WO2019146680A1 - Photosensitive resin composition, partition wall, organic electroluminescent element, image display device and lighting - Google Patents

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

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Publication number
WO2019146680A1
WO2019146680A1 PCT/JP2019/002225 JP2019002225W WO2019146680A1 WO 2019146680 A1 WO2019146680 A1 WO 2019146680A1 JP 2019002225 W JP2019002225 W JP 2019002225W WO 2019146680 A1 WO2019146680 A1 WO 2019146680A1
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PCT/JP2019/002225
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French (fr)
Japanese (ja)
Inventor
明日香 木村
和裕 中谷
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三菱ケミカル株式会社
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Priority to JP2019567137A priority Critical patent/JP7234946B2/en
Priority to KR1020207015245A priority patent/KR102636177B1/en
Priority to CN201980007829.5A priority patent/CN111566560A/en
Publication of WO2019146680A1 publication Critical patent/WO2019146680A1/en

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Classifications

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

Definitions

  • the present invention relates to a photosensitive resin composition, a partition composed of the photosensitive resin composition, an organic electroluminescent device provided with the partition, an image display apparatus including the organic electroluminescent device, and illumination.
  • organic electroluminescent devices included in organic electroluminescent display, organic electroluminescent illumination, etc. are formed by laminating various functional layers in a region surrounded by the partition after forming the partition (bank) on the substrate. It is manufactured.
  • a method of easily forming such a partition a method of forming by photolithography using a photosensitive resin composition is known.
  • an ink containing a material constituting the functional layer is prepared, and then the prepared ink is injected into the area surrounded by the partition.
  • the inkjet method is often employed because it is easy to inject a predetermined amount of ink accurately to a predetermined location.
  • the ink repellent property for the purpose of preventing the adhesion of the ink to the partition, the mixing of the ink injected between the adjacent regions, etc. It may be required to impart liquid repellency).
  • a method of imparting ink repellency to partition walls for example, a method of including a fluorine-based compound in partition walls is known (see Patent Documents 1 and 2).
  • Patent Document 3 describes that a cured product having high ink repellency can be formed by using a specific fluorocarbon resin.
  • this invention aims at providing the photosensitive resin composition which can form the partition in which ink repellency is favorable also after UV washing processing. Moreover, this invention aims at providing the partition comprised with the said photosensitive resin composition, the organic electroluminescent element provided with this partition, the image display apparatus containing this organic electroluminescent element, and illumination.
  • a liquid repellent having a specific structure is used, and a chain transfer agent is further used. It has been found that the above problems can be solved by using the present invention, and the present invention has been completed. That is, the gist of the present invention is as follows.
  • a photosensitive resin composition comprising (A) a liquid repellent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator,
  • the (A) liquid repellent agent includes an acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond
  • a photosensitive resin composition characterized by further comprising (E) a chain transfer agent.
  • the photosensitive resin according to [1] wherein the acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond has a crosslinked portion containing a poly (perfluoroalkylene ether) chain.
  • R 1 each independently represents a hydrogen atom or a methyl group.
  • X 1 represents a perfluoroalkylene group.
  • Plural X 1 contained in formula (1) may be the same or different. In the case of different ones, they may be present in a random form or in a block form, and each X 2 independently represents a direct bond or any divalent linking group, and n is one or more. Is an integer of *. * Represents a bond.
  • X 3 represents a hydrogen atom or a methyl group represents a polycyclic saturated hydrocarbon group which may have a substituent.
  • X 4 represents a urethane bond or an ester bond,
  • X 5 represents a divalent hydrocarbon group which may have a substituent, and * represents a bond.
  • the photosensitive resin according to any one of [1] to [5], wherein the (B) alkali-soluble resin comprises an epoxy (meth) acrylate resin (b1) and / or an acrylic copolymer resin (b2) Composition.
  • the epoxy (meth) acrylate resin (b1) is represented by an epoxy (meth) acrylate resin (b1-1) containing a partial structure represented by the following general formula (i), a general formula (ii) below At least one selected from the group consisting of an epoxy (meth) acrylate resin (b1-2) containing a partial structure and an epoxy (meth) acrylate resin (b1-3) containing a partial structure represented by the following general formula (iii)
  • R a represents a hydrogen atom or a methyl group
  • R b represents a divalent hydrocarbon group which may have a substituent.
  • the benzene ring in formula (i) It may be substituted by any substituent, * represents a bond.
  • each R c independently represents a hydrogen atom or a methyl group.
  • R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. .
  • R e represents a hydrogen atom or a methyl group
  • ⁇ is a single bond, —CO—, an alkylene group which may have a substituent, or 2 which may have a substituent
  • the benzene ring in the formula (iii) may be further substituted by any substituent. * Represents a bond.
  • R A and R B each independently represent a hydrogen atom or a methyl group. * Represents a bond.
  • the (D) photopolymerization initiator contains at least one selected from the group consisting of a hexaarylbiimidazole photopolymerization initiator, an oxime ester photopolymerization initiator, and an acetophenone photopolymerization initiator.
  • the photosensitive resin composition according to any one of [1] to [8].
  • the photosensitive resin composition according to any one of [1] to [10] further comprising a polymerization inhibitor.
  • the photosensitive resin composition according to any one of [1] to [11] which is for forming a partition wall.
  • a partition comprising the photosensitive resin composition according to any one of [1] to [12].
  • An organic electroluminescent device comprising the partition wall according to [13].
  • An image display comprising the organic electroluminescent device as described in [14].
  • a lighting comprising the organic electroluminescent device according to [14].
  • (meth) acrylic means “acrylic and / or methacrylic”
  • total solids means all components other than the solvent in the photosensitive resin composition. Shall be meant.
  • a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
  • a and / or B means one or both of A and B, and specifically means A, B, or A and B.
  • (co) polymer is meant to include both homopolymers (homopolymers) and copolymers (copolymers), and "polybasic acid (anhydride)" By “polybasic acid and / or polybasic acid anhydride” is meant.
  • the weight average molecular weight refers to a weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography).
  • the acid value refers to the acid value in terms of effective solid content, and is calculated by neutralization titration.
  • the partition material refers to a bank material, a wall material, and a wall material
  • the partition wall refers to a bank, a wall, and a wall.
  • the light emitting portion refers to a portion which emits light when electric energy is applied.
  • 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,
  • the liquid repellent agent (A) includes an acrylic resin (a) having a polycyclic saturated hydrocarbon backbone and an ethylenic double bond, and further includes (E) a chain transfer agent. If necessary, other components may be further contained, and for example, an ultraviolet absorber or a polymerization inhibitor may be contained.
  • the partition wall is, for example, for partitioning a functional layer (organic layer, light emitting portion) in an active drive type organic electroluminescent device, and for forming a functional layer in a partitioned region (pixel region) It is used to form pixels including a functional layer and a partition by discharging and drying the ink which is the material of the above.
  • the photosensitive resin composition of the present invention contains (A) a liquid repellent agent, (B) an alkali soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator, and further (E) a chain transfer agent And usually contain a solvent.
  • the photosensitive resin composition of the present invention contains (A) a liquid repellent.
  • the acrylic resin (a) is one having a polycyclic saturated hydrocarbon skeleton.
  • the presence of the polycyclic saturated hydrocarbon skeleton increases the ink repellency on the film surface after UV irradiation, which is considered to be due to the following effects.
  • the surface temperature of the cured product tends to rise due to the heat generated by UV absorption of the resin and the like in the cured product by the UV irradiation, and it is considered that the acrylic resin (a) segregated in the surface is susceptible to the heat generation.
  • linear structure breaks down if one place breaks, but cyclic structure does not break down unless it breaks multiple places, so it has high heat resistance because it does not break down especially when it becomes polycyclic, so heat resistance It is considered to go up.
  • a saturated cyclic hydrocarbon skeleton has no bond as a reaction starting point than an unsaturated cyclic hydrocarbon skeleton, and there is an advantage that the reactivity of the ring itself is low.
  • the presence of the polycyclic hydrocarbon skeleton itself causes steric hindrance, which makes it difficult to cut the main chain of the acrylic resin (a), and the heat resistance is further improved.
  • the acrylic resin (a) has an acrylic structure
  • compatibility with the (B) alkali-soluble resin and (C) photopolymerizable compound can be enhanced, and the storage stability of the photosensitive resin composition is also enhanced. It is considered that the generation of the residue in the pixel portion can be suppressed and the wetting and spreading property is improved.
  • the polycyclic saturated hydrocarbon skeleton may be a monovalent group or a divalent or higher group. Moreover, it may be unsubstituted or may have a substituent.
  • the carbon number of the polycyclic saturated hydrocarbon backbone is not particularly limited, but is usually 6 or more and 8 or more, preferably 9 or more, more preferably 10 or more, and preferably 20 or less, more preferably 15 or less. , 12 or less is more preferable.
  • the carbon number of the polycyclic saturated hydrocarbon skeleton is, for example, 6 to 20, preferably 8 to 20, more preferably 9 to 15, and still more preferably 10 to 12.
  • the number of rings contained in the polycyclic saturated hydrocarbon skeleton is not particularly limited as long as it is 2 or more, but 3 or more is preferable, 5 or less is preferable, and 4 or less is more preferable.
  • the number of rings possessed by the polycyclic saturated hydrocarbon skeleton is, for example, 2 to 5, and preferably 3 to 4.
  • polycyclic saturated hydrocarbon skeleton examples include an adamantane skeleton, a tricyclodecane skeleton, a norbornane skeleton, a decalin skeleton and the like, but an adamantane skeleton is preferable from the viewpoint of ink repellency after UV washing treatment.
  • the polycyclic saturated hydrocarbon skeleton may be anywhere in the chemical structure of the acrylic resin (a), for example, may be in the main chain of the acrylic resin, or may be in the side chain. It is preferably in the side chain from the viewpoint of easiness of synthesis.
  • the content ratio of the polycyclic saturated hydrocarbon skeleton in the acrylic resin (a) is not particularly limited, but 10 mass% or more is preferable, 20 mass% or more is more preferable, 25 mass% or more is more preferable, and 30% mass % Or more is particularly preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, and 35% by mass or less is more preferable.
  • the content ratio 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 30 to 35% by mass. % Is more preferred.
  • an acrylic resin (a) has a bridge
  • strand In the case of having a crosslinked portion containing a poly (perfluoroalkylene ether) chain, the crosslinked portion bonds to two or more main chains, so that the poly (perfluoroalkylene ether) chain is detached from the acrylic resin (a) even by UV washing. It is difficult that a sufficient amount of fluorine atoms can be present on the surface of the partition walls, and as a result, it is considered that the ink repellency becomes good even after the UV cleaning treatment.
  • the chemical structure of the acrylic resin (a) is not particularly limited, but from the viewpoint of showing sufficient ink repellency even after UV washing, as a partial structure having a cross-linked portion containing a poly (perfluoroalkylene ether) chain, the following general formula
  • the partial structure represented by (1) is preferably included.
  • each R 1 independently represents a hydrogen atom or a methyl group.
  • X 1 represents a perfluoroalkylene group.
  • the plurality of X 1 included in the formula (1) may be the same or different, and in the case of different ones, they may be present in a random form or in a block form.
  • Each X 2 independently represents a direct bond or any divalent linking group.
  • n is an integer of 1 or more. * Represents a bond.
  • X 1 represents a perfluoroalkylene group.
  • the carbon number of the perfluoroalkylene group is not particularly limited, but is usually 1 or more and 2 or more, preferably 5 or less, and more preferably 3 or less.
  • the perfluoroalkylene group include groups represented by the following general formulas (1-a) to (1-e).
  • the group represented by the above formula (1-a), the above formula (1-b), and the like from the viewpoint of obtaining high ink repellency.
  • Preferred groups 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) be included in the formula (1).
  • the molar ratio of the group represented by the formula (1-a) contained in the formula (1) and the group represented by the formula (1-b) is not particularly limited, but from the viewpoint of ink repellency, 1:10 to 10: 1 is preferable, 1: 4 to 4: 1 is more preferable, and 1: 2 to 2: 1 is more preferable.
  • X 2 represents a direct bond or an arbitrary divalent linking group.
  • the optional divalent linking group —O—, —CO—O—, —CO—NH—, —O—CO—NH—, or a divalent hydrocarbon group which may have a substituent can be used. It can be mentioned. At least one selected from the group consisting of -O-, -CO-O-, -CO-NH-, and -O-CO-NH-, wherein a part of -CH 2- contained in the hydrocarbon group is It may be replaced by.
  • Examples of the divalent hydrocarbon group include a divalent aliphatic group and a divalent aromatic ring group.
  • Examples of the divalent aliphatic group include linear, branched or cyclic alkylene groups, and linear, branched or cyclic alkenylene groups.
  • the carbon number of the divalent aliphatic group is not particularly limited, but is usually 1 or more and 5 or less, preferably 3 or less, and more preferably 2 or less. By setting the content to the upper limit value or less, the ink repellency tends to be high.
  • Specific examples of the divalent aliphatic group include methylene, ethylene, ethenylene, propylene, propenylene, butylene, butenylene and the like.
  • Examples of the substituent which the divalent aliphatic group may have include a hydroxyl group and an alkoxy group.
  • divalent aromatic ring group examples include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the carbon number of the divalent aromatic ring group is not particularly limited, but generally 4 or more and 5 or more is preferable, 6 or more is more preferable, 30 or less is preferable, 20 or less is more preferable, and 15 or less is more preferable.
  • compatibility with other materials tends to be good, and when the content is at the upper limit or less, the ink repellency tends to be high.
  • divalent aromatic hydrocarbon ring group examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring and a chrysene ring, which have two free valences.
  • Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like can be mentioned.
  • divalent aromatic heterocyclic group for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring having two free valences , Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine Groups such as ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sino
  • X 2 include the following.
  • a divalent aliphatic group is preferable, a methylene group and an ethylene group are more preferable, and a methylene group is more preferable. preferable.
  • n is an integer of 1 or more, but is preferably an integer of 3 to 40, more preferably an integer of 6 to 30, more preferably 10 to 20, from the viewpoint of ink repellency. More preferably, it is an integer of
  • the acrylic resin (a) has a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond, but from the viewpoint of ink repellency and sensitivity after UV washing, the polycyclic saturated hydrocarbon skeleton and It is preferable that it is a thing including the partial structure represented with following General formula (2) as a partial structure containing an ethylenic double bond.
  • R 2 and R 3 each independently represent a hydrogen atom or a methyl group.
  • X 3 represents a divalent polycyclic saturated hydrocarbon group which may have a substituent.
  • X 4 represents a urethane bond or an ester bond.
  • X 5 represents a divalent hydrocarbon group which may have a substituent. * Represents a bond.
  • X 3 represents a polycyclic saturated hydrocarbon group which may have a substituent.
  • the carbon number of the divalent polycyclic saturated hydrocarbon group is not particularly limited, but generally 6 or more and 8 or more is preferable, 9 or more is more preferable, 10 or more is more preferable, 20 or less is preferable, and 15 or less is more Preferably, 10 or less is more preferable.
  • the divalent polycyclic saturated hydrocarbon group include an adamantylene group, a dicyclopentanylene group, a norbornanylene group, and a decalinylene group.
  • Examples of the substituent which the divalent polycyclic saturated hydrocarbon group may have include an alkoxy group, a halogen atom, and a hydroxyl group.
  • X 4 represents a urethane bond (-O-CO-NH-) or an ester bond (-O-CO-).
  • a urethane bond is preferable from the viewpoint of suppressing the decrease in ink repellency after the UV cleaning treatment.
  • X 5 represents a divalent hydrocarbon group which may have a substituent.
  • the divalent hydrocarbon group include a divalent aliphatic group and a divalent aromatic ring group.
  • Examples of the divalent aliphatic group include linear, branched or cyclic alkylene groups, and linear, branched or cyclic alkenylene groups.
  • the carbon number of the divalent aliphatic group is not particularly limited, but is usually 1 or more and 2 or more, preferably 10 or less, more preferably 8 or less, still more preferably 5 or less, and particularly preferably 3 or less.
  • divalent aliphatic group examples include methylene, ethylene, ethenylene, propylene, propenylene, butylene, butenylene, cyclohexylene and adamantylene groups.
  • substituent which the divalent aliphatic group may have include a hydroxyl group, an alkoxy group, a halogen atom and the like.
  • Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the carbon number of the divalent aromatic ring group is not particularly limited, but generally 4 or more and 5 or more is preferable, 6 or more is more preferable, 30 or less is preferable, 20 or less is more preferable, and 15 or less is more preferable.
  • divalent aromatic hydrocarbon ring group examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring and a chrysene ring, which have two free valences.
  • Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like can be mentioned.
  • divalent aromatic heterocyclic group for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring having two free valences , Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine Groups such as ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sino
  • a divalent aliphatic group is preferable, a methylene group and an ethylene group are more preferable, and an ethylene group is more preferable. preferable.
  • the acrylic resin (a) may further include other partial structures, and among the other partial structures, it includes the partial structure represented by the following general formula (3) from the viewpoint of reducing the residue of the light emitting part Is preferred.
  • R 4 represents a hydrogen atom or a methyl group.
  • X 6 represents a monovalent hydrocarbon group which may have a substituent. * Represents a bond.
  • X 6 represents a monovalent hydrocarbon group which may have a substituent.
  • monovalent hydrocarbon groups include monovalent aliphatic groups and monovalent aromatic ring groups.
  • the monovalent aliphatic group includes a linear, branched or cyclic alkyl group, and a linear, branched or cyclic alkenyl group.
  • the carbon number of the monovalent aliphatic group is not particularly limited, but is usually 1 or more and 2 or more, preferably 4 or more, more preferably 6 or more, particularly preferably 8 or more, and preferably 20 or less, 15 or less Is more preferable, and 10 or less is more preferable.
  • the monovalent aliphatic group examples include a methyl group, an ethyl group, an ethenyl group, a propyl group, a propenyl group, a butyl group, a butenyl group, a cyclohexyl group and an adamantyl group.
  • substituent which the monovalent aliphatic group may have include a hydroxyl group, an alkoxy group, a halogen atom and the like.
  • Examples of the monovalent aromatic ring group include monovalent aromatic hydrocarbon ring groups and monovalent aromatic heterocyclic groups.
  • the carbon number of the monovalent aromatic ring group is not particularly limited, but generally 4 or more and 5 or more is preferable, 6 or more is more preferable, 30 or less is preferable, 20 or less is more preferable, and 15 or less is more preferable.
  • the monovalent aromatic hydrocarbon ring group is, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, having one free valence.
  • Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like can be mentioned.
  • the monovalent aromatic heterocyclic group for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring having one free valence , Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine Groups such as ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sino
  • a monovalent aliphatic group which may have a substituent is preferable, and an ethyl group which may have a substituent or a substituent is preferable.
  • the preferred adamantyl group is more preferable, and the adamantyl group which may have a substituent is more preferable.
  • the content is not limited, but 1 mol% or more is preferable, 2 mol% or more is more preferable, and 3 mol% or more More preferably, 5 mol% or more is more preferable, 7 mol% or more is particularly preferable, 20 mol% or less is preferable, 15 mol% or less is more preferable, 13 mol% or less is more preferable, 10 mol% or less Particularly preferred.
  • the content is at least the lower limit, the ink repellency tends to be high, and when the content is at the upper limit or less, compatibility with other materials tends to be good.
  • the content is, for example, 1 to 20 mol%, preferably 2 to 20 mol%, and 3 to 15 mol. % Is more preferable, 5 to 15 mol% is more preferable, and 7 to 10 mol% is even more preferable.
  • the acrylic resin (a) has a partial structure represented by the general formula (2)
  • the content is not limited, but 30 mol% or more is preferable, 40 mol% or more is more preferable, and 50 mol % Or more is more preferable, 60 mol% or more is further more preferable, 70 mol% or more is particularly preferable, 95 mol% or less is preferable, and 90 mol% or less is more preferable.
  • the content ratio is, for example, 30 to 95 mol%, preferably 40 to 95 mol%, and 50 to 90 mol. % Is more preferable, 60 to 90 mol% is more preferable, and 70 to 90 mol% is still more preferable.
  • the acrylic resin (a) has a partial structure represented by the general formula (3)
  • the content is not limited, but 1 mol% or more is preferable, 2 mol% or more is more preferable, 3 mol % Or more is more preferable, 5 mol% or more is particularly preferable, 60 mol% or less is preferable, 50 mol% or less is more preferable, 40 mol% or less is more preferable, 30 mol% or less is further more preferable, 20 mol % Or less is particularly preferred.
  • the content ratio is, for example, 1 to 60 mol%, preferably 2 to 50 mol%, and 3 to 40 mol. % Is more preferable, 5 to 30 mol% is more preferable, and 5 to 20 mol% is even more preferable.
  • the acrylic resin (a) may be a random copolymer, and a block copolymer It may be a polymer.
  • the A block including the partial structure represented by the general formula (1), the partial structure represented by the general formula (2), and / or the general structure It is preferable that it is AB block copolymer including B block containing the partial structure represented by Formula (3).
  • 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, still more preferably 8000 or more, still more preferably 10000 or more, and preferably 100,000 or less, more preferably 50,000 or less, 30,000 or less More preferably, 20000 or less is particularly preferable.
  • the weight average molecular weight of the acrylic resin (a) is, for example, 1000 to 100000, preferably 5000 to 50000, more preferably 8000 to 30000, and still more preferably 10000 to 20000.
  • the acrylic resin (a) contains a fluorine atom
  • the content is not particularly limited, and 1 mass% or more is preferable, 5 mass% or more is more preferable, 8 mass% or more is more preferable, and 50 mass% The following are preferable, and 25 mass% or less is more preferable.
  • the acrylic resin (a) contains a fluorine atom
  • the content is, for example, 1 to 50% by mass, preferably 5 to 25% by mass, and more preferably 8 to 25% by mass.
  • the content ratio of (A) liquid repellent agent in the photosensitive resin composition of this invention is not specifically limited, 0.01 mass% or more is preferable in the total solid of the photosensitive resin composition, 0.1 mass% or more 0.2 mass% or more is more preferable, 0.4 mass% or more is particularly preferable, 1 mass% or less is preferable, 0.7 mass% or less is more preferable, 0.5 mass% or less is further preferable preferable.
  • the content ratio of the (A) liquid repellent agent in the total solid content of the photosensitive resin composition is, for example, 0.01 to 1% by mass, preferably 0.1 to 0.7% by mass, and 0.2 to 7% by mass. 0.7% by mass is more preferable, and 0.4 to 0.5% by mass is more preferable.
  • the content ratio of the acrylic resin (a) in the photosensitive resin composition of the present invention is also not particularly limited, but preferably 0.01% by mass or more, and preferably 0.1% by mass or more in the total solid content of the photosensitive resin composition. 0.2 mass% or more is more preferable, 0.4 mass% or more is particularly preferable, 1 mass% or less is preferable, 0.7 mass% or less is more preferable, 0.5 mass% or less is further preferable preferable.
  • the ink repellent property tends to be increased by setting the lower limit value or more, and the outflow to the pixel portion of the acrylic resin (a) can be suppressed by setting the upper limit value or less.
  • the content ratio of the acrylic resin (a) in the total solid content of the photosensitive resin composition is, for example, 0.01 to 1% by mass, preferably 0.1 to 0.7% by mass, and 0.2 to 7% by mass. 0.7% by mass is more preferable, and 0.4 to 0.5% by mass is more preferable.
  • the liquid repellent agent (A) in the photosensitive resin composition of the present invention may contain another liquid repellent agent other than the acrylic resin (a).
  • liquid repellents include, for example, perfluoroalkylsulfonic acid, perfluoroalkylcarboxylic acid, perfluoroalkylalkylene oxide adduct, perfluoroalkyltrialkylammonium salt, perfluorocarboxylic acid ester, perfluoroalkyl phosphoric acid ester And fluorine atom-containing organic compounds such as oligomers containing a perfluoroalkyl group and oligomers containing a perfluoroalkylene group.
  • the content ratio of the acrylic resin (a) in the liquid repellent agent (A) is also not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and usually 100% by mass It is below. By setting the content to the above lower limit value or more, there is a tendency that the decrease in the ink repellency after the UV cleaning treatment is suppressed.
  • the content ratio of the acrylic resin (a) in the liquid repellent agent (A) is, for example, 50 to 100% by mass, preferably 80 to 100% by mass, and more preferably 90 to 100% by mass.
  • the content ratio of the other liquid repellent agent in (A) liquid repellent agent is not particularly limited, but 10 mass% or more is preferable, and 15 mass% or more is more preferable, 20 mass% or more is further preferable, 50 mass% or less is preferable, 40 mass% or less is more preferable, and 30 mass% or less is more preferable.
  • the content ratio of the other liquid repellent agent in (A) liquid repellent agent is, for example, 10 to 50% by mass, preferably 15 to 40% by mass, 20 to 30% by mass is more preferable.
  • 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 is a resin that can be developed with an alkali developer.
  • alkali-soluble resin various resin containing a carboxyl group and / or a hydroxyl group is mentioned. Among them, a resin having a carboxyl group is preferable from the viewpoint that a partition having an appropriate taper angle can be obtained, the outflow of the liquid repellent agent can be suppressed by heat melting of the partition surface during post baking, and the ink repellency can be maintained. .
  • the (B) alkali-soluble resin is an alkali-soluble resin (b) having an ethylenic double bond (hereinafter sometimes referred to as "alkali-soluble resin (b)"). Is preferred.
  • alkali-soluble resin (b) having an ethylenic double bond By including the alkali-soluble resin (b) having an ethylenic double bond, the sensitivity tends to be high, and the ink repellency of the partition wall obtained by suppressing the liquid repellent agent outflow during development tends to be high.
  • the specific structure of the alkali-soluble resin (b) having an ethylenic double bond is not particularly limited, but from the viewpoint of development solubility, the epoxy (meth) acrylate resin (b1) and / or the acrylic copolymer resin (b2)
  • 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.
  • 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. is there.
  • the ethylenically unsaturated bond is added to the epoxy resin via an ester bond (-COO-)
  • ester bond one in which one carboxyl group of polybasic acid anhydride is added to the hydroxyl group generated at that time is mentioned.
  • a polybasic acid anhydride what was simultaneously added and added the polyhydric alcohol is also mentioned.
  • a resin obtained by reacting a compound having a functional group capable of further reacting with the carboxyl group of the resin obtained by the above reaction is also included in the epoxy (meth) acrylate resin (b1).
  • the epoxy (meth) acrylate resin does not have an epoxy group substantially due to the chemical structure, and is not limited to "(meth) acrylate", but an epoxy compound (epoxy resin) is a raw material And because it is a representative example, "(meth) acrylate” is so named according to conventional practice.
  • epoxy resin as used herein also includes raw material compounds prior to the formation of a resin by heat curing, and the epoxy resin can be appropriately selected and used from known epoxy resins. Moreover, the epoxy resin can use the compound obtained by making a phenolic compound and an epihalohydrin react.
  • the phenolic compound is preferably a compound having a divalent or divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
  • bisphenol A epoxy resin bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, phenol and dicyclopentane
  • dihydroxyl fluorene type epoxy resin dihydroxyl alkylene oxyl fluorene type epoxy resin
  • diglycidyl ether of 9,9-bis (4'-hydroxyphenyl) fluorene 1,1-bis
  • diglycidyl ether of (4′-hydroxyphenyl) adamantane and the like there may be mentioned diglycidyl ether of (4′-hydroxyphenyl) adamantane and the like, and thus one having an aromatic ring in the main chain can be suitably used.
  • bisphenol A epoxy resin bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, epoxy compound of polymer of phenol and dicyclopentadiene, 9, 9-bis (4'-hydroxyphenyl) Epoxide compounds of fluorene and the like are preferable, and bisphenol A epoxy resin is more preferable.
  • 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 adduct, pentaerythritol trihydrate.
  • polybasic acids examples 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 And benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and anhydrides thereof.
  • succinic anhydride maleic anhydride and itaconic anhydride are preferable, and succinic anhydride is more preferable.
  • the molecular weight of the epoxy (meth) acrylate resin (b1) can be increased, branching can be introduced into the molecule, and there is a tendency to be able to balance molecular weight and viscosity.
  • the introduction rate of the acid group into the molecule can be increased, and the balance of sensitivity and adhesion tends to be easily maintained.
  • polyhydric alcohols include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane and 1,2,3-propanetriol. Is preferred.
  • the acid value of the epoxy (meth) acrylate resin (b1) is not particularly limited, but 10 mg-KOH / g or more is preferable, 20 mg-KOH / g or more is more preferable, 40 mg-KOH / g or more is more preferable, 60 mg-KOH / G or more is more preferable, 200 mg-KOH / g or less is preferable, 180 mg-KOH / g or less is more preferable, 150 mg-KOH / g or less is more preferable, 120 mg-KOH / g or less is more preferable, Particularly preferred is 100 mg-KOH / g or less.
  • the acid value of the epoxy (meth) acrylate resin (b1) is, for example, 10 to 200 mg-KOH / g, preferably 10 to 180 mg-KOH / g, more preferably 20 to 150 mg-KOH / g, and 40 to 50 120 mg-KOH / g is more preferable, and 60 to 100 mg-KOH / g is even more preferable.
  • the weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (b1) is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, still more preferably 5000 or more, Particularly preferably, it is 6,000 or more, most preferably 7,000 or more, and usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, and further preferably 10,000 or less.
  • 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, and 5000 to 15000. Are more preferred, 6000 to 10000 are particularly preferred, and 7000 to 10000 are most preferred.
  • the content of the epoxy (meth) acrylate resin (b1) contained in the (B) alkali-soluble resin is not particularly limited, but 30% by mass
  • the above is preferable, 50 mass% or more is more preferable, 70 mass% or more is more preferable, 80 mass% or more is further more preferable, 90 mass% or more is particularly preferable, and usually 100 mass% or less. Outgassing tends to be reduced by setting it to the above lower limit value or more.
  • the content of the epoxy (meth) acrylate resin (b1) contained in the (B) alkali-soluble resin is, for example, 30 to 100 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 epoxy resin is dissolved in an organic solvent, and the acid or ester compound having an ethylenic unsaturated bond is added in the coexistence of a catalyst and a thermal polymerization inhibitor to cause addition reaction, and further a polybasic acid or the acid Anhydrous can be added to continue the reaction.
  • organic solvent used for reaction 1 type (s) or 2 or more types of organic solvents, such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, are mentioned.
  • tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine, tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride and the like
  • quaternary ammonium salts phosphorus compounds such as triphenyl phosphine
  • stibines such as triphenyl stibine
  • thermal polymerization inhibitor 1 type (s) or 2 or more types, such as hydroquinone, hydroquinone monomethyl ether, a methyl hydroquinone, etc. are mentioned.
  • the acid or ester compound having an ethylenically unsaturated bond is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, per 1 chemical equivalent of the epoxy group of the epoxy resin.
  • the amount can be
  • the temperature during the addition reaction may be usually 60 to 150 ° C., preferably 80 to 120 ° C.
  • the amount of the polybasic acid (anhydride) used is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1, per 1 chemical equivalent of the hydroxyl group produced in the addition reaction.
  • the amount can be a chemical equivalent.
  • the epoxy (meth) acrylate resin (b1) is an epoxy (meth) acrylate resin (b1-1) including a partial structure represented by the following general formula (i) from the viewpoint of outgassing at the time of element light emission (hereinafter referred to as “epoxy Epoxy (meth) acrylate resin (b1-2) (hereinafter referred to as “epoxy (meth) acrylate resin (b1-1)”), which contains a partial structure represented by the following general formula (ii) Epoxy (meth) acrylate resin (b1-3) (hereinafter referred to as “epoxy (meth) acrylate resin (b1-2)”), and a partial structure represented by the following general formula (iii) It is preferable to contain at least one selected from the group consisting of (meth) acrylate resin (b1-3).
  • the epoxy (meth) acrylate resin (b1) is an epoxy (meth) acrylate resin (b1-1) including a partial structure represented by the following general formula (i) from the viewpoint of reducing outgassing at the element light emission. Is preferred.
  • One of the reasons is that it is difficult to be decomposed against heat by having a rigid main skeleton.
  • R a represents a hydrogen atom or a methyl group
  • R b represents a divalent hydrocarbon group which may have a substituent.
  • the benzene ring in formula (i) may be further substituted by any substituent. * Represents a bond.
  • R b represents a divalent hydrocarbon group which may have a substituent.
  • the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked. It can be mentioned.
  • Examples of the divalent aliphatic group include linear, branched and cyclic ones. Among them, linear ones are preferable from the viewpoint of development solubility, and cyclic ones are preferable from the viewpoint of reducing the penetration of the developer into the exposed portion.
  • the carbon number 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 still more preferably 10 or less.
  • divalent linear aliphatic group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group and the like.
  • a methylene group is preferable from the viewpoint of residue reduction.
  • divalent branched aliphatic group a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl side chain as the above-mentioned divalent linear aliphatic group can be mentioned And structures having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group and the like.
  • the number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less.
  • the residual film ratio tends to be improved by setting it to the above lower limit value, and the residue tends to be reduced by setting it to the above upper limit value.
  • Specific examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms are removed from a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring and the like Be Among these, a group in which two hydrogen atoms are removed from an adamantane ring is preferable from the viewpoint of development adhesion.
  • Examples of the substituent which the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group and the like. Among these, from the viewpoint of ease of synthesis, it is preferably unsubstituted.
  • bivalent aromatic ring group a bivalent aromatic hydrocarbon ring group and a bivalent aromatic heterocyclic group are mentioned.
  • the carbon number 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 still more preferably 10 or less.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring and a chrysene ring, which have two free valences.
  • Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like can be mentioned.
  • the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a fused ring.
  • Examples of the divalent aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole having two free valencies Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Groups such as pyrazine ring, pyridazine ring,
  • Examples of the substituent which the divalent aromatic ring group may have 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, no substitution is preferable.
  • divalent aliphatic groups and one or more divalent aromatic ring groups are linked
  • one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic groups can be used.
  • a group in which a ring group is linked to one or more is mentioned.
  • the number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less.
  • the number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less.
  • the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the following formulas (i-A) to (i-F) Can be mentioned. Among these, from the viewpoint of the rigidity of the skeleton and the hydrophobization of the film, a group represented by the following formula (i-A) is preferable. * In the chemical formula represents a bond.
  • the benzene ring in formula (i) may be further substituted by any substituent.
  • substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group.
  • the number of substituents is also not particularly limited, and may be one or two or more. Among these, from the viewpoint of curability, unsubstituted is preferable.
  • partial structure represented by the formula (i) is preferably a partial structure represented by the following formula (i-1) from the viewpoint of development solubility.
  • R a and R b are as defined in the above formula (i).
  • R 1 represents a divalent hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. * Represents a bond.
  • the benzene ring in formula (i-1) may be further substituted by any substituent.
  • R 1 represents a divalent hydrocarbon group having 1 to 4 carbon atoms which may have a substituent.
  • a bivalent hydrocarbon group an alkylene group and an alkenylene group are mentioned.
  • the alkylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility.
  • the carbon number is not particularly limited, but is usually 1 or more and 2 or more, and usually 4 or less and 3 or less.
  • the residual film ratio tends to increase by setting the lower limit value or more, and the outgas generation amount at the time of element light emission tends to decrease by setting the upper limit value or less.
  • alkylene group examples include a methylene group, an ethylene group, a propylene group and a butylene group. From the viewpoint of reducing outgassing, a methylene group or an ethylene group is preferable, and an ethylene group is more preferable.
  • the alkenylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility.
  • the carbon number is not particularly limited, but is usually 2 or more, and usually 4 or less and 3 or less is preferable.
  • the residual film ratio tends to increase by setting the lower limit value or more, and the outgas generation amount at the time of element light emission tends to decrease by setting the upper limit value or less.
  • alkenylene group examples include an ethenylene group, a propenylene group and a butyrenylene group, and from the viewpoint of outgassing, an ethenylene group is preferable.
  • the substituent which the divalent hydrocarbon group having 1 to 4 carbons may have is not particularly limited, and examples thereof include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group and the like, and the viewpoint of easiness of synthesis It is preferable that R is unsubstituted.
  • R 1 is preferably a divalent alkylene group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylene group, and still more preferably an ethylene group.
  • the partial structure represented by the formula (i-1) contained in one 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 formula (i) contained in one molecule of the epoxy (meth) acrylate resin (b1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, 3 or more is more preferable, 10 or less is preferable, and 8 or less is more preferable.
  • the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • the number of partial structures represented by the formula (i-1) contained in one molecule of the epoxy (meth) acrylate resin (b1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Preferably, it is 3 or more, more preferably 10 or less, and still more preferably 8 or less.
  • the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • epoxy (meth) acrylate resin (b1-1) Specific examples of the epoxy (meth) acrylate resin (b1-1) will be given below.
  • the epoxy (meth) acrylate resin (b1) is an epoxy (meth) acrylate resin (b1-2) including a partial structure represented by the following formula (ii) from the viewpoint of development adhesion. preferable.
  • each R c independently represents a hydrogen atom or a methyl group.
  • R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * Represents a bond.
  • R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
  • the cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
  • the number of rings possessed by the aliphatic ring group is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less.
  • the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, particularly preferably 15 or less. preferable.
  • the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring and the like.
  • an adamantane ring is preferable from the viewpoint of development adhesion.
  • the number of rings possessed by the aromatic ring group is not particularly limited, but usually 1 or more and 2 or more is preferable, 3 or more is more preferable, and usually 10 or less and 5 or less is preferable and 4 or less is more preferable.
  • the residue tends to be reduced, and by setting the content to the above upper limit value, the development adhesion tends to be improved.
  • an aromatic ring group an aromatic hydrocarbon ring group and an aromatic heterocyclic group can be mentioned.
  • the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, 30 or less.
  • the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, A fluorene ring etc. are mentioned. Among these, a fluorene ring is preferable from the viewpoint of patterning properties.
  • the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and, for example, a divalent aliphatic group, a divalent aromatic ring group, one or more And a group in which one or more divalent aromatic ring groups are connected to each other.
  • Examples of the divalent aliphatic group include linear, branched and cyclic ones. Among them, linear ones are preferable from the viewpoint of development solubility, and cyclic ones are preferable from the viewpoint of reducing the penetration of the developer into the exposed portion.
  • the carbon number 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 still more preferably 15 or less.
  • divalent linear aliphatic group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group and the like.
  • a methylene group is preferable from the viewpoint of the residue.
  • divalent branched aliphatic group a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl side chain as the above-mentioned divalent linear aliphatic group can be mentioned And structures having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group and the like.
  • the number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less.
  • the divalent cyclic aliphatic group include groups in which two hydrogen atoms are removed from a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring and the like Be Among these, a group in which two hydrogen atoms are removed from an adamantane ring is preferable from the viewpoint of development adhesion.
  • Examples of the substituent which the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group and the like. Among these, from the viewpoint of ease of synthesis, it is preferably unsubstituted.
  • bivalent aromatic ring group a bivalent aromatic hydrocarbon ring group and a bivalent aromatic heterocyclic group are mentioned.
  • the carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring and a chrysene ring, which have two free valences.
  • Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like can be mentioned.
  • the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a fused ring.
  • Examples of the divalent aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole having two free valencies Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Groups such as pyrazine ring, pyridazine ring,
  • Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. Among these, from the viewpoint of curability, no substitution is preferable.
  • divalent aliphatic groups and one or more divalent aromatic ring groups are linked
  • one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic groups can be used.
  • a group in which a ring group is linked to one or more is mentioned.
  • the number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less.
  • the number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less.
  • the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include the groups represented by the formulas (i-A) to (i-F), etc. Can be mentioned. Among them, the group represented by the formula (i-C) is preferable from the viewpoint of reducing the residue.
  • the bonding aspect of the cyclic hydrocarbon group which is a side chain is not specifically limited with respect to these bivalent hydrocarbon groups, For example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted by this side chain. And the aspect which comprised the cyclic hydrocarbon group which is a side chain including one of the carbon atom of an aliphatic group is mentioned.
  • partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-1) from the viewpoint of development adhesion.
  • R c is as defined in the above formula (ii).
  • R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • n is an integer of 1 or more.
  • the benzene ring in formula (ii-1) may be further substituted by any substituent. * Represents a bond.
  • R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
  • the number of rings contained in the aliphatic ring group is not particularly limited, but is preferably 1 or more and 2 or more, and usually 6 or less and 4 or less, and more preferably 3 or less.
  • the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, particularly preferably 15 or less. preferable.
  • the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring and the like.
  • an adamantane ring is preferable from the viewpoint of development adhesion.
  • the number of rings contained in the aromatic ring group is not particularly limited, but is usually 1 or more and 2 or more, preferably 3 or more, and usually 10 or less and 5 or less.
  • the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • an aromatic ring group an aromatic hydrocarbon ring group and an aromatic heterocyclic group can be mentioned.
  • the carbon number 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 still more preferably 15 or less.
  • the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, from the viewpoint of development adhesion, a fluorene ring is preferable.
  • the substituent which the cyclic hydrocarbon group may have, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an amyl group
  • Examples thereof include alkyl groups having 1 to 5 carbon atoms such as iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; carboxyl group and the like.
  • no substitution is preferable.
  • N represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less.
  • R ⁇ is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.
  • the benzene ring in formula (ii-1) may be further substituted by any substituent.
  • substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group.
  • the number of substituents is also not particularly limited, and may be one or two or more. Among these, from the viewpoint of curability, unsubstituted is preferable.
  • partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-2) from the viewpoint of development adhesion.
  • R c is as defined in the above formula (ii).
  • R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
  • the benzene ring in formula (ii-2) may be further substituted by any substituent. * Represents a bond.
  • R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
  • the number of rings contained in the aliphatic ring group is not particularly limited, but is usually 1 or more and 2 or more, and usually 10 or less and 5 or less.
  • the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, still more preferably 30 or less.
  • the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring and the like.
  • an adamantane ring is preferable from the viewpoint of development adhesion.
  • the number of rings contained in the aromatic ring group is not particularly limited, but is usually 1 or more and 2 or more, preferably 3 or more, and usually 10 or less and 5 or less.
  • the aromatic ring group includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, and more preferably 8 or more. The above is more preferable, and 40 or less is preferable, 30 or less is more preferable, 20 or less is more preferable, and 15 or less is particularly preferable.
  • the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, from the viewpoint of development adhesion, a fluorene ring is preferable.
  • the substituent which the cyclic hydrocarbon group may have, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an amyl group
  • Examples thereof include alkyl groups having 1 to 5 carbon atoms such as iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; carboxyl group and the like. Among these, from the viewpoint of simplicity of synthesis, no substitution is preferable.
  • R ⁇ is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group.
  • R ⁇ is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.
  • the benzene ring in formula (ii-2) may be further substituted by any substituent.
  • substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group.
  • the number of substituents is also not particularly limited, and may be one or two or more. Among these, from the viewpoint of curability, unsubstituted is preferable.
  • the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-3) from the viewpoint of curability.
  • R c and R d are as defined in the above formula (ii).
  • R 1 has the same meaning as that of the above formula (i-1). * Represents a bond.
  • the partial structure represented by the formula (ii-3) contained in one 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 formula (ii) contained in one molecule of the epoxy (meth) acrylate resin (b1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Moreover, 20 or less is preferable, 15 or less is more preferable, and 10 or less is more preferable.
  • the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • the epoxy (meth) acrylate resin (b1) is an epoxy (meth) acrylate resin (b1-3) including a partial structure represented by the following general formula (iii) from the viewpoint of reducing outgassing at the element light emission. Is preferred.
  • R e represents a hydrogen atom or a methyl group
  • ⁇ is a single bond, -CO-, an alkylene group which may have a substituent, or a bivalent which may have a substituent And a cyclic hydrocarbon group of
  • the benzene ring in Formula (iii) may be further substituted by any substituent.
  • * Represents a bond.
  • ⁇ represents a single bond, —CO—, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent.
  • the alkylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility, and is preferably branched from the viewpoint of development adhesion.
  • the carbon number is not particularly limited, but is usually 1 or more and 2 or more, and usually 6 or less and 4 or less.
  • alkylene group examples include methylene group, ethylene group, propylene group, butylene group, hexylene group and heptylene group, and from the viewpoint of achieving both development adhesion and development solubility, methylene group, ethylene group or propylene A group is preferred, and a dimethylmethylene group is more preferred.
  • Examples of the substituent which the alkylene group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group and the like. Among these, from the viewpoint of achieving both development adhesion and development solubility, it is preferable to be non-substituted.
  • bivalent cyclic hydrocarbon group a bivalent aliphatic ring group or a bivalent aromatic ring group is mentioned.
  • the number of rings contained in the aliphatic ring group is not particularly limited, but is usually 1 or more and 2 or more, and usually 10 or less and 5 or less.
  • the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, still more preferably 30 or less.
  • the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring and the like.
  • an adamantane ring is preferable from the viewpoint of development adhesion.
  • the number of rings contained in the aromatic ring group is not particularly limited, but is usually 1 or more and 2 or more, preferably 3 or more, and usually 10 or less and 5 or less.
  • the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • an aromatic ring group an aromatic hydrocarbon ring group and an aromatic heterocyclic group can be mentioned.
  • the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 40 or less, more preferably 30 or less, further 20 or less. Preferably, 15 or less is particularly preferable.
  • the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, from the viewpoint of development adhesion, a fluorene ring is preferable.
  • the substituent which the cyclic hydrocarbon group may have, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an amyl group
  • Examples thereof include alkyl groups having 1 to 5 carbon atoms such as iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; carboxyl group and the like. Among these, from the viewpoint of simplicity of synthesis, no substitution is preferable.
  • ⁇ is preferably an alkylene group which may have a substituent, and more preferably dimethylmethylene.
  • the benzene ring in formula (iii) may be further substituted by any substituent.
  • substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group.
  • the number of substituents is also not particularly limited, and may be one or two or more. Among these, from the viewpoint of curability, unsubstituted is preferable.
  • the partial structure represented by the formula (iii) is preferably a partial structure represented by the following formula (iii-1) from the viewpoint of development solubility.
  • R e and ⁇ are as defined in the above formula (iii).
  • R 1 has the same meaning as that of the above formula (i-1). * Represents a bond.
  • the benzene ring in the formula (iii-1) may be further substituted by any substituent.
  • the number of partial structures represented by the formula (iii) contained in one molecule of the epoxy (meth) acrylate resin (b1-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, 10 or more is more preferable, 18 or less is preferable, and 15 or less is more preferable.
  • the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • the number of partial structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth) acrylate resin (b1-3) is not particularly limited, but is preferably 1 or more, 3 or more is more Preferably, 5 or more is more preferable, 18 or less is preferable, and 15 or less is more preferable.
  • the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • epoxy (meth) acrylate resin (b1-3) Specific examples of the epoxy (meth) acrylate resin (b1-3) will be given below.
  • the acrylic copolymer resin (b2) is preferably one having an ethylenic double bond in the side chain from the viewpoint of curability.
  • acrylic copolymer resins (b2) acrylic copolymer resins (b2-1) containing a partial structure represented by the following general formula (I) are preferable from the viewpoint of development solubility.
  • R A and R B each independently represent a hydrogen atom or a methyl group. * Represents a bond.
  • partial structure represented by the formula (I) is preferably a partial structure represented by the following general formula (I-1) from the viewpoint of developability.
  • R A and R B have the same meaning as in the above formula (I).
  • R 1 has the same meaning as that of the above formula (i-1).
  • the partial structure represented by the formula (I) is preferably a partial structure represented by the following formula (I-2) from the viewpoint of sensitivity.
  • R A and R B have the same meaning as in the above-mentioned formula (I).
  • the acrylic copolymer resin (b2-1) contains the partial structure represented by the general formula (I)
  • the partial structure represented by the general formula (I) contained in the acrylic copolymer resin (b2-1) The content ratio of is not particularly limited, but is preferably 5 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 50 mol% or more, and particularly preferably 70 mol% or more.
  • the mole% or more is most preferable, and the 99 mole% or less is preferable, the 97 mole% or less is more preferable, and the 95 mole% or less is more preferable.
  • the acrylic copolymer resin (b2-1) contains the partial structure represented by the general formula (I)
  • the partial structure represented by the general formula (I) contained in the acrylic copolymer resin (b2-1) The content ratio of 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%.
  • 80 to 95 mol% is particularly preferred.
  • the table is represented by the above general formula (I-1) contained in the acrylic copolymer resin (b2-1)
  • the content ratio of the partial structure to be formed is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% or more, still more preferably 10 mol% or more, and 99 mol%
  • the following is preferable, 60 mol% or less is more preferable, 40 mol% or less is more preferable, 30 mol% or less is still more preferable, and 20 mol% or less is particularly preferable.
  • the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I-1), the table is represented by the above general formula (I-1) contained in the acrylic copolymer resin (b2-1)
  • the content ratio of the partial structure to be added 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 10 to 20 mol. % Is even more preferable.
  • the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I-2), the table is represented by the above general formula (I-2) contained in the acrylic copolymer resin (b2-1)
  • the content ratio of the partial structure to be formed is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, 50 mol% or more
  • Particularly preferable is 70 mol% or more, most preferable is 99 mol% or less, more preferably 95 mol% or less, still more preferably 90 mol% or less, and particularly preferably 85 mol% or less.
  • the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I-2), the table is represented by the above general formula (I-2) contained in the acrylic copolymer resin (b2-1)
  • the content ratio of the partial structure to be added 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 70 to 85 mol. % Is even more preferable.
  • the partial structure which may be contained is not particularly limited, but from the viewpoint of developing adhesion, for example, It is preferable to include a partial structure represented by the following general formula (I ′).
  • R D represents a hydrogen atom or a methyl group
  • R E is an alkyl group which may have a substituent, an aryl group which may have a substituent (aromatic ring group Or an alkenyl group which may have a substituent.
  • R E represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent.
  • the alkyl group in R E includes a linear, branched or cyclic alkyl group.
  • the carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 20 or less, more preferably 18 or less, It is more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less.
  • alkyl group examples include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, a dodecanyl group and the like.
  • a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable.
  • a substituent which the alkyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group And an acryloyl group, a methacryloyl group and the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • the aryl group (aromatic ring group) in R E includes a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.
  • the carbon number thereof is preferably 4 or more, more preferably 6 or more, and preferably 24 or less, more preferably 22 or less, still more preferably 20 or less, 18 It is particularly preferred that When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • a benzene ring for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, pyrene Rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluoranthene rings, fluorene rings and the like.
  • the aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring.
  • a benzene ring group or a naphthalene ring group is preferable, and a benzene ring group is more preferable.
  • a substituent which the aryl group may have, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligo Ethylene glycol group, phenyl group, carboxyl group and the like are mentioned, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
  • the alkenyl group in R E includes a linear, branched or cyclic alkenyl group.
  • the carbon number thereof is preferably 2 or more, 22 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less. , 14 or less is particularly preferable.
  • the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • alkenyl group examples include ethenyl group, propenyl group, butyrenyl group, cyclohexenyl group and the like. Among these, from the viewpoint of curability, an ethenyl group or a propenyl group is preferable, and an ethenyl group is more preferable.
  • an alkenyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group
  • a hydroxy group and an oligoethylene glycol group are preferred.
  • R E represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent. From the viewpoint of developability, an alkyl group or an alkenyl group is preferable, an alkyl group is more preferable, and a dicyclopentanyl group is more preferable.
  • acrylic copolymer resin (b2-1) contains the partial structure represented by said general formula (I '), it is represented by said general formula (I') contained in acrylic copolymer resin (b2-1)
  • the content of the partial structure is not particularly limited, but is preferably 0.5 mol% or more, more preferably 1 mol% or more, still more preferably 1.5 mol% or more, particularly preferably 2 mol% or more, and 90 mol % Or less is preferable, 70 mol% or less is more preferable, 50% mol or less is more preferable, 30 mol% or less is still more preferable, and 10 mol% or less is particularly preferable.
  • acrylic copolymer resin (b2-1) contains the partial structure represented by said general formula (I '), it is represented by said general formula (I') contained in acrylic copolymer resin (b2-1)
  • the content ratio of the partial structure is, for example, 0.5 to 90 mol%, preferably 1 to 70 mol%, more preferably 1.5 to 50 mol%, and still more preferably 1.5 to 30 mol%. 2 to 10 mol% is even more preferable.
  • the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I)
  • the partial structure represented by the following general formula (I ′ ′) is preferred from the viewpoint of heat resistance and film strength. It is preferable to further include.
  • R F represents a hydrogen atom or a methyl group
  • R G represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a hydroxyl group, It represents a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent.
  • t represents an integer of 0 to 5;
  • R G has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom and a substituent It may be an alkoxy group which may be substituted, a thiol group, or an alkyl sulfide group which may have a substituent.
  • the alkyl group in R G includes a linear, branched or cyclic alkyl group.
  • the carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 20 or less, more preferably 18 or less, It is more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less.
  • alkyl group examples include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, a dodecanyl group and the like.
  • a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable.
  • a substituent which the alkyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group And an acryloyl group, a methacryloyl group and the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • the alkenyl group in R G includes a linear, branched or cyclic alkenyl group.
  • the carbon number thereof is preferably 2 or more, 22 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less. , 14 or less is particularly preferable.
  • the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • alkenyl group examples include ethenyl group, propenyl group, butyrenyl group, cyclohexenyl group and the like. Among these, from the viewpoint of curability, an ethenyl group or a propenyl group is preferable, and an ethenyl group is more preferable.
  • an alkenyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group
  • a hydroxy group and an oligoethylene glycol group are preferred.
  • a fluorine atom As a halogen atom in RG , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Among these, a fluorine atom is preferable from the viewpoint of ink repellency.
  • the alkoxy group in R G includes a linear, branched or cyclic alkoxy group.
  • the carbon number thereof is preferably 1 or more, preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less. , 12 or less is particularly preferable.
  • the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • a substituent which the alkoxy group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group And an acryloyl group, a methacryloyl group and the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • alkyl sulfide group in RG a linear, branched or cyclic alkyl sulfide group can be mentioned.
  • the carbon number thereof is preferably 1 or more, preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less. , 12 or less is particularly preferable.
  • the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
  • a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group etc. are mentioned as a specific example of an alkyl sulfide group.
  • a methyl sulfide group or an ethyl sulfide group is preferable.
  • alkyl group in the alkyl sulfide group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl Groups, carboxyl groups, acryloyl groups, methacryloyl groups and the like, and from the viewpoint of developability, hydroxy groups and oligoethylene glycol groups are preferred.
  • R G is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, Or an alkyl sulfide group which may have a substituent, but among these, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable.
  • t represents an integer of 0 to 5. From the viewpoint of developability, 2 or less is preferable, 1 or less is more preferable, and 0 is more preferable.
  • the content ratio of the partial structure to be formed is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 3 mol% or more, particularly preferably 5 mol% or more, and 90 mol% or less Is preferably 70 mol% or less, more preferably 50 mol% or less, still more preferably 30 mol% or less, particularly preferably 20 mol% or less, and most preferably 10 mol% or less.
  • the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I ′ ′), a table of the above general formula (I ′ ′) contained in the acrylic copolymer resin (b2-1)
  • the content ratio of the partial structure to be added 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%, and 3 to 20 mol. % Is more preferable, and 5 to 10 mol% is particularly preferable.
  • the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I), it further includes the partial structure represented by the following general formula (I ′ ′ ′) from the viewpoint of developability. Is preferred.
  • R H represents a hydrogen atom or a methyl group.
  • the acrylic copolymer resin (b2-1) contains a partial structure represented by the above general formula (I ′ ′ ′), the above general formula (I ′ ′ ′) contained in the acrylic copolymer resin (b2-1)
  • the content ratio of the partial structure represented by is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 30 mol% or more, and preferably 90 mol% or less, 80 mol%
  • the following is more preferable, 70 mol% or less is more preferable, and 50 mol% or less is particularly preferable.
  • the acrylic copolymer resin (b2-1) contains a partial structure represented by the above general formula (I ′ ′ ′), the above general formula (I ′ ′ ′) contained in the acrylic copolymer resin (b2-1)
  • the content ratio of the partial structure represented by 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%.
  • 0% that is, it is preferable not to include the partial structure represented by the general formula (I ′ ′ ′).
  • the acid value of the acrylic copolymer resin (b2) is not particularly limited, but is preferably 5 mg-KOH / g or more, more preferably 10 mg-KOH / g or more, further preferably 20 mg-KOH / g or more, 25 mg-KOH / g
  • the above is more preferable, and 100 mg-KOH / g or less is preferable, 80 mg-KOH / g or less is more preferable, 60 mg-KOH / g or less is more preferable, and 40 mg-KOH / g or less is still more preferable.
  • the acid value of the acrylic copolymer resin (b2) is, for example, 5 to 100 mg-KOH / g, preferably 10 to 80 mg-KOH / g, more preferably 20 to 60 mg-KOH / g, and 25 to 40 mg KOH / g is more preferred.
  • 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, still more preferably 3000 or more, still more preferably 4000 or more, particularly preferably 5000 or more Also, it is usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, and still more preferably 10000 or less. Particularly preferably, it is 8000 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the 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 more preferably 5000 to 8000. More preferable.
  • the content ratio of the acrylic copolymer resin (b2) contained in the (B) alkali-soluble resin is not particularly limited, but 5% by mass or more is preferable, 10 mass% or more is more preferable, 15 mass% or more is more preferable, 20 mass% or more is particularly preferable, and usually 100 mass% or less is preferable, 80 mass% or less is more preferable, 50 mass% or less is more preferable.
  • the content is at least the lower limit, the development solubility tends to be good, and when the content is at the upper limit or less, the taper angle tends to be high.
  • the content ratio of the acrylic copolymer resin (b2) contained in the (B) alkali-soluble resin is, for example, 5 to 100% by mass. 10 to 100% by mass is preferable, 15 to 80% by mass is more preferable, and 20 to 50% by mass is more preferable.
  • alkali-soluble resin (B) either the epoxy (meth) acrylate resin (b1) or the acrylic copolymer resin (b2) may be contained alone, or both may be contained. Furthermore, alkali-soluble resins other than the alkali-soluble resin (b) may be contained in the (B) alkali-soluble resin.
  • the content ratio of the (B) alkali-soluble resin in the photosensitive resin composition of the present invention is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, based on the total solid content.
  • the content is 30% by mass or more, 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, particularly preferably 50% by mass or less.
  • the content ratio of the (B) alkali-soluble resin in the total solid content of the photosensitive resin composition is, for example, 10 to 90% by mass, preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, 40 to 50% by mass is more preferable.
  • the photosensitive resin composition of this invention contains an epoxy (meth) acrylate resin (b1)
  • the content rate of an epoxy (meth) acrylate resin (b1) is not specifically limited, In all the solid content, normally 5 % By mass, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less More preferably, it is 60% by mass or less, particularly preferably 50% by mass or less.
  • the content is at least the lower limit, developability tends to be improved, and when the content is at most the upper limit, outgas at the time of light emission of the element tends to be reduced.
  • the content ratio of the epoxy (meth) acrylate resin (b1) in the total solid content is, for example, 5 to 90% by mass 10 to 70% by mass is preferable, 20 to 60% by mass is more preferable, 30 to 50% by mass is more preferable, and 40 to 50% by mass is even more preferable.
  • the photosensitive resin composition of this invention contains an epoxy acrylic copolymer resin (b2)
  • the content rate of an acrylic copolymer resin (b2) is not specifically limited, Usually 5 mass% or more in a total solid. , Preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less, more preferably It is 60% by mass or less, particularly preferably 50% by mass or less.
  • the content is at least the lower limit, developability tends to be improved, and when the content is at most the upper limit, outgas at the time of light emission of the element tends to be reduced.
  • the content ratio of the acrylic copolymer resin (b2) in the total solid content is, for example, 5 to 90% by mass, 10 -70% by mass is preferable, 20 to 60% by mass is more preferable, 30 to 50% by mass is more preferable, and 40 to 50% by mass is even more preferable.
  • the total content of the (B) alkali-soluble resin and the (C) photopolymerizable compound 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, and further The content is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, 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.
  • the curability is improved by setting it to the above lower limit value, and there is a tendency to reduce the outgassing at the time of light emission of the device by setting it to the above upper limit value.
  • the total content of the (B) alkali-soluble resin and the (C) photopolymerizable compound in the total solid content is, for example, 5 to 99% by mass, preferably 10 to 99% by mass, and 30 to 99% by mass. Is more preferably 50 to 97% by mass, still more preferably 70 to 97% by mass, particularly preferably 80 to 95% by mass, and most preferably 90 to 95% by mass.
  • (B) alkali-soluble resin with respect to (C) photopolymerizable compound in the photosensitive resin composition 50 mass parts or more are preferable with respect to 100 mass parts of (C) photopolymerizable compounds, More preferably, it is 70 parts by mass or more, more preferably 80 parts by mass or more, and preferably 400 parts by mass or less, more preferably 300 parts by mass or less, and even more preferably 200 parts by mass or less. Part or less is particularly preferred.
  • the compounding ratio of the (B) alkali-soluble resin to 100 parts by mass of the (C) photopolymerizable compound in the photosensitive resin composition is, for example, 50 to 400 parts by mass, preferably 60 to 300 parts by mass, and 70 to 200 The mass part is more preferable, and 80 to 100 parts by mass is more preferable.
  • (C) Component; Photopolymerizable Compound The photosensitive resin composition of the present invention contains (C) a photopolymerizable compound. It is considered that the sensitivity becomes high by including the (C) photopolymerizable compound.
  • the photopolymerizable compound to be used herein means a compound having one or more ethylenically unsaturated bonds (ethylenic double bonds) in the molecule, but the polymerizability, the crosslinkability, and the exposed part associated therewith It is preferable that the compound has two or more ethylenic unsaturated bonds in the molecule from the viewpoint that the developer solubility difference in the non-exposed area can be expanded, and the unsaturated bond is (meth) acryloyloxy. It is further preferred that the group is derived from a group, that is, a (meth) acrylate compound.
  • the photosensitive resin composition of the present invention in particular, it is desirable to use a polyfunctional ethylenic monomer having two or more ethylenic unsaturated bonds in one molecule.
  • the number of ethylenically unsaturated groups contained in the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, particularly preferably 5 or more. And preferably not more than 15, more preferably not more than 10, still more preferably not more than 8, and particularly preferably not more than 7.
  • the number of ethylenically unsaturated groups possessed by 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 polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, etc. And esters obtained by the esterification reaction of the polyhydroxy compound of formula (I) with unsaturated carboxylic acid and polybasic carboxylic acid.
  • ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid examples include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate and pentaerythritol triacrylate.
  • Acrylic esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc.
  • Methacrylates wherein acrylates of these exemplified compounds are replaced by methacrylates , Itaconic acid ester similarly substituted to itaconate, ⁇ ⁇ ⁇ Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to bets and the like.
  • esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcine diacrylate, resorcine dimethacrylate, pyrogallol triacrylate and the like Etc.
  • the esters obtained by the esterification reaction of polyvalent hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily single substances, but they are representative.
  • 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, acrylic acid, adipic acid, Examples thereof include condensates of butanediol and glycerin.
  • a polyisocyanate compound, a hydroxyl group containing (meth) acrylic acid ester or polyisocyanate compound, a polyol, and a hydroxyl group containing (meth) acrylic acid ester Urethane (meth) acrylates obtained by reaction; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxyl group-containing (meth) acrylic acid ester or (meth) acrylic acid; ethylene bis acrylamide etc.
  • Acrylamides; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are useful.
  • urethane (meth) acrylates examples include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U.
  • ester (meth) acrylates or urethane (meth) acrylates as the photopolymerizable compound (C) from the viewpoint of appropriate taper angle and sensitivity, and dipentaerythritol hexa (meth) acrylate, Dipentaerythritol penta (meth) acrylate, 2-tris (meth) acryloyloxymethylethyl phthalic acid, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate dibasic It is more preferable to use an acid anhydride adduct, a dibasic acid anhydride adduct of pentaerythritol tri (meth) acrylate, or the like. One of these may be used alone, or two or more may be used in combination.
  • the molecular weight of the (C) photopolymerizable compound is not particularly limited, but it is preferably 100 or more, more preferably 150 or more, from the viewpoints of sensitivity, ink repellency and taper angle. It is preferably 200 or more, more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, preferably 1000 or less, more preferably 700 or less.
  • the molecular weight of the photopolymerizable compound (C) is, for example, 100 to 1000, preferably 150 to 700, more preferably 200 to 700, still more preferably 300 to 700, and still more preferably 400 to 700. 700 is particularly preferred.
  • the carbon number of the (C) photopolymerizable compound is not particularly limited, but is preferably 7 or more, more preferably 10 or more, still more preferably 15 or more, still more preferably from the viewpoints of sensitivity, ink repellency and taper angle. Is 20 or more, particularly preferably 25 or more, preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, particularly preferably 30 or less.
  • the carbon number 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.
  • ester (meth) acrylates, epoxy (meth) acrylates and urethane (meth) acrylates are preferable, and among them, pentaerythritol tetra (meth) acrylate and pentaerythritol Trifunctional or higher ester (meth) acrylates such as tri (meth) acrylate dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate, 2,2,2-tris (meth) acryloyloxymethylethyl phthalate Acid anhydride adducts with trifunctional or higher ester (meth) acrylates such as acid, dibasic acid anhydride adduct of dipentaerythritol penta (meth) acrylate, etc., in terms of sensitivity, ink repellency and taper angle More preferred
  • the content ratio of the (C) photopolymerizable compound in the photosensitive resin composition of the present invention is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably in the total solid content. 30% by mass or more, particularly preferably 40% by mass or more, usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, particularly preferably 50% by mass or less is there.
  • the content ratio of the (C) photopolymerizable compound in the total solid content of the photosensitive resin composition is, for example, 10 to 80% by mass, preferably 20 to 70% by mass, and more preferably 30 to 60% by mass. 40 to 55% by mass is more preferable, and 40 to 50% by mass is even more preferable.
  • the content ratio of the (C) photopolymerizable compound to 100 parts by mass of the (B) alkali-soluble resin in the photosensitive resin composition of the present invention is usually 15 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 It is not less than 80 parts by mass, particularly preferably not less than 90 parts by mass, usually not more than 150 parts by mass, preferably not more than 130 parts by mass, more preferably not more than 120 parts by mass, still more preferably not more than 110 parts by mass It is.
  • the lower limit value or more the sensitivity at the time of exposure tends to be good, the taper angle tends to be good, and by setting the upper limit value or less, the developability tends to be good.
  • the content ratio of the (C) photopolymerizable compound to 100 parts by mass of the (B) alkali-soluble resin in the photosensitive resin composition is, for example, 15 to 150 parts by mass, preferably 30 to 130 parts by mass, and 50 to 120
  • the mass part is more preferable, 80 to 120 parts by mass is more preferable, and 90 to 110 parts by mass is more preferable.
  • 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 (C) photopolymerizable compound by actinic light, and known photopolymerization initiators may be used. it can.
  • the photosensitive resin composition of this invention can use the photoinitiator normally used in this field
  • a photopolymerization initiator for example, hexaarylbiimidazole photopolymerization initiator, acyl phosphine oxide photopolymerization initiator, oxime ester photopolymerization initiator, triazine photopolymerization initiator, acetophenone photopolymerization An initiator, a benzophenone series photoinitiator, etc. are mentioned.
  • hexaarylbiimidazole photopolymerization initiator from the viewpoint of absorbance and sensitivity, and the matching property with the absorption wavelength of the ultraviolet light absorber, it is represented by the following general formula (1-1) and / or the following general formula (1-2)
  • the hexaarylbiimidazole compounds represented are preferred.
  • R 11 to R 13 each independently represent 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
  • m, n and l each independently represent an integer of 0 to 5.
  • the carbon number of the alkyl group of R 11 to R 13 is not particularly limited as long as it is within the range of 1 to 4. However, from the viewpoint of sensitivity, it is preferably 3 or less, more preferably 2 or less.
  • the alkyl group may be linear or cyclic. As a specific example of an alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group is mentioned, for example, Especially, a methyl group and an ethyl group are preferable.
  • alkyl group having 1 to 4 carbon atoms having R 11 to R 13 may have, a group of monovalent nonmetallic atomic groups other than hydrogen is used, and as a preferable example, a halogen atom (— F, -Br, -Cl, -I), a hydroxyl group and an alkoxy group can be mentioned.
  • the number of carbon atoms of the alkoxy group of R 11 to R 13 is not particularly limited as long as it is in the range of 1 to 4. However, from the viewpoint of sensitivity, it is preferably 3 or less, more preferably 2 or less.
  • the alkyl group portion of the alkoxy group may be linear or cyclic. As a specific example of an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, isopropyloxy group, butoxy group is mentioned, for example, Especially, a methoxy group and an ethoxy group are preferable.
  • Examples of the substituent which the alkoxy group having 1 to 4 carbon atoms of R 11 to R 13 may have include an alkyl group and an alkoxy group, and an alkyl group is preferable.
  • examples of the halogen atom of R 11 to R 13 include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom.
  • a chlorine atom or a fluorine atom is preferable from the viewpoint of easiness of synthesis, and a chlorine atom is more preferable. preferable.
  • R 11 to R 13 are preferably each independently a halogen atom, and more preferably a chlorine atom.
  • n, n and l each independently represent an integer of 0 to 5, but from the viewpoint of synthesisability, preferably at least one of m, n and l is an integer of 1 or more, and m, n and l More preferably, one of them is 1 and the remaining 2 are 0.
  • Examples of the hexaarylbiimidazole compound represented by the general formula (1-1) and / or the general formula (1-2) include 2,2′-bis (o-chlorophenyl) -4,5,4 ′ , 5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,5,4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4 , 4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetra (o, p- Dichlorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-fluorophenyl) biimi
  • hexaphenylbiimidazole compounds are preferable, and compounds in which the o-position of the benzene ring bonded to the 2,2'-position on the imidazole ring is substituted with a methyl group, a methoxy group or a halogen atom are more preferable, It is preferable that the benzene ring bonded to the 4,4 ′, 5,5′-position on the imidazole ring be unsubstituted or substituted with a halogen atom or a methoxy group.
  • the photopolymerization initiator either of the hexaarylbiimidazole compound represented by the general formula (1-1) and the hexaarylbiimidazole compound represented by the general formula (1-2) The two may be used in combination. When used in combination, the ratio is not particularly limited.
  • acyl phosphine oxide type photoinitiator a 2, 4, 6- trimethyl benzoyl diphenyl phosphine oxide, a bis (2, 4, 6 trimethyl benzoyl) phenyl phosphine oxide etc. can be mentioned as a preferable thing. .
  • 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.
  • an oxime ester compound having a diphenyl sulfide skeleton By containing the oxime ester compound having a diphenyl sulfide skeleton, the light absorption of short wavelength is strong and the surface curability is improved, so it is considered that the outflow of the liquid repellent during development is suppressed and the ink repellency is enhanced.
  • the chemical structure of the oxime ester compound having a diphenyl sulfide skeleton is not particularly limited, but from the viewpoint of sensitivity, it is preferable to use one represented by the following general formula (D-I).
  • R 23 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 24 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R 25 represents a hydroxyl group, a carboxyl group or a group represented by the following formula (D-II), and h represents an integer of 0 to 5.
  • the benzene ring shown in Formula (DI) may further have a substituent.
  • R 25a represents —O—, —S—, —OCO— or —COO—.
  • R 25b represents an alkylene group which may have a substituent.
  • the alkylene moiety of R 25b may be interrupted 1 to 5 times by -O-, -S-, -COO- or -OCO-.
  • the alkylene moiety of R 25 may be branched side chain and may be cyclohexylene.
  • R 25c represents a hydroxyl group or a carboxyl group.
  • the number of carbon atoms in the alkyl group in R 23 is not particularly limited, is preferably 1 or more from the viewpoint of solubility in solvents. Further, from the viewpoint of developability, it is preferably 20 or less, more preferably 10 or less, still more preferably 8 or less, still more preferably 5 or less, particularly preferably 3 or less. preferable.
  • a methyl group, a hexyl group, a cyclopentyl methyl group etc. are mentioned as a specific example of an alkyl group, Among these, a viewpoint to developability to a methyl group or a hexyl group is preferable, and a methyl group is more preferable.
  • the substituent which the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group and the like, and a hydroxyl group and a carboxyl group are preferable from the viewpoint of alkali developability Carboxyl groups are more preferred. In addition, from the viewpoint of easiness of synthesis, it is preferably unsubstituted.
  • the carbon number of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in a solvent. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less.
  • aromatic ring group examples include a phenyl group, a naphthyl group, a pyridyl group and a furyl group.
  • a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
  • substituent which the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amido group, an alkyl group, etc.
  • R 23 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably a methyl group. .
  • the carbon number of the alkyl group in R 24 is not particularly limited, but is preferably 1 or more from the viewpoint of sensitivity. Further, from the viewpoint of sensitivity, it is preferably 20 or less, more preferably 10 or less, still more preferably 5 or less, and particularly preferably 3 or less.
  • a methyl group, an ethyl group, a propyl group etc. are mentioned as a specific example of an alkyl group, From these, a viewpoint of a sensitivity to a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
  • the substituent which the alkyl group may have include a halogen atom, a hydroxyl group, a carboxyl group, an amino group and an amido group. From the viewpoint of alkali developability, a hydroxyl group and a carboxyl group are preferable, and a carboxyl group is more preferable. On the other hand, from the viewpoint of easiness of synthesis, it is preferably unsubstituted.
  • the aromatic ring group in R 24 includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the carbon number is preferably 30 or less, more preferably 12 or less, and usually 4 or more, and preferably 6 or more.
  • the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • Groups such as ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like can be mentioned.
  • the aromatic heterocyclic group may be a single ring or a condensed ring.
  • R 24 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably a methyl group.
  • R 24 is preferably an aromatic ring group which may have a substituent, more preferably an aromatic hydrocarbon group which may have a substituent. An unsubstituted aromatic hydrocarbon group is more preferable, and a phenyl group is particularly preferable.
  • R 25 is a hydroxyl group, a carboxyl group or a group represented by the above general formula (D-II), but among these, from the viewpoint of sensitivity and developability, it is represented by the above general formula (D-II) It is preferably a group.
  • R 25a represents -O-, -S-, -OCO- or -COO-, but among these, from the viewpoint of sensitivity and developability,- O- or -OCO- is preferred, and -O- is more preferred.
  • R 25b represents an alkylene group which may have a substituent.
  • the carbon number of the alkylene group in R 25b is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 20 or less from the viewpoint of solubility in the photosensitive resin composition. Is more preferably 10 or less, still more preferably 5 or less, and particularly preferably 3 or less.
  • the alkylene group may be linear, branched or may contain an aliphatic ring. Among these, from the viewpoint of solubility in the photosensitive resin composition, linear is preferable.
  • a methylene group, ethylene group, a propylene group etc. are mentioned as a specific example of an alkylene group, Among these, a methylene group is more preferable from a soluble viewpoint to the photosensitive resin composition.
  • R 25c is a hydroxyl group or a carboxyl group. From the viewpoint of development adhesion, R 25c is preferably a hydroxyl group.
  • h represents an integer of 0 to 5.
  • h is preferably 1 or more, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, or 1 from the viewpoint of developability. Most preferred.
  • h is preferably 0 from the viewpoint of synthesisability.
  • triazine-based photopolymerization initiators include halomethylated s-triazine derivatives, such as 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- ( ⁇ , ⁇ , ⁇ -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-e
  • acetophenone photopolymerization initiator for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-trichloromethyl- (p-butylphenyl) ketone, ⁇ -hydroxy-2-methylphenylpropanone, 2-methyl-1 [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) butan-1-one, 4-dimethylaminoethyl Benzoate, 4-dimethylaminois, 4-
  • benzophenone-based photopolymerization initiators include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, Michler's ketone and the like.
  • One of these photopolymerization initiators may be contained alone in the photosensitive resin composition, or two or more thereof may be contained.
  • the hexaarylbiimidazole compound is particularly preferable in that it has high surface curability due to high absorbance, and high ink repellency and high taper angle can be obtained.
  • oxime ester compounds are particularly preferable in that they have high sensitivity and ink repellency occurs even at low exposure amounts.
  • Acetophenone photopolymerization initiators are particularly preferable in that they have high internal curability and high ink repellency and a high taper angle can be obtained.
  • the content ratio of the (D) photopolymerization initiator in the photosensitive resin composition of the present invention is usually 0.01% by mass or more, preferably 0.1% by mass or more, in the total solid content of the photosensitive resin composition. More preferably, it is 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, particularly preferably 2% by mass or more, and most preferably 2.5% by mass or more. 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, particularly preferably 3% by mass or less.
  • the content ratio of the (D) photopolymerization initiator 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. 8% by mass is more preferable, and 1 to 5% by mass is more preferable. In one aspect, 1.5 to 3% by mass is preferable, in another aspect, 2 to 3% by mass is preferable, and in still another aspect, 2.5 to 5% by mass is preferable.
  • the compounding ratio of the (D) photopolymerization initiator to the (C) photopolymerizable compound in the photosensitive resin composition is preferably 1 part by mass or more with respect to 100 parts by mass of the (C) photopolymerizable compound, 2 parts by mass or more is preferable, 3 parts by mass or more is more preferable, 200 parts by mass or less is preferable, 100 parts by mass or less is more preferable, 50 parts by mass or less is more preferable, 20 parts by mass or less is more preferable, 10 parts by mass or less is particularly preferable, and 5 parts by mass or less is the most preferable.
  • the sensitivity tends to be appropriate
  • by setting the upper limit value or less a desired pattern shape tends to be easily formed.
  • the compounding ratio of the photopolymerization initiator (D) to 100 parts by mass of the photopolymerizable compound (C) in the photosensitive resin composition is, for example, 1 to 200 parts by mass, preferably 1 to 100 parts by mass, and 2 to 50 parts by mass is more preferable, 2 to 20 parts by mass is further preferable, 3 to 10 parts by mass is further more preferable, and 3 to 5 parts by mass is particularly preferable.
  • a sensitizer may be used in combination with the photopolymerization initiator. At the same time as the sensitivity is improved by the sensitizer, the light transmittance to the inside of the photosensitive resin composition is decreased, so that the taper angle tends to be increased.
  • the sensitizer those generally used in this field can be used.
  • the sensitizer is characterized in that the energy obtained by absorption is transferred to the photopolymerization initiator or electron transfer with the photopolymerization initiator occurs to efficiently promote the reaction radical polymerization reaction.
  • a sensitizer for example, unsaturated ketones represented by chalcone derivatives and dibenzalacetone etc., 1,2-diketone compounds represented by benzyl and camphorquinone etc., benzoin compounds, fluorene Compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, oxonol derivatives, etc.
  • Polymethine dyes acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds , Triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalyloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds Compounds, pyrylium compounds, thiopyrylium compounds, tetraphilin compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, benzophenone compounds and the like can be
  • thioxanthone compounds and benzophenone compounds are preferable from the viewpoint of sensitivity improvement and taper angle increase.
  • thioxanthone compound thioxanthone, 2-methyl thioxanthone, 4-methyl thioxanthone, 2,4- dimethyl thioxanthone, 2-ethyl thioxanthone, 4-ethyl thioxanthone, 2,4- diethyl thioxanthone, 2-isopropyl thioxanthone, 4- isopropyl Thioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2,4-dichlorothioxanthone and the like.
  • 2,4-diethylthioxanthone is preferable from the viewpoint of sensitivity improvement and taper angle increase.
  • benzophenone compounds include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone and the like.
  • 4,4'-bis (diethylamino) benzophenone is preferable from the viewpoint of sensitivity improvement and taper angle increase.
  • the content ratio of the sensitizer in the photosensitive resin composition is usually 0.1% by mass or more, preferably 0, in the total solid content of the photosensitive resin composition. .3 mass% or more, more preferably 0.5 mass% or more, still more preferably 0.8 mass% or more, still more preferably 1 mass% or more, particularly preferably 1.2 mass% or more, and usually 10
  • the content is at most mass%, preferably at most 7 mass%, more preferably at most 5 mass%, further preferably at most 3 mass%.
  • the content ratio of the sensitizer in the total solid content of the photosensitive resin composition is, for example, 0.1 to 10% by mass, 0.3 to 10 % By mass is preferable, 0.5 to 7% by mass is more preferable, 0.8 to 7% by mass is further preferable, 1 to 5% by mass is further more preferable, and 1.2 to 3% by mass is particularly preferable.
  • the photosensitive resin composition of the present invention contains (E) a chain transfer agent.
  • a chain transfer agent By including the chain transfer agent, radical deactivation due to oxygen inhibition or the like in the vicinity of the surface can be improved, surface curability can be enhanced, and the taper angle tends to be high. Further, by enhancing the surface hardening property, the outflow of the liquid repellent can be suppressed, and the liquid repellent can 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 include mercapto group-containing compounds and carbon tetrachloride. It is more preferable to use a compound having a mercapto group since the chain transfer effect tends to be high. The small S—H bond energy tends to cause bond cleavage and causes chain transfer reaction, so that the surface hardenability tends to be able to be enhanced.
  • chain transfer agents mercapto group-containing compounds having an aromatic ring and aliphatic mercapto group-containing compounds are preferable from the viewpoint of taper angle and surface curability.
  • a compound represented by the following general formula (E-1) is suitably used from the viewpoint of the taper angle.
  • Z represents -O-, -S- or -NH-
  • R 61 , R 62 , R 63 and R 64 each independently represent a hydrogen atom or a monovalent substituent.
  • Z is preferably -S- or -NH-, more preferably -NH-.
  • R 61 , R 62 , R 63 and R 64 are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably a hydrogen atom preferable.
  • aliphatic mercapto group-containing compound hexanedithiol, decanedithiol, or a compound represented by the following general formula (E-2) is suitably used from the viewpoint of surface curability.
  • m represents an integer of 0 to 4
  • n represents an integer of 2 to 4.
  • R 71 and R 72 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • X represents an n-valent group.
  • m is preferably 1 or 2 from the viewpoint of synthesis ease.
  • n is preferably 3 or 4 from the viewpoint of surface curability.
  • the alkyl group of R 71 and R 72 is preferably one having 1 to 3 carbon atoms, from the viewpoint of surface curability. From the viewpoint of surface curability, at least one of R 71 and R 72 , for example, R 72 is preferably a hydrogen atom, and in this case, R 71 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Is preferred.
  • X is preferably an ether bond and / or an alkylene group having 1 to 6 carbon atoms which may have a branched portion.
  • an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 4 carbon atoms is further preferable, from the viewpoint of surface curability and easiness of synthesis.
  • X be 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.
  • R 73 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a methylol group.
  • R 73 an ethyl group is preferable from the viewpoint of the taper angle.
  • R 74 represents an alkylene group having 1 to 4 carbon atoms.
  • R 74 an ethylene group is preferable from the viewpoint of the taper angle.
  • X is preferably a structure represented by the following general formula (E-2-3).
  • 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-mercaptobutyloxyethyl) -1,3,5-triazine-2, Preferred is 4,6 (1H, 3H, 5H) -trione, and more preferred is pentaerythritol tetrakis (3-mercaptopropionate) or pentaerythritol tetrakis (3-mercaptobutyrate).
  • 2-mercaptobenzothiazole 2-mercaptobenzimidazole
  • 2-mercaptobenzoxazole 2-mercaptobenzoxazole
  • a photopolymerization initiator it is preferred to use as a photoinitiator system.
  • 2-mercaptobenzothiazole may be used
  • 2-mercaptobenzimidazole may be used
  • 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination.
  • 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, and more preferably in the total solid content of the photosensitive resin composition. It is 0.05% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1% by mass or more, usually 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less.
  • the taper angle is high, the surface curability tends to be high, and the ink repellency tends to be high.
  • the desired pattern tends to be easily formed. is there.
  • the content ratio of the chain transfer agent in the total solid content of the photosensitive resin composition is, for example, 0.01 to 5% by mass, preferably 0.025 to 4% by mass, and 0.05 -4% by mass is more preferable, 0.1-3% by mass is more preferable, and 1-3% by mass is even more preferable.
  • a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound are used in combination as a chain transfer agent, 100 parts by mass of a mercapto group-containing compound having an aromatic ring
  • the amount of the aliphatic mercapto group-containing compound is usually 10 parts by mass or more, preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and usually 400 parts by mass or less, preferably 300 parts by mass or less Preferably it is 200 mass parts or less, More preferably, it is 150 mass parts or less.
  • a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound are used in combination as a chain transfer agent
  • 100 parts by mass of a mercapto group-containing compound having an aromatic ring is used as the content ratio
  • it is 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.
  • a compounding ratio of the chain transfer agent with respect to (D) photoinitiator in the photosensitive resin composition 10 mass parts or more are preferable with respect to 100 mass parts of (D) photoinitiator, and 25 mass parts
  • the above is more preferable, 50 parts by mass or more is more preferable, 80 parts by mass or more is particularly preferable, 500 parts by mass or less is preferable, 400 parts by mass or less is more preferable, 300 parts by mass or less is more preferable, 200 parts by mass or less Is more preferable, and 150 parts by mass or less is particularly preferable.
  • the taper angle is high, the surface curability tends to be high, and the ink repellency tends to be high.
  • the compounding ratio of the chain transfer agent is, for example, 10 to 500 parts by mass, preferably 25 to 400 parts by mass, and 50 to 300 parts by mass with respect to 100 parts by mass of the (D) photopolymerization initiator in the photosensitive resin composition. Is more preferable, 80 to 200 parts by mass is further preferable, and 80 to 150 parts by mass is even more preferable.
  • the photosensitive resin composition of the present invention may contain an ultraviolet absorbent.
  • the ultraviolet absorber is added for the purpose of controlling the light curing distribution by absorbing a specific wavelength of a light source used for exposure by the ultraviolet absorber.
  • an ultraviolet absorber By including an ultraviolet absorber, there is a tendency to obtain effects such as improvement of the tapered angular shape after development and reduction of the residue remaining in the non-exposed area after development.
  • a compound having an absorption maximum between wavelengths 250 nm and 400 nm can be used as the ultraviolet light absorber.
  • UV absorbers examples include benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and derivatives thereof, dinaphthalene compounds, phenanthroline compounds, dyes and the like. These ultraviolet absorbers can be used alone or in combination of two or more.
  • benzotriazole compounds and / or hydroxyphenyltriazine compounds are preferable, and benzotriazole compounds are particularly preferable.
  • benzotriazole-based compounds benzotriazole compounds described by the following general formula (Z1) are preferable from the viewpoint of taper shape.
  • R 1e and R 2e each independently represent a hydrogen atom, an alkyl group which may have a substituent, a group represented by the following general formula (Z2), or the following general formula (Z3) Represents a group represented by).
  • R 3e represents a hydrogen atom or a halogen atom.
  • R 4e represents an alkylene group which may have a substituent
  • R 5e represents an alkyl group which may have a substituent
  • R6e represents the alkylene group which may have a substituent
  • R7e represents a hydrogen atom or a methyl group.
  • R 1e and R 2e each independently represent a hydrogen atom, an alkyl group which may have a substituent, a group represented by general formula (Z2), or a general formula (Z3) Represents a group to be represented.
  • the alkyl group includes a linear, branched or cyclic alkyl group.
  • the carbon number thereof is preferably 1 or more, more preferably 2 or more, still more preferably 4 or more, and preferably 10 or less, more preferably 6 or less, More preferably, it is 4 or less.
  • the alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tert-butyl group. Among these, tert-butyl is preferable.
  • a substituent which the alkyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group And an acryloyl group and a methacryloyl group.
  • R 3e represents a hydrogen atom or a halogen atom.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned.
  • R 3e is preferably a hydrogen atom.
  • R 4e represents an alkylene group which may have a substituent.
  • alkylene group a linear, branched or cyclic alkylene group can be mentioned.
  • the carbon number is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.
  • a methylene group, ethylene group, a propylene group, a propylene group, a butylene group etc. are mentioned as a specific example of an alkylene group.
  • ethylene group is preferable.
  • a substituent which the alkylene group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group And an acryloyl group and a methacryloyl group.
  • R 4e is preferably an ethylene group.
  • R 5e In the formula (Z2), it represents an alkyl group which may have a substituent.
  • the alkyl group includes a linear, branched or cyclic alkyl group.
  • the carbon number thereof is preferably 4 or more, more preferably 5 or more, still more preferably 7 or more, and preferably 15 or less, more preferably 10 or less, More preferably, it is 9 or less.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group.
  • a substituent which the alkyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group And an acryloyl group and a methacryloyl group.
  • R 5e is preferably a heptyl group, an octyl group or a nonyl group.
  • R 6e represents an alkylene group which may have a substituent.
  • alkylene group a linear, branched or cyclic alkylene group can be mentioned.
  • the carbon number is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.
  • a methylene group, ethylene group, a propylene group, a propylene group, a butylene group etc. are mentioned as a specific example of an alkylene group.
  • ethylene group is preferable.
  • a substituent which the alkylene group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group And an acryloyl group and a methacryloyl group.
  • R 1e is tert- butyl group
  • a group R 2e is represented by the formula (Z2) (provided that R 4e is an ethylene group, and R 5e is an alkyl group having 7-9 carbon atoms
  • R 3 e is a hydrogen atom, or R 1 e is a hydrogen atom, R 2 e is a group represented by the above formula (Z 3) (wherein R 6 e is ethylene, and R 7 e is methyl), R 3 e is The compound which is a hydrogen atom is preferable, and R 1e is a tert-butyl group, R 2e is a group represented by the above formula (Z 2) (however, R 4e is an ethylene group, and R 5e is an alkyl group having 7 to 9 carbon atoms). And compounds wherein R 3e is a hydrogen atom are more preferred.
  • benzotriazole compounds include 2- (5 methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3 [3- tert-Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-) Mixture of chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3- t-Butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di) -T-amyl-2-hydroxyphenyl) benzotriazole, 2- (2-
  • benzotriazole compounds include, for example, Sumisorb (registered trademark, the same in the following) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83.
  • a hydroxyphenyl triazine compound is preferable from the viewpoint of taper angle and exposure sensitivity.
  • a triazine type compound marketed TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479 (made by BASF Corporation) etc. can be mentioned, for example.
  • UV absorbers include, for example, Sumisorb 130 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Eiko Chemical Co., Ltd.), Tomisorb 800 (manufactured by AP Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102 Benzophenone compounds such as SEESORB 103, SEESORB 105, SEESORB 106, SEESORB 107, SEESORB 151 (manufactured by Cipro Chemical Co., Ltd.); Sumisorb 400 (manufactured by Sumitomo Chemical Co., Ltd.); benzoate compounds such as phenyl salicylate; 2-ethylhexyl cinnamic acid, 2-ethylhexyl paramethoxycinnamate, Such as isopropyl methoxycinnamate and isoamyl
  • the content ratio of the ultraviolet absorber in the photosensitive resin composition is usually 0.01% by mass or more, preferably 0.05 mass%, in the total solid content. % Or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and usually 15% by mass or less, preferably 10% by mass or less, more preferably Is 5% by mass or less, more preferably 3% by mass or less.
  • the content ratio of the ultraviolet light absorber in the total solid content of the photosensitive resin composition is, for example, 0.01 to 15% by mass.
  • the content is preferably 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.
  • the photosensitive resin composition of this invention contains a ultraviolet absorber, as a compounding ratio with respect to (D) photoinitiator, as a compounding quantity of the ultraviolet absorber with respect to 100 mass parts of (D) photoinitiator, Usually, 1 part by mass or more, preferably 10 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, and usually 500 parts by mass or less, preferably 300 parts by mass
  • the content is more preferably 200 parts by mass or less, still more preferably 150 parts by mass or less.
  • the compounding ratio of the (D) photopolymerization initiator to (D) 100 parts by weight of the photopolymerization initiator is, for example, 1 to 500 parts by mass, 10 to 300 parts by mass is preferable, 30 to 200 parts by mass is more preferable, 50 to 150 parts by mass is more preferable, and 80 to 150 parts by mass is still more preferable.
  • the photosensitive resin composition of the present invention may contain a polymerization inhibitor. It is believed that the inclusion of the polymerization inhibitor can increase the taper angle of the partition obtained because it inhibits radical polymerization.
  • the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-cresol (BHT) and the like. Among these, from the viewpoint of the polymerization inhibiting ability, methylhydroquinone or methoxyphenol is preferable, and methylhydroquinone is more preferable.
  • the polymerization inhibitor preferably contains one or more kinds.
  • a polymerization inhibitor may be contained in the resin, which may be used as the polymerization inhibitor of the present invention, or in the resin.
  • the same or different polymerization inhibitor may be added at the time of photosensitive resin composition manufacture.
  • the content of the polymerization inhibitor in the photosensitive resin composition is usually 0.0005% by mass or more in the total solid content of the photosensitive resin composition.
  • it is 0.001% by mass or more, more preferably 0.01% by mass or more, and usually 0.3% by mass or less, preferably 0.2% by mass or less, more preferably 0.1% by mass or less .
  • the taper angle can be increased by setting the lower limit value or more, and there is a tendency that high sensitivity can be maintained by setting the upper limit value or less.
  • the content of the polymerization inhibitor in the total solid content of the photosensitive resin composition is, for example, 0.0005 to 0.3 mass%, The content is preferably 0.001 to 0.2% by mass, and more preferably 0.01 to 0.1% by mass.
  • the photosensitive resin composition of the present invention may contain an amino compound in order to accelerate heat curing.
  • the content ratio of the amino compound in the photosensitive resin composition is usually 40% by mass or less, preferably 30% or less in the total solid content of the photosensitive resin composition. It is less than mass%. Also, it is usually 0.5% by mass or more, preferably 1% by mass or more. There is a tendency that storage stability can be maintained by setting it to the upper limit value or less, and there is a tendency that sufficient thermosetting property can be secured by setting it to the above lower limit value.
  • the content of the amino compound in the total solid of the photosensitive resin composition is, for example, 0.5 to 40% by mass, and 1 to 30% by mass. Is preferred.
  • amino compound examples include amino compounds having at least two methylol groups as functional groups and at least two alkoxymethyl groups in which methylol groups are alcohol-condensed and modified with 1 to 8 carbon atoms.
  • a melamine resin obtained by polycondensing melamine and formaldehyde
  • a benzoguanamine resin obtained by polycondensing benzoguanamine and formaldehyde
  • a glycoluril resin obtained by polycondensing glycoluril and formaldehyde
  • urea and formaldehyde Polycondensed urea resins
  • modified resins obtained by alcohol condensation-modifying methylol groups of the above-mentioned resins examples include amino compounds having at least two methylol groups as functional groups and at least two alkoxymethyl groups in which methylol groups are alcohol-conden
  • melamine resins and modified resins thereof are preferable. Modified resins having a methylol group modification ratio of 70% or more are more preferable, and modified resins of 80% or more are particularly preferable.
  • Cymel As a specific example of the said amino compound, as a melamine resin and its modification resin, Cymel (The registered trademark, the same hereafter) 300, 301, 303, 350, 736, 738, 370, 771, 325, made by Cytec, for example is mentioned. 327, 703, 701, 266, 267, 285, 232, 238, 1141, 272, 254, 202, 1156, 1158, and Niwarak (registered trademark, hereinafter the same) MW-390 manufactured by Sanwa Chemical Co., Ltd. , MW-100 LM, MX-750 LM, MW-30 M, MX-45, MX-302 and the like.
  • etc., Made by Cytec, etc. are mentioned, for example.
  • examples of the above glycoluril resin and its modified resin include Cymel 1170, 1171, 1174, 1172 manufactured by Cytec, and Nikalac MX-270 manufactured by Sanwa Chemical Co., Ltd.
  • UFR registered trademark, the same shall apply hereinafter
  • the photosensitive resin composition of the present invention may contain a colorant for the purpose of coloring the partition walls.
  • colorants known colorants such as pigments and dyes can be used.
  • a known dispersant or dispersion aid may be used in combination so that the pigment can be stably present in the photosensitive resin composition without aggregation.
  • a black coloring agent it is effective to mix an organic pigment as well as a black dye, a black pigment, carbon black, titanium black and the like to make the color black to give low conductivity.
  • the content ratio of the coloring agent is usually 60% by mass or less, preferably 40% by mass or less, in the total solid content of the photosensitive resin composition from the viewpoint of platemaking properties and color characteristics.
  • the content ratio of the colorant is preferably 10 mass% with respect to the total solid content of the photosensitive resin composition. % Or less, more preferably 5% by mass or less, particularly preferably 0% by mass.
  • the photosensitive resin composition of the present invention contains a coatability improver and a development improver in order to improve the coatability and the development solubility. It is also good.
  • a coatability improver or the development improver for example, known cationic, anionic, nonionic, fluorine-based or silicone-based surfactants can be used.
  • the surfactant can be used for the purpose of improving the coatability as a coating liquid of the photosensitive resin composition, the developability of the coating film, etc.
  • fluorine-based or silicone-based surfactants are preferable.
  • silicone surfactants are preferred because they have the function of removing the residue of the photosensitive resin composition from the unexposed area during development and have a function of developing wettability, and polyether-modified silicones are preferred. Surfactants are more preferred.
  • the fluorosurfactant is preferably a compound having a fluoroalkyl or fluoroalkylene group at at least one of the terminal, main chain and side chain.
  • 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether
  • 1,1,2,2-tetrafluorooctylhexyl ether 1,1,2,2-tetrafluoropropyl) ether
  • octaethylene glycol di 1,1,2,2-Tetrafluorobutyl) ether hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether
  • octapropylene glycol di (1,1,2,2- Tetrafluorobutyl) ether hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether
  • sodium perfluorododecyl sulfonate 1,1,2,8,8,
  • BM-1000 and “BM-1100” manufactured by BM Chemie
  • Megafuck F470 manufactured by DIC
  • Megafuck F475 manufactured by FC430
  • FC430 manufactured by 3M Japan
  • Neos Made from “DFX-18” etc. can be mentioned.
  • silicone surfactants include “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “8032Additive”, “SH8400”, manufactured by Toray Dow Corning, Commercial products such as “BYK (registered trademark, the same as the following) 323" and “BYK 330” manufactured by Big Chemie Co., Ltd. can be mentioned.
  • the surfactant one other than the fluorine-based surfactant and the silicone-based surfactant may be contained, and as the surfactant, nonionic, anionic, cationic, amphoteric surfactant etc. may be mentioned.
  • nonionic surfactants examples 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, sorbit fatty acid esters, polyoxy acid Ethylene sorbite fatty acid ester etc. are mentioned. Examples of these commercially available products include polyoxyethylene surfactants such as "Emulgen 104P" and "Emulgen A60" manufactured by Kao Corporation, and the like.
  • anionic surfactant for example, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfate salts, alkyl sulfate ester salts, higher alcohol sulfate Ester salts, aliphatic alcohol sulfuric acid ester salts, polyoxyethylene alkyl ether sulfuric acid salts, polyoxyethylene alkyl phenyl ether sulfuric acid salts, alkyl phosphoric acid ester salts, polyoxyethylene alkyl ether phosphoric acid salts, polyoxyethylene alkyl phenyl ether phosphoric acid salts, special Polymeric surfactant etc.
  • special polymer surfactants are preferable, and special polycarboxylic acid type polymer surfactants are more preferable.
  • a commercial item can be used as such an anionic surfactant, For example, in alkyl sulfate ester salts, "Emar (registered trademark) 10" by Kao Corp. etc., and by alkyl naphthalene sulfonates by Kao Corp.
  • special polymer surfactants such as Perex (registered trademark) NB-L include “Homogen (registered trademark, the same shall apply hereinafter) L-18”, “Homogen L-100” and the like manufactured by Kao Corporation.
  • cationic surfactant quaternary ammonium salts, imidazoline derivatives, alkylamine salts and the like, and as amphoteric surfactants, betaine type compounds, imidazolium salts, imidazolines, amino acids Etc.
  • amphoteric surfactants betaine type compounds, imidazolium salts, imidazolines, amino acids Etc.
  • quaternary ammonium salts are preferable, and stearyl trimethyl ammonium salts are more preferable.
  • the surfactant may be used in combination of two or more types, and, for example, silicone surfactant / fluorinated surfactant, silicone surfactant / special polymer surfactant, fluorinated surfactant And combinations of special polymer surfactants and the like. Among them, a combination of silicone surfactant / fluorinated surfactant is preferable.
  • silicone surfactant / fluorinated surfactant for example, "DFX-18” manufactured by Neos, "BYK-300” manufactured by BIC Chemie, or “BYK-330” / “S manufactured by AGC Seimi Chemical””393", Shin-Etsu Silicone “KP340” / DIC “F-478” or “F-475”, Toray Dow Corning "SH7PA” / Daikin “DS-401”, NUC " L-77 ”/“ FC 4430 ”manufactured by 3M Japan Co., Ltd. may be mentioned. Further, as a development improver, known ones such as organic carboxylic acids or their anhydrides can also be used.
  • the content ratio of the coatability improver or the development improver is the total solid content of the photosensitive resin composition from the viewpoint of sensitivity.
  • the content is usually at most 20% by mass, preferably at most 10% by mass.
  • silane coupling agent it is also preferable to add a silane coupling agent to the photosensitive resin composition of the present invention in order to improve the adhesion to the substrate.
  • a silane coupling agent various types such as epoxy type, methacrylic type, amino type, and imidazole type can be used, but from the viewpoint of improving adhesion, epoxy type and imidazole type silane coupling agents are particularly preferable.
  • the photosensitive resin composition of the present invention contains a silane coupling agent
  • the content of the silane coupling agent is usually 20% by mass or less in the total solid content of the photosensitive resin composition from the viewpoint of adhesion. Preferably it is 15 mass% or less.
  • [1-1-12] Phosphoric Acid Adhesion Improver In order to improve the adhesion to the substrate, it is preferable to add a phosphoric acid adhesion improver to the photosensitive resin composition of the present invention.
  • a phosphoric acid adhesion improver As the phosphoric acid-based adhesion improver, (meth) acryloyloxy group-containing phosphates are preferable, and among these, those represented by the following general formulas (Va), (Vb) and (Vc) are preferable.
  • R 8 represents a hydrogen atom or a methyl group
  • r and r ′ are integers of 1 to 10, and s is 1, 2 or 3.
  • the content thereof is not particularly limited, but 0.1% by mass or more is preferable and 0.3% by mass or more in the total solid content. More preferably, it is 0.5 mass% or more, 5 mass% or less is preferable, 3 mass% or less is more preferable, and 1 mass% or less is more preferable.
  • the adhesion to the substrate tends to be improved by setting the content to the lower limit or more, and the surface curability tends to be improved by setting the content to the upper limit or less.
  • the content ratio of the phosphoric acid-based adhesion improver in the total solid content is, for example, 0.1 to 5% by mass.
  • the amount is preferably 3 to 3% by mass, and more preferably 0.5 to 1% by mass.
  • the photosensitive resin composition of the present invention is further applied with appropriate interaction (formation of matrix structure) with an alkali-soluble resin, together with improvement of strength as a cured product.
  • An inorganic filler may be contained for the purpose of improving the flatness and taper angle of the film. Examples of such an inorganic filler include talc, silica, alumina, barium sulfate, magnesium oxide, and those surface-treated with various silane coupling agents.
  • the average particle size of these inorganic fillers is usually 0.005 to 20 ⁇ m, preferably 0.01 to 10 ⁇ m.
  • the average particle size referred to in the present embodiment is a value measured by a laser diffraction scattering particle size distribution measuring apparatus such as manufactured by Beckman Coulter.
  • silica sol and silica sol modified products tend to be excellent in improvement effect of taper angle as well as dispersion stability, and therefore, they are preferably blended.
  • the photosensitive resin composition of the present invention contains an inorganic filler, the content thereof is usually 5% by mass or more, preferably 10% by mass or more, and usually 80% by mass in the total solid content from the viewpoint of sensitivity.
  • the photosensitive resin composition of the present invention contains an inorganic filler
  • the content of the inorganic filler in the total solid content is, for example, 5 to 80% by mass, preferably 10 to 70% by mass.
  • the photosensitive resin composition of the present invention usually contains a solvent, and is used in a state in which the above-described components are dissolved or dispersed in the solvent (hereinafter, photosensitive resin containing solvent)
  • the composition is sometimes referred to as "photosensitive resin composition solution”.
  • the solvent is not particularly limited, and examples thereof include the organic solvents described below.
  • Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, tri Ethylene glycol monomethyl ether , Glycol monoalkyl ethers such as triethylene glycol monoethyl ether and tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl
  • solvents corresponding to the above include Mineral Spirit, Valsol # 2, Apco # 18 Solvent, Apcosynner, Socar Solvent No. 1 and No. 2.
  • Solvesso # 150 Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl carosolve, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all are trade names) and the like.
  • the above-mentioned solvent can dissolve or disperse each component in the photosensitive resin composition, and is selected according to the method of using the photosensitive resin composition of the present invention. It is preferable to select one having a boiling point in the range of 60 to 280 ° C. under atmospheric pressure (1013.25 hPa). More preferred are those having a boiling point of 70 to 260 ° C., for example, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate.
  • the content ratio of the total solid content in the photosensitive resin composition solution 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, it is used so as to be 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
  • the content ratio 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. Solvents may be used.
  • Examples of physical properties of the photosensitive resin composition of the present invention include an acid value.
  • the acid value with respect to the total solid of the photosensitive resin composition is not particularly limited, 20 mg-KOH / g or more is preferable, 22 mg-KOH / g or more is more preferable, 24 mg-KOH / g or more is more preferable, 26 mg-KOH / G or more is more preferable, 28 mg-KOH / g or more is particularly preferable, and usually 60 mg-KOH / g or less, 55 mg-KOH / g or less is preferable, 50 mg-KOH / g or less is more preferable, 40 mg-KOH / G or less is more preferable, and 35 mg-KOH / g or less is particularly preferable.
  • the acid value of the photosensitive resin composition relative to the total solid content is, for example, 20 to 60 mg-KOH / g, preferably 22 to 55 mg-KOH / g, more preferably 24 to 50 mg-KOH / g, and 26 to 40 mg-KOH / g is more preferred, and 28-35 mg-KOH / g is even more preferred.
  • the photosensitive resin composition of the present invention is prepared by mixing the above-mentioned components with a stirrer. In addition, you may filter using a membrane filter etc. so that the prepared photosensitive resin composition may become uniform.
  • the photosensitive resin composition of the present invention can be suitably used to form a partition wall, in particular, a partition wall for partitioning an organic layer (light emitting portion) of an organic electroluminescent device.
  • the partition of the present invention is composed of the photosensitive resin composition of the present invention.
  • the method of forming a partition using the photosensitive resin composition demonstrated above is not specifically limited, A conventionally well-known method is employable.
  • the photosensitive resin composition is apply
  • a photolithographic method is mentioned as a specific example of the formation method of such a partition.
  • the photosensitive resin composition is applied on the entire surface of the region where the partition walls of the substrate are formed, to form a photosensitive resin composition layer. After exposing the formed photosensitive resin composition layer according to the pattern of a predetermined partition, the exposed photosensitive resin composition layer is developed to form a partition on the substrate.
  • a contact transfer type coating apparatus such as a roll coater, a reverse coater, a bar coater, or a spinner (rotation type) Coating device
  • the photosensitive resin composition is coated using a non-contact coating device such as a curtain flow coater, and if necessary, the solvent is removed by drying to form a photosensitive resin composition layer.
  • the photosensitive resin composition is irradiated with active energy rays such as ultraviolet light and excimer laser light using a negative mask, and the photosensitive resin composition layer is partially formed according to the pattern of the partition walls.
  • a light source emitting ultraviolet light such as a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, and a carbon arc lamp can be used for exposure.
  • the amount of exposure varies depending on the composition of the photosensitive resin composition, it is preferably, for example, about 10 to 400 mJ / cm 2 .
  • a barrier rib pattern is formed by developing the photosensitive resin composition layer exposed according to the pattern of the barrier ribs with a developer.
  • the development method is not particularly limited, and an immersion method, a spray method or the like can be used.
  • Specific examples of the developer include organic solvents such as dimethylbenzylamine, monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts. It can be mentioned.
  • an antifoamer and surfactant can also be added to a developing solution.
  • partition wall pattern after development is subjected to post-baking and heat curing to obtain partition walls.
  • Post-baking is preferably at 150 to 250 ° C. for 15 to 60 minutes.
  • a cleaning process may be performed to clean the unexposed area.
  • the cleaning method is not particularly limited, and examples include plasma irradiation, excimer light irradiation, and UV irradiation.
  • excimer light irradiation or UV irradiation active oxygen can decompose and remove an organic substance attached to a pixel portion by light irradiation.
  • the substrate used for forming the partition is not particularly limited, and is appropriately selected according to the type of the organic electroluminescent device manufactured using the substrate on which the partition is formed.
  • Suitable 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; polycarbonate; poly (meth) methacrylic resin; polysulfone; Among the materials of these substrates, glass and polyimide are preferable because they are excellent in heat resistance.
  • the organic electroluminescent device of the present invention comprises the partition wall of the present invention.
  • Various organic electroluminescent devices are manufactured using the substrate provided with the barrier rib pattern manufactured by the method described above.
  • the method of forming the organic electroluminescent element is not particularly limited, preferably, after forming the pattern of the partition on the substrate by the above method, the ink is injected into the region surrounded by the partition on the substrate to form a pixel or the like
  • An organic electroluminescent device is manufactured by forming an organic layer.
  • a type of the organic electroluminescent element a bottom emission type or a top emission type can be mentioned.
  • partition walls are formed on a glass substrate on which transparent electrodes are stacked, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are stacked in an opening surrounded by the partition walls. Ru.
  • partition walls are formed on a glass substrate on which metal electrode layers are stacked, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are stacked in an opening surrounded by the partition walls.
  • the light emitting layer include organic electroluminescent layers as described in JP-A-2009-146691 and JP-A-5734681.
  • quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.
  • Water, an organic solvent, and these mixed solvents can be used as a solvent used when forming the ink for organic layer formation.
  • the organic solvent is not particularly limited as long as it can be removed from the film formed after the injection of the ink.
  • Specific examples of the organic solvent include toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate, butyl acetate, 3-phenoxytoluene, etc.
  • a surfactant, an antioxidant, a viscosity modifier, an ultraviolet light absorber and the like can be added to the ink.
  • the ink jet method is preferable as a method of injecting the ink into the area surrounded by the partition wall, since a small amount of ink can be easily injected into a predetermined place.
  • the ink used for formation of an organic layer is suitably selected according to the kind of organic electroluminescent element manufactured.
  • the viscosity of the ink is not particularly limited as long as the ink can be favorably discharged from the ink jet head, but 4 to 20 mPa ⁇ s is preferable, and 5 to 10 mPa ⁇ s is more preferable.
  • the viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity modifier, or the like.
  • the image display device of the present invention includes the organic electroluminescent device of the present invention.
  • the type and structure of the image display device are not particularly limited as long as they include the organic electroluminescent device of the present invention, and for example, they can be assembled according to a conventional method using an active drive type organic electroluminescent device.
  • the image display device of the present invention is formed by the method as described in "Organic EL display” (Am Co., published on August 20, 2004, Shimizu Toki, Chiya Adachi, Hideyuki Murata) can do.
  • an image may be displayed by combining an organic electroluminescent element emitting white light and a color filter, or an image may be displayed by combining organic electroluminescent elements having different luminescent colors such as RGB.
  • the illumination of the present invention includes the organic electroluminescent device of the present invention.
  • the organic electroluminescent device of the present invention can be assembled according to a conventional method.
  • As an organic electroluminescent element it is good also as a simple matrix drive system, and good also as an active matrix drive system.
  • an organic electroluminescent device that emits white light may be used.
  • organic electroluminescent elements of different luminescent colors may be combined, and each color may be mixed to be white, or the color mixing ratio may be adjusted to provide a toning function.
  • the photosensitive resin composition of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
  • the components of the photosensitive resin composition used in the following examples and comparative examples are as follows.
  • Acrylic resin obtained by synthesis according to the following procedure 55 parts by mass of propylene glycol monomethyl ether acetate was charged as a solvent into a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream.
  • X is a perfluoromethylene group or a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, The average number of fluorine atoms is 46.
  • a-2 Acrylic resin (liquid repellent agent) obtained by synthesis according to the following procedure 35 parts by mass of propylene glycol monomethyl ether acetate was charged as a solvent into a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream.
  • Alkali-soluble resin (equivalent to epoxy (meth) acrylate resin (b1-3)) obtained by synthesis according to the following procedure 100 parts by mass of bisphenol A type epoxy compound (epoxy equivalent 186 g / eq, mixture of m and n in the formula is 1 to 20) represented by the following formula, 40 parts by mass of acrylic acid, p-methoxyphenol 0.06 parts
  • a reaction vessel was charged with a portion, 2.4 parts by mass of triphenylphosphine and 126 parts by mass of propylene glycol monomethyl ether acetate, and the mixture was stirred at 95 ° C. until the acid value became 5 mg-KOH / g or less.
  • b-2 The following acrylic copolymer resin (corresponding to acrylic copolymer resin (b2-1)) Acrylic acid is added in an equal amount with glycidyl methacrylate to a copolymer resin having dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio 0.02 / 0.05 / 0.93) as a constituent monomer, and further tetrahydroanhydride
  • the polystyrene equivalent weight average molecular weight (Mw) measured by GPC is 7700, and the solid content acid number is 28.5 mg-KOH / g.
  • c-1 dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)
  • d-1 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Hodogaya Chemical Co., Ltd.)
  • d-2 Irgacure 369 (BASF, compound of the following chemical structure)
  • e-1 2-mercaptobenzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • e-2 pentaerythritol tetrakis (3-mercapto propionate) (manufactured by Sakai Chemical Co., Ltd.)
  • f-1 TINUVIN 384-2 (manufactured by BASF, UV absorber)
  • g-1 KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.)
  • h-1 methyl hydroquinone (made by SEIKO CHEMICAL CO., LTD., a compound having the following chemical structure)
  • TMAH tetramethylammonium hydroxide
  • the contact angle was measured at 23 ° C. and 50% humidity using a Drop Master 500 contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. 0.7 ⁇ L of propylene glycol methyl ether acetate was dropped onto the cured product of the contact angle measurement substrate, and the contact angle after 1 second was measured. The measurement results are shown in Table 1. The larger the contact angle, the higher the ink repellency.
  • UV resistance evaluation contact angle
  • the substrate for contact angle measurement was irradiated with ultraviolet light (UV) for 3 minutes using a dry processor VUM-3073 manufactured by Oak Corporation. At this time, the intensity at a wavelength of 254 nm was 9 mW / cm 2 .
  • the contact angle of the substrate after UV irradiation was measured by the method described above. The results were evaluated from the following two types of viewpoints. 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 shows 30 degrees or more. B: The contact angle after UV irradiation shows 15 degrees or more and less than 30 degrees. C: The contact angle after UV irradiation shows less than 15 °. A is the preferred performance.
  • C The contact angle before UV irradiation showed 30 degrees or more, and the decreasing rate of the contact angle after UV irradiation showed 30% or more.
  • D The contact angle before UV irradiation did not show more than 30 °. A is the preferred performance.
  • Partition Wall Formation and Evaluation of Partition Wall
  • Formation of partition wall Each photosensitive resin composition was apply
  • the intensity at a wavelength of 365 nm was 40 mW / cm 2 and the exposure dose was 120 mJ / cm 2 under air.
  • TMAH tetramethylammonium hydroxide
  • UV resistance evaluation inkjet coating suitability for partition walls
  • the substrate having the grid-like partition walls was irradiated with ultraviolet light (UV) for 3 minutes using an Orc dry processor VUM-3073.
  • the intensity at a wavelength of 254 nm was 9 mW / cm 2 .
  • Inkjet coating was performed using DMP-2831 manufactured by Fuji Film Co., Ltd. on the pixel region surrounded by the grid-like partition walls of the substrate after UV irradiation.
  • a solvent isoamyl benzoate
  • 480 pL is applied per pixel
  • evaluation is based on the evaluation of the presence or absence of breakage (the phenomenon that the ink gets over the partition wall and mixes in the next pixel part) I went.
  • breakage tends to be suppressed.
  • the wettability and spreadability in the partition wall after ink jet coating was good, and the evaluation for breakage shown below (ink jet coating aptitude) was A.
  • A The ink could be applied in the pixel and there was no overflow out of the partition.
  • B Ink overflowed from the inside of the pixel to the entire top surface of the partition wall, and was mixed into the adjacent pixel area (broken). A is the preferred performance.
  • the coated substrates using the photosensitive resin compositions of Examples 1 to 5 have a high contact angle after UV irradiation, and good inkjet coating suitability after UV irradiation.
  • the chain transfer agent it is possible to suppress the decrease in the curability of the film surface due to oxygen inhibition, and it is possible to suppress the elution of the liquid repellent agent in the development step and fix a sufficient amount of the liquid repellent agent on the film surface. It is thought that the corner has become better.
  • the lyophobic agent one having a rigid, multi-ring saturated hydrocarbon backbone that is hard to decompose against UV irradiation is used, so the decomposition reaction of the lyophobic agent is suppressed even by UV irradiation, and after UV irradiation It is considered that the sufficient amount of fluorine atoms could be secured on the surface of the film.
  • 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 due to low surface curability due to the absence of a chain transfer agent and the outflow of the liquid repellent agent during development.
  • the coated substrate using the photosensitive resin composition of Comparative Example 2 resulted in a low contact angle after UV irradiation.
  • the lyophobic agent (a-2) used does not have a polycyclic saturated hydrocarbon skeleton, so the decomposition amount of the lyophobic agent by UV irradiation reduces the amount of fluorine atoms on the film surface, and the It is considered that this is because the ink property is not sufficiently shown.
  • the photosensitive resin composition of Example 6 was applied on a glass substrate using a spinner so as to have a thickness of 1.7 ⁇ m after heat curing. Then, 2 minutes at 95 ° C., then heated and dried on a hot plate, the resulting coating film, without a mask, using a Dainippon Research Institute Co. exposing machine MA-1100, an exposure amount 200 mJ / cm 2 Exposed the entire surface. At this time, the intensity at a wavelength of 365 nm was 40 mW / cm 2 . Next, after spray development with a 2.38 mass% aqueous solution of TMAH (tetramethylammonium hydroxide) at 24 ° C.
  • TMAH tetramethylammonium hydroxide
  • a photosensitive resin composition of Example 6 was applied on the ITO film of the glass substrate having an ITO film formed on the surface using a spinner so as to have a thickness of 1.7 ⁇ m after heat curing. After that, heat-dry on a hot plate at 95 ° C. for 2 minutes, and use a photomask (a mask having a plurality of 80 ⁇ m ⁇ 280 ⁇ m coated portions at intervals of 40 ⁇ m) for the obtained coating film. Exposure was performed using an exposure apparatus MA-1100 manufactured by Nippon Kaken Co., Ltd. At this time, the intensity at a wavelength of 365 nm was 40 mW / cm 2 and the exposure dose was 200 mJ / cm 2 under air.

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Abstract

Provided is a photosensitive resin composition which is capable of forming a partition wall that exhibits good ink repellency even after UV cleaning. A photosensitive resin composition according to the present invention contains (A) a liquid repellent agent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator. The liquid repellent agent (A) contains an acrylic resin (a) that has a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond. This photosensitive resin composition additionally contains (E) a chain transfer agent.

Description

感光性樹脂組成物、隔壁、有機電界発光素子、画像表示装置及び照明Photosensitive resin composition, partition wall, organic electroluminescent device, image display device and illumination
　本発明は、感光性樹脂組成物、該感光性樹脂組成物で構成される隔壁、該隔壁を備える有機電界発光素子、該有機電界発光素子を含む画像表示装置及び照明に関する。
　２０１８年１月２６日に日本国特許庁に出願された日本国特願２０１８－０１１０９７の明細書、特許請求の範囲及び要約書の全内容、並びに、本明細書で引用された文献等に開示された内容の一部又は全部をここに引用し、本明細書の開示内容として取り入れる。 The present invention relates to a photosensitive resin composition, a partition composed of the photosensitive resin composition, an organic electroluminescent device provided with the partition, an image display apparatus including the organic electroluminescent device, and illumination.
Disclosed in the specification, claims and abstract of Japanese Patent Application No. 2018-011097 filed with the Japanese Patent Office on January 26, 2018, as well as in the documents cited herein. A part or all of the contents described herein are incorporated herein by reference and incorporated as the disclosure contents of the present specification.
　従来から、有機電界ディスプレイや有機電界照明などに含まれる有機電界発光素子は、基板上に、隔壁（バンク）を形成した後に、隔壁に囲まれた領域内に、種々の機能層を積層して製造されている。このような隔壁を容易に形成する方法として、感光性樹脂組成物を用いるフォトリソグラフィー法により形成する方法が知られている。 2. Description of the Related Art Conventionally, organic electroluminescent devices included in organic electroluminescent display, organic electroluminescent illumination, etc. are formed by laminating various functional layers in a region surrounded by the partition after forming the partition (bank) on the substrate. It is manufactured. As a method of easily forming such a partition, a method of forming by photolithography using a photosensitive resin composition is known.
　また、隔壁に囲まれた領域内に種々の機能層を積層する方法としては、まず機能層を構成する材料を含むインクを調製し、次いで、調製したインクを隔壁に囲まれた領域内に注入する方法が知られている。この方法の中でも、所定量のインクを所定の箇所に正確に注入しやすいことから、インクジェット法が採用されることが多い。 In addition, as a method of laminating various functional layers in the area surrounded by the partition, first, an ink containing a material constituting the functional layer is prepared, and then the prepared ink is injected into the area surrounded by the partition The way to do it is known. Among these methods, the inkjet method is often employed because it is easy to inject a predetermined amount of ink accurately to a predetermined location.
　さらに、インクを用いて機能層を形成する場合、隔壁へのインクの付着の予防や、隣接する領域間に注入されるインク同士が混合されることを防ぐ目的等で、隔壁に撥インク性（撥液性）を付与することが求められる場合がある。隔壁に撥インク性を付与する方法としては、例えば、隔壁にフッ素系化合物を含有させる方法が知られている（特許文献１及び２参照）。 Furthermore, when forming a functional layer using an ink, the ink repellent property (for the purpose of preventing the adhesion of the ink to the partition, the mixing of the ink injected between the adjacent regions, etc. It may be required to impart liquid repellency). As a method of imparting ink repellency to partition walls, for example, a method of including a fluorine-based compound in partition walls is known (see Patent Documents 1 and 2).
　また、特許文献３には、特定のフッ素樹脂を用いることで、高い撥インク性を有する硬化物が形成可能であると記載されている。 Further, Patent Document 3 describes that a cured product having high ink repellency can be formed by using a specific fluorocarbon resin.
国際公開第２０１３／１６１８２９号International Publication No. 2013/161829 日本国特開２０１５－１７９２５７号公報Japanese Patent Laid-Open Publication No. 2015-179257 日本国特開２０１２－０９２３０８号公報Japan JP 2012-092308 gazette
　感光性樹脂組成物を用いて隔壁を形成する場合、隔壁で囲まれた画素領域に該組成物の残渣が発生すると、画素部の一部が発光しなくなる場合がある。このため、隔壁形成後に残渣の除去等を目的としてＵＶ洗浄処理を行うことがあるが、残渣が除去される一方で、隔壁の撥インク性が低下するという問題があった。
　本発明者らが検討したところ、特許文献１に記載の感光性樹脂組成物では、ＵＶ洗浄処理後の撥インク性が十分ではないことがわかった。
　また、特許文献２及び３に記載の感光性樹脂組成物では、撥インク性が十分ではないことがわかった。 When forming a partition using a photosensitive resin composition, when the residue of this composition generate | occur | produces in the pixel area | region enclosed by the partition, a part of pixel part may stop light emission. For this reason, although UV cleaning may be performed for the purpose of removing the residue, etc. after the partition is formed, there is a problem that while the residue is removed, the ink repellency of the partition is lowered.
When the present inventors examined, in the photosensitive resin composition of patent document 1, it turned out that the ink repellency after UV washing processing is not enough.
Moreover, in the photosensitive resin composition of patent document 2 and 3, it turned out that ink repellency is not enough.
　そこで、本発明では、ＵＶ洗浄処理後も撥インク性が良好である隔壁を形成可能な感光性樹脂組成物を提供することを目的とする。
　また本発明は、当該感光性樹脂組成物で構成される隔壁や、該隔壁を備える有機電界発光素子、該有機電界発光素子を含む画像表示装置及び照明を提供することを目的とする。 So, in this invention, it aims at providing the photosensitive resin composition which can form the partition in which ink repellency is favorable also after UV washing processing.
Moreover, this invention aims at providing the partition comprised with the said photosensitive resin composition, the organic electroluminescent element provided with this partition, the image display apparatus containing this organic electroluminescent element, and illumination.
　本発明者らが鋭意検討した結果、撥液剤、アルカリ可溶性樹脂、光重合性化合物、光重合開始剤を含有する感光性樹脂組成物において、特定の構造を有する撥液剤を用い、さらに連鎖移動剤を用いることで上記課題を解決できることを見出し、本発明を完成するに至った。
　即ち本発明の要旨は以下の通りである。 As a result of intensive investigations by the present inventors, in a photosensitive resin composition containing a liquid repellent, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, a liquid repellent having a specific structure is used, and a chain transfer agent is further used. It has been found that the above problems can be solved by using the present invention, and the present invention has been completed.
That is, the gist of the present invention is as follows.
［１］　（Ａ）撥液剤、（Ｂ）アルカリ可溶性樹脂、（Ｃ）光重合性化合物、及び（Ｄ）光重合開始剤を含有する感光性樹脂組成物であって、
　前記（Ａ）撥液剤が、多環式飽和炭化水素骨格及びエチレン性二重結合を有するアクリル樹脂（ａ）を含み、
　さらに（Ｅ）連鎖移動剤を含むことを特徴とする感光性樹脂組成物。
［２］　前記多環式飽和炭化水素骨格及びエチレン性二重結合を有するアクリル樹脂（ａ）が、ポリ（パーフルオロアルキレンエーテル）鎖を含む架橋部を有する、［１］に記載の感光性樹脂組成物。 [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 (A) liquid repellent agent includes an acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond,
A photosensitive resin composition characterized by further comprising (E) a chain transfer agent.
[2] The photosensitive resin according to [1], wherein the acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond has a crosslinked portion containing a poly (perfluoroalkylene ether) chain. Composition.
［３］　前記多環式飽和炭化水素骨格及びエチレン性二重結合を有するアクリル樹脂（ａ）が、下記一般式（１）で表される部分構造を含む、［２］に記載の感光性樹脂組成物。 [3] The photosensitive resin according to [2], wherein the acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond contains a partial structure represented by the following general formula (1) Composition.
Figure JPOXMLDOC01-appb-C000007
  
Figure JPOXMLDOC01-appb-C000007
  
（式（１）中、Ｒ1は各々独立に、水素原子又はメチル基を表す。Ｘ1はパーフルオロアルキレン基を表す。式（１）中に含まれる複数のＸ1は同一のものでも異なるものでもよく、異なるものの場合にはランダム状に存在してもブロック状に存在していてもよい。Ｘ2は各々独立に、直接結合又は任意の２価の連結基を表す。ｎは１以上の整数である。＊は結合手を表す。） (In formula (1), R 1 each independently represents a hydrogen atom or a methyl group. X 1 represents a perfluoroalkylene group. Plural X 1 contained in formula (1) may be the same or different. In the case of different ones, they may be present in a random form or in a block form, and each X 2 independently represents a direct bond or any divalent linking group, and n is one or more. Is an integer of *. * Represents a bond.)
［４］　前記多環式飽和炭化水素骨格が、アダマンタン骨格である、［１］～［３］のいずれかに記載の感光性樹脂組成物。
［５］　前記多環式飽和炭化水素骨格及びエチレン性二重結合を有するアクリル樹脂（ａ）が、下記一般式（２）で表される部分構造を含む、［１］～［４］のいずれかに記載の感光性樹脂組成物。 [4] The photosensitive resin composition according to any one of [1] to [3], wherein the polycyclic saturated hydrocarbon skeleton is an adamantane skeleton.
[5] Any one of [1] to [4], wherein the acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond contains a partial structure represented by the following general formula (2) The photosensitive resin composition according to claim 1.
Figure JPOXMLDOC01-appb-C000008
  
Figure JPOXMLDOC01-appb-C000008
  
（式（２）中、Ｒ2及びＲ3は各々独立に、水素原子又はメチル基を表す。Ｘ3は置換基を有していてもよい２価の多環式飽和炭化水素基を表す。Ｘ4はウレタン結合又はエステル結合を表す。Ｘ5は置換基を有していてもよい２価の炭化水素基を表す。＊は結合手を表す。） (In the formula (2), each independently R 2 and R 3, .X 3 represents a hydrogen atom or a methyl group represents a polycyclic saturated hydrocarbon group which may have a substituent. X 4 represents a urethane bond or an ester bond, X 5 represents a divalent hydrocarbon group which may have a substituent, and * represents a bond.
［６］　前記（Ｂ）アルカリ可溶性樹脂が、エポキシ（メタ）アクリレート樹脂（ｂ１）及び／又はアクリル共重合樹脂（ｂ２）を含む、［１］～［５］のいずれかに記載の感光性樹脂組成物。
［７］　前記エポキシ（メタ）アクリレート樹脂（ｂ１）が、下記一般式（ｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂（ｂ１－１）、下記一般式（ｉｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂（ｂ１－２）、及び下記一般式（ｉｉｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂（ｂ１－３）からなる群から選ばれる少なくとも１種である、［６］に記載の感光性樹脂組成物。 [6] The photosensitive resin according to any one of [1] to [5], wherein the (B) alkali-soluble resin comprises an epoxy (meth) acrylate resin (b1) and / or an acrylic copolymer resin (b2) Composition.
[7] The epoxy (meth) acrylate resin (b1) is represented by an epoxy (meth) acrylate resin (b1-1) containing a partial structure represented by the following general formula (i), a general formula (ii) below At least one selected from the group consisting of an epoxy (meth) acrylate resin (b1-2) containing a partial structure and an epoxy (meth) acrylate resin (b1-3) containing a partial structure represented by the following general formula (iii) The photosensitive resin composition as described in [6] which is 1 type.
Figure JPOXMLDOC01-appb-C000009
  
Figure JPOXMLDOC01-appb-C000009
  
（式（ｉ）中、Ｒaは水素原子又はメチル基を表し、Ｒbは置換基を有していてもよい２価の炭化水素基を表す。式（ｉ）中のベンゼン環は、更に任意の置換基により置換されていてもよい。＊は結合手を表す。） (In formula (i), R a represents a hydrogen atom or a methyl group, R b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) It may be substituted by any substituent, * represents a bond.)
Figure JPOXMLDOC01-appb-C000010
  
（式（ｉｉ）中、Ｒcは各々独立に、水素原子又はメチル基を表す。Ｒdは、環状炭化水素基を側鎖として有する２価の炭化水素基を表す。＊は結合手を表す。）
Figure JPOXMLDOC01-appb-C000010
(In formula (ii), each R c independently represents a hydrogen atom or a methyl group. R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. .)
Figure JPOXMLDOC01-appb-C000011
  
Figure JPOXMLDOC01-appb-C000011
  
（式（ｉｉｉ）中、Ｒeは水素原子又はメチル基を表し、γは単結合、－ＣＯ－、置換基を有していてもよいアルキレン基、又は置換基を有していてもよい２価の環状炭化水素基を表す。式（ｉｉｉ）中のベンゼン環は、更に任意の置換基により置換されていてもよい。＊は結合手を表す。） (In formula (iii), R e represents a hydrogen atom or a methyl group, and γ is a single bond, —CO—, an alkylene group which may have a substituent, or 2 which may have a substituent And the benzene ring in the formula (iii) may be further substituted by any substituent. * Represents a bond.)
［８］　前記アクリル共重合樹脂（ｂ２）が、下記一般式（Ｉ）で表される部分構造を含むアクリル共重合樹脂（ｂ２－１）である、［６］又は［７］に記載の感光性樹脂組成物。 [8] The photosensitivity 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) Resin composition.
Figure JPOXMLDOC01-appb-C000012
  
Figure JPOXMLDOC01-appb-C000012
  
（式（Ｉ）中、ＲA及びＲBは各々独立に、水素原子又はメチル基を表す。＊は結合手を表す。） (In formula (I), R A and R B each independently represent a hydrogen atom or a methyl group. * Represents a bond.)
［９］　前記（Ｄ）光重合開始剤が、ヘキサアリールビイミダゾール系光重合開始剤、オキシムエステル系光重合開始剤及びアセトフェノン系光重合開始剤からなる群から選ばれる少なくとも１種を含有する、［１］～［８］のいずれかに記載の感光性樹脂組成物。
［１０］　さらに紫外線吸収剤を含有する、［１］～［９］のいずれかに記載の感光性樹脂組成物。
［１１］　さらに重合禁止剤を含有する、［１］～［１０］のいずれかに記載の感光性樹脂組成物。
［１２］　隔壁形成用である［１］～［１１］のいずれかに記載の感光性樹脂組成物。
［１３］　［１］～［１２］のいずれかに記載の感光性樹脂組成物で構成される隔壁。
［１４］　［１３］に記載の隔壁を備える有機電界発光素子。
［１５］　［１４］に記載の有機電界発光素子を含む画像表示装置。
［１６］　［１４］に記載の有機電界発光素子を含む照明。 [9] The (D) photopolymerization initiator contains at least one selected from the group consisting of a hexaarylbiimidazole photopolymerization initiator, an oxime ester photopolymerization initiator, and an acetophenone photopolymerization initiator. The photosensitive resin composition according to any one of [1] to [8].
[10] The photosensitive resin composition according to any one of [1] to [9], further containing an ultraviolet absorber.
[11] The photosensitive resin composition according to any one of [1] to [10], further comprising a polymerization inhibitor.
[12] The photosensitive resin composition according to any one of [1] to [11], which is for forming a partition wall.
[13] A partition comprising the photosensitive resin composition according to any one of [1] to [12].
[14] An organic electroluminescent device comprising the partition wall according to [13].
[15] An image display comprising the organic electroluminescent device as described in [14].
[16] A lighting comprising the organic electroluminescent device according to [14].
　本発明により、ＵＶ洗浄処理後も撥インク性が良好である隔壁を形成可能な感光性樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a photosensitive resin composition capable of forming partition walls having good ink repellency even after UV cleaning treatment.
　以下、本発明を詳細に説明する。なお、以下の記載は本発明の実施形態の一例であり、本発明はその要旨を超えない限り、これらに特定されない。
　なお、本発明において、「（メタ）アクリル」とは、「アクリル及び／又はメタクリル」を意味するものとし、また、「全固形分」とは、感光性樹脂組成物における溶剤以外の全成分を意味するものとする。さらに、本発明において「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。また、「Ａ及び／又はＢ」とは、Ａ及びＢの一方または両方を意味し、具体的には、Ａ、Ｂ、又はＡ及びＢを意味する。
　また、本発明において、「（共）重合体」とは、単一重合体（ホモポリマー）と共重合体（コポリマー）の双方を含むことを意味し、また、「多塩基酸（無水物）」とは、「多塩基酸及び／又は多塩基酸無水物」を意味する。
　本発明において、重量平均分子量とは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によるポリスチレン換算の重量平均分子量（Ｍｗ）をさす。
　本発明において酸価とは、有効固形分換算の酸価を表し、中和滴定により算出される。 Hereinafter, the present invention will be described in detail. In addition, the following description is an example of embodiment of this invention, and this invention is not specified in these, unless the summary is exceeded.
In the present invention, "(meth) acrylic" means "acrylic and / or methacrylic", and "total solids" means all components other than the solvent in the photosensitive resin composition. Shall be meant. Furthermore, in the present invention, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value. Moreover, "A and / or B" means one or both of A and B, and specifically means A, B, or A and B.
In the present invention, "(co) polymer" is meant to include both homopolymers (homopolymers) and copolymers (copolymers), and "polybasic acid (anhydride)" By "polybasic acid and / or polybasic acid anhydride" is meant.
In the present invention, the weight average molecular weight refers to a weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography).
In the present invention, the acid value refers to the acid value in terms of effective solid content, and is calculated by neutralization titration.
　本発明において、隔壁材とはバンク材、壁材、ウォール材をさし、同様に、隔壁とはバンク、壁、ウォールをさす。
　また本発明において、発光部（画素部）とは電気エネルギーを与えた場合に光を放出する部分をさす。 In the present invention, the partition material refers to a bank material, a wall material, and a wall material, and similarly, the partition wall refers to a bank, a wall, and a wall.
In the present invention, the light emitting portion (pixel portion) refers to a portion which emits light when electric energy is applied.
［１］感光性樹脂組成物
　本発明の感光性樹脂組成物は、（Ａ）撥液剤、（Ｂ）アルカリ可溶性樹脂、（Ｃ）光重合性化合物、（Ｄ）光重合開始剤を含有し、前記（Ａ）撥液剤が、多環式飽和炭化水素骨格及びエチレン性二重結合を有するアクリル樹脂（ａ）を含み、さらに（Ｅ）連鎖移動剤を含むことを特徴とする。必要に応じてさらにその他の成分を含んでいてもよく、例えば紫外線吸収剤や、重合禁止剤を含んでいてもよい。 [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, The liquid repellent agent (A) includes an acrylic resin (a) having a polycyclic saturated hydrocarbon backbone and an ethylenic double bond, and further includes (E) a chain transfer agent. If necessary, other components may be further contained, and for example, an ultraviolet absorber or a polymerization inhibitor may be contained.
　本発明において隔壁とは、例えば、アクティブ駆動型有機電界発光素子における機能層（有機層、発光部）を区画するためのものであり、区画された領域（画素領域）に機能層を構成するための材料であるインクを吐出、乾燥することで、機能層及び隔壁を含む画素等を形成させていくために使用されるものである。 In the present invention, the partition wall is, for example, for partitioning a functional layer (organic layer, light emitting portion) in an active drive type organic electroluminescent device, and for forming a functional layer in a partitioned region (pixel region) It is used to form pixels including a functional layer and a partition by discharging and drying the ink which is the material of the above.
［１－１］感光性樹脂組成物の成分及び組成
　本発明の感光性樹脂組成物を構成する成分およびその組成について説明する。
　本発明の感光性樹脂組成物は、（Ａ）撥液剤、（Ｂ）アルカリ可溶性樹脂、（Ｃ）光重合性化合物、及び（Ｄ）光重合開始剤を含有し、さらに（Ｅ）連鎖移動剤を含有し、通常は溶剤も含有する。 [1-1] Components and Composition of Photosensitive Resin Composition The components constituting the photosensitive resin composition of the present invention and the composition thereof will be described.
The photosensitive resin composition of the present invention contains (A) a liquid repellent agent, (B) an alkali soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator, and further (E) a chain transfer agent And usually contain a solvent.
［１－１－１］（Ａ）成分；撥液剤
　本発明の感光性樹脂組成物は、（Ａ）撥液剤を含有する。（Ａ）撥液剤を含有することで、得られる隔壁の表面に撥インク性（撥液性）を付与できることから、インクジェット法で有機電界発光素子を作成する際には、隔壁へのインクの付着が予防され、また、隣接する領域間に注入されるインク同士が混合されることが予防できると考えられる。 [1-1-1] (A) Component; Liquid Repellent The photosensitive resin composition of the present invention contains (A) a liquid repellent. (A) By containing a liquid repellent agent, since ink repellency (liquid repellency) can be imparted to the surface of the obtained partition, when the organic electroluminescent element is formed by the inkjet method, adhesion of the ink to the partition It is believed that it is possible to prevent the mixing of inks injected between adjacent areas.
［多環式飽和炭化水素骨格及びエチレン性二重結合を有するアクリル樹脂（ａ）］
　本発明の感光性樹脂組成物における（Ａ）撥液剤は、多環式飽和炭化水素骨格及びエチレン性二重結合を有するアクリル樹脂（ａ）（以下、「アクリル樹脂（ａ）」と略記する場合がある。）を含む。
　アクリル樹脂（ａ）がエチレン性二重結合を有することで、塗布膜を露光した際にその表面にアクリル樹脂（ａ）が固定されるため、アクリル樹脂（ａ）が現像処理時に流出しにくくなり、その結果、得られる隔壁の撥インク性を高くすることができると考えられる。 [Acrylate resin having a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond (a)]
When (A) liquid repellent agent in the photosensitive resin composition of the present invention is abbreviated as acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond (hereinafter referred to as "acrylic resin (a)" There is.
When the acrylic resin (a) has an ethylenic double bond, the acrylic resin (a) is fixed to the surface when the coating film is exposed, so the acrylic resin (a) is less likely to flow out during development processing. As a result, it is considered that the ink repellency of the obtained partition can be enhanced.
　また、アクリル樹脂（ａ）は多環式飽和炭化水素骨格を有するものである。多環式飽和炭化水素骨格を有することでＵＶ照射後の膜表面において撥インク性が高くなるが、それは以下の作用によるものと考えられる。
　ＵＶ照射により、硬化物中の樹脂等のＵＶ吸収による発熱で硬化物の表層温度は上昇する傾向にあり、表層に偏析するアクリル樹脂（ａ）はその発熱の影響を受けやすいと考えられる。
　熱に対し、直鎖構造は１箇所が切れると分解してしまうが、環状構造は複数箇所が切れないと分解しないため耐熱性が高く、特に多環式になるとさらに分解しにくくなり耐熱性が上がると考えられる。また、不飽和環状炭化水素骨格よりも飽和環状炭化水素骨格の方が反応起点となる結合がなく、環自体の反応性が低い利点があると考えられる。
　また多環式炭化水素骨格を有することで、それ自身が立体障害となり、アクリル樹脂（ａ）の主鎖も切れにくくなり、より耐熱性が上がると考えられる。 The acrylic resin (a) is one having a polycyclic saturated hydrocarbon skeleton. The presence of the polycyclic saturated hydrocarbon skeleton increases the ink repellency on the film surface after UV irradiation, which is considered to be due to the following effects.
The surface temperature of the cured product tends to rise due to the heat generated by UV absorption of the resin and the like in the cured product by the UV irradiation, and it is considered that the acrylic resin (a) segregated in the surface is susceptible to the heat generation.
For heat, linear structure breaks down if one place breaks, but cyclic structure does not break down unless it breaks multiple places, so it has high heat resistance because it does not break down especially when it becomes polycyclic, so heat resistance It is considered to go up. In addition, it is considered that a saturated cyclic hydrocarbon skeleton has no bond as a reaction starting point than an unsaturated cyclic hydrocarbon skeleton, and there is an advantage that the reactivity of the ring itself is low.
In addition, it is considered that the presence of the polycyclic hydrocarbon skeleton itself causes steric hindrance, which makes it difficult to cut the main chain of the acrylic resin (a), and the heat resistance is further improved.
　さらに、アクリル樹脂（ａ）がアクリル構造であることによって、（Ｂ）アルカリ可溶性樹脂や（Ｃ）光重合性化合物との相溶性を高めることができ、感光性樹脂組成物の保存性も高めることができるととともに、画素部の残渣発生を抑制できて濡れ広がり性が良好になると考えられる。 Furthermore, when the acrylic resin (a) has an acrylic structure, compatibility with the (B) alkali-soluble resin and (C) photopolymerizable compound can be enhanced, and the storage stability of the photosensitive resin composition is also enhanced. It is considered that the generation of the residue in the pixel portion can be suppressed and the wetting and spreading property is improved.
　前記多環式飽和炭化水素骨格は、１価の基でもよく、２価以上の基でもよい。また、無置換でもよいし、置換基を有していてもよい。 The polycyclic saturated hydrocarbon skeleton may be a monovalent group or a divalent or higher group. Moreover, it may be unsubstituted or may have a substituent.
　前記多環式飽和炭化水素骨格の炭素数は特に限定されないが、通常６以上、８以上が好ましく、９以上がより好ましく、１０以上がさらに好ましく、また、２０以下が好ましく、１５以下がより好ましく、１２以下がさらに好ましい。前記下限値以上とすることでＵＶ洗浄処理後の撥インク性が良好となる傾向があり、また、前記上限値以下とすることで感光性樹脂組成物中の相溶性が良好となる傾向がある。前記多環式飽和炭化水素骨格の炭素数としては、例えば、６～２０であり、８～２０が好ましく、９～１５がより好ましく、１０～１２がさらに好ましい。
　また、前記多環式飽和炭化水素骨格が有する環の数は２以上であれば特に限定されないが、３以上が好ましく、また、５以下が好ましく、４以下がより好ましい。前記下限値以上とすることでＵＶ洗浄処理後の撥インク性が良好となる傾向があり、また、前記上限値以下とすることで感光性樹脂組成物中の相溶性が良好となる傾向がある。前記多環式飽和炭化水素骨格が有する環の数としては、例えば、２～５であり、３～４が好ましい。
　前記多環式飽和炭化水素骨格の具体例としては、アダマンタン骨格、トリシクロデカン骨格、ノルボルナン骨格、デカリン骨格などが挙げられるが、ＵＶ洗浄処理後の撥インク性の観点からアダマンタン骨格が好ましい。 The carbon number of the polycyclic saturated hydrocarbon backbone is not particularly limited, but is usually 6 or more and 8 or more, preferably 9 or more, more preferably 10 or more, and preferably 20 or less, more preferably 15 or less. , 12 or less is more preferable. By setting the content to the above lower limit or more, the ink repellency after UV cleaning tends to be good, and by setting the above upper limit or less, the compatibility in the photosensitive resin composition tends to be good. . The carbon number of the polycyclic saturated hydrocarbon skeleton is, for example, 6 to 20, preferably 8 to 20, more preferably 9 to 15, and still more preferably 10 to 12.
The number of rings contained in the polycyclic saturated hydrocarbon skeleton is not particularly limited as long as it is 2 or more, but 3 or more is preferable, 5 or less is preferable, and 4 or less is more preferable. By setting the content to the above lower limit or more, the ink repellency after UV cleaning tends to be good, and by setting the above upper limit or less, the compatibility in the photosensitive resin composition tends to be good. . The number of rings possessed by the polycyclic saturated hydrocarbon skeleton is, for example, 2 to 5, and preferably 3 to 4.
Specific examples of the polycyclic saturated hydrocarbon skeleton include an adamantane skeleton, a tricyclodecane skeleton, a norbornane skeleton, a decalin skeleton and the like, but an adamantane skeleton is preferable from the viewpoint of ink repellency after UV washing treatment.
　前記多環式飽和炭化水素骨格は、アクリル樹脂（ａ）の化学構造のどこにあってもよく、例えば、アクリル樹脂の主鎖中にあってもよく、側鎖中にあってもよい。合成しやすさの観点から、側鎖中にあることが好ましい。 The polycyclic saturated hydrocarbon skeleton may be anywhere in the chemical structure of the acrylic resin (a), for example, may be in the main chain of the acrylic resin, or may be in the side chain. It is preferably in the side chain from the viewpoint of easiness of synthesis.
　また、アクリル樹脂（ａ）における多環式飽和炭化水素骨格の含有割合は特に限定されないが、１０質量％以上が好ましく、２０質量％以上がより好ましく、２５質量％以上がさらに好ましく、３０％質量％以上が特に好ましく、また、５０質量％以下が好ましく、４０質量％以下がより好ましく、３５質量％以下がさらに好ましい。前記下限値以上とすることでＵＶ洗浄処理後の撥インク性が良好となる傾向があり、また、前記上限値以下とすることで感光性樹脂組成物中の相溶性が良好となる傾向がある。アクリル樹脂（ａ）における多環式飽和炭化水素骨格の含有割合としては、例えば、１０～５０質量％であり、２０～４０質量％が好ましく、２５～３５質量％がより好ましく、３０～３５質量％がさらに好ましい。 Further, the content ratio of the polycyclic saturated hydrocarbon skeleton in the acrylic resin (a) is not particularly limited, but 10 mass% or more is preferable, 20 mass% or more is more preferable, 25 mass% or more is more preferable, and 30% mass % Or more is particularly preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, and 35% by mass or less is more preferable. By setting the content to the above lower limit or more, the ink repellency after UV cleaning tends to be good, and by setting the above upper limit or less, the compatibility in the photosensitive resin composition tends to be good. . The content ratio 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 30 to 35% by mass. % Is more preferred.
　また、アクリル樹脂（ａ）は、ポリ（パーフルオロアルキレンエーテル）鎖を含む架橋部を有することが好ましい。ポリ（パーフルオロアルキレンエーテル）鎖を含む架橋部を有する場合、架橋部が２以上の主鎖と結合するので、ＵＶ洗浄によってもポリ（パーフルオロアルキレンエーテル）鎖がアクリル樹脂（ａ）から脱離しにくく、隔壁表面に十分な量のフッ素原子を存在させることができ、その結果、ＵＶ洗浄処理後も撥インク性が良好となると考えられる。 Moreover, it is preferable that an acrylic resin (a) has a bridge | crosslinking part containing a poly (perfluoro alkylene ether) chain | strand. In the case of having a crosslinked portion containing a poly (perfluoroalkylene ether) chain, the crosslinked portion bonds to two or more main chains, so that the poly (perfluoroalkylene ether) chain is detached from the acrylic resin (a) even by UV washing. It is difficult that a sufficient amount of fluorine atoms can be present on the surface of the partition walls, and as a result, it is considered that the ink repellency becomes good even after the UV cleaning treatment.
　アクリル樹脂（ａ）の化学構造は特に限定されないが、ＵＶ洗浄後においても十分な撥インク性を示す観点から、ポリ（パーフルオロアルキレンエーテル）鎖を含む架橋部を有する部分構造として、下記一般式（１）で表される部分構造を含むものであることが好ましい。 The chemical structure of the acrylic resin (a) is not particularly limited, but from the viewpoint of showing sufficient ink repellency even after UV washing, as a partial structure having a cross-linked portion containing a poly (perfluoroalkylene ether) chain, the following general formula The partial structure represented by (1) is preferably included.
Figure JPOXMLDOC01-appb-C000013
  
Figure JPOXMLDOC01-appb-C000013
  
　式（１）中、Ｒ1は各々独立に、水素原子又はメチル基を表す。Ｘ1はパーフルオロアルキレン基を表す。式（１）中に含まれる複数のＸ1は同一のものでも異なるものでもよく、異なるものの場合にはランダム状に存在してもブロック状に存在していてもよい。Ｘ2は各々独立に、直接結合又は任意の２価の連結基を表す。ｎは１以上の整数である。＊は結合手を表す。 In formula (1), each R 1 independently represents a hydrogen atom or a methyl group. X 1 represents a perfluoroalkylene group. The plurality of X 1 included in the formula (1) may be the same or different, and in the case of different ones, they may be present in a random form or in a block form. Each X 2 independently represents a direct bond or any divalent linking group. n is an integer of 1 or more. * Represents a bond.
（Ｘ1）
　前記式（１）において、Ｘ1はパーフルオロアルキレン基を表す。
　パーフルオロアルキレン基の炭素数は特に限定されないが、通常１以上、２以上が好ましく、また、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで十分な撥インク性を示す傾向があり、前記上限値以下とすることで他の材料との相溶性が良好となる傾向がある。
　パーフルオロアルキレン基の具体例としては、下記一般式（１－ａ）～（１－ｅ）で表される基が挙げられる。 (X 1 )
In the formula (1), X 1 represents a perfluoroalkylene group.
The carbon number of the perfluoroalkylene group is not particularly limited, but is usually 1 or more and 2 or more, preferably 5 or less, and more preferably 3 or less. By setting it to the above lower limit value or the like, there is a tendency to show sufficient ink repellency, and by setting it to the above upper limit value, compatibility with other materials tends to be good.
Specific examples of the perfluoroalkylene group include groups represented by the following general formulas (1-a) to (1-e).
Figure JPOXMLDOC01-appb-C000014
  
Figure JPOXMLDOC01-appb-C000014
  
　式（１－ａ）～（１－ｅ）中、＊は結合手を表す。 In formulas (1-a) to (1-e), * represents a bond.
　前記式（１－ａ）～（１－ｅ）の中でも、高い撥インク性が得られるとの観点から、前記式（１－ａ）で表される基、前記式（１－ｂ）で表される基が好ましい。
　また、撥インク性の観点から、式（１）中に前記式（１－ａ）で表される基と前記式（１－ｂ）で表される基との両者が含まれることがより好ましい。前記式（１）中に含まれる前記式（１－ａ）で表される基と前記式（１－ｂ）で表される基のモル比は特に限定されないが、撥インク性の観点から、１：１０～１０：１が好ましく、１：４～４：１がより好ましく、１：２～２：１がさらに好ましい。 Among the above formulas (1-a) to (1-e), the group represented by the above formula (1-a), the above formula (1-b), and the like, from the viewpoint of obtaining high ink repellency. Preferred groups.
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) be included in the formula (1). . The molar ratio of the group represented by the formula (1-a) contained in the formula (1) and the group represented by the formula (1-b) is not particularly limited, but from the viewpoint of ink repellency, 1:10 to 10: 1 is preferable, 1: 4 to 4: 1 is more preferable, and 1: 2 to 2: 1 is more preferable.
（Ｘ2）
　前記式（１）中、Ｘ2は直接結合又は任意の２価の連結基を表す。
　任意の２価の連結基としては、－Ｏ－、－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－Ｏ－ＣＯ－ＮＨ－、置換基を有していてもよい２価の炭化水素基が挙げられる。該炭化水素基中に含まれる－ＣＨ2－の一部が、－Ｏ－、－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、及び－Ｏ－ＣＯ－ＮＨ－からなる群から選ばれる少なくとも１種で置き換えられていてもよい。 (X 2 )
In Formula (1), X 2 represents a direct bond or an arbitrary divalent linking group.
As the optional divalent linking group, —O—, —CO—O—, —CO—NH—, —O—CO—NH—, or a divalent hydrocarbon group which may have a substituent can be used. It can be mentioned. At least one selected from the group consisting of -O-, -CO-O-, -CO-NH-, and -O-CO-NH-, wherein a part of -CH 2- contained in the hydrocarbon group is It may be replaced by.
　２価の炭化水素基としては、２価の脂肪族基、２価の芳香族環基が挙げられる。
　２価の脂肪族基としては、直鎖状、分岐鎖状、又は環状のアルキレン基や、直鎖状、分岐鎖状、又は環状のアルケニレン基が挙げられる。
　２価の脂肪族基の炭素数は特に限定されないが、通常１以上、また５以下が好ましく、３以下がより好ましく、２以下がさらに好ましい。前記上限値以下とすることで撥インク性が高くなる傾向がある。
　２価の脂肪族基の具体例としては、メチレン基、エチレン基、エテニレン基、プロピレン基、プロペニレン基、ブチレン基、ブテニレン基などが挙げられる。
　２価の脂肪族基が有していてもよい置換基としては、水酸基、アルコキシ基などが挙げられる。 Examples of the divalent hydrocarbon group include a divalent aliphatic group and a divalent aromatic ring group.
Examples of the divalent aliphatic group include linear, branched or cyclic alkylene groups, and linear, branched or cyclic alkenylene groups.
The carbon number of the divalent aliphatic group is not particularly limited, but is usually 1 or more and 5 or less, preferably 3 or less, and more preferably 2 or less. By setting the content to the upper limit value or less, the ink repellency tends to be high.
Specific examples of the divalent aliphatic group include methylene, ethylene, ethenylene, propylene, propenylene, butylene, butenylene and the like.
Examples of the substituent which the divalent aliphatic group may have include a hydroxyl group and an alkoxy group.
　２価の芳香族環基としては、２価の芳香族炭化水素環基、２価の芳香族複素環基が挙げられる。
　２価の芳香族環基の炭素数は特に限定されないが、通常４以上、５以上が好ましく、６以上がより好ましく、また、３０以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。前記下限値以上とすることで他の材料との相溶性が良好となる傾向があり、また、前記上限値以下とすることで撥インク性が高くなる傾向がある。
　２価の芳香族炭化水素環基としては、例えば、２個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。
　また、２価の芳香族複素環基としては、例えば、２個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
　２価の芳香族環基が有していてもよい置換基としては、水酸基、アルキル基、アルコキシ基などが挙げられる。 Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
The carbon number of the divalent aromatic ring group is not particularly limited, but generally 4 or more and 5 or more is preferable, 6 or more is more preferable, 30 or less is preferable, 20 or less is more preferable, and 15 or less is more preferable. When the content is at least the lower limit, compatibility with other materials tends to be good, and when the content is at the upper limit or less, the ink repellency tends to be high.
Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring and a chrysene ring, which have two free valences. Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like can be mentioned.
Also, as the divalent aromatic heterocyclic group, for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring having two free valences , Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine Groups such as ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like can be mentioned.
Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, an alkyl group and an alkoxy group.
　Ｘ2の具体例としては、以下のものが挙げられる。 Specific examples of X 2 include the following.
Figure JPOXMLDOC01-appb-C000015
  
Figure JPOXMLDOC01-appb-C000015
  
　これらの中でも、撥インク性確保の観点、及び現像時の画素部における撥液剤の残存抑制の観点からは、２価の脂肪族基が好ましく、メチレン基、エチレン基がより好ましく、メチレン基がさらに好ましい。 Among these, from the viewpoint of securing the ink repellency and from the viewpoint of suppressing the remaining of the liquid repellent agent in the pixel portion during development, a divalent aliphatic group is preferable, a methylene group and an ethylene group are more preferable, and a methylene group is more preferable. preferable.
（ｎ）
　前記式（１）中、ｎは１以上の整数であるが、撥インク性の観点から、３～４０の整数であることが好ましく、６～３０の整数であることがより好ましく、１０～２０の整数であることがさらに好ましい。 (N)
In the above formula (1), n is an integer of 1 or more, but is preferably an integer of 3 to 40, more preferably an integer of 6 to 30, more preferably 10 to 20, from the viewpoint of ink repellency. More preferably, it is an integer of
　また、アクリル樹脂（ａ）は、多環式飽和炭化水素骨格及びエチレン性二重結合を有するものであるが、ＵＶ洗浄後の撥インク性と感度の観点から、多環式飽和炭化水素骨格及びエチレン性二重結合を含む部分構造として、下記一般式（２）で表される部分構造を含むものであることが好ましい。 The acrylic resin (a) has a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond, but from the viewpoint of ink repellency and sensitivity after UV washing, the polycyclic saturated hydrocarbon skeleton and It is preferable that it is a thing including the partial structure represented with following General formula (2) as a partial structure containing an ethylenic double bond.
Figure JPOXMLDOC01-appb-C000016
  
Figure JPOXMLDOC01-appb-C000016
  
　式（２）中、Ｒ2及びＲ3は各々独立に、水素原子又はメチル基を表す。Ｘ3は置換基を有していてもよい２価の多環式飽和炭化水素基を表す。Ｘ4はウレタン結合又はエステル結合を表す。Ｘ5は置換基を有していてもよい２価の炭化水素基を表す。＊は結合手を表す。 In formula (2), R 2 and R 3 each independently represent a hydrogen atom or a methyl group. X 3 represents a divalent polycyclic saturated hydrocarbon group which may have a substituent. X 4 represents a urethane bond or an ester bond. X 5 represents a divalent hydrocarbon group which may have a substituent. * Represents a bond.
（Ｘ3）
　前記式（２）中、Ｘ3は置換基を有していてもよい２価の多環式飽和炭化水素基を表す。 (X 3 )
In the formula (2), X 3 represents a polycyclic saturated hydrocarbon group which may have a substituent.
　２価の多環式飽和炭化水素基の炭素数は特に限定されないが、通常６以上、８以上が好ましく、９以上がより好ましく、１０以上がさらに好ましく、また２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記下限値以上とすることでＵＶ洗浄処理後の撥インク性の低下が抑制できる傾向があり、また、前記上限値以下とすることで撥インク性が高くなる傾向がある。
　２価の多環式飽和炭化水素基の具体例としては、アダマンチレン基、ジシクロペンタニレン基、ノルボルナニレン基、デカリニレン基などが挙げられ、これらの中でもＵＶ洗浄処理後の撥インク性の観点からアダマンチレン基が好ましい。
　２価の多環式飽和炭化水素基が有していてもよい置換基としては、アルコキシ基、ハロゲン原子、水酸基などが挙げられる。 The carbon number of the divalent polycyclic saturated hydrocarbon group is not particularly limited, but generally 6 or more and 8 or more is preferable, 9 or more is more preferable, 10 or more is more preferable, 20 or less is preferable, and 15 or less is more Preferably, 10 or less is more preferable. By setting the content to the above lower limit or more, the decrease in ink repellency after UV cleaning tends to be suppressed, and by setting the above upper limit or less, the ink repellency tends to be high.
Specific examples of the divalent polycyclic saturated hydrocarbon group include an adamantylene group, a dicyclopentanylene group, a norbornanylene group, and a decalinylene group. Among these, from the viewpoint of ink repellency after a UV washing treatment An adamantylene group is preferred.
Examples of the substituent which the divalent polycyclic saturated hydrocarbon group may have include an alkoxy group, a halogen atom, and a hydroxyl group.
（Ｘ4）
　前記式（２）中、Ｘ4はウレタン結合（－Ｏ－ＣＯ－ＮＨ－）又はエステル結合（－Ｏ－ＣＯ－）を表す。これらの中でもＵＶ洗浄処理後の撥インク性の低下抑制の観点から、ウレタン結合が好ましい。 (X 4 )
In the formula (2), X 4 represents a urethane bond (-O-CO-NH-) or an ester bond (-O-CO-). Among these, a urethane bond is preferable from the viewpoint of suppressing the decrease in ink repellency after the UV cleaning treatment.
（Ｘ5）
　前記式（２）中、Ｘ5は置換基を有していてもよい２価の炭化水素基を表す。
　２価の炭化水素基としては、２価の脂肪族基、２価の芳香族環基が挙げられる。 (X 5 )
In the formula (2), X 5 represents a divalent hydrocarbon group which may have a substituent.
Examples of the divalent hydrocarbon group include a divalent aliphatic group and a divalent aromatic ring group.
　２価の脂肪族基としては、直鎖状、分岐鎖状、又は環状のアルキレン基や、直鎖状、分岐鎖状、又は環状のアルケニレン基が挙げられる。
　２価の脂肪族基の炭素数は特に限定されないが、通常１以上、２以上が好ましく、また１０以下が好ましく、８以下がより好ましく、５以下がさらに好ましく、３以下が特に好ましい。前記下限値以上とすることでＵＶ洗浄処理後の撥インク性の低下が抑制できる傾向があり、前記上限値以下とすることで撥インク性が高くなる傾向がある。
　２価の脂肪族基の具体例としては、メチレン基、エチレン基、エテニレン基、プロピレン基、プロペニレン基、ブチレン基、ブテニレン基、シクロヘキシレン基、アダマンチレン基などが挙げられる。
　２価の脂肪族基が有していてもよい置換基としては、水酸基、アルコキシ基、ハロゲン原子などが挙げられる Examples of the divalent aliphatic group include linear, branched or cyclic alkylene groups, and linear, branched or cyclic alkenylene groups.
The carbon number of the divalent aliphatic group is not particularly limited, but is usually 1 or more and 2 or more, preferably 10 or less, more preferably 8 or less, still more preferably 5 or less, and particularly preferably 3 or less. By setting the content to the above lower limit or more, the decrease in ink repellency after UV cleaning tends to be suppressed, and by setting the above upper limit or less, the ink repellency tends to be high.
Specific examples of the divalent aliphatic group include methylene, ethylene, ethenylene, propylene, propenylene, butylene, butenylene, cyclohexylene and adamantylene groups.
Examples of the substituent which the divalent aliphatic group may have include a hydroxyl group, an alkoxy group, a halogen atom and the like.
　２価の芳香族環基としては、２価の芳香族炭化水素環基、２価の芳香族複素環基が挙げられる。
　２価の芳香族環基の炭素数は特に限定されないが、通常４以上、５以上が好ましく、６以上がより好ましく、また、３０以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。前記下限値以上とすることでＵＶ洗浄処理後の撥インク性の低下が抑制できる傾向があり、また、前記上限値以下とすることで撥インク性が高くなる傾向がある。
　２価の芳香族炭化水素環基としては、例えば、２個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。
　また、２価の芳香族複素環基としては、例えば、２個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
　２価の芳香族環基が有していてもよい置換基としては、水酸基、アルキル基、アルコキシ基、ハロゲン原子などが挙げられる。 Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
The carbon number of the divalent aromatic ring group is not particularly limited, but generally 4 or more and 5 or more is preferable, 6 or more is more preferable, 30 or less is preferable, 20 or less is more preferable, and 15 or less is more preferable. By setting the content to the above lower limit or more, the decrease in ink repellency after UV cleaning tends to be suppressed, and by setting the above upper limit or less, the ink repellency tends to be high.
Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring and a chrysene ring, which have two free valences. Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like can be mentioned.
Also, as the divalent aromatic heterocyclic group, for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring having two free valences , Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine Groups such as ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like can be mentioned.
Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, an alkyl group, an alkoxy group and a halogen atom.
　これらの中でも、撥インク性確保の観点、及び現像時の画素部における撥液剤の残存抑制の観点からは、２価の脂肪族基が好ましく、メチレン基、エチレン基がより好ましく、エチレン基がさらに好ましい。 Among these, from the viewpoint of securing the ink repellency and from the viewpoint of suppressing the remaining of the liquid repellent agent in the pixel portion during development, a divalent aliphatic group is preferable, a methylene group and an ethylene group are more preferable, and an ethylene group is more preferable. preferable.
　また、アクリル樹脂（ａ）はさらにその他の部分構造を含んでいてもよく、その他の部分構造の中でも発光部の残渣低減の観点から、下記一般式（３）で表される部分構造を含むものであることが好ましい。 In addition, the acrylic resin (a) may further include other partial structures, and among the other partial structures, it includes the partial structure represented by the following general formula (3) from the viewpoint of reducing the residue of the light emitting part Is preferred.
Figure JPOXMLDOC01-appb-C000017
  
Figure JPOXMLDOC01-appb-C000017
  
　式（３）中、Ｒ4は水素原子又はメチル基を表す。Ｘ6は置換基を有していてもよい１価の炭化水素基を表す。＊は結合手を表す。 In formula (3), R 4 represents a hydrogen atom or a methyl group. X 6 represents a monovalent hydrocarbon group which may have a substituent. * Represents a bond.
（Ｘ6）
　前記式（３）中、Ｘ6は置換基を有していてもよい１価の炭化水素基を表す。
　１価の炭化水素基としては、１価の脂肪族基、１価の芳香族環基が挙げられる。 (X 6 )
In the formula (3), X 6 represents a monovalent hydrocarbon group which may have a substituent.
Examples of monovalent hydrocarbon groups include monovalent aliphatic groups and monovalent aromatic ring groups.
　１価の脂肪族基としては、直鎖状、分岐鎖状、又は環状のアルキル基や、直鎖状、分岐鎖状、又は環状のアルケニル基が挙げられる。
　１価の脂肪族基の炭素数は特に限定されないが、通常１以上、２以上が好ましく、４以上がより好ましく、６以上がさらに好ましく、８以上が特に好ましく、また２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記下限値以上とすることでＵＶ洗浄処理後の撥インク性の低下が抑制できる傾向があり、また、前記上限値以下とすることで撥インク性が高くなる傾向がある。
　１価の脂肪族基の具体例としては、メチル基、エチル基、エテニル基、プロピル基、プロペニル基、ブチル基、ブテニル基、シクロヘキシル基、アダマンチル基などが挙げられる。
　１価の脂肪族基が有していてもよい置換基としては、水酸基、アルコキシ基、ハロゲン原子などが挙げられる The monovalent aliphatic group includes a linear, branched or cyclic alkyl group, and a linear, branched or cyclic alkenyl group.
The carbon number of the monovalent aliphatic group is not particularly limited, but is usually 1 or more and 2 or more, preferably 4 or more, more preferably 6 or more, particularly preferably 8 or more, and preferably 20 or less, 15 or less Is more preferable, and 10 or less is more preferable. By setting the content to the above lower limit or more, the decrease in ink repellency after UV cleaning tends to be suppressed, and by setting the above upper limit or less, the ink repellency tends to be high.
Specific examples of the monovalent aliphatic group include a methyl group, an ethyl group, an ethenyl group, a propyl group, a propenyl group, a butyl group, a butenyl group, a cyclohexyl group and an adamantyl group.
Examples of the substituent which the monovalent aliphatic group may have include a hydroxyl group, an alkoxy group, a halogen atom and the like.
　１価の芳香族環基としては、１価の芳香族炭化水素環基、１価の芳香族複素環基が挙げられる。
　１価の芳香族環基の炭素数は特に限定されないが、通常４以上、５以上が好ましく、６以上がより好ましく、また、３０以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。前記下限値以上とすることでＵＶ洗浄処理後の撥インク性の低下が抑制できる傾向があり、また、前記上限値以下とすることで撥インク性が高くなる傾向がある。
　１価の芳香族炭化水素環基としては、例えば、１個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。
　また、１価の芳香族複素環基としては、例えば、１個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
　１価の芳香族環基が有していてもよい置換基としては、水酸基、アルキル基、アルコキシ基などが挙げられる。 Examples of the monovalent aromatic ring group include monovalent aromatic hydrocarbon ring groups and monovalent aromatic heterocyclic groups.
The carbon number of the monovalent aromatic ring group is not particularly limited, but generally 4 or more and 5 or more is preferable, 6 or more is more preferable, 30 or less is preferable, 20 or less is more preferable, and 15 or less is more preferable. By setting the content to the above lower limit or more, the decrease in ink repellency after UV cleaning tends to be suppressed, and by setting the above upper limit or less, the ink repellency tends to be high.
The monovalent aromatic hydrocarbon ring group is, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, having one free valence. Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like can be mentioned.
In addition, as the monovalent aromatic heterocyclic group, for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring having one free valence , Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine Groups such as ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like can be mentioned.
Examples of the substituent which the monovalent aromatic ring group may have include a hydroxyl group, an alkyl group and an alkoxy group.
　これらの中でも、撥インク性の観点からは、置換基を有していてもよい１価の脂肪族基が好ましく、置換基を有していてもよいエチル基、置換基を有していてもよいアダマンチル基がより好ましく、置換基を有していてもよいアダマンチル基がさらに好ましい。 Among these, from the viewpoint of ink repellency, a monovalent aliphatic group which may have a substituent is preferable, and an ethyl group which may have a substituent or a substituent is preferable. The preferred adamantyl group is more preferable, and the adamantyl group which may have a substituent is more preferable.
　アクリル樹脂（ａ）が前記一般式（１）で表される部分構造を有する場合、その含有割合は限定されないが、１モル％以上が好ましく、２モル％以上がより好ましく、３モル％以上がさらに好ましく、５モル％以上がよりさらに好ましく、７モル％以上が特に好ましく、また、２０モル％以下が好ましく、１５モル％以下がより好ましく、１３モル％以下がさらに好ましく、１０モル％以下が特に好ましい。前記下限値以上とすることで撥インク性が高くなる傾向があり、前記上限値以下とすることで他の材料との相溶性が良好となる傾向がある。アクリル樹脂（ａ）が前記一般式（１）で表される部分構造を有する場合、その含有割合としては、例えば、１～２０モル％であり、２～２０モル％が好ましく、３～１５モル％がより好ましく、５～１５モル％がさらに好ましく、７～１０モル％がよりさらに好ましい。 When the acrylic resin (a) has a partial structure represented by the general formula (1), the content is not limited, but 1 mol% or more is preferable, 2 mol% or more is more preferable, and 3 mol% or more More preferably, 5 mol% or more is more preferable, 7 mol% or more is particularly preferable, 20 mol% or less is preferable, 15 mol% or less is more preferable, 13 mol% or less is more preferable, 10 mol% or less Particularly preferred. When the content is at least the lower limit, the ink repellency tends to be high, and when the content is at the upper limit or less, compatibility with other materials tends to be good. When the acrylic resin (a) has a partial structure represented by the above general formula (1), the content is, for example, 1 to 20 mol%, preferably 2 to 20 mol%, and 3 to 15 mol. % Is more preferable, 5 to 15 mol% is more preferable, and 7 to 10 mol% is even more preferable.
　一方で、アクリル樹脂（ａ）が前記一般式（２）で表される部分構造を有する場合、その含有割合は限定されないが、３０モル％以上が好ましく、４０モル％以上がより好ましく、５０モル％以上がさらに好ましく、６０モル％以上がよりさらに好ましく、７０モル％以上が特に好ましく、また、９５モル％以下が好ましく、９０モル％以下がより好ましい。前記下限値以上とすることで現像時の撥液剤の流出を抑制でき、撥インク性が高くなる傾向があり、また、前記上限値以下とすることで相対的に撥液剤中のフッ素原子の含有割合が高くなり、撥インク性が高くなる傾向がある。アクリル樹脂（ａ）が前記一般式（２）で表される部分構造を有する場合、その含有割合としては、例えば、３０～９５モル％であり、４０～９５モル％が好ましく、５０～９０モル％がより好ましく、６０～９０モル％がさらに好ましく、７０～９０モル％がよりさらに好ましい。 On the other hand, when the acrylic resin (a) has a partial structure represented by the general formula (2), the content is not limited, but 30 mol% or more is preferable, 40 mol% or more is more preferable, and 50 mol % Or more is more preferable, 60 mol% or more is further more preferable, 70 mol% or more is particularly preferable, 95 mol% or less is preferable, and 90 mol% or less is more preferable. By setting the content to the above lower limit or more, the outflow of the liquid repellent can be suppressed at the time of development, and the ink repellency tends to be high. Further, by setting the content to the above upper limit, the content of fluorine atoms in the liquid repellent is relatively contained. The proportion tends to be high, and the ink repellency tends to be high. When the acrylic resin (a) has a partial structure represented by the above general formula (2), the content ratio is, for example, 30 to 95 mol%, preferably 40 to 95 mol%, and 50 to 90 mol. % Is more preferable, 60 to 90 mol% is more preferable, and 70 to 90 mol% is still more preferable.
　一方で、アクリル樹脂（ａ）が前記一般式（３）で表される部分構造を有する場合、その含有割合は限定されないが、１モル％以上が好ましく、２モル％以上がより好ましく、３モル％以上がさらに好ましく、５モル％以上が特に好ましく、また、６０モル％以下が好ましく、５０モル％以下がより好ましく、４０モル％以下がさらに好ましく、３０モル％以下がよりさらに好ましく、２０モル％以下が特に好ましい。前記下限値以上とすることで発光部の残渣が低減できる傾向があり、前記上限値以下とすることで撥インク性が高くなる傾向がある。アクリル樹脂（ａ）が前記一般式（３）で表される部分構造を有する場合、その含有割合としては、例えば、１～６０モル％であり、２～５０モル％が好ましく、３～４０モル％がより好ましく、５～３０モル％がさらに好ましく、５～２０モル％がよりさらに好ましい。 On the other hand, when the acrylic resin (a) has a partial structure represented by the general formula (3), the content is not limited, but 1 mol% or more is preferable, 2 mol% or more is more preferable, 3 mol % Or more is more preferable, 5 mol% or more is particularly preferable, 60 mol% or less is preferable, 50 mol% or less is more preferable, 40 mol% or less is more preferable, 30 mol% or less is further more preferable, 20 mol % Or less is particularly preferred. By setting the content to the above lower limit or more, the residue of the light emitting portion tends to be reduced, and by setting the above upper limit or less, the ink repellency tends to be high. When the acrylic resin (a) has a partial structure represented by the above general formula (3), the content ratio is, for example, 1 to 60 mol%, preferably 2 to 50 mol%, and 3 to 40 mol. % Is more preferable, 5 to 30 mol% is more preferable, and 5 to 20 mol% is even more preferable.
　アクリル樹脂（ａ）が前記一般式（１）～（３）からなる群から選ばれる２種以上の部分構造を含む場合、アクリル樹脂（ａ）はランダム共重合体であってもよく、ブロック共重合体であってもよい。ブロック共重合体である場合、撥インク性の観点から、前記一般式（１）で表される部分構造を含むＡブロックと、前記一般式（２）で表される部分構造及び／又は前記一般式（３）で表される部分構造を含むＢブロックとを含む、ＡＢブロック共重合体であることが好ましい。 When the acrylic resin (a) contains two or more partial structures selected from the group consisting of the general formulas (1) to (3), the acrylic resin (a) may be a random copolymer, and a block copolymer It may be a polymer. When it is a block copolymer, from the viewpoint of ink repellency, the A block including the partial structure represented by the general formula (1), the partial structure represented by the general formula (2), and / or the general structure It is preferable that it is AB block copolymer including B block containing the partial structure represented by Formula (3).
　アクリル樹脂（ａ）の重量平均分子量は特に制限されず、低分子量の化合物でも、高分子量体であってもよい。アクリル樹脂（ａ）の重量平均分子量は、１０００以上が好ましく、５０００以上がより好ましく、８０００以上がよりさらに好ましく、１００００以上がさらに好ましく、また１０００００以下が好ましく、５００００以下がより好ましく、３００００以下がさらに好ましく、２００００以下が特に好ましい。前記範囲内とすることで、ポストベークによる撥液剤の流動性が抑えられ、隔壁から撥液剤が流出することを抑制できる傾向がある。アクリル樹脂（ａ）の重量平均分子量としては、例えば、１０００～１０００００であり、５０００～５００００が好ましく、８０００～３００００がより好ましく、１００００～２００００がさらに好ましい。 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, still more preferably 8000 or more, still more preferably 10000 or more, and preferably 100,000 or less, more preferably 50,000 or less, 30,000 or less More preferably, 20000 or less is particularly preferable. By setting the content in the above-mentioned range, the fluidity of the liquid repellent agent after the post-baking is suppressed, and the outflow of the liquid repellent agent from the partition wall tends to be suppressed. The weight average molecular weight of the acrylic resin (a) is, for example, 1000 to 100000, preferably 5000 to 50000, more preferably 8000 to 30000, and still more preferably 10000 to 20000.
　アクリル樹脂（ａ）がフッ素原子を含有する場合、その含有割合は特に限定されず、１質量％以上が好ましく、５質量％以上がより好ましく、８質量％以上がさらに好ましく、また、５０質量％以下が好ましく、２５質量％以下がより好ましい。前記下限値以上とすることで高い撥インク性が得られる傾向があり、前記上限値以下とすることで発光部におけるアクリル樹脂（ａ）の残存を抑制できる傾向がある。アクリル樹脂（ａ）がフッ素原子を含有する場合、その含有割合としては、例えば、１～５０質量％であり、５～２５質量％が好ましく、８～２５質量％がより好ましい。 When the acrylic resin (a) contains a fluorine atom, the content is not particularly limited, and 1 mass% or more is preferable, 5 mass% or more is more preferable, 8 mass% or more is more preferable, and 50 mass% The following are preferable, and 25 mass% or less is more preferable. There is a tendency for high ink repellency to be obtained by setting it to the above lower limit value, and there is a tendency to be able to suppress the remaining of the acrylic resin (a) in the light emitting part by setting it to the above upper limit value. When the acrylic resin (a) contains a fluorine atom, the content is, for example, 1 to 50% by mass, preferably 5 to 25% by mass, and more preferably 8 to 25% by mass.
　本発明の感光性樹脂組成物における（Ａ）撥液剤の含有割合は特に限定されないが、感光性樹脂組成物の全固形分中に０．０１質量％以上が好ましく、０．１質量％以上がより好ましく、０．２質量％以上がさらに好ましく、０．４質量％以上が特に好ましく、また、１質量％以下が好ましく、０．７質量％以下がより好ましく、０．５質量％以下がさらに好ましい。前記下限値以上とすることで高い撥インク性を示す傾向があり、また、前記上限値以下とすることで撥液剤の画素部への流出を抑制できる傾向がある。感光性樹脂組成物の全固形分中における（Ａ）撥液剤の含有割合としては、例えば、０．０１～１質量％であり、０．１～０．７質量％が好ましく、０．２～０．７質量％がより好ましく、０．４～０．５質量％がさらに好ましい。 Although the content ratio of (A) liquid repellent agent in the photosensitive resin composition of this invention is not specifically limited, 0.01 mass% or more is preferable in the total solid of the photosensitive resin composition, 0.1 mass% or more 0.2 mass% or more is more preferable, 0.4 mass% or more is particularly preferable, 1 mass% or less is preferable, 0.7 mass% or less is more preferable, 0.5 mass% or less is further preferable preferable. There is a tendency to show high ink repellency by setting it to the above lower limit value, and there is a tendency to be able to control the outflow of the liquid repellent to the pixel portion by setting it to the above upper limit value. The content ratio of the (A) liquid repellent agent in the total solid content of the photosensitive resin composition is, for example, 0.01 to 1% by mass, preferably 0.1 to 0.7% by mass, and 0.2 to 7% by mass. 0.7% by mass is more preferable, and 0.4 to 0.5% by mass is more preferable.
　本発明の感光性樹脂組成物におけるアクリル樹脂（ａ）の含有割合も特に限定されないが、感光性樹脂組成物の全固形分中に０．０１質量％以上が好ましく、０．１質量％以上がより好ましく、０．２質量％以上がさらに好ましく、０．４質量％以上が特に好ましく、また、１質量％以下が好ましく、０．７質量％以下がより好ましく、０．５質量％以下がさらに好ましい。前記下限値以上とすることで撥インク性が高くなる傾向があり、また、前記上限値以下とすることでアクリル樹脂（ａ）の画素部への流出を抑制できる傾向がある。感光性樹脂組成物の全固形分中におけるアクリル樹脂（ａ）の含有割合としては、例えば、０．０１～１質量％であり、０．１～０．７質量％が好ましく、０．２～０．７質量％がより好ましく、０．４～０．５質量％がさらに好ましい。 The content ratio of the acrylic resin (a) in the photosensitive resin composition of the present invention is also not particularly limited, but preferably 0.01% by mass or more, and preferably 0.1% by mass or more in the total solid content of the photosensitive resin composition. 0.2 mass% or more is more preferable, 0.4 mass% or more is particularly preferable, 1 mass% or less is preferable, 0.7 mass% or less is more preferable, 0.5 mass% or less is further preferable preferable. The ink repellent property tends to be increased by setting the lower limit value or more, and the outflow to the pixel portion of the acrylic resin (a) can be suppressed by setting the upper limit value or less. The content ratio of the acrylic resin (a) in the total solid content of the photosensitive resin composition is, for example, 0.01 to 1% by mass, preferably 0.1 to 0.7% by mass, and 0.2 to 7% by mass. 0.7% by mass is more preferable, and 0.4 to 0.5% by mass is more preferable.
　本発明の感光性樹脂組成物における（Ａ）撥液剤は、アクリル樹脂（ａ）以外のその他の撥液剤を含有してもよい。 The liquid repellent agent (A) in the photosensitive resin composition of the present invention may contain another liquid repellent agent other than the acrylic resin (a).
　その他の撥液剤の具体例としては、例えばパーフルオロアルキルスルホン酸、パーフルオロアルキルカルボン酸、パーフルオロアルキルアルキレンオキシド付加物、パーフルオロアルキルトリアルキルアンモニウム塩、パーフルオロカルボン酸エステル、パーフルオロアルキル燐酸エステル、パーフルオロアルキル基を含むオリゴマー、パーフルオロアルキレン基を含むオリゴマーなどのフッ素原子含有有機化合物を挙げることができる。 Specific examples of other liquid repellents include, for example, perfluoroalkylsulfonic acid, perfluoroalkylcarboxylic acid, perfluoroalkylalkylene oxide adduct, perfluoroalkyltrialkylammonium salt, perfluorocarboxylic acid ester, perfluoroalkyl phosphoric acid ester And fluorine atom-containing organic compounds such as oligomers containing a perfluoroalkyl group and oligomers containing a perfluoroalkylene group.
　これらのフッ素原子含有有機化合物の市販品としては、ＤＩＣ社製「メガファック（登録商標、以下同じ。）Ｆ１１６」、「メガファックＦ１２０」、「メガファックＦ１４２Ｄ」、「メガファックＦ１４４Ｄ」、「メガファックＦ１５０」、「メガファックＦ１６０」、「メガファックＦ１７１」、「メガファックＦ１７２」、「メガファックＦ１７３」、「メガファックＦ１７７」、「メガファックＦ１７８Ａ」、「メガファックＦ１７８Ｋ」、「メガファックＦ１７９」、「メガファックＦ１８３」、「メガファックＦ１８４」、「メガファックＦ１９１」、「メガファックＦ８１２」、「メガファックＦ８１５」、「メガファックＦ８２４」、「メガファックＦ８３３」、「メガファックＲＳ１０１」、「メガファックＲＳ１０２」「メガファックＲＳ１０５」、「メガファックＲＳ２０１」、「メガファックＲＳ２０２」、「メガファックＲＳ３０１」、「メガファックＲＳ３０３」「メガファックＲＳ３０４」、「メガファックＲＳ４０１」、「メガファックＲＳ４０２」、「メガファックＲＳ５０１」、「メガファックＲＳ５０２」、「メガファックＲＳ－５６」、「メガファックＲＳ－７２－Ｋ」、「ＤＥＦＥＮＳＡ（登録商標、以下同じ。）　ＭＣＦ３００」、「ＤＥＦＥＮＳＡ　ＭＣＦ３１０」、「ＤＥＦＥＮＳＡ　ＭＣＦ３１２」、「ＤＥＦＥＮＳＡ　ＭＣＦ３２３」、スリーエムジャパン社製「フロラードＦＣ－４３０」、「フロラードＦＣ－４３１」、「ＦＣ－４４３０」、「ＦＣ－４４３２」、ＡＧＣ社製「アサヒガード（登録商標。）ＡＧ－７１０」、ＡＧＣセイミケミカル社製「サーフロン（登録商標、以下同じ。）Ｓ－３８２」、「サーフロンＳＣ－１０１」、「サーフロンＳＣ－１０２」、「サーフロンＳＣ－１０３」、「サーフロンＳＣ－１０４」、「サーフロンＳＣ－１０５」、「サーフロンＳＣ－１０６」、ダイキン工業社製「オプツール（登録商標。）ＤＡＣ－ＨＰ」などの商品名で市販されているフッ素原子含有有機化合物を使用することができる。 As commercial products of these fluorine atom-containing organic compounds, "Megafuck (registered trademark, the same as the following) F116", "Megafuck F120", "Megafuck F142D", "Megafuck F144D", "Megafuck (registered trademark), the same below" Fuck F150 "," Megafuck F160 "," Megafuck F171 "," Megafuck F173 "," Megafuck F177 "," Megafuck F178A "," Megafuck F178K "," Megafuck F179 " “Megafuck F183”, “Megafuck F184”, “Megafuck F191”, “Megafuck F812”, “Megafuck F824”, “Megafuck F833”, “Megafuck RS101”, "Megafuck RS102 "Megafuck RS105", "Megafuck RS201", "Megafuck RS202", "Megafuck RS303", "Megafuck RS304", "Megafuck RS401", "Megafuck RS402", "Megafuck "RS501", "Megafuck RS502", "Megafuck RS-56", "Megafuck RS-72-K", "DEFENSA (registered trademark, the same applies hereinafter) MCF 300", "DEFENSA MCF 310", "DEFENSA MCF 312", “DEFENSA MCF 323”, “Florard FC-430” manufactured by 3M Japan Ltd., “Florrad FC-431”, “FC-4430”, “FC-4432”, “Asahi Guard (registered trademark)” AG-71 manufactured by AGC “AGA SEIMICHEMIC Co., Ltd.“ Surflon (registered trademark, the same as the following) S-382 ”,” “Surfron SC-101,” “Surfron SC-102,” “Surfron SC-103,” “Surflon SC-104,” A fluorine atom-containing organic compound commercially available under a trade name such as "Surflon SC-105", "Surflon SC-106", "Optool (registered trademark) DAC-HP" manufactured by Daikin Industries, Ltd. can be used.
　（Ａ）撥液剤中のアクリル樹脂（ａ）の含有割合も特に限定されないが、５０質量％以上が好ましく、８０質量％以上がより好ましく、９０質量％以上がさらに好ましく、また、通常１００質量％以下である。前記下限値以上とすることでＵＶ洗浄処理後の撥インク性の低下が抑制される傾向がある。（Ａ）撥液剤中のアクリル樹脂（ａ）の含有割合としては、例えば、５０～１００質量％であり、８０～１００質量％が好ましく、９０～１００質量％がより好ましい。 The content ratio of the acrylic resin (a) in the liquid repellent agent (A) is also not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and usually 100% by mass It is below. By setting the content to the above lower limit value or more, there is a tendency that the decrease in the ink repellency after the UV cleaning treatment is suppressed. The content ratio of the acrylic resin (a) in the liquid repellent agent (A) is, for example, 50 to 100% by mass, preferably 80 to 100% by mass, and more preferably 90 to 100% by mass.
　（Ａ）撥液剤がその他の撥液剤を含有する場合、（Ａ）撥液剤中のその他の撥液剤の含有割合は特に限定されないが、１０質量％以上が好ましく、１５質量％以上がより好ましく、２０質量％以上がさらに好ましく、また、５０質量％以下が好ましく、４０質量％以下がより好ましく、３０質量％以下がさらに好ましい。前記下限値以上とすることで画素部の残渣が抑制できる傾向があり、また、前記上限値以下とすることでＵＶ洗浄処理後の撥インク性の低下が抑制される傾向がある。（Ａ）撥液剤がその他の撥液剤を含有する場合、（Ａ）撥液剤中のその他の撥液剤の含有割合としては、例えば、１０～５０質量％であり、１５～４０質量％が好ましく、２０～３０質量％がより好ましい。 When the liquid repellent agent contains (A) another liquid repellent agent, the content ratio of the other liquid repellent agent in (A) liquid repellent agent is not particularly limited, but 10 mass% or more is preferable, and 15 mass% or more is more preferable, 20 mass% or more is further preferable, 50 mass% or less is preferable, 40 mass% or less is more preferable, and 30 mass% or less is more preferable. By setting the lower limit value or more, the residue of the pixel portion tends to be suppressed, and by setting the upper limit value or less, the decrease in the ink repellency after the UV cleaning processing tends to be suppressed. When the liquid repellent agent contains (A) another liquid repellent agent, the content ratio of the other liquid repellent agent in (A) liquid repellent agent is, for example, 10 to 50% by mass, preferably 15 to 40% by mass, 20 to 30% by mass is more preferable.
［１－１－２］（Ｂ）成分；アルカリ可溶性樹脂
　本発明の感光性樹脂組成物は、（Ｂ）アルカリ可溶性樹脂を含有する。アルカリ可溶性樹脂としてはアルカリ現像液で現像可能な樹脂であれば特に限定されない。アルカリ可溶性樹脂としては、カルボキシル基及び／又は水酸基を含有する各種樹脂が挙げられる。その中でも、適度なテーパー角の隔壁が得られ、ポストベーク時の隔壁表面の熱溶融による撥液剤の流出が抑えられて撥インク性を保持できるなどの観点から、カルボキシル基を含有する樹脂が好ましい。 [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 is a resin that can be developed with an alkali developer. As alkali-soluble resin, various resin containing a carboxyl group and / or a hydroxyl group is mentioned. Among them, a resin having a carboxyl group is preferable from the viewpoint that a partition having an appropriate taper angle can be obtained, the outflow of the liquid repellent agent can be suppressed by heat melting of the partition surface during post baking, and the ink repellency can be maintained. .
［エチレン性二重結合を有するアルカリ可溶性樹脂（ｂ）］
　本発明の感光性樹脂組成物において、（Ｂ）アルカリ可溶性樹脂は、エチレン性二重結合を有するアルカリ可溶性樹脂（ｂ）（以下、「アルカリ可溶性樹脂（ｂ）」と略記する場合がある。）を含むことが好ましい。エチレン性二重結合を有するアルカリ可溶性樹脂（ｂ）を含むことで、感度が高くなり、現像時の撥液剤流出を抑制することで得られる隔壁の撥インク性が高くなる傾向がある。 [Alkali-soluble resin (b) having an ethylenic double bond]
In the photosensitive resin composition of the present invention, the (B) alkali-soluble resin is an alkali-soluble resin (b) having an ethylenic double bond (hereinafter sometimes referred to as "alkali-soluble resin (b)"). Is preferred. By including the alkali-soluble resin (b) having an ethylenic double bond, the sensitivity tends to be high, and the ink repellency of the partition wall obtained by suppressing the liquid repellent agent outflow during development tends to be high.
　エチレン性二重結合を有するアルカリ可溶性樹脂（ｂ）の具体的構造は特に限定されないが、現像溶解性の観点から、エポキシ（メタ）アクリレート樹脂（ｂ１）及び／又はアクリル共重合樹脂（ｂ２）が好ましく、アウトガス低減の観点からはエポキシ（メタ）アクリレート樹脂（ｂ１）がより好ましい。
　以下に、エポキシ（メタ）アクリレート樹脂（ｂ１）について詳述する。 The specific structure of the alkali-soluble resin (b) having an ethylenic double bond is not particularly limited, but from the viewpoint of development solubility, the epoxy (meth) acrylate resin (b1) and / or the acrylic copolymer resin (b2) 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.
［エポキシ（メタ）アクリレート樹脂（ｂ１）］
　エポキシ（メタ）アクリレート樹脂（ｂ１）は、エポキシ樹脂にエチレン性不飽和結合（エチレン性二重結合）を有する酸又はエステル化合物を付加し、更に多塩基酸又はその無水物を付加させた樹脂である。例えば、エポキシ樹脂のエポキシ基に、エチレン性不飽和結合を有する酸のカルボキシル基が開環付加されることにより、エポキシ樹脂にエステル結合（－ＣＯＯ－）を介してエチレン性不飽和結合が付加されると共に、その際生じた水酸基に、多塩基酸無水物の一方のカルボキシル基が付加されたものが挙げられる。また多塩基酸無水物を付加するときに、多価アルコールを同時に添加して付加されたものも挙げられる。さらに、上記反応で得られた樹脂のカルボキシル基に、更に反応し得る官能基を有する化合物を反応させて得られる樹脂も、上記エポキシ（メタ）アクリレート樹脂（ｂ１）に含まれる。
　このように、エポキシ（メタ）アクリレート樹脂は化学構造上、実質的にエポキシ基を有さず、かつ「（メタ）アクリレート」に限定されるものではないが、エポキシ化合物（エポキシ樹脂）が原料であり、かつ、「（メタ）アクリレート」が代表例であるので慣用に従いこのように命名されている。 [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. is there. For example, by the ring-opening addition of the carboxyl group of the acid having an ethylenically unsaturated bond to the epoxy group of the epoxy resin, the ethylenically unsaturated bond is added to the epoxy resin via an ester bond (-COO-) In addition to the above, one in which one carboxyl group of polybasic acid anhydride is added to the hydroxyl group generated at that time is mentioned. Moreover, when adding a polybasic acid anhydride, what was simultaneously added and added the polyhydric alcohol is also mentioned. Furthermore, a resin obtained by reacting a compound having a functional group capable of further reacting with the carboxyl group of the resin obtained by the above reaction is also included in the epoxy (meth) acrylate resin (b1).
Thus, the epoxy (meth) acrylate resin does not have an epoxy group substantially due to the chemical structure, and is not limited to "(meth) acrylate", but an epoxy compound (epoxy resin) is a raw material And because it is a representative example, "(meth) acrylate" is so named according to conventional practice.
　ここでエポキシ樹脂とは、熱硬化により樹脂を形成する以前の原料化合物をも含めて言うこととし、そのエポキシ樹脂としては、公知のエポキシ樹脂の中から適宜選択して用いることができる。また、エポキシ樹脂は、フェノール性化合物とエピハロヒドリンとを反応させて得られる化合物を用いることができる。フェノール性化合物としては、２価もしくは２価以上のフェノール性水酸基を有する化合物が好ましく、単量体でも重合体でもよい。
　具体的には、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、ビフェニルノボラックエポキシ樹脂、トリスフェノールエポキシ樹脂、フェノールとジシクロペンタンとの重合体のエポキシ化物、ジハイドロオキシルフルオレン型エポキシ樹脂、ジハイドロオキシルアルキレンオキシルフルオレン型エポキシ樹脂、９，９－ビス（４’－ヒドロキシフェニル）フルオレンのジグリシジルエーテル化物、１，１－ビス（４’－ヒドロキシフェニル）アダマンタンのジグリシジルエーテル化物などが挙げられ、このように主鎖に芳香族環を有するものを好適に用いることができる。 The term "epoxy resin" as used herein also includes raw material compounds prior to the formation of a resin by heat curing, and the epoxy resin can be appropriately selected and used from known epoxy resins. Moreover, the epoxy resin can use the compound obtained by making a phenolic compound and an epihalohydrin react. The phenolic compound is preferably a compound having a divalent or divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, phenol and dicyclopentane Of epoxidized polymers of polymers, dihydroxyl fluorene type epoxy resin, dihydroxyl alkylene oxyl fluorene type epoxy resin, diglycidyl ether of 9,9-bis (4'-hydroxyphenyl) fluorene, 1,1-bis There may be mentioned diglycidyl ether of (4′-hydroxyphenyl) adamantane and the like, and thus one having an aromatic ring in the main chain can be suitably used.
　中でも、硬化膜強度の観点から、ビスフェノールＡ型エポキシ樹脂、フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、フェノールとジシクロペンタジエンとの重合体のエポキシ化物、９，９－ビス（４’－ヒドロキシフェニル）フルオレンのエポキシ化物、などが好ましく、ビスフェノールＡ型エポキシ樹脂が更に好ましい。 Among them, from the viewpoint of cured film strength, bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, epoxy compound of polymer of phenol and dicyclopentadiene, 9, 9-bis (4'-hydroxyphenyl) Epoxide compounds of fluorene and the like are preferable, and bisphenol A epoxy resin is more preferable.
　エチレン性不飽和結合を有する酸としては、例えば、（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、シトラコン酸等、および、ペンタエリスリトールトリ（メタ）アクリレート無水コハク酸付加物、ペンタエリスリトールトリ（メタ）アクリレートテトラヒドロ無水フタル酸付加物、ジペンタエリスリトールペンタ（メタ）アクリレート無水コハク酸付加物、ジペンタエリスリトールペンタ（メタ）アクリレート無水フタル酸付加物、ジペンタエリスリトールペンタ（メタ）アクリレートテトラヒドロ無水フタル酸付加物、（メタ）アクリル酸とε－カプロラクトンとの反応生成物などが挙げられる。中でも、感度の観点から、（メタ）アクリル酸が好ましい。 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 adduct, pentaerythritol trihydrate. (Meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride Examples include acid adducts and reaction products of (meth) acrylic acid and ε-caprolactone. Among them, (meth) acrylic acid is preferable from the viewpoint of sensitivity.
　多塩基酸（無水物）としては、例えば、コハク酸、マレイン酸、イタコン酸、フタル酸、テトラヒドロフタル酸、３－メチルテトラヒドロフタル酸、４－メチルテトラヒドロフタル酸、３－エチルテトラヒドロフタル酸、４－エチルテトラヒドロフタル酸、ヘキサヒドロフタル酸、３－メチルヘキサヒドロフタル酸、４－メチルヘキサヒドロフタル酸、３－エチルヘキサヒドロフタル酸、４－エチルヘキサヒドロフタル酸、トリメリット酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸、ビフェニルテトラカルボン酸、およびそれらの無水物などが挙げられる。これらは１種を単独でも用いてもよく、２種以上を併用して用いてもよい。これらの中でも、現像後の画素部の残渣低減の観点から、コハク酸無水物、マレイン酸無水物、イタコン酸無水物が好ましく、コハク酸無水物がより好ましい。 Examples of polybasic acids (anhydrides) 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 And benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and anhydrides thereof. One of these may be used alone, or two or more of these may be used in combination. Among these, from the viewpoint of reducing the residue in the pixel portion after development, succinic anhydride, maleic anhydride and itaconic anhydride are preferable, and succinic anhydride is more preferable.
　多価アルコールを用いることで、エポキシ（メタ）アクリレート樹脂（ｂ１）の分子量を増大させ、分子中に分岐を導入することが出来、分子量と粘度のバランスをとることができる傾向がある。また、分子中への酸基の導入率を増やすことができ、感度や密着性等のバランスがとれやすい傾向がある。
　多価アルコールとしては、例えばトリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリメチロールエタン、１，２，３－プロパントリオールの中から選ばれる１種又は２種以上の多価アルコールであることが好ましい。 By using a polyhydric alcohol, the molecular weight of the epoxy (meth) acrylate resin (b1) can be increased, branching can be introduced into the molecule, and there is a tendency to be able to balance molecular weight and viscosity. In addition, the introduction rate of the acid group into the molecule can be increased, and the balance of sensitivity and adhesion tends to be easily maintained.
Examples of polyhydric alcohols include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane and 1,2,3-propanetriol. Is preferred.
　エポキシ（メタ）アクリレート樹脂（ｂ１）の酸価は特に限定されないが、１０ｍｇ－ＫＯＨ／ｇ以上が好ましく、２０ｍｇ－ＫＯＨ／ｇ以上がより好ましく、４０ｍｇ－ＫＯＨ／ｇ以上がさらに好ましく、６０ｍｇ－ＫＯＨ／ｇ以上がよりさらに好ましく、また、２００ｍｇ－ＫＯＨ／ｇ以下が好ましく、１８０ｍｇ－ＫＯＨ／ｇ以下がより好ましく、１５０ｍｇ－ＫＯＨ／ｇ以下がさらに好ましく、１２０ｍｇ－ＫＯＨ／ｇ以下がよりさらに好ましく、１００ｍｇ－ＫＯＨ／ｇ以下が特に好ましい。前記下限値以上とすることで残渣が低減し、テーパー角が高くなる傾向があり、また、前記上限値以下とすることで素子発光時のアウトガスが低減する傾向がある。エポキシ（メタ）アクリレート樹脂（ｂ１）の酸価としては、例えば、１０～２００ｍｇ－ＫＯＨ／ｇであり、１０～１８０ｍｇ－ＫＯＨ／ｇが好ましく、２０～１５０ｍｇ－ＫＯＨ／ｇがより好ましく、４０～１２０ｍｇ－ＫＯＨ／ｇがさらに好ましく、６０～１００ｍｇ－ＫＯＨ／ｇがよりさらに好ましい。 The acid value of the epoxy (meth) acrylate resin (b1) is not particularly limited, but 10 mg-KOH / g or more is preferable, 20 mg-KOH / g or more is more preferable, 40 mg-KOH / g or more is more preferable, 60 mg-KOH / G or more is more preferable, 200 mg-KOH / g or less is preferable, 180 mg-KOH / g or less is more preferable, 150 mg-KOH / g or less is more preferable, 120 mg-KOH / g or less is more preferable, Particularly preferred is 100 mg-KOH / g or less. By setting the lower limit value or more, the residue tends to be reduced and the taper angle tends to be high, and by setting the upper limit value or less, outgassing at the time of element light emission tends to be reduced. The acid value of the epoxy (meth) acrylate resin (b1) is, for example, 10 to 200 mg-KOH / g, preferably 10 to 180 mg-KOH / g, more preferably 20 to 150 mg-KOH / g, and 40 to 50 120 mg-KOH / g is more preferable, and 60 to 100 mg-KOH / g is even more preferable.
　エポキシ（メタ）アクリレート樹脂（ｂ１）の重量平均分子量（Ｍｗ）は特に限定されないが、通常１０００以上、好ましくは２０００以上、より好ましくは３０００以上、さらに好ましくは４０００以上、よりさらに好ましくは５０００以上、特に好ましくは６０００以上、最も好ましくは７０００以上であり、また、通常３００００以下、好ましくは２００００以下、より好ましくは１５０００以下、さらに好ましくは１００００以下である。前記下限値以上とすることで素子発光時のアウトガスが低減する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。エポキシ（メタ）アクリレート樹脂（ｂ１）の重量平均分子量（Ｍｗ）としては、例えば、１０００～３００００であり、２０００～２００００が好ましく、３０００～２００００がより好ましく、４０００～１５０００がさらに好ましく、５０００～１５０００がよりさらに好ましく、６０００～１００００が特に好ましく、７０００～１００００が最も好ましい。 The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (b1) is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, still more preferably 5000 or more, Particularly preferably, it is 6,000 or more, most preferably 7,000 or more, and usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, and further preferably 10,000 or less. By setting the lower limit value or more, outgassing at the time of element light emission tends to be reduced, and by setting the upper limit value or less, the 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, and 5000 to 15000. Are more preferred, 6000 to 10000 are particularly preferred, and 7000 to 10000 are most preferred.
　（Ｂ）アルカリ可溶性樹脂がエポキシ（メタ）アクリレート樹脂（ｂ１）を含む場合、（Ｂ）アルカリ可溶性樹脂に含まれるエポキシ（メタ）アクリレート樹脂（ｂ１）の含有割合は特に限定されないが、３０質量％以上が好ましく、５０質量％以上がより好ましく、７０質量％以上がさらに好ましく、８０質量％以上がよりさらに好ましく、９０質量％以上が特に好ましく、また、通常１００質量％以下である。前記下限値以上とすることでアウトガスが低減する傾向がある。（Ｂ）アルカリ可溶性樹脂がエポキシ（メタ）アクリレート樹脂（ｂ１）を含む場合、（Ｂ）アルカリ可溶性樹脂に含まれるエポキシ（メタ）アクリレート樹脂（ｂ１）の含有割合としては、例えば、３０～１００質量％であり、５０～１００質量％が好ましく、７０～１００質量％がより好ましく、８０～１００質量％がさらに好ましく、９０～１００質量％がよりさらに好ましい。 When the alkali-soluble resin (B) contains an 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 30% by mass The above is preferable, 50 mass% or more is more preferable, 70 mass% or more is more preferable, 80 mass% or more is further more preferable, 90 mass% or more is particularly preferable, and usually 100 mass% or less. Outgassing tends to be reduced by setting it to the above lower limit value or more. When the alkali-soluble resin (B) contains an epoxy (meth) acrylate resin (b1), the content of the epoxy (meth) acrylate resin (b1) contained in the (B) alkali-soluble resin is, for example, 30 to 100 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.
　エポキシ（メタ）アクリレート樹脂（ｂ１）は、従来公知の方法により合成することができる。具体的には、前記エポキシ樹脂を有機溶剤に溶解させ、触媒と熱重合禁止剤の共存下、前記エチレン性不飽和結合を有する酸又はエステル化合物を加えて付加反応させ、更に多塩基酸又はその無水物を加えて反応を続ける方法を用いることができる。 The epoxy (meth) acrylate resin (b1) can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and the acid or ester compound having an ethylenic unsaturated bond is added in the coexistence of a catalyst and a thermal polymerization inhibitor to cause addition reaction, and further a polybasic acid or the acid Anhydrous can be added to continue the reaction.
　ここで、反応に用いる有機溶剤としては、メチルエチルケトン、シクロヘキサノン、ジエチレングリコールエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテートなどの有機溶剤の１種または２種以上が挙げられる。また、上記触媒としては、トリエチルアミン、ベンジルジメチルアミン、トリベンジルアミン等の第３級アミン類、テトラメチルアンモニウムクロライド、メチルトリエチルアンモニウムクロライド、テトラエチルアンモニウムクロライド、テトラブチルアンモニウムクロライド、トリメチルベンジルアンモニウムクロライドなどの第４級アンモニウム塩類、トリフェニルホスフィンなどの燐化合物、トリフェニルスチビンなどのスチビン類などの１種または２種以上が挙げられる。更に、熱重合禁止剤としては、ハイドロキノン、ハイドロキノンモノメチルエーテル、メチルハイドロキノンなどの１種または２種以上が挙げられる。 Here, as an organic solvent used for reaction, 1 type (s) or 2 or more types of organic solvents, such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, are mentioned. Further, as the above catalyst, tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine, tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride and the like One or more of quaternary ammonium salts, phosphorus compounds such as triphenyl phosphine, and stibines such as triphenyl stibine may be used. Furthermore, as a thermal polymerization inhibitor, 1 type (s) or 2 or more types, such as hydroquinone, hydroquinone monomethyl ether, a methyl hydroquinone, etc. are mentioned.
　また、エチレン性不飽和結合を有する酸又はエステル化合物としては、エポキシ樹脂のエポキシ基の１化学当量に対して通常０．７～１．３化学当量、好ましくは０．９～１．１化学当量となる量とすることができる。また、付加反応時の温度としては、通常６０～１５０℃、好ましくは８０～１２０℃の温度とすることができる。更に、多塩基酸（無水物）の使用量としては、前記付加反応で生じた水酸基の１化学当量に対して、通常０．１～１．２化学当量、好ましくは０．２～１．１化学当量となる量とすることができる。 The acid or ester compound having an ethylenically unsaturated bond is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, per 1 chemical equivalent of the epoxy group of the epoxy resin. The amount can be The temperature during the addition reaction may be usually 60 to 150 ° C., preferably 80 to 120 ° C. Furthermore, the amount of the polybasic acid (anhydride) used is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1, per 1 chemical equivalent of the hydroxyl group produced in the addition reaction. The amount can be a chemical equivalent.
　エポキシ（メタ）アクリレート樹脂（ｂ１）は、素子発光時のアウトガスの観点から、下記一般式（ｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂（ｂ１－１）（以下、「エポキシ（メタ）アクリレート樹脂（ｂ１－１）」と称する場合がある。）、下記一般式（ｉｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂（ｂ１－２）（以下、「エポキシ（メタ）アクリレート樹脂（ｂ１－２）」と称する場合がある。）、及び下記一般式（ｉｉｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂（ｂ１－３）（以下、「エポキシ（メタ）アクリレート樹脂（ｂ１－３）」と称する場合がある。）からなる群から選ばれる少なくとも１種を含有することが好ましい。 The epoxy (meth) acrylate resin (b1) is an epoxy (meth) acrylate resin (b1-1) including a partial structure represented by the following general formula (i) from the viewpoint of outgassing at the time of element light emission (hereinafter referred to as “epoxy Epoxy (meth) acrylate resin (b1-2) (hereinafter referred to as “epoxy (meth) acrylate resin (b1-1)”), which contains a partial structure represented by the following general formula (ii) Epoxy (meth) acrylate resin (b1-3) (hereinafter referred to as “epoxy (meth) acrylate resin (b1-2)”), and a partial structure represented by the following general formula (iii) It is preferable to contain at least one selected from the group consisting of (meth) acrylate resin (b1-3).
　エポキシ（メタ）アクリレート樹脂（ｂ１）は、これらの中でも素子発光時のアウトガス低減の観点から、下記一般式（ｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂（ｂ１－１）であることが好ましい。理由の一つとしては、剛直な主骨格を有することで熱に対して分解しづらいことなどが推測される。 Among them, the epoxy (meth) acrylate resin (b1) is an epoxy (meth) acrylate resin (b1-1) including a partial structure represented by the following general formula (i) from the viewpoint of reducing outgassing at the element light emission. Is preferred. One of the reasons is that it is difficult to be decomposed against heat by having a rigid main skeleton.
Figure JPOXMLDOC01-appb-C000018
  
Figure JPOXMLDOC01-appb-C000018
  
　式（ｉ）中、Ｒaは水素原子又はメチル基を表し、Ｒbは置換基を有していてもよい２価の炭化水素基を表す。式（ｉ）中のベンゼン環は、更に任意の置換基により置換されていてもよい。＊は結合手を表す。 In formula (i), R a represents a hydrogen atom or a methyl group, and R b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) may be further substituted by any substituent. * Represents a bond.
（Ｒb）
　前記式（ｉ）において、Ｒbは置換基を有していてもよい２価の炭化水素基を表す。
　２価の炭化水素基としては、２価の脂肪族基、２価の芳香族環基、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基が挙げられる。 (R b )
In the formula (i), R b represents a divalent hydrocarbon group which may have a substituent.
Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked. It can be mentioned.
　２価の脂肪族基は、直鎖状、分岐鎖状、環状のものが挙げられる。これらの中でも現像溶解性の観点からは直鎖状のものが好ましく、一方で露光部への現像液の浸透低減の観点からは環状のものが好ましい。その炭素数は通常１以上であり、３以上が好ましく、６以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 Examples of the divalent aliphatic group include linear, branched and cyclic ones. Among them, linear ones are preferable from the viewpoint of development solubility, and cyclic ones are preferable from the viewpoint of reducing the penetration of the developer into the exposed portion. The carbon number 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 still more preferably 10 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　２価の直鎖状脂肪族基の具体例としては、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ヘキシレン基、ｎ－ヘプチレン基等が挙げられる。これらの中でも残渣低減の観点から、メチレン基が好ましい。
　２価の分岐鎖状脂肪族基の具体例としては、前述の２価の直鎖状脂肪族基に、側鎖としてメチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｉｓｏ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等を有する構造が挙げられる。
　２価の環状の脂肪族基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、通常１０以下、５以下が好ましい。前記下限値以上とすることで残膜率が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。２価の環状の脂肪族基の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環等の環から水素原子を２つ除した基が挙げられる。これらの中でも現像密着性の観点から、アダマンタン環から水素原子を２つ除した基が好ましい。 Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group and the like. Among these, a methylene group is preferable from the viewpoint of residue reduction.
As specific examples of the divalent branched aliphatic group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl side chain as the above-mentioned divalent linear aliphatic group can be mentioned And structures having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group and the like.
The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less. The residual film ratio tends to be improved by setting it to the above lower limit value, and the residue tends to be reduced by setting it to the above upper limit value. Specific examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms are removed from a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring and the like Be Among these, a group in which two hydrogen atoms are removed from an adamantane ring is preferable from the viewpoint of development adhesion.
　２価の脂肪族基が有していてもよい置換基としては、メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成容易性の観点から、無置換であることが好ましい。 Examples of the substituent which the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group and the like. Among these, from the viewpoint of ease of synthesis, it is preferably unsubstituted.
　また、２価の芳香族環基としては、２価の芳香族炭化水素環基及び２価の芳香族複素環基が挙げられる。その炭素数は通常４以上であり、５以上が好ましく、６以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 Moreover, as a bivalent aromatic ring group, a bivalent aromatic hydrocarbon ring group and a bivalent aromatic heterocyclic group are mentioned. The carbon number 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 still more preferably 10 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　２価の芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。２価の芳香族炭化水素環基としては、例えば、２個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。
　また、２価の芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。２価の芳香族複素環基としては、例えば、２個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。これらの中でも光硬化性の観点から、２個の遊離原子価を有するベンゼン環又はナフタレン環が好ましく、２個の遊離原子価を有するベンゼン環がより好ましい。 The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring and a chrysene ring, which have two free valences. Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like can be mentioned.
The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a fused ring. Examples of the divalent aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole having two free valencies Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Groups such as pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like can be mentioned. Among these, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.
　２価の芳香族環基が有していてもよい置換基としては、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基、グリシジルエーテル基等が挙げられる。これらの中でも硬化性の観点から、無置換が好ましい。 Examples of the substituent which the divalent aromatic ring group may have 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, no substitution is preferable.
　また、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基としては、前述の２価の脂肪族基を１以上と、前述の２価の芳香族環基を１以上とを連結した基が挙げられる。
　２価の脂肪族基の数は特に限定されないが、通常１以上、２以上が好ましく、通常１０以下、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　２価の芳香族環基の数は特に限定されないが、通常１以上、２以上が好ましく、通常１０以下、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 Further, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic groups can be used. A group in which a ring group is linked to one or more is mentioned.
The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基の具体例としては、下記式（ｉ－Ａ）～（ｉ－Ｆ）で表される基等が挙げられる。これらの中でも骨格の剛直性と膜の疎水化の観点から、下記式（ｉ－Ａ）で表される基が好ましい。化学式中の＊は結合手を表す。 Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the following formulas (i-A) to (i-F) Can be mentioned. Among these, from the viewpoint of the rigidity of the skeleton and the hydrophobization of the film, a group represented by the following formula (i-A) is preferable. * In the chemical formula represents a bond.
Figure JPOXMLDOC01-appb-C000019
  
Figure JPOXMLDOC01-appb-C000019
  
　前記のとおり、式（ｉ）中のベンゼン環は、更に任意の置換基により置換されていてもよい。該置換基としては、例えば、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基等が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。
　これらの中でも硬化性の観点から、無置換であることが好ましい。 As mentioned above, the benzene ring in formula (i) may be further substituted by any substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is also not particularly limited, and may be one or two or more.
Among these, from the viewpoint of curability, unsubstituted is preferable.
　また、前記式（ｉ）で表される部分構造は、現像溶解性の観点から、下記式（ｉ－１）で表される部分構造であることが好ましい。 Further, the partial structure represented by the formula (i) is preferably a partial structure represented by the following formula (i-1) from the viewpoint of development solubility.
Figure JPOXMLDOC01-appb-C000020
  
Figure JPOXMLDOC01-appb-C000020
  
　式（ｉ－１）中、Ｒa及びＲbは、前記式（ｉ）のものと同義である。Ｒ1は置換基を有していてもよい炭素数１～４の２価の炭化水素基を表す。＊は結合手を表す。式（ｉ－１）中のベンゼン環は、更に任意の置換基により置換されていてもよい。 In formula (i-1), R a and R b are as defined in the above formula (i). R 1 represents a divalent hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. * Represents a bond. The benzene ring in formula (i-1) may be further substituted by any substituent.
（Ｒ1）
　前記一般式（ｉ－１）において、Ｒ1は置換基を有していてもよい炭素数１～４の２価の炭化水素基を表す。２価の炭化水素基としては、アルキレン基、アルケニレン基が挙げられる。 (R 1 )
In the general formula (i-1), R 1 represents a divalent hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. As a bivalent hydrocarbon group, an alkylene group and an alkenylene group are mentioned.
　アルキレン基は直鎖でも、分岐鎖でもよいが、現像溶解性の観点から直鎖であることが好ましい。その炭素数は特に限定されないが、通常１以上、２以上が好ましく、また通常４以下、３以下が好ましい。前記下限値以上とすることで残膜率が高くなる傾向があり、また、前記上限値以下とすることで素子発光時のアウトガス発生量が少なくなる傾向がある。 The alkylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility. The carbon number is not particularly limited, but is usually 1 or more and 2 or more, and usually 4 or less and 3 or less. The residual film ratio tends to increase by setting the lower limit value or more, and the outgas generation amount at the time of element light emission tends to decrease by setting the upper limit value or less.
　アルキレン基の具体例としては、メチレン基、エチレン基、プロピレン基、ブチレン基が挙げられ、アウトガス低減の観点から、メチレン基又はエチレン基が好ましく、エチレン基がより好ましい。 Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group and a butylene group. From the viewpoint of reducing outgassing, a methylene group or an ethylene group is preferable, and an ethylene group is more preferable.
　また、アルケニレン基は直鎖でも、分岐鎖でもよいが、現像溶解性の観点から直鎖であることが好ましい。その炭素数は特に限定されないが、通常２以上であり、また通常４以下、３以下が好ましい。前記下限値以上とすることで残膜率が高くなる傾向があり、また、前記上限値以下とすることで素子発光時のアウトガス発生量が少なくなる傾向がある。 The alkenylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility. The carbon number is not particularly limited, but is usually 2 or more, and usually 4 or less and 3 or less is preferable. The residual film ratio tends to increase by setting the lower limit value or more, and the outgas generation amount at the time of element light emission tends to decrease by setting the upper limit value or less.
　アルケニレン基の具体例としては、エテニレン基、プロペニレン基、ブチレニレン基が挙げられ、アウトガスの観点から、エテニレン基が好ましい。 Specific examples of the alkenylene group include an ethenylene group, a propenylene group and a butyrenylene group, and from the viewpoint of outgassing, an ethenylene group is preferable.
　炭素数１～４の２価の炭化水素基が有していてもよい置換基は特に限定されないが、例えば、ハロゲン原子、アルコキシ基、ベンゾイル基、水酸基などが挙げられ、合成の容易さの観点からは無置換であることが好ましい。 The substituent which the divalent hydrocarbon group having 1 to 4 carbons may have is not particularly limited, and examples thereof include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group and the like, and the viewpoint of easiness of synthesis It is preferable that R is unsubstituted.
　これらの中でもアウトガス低減の観点から、Ｒ1が炭素数１～４の２価のアルキレン基であることが好ましく、メチレン基又はエチレン基であることがより好ましく、エチレン基であることがさらに好ましい。 Among them, from the viewpoint of reducing outgassing, R 1 is preferably a divalent alkylene group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylene group, and still more preferably an ethylene group.
　エポキシ（メタ）アクリレート樹脂（ｂ１－１）１分子中に含まれる、前記式（ｉ－１）で表される部分構造は、１種でも２種以上でもよい。 The partial structure represented by the formula (i-1) contained in one molecule of the epoxy (meth) acrylate resin (b1-1) may be one kind or two or more kinds.
　また、エポキシ（メタ）アクリレート樹脂（ｂ１－１）１分子中に含まれる、前記式（ｉ）で表される部分構造の数は特に限定されないが、１以上が好ましく、２以上がより好ましく、３以上がさらに好ましく、また、１０以下が好ましく、８以下がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 The number of partial structures represented by the formula (i) contained in one molecule of the epoxy (meth) acrylate resin (b1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, 3 or more is more preferable, 10 or less is preferable, and 8 or less is more preferable. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　また、エポキシ（メタ）アクリレート樹脂（ｂ１－１）１分子中に含まれる、前記式（ｉ－１）で表される部分構造の数は特に限定されないが、１以上が好ましく、２以上がより好ましく、３以上がさらに好ましく、また、１０以下が好ましく、８以下がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 Further, the number of partial structures represented by the formula (i-1) contained in one molecule of the epoxy (meth) acrylate resin (b1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Preferably, it is 3 or more, more preferably 10 or less, and still more preferably 8 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　以下にエポキシ（メタ）アクリレート樹脂（ｂ１－１）の具体例を挙げる。 Specific examples of the epoxy (meth) acrylate resin (b1-1) will be given below.
Figure JPOXMLDOC01-appb-C000021
  
Figure JPOXMLDOC01-appb-C000021
  
Figure JPOXMLDOC01-appb-C000022
  
Figure JPOXMLDOC01-appb-C000022
  
Figure JPOXMLDOC01-appb-C000023
  
Figure JPOXMLDOC01-appb-C000023
  
Figure JPOXMLDOC01-appb-C000024
  
Figure JPOXMLDOC01-appb-C000024
  
Figure JPOXMLDOC01-appb-C000025
  
Figure JPOXMLDOC01-appb-C000025
  
Figure JPOXMLDOC01-appb-C000026
  
Figure JPOXMLDOC01-appb-C000026
  
Figure JPOXMLDOC01-appb-C000027
  
Figure JPOXMLDOC01-appb-C000027
  
　また一方で、エポキシ（メタ）アクリレート樹脂（ｂ１）は、現像密着性の観点から、下記式（ｉｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂（ｂ１－２）であることが好ましい。 On the other hand, the epoxy (meth) acrylate resin (b1) is an epoxy (meth) acrylate resin (b1-2) including a partial structure represented by the following formula (ii) from the viewpoint of development adhesion. preferable.
Figure JPOXMLDOC01-appb-C000028
  
Figure JPOXMLDOC01-appb-C000028
  
　式（ｉｉ）中、Ｒcは各々独立に、水素原子又はメチル基を表す。Ｒdは、環状炭化水素基を側鎖として有する２価の炭化水素基を表す。＊は結合手を表す。 In formula (ii), each R c independently represents a hydrogen atom or a methyl group. R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * Represents a bond.
（Ｒd）
　前記式（ｉｉ）において、Ｒdは、環状炭化水素基を側鎖として有する２価の炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 (R d )
In the formula (ii), R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
　脂肪族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、通常１０以下、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　また、脂肪族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　脂肪族環基における脂肪族環の具体例としてはシクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環等が挙げられる。これらの中でも現像密着性の観点から、アダマンタン環が好ましい。 The number of rings possessed by the aliphatic ring group is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, particularly preferably 15 or less. preferable. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.
　一方で、芳香族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、３以上がより好ましく、また、通常１０以下、５以下が好ましく、４以下がより好ましい。前記下限値以上とすることで残渣が低減する傾向があり、また、前記上限値以下とすることで現像密着性が向上する傾向がある。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、１０以上がよりさらに好ましく、１２以上が特に好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記下限値以上とすることで残渣が低減する傾向があり、また、前記上限値以下とすることで現像密着性が向上する傾向がある。
　芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環等が挙げられる。これらの中でもパターニング特性の観点から、フルオレン環が好ましい。 On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but usually 1 or more and 2 or more is preferable, 3 or more is more preferable, and usually 10 or less and 5 or less is preferable and 4 or less is more preferable. By setting the content to the above lower limit value, the residue tends to be reduced, and by setting the content to the above upper limit value, the development adhesion tends to be improved.
As an aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group can be mentioned. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, 30 or less. More preferably, 20 or less is more preferable, and 15 or less is particularly preferable. By setting the content to the above lower limit value, the residue tends to be reduced, and by setting the content to the above 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, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, A fluorene ring etc. are mentioned. Among these, a fluorene ring is preferable from the viewpoint of patterning properties.
　また、環状炭化水素基を側鎖として有する２価の炭化水素基における、２価の炭化水素基は特に限定されないが、例えば、２価の脂肪族基、２価の芳香族環基、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基が挙げられる。 Further, the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and, for example, a divalent aliphatic group, a divalent aromatic ring group, one or more And a group in which one or more divalent aromatic ring groups are connected to each other.
　２価の脂肪族基は、直鎖状、分岐鎖状、環状のものが挙げられる。これらの中でも現像溶解性の観点からは直鎖状のものが好ましく、一方で露光部への現像液の浸透低減の観点からは環状のものが好ましい。その炭素数は通常１以上であり、３以上が好ましく、６以上がより好ましく、また、２５以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 Examples of the divalent aliphatic group include linear, branched and cyclic ones. Among them, linear ones are preferable from the viewpoint of development solubility, and cyclic ones are preferable from the viewpoint of reducing the penetration of the developer into the exposed portion. The carbon number 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 still more preferably 15 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　２価の直鎖状脂肪族基の具体例としては、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ヘキシレン基、ｎ－ヘプチレン基等が挙げられる。これらの中でも残渣の観点から、メチレン基が好ましい。
　２価の分岐鎖状脂肪族基の具体例としては、前述の２価の直鎖状脂肪族基に、側鎖としてメチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｉｓｏ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等を有する構造が挙げられる。
　２価の環状の脂肪族基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、通常１０以下、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。２価の環状の脂肪族基の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環等の環から水素原子を２つ除した基が挙げられる。これらの中でも現像密着性の観点から、アダマンタン環から水素原子を２つ除した基が好ましい。 Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group and the like. Among these, a methylene group is preferable from the viewpoint of the residue.
As specific examples of the divalent branched aliphatic group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl side chain as the above-mentioned divalent linear aliphatic group can be mentioned And structures having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group and the like.
The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced. Specific examples of the divalent cyclic aliphatic group include groups in which two hydrogen atoms are removed from a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring and the like Be Among these, a group in which two hydrogen atoms are removed from an adamantane ring is preferable from the viewpoint of development adhesion.
　２価の脂肪族基が有していてもよい置換基としては、メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成容易性の観点から、無置換であることが好ましい。 Examples of the substituent which the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group and the like. Among these, from the viewpoint of ease of synthesis, it is preferably unsubstituted.
　また、２価の芳香族環基としては、２価の芳香族炭化水素環基及び２価の芳香族複素環基が挙げられる。その炭素数は通常４以上であり、５以上が好ましく、６以上がより好ましく、また、３０以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 Moreover, as a bivalent aromatic ring group, a bivalent aromatic hydrocarbon ring group and a bivalent aromatic heterocyclic group are mentioned. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　２価の芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。２価の芳香族炭化水素環基としては、例えば、２個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。
　また、２価の芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。２価の芳香族複素環基としては、例えば、２個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。これらの中でも光硬化性の観点から、２個の遊離原子価を有するベンゼン環又はナフタレン環が好ましく、２個の遊離原子価を有するベンゼン環がより好ましい。 The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring and a chrysene ring, which have two free valences. Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like can be mentioned.
The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a fused ring. Examples of the divalent aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole having two free valencies Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Groups such as pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like can be mentioned. Among these, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.
　２価の芳香族環基が有していてもよい置換基としては、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基等が挙げられる。これらの中でも硬化性の観点から、無置換が好ましい。 Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. Among these, from the viewpoint of curability, no substitution is preferable.
　また、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基としては、前述の２価の脂肪族基を１以上と、前述の２価の芳香族環基を１以上とを連結した基が挙げられる。
　２価の脂肪族基の数は特に限定されないが、通常１以上、２以上が好ましく、通常１０以下、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　２価の芳香族環基の数は特に限定されないが、通常１以上、２以上が好ましく、通常１０以下、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 Further, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic groups can be used. A group in which a ring group is linked to one or more is mentioned.
The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基の具体例としては、前記式（ｉ－Ａ）～（ｉ－Ｆ）で表される基等が挙げられる。これらの中でも残渣低減の観点から、前記式（ｉ－Ｃ）で表される基が好ましい。 Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include the groups represented by the formulas (i-A) to (i-F), etc. Can be mentioned. Among them, the group represented by the formula (i-C) is preferable from the viewpoint of reducing the residue.
　これらの２価の炭化水素基に対して、側鎖である環状炭化水素基の結合態様は特に限定されないが、例えば、脂肪族基や芳香族環基の水素原子１つを該側鎖で置換した態様や、脂肪族基の炭素原子の１つを含めて側鎖である環状炭化水素基を構成した態様が挙げられる。 Although the bonding aspect of the cyclic hydrocarbon group which is a side chain is not specifically limited with respect to these bivalent hydrocarbon groups, For example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted by this side chain. And the aspect which comprised the cyclic hydrocarbon group which is a side chain including one of the carbon atom of an aliphatic group is mentioned.
　また、前記式（ｉｉ）で表される部分構造は、現像密着性の観点から、下記式（ｉｉ－１）で表される部分構造であることが好ましい。 Further, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-1) from the viewpoint of development adhesion.
Figure JPOXMLDOC01-appb-C000029
  
Figure JPOXMLDOC01-appb-C000029
  
　式（ｉｉ－１）中、Ｒcは前記式（ｉｉ）と同義である。Ｒαは、置換基を有していてもよい１価の環状炭化水素基を表す。ｎは１以上の整数である。式（ｉｉ－１）中のベンゼン環は、更に任意の置換基により置換されていてもよい。＊は結合手を表す。 In formula (ii-1), R c is as defined in the above formula (ii). R α represents a monovalent cyclic hydrocarbon group which may have a substituent. n is an integer of 1 or more. The benzene ring in formula (ii-1) may be further substituted by any substituent. * Represents a bond.
（Ｒα）
　前記式（ｉｉ－１）において、Ｒαは、置換基を有していてもよい１価の環状炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 (R α )
In the formula (ii-1), R α represents a monovalent cyclic hydrocarbon group which may have a substituent.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
　脂肪族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、通常６以下、４以下が好ましく、３以下がより好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　また、脂肪族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　脂肪族環基における脂肪族環の具体例としてはシクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環等が挙げられる。これらの中でも現像密着性の観点から、アダマンタン環が好ましい。 The number of rings contained in the aliphatic ring group is not particularly limited, but is preferably 1 or more and 2 or more, and usually 6 or less and 4 or less, and more preferably 3 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, particularly preferably 15 or less. preferable. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.
　一方で、芳香族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、３以上がより好ましく、また、通常１０以下、５以下が好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常４以上であり、５以上が好ましく、６以上がより好ましく、また、３０以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環等が挙げられる。これらの中でも現像密着性の観点から、フルオレン環が好ましい。 On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is usually 1 or more and 2 or more, preferably 3 or more, and usually 10 or less and 5 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
As an aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group can be mentioned. The carbon number 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 still more preferably 15 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, from the viewpoint of development adhesion, a fluorene ring is preferable.
　環状炭化水素基が有していてもよい置換基としては、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、アミル基、ｉｓｏ－アミル基等の炭素数１～５のアルキル基；メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成の容易性の観点から、無置換が好ましい。 As the substituent which the cyclic hydrocarbon group may have, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an amyl group, Examples thereof include alkyl groups having 1 to 5 carbon atoms such as iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; carboxyl group and the like. Among these, from the viewpoint of easiness of synthesis, no substitution is preferable.
　ｎは１以上の整数を表すが、２以上が好ましく、また、３以下が好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 N represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　これらの中でも、強固な膜硬化度と電気特性の観点から、Ｒαが１価の脂肪族環基であることが好ましく、アダマンチル基であることがより好ましい。 Among these, from the viewpoint of firm film hardness and electrical properties, R α is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.
　前記のとおり、式（ｉｉ－１）中のベンゼン環は、更に任意の置換基により置換されていてもよい。該置換基としては、例えば、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基等が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。これらの中でも硬化性の観点から、無置換であることが好ましい。 As described above, the benzene ring in formula (ii-1) may be further substituted by any substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is also not particularly limited, and may be one or two or more. Among these, from the viewpoint of curability, unsubstituted is preferable.
　以下に前記式（ｉｉ－１）で表される部分構造の具体例を挙げる。 Specific examples of the partial structure represented by the formula (ii-1) will be given below.
Figure JPOXMLDOC01-appb-C000030
  
Figure JPOXMLDOC01-appb-C000030
  
Figure JPOXMLDOC01-appb-C000031
  
Figure JPOXMLDOC01-appb-C000031
  
Figure JPOXMLDOC01-appb-C000032
  
Figure JPOXMLDOC01-appb-C000032
  
Figure JPOXMLDOC01-appb-C000033
  
Figure JPOXMLDOC01-appb-C000033
  
Figure JPOXMLDOC01-appb-C000034
  
Figure JPOXMLDOC01-appb-C000034
  
　また、前記式（ｉｉ）で表される部分構造は、現像密着性の観点から、下記式（ｉｉ－２）で表される部分構造であることが好ましい。 Further, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-2) from the viewpoint of development adhesion.
Figure JPOXMLDOC01-appb-C000035
  
Figure JPOXMLDOC01-appb-C000035
  
　式（ｉｉ－２）中、Ｒcは前記式（ｉｉ）と同義である。Ｒβは、置換基を有していてもよい２価の環状炭化水素基を表す。式（ｉｉ－２）中のベンゼン環は、更に任意の置換基により置換されていてもよい。＊は結合手を表す。 In formula (ii-2), R c is as defined in the above formula (ii). R β represents a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (ii-2) may be further substituted by any substituent. * Represents a bond.
（Ｒβ）
　前記式（ｉｉ－２）において、Ｒβは、置換基を有していてもよい２価の環状炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 (R β )
In Formula (ii-2) above, R β represents a divalent cyclic hydrocarbon group which may have a substituent.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
　脂肪族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、通常１０以下、５以下が好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　また、脂肪族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、また、４０以下が好ましく、３５以下がより好ましく、３０以下がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　脂肪族環基における脂肪族環の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環等が挙げられる。これらの中でも現像密着性の観点から、アダマンタン環が好ましい。 The number of rings contained in the aliphatic ring group is not particularly limited, but is usually 1 or more and 2 or more, and usually 10 or less and 5 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.
　一方で、芳香族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、３以上がより好ましく、また、通常１０以下、５以下が好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられるまた、芳香族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、１０以上がさらに好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環等が挙げられる。これらの中でも現像密着性の観点から、フルオレン環が好ましい。 On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is usually 1 or more and 2 or more, preferably 3 or more, and usually 10 or less and 5 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
The aromatic ring group includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, and more preferably 8 or more. The above is more preferable, and 40 or less is preferable, 30 or less is more preferable, 20 or less is more preferable, and 15 or less is particularly preferable. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, from the viewpoint of development adhesion, a fluorene ring is preferable.
　環状炭化水素基が有していてもよい置換基としては、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、アミル基、ｉｓｏ－アミル基等の炭素数１～５のアルキル基；メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成の簡易性の観点から、無置換が好ましい。 As the substituent which the cyclic hydrocarbon group may have, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an amyl group, Examples thereof include alkyl groups having 1 to 5 carbon atoms such as iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; carboxyl group and the like. Among these, from the viewpoint of simplicity of synthesis, no substitution is preferable.
　これらの中でも、硬化性の観点から、Ｒβが２価の脂肪族環基であることが好ましく、２価のアダマンタン環基であることがより好ましい。
　一方で、現像密着性の観点から、Ｒβが２価の芳香族環基であることが好ましく、２価のフルオレン環基であることがより好ましい。 Among these, from the viewpoint of curability, R β is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group.
On the other hand, from the viewpoint of development adhesion, R β is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.
　前記のとおり、式（ｉｉ－２）中のベンゼン環は、更に任意の置換基により置換されていてもよい。該置換基としては、例えば、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基等が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。これらの中でも硬化性の観点から、無置換であることが好ましい。 As described above, the benzene ring in formula (ii-2) may be further substituted by any substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is also not particularly limited, and may be one or two or more. Among these, from the viewpoint of curability, unsubstituted is preferable.
　以下に前記式（ｉｉ－２）で表される部分構造の具体例を挙げる。 Specific examples of the partial structure represented by the formula (ii-2) will be given below.
Figure JPOXMLDOC01-appb-C000036
  
Figure JPOXMLDOC01-appb-C000036
  
Figure JPOXMLDOC01-appb-C000037
  
Figure JPOXMLDOC01-appb-C000037
  
Figure JPOXMLDOC01-appb-C000038
  
Figure JPOXMLDOC01-appb-C000038
  
Figure JPOXMLDOC01-appb-C000039
  
Figure JPOXMLDOC01-appb-C000039
  
　一方で、前記式（ｉｉ）で表される部分構造は、硬化性の観点から、下記式（ｉｉ－３）で表される部分構造であることが好ましい。 On the other hand, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-3) from the viewpoint of curability.
Figure JPOXMLDOC01-appb-C000040
  
Figure JPOXMLDOC01-appb-C000040
  
　式（ｉｉ－３）中、Ｒc及びＲdは前記式（ｉｉ）と同義である。Ｒ1は前記式（ｉ－１）と同義である。＊は結合手を表す。 In formula (ii-3), R c and R d are as defined in the above formula (ii). R 1 has the same meaning as that of the above formula (i-1). * Represents a bond.
　エポキシ（メタ）アクリレート樹脂（ｂ１－２）１分子中に含まれる、前記式（ｉｉ－３）で表される部分構造は、１種でも２種以上でもよい。 The partial structure represented by the formula (ii-3) contained in one molecule of the epoxy (meth) acrylate resin (b1-2) may be one kind or two or more kinds.
　また、エポキシ（メタ）アクリレート樹脂（ｂ１－２）１分子中に含まれる、前記式（ｉｉ）で表される部分構造の数は特に限定されないが、１以上が好ましく、３以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 Further, the number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth) acrylate resin (b1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Moreover, 20 or less is preferable, 15 or less is more preferable, and 10 or less is more preferable. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　また一方で、エポキシ（メタ）アクリレート樹脂（ｂ１）は、素子発光時のアウトガス低減の観点から、下記一般式（ｉｉｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂（ｂ１－３）であることが好ましい。 On the other hand, the epoxy (meth) acrylate resin (b1) is an epoxy (meth) acrylate resin (b1-3) including a partial structure represented by the following general formula (iii) from the viewpoint of reducing outgassing at the element light emission. Is preferred.
Figure JPOXMLDOC01-appb-C000041
  
Figure JPOXMLDOC01-appb-C000041
  
　式（ｉｉｉ）中、Ｒeは水素原子又はメチル基を表し、γは単結合、－ＣＯ－、置換基を有していてもよいアルキレン基、又は置換基を有していてもよい２価の環状炭化水素基を表す。式（ｉｉｉ）中のベンゼン環は、更に任意の置換基により置換されていてもよい。＊は結合手を表す。 In formula (iii), R e represents a hydrogen atom or a methyl group, and γ is a single bond, -CO-, an alkylene group which may have a substituent, or a bivalent which may have a substituent And a cyclic hydrocarbon group of The benzene ring in Formula (iii) may be further substituted by any substituent. * Represents a bond.
（γ）
　前記式（ｉｉｉ）において、γは単結合、－ＣＯ－、置換基を有していてもよいアルキレン基、又は置換基を有していてもよい２価の環状炭化水素基を表す。 (Γ)
In the formula (iii), γ represents a single bond, —CO—, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent.
　アルキレン基は直鎖状でも、分岐鎖状でもよいが、現像溶解性の観点からは直鎖状であることが好ましく、現像密着性の観点からは分岐鎖状であることが好ましい。その炭素数は特に限定されないが、通常１以上、２以上が好ましく、また通常６以下、４以下が好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 The alkylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility, and is preferably branched from the viewpoint of development adhesion. The carbon number is not particularly limited, but is usually 1 or more and 2 or more, and usually 6 or less and 4 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　アルキレン基の具体例としては、メチレン基、エチレン基、プロピレン基、ブチレン基、へキシレン基、ヘプチレン基が挙げられ、現像密着性と現像溶解性の両立の観点から、メチレン基、エチレン基又はプロピレン基が好ましく、ジメチルメチレン基がより好ましい。 Specific examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, hexylene group and heptylene group, and from the viewpoint of achieving both development adhesion and development solubility, methylene group, ethylene group or propylene A group is preferred, and a dimethylmethylene group is more preferred.
　アルキレン基が有していてもよい置換基としては、メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも現像密着性と現像溶解性の両立の観点から、無置換であることが好ましい。 Examples of the substituent which the alkylene group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group and the like. Among these, from the viewpoint of achieving both development adhesion and development solubility, it is preferable to be non-substituted.
　２価の環状炭化水素基としては、２価の脂肪族環基又は２価の芳香族環基が挙げられる。 As a bivalent cyclic hydrocarbon group, a bivalent aliphatic ring group or a bivalent aromatic ring group is mentioned.
　脂肪族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、通常１０以下、５以下が好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　また、脂肪族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、また、４０以下が好ましく、３５以下がより好ましく、３０以下がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　脂肪族環基における脂肪族環の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環等が挙げられる。これらの中でも現像密着性の観点から、アダマンタン環が好ましい。 The number of rings contained in the aliphatic ring group is not particularly limited, but is usually 1 or more and 2 or more, and usually 10 or less and 5 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.
　一方で、芳香族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、３以上がより好ましく、また、通常１０以下、５以下が好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、１０以上がさらに好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環等が挙げられる。これらの中でも現像密着性の観点から、フルオレン環が好ましい。 On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is usually 1 or more and 2 or more, preferably 3 or more, and usually 10 or less and 5 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
As an aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group can be mentioned. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 40 or less, more preferably 30 or less, further 20 or less. Preferably, 15 or less is particularly preferable. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, from the viewpoint of development adhesion, a fluorene ring is preferable.
　環状炭化水素基が有していてもよい置換基としては、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、アミル基、ｉｓｏ－アミル基等の炭素数１～５のアルキル基；メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成の簡易性の観点から、無置換が好ましい。 As the substituent which the cyclic hydrocarbon group may have, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an amyl group, Examples thereof include alkyl groups having 1 to 5 carbon atoms such as iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; carboxyl group and the like. Among these, from the viewpoint of simplicity of synthesis, no substitution is preferable.
　これらの中でも、残渣低減の観点から、γが置換基を有していてもよいアルキレン基であることが好ましく、ジメチルメチレンであることがより好ましい。 Among these, from the viewpoint of residue reduction, γ is preferably an alkylene group which may have a substituent, and more preferably dimethylmethylene.
　前記のとおり、式（ｉｉｉ）中のベンゼン環は、更に任意の置換基により置換されていてもよい。該置換基としては、例えば、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基等が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。これらの中でも硬化性の観点から、無置換であることが好ましい。 As described above, the benzene ring in formula (iii) may be further substituted by any substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is also not particularly limited, and may be one or two or more. Among these, from the viewpoint of curability, unsubstituted is preferable.
　一方で、前記式（ｉｉｉ）で表される部分構造は、現像溶解性の観点から、下記式（ｉｉｉ－１）で表される部分構造であることが好ましい。 On the other hand, the partial structure represented by the formula (iii) is preferably a partial structure represented by the following formula (iii-1) from the viewpoint of development solubility.
Figure JPOXMLDOC01-appb-C000042
  
Figure JPOXMLDOC01-appb-C000042
  
　式（ｉｉｉ－１）中、Ｒe及びγは前記式（ｉｉｉ）と同義である。Ｒ1は前記式（ｉ－１）のものと同義である。＊は結合手を表す。式（ｉｉｉ－１）中のベンゼン環は、更に任意の置換基により置換されていてもよい。 In formula (iii-1), R e and γ are as defined in the above formula (iii). R 1 has the same meaning as that of the above formula (i-1). * Represents a bond. The benzene ring in the formula (iii-1) may be further substituted by any substituent.
　また、エポキシ（メタ）アクリレート樹脂（ｂ１－３）１分子中に含まれる、前記式（ｉｉｉ）で表される部分構造の数は特に限定されないが、１以上が好ましく、５以上がより好ましく、１０以上がさらに好ましく、また、１８以下が好ましく、１５以下がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 Further, the number of partial structures represented by the formula (iii) contained in one molecule of the epoxy (meth) acrylate resin (b1-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, 10 or more is more preferable, 18 or less is preferable, and 15 or less is more preferable. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　また、エポキシ（メタ）アクリレート樹脂（ｂ１－３）１分子中に含まれる、前記式（ｉｉｉ－１）で表される部分構造の数は特に限定されないが、１以上が好ましく、３以上がより好ましく、５以上がさらに好ましく、また、１８以下が好ましく、１５以下がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 Further, the number of partial structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth) acrylate resin (b1-3) is not particularly limited, but is preferably 1 or more, 3 or more is more Preferably, 5 or more is more preferable, 18 or less is preferable, and 15 or less is more preferable. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　以下にエポキシ（メタ）アクリレート樹脂（ｂ１－３）の具体例を挙げる。 Specific examples of the epoxy (meth) acrylate resin (b1-3) will be given below.
Figure JPOXMLDOC01-appb-C000043
  
Figure JPOXMLDOC01-appb-C000043
  
Figure JPOXMLDOC01-appb-C000044
  
Figure JPOXMLDOC01-appb-C000044
  
Figure JPOXMLDOC01-appb-C000045
  
Figure JPOXMLDOC01-appb-C000045
  
［アクリル共重合樹脂（ｂ２）］
　次に、アクリル共重合樹脂（ｂ２）について詳述する。アクリル共重合樹脂（ｂ２）は、硬化性の観点から、側鎖にエチレン性二重結合を有するものであることが好ましい。 [Acrylic copolymer resin (b2)]
Next, the acrylic copolymer resin (b2) will be described in detail. The acrylic copolymer resin (b2) is preferably one having an ethylenic double bond in the side chain from the viewpoint of curability.
　アクリル共重合樹脂（ｂ２）の中でも、現像溶解性の観点から、下記一般式（Ｉ）で表される部分構造を含むアクリル共重合樹脂（ｂ２－１）が好ましい。 Among the acrylic copolymer resins (b2), acrylic copolymer resins (b2-1) containing a partial structure represented by the following general formula (I) are preferable from the viewpoint of development solubility.
Figure JPOXMLDOC01-appb-C000046
  
Figure JPOXMLDOC01-appb-C000046
  
　式（Ｉ）中、ＲA及びＲBは各々独立に、水素原子又はメチル基を表す。＊は結合手を表す。 In formula (I), R A and R B each independently represent a hydrogen atom or a methyl group. * Represents a bond.
　また、前記式（Ｉ）で表される部分構造は、現像性の観点から、下記一般式（Ｉ－１）で表される部分構造であることが好ましい。 Further, the partial structure represented by the formula (I) is preferably a partial structure represented by the following general formula (I-1) from the viewpoint of developability.
Figure JPOXMLDOC01-appb-C000047
  
Figure JPOXMLDOC01-appb-C000047
  
　式（Ｉ－１）中、ＲA及びＲBは、前記式（Ｉ）のものと同義である。Ｒ1は前記式（ｉ－１）のものと同義である。 In formula (I-1), R A and R B have the same meaning as in the above formula (I). R 1 has the same meaning as that of the above formula (i-1).
　また、前記式（Ｉ）で表される部分構造は、感度の観点から、下記式（Ｉ－２）で表される部分構造であることが好ましい。 The partial structure represented by the formula (I) is preferably a partial structure represented by the following formula (I-2) from the viewpoint of sensitivity.
Figure JPOXMLDOC01-appb-C000048
  
Figure JPOXMLDOC01-appb-C000048
  
　式（Ｉ－２）中、ＲA及びＲBは、前記式（Ｉ）のものと同義である。 In formula (I-2), R A and R B have the same meaning as in the above-mentioned formula (I).
　アクリル共重合樹脂（ｂ２－１）が前記一般式（Ｉ）で表される部分構造を含む場合、アクリル共重合樹脂（ｂ２－１）に含まれる前記一般式（Ｉ）で表される部分構造の含有割合は特に限定されないが、５モル％以上が好ましく、２０モル％以上がより好ましく、３０モル％以上がさらに好ましく、５０モル％以上がよりさらに好ましく、７０モル％以上が特に好ましく、８０モル％以上が最も好ましく、また、９９モル％以下が好ましく、９７モル％以下がより好ましく、９５モル％以下がさらに好ましい。前記下限値以上とすることで残渣が低減する傾向があり、また、前記上限値以下とすることで現像密着性が向上する傾向がある。アクリル共重合樹脂（ｂ２－１）が前記一般式（Ｉ）で表される部分構造を含む場合、アクリル共重合樹脂（ｂ２－１）に含まれる前記一般式（Ｉ）で表される部分構造の含有割合としては、例えば、５～９９モル％であり、２０～９９モル％が好ましく、３０～９７モル％がより好ましく、５０～９７モル％がさらに好ましく、７０～９５モル％がよりさらに好ましく、８０～９５モル％が特に好ましい。 When the acrylic copolymer resin (b2-1) contains the partial structure represented by the general formula (I), the partial structure represented by the general formula (I) contained in the acrylic copolymer resin (b2-1) The content ratio of is not particularly limited, but is preferably 5 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 50 mol% or more, and particularly preferably 70 mol% or more. The mole% or more is most preferable, and the 99 mole% or less is preferable, the 97 mole% or less is more preferable, and the 95 mole% or less is more preferable. By setting the content to the above lower limit value, the residue tends to be reduced, and by setting the content to the above upper limit value, the development adhesion tends to be improved. When the acrylic copolymer resin (b2-1) contains the partial structure represented by the general formula (I), the partial structure represented by the general formula (I) contained in the acrylic copolymer resin (b2-1) The content ratio of 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%. Preferably, 80 to 95 mol% is particularly preferred.
　アクリル共重合樹脂（ｂ２－１）が前記一般式（Ｉ－１）で表される部分構造を含む場合、アクリル共重合樹脂（ｂ２－１）に含まれる前記一般式（Ｉ－１）で表される部分構造の含有割合は特に限定されないが、１モル％以上が好ましく、５モル％以上がより好ましく、８モル％以上がさらに好ましく、１０モル％以上がよりさらに好ましく、また、９９モル％以下が好ましく、６０モル％以下がより好ましく、４０モル％以下がさらに好ましく、３０モル％以下がよりさらに好ましく、２０モル％以下が特に好ましい。前記下限値以上とすることで感度が高くなり、残渣が低減する傾向があり、また、前記上限値以下とすることで現像密着性が向上する傾向がある。アクリル共重合樹脂（ｂ２－１）が前記一般式（Ｉ－１）で表される部分構造を含む場合、アクリル共重合樹脂（ｂ２－１）に含まれる前記一般式（Ｉ－１）で表される部分構造の含有割合としては、例えば、１～９９モル％であり、５～６０モル％が好ましく、５～４０モル％がより好ましく、８～４０モル％がさらに好ましく、１０～２０モル％がよりさらに好ましい。 When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I-1), the table is represented by the above general formula (I-1) contained in the acrylic copolymer resin (b2-1) The content ratio of the partial structure to be formed is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% or more, still more preferably 10 mol% or more, and 99 mol% The following is preferable, 60 mol% or less is more preferable, 40 mol% or less is more preferable, 30 mol% or less is still more preferable, and 20 mol% or less is particularly preferable. By setting the content to the above lower limit value, the sensitivity tends to be high and the residue tends to be reduced, and by setting the content to the above upper limit value, the development adhesion tends to be improved. When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I-1), the table is represented by the above general formula (I-1) contained in the acrylic copolymer resin (b2-1) The content ratio of the partial structure to be added 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 10 to 20 mol. % Is even more preferable.
　アクリル共重合樹脂（ｂ２－１）が前記一般式（Ｉ－２）で表される部分構造を含む場合、アクリル共重合樹脂（ｂ２－１）に含まれる前記一般式（Ｉ－２）で表される部分構造の含有割合は特に限定されないが、１０モル％以上が好ましく、２０モル％以上がより好ましく、３０モル％以上がさらに好ましく、４０モル％以上がよりさらに好ましく、５０モル％以上が特に好ましく、７０モル％以上が最も好ましく、また、９９モル％以下が好ましく、９５モル％以下がより好ましく、９０モル％以下がさらに好ましく、８５モル％以下が特に好ましい。前記下限値以上とすることで感度が高くなる傾向があり、また、前記上限値以下とすることで現像性が向上する傾向がある。アクリル共重合樹脂（ｂ２－１）が前記一般式（Ｉ－２）で表される部分構造を含む場合、アクリル共重合樹脂（ｂ２－１）に含まれる前記一般式（Ｉ－２）で表される部分構造の含有割合としては、例えば、１０～９９モル％であり、３０～９５モル％が好ましく、５０～９０モル％がより好ましく、７０～９０モル％がさらに好ましく、７０～８５モル％がよりさらに好ましい。 When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I-2), the table is represented by the above general formula (I-2) contained in the acrylic copolymer resin (b2-1) The content ratio of the partial structure to be formed is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, 50 mol% or more Particularly preferable is 70 mol% or more, most preferable is 99 mol% or less, more preferably 95 mol% or less, still more preferably 90 mol% or less, and particularly preferably 85 mol% or less. When the content is at least the lower limit, the sensitivity tends to be high, and when the content is at the upper limit or less, the developability tends to be improved. When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I-2), the table is represented by the above general formula (I-2) contained in the acrylic copolymer resin (b2-1) The content ratio of the partial structure to be added 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 70 to 85 mol. % Is even more preferable.
　アクリル共重合樹脂（ｂ２－１）が前記一般式（Ｉ）で表される部分構造を含む場合、他に含んでいてもよい部分構造は特に限定されないが、現像密着性の観点から、例えば、下記一般式（Ｉ’）で表される部分構造を含むことが好ましい。 When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I), the partial structure which may be contained is not particularly limited, but from the viewpoint of developing adhesion, for example, It is preferable to include a partial structure represented by the following general formula (I ′).
Figure JPOXMLDOC01-appb-C000049
  
Figure JPOXMLDOC01-appb-C000049
  
　上記式（Ｉ’）中、ＲDは水素原子又はメチル基を表し、ＲEは置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基（芳香族環基）、又は置換基を有していてもよいアルケニル基を表す。 In the above formula (I ′), R D represents a hydrogen atom or a methyl group, R E is an alkyl group which may have a substituent, an aryl group which may have a substituent (aromatic ring group Or an alkenyl group which may have a substituent.
（ＲE）
　前記式（Ｉ’）において、ＲEは置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアルケニル基を表す。
　ＲEにおけるアルキル基としては直鎖状、分岐鎖状又は環状のアルキル基が挙げられる。その炭素数は、１以上であることが好ましく、３以上であることがより好ましく、５以上であることがさらに好ましく、また、２０以下であることが好ましく、１８以下であることがより好ましく、１６以下であることがさらに好ましく、１４以下であることがよりさらに好ましく、１２以下であることが特に好ましい。前記下限値以上とすることで膜強度が高くなり、現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 (R E )
In Formula (I ′), R E represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent.
The alkyl group in R E includes a linear, branched or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 20 or less, more preferably 18 or less, It is more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. By setting the content to the above lower limit or more, the film strength tends to be high, the development adhesion tends to be improved, and the content to the above upper limit or less tends to reduce the residue.
　アルキル基の具体例としては、メチル基、エチル基、シクロヘキシル基、ジシクロペンタニル基、ドデカニル基等が挙げられる。これらの中でも膜強度の観点から、ジシクロペンタニル基又はドデカニル基が好ましく、ジシクロペンタニル基がより好ましい。
　また、アルキル基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基などが挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, a dodecanyl group and the like. Among these, from the viewpoint of film strength, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable.
Moreover, as a substituent which the alkyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group And an acryloyl group, a methacryloyl group and the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
　ＲEにおけるアリール基（芳香族環基）としては、１価の芳香族炭化水素環基及び１価の芳香族複素環基が挙げられる。その炭素数は４以上であることが好ましく、６以上であることがより好ましく、また、２４以下であることが好ましく、２２以下であることがより好ましく、２０以下であることがさらに好ましく、１８以下であることが特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。
　芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよく、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などが挙げられる。
　また、芳香族複素環基における芳香族複素環基としては、単環であっても縮合環であってもよく、例えば、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などが挙げられる。これらの中でも硬化性の観点から、ベンゼン環基、又はナフタレン環基が好ましく、ベンゼン環基がより好ましい。
　また、アリール基が有していてもよい置換基としては、メチル基、エチル基、プロピル基、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基などが挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 The aryl group (aromatic ring group) in R E includes a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The carbon number thereof is preferably 4 or more, more preferably 6 or more, and preferably 24 or less, more preferably 22 or less, still more preferably 20 or less, 18 It is particularly preferred that When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, pyrene Rings, benzpyrene rings, chrysene rings, triphenylene rings, acenaphthene rings, fluoranthene rings, fluorene rings and the like.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring. For example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring , Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzoiso Thiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring etc It is below. 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.
Moreover, as a substituent which the aryl group may have, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligo Ethylene glycol group, phenyl group, carboxyl group and the like are mentioned, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
　ＲEにおけるアルケニル基としては、直鎖状、分岐鎖状又は環状のアルケニル基が挙げられる。その炭素数は、２以上であることが好ましく、また、２２以下であることが好ましく、２０以下であることがより好ましく、１８以下であることがさらに好ましく、１６以下であることがよりさらに好ましく、１４以下であることが特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 The alkenyl group in R E includes a linear, branched or cyclic alkenyl group. The carbon number thereof is preferably 2 or more, 22 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less. , 14 or less is particularly preferable. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　アルケニル基の具体例としては、エテニル基、プロペニル基、ブチレニル基、シクロヘキセニル基等が挙げられる。これらの中でも硬化性の観点から、エテニル基又はプロペニル基が好ましく、エテニル基がより好ましい。
　また、アルケニル基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基などが挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Specific examples of the alkenyl group include ethenyl group, propenyl group, butyrenyl group, cyclohexenyl group and the like. Among these, from the viewpoint of curability, an ethenyl group or a propenyl group is preferable, and an ethenyl group is more preferable.
Moreover, as a substituent which an alkenyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　このように、ＲEは置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアルケニル基を表すが、これらの中でも現像性の観点から、アルキル基又はアルケニル基が好ましく、アルキル基がより好ましく、ジシクロペンタニル基がさらに好ましい。 Thus, R E represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent. From the viewpoint of developability, an alkyl group or an alkenyl group is preferable, an alkyl group is more preferable, and a dicyclopentanyl group is more preferable.
　アクリル共重合樹脂（ｂ２－１）が前記一般式（Ｉ’）で表される部分構造を含む場合、アクリル共重合樹脂（ｂ２－１）に含まれる前記一般式（Ｉ’）で表される部分構造の含有割合は特に限定されないが、０．５モル％以上が好ましく、１モル％以上がより好ましく、１．５モル％以上がさらに好ましく、２モル％以上が特に好ましく、また、９０モル％以下が好ましく、７０モル％以下がより好ましく、５０％モル以下がさらに好ましく、３０モル％以下がよりさらに好ましく、１０モル％以下が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。アクリル共重合樹脂（ｂ２－１）が前記一般式（Ｉ’）で表される部分構造を含む場合、アクリル共重合樹脂（ｂ２－１）に含まれる前記一般式（Ｉ’）で表される部分構造の含有割合としては、例えば、０．５～９０モル％であり、１～７０モル％が好ましく、１．５～５０モル％がより好ましく、１．５～３０モル％がさらに好ましく、２～１０モル％がよりさらに好ましい。 When acrylic copolymer resin (b2-1) contains the partial structure represented by said general formula (I '), it is represented by said general formula (I') contained in acrylic copolymer resin (b2-1) The content of the partial structure is not particularly limited, but is preferably 0.5 mol% or more, more preferably 1 mol% or more, still more preferably 1.5 mol% or more, particularly preferably 2 mol% or more, and 90 mol % Or less is preferable, 70 mol% or less is more preferable, 50% mol or less is more preferable, 30 mol% or less is still more preferable, and 10 mol% or less is particularly preferable. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced. When acrylic copolymer resin (b2-1) contains the partial structure represented by said general formula (I '), it is represented by said general formula (I') contained in acrylic copolymer resin (b2-1) The content ratio of the partial structure is, for example, 0.5 to 90 mol%, preferably 1 to 70 mol%, more preferably 1.5 to 50 mol%, and still more preferably 1.5 to 30 mol%. 2 to 10 mol% is even more preferable.
　アクリル共重合樹脂（ｂ２－１）が前記一般式（Ｉ）で表される部分構造を含む場合、耐熱性、膜強度の観点から、下記一般式（Ｉ’’）で表される部分構造をさらに含むことが好ましい。 When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I), the partial structure represented by the following general formula (I ′ ′) is preferred from the viewpoint of heat resistance and film strength. It is preferable to further include.
Figure JPOXMLDOC01-appb-C000050
  
Figure JPOXMLDOC01-appb-C000050
  
　上記式（Ｉ’’）中、ＲFは水素原子又はメチル基を表し、ＲGは置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、ヒドロキシル基、カルボキシル基、ハロゲン原子、置換基を有していてもよいアルコキシ基、チオール基、又は置換基を有していてもよいアルキルスルフィド基を表す。ｔは０～５の整数を表す。 In the above formula (I ′ ′), R F represents a hydrogen atom or a methyl group, R G represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a hydroxyl group, It represents a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent. t represents an integer of 0 to 5;
（ＲG）
　前記式（Ｉ’’）においてＲGは置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、ヒドロキシル基、カルボキシル基、ハロゲン原子、置換基を有していてもよいアルコキシ基、チオール基、又は置換基を有していてもよいアルキルスルフィド基を表す。
　ＲGにおけるアルキル基としては、直鎖状、分岐鎖状又は環状のアルキル基が挙げられる。その炭素数は、１以上であることが好ましく、３以上であることがより好ましく、５以上であることがさらに好ましく、また、２０以下であることが好ましく、１８以下であることがより好ましく、１６以下であることがさらに好ましく、１４以下であることがよりさらに好ましく、１２以下であることが特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 (R G )
In the above formula (I ′ ′), R G has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom and a substituent It may be an alkoxy group which may be substituted, a thiol group, or an alkyl sulfide group which may have a substituent.
The alkyl group in R G includes a linear, branched or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 20 or less, more preferably 18 or less, It is more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　アルキル基の具体例としては、メチル基、エチル基、シクロヘキシル基、ジシクロペンタニル基、ドデカニル基等が挙げられる。これらの中でも現像密着性の観点から、ジシクロペンタニル基又はドデカニル基が好ましく、ジシクロペンタニル基がより好ましい。
　また、アルキル基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基などが挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, a dodecanyl group and the like. Among these, from the viewpoint of development adhesion, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable.
Moreover, as a substituent which the alkyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group And an acryloyl group, a methacryloyl group and the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
　ＲGにおけるアルケニル基としては、直鎖状、分岐鎖状又は環状のアルケニル基が挙げられる。その炭素数は、２以上であることが好ましく、また、２２以下であることが好ましく、２０以下であることがより好ましく、１８以下であることがさらに好ましく、１６以下であることがよりさらに好ましく、１４以下であることが特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 The alkenyl group in R G includes a linear, branched or cyclic alkenyl group. The carbon number thereof is preferably 2 or more, 22 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less. , 14 or less is particularly preferable. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　アルケニル基の具体例としては、エテニル基、プロペニル基、ブチレニル基、シクロヘキセニル基等が挙げられる。これらの中でも硬化性の観点から、エテニル基又はプロペニル基が好ましく、エテニル基がより好ましい。
　また、アルケニル基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基などが挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Specific examples of the alkenyl group include ethenyl group, propenyl group, butyrenyl group, cyclohexenyl group and the like. Among these, from the viewpoint of curability, an ethenyl group or a propenyl group is preferable, and an ethenyl group is more preferable.
Moreover, as a substituent which an alkenyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　ＲGにおけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、これらの中でも撥インク性の観点からはフッ素原子が好ましい。 As a halogen atom in RG , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Among these, a fluorine atom is preferable from the viewpoint of ink repellency.
　ＲGにおけるアルコキシ基としては、直鎖状、分岐鎖状又は環状のアルコキシ基が挙げられる。その炭素数は、１以上であることが好ましく、また、２０以下であることが好ましく、１８以下であることがより好ましく、１６以下であることがさらに好ましく、１４以下であることがよりさらに好ましく、１２以下であることが特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 The alkoxy group in R G includes a linear, branched or cyclic alkoxy group. The carbon number thereof is preferably 1 or more, preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less. , 12 or less is particularly preferable. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　また、アルコキシ基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基などが挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Moreover, as a substituent which the alkoxy group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group And an acryloyl group, a methacryloyl group and the like, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
　ＲGにおけるアルキルスルフィド基としては、直鎖状、分岐鎖状又は環状のアルキルスルフィド基が挙げられる。その炭素数は、１以上であることが好ましく、また、２０以下であることが好ましく、１８以下であることがより好ましく、１６以下であることがさらに好ましく、１４以下であることがよりさらに好ましく、１２以下であることが特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。 As an alkyl sulfide group in RG , a linear, branched or cyclic alkyl sulfide group can be mentioned. The carbon number thereof is preferably 1 or more, preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less. , 12 or less is particularly preferable. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced.
　アルキルスルフィド基の具体例としては、メチルスルフィド基、エチルスルフィド基、プロピルスルフィド基、ブチルスルフィド基等が挙げられる。これらの中でも現像性の観点から、メチルスルフィド基又はエチルスルフィド基が好ましい。
　また、アルキルスルフィド基におけるアルキル基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基などが挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 A methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group etc. are mentioned as a specific example of an alkyl sulfide group. Among these, from the viewpoint of developability, a methyl sulfide group or an ethyl sulfide group is preferable.
Moreover, as a substituent which the alkyl group in the alkyl sulfide group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl Groups, carboxyl groups, acryloyl groups, methacryloyl groups and the like, and from the viewpoint of developability, hydroxy groups and oligoethylene glycol groups are preferred.
　このように、ＲGは置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、ヒドロキシル基、カルボキシル基、ハロゲン原子、アルコキシ基、ヒドロキシアルキル基、チオール基、又は置換基を有していてもよいアルキルスルフィド基を表すが、これらの中でも現像性の観点から、ヒドロキシル基又はカルボキシル基が好ましく、カルボキシル基がより好ましい。 Thus, R G is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, Or an alkyl sulfide group which may have a substituent, but among these, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable.
（ｔ）
　前記式（Ｉ’’）においてｔは０～５の整数を表す。現像性の観点から、２以下が好ましく、１以下がより好ましく、０がさらに好ましい。 (T)
In the formula (I ′ ′), t represents an integer of 0 to 5. From the viewpoint of developability, 2 or less is preferable, 1 or less is more preferable, and 0 is more preferable.
　アクリル共重合樹脂（ｂ２－１）が前記一般式（Ｉ’’）で表される部分構造を含む場合、アクリル共重合樹脂（ｂ２－１）に含まれる前記一般式（Ｉ’’）で表される部分構造の含有割合は特に限定されないが、１モル％以上が好ましく、２モル％以上がより好ましく、３モル％以上がさらに好ましく、５モル％以上が特に好ましく、また、９０モル％以下が好ましく、７０モル％以下がより好ましく、５０モル％以下がさらに好ましく、３０モル％以下がよりさらに好ましく、２０モル％以下が特に好ましく、１０モル％以下が最も好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。アクリル共重合樹脂（ｂ２－１）が前記一般式（Ｉ’’）で表される部分構造を含む場合、アクリル共重合樹脂（ｂ２－１）に含まれる前記一般式（Ｉ’’）で表される部分構造の含有割合としては、例えば、１～９０モル％であり、２～７０モル％が好ましく、２～５０モル％がより好ましく、３～３０モル％がさらに好ましく、３～２０モル％がよりさらに好ましく、５～１０モル％が特に好ましい。 When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I ′ ′), a table of the above general formula (I ′ ′) contained in the acrylic copolymer resin (b2-1) The content ratio of the partial structure to be formed is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 3 mol% or more, particularly preferably 5 mol% or more, and 90 mol% or less Is preferably 70 mol% or less, more preferably 50 mol% or less, still more preferably 30 mol% or less, particularly preferably 20 mol% or less, and most preferably 10 mol% or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the residue tends to be reduced. When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I ′ ′), a table of the above general formula (I ′ ′) contained in the acrylic copolymer resin (b2-1) The content ratio of the partial structure to be added 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%, and 3 to 20 mol. % Is more preferable, and 5 to 10 mol% is particularly preferable.
　アクリル共重合樹脂（ｂ２－１）が前記一般式（Ｉ）で表される部分構造を含む場合、現像性の観点から下記一般式（Ｉ’’’）で表される部分構造をさらに含むことが好ましい。 When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I), it further includes the partial structure represented by the following general formula (I ′ ′ ′) from the viewpoint of developability. Is preferred.
Figure JPOXMLDOC01-appb-C000051
  
Figure JPOXMLDOC01-appb-C000051
  
　上記式（Ｉ’’’）中、ＲHは水素原子又はメチル基を表す。 In the above formula (I ′ ′ ′), R H represents a hydrogen atom or a methyl group.
　アクリル共重合樹脂（ｂ２－１）が前記一般式（Ｉ’’’）で表される部分構造を含む場合、アクリル共重合樹脂（ｂ２－１）に含まれる前記一般式（Ｉ’’’）で表される部分構造の含有割合は特に限定されないが、５モル％以上が好ましく、１０モル％以上がより好ましく、３０モル％以上がさらに好ましく、また、９０モル％以下が好ましく、８０モル％以下がより好ましく、７０モル％以下がさらに好ましく、５０モル％以下が特に好ましい。前記下限値以上とすることで残渣が低減する傾向があり、また、前記上限値以下とすることで現像密着性が向上する傾向がある。アクリル共重合樹脂（ｂ２－１）が前記一般式（Ｉ’’’）で表される部分構造を含む場合、アクリル共重合樹脂（ｂ２－１）に含まれる前記一般式（Ｉ’’’）で表される部分構造の含有割合としては、例えば、５～９０モル％であり、５～８０モル％が好ましく、１０～７０モル％がより好ましく、３０～５０モル％がさらに好ましい。一方で、アウトガスの観点から、０％、つまり、前記一般式（Ｉ’’’）で表される部分構造を含まないことが好ましい。 When the acrylic copolymer resin (b2-1) contains a partial structure represented by the above general formula (I ′ ′ ′), the above general formula (I ′ ′ ′) contained in the acrylic copolymer resin (b2-1) The content ratio of the partial structure represented by is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 30 mol% or more, and preferably 90 mol% or less, 80 mol% The following is more preferable, 70 mol% or less is more preferable, and 50 mol% or less is particularly preferable. By setting the content to the above lower limit value, the residue tends to be reduced, and by setting the content to the above upper limit value, the development adhesion tends to be improved. When the acrylic copolymer resin (b2-1) contains a partial structure represented by the above general formula (I ′ ′ ′), the above general formula (I ′ ′ ′) contained in the acrylic copolymer resin (b2-1) The content ratio of the partial structure represented by 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 outgassing, 0%, that is, it is preferable not to include the partial structure represented by the general formula (I ′ ′ ′).
　アクリル共重合樹脂（ｂ２）の酸価は特に限定されないが、５ｍｇ－ＫＯＨ／ｇ以上が好ましく、１０ｍｇ－ＫＯＨ／ｇ以上がより好ましく、２０ｍｇ－ＫＯＨ／ｇ以上がさらに好ましく、２５ｍｇ－ＫＯＨ／ｇ以上がよりさらに好ましく、また、１００ｍｇ－ＫＯＨ／ｇ以下が好ましく、８０ｍｇ－ＫＯＨ／ｇ以下がより好ましく、６０ｍｇ－ＫＯＨ／ｇ以下がさらに好ましく、４０ｍｇ－ＫＯＨ／ｇ以下がよりさらに好ましい。前記下限値以上とすることで残渣が低減する傾向があり、また、前記上限値以下とすることで現像密着性が向上する傾向がある。アクリル共重合樹脂（ｂ２）の酸価としては、例えば、５～１００ｍｇ－ＫＯＨ／ｇであり、１０～８０ｍｇ－ＫＯＨ／ｇが好ましく、２０～６０ｍｇ－ＫＯＨ／ｇがより好ましく、２５～４０ｍｇ－ＫＯＨ／ｇがさらに好ましい。 The acid value of the acrylic copolymer resin (b2) is not particularly limited, but is preferably 5 mg-KOH / g or more, more preferably 10 mg-KOH / g or more, further preferably 20 mg-KOH / g or more, 25 mg-KOH / g The above is more preferable, and 100 mg-KOH / g or less is preferable, 80 mg-KOH / g or less is more preferable, 60 mg-KOH / g or less is more preferable, and 40 mg-KOH / g or less is still more preferable. By setting the content to the above lower limit value, the residue tends to be reduced, and by setting the content to the above upper limit value, the development adhesion tends to be improved. The acid value of the acrylic copolymer resin (b2) is, for example, 5 to 100 mg-KOH / g, preferably 10 to 80 mg-KOH / g, more preferably 20 to 60 mg-KOH / g, and 25 to 40 mg KOH / g is more preferred.
　アクリル共重合樹脂（ｂ２）の重量平均分子量（Ｍｗ）は特に限定されないが、好ましくは１０００以上、より好ましくは２０００以上、さらに好ましくは３０００以上、よりさらに好ましくは４０００以上、特に好ましくは５０００以上であり、また、通常３００００以下、好ましくは２００００以下、より好ましくは１５０００以下、さらに好ましくは１００００以下である。特に好ましくは８０００以下である。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで残渣が低減する傾向がある。アクリル共重合樹脂（ｂ２）の重量平均分子量（Ｍｗ）としては、例えば、１０００～３００００であり、２０００～２００００が好ましく、３０００～１５０００がより好ましく、４０００～１００００がさらに好ましく、５０００～８０００がよりさらに好ましい。 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, still more preferably 3000 or more, still more preferably 4000 or more, particularly preferably 5000 or more Also, it is usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, and still more preferably 10000 or less. Particularly preferably, it is 8000 or less. When the content is at least the lower limit value, the development adhesion tends to be improved, and when the content is at most the upper limit value, the 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 more preferably 5000 to 8000. More preferable.
　（Ｂ）アルカリ可溶性樹脂がアクリル共重合樹脂（ｂ２）を含む場合、（Ｂ）アルカリ可溶性樹脂に含まれるアクリル共重合樹脂（ｂ２）の含有割合は特に限定されないが、５質量％以上が好ましく、１０質量％以上がより好ましく、１５質量％以上がさらに好ましく、２０質量％以上が特に好ましく、また、通常１００質量％以下が好ましく、８０質量％以下がより好ましく、５０質量％以下がさらに好ましい。前記下限値以上とすることで現像溶解性が良好となる傾向があり、前記上限値以下とすることでテーパー角が高くなる傾向がある。（Ｂ）アルカリ可溶性樹脂がアクリル共重合樹脂（ｂ２）を含む場合、（Ｂ）アルカリ可溶性樹脂に含まれるアクリル共重合樹脂（ｂ２）の含有割合としては、例えば、５～１００質量％であり、１０～１００質量％が好ましく、１５～８０質量％がより好ましく、２０～５０質量％がさらに好ましい。 When the alkali-soluble resin (B) contains an acrylic copolymer resin (b2), the content ratio of the acrylic copolymer resin (b2) contained in the (B) alkali-soluble resin is not particularly limited, but 5% by mass or more is preferable, 10 mass% or more is more preferable, 15 mass% or more is more preferable, 20 mass% or more is particularly preferable, and usually 100 mass% or less is preferable, 80 mass% or less is more preferable, 50 mass% or less is more preferable. When the content is at least the lower limit, the development solubility tends to be good, and when the content is at the upper limit or less, the taper angle tends to be high. When the alkali-soluble resin (B) contains the acrylic copolymer resin (b2), the content ratio of the acrylic copolymer resin (b2) contained in the (B) alkali-soluble resin is, for example, 5 to 100% by mass. 10 to 100% by mass is preferable, 15 to 80% by mass is more preferable, and 20 to 50% by mass is more preferable.
　（Ｂ）アルカリ可溶性樹脂中には、エポキシ（メタ）アクリレート樹脂（ｂ１）及びアクリル共重合樹脂（ｂ２）のいずれかが単独で含まれていてもよく、両者が含まれていてもよい。さらに、（Ｂ）アルカリ可溶性樹脂中にはアルカリ可溶性樹脂（ｂ）以外のアルカリ可溶性樹脂が含まれていてもよい。 In the alkali-soluble resin (B), either the epoxy (meth) acrylate resin (b1) or the acrylic copolymer resin (b2) may be contained alone, or both may be contained. Furthermore, alkali-soluble resins other than the alkali-soluble resin (b) may be contained in the (B) alkali-soluble resin.
　本発明の感光性樹脂組成物における（Ｂ）アルカリ可溶性樹脂の含有割合は、全固形分中に、通常５質量％以上、好ましくは１０質量％以上、より好ましくは２０質量％以上、さらに好ましくは３０質量％以上、特に好ましくは４０質量％以上、また、通常９０質量％以下、好ましくは７０質量％以下、より好ましくは６０質量％以下、特に好ましくは５０質量％以下である。前記下限値以上とすることで現像性が向上する傾向があり、また、前記上限値以下とすることで素子発光時のアウトガスを低減する傾向がある。感光性樹脂組成物の全固形分中における（Ｂ）アルカリ可溶性樹脂の含有割合としては、例えば、１０～９０質量％であり、２０～７０質量％が好ましく、３０～６０質量％がより好ましく、４０～５０質量％がさらに好ましい。 The content ratio of the (B) alkali-soluble resin in the photosensitive resin composition of the present invention is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, based on the total solid content. The content is 30% by mass or more, 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, particularly preferably 50% by mass or less. When the content is at least the lower limit, developability tends to be improved, and when the content is at most the upper limit, outgas at the time of light emission of the element tends to be reduced. The content ratio of the (B) alkali-soluble resin in the total solid content of the photosensitive resin composition is, for example, 10 to 90% by mass, preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, 40 to 50% by mass is more preferable.
　また、本発明の感光性樹脂組成物がエポキシ（メタ）アクリレート樹脂（ｂ１）を含む場合、エポキシ（メタ）アクリレート樹脂（ｂ１）の含有割合は特に限定されないが、全固形分中に、通常５質量％以上、好ましくは１０質量％以上、より好ましくは２０質量％以上、さらに好ましくは３０質量％以上、特に好ましくは４０質量％以上、また、通常９０質量％以下、好ましくは７０質量％以下、より好ましくは６０質量％以下、特に好ましくは５０質量％以下である。前記下限値以上とすることで現像性が向上する傾向があり、また、前記上限値以下とすることで素子発光時のアウトガスを低減する傾向がある。本発明の感光性樹脂組成物がエポキシ（メタ）アクリレート樹脂（ｂ１）を含む場合、エポキシ（メタ）アクリレート樹脂（ｂ１）の全固形分中の含有割合としては、例えば、５～９０質量％であり、１０～７０質量％が好ましく、２０～６０質量％がより好ましく、３０～５０質量％がさらに好ましく、４０～５０質量％がよりさらに好ましい。 Moreover, when the photosensitive resin composition of this invention contains an epoxy (meth) acrylate resin (b1), although the content rate of an epoxy (meth) acrylate resin (b1) is not specifically limited, In all the solid content, normally 5 % By mass, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less More preferably, it is 60% by mass or less, particularly preferably 50% by mass or less. When the content is at least the lower limit, developability tends to be improved, and when the content is at most the upper limit, outgas at the time of light emission of the element tends to be reduced. When the photosensitive resin composition of the present invention contains an epoxy (meth) acrylate resin (b1), the content ratio of the epoxy (meth) acrylate resin (b1) in the total solid content is, for example, 5 to 90% by mass 10 to 70% by mass is preferable, 20 to 60% by mass is more preferable, 30 to 50% by mass is more preferable, and 40 to 50% by mass is even more preferable.
　また、本発明の感光性樹脂組成物がエポキシアクリル共重合樹脂（ｂ２）を含む場合、アクリル共重合樹脂（ｂ２）の含有割合は特に限定されないが、全固形分中に、通常５質量％以上、好ましくは１０質量％以上、より好ましくは２０質量％以上、さらに好ましくは３０質量％以上、特に好ましくは４０質量％以上、また、通常９０質量％以下、好ましくは７０質量％以下、より好ましくは６０質量％以下、特に好ましくは５０質量％以下である。前記下限値以上とすることで現像性が向上する傾向があり、また、前記上限値以下とすることで素子発光時のアウトガスを低減する傾向がある。本発明の感光性樹脂組成物がエポキシアクリル共重合樹脂（ｂ２）を含む場合、アクリル共重合樹脂（ｂ２）の全固形分中の含有割合としては、例えば、５～９０質量％であり、１０～７０質量％が好ましく、２０～６０質量％がより好ましく、３０～５０質量％がさらに好ましく、４０～５０質量％がよりさらに好ましい。 Moreover, when the photosensitive resin composition of this invention contains an epoxy acrylic copolymer resin (b2), although the content rate of an acrylic copolymer resin (b2) is not specifically limited, Usually 5 mass% or more in a total solid. , Preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less, more preferably It is 60% by mass or less, particularly preferably 50% by mass or less. When the content is at least the lower limit, developability tends to be improved, and when the content is at most the upper limit, outgas 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 ratio of the acrylic copolymer resin (b2) in the total solid content is, for example, 5 to 90% by mass, 10 -70% by mass is preferable, 20 to 60% by mass is more preferable, 30 to 50% by mass is more preferable, and 40 to 50% by mass is even more preferable.
　また、全固形分中における（Ｂ）アルカリ可溶性樹脂及び（Ｃ）光重合性化合物の含有割合の合計は、通常５質量％以上、好ましくは１０質量％以上、より好ましくは３０質量％以上、さらに好ましくは５０質量％以上、よりさらに好ましくは７０質量％以上、特に好ましくは８０質量％以上であり、最も好ましくは９０質量％以上であり、また、通常９９質量％以下、好ましくは９７質量％以下、より好ましくは９５質量％以下である。前記下限値以上とすることで硬化性が向上する傾向があり、また、前記上限値以下とすることで素子発光時のアウトガス低減する傾向がある。全固形分中における（Ｂ）アルカリ可溶性樹脂及び（Ｃ）光重合性化合物の含有割合の合計としては、例えば、５～９９質量％であり、１０～９９質量％が好ましく、３０～９９質量％がより好ましく、５０～９７質量％がさらに好ましく、７０～９７質量％がよりさらに好ましく、８０～９５質量％が特に好ましく、９０～９５質量％が最も好ましい。 The total content of the (B) alkali-soluble resin and the (C) photopolymerizable compound 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, and further The content is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, 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. There is a tendency for the curability to be improved by setting it to the above lower limit value, and there is a tendency to reduce the outgassing at the time of light emission of the device by setting it to the above upper limit value. The total content of the (B) alkali-soluble resin and the (C) photopolymerizable compound in the total solid content is, for example, 5 to 99% by mass, preferably 10 to 99% by mass, and 30 to 99% by mass. Is more preferably 50 to 97% by mass, still more preferably 70 to 97% by mass, particularly preferably 80 to 95% by mass, and most preferably 90 to 95% by mass.
　また、感光性樹脂組成物における（Ｃ）光重合性化合物に対する（Ｂ）アルカリ可溶性樹脂の配合比としては、（Ｃ）光重合性化合物１００質量部に対して、５０質量部以上が好ましく、６０質量部以上がより好ましく、７０質量部以上がさらに好ましく、８０質量部以上が特に好ましく、また、４００質量部以下が好ましく、３００質量部以下がより好ましく、２００質量部以下がさらに好ましく、１００質量部以下が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向があり、また、前記上限値以下とすることで硬化性が向上する傾向がある。感光性樹脂組成物における（Ｃ）光重合性化合物１００質量部に対する（Ｂ）アルカリ可溶性樹脂の配合比としては、例えば、５０～４００質量部であり、６０～３００質量部が好ましく、７０～２００質量部がより好ましく、８０～１００質量部がさらに好ましい。 Moreover, as a compounding ratio of (B) alkali-soluble resin with respect to (C) photopolymerizable compound in the photosensitive resin composition, 50 mass parts or more are preferable with respect to 100 mass parts of (C) photopolymerizable compounds, More preferably, it is 70 parts by mass or more, more preferably 80 parts by mass or more, and preferably 400 parts by mass or less, more preferably 300 parts by mass or less, and even more preferably 200 parts by mass or less. Part or less is particularly preferred. By setting the amount to the above lower limit value or more, the development adhesion tends to be improved, and by setting the amount to the above upper limit value, the curability tends to be improved. The compounding ratio of the (B) alkali-soluble resin to 100 parts by mass of the (C) photopolymerizable compound in the photosensitive resin composition is, for example, 50 to 400 parts by mass, preferably 60 to 300 parts by mass, and 70 to 200 The mass part is more preferable, and 80 to 100 parts by mass is more preferable.
［１－１－３］（Ｃ）成分；光重合性化合物
　本発明の感光性樹脂組成物は、（Ｃ）光重合性化合物を含有する。（Ｃ）光重合性化合物を含むことで、高感度となると考えられる。
　ここで使用される光重合性化合物としては、エチレン性不飽和結合（エチレン性二重結合）を分子内に１個以上有する化合物を意味するが、重合性、架橋性、およびそれに伴う露光部と非露光部の現像液溶解性の差異を拡大できる等の点から、エチレン性不飽和結合を分子内に２個以上有する化合物であることが好ましく、また、その不飽和結合は（メタ）アクリロイルオキシ基に由来するもの、つまり、（メタ）アクリレート化合物であることがさらに好ましい。 [1-1-3] (C) Component; Photopolymerizable Compound The photosensitive resin composition of the present invention contains (C) a photopolymerizable compound. It is considered that the sensitivity becomes high by including the (C) photopolymerizable compound.
The photopolymerizable compound to be used herein means a compound having one or more ethylenically unsaturated bonds (ethylenic double bonds) in the molecule, but the polymerizability, the crosslinkability, and the exposed part associated therewith It is preferable that the compound has two or more ethylenic unsaturated bonds in the molecule from the viewpoint that the developer solubility difference in the non-exposed area can be expanded, and the unsaturated bond is (meth) acryloyloxy. It is further preferred that the group is derived from a group, that is, a (meth) acrylate compound.
　本発明の感光性樹脂組成物においては、特に、１分子中にエチレン性不飽和結合を２個以上有する多官能エチレン性単量体を使用することが望ましい。多官能エチレン性単量体が有するエチレン性不飽和基の数は特に限定されないが、好ましくは２個以上、より好ましくは３個以上、さらに好ましくは４個以上、特に好ましくは５個以上であり、また、好ましくは１５個以下、より好ましくは１０個以下、さらに好ましくは８個以下、特に好ましくは７個以下である。前記下限値以上とすることで重合性が向上して高感度となる傾向があり、前記上限値以下とすることで現像性がより良好となる傾向がある。多官能エチレン性単量体が有するエチレン性不飽和基の数としては、例えば、２～１５個であり、３～１０個が好ましく、４～８個がより好ましく、５～７個がさらに好ましい。
　光重合性化合物の具体例としては、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と、不飽和カルボン酸及び多塩基性カルボン酸とのエステル化反応により得られるエステルなどが挙げられる。 In the photosensitive resin composition of the present invention, in particular, it is desirable to use a polyfunctional ethylenic monomer having two or more ethylenic unsaturated bonds in one molecule. The number of ethylenically unsaturated groups contained in the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, particularly preferably 5 or more. And preferably not more than 15, more preferably not more than 10, still more preferably not more than 8, and particularly preferably not more than 7. By setting the content to the above lower limit or more, the polymerizability tends to be improved and the sensitivity becomes high, and by setting the content to the above upper limit or less, the developability tends to be better. The number of ethylenically unsaturated groups possessed by 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 polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, etc. And esters obtained by the esterification reaction of the polyhydroxy compound of formula (I) with unsaturated carboxylic acid and polybasic carboxylic acid.
　前記脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールエタントリアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、グリセロールアクリレート等の脂肪族ポリヒドロキシ化合物のアクリル酸エステル、これら例示化合物のアクリレートをメタクリレートに代えたメタクリル酸エステル、同様にイタコネートに代えたイタコン酸エステル、クロネートに代えたクロトン酸エステルもしくはマレエートに代えたマレイン酸エステル等が挙げられる。 Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate and pentaerythritol triacrylate. Acrylic esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. Methacrylates wherein acrylates of these exemplified compounds are replaced by methacrylates , Itaconic acid ester similarly substituted to itaconate, ク ロ ネMaleic acid esters in which instead of the crotonic acid ester or maleate was changed to bets and the like.
　芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、ハイドロキノンジアクリレート、ハイドロキノンジメタクリレート、レゾルシンジアクリレート、レゾルシンジメタクリレート、ピロガロールトリアクリレート等の芳香族ポリヒドロキシ化合物のアクリル酸エステル及びメタクリル酸エステル等が挙げられる。
　脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と、不飽和カルボン酸及び多塩基性カルボン酸とのエステル化反応により得られるエステルとしては必ずしも単一物ではないが、代表的な具体例を挙げれば、アクリル酸、フタル酸、及びエチレングリコールの縮合物、アクリル酸、マレイン酸、及びジエチレングリコールの縮合物、メタクリル酸、テレフタル酸及びペンタエリスリトールの縮合物、アクリル酸、アジピン酸、ブタンジオール及びグリセリンの縮合物等が挙げられる。 As esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcine diacrylate, resorcine dimethacrylate, pyrogallol triacrylate and the like Etc.
The esters obtained by the esterification reaction of polyvalent hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily single substances, but they are representative. Specific 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, acrylic acid, adipic acid, Examples thereof include condensates of butanediol and glycerin.
　その他、本発明の感光性樹脂組成物に用いられる光重合性化合物の例としては、ポリイソシアネート化合物と水酸基含有（メタ）アクリル酸エステル又はポリイソシアネート化合物とポリオール及び水酸基含有（メタ）アクリル酸エステルを反応させて得られるようなウレタン（メタ）アクリレート類；多価エポキシ化合物と水酸基含有（メタ）アクリル酸エステル又は（メタ）アクリル酸との付加反応物のようなエポキシアクリレート類；エチレンビスアクリルアミド等のアクリルアミド類；フタル酸ジアリル等のアリルエステル類；ジビニルフタレート等のビニル基含有化合物等が有用である。
　上記ウレタン（メタ）アクリレート類としては、例えば、ＤＰＨＡ－４０Ｈ、ＵＸ－５０００、ＵＸ－５００２Ｄ－Ｐ２０、ＵＸ－５００３Ｄ、ＵＸ－５００５（日本化薬社製）、Ｕ－２ＰＰＡ、Ｕ－６ＬＰＡ、Ｕ－１０ＰＡ、Ｕ－３３Ｈ、ＵＡ－５３Ｈ、ＵＡ－３２Ｐ、ＵＡ－１１００Ｈ（新中村化学工業社製）、ＵＡ－３０６Ｈ、ＵＡ－５１０Ｈ、ＵＦ－８００１Ｇ（協栄社化学社製）、ＵＶ－１７００Ｂ、ＵＶ－７６００Ｂ、ＵＶ－７６０５Ｂ、ＵＶ－７６３０Ｂ、ＵＶ７６４０Ｂ（日本合成化学工業社製）等が挙げられる。 In addition, as an example of the photopolymerizable compound used for the photosensitive resin composition of this invention, a polyisocyanate compound, a hydroxyl group containing (meth) acrylic acid ester or polyisocyanate compound, a polyol, and a hydroxyl group containing (meth) acrylic acid ester Urethane (meth) acrylates obtained by reaction; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxyl group-containing (meth) acrylic acid ester or (meth) acrylic acid; ethylene bis acrylamide etc. Acrylamides; 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 Kayaku Co., Ltd.), U-2PPA, U-6LPA, U. -10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B , UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and the like.
　これらの中でも、適正なテーパー角と感度の観点から（Ｃ）光重合性化合物として、エステル（メタ）アクリレート類又はウレタン（メタ）アクリレート類を用いることが好ましく、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、２－トリス（メタ）アクリロイロキシメチルエチルフタル酸、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレートの二塩基酸無水物付加物、ペンタエリスリトールトリ（メタ）アクリレートの二塩基酸無水物付加物等を用いることがより好ましい。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Among these, it is preferable to use ester (meth) acrylates or urethane (meth) acrylates as the photopolymerizable compound (C) from the viewpoint of appropriate taper angle and sensitivity, and dipentaerythritol hexa (meth) acrylate, Dipentaerythritol penta (meth) acrylate, 2-tris (meth) acryloyloxymethylethyl phthalic acid, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate dibasic It is more preferable to use an acid anhydride adduct, a dibasic acid anhydride adduct of pentaerythritol tri (meth) acrylate, or the like.
One of these may be used alone, or two or more may be used in combination.
　本発明の感光性樹脂組成物において、（Ｃ）光重合性化合物の分子量は特に限定されないが、感度、撥インク性、テーパー角の観点から、好ましくは１００以上、より好ましくは１５０以上で、さらに好ましくは２００以上、よりさらに好ましくは３００以上、特に好ましくは４００以上、最も好ましくは５００以上であり、好ましくは１０００以下、より好ましくは７００以下である。（Ｃ）光重合性化合物の分子量としては、例えば、１００～１０００であり、１５０～７００が好ましく、２００～７００がより好ましく、３００～７００がさらに好ましく、４００～７００がよりさらに好ましく、５００～７００が特に好ましい。
　また、（Ｃ）光重合性化合物の炭素数は特に限定されないが、感度、撥インク性、テーパー角の観点から、好ましくは７以上、より好ましくは１０以上、さらに好ましくは１５以上、よりさらに好ましくは２０以上、特に好ましくは２５以上であり、好ましくは５０以下、より好ましくは４０以下、さらに好ましくは３５以下、特に好ましくは３０以下である。（Ｃ）光重合性化合物の炭素数としては、例えば、７～５０であり、１０～４０が好ましく、１５～３５がより好ましく、２０～３０がさらに好ましく、２５～３０がよりさらに好ましい。
　また、感度、撥インク性、テーパー角の観点から、エステル（メタ）アクリレート類、エポキシ（メタ）アクリレート類、およびウレタン（メタ）アクリレート類が好ましく、中でも、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレートなど３官能以上のエステル（メタ）アクリレート類、２，２，２－トリス（メタ）アクリロイロキシメチルエチルフタル酸、ジペンタエリスリトールペンタ（メタ）アクリレートの二塩基酸無水物付加物等の３官能以上のエステル（メタ）アクリレート類への酸無水物の付加物が、感度、撥インク性、テーパー角の観点でさらに好ましい。 In the photosensitive resin composition of the present invention, the molecular weight of the (C) photopolymerizable compound is not particularly limited, but it is preferably 100 or more, more preferably 150 or more, from the viewpoints of sensitivity, ink repellency and taper angle. It is preferably 200 or more, more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, preferably 1000 or less, more preferably 700 or less. The molecular weight of the photopolymerizable compound (C) is, for example, 100 to 1000, preferably 150 to 700, more preferably 200 to 700, still more preferably 300 to 700, and still more preferably 400 to 700. 700 is particularly preferred.
The carbon number of the (C) photopolymerizable compound is not particularly limited, but is preferably 7 or more, more preferably 10 or more, still more preferably 15 or more, still more preferably from the viewpoints of sensitivity, ink repellency and taper angle. Is 20 or more, particularly preferably 25 or more, preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, particularly preferably 30 or less. The carbon number 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.
In addition, from the viewpoints of sensitivity, ink repellency and taper angle, ester (meth) acrylates, epoxy (meth) acrylates and urethane (meth) acrylates are preferable, and among them, pentaerythritol tetra (meth) acrylate and pentaerythritol Trifunctional or higher ester (meth) acrylates such as tri (meth) acrylate dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate, 2,2,2-tris (meth) acryloyloxymethylethyl phthalate Acid anhydride adducts with trifunctional or higher ester (meth) acrylates such as acid, dibasic acid anhydride adduct of dipentaerythritol penta (meth) acrylate, etc., in terms of sensitivity, ink repellency and taper angle More preferred.
　本発明の感光性樹脂組成物における（Ｃ）光重合性化合物の含有割合は、全固形分中に通常５質量％以上、好ましくは１０質量％以上、より好ましくは２０質量％以上、さらに好ましくは３０質量％以上、特に好ましくは４０質量％以上、通常８０質量％以下、好ましくは７０質量％以下、より好ましくは６０質量％以下、さらに好ましくは５５質量％以下、特に好ましくは５０質量％以下である。前記下限値以上とすることで露光時の感度やテーパー角が良好となる傾向があり、前記上限値以下とすることで現像性が良好となる傾向がある。感光性樹脂組成物の全固形分中における（Ｃ）光重合性化合物の含有割合としては、例えば、１０～８０質量％であり、２０～７０質量％が好ましく、３０～６０質量％がより好ましく、４０～５５質量％がさらに好ましく、４０～５０質量％がよりさらに好ましい。 The content ratio of the (C) photopolymerizable compound in the photosensitive resin composition of the present invention is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably in the total solid content. 30% by mass or more, particularly preferably 40% by mass or more, usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, particularly preferably 50% by mass or less is there. By setting the content to the above lower limit or more, the sensitivity and the taper angle at the time of exposure tend to be good, and by setting the above upper limit or less, the developability tends to be favorable. The content ratio of the (C) photopolymerizable compound in the total solid content of the photosensitive resin composition is, for example, 10 to 80% by mass, preferably 20 to 70% by mass, and more preferably 30 to 60% by mass. 40 to 55% by mass is more preferable, and 40 to 50% by mass is even more preferable.
　また、本発明の感光性樹脂組成物における（Ｂ）アルカリ可溶性樹脂１００質量部に対する（Ｃ）光重合性化合物の含有割合は、通常１５質量部以上、好ましくは３０質量部以上、より好ましくは５０質量部以上、さらに好ましくは８０質量部以上、特に好ましくは９０質量部以上であり、通常１５０質量部以下、好ましくは１３０質量部以下、より好ましくは１２０質量部以下、さらに好ましくは１１０質量部以下である。前記下限値以上とすることで露光時に感度が良好となり、テーパー角が良好となる傾向があり、前記上限値以下とすることで現像性が良好となる傾向がある。感光性樹脂組成物における（Ｂ）アルカリ可溶性樹脂１００質量部に対する（Ｃ）光重合性化合物の含有割合としては、例えば、１５～１５０質量部であり、３０～１３０質量部が好ましく、５０～１２０質量部がより好ましく、８０～１２０質量部がさらに好ましく、９０～１１０質量部がよりさらに好ましい。 The content ratio of the (C) photopolymerizable compound to 100 parts by mass of the (B) alkali-soluble resin in the photosensitive resin composition of the present invention is usually 15 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 It is not less than 80 parts by mass, particularly preferably not less than 90 parts by mass, usually not more than 150 parts by mass, preferably not more than 130 parts by mass, more preferably not more than 120 parts by mass, still more preferably not more than 110 parts by mass It is. By setting the lower limit value or more, the sensitivity at the time of exposure tends to be good, the taper angle tends to be good, and by setting the upper limit value or less, the developability tends to be good. The content ratio of the (C) photopolymerizable compound to 100 parts by mass of the (B) alkali-soluble resin in the photosensitive resin composition is, for example, 15 to 150 parts by mass, preferably 30 to 130 parts by mass, and 50 to 120 The mass part is more preferable, 80 to 120 parts by mass is more preferable, and 90 to 110 parts by mass is more preferable.
［１－１－４］（Ｄ）成分；光重合開始剤
　本発明の感光性樹脂組成物は、（Ｄ）光重合開始剤を含有する。光重合開始剤は、活性光線により、前記（Ｃ）光重合性化合物が有するエチレン性不飽和結合を重合させる化合物であれば特に限定されるものではなく、公知の光重合開始剤を用いることができる。 [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 (C) photopolymerizable compound by actinic light, and known photopolymerization initiators may be used. it can.
　本発明の感光性樹脂組成物は、（Ｄ）光重合開始剤として、この分野で通常用いられている光重合開始剤を使用することができる。このような光重合開始剤としては、例えば、ヘキサアリールビイミダゾール系光重合開始剤、アシルホスフィンオキサイド系光重合開始剤、オキシムエステル系光重合開始剤、トリアジン系光重合開始剤、アセトフェノン系光重合開始剤、ベンゾフェノン系光重合開始剤、が挙げられる。 The photosensitive resin composition of this invention can use the photoinitiator normally used in this field | area as a (D) photoinitiator. As such a photopolymerization initiator, for example, hexaarylbiimidazole photopolymerization initiator, acyl phosphine oxide photopolymerization initiator, oxime ester photopolymerization initiator, triazine photopolymerization initiator, acetophenone photopolymerization An initiator, a benzophenone series photoinitiator, etc. are mentioned.
　ヘキサアリールビイミダゾール系光重合開始剤としては、吸光度および感度、紫外線吸収剤の吸収波長とのマッチング性の観点から、下記一般式（１－１）及び／又は下記一般式（１－２）で表されるヘキサアリールビイミダゾール系化合物が好ましい。 As the hexaarylbiimidazole photopolymerization initiator, from the viewpoint of absorbance and sensitivity, and the matching property with the absorption wavelength of the ultraviolet light absorber, it is represented by the following general formula (1-1) and / or the following general formula (1-2) The hexaarylbiimidazole compounds represented are preferred.
Figure JPOXMLDOC01-appb-C000052
  
Figure JPOXMLDOC01-appb-C000052
  
　上記式中、Ｒ11～Ｒ13は、各々独立に置換基を有してもよい炭素数１～４のアルキル基、置換基を有してもよい炭素数１～４のアルコキシ基、又はハロゲン原子を表し、ｍ、ｎ及びｌは、各々独立に０～５の整数を表す。 In the above formulas, R 11 to R 13 each independently represent 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 And m, n and l each independently represent an integer of 0 to 5.
　Ｒ11～Ｒ13のアルキル基の炭素数は１～４の範囲内であれば特に限定されないが、感度の観点から、好ましくは３以下、より好ましくは２以下である。アルキル基は鎖状のものでも、環状のものでもよい。アルキル基の具体例としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基が挙げられ、中でもメチル基、エチル基が好ましい。Ｒ11～Ｒ13の炭素数１～４のアルキル基が有してもよい置換基としては、水素を除く１価の非金属原子団の基が用いられ、好ましい例としては、ハロゲン原子（－Ｆ、－Ｂｒ、－Ｃｌ、－Ｉ）、ヒドロキシル基、アルコキシ基が挙げられる。 The carbon number of the alkyl group of R 11 to R 13 is not particularly limited as long as it is within the range of 1 to 4. However, from the viewpoint of sensitivity, it is preferably 3 or less, more preferably 2 or less. The alkyl group may be linear or cyclic. As a specific example of an alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group is mentioned, for example, Especially, a methyl group and an ethyl group are preferable. As a substituent which the alkyl group having 1 to 4 carbon atoms having R 11 to R 13 may have, a group of monovalent nonmetallic atomic groups other than hydrogen is used, and as a preferable example, a halogen atom (— F, -Br, -Cl, -I), a hydroxyl group and an alkoxy group can be mentioned.
　また、Ｒ11～Ｒ13のアルコキシ基の炭素数は１～４の範囲内であれば特に限定されないが、感度の観点から、好ましくは３以下、より好ましくは２以下である。アルコキシ基のアルキル基部分は鎖状のものでも、環状のものでもよい。アルコキシ基の具体例とは、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロピルオキシ基、ブトキシ基が挙げられ、中でもメトキシ基、エトキシ基が好ましい。Ｒ11～Ｒ13の炭素数１～４のアルコキシ基が有してもよい置換基としてはアルキル基、アルコキシ基が挙げられるが、好ましくはアルキル基である。 The number of carbon atoms of the alkoxy group of R 11 to R 13 is not particularly limited as long as it is in the range of 1 to 4. However, from the viewpoint of sensitivity, it is preferably 3 or less, more preferably 2 or less. The alkyl group portion of the alkoxy group may be linear or cyclic. As a specific example of an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, isopropyloxy group, butoxy group is mentioned, for example, Especially, a methoxy group and an ethoxy group are preferable. Examples of the substituent which the alkoxy group having 1 to 4 carbon atoms of R 11 to R 13 may have include an alkyl group and an alkoxy group, and an alkyl group is preferable.
　また、Ｒ11～Ｒ13のハロゲン原子とは、例えば、塩素原子、ヨウ素原子、臭素原子、フッ素原子が挙げられ、中でも合成容易性の観点から、塩素原子又はフッ素原子が好ましく、塩素原子がより好ましい。
　これらの中でも、感度や合成容易性の観点から、Ｒ11～Ｒ13は各々独立にハロゲン原子であることが好ましく、塩素原子であることがより好ましい。 Further, examples of the halogen atom of R 11 to R 13 include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom. Among them, a chlorine atom or a fluorine atom is preferable from the viewpoint of easiness of synthesis, and a chlorine atom is more preferable. preferable.
Among these, from the viewpoint of sensitivity and easiness of synthesis, R 11 to R 13 are preferably each independently a halogen atom, and more preferably a chlorine atom.
　ｍ、ｎ及びｌは、各々独立に０～５の整数を表すが、合成容易性の観点から、ｍ、ｎ及びｌの少なくとも１つが１以上の整数であることが好ましく、ｍ、ｎ及びｌのうちいずれか１つが１であり、かつ、残りの２つが０であることがより好ましい。 m, n and l each independently represent an integer of 0 to 5, but from the viewpoint of synthesisability, preferably at least one of m, n and l is an integer of 1 or more, and m, n and l More preferably, one of them is 1 and the remaining 2 are 0.
　一般式（１－１）及び／又は一般式（１－２）で表されるヘキサアリールビイミダゾール系化合物としては、例えば、２，２’－ビス（ｏ－クロロフェニル）－４，５，４’，５’－テトラフェニルビイミダゾール、２，２’－ビス（ｏ－メチルフェニル）－４，５，４’，５’－テトラフェニルビイミダゾール、２，２’－ビス（ｏ－クロロフェニル）－４，４’，５，５’－テトラ（ｏ，ｐ－ジクロロフェニル）ビイミダゾール、２，２’－ビス（ｏ，ｐ－ジクロロフェニル）－４，４’，５，５’－テトラ（ｏ，ｐ－ジクロロフェニル）ビイミダゾール、２，２’－ビス（ｏ－クロロフェニル）－４，４’，５，５’－テトラ（ｐ－フルオロフェニル）ビイミダゾール、２，２’－ビス（ｏ－クロロフェニル）－４，４’，５，５’－テトラ（ｏ，ｐ－ジブロモフェニル）ビイミダゾール、２，２’－ビス（ｏ－ブロモフェニル）－４，４’，５，５’－テトラ（ｏ，ｐ－ジクロロフェニル）ビイミダゾール、２，２’－ビス（ｏ－クロロフェニル）－４，４’，５，５’－テトラ（ｐ－クロロナフチル）ビイミダゾール等が挙げられる。中でも、ヘキサフェニルビイミダゾール化合物が好ましく、そのイミダゾール環上の２，２’－位に結合したベンゼン環のｏ－位がメチル基、メトキシ基、又はハロゲン原子で置換されたものが更に好ましく、そのイミダゾール環上の４，４’，５，５’－位に結合したベンゼン環が無置換、又は、ハロゲン原子若しくはメトキシ基で置換されたもの等が好ましい。 Examples of the hexaarylbiimidazole compound represented by the general formula (1-1) and / or the general formula (1-2) include 2,2′-bis (o-chlorophenyl) -4,5,4 ′ , 5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,5,4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4 , 4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetra (o, p- Dichlorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-fluorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4 , 4 ', 5, 5' Tetra (o, p-dibromophenyl) biimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, 2,2 ′ And -bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-chloronaphthyl) biimidazole and the like. Among them, hexaphenylbiimidazole compounds are preferable, and compounds in which the o-position of the benzene ring bonded to the 2,2'-position on the imidazole ring is substituted with a methyl group, a methoxy group or a halogen atom are more preferable, It is preferable that the benzene ring bonded to the 4,4 ′, 5,5′-position on the imidazole ring be unsubstituted or substituted with a halogen atom or a methoxy group.
　（Ｄ）光重合開始剤として、一般式（１－１）で表されるヘキサアリールビイミダゾール系化合物と一般式（１－２）で表されるヘキサアリールビイミダゾール系化合物のいずれかを用いてもよく、両者を併用して用いてもよい。併用して用いる場合には、その比率については特に限定されない。 (D) As the photopolymerization initiator, either of the hexaarylbiimidazole compound represented by the general formula (1-1) and the hexaarylbiimidazole compound represented by the general formula (1-2) The two may be used in combination. When used in combination, the ratio is not particularly limited.
　また、アシルホスフィンオキサイド系光重合開始剤としては、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）フェニルフォスフィンオキサイド等を好ましいものとして挙げることができる。 Moreover, as an acyl phosphine oxide type photoinitiator, a 2, 4, 6- trimethyl benzoyl diphenyl phosphine oxide, a bis (2, 4, 6 trimethyl benzoyl) phenyl phosphine oxide etc. can be mentioned as a preferable thing. .
　オキシムエステル系光重合開始剤としては、カルバゾール骨格やジフェニルスルフィド骨格を有するオキシムエステル系化合物を含むことが好ましく、ジフェニルスルフィド骨格を有するオキシムエステル系化合物がより好ましい。ジフェニルスルフィド骨格を有するオキシムエステル系化合物を含むことにより、短波長の光吸収が強く、表面硬化性が向上するため、撥液剤の現像時の流出を抑制し、撥インク性が高まると考えられる。 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. By containing the oxime ester compound having a diphenyl sulfide skeleton, the light absorption of short wavelength is strong and the surface curability is improved, so it is considered that the outflow of the liquid repellent during development is suppressed and the ink repellency is enhanced.
　ジフェニルスルフィド骨格を有するオキシムエステル系化合物の化学構造は特に限定されないが、感度の観点から、下記一般式（Ｄ－Ｉ）で表されるものを用いることが好ましい。 The chemical structure of the oxime ester compound having a diphenyl sulfide skeleton is not particularly limited, but from the viewpoint of sensitivity, it is preferable to use one represented by the following general formula (D-I).
Figure JPOXMLDOC01-appb-C000053
  
Figure JPOXMLDOC01-appb-C000053
  
　上記一般式（Ｄ－Ｉ）において、Ｒ23は、置換基を有していてもよいアルキル基、又は置換基を有していてもよい芳香族環基を表す。
　Ｒ24は、置換基を有していてもよいアルキル基、又は置換基を有していてもよい芳香族環基を表す。
　Ｒ25は、水酸基、カルボキシル基又は下記一般式（Ｄ－ＩＩ）で表される基を表し、ｈは０～５の整数を表す。
　式（Ｄ－Ｉ）中に示されるベンゼン環はさらに置換基を有していてもよい。 In Formula (DI), R 23 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R 24 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R 25 represents a hydroxyl group, a carboxyl group or a group represented by the following formula (D-II), and h represents an integer of 0 to 5.
The benzene ring shown in Formula (DI) may further have a substituent.
Figure JPOXMLDOC01-appb-C000054
  
Figure JPOXMLDOC01-appb-C000054
  
　式（Ｄ－ＩＩ）中、Ｒ25aは、－Ｏ－、－Ｓ－、－ＯＣＯ－又は－ＣＯＯ－を表す。
　Ｒ25bは、置換基を有していてもよいアルキレン基を表す。
　Ｒ25bのアルキレン部分は、－Ｏ－、－Ｓ－、－ＣＯＯ－又は－ＯＣＯ－により１～５回中断されていてもよい。Ｒ25のアルキレン部分は分岐側鎖があってもよく、シクロヘキシレンであってもよい。
　Ｒ25cは、水酸基又はカルボキシル基を表す。 In formula (D-II), R 25a represents —O—, —S—, —OCO— or —COO—.
R 25b represents an alkylene group which may have a substituent.
The alkylene moiety of R 25b may be interrupted 1 to 5 times by -O-, -S-, -COO- or -OCO-. The alkylene moiety of R 25 may be branched side chain and may be cyclohexylene.
R 25c represents a hydroxyl group or a carboxyl group.
　Ｒ23におけるアルキル基の炭素数は特に限定されないが、溶剤への溶解性の観点から１以上であることが好ましい。また、現像性の観点から２０以下であることが好ましく、１０以下であることがより好ましく、８以下であることがさらに好ましく、５以下であることがよりさらに好ましく、３以下であることが特に好ましい。 The number of carbon atoms in the alkyl group in R 23 is not particularly limited, is preferably 1 or more from the viewpoint of solubility in solvents. Further, from the viewpoint of developability, it is preferably 20 or less, more preferably 10 or less, still more preferably 8 or less, still more preferably 5 or less, particularly preferably 3 or less. preferable.
　アルキル基の具体例としては、メチル基、ヘキシル基、シクロペンチルメチル基などが挙げられ、これらの中でも現像性の観点から、メチル基又はへキシル基が好ましく、メチル基がより好ましい。
　アルキル基が有していてもよい置換基としては、芳香族環基、水酸基、カルボキシル基、ハロゲン原子、アミノ基、アミド基などが挙げられ、アルカリ現像性の観点から水酸基、カルボキシル基が好ましく、カルボキシル基がより好ましい。また、合成容易性の観点からは、無置換であることが好ましい。 A methyl group, a hexyl group, a cyclopentyl methyl group etc. are mentioned as a specific example of an alkyl group, Among these, a viewpoint to developability to a methyl group or a hexyl group is preferable, and a methyl group is more preferable.
Examples of the substituent which the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group and the like, and a hydroxyl group and a carboxyl group are preferable from the viewpoint of alkali developability Carboxyl groups are more preferred. In addition, from the viewpoint of easiness of synthesis, it is preferably unsubstituted.
　Ｒ23における芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。芳香族環基の炭素数は特に限定されないが、溶剤への溶解性の観点から５以上であることが好ましい。また、現像性の観点から３０以下であることが好ましく、２０以下であることがより好ましく、１２以下であることがさらに好ましい。 The aromatic ring group in R 23, an aromatic hydrocarbon ring group and aromatic heterocyclic group. The carbon number of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in a solvent. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less.
　芳香族環基の具体例としては、フェニル基、ナフチル基、ピリジル基、フリル基などが挙げられ、これらの中でも現像性の観点から、フェニル基又はナフチル基が好ましく、フェニル基がより好ましい。
　芳香族環基が有していてもよい置換基としては、水酸基、カルボキシル基、ハロゲン原子、アミノ基、アミド基、アルキル基などが挙げられ、現像性の観点から水酸基、カルボキシル基が好ましく、カルボキシル基がより好ましい。
　これらの中でも、現像性の観点から、Ｒ23が置換基を有していてもよいアルキル基であることが好ましく、無置換のアルキル基であることがより好ましく、メチル基であることがさらに好ましい。 Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group and a furyl group. Among these, from the viewpoint of developability, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
Examples of the substituent which the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amido group, an alkyl group, etc. From the viewpoint of developability, a hydroxyl group and a carboxyl group are preferable, and a carboxyl Groups are more preferred.
Among these, from the viewpoint of developability, R 23 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably a methyl group. .
　Ｒ24におけるアルキル基の炭素数は特に限定されないが、感度の観点から１以上であることが好ましい。また、感度の観点から２０以下であることが好ましく、１０以下であることがより好ましく、５以下であることがさらに好ましく、３以下であることが特に好ましい。 The carbon number of the alkyl group in R 24 is not particularly limited, but is preferably 1 or more from the viewpoint of sensitivity. Further, from the viewpoint of sensitivity, it is preferably 20 or less, more preferably 10 or less, still more preferably 5 or less, and particularly preferably 3 or less.
　アルキル基の具体例としては、メチル基、エチル基、プロピル基などが挙げられ、これらの中でも感度の観点から、メチル基又はエチル基が好ましく、メチル基がより好ましい。
　アルキル基が有していてもよい置換基としては、ハロゲン原子、水酸基、カルボキシル基、アミノ基、アミド基などが挙げられ、アルカリ現像性の観点から水酸基、カルボキシル基が好ましく、カルボキシル基がより好ましく、他方合成容易性の観点からは無置換であることが好ましい。 A methyl group, an ethyl group, a propyl group etc. are mentioned as a specific example of an alkyl group, From these, a viewpoint of a sensitivity to a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
Examples of the substituent which the alkyl group may have include a halogen atom, a hydroxyl group, a carboxyl group, an amino group and an amido group. From the viewpoint of alkali developability, a hydroxyl group and a carboxyl group are preferable, and a carboxyl group is more preferable. On the other hand, from the viewpoint of easiness of synthesis, it is preferably unsubstituted.
　Ｒ24における芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。その炭素数は３０以下であることが好ましく１２以下であることがより好ましく、通常４以上であり、６以上であることが好ましい。前記上限値以下とすることで、高感度となる傾向があり、前記下限値以上とすることで低昇華性となる傾向がある。 The aromatic ring group in R 24 includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is preferably 30 or less, more preferably 12 or less, and usually 4 or more, and preferably 6 or more. By setting the upper limit value or less, the sensitivity tends to be high, and by setting the lower limit value or more, the sublimation property tends to be low.
　芳香族炭化水素環基としては、単環であっても縮合環であってもよく、例えば、１個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。
　また、芳香族複素環基としては、単環であっても縮合環であってもよく、例えば、１個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
　芳香族環基が有していてもよい置換基としては、アルキル基、ハロゲン原子、水酸基、カルボキシル基などが挙げられる。
　これらの中でも、感度の観点から、Ｒ24が置換基を有していてもよいアルキル基であることが好ましく、無置換のアルキル基であることがより好ましく、メチル基であることがさらに好ましい。
　他方、製版性の観点から、Ｒ24が置換基を有していてもよい芳香族環基であることが好ましく、置換基を有していてもよい芳香族炭化水素基であることがより好ましく、無置換の芳香族炭化水素基であることがさらに好ましく、フェニル基であることが特に好ましい。 The aromatic hydrocarbon ring group may be a single ring or a condensed ring. For example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene having one free valence. Groups such as ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like can be mentioned.
The aromatic heterocyclic group may be a single ring or a condensed ring. For example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring having one free valence , Pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring , Benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, quinoline ring, isoquinoline ring, quinoline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring , Azulene ring It includes the groups.
Examples of the substituent which the aromatic ring group may have include an alkyl group, a halogen atom, a hydroxyl group and a carboxyl group.
Among these, from the viewpoint of sensitivity, R 24 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably a methyl group.
On the other hand, from the viewpoint of plate-making property, R 24 is preferably an aromatic ring group which may have a substituent, more preferably an aromatic hydrocarbon group which may have a substituent. An unsubstituted aromatic hydrocarbon group is more preferable, and a phenyl group is particularly preferable.
　Ｒ25は、水酸基、カルボキシル基又は前記一般式（Ｄ－ＩＩ）で表される基であるが、これらの中でも、感度及び現像性の観点から、前記一般式（Ｄ－ＩＩ）で表される基であることが好ましい。
　前記一般式（Ｄ－ＩＩ）において、前述のとおり、Ｒ25aは、－Ｏ－、－Ｓ－、－ＯＣＯ－又は－ＣＯＯ－を表すが、これらの中でも、感度及び現像性の観点から、－Ｏ－又は－ＯＣＯ－が好ましく、－Ｏ－がより好ましい。 R 25 is a hydroxyl group, a carboxyl group or a group represented by the above general formula (D-II), but among these, from the viewpoint of sensitivity and developability, it is represented by the above general formula (D-II) It is preferably a group.
In the general formula (D-II), as described above, R 25a represents -O-, -S-, -OCO- or -COO-, but among these, from the viewpoint of sensitivity and developability,- O- or -OCO- is preferred, and -O- is more preferred.
　前述のとおり、Ｒ25bは、置換基を有していてもよいアルキレン基を表す。
　Ｒ25bにおけるアルキレン基の炭素数は特に限定されないが、感光性樹脂組成物への溶解性の観点から１以上であることが好ましく、２以上であることがより好ましく、また、２０以下であることが好ましく、１０以下であることがより好ましく、５以下であることがさらに好ましく、３以下であることが特に好ましい。
　アルキレン基は、直鎖でもよく、分岐していてもよく、脂肪族環を含むものであってもよい。これらの中でも、感光性樹脂組成物への溶解性の観点から、直鎖であることが好ましい。 As described above, R 25b represents an alkylene group which may have a substituent.
The carbon number of the alkylene group in R 25b is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 20 or less from the viewpoint of solubility in the photosensitive resin composition. Is more preferably 10 or less, still more preferably 5 or less, and particularly preferably 3 or less.
The alkylene group may be linear, branched or may contain an aliphatic ring. Among these, from the viewpoint of solubility in the photosensitive resin composition, linear is preferable.
　アルキレン基の具体例としては、メチレン基、エチレン基、プロピレン基などが挙げられ、これらの中でも感光性樹脂組成物への溶解性の観点から、メチレン基がより好ましい。 A methylene group, ethylene group, a propylene group etc. are mentioned as a specific example of an alkylene group, Among these, a methylene group is more preferable from a soluble viewpoint to the photosensitive resin composition.
　前述のとおりＲ25cは、水酸基又はカルボキシル基である。現像密着性の観点からは、Ｒ25cが水酸基であることが好ましい。 As mentioned above, R 25c is a hydroxyl group or a carboxyl group. From the viewpoint of development adhesion, R 25c is preferably a hydroxyl group.
　前記一般式（Ｄ－Ｉ）において、ｈは０～５の整数を表す。特に、現像性の観点からはｈは１以上であることが好ましく、また４以下であることが好ましく、３以下であることがより好ましく、２以下であることがさらに好ましく、１であることが最も好ましい。
　他方、合成容易性の観点からは、ｈは０であることが好ましい。 In the general formula (DI), h represents an integer of 0 to 5. In particular, h is preferably 1 or more, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, or 1 from the viewpoint of developability. Most preferred.
On the other hand, h is preferably 0 from the viewpoint of synthesisability.
　トリアジン系光重合開始剤としては、ハロメチル化ｓ－トリアジン誘導体類が挙げられ、例えば、２，４，６－トリス（モノクロロメチル）－ｓ－トリアジン、２，４，６－トリス（ジクロロメチル）－ｓ－トリアジン、２，４，６－トリス（トリクロロメチル）－ｓ－トリアジン、２－メチル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－ｎ－プロピル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（α，α，β－トリクロロエチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－フェニル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（３，４－エポキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－クロロフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－〔１－（ｐ－メトキシフェニル）－２，４－ブタジエニル〕－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－スチリル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－メトキシスチリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－メトキシ－ｍ－ヒドロキシスチリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－ｉ－プロピルオキシスチリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－トリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－メトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－エトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（ｐ－エトキシカルボニルナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－フェニルチオ－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－ベンジルチオ－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２，４，６－トリス（ジブロモメチル）－ｓ－トリアジン、２，４，６－トリス（トリブロモメチル）－ｓ－トリアジン、２－メチル－４，６－ビス（トリブロモメチル）－ｓ－トリアジン、２－メトキシ－４，６－ビス（トリブロモメチル）－ｓ－トリアジン、２－（４－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン等のハロメチル化ｓ－トリアジン誘導体類が挙げられ、中でも感度の観点から、ビス（トリハロメチル）－ｓ－トリアジン類が好ましい。 Examples of triazine-based photopolymerization initiators include halomethylated s-triazine derivatives, such as 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- (α, α, β-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 (to) Chloromethyl) -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-methoxy-m-hydroxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxynaphthyl) -4,6-bis ( Lichloromethyl) -s-triazine, 2- (p-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl)- s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-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- Halomethyl compounds such as bis (tribromomethyl) -s-triazine and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine And s-triazine derivatives. Among these, bis (trihalomethyl) -s-triazines are preferred from the viewpoint of sensitivity.
　アセトフェノン系光重合開始剤としては、例えば、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、１－ヒドロキシ－１－（ｐ－ドデシルフェニル）ケトン、１－ヒドロキシ－１－メチルエチル－（ｐ－イソプロピルフェニル）ケトン、１－トリクロロメチル－（ｐ－ブチルフェニル）ケトン、α－ヒドロキシ－２－メチルフェニルプロパノン、２－メチル－１［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタノン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタン－１－オン、４－ジメチルアミノエチルベンゾエート、４－ジメチルアミノイソアミルベンゾエート、４－ジエチルアミノアセトフェノン、４－ジメチルアミノプロピオフェノン、２－エチルヘキシル－１，４－ジメチルアミノベンゾエート、２，５－ビス（４－ジエチルアミノベンザル）シクロヘキサノン、４－（ジエチルアミノ）カルコン等が挙げられる。
　ベンゾフェノン系光重合開始剤としては、例えば、ベンゾフェノン、２－メチルベンゾフェノン、３－メチルベンゾフェノン、４－メチルベンゾフェノン、２－カルボキシベンゾフェノン、２－クロロベンゾフェノン、４－ブロモベンゾフェノン、ミヒラーケトン等が挙げられる。 As an acetophenone photopolymerization initiator, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-trichloromethyl- (p-butylphenyl) ketone, α-hydroxy-2-methylphenylpropanone, 2-methyl-1 [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) butan-1-one, 4-dimethylaminoethyl Benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 4- 4- (Diethylamino) chalcone etc. are mentioned.
Examples of benzophenone-based photopolymerization initiators include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, Michler's ketone and the like.
　これらの光重合開始剤は、感光性樹脂組成物中にその１種が単独で含まれていてもよく、２種以上が含まれていてもよい。これらの光重合開始剤の中で、ヘキサアリールビイミダゾール系光重合開始剤、オキシムエステル系光重合開始剤及びアセトフェノン系光重合開始剤からなる群から選ばれる少なくとも１種を含有することが好ましい。ヘキサアリールビイミダゾール化合物は、吸光度が高いことから表面硬化性が高く、また、高い撥インク性と高いテーパー角が得られる点で特に好ましい。また、オキシムエステル系化合物は感度が高く、低い露光量でも撥インク性が生じる点で特に好ましい。また、アセトフェノン系光重合開始剤は、内部硬化性が高く、高い撥インク性と高いテーパー角が得られる点で特に好ましい。 One of these photopolymerization initiators may be contained alone in the photosensitive resin composition, or two or more thereof may be contained. Among these photopolymerization initiators, it is preferable to contain at least one selected from the group consisting of a hexaarylbiimidazole photopolymerization initiator, an oxime ester photopolymerization initiator, and an acetophenone photopolymerization initiator. The hexaarylbiimidazole compound is particularly preferable in that it has high surface curability due to high absorbance, and high ink repellency and high taper angle can be obtained. Furthermore, oxime ester compounds are particularly preferable in that they have high sensitivity and ink repellency occurs even at low exposure amounts. Acetophenone photopolymerization initiators are particularly preferable in that they have high internal curability and high ink repellency and a high taper angle can be obtained.
　本発明の感光性樹脂組成物における（Ｄ）光重合開始剤の含有割合としては、感光性樹脂組成物の全固形分中に、通常０．０１質量％以上、好ましくは０．１質量％以上、より好ましくは０．５質量％以上、さらに好ましくは１質量％以上、よりさらに好ましくは１．５質量％以上、特に好ましくは２質量％以上、最も好ましくは２．５質量％以上であり、通常２５質量％以下、好ましくは１０質量％以下、より好ましくは８質量％以下、さらに好ましくは５質量％以下、特に好ましくは３質量％以下である。前記下限値以上とすることで現像時に膜減りを生じず塗膜が形成され、また十分な撥インク性が生じる傾向があり、また、前記上限値以下とすることで所望のパターン形状が形成しやすくなる傾向がある。感光性樹脂組成物の全固形分中における（Ｄ）光重合開始剤の含有割合としては、例えば、０．０１～２５質量％であり、０．１～１０質量％が好ましく、０．５～８質量％がより好ましく、１～５質量％がさらに好ましい。ある態様としては１．５～３質量％が好ましく、別の態様としては２～３質量％が好ましく、さらに別の態様としては２．５～５質量％が好ましい。 The content ratio of the (D) photopolymerization initiator in the photosensitive resin composition of the present invention is usually 0.01% by mass or more, preferably 0.1% by mass or more, in the total solid content of the photosensitive resin composition. More preferably, it is 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, particularly preferably 2% by mass or more, and most preferably 2.5% by mass or more. 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, particularly preferably 3% by mass or less. By setting the lower limit value or more, a film is not reduced at the time of development, a coating film is formed, and a sufficient ink repellent property tends to occur, and by setting the upper limit value or less, a desired pattern shape is formed. It tends to be easier. The content ratio of the (D) photopolymerization initiator 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. 8% by mass is more preferable, and 1 to 5% by mass is more preferable. In one aspect, 1.5 to 3% by mass is preferable, in another aspect, 2 to 3% by mass is preferable, and in still another aspect, 2.5 to 5% by mass is preferable.
　また、感光性樹脂組成物における（Ｃ）光重合性化合物に対する（Ｄ）光重合開始剤の配合比としては、（Ｃ）光重合性化合物１００質量部に対して、１質量部以上が好ましく、２質量部以上がより好ましく、３質量部以上がさらに好ましく、また、２００質量部以下が好ましく、１００質量部以下がより好ましく、５０質量部以下がさらに好ましく、２０質量部以下がよりさらに好ましく、１０質量部以下が特に好ましく、５質量部以下が最も好ましい。前記下限値以上とすることで適切な感度となる傾向があり、また、前記上限値以下とすることで所望のパターン形状が形成しやすくなる傾向がある。感光性樹脂組成物における（Ｃ）光重合性化合物１００質量部に対する（Ｄ）光重合開始剤の配合比としては、例えば、１～２００質量部であり、１～１００質量部が好ましく、２～５０質量部がより好ましく、２～２０質量部がさらに好ましく、３～１０質量部がよりさらに好ましく、３～５質量部が特に好ましい。 The compounding ratio of the (D) photopolymerization initiator to the (C) photopolymerizable compound in the photosensitive resin composition is preferably 1 part by mass or more with respect to 100 parts by mass of the (C) photopolymerizable compound, 2 parts by mass or more is preferable, 3 parts by mass or more is more preferable, 200 parts by mass or less is preferable, 100 parts by mass or less is more preferable, 50 parts by mass or less is more preferable, 20 parts by mass or less is more preferable, 10 parts by mass or less is particularly preferable, and 5 parts by mass or less is the most preferable. By setting the lower limit value or more, the sensitivity tends to be appropriate, and by setting the upper limit value or less, a desired pattern shape tends to be easily formed. The compounding ratio of the photopolymerization initiator (D) to 100 parts by mass of the photopolymerizable compound (C) in the photosensitive resin composition is, for example, 1 to 200 parts by mass, preferably 1 to 100 parts by mass, and 2 to 50 parts by mass is more preferable, 2 to 20 parts by mass is further preferable, 3 to 10 parts by mass is further more preferable, and 3 to 5 parts by mass is particularly preferable.
　また上記光重合開始剤と併用して、増感剤を用いてもよい。増感剤により感度が向上すると同時に、感光性樹脂組成物内部への光透過率が減少することで、テーパー角が大きくなる傾向がある。 In addition, a sensitizer may be used in combination with the photopolymerization initiator. At the same time as the sensitivity is improved by the sensitizer, the light transmittance to the inside of the photosensitive resin composition is decreased, so that the taper angle tends to be increased.
　増感剤としては、この分野で通常用いられている増感剤を使用することができる。増感剤は、吸収して得たエネルギーを光重合開始剤に移行、もしくは光重合開始剤との電子の授受を起こし、効率よく反応ラジカル重合反応を促進させる特徴がある。このような増感剤としては、例えば、カルコン誘導体やジベンザルアセトン等に代表される不飽和ケトン類、ベンジルやカンファーキノン等に代表される１，２－ジケトン系化合物、ベンゾイン系化合物、フルオレン系化合物、ナフトキノン系化合物、アントラキノン系化合物、キサンテン系化合物、チオキサンテン系化合物、キサントン系化合物、チオキサントン系化合物、クマリン系化合物、ケトクマリン系化合物、シアニン系化合物、メロシアニン系化合物、オキソノ－ル誘導体等のポリメチン色素、アクリジン系化合物、アジン系化合物、チアジン系化合物、オキサジン系化合物、インドリン系化合物、アズレン系化合物、アズレニウム系化合物、スクアリリウム系化合物、ポルフィリン系化合物、テトラフェニルポルフィリン系化合物、トリアリールメタン系化合物、テトラベンゾポルフィリン系化合物、テトラピラジノポルフィラジン系化合物、フタロシアニン系化合物、テトラアザポルフィラジン系化合物、テトラキノキサリロポルフィラジン系化合物、ナフタロシアニン系化合物、サブフタロシアニン系化合物、ピリリウム系化合物、チオピリリウム系化合物、テトラフィリン系化合物、アヌレン系化合物、スピロピラン系化合物、スピロオキサジン系化合物、チオスピロピラン系化合物、金属アレーン錯体、有機ルテニウム錯体、ベンゾフェノン系化合物等が挙げられる。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 As the sensitizer, those generally used in this field can be used. The sensitizer is characterized in that the energy obtained by absorption is transferred to the photopolymerization initiator or electron transfer with the photopolymerization initiator occurs to efficiently promote the reaction radical polymerization reaction. As such a sensitizer, for example, unsaturated ketones represented by chalcone derivatives and dibenzalacetone etc., 1,2-diketone compounds represented by benzyl and camphorquinone etc., benzoin compounds, fluorene Compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, oxonol derivatives, etc. Polymethine dyes, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds , Triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalyloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds Compounds, pyrylium compounds, thiopyrylium compounds, tetraphilin compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, benzophenone compounds and the like can be mentioned.
One of these may be used alone, or two or more may be used in combination.
　これらの中でも、感度向上とテーパー角増大の観点から、チオキサントン系化合物、ベンゾフェノン系化合物が好ましい。 Among these, thioxanthone compounds and benzophenone compounds are preferable from the viewpoint of sensitivity improvement and taper angle increase.
　チオキサントン系化合物としては、チオキサントン、２－メチルチオキサントン、４－メチルチオキサントン、２，４－ジメチルチオキサントン、２－エチルチオキサントン、４－エチルチオキサントン、２，４－ジエチルチオキサントン、２－イソプロピルチオキサントン、４－イソプロピルチオキサントン、２，４－ジイソプロピルチオキサントン、２－クロロチオキサントン、４－クロロチオキサントン、２，４－ジクロロチオキサントンなどが挙げられる。これらの中でも、感度向上とテーパー角増大の観点から２，４－ジエチルチオキサントンが好ましい。 As a thioxanthone compound, thioxanthone, 2-methyl thioxanthone, 4-methyl thioxanthone, 2,4- dimethyl thioxanthone, 2-ethyl thioxanthone, 4-ethyl thioxanthone, 2,4- diethyl thioxanthone, 2-isopropyl thioxanthone, 4- isopropyl Thioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2,4-dichlorothioxanthone and the like. Among these, 2,4-diethylthioxanthone is preferable from the viewpoint of sensitivity improvement and taper angle increase.
　ベンゾフェノン系化合物としては、ベンゾフェノン、４，４’－ビス（ジメチルアミノ）ベンゾフェノン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、４，４’－ビス（エチルメチルアミノ）ベンゾフェノンなどが挙げられる。これらの中でも、感度向上とテーパー角増大の観点から４，４’－ビス（ジエチルアミノ）ベンゾフェノンが好ましい。 Examples of benzophenone compounds include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone and the like. Among these, 4,4'-bis (diethylamino) benzophenone is preferable from the viewpoint of sensitivity improvement and taper angle increase.
　感光性樹脂組成物が増感剤を含む場合、感光性樹脂組成物における増感剤の含有割合は、感光性樹脂組成物の全固形分中に、通常０．１質量％以上、好ましくは０．３質量％以上、より好ましくは０．５質量％以上、さらに好ましくは０．８質量％以上、よりさらに好ましくは１質量％以上、特に好ましくは１．２質量％以上であり、また通常１０質量％以下、好ましくは７質量％以下、より好ましくは５質量％以下、さらに好ましくは３質量％以下である。前記下限値以上とすることで感度を向上し、テーパー角を高くすることができる傾向があり、また、前記上限値以下とすることで所望のパターンを形成しやすくなる傾向がある。感光性樹脂組成物が増感剤を含む場合、感光性樹脂組成物の全固形分中における増感剤の含有割合としては、例えば、０．１～１０質量％であり、０．３～１０質量％が好ましく、０．５～７質量％がより好ましく、０．８～７質量％がさらに好ましく、１～５質量％がよりさらに好ましく、１．２～３質量％が特に好ましい。 When the photosensitive resin composition contains a sensitizer, the content ratio of the sensitizer in the photosensitive resin composition is usually 0.1% by mass or more, preferably 0, in the total solid content of the photosensitive resin composition. .3 mass% or more, more preferably 0.5 mass% or more, still more preferably 0.8 mass% or more, still more preferably 1 mass% or more, particularly preferably 1.2 mass% or more, and usually 10 The content is at most mass%, preferably at most 7 mass%, more preferably at most 5 mass%, further preferably at most 3 mass%. By setting the lower limit value or more, the sensitivity tends to be improved and the taper angle tends to be increased. When the upper limit value is set, the desired pattern tends to be formed easily. When the photosensitive resin composition contains a sensitizer, the content ratio of the sensitizer in the total solid content of the photosensitive resin composition is, for example, 0.1 to 10% by mass, 0.3 to 10 % By mass is preferable, 0.5 to 7% by mass is more preferable, 0.8 to 7% by mass is further preferable, 1 to 5% by mass is further more preferable, and 1.2 to 3% by mass is particularly preferable.
［１－１－５］（Ｅ）連鎖移動剤
　本発明の感光性樹脂組成物は、（Ｅ）連鎖移動剤を含む。連鎖移動剤を含むことで、表面近傍における酸素阻害等によるラジカル失活が改善されて表面硬化性を高めることができ、テーパー角が高くなる傾向がある。また、表面硬化性を高めることによって撥液剤の流出を抑制でき、撥液剤を隔壁の表面近傍に固定しやすく接触角が高くなる傾向がある。
　連鎖移動剤としてはメルカプト基含有化合物や、四塩化炭素等が挙げられ、連鎖移動効果が高い傾向があることからメルカプト基を有する化合物を用いることがより好ましい。Ｓ－Ｈ結合エネルギーが小さいことによって結合開裂が起こりやすく、連鎖移動反応を起こしやすいため、表面硬化性を高めることができる傾向がある。 [1-1-5] (E) Chain Transfer Agent The photosensitive resin composition of the present invention contains (E) a chain transfer agent. By including the chain transfer agent, radical deactivation due to oxygen inhibition or the like in the vicinity of the surface can be improved, surface curability can be enhanced, and the taper angle tends to be high. Further, by enhancing the surface hardening property, the outflow of the liquid repellent can be suppressed, and the liquid repellent can be easily fixed in the vicinity of the surface of the partition wall, and the contact angle tends to be high.
Examples of the chain transfer agent include mercapto group-containing compounds and carbon tetrachloride. It is more preferable to use a compound having a mercapto group since the chain transfer effect tends to be high. The small S—H bond energy tends to cause bond cleavage and causes chain transfer reaction, so that the surface hardenability tends to be able to be enhanced.
　連鎖移動剤の中でも、テーパー角、表面硬化性の観点から、芳香族環を有するメルカプト基含有化合物と脂肪族系のメルカプト基含有化合物が好ましい。 Among the chain transfer agents, mercapto group-containing compounds having an aromatic ring and aliphatic mercapto group-containing compounds are preferable from the viewpoint of taper angle and surface curability.
　芳香族環を有するメルカプト基含有化合物としては、テーパー角の観点から、下記一般式（Ｅ－１）で表される化合物が好適に用いられる。 As the mercapto group-containing compound having an aromatic ring, a compound represented by the following general formula (E-1) is suitably used from the viewpoint of the taper angle.
Figure JPOXMLDOC01-appb-C000055
  
Figure JPOXMLDOC01-appb-C000055
  
　式（Ｅ－１）中、Ｚは－Ｏ－、－Ｓ－又は－ＮＨ－を表し、Ｒ61、Ｒ62、Ｒ63及びＲ64は各々独立に、水素原子又は１価の置換基を表す。
　このうち、テーパー角の観点から、Ｚは－Ｓ－又は－ＮＨ－が好ましく、－ＮＨ－がより好ましい。
　またテーパー角の観点から、Ｒ61、Ｒ62、Ｒ63及びＲ64は各々独立に、水素原子、炭素数１～４のアルキル基又は炭素数１～４のアルコキシ基が好ましく、水素原子がより好ましい。 In formula (E-1), Z represents -O-, -S- or -NH-, and R 61 , R 62 , R 63 and R 64 each independently represent a hydrogen atom or a monovalent substituent. .
Among these, from the viewpoint of the taper angle, Z is preferably -S- or -NH-, more preferably -NH-.
Further, from the viewpoint of taper angle, R 61 , R 62 , R 63 and R 64 are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably a hydrogen atom preferable.
　具体的には、２－メルカプトベンゾチアゾール、２－メルカプトベンゾイミダゾール、２－メルカプトベンゾオキサゾール、３－メルカプト－１，２，４－トリアゾール、２－メルカプト－４（３Ｈ）－キナゾリン、β－メルカプトナフタレン、１，４－ジメチルメルカプトベンゼン等の芳香族環を有するメルカプト基含有化合物が挙げられ、テーパー角の観点から、２－メルカプトベンゾチアゾール、２－メルカプトベンゾイミダゾールが好ましい。 Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene And mercapto group-containing compounds having an aromatic ring such as 1,4-dimethyl mercaptobenzene. From the viewpoint of taper angle, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable.
　一方で脂肪族系のメルカプト基含有化合物としては、表面硬化性の観点から、へキサンジチオール、デカンジチオール、または下記一般式（Ｅ－２）で表される化合物が好適に用いられる。 On the other hand, as the aliphatic mercapto group-containing compound, hexanedithiol, decanedithiol, or a compound represented by the following general formula (E-2) is suitably used from the viewpoint of surface curability.
Figure JPOXMLDOC01-appb-C000056
  
Figure JPOXMLDOC01-appb-C000056
  
　式（Ｅ－２）中、ｍは０～４の整数、ｎは２～４の整数を表す。Ｒ71及びＲ72は各々独立に、水素原子又は炭素数１～４のアルキル基を表す。Ｘはｎ価の基を表す。 In formula (E-2), m represents an integer of 0 to 4, and n represents an integer of 2 to 4. Each of R 71 and R 72 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X represents an n-valent group.
　前記一般式（Ｅ－２）において、合成容易性の観点から、ｍは１又は２であることが好ましい。また、表面硬化性の観点から、ｎは３又は４であることが好ましい。
　また、Ｒ71及びＲ72のアルキル基としては、表面硬化性の観点から、炭素数１～３のものが好ましい。表面硬化性の観点から、Ｒ71及びＲ72のうちの少なくとも一方、例えばＲ72は水素原子であることが好ましく、この場合において、Ｒ71は水素原子又は炭素数１～３のアルキル基であることが好ましい。 In the general formula (E-2), m is preferably 1 or 2 from the viewpoint of synthesis ease. In addition, n is preferably 3 or 4 from the viewpoint of surface curability.
The alkyl group of R 71 and R 72 is preferably one having 1 to 3 carbon atoms, from the viewpoint of surface curability. From the viewpoint of surface curability, at least one of R 71 and R 72 , for example, R 72 is preferably a hydrogen atom, and in this case, R 71 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Is preferred.
　ｎが２である場合、表面硬化性の観点から、Ｘはエーテル結合及び／又は枝分かれ部を有してもよい炭素数１～６のアルキレン基が好ましい。表面硬化性、合成容易性の観点から、中でも炭素数１～６のアルキレン基がより好ましく、炭素数４のアルキレン基がさらに好ましい。 When n is 2, from the viewpoint of surface curability, X is preferably an ether bond and / or an alkylene group having 1 to 6 carbon atoms which may have a branched portion. Among them, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 4 carbon atoms is further preferable, from the viewpoint of surface curability and easiness of synthesis.
　ｎが３である場合、表面硬化性、合成容易性の観点から、Ｘは下記一般式（Ｅ－２－１）又は（Ｅ－２－２）で表される構造であることが好ましい。 When n is 3, it is preferable that X be 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.
Figure JPOXMLDOC01-appb-C000057
  
Figure JPOXMLDOC01-appb-C000057
  
　式（Ｅ－２－１）中、Ｒ73は水素原子、炭素数１～６のアルキル基、又はメチロール基を表す。Ｒ73の中でも、テーパー角の観点から、エチル基が好ましい。 In formula (E-2-1), R 73 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a methylol group. Among R 73 , an ethyl group is preferable from the viewpoint of the taper angle.
Figure JPOXMLDOC01-appb-C000058
  
Figure JPOXMLDOC01-appb-C000058
  
　式（Ｅ－２－２）中、Ｒ74は炭素数１～４のアルキレン基を表す。Ｒ74の中でも、テーパー角の観点から、エチレン基が好ましい。 In formula (E-2-2), R 74 represents an alkylene group having 1 to 4 carbon atoms. Among R 74 , an ethylene group is preferable from the viewpoint of the taper angle.
　一方で、ｎが４である場合、Ｘは下記一般式（Ｅ－２－３）で表される構造であることが好ましい。 On the other hand, when n is 4, X is preferably a structure represented by the following general formula (E-2-3).
Figure JPOXMLDOC01-appb-C000059
  
Figure JPOXMLDOC01-appb-C000059
  
　具体的には、ブタンジオールビス（３－メルカプトプロピオネート）、ブタンジオールビスチオグリコレート、エチレングリコールビス（３－メルカプトプロピオネート）、エチレングリコールビスチオグリコレート、トリメチロールプロパントリス（３－メルカプトプロピオネート）、トリメチロールプロパントリスチオグリコレート、トリスヒドロキシエチルトリスチオプロピオネート、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールトリス（３－メルカプトプロピオネート）、ブタンジオールビス（３－メルカプトブチレート）、エチレングリコールビス（３－メルカプトブチレート）、トリメチロールプロパントリス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、ペンタエリスリトールトリス（３－メルカプトブチレート）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン等が挙げられる。 Specifically, butanediol bis (3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis (3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris (3- Mercaptopropionate), trimethylolpropane tristhioglycollate, trishydroxyethyltristhiopropionate, 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-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like.
　このうち、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールトリス（３－メルカプトプロピオネート）、トリメチロールプロパントリス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、ペンタエリスリトールトリス（３－メルカプトブチレート）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオンが好ましく、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）がより好ましい。 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-mercaptobutyloxyethyl) -1,3,5-triazine-2, Preferred is 4,6 (1H, 3H, 5H) -trione, and more preferred is pentaerythritol tetrakis (3-mercaptopropionate) or pentaerythritol tetrakis (3-mercaptobutyrate).
　これらは種々のものが１種を単独で、或いは２種以上を混合して使用できる。 These can be used singly or in combination of two or more.
　これらの中でも、撥インク性を高める観点から、２－メルカプトベンゾチアゾール、２－メルカプトベンゾイミダゾール、及び２－メルカプトベンゾオキサゾールからなる群から選択された１以上と、光重合開始剤とを組み合わせて、光重合開始剤系として使用することが好適である。例えば、２－メルカプトベンゾチアゾールを用いてもよく、２－メルカプトベンゾイミダゾールを用いてもよく、２－メルカプトベンゾチアゾールと２－メルカプトベンゾイミダゾールとを併用して用いてもよい。
　また、表面硬化性の観点から、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、及びペンタエリスリトールテトラキス（３－メルカプトブチレート）からなる群から選択された１又は２以上を用いることが好ましい。 Among these, from the viewpoint of enhancing ink repellency, one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, and a photopolymerization initiator are combined, It is preferred to use as a photoinitiator system. For example, 2-mercaptobenzothiazole may be used, 2-mercaptobenzimidazole may be used, and 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination.
In addition, from the viewpoint of surface hardenability, it is preferable to use one or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate).
　本発明の感光性樹脂組成物における連鎖移動剤の含有割合としては、感光性樹脂組成物の全固形分中に、通常０．０１質量％以上、好ましくは０．０２５質量％以上、より好ましくは０．０５質量％以上、さらに好ましくは０．１質量％以上、特に好ましくは１質量％以上であり、通常５質量％以下、好ましくは４質量％以下、より好ましくは３質量％以下である。前記下限値以上とすることでテーパー角が高く、表面硬化性が高くなり、撥インク性が高くなる傾向があり、また、前記上限値以下とすることで所望のパターンを形成しやすくなる傾向がある。感光性樹脂組成物の全固形分中における連鎖移動剤の全固形分中の含有割合としては、例えば、０．０１～５質量％であり、０．０２５～４質量％が好ましく、０．０５～４質量％がより好ましく、０．１～３質量％がさらに好ましく、１～３質量％がよりさらに好ましい。 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, and more preferably in the total solid content of the photosensitive resin composition. It is 0.05% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1% by mass or more, usually 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less. By setting the lower limit value or more, the taper angle is high, the surface curability tends to be high, and the ink repellency tends to be high. By setting the upper limit value or less, the desired pattern tends to be easily formed. is there. The content ratio of the chain transfer agent in the total solid content of the photosensitive resin composition is, for example, 0.01 to 5% by mass, preferably 0.025 to 4% by mass, and 0.05 -4% by mass is more preferable, 0.1-3% by mass is more preferable, and 1-3% by mass is even more preferable.
　また連鎖移動剤として、芳香族環を有するメルカプト基含有化合物と脂肪族系のメルカプト基含有化合物を併用して使用するときのその含有割合としては、芳香族環を有するメルカプト基含有化合物１００質量部に対して、脂肪族系のメルカプト基含有化合物を通常１０質量部以上、好ましくは５０質量部以上、より好ましくは８０質量部以上であり、通常４００質量部以下、好ましくは３００質量部以下、より好ましくは２００質量部以下、さらに好ましくは１５０質量部以下である。前記下限値以上とすることで撥インク性が高くなる傾向があり、また、前記上限値以下とすることで感度が高くなる傾向がある。連鎖移動剤として、芳香族環を有するメルカプト基含有化合物と脂肪族系のメルカプト基含有化合物を併用して使用するときのその含有割合としては、芳香族環を有するメルカプト基含有化合物１００質量部に対して、例えば、１０～４００質量部であり、５０～３００質量部が好ましく、８０～２００質量部がより好ましく、８０～１５０質量部がさらに好ましい。 When a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound are used in combination as a chain transfer agent, 100 parts by mass of a mercapto group-containing compound having an aromatic ring The amount of the aliphatic mercapto group-containing compound is usually 10 parts by mass or more, preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and usually 400 parts by mass or less, preferably 300 parts by mass or less Preferably it is 200 mass parts or less, More preferably, it is 150 mass parts or less. When the lower limit value or more is used, the ink repellency tends to be high, and when the upper limit value or less is used, the sensitivity tends to be high. When a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound are used in combination as a chain transfer agent, 100 parts by mass of a mercapto group-containing compound having an aromatic ring is used as the content ratio For example, it is 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.
　また、感光性樹脂組成物における（Ｄ）光重合開始剤に対する、連鎖移動剤の配合比としては、（Ｄ）光重合開始剤１００質量部に対して、１０質量部以上が好ましく、２５質量部以上がより好ましく、５０質量部以上がさらに好ましく、８０質量部以上が特に好ましく、また、５００質量部以下が好ましく、４００質量部以下がより好ましく、３００質量部以下がさらに好ましく、２００質量部以下がよりさらに好ましく、１５０質量部以下が特に好ましい。前記下限値以上とすることでテーパー角が高く、表面硬化性が高くなり、撥インク性が高くなる傾向があり、また、前記上限値以下とすることで所望のパターンを形成しやすくなる傾向がある。感光性樹脂組成物における（Ｄ）光重合開始剤１００質量部に対する、連鎖移動剤の配合比としては、例えば、１０～５００質量部であり、２５～４００質量部が好ましく、５０～３００質量部がより好ましく、８０～２００質量部がさらに好ましく、８０～１５０質量部がよりさらに好ましい。 Moreover, as a compounding ratio of the chain transfer agent with respect to (D) photoinitiator in the photosensitive resin composition, 10 mass parts or more are preferable with respect to 100 mass parts of (D) photoinitiator, and 25 mass parts The above is more preferable, 50 parts by mass or more is more preferable, 80 parts by mass or more is particularly preferable, 500 parts by mass or less is preferable, 400 parts by mass or less is more preferable, 300 parts by mass or less is more preferable, 200 parts by mass or less Is more preferable, and 150 parts by mass or less is particularly preferable. By setting the lower limit value or more, the taper angle is high, the surface curability tends to be high, and the ink repellency tends to be high. By setting the upper limit value or less, the desired pattern tends to be easily formed. is there. The compounding ratio of the chain transfer agent is, for example, 10 to 500 parts by mass, preferably 25 to 400 parts by mass, and 50 to 300 parts by mass with respect to 100 parts by mass of the (D) photopolymerization initiator in the photosensitive resin composition. Is more preferable, 80 to 200 parts by mass is further preferable, and 80 to 150 parts by mass is even more preferable.
［１－１－６］紫外線吸収剤
　本発明の感光性樹脂組成物は、紫外線吸収剤を含有してもよい。紫外線吸収剤は、露光に用いられる光源の特定の波長を紫外線吸収剤によって吸収させることにより、光硬化分布を制御する目的で添加されるものである。紫外線吸収剤を含むことにより、現像後のテーパー角形状を改善したり、現像後に非露光部に残る残渣を低減したりするなどの効果が得られる傾向がある。紫外線吸収剤としては、光重合開始剤による光吸収を阻害するとの観点から、例えば、波長２５０ｎｍから４００ｎｍの間に吸収極大を有する化合物を用いることができる。
　紫外線吸収剤の例としては、ベンゾトリアゾール系化合物、トリアジン系化合物、ベンゾフェノン化合物、ベンゾエート化合物、桂皮酸誘導体、ナフタレン誘導体、アントラセン及びその誘導体、ジナフタレン化合物、フェナントロリン化合物、染料等が挙げられる。
　これらの紫外線吸収剤は、単独又は２種以上組み合わせて用いることができる。 [1-1-6] Ultraviolet Absorbent The photosensitive resin composition of the present invention may contain an ultraviolet absorbent. The ultraviolet absorber is added for the purpose of controlling the light curing distribution by absorbing a specific wavelength of a light source used for exposure by the ultraviolet absorber. By including an ultraviolet absorber, there is a tendency to obtain effects such as improvement of the tapered angular shape after development and reduction of the residue remaining in the non-exposed area after development. From the viewpoint of inhibiting light absorption by the photopolymerization initiator, for example, a compound having an absorption maximum between wavelengths 250 nm and 400 nm can be used as the ultraviolet light absorber.
Examples of UV absorbers include benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and derivatives thereof, dinaphthalene compounds, phenanthroline compounds, dyes and the like.
These ultraviolet absorbers can be used alone or in combination of two or more.
　これらの中でも、テーパー角を高める観点から、ベンゾトリアゾール化合物及び／又はヒドロキシフェニルトリアジン化合物が好ましく、ベンゾトリアゾール化合物が特に好ましい。 Among these, from the viewpoint of increasing the taper angle, benzotriazole compounds and / or hydroxyphenyltriazine compounds are preferable, and benzotriazole compounds are particularly preferable.
　ベンゾトリアゾール系化合物の中でも、テーパー形状の点から、下記の一般式（Ｚ１）で記載されるベンゾトリアゾール化合物が好ましい。 Among the benzotriazole-based compounds, benzotriazole compounds described by the following general formula (Z1) are preferable from the viewpoint of taper shape.
Figure JPOXMLDOC01-appb-C000060
  
Figure JPOXMLDOC01-appb-C000060
  
　上記式（Ｚ１）中、Ｒ1e及びＲ2eは各々独立に、水素原子、置換基を有していてもよいアルキル基、下記一般式（Ｚ２）で表される基、又は下記一般式（Ｚ３）で表される基を表す。Ｒ3eは、水素原子又はハロゲン原子を表す。 In the above formula (Z1), R 1e and R 2e each independently represent a hydrogen atom, an alkyl group which may have a substituent, a group represented by the following general formula (Z2), or the following general formula (Z3) Represents a group represented by). R 3e represents a hydrogen atom or a halogen atom.
Figure JPOXMLDOC01-appb-C000061
  
Figure JPOXMLDOC01-appb-C000061
  
　上記式（Ｚ２）中、Ｒ4eは置換基を有していてもよいアルキレン基を表し、Ｒ5eは置換基を有していてもよいアルキル基を表す。 In formula (Z2), R 4e represents an alkylene group which may have a substituent, and R 5e represents an alkyl group which may have a substituent.
Figure JPOXMLDOC01-appb-C000062
  
Figure JPOXMLDOC01-appb-C000062
  
　上記式（Ｚ３）中、Ｒ6eは置換基を有していてもよいアルキレン基を表し、Ｒ7eは水素原子またはメチル基を表す。 In said formula (Z3), R6e represents the alkylene group which may have a substituent, R7e represents a hydrogen atom or a methyl group.
（Ｒ1e及びＲ2e）
　前記式（Ｚ１）において、Ｒ1e及びＲ2eは各々独立に、水素原子、置換基を有していてもよいアルキル基、一般式（Ｚ２）で表される基、又は一般式（Ｚ３）で表される基を表す。
　アルキル基としては、直鎖状、分岐鎖状又は環状のアルキル基が挙げられる。その炭素数は、１以上であることが好ましく、２以上であることがより好ましく、４以上であることがさらに好ましく、また、１０以下であることが好ましく、６以下であることがより好ましく、４以下であることがさらに好ましい。 (R 1e and R 2e )
In the formula (Z1), R 1e and R 2e each independently represent a hydrogen atom, an alkyl group which may have a substituent, a group represented by general formula (Z2), or a general formula (Z3) Represents a group to be represented.
The alkyl group includes a linear, branched or cyclic alkyl group. The carbon number thereof is preferably 1 or more, more preferably 2 or more, still more preferably 4 or more, and preferably 10 or less, more preferably 6 or less, More preferably, it is 4 or less.
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基等が挙げられる。これらの中でもｔｅｒｔ－ブチル基が好ましい。
　また、アルキル基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基などが挙げられる。 Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tert-butyl group. Among these, tert-butyl is preferable.
Moreover, as a substituent which the alkyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group And an acryloyl group and a methacryloyl group.
（Ｒ3e）
　前記式（Ｚ１）において、Ｒ3eは、水素原子又はハロゲン原子を表す。
　ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子などが挙げられる。
　これらの中でも合成の観点から、Ｒ3eが水素原子であることが好ましい。 (R 3e )
In Formula (Z1), R 3e represents a hydrogen atom or a halogen atom.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned.
Among these, from the viewpoint of synthesis, R 3e is preferably a hydrogen atom.
（Ｒ4e）
　前記式（Ｚ２）において、Ｒ4eは置換基を有していてもよいアルキレン基を表す。
　アルキレン基としては、直鎖状、分岐鎖状又は環状のアルキレン基が挙げられる。その炭素数は通常１以上であり、２以上が好ましく、また６以下が好ましく、４以下がより好ましく、３以下がさらに好ましい。 (R 4e )
In Formula (Z2), R 4e represents an alkylene group which may have a substituent.
As the alkylene group, a linear, branched or cyclic alkylene group can be mentioned. The carbon number is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.
　アルキレン基の具体例としては、メチレン基、エチレン基、プロピレン基、プロピレン基、ブチレン基等が挙げられる。これらの中でもエチレン基が好ましい。
　また、アルキレン基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基などが挙げられる。 A methylene group, ethylene group, a propylene group, a propylene group, a butylene group etc. are mentioned as a specific example of an alkylene group. Among these, ethylene group is preferable.
Moreover, as a substituent which the alkylene group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group And an acryloyl group and a methacryloyl group.
　これらの中でも、Ｒ4eがエチレン基であることが好ましい。 Among these, R 4e is preferably an ethylene group.
（Ｒ5e）
　前記式（Ｚ２）において、置換基を有していてもよいアルキル基を表す。
　アルキル基としては、直鎖状、分岐鎖状又は環状のアルキル基が挙げられる。その炭素数は、４以上であることが好ましく、５以上であることがより好ましく、７以上であることがさらに好ましく、また、１５以下であることが好ましく、１０以下であることがより好ましく、９以下であることがさらに好ましい。 (R 5e )
In the formula (Z2), it represents an alkyl group which may have a substituent.
The alkyl group includes a linear, branched or cyclic alkyl group. The carbon number thereof is preferably 4 or more, more preferably 5 or more, still more preferably 7 or more, and preferably 15 or less, more preferably 10 or less, More preferably, it is 9 or less.
　アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプシル基、オクチル基、ノニル基等が挙げられる。
　また、アルキル基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基などが挙げられる。
　これらの中でもテーパー形状の観点から、Ｒ5eがヘプチル基、オクチル基、ノニル基であることが好ましい。 Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group.
Moreover, as a substituent which the alkyl group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group And an acryloyl group and a methacryloyl group.
Among these, from the viewpoint of the tapered shape, R 5e is preferably a heptyl group, an octyl group or a nonyl group.
（Ｒ6e）
　前記式（Ｚ３）において、Ｒ6eは置換基を有していてもよいアルキレン基を表す。
　アルキレン基としては、直鎖状、分岐鎖状又は環状のアルキレン基が挙げられる。その炭素数は通常１以上であり、２以上が好ましく、また６以下が好ましく、４以下がより好ましく、３以下がさらに好ましい。 (R 6e )
In Formula (Z3), R 6e represents an alkylene group which may have a substituent.
As the alkylene group, a linear, branched or cyclic alkylene group can be mentioned. The carbon number is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.
　アルキレン基の具体例としては、メチレン基、エチレン基、プロピレン基、プロピレン基、ブチレン基等が挙げられる。これらの中でもエチレン基が好ましい。
　また、アルキレン基が有していてもよい置換基としては、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシル基、アクリロイル基、メタクリロイル基などが挙げられる。 A methylene group, ethylene group, a propylene group, a propylene group, a butylene group etc. are mentioned as a specific example of an alkylene group. Among these, ethylene group is preferable.
Moreover, as a substituent which the alkylene group may have, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, a carboxyl group And an acryloyl group and a methacryloyl group.
　これらの中でもテーパー形状の観点から、Ｒ1eがｔｅｒｔ－ブチル基、Ｒ2eが前記式（Ｚ２）で表される基（ただしＲ4eがエチレン基、及びＲ5eが炭素数７～９のアルキル基）、Ｒ3eが水素原子である化合物、またはＲ1eが水素原子、Ｒ2eが前記式（Ｚ３）で表される基（ただしＲ6eがエチレン基、及びＲ7eがメチル基）、Ｒ3eが水素原子である化合物が好ましく、Ｒ1eがｔｅｒｔ－ブチル基、Ｒ2eが前記式（Ｚ２）で表される基（ただしＲ4eがエチレン基、及びＲ5eが炭素数７～９のアルキル基）、Ｒ3eが水素原子である化合物がより好ましい。 From the viewpoint of tapered Among these, R 1e is tert- butyl group, a group R 2e is represented by the formula (Z2) (provided that R 4e is an ethylene group, and R 5e is an alkyl group having 7-9 carbon atoms And R 3 e is a hydrogen atom, or R 1 e is a hydrogen atom, R 2 e is a group represented by the above formula (Z 3) (wherein R 6 e is ethylene, and R 7 e is methyl), R 3 e is The compound which is a hydrogen atom is preferable, and R 1e is a tert-butyl group, R 2e is a group represented by the above formula (Z 2) (however, R 4e is an ethylene group, and R 5e is an alkyl group having 7 to 9 carbon atoms). And compounds wherein R 3e is a hydrogen atom are more preferred.
　ベンゾトリアゾール系化合物の具体例としては、２－（５メチル－２－ヒドロキシフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－５－ｔ－ブチルフェニル）－２Ｈ－ベンゾトリアゾール、オクチル－３［３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－（５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル）フェニル］プロピオネートと２－エチルヘキシル－３－［３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－（５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル）フェニル］プロピオネートの混合物、２－［２－ヒドロキシ－３，５－ビス（α，α－ジメチルベンジル）フェニル］－２Ｈ－ベンゾトリアゾール、２－（３－ｔブチル－５－メチル－２－ヒドロキシフェニル）－５－クロロベンゾトリアゾール、２－（３，５－ジ－ｔ－アミル－２－ヒドロキシフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－５’－ｔ－オクチルフェニル）ベンゾトリアゾール、ベンゼンプロパン酸，３－（２Ｈ－ベンゾトリアゾール－２－イル）－（１，１－ジメチルエチル）－４－ヒドロキシ，Ｃ７－９側鎖及び直鎖アルキルエステルの化合物、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ビス（１－メチル－１－フェニルエチル）フェノール、２－（２Ｈ－ベンゾトリアゾール－２－イル）－６－（１－メチル－１－フェニルエチル）－４－（１，１，３，３－テトラメチルブチル）フェノール、が挙げられる。これらの中でも、テーパー角と露光感度の観点から、３－（２Ｈ－ベンゾトリアゾール－２－イル）－（１，１－ジメチルエチル）－４－ヒドロキシ，Ｃ７－９側鎖及び直鎖アルキルエステルの化合物が好ましい。 Specific examples of benzotriazole compounds include 2- (5 methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3 [3- tert-Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-) Mixture of chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3- t-Butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di) -T-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, benzenepropanoic acid, 3- (2H-benzotriazol-2-yl)-( 1,1-Dimethylethyl) -4-hydroxy, compound of C7-9 side chain and linear alkyl ester, 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 is mentioned Be Among them, from the viewpoint of taper angle and exposure sensitivity, 3- (2H-benzotriazol-2-yl)-(1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester Compounds are preferred.
　市販されているベンゾトリアゾール系化合物としては例えば、スミソーブ（登録商標、以下同じ。）２００、スミソーブ２５０、スミソーブ３００、スミソーブ３４０、スミソーブ３５０（住友化学社製）、ＪＦ７７、ＪＦ７８、ＪＦ７９、ＪＦ８０、ＪＦ８３（城北化学工業社製）、ＴＩＮＵＶＩＮ（登録商標、以下同じ。）　ＰＳ、ＴＩＮＵＶＩＮ９９－２、ＴＩＮＵＶＩＮ１０９、ＴＩＮＵＶＩＮ３８４－２、ＴＩＮＵＶＩＮ　３２６、ＴＩＮＵＶＩＮ９００、ＴＩＮＵＶＩＮ９２８、ＴＩＮＵＶＩＮ１１３０（ＢＡＳＦ社製）、ＥＶＥＲＳＯＲＢ７０、ＥＶＥＲＳＯＲＢ７１、ＥＶＥＲＳＯＲＢ７２、ＥＶＥＲＳＯＲＢ７３、ＥＶＥＲＳＯＲＢ７４、ＥＶＥＲＳＯＲＢ７５、ＥＶＥＲＳＯＲＢ７６、ＥＶＥＲＳＯＲＢ２３４、ＥＶＥＲＳＯＲＢ７７、ＥＶＥＲＳＯＲＢ７８、ＥＶＥＲＳＯＲＢ８０、ＥＶＥＲＳＯＲＢ８１（台湾永光化学工業社製）、トミソーブ（登録商標、以下同じ。）１００、トミソーブ６００（エーピーアイコーポレーション社製）、ＳＥＥＳＯＲＢ（登録商標、以下同じ。）７０１、ＳＥＥＳＯＲＢ７０２、ＳＥＥＳＯＲＢ７０３、ＳＥＥＳＯＲＢ７０４、ＳＥＥＳＯＲＢ７０６、ＳＥＥＳＯＲＢ７０７、ＳＥＥＳＯＲＢ７０９（シプロ化成社製）、ＲＵＶＡ－９３（大塚化学社製）などが挙げられる。 Commercially available benzotriazole compounds include, for example, Sumisorb (registered trademark, the same in the following) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83. (Johoku Chemical Industry Co., Ltd.), TINUVIN (registered trademark, the same below) PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 326, TINUVIN 900, TINUVIN 928, TINUVIN 1130 (manufactured by BASF), EVERSORB 70, EVERSORB 71, EVERSORB 72, EVERSORB73 , EVERSORB 74, EVERSORB 75, EVERSORB 76, EVERSORB 234, EV RSORB 77, EVERSORB 78, EVERSORB 80, EVERSORB 81 (manufactured by Taiwan Eiko Chemical Co., Ltd.), Tomisorb (registered trademark, the same as the following) 100, Tomisorb 600 (manufactured by AP Corporation), SEESORB (registered trademark, the same below) SEESORB 703, SEESORB 704, SEESORB 706, SEESORB 707, SEESORB 709 (manufactured by Shipro Kasei Co., Ltd.), RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.), and the like.
　トリアジン系化合物としては、２－［４，６－ジ（２，４－キシリル）－１，３，５－トリアジン－２－イル］－５－オクチルオキシフェノール、２－［４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン－２－イル］－５－［３－（ドデシルオキシ）－２－ヒドロキシプロポキシ］フェノール、２－（２，４－ジヒドロキシフェニル）－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジンと（２－エチルヘキシル）グリシド酸エステルの反応生成物、２，４－ビス［２－ヒドロキシ－４－ブトキシフェニル］－６－（２，４－ジブトキシフェニル）－１，３，５－トリアジン等が挙げられる。これらの中でも、テーパー角と露光感度の観点から、ヒドロキシフェニルトリアジン化合物が好ましい。
　市販されているトリアジン系化合物としては例えば、ＴＩＮＵＶＩＮ４００、ＴＩＮＵＶＩＮ４０５、ＴＩＮＵＶＩＮ４６０、ＴＩＮＵＶＩＮ４７７、ＴＩＮＵＶＩＮ４７９（ＢＡＳＦ社製）などを挙げることができる。 As the triazine compounds, 2- [4,6-di (2,4-xylyl) -1,3,5-triazin-2-yl] -5-octyloxyphenol, 2- [4,6-bis ( 2,4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl) -4 The reaction product of 2,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) glycidate, 2,4-bis [2-hydroxy-4-butoxyphenyl]- 6- (2,4-dibutoxyphenyl) -1,3,5-triazine and the like. Among these, a hydroxyphenyl triazine compound is preferable from the viewpoint of taper angle and exposure sensitivity.
As a triazine type compound marketed, TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479 (made by BASF Corporation) etc. can be mentioned, for example.
　その他の紫外線吸収剤としては、例えば、スミソーブ１３０（住友化学社製）、ＥＶＥＲＳＯＲＢ１０、ＥＶＥＲＳＯＲＢ１１、ＥＶＥＲＳＯＲＢ１２（台湾永光化学工業社製）、トミソーブ８００（エーピーアイコーポレーション社製）、ＳＥＥＳＯＲＢ１００、ＳＥＥＳＯＲＢ１０１、ＳＥＥＳＯＲＢ１０１Ｓ、ＳＥＥＳＯＲＢ１０２、ＳＥＥＳＯＲＢ１０３、ＳＥＥＳＯＲＢ１０５、ＳＥＥＳＯＲＢ１０６、ＳＥＥＳＯＲＢ１０７、ＳＥＥＳＯＲＢ１５１（シプロ化成社製）などのベンゾフェノン化合物；スミソーブ４００（住友化学社製）、サリチル酸フェニルなどのベンゾエート化合物；桂皮酸２－エチルヘキシル、パラメトキシ桂皮酸２－エチルヘキシル、メトキシケイ皮酸イソプロピル、メトキシケイ皮酸イソアミル等の桂皮酸誘導体；α－ナフトール、β－ナフトール、α－ナフトールメチルエーテル、α－ナフトールエチルエーテル、１，２－ジヒドロキシナフタレン、１，３－ジヒドロキシナフタレン、１，４－ジヒドロキシナフタレン、１，５－ジヒドロキシナフタレン、１，６－ジヒドロキシナフタレン、１，７－ジヒドロキシナフタレン、１，８－ジヒドロキシナフタレン、２，３－ジヒドロキシナフタレン、２，６－ジヒドロキシナフタレン、２，７－ジヒドロキシナフタレン等のナフタレン誘導体；アントラセン、９，１０－ジヒドロキシアントラセン等のアントラセン及びその誘導体；アゾ系染料、ベンゾフェノン系染料、アミノケトン系染料、キノリン系染料、アントラキノン系染料、ジフェニルシアノアクリレート系染料、トリアジン系染料、ｐ－アミノ安息香酸系染料等の染料；等が挙げられる。これらの中でも、露光感度の観点から、桂皮酸誘導体、ナフタレン誘導体を用いることが好ましく、桂皮酸誘導体を用いることが特に好ましい。 Other UV absorbers include, for example, Sumisorb 130 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Eiko Chemical Co., Ltd.), Tomisorb 800 (manufactured by AP Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102 Benzophenone compounds such as SEESORB 103, SEESORB 105, SEESORB 106, SEESORB 107, SEESORB 151 (manufactured by Cipro Chemical Co., Ltd.); Sumisorb 400 (manufactured by Sumitomo Chemical Co., Ltd.); benzoate compounds such as phenyl salicylate; 2-ethylhexyl cinnamic acid, 2-ethylhexyl paramethoxycinnamate, Such as isopropyl methoxycinnamate and isoamyl methoxycinnamate Acid derivatives; α-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene Naphthalene derivatives such as 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene; anthracene 9, Anthracene and its derivatives such as 10-dihydroxy anthracene; azo dyes, benzophenone dyes, amino ketone dyes, quinoline dyes, anthraquinone dyes, diphenyl cyanoacrylate dyes, triazine dyes, and dyes such as p-aminobenzoic acid dyes. Among these, from the viewpoint of exposure sensitivity, it is preferable to use a cinnamic acid derivative or a naphthalene derivative, and it is particularly preferable to use a cinnamic acid derivative.
　本発明の感光性樹脂組成物が紫外線吸収剤を含む場合、感光性樹脂組成物における紫外線吸収剤の含有割合は、全固形分中に、通常０．０１質量％以上、好ましくは０．０５質量％以上、より好ましくは０．１質量％以上、さらに好ましくは０．５質量％以上、特に好ましくは１質量％以上であり、また、通常１５質量％以下、好ましくは１０質量％以下、より好ましくは５質量％以下、さらに好ましくは３質量％以下である。前記下限値以上とすることでテーパー角が大きくなる傾向があり、また、前記上限値以下とすることで高感度となる傾向がある。本発明の感光性樹脂組成物が紫外線吸収剤を含む場合、感光性樹脂組成物の全固形分中における紫外線吸収剤の含有割合としては、例えば、０．０１～１５質量％であり、０．０５～１０質量％が好ましく、０．１～５質量％がより好ましく、０．５～３質量％がさらに好ましく、１～３質量％がよりさらに好ましい。 When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the content ratio of the ultraviolet absorber in the photosensitive resin composition is usually 0.01% by mass or more, preferably 0.05 mass%, in the total solid content. % Or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and usually 15% by mass or less, preferably 10% by mass or less, more preferably Is 5% by mass or less, more preferably 3% by mass or less. By setting the lower limit value or more, the taper angle tends to be large, and by setting the upper limit value or less, the sensitivity tends to be high. When the photosensitive resin composition of the present invention contains an ultraviolet light absorber, the content ratio of the ultraviolet light absorber in the total solid content of the photosensitive resin composition is, for example, 0.01 to 15% by mass. The content is preferably 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.
　また、本発明の感光性樹脂組成物が紫外線吸収剤を含む場合、（Ｄ）光重合開始剤に対する配合比としては、（Ｄ）光重合開始剤１００質量部に対する紫外線吸収剤の配合量として、通常１質量部以上、好ましくは１０質量部以上、より好ましくは３０質量部以上、さらに好ましくは５０質量部以上、特に好ましくは８０質量部以上であり、通常５００質量部以下、好ましくは３００質量部以下、より好ましくは２００質量部以下、さらに好ましくは１５０質量部以下である。前記下限値以上とすることでテーパー角が大きくなる傾向があり、また、前記上限値以下とすることで高感度となる傾向がある。本発明の感光性樹脂組成物が紫外線吸収剤を含む場合、（Ｄ）光重合開始剤１００質量部に対する（Ｄ）光重合開始剤の配合比としては、例えば、１～５００質量部であり、１０～３００質量部が好ましく、３０～２００質量部がより好ましく、５０～１５０質量部がさらに好ましく、８０～１５０質量部がよりさらに好ましい。 Moreover, when the photosensitive resin composition of this invention contains a ultraviolet absorber, as a compounding ratio with respect to (D) photoinitiator, as a compounding quantity of the ultraviolet absorber with respect to 100 mass parts of (D) photoinitiator, Usually, 1 part by mass or more, preferably 10 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, and usually 500 parts by mass or less, preferably 300 parts by mass The content is more preferably 200 parts by mass or less, still more preferably 150 parts by mass or less. By setting the lower limit value or more, the taper angle tends to be large, and by setting the upper limit value or less, the sensitivity tends to be high. When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the compounding ratio of the (D) photopolymerization initiator to (D) 100 parts by weight of the photopolymerization initiator is, for example, 1 to 500 parts by mass, 10 to 300 parts by mass is preferable, 30 to 200 parts by mass is more preferable, 50 to 150 parts by mass is more preferable, and 80 to 150 parts by mass is still more preferable.
［１－１－７］重合禁止剤
　本発明の感光性樹脂組成物は、重合禁止剤を含有してもよい。重合禁止剤を含有することでそれがラジカル重合を阻害することから、得られる隔壁のテーパー角を大きくすることができると考えられる。
　重合禁止剤としては、ハイドロキノン、ハイドロキノンモノメチルエーテル、メチルハイドロキノン、メトキシフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－クレゾール（ＢＨＴ）などが挙げられる。これらの中でも重合禁止能力の観点から、メチルハイドロキノン又はメトキシフェノールが好ましく、メチルハイドロキノンがより好ましい。 [1-1-7] Polymerization Inhibitor The photosensitive resin composition of the present invention may contain a polymerization inhibitor. It is believed that the inclusion of the polymerization inhibitor can increase the taper angle of the partition obtained because it inhibits radical polymerization.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-cresol (BHT) and the like. Among these, from the viewpoint of the polymerization inhibiting ability, methylhydroquinone or methoxyphenol is preferable, and methylhydroquinone is more preferable.
　重合禁止剤は、１種又は２種以上を含有することが好ましい。通常、（Ｂ）アルカリ可溶性樹脂を製造する際に、当該樹脂中に重合禁止剤が含まれることがあり、それを本発明の重合禁止剤として用いてもよいし、樹脂中に重合禁止剤の他に、それと同一、又は異なる重合禁止剤を感光性樹脂組成物製造時に添加してもよい。 The polymerization inhibitor preferably contains one or more kinds. Usually, when (B) an alkali-soluble resin is produced, a polymerization inhibitor may be contained in the resin, which may be used as the polymerization inhibitor of the present invention, or in the resin In addition, the same or different polymerization inhibitor may be added at the time of photosensitive resin composition manufacture.
　本発明の感光性樹脂組成物が重合禁止剤を含む場合、感光性樹脂組成物における重合禁止剤の含有割合は、感光性樹脂組成物の全固形分中に、通常０．０００５質量％以上、好ましくは０．００１質量％以上、より好ましくは０．０１質量％以上であり、また通常０．３質量％以下、好ましくは０．２質量％以下、より好ましくは０．１質量％以下である。前記下限値以上とすることでテーパー角を高くすることができる傾向があり、また、前記上限値以下とすることで高感度を保つことができる傾向がある。本発明の感光性樹脂組成物が重合禁止剤を含む場合、感光性樹脂組成物の全固形分中における重合禁止剤の含有割合としては、例えば、０．０００５～０．３質量％であり、０．００１～０．２質量％が好ましく、０．０１～０．１質量％がより好ましい。 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% by mass or more in the total solid content of the photosensitive resin composition. Preferably, it is 0.001% by mass or more, more preferably 0.01% by mass or more, and usually 0.3% by mass or less, preferably 0.2% by mass or less, more preferably 0.1% by mass or less . There is a tendency that the taper angle can be increased by setting the lower limit value or more, and there is a tendency that high sensitivity can be maintained by setting the upper limit value or less. When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor in the total solid content of the photosensitive resin composition is, for example, 0.0005 to 0.3 mass%, The content is preferably 0.001 to 0.2% by mass, and more preferably 0.01 to 0.1% by mass.
［１－１－８］アミノ化合物
　本発明の感光性樹脂組成物には、熱硬化を促進するためにアミノ化合物が含まれていてもよい。
　本発明の感光性樹脂組成物がアミノ化合物を含む場合、感光性樹脂組成物におけるアミノ化合物の含有割合としては、感光性樹脂組成物の全固形分中に、通常４０質量％以下、好ましくは３０質量％以下である。また、通常０．５質量％以上、好ましくは１質量％以上である。前記上限値以下とすることで保存安定性を維持できる傾向があり、前記下限値以上とすることで十分な熱硬化性を確保できる傾向がある。本発明の感光性樹脂組成物がアミノ化合物を含む場合、感光性樹脂組成物におけるアミノ化合物の全固形分中の含有割合は、例えば、０．５～４０質量％であり、１～３０質量％が好ましい。 [1-1-8] Amino Compound The photosensitive resin composition of the present invention may contain an amino compound in order to accelerate heat curing.
When the photosensitive resin composition of the present invention contains an amino compound, the content ratio of the amino compound in the photosensitive resin composition is usually 40% by mass or less, preferably 30% or less in the total solid content of the photosensitive resin composition. It is less than mass%. Also, it is usually 0.5% by mass or more, preferably 1% by mass or more. There is a tendency that storage stability can be maintained by setting it to the upper limit value or less, and there is a tendency that sufficient thermosetting property can be secured by setting it to the above lower limit value. When the photosensitive resin composition of the present invention contains an amino compound, the content of the amino compound in the total solid of the photosensitive resin composition is, for example, 0.5 to 40% by mass, and 1 to 30% by mass. Is preferred.
　アミノ化合物としては、例えば、官能基としてメチロール基や、メチロール基を炭素数１～８のアルコール縮合変性したアルコキシメチル基を少なくとも２個有するアミノ化合物が挙げられる。具体的には、例えば、メラミンとホルムアルデヒドとを重縮合させたメラミン樹脂；ベンゾグアナミンとホルムアルデヒドとを重縮合させたベンゾグアナミン樹脂；グリコールウリルとホルムアルデヒドとを重縮合させたグリコールウリル樹脂；尿素とホルムアルデヒドとを重縮合させた尿素樹脂；メラミン、ベンゾグアナミン、グリコールウリル、または尿素などの２種以上とホルムアルデヒドとを共重縮合させた樹脂；上述の樹脂のメチロール基をアルコール縮合変性した変性樹脂などが挙げられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。アミノ化合物としては中でも、メラミン樹脂およびその変性樹脂が好ましく、メチロール基の変性割合が、７０％以上の変性樹脂が更に好ましく、８０％以上の変性樹脂が特に好ましい。 Examples of the amino compound include amino compounds having at least two methylol groups as functional groups and at least two alkoxymethyl groups in which methylol groups are alcohol-condensed and modified with 1 to 8 carbon atoms. Specifically, for example, a melamine resin obtained by polycondensing melamine and formaldehyde; a benzoguanamine resin obtained by polycondensing benzoguanamine and formaldehyde; a glycoluril resin obtained by polycondensing glycoluril and formaldehyde; urea and formaldehyde Polycondensed urea resins; resins obtained by copolycondensing formaldehyde with two or more kinds of melamine, benzoguanamine, glycoluril, or urea; and modified resins obtained by alcohol condensation-modifying methylol groups of the above-mentioned resins. One of these may be used alone, or two or more may be used in combination. Among the amino compounds, melamine resins and modified resins thereof are preferable. Modified resins having a methylol group modification ratio of 70% or more are more preferable, and modified resins of 80% or more are particularly preferable.
　上記アミノ化合物の具体例として、メラミン樹脂およびその変性樹脂としては、例えば、サイテック社製のサイメル（登録商標、以下同じ。）３００、３０１、３０３、３５０、７３６、７３８、３７０、７７１、３２５、３２７、７０３、７０１、２６６、２６７、２８５、２３２、２３５、２３８、１１４１、２７２、２５４、２０２、１１５６、１１５８、および、三和ケミカル社製のニカラック（登録商標、以下同じ。）ＭＷ－３９０、ＭＷ－１００ＬＭ、ＭＸ－７５０ＬＭ、ＭＷ－３０Ｍ、ＭＸ－４５、ＭＸ－３０２などが挙げられる。また、上記ベンゾグアナミン樹脂およびその変性樹脂としては、例えば、サイテック社製のサイメル１１２３、１１２５、１１２８などが挙げられる。また、上記グリコールウリル樹脂およびその変性樹脂としては、例えば、サイテック社製のサイメル１１７０、１１７１、１１７４、１１７２、および、三和ケミカル社製のニカラックＭＸ－２７０などが挙げられる。また、上記尿素樹脂およびその変性樹脂としては、例えば、サイテック社製のＵＦＲ（登録商標、以下同じ。）６５、３００、および、三和ケミカル社製のニカラックＭＸ－２９０などが挙げられる。 As a specific example of the said amino compound, as a melamine resin and its modification resin, Cymel (The registered trademark, the same hereafter) 300, 301, 303, 350, 736, 738, 370, 771, 325, made by Cytec, for example is mentioned. 327, 703, 701, 266, 267, 285, 232, 238, 1141, 272, 254, 202, 1156, 1158, and Niwarak (registered trademark, hereinafter the same) MW-390 manufactured by Sanwa Chemical Co., Ltd. , MW-100 LM, MX-750 LM, MW-30 M, MX-45, MX-302 and the like. Moreover, as said benzoguanamine resin and its modification | denaturation resin, the Cymel 1123, 1125, 1128 grade | etc., Made by Cytec, etc. are mentioned, for example. Further, examples of the above glycoluril resin and its modified resin include Cymel 1170, 1171, 1174, 1172 manufactured by Cytec, and Nikalac MX-270 manufactured by Sanwa Chemical Co., Ltd. Further, as the above-mentioned urea resin and its modified resin, for example, UFR (registered trademark, the same shall apply hereinafter) 65, 300 manufactured by Cytec Co., Ltd., Nikalac MX-290 manufactured by Sanwa Chemical Co., Ltd., etc. may be mentioned.
［１－１－９］着色剤
　本発明の感光性樹脂組成物には、隔壁を着色させる目的で着色剤が含まれていてもよい。着色剤としては、顔料、染料等公知の着色剤を用いることができる。また、例えば、顔料を用いる際に、その顔料が凝集したりせずに安定して感光性樹脂組成物中に存在できるように、公知の分散剤や分散助剤が併用されてもよい。特に撥インク性隔壁を黒色に着色することで、鮮明な画素表示が得られる効果がある。黒色着色剤としては黒色染料や黒色顔料、カーボンブラック、チタンブラックなどの他、有機顔料を混合させて黒く着色することも低導電性を持たせる効果として有効である。着色剤の含有割合としては製版性と色特性の観点から、感光性樹脂組成物の全固形分中に、通常６０質量％以下、好ましくは４０質量％以下である。
　一方で、隔壁からのアウトガスを低減させる目的の場合、隔壁を透明にすることが望ましく、その場合の着色剤の含有割合は、感光性樹脂組成物の全固形分に対して、好ましくは１０質量％以下、より好ましくは５質量％以下、特に好ましくは０質量％である。 [1-1-9] Colorant The photosensitive resin composition of the present invention may contain a colorant for the purpose of coloring the partition walls. As colorants, known colorants such as pigments and dyes can be used. Also, for example, when a pigment is used, a known dispersant or dispersion aid may be used in combination so that the pigment can be stably present in the photosensitive resin composition without aggregation. In particular, by coloring the ink repellent partition wall black, there is an effect that a clear pixel display can be obtained. As a black coloring agent, it is effective to mix an organic pigment as well as a black dye, a black pigment, carbon black, titanium black and the like to make the color black to give low conductivity. The content ratio of the coloring agent is usually 60% by mass or less, preferably 40% by mass or less, in the total solid content of the photosensitive resin composition from the viewpoint of platemaking properties and color characteristics.
On the other hand, for the purpose of reducing the outgassing from the partition walls, it is desirable to make the partition walls transparent, in which case the content ratio of the colorant is preferably 10 mass% with respect to the total solid content of the photosensitive resin composition. % Or less, more preferably 5% by mass or less, particularly preferably 0% by mass.
［１－１－１０］塗布性向上剤、現像改良剤
　本発明の感光性樹脂組成物には、塗布性や現像溶解性を向上するために塗布性向上剤や現像改良剤が含まれていてもよい。塗布性向上剤あるいは現像改良剤としては、例えば公知の、カチオン性、アニオン性、ノニオン性、フッ素系、シリコーン系界面活性剤を用いることができる。界面活性剤は、感光性樹脂組成物の塗布液としての塗布性、および塗布膜の現像性の向上などを目的として用いることができ、中でもフッ素系又はシリコーン系の界面活性剤が好ましい。
　特に、現像の際、未露光部から感光性樹脂組成物の残渣を除去する作用があり、また、濡れ性を発現する機能を有することから、シリコーン系界面活性剤が好ましく、ポリエーテル変性シリコーン系界面活性剤がさらに好ましい。 [1-1-10] Coatability Improver, Development Improver The photosensitive resin composition of the present invention contains a coatability improver and a development improver in order to improve the coatability and the development solubility. It is also good. As the coatability improver or the development improver, for example, known cationic, anionic, nonionic, fluorine-based or silicone-based surfactants can be used. The surfactant can be used for the purpose of improving the coatability as a coating liquid of the photosensitive resin composition, the developability of the coating film, etc. Among these, fluorine-based or silicone-based surfactants are preferable.
In particular, silicone surfactants are preferred because they have the function of removing the residue of the photosensitive resin composition from the unexposed area during development and have a function of developing wettability, and polyether-modified silicones are preferred. Surfactants are more preferred.
　フッ素系界面活性剤としては、末端、主鎖および側鎖の少なくとも何れかの部位にフルオロアルキルまたはフルオロアルキレン基を有する化合物が好適である。具体的には、１，１，２，２－テトラフロロオクチル（１，１，２，２－テトラフロロプロピル）エーテル、１，１，２，２－テトラフロロオクチルヘキシルエーテル、オクタエチレングリコールジ（１，１，２，２－テトラフロロブチル）エーテル、ヘキサエチレングリコールジ（１，１，２，２，３，３－ヘキサフロロペンチル）エーテル、オクタプロピレングリコールジ（１，１，２，２－テトラフロロブチル）エーテル、ヘキサプロピレングリコールジ（１，１，２，２，３，３－ヘキサフロロペンチル）エーテル、パーフロロドデシルスルホン酸ナトリウム、１，１，２，２，８，８，９，９，１０，１０－デカフロロドデカン、１，１，２，２，３，３－ヘキサフロロデカンなどを挙げることができる。これらの市販品としては、例えば、ＢＭ　Ｃｈｅｍｉｅ社製「ＢＭ－１０００」、「ＢＭ－１１００」、ＤＩＣ社製「メガファックＦ４７０」、「メガファックＦ４７５」、スリーエムジャパン社製「ＦＣ４３０」、ネオス社製「ＤＦＸ－１８」などを挙げることができる。 The fluorosurfactant is preferably a compound having a fluoroalkyl or fluoroalkylene group at at least one of the terminal, main chain and side chain. Specifically, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di 1,1,2,2-Tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2- Tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8,9, Examples include 9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane and the like. Examples of these commercial products include “BM-1000” and “BM-1100” manufactured by BM Chemie, “Megafuck F470” manufactured by DIC, “Megafuck F475”, “FC430” manufactured by 3M Japan, and Neos Made from "DFX-18" etc. can be mentioned.
　また、シリコーン系界面活性剤としては、例えば、東レ・ダウコーニング社製「ＤＣ３ＰＡ」、「ＳＨ７ＰＡ」、「ＤＣ１１ＰＡ」、「ＳＨ２１ＰＡ」、「ＳＨ２８ＰＡ」、「ＳＨ２９ＰＡ」、「８０３２Ａｄｄｉｔｉｖｅ」、「ＳＨ８４００」、ビックケミー社製「ＢＹＫ（登録商標、以下同じ。）３２３」、「ＢＹＫ３３０」などの市販品を挙げることができる。
　界面活性剤として、フッ素系界面活性剤及びシリコーン系界面活性剤以外のものを含んでいてもよく、その他、界面活性剤としては、ノニオン性、アニオン性、カチオン性、両性界面活性剤などが挙げられる。 Further, examples of silicone surfactants include “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “8032Additive”, “SH8400”, manufactured by Toray Dow Corning, Commercial products such as "BYK (registered trademark, the same as the following) 323" and "BYK 330" manufactured by Big Chemie Co., Ltd. can be mentioned.
As the surfactant, one other than the fluorine-based surfactant and the silicone-based surfactant may be contained, and as the surfactant, nonionic, anionic, cationic, amphoteric surfactant etc. may be mentioned. Be
　上記ノニオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンポリオキシプロピレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンアルキルエステル類、ポリオキシエチレン脂肪酸エステル類、グリセリン脂肪酸エステル類、ポリオキシエチレングリセリン脂肪酸エステル類、ペンタエリスリット脂肪酸エステル類、ポリオキシエチレンペンタエリスリット脂肪酸エステル類、ソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタン脂肪酸エステル類、ソルビット脂肪酸エステル類、ポリオキシエチレンソルビット脂肪酸エステル類などが挙げられる。これらの市販品としては、例えば、花王社製の「エマルゲン１０４Ｐ」、「エマルゲンＡ６０」などのポリオキシエチレン系界面活性剤などが挙げられる。 Examples of the nonionic surfactants 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, sorbit fatty acid esters, polyoxy acid Ethylene sorbite fatty acid ester etc. are mentioned. Examples of these commercially available products include polyoxyethylene surfactants such as "Emulgen 104P" and "Emulgen A60" manufactured by Kao Corporation, and the like.
　また、上記アニオン性界面活性剤としては、例えば、アルキルスルホン酸塩類、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、ポリオキシエチレンアルキルエーテルスルホン酸塩類、アルキル硫酸塩類、アルキル硫酸エステル塩類、高級アルコール硫酸エステル塩類、脂肪族アルコール硫酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸塩類、ポリオキシエチレンアルキルフェニルエーテル硫酸塩類、アルキル燐酸エステル塩類、ポリオキシエチレンアルキルエーテル燐酸塩類、ポリオキシエチレンアルキルフェニルエーテル燐酸塩類、特殊高分子系界面活性剤などが挙げられる。中でも、特殊高分子系界面活性剤が好ましく、特殊ポリカルボン酸型高分子系界面活性剤がさらに好ましい。このようなアニオン性界面活性剤としては市販品を用いることができ、例えば、アルキル硫酸エステル塩類では、花王社製「エマール（登録商標。）１０」等、アルキルナフタレンスルホン酸塩類では花王社製「ペレックス（登録商標。）ＮＢ－Ｌ」など、特殊高分子系界面活性剤では花王社製「ホモゲノール（登録商標、以下同じ。）Ｌ－１８」、「ホモゲノールＬ－１００」などが挙げられる。 Further, as the above-mentioned anionic surfactant, for example, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfate salts, alkyl sulfate ester salts, higher alcohol sulfate Ester salts, aliphatic alcohol sulfuric acid ester salts, polyoxyethylene alkyl ether sulfuric acid salts, polyoxyethylene alkyl phenyl ether sulfuric acid salts, alkyl phosphoric acid ester salts, polyoxyethylene alkyl ether phosphoric acid salts, polyoxyethylene alkyl phenyl ether phosphoric acid salts, special Polymeric surfactant etc. are mentioned. Among them, special polymer surfactants are preferable, and special polycarboxylic acid type polymer surfactants are more preferable. A commercial item can be used as such an anionic surfactant, For example, in alkyl sulfate ester salts, "Emar (registered trademark) 10" by Kao Corp. etc., and by alkyl naphthalene sulfonates by Kao Corp. Examples of special polymer surfactants such as Perex (registered trademark) NB-L include “Homogen (registered trademark, the same shall apply hereinafter) L-18”, “Homogen L-100” and the like manufactured by Kao Corporation.
　さらに、上記カチオン性界面活性剤としては、第４級アンモニウム塩類、イミダゾリン誘導体類、アルキルアミン塩類などが、また、両性界面活性剤としては、ベタイン型化合物類、イミダゾリウム塩類、イミダゾリン類、アミノ酸類などが挙げられる。これらのうち、第４級アンモニウム塩類が好ましく、ステアリルトリメチルアンモニウム塩類がさらに好ましい。市販のものとしては、例えば、アルキルアミン塩類では花王社製「アセタミン（登録商標。）２４」など、第４級アンモニウム塩類では花王社製「コータミン（登録商標、以下同じ。）２４Ｐ」、「コータミン８６Ｗ」などが挙げられる。
　また、界面活性剤は２種類以上の組み合わせで用いてもよく、例えば、シリコーン系界面活性剤／フッ素系界面活性剤、シリコーン系界面活性剤／特殊高分子系界面活性剤、フッ素系界面活性剤／特殊高分子系界面活性剤の組み合わせなどが挙げられる。中でも、シリコーン系界面活性剤／フッ素系界面活性剤の組み合わせが好ましい。このシリコーン系界面活性剤／フッ素系界面活性剤の組み合わせでは、例えば、／ネオス社製「ＤＦＸ－１８」、ビックケミー社製「ＢＹＫ－３００」または「ＢＹＫ－３３０」／ＡＧＣセイミケミカル社製「Ｓ－３９３」、信越シリコーン社製「ＫＰ３４０」／ＤＩＣ社製「Ｆ－４７８」または「Ｆ－４７５」、東レ・ダウコーニング社製「ＳＨ７ＰＡ」／ダイキン社製「ＤＳ－４０１」、ＮＵＣ社製「Ｌ－７７」／スリーエムジャパン社製「ＦＣ４４３０」などが挙げられる。
　また、現像改良剤として、有機カルボン酸或いはその無水物など公知のものを用いることもできる。
　また、本発明の感光性樹脂組成物が塗布性向上剤や現像改良剤を含む場合、塗布性向上剤や現像改良剤の含有割合は、感度の観点から、感光性樹脂組成物の全固形分中に、通常それぞれ２０質量％以下、好ましくはそれぞれ１０質量％以下である。 Furthermore, as the above-mentioned cationic surfactant, quaternary ammonium salts, imidazoline derivatives, alkylamine salts and the like, and as amphoteric surfactants, betaine type compounds, imidazolium salts, imidazolines, amino acids Etc. Among these, quaternary ammonium salts are preferable, and stearyl trimethyl ammonium salts are more preferable. As commercially available products, for example, alkylamine salts such as "Acetamine (registered trademark) 24" manufactured by Kao Corporation, and quaternary ammonium salts such as "Cortamine (registered trademark, the same as the following) 24P" manufactured by Kao Corporation, "Cortamine 86 W "and the like.
Also, the surfactant may be used in combination of two or more types, and, for example, silicone surfactant / fluorinated surfactant, silicone surfactant / special polymer surfactant, fluorinated surfactant And combinations of special polymer surfactants and the like. Among them, a combination of silicone surfactant / fluorinated surfactant is preferable. In this combination of silicone surfactant / fluorinated surfactant, for example, "DFX-18" manufactured by Neos, "BYK-300" manufactured by BIC Chemie, or "BYK-330" / "S manufactured by AGC Seimi Chemical""393", Shin-Etsu Silicone "KP340" / DIC "F-478" or "F-475", Toray Dow Corning "SH7PA" / Daikin "DS-401", NUC " L-77 ”/“ FC 4430 ”manufactured by 3M Japan Co., Ltd. may be mentioned.
Further, as a development improver, known ones such as organic carboxylic acids or their anhydrides can also be used.
When the photosensitive resin composition of the present invention contains a coatability improver or a development improver, the content ratio of the coatability improver or the development improver is the total solid content of the photosensitive resin composition from the viewpoint of sensitivity. The content is usually at most 20% by mass, preferably at most 10% by mass.
［１－１－１１］シランカップリング剤
　本発明の感光性樹脂組成物には、基板との密着性を改善するため、シランカップリング剤を添加することも好ましい。シランカップリング剤の種類としては、エポキシ系、メタクリル系、アミノ系、イミダゾール系など種々の物が使用できるが、密着性向上の観点から、特にエポキシ系、イミダゾール系のシランカップリング剤が好ましい。
　本発明の感光性樹脂組成物がシランカップリング剤を含む場合、シランカップリング剤の含有割合は、密着性の観点から、感光性樹脂組成物の全固形分中に、通常２０質量％以下、好ましくは１５質量％以下である。 [1-1-11] Silane Coupling Agent It is also preferable to add a silane coupling agent to the photosensitive resin composition of the present invention in order to improve the adhesion to the substrate. As the type of silane coupling agent, various types such as epoxy type, methacrylic type, amino type, and imidazole type can be used, but from the viewpoint of improving adhesion, epoxy type and imidazole type silane coupling agents are particularly preferable.
When the photosensitive resin composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is usually 20% by mass or less in the total solid content of the photosensitive resin composition from the viewpoint of adhesion. Preferably it is 15 mass% or less.
［１－１－１２］リン酸系密着向上剤
　本発明の感光性樹脂組成物には、基板との密着性を改善するため、リン酸系密着向上剤を添加することも好ましい。リン酸系密着向上剤としては、（メタ）アクリロイルオキシ基含有ホスフェート類が好ましく、中でも下記一般式（Ｖａ）、（Ｖｂ）、（Ｖｃ）で表されるものが好ましい。 [1-1-12] Phosphoric Acid Adhesion Improver In order to improve the adhesion to the substrate, it is preferable to add a phosphoric acid adhesion improver to the photosensitive resin composition of the present invention. As the phosphoric acid-based adhesion improver, (meth) acryloyloxy group-containing phosphates are preferable, and among these, those represented by the following general formulas (Va), (Vb) and (Vc) are preferable.
Figure JPOXMLDOC01-appb-C000063
  
Figure JPOXMLDOC01-appb-C000063
  
　上記一般式（Ｖａ）、（Ｖｂ）、（Ｖｃ）において、Ｒ8は水素原子又はメチル基を示し、ｒ及びｒ’は１～１０の整数、ｓは１、２又は３である。 In the general formulas (Va), (Vb) and (Vc), R 8 represents a hydrogen atom or a methyl group, r and r ′ are integers of 1 to 10, and s is 1, 2 or 3.
　本発明の感光性樹脂組成物がリン酸系密着向上剤を含有する場合、その含有割合は特に限定されないが、全固形分中に０．１質量％以上が好ましく、０．３質量％以上がより好ましく、０．５質量％以上がさらに好ましく、また、５質量％以下が好ましく、３質量％以下がより好ましく、１質量％以下がさらに好ましい。前記下限値以上とすることで基板との密着性が向上する傾向があり、また、前記上限値以下とすることで表面硬化性が向上する傾向がある。本発明の感光性樹脂組成物がリン酸系密着向上剤を含有する場合、リン酸系密着向上剤の全固形分中の含有割合は、例えば、０．１～５質量％であり、０．３～３質量％が好ましく、０．５～１質量％がより好ましい。 When the photosensitive resin composition of the present invention contains a phosphoric acid-based adhesion improver, the content thereof is not particularly limited, but 0.1% by mass or more is preferable and 0.3% by mass or more in the total solid content. More preferably, it is 0.5 mass% or more, 5 mass% or less is preferable, 3 mass% or less is more preferable, and 1 mass% or less is more preferable. The adhesion to the substrate tends to be improved by setting the content to the lower limit or more, and the surface curability tends to be improved by setting the content to the upper limit or less. When the photosensitive resin composition of the present invention contains a phosphoric acid-based adhesion improver, the content ratio of the phosphoric acid-based adhesion improver in the total solid content is, for example, 0.1 to 5% by mass. The amount is preferably 3 to 3% by mass, and more preferably 0.5 to 1% by mass.
［１－１－１３］無機充填剤
　また、本発明の感光性樹脂組成物は、さらに、硬化物としての強度の向上と共に、アルカリ可溶性樹脂との適度な相互作用（マトリックス構造の形成）による塗布膜の優れた平坦性とテーパー角の向上等を目的として、無機充填剤を含有していてもよい。そのような無機充填剤としては、例えば、タルク、シリカ、アルミナ、硫酸バリウム、酸化マグネシウム、或いは、これらを各種シランカップリング剤により表面処理したものなどが挙げられる。 [1-1-13] Inorganic Filler Furthermore, the photosensitive resin composition of the present invention is further applied with appropriate interaction (formation of matrix structure) with an alkali-soluble resin, together with improvement of strength as a cured product. An inorganic filler may be contained for the purpose of improving the flatness and taper angle of the film. Examples of such an inorganic filler include talc, silica, alumina, barium sulfate, magnesium oxide, and those surface-treated with various silane coupling agents.
　これら無機充填剤の平均粒子径としては、通常０．００５～２０μｍ、好ましくは０．０１～１０μｍである。ここで本実施の形態にいう平均粒子径とは、ベックマン・コールター社製などのレーザ回折散乱粒度分布測定装置にて測定した値である。これらの無機充填剤のうち、特に、シリカゾルおよびシリカゾル変性物は、分散安定性と共にテーパー角の向上効果に優れる傾向があるため、好ましく配合される。
　本発明の感光性樹脂組成物が無機充填剤を含む場合、その含有量としては、感度の観点から、全固形分中に、通常５質量％以上、好ましくは１０質量％以上であり、通常８０質量％以下、好ましくは７０質量％以下である。本発明の感光性樹脂組成物が無機充填剤を含む場合、無機充填剤の全固形分中の含有量としては、例えば、５～８０質量％であり、１０～７０質量％が好ましい。 The average particle size of these inorganic fillers is usually 0.005 to 20 μm, preferably 0.01 to 10 μm. Here, the average particle size referred to in the present embodiment is a value measured by a laser diffraction scattering particle size distribution measuring apparatus such as manufactured by Beckman Coulter. Among these inorganic fillers, in particular, silica sol and silica sol modified products tend to be excellent in improvement effect of taper angle as well as dispersion stability, and therefore, they are preferably blended.
When the photosensitive resin composition of the present invention contains an inorganic filler, the content thereof is usually 5% by mass or more, preferably 10% by mass or more, and usually 80% by mass in the total solid content from the viewpoint of sensitivity. It is at most mass%, preferably at most 70 mass%. When the photosensitive resin composition of the present invention contains an inorganic filler, the content of the inorganic filler in the total solid content is, for example, 5 to 80% by mass, preferably 10 to 70% by mass.
［１－１－１４］溶剤
　本発明の感光性樹脂組成物は、通常溶剤を含有し、前述の各成分を溶剤に溶解または分散させた状態で使用される（以下、溶剤を含む感光性樹脂組成物を「感光性樹脂組成物溶液」と記すことがある）。その溶剤としては、特に制限は無いが、例えば、以下に記載する有機溶剤が挙げられる。 [1-1-14] Solvent The photosensitive resin composition of the present invention usually contains a solvent, and is used in a state in which the above-described components are dissolved or dispersed in the solvent (hereinafter, photosensitive resin containing solvent) The composition is sometimes referred to as "photosensitive resin composition solution". The solvent is not particularly limited, and examples thereof include the organic solvents described below.
　エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ－ｎ－ブチルエーテル、プロピレングリコール－ｔ－ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ－ｎ－ブチルエーテル、メトキシメチルペンタノール、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、３－メチル－３－メトキシブタノール、３－メトキシ－１－ブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリプロピレングリコールメチルエーテルのようなグリコールモノアルキルエーテル類；エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジメチルエーテルのようなグリコールジアルキルエーテル類；エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ－ｎ－ブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、メトキシブチルアセテート、３－メトキシブチルアセテート、メトキシペンチルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノ－ｎ－ブチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノエチルエーテルアセテート、３－メチル－３－メトキシブチルアセテート、３－メトキシ－１－ブチルアセテートのようなグリコールアルキルエーテルアセテート類；エチレングリコールジアセテート、１，３－ブチレングリコールジアセテート、１，６－ヘキサノールジアセテートなどのグリコールジアセテート類；シクロヘキサノールアセテートなどのアルキルアセテート類；アミルエーテル、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジアミルエーテル、エチルイソブチルエーテル、ジヘキシルエーテルのようなエーテル類；アセトン、メチルエチルケトン、メチルアミルケトン、メチルイソプロピルケトン、メチルイソアミルケトン、ジイソプロピルケトン、ジイソブチルケトン、メチルイソブチルケトン、シクロヘキサノン、エチルアミルケトン、メチルブチルケトン、メチルヘキシルケトン、メチルノニルケトン、メトキシメチルペンタノンのようなケトン類；メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、メトキシメチルペンタノール、グリセリン、ベンジルアルコールのような１価又は多価アルコール類；ｎ－ペンタン、ｎ－オクタン、ジイソブチレン、ｎ－ヘキサン、ヘキセン、イソプレン、ジペンテン、ドデカンのような脂肪族炭化水素類；シクロヘキサン、メチルシクロヘキサン、メチルシクロヘキセン、ビシクロヘキシルのような脂環式炭化水素類；ベンゼン、トルエン、キシレン、クメンのような芳香族炭化水素類；アミルホルメート、エチルホルメート、酢酸エチル、酢酸ブチル、酢酸プロピル、酢酸アミル、メチルイソブチレート、エチレングリコールアセテート、エチルプロピオネート、プロピルプロピオネート、酪酸ブチル、酪酸イソブチル、イソ酪酸メチル、エチルカプリレート、ブチルステアレート、エチルベンゾエート、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、γ－ブチロラクトンのような鎖状又は環状エステル類；３－メトキシプロピオン酸、３－エトキシプロピオン酸のようなアルコキシカルボン酸類；ブチルクロライド、アミルクロライドのようなハロゲン化炭化水素類；メトキシメチルペンタノンのようなエーテルケトン類；アセトニトリル、ベンゾニトリルのようなニトリル類：テトラヒドロフラン、ジメチルテトラヒドロフラン、ジメトキシテトラヒドロフランのようなテトラヒドロフラン類などである。 Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, tri Ethylene glycol monomethyl ether , Glycol monoalkyl ethers such as triethylene glycol monoethyl ether and tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol Glycol dialkyl ethers such as dimethyl ether; 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 alkyl ether acetates such as glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-1-butyl acetate; ethylene glycol di acetate, Glycol diacetates such as 1,3-butylene glycol diacetate and 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ester Ethers such as ether, ethyl isobutyl ether and dihexyl ether; 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, Methylhexyl ketone, methylnonyl ketone, ketones such as methoxymethylpentanone; methanol, ethanol Monohydric or polyhydric alcohols such as propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethyl pentanol, glycerin and benzyl alcohol; n Aliphatic hydrocarbons such as pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl; Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl Sobutylate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate , Linear or cyclic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone; 3-methoxypropionic acid, 3- Alkoxycarboxylic acids such as ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethyl pentanone; acetonitrile, benzonitrile UNA nitriles: is tetrahydrofuran, dimethyl tetrahydrofuran, tetrahydrofuran, such as dimethoxytetrahydrofuran.
　上記に該当する市販の溶剤としては、ミネラルスピリット、バルソル＃２、アプコ＃１８ソルベント、アプコシンナー、ソーカルソルベントＮｏ．１およびＮｏ．２、ソルベッソ＃１５０、シェルＴＳ２８　ソルベント、カルビトール、エチルカルビトール、ブチルカルビトール、メチルセロソルブ、エチルセロソルブ、エチルセロソルブアセテート、メチルセロソルブアセテート、ジグライム（いずれも商品名）などが挙げられる。 Commercially available solvents corresponding to the above include Mineral Spirit, Valsol # 2, Apco # 18 Solvent, Apcosynner, Socar Solvent No. 1 and No. 2. Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl carosolve, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all are trade names) and the like.
　上記溶剤は、感光性樹脂組成物中の各成分を溶解または分散させることができるもので、本発明の感光性樹脂組成物の使用方法に応じて選択されるが、塗布性の観点から、大気圧下（１０１３．２５ｈＰａ）における沸点が６０～２８０℃の範囲のものを選択することが好ましい。より好ましくは７０～２６０℃の沸点をもつものであり、例えばプロピレングリコールモノメチルエーテル、３－メトキシ－１－ブタノール、プロピレングリコールモノメチルエーテルアセテート、３－メトキシ－１－ブチルアセテートが好ましい。 The above-mentioned solvent can dissolve or disperse each component in the photosensitive resin composition, and is selected according to the method of using the photosensitive resin composition of the present invention. It is preferable to select one having a boiling point in the range of 60 to 280 ° C. under atmospheric pressure (1013.25 hPa). More preferred are those having a boiling point of 70 to 260 ° C., for example, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate.
　これらの溶剤は１種を単独でもしくは２種以上を混合して使用することができる。また、これらの溶剤は、感光性樹脂組成物溶液中の全固形分の含有割合が、通常１０質量％以上、好ましくは１５質量％以上、より好ましくは１８質量％以上、通常９０質量％以下、好ましくは５０質量％以下、より好ましくは４０質量％以下、さらに好ましくは３０質量％以下となるように使用されることが好ましい。前記下限値以上とすることで高い膜厚に対しても塗膜が得られる傾向があり、また、前記上限値以下とすることで適度な塗布均一性が得られる傾向がある。例えば、感光性樹脂組成物中の全固形分の含有割合が１０～９０質量％、好ましくは１０～５０質量％、より好ましくは１５～４０質量％、さらに好ましくは１８～３０質量％となるように、溶媒が使用されうる。 These solvents may be used alone or in combination of two or more. In these solvents, the content ratio of the total solid content in the photosensitive resin composition solution 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, it is used so as to be 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. By setting the content to the above lower limit or more, a coating film tends to be obtained even for a high film thickness, and by setting the above upper limit or less, appropriate coating uniformity tends to be obtained. For example, the content ratio 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. Solvents may be used.
［１－２］感光性樹脂組成物の物性
　本発明の感光性樹脂組成物の物性としては、例えば酸価が挙げられる。
　感光性樹脂組成物の全固形分に対する酸価は特に限定されないが、２０ｍｇ－ＫＯＨ／ｇ以上が好ましく、２２ｍｇ－ＫＯＨ／ｇ以上がより好ましく、２４ｍｇ－ＫＯＨ／ｇ以上がさらに好ましく、２６ｍｇ－ＫＯＨ／ｇ以上がよりさらに好ましく、２８ｍｇ－ＫＯＨ／ｇ以上が特に好ましく、また、通常６０ｍｇ－ＫＯＨ／ｇ以下、５５ｍｇ－ＫＯＨ／ｇ以下が好ましく、５０ｍｇ－ＫＯＨ／ｇ以下がより好ましく、４０ｍｇ－ＫＯＨ／ｇ以下がさらに好ましく、３５ｍｇ－ＫＯＨ／ｇ以下が特に好ましい。前記下限値以上とすることで現像液への溶解性が高く、未露光部が十分に溶解、除去できることでテーパー角が高くなる傾向があり、また、前記上限値以下とすることで現像密着性が良好となる傾向がある。感光性樹脂組成物の全固形分に対する酸価としては、例えば、２０～６０ｍｇ－ＫＯＨ／ｇであり、２２～５５ｍｇ－ＫＯＨ／ｇが好ましく、２４～５０ｍｇ－ＫＯＨ／ｇがより好ましく、２６～４０ｍｇ－ＫＯＨ／ｇがさらに好ましく、２８～３５ｍｇ－ＫＯＨ／ｇがよりさらに好ましい。 [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.
Although the acid value with respect to the total solid of the photosensitive resin composition is not particularly limited, 20 mg-KOH / g or more is preferable, 22 mg-KOH / g or more is more preferable, 24 mg-KOH / g or more is more preferable, 26 mg-KOH / G or more is more preferable, 28 mg-KOH / g or more is particularly preferable, and usually 60 mg-KOH / g or less, 55 mg-KOH / g or less is preferable, 50 mg-KOH / g or less is more preferable, 40 mg-KOH / G or less is more preferable, and 35 mg-KOH / g or less is particularly preferable. By setting the lower limit value or more, the solubility in the developer is high, and the unexposed area can be sufficiently dissolved and removed, so that the taper angle tends to be high, and by making the upper limit value or less, the development adhesion Tend to be good. The acid value of the photosensitive resin composition relative to the total solid content is, for example, 20 to 60 mg-KOH / g, preferably 22 to 55 mg-KOH / g, more preferably 24 to 50 mg-KOH / g, and 26 to 40 mg-KOH / g is more preferred, and 28-35 mg-KOH / g is even more preferred.
［１－３］感光性樹脂組成物の調製方法
　本発明の感光性樹脂組成物は、上記の各成分を撹拌機で混合することにより調製される。なお、調製された感光性樹脂組成物が均一なものとなるよう、メンブランフィルタ等を用いて濾過してもよい。 [1-3] Preparation Method of Photosensitive Resin Composition The photosensitive resin composition of the present invention is prepared by mixing the above-mentioned components with a stirrer. In addition, you may filter using a membrane filter etc. so that the prepared photosensitive resin composition may become uniform.
［２］隔壁及び隔壁の形成方法
　本発明の感光性樹脂組成物は隔壁、特に有機電界発光素子の有機層（発光部）を区画するための隔壁を形成するために好適に用いることができる。本発明の隔壁は、本発明の感光性樹脂組成物で構成される。
　以上説明した感光性樹脂組成物を用いて隔壁を形成する方法は特に限定されず、従来公知の方法を採用することができる。隔壁の形成方法としては、例えば、感光性樹脂組成物を、基板上に塗布し、感光性樹脂組成物層を形成する塗布工程と、感光性樹脂組成物層を露光する露光工程と、を含む方法が挙げられる。このような隔壁の形成方法の具体例としては、フォトリソグラフィー法が挙げられる。 [2] Method of Forming Partition Walls and Partition Walls The photosensitive resin composition of the present invention can be suitably used to form a partition wall, in particular, a partition wall for partitioning an organic layer (light emitting portion) of an organic electroluminescent device. The partition of the present invention is composed of the photosensitive resin composition of the present invention.
The method of forming a partition using the photosensitive resin composition demonstrated above is not specifically limited, A conventionally well-known method is employable. As a formation method of a partition, the photosensitive resin composition is apply | coated on a board | substrate, for example, the application process of forming the photosensitive resin composition layer, and the exposure process of exposing the photosensitive resin composition layer are included. The method is mentioned. A photolithographic method is mentioned as a specific example of the formation method of such a partition.
　フォトリソグラフィー法では、感光性樹脂組成物を、基板の隔壁が形成される領域全面に塗布して感光性樹脂組成物層を形成する。形成された感光性樹脂組成物層を、所定の隔壁のパターンに応じて露光した後、露光された感光性樹脂組成物層を現像して、基板上に隔壁が形成される。 In the photolithography method, the photosensitive resin composition is applied on the entire surface of the region where the partition walls of the substrate are formed, to form a photosensitive resin composition layer. After exposing the formed photosensitive resin composition layer according to the pattern of a predetermined partition, the exposed photosensitive resin composition layer is developed to form a partition on the substrate.
　フォトリソグラフィー法における、感光性樹脂組成物を基板上に塗布する塗布工程では、隔壁が形成されるべき基板上に、ロールコーター、リバースコーター、バーコーター等の接触転写型塗布装置やスピナー（回転式塗布装置）、カーテンフローコーター等の非接触型塗布装置を用いて感光性樹脂組成物を塗布し、必要に応じて、乾燥により溶媒を除去して、感光性樹脂組成物層を形成する。 In the coating step of coating the photosensitive resin composition on the substrate in the photolithography method, a contact transfer type coating apparatus such as a roll coater, a reverse coater, a bar coater, or a spinner (rotation type) Coating device) The photosensitive resin composition is coated using a non-contact coating device such as a curtain flow coater, and if necessary, the solvent is removed by drying to form a photosensitive resin composition layer.
　次いで、露光工程では、ネガ型のマスクを利用して、感光性樹脂組成物に紫外線、エキシマレーザー光等の活性エネルギー線を照射し、感光性樹脂組成物層を隔壁のパターンに応じて部分的に露光する。露光には、高圧水銀灯、超高圧水銀灯、キセノンランプ、カーボンアーク灯等の紫外線を発する光源を用いることができる。露光量は感光性樹脂組成物の組成によっても異なるが、例えば１０～４００ｍＪ／ｃｍ2程度が好ましい。 Next, in the exposure step, the photosensitive resin composition is irradiated with active energy rays such as ultraviolet light and excimer laser light using a negative mask, and the photosensitive resin composition layer is partially formed according to the pattern of the partition walls. Exposure. A light source emitting ultraviolet light such as a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, and a carbon arc lamp can be used for exposure. Although the amount of exposure varies depending on the composition of the photosensitive resin composition, it is preferably, for example, about 10 to 400 mJ / cm 2 .
　次いで、現像工程では、隔壁のパターンに応じて露光された感光性樹脂組成物層を現像液で現像することにより隔壁パターンを形成する。現像方法は特に限定されず、浸漬法、スプレー法等を用いることができる。現像液の具体例としては、ジメチルベンジルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等の有機系のものや、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、アンモニア、４級アンモニウム塩等の水溶液が挙げられる。又、現像液には、消泡剤や界面活性剤を添加することもできる。 Next, in the developing step, a barrier rib pattern is formed by developing the photosensitive resin composition layer exposed according to the pattern of the barrier ribs with a developer. The development method is not particularly limited, and an immersion method, a spray method or the like can be used. Specific examples of the developer include organic solvents such as dimethylbenzylamine, monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts. It can be mentioned. Moreover, an antifoamer and surfactant can also be added to a developing solution.
　その後、現像後の隔壁パターンにポストベークを施して加熱硬化することで隔壁が得られる。ポストベークは、１５０～２５０℃で１５～６０分間が好ましい。 Thereafter, the partition wall pattern after development is subjected to post-baking and heat curing to obtain partition walls. Post-baking is preferably at 150 to 250 ° C. for 15 to 60 minutes.
　隔壁形成後に未露光部の洗浄を目的とした洗浄処理を行うこともできる。洗浄方法は、特に限定されず、プラズマ照射、エキシマ光照射、ＵＶ照射があげられる。エキシマ光照射やＵＶ照射では、光照射によって活性酸素が画素部に付着した有機物を分解して除去することができる。 After the formation of the partition walls, a cleaning process may be performed to clean the unexposed area. The cleaning method is not particularly limited, and examples include plasma irradiation, excimer light irradiation, and UV irradiation. In excimer light irradiation or UV irradiation, active oxygen can decompose and remove an organic substance attached to a pixel portion by light irradiation.
　隔壁の形成に用いる基板は特に限定されず、隔壁が形成された基板を用いて製造される有機電界発光素子の種類に合わせて適宜選択される。好適な基板の材料としては、ガラスや、各種の樹脂材料が挙げられる。樹脂材料の具体例としては、ポリエチレンテレフタレート等のポリエステル；ポリエチレン、及びポリプロピレン等のポリオレフィン；ポリカーボネート；ポリ（メタ）メタアクリル樹脂；ポリスルホン；ポリイミドが挙げられる。これらの基板の材料の中では、耐熱性に優れることからガラス、及びポリイミドが好ましい。また、製造される有機電界発光素子の種類に応じて、隔壁が形成される基板の表面には、予めＩＴＯやＺｎＯ等の透明電極層を設けておいてもよい。 The substrate used for forming the partition is not particularly limited, and is appropriately selected according to the type of the organic electroluminescent device manufactured using the substrate on which the partition is formed. Suitable 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; polycarbonate; poly (meth) methacrylic resin; polysulfone; Among the materials of these substrates, glass and polyimide are preferable because they are excellent in heat resistance. Moreover, according to the kind of organic electroluminescent element manufactured, you may provide transparent electrode layers, such as ITO and ZnO, in advance on the surface of the board | substrate in which a partition is formed.
［３］有機電界発光素子
　本発明の有機電界発光素子は、本発明の隔壁を備える。
　以上説明した方法により製造された隔壁パターンを備える基板を用いて、種々の有機電界発光素子が製造される。有機電界発光素子を形成する方法は特に限定されないが、好ましくは、上記方法により基板上に隔壁のパターンを形成した後に、基板上の隔壁によって囲まれた領域内にインクを注入して画素等の有機層を形成することによって、有機電界発光素子が製造される。
　有機電界発光素子のタイプとしては、ボトムエミッション型やトップエミッション型が挙げられる。
　ボトムエミッション型では、例えば、透明電極を積層したガラス基板上に隔壁を形成し、隔壁で囲まれた開口部に正孔輸送層、発光層、電子輸送層、金属電極層を積層して作成される。一方でトップエミッション型では、例えば、金属電極層を積層したガラス基板上に隔壁を形成し、隔壁で囲まれた開口部に電子輸送層、発光層、正孔輸送層、透明電極層を積層して作成される。
　なお、発光層としては、日本国特開２００９－１４６６９１号公報や日本国特許第５７３４６８１号公報に記載されているような有機電界発光層が挙げられる。また、日本国特許第５６５３３８７号公報や日本国特許第５６５３１０１号公報に記載されているような量子ドットを用いてもよい。 [3] Organic Electroluminescent Device The organic electroluminescent device of the present invention comprises the partition wall of the present invention.
Various organic electroluminescent devices are manufactured using the substrate provided with the barrier rib pattern manufactured by the method described above. Although the method of forming the organic electroluminescent element is not particularly limited, preferably, after forming the pattern of the partition on the substrate by the above method, the ink is injected into the region surrounded by the partition on the substrate to form a pixel or the like An organic electroluminescent device is manufactured by forming an organic layer.
As a type of the organic electroluminescent element, a bottom emission type or a top emission type can be mentioned.
In the bottom emission type, for example, partition walls are formed on a glass substrate on which transparent electrodes are stacked, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are stacked in an opening surrounded by the partition walls. Ru. On the other hand, in the top emission type, for example, partition walls are formed on a glass substrate on which metal electrode layers are stacked, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are stacked in an opening surrounded by the partition walls. Is created.
Examples of the light emitting layer include organic electroluminescent layers as described in JP-A-2009-146691 and JP-A-5734681. Alternatively, quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.
　有機層形成用のインクを形成する際に使用される溶媒としては、水、有機溶剤、及びこれらの混合溶剤を用いることができる。有機溶剤は、インクの注入後に形成された皮膜から除去可能であれば特に限定されない。有機溶剤の具体例としては、トルエン、キシレン、アニソール、メシチレン、テトラリン、シクロヘキシルベンゼン、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、メタノール、エタノール、イソプロピルアルコール、酢酸エチル、酢酸ブチル、３－フェノキシトルエン、等が挙げられる。また、インクには、界面活性剤、酸化防止剤、粘度調整剤、紫外線吸収剤等を添加することができる。 Water, an organic solvent, and these mixed solvents can be used as a solvent used when forming the ink for organic layer formation. The organic solvent is not particularly limited as long as it can be removed from the film formed after the injection of the ink. Specific examples of the organic solvent include toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate, butyl acetate, 3-phenoxytoluene, etc. Can be mentioned. Further, to the ink, a surfactant, an antioxidant, a viscosity modifier, an ultraviolet light absorber and the like can be added.
　隔壁により囲まれた領域内にインクを注入する方法としては、少量のインクを所定の箇所に容易に注入可能であることから、インクジェット法が好ましい。有機層の形成に使用されるインクは、製造される有機電界発光素子の種類に応じて適宜選択される。インクをインクジェット法により注入する場合、インクの粘度はインクをインクジェットヘッドから良好に吐出できる限り特に限定されないが、４～２０ｍＰａ・ｓが好ましく、５～１０ｍＰａ・ｓがより好ましい。インクの粘度は、インク中の固形分含有量の調整、溶媒の変更、粘度調整剤の添加等により調整することができる。 The ink jet method is preferable as a method of injecting the ink into the area surrounded by the partition wall, since a small amount of ink can be easily injected into a predetermined place. The ink used for formation of an organic layer is suitably selected according to the kind of organic electroluminescent element 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 favorably discharged from the ink jet head, but 4 to 20 mPa · s is preferable, and 5 to 10 mPa · s is more preferable. The viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity modifier, or the like.
［４］画像表示装置
　本発明の画像表示装置は、本発明の有機電界発光素子を含む。本発明の有機電界発光素子を含むものであれば、画像表示装置の型式や構造については特に制限はなく、例えばアクティブ駆動型有機電界発光素子を用いて常法に従って組み立てることができる。例えば、「有機ＥＬディスプレイ」（オーム社、平成１６年８月２０日発行、時任静士、安達千波矢、村田英幸著）に記載されているような方法で、本発明の画像表示装置を形成することができる。例えば、白色光を発光する有機電界発光素子とカラーフィルターとを組み合わせて画像表示させてもよいし、ＲＧＢ等の発光色の異なる有機電界発光素子を組み合わせて画像表示させてもよい。 [4] Image Display Device The image display device of the present invention includes the organic electroluminescent device of the present invention. The type and structure of the image display device are not particularly limited as long as they include the organic electroluminescent device of the present invention, and for example, they can be assembled according to a conventional method using an active drive type organic electroluminescent device. For example, the image display device of the present invention is formed by the method as described in "Organic EL display" (Am Co., published on August 20, 2004, Shimizu Toki, Chiya Adachi, Hideyuki Murata) can do. For example, an image may be displayed by combining an organic electroluminescent element emitting white light and a color filter, or an image may be displayed by combining organic electroluminescent elements having different luminescent colors such as RGB.
［５］照明
　本発明の照明は、本発明の有機電界発光素子を含む。型式や構造については特に制限はなく、本発明の有機電界発光素子を用いて常法に従って組み立てることができる。有機電界発光素子としては、単純マトリックス駆動方式としてもよいし、アクティブマトリックス駆動方式としてもよい。
　本発明の照明が白色光を発光するものとするために、白色光を発光する有機電界発光素子を用いてもよい。また、発光色の異なる有機電界発光素子を組み合わせて、各色が混色して白色となるよう構成してもよいし、混色比率を調整できるように構成して調色機能を付与してもよい。 [5] Illumination The illumination of the present invention includes the organic electroluminescent device of the present invention. There is no particular limitation on the type and the structure, and the organic electroluminescent device of the present invention can be assembled according to a conventional method. As an organic electroluminescent element, it is good also as a simple matrix drive system, and good also as an active matrix drive system.
In order for the illumination of the present invention to emit white light, an organic electroluminescent device that emits white light may be used. In addition, organic electroluminescent elements of different luminescent colors may be combined, and each color may be mixed to be white, or the color mixing ratio may be adjusted to provide a toning function.
　以下、本発明の感光性樹脂組成物について、具体的な実施例を挙げて説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。
　以下の実施例及び比較例で用いた感光性樹脂組成物の構成成分は次の通りである。 Hereinafter, the photosensitive resin composition of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
The components of the photosensitive resin composition used in the following examples and comparative examples are as follows.
ａ－１：以下の手順で合成して得られた、アクリル樹脂（撥液剤）
　撹拌装置、温度計、冷却管、滴下装置を備えたガラスフラスコに、溶媒としてプロピレングリコールモノメチルエーテルアセテート５５質量部を仕込み、窒素気流下にて攪拌しながら１０５℃に昇温した。次いで、以下に示す化学構造を有するポリ（パーフルオロアルキレンエーテル）鎖を含む化合物（ａａ－１）２０質量部と、３－ヒドロキシ－１－アダマンチルメタクリレート５０．１質量部をプロピレングリコールモノメチルエーテルアセテート８４．６質量部に溶解したモノマー溶液と、重合開始剤としてｔ－ブチルペルオキシ－２－エチルヘキサノエート１０．６質量部をプロピレングリコールモノメチルエーテルアセテート１０．６質量部に溶解した重合開始剤溶液との３種類の滴下液をそれぞれ別々の滴下装置にセットし、前記ガラスフラスコ内を１０５℃に保ちながら同時に２時間かけて滴下した。滴下終了後、１０５℃で５時間攪拌した後、減圧下で溶媒１０３．５質量部を留去することによって、重合体（ａａ－２）溶液を得た。 a-1: Acrylic resin (liquid repellent agent) obtained by synthesis according to the following procedure
55 parts by mass of propylene glycol monomethyl ether acetate was charged as a solvent into a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Next, 20 parts by mass of a compound (aa-1) containing a poly (perfluoroalkylene ether) chain having a chemical structure shown below, and 50.1 parts by mass of 3-hydroxy-1-adamantyl methacrylate as propylene glycol monomethyl ether acetate 84 A monomer solution dissolved in 6 parts by mass, and a polymerization initiator solution obtained by dissolving 10.6 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator in 10.6 parts by mass of propylene glycol monomethyl ether acetate The three types of drops were set in separate dropping devices, and were dropped simultaneously over 2 hours while maintaining the inside of the glass flask at 105 ° C. After completion of the dropwise addition, the mixture was stirred at 105 ° C. for 5 hours, and 103.5 parts by mass of the solvent was distilled off under reduced pressure to obtain a polymer (aa-2) solution.
Figure JPOXMLDOC01-appb-C000064
  
Figure JPOXMLDOC01-appb-C000064
  
（式（ａａ－１）中、Ｘはパーフルオロメチレン基又はパーフルオロエチレン基であり、１分子あたり、パーフルオロメチレン基が平均７個、パーフルオロエチレン基が平均８個存在するものであり、フッ素原子の数が平均４６個である。） (In the formula (aa-1), X is a perfluoromethylene group or a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, The average number of fluorine atoms is 46.)
　次いで、上記で得られた重合体（ａａ－２）溶液に、重合禁止剤としてｐ－メトキシフェノール０．１質量部、ウレタン化触媒としてオクチル酸錫０．０３質量部を仕込み、空気気流下で攪拌を開始し、６０℃を保ちながら、２－アクリロイルオキシエチルイソシアネート２９．９質量部を１時間で滴下した。滴下終了後、６０℃で２時間攪拌した後、８０℃に昇温して１０時間攪拌し、ＩＲスペクトル測定でイソシアネート基の消失を確認し、プロピレングリコールモノメチルエーテルアセテート５３．３質量部を加えて、アダマンタン骨格、ポリ（パーフルオロアルキレンエーテル）鎖を含む架橋部、及びエチレン性二重結合を有するアクリル樹脂（ａ－１）を５０質量％含有するプロピレングリコールモノメチルエーテルアセテート溶液を得た。得られたアクリル樹脂（ａ－１）の、ＧＰＣで測定したポリスチレン換算の重量平均分子量（Ｍｗ）は１００００であった。 Next, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 parts by mass of tin octylate as a urethanization catalyst are added to the solution of the polymer (aa-2) obtained above, under an air stream Stirring was started, and 29.9 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. After completion of dropwise addition, the mixture is stirred at 60 ° C. for 2 hours, heated to 80 ° C. and stirred for 10 hours, IR spectrum measurement confirms disappearance of isocyanate group, and 53.3 parts by mass of propylene glycol monomethyl ether acetate is added There was obtained a propylene glycol monomethyl ether acetate solution containing 50% by mass of an acrylic resin (a-1) having an adamantane skeleton, a crosslinked portion containing a poly (perfluoroalkylene ether) chain, and an ethylenic double bond. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC of the obtained acrylic resin (a-1) was 10000.
ａ－２：以下の手順で合成して得られた、アクリル樹脂（撥液剤）
　撹拌装置、温度計、冷却管、滴下装置を備えたガラスフラスコに、溶媒としてプロピレングリコールモノメチルエーテルアセテート３５質量部を仕込み、窒素気流下にて攪拌しながら１０５℃に昇温した。次いで、前記化合物（ａａ－１）２０質量部と、２－ヒドロキシエチルメタクリレート４６．１質量部をプロピレングリコールモノメチルエーテルアセテート８４．６質量部に溶解したモノマー溶液と、重合開始剤としてｔ－ブチルペルオキシ－２－エチルヘキサノエート１０．６質量部をプロピレングリコールモノメチルエーテルアセテート１０．６質量部に溶解した重合開始剤溶液との３種類の滴下液をそれぞれ別々の滴下装置にセットし、前記ガラスフラスコ内を１０５℃に保ちながら同時に２時間かけて滴下した。滴下終了後、１０５℃で５時間攪拌した後、減圧下で溶媒８３．５質量部を留去することによって、重合体（ａｂ－２）溶液を得た。 a-2: Acrylic resin (liquid repellent agent) obtained by synthesis according to the following procedure
35 parts by mass of propylene glycol monomethyl ether acetate was charged as a solvent into a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Then, a monomer solution in which 20 parts by mass of the compound (aa-1) and 46.1 parts by mass of 2-hydroxyethyl methacrylate are dissolved in 84.6 parts by mass of propylene glycol monomethyl ether acetate, and t-butylperoxy as a polymerization initiator Three kinds of dropping solutions with a polymerization initiator solution in which 10.6 parts by mass of -2-ethylhexanoate are dissolved in 10.6 parts by mass of propylene glycol monomethyl ether acetate are respectively set in separate dropping devices, and the glass flask It dripped over 2 hours simultaneously, maintaining the inside at 105 degreeC. After completion of the dropwise addition, the solution was stirred at 105 ° C. for 5 hours, and 83.5 parts by mass of the solvent was distilled off under reduced pressure to obtain a polymer (ab-2) solution.
　次いで、上記で得られた重合体（ａｂ－２）溶液に、重合禁止剤としてｐ－メトキシフェノール０．１質量部、ウレタン化触媒としてオクチル酸錫０．０３質量部を仕込み、空気気流下で攪拌を開始し、６０℃を保ちながら、２－アクリロイルオキシエチルイソシアネート３３．３質量部を１時間で滴下した。滴下終了後、６０℃で２時間攪拌した後、８０℃に昇温して１０時間攪拌し、ＩＲスペクトル測定でイソシアネート基の消失を確認し、プロピレングリコールモノメチルエーテルアセテート５０．０質量部を加えて、ポリ（パーフルオロアルキレンエーテル）鎖を含む架橋部及びエチレン性二重結合を有するアクリル樹脂（ａ－２）を５０質量％含有するプロピレングリコールモノメチルエーテルアセテート溶液を得た。得られたアクリル樹脂（ａ－２）の、ＧＰＣで測定したポリスチレン換算の重量平均分子量（Ｍｗ）は１２０００であった。 Next, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 parts by mass of tin octylate as a urethanization catalyst are added to the solution of the polymer (ab-2) obtained above, under an air stream Stirring was started, and 33.3 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. After completion of dropwise addition, the mixture is stirred at 60 ° C. for 2 hours, heated to 80 ° C. and stirred for 10 hours, IR spectrum measurement confirms disappearance of isocyanate group, and 50.0 parts by mass of propylene glycol monomethyl ether acetate is added There was obtained a propylene glycol monomethyl ether acetate solution containing 50% by mass of an acrylic resin (a-2) having a crosslinked portion containing a poly (perfluoroalkylene ether) chain and an ethylenic double bond. The weight-average molecular weight (Mw) in terms of polystyrene measured by GPC of the obtained acrylic resin (a-2) was 12,000.
ｂ－１：以下の手順で合成して得られた、アルカリ可溶性樹脂（エポキシ（メタ）アクリレート樹脂（ｂ１－３）に相当）
　下記式で表されるビスフェノールＡ型エポキシ化合物（エポキシ当量１８６ｇ／ｅｑ、式中のｍ及びｎが１～２０のものの混合物）１００質量部、アクリル酸４０質量部、ｐ－メトキシフェノール０．０６質量部、トリフェニルホスフィン２．４質量部、プロピレングリコールモノメチルエーテルアセテート１２６質量部を反応容器に仕込み、酸価が５ｍｇ－ＫＯＨ／ｇ以下になるまで９５℃で撹拌した。次いで、上記反応により得られた反応液８０質量部にプロピレングリコールモノメチルエーテルアセテート１２質量部を加え、無水コハク酸を添加し、９５℃で３時間反応させ、固形分酸価６０ｍｇ－ＫＯＨ／ｇ、ＧＰＣで測定したポリスチレン換算の重量平均分子量（Ｍｗ）が８０００のアルカリ可溶性樹脂（ｂ－１）溶液を得た。 b-1: Alkali-soluble resin (equivalent to epoxy (meth) acrylate resin (b1-3)) obtained by synthesis according to the following procedure
100 parts by mass of bisphenol A type epoxy compound (epoxy equivalent 186 g / eq, mixture of m and n in the formula is 1 to 20) represented by the following formula, 40 parts by mass of acrylic acid, p-methoxyphenol 0.06 parts A reaction vessel was charged with a portion, 2.4 parts by mass of triphenylphosphine and 126 parts by mass of propylene glycol monomethyl ether acetate, and the mixture was stirred at 95 ° C. until the acid value became 5 mg-KOH / g or less. Next, 12 parts by mass of propylene glycol monomethyl ether acetate is added to 80 parts by mass of the reaction liquid obtained by the above reaction, succinic anhydride is added, and reaction is carried out at 95 ° C. for 3 hours. An alkali-soluble resin (b-1) solution having a polystyrene-reduced weight average molecular weight (Mw) measured by GPC of 8,000 was obtained.
Figure JPOXMLDOC01-appb-C000065
  
Figure JPOXMLDOC01-appb-C000065
  
ｂ－２：以下のアクリル共重合樹脂（アクリル共重合樹脂（ｂ２－１）に相当）
　ジシクロペンタニルメタクリレート／スチレン／グリシジルメタクリレート（モル比０．０２／０．０５／０．９３）を構成モノマーとする共重合樹脂に、アクリル酸をグリシジルメタクリレートと等量付加反応させ、さらに無水テトラヒドロフタル酸を上記の共重合樹脂１モルに対してモル比０．１になるように付加した、アルカリ可溶性のアクリル共重合樹脂（ｂ－２）。ＧＰＣで測定したポリスチレン換算の重量平均分子量（Ｍｗ）は７７００、固形分酸価は２８．５ｍｇ－ＫＯＨ／ｇ。 b-2: The following acrylic copolymer resin (corresponding to acrylic copolymer resin (b2-1))
Acrylic acid is added in an equal amount with glycidyl methacrylate to a copolymer resin having dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio 0.02 / 0.05 / 0.93) as a constituent monomer, and further tetrahydroanhydride An alkali-soluble acrylic copolymer resin (b-2) in which phthalic acid is added to have a molar ratio of 0.1 with respect to 1 mol of the above-mentioned copolymer resin. The polystyrene equivalent weight average molecular weight (Mw) measured by GPC is 7700, and the solid content acid number is 28.5 mg-KOH / g.
ｃ－１：ジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ、日本化薬社製）
ｄ－１：２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニル－１，２’－ビイミダゾール（保土ヶ谷化学社製）
ｄ－２：イルガキュア３６９（ＢＡＳＦ社製、下記の化学構造の化合物） c-1: dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)
d-1: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Hodogaya Chemical Co., Ltd.)
d-2: Irgacure 369 (BASF, compound of the following chemical structure)
Figure JPOXMLDOC01-appb-C000066
  
Figure JPOXMLDOC01-appb-C000066
  
ｅ－１：２－メルカプトベンゾイミダゾール（東京化成社製）
ｅ－２：ペンタエリスリトールテトラキス（３－メルカプトプロピオナート）（淀化学社製）
ｆ－１：ＴＩＮＵＶＩＮ３８４－２（ＢＡＳＦ社製、紫外線吸収剤）
ｇ－１：ＫＡＹＡＭＥＲ　ＰＭ－２１（日本化薬社製）
ｈ－１：メチルヒドロキノン（精工化学社製、下記の化学構造の化合物） e-1: 2-mercaptobenzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
e-2: pentaerythritol tetrakis (3-mercapto propionate) (manufactured by Sakai Chemical Co., Ltd.)
f-1: TINUVIN 384-2 (manufactured by BASF, UV absorber)
g-1: KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.)
h-1: methyl hydroquinone (made by SEIKO CHEMICAL CO., LTD., a compound having the following chemical structure)
Figure JPOXMLDOC01-appb-C000067
  
Figure JPOXMLDOC01-appb-C000067
  
［１］　感光性樹脂組成物の作製及び評価
　各成分を表１に記載の配合割合で用い、かつ、全固形分の含有割合が１９質量％となるようにプロピレングリコールモノメチルエーテルアセテートを用いて、各成分を均一になるまで撹拌して実施例１～５及び比較例１～２の感光性樹脂組成物を調製した。なお、表１中の各成分の配合割合（質量％）は、全固形分中における各成分の固形分の値を意味する。 [1] Preparation and Evaluation of Photosensitive Resin Composition Using each component at the blend ratio described in Table 1, and using propylene glycol monomethyl ether acetate so that the content ratio of the total solid content is 19% by mass, The components were stirred until uniform to prepare photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 2. In addition, the compounding ratio (mass%) of each component in Table 1 means the value of the solid content of each component in all the solid content.
Figure JPOXMLDOC01-appb-T000068
  
Figure JPOXMLDOC01-appb-T000068
  
　実施例１～５及び比較例１～２の感光性樹脂組成物の物性評価を以下に記載の方法で行った。
（接触角の測定）
　ガラス基板上にスピナーを用いて、加熱硬化後に１．７μｍの厚みになるように各感光性樹脂組成物を塗布した。その後、９５℃で２分間、ホットプレート上で加熱乾燥し、得られた塗膜を、マスクを使用せずに、大日本科研社製露光機ＭＡ－１１００を用いて、露光量１２０ｍＪ／ｃｍ2で全面露光した。この時の波長３６５ｎｍにおける強度は４０ｍＷ／ｃｍ2であった。次いで、２４℃の２．３８質量％ＴＭＡＨ（水酸化テトラメチルアンモニウム）水溶液で６０秒間スプレー現像した後、純水で１０秒間洗浄した。この基板を、オーブン中２３０℃で３０分間加熱硬化させ、硬化物付きの接触角測定用基板を得た。 Physical properties of the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were evaluated by the methods described below.
(Measurement of contact angle)
Each photosensitive resin composition was apply | coated so that it might become 1.7 micrometers in thickness after heat-hardening using a spinner on a glass substrate. Thereafter, the film is dried by heating on a hot plate at 95 ° C. for 2 minutes, and the obtained coating film is exposed using an exposure apparatus MA-1100 manufactured by Dainippon Kagaku Co., Ltd., at a dose of 120 mJ / cm 2. Exposed the entire surface. At this time, the intensity at a wavelength of 365 nm was 40 mW / cm 2 . Next, after spray development with a 2.38 mass% aqueous solution of TMAH (tetramethylammonium hydroxide) at 24 ° C. for 60 seconds, the resultant was washed with pure water for 10 seconds. The substrate was heat cured in an oven at 230 ° C. for 30 minutes to obtain a substrate for contact angle measurement with a cured product.
　接触角の測定は協和界面科学社製Ｄｒｏｐ　Ｍａｓｔｅｒ　５００接触角測定装置を用いて、２３℃湿度５０％の条件下で行った。接触角測定用基板の硬化物上にプロピレングリコールメチルエーテルアセテートを０．７μＬ滴下し、１秒後の接触角を測定した。測定結果を表１に示す。接触角が大きい方が、撥インク性が高いことを表す。 The contact angle was measured at 23 ° C. and 50% humidity using a Drop Master 500 contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. 0.7 μL of propylene glycol methyl ether acetate was dropped onto the cured product of the contact angle measurement substrate, and the contact angle after 1 second was measured. The measurement results are shown in Table 1. The larger the contact angle, the higher the ink repellency.
（ＵＶ耐性評価（接触角））
　前記接触角測定用基板に対して、オーク社製ドライプロセッサーＶＵＭ-３０７３を用いて、紫外線（ＵＶ）を３分間照射した。この時の波長２５４ｎｍにおける強度は９ｍＷ／ｃｍ2であった。
　ＵＶ照射後の基板に対して、前述の方法で接触角の測定を行った。この結果に関し、以下の２種類の観点で評価を行った。測定結果と評価結果を表１に示す。 (UV resistance evaluation (contact angle))
The substrate for contact angle measurement was irradiated with ultraviolet light (UV) for 3 minutes using a dry processor VUM-3073 manufactured by Oak Corporation. At this time, the intensity at a wavelength of 254 nm was 9 mW / cm 2 .
The contact angle of the substrate after UV irradiation was measured by the method described above. The results were evaluated from the following two types of viewpoints. The measurement results and the evaluation results are shown in Table 1.
［接触角評価－１］
　ＵＶ照射後の接触角につき、以下の基準にて評価した。
Ａ：ＵＶ照射後の接触角が３０°以上を示す。
Ｂ：ＵＶ照射後の接触角が１５°以上３０°未満を示す。
Ｃ：ＵＶ照射後の接触角が１５°未満を示す。
　Ａが好ましい性能である。 [Contact angle evaluation-1]
The contact angle after UV irradiation was evaluated according to the following criteria.
A: The contact angle after UV irradiation shows 30 degrees or more.
B: The contact angle after UV irradiation shows 15 degrees or more and less than 30 degrees.
C: The contact angle after UV irradiation shows less than 15 °.
A is the preferred performance.
［接触角評価－２］
　接触角の低下率を下記式により導出し、以下の基準にて評価した。ただし、ＵＶ照射前の時点で接触角が３０°未満のものは、接触角の低下率を算出せずＮＡ（Ｎｏｔ　Ａｖａｉｌａｂｌｅ）とした。
　　接触角の低下率（％）＝１００－｛（ＵＶ照射後の接触角）／（ＵＶ照射前の接触角）｝×１００
Ａ：ＵＶ照射前の接触角が３０°以上を示し、ＵＶ照射後の接触角の低下率が２０％未満を示した。
Ｂ：ＵＶ照射前の接触角が３０°以上を示し、ＵＶ照射後の接触角の低下率が２０％以上３０％未満を示した。
Ｃ：ＵＶ照射前の接触角が３０°以上を示し、ＵＶ照射後の接触角の低下率が３０％以上を示した。
Ｄ：ＵＶ照射前の接触角が３０°以上を示さなかった。
　Ａが好ましい性能である。 [Contact angle evaluation-2]
The reduction rate of the contact angle was derived by the following equation, and evaluated according to the following criteria. However, when the contact angle was less than 30 ° before UV irradiation, the decrease rate of the contact angle was not calculated and it was regarded as NA (Not Available).
Reduction rate of contact angle (%) = 100 − {(contact angle after UV irradiation) / (contact angle before UV irradiation)} × 100
A: The contact angle before UV irradiation showed 30 degrees or more, and the decreasing rate of the contact angle after UV irradiation showed less than 20%.
B: The contact angle before UV irradiation showed 30 degrees or more, and the decreasing rate of the contact angle after UV irradiation showed 20% or more and less than 30%.
C: The contact angle before UV irradiation showed 30 degrees or more, and the decreasing rate of the contact angle after UV irradiation showed 30% or more.
D: The contact angle before UV irradiation did not show more than 30 °.
A is the preferred performance.
［２］　隔壁の形成及び評価
　実施例１～５の感光性樹脂組成物を用いて、以下に記載した方法で隔壁の形成と性能評価を行った。
（隔壁の形成）
　表面にＩＴＯ膜を形成したガラス基板の該ＩＴＯ膜上にスピナーを用いて、加熱硬化後に１．７μｍの厚みになるように各感光性樹脂組成物を塗布した。その後、９５℃で２分間、ホットプレート上で加熱乾燥して、得られた塗膜に、フォトマスク（８０μｍ×２８０μｍの被覆部を４０μｍ間隔で複数有するマスク）を用い、露光ギャップ１６μｍで、大日本科研社製露光機ＭＡ－１１００を用いて露光した。この時の波長３６５ｎｍにおける強度は４０ｍＷ／ｃｍ2、露光量は１２０ｍＪ／ｃｍ2、空気下で行った。次いで、２４℃の２．３８質量％ＴＭＡＨ（水酸化テトラメチルアンモニウム）水溶液で６０秒間スプレー現像した後、純水で１分間洗浄した。これらの操作により、不要な部分が除去されてパターンが形成された基板を、オーブン中２３０℃で３０分間加熱硬化させ、格子状の隔壁を有する基板を得た。 [2] Formation and Evaluation of Partition Wall The formation of the partition wall and the performance evaluation were performed by the methods described below using the photosensitive resin compositions of Examples 1 to 5.
(Formation of partition wall)
Each photosensitive resin composition was apply | coated so that it might become 1.7 micrometers in thickness after heat-hardening using spinner on this ITO film | membrane of the glass substrate in which the ITO film | membrane was formed in the surface. After that, heat-dry on a hot plate at 95 ° C. for 2 minutes, and use a photomask (a mask having a plurality of 80 μm × 280 μm coated portions at intervals of 40 μm) for the obtained coating film. Exposure was performed using an exposure apparatus MA-1100 manufactured by Nippon Kaken Co., Ltd. At this time, the intensity at a wavelength of 365 nm was 40 mW / cm 2 and the exposure dose was 120 mJ / cm 2 under air. Next, after spray development with a 2.38 mass% aqueous solution of TMAH (tetramethylammonium hydroxide) at 24 ° C. for 60 seconds, the resultant was washed with pure water for 1 minute. By these operations, unnecessary portions were removed, and the patterned substrate was heat-cured in an oven at 230 ° C. for 30 minutes to obtain a substrate having grid-like partition walls.
（ＵＶ耐性評価（隔壁のインクジェット塗布適性））
　前記格子状の隔壁を有する基板に対して、オーク社製ドライプロセッサーＶＵＭ-３０７３を用いて、紫外線（ＵＶ）を３分間照射した。この時の波長２５４ｎｍにおける強度は９ｍＷ／ｃｍ2であった。
　ＵＶ照射後の基板の格子状の隔壁で囲われた画素領域に対して、富士フィルム社製ＤＭＰ－２８３１を用いてインクジェット塗布を行った。インクとして、溶剤（安息香酸イソアミル）を単独で使用し、１画素あたり４８０ｐＬの塗布を行い、決壊（インクが隔壁を乗り越えて隣の画素部に混入する現象）の有無の評価を以下の基準にて行った。隔壁の撥インク性が高いほど、決壊が抑制される傾向がある。なお、実施例１～５の全てにおいて、インクジェット塗布後の隔壁内の濡れ広がり性は良好であり、かつ、以下に示す決壊評価（インクジェット塗布適性）はＡであった。 (UV resistance evaluation (inkjet coating suitability for partition walls))
The substrate having the grid-like partition walls was irradiated with ultraviolet light (UV) for 3 minutes using an Orc dry processor VUM-3073. At this time, the intensity at a wavelength of 254 nm was 9 mW / cm 2 .
Inkjet coating was performed using DMP-2831 manufactured by Fuji Film Co., Ltd. on the pixel region surrounded by the grid-like partition walls of the substrate after UV irradiation. A solvent (isoamyl benzoate) is used alone as an ink, 480 pL is applied per pixel, and evaluation is based on the evaluation of the presence or absence of breakage (the phenomenon that the ink gets over the partition wall and mixes in the next pixel part) I went. As the ink repellency of the partition wall is higher, breakage tends to be suppressed. In all of Examples 1 to 5, the wettability and spreadability in the partition wall after ink jet coating was good, and the evaluation for breakage shown below (ink jet coating aptitude) was A.
［決壊評価（インクジェット塗布適性）］
Ａ：インクを画素内に塗布することができ、隔壁外へのあふれ出しがなかった。
Ｂ：インクが画素内から隔壁の上面の全面にあふれ出し、隣の画素領域に混入してしまった（決壊）。
　Ａが好ましい性能である。 [Destructive evaluation (inkjet coating suitability)]
A: The ink could be applied in the pixel and there was no overflow out of the partition.
B: Ink overflowed from the inside of the pixel to the entire top surface of the partition wall, and was mixed into the adjacent pixel area (broken).
A is the preferred performance.
　実施例１～５の感光性樹脂組成物を用いた塗布基板は、ＵＶ照射後の接触角が高く、ＵＶ照射後のインクジェット塗布適性が良好であることが確認された。連鎖移動剤を含むことで、酸素阻害による膜表面の硬化性の低下が抑制でき、現像工程における撥液剤の溶出が抑制されて膜表面に十分な量の撥液剤を固定することができ、接触角が良好になったと考えられる。そして、撥液剤として、ＵＶ照射に対して分解しづらい剛直な多環式飽和炭化水素骨格を有するものを使用しているため、ＵＶ照射によっても撥液剤の分解反応が抑制されて、ＵＶ照射後の膜表面においてフッ素原子の存在量を十分に確保できたものと考えられる。 It was confirmed that the coated substrates using the photosensitive resin compositions of Examples 1 to 5 have a high contact angle after UV irradiation, and good inkjet coating suitability after UV irradiation. By including the chain transfer agent, it is possible to suppress the decrease in the curability of the film surface due to oxygen inhibition, and it is possible to suppress the elution of the liquid repellent agent in the development step and fix a sufficient amount of the liquid repellent agent on the film surface. It is thought that the corner has become better. And, as the lyophobic agent, one having a rigid, multi-ring saturated hydrocarbon backbone that is hard to decompose against UV irradiation is used, so the decomposition reaction of the lyophobic agent is suppressed even by UV irradiation, and after UV irradiation It is considered that the sufficient amount of fluorine atoms could be secured on the surface of the film.
　これに対して比較例１の感光性樹脂組成物を用いた塗布基板は、ＵＶ照射前から十分な撥インク性を示さなかった。これは、連鎖移動剤を含まないことによって表面硬化性が低く、現像時に撥液剤が流出したためと考えられる。 On the other hand, 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 due to low surface curability due to the absence of a chain transfer agent and the outflow of the liquid repellent agent during development.
　また、比較例２の感光性樹脂組成物を用いた塗布基板は、ＵＶ照射後の接触角が低い結果となった。これは、使用した撥液剤（ａ－２）が多環式飽和炭化水素骨格を有さないものであるため、ＵＶ照射による撥液剤の分解によって膜表面におけるフッ素原子の存在量が少なくなり、撥インク性を十分に示さなくなったからであると考えられる。 Moreover, the coated substrate using the photosensitive resin composition of Comparative Example 2 resulted in a low contact angle after UV irradiation. This is because the lyophobic agent (a-2) used does not have a polycyclic saturated hydrocarbon skeleton, so the decomposition amount of the lyophobic agent by UV irradiation reduces the amount of fluorine atoms on the film surface, and the It is considered that this is because the ink property is not sufficiently shown.
［３］　感光性樹脂組成物の作成及び評価、並びに隔壁の作成及び評価
　全固形分中における各成分の固形分の値が以下の配合割合（質量部）になるようにし、かつ、全固形分の含有割合が１９質量％となるように、プロピレングリコールモノメチルエーテルアセテートを用いて、各成分を均一になるまで撹拌して実施例６の感光性樹脂組成物を調製した。
　アクリル樹脂（ａ－１）　　　　　０．５質量部
　アルカリ可溶性樹脂（ｂ－１）　４７．０質量部
　光重合性化合物（ｃ－１）　　　４７．０質量部
　光重合開始剤（ｄ－１）　　　　　２．０質量部
　連鎖鎖移動剤（ｅ－１）　　　　　１．０質量部
　紫外線吸収剤（ｆ－１）　　　　　２．０質量部
　添加剤（ｇ－１）　　　　　　　　０．５質量部
　重合禁止剤（ｈ－１）　　　　　０．０４質量部 [3] Preparation and Evaluation of Photosensitive Resin Composition, and Preparation and Evaluation of Partition Walls The value of the solid content of each component in the total solid content is such that the following blending ratio (parts by mass), and the total solid content The photosensitive resin composition of Example 6 was prepared by stirring each component with propylene glycol monomethyl ether acetate until the content ratio of 19% by mass was obtained.
Acrylic resin (a-1) 0.5 parts by mass Alkali-soluble resin (b-1) 47.0 parts by mass Photopolymerizable compound (c-1) 47.0 parts by mass Photopolymerization initiator (d-1) 2. 0 parts by mass Chain transfer agent (e-1) 1.0 parts by mass Ultraviolet absorber (f-1) 2.0 parts by mass Additives (g-1) 0.5 parts by mass Polymerization inhibitor (h-1) 0.04 parts by mass
（接触角の測定）
　ガラス基板上にスピナーを用いて、加熱硬化後に１．７μｍの厚みになるように実施例６の感光性樹脂組成物を塗布した。その後、９５℃で２分間、ホットプレート上で加熱乾燥し、得られた塗膜を、マスクを使用せずに、大日本科研社製露光機ＭＡ－１１００を用いて、露光量２００ｍＪ／ｃｍ2で全面露光した。この時の波長３６５ｎｍにおける強度は４０ｍＷ／ｃｍ2であった。次いで、２４℃の２．３８質量％ＴＭＡＨ（水酸化テトラメチルアンモニウム）水溶液で６０秒間スプレー現像した後、純水で１０秒間洗浄した。この基板を、オーブン中２３０℃で３０分間加熱硬化させ、硬化物付きの接触角測定用基板が得られた。
　前述と同様の方法で、接触角測定およびＵＶ耐性評価（隔壁のインクジェット塗布適性）を行い、以下の結果が得られた。
　接触角（°／ＵＶ照射前）　　：４２°
　接触角（°／ＵＶ照射後）　　：３６°
　接触角評価－１　　　　　　　：Ａ
　ＵＶ照射による接触角の低下率：１４％
　接触角評価－２　　　　　　　：Ａ (Measurement of contact angle)
The photosensitive resin composition of Example 6 was applied on a glass substrate using a spinner so as to have a thickness of 1.7 μm after heat curing. Then, 2 minutes at 95 ° C., then heated and dried on a hot plate, the resulting coating film, without a mask, using a Dainippon Research Institute Co. exposing machine MA-1100, an exposure amount 200 mJ / cm 2 Exposed the entire surface. At this time, the intensity at a wavelength of 365 nm was 40 mW / cm 2 . Next, after spray development with a 2.38 mass% aqueous solution of TMAH (tetramethylammonium hydroxide) at 24 ° C. for 60 seconds, the resultant was washed with pure water for 10 seconds. The substrate was heat cured in an oven at 230 ° C. for 30 minutes to obtain a substrate for contact angle measurement with a cured product.
In the same manner as described above, contact angle measurement and UV resistance evaluation (inkjet coatability of partition wall) were performed, and the following results were obtained.
Contact angle (° / before UV irradiation): 42 °
Contact angle (° / UV irradiation): 36 °
Contact angle evaluation-1: A
14% reduction in contact angle due to UV irradiation
Contact angle evaluation-2: A
（隔壁の形成）
　表面にＩＴＯ膜を形成したガラス基板の該ＩＴＯ膜上にスピナーを用いて、加熱硬化後に１．７μｍの厚みになるように実施例６の感光性樹脂組成物を塗布した。その後、９５℃で２分間、ホットプレート上で加熱乾燥して、得られた塗膜に、フォトマスク（８０μｍ×２８０μｍの被覆部を４０μｍ間隔で複数有するマスク）を用い、露光ギャップ１６μｍで、大日本科研社製露光機ＭＡ－１１００を用いて露光した。この時の波長３６５ｎｍにおける強度は４０ｍＷ／ｃｍ2、露光量は２００ｍＪ／ｃｍ2、空気下で行った。次いで、２４℃の２．３８質量％ＴＭＡＨ（水酸化テトラメチルアンモニウム）水溶液で６０秒間スプレー現像した後、純水で１分間洗浄した。これらの操作により、不要な部分が除去されてパターンが形成された基板を、オーブン中２３０℃で３０分間加熱硬化させ、格子状の隔壁を有する基板を得た。
　前述と同様の方法で、ＵＶ耐性評価（隔壁のインクジェット塗布適性）を行い、以下の結果が得られた。
　インクジェット塗布適性（ＵＶ照射後）　：Ａ (Formation of partition wall)
A photosensitive resin composition of Example 6 was applied on the ITO film of the glass substrate having an ITO film formed on the surface using a spinner so as to have a thickness of 1.7 μm after heat curing. After that, heat-dry on a hot plate at 95 ° C. for 2 minutes, and use a photomask (a mask having a plurality of 80 μm × 280 μm coated portions at intervals of 40 μm) for the obtained coating film. Exposure was performed using an exposure apparatus MA-1100 manufactured by Nippon Kaken Co., Ltd. At this time, the intensity at a wavelength of 365 nm was 40 mW / cm 2 and the exposure dose was 200 mJ / cm 2 under air. Next, after spray development with a 2.38 mass% aqueous solution of TMAH (tetramethylammonium hydroxide) at 24 ° C. for 60 seconds, the resultant was washed with pure water for 1 minute. By these operations, unnecessary portions were removed, and the patterned substrate was heat-cured in an oven at 230 ° C. for 30 minutes to obtain a substrate having grid-like partition walls.
In the same manner as described above, UV resistance evaluation (inkjet coating suitability for partition walls) was performed, and the following results were obtained.
Ink jet coating suitability (after UV irradiation): A

Claims (16)

  1. 　（Ａ）撥液剤、（Ｂ）アルカリ可溶性樹脂、（Ｃ）光重合性化合物、及び（Ｄ）光重合開始剤を含有する感光性樹脂組成物であって、
    　前記（Ａ）撥液剤が、多環式飽和炭化水素骨格及びエチレン性二重結合を有するアクリル樹脂（ａ）を含み、
    　さらに（Ｅ）連鎖移動剤を含むことを特徴とする感光性樹脂組成物。     A photosensitive resin composition comprising (A) a liquid repellent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator,
    The (A) liquid repellent agent includes an acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond,
    A photosensitive resin composition characterized by further comprising (E) a chain transfer agent.
  2. 　前記多環式飽和炭化水素骨格及びエチレン性二重結合を有するアクリル樹脂（ａ）が、ポリ（パーフルオロアルキレンエーテル）鎖を含む架橋部を有する、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond has a crosslinked portion containing a poly (perfluoroalkylene ether) chain.
  3. 　前記多環式飽和炭化水素骨格及びエチレン性二重結合を有するアクリル樹脂（ａ）が、下記一般式（１）で表される部分構造を含む、請求項２に記載の感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
      
    （式（１）中、Ｒ1は各々独立に、水素原子又はメチル基を表す。Ｘ1はパーフルオロアルキレン基を表す。式（１）中に含まれる複数のＸ1は同一のものでも異なるものでもよく、異なるものの場合にはランダム状に存在してもブロック状に存在していてもよい。Ｘ2は各々独立に、直接結合又は任意の２価の連結基を表す。ｎは１以上の整数である。＊は結合手を表す。）     The photosensitive resin composition according to claim 2, wherein the acrylic resin (a) having a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond contains a partial structure represented by the following general formula (1).
    Figure JPOXMLDOC01-appb-C000001
    (In formula (1), R 1 each independently represents a hydrogen atom or a methyl group. X 1 represents a perfluoroalkylene group. Plural X 1 contained in formula (1) may be the same or different. In the case of different ones, they may be present in a random form or in a block form, and each X 2 independently represents a direct bond or any divalent linking group, and n is one or more. Is an integer of *. * Represents a bond.)
  4. 　前記多環式飽和炭化水素骨格が、アダマンタン骨格である、請求項１～３のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 3, wherein the polycyclic saturated hydrocarbon skeleton is an adamantane skeleton.
  5. 　前記多環式飽和炭化水素骨格及びエチレン性二重結合を有するアクリル樹脂（ａ）が、下記一般式（２）で表される部分構造を含む、請求項１～４のいずれか１項に記載の感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000002
      
    （式（２）中、Ｒ2及びＲ3は各々独立に、水素原子又はメチル基を表す。Ｘ3は置換基を有していてもよい２価の多環式飽和炭化水素基を表す。Ｘ4はウレタン結合又はエステル結合を表す。Ｘ5は置換基を有していてもよい２価の炭化水素基を表す。＊は結合手を表す。）     The acrylic resin (a) having a polycyclic saturated hydrocarbon backbone and an ethylenic double bond according to any one of claims 1 to 4, which contains a partial structure represented by the following general formula (2). Photosensitive resin composition.
    Figure JPOXMLDOC01-appb-C000002
    (In the formula (2), each independently R 2 and R 3, .X 3 represents a hydrogen atom or a methyl group represents a polycyclic saturated hydrocarbon group which may have a substituent. X 4 represents a urethane bond or an ester bond, X 5 represents a divalent hydrocarbon group which may have a substituent, and * represents a bond.
  6. 　前記（Ｂ）アルカリ可溶性樹脂が、エポキシ（メタ）アクリレート樹脂（ｂ１）及び／又はアクリル共重合樹脂（ｂ２）を含む、請求項１～５のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 5, wherein the (B) alkali-soluble resin contains an epoxy (meth) acrylate resin (b1) and / or an acrylic copolymer resin (b2).
  7. 　前記エポキシ（メタ）アクリレート樹脂（ｂ１）が、下記一般式（ｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂（ｂ１－１）、下記一般式（ｉｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂（ｂ１－２）、及び下記一般式（ｉｉｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂（ｂ１－３）からなる群から選ばれる少なくとも１種である、請求項６に記載の感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000003
      
    （式（ｉ）中、Ｒaは水素原子又はメチル基を表し、Ｒbは置換基を有していてもよい２価の炭化水素基を表す。式（ｉ）中のベンゼン環は、更に任意の置換基により置換されていてもよい。＊は結合手を表す。）
    Figure JPOXMLDOC01-appb-C000004
      
    （式（ｉｉ）中、Ｒcは各々独立に、水素原子又はメチル基を表す。Ｒdは、環状炭化水素基を側鎖として有する２価の炭化水素基を表す。＊は結合手を表す。）
    Figure JPOXMLDOC01-appb-C000005
      
    （式（ｉｉｉ）中、Ｒeは水素原子又はメチル基を表し、γは単結合、－ＣＯ－、置換基を有していてもよいアルキレン基、又は置換基を有していてもよい２価の環状炭化水素基を表す。式（ｉｉｉ）中のベンゼン環は、更に任意の置換基により置換されていてもよい。＊は結合手を表す。）     Epoxy (meth) acrylate resin (b1-1) containing the partial structure represented by the following general formula (i), the partial structure represented by the following general formula (ii) And at least one selected from the group consisting of an epoxy (meth) acrylate resin (b1-2) containing the following, and an epoxy (meth) acrylate resin (b1-3) containing the partial structure represented by the following general formula (iii) The photosensitive resin composition according to claim 6.
    Figure JPOXMLDOC01-appb-C000003
    (In formula (i), R a represents a hydrogen atom or a methyl group, R b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) It may be substituted by any substituent, * represents a bond.)
    Figure JPOXMLDOC01-appb-C000004
    (In formula (ii), each R c independently represents a hydrogen atom or a methyl group. R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. .)
    Figure JPOXMLDOC01-appb-C000005
    (In formula (iii), R e represents a hydrogen atom or a methyl group, and γ is a single bond, —CO—, an alkylene group which may have a substituent, or 2 which may have a substituent And the benzene ring in the formula (iii) may be further substituted by any substituent. * Represents a bond.)
  8. 　前記アクリル共重合樹脂（ｂ２）が、下記一般式（Ｉ）で表される部分構造を含むアクリル共重合樹脂（ｂ２－１）である、請求項６又は７に記載の感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000006
      
    （式（Ｉ）中、ＲA及びＲBは各々独立に、水素原子又はメチル基を表す。＊は結合手を表す。）     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 JPOXMLDOC01-appb-C000006
    (In formula (I), R A and R B each independently represent a hydrogen atom or a methyl group. * Represents a bond.)
  9. 　前記（Ｄ）光重合開始剤が、ヘキサアリールビイミダゾール系光重合開始剤、オキシムエステル系光重合開始剤及びアセトフェノン系光重合開始剤からなる群から選ばれる少なくとも１種を含有する、請求項１～８のいずれか１項に記載の感光性樹脂組成物。 The photopolymerization initiator (D) contains at least one selected from the group consisting of a hexaarylbiimidazole photopolymerization initiator, an oxime ester photopolymerization initiator, and an acetophenone photopolymerization initiator. 8. The photosensitive resin composition according to any one of to 8.
  10. 　さらに紫外線吸収剤を含有する、請求項１～９のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 9, further comprising an ultraviolet absorber.
  11. 　さらに重合禁止剤を含有する、請求項１～１０のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 10, further comprising a polymerization inhibitor.
  12. 　隔壁形成用である請求項１～１１のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 11, which is for forming a partition wall.
  13. 　請求項１～１２のいずれか１項に記載の感光性樹脂組成物で構成される隔壁。 A partition comprising the photosensitive resin composition according to any one of claims 1 to 12.
  14. 　請求項１３に記載の隔壁を備える有機電界発光素子。 The organic electroluminescent element provided with the partition of Claim 13.
  15. 　請求項１４に記載の有機電界発光素子を含む画像表示装置。 An image display comprising the organic electroluminescent device according to claim 14.
  16. 　請求項１４に記載の有機電界発光素子を含む照明。 An illumination comprising the organic electroluminescent device according to claim 14.
PCT/JP2019/002225 2018-01-26 2019-01-24 Photosensitive resin composition, partition wall, organic electroluminescent element, image display device and lighting WO2019146680A1 (en)

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