower limit value, residue in the pixel portion tends to be suppressed, and when the upper limit value is not more than the above-described upper limit value, ink repellency after the UV cleaning treatment tends to be suppressed from decreasing. (A) When the liquid repellent contains another liquid repellent, the content of the other liquid repellent in the liquid repellent (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 developing solution. Examples of the alkali-soluble resin include various resins containing a carboxyl group and/or a hydroxyl group. Among them, a carboxyl group-containing resin is preferable from the viewpoint of obtaining a partition wall having an appropriate taper angle, suppressing the flow-out of a liquid repellent due to thermal fusion of the surface of the partition wall at the time of post baking, and maintaining ink repellency.
[ alkali-soluble resin (b) having an ethylenic 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 ethylenic double bond (hereinafter, may be simply referred to as "alkali-soluble resin (B)"). The alkali-soluble resin (b) having an ethylenic double bond is included, and therefore, the sensitivity is improved, and the outflow of the liquid repellent during development is suppressed, and the ink repellency of the partition walls obtained tends to be improved.
The specific structure of the alkali-soluble resin (b) having an ethylenic double bond is not particularly limited, and the epoxy (meth) acrylate resin (b1) and/or the acrylic copolymer resin (b2) are preferable from the viewpoint of developing solubility, and the epoxy (meth) acrylate resin (b1) is more preferable from the viewpoint of reducing outgassing.
The epoxy (meth) acrylate resin (b1) will be described in detail below.
[ epoxy (meth) acrylate resin (b1) ]
The epoxy (meth) acrylate resin (b1) is a resin obtained by adding an acid or ester compound having an ethylenically unsaturated bond (ethylenic double bond) to an epoxy resin and further adding a polybasic acid or an 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 to add the ethylenically unsaturated bond to the epoxy resin via an ester bond (-COO-) and simultaneously add a hydroxyl group generated at this time to one carboxyl group of a polybasic acid anhydride is exemplified. Further, a resin obtained by adding a polyhydric alcohol simultaneously with the addition of a polybasic acid anhydride may be mentioned. Further, a resin obtained by further reacting a carboxyl group of the resin obtained in the above reaction with a compound having a reactive functional group is also included in the above epoxy (meth) acrylate resin (b 1).
As described above, the epoxy (meth) acrylate resin is not limited to "(meth) acrylate" because it has substantially no epoxy group in its chemical structure, but is conventionally named because an epoxy compound (epoxy resin) is used as 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 thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. In addition, as the epoxy resin, a compound obtained by reacting a phenolic compound with epichlorohydrin may be used. The phenolic compound is preferably a 2-or more-membered compound having a phenolic hydroxyl group, and may be a monomer or a polymer.
Specific examples thereof include: bisphenol a-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, biphenol-aldehyde epoxy resins, trisphenol epoxy resins, epoxides of polymers of phenol and dicyclopentadiene, dihydroxyfluorene-type epoxy resins, dihydroxyalkyleneoxyfluorene-type epoxy resins, diglycidyl etherate of 9, 9-bis (4 '-hydroxyphenyl) fluorene, diglycidyl etherate of 1, 1-bis (4' -hydroxyphenyl) adamantane, and the like, and compounds having an aromatic ring in the main chain as described above can be preferably used.
Among these, 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 cured film strength.
Examples of the acid having an ethylenically unsaturated bond include: (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, and the like, and pentaerythritol tri (meth) acrylate succinic anhydride adducts, pentaerythritol tri (meth) acrylate tetrahydrophthalic anhydride adducts, dipentaerythritol penta (meth) acrylate succinic anhydride adducts, dipentaerythritol penta (meth) acrylate phthalic anhydride adducts, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride adducts, reaction products of (meth) acrylic acid and 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, and acid anhydrides thereof. These polybasic acids (anhydrides) may be used alone or in combination of two or more. Among these, from the viewpoint of reducing residues in the pixel portion after development, succinic anhydride, maleic anhydride, and itaconic anhydride are preferable, and succinic anhydride is more preferable.
By using a polyol, the molecular weight of the epoxy (meth) acrylate resin (b1) tends to be increased, and a balance between the molecular weight and the viscosity tends to be obtained by introducing a branch into the molecule. Further, the introduction rate of an acid group into a molecule tends to be increased, and a balance between sensitivity, adhesion, and the like tends to be easily obtained.
The polyol is preferably one or two or more polyols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2, 3-propanetriol, for example.
The acid value of the epoxy (meth) acrylate resin (b1) 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 not less than the above-described lower limit value, the residue tends to be reduced and the taper angle tends to be high, and when the upper limit value is not more than the above-described upper limit value, the outgassing during the light emission of the device tends to be reduced. The acid value of the epoxy (meth) acrylate resin (b1) 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 yet more preferably 60 to 100 mg-KOH/g.
The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (b1) is not particularly limited, and is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, further preferably 4000 or more, further preferably 5000 or more, particularly preferably 6000 or more, and most preferably 7000 or more, and is usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, and further preferably 10000 or less. When the lower limit value is not less than the above-mentioned lower limit value, outgassing tends to be reduced when the element emits light, and when the upper limit value is not more than the above-mentioned upper limit value, residue tends to be reduced. The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (b1) 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 (B) alkali-soluble resin is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, and usually 100% by mass or less. When the lower limit value is not less than the above-described lower limit value, the degassing tends to be reduced. (B) When the alkali-soluble resin includes 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 (b1) can be synthesized by a conventionally known method. Specifically, the following method may be employed: the epoxy resin is dissolved in an organic solvent, the acid or ester compound having an ethylenically unsaturated bond is added in the presence of a catalyst and a thermal polymerization inhibitor to cause an addition reaction, and a polybasic acid or an 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, etc. Further, as the catalyst, there may be mentioned: one or more of tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine, quaternary ammonium salts such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride and trimethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and antimony compounds such as triphenylantimony. The thermal polymerization inhibitor may be one or more selected from hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone.
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 1 chemical equivalent of the epoxy group of the epoxy resin. The temperature during the addition reaction may be generally 60 to 150 ℃, preferably 80 to 120 ℃. The amount of the polybasic acid (anhydride) used may be usually 0.1 to 1.2 stoichiometric equivalents, preferably 0.2 to 1.1 stoichiometric equivalents, based on 1 stoichiometric equivalent of the hydroxyl group formed in the addition reaction.
From the viewpoint of outgassing when the element emits light, the epoxy (meth) acrylate resin (b1) preferably contains at least one selected from the group consisting of: an epoxy (meth) acrylate resin (b1-1) (hereinafter, may be abbreviated as "epoxy (meth) acrylate resin (b 1-1)") having a partial structure represented by the following general formula (i), an epoxy (meth) acrylate resin (b1-2) (hereinafter, may be abbreviated as "epoxy (meth) acrylate resin (b 1-2)") having a partial structure represented by the following general formula (ii), and an epoxy (meth) acrylate resin (b1-3) (hereinafter, may be abbreviated as "epoxy (meth) acrylate resin (b 1-3)") having a partial structure represented by the following general formula (iii).
Among the above, the epoxy (meth) acrylate resin (b1) is preferably an epoxy (meth) acrylate resin (b1-1) containing a partial structure represented by the following general formula (i) from the viewpoint of reducing outgassing during light emission of the device. One reason for this is that the steel sheet has a rigid main skeleton and is therefore less likely to be decomposed by heat.
[ chemical formula 12]
Figure BDA0002576772040000231
In the formula (i), RaRepresents a hydrogen atom or a methyl group, RbRepresents a 2-valent hydrocarbon group optionally having a substituent, the benzene ring in the formula (i) is optionally further substituted with an optional substituent, and represents a bonding position.
(Rb)
In the above formula (i), RbRepresents a 2-valent hydrocarbon group optionally having a substituent.
As the 2-valent hydrocarbon group, there may be mentioned: a 2-valent aliphatic group, a 2-valent aromatic group, and a group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic groups are linked.
Examples of the 2-valent aliphatic group include linear, branched and cyclic groups. Among 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 permeation 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 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 above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, 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 the residue.
Specific examples of the 2-valent branched aliphatic group include: the aforementioned 2-valent linear aliphatic group has a structure having a side chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or the like.
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 usually 10 or less, preferably 5 or less. When the lower limit value is not less than the above-described lower limit value, the residual film ratio tends to be improved, and when the upper limit value is not more than the above-described upper limit value, the residual film 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 isoborneol ring, or an adamantane ring. Among these groups, from the viewpoint of development adhesion, a group obtained by removing 2 hydrogen atoms from the adamantane ring is preferable.
As the substituent optionally having the 2-valent aliphatic group, there can be mentioned: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
Examples of the 2-valent aromatic ring group include a 2-valent aromatic 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 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 above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, 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. As the 2-valent aromatic hydrocarbon ring group, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,
Figure BDA0002576772040000241
A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, etc., having 2 free valences.
The aromatic heterocyclic ring in the 2-valent aromatic heterocyclic group may be a monocyclic 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, or the like,
Figure BDA0002576772040000242
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring
Figure BDA0002576772040000243
An 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,
Figure BDA0002576772040000244
a group having 2 free valences such as a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, etc. Among these, from the viewpoint of photocurability, a benzene ring or a 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 aromatic ring group having a valence of 2 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, the resin is preferably unsubstituted.
Examples of the group in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked include groups in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked.
The number of the 2-valent aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, 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 usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Specific examples of the group in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked include: groups represented by the following formulae (i-A) to (i-F), and the like. Among these groups, from the viewpoint of rigidity of the skeleton and hydrophobization of the film, a group represented by the following formula (i-a) is preferable. In the formula,. indicates a bonding site.
[ chemical formula 13]
Figure BDA0002576772040000261
As mentioned above, the phenyl ring in formula (i) is optionally further substituted with any substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of the substituents is not particularly limited, and may be 1 or 2 or more.
Among these, from the viewpoint of curability, the resin is preferably unsubstituted.
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]
Figure BDA0002576772040000271
In the formula (i-1), RaAnd RbAnd R in the above formula (i)aAnd RbSynonymy, R1Represents a C1-4 valent hydrocarbon group 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), R1Represents an optionally substituted C1-4 valent hydrocarbon group. 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, and is usually 1 or more, preferably 2 or more, and usually 4 or less, preferably 3 or less. When the lower limit value is set to be equal to or higher than the lower limit value, the residual film ratio tends to be improved, and when the upper limit value is set to be equal to or lower than the lower limit value, the amount of outgas in light emission of the device tends to be reduced.
Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group, and from the viewpoint of reducing degassing, the methylene group or the ethylene group is preferable, and the ethylene group 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 2 or more, and usually 4 or less, preferably 3 or less. When the lower limit value is set to be equal to or higher than the lower limit value, the residual film ratio tends to be improved, and when the upper limit value is set to be equal to or lower than the lower limit value, the amount of outgas in light emission of the device tends to be reduced.
Specific examples of the alkenylene group include a vinylene group, a propenylene group, and a butenylene group, and the vinylene group is preferable from the viewpoint of degassing.
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.
Of these, R is from the viewpoint of reducing outgassing1The alkylene group is preferably a C1-4 alkylene group having a valence of 2, more preferably a methylene group or an ethylene group, and still more preferably an ethylene group.
The partial structure represented by the above formula (i-1) contained in1 molecule of the epoxy (meth) acrylate resin (b1-1) may be one kind, or two or more kinds.
The number of partial structures represented by the above formula (i) contained in1 molecule of the epoxy (meth) acrylate resin (b1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further 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 above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
The number of partial structures represented by the above formula (i-1) contained in1 molecule of the epoxy (meth) acrylate resin (b1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, further 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 above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Specific examples of the epoxy (meth) acrylate resin (b1-1) are described below.
[ chemical formula 15]
Figure BDA0002576772040000281
[ chemical formula 16]
Figure BDA0002576772040000282
[ chemical formula 17]
Figure BDA0002576772040000291
[ chemical formula 18]
Figure BDA0002576772040000292
[ chemical formula 19]
Figure BDA0002576772040000293
[ chemical formula 20]
Figure BDA0002576772040000294
[ chemical formula 21]
Figure BDA0002576772040000301
On the other hand, from the viewpoint of development adhesion, the epoxy (meth) acrylate resin (b1) is preferably an epoxy (meth) acrylate resin (b1-2) containing a partial structure represented by the following formula (ii).
[ chemical formula 22]
Figure BDA0002576772040000302
In the formula (ii)，RcEach independently represents a hydrogen atom or a methyl group, RdRepresents 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), RdRepresents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less carbon atoms. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Specific examples of the alicyclic ring in the alicyclic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isoborneol ring, adamantane ring, etc. Among these, an adamantane ring is preferable from the viewpoint of film strength and development adhesion.
On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and more preferably 3 or more, and is usually 10 or less, preferably 5 or less, and more preferably 4 or less. When the lower limit value is not less than the above-described lower limit value, the residue tends to be reduced, and when the upper limit value is not more than the above-described upper limit value, the development adhesion tends to be improved.
Examples of the aromatic ring group include an aromatic 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, further preferably 10 or more, and particularly preferably 12 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. When the lower limit value is not less than the above-described lower limit value, the residue tends to be reduced, and when the upper limit value is not more than the above-described 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,
Figure BDA0002576772040000311
A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, etc. Among these, the fluorene ring is preferable from the viewpoint of patterning characteristics.
In addition, the 2-valent hydrocarbon group in the 2-valent hydrocarbon group 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 group, and a group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic groups are linked.
Examples of the 2-valent aliphatic group include linear, branched and cyclic groups. Among 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 permeation 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 preferably 25 or less, more preferably 20 or less, and further preferably 15 or less. When the lower limit value is not less than the above-described lower limit value, the development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, the residue tends to be reduced and killed.
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 the residue.
Specific examples of the 2-valent branched aliphatic group include: the aforementioned 2-valent linear aliphatic group has a structure having a side chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl.
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 usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, 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 isoborneol ring, or an adamantane ring. Among these, from the viewpoint of development adhesion, a group obtained by removing 2 hydrogen atoms from an adamantane ring is preferable.
As the substituent optionally having the 2-valent aliphatic group, there can be mentioned: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
Examples of the 2-valent aromatic ring group include a 2-valent aromatic 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 preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, 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. As the 2-valent aromatic hydrocarbon ring group, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,
Figure BDA0002576772040000321
A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, etc., having 2 free valences.
In addition, as 2-valent aromaticThe aromatic heterocycle of the heterocyclic group may be a monocyclic 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, or the like,
Figure BDA0002576772040000322
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring
Figure BDA0002576772040000323
An 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,
Figure BDA0002576772040000324
a group having 2 free valences such as a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, etc. Among these, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having 2 free valences is preferable, and a benzene ring having 2 free valences is more preferable.
As the substituent optionally having a 2-valent aromatic ring group, there can be mentioned: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.
Examples of the group in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked include: a group in which 1 or more of the aforementioned 2-valent aliphatic groups are linked to 1 or more of the aforementioned 2-valent aromatic ring groups.
The number of the 2-valent aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, 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 usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Specific examples of the group in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked include: and groups represented by the above formulae (i-A) to (i-F). Among these groups, the group represented by the above formula (i-C) is preferable from the viewpoint of reducing the residue.
The bonding form of the cyclic hydrocarbon group as the side chain to these 2-valent hydrocarbon groups is not particularly limited, and examples thereof include: the side chain is substituted with an aliphatic group or 1 hydrogen atom of an aromatic ring group, or a cyclic hydrocarbon group having 1 carbon atom of the aliphatic group as a side chain.
In addition, the partial structure represented by the above formula (ii) is preferably a partial structure represented by the following formula (ii-1) from the viewpoint of development adhesion.
[ chemical formula 23]
Figure BDA0002576772040000331
In the formula (ii-1), RcSynonymous with the above formula (ii), RαRepresents an optionally substituted 1-valent cyclic hydrocarbon group, 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, and represents a bonding position.
(Rα)
In the above formula (ii-1), RαRepresents an optionally substituted 1-valent cyclic hydrocarbon group.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less carbon atoms. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Specific examples of the alicyclic ring in the alicyclic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isoborneol ring, adamantane ring, etc. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.
On the other hand, the number of rings of 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 above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Examples of the aromatic ring group include an aromatic 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 preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, 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, etc. Among these, the fluorene ring is preferable from the viewpoint of development adhesion.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, etc.; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; hydroxyl and nitro; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Of these, R is R from the viewpoint of firm film curability and electrical characteristicsαPreferably a 1-valent aliphatic ring group, more preferably an adamantyl group.
As described above, the benzene ring in the formula (ii-1) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of the substituents is also not particularly limited, and may be 1 or 2 or more. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.
Specific examples of the partial structure represented by the above formula (ii-1) are shown below.
[ chemical formula 24]
Figure BDA0002576772040000351
[ chemical formula 25]
Figure BDA0002576772040000352
[ chemical formula 26]
Figure BDA0002576772040000353
[ chemical formula 27]
Figure BDA0002576772040000354
[ chemical formula 28]
Figure BDA0002576772040000355
In addition, the partial structure represented by the above formula (ii) is preferably a partial structure represented by the following formula (ii-2) from the viewpoint of development adhesion.
[ chemical formula 29]
Figure BDA0002576772040000361
In the formula (ii-2), RcSynonymous with the above formula (ii), RβRepresents a 2-valent cyclic hydrocarbon group optionally having a substituent, the benzene ring in the formula (ii-2) is optionally further substituted with an optional substituent, and represents a bonding position.
(Rβ)
In the above formula (ii-2), RβRepresents an optionally substituted 2-valent cyclic hydrocarbon group.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less carbon atoms. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Specific examples of the alicyclic ring in the alicyclic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isoborneol ring, adamantane ring, etc. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.
On the other hand, the number of rings of 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 above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Examples of the aromatic ring group include an aromatic 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, further preferably 10 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, 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, etc. Among these, the fluorene ring is preferable from the viewpoint of development adhesion.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, etc.; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
Among these, R is R from the viewpoint of curabilityβPreferably a 2-valent aliphatic ring group, more preferably a 2-valent adamantyl ring group.
On the other hand, from the viewpoint of development adhesion, RβPreferably a 2-valent aromatic ring group, more preferably a 2-valent fluorene ring group.
As described above, the benzene ring in the formula (ii-2) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of the substituents is also not particularly limited, and may be 1 or 2 or more. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.
Specific examples of the partial structure represented by the above formula (ii-2) are shown below.
[ chemical formula 30]
Figure BDA0002576772040000371
[ chemical formula 31]
Figure BDA0002576772040000372
[ chemical formula 32]
Figure BDA0002576772040000373
[ chemical formula 33]
Figure BDA0002576772040000381
On the other hand, the partial structure represented by the above formula (ii) is preferably a partial structure represented by the following formula (ii-3) from the viewpoint of curability.
[ chemical formula 34]
Figure BDA0002576772040000382
In the formula (ii-3), RcAnd RdSynonymous with the above formula (ii), R1The same meaning as in the above formula (i-1) indicates a bonding site.
The partial structure represented by the above formula (ii-3) contained in1 molecule of the epoxy (meth) acrylate resin (b1-2) may be one kind, or two or more kinds.
The number of partial structures represented by the above formula (ii) contained in1 molecule of the epoxy (meth) acrylate resin (b1-2) 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 still more preferably 10 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
On the other hand, from the viewpoint of reducing outgassing during light emission of the device, the epoxy (meth) acrylate resin (b1) is preferably an epoxy (meth) acrylate resin (b1-3) containing a partial structure represented by the following general formula (iii).
[ chemical formula 35]
Figure BDA0002576772040000391
In the formula (iii), ReRepresents 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 the formula (iii) is optionally further substituted with an optional substituent, and x represents a bonding position.
(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 development solubility, and is preferably branched from the viewpoint of development adhesion. The number of carbon atoms is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, 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 a methylene group, ethylene group, or propylene group, and more preferably a dimethylmethylene group, from the viewpoint of achieving both 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; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of satisfying both development adhesion and development solubility, the non-substituted is preferable.
Examples of the 2-valent cyclic hydrocarbon group include a 2-valent aliphatic ring group and a 2-valent aromatic ring group.
The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less carbon atoms. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Specific examples of the alicyclic ring in the alicyclic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isoborneol ring, adamantane ring, etc. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.
On the other hand, the number of rings of 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 above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Examples of the aromatic ring group include an aromatic 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, further preferably 10 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, 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, etc. Among these, the fluorene ring is preferable from the viewpoint of development adhesion.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, etc.; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
Among these, γ is preferably an alkylene group optionally having a substituent, more preferably dimethylmethylene group, from the viewpoint of reducing the residue.
As mentioned above, the phenyl ring in formula (iii) is optionally further substituted with any substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of the substituents is also not particularly limited, and may be 1 or 2 or more. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.
On the other hand, the partial structure represented by the above formula (iii) is preferably a partial structure represented by the following formula (iii-1) from the viewpoint of developing solubility.
[ chemical formula 36]
Figure BDA0002576772040000411
In the formula (iii-1), ReAnd γ is the same as in the above formula (iii), R1And R in the above formula (i-1)1Synonymously, indicates the bonding position. The benzene ring in the formula (iii-1) is optionally further substituted with an optional substituent.
The number of partial structures represented by the above formula (iii) contained in1 molecule of the epoxy (meth) acrylate resin (b1-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, and still more preferably 10 or more, and is preferably 18 or less, and still more preferably 15 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
The number of partial structures represented by the above formula (iii-1) contained in1 molecule of the epoxy (meth) acrylate resin (b1-3) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and further preferably 18 or less, further preferably 15 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Specific examples of the epoxy (meth) acrylate resin (b1-3) are described below.
[ chemical formula 37]
Figure BDA0002576772040000412
[ chemical formula 38]
Figure BDA0002576772040000421
[ chemical formula 39]
Figure BDA0002576772040000422
[ acrylic copolymer resin (b2) ]
Next, the acrylic copolymer resin (b2) will be described in detail. From the viewpoint of curability, the acrylic copolymer resin (b2) is preferably an acrylic copolymer resin having an ethylenic double bond in a side chain.
Among the acrylic copolymer resins (b2), from the viewpoint of developing solubility, an acrylic copolymer resin (b2-1) containing a partial structure represented by the following general formula (I) is preferable.
[ chemical formula 40]
Figure BDA0002576772040000423
In the formula (I), RAAnd RBEach independently represents a hydrogen atom or a methyl group, and represents a bonding position.
In addition, the partial structure represented by the above formula (I) is preferably a partial structure represented by the following general formula (I-1) from the viewpoint of developability.
[ chemical formula 41]
Figure BDA0002576772040000431
In the formula (I-1), RAAnd RBSynonymous with in the above formula (I), R1The same meaning as in the above formula (i-1).
From the viewpoint of sensitivity, the partial structure represented by the formula (I) is preferably a partial structure represented by the following formula (I-2).
[ chemical formula 42]
Figure BDA0002576772040000432
In the formula (I-2), RAAnd RBThe same meaning as in the above formula (I).
When the acrylic copolymer resin (b2-1) includes a partial structure represented by the above general formula (I), the content ratio of the partial structure represented by the above general formula (I) in the acrylic copolymer resin (b2-1) is not particularly limited, but is preferably 5 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, further 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, and further preferably 95 mol% or less. When the lower limit value is not less than the above-described lower limit value, the residue tends to be reduced, and when the upper limit value is not more than the above-described upper limit value, the development adhesion tends to be improved. When the acrylic copolymer resin (b2-1) includes the 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 (b2-1) 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 (b2-1) contains a partial structure represented by the above general formula (I-1), the content ratio of the partial structure represented by the above general formula (I-1) contained in the acrylic copolymer resin (b2-1) is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% or more, and yet more preferably 10 mol% or more, and is preferably 99 mol% or less, more preferably 60 mol% or less, still more preferably 40 mol% or less, yet more preferably 30 mol% or less, and particularly preferably 20 mol% or less. When the lower limit value is not less than the above-described lower limit value, sensitivity tends to be improved and residue tends to be reduced, and when the upper limit value is not more than the above-described upper limit value, development adhesion tends to be improved. When the acrylic copolymer resin (b2-1) contains the partial structure represented by the general formula (I-1), the content of the partial structure represented by the general formula (I-1) contained in the acrylic copolymer resin (b2-1) 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 (b2-1) contains a partial structure represented by the above general formula (I-2), the content ratio of the partial structure represented by the above general formula (I-2) contained in the acrylic copolymer resin (b2-1) is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, further 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, further preferably 90 mol% or less, and particularly preferably 85 mol% or less. When the lower limit value is not less than the lower limit value, sensitivity tends to be improved, and when the upper limit value is not more than the upper limit value, developability tends to be improved. When the acrylic copolymer resin (b2-1) contains the partial structure represented by the general formula (I-2), the content of the partial structure represented by the general formula (I-2) contained in the acrylic copolymer resin (b2-1) 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 (b2-1) contains a partial structure represented by the above general formula (I), the partial structure that may be contained separately is not particularly limited, and from the viewpoint of development adhesion, it is preferable to contain a partial structure represented by the following general formula (I'), for example.
[ chemical formula 43]
Figure BDA0002576772040000451
In the above formula (I'), RDRepresents a hydrogen atom or a methyl group, RERepresents an alkyl group optionally having a substituent, an aryl group (aromatic ring group) optionally having a substituent, or an alkenyl group optionally having a substituent.
(RE)
In the above formula (I'), RERepresents an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an alkenyl group optionally having a substituent.
As REExamples of the alkyl group in (1) include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and further preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the lower limit value is not less than the above-described lower limit value, the film strength tends to be improved and the development adhesion tends to be improved, and when the upper limit value is not more than the above-described 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, from the viewpoint of membrane strength, dicyclopentyl or dodecyl is preferable, and dicyclopentyl is more preferable.
Further, as the substituent optionally contained in the alkyl group, there may be mentioned: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl group, methacryloyl group, etc., and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
As REExamples of the aryl group (aromatic ring group) in (1) 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 also preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, 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,
Figure BDA0002576772040000452
A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, etc.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and examples thereof include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, or the like,
Figure BDA0002576772040000461
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring
Figure BDA0002576772040000462
An 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,
Figure BDA0002576772040000463
Pyridine ring, quinazoline ring, azulene ring, etc. 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.
Further, as the substituent optionally having an aryl group, there may be mentioned: methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, etc., and from the viewpoint of developability, hydroxyl group and oligoethylene glycol group are preferable.
As REExamples of the alkenyl group in (1) include straight-chain, branched or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, and is preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Specific examples of the alkenyl group include: ethenyl, propenyl, butenyl, cyclohexenyl, and the like. Among these, from the viewpoint of curability, an ethylene group or an propylene group is preferable, and an ethylene group is more preferable.
In addition, as the substituent optionally having an alkenyl group, there may be mentioned: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, etc., and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
Like this, RERepresents 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 even more preferable.
When the acrylic copolymer resin (b2-1) includes the 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 (b2-1) is not particularly limited, but is preferably 0.5 mol% or more, more preferably 1 mol% or more, further preferably 1.5 mol% or more, particularly preferably 2 mol% or more, and further preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, further preferably 30 mol% or less, and particularly preferably 10 mol% or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced. When the acrylic copolymer resin (b2-1) includes the partial structure represented by the general formula (I '), the content of the partial structure represented by the general formula (I') included in the acrylic copolymer resin (b2-1) 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 (b2-1) contains a partial structure represented by the above general formula (I), it is preferable that the acrylic copolymer resin further contains a partial structure represented by the following general formula (I ") from the viewpoint of heat resistance and film strength.
[ chemical formula 44]
Figure BDA0002576772040000471
In the above formula (I'), RFRepresents a hydrogen atom or a methyl group, RGRepresents 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'), RGRepresents an optionally substituted alkyl group, an optionally substituted alkenyl group, a hydroxyl group, a carboxyl group, a halogen atom, an optionally substituted alkyl groupAn alkoxy group, a thiol group, or an alkylthio group optionally having a substituent.
As RGExamples of the alkyl group in (1) include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and further preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Specific examples of the alkyl group include: methyl, ethyl, cyclohexyl, dicyclopentyl, dodecyl and the like. Among these groups, from the viewpoint of development adhesion, dicyclopentyl group or dodecyl group is preferable, and dicyclopentyl group is more preferable.
Further, as the substituent optionally contained in the alkyl group, there may be mentioned: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl group, methacryloyl group, etc., and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
As RGExamples of the alkenyl group in (1) include straight-chain, branched or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, and is preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Specific examples of the alkenyl group include: ethenyl, propenyl, butenyl, cyclohexenyl, and the like. Among these, from the viewpoint of curability, an ethylene group or an propylene group is preferable, and an ethylene group is more preferable.
In addition, as the substituent optionally having an alkenyl group, there may be mentioned: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, etc., and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
As RGThe halogen atom in (b) may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and among these, a fluorine atom is preferable from the viewpoint of ink repellency.
As RGExamples of the alkoxy group in (1) include linear, branched or cyclic alkoxy groups. The number of carbon atoms is preferably 1 or more, and is preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Further, as the substituent optionally having an alkoxy group, there may be mentioned: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl group, methacryloyl group, etc., and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
As RGThe alkylthio group in (1) may be a straight-chain, branched or cyclic alkylthio group. The number of carbon atoms is preferably 1 or more, and is preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced.
Specific examples of the alkylthio group include: methylthio, ethylthio, propylthio, butylthio, and the like. Among these, methylthio and ethylthio are preferable from the viewpoint of developability.
In addition, as the substituent optionally having an alkyl group in the alkylthio group, there can be mentioned: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl group, methacryloyl group, etc., and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
Like this, RGRepresents 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, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable.
(t)
In the formula (I ″), t represents an integer of 0 to 5, and is preferably 2 or less, more preferably 1 or less, and even more preferably 0, from the viewpoint of developability.
When the acrylic copolymer resin (b2-1) includes a partial structure represented by the above general formula (I ″), the content ratio of the partial structure represented by the above general formula (I ″) included in the acrylic copolymer resin (b2-1) is not particularly 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 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, further 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 above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced. When the acrylic copolymer resin (b2-1) includes the partial structure represented by the general formula (I ″), the content of the partial structure represented by the general formula (I ″) included in the acrylic copolymer resin (b2-1) 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 (b2-1) contains a partial structure represented by the above general formula (I), it is preferable from the viewpoint of developability to further contain a partial structure represented by the following general formula (I' ").
[ chemical formula 45]
Figure BDA0002576772040000491
In the above formula (I'), RHRepresents a hydrogen atom or a methyl group.
When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I '"), the content ratio of the partial structure represented by the above general formula (I'") contained in the acrylic copolymer resin (b2-1) is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 30 mol% or more, and further preferably 90 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, and particularly preferably 50 mol% or less. When the lower limit value is not less than the above-described lower limit value, the residue tends to be reduced, and when the upper limit value is not more than the above-described upper limit value, the development adhesion tends to be improved. When the acrylic copolymer resin (b2-1) includes the partial structure represented by the general formula (I '"), the content of the partial structure represented by the general formula (I'") included in the acrylic copolymer resin (b2-1) is, for example, 5 to 90 mol%, preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and still 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 (b2) 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, yet 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, and still more preferably 40mg-KOH/g or less. When the lower limit value is not less than the above-described lower limit value, the residue tends to be reduced, and when the upper limit value is not more than the above-described upper limit value, the development adhesion tends to be improved. The acid value of the acrylic copolymer resin (b2) 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 40 mg-KOH/g.
The weight average molecular weight (Mw) of the acrylic copolymer resin (b2) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, further preferably 3000 or more, further preferably 4000 or more, and particularly preferably 5000 or more, and is usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, further preferably 10000 or less, and particularly preferably 8000 or less. When the lower limit value is not less than the above-described lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-described upper limit value, residue tends to be reduced. The weight average molecular weight (Mw) of the acrylic copolymer resin (b2) is, for example, 1000 to 30000, preferably 2000 to 20000, more preferably 3000 to 15000, still more preferably 4000 to 10000, and still more preferably 5000 to 8000.
(B) When the alkali-soluble resin includes the acrylic copolymer resin (B2), the content of the acrylic copolymer resin (B2) included in the (B) 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 usually 100% by mass or less, preferably 80% by mass or less, further preferably 50% by mass or less. When the lower limit value is set to be equal to or higher than the upper limit value, the developing solubility tends to be good, and when the upper limit value is set to be equal to or lower than the lower limit value, the taper angle tends to be high. (B) When the alkali-soluble resin includes the acrylic copolymer resin (B2), the content of the acrylic copolymer resin (B2) contained as the alkali-soluble resin (B) is, for example, 5 to 100 mass%, preferably 10 to 100 mass%, more preferably 15 to 80 mass%, and further preferably 20 to 50 mass%.
(B) The alkali-soluble resin may contain either one of the epoxy (meth) acrylate resin (b1) and the acrylic copolymer resin (b2) 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 content of the total solid content is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less. When the lower limit value is not less than the above-mentioned lower limit value, the developing property tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the outgassing at the time of 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.
When the photosensitive resin composition of the present invention contains the epoxy (meth) acrylate resin (b1), the content of the epoxy (meth) acrylate resin (b1) is not particularly limited, and is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and 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, and particularly preferably 50% by mass or less, of the total solid content. When the lower limit value is not less than the above-mentioned lower limit value, the developing property tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the outgassing at the time of light emission of the element tends to be reduced. When the photosensitive resin composition of the present invention contains the epoxy (meth) acrylate resin (b1), the content of the epoxy (meth) acrylate resin (b1) 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.
When the photosensitive resin composition of the present invention contains the epoxy acrylic copolymer resin (b2), the content of the acrylic copolymer resin (b2) is not particularly limited, and is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more, and is usually 90% by mass or less, preferably 70% by mass or less, more preferably は 60% by mass or less, and particularly preferably 50% by mass or less in the total solid content. When the lower limit value is not less than the above-mentioned lower limit value, the developing property tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the outgassing at the time of light emission of the element tends to be reduced. When the photosensitive resin composition of the present invention contains the epoxy acrylic copolymer resin (b2), the content of the acrylic copolymer resin (b2) 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.
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, further preferably 50% by mass or more, further preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more, and usually 99% by mass or less, preferably 97% by mass or less, and more preferably 95% by mass or less. When the lower limit value is not less than the above-mentioned lower limit value, curability tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, outgassing tends to be reduced when the device emits light. The total content of the alkali-soluble resin (B) and the photopolymerizable compound (C) in all the solid components is, for example, 5 to 99% by mass, preferably 10 to 99% by mass, more preferably 30 to 99% by mass, even more preferably 50 to 97% by mass, even 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, further preferably 70 parts by mass or more, and 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, further preferably 200 parts by mass or less, and particularly preferably 100 parts by mass or less, with respect to 100 parts by mass of the photopolymerizable compound (C). When the lower limit value is not less than the above-mentioned lower limit value, development adhesion tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, curability tends to be improved. The compounding ratio of the alkali-soluble resin (B) to 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 incorporation of (C) a photopolymerizable compound is considered to result in high sensitivity.
The photopolymerizable compound used herein is a compound having 1 or more ethylenically unsaturated bonds (ethylenic double bonds) in the molecule, and is preferably a compound having 2 or more ethylenically unsaturated bonds in the molecule from the viewpoints of polymerizability, crosslinkability, and the accompanying enlargement of the difference in solubility of the developer between the exposed portion and the unexposed portion, and is also preferably a compound whose unsaturated bond is derived from a (meth) acryloyloxy group, that is, a (meth) acrylate compound.
In the photosensitive resin composition of the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having 2 or more ethylenically unsaturated bonds in1 molecule. The number of the ethylenically unsaturated groups of the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, and particularly preferably 5 or more, and is preferably 15 or less, more preferably 10 or less, further preferably 8 or less, and particularly preferably 7 or less. When the lower limit value is not less than the above-mentioned lower limit value, the polymerizability tends to be improved and the sensitivity tends to be high, and when the upper limit value is not more than the above-mentioned upper limit value, the developability tends to be more excellent. The number of the ethylenically unsaturated groups contained in the polyfunctional ethylenic monomer is, for example, 2 to 15, preferably 3 to 10, more preferably 4 to 8, and still more preferably 5 to 7.
Specific examples of the photopolymerizable compound include: esters of aliphatic polyols with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; esters 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.
Examples of the ester of the aliphatic polyhydric compound and the unsaturated carboxylic acid include: examples of the acrylate include acrylates of aliphatic polyhydric compounds 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 replacing acrylates of the above exemplified compounds with methacrylates, itaconates similarly replaced with itaconates, crotonates replaced with crotonates, and maleates replaced with maleates.
As the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, there can be mentioned: acrylic acid esters and methacrylic acid esters 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 one, and representative examples thereof include: condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerol, and the like.
Further, examples of the photopolymerizable compound used in the photosensitive resin composition of the present invention include urethane (meth) acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or a polyol and a hydroxyl group-containing (meth) acrylate; epoxy acrylates such as addition reaction products of a polyhydric 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 group-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 Ningmura Kagaku K.K.), UA-306H, UA-510H, UF-8001G (manufactured by Kaishi Kagaku K.K.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640 76 7640B (manufactured by Nippon Kagaku K.K.), and the like.
Among these, from the viewpoint of appropriate taper angle and sensitivity, ester (meth) acrylates or urethane (meth) acrylates are preferably used as the photopolymerizable compound (C), and dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2-tris (meth) acryloyloxymethyl ethyl phthalate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, a dibasic anhydride adduct of dipentaerythritol penta (meth) acrylate, a dibasic anhydride adduct of pentaerythritol tri (meth) acrylate, and the like are more preferably used.
These compounds may be used alone 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, further preferably 200 or more, further preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, and preferably 1000 or less, more preferably 700 or less, from the viewpoint of sensitivity, ink repellency, and taper angle. The photopolymerizable compound (C) has a molecular weight of, 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, further preferably 15 or more, further preferably 20 or more, particularly preferably 25 or more, and preferably 50 or less, more preferably 40 or less, further preferably 35 or less, and particularly preferably 30 or less, from the viewpoint 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, and still more preferably 25 to 30.
Further, ester (meth) acrylates, epoxy (meth) acrylates, and urethane (meth) acrylates are preferable from the viewpoint of sensitivity, ink repellency, and cone angle, and among them, 3-functional or higher ester (meth) acrylates such as pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate, and anhydride adducts of 3-functional ester (meth) acrylates such as 2,2, 2-tris (meth) acryloyloxymethylethyl phthalate, and dibasic anhydride adducts of dipentaerythritol penta (meth) acrylate are more preferable from the viewpoint of sensitivity, ink repellency, and cone angle.
The content of the photopolymerizable compound (C) in the photosensitive resin composition of the invention is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more, and is usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 55% by mass or less, and particularly preferably 50% by mass or less, in the total solid content. When the lower limit value is set to be equal to or higher than the lower limit value, sensitivity and a taper angle at the time of exposure tend to be good, and when the upper limit value is set to be equal to or lower 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, and particularly preferably 90 parts by mass or more, and is usually 150 parts by mass or less, preferably 130 parts by mass or less, more preferably 120 parts by mass or less, and further preferably 110 parts by mass or less, relative to 100 parts by mass of the alkali-soluble resin (B). When the lower limit value is set to be equal to or higher than the lower limit value, 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 set to be equal to or lower than the upper limit value, developability 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 yet 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 is a compound capable of polymerizing the ethylenically unsaturated bond of the photopolymerizable compound (C) with actinic rays, and a known photopolymerization initiator can be used.
In the photosensitive resin composition of the present invention, as the (D) photopolymerization initiator, a photopolymerization initiator generally used in the field can be used. Examples of such photopolymerization initiators include: hexaarylbisimidazole photopolymerization initiator, acylphosphine oxide photopolymerization initiator, oxime ester photopolymerization initiator, triazine photopolymerization initiator, acetophenone photopolymerization initiator and benzophenone photopolymerization initiator.
The hexaarylbisimidazole-based photopolymerization initiator is preferably a hexaarylbisimidazole-based compound represented by the following general formula (1-1) and/or the following general formula (1-2) from the viewpoint of absorbance, sensitivity, and compatibility with the absorption wavelength of an ultraviolet absorber.
[ chemical formula 46]
Figure BDA0002576772040000561
In the above formula, R11～R13Each independently represents an alkyl group having 1 to 4 carbon atoms which may have a substituent, an alkoxy group having 1 to 4 carbon atoms which may have a substituent, or a halogen atom, and m, n, and l each independently represent an integer of 0 to 5.
R11～R13The number of carbon atoms of the alkyl group (b) is not particularly limited as long as it is in the 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 linear or cyclic. Specific examples of the alkyl group include methyl, ethyl, propyl and isopropyl groups, and among these, methyl and ethyl groups are preferable. As R11～R13As the substituent optionally having the alkyl group having 1 to 4 carbon atoms, a group having a nonmetallic atom group of 1 valence other than hydrogen can be used, and preferable examples thereof include a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group and an alkoxy group.
In addition, R11～R13The number of carbon atoms of the alkoxy group(s) 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 moiety of the alkoxy group may be linear or cyclic. Specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group and butoxy group, and among these, methoxy group and ethoxy group are preferable. As R11～R13The substituent optionally having the alkoxy group having 1 to 4 carbon atoms in (b) includes an alkyl group and an alkoxy group, and is preferably an alkyl group.
In addition, as R11～R13Examples of the halogen atom of (b) include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom, among which, from the viewpoint of ease of synthesis, a chlorine atom or a fluorine atom is preferable, and a chlorine atom is more preferable.
Of theseR is from the viewpoint of sensitivity and ease of synthesis11～R13Each independently is preferably a halogen atom, more preferably a chlorine atom.
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, and 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', 5,5 '-tetrakis (o, p-dichlorophenyl) biimidazole, 2' -bis (o, p-dichlorophenyl) -4,4 ', 5, 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, 5' -tetrakis (o, p-dibromophenyl) biimidazole, 2,2 '-bis (o-bromophenyl) -4, 4', 5,5 '-tetrakis (o, p-dichlorophenyl) biimidazole, 2' -bis (o-chlorophenyl) -4,4 ', 5, 5' -tetrakis (p-chloronaphthyl) biimidazole, and the like. Among these compounds, preferred are hexaphenylbiimidazole compounds, more preferred are compounds in which the ortho position of the benzene ring bonded to the 2,2 ' -position of the imidazole ring is substituted with a methyl group, a methoxy group or a halogen atom, and preferred are compounds in which the benzene ring bonded to the 4,4 ', 5,5 ' -position of the imidazole ring is unsubstituted or substituted with a halogen atom or a methoxy group.
As the photopolymerization initiator (D), either one of the hexaarylbisimidazole compound represented by the general formula (1-1) and the hexaarylbisimidazole compound represented by the general formula (1-2) may be used, or both may be used in combination. When used in combination, the ratio thereof is not particularly limited.
Further, as the acylphosphine oxide-based photopolymerization initiator, preferred are: 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and the like.
The oxime ester photopolymerization initiator preferably contains an oxime ester compound having a carbazole skeleton or a diphenyl sulfide skeleton, and more preferably an oxime ester compound having a diphenyl sulfide skeleton. It is considered that the inclusion of the oxime ester compound having a diphenyl sulfide skeleton enhances light absorption at short wavelengths and improves surface curability, and therefore, the flow-out of the liquid repellent during development is suppressed, and the ink repellency is improved.
The chemical structure of the oxime ester compound having a diphenyl sulfide skeleton is not particularly limited, and an oxime ester compound represented by the following general formula (D-I) is preferably used from the viewpoint of sensitivity.
[ chemical formula 47]
Figure BDA0002576772040000581
In the above general formula (D-I), R23Represents an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent;
R24represents an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent;
R25represents 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 shown in the formula (D-I) may further have a substituent.
[ chemical formula 48]
R25c-R25b-R25a-* (D-II)
In the formula (D-II), R25arepresents-O-, -S-, -OCO-or-COO-;
R25brepresents an alkylene group optionally having a substituent;
R25bthe alkylene moiety of (A) may be interrupted 1 to 5 times by-O-, -S-, -COO-or-OCO-, R25The alkylene moiety of (a) may have a branched side chain, or may be a cycloalkylene group;
R25crepresents a hydroxyl group or a carboxyl group.
R23The number of carbon atoms of the alkyl group in (b) 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, and further more preferably 10 or less from the viewpoint of developabilityPreferably 8 or less, more preferably 5 or less, and particularly preferably 3 or less.
Specific examples of the alkyl group include a methyl group, a hexyl group, a cyclopentylmethyl group, and the like, and among these, from the viewpoint of developability, a methyl group or a hexyl group is preferable, and a methyl group is more preferable.
Examples of the substituent optionally contained in the alkyl group include: aromatic ring group, hydroxyl group, carboxyl group, halogen atom, amino group, amide group and the like, and from the viewpoint of alkali developability, hydroxyl group and carboxyl group are preferred, and carboxyl group is more preferred. In addition, from the viewpoint of ease of synthesis, it is preferably unsubstituted.
As R23As the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. 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 and the like, and among these, from the viewpoint of developability, phenyl or naphthyl is preferred, and phenyl is more preferred.
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 preferred, and carboxyl group is more preferred.
Among these, R is R from the viewpoint of developability23Preferred is an alkyl group optionally having a substituent, more preferred is an unsubstituted alkyl group, and further preferred is a methyl group.
R24The number of carbon atoms of the alkyl group in (b) 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, and particularly preferably 3 or less from the viewpoint of sensitivity.
Specific examples of the alkyl group include: methyl group, ethyl group, propyl group, etc., of these, methyl group or ethyl group is preferred, and methyl group is more preferred, from the viewpoint of sensitivity.
Examples of the substituent optionally contained in the alkyl group include: a halogen atom, a hydroxyl group, a carboxyl group, an amino group, an amide group, and the like, and preferably a hydroxyl group or a carboxyl group, more preferably a carboxyl group, from the viewpoint of alkali developability, and preferably unsubstituted from the viewpoint of ease of synthesis.
As R24As the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. The number of carbon atoms is preferably 30 or less, more preferably 12 or less, and usually 4 or more, preferably 6 or more. When the upper limit value is less than the upper limit value, sensitivity tends to be high, and when the lower limit value is more than the lower limit value, sublimation tends to be low.
The aromatic hydrocarbon ring group may be a monocyclic 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,
Figure BDA0002576772040000591
A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, etc., having 1 free valence.
The aromatic heterocyclic group may be a monocyclic or condensed ring, and examples thereof include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, or the like,
Figure BDA0002576772040000592
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring
Figure BDA0002576772040000601
An 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,
Figure BDA0002576772040000602
a group having 1 free valence of the pyridine ring, quinazoline ring, quinazolinone ring, azulene ring, etc.
Examples of the substituent optionally contained in the aromatic ring group include: alkyl groups, halogen atoms, hydroxyl groups, carboxyl groups, and the like.
Of these, R is from the viewpoint of sensitivity24Preferred is an alkyl group optionally having a substituent, more preferred is an unsubstituted alkyl group, and further preferred is a methyl group.
On the other hand, from the viewpoint of platemaking property, R24Preferred is an optionally substituted aromatic ring group, more preferred is an optionally substituted aromatic ring group, still more preferred is an unsubstituted aromatic ring group, and particularly preferred is a phenyl group.
R25The hydroxyl group, the carboxyl group or the group represented by the general formula (D-II) is preferred, from the viewpoint of sensitivity and developability.
In the above general formula (D-II), R is as defined above25arepresents-O-, -S-, -OCO-or-COO-, among these, from the viewpoint of sensitivity and developability, -O-or-OCO-is preferable, and-O-is more preferable.
As previously mentioned, R25bRepresents an alkylene group optionally having a substituent.
R25bThe number of carbon atoms of the alkylene group in (b) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 20 or less, more preferably 10 or less, further 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. Among these, from the viewpoint of solubility in the photosensitive resin composition, a linear one is preferable.
Specific examples of the alkylene group include: methylene, ethylene, propylene and the like, and among these, ethylene is more preferable from the viewpoint of solubility in the photosensitive resin composition.
As previously mentioned, R25cIs hydroxyOr a carboxyl group. From the viewpoint of development adhesion, R25cHydroxyl groups are preferred.
In the 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.
Examples of the triazine photopolymerization initiator include halomethylated s-triazine derivatives, 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-methoxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-methoxym-hydroxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-isopropoxystyryl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (p-methoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, Halomethylated s-triazine derivatives such as 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-benzylthio-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 the like, among them, bis (trihalomethyl) s-triazines are preferable from the viewpoint of sensitivity.
Examples of the acetophenone-based 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-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-1- (p-dodecylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl, Ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 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-methyl benzophenone, 3-methyl benzophenone, 4-methyl benzophenone, 2-carboxyl benzophenone, 2-chlorine benzophenone, 4-bromine benzophenone, Michler's ketone etc..
These photopolymerization initiators may be contained in the photosensitive resin composition alone, or may be contained in two or more kinds. Among these photopolymerization initiators, it is preferable to contain at least one selected from the group consisting of hexaarylbisimidazole-based photopolymerization initiators, oxime ester-based photopolymerization initiators and acetophenone-based photopolymerization initiators. The hexaarylbiimidazole compound is particularly preferable in that it has high absorbance, high surface curability, and high ink repellency and a high cone angle. The oxime ester compounds are particularly preferable in that they have high sensitivity and exhibit ink repellency even with a low exposure amount. The acetophenone-based photopolymerization initiator is particularly preferable in that it has high internal curability and can achieve high ink repellency and a high cone 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, further preferably 1% by mass or more, further preferably 1.5% by mass or more, particularly preferably 2% by mass or more, and most preferably 2.5% by mass or more, and is usually 25% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 5% by mass or less, and particularly preferably 3% by mass or less, in the entire solid content of the photosensitive resin composition. When the lower limit value is not less than the lower limit value, a coating film is formed without causing film reduction during development, and sufficient ink repellency tends to be generated. 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 addition, in the photosensitive resin composition, the blending ratio of the photopolymerization initiator (D) to the photopolymerizable compound (C) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, further preferably 3 parts by mass or more, and further preferably 200 parts by mass or less, more preferably 100 parts by mass or less, further preferably 50 parts by mass or less, further preferably 20 parts by mass or less, particularly preferably 10 parts by mass or less, and most preferably 5 parts by mass or less, relative to 100 parts by mass of the photopolymerizable compound (C). When the lower limit value is not less than the lower limit value, there is a tendency that the sensitivity becomes appropriate, and when the upper limit value is not more than the upper limit value, there is a tendency that a desired pattern shape is easily formed. The mixing ratio of the photopolymerization initiator (D) to 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, relative to 100 parts by mass of the photopolymerizable compound (C).
In addition, a sensitizer may be used in combination with the photopolymerization initiator. The sensitivity is improved by the sensitizer, and the light transmittance into the photosensitive resin composition is reduced, so that the taper angle tends to increase.
As the sensitizer, one commonly used in this field can be used. The sensitizer has a characteristic of transferring energy obtained by absorption to the photopolymerization initiator or generating transfer of electrons to and from the photopolymerization initiator, thereby effectively promoting a radical polymerization reaction. Examples of such a sensitizer include: unsaturated ketones typified by chalcone derivatives and dibenzylideneacetone, 1, 2-diketones typified by benzil and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, coumarone compounds, cyanine compounds, merocyanine compounds, oxonol derivatives and other polymethine pigments, acridine compounds, azine compounds, thiazine compounds, azone compounds, dihydropyrane,
Figure BDA0002576772040000631
Oxazine compound, indoline compound, azulene compound and azulene
Figure BDA0002576772040000632
Class compounds, squarylium cyanine compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetraphenylporphyrin compounds, tetrapyrazino-tetraazaporphyrin compounds, phthalocyanine compounds, tetraazaporphyrin compounds, tetraquinoxalino-tetraazaporphyrin compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrane compounds
Figure BDA0002576772040000633
Compound and thiopyran
Figure BDA0002576772040000634
Compounds, porphyrins, annulenes, spiropyrans, and spiros
Figure BDA0002576772040000635
Oxazine compound and thiospiropyran compoundMetal arene complexes, organic ruthenium complexes, benzophenone compounds and the like.
These sensitizers may be used singly or in combination of two or more.
Among these, from the viewpoint of improving sensitivity and increasing the taper angle, a thioxanthone-based compound and a benzophenone-based compound are preferable.
Examples of the thioxanthone compound include: thioxanthone, 2-methylthioxanthone, 4-methylthioxanthone, 2, 4-dimethylthioxanthone, 2-ethylthioxanthone, 4-ethylthioxanthone, 2, 4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diisopropylthioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2, 4-dichlorothioxanthone, and the like. Among these compounds, 2, 4-diethylthioxanthone is preferable from the viewpoint of improving sensitivity and increasing the 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 viewpoint of improving sensitivity and increasing the cone angle.
When the photosensitive resin composition contains a sensitizer, the content of the sensitizer in the photosensitive resin composition, は, is usually 0.1 mass% or more, preferably 0.3 mass% or more, more preferably 0.5 mass% or more, further preferably 0.8 mass% or more, further preferably 1 mass% or more, and particularly preferably 1.2 mass% or more, in the entire solid content of the photosensitive resin composition, and is usually 10 mass% or less, preferably 7 mass% or less, more preferably 5 mass% or less, and further preferably 3 mass% or less. When the lower limit value is set to be equal to or higher than the above-described lower limit value, the sensitivity is likely to be improved, and the taper angle tends to be improved. When the photosensitive resin composition contains a sensitizer, the content of the sensitizer in the entire 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 a chain transfer agent, the deactivation of radicals in the vicinity of the surface due to oxygen inhibition or the like is improved, the surface curability is improved, and the taper angle tends to be increased. Further, by improving the surface curability, the flowing-out of the liquid repellent can be suppressed, and the liquid repellent tends to be easily fixed in the vicinity of the surface of the partition wall, and the contact angle tends to be high.
The chain transfer agent may be a mercapto group-containing compound, carbon tetrachloride or the like, and the mercapto group-containing compound is more preferably used because the chain transfer effect tends to be high. The mercapto group-containing compound tends to have improved surface curability because it is likely to undergo bond cleavage and chain transfer reaction due to its small S — H bond energy.
Among the chain transfer agents, mercapto compounds having an aromatic ring and aliphatic mercapto compounds are preferable from the viewpoint 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 cone angle.
[ chemical formula 49]
Figure BDA0002576772040000641
In the formula (E-1), Z represents-O-, -S-or-NH-, R61、R62、R63And R64Each independently represents a hydrogen atom or a 1-valent substituent.
Among these, from the viewpoint of the taper angle, Z is preferably-S-or-NH-, and more preferably-NH-.
In addition, from the viewpoint of taper angle, R61、R62、R63And R64Each independently preferably being a hydrogen atom, carbonAn alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.
Specific examples thereof include: 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzo
Figure BDA0002576772040000642
Thiol-containing compounds having an aromatic ring such as oxazole, 3-mercapto-1, 2, 4-triazole, 2-mercapto-4 (3H) -quinazoline, β -mercaptonaphthalene, and 1, 4-dimethylmercaptobenzene, and 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable from the viewpoint of the cone angle.
On the other hand, as the aliphatic mercapto 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]
Figure BDA0002576772040000651
In the formula (E-2), m represents an integer of 0 to 4, n represents an integer of 2 to 4, R71And R72Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents an n-valent group.
In the general formula (E-2), m is preferably 1 or 2 from the viewpoint of ease of synthesis. In addition, n is preferably 3 or 4 from the viewpoint of surface curability.
In addition, as R71And R72The alkyl group of (2) is preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of surface curability. From the viewpoint of surface curability, R is preferred71And R72At least one of, e.g. R72Is a hydrogen atom, in which case R is preferably71Is 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 branched 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 even more preferable, from the viewpoint 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 viewpoint of surface curability and ease of synthesis.
[ chemical formula 51]
Figure BDA0002576772040000652
In the formula (E-2-1), R73Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxymethyl group. At R73Among them, ethyl is preferable from the viewpoint of the taper angle.
[ chemical formula 52]
Figure BDA0002576772040000661
In the formula (E-2-2), R74Represents an alkylene group having 1 to 4 carbon atoms. At R74Among them, ethylene is preferable from the viewpoint of the 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]
Figure BDA0002576772040000662
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), trihydroxyethyltris (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 these, 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.
Among these, one of various compounds may be used alone, or two or more of them may be used in combination.
Of these, from the viewpoint of improving ink repellency, it is preferable to use a compound selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole and 2-mercaptobenz
Figure BDA0002576772040000663
One or more of azoles and a photopolymerization initiator are used in combination as a photopolymerization initiator system. For example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, or a combination of 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used.
In addition, from the viewpoint of surface curability, one or two 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, further preferably 0.1% by mass or more, and particularly preferably 1% by mass or more, and is usually 5% by mass or less, preferably 4% by mass or less, and more preferably 3% by mass or less, of the total solid content of the photosensitive resin composition. When the lower limit value is not less than the above-mentioned lower limit value, the taper angle tends to be high, the surface curability tends to be improved, and the ink repellency tends to be improved. The content of the chain transfer agent in the entire 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 aromatic ring-containing mercapto compound and the aliphatic mercapto compound are used in combination as the chain transfer agent, the content ratio of these compounds is usually 10 parts by mass or more, preferably 50 parts by mass or more, and more preferably 80 parts by mass or more, and usually 400 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and further preferably 150 parts by mass or less, relative to 100 parts by mass of the aromatic ring-containing mercapto compound. When the lower limit is not less than the above-described lower limit, ink repellency tends to be improved, and when the upper limit is not more than the above-described upper limit, sensitivity tends to be improved. The content ratio of the aromatic ring-containing mercapto compound and the aliphatic mercapto compound used in combination as the chain transfer agent 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 still more preferably 80 to 150 parts by mass, based on 100 parts by mass of the aromatic ring-containing mercapto compound.
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, further preferably 50 parts by mass or more, and particularly preferably 80 parts by mass or more, and is preferably 500 parts by mass or less, more preferably 400 parts by mass or less, further preferably 300 parts by mass or less, further preferably 200 parts by mass or less, and particularly preferably 150 parts by mass or less, with respect to 100 parts by mass of the photopolymerization initiator (D). When the lower limit value is not less than the above-mentioned lower limit value, the taper angle tends to be high, the surface curability tends to be improved, and the ink repellency tends to be improved. 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 purpose: the photocuring profile 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 improvement of the taper shape after development and elimination of residue remaining in the unexposed portion after development can be obtained. As the ultraviolet absorber, for example, a compound having an absorption maximum in a wavelength range of 250nm to 400nm can be used from the viewpoint of inhibiting 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, dinaphthalene compounds, phenanthroline compounds, dyes, and the like.
These ultraviolet absorbers may be used alone or in combination of two or more.
Among these, from the viewpoint of increasing the taper angle, benzotriazole-based compounds and/or hydroxyphenyltriazine-based compounds are preferable, and benzotriazole-based compounds are particularly preferable.
Among the benzotriazole-based compounds, preferred is a benzotriazole compound represented by the following general formula (Z1) from the viewpoint of tapered shape.
[ chemical formula 54]
Figure BDA0002576772040000681
In the above formula (Z1), R1eAnd R2eEach independently represents 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). R3eRepresents a hydrogen atom or a halogen atom.
[ chemical formula 55]
Figure BDA0002576772040000682
In the above formula (Z2), R4eRepresents an alkylene group optionally having a substituent, R5eRepresents an alkyl group optionally having a substituent.
[ chemical formula 56]
Figure BDA0002576772040000691
In the above formula (Z3), R6eRepresents an alkylene group optionally having a substituent, R7eRepresents a hydrogen atom or a methyl group.
(R1eAnd R2e)
In the above formula (Z1), R1eAnd R2eEach independently represents 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 linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 2 or more, and even more preferably 4 or more, and is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less.
Specific examples of the alkyl group include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like. Among these alkyl groups, a tert-butyl group is preferable.
Further, as the substituent optionally contained in the alkyl group, there may be mentioned: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxy, acryloyl, methacryloyl, and the like.
(R3e)
In the above formula (Z1), R3eRepresents a hydrogen atom or a halogen atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Of these, R is preferred from the viewpoint of synthesis3eIs a hydrogen atom.
(R4e)
In the above formula (Z2), R4eDenotes optionalAn alkylene group 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 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 preferred.
Further, as the substituent optionally having the alkylene group, there may be mentioned: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxy, acryloyl, methacryloyl, and the like.
Of these, R is preferred4eIs an ethylene group.
(R5e)
In the above formula (Z2), an alkyl group which may have a substituent is represented.
Examples of the alkyl group include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 4 or more, more preferably 5 or more, further preferably 7 or more, and further preferably 15 or less, more preferably 10 or less, further preferably 9 or less.
Specific examples of the alkyl group include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and the like.
Further, as the substituent optionally contained in the alkyl group, there may be mentioned: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxy, acryloyl, methacryloyl, and the like.
Of these, R is preferable from the viewpoint of taper shape5eHeptyl, octyl and nonyl.
(R6e)
In the above formula (Z3), R6eRepresents 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 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 preferred.
Further, as the substituent optionally having the alkylene group, there may be mentioned: methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxy, acryloyl, methacryloyl, and the like.
Of these, R is preferable from the viewpoint of taper shape1eIs tert-butyl, R2eIs a group represented by the above formula (Z2) (wherein, R4eIs ethylene, R5eAlkyl with 7-9 carbon atoms), R3eA compound being a hydrogen atom, or R1eIs a hydrogen atom, R2eIs a group represented by the above formula (Z3) (wherein, R6eIs ethylene, and R7eIs methyl), R3eCompounds which are hydrogen atoms, more preferably R1eIs tert-butyl, R2eIs a group represented by the above formula (Z2) (wherein, R4eIs ethylene, and R5eAlkyl with 7-9 carbon atoms), R3eA compound which is a hydrogen atom.
Specific examples of the benzotriazole compound include: 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, a mixture of octyl-3- [ 3-t-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate and 2-ethylhexyl-3- [ 3-t-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate, 2- [ 2-hydroxy-3, 5-bis (. alpha.,. alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole, a salt thereof, a hydrate thereof, and a pharmaceutical composition, 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, C7-9 side chain and linear alkyl ester compounds, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3, 3-tetramethylbutyl) phenol. Among these, from the viewpoint of the cone angle and the exposure sensitivity, a compound of 3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester is preferable.
Examples of commercially available benzotriazole compounds include: SUMISORB (registered trademark, hereinafter the same) 200, SUMISORB 250, SUMISORB 300, SUMISORB 340, SUMISORB 350 (manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83 (manufactured by North City Chemical industry Co., Ltd.), TINUVIN (registered trademark, hereinafter the same) PS, TINU 99-2, TINUVIN109, TINUVIN384-2, TINUVIN 326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF Co., Ltd.), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB 8238, EVERSORB75, EVERSORB 702, SEORB (manufactured by SEORB), SEORB 701, SEISOB, SEORB 706, SEORB (manufactured by North Chemical Co., registered trademark, SEORB), SEISOB, SEORB, SEOR.
Examples of the triazine compound include: 2- [4, 6-bis (2, 4-dimethylphenyl) -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 (2-ethylhexyl) glycidate, 2, 4-bis [ 2-hydroxy-4-butoxyphenyl ] -6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine, and the like. Among these, from the viewpoint of the taper angle and the exposure sensitivity, a hydroxyphenyltriazine compound is preferable.
Examples of commercially available triazine compounds include: TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479(BASF corporation), and the like.
Examples of other ultraviolet absorbers include: benzophenone compounds such as SUMISORB 130 (manufactured by Sumitomo chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Yongshioto industries Co., Ltd.), Tomisorb 800 (manufactured by APICorporation), SEESORB100, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by SHIPRO KASEI Co., Ltd.); a benzoate compound such as SUMISORB 400 (manufactured by Sumitomo chemical Co., Ltd.) and phenyl salicylate; 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, p-aminobenzoic acid dyes, and the like; and so on. Among these, cinnamic acid derivatives and naphthalene derivatives are preferably used from the viewpoint of exposure sensitivity, and cinnamic acid derivatives are particularly preferably used.
When the photosensitive resin composition of the present invention contains an ultraviolet absorber, 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, further preferably 0.5% by mass or more, and 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, and further preferably 3% by mass or less, in the total solid content. When the lower limit value is set to be equal to or higher than the lower limit value, the taper angle tends to be increased, and when the upper limit value is set to be 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 entire 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.
When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the blending ratio of the ultraviolet absorber to the (D) photopolymerization initiator is usually 1 part by mass or more, preferably 10 parts by mass or more, more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, and particularly preferably 80 parts by mass or more, and is usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and further preferably 150 parts by mass or less, based on 100 parts by mass of the ultraviolet absorber to the (D) photopolymerization initiator. When the lower limit value is set to be equal to or higher than the lower limit value, the taper angle tends to be increased, and when the upper limit value is set to be 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. Since the inclusion of the polymerization inhibitor inhibits radical polymerization, it is considered that the taper angle of the obtained partition wall can be increased.
As the polymerization inhibitor, there may be mentioned: hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, 2, 6-di-tert-butyl-4-cresol (BHT), and the like. Among these polymerization inhibitors, from the viewpoint of polymerization inhibiting ability, methylhydroquinone or methoxyphenol are preferable, and methylhydroquinone is more preferable.
The polymerization inhibitor preferably contains one or more species. In general, when the alkali-soluble resin (B) is produced, a polymerization inhibitor may be contained in the resin, and the resin may be used as the polymerization inhibitor of the present invention.
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 usually 0.3 mass% or less, preferably 0.2 mass% or less, more preferably 0.1 mass% or less, of the total solid content of the photosensitive resin composition. By setting the lower limit value or more, the taper angle tends to be increased, and by setting the upper limit value or less, high 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 entire 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 to promote thermal curing.
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% by mass or less, preferably 30% by mass or less, and usually 0.5% by mass or more, preferably 1% by mass or more, of the total solid content of the photosensitive resin composition. When the upper limit value is less than the upper limit value, the storage stability tends to be maintained, and when the lower limit value is more than the lower limit value, sufficient thermosetting properties tend to be secured. When the photosensitive resin composition of the present invention contains an amino compound, the content of the amino compound in the entire solid content of 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 at least 2 of methylol groups and alkoxymethyl groups obtained by condensation-modifying a methylol group with an alcohol having 1 to 8 carbon atoms as a functional group. Specific examples thereof include: a melamine resin obtained by polycondensation of melamine and formaldehyde; benzoguanamine resin obtained by condensation polymerization of benzoguanamine and formaldehyde; glycoluril resin obtained by polycondensation of glycoluril with formaldehyde; urea resin obtained by condensation polymerization of urea and formaldehyde; a resin obtained by copolycondensating two or more of melamine, benzoguanamine, glycoluril, urea, or the like with formaldehyde; modified resins obtained by modifying methylol groups of the above resins by alcohol condensation. These amino compounds may be used alone or in combination of two or more. Among these, the amino compound is preferably a melamine resin and a modified resin thereof, more preferably a modified resin having a methylol group modification ratio of 70% or more, and particularly preferably a modified resin having a methylol group modification ratio of 80% or more.
Specific examples of the amino compound include melamine resins and modified resins thereof, for example: "Cymel" (registered trademark, the same hereinafter) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, manufactured by SaiTech corporation, and "Nicarac" (registered trademark, the same hereinafter) MW-390, MW-100LM, MX-750LM, MW-30M, MX-45, MX-302, manufactured by sanwa chemical corporation, and the like. Examples of the benzoguanamine resin and modified resins thereof include: cymel 1123, 1125, 1128, etc., manufactured by SaiTech corporation. Examples of the glycoluril resin and its modified resin include: cymel 1170, 1171, 1174, 1172 manufactured by SaiTech corporation, and Nicarac MX-270 manufactured by Sanwa Chemical corporation, and the like. Examples of the urea resin and modified resin thereof include: "UFR" (registered trademark, the same applies hereinafter) 65 and 300 manufactured by SaiTech corporation, Nicarac MX-290 manufactured by Sanwa Chemical corporation, and the like.
[1-1-9] coloring agent
The photosensitive resin composition of the present invention may contain a colorant for coloring the partition walls. As the colorant, known colorants such as pigments and dyes can be used. When a pigment is used, for example, 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 causing aggregation or the like. In particular, coloring the ink-repellent partition walls black has an effect of obtaining a clear pixel display. As the black colorant, in addition to a black dye or a black pigment, carbon black, titanium black, and the like, coloring to black by mixing an organic pigment 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, in the entire solid content of the photosensitive resin composition, from the viewpoint of platemaking properties and color characteristics.
On the other hand, in order to reduce the degassing from the partition wall, preferably the partition wall is transparent, and in this case, the content ratio of the colorant is preferably 10 mass% or less, more preferably 5 mass% or less, and particularly preferably 0 mass% relative to the total solid content of the photosensitive resin composition.
[1-1-10] coating property improver and development improver
The photosensitive resin composition of the present invention may contain a coating property improving agent and a development improving agent for improving coating property and development solubility. As the coating property improving agent or the development improving agent, for example, a known cationic, anionic, nonionic, fluorine-based, or silicone-based surfactant can be used. The surfactant can be used for the purpose of improving coatability of a coating solution as a photosensitive resin composition, developability of a coating film, and the like, and among them, a fluorine-based or silicone-based surfactant is preferable.
In particular, the silicone surfactant is preferable, and the polyether-modified silicone surfactant is more preferable, because it has a function of removing the residue of the photosensitive resin composition from unexposed portions during development and a function of exhibiting wettability.
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: 1,1,2, 2-tetrafluorooctyl (1,1,2, 2-tetrafluoropropyl) ether, 1,2, 2-tetrafluorooctylhexyl ether, octaethyleneglycol bis (1,1,2, 2-tetrafluorobutyl) ether, hexaethyleneglycol bis (1,1,2,2,3, 3-hexafluoropentyl) ether, octapropyleneglycol bis (1,1,2, 2-tetrafluorobutyl) ether, hexapropyleneglycol bis (1,1,2,2,3, 3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,2,2,8,8,9,9,10, 10-decafluorododecane, 1,2,2,3, 3-hexafluorodecane, and the like. Examples of commercially available products of these include: BM-1000 and BM-1100 manufactured by BM Chemie, Megafac F470 and Megafac F475 manufactured by DIC, FC430 manufactured by 3M Japan, and DFX-18 manufactured by Neos, and the like.
Examples of the silicone surfactant include: commercially available products such as "DC 3 PA", "SH 7 PA", "DC 11 PA", "SH 21 PA", "SH 28 PA", "SH 29 PA", "8032 Additive", "SH 8400", and "BYK (registered trademark, the same shall apply hereinafter)" 323 "and" BYK330 ", manufactured by Dow Corning Toray.
The surfactant may contain surfactants other than the fluorine-based surfactant and the silicone-based surfactant, and examples of the other surfactants include nonionic, anionic, cationic, and amphoteric surfactants.
Examples of the nonionic surfactant include: polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl 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 commercially available products of these include: polyoxyethylene surfactants such as "EMULGEN 104P" and "EMULGEN A60" manufactured by Kao corporation, and the like.
Examples of the anionic surfactant include: alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, polyoxyethylene alkylethersulfonic acid salts, alkylsulfuric acid ester salts, higher alcohol sulfuric acid ester salts, fatty alcohol sulfuric acid ester salts, polyoxyethylene alkylethersulfuric acid salts, polyoxyethylene alkylphenylether sulfuric acid salts, alkylphosphoric acid ester salts, polyoxyethylene alkyletherphosphoric acid salts, polyoxyethylene alkylphenylether phosphoric acid ester salts, special polymer 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 an anionic surfactant, commercially available ones can be used, and examples of the alkyl sulfate salt include "Emal (registered trademark) 10" manufactured by Kao corporation, the alkyl naphthalene sulfonate salt include "Perex (registered trademark) NB-L" manufactured by Kao corporation, and the special polymer surfactant include "Homogenol (registered trademark, the same applies hereinafter) L-18" and "Homogenol L-100" manufactured by Kao corporation.
Further, the cationic surfactant may be exemplified by quaternary ammonium salts, imidazoline derivatives, alkylamine salts, etc., and the amphoteric surfactant may be exemplified by betaine type compounds, imidazole, etc
Figure BDA0002576772040000761
Salts, imidazolines, amino acids, and the like. Of these, quaternary ammonium salts are preferable, and stearyl trimethylammonium salts are more preferable. Examples of commercially available products include alkylamine salts such as "Acetamin (registered trademark) 24" manufactured by Kao corporation, and quaternary ammonium salts such as "KOTAMIN (registered trademark, the same applies hereinafter) 24P" and "KOTAMIN 86W" manufactured by Kao corporation.
In addition, two or more kinds of surfactants may be used in combination, and examples thereof include: silicone surfactant/fluorine surfactant, silicone surfactant/special polymer surfactant, and a combination of fluorine surfactant/special polymer surfactant. Among these, a combination of a silicone surfactant and a fluorine surfactant is preferable. In the combination of the silicone surfactant and the fluorine surfactant, for example: "DFX-18" manufactured by Neos, "BYK-300" manufactured by BYK Chemie, "S-393" manufactured by BYK-330 "/AGC SEIMI CHEMICAL," F-478 "manufactured by" KP340 "/DIC," F-475 "manufactured by Shin-Etsu Silicone," SH7PA "/DS-401 manufactured by Dow Corning Toray," L-77 "manufactured by NUC,"/FC 4430 "manufactured by 3M Japan, and the like.
Further, as the development improving agent, a known development improving agent such as an organic carboxylic acid or an acid anhydride thereof may be used.
When the photosensitive resin composition of the present invention contains the coatability improver and the development modifier, the content ratio of the coatability improver and the development modifier is usually 20% by mass or less, preferably 10% by mass or less, respectively, in the entire solid content of the photosensitive resin composition, from the viewpoint of sensitivity.
[1-1-11] silane coupling agent
In order to improve adhesion to a substrate, it is also preferable to add a silane coupling agent to the photosensitive resin composition of the present invention. Various silane coupling agents such as epoxy, methacrylic, amino, and imidazole can be used as the silane coupling agent, 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 in the entire solid content of the photosensitive resin composition is usually 20 mass% or less, preferably 15 mass% or less, from the viewpoint of adhesion.
[1-1-12] phosphoric acid adhesion improver
In order to improve the adhesion to the substrate, a phosphoric acid-based adhesion improver is preferably added to the photosensitive resin composition of the present invention. The phosphate adhesion improver is preferably a phosphate containing a (meth) acryloyloxy group, and particularly preferably a phosphate adhesion improver represented by the following general formulae (Va), (Vb) and (Vc).
[ chemical formula 57]
Figure BDA0002576772040000771
In the above general formulae (Va), (Vb), (Vc), R8Represents 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 a phosphoric acid-based adhesion improver, the content thereof is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more, and is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less of the total solid content. When the lower limit value is not less than the above-mentioned lower limit value, the adhesion to the substrate tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the surface curability tends to be improved. When the photosensitive resin composition of the present invention contains a phosphoric acid adhesion improver, the content of the phosphoric acid adhesion improver in the entire 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
The photosensitive resin composition of the present invention may further contain an inorganic filler in order to improve the strength as a cured product and to improve the excellent flatness, taper angle, and the like of a coating film due to a proper interaction (formation of a matrix structure) with an alkali-soluble resin. Examples of such inorganic fillers include: talc, silica, alumina, barium sulfate, magnesium oxide, and a surface-treated product thereof with various silane coupling agents.
The average particle diameter of these inorganic fillers is usually 0.005 to 20 μm, preferably 0.01 to 10 μm. The average particle diameter in the present embodiment is a value measured by a laser diffraction scattering particle size distribution measuring apparatus manufactured by Beckman Coulter corporation and the like. Among these inorganic fillers, silica sol and silica sol modified products are particularly preferable because they tend to have excellent dispersion stability and an excellent effect of improving the cone angle.
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 usually contains a solvent, and the above-mentioned components can be used in a state of being dissolved or dispersed in the solvent (hereinafter, the photosensitive resin composition containing the solvent is also referred to as "photosensitive resin composition solution"). The solvent is not particularly limited, and examples thereof include the following organic solvents.
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 tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, 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 alkyl ether acetates such as ethylene 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, and 3-methoxy-1-butyl acetate; glycol diacetate esters 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, diamyl ether, ethyl isobutyl 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 bicyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; linear 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 γ -butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and pentyl chloride; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile; and tetrahydrofuran compounds such as tetrahydrofuran, dimethyltetrahydrofuran, and dimethoxytetrahydrofuran.
Examples of commercially available solvents corresponding to the above include: mineral Spirit, Valsol #2, Apco #18Solvent, Apco thinker, Socal Solvent No.1 and No.2, Solvesso #150, Shell TS Solvent28, 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 each component in the photosensitive resin composition, and can 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 ℃ under 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. These solvents are preferably used so that the content of the total solid content 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 is not less than the above-mentioned lower limit, a coating film tends to be obtained even with a high film thickness, and when the upper limit is not more than the above-mentioned upper limit, appropriate 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
Examples of physical properties of the photosensitive resin composition of the present invention include an acid value.
The acid value of the total solid content of the photosensitive resin composition is not particularly limited, but is preferably 20mg-KOH/g or more, more preferably 22mg-KOH/g or more, further preferably 24mg-KOH/g or more, further preferably 26mg-KOH/g or more, particularly preferably 28mg-KOH/g or more, and is usually 60mg-KOH/g or less, preferably 55mg-KOH/g or less, more preferably 50mg-KOH/g or less, further preferably 40mg-KOH/g or less, particularly preferably 35mg-KOH/g or less. When the lower limit value is not less than the above-mentioned lower limit value, 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 upper limit value is not more than the above-mentioned upper limit value, the development adhesion tends to be good. The acid value of the total solid content 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 35 mg-KOH/g.
[1-3] method for producing photosensitive resin composition
The photosensitive resin composition of the present invention can be prepared by mixing the above components with a stirrer. The photosensitive resin composition to be prepared may be filtered by using a membrane filter or the like to make the composition uniform.
[2] Spacer and method for forming spacer
The photosensitive resin composition of the present invention can be used for forming partition walls, particularly partition walls for partitioning an organic layer (light emitting section) of an organic electroluminescent device. 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 used. Examples of the method for forming the partition wall include a method including a coating step of coating a photosensitive resin composition on a substrate to form a photosensitive resin composition layer and an exposure step of exposing the photosensitive resin composition layer to light. A specific example of a method for forming such a partition wall is photolithography.
In the photolithography method, a photosensitive resin composition is applied to the entire surface of a region of a substrate where partition walls are to be formed, thereby forming a photosensitive resin composition layer. After the formed photosensitive resin composition layer is exposed to light corresponding to a pattern of the partition walls, the exposed photosensitive resin composition layer is developed to form the partition walls on the substrate.
In a coating step of applying a photosensitive resin composition onto a substrate in a photolithography method, a photosensitive resin composition is applied onto a substrate to be formed with partition walls using a contact transfer type coating apparatus such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating apparatus such as a spin coater (a spin coater) or a curtain flow coater, and the solvent is removed by drying as necessary, thereby forming a photosensitive resin composition layer.
Next, in the exposure step, the photosensitive resin composition is irradiated with active energy rays such as ultraviolet rays or excimer laser light through a negative mask, and the photosensitive resin composition layer is partially exposed in accordance with the pattern of the partition walls. For the exposure, a light source emitting ultraviolet rays such as a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. The exposure amount varies depending on the composition of the photosensitive resin composition, but is preferably, for example, 10 to 400mJ/cm2Left and right.
Next, in a developing step, the photosensitive resin composition layer exposed to light according to the pattern of the partition walls is developed in a developing solution to form the partition walls. The developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developer include: organic developers such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. In addition, a defoaming agent and a surfactant may be added to the developer.
Thereafter, the developed partition walls are post-baked and heat-cured. The post-baking is preferably carried out at 150 to 250 ℃ for 15 to 60 minutes.
After the formation of the partition walls, a cleaning process may be performed for the purpose of cleaning the unexposed portions. The cleaning method is not particularly limited, and plasma irradiation, excimer light irradiation, and UV irradiation can be mentioned. In excimer light irradiation or UV light irradiation, active oxygen can decompose and remove organic substances attached to the pixel portion by light irradiation.
The substrate for forming the partition walls is not particularly limited, and may be appropriately selected according to the kind of organic electroluminescent element manufactured using the substrate with the partition walls formed. Preferable substrate materials include glass and various resin materials. Specific examples of the resin material include: polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; a polycarbonate; a poly (meth) acrylic resin; polysulfones; and (3) a polyimide. Among these substrate materials, glass and polyimide are preferable because of their excellent heat resistance. In addition, a transparent electrode layer of ITO, ZnO, or the like may be provided in advance on the surface of the substrate on which the partition walls are to be formed, depending on the type of the organic electroluminescent element to be manufactured.
[3] Organic electroluminescent element
The organic electroluminescent element of the present invention comprises the partition wall of the present invention.
Various organic electroluminescent elements can be manufactured using the substrate having the partition wall pattern manufactured by the above-described method. The method of forming the organic electroluminescent element is not particularly limited, but it is preferable to form an organic layer such as a pixel by injecting ink into a region surrounded by the partition walls on the substrate after forming the pattern of the partition walls on the substrate by the above-mentioned method.
Examples of the type of the organic electroluminescent element include 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 in an opening surrounded by the partition wall. On the other hand, in the top emission type, for example, a partition wall 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 in an opening surrounded by the partition wall.
The light-emitting layer may be an organic electroluminescent layer as described in japanese patent laid-open nos. 2009-146691 and 5734681. In addition, 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 film after the ink is injected. Specific examples of the organic solvent include: toluene, xylene, anisole, mesitylene, tetralin, 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 modifier, 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 walls, an ink jet method is preferable because a small amount of ink can be easily injected into a predetermined portion. The ink used for forming the organic layer may be appropriately selected depending on the kind of the organic electroluminescent element to be manufactured. When the ink is injected by the ink jet method, the viscosity of the ink is not particularly limited as long as the ink can be ejected well from the ink jet 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 modifier, and the like.
[4] Image display device
The image display device of the present invention comprises 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, an active-drive type organic electroluminescent element can be used and assembled by 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, 16 years, 8 months, 20 days, waiter, andkyush, village english to lucky). For example, an image may be displayed by combining an organic electroluminescent element that emits white light with a color filter, or an image may be displayed by combining organic electroluminescent elements having different luminescent colors such as RGB.
[5] Illumination device
The lighting 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 can be assembled by a conventional method. The organic electroluminescent element may be of a simple matrix driving type or an active matrix driving type.
In order to make the illumination of the present invention emit white light, an organic electroluminescent element that emits white light may be used. Further, the color mixing function may be provided by combining organic electroluminescent elements having different emission colors so that the color mixture of the respective colors becomes white, or by adjusting the ratio of the color mixture.
Examples
The photosensitive resin composition of the present invention will be described below with reference to specific examples, but the present invention is not limited to the following examples within the scope 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: the resulting acrylic resin (liquid repellent) was synthesized in the following manner
55 parts by mass of propylene glycol monomethyl ether acetate as a solvent was placed in a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, and the temperature was raised to 105 ℃ under stirring in a nitrogen gas stream. Next, 20 parts by mass of a compound (aa-1) containing a poly (perfluoroalkylene ether) chain having a chemical structure shown below, a monomer solution in which 50.1 parts by mass of 3-hydroxy-1-adamantyl methacrylate was dissolved in 84.6 parts by mass of propylene glycol monomethyl ether acetate, and 3 dropping solutions 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 separately set in respective dropping devices, and the glass flask was kept at 105 ℃ and dropped over 2 hours. After completion of the dropwise addition, the mixture was stirred at 105 ℃ for 5 hours, and then 103.5 parts by mass of the solvent was distilled off under reduced pressure, thereby obtaining a polymer (aa-2) solution.
[ chemical formula 58]
Figure BDA0002576772040000841
(in the formula (aa-1), X is a perfluoromethylene group or a perfluoroethylene group, 7 perfluoromethylene groups and 8 perfluoroethylene groups are present in an average number per 1 molecule, and the number of fluorine atoms is 46 on average.)
Then, 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 octylate as a urethane-forming catalyst were added, and stirring was started under an air stream, and 29.9 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 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 then the disappearance of isocyanate groups was confirmed by IR spectroscopy, 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 mass% of an acrylic resin (a-1) having an adamantane skeleton, a crosslinked portion containing a poly (perfluoroalkylene ether) chain, and an olefinic double bond. The weight average molecular weight (Mw) of the obtained acrylic resin (a-1) in terms of polystyrene measured by GPC was 10000.
a-2: the resulting acrylic resin (liquid repellent) was synthesized in the following manner
In a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 35 parts by mass of propylene glycol monomethyl ether acetate as a solvent was charged, and the temperature was raised to 105 ℃ under stirring in a nitrogen gas stream. Next, 20 parts by mass of the compound (aa-1), 46.1 parts by mass of a monomer solution in which 2-hydroxyethyl methacrylate was dissolved in 84.6 parts by mass of propylene glycol monomethyl ether acetate, and 3 kinds of dropping solutions 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 placed in respective dropping devices, and the glass flask was kept at 105 ℃ and dropped over 2 hours. After completion of the dropwise addition, the mixture was stirred at 105 ℃ for 5 hours, and 83.5 parts by mass of the solvent was distilled off under reduced pressure, thereby obtaining a polymer (ab-2) solution.
Then, to the polymer (ab-2) solution obtained above, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 part by mass of tin octylate as a urethane-forming catalyst were added, and stirring was started under an air stream, and 33.3 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 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 then, after confirming disappearance of isocyanate groups by IR spectroscopy, 50.0 parts by mass of propylene glycol monomethyl ether acetate was added to obtain a propylene glycol monomethyl ether acetate solution containing 50 mass% of an acrylic resin (a-2) having a crosslinked portion 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 in terms of polystyrene as measured by GPC.
b-1: an alkali-soluble resin (corresponding to epoxy (meth) acrylate resin (b1-3)) synthesized in the following order
100 parts by mass of a bisphenol A type epoxy compound (a mixture of compounds having an epoxy equivalent of 186g/eq and m and n in the formula of 1 to 20), 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 put into a reaction vessel, and stirred at 95 ℃ until the acid value reached 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 reaction mixture was reacted at 95 ℃ for 3 hours to obtain an alkali-soluble resin (b-1) solution having a solid acid value of 60mg-KOH/g and a weight average molecular weight (Mw) of 8,000 in terms of polystyrene as measured by GPC.
[ chemical formula 59]
Figure BDA0002576772040000851
(G represents a glycidyl group)
b-2: the following acrylic copolymer resin (corresponding to acrylic copolymer resin (b2-1))
An alkali-soluble acrylic copolymer resin (b-2) obtained by adding acrylic acid to a copolymer resin containing dicyclopentyl methacrylate/styrene/glycidyl methacrylate (molar ratio 0.02/0.05/0.93) as a constituent monomer so as to cause an equivalent addition reaction with glycidyl methacrylate, and further adding tetrahydrophthalic anhydride so as to achieve a molar ratio of 0.1 to 1 mol of the copolymer resin. The polystyrene-equivalent weight average molecular weight (Mw) measured by GPC was 7700, and the solid acid value was 28.5 mg-KOH/g.
c-1: dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kabushiki Kaisha)
d-1: 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -biimidazole (manufactured by Baotu chemical Co., Ltd.)
d-2: irgacure 369 (Compound having the following chemical Structure, manufactured by BASF Corp.)
[ chemical formula 60]
Figure BDA0002576772040000861
e-1: 2-mercaptobenzimidazole (manufactured by Tokyo Kasei K.K.)
e-2: pentaerythritol tetrakis (3-mercaptopropionate) (product of lake chemical Co., Ltd.)
f-1: TINUVIN384-2 (ultraviolet absorber manufactured by BASF corporation)
g-1: KAYAMER PM-21 (manufactured by Nippon Kabushiki Kaisha)
h-1: methylhydroquinone (Compound of the following chemical Structure, available from Seiko chemical Co., Ltd.)
[ chemical formula 61]
Figure BDA0002576772040000862
[1] Production and evaluation of photosensitive resin composition
Photosensitive resin compositions of examples 1 to 5 and comparative examples 1 to 2 were prepared by using the respective components in the blending ratios shown in Table 1 and using propylene glycol monomethyl ether acetate so that the content of the total solid content became 19 mass%, and stirring was carried out until the respective components became uniform. In table 1, the blending ratio (% by mass) of each component means a value of a solid content of each component in the total solid content.
[ Table 1]
Figure BDA0002576772040000871
The photosensitive resin compositions of examples 1 to 5 and comparative examples 1 to 2 were evaluated for physical properties by the following methods.
(measurement of contact Angle)
Each photosensitive resin composition was applied onto a glass substrate using a spin coater so as to have a thickness of 1.7 μm after heat curing. Then, the resultant was dried by heating at 95 ℃ for 2 minutes on a hot plate, and the obtained coating film was exposed to light at an amount of 120mJ/cm without using a mask by using an exposure machine MA-1100 manufactured by Dainippon scientific research Co., Ltd2The entire surface was exposed. The intensity at a wavelength of 365nm in this case was 40mW/cm2. Subsequently, the resultant was subjected to spray development with a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 24 ℃ for 60 seconds, and then 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 a Drop Master 500 contact angle measuring apparatus manufactured by Kyowa Kagaku K.K. under conditions of 23 ℃ and 50% humidity. To the contact angle measurement substrate of the cured product of 0.7L, propylene glycol methyl ether acetate was added dropwise, measuring the contact angle after 1 second. The measurement results are shown in Table 1. The case where the contact angle is large indicates that the ink repellency is high.
(evaluation of UV resistance (contact Angle))
The substrate for contact angle measurement was irradiated with Ultraviolet (UV) light for 3 minutes using a drying processor VUM-3073 manufactured by Oak Corporation. The intensity at a wavelength of 254nm was 9mW/cm2。
The contact angle of the substrate after UV irradiation was measured in the same manner as described above. The results were evaluated from the following 2 viewpoints, and the measurement results and the 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 30 ° or more.
B: the contact angle after UV irradiation was 15 ° or more and less than 30 °.
C: the contact angle after UV irradiation was shown to be less than 15 °.
A is the desired property.
[ contact Angle evaluation-2 ]
The decrease rate of the contact angle was derived according to the following formula, and evaluated according to the following criteria. In the case where the contact angle at the time before UV irradiation is less than 30 °, the decrease rate of the contact angle is not calculated as na (not available).
The decreasing rate (%) of the contact angle was 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 DEG 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 is 30 DEG or more, and the reduction rate of the contact angle after UV irradiation is 30% or more.
D: the contact angle before UV irradiation did not show 30 ° or more.
A is the desired property.
[2] Formation and evaluation of partition wall
Using the photosensitive resin compositions of examples 1 to 5, partition wall formation and performance evaluation were carried out according to the methods described below.
(formation of partition wall)
Use ofThe coating machine on the surface of the ITO film formed on the glass substrate of the ITO film, in order to heat curing to reach 1.7 m thickness of the way of coating each photosensitive resin composition, then, on a hot plate at 95 degrees C for 2 minutes heating drying, the coating film, using a photomask (40 m interval with a plurality of 80 m × 280 m coating part of the mask), in the exposure gap of 16 m, using Japan scientific research company, make exposure machine MA-1100 exposure, the wavelength of 365nm at 40mW/cm intensity2The exposure amount was 120mJ/cm2In air. Subsequently, the resultant was subjected to spray development with a 2.38 mass% aqueous solution of TMAH (tetramethylammonium hydroxide) at 24 ℃ for 60 seconds, and then washed with pure water for 1 minute. The substrate from which the unnecessary portions were removed and the pattern was formed was heated and cured at 230 ℃ for 30 minutes in an oven, to obtain a substrate having lattice-shaped partition walls.
(evaluation of UV resistance (suitability for ink jet coating on partition wall))
The substrate having the lattice-shaped partition walls was irradiated with Ultraviolet (UV) rays for 3 minutes using a drying processor VUM-3073 manufactured by Oak Corporation. The intensity at a wavelength of 254nm was 9mW/cm2。
The pixel portion surrounded by the lattice-shaped partition walls of the substrate after UV irradiation was subjected to ink-jet coating using DMP-2831 manufactured by Fuji Film corporation. As an ink, 480pL was applied to 1 pixel using a solvent (isoamyl benzoate) alone, and whether or not there was a collapse (a phenomenon in which the ink crossed the partition walls and mixed into the adjacent pixel portion) was evaluated according to the following criteria.
The higher the ink repellency of the partition walls, the more likely the collapse is suppressed. In examples 1 to 5, the wetting extension property in the partition walls after the ink jet coating was good, and the following evaluation of the collapse (ink jet coating suitability) was a.
[ burst evaluation (ink jet coating suitability) ]
A: the ink can be applied to the inside of the pixel without overflowing the partition wall.
B: the ink overflows from the pixel to the entire upper surface of the partition wall, and is mixed into the adjacent pixel portion (collapse).
A is the desired property.
The coated substrates using the photosensitive resin compositions of examples 1 to 5 were confirmed to have a high contact angle after UV irradiation and good suitability for inkjet coating after UV irradiation. It is considered that the chain transfer agent is contained, whereby the decrease in the curability of the film surface due to the inhibition of oxygen can be suppressed, the elution of the liquid repellent in the developing step can be suppressed, a sufficient amount of the liquid repellent can be fixed to the film surface, and the contact angle becomes good. 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 amount of fluorine atoms present on the film surface after UV irradiation can be sufficiently secured.
In contrast, the coated substrate using the photosensitive resin composition of comparative example 1 did not exhibit sufficient ink repellency before UV irradiation. This is considered to be because the surface curability is low and the liquid repellent flows out during development because the composition does not contain a chain transfer agent.
In addition, the coated substrate using the photosensitive resin composition of comparative example 2 had 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 is reduced by decomposition of the liquid repellent by UV irradiation, and sufficient ink repellency is not exhibited.
[3] Production and evaluation of photosensitive resin composition, and production and evaluation of partition wall
The photosensitive resin composition of example 6 was prepared by stirring propylene glycol monomethyl ether acetate so that the solid content of each component in the total solid content became the following blending ratio (parts by mass) and the content of the total solid content became 19% by mass, until the components became homogeneous.
Figure BDA0002576772040000901
(measurement of contact Angle)
The photosensitive resin composition of example 6 was applied onto a glass substrate using a spin coater so as to have a thickness of 1.7 μm after heat curing. Then, the resultant was dried by heating at 95 ℃ for 2 minutes on a hot plate, and the obtained coating film was exposed to an exposure of 200mJ/cm without using a mask by using an exposure machine MA-1100 manufactured by Dainippon scientific research Co., Ltd2The entire surface was exposed. The intensity at a wavelength of 365nm in this case was 40mW/cm2. Subsequently, the resultant was subjected to spray development with a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution at 24 ℃ for 60 seconds, and then 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.
Contact angle measurement and UV resistance evaluation (suitability for inkjet coating of partition walls) were performed in the same manner as described above, and the following results were obtained.
Figure BDA0002576772040000902
Figure BDA0002576772040000911
(formation of partition wall)
The glass substrate having an ITO film formed on the surface thereof was coated with the photosensitive resin composition of example 6 using a spin coater so as to be cured by heating to a thickness of 1.7 μm, and then dried by heating at 95 ℃ for 2 minutes on a hot plate, and the resulting coating film was exposed to light at an exposure gap of 16 μm using a photomask (a mask having a plurality of coating portions of 80 μm × 280 μm at 40 μm intervals) using an exposure machine MA-1100 manufactured by Dainippon scientific research Co., Ltd. at an intensity of 40mW/cm at a wavelength of 365nm2The exposure amount was 200mJ/cm2In air. Subsequently, the resultant was subjected to spray development with a 2.38 mass% aqueous solution of TMAH (tetramethylammonium hydroxide) at 24 ℃ for 60 seconds, and then washed with pure water for 1 minute. So that unnecessary portions are removed and a pattern is formed by these operationsThe substrate of (2) was cured by heating at 230 ℃ for 30 minutes in an oven to obtain a substrate having lattice-shaped partition walls.
The UV resistance evaluation (suitability for inkjet coating of partition walls) was performed in the same manner as described above, and the following results were obtained.
Inkjet coating suitability (after UV irradiation): A.

Claims (16)

1. a photosensitive resin composition comprising: (A) a liquid repellent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator,
the liquid repellent (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 claim 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 claim 2, wherein the acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an olefinic double bond has a partial structure represented by the following general formula (1),
Figure FDA0002576772030000011
in the formula (1), R1Each independently represents a hydrogen atom or a methyl group, X1Represents a perfluoroalkylene group, a plurality of X's contained in the formula (1)1Optionally the same or different at a plurality of X1In each case optionally present in random or block form, X2Each 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.
4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the polycyclic saturated hydrocarbon skeleton is an adamantane skeleton.
5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an olefinic double bond has a partial structure represented by the following general formula (2),
Figure FDA0002576772030000012
in the formula (2), R2And R3Each independently represents a hydrogen atom or a methyl group, X3Represents an optionally substituted 2-valent polycyclic saturated hydrocarbon group, X4Represents a urethane bond or an ester bond, X5Represents a 2-valent hydrocarbon group optionally having a substituent, and represents a bonding position.
6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the (B) alkali-soluble resin comprises an epoxy (meth) acrylate resin (B1) and/or an acrylic copolymer resin (B2).
7. The photosensitive resin composition according to claim 6, wherein the epoxy (meth) acrylate resin (b1) is at least one selected from the group consisting of an epoxy (meth) acrylate resin (b1-1) having a partial structure represented by the following general formula (i), an epoxy (meth) acrylate resin (b1-2) having a partial structure represented by the following general formula (ii), and an epoxy (meth) acrylate resin (b1-3) having a partial structure represented by the following general formula (iii),
Figure FDA0002576772030000021
in the formula (i), RaRepresents a hydrogen atom or a methyl group, RbRepresents an optionally substituted 2-valent hydrocarbon group, the benzene ring in the formula (i) is optionally further substituted by an optional substituentThe position of the bonding is determined by the position of the bonding,
Figure FDA0002576772030000022
in the formula (ii), RcEach independently represents a hydrogen atom or a methyl group, RdRepresents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain, represents a bonding position,
Figure FDA0002576772030000031
in the formula (iii), ReRepresents 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 the formula (iii) is optionally further substituted with an optional substituent, and x represents a bonding position.
8. The photosensitive resin composition according to claim 6 or 7, wherein the acrylic copolymer resin (b2) is an acrylic copolymer resin (b2-1) containing a partial structure represented by the following general formula (I),
Figure FDA0002576772030000032
in the formula (I), RAAnd RBEach independently represents a hydrogen atom or a methyl group, and represents a bonding position.
9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the photopolymerization initiator (D) contains at least one selected from the group consisting of hexaarylbisimidazole-based photopolymerization initiators, oxime ester-based photopolymerization initiators and acetophenone-based photopolymerization initiators.
10. The photosensitive resin composition according to any one of claims 1 to 9, which further contains an ultraviolet absorber.
11. The photosensitive resin composition according to any one of claims 1 to 10, further comprising a polymerization inhibitor.
12. The photosensitive resin composition according to any one of claims 1 to 11, which is used for forming partition walls.
13. A partition wall comprising the photosensitive resin composition according to any one of claims 1 to 12.
14. An organic electroluminescent element comprising the partition wall as claimed in claim 13.
15. An image display device comprising the organic electroluminescent element according to claim 14.
16. A lighting comprising the organic electroluminescent element according to claim 14.
CN201980007829.5A 2018-01-26 2019-01-24 Photosensitive resin composition, partition wall, organic electroluminescent element, image display device, and illumination Pending CN111566560A (en)

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