WO2018101314A1 - 着色感光性樹脂組成物、顔料分散液、隔壁、有機電界発光素子、画像表示装置及び照明 - Google Patents

着色感光性樹脂組成物、顔料分散液、隔壁、有機電界発光素子、画像表示装置及び照明 Download PDF

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WO2018101314A1
WO2018101314A1 PCT/JP2017/042773 JP2017042773W WO2018101314A1 WO 2018101314 A1 WO2018101314 A1 WO 2018101314A1 JP 2017042773 W JP2017042773 W JP 2017042773W WO 2018101314 A1 WO2018101314 A1 WO 2018101314A1
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group
mass
less
resin composition
colored photosensitive
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PCT/JP2017/042773
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English (en)
French (fr)
Japanese (ja)
Inventor
由香子 小野
良尚 沢井
敦哉 伊藤
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三菱ケミカル株式会社
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=62242563&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2018101314(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to KR1020247039138A priority Critical patent/KR20240172762A/ko
Priority to KR1020237014487A priority patent/KR102739353B1/ko
Priority to KR1020197012591A priority patent/KR20190088972A/ko
Priority to KR1020207006805A priority patent/KR102131590B1/ko
Priority to CN201780070424.7A priority patent/CN109952535A/zh
Priority to JP2018553266A priority patent/JP6451918B2/ja
Priority to CN202410172111.4A priority patent/CN118151488A/zh
Publication of WO2018101314A1 publication Critical patent/WO2018101314A1/ja

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    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F220/32—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
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1063—Esters of polycondensation macromers of alcohol terminated polyethers
    • 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
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C09B67/0063—Preparation of organic pigments of organic pigments with only macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/008—Preparations of disperse dyes or solvent dyes
    • C09B67/0082—Preparations of disperse dyes or solvent dyes in liquid form
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G03F7/032—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
    • G03F7/09—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

Definitions

  • the present invention relates to a colored photosensitive resin composition, and also includes a pigment dispersion used in the colored photosensitive resin composition, a partition composed of the colored photosensitive resin composition, an organic electroluminescent device including the partition, an image
  • the present invention relates to a display device and illumination.
  • Liquid crystal display utilizes the property that the arrangement of liquid crystal molecules is switched by turning on and off the voltage applied to the liquid crystal.
  • each member constituting the LCD cell is often formed by a method using a photosensitive composition typified by photolithography.
  • This photosensitive composition tends to form a fine structure and can be easily applied to a substrate for a large screen, so that the application range of the photosensitive composition tends to further expand in the future.
  • Patent Document 1 describes a photosensitive coloring composition having excellent dispersibility and light shielding properties by combining a specific organic black pigment and a dispersant, and having a low relative dielectric constant.
  • an image display device including an organic electroluminescent element (also referred to as organic electroluminescence or organic EL) is excellent in visibility and responsiveness such as contrast and viewing angle, and has low power consumption, thin and light weight, and Since the display body can be made flexible, it is attracting attention as a next-generation flat panel display (FPD).
  • An organic electroluminescent element has a structure in which an organic layer including a light emitting layer or various functional layers is sandwiched between a pair of electrodes, at least one of which has translucency.
  • the image display device displays an image by driving a panel in which an organic electroluminescent element is arranged for each pixel.
  • such an organic electroluminescent element has been manufactured by forming a partition (bank) on a substrate and then laminating a light emitting layer or various functional layers in a region surrounded by the partition.
  • a vapor deposition method in which a material is sublimated in a vacuum state and deposited on a substrate is mainly applied.
  • a method of forming a film by a wet process such as a casting method, a spin coating method, or an ink jet printing method has attracted attention.
  • the ink-jet printing method can reduce film thickness unevenness when the area is large, and can increase the definition of the display, reduce the amount of material used, and improve the yield by separately coating during application. Therefore, it is suitable as a method for forming an organic layer in a large panel.
  • Patent Document 1 As a result of investigations by the present inventors, it has been found that the photosensitive coloring composition described in Patent Document 1 has a large amount of outgas and has practical problems. In addition, Patent Document 1 has no description or suggestion about application of organic electroluminescent elements to barrier ribs, and the present inventors have examined a use for barrier rib formation of organic electroluminescent elements and are required to have a general resolution model. However, it was found that the fine pattern adhesion required for a high-resolution model was not sufficient.
  • the 2nd subject of this invention is providing the colored photosensitive resin composition for forming the partition of an organic electroluminescent element which has few outgas amounts after hardened
  • Another object of the present invention is to provide a partition formed using the colored photosensitive resin composition, an organic electroluminescence device including the partition, an image display device including the organic electroluminescence device, and illumination.
  • a third problem of the present invention is to provide a pigment dispersion for constituting a photosensitive resin composition that solves the first problem.
  • the gist of the present invention is as follows.
  • a colored photosensitive resin composition comprising (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, and (E) a photopolymerization initiator,
  • the (A) colorant is at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound (A1) containing an organic black pigment containing
  • the (B) dispersant includes an acrylic dispersant,
  • R a1 and R a6 each independently represents a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
  • the (C1) epoxy (meth) acrylate resin has an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and a partial structure represented by the following general formula (III):
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 represents a divalent hydrocarbon group which may have a substituent
  • the benzene ring in formula (II) may be further substituted with an optional substituent
  • each R 13 independently represents a hydrogen atom or a methyl group
  • R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
  • R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent
  • m and n each independently represents an integer of 0 to 2
  • a colored photosensitive resin composition comprising: The (A) colorant is at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound (A1) containing an organic black pigment containing The colored photosensitive resin composition, wherein the (C) binder resin contains 75% by mass or more of (C1) epoxy (meth) acrylate resin.
  • R a1 and R a6 each independently represents a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
  • the (C1) epoxy (meth) acrylate resin has an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and a partial structure represented by the following general formula (III):
  • the colored photosensitive resin composition according to [9] or [10] which includes one or both of epoxy (meth) acrylate resins having.
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 represents a divalent hydrocarbon group which may have a substituent
  • the benzene ring in formula (II) may be further substituted with an optional substituent
  • each R 13 independently represents a hydrogen atom or a methyl group
  • R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
  • R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent
  • m and n each independently represents an integer of 0 to 2
  • An organic electroluminescence device comprising the partition wall according to [15].
  • An image display device comprising the organic electroluminescent element as described in [16].
  • a pigment dispersion containing (A) a colorant, (B) a dispersant, and (C) a binder resin is at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound (A1) containing an organic black pigment containing
  • the (B) dispersant includes an acrylic dispersant
  • the pigment dispersion, wherein the (C) binder resin contains (C1) an epoxy (meth) acrylate resin.
  • R a1 and R a6 each independently represents a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
  • the (C1) epoxy (meth) acrylate resin has an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and a partial structure represented by the following general formula (III):
  • the pigment dispersion liquid according to [19] or [20] which includes one or both of epoxy (meth) acrylate resins having.
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 represents a divalent hydrocarbon group which may have a substituent
  • the benzene ring in formula (II) may be further substituted with an optional substituent
  • each R 13 independently represents a hydrogen atom or a methyl group
  • R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
  • R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent
  • m and n each independently represents an integer of 0 to 2
  • a colored photosensitive resin composition that has a small amount of outgas after formation of a cured product, is excellent in reliability, and has good pattern adhesion in a development process during the creation of the cured product. Can do.
  • the cured product formed from the colored photosensitive resin composition of the present invention has a small amount of outgas during operation, has a short lifetime, and is excellent in reliability as a light emitting device.
  • a colored photosensitive resin composition for forming a partition wall of an organic electroluminescence device which has a small amount of outgas after forming a cured product and is excellent in reliability.
  • the cured product formed from the colored photosensitive resin composition of the present invention has a small amount of outgas during operation, has a short lifetime, and is excellent in reliability as a light emitting device.
  • the colored photosensitive resin composition can be provided by the pigment dispersion of the present invention.
  • (meth) acryl means “acryl and / or methacryl”
  • total solid content means in the colored photosensitive resin composition or pigment dispersion, It shall mean all components other than the solvent.
  • a numerical range represented by using “to” in the present invention means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the term “(co) polymer” means that both a single polymer (homopolymer) and a copolymer (copolymer) are included, and “(acid) anhydride”, “ The term “(anhydrous)... Acid” means to include both an acid and its anhydride.
  • the partition material refers to bank material, wall material, and wall material, and similarly, the partition material refers to bank, wall, and wall.
  • the partition wall is, for example, for partitioning a functional layer (organic layer) in an active drive organic electroluminescence device, and deposits or inkjets a material for forming the functional layer in the partitioned region (pixel region).
  • the weight average molecular weight refers to a polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
  • reliability means reliability at the time of driving an organic electroluminescence element, and particularly means display reliability for an image display device and light emission reliability for illumination.
  • the colored photosensitive resin composition according to the first aspect of the present invention solves the first problem
  • the (A) colorant is a compound represented by the following general formula (I): (A1) containing an organic black pigment containing at least one selected from the group consisting of the geometric isomer of the compound, the salt of the compound, and the salt of the geometric isomer of the compound, and the dispersant (B), An acrylic dispersant is included, and the (C) binder resin contains 75% by mass or more of (C1) epoxy (meth) acrylate resin.
  • the colored photosensitive resin composition according to the second aspect of the present invention solves the second problem, and is a colored photosensitive resin composition for forming partition walls of an organic electroluminescent element
  • the (A) colorant is at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound. It contains (A1) an organic black pigment containing seeds, and the (C) binder resin contains 75% by mass or more of (C1) epoxy (meth) acrylate resin.
  • the pigment dispersion according to the third aspect of the present invention solves the third problem, wherein the colorant (A) is a compound represented by the following general formula (I), (A1) containing an organic black pigment containing at least one selected from the group consisting of a geometric isomer, a salt of the compound, and a salt of the geometric isomer of the compound, and the dispersant (B) is an acrylic dispersion
  • the (C) binder resin contains an agent, and (C1) an epoxy (meth) acrylate resin.
  • the “colored photosensitive resin composition of the present invention” means both the colored photosensitive resin composition according to the first aspect and the colored photosensitive resin composition according to the second aspect. Point to.
  • the colored photosensitive resin composition of the present invention includes (A) a colorant, (B) a dispersant, (C) a binder resin, and (D) a photopolymerization. And (E) a photopolymerization initiator, and usually also contains a solvent.
  • A) Colorant A
  • the colorant in the colored photosensitive resin composition and the pigment dispersion of the present invention is a compound represented by the following general formula (I) (hereinafter referred to as “Compound (I)”).
  • Compound (I) an organic black pigment (hereinafter referred to as “A1”) containing at least one selected from the group consisting of a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound.
  • A1 organic black pigment
  • a cured product having a color tone closer to black can be obtained, it can be suitably used as a colorant for forming partition walls of an organic electroluminescent element having a large area ratio in the image display region of the image display device.
  • R a1 and R a6 each independently represents a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
  • the geometric isomer of the compound represented by the general formula (I) has the following core structure (however, the substituents in the structural formula are omitted), and the trans-trans isomer is probably the most stable. .
  • the compound represented by general formula (I) When the compound represented by general formula (I) is anionic, its charge can be any known suitable cation, such as a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal A salt compensated by a transition metal, a tertiary ammonium such as primary ammonium, secondary ammonium or trialkylammonium, a quaternary ammonium such as tetraalkylammonium, or an organometallic complex. Further, when the geometric isomer of the compound represented by the general formula (I) is anionic, it is preferably a similar salt.
  • a metal, organic, inorganic or metal organic cation specifically an alkali metal, alkaline earth metal A salt compensated by a transition metal, a tertiary ammonium such as primary ammonium, secondary ammonium or trialkylammonium, a quaternary ammonium such as tetraalkylammonium
  • R a2 , R a4 , R a5 , R a7 , R a9 and R a10 are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
  • R a3 and R a8 are each independently preferably a hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N (CH 3 ) 2 , N (CH 3 ) (C 2 H 5 ), N (C 2 H 5 ) 2 , ⁇ -naphthyl, ⁇ -naphthyl, SO 3 H or SO 3 — , more preferably a hydrogen atom or SO 3 H.
  • R 1 and R 6 are each independently preferably a hydrogen atom, CH 3 or CF 3 , more preferably a hydrogen atom.
  • at least one combination selected from the group consisting of R 1 and R 6 , R 2 and R 7 , R 3 and R 8 , R 4 and R 9 , and R 5 and R 10 is the same, more preferably R 1 is the same as R 6 , R 2 is the same as R 7 , R 3 is the same as R 8 , R 4 is the same as R 9 , and R 5 is the same as R 10 Are the same.
  • alkyl group having 1 to 12 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n- Pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2-ethylhexyl Group, nonyl group, decyl group, undecyl group or dodecyl group.
  • Examples of the cycloalkyl group having 3 to 12 carbon atoms include cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, trimethylcyclohexyl group, tuzyl group, norbornyl group, bornyl group, norcaryl group. , Caryl group, menthyl group, norpinyl group, pinyl group, 1-adamantyl group or 2-adamantyl group.
  • alkenyl group having 2 to 12 carbon atoms examples include vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, and 1,3-butadiene.
  • Examples of the cycloalkenyl group having 3 to 12 carbon atoms include a 2-cyclobuten-1-yl group, a 2-cyclopenten-1-yl group, a 2-cyclohexen-1-yl group, a 3-cyclohexen-1-yl group, , 4-Cyclohexadien-1-yl group, 1-p-menten-8-yl group, 4 (10) -tgen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene-1 -An yl group, a 7,7-dimethyl-2,4-norcaradien-3-yl group or a camphenyl group.
  • alkynyl group having 2 to 12 carbon atoms examples include 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, and 2-methyl-3-butyn-2-yl.
  • the halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • the (A1) organic black pigment is preferably a compound represented by the following general formula (I-1) (hereinafter sometimes referred to as “compound (I-1)”), and geometric isomers of the compound Is at least one selected from the group consisting of
  • organic black pigments include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) under the trade name.
  • This organic black pigment is preferably used after being dispersed by a dispersant, a solvent and a method described later. Further, at the time of dispersion, the sulfonic acid derivative (sulfonic acid substitution product) of the compound (I), the sulfonic acid derivative of the geometric isomer of the compound (I), particularly the sulfonic acid derivative of the compound (I-1), or When the sulfonic acid derivative of the geometric isomer of the compound (I-1) is present, dispersibility and storage stability may be improved.
  • the (A) colorant used in the present invention may contain other colorants in addition to the (A1) organic black pigment.
  • a pigment is preferably used, and the pigment may be an organic pigment or an inorganic pigment, but from the viewpoint of high resistance and low dielectric constant, it is more preferable to use an organic pigment.
  • an organic coloring pigment hereinafter sometimes referred to as “(A2) organic coloring pigment”.
  • organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene can be used.
  • organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene
  • pigment numbers specific examples of usable organic pigments are indicated by pigment numbers.
  • Terms such as “CI Pigment Red 2” mentioned below mean the color index (CI).
  • red pigments examples include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 185, 187, 188, 190, 193, 194, 200
  • C.I. I. Pigment Red 48 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.
  • C.I. I. Pigment Red 177, 254, and 272 are preferably used.
  • a red pigment having a low ultraviolet absorption rate From C.I. I. More preferably, CI pigment red 254 and 272 are used.
  • C.I. I. Pigment Orange 1 As orange (orange) pigments, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79.
  • C.I. I. Pigment Orange 13, 43, 64, 72 are preferably used, and when the colored photosensitive resin composition of the present invention is cured with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate, From this point of view, C.I. I. More preferably, CI pigment oranges 64 and 72 are used.
  • I. Pigment Orange 64 is particularly preferable.
  • blue pigments examples include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79.
  • C.I. I. Pigment Blue 15: 6, 16, and 60 are preferably used.
  • the colored photosensitive resin composition of the present invention is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate, From this point of view, C.I. I. More preferably, CI Pigment Blue 60 is used.
  • Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50.
  • C.C. I. Pigment Violet 19 and 23 are preferably used.
  • C.I. I. Pigment Violet 23 and 29 are preferably used, and when the colored photosensitive resin composition of the present invention is cured with ultraviolet rays, it is preferable to use a violet pigment having a low ultraviolet absorptivity.
  • C. I. More preferably, pigment violet 29 is used.
  • organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and purple pigments include green pigments and yellow pigments.
  • green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58. Of these, C.I. I. And CI Pigment Green 7 and 36.
  • yellow pigments include C.I. I.
  • C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.
  • pigments it is preferable to use a combination of at least one selected from the group consisting of a red pigment and an orange pigment and at least one selected from the group consisting of a blue pigment and a purple pigment.
  • a combination of at least one selected from the group consisting of a red pigment and an orange pigment and at least one selected from the group consisting of a blue pigment and a purple pigment it is preferable to use a combination of at least one selected from the group consisting of a red pigment and an orange pigment and at least one selected from the group consisting of a blue pigment and a purple pigment.
  • Red pigment C.I. I. Pigment Red 177, 254, 272
  • Orange pigment C.I. I. Pigment Orange 43, 64, 72
  • Blue pigment C.I. I. Pigment Blue 15: 6, 60 Purple pigment: C.I. I. Pigment Violet 23, 29
  • the combination of colors is not particularly limited, but from the viewpoint of light shielding properties, for example, a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, a combination of a blue pigment, an orange pigment, and a purple pigment can be mentioned. .
  • organic colorants can be used as other colorants.
  • other organic black pigments other than those represented by the general formula (I) may be used from the viewpoint of light shielding properties and color tone.
  • examples of other organic black pigments include aniline black, perylene black, and cyanine black.
  • an inorganic black pigment can be used.
  • the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, titanium black, and the like.
  • carbon black (hereinafter sometimes referred to as “(A3) carbon black”) can be preferably used from the viewpoint of light shielding properties and image characteristics.
  • Examples of carbon black include the following carbon black.
  • Carbon black coated with resin may be used.
  • Use of carbon black coated with a resin has the effect of improving adhesion to a glass substrate and volume resistance.
  • carbon black coated with the resin for example, carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be preferably used.
  • Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.
  • the total content of Na and Ca is preferably 100 ppm or less.
  • Carbon black is usually raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulated water, Na mixed from furnace materials of the reactor, Ca, K, Mg, Al, Fe.
  • the ash content of etc. is contained on the order of percent.
  • Na and Ca are generally contained in a few hundred ppm or more, but by reducing these, penetration into the transparent electrode (ITO) and other electrodes is suppressed, and electricity Tend to prevent mechanical short circuit.
  • the resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water is small, it is possible to cover fine units. Furthermore, it is preferable that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption is 140 mL / 100 g or less. By setting it within the above range, a coating film having good light shielding properties tends to be obtained.
  • the average particle diameter means the number average particle diameter, which is obtained by taking several fields of view at a magnification of tens of thousands by electron microscope observation, and measuring about 2000 to 3000 carbon black particles in the obtained photograph with an image processing apparatus. This means the equivalent circle diameter obtained by image analysis.
  • the method for preparing carbon black coated with resin is not particularly limited. For example, after appropriately adjusting the blending amount of carbon black and resin, After mixing and stirring a resin solution obtained by mixing a resin and a solvent such as cyclohexanone, toluene, xylene and the like, and a suspension obtained by mixing carbon black and water, the carbon black and water are separated, 1. A method in which the composition obtained by removing water and heating and kneading is formed into a sheet, pulverized and then dried; A method of mixing and stirring the resin solution and suspension prepared in the same manner as above to granulate carbon black and the resin, then separating and heating the obtained granular material, and removing the remaining solvent and water; 3.
  • Dissolve carboxylic acid such as maleic acid and fumaric acid in solvent add carbon black, mix and dry, remove solvent to obtain carboxylic acid-impregnated carbon black, add resin to this and dry blend
  • a reactive group-containing monomer component constituting the resin to be coated and water are stirred at a high speed to prepare a suspension. After polymerization, the suspension is cooled to obtain a reactive group-containing resin from the polymer suspension.
  • a method of adding carbon black and kneading, reacting carbon black with a reactive group (grafting carbon black), cooling and pulverizing, and the like can be employed.
  • the type of resin to be coated is not particularly limited, but a synthetic resin is common, and a resin having a benzene ring in its structure has a stronger function as an amphoteric surfactant. From the viewpoint of dispersibility and dispersion stability.
  • Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene.
  • Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamide imide, polyimide, polyamino bismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, polyether ether ketone, can be used.
  • the amount of the coating resin is preferably 1 to 30% by mass with respect to the total amount of carbon black and the coating resin. There exists a tendency which can make coating
  • Carbon black formed by coating with a resin in this way can be used as a light shielding material such as a partition and a colored spacer according to a conventional method.
  • An organic light emitting device and a color filter having the partition and the colored spacer as constituent elements are used. It can be created by conventional methods. When such carbon black is used, there is a tendency that a high light shielding rate and a low cost can be achieved. Further, by coating the carbon black surface with a resin, a light shielding material such as a high-resistance, low-dielectric-constant partition or colored spacer can be produced.
  • dyes may be used as other colorants.
  • the dye that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
  • the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I.
  • anthraquinone dyes examples include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
  • Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.
  • organic black pigment (A2) organic color pigment, black colorant and other pigments have an average particle size of usually 1 ⁇ m or less, preferably 0.5 ⁇ m or less, more preferably 0.25 ⁇ m or less. It is preferable to use in a dispersed manner.
  • the standard of the average particle diameter is the number of pigment particles.
  • the average particle diameter of this pigment is a value obtained from the pigment particle diameter measured by dynamic light scattering (DLS).
  • the particle size is measured with a sufficiently diluted colored photosensitive resin composition (usually diluted to a pigment content of about 0.005 to 0.2% by weight, provided that there is a concentration recommended by the measuring instrument. , According to the concentration) and measured at 25 ° C.
  • the dispersant contains an acrylic dispersant.
  • Acrylic dispersants have a flexible main skeleton with a linear molecular structure, so that most of the adsorbing groups are adsorbed to the colorant, so that the colorant is uniformly distributed in the colored photosensitive resin composition and the pigment dispersion. It is considered to be dispersed.
  • the coating film becomes a dense film, and further, the colorant that is an insoluble component in the alkali developer is uniformly arranged in the coating film. It is considered that the penetration of the developer into the coating film is suppressed during the development process and the pattern adhesiveness is improved. In particular, the adhesiveness is improved even with a fine pattern.
  • a polymer dispersant having a functional group is preferable. From the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; an acrylic dispersant containing a nitrogen atom is preferable, and an acrylic dispersant containing a nitrogen atom is particularly preferable. Furthermore, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, pyrazine, etc.
  • the colorant can be dispersed with a small amount of a dispersant.
  • These functional groups act as adsorbing groups that adsorb to the colorant.
  • acrylic dispersants include DISPERBYK-2000, DISPERBYK-2001, BYK-LPN21116, BYK-LPN6919, and the like (all manufactured by BYK Chemie).
  • an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant). It is preferable to use a random copolymer, a graft copolymer, or a block copolymer of the polymer and an unsaturated group-containing monomer having no functional group. These copolymers can be produced by a known method.
  • Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, and 2- (meth) acryloyloxyethyl.
  • Unsaturated monomer having a carboxyl group such as hexahydrophthalic acid and acrylic acid dimer; tertiary amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof, quaternary ammonium
  • Specific examples include unsaturated monomers having a base. These may be used alone or in combination of two or more.
  • Examples of the unsaturated group-containing monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives
  • the acrylic dispersant is an AB or BAB block copolymer composed of an A block having a functional group and a B block having no functional group, from the viewpoint of dispersibility.
  • the A block contains a partial structure derived from an unsaturated group-containing monomer not containing the functional group in addition to the partial structure derived from the unsaturated group-containing monomer containing the functional group. These may be contained in the A block in any form of random copolymerization or block copolymerization.
  • the content ratio in the A block of the partial structure not containing a functional group is usually 80% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass or less, Most preferably, it is 0 mass%.
  • the B block is preferably composed only of a partial structure derived from an unsaturated group-containing monomer that does not contain the functional group, and two or more kinds of single units are contained in one B block.
  • the partial structure derived from a body may be contained, and these may be contained in any form of random copolymerization or block copolymerization in the B block.
  • the AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.
  • the living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method.
  • the anion living polymerization method has a polymerization active species as an anion, and is represented by the following scheme, for example.
  • Ar 1 is a monovalent organic group
  • Ar 2 is a monovalent organic group different from Ar 1
  • M is a metal atom
  • s and t are each an integer of 1 or more.
  • the polymerization active species is a radical, and is represented by the following scheme, for example.
  • Ar 1 is a monovalent organic group
  • Ar 2 is a monovalent organic group different from Ar 1
  • j and k are each an integer of 1 or more
  • R a is a hydrogen atom or 1
  • R b is a hydrogen atom different from R a or a monovalent organic group.
  • the acrylic dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and constitutes the copolymer.
  • the A block / B block ratio is not particularly limited, and is preferably 1/99 to 80/20 (mass ratio), more preferably 5/95 to 60/40 (mass ratio). By making it within this range, it tends to be easy to secure a balance between dispersibility and storage stability.
  • the amount of the quaternary ammonium base in 1 g of the AB block copolymer or BAB block copolymer that can be used in the present invention is usually preferably 0.1 to 10 mmol. By making it within this range, it tends to ensure good dispersibility.
  • such an acrylic dispersant may contain an amino group.
  • the amine value of the acrylic dispersant is usually about 1 to 130 mgKOH / g. 10 mgKOH / g or more is preferred, 30 mgKOH / g or more is more preferred, 50 mgKOH / g or more is more preferred, 60 mgKOH / g or more is particularly preferred, 120 mgKOH / g or less is preferred, 100 mgKOH / g or less is more preferred, 90 mgKOH / g or less g or less is more preferable, and 80 mgKOH / g or less is particularly preferable.
  • the combination of the upper limit and the lower limit is preferably 10 to 120 mgKOH / g, more preferably 30 to 100 mgKOH / g, further preferably 50 to 90 mgKOH / g, and particularly preferably 60 to 80 mgKOH / g.
  • the amine value of the acrylic dispersant is expressed by the mass of KOH equivalent to the base amount per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
  • Amine value [mgKOH / g] (561 ⁇ V) / (W ⁇ S) [However, W: Weighing amount of dispersant sample [g], V: Titration amount at the end of titration [mL], S: Solid content concentration [mass%] of the dispersant sample. ]
  • the weight average molecular weight (Mw) of the acrylic dispersant is not particularly limited, but is preferably 1000 or more, more preferably 3000 or more, further preferably 4000 or more, particularly preferably 5000 or more, and preferably 50000 or less, preferably 20000 or less. More preferred is 15000 or less.
  • Mw weight average molecular weight
  • the combination of the upper limit and the lower limit is preferably 1000 to 50000, more preferably 3000 to 20000, still more preferably 4000 to 15000, and particularly preferably 5000 to 15000.
  • the acrylic dispersant has a quaternary ammonium base as a functional group
  • the chemical structure of the repeating unit containing the quaternary ammonium base is not particularly limited, but from the viewpoint of dispersibility, the acrylic dispersant is represented by the following general formula (V It is preferable to have a repeating unit represented by the following (hereinafter sometimes referred to as “repeating unit (V)”).
  • R 31 to R 33 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent.
  • R 34 is a hydrogen atom or a methyl group;
  • X is a divalent linking group;
  • Y ⁇ is a counter anion.
  • the number of carbon atoms of the alkyl group which may have a substituent in R 31 to R 33 in the above formula (V) is not particularly limited, but is usually 1 or more, preferably 10 or less, More preferably, it is more preferably 4 or less, and particularly preferably 2 or less.
  • 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, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified.
  • Group, pentyl group, or hexyl group is preferred, methyl group, ethyl group, propyl group, or butyl group is more preferred, and methyl group or ethyl group is still more preferred. Further, it may be either linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • the number of carbon atoms of the aryl group which may have a substituent in R 31 to R 33 in the above formula (V) is not particularly limited, but is usually 6 or more and preferably 16 or less. The following is more preferable.
  • Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group.
  • a phenyl group, a methylphenyl group, and an ethylphenyl group A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.
  • the carbon number of the aralkyl group which may have a substituent in R 31 to R 33 in the above formula (V) is not particularly limited, but is usually 7 or more and preferably 16 or less. More preferably, it is more preferably 10 or less, and particularly preferably 8 or less.
  • Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group.
  • a phenylmethyl group and a phenylethyl group Group a phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.
  • R 31 to R 33 are preferably each independently an alkyl group or an aralkyl group. Specifically, R 31 and R 33 are each independently a methyl group or an ethyl group. And R 32 is preferably a phenylmethyl group or a phenylethyl group, more preferably R 31 and R 33 are a methyl group, and R 32 is a phenylmethyl group.
  • repeating unit (VI) When the polymer dispersant has a tertiary amine as a functional group, from the viewpoint of dispersibility, the repeating unit represented by the following general formula (VI) (hereinafter referred to as “repeating unit (VI)”) It is preferable to have.
  • R 35 and R 36 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent.
  • An aralkyl group which may be optionally bonded, R 35 and R 36 may be bonded together to form a cyclic structure;
  • R 37 is a hydrogen atom or a methyl group;
  • Z is a divalent linking group.
  • alkyl group which may have a substituent in R 35 and R 36 in the above formula (VI) those exemplified as R 31 to R 33 in the above formula (V) may be preferably employed. it can.
  • aryl group which may have a substituent in R 35 and R 36 in the above formula (VI) those exemplified as R 31 to R 33 in the above formula (V) should be preferably employed. Can do.
  • R 35 and R 36 in the above formula (VI) which may have a substituent those exemplified as R 31 to R 33 in the above formula (V) may be preferably employed. it can.
  • R 35 and R 36 are each preferably an alkyl group which may have a substituent, and more preferably a methyl group, or ethyl group.
  • alkyl group, aralkyl group or aryl group in R 31 to R 33 of the above formula (V) and R 35 and R 36 of the above formula (VI) may have include a halogen atom, an alkoxy group, A benzoyl group, a hydroxyl group, etc. are mentioned.
  • examples of the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R 43 — group, A —COOR 44 — group (wherein R 43 and R 44 are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms). Is a —COO—R 44 — group, more preferably a —COO—C 2 H 4 — group.
  • examples of Y ⁇ of the counter anion include Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , CH 3 COO ⁇ , PF 6 ⁇ and the like.
  • the content rate of the repeating unit represented by the said formula (V) is not specifically limited, From a dispersible viewpoint, it is represented by the content rate of the repeating unit represented by the said formula (V), and the said formula (VI).
  • it is 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, based on the total content of repeating units.
  • the amount is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and particularly preferably 30 mol% or more.
  • the combination of the upper limit and the lower limit is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, still more preferably 20 to 40 mol%, particularly preferably 30 to 35 mol%.
  • the content of the repeating unit represented by the formula (V) in the total repeating units of the dispersant is not particularly limited, but is preferably 1 mol% or more from the viewpoint of dispersibility, and is 5 mol% or more. Is more preferably 8 mol% or more, particularly preferably 10 mol% or more, more preferably 50 mol% or less, and more preferably 30 mol% or less. Preferably, it is 20 mol% or less, more preferably 15 mol% or less.
  • the combination of the upper limit and the lower limit is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, further preferably 8 to 20 mol%, and particularly preferably 10 to 15 mol%.
  • the content rate of the repeating unit represented by the said formula (VI) is not specifically limited, From a dispersible viewpoint, it is represented by the content rate of the repeating unit represented by the said formula (V), and the said formula (VI).
  • it is 100 mol% or less, more preferably 90 mol% or less, still more preferably 80 mol% or less, particularly preferably 70 mol% or less, based on the total content of repeating units.
  • the amount is preferably 10 mol% or more, more preferably 30 mol% or more, still more preferably 50 mol% or more, and particularly preferably 60 mol% or more.
  • the combination of the upper limit and the lower limit is preferably 10 to 100 mol%, more preferably 30 to 90 mol%, still more preferably 50 to 80 mol%, and particularly preferably 60 to 70 mol%.
  • the content of the repeating unit represented by the formula (VI) in all the repeating units of the dispersant is not particularly limited, but is preferably 5 mol% or more from the viewpoint of dispersibility, and is preferably 10 mol% or more. More preferably, it is 15 mol% or more, more preferably 20 mol% or more, more preferably 60 mol% or less, and more preferably 40 mol% or less. Preferably, it is 30 mol% or less, more preferably 25 mol% or less.
  • the combination of the upper limit and the lower limit is preferably 5 to 600 mol%, more preferably 10 to 40 mol%, still more preferably 15 to 30 mol%, and particularly preferably 20 to 25 mol%.
  • the acrylic dispersant is a repeating unit represented by the following general formula (VII) (hereinafter referred to as “repeating unit (VII)” from the viewpoint of enhancing the compatibility with a binder component such as a solvent and improving dispersion stability. ) ").).
  • R 40 is an ethylene group or a propylene group
  • R 41 is an alkyl group which may have a substituent
  • R 42 is a hydrogen atom or a methyl group
  • n is an integer of 1 to 20.
  • the number of carbon atoms of the alkyl group which may have a substituent in R 41 of the above formula (VII) is not particularly limited, but is usually 1 or more, preferably 2 or more, and 10 or less. Is preferably 6 or less, more preferably 4 or less.
  • 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, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified.
  • It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be either linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • n in the above formula (VII) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less from the viewpoint of compatibility and dispersibility with respect to a binder component such as a solvent. More preferably, it is 5 or less.
  • the combination of the upper limit and the lower limit is preferably an integer of 1 to 10, more preferably an integer of 2 to 5.
  • the content ratio of the repeating unit represented by the formula (VII) in all the repeating units of the dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more. 4 mol% or more is more preferable, 30 mol% or less is preferable, 20 mol% or less is more preferable, and 10 mol% or less is more preferable. In the case of the above range, there is a tendency that compatibility with the binder component such as a solvent and dispersion stability are easily achieved.
  • the combination of the upper limit and the lower limit is preferably 1 to 30% by mole, more preferably 2 to 20% by mole, and further preferably 4 to 10% by mole.
  • the acrylic dispersant is one or more repeating units represented by the following general formula (VIII) (hereinafter referred to as the following general formula (VIII)) from the viewpoint of improving the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability. It may preferably be referred to as “repeating unit (VIII)”.
  • R 38 is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent;
  • R 39 is a hydrogen atom or a methyl group.
  • the number of carbon atoms of the alkyl group which may have a substituent in R 38 in the above formula (VIII) is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 4 or more. More preferably, it is preferably 10 or less, and more preferably 8 or less.
  • 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 2-ethylhexyl group.
  • a methyl group, an ethyl group , A propyl group, a butyl group, a pentyl group, a hexyl group, or a 2-ethylhexyl group and more preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a 2-ethylhexyl group.
  • it may be either linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • the number of carbon atoms of the aryl group which may have a substituent in R 38 in the above formula (VIII) is not particularly limited, but is usually 6 or more, preferably 16 or less, and preferably 12 or less. More preferably, it is more preferably 8 or less.
  • Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group.
  • a phenyl group, a methylphenyl group, and an ethylphenyl group A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.
  • the carbon number of the aralkyl group which may have a substituent in R 38 of the above formula (VIII) is not particularly limited, but is usually 7 or more, preferably 16 or less, and preferably 12 or less. More preferred is 10 or less.
  • Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group.
  • a phenylmethyl group and a phenylethyl group Group a phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.
  • R 38 is preferably an alkyl group or an aralkyl group, and is a methyl group, an ethyl group, a butyl group, a 2-ethylhexyl group or a phenylmethyl group. Is more preferable.
  • the substituent that the alkyl group may have in R 38 include a halogen atom and an alkoxy group.
  • the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group.
  • the linear alkyl group represented by R 38 includes both linear and branched chains.
  • the content rate of the repeating unit represented by the said formula (VIII) which occupies for all the repeating units of a dispersing agent (when the 2 or more types of repeating unit represented by the said formula (VIII) is included, the total content rate) Is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and 80 mol% or less from the viewpoint of dispersibility. Preferably, it is 70 mol% or less.
  • the combination of the upper limit and the lower limit is preferably 30 to 80 mol%, more preferably 40 to 70 mol%, and further preferably 50 to 70 mol%.
  • the acrylic dispersant may have a repeating unit other than the repeating unit (V), the repeating unit (VI), the repeating unit (VII) and the repeating unit (VIII).
  • repeating units include styrene monomers such as styrene and ⁇ -methylstyrene; (meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N- (Meth) acrylamide monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from monomers such as N-methacryloylmorpholine.
  • the acrylic dispersant is an A block having a repeating unit (V) and a repeating unit (VI), and a B block having no repeating unit (V) and a repeating unit (VI). It is preferable that it is a block copolymer which has these.
  • the block copolymer is preferably an AB block copolymer or a BAB block copolymer. By introducing not only a quaternary ammonium base but also a tertiary amino group into the A block, the dispersing ability of the dispersant tends to be remarkably improved.
  • the B block preferably has a repeating unit (VII), and more preferably has a repeating unit (VIII).
  • the repeating unit (V) and the repeating unit (VI) may be contained in any form of random copolymerization and block copolymerization. Further, the repeating unit (V) and the repeating unit (VI) may be contained in two or more kinds in one A block, in which case each repeating unit is randomly copolymerized in the A block, It may be contained in any form of block copolymerization.
  • a repeating unit other than the repeating unit (V) and the repeating unit (VI) may be contained in the A block.
  • Examples of such a repeating unit include the (meth) acrylic acid ester-based unit described above.
  • Examples include a repeating unit derived from a monomer.
  • the content of the repeating unit other than the repeating unit (V) and the repeating unit (VI) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably it is not contained in the block.
  • Repeating units other than the repeating units (VII) and (VIII) may be contained in the B block.
  • repeating units include styrene monomers such as styrene and ⁇ -methylstyrene; (Meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonic acid Ether; repeating units derived from monomers such as N-methacryloylmorpholine.
  • the content of the repeating units other than the repeating unit (VII) and the repeating unit (VIII) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably it is not contained in the block.
  • These acrylic dispersants may be used alone or in combination of two or more.
  • the dispersant is the following in addition to the acrylic dispersant described above. Other polymer dispersants shown may be included.
  • polymer dispersants include, for example, urethane-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants composed of amino group-containing monomers and macromonomers, polyoxyethylene alkyl ether-based dispersants, Examples thereof include oxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
  • a dispersant examples include trade names of EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK Chemie), Disparon (registered trademark, manufactured by Enomoto Kasei), and SOLPERSE. (Registered trademark, manufactured by Lubrizol Corp.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Co., Inc.) and the like.
  • EFKA registered trademark, manufactured by BASF
  • DISPERBYK registered trademark, manufactured by BYK Chemie
  • Disparon registered trademark, manufactured by Enomoto Kasei
  • SOLPERSE SOLPERSE.
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • Ajisper registered trademark, manufactured
  • the weight average molecular weight (Mw) of the other polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.
  • urethane polymer dispersants are preferable from the viewpoint of pigment dispersibility.
  • a polymer dispersant having a basic functional group and having a polyester bond and / or a polyether bond is preferable from the viewpoint of dispersibility and storage stability.
  • urethane polymer dispersants examples include DISPERBYK 160-167 and 182 series.
  • Specific examples of a preferable chemical structure as a urethane-based polymer dispersant include, for example, a polyisocyanate compound, a compound having one or two hydroxyl groups in the molecule, and a compound having a number average molecular weight of 300 to 10,000.
  • a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting active hydrogen with a compound having a tertiary amino group.
  • a quaternizing agent such as benzyl chloride, all or part of the tertiary amino group can be converted to a quaternary ammonium base.
  • polyisocyanate compounds examples include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate.
  • Aromatic diisocyanates hexamethylene diisocyanates, lysine methyl ester diisocyanates, 2,4,4-trimethylhexamethylene diisocyanates, dimer acid diisocyanates and other aliphatic diisocyanates, isophorone diisocyanates, 4,4'-methylenebis (cyclohexyl isocyanate), ⁇ , ⁇ Alicyclic diisocyanates such as ′ -diisocyanate dimethylcyclohexane, xylylene diisocyanate, ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetra Aliphatic diisocyanates having an aromatic ring such as tilxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate Examples thereof include tri
  • polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.
  • the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.
  • an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like.
  • Examples of the compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and one terminal hydroxyl group of these compounds has 1 to 1 carbon atoms. Examples thereof include those alkoxylated with 25 alkyl groups and mixtures of two or more thereof.
  • Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these.
  • polyether diols are those obtained by homopolymerizing or copolymerizing alkylene oxides such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned.
  • Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate.
  • alkylene oxides such as poly (poly And oxytetramethylene) adipate.
  • the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
  • Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, , 6-hexanediol, 2-methyl-2,4 Pentanediol, 2,2,
  • Polycarbonate glycol includes poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate.
  • Polyolefin glycol includes polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, and the like. Is mentioned. These may be used alone or in combination of two or more.
  • the number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10000, preferably 500 to 6000, more preferably 1000 to 4000.
  • Active hydrogen that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred.
  • the tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
  • Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl
  • examples of the nitrogen-containing heterocyclic ring include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo Nitrogen-containing hetero 6-membered rings such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc., pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring A ring is mentioned.
  • nitrogen-containing heterocycles preferred are an imidazole ring or a triazole ring.
  • these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like.
  • specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like.
  • N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, and 3-amino-1,2,4-triazole preferable. These may be used alone or in combination of two or more.
  • the preferred blending ratio of the raw materials for producing the urethane-based polymer dispersant is 10 to 200 of a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound. Parts by weight, preferably 20 to 190 parts by weight, more preferably 30 to 180 parts by weight, and 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight of the compound having an active hydrogen and a tertiary amino group in the same molecule. Part by mass.
  • the production of the urethane-based polymer dispersant can be performed according to a known polyurethane resin production method.
  • a solvent for production usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. These may be used alone or in combination of two or
  • a urethanization reaction catalyst is usually used.
  • the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. Secondary amine type and the like can be mentioned. These may be used alone or in combination of two or more.
  • the introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is in the range of 5 to 95 mgKOH / g.
  • the amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amount is not less than the lower limit, the dispersing ability tends to be improved, and when the amount is not more than the upper limit, the developability tends to be good.
  • the weight average molecular weight (Mw) of the urethane polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. Dispersibility and dispersion stability tend to be good when the lower limit or more, and the solubility is improved and dispersibility becomes good when the upper limit or less, the reaction tends to be easy to control. is there.
  • the dispersant is preferably used in combination with a pigment derivative described later.
  • the (B) dispersant in the colored photosensitive resin composition according to the second aspect of the present invention is not limited as long as it can disperse the (A) colorant.
  • the above-mentioned acrylic dispersant may be used, and the other polymer dispersants described above may be used.
  • an acrylic type dispersing agent or a urethane type polymer dispersing agent is included from a dispersible viewpoint.
  • the colored photosensitive resin composition and the pigment dispersion of the present invention contain (C) a binder resin.
  • C) a binder resin By containing a binder resin, it becomes possible to obtain a homogeneous film.
  • the binder resin is not particularly limited as long as a homogeneous film can be obtained, but is preferably an alkali-soluble resin from the viewpoint of solubility in an alkali developer.
  • the (C) binder resin contains (C1) an epoxy (meth) acrylate resin from the viewpoint of reducing outgas.
  • (C1) Epoxy (meth) acrylate resin has a rigid skeleton, is highly heat resistant and difficult to thermally decompose, and since the skeleton is rigid, a film with high crosslinkability is formed by taking an array structure at the time of curing. Therefore, it is considered that the amount of outgas generated after the cured product is formed is reduced.
  • the (C1) epoxy (meth) acrylate resin preferably contains a carboxyl group or a hydroxyl group.
  • the (C1) epoxy (meth) acrylate resin is preferably a resin obtained by adding an acid or ester compound having an ethylenically unsaturated bond to an epoxy resin and further reacting with a polybasic acid or its anhydride.
  • an ethylenically unsaturated bond is added to an epoxy compound via an ester bond (—COO—) by ring-opening addition of an acid carboxyl group having an ethylenically unsaturated bond to the epoxy group of the epoxy resin.
  • one carboxyl group of the polybasic acid anhydride is added to the hydroxyl group generated at that time.
  • the resin obtained by making the carboxyl group of the resin obtained by the said reaction react with the compound which has a functional group which can react further is also contained in the said (C1) epoxy (meth) acrylate resin.
  • the epoxy (meth) acrylate resin has substantially no epoxy group in terms of chemical structure and is not limited to “(meth) acrylate”, but an epoxy compound (epoxy resin) is a raw material.
  • (meth) acrylate” is a representative example, it is named in accordance with conventional usage.
  • the epoxy resin includes the raw material compound before the resin is formed by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Moreover, the epoxy resin can use the compound obtained by making a phenolic compound and epihalohydrin react.
  • the phenolic compound is preferably a compound having a divalent or trivalent 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, polymerization of phenol and dicyclopentane Epoxy resin, dihydroxyoxyfluorene type epoxy resin, dihydroxyalkyleneoxyl fluorene type epoxy resin, diglycidyl etherified product of 9,9-bis (4′-hydroxyphenyl) fluorene, 1,1-bis (4′-hydroxy) Phenyl) adamantane diglycidyl ether, and the like, and those having an aromatic ring in the main chain can be suitably used.
  • bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, epoxidized polymer of phenol and dicyclopentadiene, 9,9-bis (4′-hydroxyphenyl) Preferred are fluorene epoxidized products (diglycidyl etherified products), epoxy resins having adamantyl groups, epoxidized products of polymers of phenol and dicyclopentadiene, epoxidized products of 9,9-bis (4′-hydroxyphenyl) fluorene
  • An epoxy resin having an adamantyl group is more preferable.
  • ethylenically unsaturated monocarboxylic acid is preferable.
  • the acid having an ethylenically unsaturated bond include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, pentaerythritol tri (meth) acrylate succinic anhydride adduct, and pentaerythritol tris.
  • polybasic acid 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 , Benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and anhydrides thereof.
  • succinic anhydride succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, succinic anhydride or tetrahydrophthalic anhydride is more preferable, and tetrahydrophthalic acid is more preferable.
  • An acid anhydride is more preferable.
  • the molecular weight of the (C1) epoxy (meth) acrylate resin can be increased, branching can be introduced into the molecule, and the molecular weight and viscosity tend to be balanced.
  • the rate of introduction of acid groups into the molecule can be increased, and there is a tendency that balances such as sensitivity and adhesiveness are easily obtained.
  • the polyhydric alcohol include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. Preferably there is.
  • the acid value of the (C1) epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, more preferably 60 mgKOH / g or more, 80 mgKOH / g or more is particularly preferred, 200 mgKOH / g or less is preferred, 180 mgKOH / g or less is more preferred, 150 mgKOH / g or less is more preferred, 130 mgKOH / g or less is even more preferred, and 120 mgKOH / g or less is particularly preferred.
  • the combination of the upper limit and the lower limit is preferably 10 to 200 mgKOH / g, more preferably 20 to 180 mgKOH / g, still more preferably 40 to 150 mgKOH / g, still more preferably 60 to 130 mgKOH / g, and 80 to 120 mgKOH / g. Particularly preferred is mentioned.
  • the weight average molecular weight (Mw) of the (C1) epoxy (meth) acrylate resin 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, particularly preferably 5000 or more. Usually, it is 30000 or less, preferably 20000 or less, more preferably 15000 or less, further preferably 10,000 or less, and particularly preferably 8000 or less.
  • the combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 2000 to 20000, still more preferably 3000 to 15000, still more preferably 4000 to 10,000, and particularly preferably 5000 to 8000.
  • the epoxy (meth) acrylate resin can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the presence of a catalyst and a thermal polymerization inhibitor, the acid or ester compound having an ethylenically unsaturated bond is added to cause addition reaction, and further a polybasic acid or its A method of continuing the reaction by adding an anhydride can be used.
  • examples of the organic solvent used in the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.
  • examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine, and tertiary amines such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride.
  • thermal polymerization inhibitor examples include one or more of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone and the like.
  • 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, relative to one chemical equivalent of the epoxy group of the epoxy resin.
  • the amount can be.
  • the temperature during the addition reaction is usually 60 to 150 ° C., preferably 80 to 120 ° C.
  • the polybasic acid (anhydride) is used in an amount of usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1, based on 1 chemical equivalent of the hydroxyl group generated in the addition reaction.
  • the amount can be a chemical equivalent.
  • the chemical structure of the epoxy (meth) acrylate resin is not particularly limited, but from the viewpoint of reducing outgas, an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and / or the following general structure It is preferable to contain an epoxy (meth) acrylate resin having a partial structure represented by the formula (III).
  • the epoxy (meth) acrylate resin has high sensitivity, and therefore has good patterning performance, has a hydrophobic skeleton, and has a mild dissolution rate, and thus has good substrate adhesion.
  • an acrylic resin unlike an acrylic resin, it has a rigid skeleton, and takes an array structure at the time of curing and is closely cross-linked, so that it is considered that generation of outgas can be suppressed.
  • an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and / or an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (III) is a central portion. Since it has a bulky and rigid skeleton, hydrophilic portions such as a (meth) acryloyl group are developed outward and the developability is considered to be good.
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 represents a divalent hydrocarbon group which may have a substituent
  • the benzene ring in formula (II) may be further substituted with an optional substituent
  • each R 13 independently represents a hydrogen atom or a methyl group
  • R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
  • R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent
  • m and n each independently represents an integer of 0 to 2
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 represents a divalent hydrocarbon group which may have a substituent
  • the benzene ring in formula (II) may be further substituted with an optional substituent
  • R 12 represents a divalent hydrocarbon group which may have a substituent.
  • the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups. Can be mentioned.
  • Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing penetration of the developer into the exposed portion.
  • the number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and further preferably 6 to 10.
  • divalent linear aliphatic group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group.
  • a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
  • divalent branched aliphatic group examples include iso-propyl group, sec-butyl group, tert-butyl group, iso-amyl group and the like.
  • the number of rings of the divalent cyclic aliphatic group is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 12 or less and 10 or less.
  • the divalent cyclic aliphatic group include a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, tricyclodecane ring, adamantane ring, cyclododecane ring, dicyclopentadiene, and the like.
  • a group obtained by removing two hydrogen atoms from the ring is preferable from the viewpoint of the rigidity of the skeleton.
  • Examples of the substituent that 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, unsubstituted is preferable from the viewpoint of ease of synthesis.
  • examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.
  • 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, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
  • the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
  • the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences.
  • Examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
  • a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.
  • Examples of the substituent that 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.
  • unsubstituted is preferable from the viewpoints of development solubility and moisture absorption resistance.
  • divalent aliphatic groups and one or more divalent aromatic ring groups are linked
  • one or more of the above divalent aliphatic groups and the above divalent aromatic group are used.
  • the number of divalent aliphatic groups is not particularly limited, but is usually preferably 1 or more and 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.
  • the number of divalent aromatic ring groups is not particularly limited, but is usually preferably 1 or more and 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.
  • 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 (II-A) to (II-F), etc. Is mentioned. Among these, a group represented by the following formula (II-A) is preferable from the viewpoint of skeleton rigidity and membrane hydrophobicity. * In the chemical formula represents a bond.
  • the benzene ring in formula (II) may be further substituted with an arbitrary 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 not particularly limited, either one or two or more. Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.
  • the repeating unit structure represented by the formula (II) is preferably a repeating unit structure represented by the following formula (II-1) from the viewpoint of simplicity of synthesis.
  • R 11 and R 12 have the same meaning as in formula (II);
  • R X represents a hydrogen atom or a polybasic acid residue; * Represents a bond;
  • the benzene ring in formula (II-1) may be further substituted with an arbitrary substituent.
  • the polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
  • Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, end methylenetetrahydrophthalic acid
  • One type or two or more types selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid may be mentioned.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable.
  • tetrahydrophthalic acid and biphenyltetracarboxylic acid more preferably tetrahydrophthalic anhydride.
  • the repeating unit structure represented by the formula (II-1) contained in one molecule of the epoxy (meth) acrylate resin may be one type or two or more types.
  • R X is a hydrogen atom.
  • those in which R X is a polybasic acid residue may be mixed.
  • the number of repeating unit structures represented by the formula (II) contained in one molecule of the (C1-1) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Moreover, 20 or less is preferable and 15 or less is more preferable. It is easy to obtain a strong film by making it the above lower limit or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of the surface smoothness and sensitivity of the film by making the upper limit or less, The resolution tends to improve.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the (C1-1) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, 2000 or more is further preferable, 3000 or more is particularly preferable, 30000 or less is preferable, 20000 or less is more preferable, 10,000 or less is further preferable, and 8000 or less is particularly preferable.
  • the combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 1500 to 20000, still more preferably 2000 to 10000, and particularly preferably 3000 to 8000.
  • the acid value of the (C1-1) epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, more preferably 50 mgKOH / g or more. More preferably, 80 mgKOH / g or more is particularly preferable, 200 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, 130 mgKOH / g or less is more preferable, and 100 mgKOH / g or less is particularly preferable.
  • the combination of the upper limit and the lower limit is preferably 10 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g, further preferably 40 to 130 mgKOH / g, still more preferably 50 to 100 mgKOH / g, and 80 to 100 mgKOH / g. Particularly preferred is mentioned.
  • each R 13 independently represents a hydrogen atom or a methyl group
  • R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
  • R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent
  • m and n each independently represents an integer of 0 to 2
  • R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings that the aliphatic ring group has is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. It is easy to obtain a strong film by making it the above lower limit or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of the surface smoothness and sensitivity of the film by making the upper limit or less, The resolution tends to improve.
  • the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
  • the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable. It is easy to obtain a strong film by making it the above lower limit or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of the surface smoothness and sensitivity of the film by making the upper limit or less, There is a tendency that the resolution is improved.
  • the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, further preferably 8 to 20, and particularly preferably 8 to 15.
  • 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 a cyclododecane ring.
  • an adamantane ring is preferable from the viewpoint of the remaining film ratio and resolution of the colored photosensitive resin composition.
  • the number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, 5 or less, and more preferably 4 or less. It is easy to obtain a strong film by making it the above lower limit or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of the surface smoothness and sensitivity of the film by making the upper limit or less, There is a tendency that the resolution is improved.
  • the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 3 to 4.
  • the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in 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, preferably 30 or less. More preferably, it is more preferably 20 or less, and particularly preferably 15 or less.
  • the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, further preferably 8 to 20, still more preferably 10 to 15, and particularly preferably 12 to 15.
  • aromatic ring in the aromatic ring group examples 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, Examples include fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of patterning characteristics.
  • the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited.
  • Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing penetration of the developer into the exposed portion.
  • the number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 25 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.
  • divalent linear aliphatic group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group.
  • a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
  • divalent branched aliphatic group examples include the above-mentioned divalent linear aliphatic group, a side chain of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group.
  • the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 10 or less, 5 or less, more preferably 3 or less.
  • the amount is not less than the lower limit value, a strong film tends to be obtained and the substrate adhesion tends to be good.
  • the value is not more than the upper limit value, it is easy to suppress deterioration of the surface smoothness and sensitivity of the film, and resolution. Tend to improve.
  • divalent aliphatic group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and the like, by removing two hydrogen atoms.
  • a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of the rigidity of the skeleton.
  • Examples of the substituent that 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, unsubstituted is preferable from the viewpoint of ease of synthesis.
  • examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.
  • 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, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
  • the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
  • the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences.
  • Examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
  • a benzene ring or a naphthalene ring having two free valences is preferable, and a fluorene ring having two free valences is more preferable.
  • Examples of the substituent that 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, unsubstituted is preferable from the viewpoint of development solubility.
  • divalent aliphatic groups and one or more divalent aromatic ring groups are linked
  • one or more of the above divalent aliphatic groups and the above divalent aromatic group are used.
  • the number of divalent aliphatic groups is not particularly limited, but is usually preferably 1 or more and 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.
  • the number of divalent aromatic ring groups is not particularly limited, but is usually preferably 1 or more and 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.
  • 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 above formulas (II-A) to (II-F) Is mentioned.
  • the group represented by the formula (II-C) or the group represented by the formula (II-D) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobicity of the film.
  • the bonding mode of the cyclic hydrocarbon group which is a side chain with respect to these divalent hydrocarbon groups is not particularly limited. For example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with the side chain. And a mode in which a cyclic hydrocarbon group which is a side chain including one of the carbon atoms of the aliphatic group is formed.
  • R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent.
  • Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing penetration of the developer into the exposed portion.
  • the number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the amount is not less than the lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be favorable. And the deterioration of sensitivity tends to be suppressed, and the resolution tends to be improved.
  • divalent linear aliphatic group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group.
  • a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
  • divalent branched aliphatic group examples include the above-mentioned divalent linear aliphatic group, a side chain of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group.
  • the number of rings of the divalent cyclic aliphatic group is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 12 or less and 10 or less.
  • the amount is not less than the lower limit value, a strong film tends to be obtained and the substrate adhesion tends to be good.
  • the value is not more than the upper limit value, it is easy to suppress deterioration of the surface smoothness and sensitivity of the film, and resolution. Tend to improve.
  • divalent cyclic aliphatic group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, a dicyclopentadiene, and a hydrogen atom.
  • a group in which two are removed Among these, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable from the viewpoint of skeleton rigidity.
  • Examples of the substituent that 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, unsubstituted is preferable from the viewpoint of ease of synthesis.
  • m and n each independently represents an integer of 0 to 2.
  • m and n are preferably 0.
  • m and n are each independently 1 or more from the viewpoint of patterning suitability and surface roughness.
  • the partial structure represented by the general formula (III) is preferably a partial structure represented by the following general formula (III-1) from the viewpoint of adhesion to the substrate.
  • R 13 , R 15 , R 16 , m and n are as defined in the formula (III);
  • R alpha represents optionally may be monovalent cyclic hydrocarbon group having a substituent;
  • p is an integer greater than or equal to 1;
  • the benzene ring in formula (III-1) may be further substituted with an optional substituent; * Represents a bond.
  • R ⁇ represents a monovalent cyclic hydrocarbon group.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings that the aliphatic cyclic group has is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less.
  • the combination of the upper limit and the lower limit is preferably 1 to 6, more preferably 2 to 4, and further preferably 2 to 3.
  • the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable.
  • the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, further preferably 8 to 20, and particularly preferably 8 to 15.
  • 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 a cyclododecane ring.
  • an adamantane ring is preferable from the viewpoint of strong film characteristics.
  • the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less.
  • the lower limit value or more By setting it to the lower limit value or more, a strong film is likely to be obtained and surface roughness tends to be less likely to occur, and by setting the upper limit value or less, patterning characteristics tend to be good.
  • the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 3 to 5.
  • the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the carbon number of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the combination of the upper limit and the lower limit is preferably 4 to 30, more preferably 5 to 20, and further preferably 6 to 15.
  • Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of development solubility.
  • Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, 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, Examples thereof include alkyl groups having 1 to 5 carbon atoms such as amyl group and iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.
  • P represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less.
  • R ⁇ is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.
  • the benzene ring in formula (III-1) may be further substituted with an arbitrary 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 not particularly limited, either one or two or more. Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.
  • the partial structure represented by the general formula (III) is preferably a partial structure represented by the following general formula (III-2) from the viewpoints of skeleton rigidity and membrane hydrophobization.
  • R 13 , R 15 , R 16 , m and n are as defined in the formula (III); R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent; The benzene ring in formula (III-2) may be further substituted with an optional substituent; * Represents a bond.
  • R ⁇ represents a divalent cyclic hydrocarbon group.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings that the aliphatic ring group has is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 10 or less and 5 or less. It is easy to obtain a strong film by making it the above lower limit or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of the surface smoothness and sensitivity of the film by making the upper limit or less, The resolution tends to improve.
  • the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5.
  • carbon number of an aliphatic cyclic group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 40 or less are preferable, 35 or less are more preferable, and 30 or less are more preferable.
  • the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 35, and still more preferably 8 to 30.
  • 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 a cyclododecane ring.
  • an adamantane ring is preferable from the viewpoint of storage stability.
  • the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. It is easy to obtain a strong film by making it the above lower limit or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of the surface smoothness and sensitivity of the film by making the upper limit or less, The resolution tends to improve.
  • the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 3 to 5.
  • the aromatic ring group include 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, more preferably 8 or more, and 10
  • the above is more preferable, 40 or less is preferable, 30 or less is more preferable, 20 or less is further preferable, and 15 or less is particularly preferable. It is easy to obtain a strong film by making it the above lower limit or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of the surface smoothness and sensitivity of the film by making the upper limit or less, The resolution tends to improve.
  • the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, and particularly preferably 10 to 15.
  • aromatic ring in the aromatic ring group examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
  • a fluorene ring is preferable from the viewpoint of developability.
  • Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, 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, Examples thereof include alkyl groups having 1 to 5 carbon atoms such as amyl group and iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; Among these, unsubstituted is preferable from the viewpoint of simplicity of synthesis.
  • R beta is a divalent aliphatic cyclic group, and more preferably a divalent adamantane ring group.
  • R beta is a divalent aromatic ring group, and more preferably a divalent fluorene ring group.
  • the benzene ring in formula (III-2) may be further substituted with an arbitrary 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 not particularly limited, either one or two or more.
  • two benzene rings in formula (III-2) may be linked via these substituents. Among these, unsubstituted is preferable from the viewpoint of patterning characteristics. Moreover, it is preferable that it is methyl group substitution from a viewpoint of making it hard to produce film reduction.
  • the partial structure represented by the formula (III) is preferably a partial structure represented by the following formula (III-3) from the viewpoint of the remaining film ratio and patterning characteristics.
  • R 13 , R 14 , R 15 , R 16 , m and n are as defined in the formula (III);
  • R Z represents a hydrogen atom or a polybasic acid residue.
  • the polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Further, another OH group may be removed and shared with R Z in other molecules represented by the formula (III-3), that is, a plurality of formulas (III-3) are bonded via R Z. ) May be linked.
  • Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, end methylenetetrahydrophthalic acid
  • One type or two or more types selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid may be mentioned.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable.
  • tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable.
  • the partial structure represented by the formula (III-3) contained in one molecule of the epoxy (meth) acrylate resin may be one type or two or more types.
  • R Z is a hydrogen atom.
  • those in which R Z is a polybasic acid residue may be mixed.
  • the number of partial structures represented by the formula (III) contained in one molecule of (C1-2) epoxy (meth) acrylate resin 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 further more preferable.
  • the lower limit value or more it is easy to obtain a strong film, surface roughness is less likely to occur, and the electric characteristics tend to be good, and by setting the upper limit value or less, the surface smoothness and sensitivity of the film are reduced. Deterioration is easy to suppress and the resolution tends to improve.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the (C1-2) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, 3000 or more are more preferable, 3500 or more are particularly preferable, 30000 or less is preferable, 20000 or less is more preferable, 10,000 or less is further preferable, 7000 or less is further more preferable, and 5000 or less is particularly preferable.
  • the combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 2000 to 20000, still more preferably 3000 to 10000, still more preferably 3500 to 7000, and particularly preferably 3500 to 5000.
  • the acid value of the (C1-2) epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, and more preferably 60 mgKOH / g or more.
  • 80 mgKOH / g or more is particularly preferable, 200 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, and 120 mgKOH / g or less is more preferable.
  • the combination of the upper limit and the lower limit is preferably 10 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g, further preferably 40 to 150 mgKOH / g, still more preferably 60 to 120 mgKOH / g, and 80 to 120 mgKOH / g. Particularly preferred is mentioned.
  • the (C) binder resin contained in the colored photosensitive resin composition and the pigment dispersion of the present invention is abbreviated as a binder resin other than (C1) epoxy (meth) acrylate resin (hereinafter referred to as “(C2) other binder resin”). May be included).
  • (C2) Other binder resins include, for example, acrylic resins, carboxyl group-containing epoxy resins, carboxy group-containing urethane resins, novolac resins, polyvinylphenol resins, etc., and these may be used alone. Alternatively, a plurality of types may be mixed and used.
  • the (C) binder resin contains 75% by mass or more of (C1) epoxy (meth) acrylate resin.
  • (C) It is thought that heat resistance of hardened
  • the content ratio of (C1) epoxy (meth) acrylate resin to (C) binder resin is not particularly limited as long as it is 75% by mass or more, preferably 80% by weight or more, more preferably 85% by weight or more, and 90% by weight or more. Is more preferable, and 95% by mass or more is particularly preferable.
  • the combination of the upper limit and the lower limit is preferably 75 to 100% by mass, more preferably 80 to 100% by mass, further preferably 85 to 100% by mass, still more preferably 90 to 100% by mass, and 95 to 100% by mass. Particularly preferred is mentioned.
  • the colored photosensitive resin composition of the present invention contains (D) a photopolymerizable monomer.
  • the (D) photopolymerizable monomer used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond, ester of polyhydric or monohydric alcohol, and the like can be mentioned. It is done.
  • a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule is particularly desirable.
  • the number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably It is 8 or less, more preferably 7 or less.
  • the combination of the upper limit and the lower limit is preferably 2 to 8, more preferably 4 to 8, and further preferably 5 to 7.
  • polyfunctional ethylenic monomer examples include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, and an aromatic polyhydroxy compound.
  • esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a hydroxy compound with an unsaturated carboxylic acid and a 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, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc.
  • itaconic acid ester replaced by itaconate
  • ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid examples include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.
  • the ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.
  • a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted.
  • urethane (meth) acrylates examples include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003, 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.
  • a photopolymerizable monomer is preferably (meth) acrylic acid alkyl ester, and more preferably dipentaerythritol hexaacrylate. These may be used alone or in combination of two or more.
  • the colored photosensitive resin composition of the present invention contains (E) a photopolymerization initiator.
  • the photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. If necessary, an additive such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added and used.
  • Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, and JP-A-2000-56118.
  • N-aryl- ⁇ -amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in JP-A-10-39503; Radical activators such as -aryl- ⁇ -amino acid salts and N-aryl- ⁇ -amino acid esters, ⁇ -aminoalkylphenone derivatives; Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2006-36750, etc. And the oxime ester derivatives described in the above.
  • titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny) 1-yl), dicyclopentadienyltitanium di (2,6-difluorophen-1-yl), dicyclopentadienyltitanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadieny
  • Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole. Dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like.
  • halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [ ⁇ - (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [ ⁇ - (2 ′-(6 ′′ -benzofuryl) vinyl)]-1,3,4-oxadiazole, And 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
  • halomethyl-s-triazine derivatives examples include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-triazine and the like.
  • ⁇ -aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. It is
  • oxime ester derivatives are particularly effective in terms of sensitivity and plate-making properties, and when an alkali-soluble resin containing a phenolic hydroxyl group is used. Since it is disadvantageous in terms of sensitivity, oxime ester derivatives (oxime ester compounds and ketoxime ester compounds) that are particularly excellent in such sensitivity are particularly useful.
  • the oxime ester compound include compounds having a partial structure represented by the following general formula (IX), and preferably an oxime ester compound represented by the following general formula (IX-A).
  • R 22 is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and 3 carbon atoms.
  • R 21a is a hydrogen atom, or an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroaryl having 1 to 20 carbon atoms.
  • Aminoalkyl group alkanoyl group having 2 to 12 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, cycloalkanoyl group having 3 to 8 carbon atoms, aryloyl group having 7 to 20 carbon atoms, heteroarylloyl having 1 to 20 carbon atoms Group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or 1 to 10 carbon atoms
  • a cycloalkylalkyl group of R 21b represents an arbitrary substituent containing an aromatic hydrocarbon ring or an aromatic heterocyclic ring (heteroaromatic ring).
  • R 21a may be linked to R 21b to form a ring, and each of the linking groups may have a substituent, an alkylene group having 1 to 10 carbon atoms, a polyethylene group (— (CH ⁇ CH) r —), a polyethynylene group (— (C ⁇ C) r —) or a group formed by a combination thereof (where r is an integer of 0 to 3).
  • R 22a is each optionally substituted alkanoyl group having 2 to 12 carbon atoms, heteroarylalkanoyl group having 1 to 20 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, carbon A cycloalkanoyl group having 3 to 8 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxyoxycarbonylalkanoyl group having 3 to 20 carbon atoms, and 2 to 10 carbon atoms
  • R 22 in the general formula (IX) and R 22a in the general formula (IX-A) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or 3 carbon atoms. ⁇ 8 cycloalkanoyl groups.
  • R 21a in the general formula (IX-A) is preferably an unsubstituted methyl group, ethyl group, propyl group, or a propyl group substituted with an N-acetyl-N-acetoxyamino group.
  • R 21b is preferably an optionally substituted carbazoyl group, an optionally substituted fluorenyl group, an optionally substituted thioxanthonyl group, or an optionally substituted group.
  • Good phenyl sulfide groups are mentioned.
  • the optional substituents in the general formulas (IX) and (IX-A) include an alkyl group, an aromatic hydrocarbon ring group (aryl group), an aliphatic ring group, an aromatic heterocyclic group, a halogen group, Examples include a hydroxyl group, a carboxyl group, an amino group, and an amide group.
  • Specific examples of the oxime ester-based compound suitable for the present invention include the compounds exemplified below, but the oxime ester-based compound is not limited to these compounds.
  • ketoxime ester compound examples include a compound having a partial structure represented by the following general formula (X), and preferably a ketoxime ester compound represented by the following general formula (XA).
  • R 24 has the same meaning as R 22 in the general formula (IX).
  • R 23a is a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heterocycle having 1 to 20 carbon atoms, which may be substituted.
  • R 23a may be linked to R 23b to form a ring, and each of the linking groups may have a substituent, an alkylene group having 1 to 10 carbon atoms, a polyethylene group (— (CH ⁇ CH) r —), a polyethynylene group (— (C ⁇ C) r —) or a group formed by a combination thereof (where r is an integer of 0 to 3).
  • R 24a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, carbon A benzoyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, Or represents an alkylaminocarbonyl group having 2 to 20 carbon atoms.
  • R 24 in the general formula (X) and R 24a in the general formula ( XA ) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or a carbon number of 3 A cycloalkanoyl group having 8 to 8 carbon atoms, and an aryloyl group having 7 to 20 carbon atoms.
  • R 23a in the general formula ( XA ) is preferably an unsubstituted ethyl group, propyl group, butyl group, or an ethyl group or propyl group substituted with a methoxycarbonyl group.
  • R 23b in the above general formula ( XA ) is preferably an optionally substituted carbazoyl group, an optionally substituted fluorenyl group, or an optionally substituted phenyl sulfide group.
  • the optional substituents in the general formulas (X) and (XA) include an alkyl group, an aromatic hydrocarbon ring group (aryl group), an aliphatic ring group, an aromatic heterocyclic group, a halogen group, Examples include a hydroxyl group, a carboxyl group, an amino group, and an amide group.
  • Specific examples of the ketoxime ester-based compound suitable for the present invention include compounds exemplified below, but the ketoxime ester-based compound is not limited to these compounds.
  • oxime ester compounds and ketoxime ester compounds are known compounds per se, for example, a series described in Japanese Unexamined Patent Publication No. 2000-80068 and Japanese Unexamined Patent Publication No. 2006-36750. It is a kind of compound. From the viewpoint of sensitivity, in the present invention, it is preferable that (E) the photopolymerization initiator is an oxime ester compound and / or a ketoxime ester compound.
  • the said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
  • benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether; 2-methylanthraquinone, 2-ethylanthraquinone, 2- Anthraquinone derivatives such as t-butylanthraquinone and 1-chloroanthraquinone; benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, etc.
  • Benzophenone derivatives 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylpheni Ketone, ⁇ -hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 Acetophenone derivatives such as' -methylthiophenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2- Thioxanthone derivatives such as chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl
  • a photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more types.
  • a sensitizing dye and a polymerization accelerator according to the wavelength of the image exposure light source can be blended with the photopolymerization initiator as necessary for the purpose of increasing the sensitivity.
  • sensitizing dyes xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958, Japanese Patent Application Laid-Open No. 4-219756, Japanese Patent Application Laid-Open No. 3-239703, and Japanese Patent Application Laid-Open No. 5-289335 are described.
  • amino group-containing sensitizing dyes preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone.
  • Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) ) Benzothiazole, 2- (p-diethi) Ruaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazol
  • polymerization accelerator examples include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds described later. It is done.
  • a polymerization accelerator may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the colored photosensitive resin composition of the present invention includes an adhesion improver such as a silane coupling agent, a coating property improver, and development.
  • an improver, an ultraviolet absorber, an antioxidant, a surfactant, a pigment derivative, and the like can be appropriately blended.
  • the colored photosensitive resin composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate.
  • an adhesion improver a silane coupling agent, a phosphoric acid group-containing compound and the like are preferable.
  • the type of silane coupling agent various types such as epoxy, (meth) acrylic, amino and the like can be used alone or in combination of two or more.
  • Preferred silane coupling agents include, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • Epoxy silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and ureidosilanes such as 3-ureidopropyltriethoxysilane, Isocyanate silanes such as 3-isocyanatopropyltriethoxysilane are mentioned, and epoxy silane silane coupling agents are particularly preferable.
  • the phosphoric acid group-containing compound (meth) acryloyl group-containing phosphates are preferable, and those represented by the following general formula (XI-A), (XI-B) or (XI-C) are preferable.
  • R 51 represents a hydrogen atom or a methyl group
  • l and l ′ represent an integer of 1 to 10
  • m represents 1, 2 or 3.
  • These phosphoric acid group-containing compounds may be used alone or in combination of two or more.
  • the colored photosensitive resin composition of the present invention may contain a pigment derivative as a dispersion aid in order to improve dispersibility and storage stability.
  • a pigment derivative as a dispersion aid
  • As pigment derivatives azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine
  • derivatives such as phthalocyanines and quinophthalones are preferable.
  • Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.
  • pigment derivatives include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These may be used alone or in combination of two or more.
  • Photoacid generator is a compound capable of generating an acid by ultraviolet rays.
  • a crosslinking agent such as a melamine compound. If there is, it will advance a crosslinking reaction.
  • photoacid generators those having a high solubility in a solvent, particularly in a solvent used in a photosensitive coloring composition, are preferable, for example, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl).
  • Iodonium bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl (p-tolyl) iodonium, p Diaryl iodonium such as isopropylphenyl (p-tolyl) iodonium, or triarylsulfonium chloride such as triphenylsulfonium, bromide, borofluoride, hexafluorophosphate salt, hexafluoroa Senate salts, aromatic sulfonates, tetrakis (pentafluorophenyl) borate salts and the like, sulfonium organoboron complexes such as diphenylphenacylsulfonium (n-butyl) triphen
  • Crosslinking Agent A crosslinked agent can be further added to the colored photosensitive resin composition of the present invention.
  • a melamine or guanamine compound can be used.
  • these crosslinking agents include melamine or guanamine compounds represented by the following general formula (XII).
  • R 61 represents a —NR 66 R 67 group or an aryl group having 6 to 12 carbon atoms;
  • R 61 is a —NR 66 R 67 group, one of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 , and when R 61 is an aryl group having 6 to 12 carbon atoms, R 62 , R 63 , R 64 and R 65 represent a —CH 2 OR 68 group;
  • the rest of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 each independently represents a hydrogen atom or a —CH 2 OR 68 group;
  • R 68 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the aryl group having 6 to 12 carbon atoms is typically a phenyl group, 1-naphthyl group or 2-naphthyl group, and these phenyl group and naphthyl group include an alkyl group, an alkoxy group, a halogen atom, etc. May be bonded to each other.
  • Each of the alkyl group and the alkoxy group may have about 1 to 6 carbon atoms.
  • Alkyl group represented by R 68 is, among the above, preferably a methyl group or an ethyl group, more preferably a methyl group.
  • Melamine compounds corresponding to the general formula (XII), that is, compounds of the following general formula (XII-A) include hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, tetramethoxy Methyl melamine, hexaethoxymethyl melamine and the like are included.
  • R 62 , R 63 , R 64 , R 65 , R 66 and R 67 when one of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 is an aryl group, one of R 62 , R 63 , R 64 and R 65 is —CH 2 Represents the OR 68 group;
  • the rest of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 each independently represents a hydrogen atom or a —CH 2 OR 68 group;
  • R 68 represents a hydrogen atom or an alkyl group.
  • guanamine compounds corresponding to the general formula (XII), that is, compounds in which R 61 in the general formula (XII) is aryl include tetramethylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxymethyl benzoguanamine, tetraethoxymethyl benzoguanamine. Etc. are included.
  • a crosslinking agent having a methylol group or a methylol alkyl ether group can also be used. Examples are given below. 2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3 , 5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3,5-bis (hydroxymethyl) perhydro-1,3,5- Oxadiazin-4-one (commonly called dimethyloluron) or a dimethyl ether thereof, tetramethylol glyoxal diurein or a tetramethyl ether thereof.
  • crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the amount of the crosslinking agent used is preferably 0.1 to 15% by mass, particularly preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive coloring composition.
  • Mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bis Thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropioate , Pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, ethylene glycol (3-mercaptobutyrate), butanediol bis (3-mercapto
  • the colored photosensitive resin composition of the present invention may contain a surfactant in order to improve coatability.
  • the surfactant for example, various types such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used.
  • nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and among them, fluorine-based and silicone-based surfactants are effective in terms of coatability.
  • fluorine-based and silicone-based surfactants are effective in terms of coatability.
  • these commercially available products include “BM-1000” and “BM-1100” manufactured by BM Chemie, “Megafuck F-142D”, “Megafuck F-172”, and “Megafuck F-173” manufactured by DIC.
  • silicone surfactant examples include “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “8032Additive”, “SH8400” manufactured by Toray Dow Corning, Commercial products such as “BYK300”, “BYK323”, “BYK325”, “BYK330”, and “KP340” manufactured by Shin-Etsu Silicone are available.
  • Surfactants may include those other than fluorosurfactants and silicone surfactants.
  • Other surfactants include nonionic surfactants, anionic surfactants, and cationic surfactants. An activator, an amphoteric surfactant, etc. are mentioned.
  • surfactant may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
  • a combination of silicone surfactant / fluorine surfactant is preferable.
  • this silicone surfactant / fluorine surfactant combination for example, “BYK-300” or “BYK-330” manufactured by Big Chemie / “F-475”, “F-478”, “F-554” manufactured by DIC Or “F-559”.
  • the colored photosensitive resin composition of the present invention may contain a liquid repellent agent.
  • a liquid repellent By containing a liquid repellent, it can impart liquid repellency to the surface of the partition wall, and thus the resulting partition wall can prevent color mixing for each pixel of the organic layer.
  • the liquid repellent include a silicone-containing compound and a fluorine-based compound, and preferably include a liquid repellent having a crosslinking group (hereinafter sometimes referred to as “crosslinking group-containing liquid repellent”).
  • crosslinking group examples include an epoxy group or an ethylenically unsaturated group, and an ethylenically unsaturated group is preferable from the viewpoint of suppressing the outflow of the liquid repellent component of the developer.
  • the crosslinkable group-containing liquid repellent when used, when the formed coating film is exposed, the cross-linking reaction on the surface can be accelerated, and the liquid repellent is less likely to flow out during the development process. Can be considered to exhibit high liquid repellency.
  • the fluorine-based compound When a fluorine-based compound is used as the liquid repellent, the fluorine-based compound tends to be aligned on the surface of the partition wall and function to prevent ink bleeding and color mixing. More specifically, the group having a fluorine atom tends to function to repel ink and prevent ink bleeding and color mixing due to the ink entering the adjacent region beyond the partition wall.
  • crosslinkable group-containing liquid repellent particularly the ethylenically unsaturated group-containing fluorine-based compound
  • the crosslinkable group-containing liquid repellent particularly the ethylenically unsaturated group-containing fluorine-based compound
  • the crosslinkable group-containing liquid repellent particularly the ethylenically unsaturated group-containing fluorine-based compound
  • the crosslinkable group-containing liquid repellent particularly the ethylenically unsaturated group-containing fluorine-based compound
  • the crosslinkable group-containing liquid repellent particularly the ethylenically unsaturated group-containing fluorine-based compound
  • perfluoroalkylsulfonic acid perfluoroalkylcarboxylic acid
  • perfluoroalkylalkylene oxide adduct perfluoroalkyltrialkylammonium salt
  • Oligomers containing perfluoroalkyl groups and hydrophilic groups Oligomers containing perfluoroalkyl groups and lipophilic groups, oligomers containing perfluoroalkyl groups, hydrophilic groups and lipophilic groups, urethanes containing perfluoroalkyl groups and hydrophilic groups, Mention may be made of fluorine-containing organic compounds such as fluoroalkyl esters and perfluoroalkyl phosphate esters.
  • fluorine-containing compounds include “DEFENSAMCF-300”, “DEFENSAMCF-310”, “DEFENSAMCF-312”, “DEFENSAMCF-323”, “Megafuck RS-72-K” manufactured by DIC, 3M Japan “FLORARD FC-431”, “FLORARD FC-4430”, “FLORARD FC-4432” manufactured by Asahi Glass Co., Ltd.
  • the fluorine atom content ratio in the liquid repellent is not particularly limited, but the fluorine atom content ratio is preferably 1% by mass or more, more preferably 5% by mass or more. Moreover, 50 mass% or less is preferable, and 25 mass% or less is more preferable. There exists a tendency which shows a high contact angle by setting it as the said lower limit or more, and there exists a tendency which can suppress the outflow to a pixel part by setting it as the said upper limit or less.
  • the molecular weight of the liquid repellent is not particularly limited, and may be a low molecular weight compound or a high molecular weight substance.
  • the high molecular weight liquid repellent is preferable because the flow of the liquid repellent due to firing is suppressed, and thus the liquid repellent tends to be prevented from flowing out of the partition wall.
  • the number average molecular weight of the liquid repellent is 100 or more, 500 or more is more preferable, 100,000 or less is preferable, and 10,000 or less is more preferable.
  • the content ratio of the liquid repellent in the colored photosensitive resin composition of the present invention is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more with respect to the total solid content.
  • the amount is usually 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.3% by mass or less.
  • the colored photosensitive resin composition of the present invention may contain an ultraviolet absorber.
  • the ultraviolet absorber is added for the purpose of controlling the photocuring distribution by absorbing a specific wavelength of a light source used for exposure by the ultraviolet absorber.
  • the addition of the ultraviolet absorber tends to improve the taper angle and shape after development, or eliminate the residue remaining in the non-exposed area after development.
  • the ultraviolet absorber from the viewpoint of inhibiting the light absorption of the initiator, for example, a compound having an absorption maximum between wavelengths of 250 nm to 400 nm can be used.
  • a benzotriazole compound and / or a triazine compound is desirable.
  • benzotriazole compounds examples include 2- (5 methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, and octyl-3 [3-tert-butyl.
  • benzotriazole-based compounds examples include Sumisorb 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83 (manufactured by Johoku Chemical Industry Co., Ltd.), TINUVIN PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN 326, TINUVIN900, TINUVIN 928, TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSO B78, EVERSORB80, EVERSORB81 (manufactured by Taiwan Eiko Chemical Industry Co., Ltd.), Tomi
  • Triazine compounds include 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 , 6-Bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl-glycidic acid ester reaction product, 2,4-bis "2-hydroxy-4-butoxyphenyl"- Examples include 6- (2,4-dibutoxyphenyl) -1,3-5-triazine, etc.
  • hydroxyphenyltriazine compounds are preferable from the viewpoint of taper angle and exposure sensitivity.
  • examples of commercially available triazine compounds include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479 (manufactured by BASF).
  • the colored photosensitive resin composition of the present invention may contain a polymerization inhibitor. Since it inhibits radical polymerization by containing a polymerization inhibitor, the taper angle of the resulting cured product tends to be increased.
  • the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, 2,6-di-tert-butyl-4-cresol, hydroquinone or methoxyphenol is preferable from the viewpoint of the ability to inhibit polymerization.
  • the polymerization inhibitor preferably contains one or more kinds.
  • a polymerization inhibitor may be contained in the resin, and in addition to the polymerization inhibitor contained in the resin, the same or different polymerization inhibitor is photosensitive. You may add at the time of resin composition manufacture.
  • the content of the polymerization inhibitor in the colored photosensitive resin composition is usually 0.0005% by mass or more, preferably 0.001% by mass or more, more preferably based on the total solid content of the colored photosensitive resin composition. It is 0.01 mass% or more, and is 0.1 mass% or less normally, Preferably it is 0.08 mass% or less, More preferably, it is 0.05 mass% or less. There exists a tendency which can make a taper angle high by setting it as the said lower limit or more, and there exists a tendency which can maintain a high sensitivity by setting it as the said upper limit or less.
  • the colored photosensitive resin composition of the present invention further improves the strength of the cured product and (C) moderate interaction with the binder resin (formation of a matrix structure).
  • an inorganic filler may be contained. Examples of such inorganic fillers include talc, silica, alumina, barium sulfate, magnesium oxide, and those obtained by surface treatment 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 diameter referred to in the present embodiment is a value measured with a laser diffraction / scattering particle size distribution measuring device such as manufactured by Beckman Coulter.
  • silica sol and silica sol modified product are particularly preferably blended because they tend to be excellent in the effect of improving the taper angle as well as the dispersion stability.
  • the content is usually 5% by mass or more, preferably 10% by mass or more, based on the total solid content, from the viewpoint of sensitivity. Yes, usually 80% by mass or less, preferably 70% by mass or less.
  • the colored photosensitive resin composition and the pigment dispersion of the present invention usually contain a solvent. By including a solvent, a colorant such as a pigment can be dispersed in the solvent, and the coating becomes easy.
  • the colored photosensitive resin composition of the present invention usually contains (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, (E) a photopolymerization initiator, and as necessary.
  • Various other materials used are used in a state of being dissolved or dispersed in a solvent.
  • a colorant (B) a dispersant, (C) a binder resin and other various materials used as necessary are usually dissolved or dispersed in a solvent. Used in state.
  • organic solvents are preferable from the viewpoints of dispersibility and coatability.
  • organic solvents those having a boiling point in the range of 100 to 300 ° C. (under a pressure of 101.25 hPa, hereinafter the same applies to the boiling points) are preferably selected from the viewpoint of applicability, and the boiling point is 120 to 280 ° C. It is more preferable to select the thing of the range.
  • organic solvents include the following. 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, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl Ether, tri Chi glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether; Glycol dialkyl ethers such as ethylene glycol mono
  • acetone Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones; Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol; aliphatic hydrocarbons such as n-pentan
  • Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, ⁇ -butyrolactone; Alkoxycarboxylic acids such as 3-methoxy
  • organic solvents corresponding to the above include mineral spirits, Valsol # 2, Apco # 18 solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“Cerosolve” is a registered trademark, the same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any Product name). These organic solvents may be used alone or in combination of two or more.
  • an organic solvent having a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120 to 170 ° C.
  • glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.
  • glycol alkyl ether acetates may be used alone or in combination with other organic solvents.
  • glycol monoalkyl ethers are particularly preferable.
  • propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition.
  • glycol monoalkyl ethers are highly polar, and if the addition amount is too large, the pigment is likely to aggregate, and the storage stability such as the viscosity of the colored photosensitive resin composition obtained later tends to decrease. Therefore, the proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.
  • an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”).
  • high boiling point solvent an organic solvent having a boiling point of 150 ° C. or higher
  • the colored photosensitive resin composition is difficult to dry, but has an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. . That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation or solidification of a colorant or the like at the tip of the slit nozzle.
  • diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred because of their high effects.
  • the content of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass.
  • the drying temperature of the composition Tends to be able to suppress slowing down and to prevent problems such as tact failure in the vacuum drying process and pre-baked pin marks
  • the high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is separately contained. It doesn't have to be.
  • Preferred high boiling solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.
  • the content ratio of (A) the colorant is usually 20% by mass or more and preferably 25% by mass or more with respect to the total solid content in the colored photosensitive resin composition. 30% by mass or more, more preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass or less, and 40% by mass or less. Even more preferably.
  • a sufficient optical density (OD) tends to be obtained, and when it is at most the upper limit, sufficient image formability tends to be ensured.
  • the combination of the upper limit and the lower limit is preferably 20 to 60% by mass, more preferably 25 to 50% by mass, further preferably 30 to 45% by mass, and particularly preferably 30 to 40% by mass.
  • the content ratio of (A1) organic black pigment to (A) colorant is usually 10% by mass or more, preferably 30% by mass or more, more preferably. It is 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and usually 100% by mass or less.
  • the combination of the upper limit and the lower limit is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, further preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, and 80 to 100% by mass. Particularly preferred is 90 to 100% by mass.
  • the (A) colorant may contain (A2) an organic color pigment together with (A1) the organic black pigment.
  • the content ratio of (A1) organic black pigment to (A) colorant is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and usually 90% by mass or less, preferably It is 80 mass% or less, More preferably, it is 60 mass% or less.
  • the content ratio of the (A2) organic coloring pigment is usually 10% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, and usually 90% by mass or less, preferably 80% by mass or less. More preferably, it is 70 mass% or less.
  • the taper angle tends to be lowered by setting it to the lower limit value or more, and a black-colored coating film tends to be obtained by setting the upper limit value or less.
  • the content ratio of (A1) organic black pigment to (A2) 100 parts by weight of organic color pigment is usually 15 parts by weight or more, preferably 20 parts by weight or more, usually 900 parts by weight or less, preferably 800 parts by weight or less. Preferably it is 500 mass parts or less, More preferably, it is 200 mass parts or less.
  • the colorant may contain (A3) carbon black together with (A1) the organic black pigment.
  • the content ratio of the (A1) organic black pigment to (A) the colorant is usually 50% by mass or more, preferably 60% by mass or more, and usually 95% by mass or less, preferably 90% by mass or less.
  • the content of (A3) carbon black is usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less.
  • the content ratio of (A1) organic black pigment to (A3) 100 parts by mass of carbon black is usually 100 parts by mass or more, preferably 150 parts by mass or more, and usually 2000 parts by mass or less, preferably 1000 parts by mass or less.
  • the colorant may contain (A2) an organic color pigment and (A3) carbon black together with (A1) the organic black pigment.
  • the content ratio of the (A1) organic black pigment to (A) the colorant is usually 10% by mass or more, preferably 20% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less.
  • the content rate of (A2) organic coloring pigment is 10 mass% or more normally, Preferably it is 20 mass% or more, and is 60 mass% or less normally, Preferably it is 50 mass% or less.
  • the content ratio of (A3) carbon black is usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less.
  • the content ratio of (A1) organic black pigment to 100 parts by mass of (A2) organic coloring pigment is usually 15 parts by mass or more, preferably 20 parts by mass or more, usually 800 parts by mass or less, preferably 700 parts by mass or less. is there.
  • the content ratio of (A1) organic black pigment to (A3) 100 parts by mass of carbon black is usually 40 parts by mass or more, preferably 50 parts by mass or more, and usually 1000 parts by mass or less, preferably 900 parts by mass or less.
  • the content rate of a dispersing agent is 1 mass% or more normally in solid content of a coloring photosensitive resin composition, 3 mass% or more is preferable, 5 mass% or more is more preferable, and usually 30 mass% or less. 20 mass% or less is preferable, 15 mass% or less is more preferable, and 10 mass% or less is further more preferable.
  • the combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, further preferably 5 to 15% by mass, and particularly preferably 5 to 10% by mass.
  • the content ratio of the (B) dispersant with respect to 100 parts by mass of the (A) colorant is usually preferably 5 parts by mass or more and 10 parts by mass or more, and is usually preferably 50 parts by mass or less and 30 parts by mass or less.
  • the amount is not less than the lower limit, dispersibility tends to be good, and when the amount is not more than the upper limit, excess dispersant can be reduced, and developability tends to be good.
  • the combination of the upper limit and the lower limit is preferably 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass.
  • the content ratio of the acrylic dispersant is not particularly limited, but is usually 1% by mass or more in the solid content of the colored photosensitive resin composition. It is preferably at least 5% by mass, more preferably at least 5% by mass, usually at most 30% by mass and at most 20% by mass, more preferably at most 15% by mass and even more preferably at most 10% by mass.
  • the amount is not less than the lower limit, dispersibility tends to be good, and when the amount is not more than the upper limit, excess dispersant can be reduced, and developability tends to be good.
  • the combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, further preferably 5 to 15% by mass, and particularly preferably 5 to 10% by mass.
  • (A) the content ratio of the acrylic dispersant to 100 parts by mass of the colorant is: Usually 5 parts by mass or more and 10 parts by mass or more are preferable, and usually 50 parts by mass or less and 30 parts by mass or less are preferable.
  • the combination of the upper limit and the lower limit is preferably 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass.
  • the content rate of binder resin is not specifically limited, It is 5 mass% or more normally with respect to the total solid of the colored photosensitive resin composition of this invention, Preferably it is 10 mass% or more, More preferably, it is 20 mass%. Or more, more preferably 30% by mass or more, particularly preferably 40% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less. .
  • the amount is not less than the lower limit value, a strong film tends to be obtained, and when the amount is not more than the upper limit value, the penetration of the developer into the exposed area is suppressed, and the surface smoothness and sensitivity of the film are reduced.
  • the combination of the upper limit and the lower limit is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, further preferably 20 to 60% by mass, still more preferably 30 to 50% by mass, and 40 to 50% by mass. Particularly preferred is mentioned.
  • the content ratio of the (C1) epoxy (meth) acrylate resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass with respect to the total solid content of the colored photosensitive resin composition of the present invention. Or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, particularly preferably 40% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, More preferably, it is 50 mass% or less.
  • the combination of the upper limit and the lower limit is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, further preferably 20 to 60% by mass, still more preferably 30 to 60% by mass, and 35 to 60% by mass. Particularly preferred is 40 to 50% by mass.
  • the content ratio of the meth) acrylate resin is not particularly limited, but is preferably 75% by mass or more, more preferably 80% by mass or more, and 85% by mass or more. Is more preferably 90% by mass or more, and particularly preferably 95% by mass or more. Moreover, it is 100 mass% or less normally. There exists a tendency for outgas suitability to become favorable by setting it as the said lower limit or more.
  • the combination of the upper limit and the lower limit is preferably 75 to 100% by mass, more preferably 80 to 100% by mass, further preferably 85 to 100% by mass, still more preferably 90 to 100% by mass, and 95 to 100% by mass. Particularly preferred is mentioned.
  • the content of the photopolymerizable monomer is usually 1% by mass or more, preferably 5% by mass or more, more preferably 8% by mass or more, based on the total solid content of the colored photosensitive resin composition. Usually, it is 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less. When it is at least the lower limit, the sensitivity tends to be high, and when it is at most the upper limit, the developability tends to be good.
  • the combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, and further preferably 8 to 15% by mass.
  • the content rate of a photoinitiator is 0.1 mass% or more normally with respect to the total solid of the colored photosensitive resin composition of this invention, Preferably it is 0.5 mass% or more, More preferably, it is 1 % By mass or more, more preferably 2% by mass or more, particularly preferably 3% by mass or more, and usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less. It is. There exists a tendency for favorable sensitivity to be acquired by setting it as the said lower limit or more, and there exists a tendency which can ensure the quantity of binder resin and photopolymerizable monomer suitable for image development by setting it as the said upper limit or less.
  • the combination of the upper limit and the lower limit is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, further preferably 1 to 8% by mass, still more preferably 2 to 5% by mass, and 3 to 3% by mass. 5% by mass is particularly preferable.
  • the content of the polymerization accelerator is preferably 0.05% by mass or more based on the total solid content of the colored photosensitive resin composition of the present invention.
  • the amount is usually 10% by mass or less, preferably 5% by mass or less.
  • the polymerization accelerator is usually 0.1 parts by mass or more, preferably 0.2 parts by mass or more, and usually 100 parts by mass or less, preferably 50 parts by weight with respect to 100 parts by mass of the photopolymerization initiator (D). It is as follows.
  • the blending ratio of the sensitizing dye in the colored photosensitive resin composition of the present invention is usually 0.5% by mass or more, preferably in the total solid content in the colored photosensitive resin composition, from the viewpoint of sensitivity. 1% by mass or less, usually 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less.
  • the content ratio is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.8% by mass with respect to the total solid content in the colored photosensitive resin composition. 4 to 2% by mass.
  • the content is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably the total solid content in the colored photosensitive resin composition. 0.01 to 0.5% by mass, most preferably 0.03 to 0.3% by mass.
  • the content of the surfactant is not less than the above lower limit value, the coating film tends to have smoothness and uniformity, and when it is not more than the upper limit value, the occurrence of unevenness tends to be suppressed.
  • the colored photosensitive resin composition of the present invention is prepared using the above-mentioned organic solvent so that the solid content concentration is usually 5 to 50% by mass, preferably 10 to 30% by mass.
  • the colored photosensitive resin composition of the present invention can be suitably used for forming a black matrix in addition to the partition walls and the colored spacers. From this viewpoint, the colored photosensitive resin composition is preferably black and has a coating film thickness of 1 ⁇ m.
  • the hit optical density (OD) is preferably 0.5 or more, more preferably 0.8 or more, further preferably 1.0 or more, and particularly preferably 1.3 or more. .
  • the color tone when applied to a member having a high area ratio in the image display area of the image display device, such as a partition wall of an organic electroluminescent element, the color tone is preferably closer to black.
  • the chromaticity x when cured is preferably 0.20 or more, more preferably 0.25 or more, further preferably 0.30 or more, and It is preferably 50 or less, more preferably 0.45 or less, and further preferably 0.40 or less.
  • the chromaticity y is preferably 0.20 or more, more preferably 0.25 or more, further preferably 0.30 or more, and preferably 0.50 or less. 0.45 or less, more preferably 0.40 or less.
  • pigment dispersion liquid of the present invention contains (A) a colorant, (B) a dispersant, and (C) a binder resin. Usually, it also contains a solvent. Moreover, the pigment dispersion liquid of this invention can be conveniently used as one of the raw materials used when manufacturing a colored photosensitive resin composition as mentioned later.
  • the colorant contains the aforementioned (A1) organic black pigment.
  • a coating film obtained by applying a colored photosensitive resin composition produced using a pigment dispersion containing an organic black pigment can achieve a high resistance, a low dielectric constant and a high light-shielding rate. There is a tendency to be a cured product having a close color tone.
  • a dispersing agent contains an acrylic type dispersing agent. There exists a tendency for the pattern adhesiveness at the time of image development to become favorable by manufacturing a coloring photosensitive resin composition using the pigment dispersion liquid containing an acrylic type dispersing agent.
  • (C) binder resin contains (C1) epoxy (meth) acrylate resin. (C1) By producing a colored photosensitive resin composition using a pigment dispersion containing an epoxy (meth) acrylate resin, the amount of outgas generated after the cured product tends to be reduced.
  • the content ratio of (A) the colorant is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, based on the total solid content in the pigment dispersion. More preferably 40% by weight or more, still more preferably 50% by weight or more, particularly preferably 55% by weight or more, and usually 100% by weight or less, preferably 80% by weight or less, more preferably 70% by weight or less, and further preferably. Is 60% by mass or less.
  • a coloring photosensitive resin composition can be manufactured with suitable solid content concentration, and there exists a tendency for a dispersibility to become favorable by setting it as the said upper limit or less.
  • the combination of the upper limit and the lower limit is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, further preferably 30 to 70% by mass, still more preferably 40 to 70% by mass, and 50 to 60% by mass. Particularly preferred is 55 to 60 mass.
  • the content of the (B) dispersant is usually 2% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content in the pigment dispersion. Moreover, it is 50 mass% or less normally, Preferably it is 40 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less, Most preferably, it is 15 mass% or less. Dispersibility tends to be good when the amount is not less than the lower limit value, and excess dispersant can be reduced by being not more than the upper limit value, and the developability of the resulting colored photosensitive resin composition becomes good.
  • the combination of the upper limit and the lower limit is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, further preferably 5 to 30% by mass, still more preferably 5 to 20% by mass, and more preferably 10 to 15% by mass. Particularly preferred is mentioned.
  • the content of the acrylic dispersant is usually 2% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content in the pigment dispersion.
  • the amount is usually 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less.
  • the dispersibility is good when the amount is not less than the lower limit and the pattern adhesiveness is good when the cured product is developed, and the colored photosensitive resin composition obtained by being not more than the upper limit is used.
  • the combination of the upper limit and the lower limit is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, further preferably 5 to 30% by mass, still more preferably 5 to 20% by mass, and more preferably 10 to 15% by mass. Particularly preferred is mentioned.
  • the content ratio of (C) the binder resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, based on the total solid content in the pigment dispersion. More preferably, it is 20% by mass or more, particularly preferably 25% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less. Dispersibility tends to be good when the amount is not less than the above lower limit value, and the amount of the colorant in the colored photosensitive resin composition obtained by being not more than the above upper limit value can be optimized, and sufficient light shielding properties can be obtained. Tends to be secured.
  • the combination of the upper limit and the lower limit is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, further preferably 15 to 35% by mass, still more preferably 20 to 35% by mass, and 25 to 30% by mass. Particularly preferred is mentioned.
  • the content ratio of the (C1) epoxy (meth) acrylate resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% with respect to the total solid content in the pigment dispersion.
  • % By mass or more, more preferably 20% by mass or more, particularly preferably 25% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less. It is. There is a tendency that the outgas suitability of the cured product is good by setting it to the lower limit value or more, and the amount of the colorant in the colored photosensitive resin composition obtained by setting the upper limit value or less can be optimized.
  • the combination of the upper limit and the lower limit is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, further preferably 15 to 35% by mass, still more preferably 20 to 35% by mass, and 25 to 30% by mass. Particularly preferred is mentioned.
  • the pigment dispersion of the present invention is prepared using the above-mentioned organic solvent so that the solid content concentration is usually 5 to 50% by mass, preferably 10 to 30% by mass.
  • the colored photosensitive resin composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method. Usually, it is preferable to disperse the colorant (A) in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the colorant (A) is finely divided by the dispersion treatment, the coating characteristics of the resist are improved.
  • the dispersion treatment is usually preferably carried out in a system in which (A) a colorant, an organic solvent, (B) a dispersant, and (C) a part or all of a binder resin are used in combination (hereinafter, the dispersion treatment is used.
  • the mixture and the composition obtained by the treatment may be referred to as “ink” or “pigment dispersion”).
  • a polymer dispersant as the dispersant (B) because the resulting ink and resist are prevented from thickening with time (excellent in dispersion stability).
  • a pigment dispersion containing at least (A) a colorant, an organic solvent, and (B) a dispersant.
  • a highly reactive component may be denatured due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
  • the colorant (A) is dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used.
  • the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C.
  • the dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment apparatus, and the like.
  • the standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the resist is in the range of 50 to 300.
  • the glossiness of the resist By setting the glossiness of the resist to the above lower limit or more, the dispersion treatment is not sufficient, and the remaining of the rough pigment (colorant) particles can be suppressed, and the developability, adhesion, resolution, and the like tend to be sufficient.
  • the gloss value to be equal to or less than the above upper limit value, it is possible to avoid the occurrence of a large number of ultrafine particles by crushing the pigment, and the dispersion stability tends to be maintained.
  • the dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 ⁇ m, and is measured by a dynamic light scattering method or the like.
  • the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution.
  • fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered by a filter or the like.
  • Cured product and formation method thereof [4] Cured product A cured product can be obtained by curing the colored photosensitive resin composition of the present invention.
  • the cured product composed of the colored photosensitive resin composition can be suitably used as a partition wall and a colored spacer.
  • the colored photosensitive resin composition of the present invention can be suitably used for forming a partition wall, particularly a partition wall for partitioning an organic layer of an organic electroluminescence device.
  • the organic layer used in the organic electroluminescence device include a hole injection layer, a hole transport layer, or a hole transport layer on the hole injection layer as described in Japanese Patent Application Laid-Open No. 2016-165396. The organic layer to be used is mentioned.
  • the colored photosensitive resin composition of the present invention can be suitably used as a resist for colored spacers other than the partition walls.
  • the TFT may malfunction as a switching element due to light incident on the TFT, and a colored spacer is used to prevent this (for example, Japanese Patent Laid-Open No. 8-234212). Issue gazette).
  • the support for forming the partition walls and the colored spacer is not particularly limited as long as it has an appropriate strength.
  • a transparent substrate is mainly used, but the material is, for example, a polyester resin such as polyethylene terephthalate, a polyolefin resin such as polypropylene or polyethylene, a sheet made of a thermoplastic resin such as polycarbonate, polymethyl methacrylate or polysulfone, or an epoxy resin. And thermosetting resin sheets such as unsaturated polyester resins and poly (meth) acrylic resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.
  • a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Other than the transparent substrate, it can be formed on the TFT array.
  • the support may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc., if necessary, in order to improve surface properties such as adhesiveness.
  • the thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. When a thin film forming process of various resins is performed, the film thickness is usually 0.01 to 10 ⁇ m, preferably 0.05 to 5 ⁇ m.
  • the coating of the colored photosensitive resin composition on the substrate is performed by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, or a spray coating. This can be done by law.
  • the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.
  • the thickness of the coating film is usually preferably in the range of 0.2 to 10 ⁇ m, more preferably in the range of 0.5 to 6 ⁇ m, and still more preferably in the range of 1 to 4 ⁇ m, as the film thickness after drying. is there.
  • the coating film after the colored photosensitive resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, IR oven, or convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like.
  • the drying time is usually selected within the range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes. The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate.
  • the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.
  • Exposure Image exposure is performed by overlaying a negative mask pattern on the coating film of the colored photosensitive resin composition and irradiating a UV or visible light source through this mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen.
  • the light source used for said image exposure is not specifically limited.
  • a xenon lamp, a halogen lamp, a tungsten lamp for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser
  • Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser.
  • An optical filter can also be used
  • the partition walls and colored spacers according to the present invention are obtained by subjecting a coating film made of a colored photosensitive resin composition to image exposure with the above-mentioned light source, and then an organic solvent or a surfactant and an alkaline property.
  • An image can be formed on a substrate by development using an aqueous solution containing a compound.
  • This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
  • Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate
  • Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine , Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc.
  • Organic alkaline compounds. These alkaline compounds may be a mixture of two or more.
  • surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids.
  • nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids.
  • anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters
  • amphoteric surfactants such as alkylbetaines and amino acids.
  • organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like.
  • the organic solvent may be used alone or in combination with an aqueous solution.
  • the development processing conditions are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C., particularly 15 to 45 ° C., particularly preferably 20 to 40 ° C.
  • the development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.
  • thermosetting treatment The substrate after development is subjected to thermosetting treatment or photocuring treatment, preferably thermosetting treatment.
  • the thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C., preferably in the range of 150 to 250 ° C., and the time is in the range of 5 to 60 minutes.
  • Organic electroluminescent device includes a cured product composed of the above-mentioned colored photosensitive resin composition, for example, a partition.
  • various organic electroluminescent elements are manufactured using a substrate having a partition pattern manufactured by the method described above.
  • the method for forming the organic electroluminescent element is not particularly limited, but preferably, after the pattern of the partition is formed on the substrate by the above method, the functional material is sublimated in a vacuum state, and the region within the region surrounded by the partition on the substrate is formed.
  • An organic electroluminescent element is manufactured by forming an organic layer such as a pixel by a wet process such as a vapor deposition method in which a film is attached to the film, a casting method, a spin coating method, or an ink jet printing method.
  • an organic electroluminescent element When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent light from the light emitting layer of a certain pixel from leaking to other pixels. Since it is necessary to prevent deterioration of image quality due to light reflection, it is preferable to provide light shielding properties to the partition walls constituting the organic electroluminescent element. Moreover, in an organic electroluminescent element, since it is necessary to provide an electrode on the upper surface and lower surface of a partition, it is preferable that a partition has high resistance and a low dielectric constant from an insulating viewpoint. Therefore, when a colorant is used to impart light shielding properties to the partition walls, it is preferable to use the (A1) organic black pigment having a high resistance and a low dielectric constant.
  • the image display device of the present invention is not particularly limited as long as it is a device that displays an image or video, and examples thereof include a liquid crystal display device and an organic EL display device.
  • a liquid crystal display device containing the above-mentioned coloring spacer
  • the organic EL display device containing the above-mentioned organic electroluminescent element, etc. are mentioned.
  • the liquid crystal display device is not particularly limited in type and structure as long as it includes the above-described colored spacer.
  • the black matrix of the present invention is provided on a TFT element substrate, red, green and blue pixels are formed, an overcoat layer is formed as necessary, and further, ITO and IZO are formed on the image.
  • ITO and IZO are formed on the image.
  • the transparent electrode may not be formed.
  • an alignment film is formed on a color filter, a photo spacer is formed on the alignment film, and then a liquid crystal cell is formed by bonding to a counter substrate. A liquid crystal is injected into the formed liquid crystal cell and connected to a counter electrode. And completed.
  • a resin film such as polyimide is suitable.
  • a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm.
  • the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.
  • Organic EL display device As long as the organic EL display device includes the organic electroluminescence element described above, there is no particular limitation on the type and structure of the image display device.
  • the device can be assembled according to a conventional method.
  • the image display device of the present invention is formed by a method as described in “Organic EL Display” (Ohm, published on August 20, 2004, by Shizushi Tokito, Chiba Adachi, and Hideyuki Murata). can do.
  • an organic electroluminescent element that emits white light and a color filter may be combined to display an image, or organic electroluminescent elements having different emission colors such as RGB may be combined to display an image.
  • the illumination of the present invention includes the organic electroluminescent element described above. There is no restriction
  • the organic electroluminescence element may be a simple matrix driving method or an active matrix driving method.
  • an organic electroluminescent element that emits white light may be used.
  • organic electroluminescent elements having different emission colors may be combined so that each color is mixed to become white, or the color mixing ratio can be adjusted to provide a color adjustment function.
  • ⁇ Binder resin-I> “ZCR-1642H” weight average molecular weight (Mw) 6500, acid value 98 mgKOH / g, carboxyl group-containing epoxy (meth) acrylate resin) manufactured by Nippon Kayaku Co., Ltd.
  • This resin corresponds to (C1-1), has a repeating unit structure represented by the chemical formula (II-1), R 11 is a methyl group, and R 12 is represented by the formula (II-A).
  • R X is a tetrahydrophthalic acid residue.
  • Binder Resin-IV having an acid value of 110 mgKOH / g and a weight average molecular weight (Mw) of 2800. This resin corresponds to (C1-2).
  • the binder resin-V thus obtained had a weight average molecular weight (Mw) of about 8400, an acid value of 80 mgKOH / g, and a double bond equivalent of 480 g / mol.
  • Acrylic AB block consisting of A block having quaternary ammonium base and tertiary amino group in the side chain and B block having no quaternary ammonium base and tertiary amino group
  • Polymer.Amine value is 70 mgKOH / g.
  • Acid value is 1 mgKOH / g or less.
  • the A block of Dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains repeating units of the following formula (3a).
  • the content of the repeating units of the following formulas (1a), (2a), and (3a) in all the repeating units of Dispersant-I is 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. is there.
  • ⁇ Oxime ester body> The oxime (2.22 g, 4.77 mmol) and acetyl chloride (1.34 g, 17.0 mmol) were added to 20 mL of dichloromethane and ice-cooled. Triethylamine (1.77 g, 17.5 mmol) was added dropwise, and 1 Reacted for hours. After confirming disappearance of the raw material by thin layer chromatography, water was added to stop the reaction. The reaction mixture was washed twice with 5 mL of saturated aqueous sodium hydrogen carbonate solution, twice with 5 mL of saturated brine, and dried over anhydrous sodium sulfate.
  • This solution was subjected to a dispersion treatment in the range of 25 to 45 ° C. for 3 hours using a paint shaker.
  • the beads 0.5 mm ⁇ zirconia beads were used, and 2.5 times the mass of the dispersion was added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare pigment dispersions 1 to 6.
  • Examples 1 to 6 Reference Example 1, and Comparative Example 1
  • each component was added so that the ratio in the solid content was the mixing ratio shown in Table 2, and PGMEA was further adjusted so that the total solid content was 22% by mass.
  • the mixture was stirred and dissolved to prepare a colored photosensitive resin composition.
  • a pattern was prepared by the method described later and evaluated.
  • Each colored photosensitive resin composition was applied onto an ITO substrate (a glass substrate on which ITO having a thickness of 1500 mm was deposited) using a spinner. Subsequently, it heated and dried on the hotplate at 100 degreeC for 80 second, and the coating film was formed.
  • the obtained coating film was subjected to an exposure treatment using an exposure mask having line-shaped openings having various opening widths of 5 to 50 ⁇ m (5 to 20 ⁇ m: every 1 ⁇ m, 25 to 50 ⁇ m: every 5 ⁇ m).
  • the exposure gap (distance between the exposure mask and the coated surface) was 5 ⁇ m.
  • the irradiation light intensity at a wavelength 365nm is used ultraviolet is 32 mW / cm 2, the exposure amount was 60 mJ / cm 2. Moreover, ultraviolet irradiation was performed under air.
  • ⁇ Outgas evaluation method About 3 mg of the coating film was cut out from the substrate of pattern 2 to obtain a sample for outgas measurement. Using TG-DTA6300 (manufactured by Hitachi High-Tech Science Co., Ltd.), the sample was heated from room temperature to 500 ° C. at 10 ° C./min in an air atmosphere (Flow 200 ml / min), and the weight loss at that time was measured. Table 2 shows the weight loss (% by mass) when the temperature increased from room temperature to 400 ° C. with respect to the total amount of binder resin contained in each colored photosensitive resin composition.
  • Example 1 weight reduction amount (mass%) when it rose from room temperature to 400 degreeC with respect to the total solid of each coloring photosensitive resin composition is Example 1: 26.8, Example 2: 30.2, implementation.
  • ⁇ Chromaticity> Using the substrate of the pattern 2 of Example 1, a spectrophotometer UV-3100 (manufactured by Shimadzu Corporation), using an aluminum vapor-deposited plate as a reference plate, and having a specular reflectance of 5 degrees at a wavelength of 380 to 780 nm. Measured from the side, the chromaticity (D65 light source) in the XYZ color system was calculated.
  • the coated substrates using the colored photosensitive resin compositions of Examples 1 to 6 and Reference Example 1 were excellent in outgas characteristics.
  • the coated substrate using the colored photosensitive resin composition of Comparative Example 1 has poor outgas characteristics.
  • the colored photosensitive resin compositions of Examples 1 to 6 and Reference Example 1 have a higher content of epoxy (meth) acrylate resin in the binder resin.
  • Epoxy (meth) acrylate resins have a rigid skeleton and are difficult to be thermally decomposed. Also, since the skeleton is rigid, a film having a high crosslinkability is formed by taking an arrangement structure at the time of curing. It is considered that the outgas characteristics were improved by increasing the content of acrylate resin.
  • the coated substrate using the colored photosensitive resin composition of Reference Example 1 has better development adhesion of the fine line pattern.
  • the colored photosensitive resin composition of Reference Example 1 can be sufficiently applied as a partition wall of an organic electroluminescence device having a general resolution.
  • the colored photosensitive resin composition of Examples 1 to 6 has a high resolution. It was suggested that the present invention can also be applied to the partition walls of organic electroluminescence devices. Since the dispersant contained in the colored photosensitive resin composition of Reference Example 1 is not an acrylic dispersant, it is considered that the developer easily penetrates into the film during development, and the fine line pattern hardly remained on the substrate.
  • the dispersant contained in the colored photosensitive resin compositions of Examples 1 to 6 is an acrylic dispersant, it has a flexible main skeleton with a linear molecular structure, so that many of the adsorbing groups are present.
  • the colorant is uniformly dispersed in the colored photosensitive resin composition, and in the resulting coating film, the colorant that is a developer-insoluble component is uniformly arranged to form a dense film, It is considered that the penetration of the developer into the film during development was suppressed, and even a fine line pattern could be formed on the substrate.
  • the colored photosensitive resin compositions of Examples 1 to 6 the colored photosensitive resin compositions obtained by using pigment dispersions 1 to 5 containing an epoxy (meth) acrylate resin as a binder resin were prepared. The content ratio of the epoxy (meth) acrylate resin contained in the product could be increased.

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PCT/JP2017/042773 2016-12-02 2017-11-29 着色感光性樹脂組成物、顔料分散液、隔壁、有機電界発光素子、画像表示装置及び照明 WO2018101314A1 (ja)

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KR1020237014487A KR102739353B1 (ko) 2016-12-02 2017-11-29 착색 감광성 수지 조성물, 안료 분산액, 격벽, 유기 전계 발광 소자, 화상 표시 장치 및 조명
KR1020197012591A KR20190088972A (ko) 2016-12-02 2017-11-29 착색 감광성 수지 조성물, 안료 분산액, 격벽, 유기 전계 발광 소자, 화상 표시 장치 및 조명
KR1020207006805A KR102131590B1 (ko) 2016-12-02 2017-11-29 착색 감광성 수지 조성물, 안료 분산액, 격벽, 유기 전계 발광 소자, 화상 표시 장치 및 조명
CN201780070424.7A CN109952535A (zh) 2016-12-02 2017-11-29 着色感光性树脂组合物、颜料分散液、间隔壁、有机场致发光元件、图像显示装置及照明
JP2018553266A JP6451918B2 (ja) 2016-12-02 2017-11-29 着色感光性樹脂組成物、顔料分散液、隔壁、有機電界発光素子、画像表示装置及び照明
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JPWO2020017576A1 (ja) * 2018-07-20 2021-08-12 三菱ケミカル株式会社 感光性着色樹脂組成物、硬化物、画像表示装置及び照明
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JP2022065931A (ja) * 2020-10-16 2022-04-28 山陽色素株式会社 黒色顔料分散体
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JP2019082692A (ja) 2019-05-30
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