WO2018101314A1 - Colored photosensitive resin composition, pigment dispersion, partition, organic electroluminescent element, image display device, and illumination - Google Patents

Colored photosensitive resin composition, pigment dispersion, partition, organic electroluminescent element, image display device, and illumination Download PDF

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Publication number
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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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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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 KR1020237014487A priority Critical patent/KR20230062678A/en
Priority to CN201780070424.7A priority patent/CN109952535A/en
Priority to KR1020207006805A priority patent/KR102131590B1/en
Priority to JP2018553266A priority patent/JP6451918B2/en
Priority to KR1020197012591A priority patent/KR20190088972A/en
Publication of WO2018101314A1 publication Critical patent/WO2018101314A1/en

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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
    • 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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Abstract

A first problem addressed by the present invention is to provide a colored photosensitive resin composition that is highly reliable due to the amount of outgas after a cured product is formed being less, and that provides excellent adhesion of patterns in a development step during formation of the cured product. The colored photosensitive resin composition according to a first embodiment of the present invention comprises a colorant (A), a dispersant (B), a binder resin (C), a photopolymerizable monomer (D), and a photopolymerization initiator (E), wherein: the colorant (A) contains an organic black pigment (A1) that comprises at least one member selected from the group consisting of a compound represented by general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound; the dispersant (B) contains an acrylic dispersant; and the binder resin (C) contains at least 75 mass% of an epoxy (meth)acrylate resin (C1).

Description

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Colored photosensitive resin composition, pigment dispersion, partition, organic electroluminescent device, image display device and illumination
　本発明は、着色感光性樹脂組成物に関し、また該着色感光性樹脂組成物に用いられる顔料分散液、該着色感光性樹脂組成物で構成される隔壁、該隔壁を備える有機電界発光素子、画像表示装置及び照明に関する。 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.
　液晶ディスプレイ（ＬＣＤ）は液晶への印加電圧のオン・オフにより液晶分子の並び方が切り替わる性質を利用している。一方、ＬＣＤのセルを構成する各部材は、フォトリソグラフィーに代表される、感光性組成物を利用した方法によって形成されるものが多い。この感光性組成物は、微細な構造を形成し易い、大画面用の基板に対して処理がし易いといった理由からも、今後さらに感光性組成物の適用範囲は広がる傾向にある。 Liquid crystal display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by turning on and off the voltage applied to the liquid crystal. On the other hand, 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.
　また、パネル構造及び製造工程の簡便化に伴い、液晶パネルにおける２枚の基板の間隔を一定に保つために使用される、所謂、柱状スペーサーをフォトリソグラフィーで形成する方法が検討され、近年ではフォトスペーサーとブラックマトリクスを一体化した着色スペーサーも開発されている。ただし、この様な着色スペーサーには、通常の形状や圧縮特性以外に、ＴＦＴ素子の上に直接搭載させても電気回路の短絡を起こさない様に、一定以上の体積抵抗率や一定以下の比誘電率を持つことが求められる。
　このような着色スペーサーとしては、顔料に複数種の有機着色顔料を用いたものや、有機黒色顔料を用いたものが提案されている。特許文献１には特定の有機黒色顔料と分散剤を組み合わせることにより優れた分散性、遮光性を有し、また低い比誘電率を有する感光性着色組成物が記載されている。 In addition, with the simplification of the panel structure and manufacturing process, a method for forming a so-called columnar spacer by photolithography, which is used to keep the distance between two substrates in a liquid crystal panel constant, has been studied. A colored spacer that integrates a spacer and a black matrix has also been developed. However, in addition to the normal shape and compression characteristics, such colored spacers have a volume resistivity above a certain level and a ratio below a certain level so as not to cause a short circuit of an electric circuit even when directly mounted on a TFT element. It is required to have a dielectric constant.
As such coloring spacers, those using a plurality of types of organic coloring pigments as pigments and those using organic black pigments have been proposed. 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.
　一方で有機電界発光素子（有機エレクトロルミネセンス、有機ＥＬともいう。）を含む画像表示装置は、コントラストや視野角等の視認性や応答性に優れ、低消費電力化、薄型軽量化、及び、ディスプレイ本体のフレキシブル化が可能であることから、次世代のフラットパネルディスプレイ（ＦＰＤ）として注目を集めている。
　有機電界発光素子は、少なくとも一方が透光性を有する一対の電極間に、発光層あるいは種々の機能層を含む有機層が狭持された構造を有するものである。画像表示装置は画素毎に有機電界発光素子が配置されたパネルを駆動させることにより、画像表示を行うものである。
　従来からこのような有機電界発光素子は、基板上に、隔壁（バンク）を形成した後に、隔壁に囲まれた領域内に、発光層あるいは種々の機能層を積層して製造されている。 On the other hand, 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.
Conventionally, 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.
　隔壁に囲まれた領域内に発光層等を成膜するには、材料を真空状態で昇華させ、基板上に付着させて成膜する蒸着法が主に適用されている。また近年では、キャスト法、スピンコート法、インクジェット印刷法といったウェットプロセスにて成膜する方法が注目されている。特に、インクジェット印刷法は、大面積にした場合の膜厚ムラを低減することができるとともに、塗布時の塗り分けによるディスプレイの高精細化、材料の使用量の削減、歩留まりの向上を図ることが可能となるため、大型パネルにおける有機層の成膜方法として好適である。 In order to form a light emitting layer or the like in a region surrounded by a partition wall, a vapor deposition method in which a material is sublimated in a vacuum state and deposited on a substrate is mainly applied. In recent years, 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. In particular, 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.
　またこれらの隔壁を容易に形成する方法としては、感光性樹脂組成物を用いたフォトリソグラフィー法により形成する方法が知られている。 In addition, as a method of easily forming these partition walls, a method of forming by a photolithography method using a photosensitive resin composition is known.
国際公開第２０１５／０４６１７８号International Publication No. 2015/046178
　近年、画像表示装置等を構成する硬化物を形成した後に、該硬化物から発生するアウトガスを低減する要望がある。特に有機電界発光素子においては、素子発光時に隔壁から発生するアウトガスを低減する要望が強い。有機電界発光素子においては、隔壁等の硬化物から発生するアウトガス量が多いと、素子の寿命の低下を引き起こしてしまう可能性があるからである。 In recent years, there has been a demand to reduce the outgas generated from a cured product that forms an image display device or the like. In particular, in an organic electroluminescence device, there is a strong demand for reducing outgas generated from the partition during device light emission. This is because in an organic electroluminescent device, if the amount of outgas generated from a cured product such as a partition wall is large, the lifetime of the device may be reduced.
　一方で、画像表示装置の中でも高解像度のモデルにおいては、それを構成する硬化物を微細化する必要があり、微細なパターンであっても現像工程において基板等に十分に密着することが要求されている。 On the other hand, in a high-resolution model among image display devices, it is necessary to refine the cured product that constitutes the image display device, and even a fine pattern is required to sufficiently adhere to a substrate or the like in a development process. ing.
　本発明者らが検討したところ、特許文献１に記載の感光性着色組成物では、アウトガスが多く、実用上問題があることが見出された。
　また、特許文献１には有機電界発光素子の隔壁への適用については記載も示唆もなく、本発明者らが有機電界発光素子の隔壁形成用途に検討したところ一般的な解像度のモデルに要求されるサイズのパターンの密着性が十分であることが見出されたものの、高解像度なモデルに要求されるような微細パターンの密着性は十分ではないことが見出された。 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.
　本発明の第１の課題は、硬化物形成後のアウトガス量が少なく信頼性に優れており、また硬化物作成時の現像工程における微細パターンの密着性が良好である着色感光性樹脂組成物を提供することにある。
　また、該着色感光性樹脂組成物を用いて形成された隔壁、該隔壁を備える有機電界発光素子、該有機電界発光素子を含む画像表示装置及び照明を提供することにある。 A first problem of the present invention is a colored photosensitive resin composition that is excellent in reliability with a small amount of outgas after formation of a cured product, and that has good adhesion of a fine pattern in a development process at the time of creating the cured product. It is to provide.
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.
　また本発明の第２の課題は、硬化物形成後のアウトガス量が少なく信頼性に優れる、有機電界発光素子の隔壁を形成するための着色感光性樹脂組成物を提供することにある。
　また、該着色感光性樹脂組成物を用いて形成された隔壁、該隔壁を備える有機電界発光素子、該有機電界発光素子を含む画像表示装置及び照明を提供することにある。 Moreover, 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 | cured material formation, and is excellent in reliability.
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.
　さらに本発明の第３の課題は、第１の課題を解決する感光性樹脂組成物を構成するための顔料分散液を提供することにある。 Furthermore, a third problem of the present invention is to provide a pigment dispersion for constituting a photosensitive resin composition that solves the first problem.
　本発明者らが鋭意検討した結果、特定の有機黒色顔料を含有し、さらに特定のバインダー樹脂を一定量以上含有する着色感光性樹脂組成物等により、上記課題を解決できることを見出し、本発明に至った。
　即ち本発明の要旨は以下の通りである。 As a result of intensive studies by the present inventors, it has been found that the above-mentioned problems can be solved by a colored photosensitive resin composition containing a specific organic black pigment and further containing a specific amount of a specific binder resin. It came.
That is, the gist of the present invention is as follows.
［１］（Ａ）着色剤、（Ｂ）分散剤、（Ｃ）バインダー樹脂、（Ｄ）光重合性モノマー及び（Ｅ）光重合開始剤を含有する着色感光性樹脂組成物であって、
　前記（Ａ）着色剤が、下記一般式（Ｉ）で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも１種を含有する（Ａ１）有機黒色顔料を含み、
　前記（Ｂ）分散剤が、アクリル系分散剤を含み、
　前記（Ｃ）バインダー樹脂が、（Ｃ１）エポキシ（メタ）アクリレート樹脂を７５質量％以上含むことを特徴とする着色感光性樹脂組成物。 [1] 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,
The colored photosensitive resin composition, wherein the (C) binder resin contains 75% by mass or more of (C1) epoxy (meth) acrylate resin.
Figure JPOXMLDOC01-appb-C000010
  
Figure JPOXMLDOC01-appb-C000010
  
（式（Ｉ）中、Ｒａ1及びＲａ6は各々独立に、水素原子、ＣＨ3、ＣＦ3、フッ素原子又は塩素原子を表し；
Ｒａ2、Ｒａ3、Ｒａ4、Ｒａ5、Ｒａ7、Ｒａ8、Ｒａ9及びＲａ10は各々独立に、水素原子、ハロゲン原子、Ｒａ11、ＣＯＯＨ、ＣＯＯＲａ11、ＣＯＯ-、ＣＯＮＨ2、ＣＯＮＨＲａ11、ＣＯＮＲａ11Ｒａ12、ＣＮ、ＯＨ、ＯＲａ11、ＣＯＣＲａ11、ＯＯＣＮＨ2、ＯＯＣＮＨＲａ11、ＯＯＣＮＲａ11Ｒａ12、ＮＯ2、ＮＨ2、ＮＨＲａ11、ＮＲａ11Ｒａ12、ＮＨＣＯＲａ12、ＮＲａ11ＣＯＲａ12、Ｎ＝ＣＨ2、Ｎ＝ＣＨＲａ11、Ｎ＝ＣＲａ11Ｒａ12、ＳＨ、ＳＲａ11、ＳＯＲａ11、ＳＯ2Ｒａ11、ＳＯ3Ｒａ11、ＳＯ3Ｈ、ＳＯ3 -、ＳＯ2ＮＨ2、ＳＯ2ＮＨＲａ11又はＳＯ2ＮＲａ11Ｒａ12を表し；
且つ、Ｒａ2とＲａ3、Ｒａ3とＲａ4、Ｒａ4とＲａ5、Ｒａ7とＲａ8、Ｒａ8とＲａ9、及びＲａ9とＲａ10からなる群から選ばれる少なくとも１つの組み合わせは、互いに直接結合してもよく、又は酸素原子、硫黄原子、ＮＨ若しくはＮＲａ11ブリッジによって互いに結合してもよく；
Ｒａ11及びＲａ12は各々独立に、炭素数１～１２のアルキル基、炭素数３～１２のシクロアルキル基、炭素数２～１２のアルケニル基、炭素数３～１２のシクロアルケニル基又は炭素数２～１２のアルキニル基を表す。）
［２］前記（Ｃ）バインダー樹脂における前記（Ｃ１）エポキシ（メタ）アクリレート樹脂の含有割合が８５質量％以上である、［１］に記載の着色感光性樹脂組成物。
［３］前記（Ｃ１）エポキシ（メタ）アクリレート樹脂が、下記一般式（ＩＩ）で表される繰り返し単位構造を有するエポキシ（メタ）アクリレート樹脂及び下記一般式（ＩＩＩ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂の一方又は両方を含む、［１］又は［２］に記載の着色感光性樹脂組成物。 (In formula (I), R a1 and R a6 each independently represents a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
R a2 , R a3 , R a4 , R a5 , R a7 , R a8 , R a9 and R a10 are each independently a hydrogen atom, a halogen atom, R a11 , COOH, COOR a11 , COO − , CONH 2 , CONHR a11 , CONR a11 R a12, CN, OH, OR a11, COCR a11, OOCNH 2, OOCNHR a11, OOCNR a11 R a12, NO 2, NH 2, NHR a11, NR a11 R a12, NHCOR a12, NR a11 COR a12, N = CH 2 , N = CHR a11 , N = CR a11 R a12 , SH, SR a11 , SOR a11 , SO 2 R a11 , SO 3 R a11 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR represents a11 or SO 2 NR a11 R a12 ;
And at least one combination selected from the group consisting of R a2 and R a3 , R a3 and R a4 , R a4 and R a5 , R a7 and R a8 , R a8 and R a9 , and R a9 and R a10 , May be bonded directly to each other, or may be bonded to each other by oxygen, sulfur, NH or NR a11 bridges;
R a11 and R a12 each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a carbon number Represents 2 to 12 alkynyl groups. )
[2] The colored photosensitive resin composition according to [1], wherein a content ratio of the (C1) epoxy (meth) acrylate resin in the (C) binder resin is 85% by mass or more.
[3] 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 coloring photosensitive resin composition as described in [1] or [2] containing one or both of the epoxy (meth) acrylate resin which has.
Figure JPOXMLDOC01-appb-C000011
  
Figure JPOXMLDOC01-appb-C000011
  
（式（ＩＩ）中、Ｒ11は水素原子又はメチル基を表し；
Ｒ12は置換基を有していてもよい２価の炭化水素基を表し；
式（ＩＩ）中のベンゼン環は、更に任意の置換基により置換されていてもよく；
＊は結合手を表す。） (In formula (II), 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;
* Represents a bond. )
Figure JPOXMLDOC01-appb-C000012
  
Figure JPOXMLDOC01-appb-C000012
  
（式（ＩＩＩ）中、Ｒ13は各々独立に、水素原子又はメチル基を表し；
Ｒ14は、環状炭化水素基を側鎖として有する２価の炭化水素基を表し；
Ｒ15及びＲ16は各々独立に、置換基を有していてもよい２価の脂肪族基を表し；
ｍ及びｎは各々独立に０～２の整数を表し；
＊は結合手を表す。）
［４］前記アクリル系分散剤が、窒素原子を含有するアクリル系分散剤である、［１］～［３］のいずれか１項に記載の着色感光性樹脂組成物。
［５］前記（Ａ）着色剤の含有割合が、前記着色感光性樹脂組成物の全固形分あたり６０質量％以下である、［１］～［４］のいずれか１項に記載の着色感光性樹脂組成物。
［６］前記（Ａ）着色剤が、さらに（Ａ２）有機着色顔料及び（Ａ３）カーボンブラックの一方又は両方を含む、［１］～［５］のいずれか１項に記載の着色感光性樹脂組成物。
［７］前記（Ａ）着色剤における（Ａ１）有機黒色顔料の含有割合が１０質量％以上である、［１］～［６］のいずれか１項に記載の着色感光性樹脂組成物。
［８］有機電界発光素子の隔壁を形成するために用いられる、［１］～［７］のいずれか１項に記載の着色感光性樹脂組成物。 (In formula (III), 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;
* Represents a bond. )
[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein the acrylic dispersant is an acrylic dispersant containing a nitrogen atom.
[5] The colored photosensitive composition according to any one of [1] to [4], wherein the content ratio of the (A) coloring agent is 60% by mass or less based on the total solid content of the colored photosensitive resin composition. Resin composition.
[6] The colored photosensitive resin according to any one of [1] to [5], wherein the (A) colorant further contains one or both of (A2) an organic color pigment and (A3) carbon black. Composition.
[7] The colored photosensitive resin composition according to any one of [1] to [6], wherein the content of the (A1) organic black pigment in the (A) colorant is 10% by mass or more.
[8] The colored photosensitive resin composition according to any one of [1] to [7], which is used to form a partition wall of an organic electroluminescence device.
［９］（Ａ）着色剤、（Ｂ）分散剤、（Ｃ）バインダー樹脂、（Ｄ）光重合性モノマー及び（Ｅ）光重合開始剤を含有する、有機電界発光素子の隔壁を形成するための着色感光性樹脂組成物であって、
　前記（Ａ）着色剤が、下記一般式（Ｉ）で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも１種を含有する（Ａ１）有機黒色顔料を含み、
　前記（Ｃ）バインダー樹脂が、（Ｃ１）エポキシ（メタ）アクリレート樹脂を７５質量％以上含むことを特徴とする着色感光性樹脂組成物。 [9] In order to form a partition wall of an organic electroluminescence device containing (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, and (E) a photopolymerization initiator. 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.
Figure JPOXMLDOC01-appb-C000013
  
Figure JPOXMLDOC01-appb-C000013
  
（式（Ｉ）中、Ｒａ1及びＲａ6は各々独立に、水素原子、ＣＨ3、ＣＦ3、フッ素原子又は塩素原子を表し；
Ｒａ2、Ｒａ3、Ｒａ4、Ｒａ5、Ｒａ7、Ｒａ8、Ｒａ9及びＲａ10は各々独立に、水素原子、ハロゲン原子、Ｒａ11、ＣＯＯＨ、ＣＯＯＲａ11、ＣＯＯ-、ＣＯＮＨ2、ＣＯＮＨＲａ11、ＣＯＮＲａ11Ｒａ12、ＣＮ、ＯＨ、ＯＲａ11、ＣＯＣＲａ11、ＯＯＣＮＨ2、ＯＯＣＮＨＲａ11、ＯＯＣＮＲａ11Ｒａ12、ＮＯ2、ＮＨ2、ＮＨＲａ11、ＮＲａ11Ｒａ12、ＮＨＣＯＲａ12、ＮＲａ11ＣＯＲａ12、Ｎ＝ＣＨ2、Ｎ＝ＣＨＲａ11、Ｎ＝ＣＲａ11Ｒａ12、ＳＨ、ＳＲａ11、ＳＯＲａ11、ＳＯ2Ｒａ11、ＳＯ3Ｒａ11、ＳＯ3Ｈ、ＳＯ3 -、ＳＯ2ＮＨ2、ＳＯ2ＮＨＲａ11又はＳＯ2ＮＲａ11Ｒａ12を表し；
且つ、Ｒａ2とＲａ3、Ｒａ3とＲａ4、Ｒａ4とＲａ5、Ｒａ7とＲａ8、Ｒａ8とＲａ9、及びＲａ9とＲａ10からなる群から選ばれる少なくとも１つの組み合わせは、互いに直接結合してもよく、又は酸素原子、硫黄原子、ＮＨ若しくはＮＲａ11ブリッジによって互いに結合してもよく；
Ｒａ11及びＲａ12は各々独立に、炭素数１～１２のアルキル基、炭素数３～１２のシクロアルキル基、炭素数２～１２のアルケニル基、炭素数３～１２のシクロアルケニル基又は炭素数２～１２のアルキニル基を表す。）
［１０］前記（Ｃ）バインダー樹脂における前記（Ｃ１）エポキシ（メタ）アクリレート樹脂の含有割合が８５質量％以上である、［９］に記載の着色感光性樹脂組成物。
［１１］前記（Ｃ１）エポキシ（メタ）アクリレート樹脂が、下記一般式（ＩＩ）で表される繰り返し単位構造を有するエポキシ（メタ）アクリレート樹脂及び下記一般式（ＩＩＩ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂の一方又は両方を含む、［９］又は［１０］に記載の着色感光性樹脂組成物。 (In formula (I), R a1 and R a6 each independently represents a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
R a2 , R a3 , R a4 , R a5 , R a7 , R a8 , R a9 and R a10 are each independently a hydrogen atom, a halogen atom, R a11 , COOH, COOR a11 , COO − , CONH 2 , CONHR a11 , CONR a11 R a12, CN, OH, OR a11, COCR a11, OOCNH 2, OOCNHR a11, OOCNR a11 R a12, NO 2, NH 2, NHR a11, NR a11 R a12, NHCOR a12, NR a11 COR a12, N = CH 2 , N = CHR a11 , N = CR a11 R a12 , SH, SR a11 , SOR a11 , SO 2 R a11 , SO 3 R a11 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR represents a11 or SO 2 NR a11 R a12 ;
And at least one combination selected from the group consisting of R a2 and R a3 , R a3 and R a4 , R a4 and R a5 , R a7 and R a8 , R a8 and R a9 , and R a9 and R a10 , May be bonded directly to each other, or may be bonded to each other by oxygen, sulfur, NH or NR a11 bridges;
R a11 and R a12 each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a carbon number Represents 2 to 12 alkynyl groups. )
[10] The colored photosensitive resin composition according to [9], wherein a content ratio of the (C1) epoxy (meth) acrylate resin in the (C) binder resin is 85% by mass or more.
[11] 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.
Figure JPOXMLDOC01-appb-C000014
  
Figure JPOXMLDOC01-appb-C000014
  
（式（ＩＩ）中、Ｒ11は水素原子又はメチル基を表し；
Ｒ12は置換基を有していてもよい２価の炭化水素基を表し；
式（ＩＩ）中のベンゼン環は、更に任意の置換基により置換されていてもよく；
＊は結合手を表す。） (In formula (II), 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;
* Represents a bond. )
Figure JPOXMLDOC01-appb-C000015
  
Figure JPOXMLDOC01-appb-C000015
  
（式（ＩＩＩ）中、Ｒ13は各々独立に、水素原子又はメチル基を表し；
Ｒ14は、環状炭化水素基を側鎖として有する２価の炭化水素基を表し；
Ｒ15及びＲ16は各々独立に、置換基を有していてもよい２価の脂肪族基を表し；
ｍ及びｎは各々独立に０～２の整数を表し；
＊は結合手を表す。）
［１２］前記（Ａ）着色剤の含有割合が、前記着色感光性樹脂組成物の全固形分あたり６０質量％以下である、［９］～［１１］のいずれか１項に記載の着色感光性樹脂組成物。
［１３］前記（Ａ）着色剤が、さらに（Ａ２）有機着色顔料及び（Ａ３）カーボンブラックの一方又は両方を含む、［９］～［１２］のいずれか１項に記載の着色感光性樹脂組成物。
［１４］前記（Ａ）着色剤における（Ａ１）有機黒色顔料の含有割合が１０質量％以上である、［９］～［１３］のいずれか１項に記載の着色感光性樹脂組成物。 (In formula (III), 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;
* Represents a bond. )
[12] The colored photosensitive composition according to any one of [9] to [11], wherein the content ratio of the colorant (A) is 60% by mass or less based on the total solid content of the colored photosensitive resin composition. Resin composition.
[13] The colored photosensitive resin according to any one of [9] to [12], wherein the (A) colorant further contains one or both of (A2) an organic color pigment and (A3) carbon black. Composition.
[14] The colored photosensitive resin composition according to any one of [9] to [13], wherein the content of the (A1) organic black pigment in the (A) colorant is 10% by mass or more.
［１５］［１］～［１４］のいずれか１項に記載の着色感光性樹脂組成物で構成される隔壁。
［１６］［１５］に記載の隔壁を備える有機電界発光素子。
［１７］［１６］に記載の有機電界発光素子を含む画像表示装置。
［１８］［１６］に記載の有機電界発光素子を含む照明。 [15] A partition composed of the colored photosensitive resin composition according to any one of [1] to [14].
[16] An organic electroluminescence device comprising the partition wall according to [15].
[17] An image display device comprising the organic electroluminescent element as described in [16].
[18] Illumination including the organic electroluminescent element according to [16].
［１９］（Ａ）着色剤、（Ｂ）分散剤及び（Ｃ）バインダー樹脂を含有する顔料分散液であって、
　前記（Ａ）着色剤が、下記一般式（Ｉ）で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも１種を含有する（Ａ１）有機黒色顔料を含み、
　前記（Ｂ）分散剤が、アクリル系分散剤を含み、
　前記（Ｃ）バインダー樹脂が、（Ｃ１）エポキシ（メタ）アクリレート樹脂を含むことを特徴とする顔料分散液。 [19] A pigment dispersion containing (A) a colorant, (B) a dispersant, and (C) a binder resin,
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,
The pigment dispersion, wherein the (C) binder resin contains (C1) an epoxy (meth) acrylate resin.
Figure JPOXMLDOC01-appb-C000016
  
Figure JPOXMLDOC01-appb-C000016
  
（式（Ｉ）中、Ｒａ1及びＲａ6は各々独立に、水素原子、ＣＨ3、ＣＦ3、フッ素原子又は塩素原子を表し；
Ｒａ2、Ｒａ3、Ｒａ4、Ｒａ5、Ｒａ7、Ｒａ8、Ｒａ9及びＲａ10は各々独立に、水素原子、ハロゲン原子、Ｒ11、ＣＯＯＨ、ＣＯＯＲａ11、ＣＯＯ-、ＣＯＮＨ2、ＣＯＮＨＲａ11、ＣＯＮＲａ11Ｒａ12、ＣＮ、ＯＨ、ＯＲａ11、ＣＯＣＲａ11、ＯＯＣＮＨ2、ＯＯＣＮＨＲａ11、ＯＯＣＮＲａ11Ｒａ12、ＮＯ2、ＮＨ2、ＮＨＲａ11、ＮＲａ11Ｒａ12、ＮＨＣＯＲａ12、ＮＲａ11ＣＯＲａ12、Ｎ＝ＣＨ2、Ｎ＝ＣＨＲａ11、Ｎ＝ＣＲａ11Ｒａ12、ＳＨ、ＳＲａ11、ＳＯＲａ11、ＳＯ2Ｒａ11、ＳＯ3Ｒａ11、ＳＯ3Ｈ、ＳＯ3 -、ＳＯ2ＮＨ2、ＳＯ2ＮＨＲａ11又はＳＯ2ＮＲａ11Ｒａ12を表し；
且つ、Ｒａ2とＲａ3、Ｒａ3とＲａ4、Ｒａ4とＲａ5、Ｒａ7とＲａ8、Ｒａ8とＲａ9、及びＲａ9とＲａ10からなる群から選ばれる少なくとも１つの組み合わせは、互いに直接結合してもよく、又は酸素原子、硫黄原子、ＮＨ若しくはＮＲａ11ブリッジによって互いに結合してもよく；
Ｒａ11及びＲａ12は各々独立に、炭素数１～１２のアルキル基、炭素数３～１２のシクロアルキル基、炭素数２～１２のアルケニル基、炭素数３～１２のシクロアルケニル基又は炭素数２～１２のアルキニル基を表す。）
［２０］前記（Ｂ）分散剤の含有割合が、（Ａ）着色剤１００質量部に対して１０質量部以上である、［１９］に記載の顔料分散液。
［２１］前記（Ｃ１）エポキシ（メタ）アクリレート樹脂が、下記一般式（ＩＩ）で表される繰り返し単位構造を有するエポキシ（メタ）アクリレート樹脂及び下記一般式（ＩＩＩ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂の一方又は両方を含む、［１９］又は［２０］に記載の顔料分散液。 (In formula (I), R a1 and R a6 each independently represents a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
R a2 , R a3 , R a4 , R a5 , R a7 , R a8 , R a9 and R a10 are each independently a hydrogen atom, a halogen atom, R 11 , COOH, COOR a11 , COO − , CONH 2 , CONHR a11 , CONR a11 R a12, CN, OH, OR a11, COCR a11, OOCNH 2, OOCNHR a11, OOCNR a11 R a12, NO 2, NH 2, NHR a11, NR a11 R a12, NHCOR a12, NR a11 COR a12, N = CH 2 , N = CHR a11 , N = CR a11 R a12 , SH, SR a11 , SOR a11 , SO 2 R a11 , SO 3 R a11 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR represents a11 or SO 2 NR a11 R a12 ;
And at least one combination selected from the group consisting of R a2 and R a3 , R a3 and R a4 , R a4 and R a5 , R a7 and R a8 , R a8 and R a9 , and R a9 and R a10 , May be bonded directly to each other, or may be bonded to each other by oxygen, sulfur, NH or NR a11 bridges;
R a11 and R a12 each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a carbon number Represents 2 to 12 alkynyl groups. )
[20] The pigment dispersion according to [19], wherein the content ratio of the (B) dispersant is 10 parts by mass or more with respect to 100 parts by mass of the (A) colorant.
[21] 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.
Figure JPOXMLDOC01-appb-C000017
  
Figure JPOXMLDOC01-appb-C000017
  
（式（ＩＩ）中、Ｒ11は水素原子又はメチル基を表し；
Ｒ12は置換基を有していてもよい２価の炭化水素基を表し；
式（ＩＩ）中のベンゼン環は、更に任意の置換基により置換されていてもよく；
＊は結合手を表す。） (In formula (II), 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;
* Represents a bond. )
Figure JPOXMLDOC01-appb-C000018
  
Figure JPOXMLDOC01-appb-C000018
  
（式（ＩＩＩ）中、Ｒ13は各々独立に、水素原子又はメチル基を表し；
Ｒ14は、環状炭化水素基を側鎖として有する２価の炭化水素基を表し；
Ｒ15及びＲ16は各々独立に、置換基を有していてもよい２価の脂肪族基を表し；
ｍ及びｎは各々独立に０～２の整数を表し；
＊は結合手を表す。）
［２２］前記アクリル系分散剤が、窒素原子を含有するアクリル系分散剤である、［１９］～［２１］のいずれか１項に記載の顔料分散液。
［２３］着色感光性樹脂組成物を製造するために用いられる、［１９］～［２２］のいずれか１項に記載の顔料分散液。 (In formula (III), 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;
* Represents a bond. )
[22] The pigment dispersion according to any one of [19] to [21], wherein the acrylic dispersant is an acrylic dispersant containing a nitrogen atom.
[23] The pigment dispersion according to any one of [19] to [22], which is used for producing a colored photosensitive resin composition.
　本発明のある態様により、硬化物形成後のアウトガス量が少なく信頼性に優れており、また硬化物作成時の現像工程におけるパターンの密着性が良好である着色感光性樹脂組成物を提供することができる。また本発明の着色感光性樹脂組成物から形成される硬化物は稼働時のアウトガス量が少なく、発光素子としては寿命の低下が少なく、信頼性に優れる。 According to an aspect of the present invention, there is provided 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. In addition, 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.
　また本発明の別の態様により、硬化物形成後のアウトガス量が少なく信頼性に優れる、有機電界発光素子の隔壁を形成するための着色感光性樹脂組成物を提供することができる。また本発明の着色感光性樹脂組成物から形成される硬化物は稼働時のアウトガス量が少なく、発光素子としては寿命の低下が少なく、信頼性に優れる。 Further, according to another aspect of the present invention, it is possible to provide 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. In addition, 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.
　また本発明の顔料分散液により前記着色感光性樹脂組成物を提供することが可能となる。 Also, the colored photosensitive resin composition can be provided by the pigment dispersion of the present invention.
　以下、本発明を詳細に説明する。なお、以下の記載は本発明の実施形態の一例であり、本発明はその要旨を超えない限り、これらに特定されない。
　なお、本発明において、「（メタ）アクリル」とは、「アクリル及び／又はメタクリル」を意味するものとし、また、「全固形分」とは、着色感光性樹脂組成物又は顔料分散液における、溶剤以外の全成分を意味するものとする。さらに、本発明において「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
　また、本発明において、「（共）重合体」とは、単一重合体（ホモポリマー）と共重合体（コポリマー）の双方を含むことを意味し、また、「（酸）無水物」、「（無水）…酸」とは、酸とその無水物の双方を含むことを意味する。
　本発明において、隔壁材とはバンク材、壁材、ウォール材をさし、同様に、隔壁とはバンク、壁、ウォールをさす。隔壁とは、例えば、アクティブ駆動型有機電界発光素子における機能層（有機層）を区画するためのものであり、区画された領域（画素領域）に機能層を構成するための材料を蒸着あるいはインクジェット等による塗布、乾燥を行うことで、機能層及び隔壁からなる画素等を形成させていくために使用されるものである。
　本発明において、重量平均分子量とは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によるポリスチレン換算の重量平均分子量（Ｍｗ）をさす。
　本発明において、信頼性とは、有機電界発光素子の駆動時の信頼性を意味し、特に、画像表示装置に関しては表示信頼性を、照明に関しては発光信頼性を意味する。 Hereinafter, the present invention will be described in detail. In addition, the following description is an example of embodiment of this invention, and this invention is not specified to these, unless the summary is exceeded.
In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and “total solid content” means in the colored photosensitive resin composition or pigment dispersion, It shall mean all components other than the solvent. Furthermore, 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.
In the present invention, 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.
In the present invention, 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). It is used to form pixels and the like composed of functional layers and partition walls by applying and drying with the like.
In the present invention, the weight average molecular weight refers to a polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
In the present invention, 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.
　本発明の第１の態様に係る着色感光性樹脂組成物は、前記第１の課題を解決するものであり、前記（Ａ）着色剤が、後述の一般式（Ｉ）で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも１種を含有する（Ａ１）有機黒色顔料を含み、前記（Ｂ）分散剤が、アクリル系分散剤を含み、前記（Ｃ）バインダー樹脂が、（Ｃ１）エポキシ（メタ）アクリレート樹脂を７５質量％以上含むものである。 The colored photosensitive resin composition according to the first aspect of the present invention solves the first problem, and 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.
　本発明の第２の態様に係る着色感光性樹脂組成物は、前記第２の課題を解決するものであり、有機電界発光素子の隔壁を形成するための着色感光性樹脂組成物であって、前記（Ａ）着色剤が、後述の一般式（Ｉ）で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも１種を含有する（Ａ１）有機黒色顔料を含み、前記（Ｃ）バインダー樹脂が、（Ｃ１）エポキシ（メタ）アクリレート樹脂を７５質量％以上含むものである。 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.
　本発明の第３の態様に係る顔料分散液は、前記第３の課題を解決するものであり、前記（Ａ）着色剤が、後述の一般式（Ｉ）で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも１種を含有する（Ａ１）有機黒色顔料を含み、前記（Ｂ）分散剤が、アクリル系分散剤を含み、前記（Ｃ）バインダー樹脂が、（Ｃ１）エポキシ（メタ）アクリレート樹脂を含むものである。 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.
　以下、特に断りがない限り、「本発明の着色感光性樹脂組成物」は、前記第１の態様に係る着色感光性樹脂組成物、及び第２の態様に係る着色感光性樹脂組成物の両者を指す。 Hereinafter, unless otherwise specified, 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.
［１］着色感光性樹脂組成物の成分及び組成
　本発明の着色感光性樹脂組成物を構成する成分及びその組成について説明する。
　本発明の着色感光性樹脂組成物（以下、単に「感光性樹脂組成物」という場合がある）は、（Ａ）着色剤、（Ｂ）分散剤、（Ｃ）バインダー樹脂、（Ｄ）光重合性モノマー及び（Ｅ）光重合開始剤を含有し、さらに通常は、溶剤も含有する。 [1] Components and composition of colored photosensitive resin composition The components and composition of the colored photosensitive resin composition of the present invention will be described.
The colored photosensitive resin composition of the present invention (hereinafter sometimes simply referred to as “photosensitive resin composition”) 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.
［１－１］（Ａ）着色剤
　本発明の着色感光性樹脂組成物及び顔料分散液における（Ａ）着色剤は、下記一般式（Ｉ）で表される化合物（以下、「化合物（Ｉ）」と称する場合がある。）、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも１種を含有する（Ａ１）有機黒色顔料（以下、「（Ａ１）有機黒色顔料」と称する場合がある。）を含む。
　このように、（Ａ１）有機黒色顔料を含むことで、高抵抗、低誘電率かつ高遮光率を実現できると考えられる。さらに、より黒色に近い色調の硬化物が得られることから、画像表示装置の画像表示領域に占める面積割合が大きい、有機電界発光素子の隔壁を形成するための着色剤として好適に用いることができる。また（Ａ１）有機黒色顔料を用いることで分散性、保存性も良好であり、これを含有する着色感光性樹脂組成物においては現像時のパターニング適性も良好である。 [1-1] (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)”). And (A1) 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. And “(A1) Organic black pigment”.
Thus, (A1) It is thought that high resistance, a low dielectric constant, and a high light-shielding rate are realizable by including an organic black pigment. Furthermore, since 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. . In addition, (A1) by using an organic black pigment, dispersibility and storage stability are also good, and a colored photosensitive resin composition containing this has good patterning suitability during development.
Figure JPOXMLDOC01-appb-C000019
  
Figure JPOXMLDOC01-appb-C000019
  
　式（Ｉ）中、Ｒａ1及びＲａ6は各々独立に、水素原子、ＣＨ3、ＣＦ3、フッ素原子又は塩素原子を表し；
　Ｒａ2、Ｒａ3、Ｒａ4、Ｒａ5、Ｒａ7、Ｒａ8、Ｒａ9及びＲａ10は各々独立に、水素原子、ハロゲン原子、Ｒａ11、ＣＯＯＨ、ＣＯＯＲａ11、ＣＯＯ-、ＣＯＮＨ2、ＣＯＮＨＲａ11、ＣＯＮＲａ11Ｒａ12、ＣＮ、ＯＨ、ＯＲａ11、ＣＯＣＲａ11、ＯＯＣＮＨ2、ＯＯＣＮＨＲａ11、ＯＯＣＮＲａ11Ｒａ12、ＮＯ2、ＮＨ2、ＮＨＲａ11、ＮＲａ11Ｒａ12、ＮＨＣＯＲａ12、ＮＲａ11ＣＯＲａ12、Ｎ＝ＣＨ2、Ｎ＝ＣＨＲａ11、Ｎ＝ＣＲａ11Ｒａ12、ＳＨ、ＳＲａ11、ＳＯＲａ11、ＳＯ2Ｒａ11、ＳＯ3Ｒａ11、ＳＯ3Ｈ、ＳＯ3 -、ＳＯ2ＮＨ2、ＳＯ2ＮＨＲａ11又はＳＯ2ＮＲａ11Ｒａ12を表し；
　且つ、Ｒａ2とＲａ3、Ｒａ3とＲａ4、Ｒａ4とＲａ5、Ｒａ7とＲａ8、Ｒａ8とＲａ9、及びＲａ9とＲａ10からなる群から選ばれる少なくとも１つの組み合わせは、互いに直接結合してもよく、又は酸素原子、硫黄原子、ＮＨ若しくはＮＲ11ブリッジによって互いに結合してもよく；
　Ｒａ11及びＲａ12は各々独立に、炭素数１～１２のアルキル基、炭素数３～１２のシクロアルキル基、炭素数２～１２のアルケニル基、炭素数３～１２のシクロアルケニル基又は炭素数２～１２のアルキニル基を表す。 In formula (I), R a1 and R a6 each independently represents a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
R a2 , R a3 , R a4 , R a5 , R a7 , R a8 , R a9 and R a10 are each independently a hydrogen atom, a halogen atom, R a11 , COOH, COOR a11 , COO − , CONH 2 , CONHR a11 , CONR a11 R a12, CN, OH, OR a11, COCR a11, OOCNH 2, OOCNHR a11, OOCNR a11 R a12, NO 2, NH 2, NHR a11, NR a11 R a12, NHCOR a12, NR a11 COR a12, N = CH 2 , N = CHR a11 , N = CR a11 R a12 , SH, SR a11 , SOR a11 , SO 2 R a11 , SO 3 R a11 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR represents a11 or SO 2 NR a11 R a12 ;
And at least one combination selected from the group consisting of R a2 and R a3 , R a3 and R a4 , R a4 and R a5 , R a7 and R a8 , R a8 and R a9 , and R a9 and R a10 , May be bonded directly to each other, or may be bonded to each other by oxygen, sulfur, NH or NR 11 bridges;
R a11 and R a12 each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a carbon number Represents 2 to 12 alkynyl groups.
　一般式（Ｉ）で表される化合物の幾何異性体は、以下のコア構造を有し（ただし、構造式中の置換基は省略している）、トランス－トランス異性体が恐らく最も安定である。 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. .
Figure JPOXMLDOC01-appb-C000020
  
Figure JPOXMLDOC01-appb-C000020
  
　一般式（Ｉ）で表される化合物がアニオン性である場合、その電荷を任意の公知の適したカチオン、例えば金属、有機、無機又は金属有機カチオン、具体的にはアルカリ金属、アルカリ土類金属、遷移金属、一級アンモニウム、二級アンモニウム、トリアルキルアンモニウムなどの三級アンモニウム、テトラアルキルアンモニウムなどの四級アンモニウム又は有機金属錯体によって補償した塩であることが好ましい。また、一般式（Ｉ）で表される化合物の幾何異性体がアニオン性である場合、同様の塩であることが好ましい。 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.
　一般式（Ｉ）の置換基に関しては、遮蔽率が高くなる傾向があることから、以下のものが好ましい。これは、以下の置換基は吸収がなく、顔料の色相に影響しないと考えられるからである。
　Ｒａ2、Ｒａ4、Ｒａ5、Ｒａ7、Ｒａ9及びＲａ10は各々独立に、好ましくは水素原子、フッ素原子、又は塩素原子であり、さらに好ましくは水素原子である。
　Ｒａ3及びＲａ8は各々独立に、好ましくは水素原子、ＮＯ2、ＯＣＨ3、ＯＣ2Ｈ5、臭素原子、塩素原子、ＣＨ3、Ｃ2Ｈ5、Ｎ（ＣＨ3）2、Ｎ（ＣＨ3）（Ｃ2Ｈ5）、Ｎ（Ｃ2Ｈ5）2、α－ナフチル、β－ナフチル、ＳＯ3Ｈ又はＳＯ3 -であり、さらに好ましくは水素原子又はＳＯ3Ｈである。 With respect to the substituent of the general formula (I), the following are preferable because the shielding rate tends to increase. This is because the following substituents are considered not to absorb and affect the hue of the pigment.
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 , α-naphthyl, β-naphthyl, SO 3 H or SO 3 — , more preferably a hydrogen atom or SO 3 H.
　Ｒ1及びＲ6は各々独立に、好ましくは水素原子、ＣＨ3又はＣＦ3であり、さらに好ましくは水素原子である。
　好ましくは、Ｒ1とＲ6、Ｒ2とＲ7、Ｒ3とＲ8、Ｒ4とＲ9、及びＲ5とＲ10からなる群から選ばれる少なくとも１つの組み合わせが同一であり、より好ましくは、Ｒ1はＲ6と同一であり、Ｒ2はＲ7と同一であり、Ｒ3はＲ8と同一であり、Ｒ4はＲ9と同一であり、かつ、Ｒ5はＲ10と同一である。 R 1 and R 6 are each independently preferably a hydrogen atom, CH 3 or CF 3 , more preferably a hydrogen atom.
Preferably, 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.
　炭素数１～１２のアルキル基は、例えばメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、２－メチルブチル基、ｎ－ペンチル基、２－ペンチル基、３－ペンチル基、２，２－ジメチルプロピル基、ｎ－ヘキシル基、ヘプチル基、ｎ－オクチル基、１，１，３，３－テトラメチルブチル基、２－エチルヘキシル基、ノニル基、デシル基、ウンデシル基又はドデシル基である。 Examples of the alkyl group having 1 to 12 carbon atoms 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.
　炭素数３～１２のシクロアルキル基は、例えば、シクロプロピル基、シクロプロピルメチル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘキシルメチル基、トリメチルシクロヘキシル基、ツジル基、ノルボルニル基、ボルニル基、ノルカリル基、カリル基、メンチル基、ノルピニル基、ピニル基、１－アダマンチル基又は２－アダマンチル基である。 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.
　炭素数２～１２のアルケニル基は、例えば、ビニル基、アリル基、２－プロペン－２－イル基、２－ブテン－１－イル基、３－ブテン－１－イル基、１，３－ブタジエン－２－イル基、２－ペンテン－１－イル基、３－ペンテン－２－イル基、２－メンチル－１－ブテン－３－イル基、２－メチル－３－ブテン－２－イル基、３－メチル－２－ブテン－１－イル基、１，４－ペンタジエン－３－イル基、ヘキセニル基、オクテニル基、ノネニル基、デセニル基又はドデセニル基である。 Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, and 1,3-butadiene. -2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-menthyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, A 3-methyl-2-buten-1-yl group, a 1,4-pentadien-3-yl group, a hexenyl group, an octenyl group, a nonenyl group, a decenyl group or a dodecenyl group;
　炭素数３～１２のシクロアルケニル基は、例えば、２－シクロブテン－１－イル基、２－シクロペンテン－１－イル基、２－シクロヘキセン－１－イル基、３－シクロヘキセン－１－イル基、２，４－シクロヘキサジエン－１－イル基、１－ｐ－メンテン－８－イル基、４（１０）－ツジェン－１０－イル基、２－ノルボルネン－１－イル基、２，５－ノルボルナジエン－１－イル基、７，７－ジメチル－２，４－ノルカラジエン－３－イル基又はカンフェニル基である。 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.
　炭素数２～１２のアルキニル基は、例えば、１－プロピン－３－イル基、１－ブチン－４－イル基、１－ペンチン－５－イル基、２－メチル－３－ブチン－２－イル基、１，４－ペンタジイン－３－イル基、１，３－ペンタジイン－５－イル基、１－ヘキシン－６－イル基、シス－３－メチル－２－ペンテン－４－イン－１－イル基、トランス－３－メチル－２－ペンテン－４－イン－１－イル基、１，３－ヘキサジイン－５－イル基、１－オクチン－８－イル基、１－ノニン－９－イル基、１－デシン－１０－イル基又は１－ドデシン－１２－イル基である。 Examples of the alkynyl group having 2 to 12 carbon atoms include 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, and 2-methyl-3-butyn-2-yl. Group, 1,4-pentadiin-3-yl group, 1,3-pentadiin-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-in-1-yl Group, trans-3-methyl-2-penten-4-in-1-yl group, 1,3-hexadiin-5-yl group, 1-octin-8-yl group, 1-nonin-9-yl group, 1-decyn-10-yl group or 1-dodecin-12-yl group.
　ハロゲン原子は、例えば、フッ素原子、塩素原子、臭素原子又はヨウ素原子である。 The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
　前記（Ａ１）有機黒色顔料は、好ましくは下記一般式（Ｉ－１）で表される化合物（以下、「化合物（Ｉ－１）」と称する場合がある。）、及び該化合物の幾何異性体からなる群から選ばれる少なくとも１種である。 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
Figure JPOXMLDOC01-appb-C000021
  
Figure JPOXMLDOC01-appb-C000021
  
　このような有機黒色顔料の具体例としては、商品名で、Ｉｒｇａｐｈｏｒ（登録商標）　Ｂｌａｃｋ　Ｓ　０１００　ＣＦ（ＢＡＳＦ社製）が挙げられる。
　この有機黒色顔料は、好ましくは後述される分散剤、溶剤、方法によって分散して使用される。また、分散の際に前記化合物（Ｉ）のスルホン酸誘導体（スルホン酸置換体）、又は化合物（Ｉ）の幾何異性体のスルホン酸誘導体、特に前記化合物（Ｉ－１）のスルホン酸誘導体、又は前記化合物（Ｉ－１）の幾何異性体のスルホン酸誘導体が存在すると、分散性や保存性が向上する場合がある。 Specific examples of such 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.
　本発明で用いる（Ａ）着色剤は、前記（Ａ１）有機黒色顔料以外にその他の着色剤を含有していてもよい。その他の着色剤としては、顔料を用いることが好ましく、顔料は有機顔料であっても無機顔料であってもよいが、高抵抗、低誘電率の観点からは、有機顔料を用いることがより好ましく、特に有機着色顔料（以下「（Ａ２）有機着色顔料」と称する場合がある。）を用いることがさらに好ましい。 The (A) colorant used in the present invention may contain other colorants in addition to the (A1) organic black pigment. As the other colorant, 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. In particular, it is more preferable to use an organic coloring pigment (hereinafter sometimes referred to as “(A2) organic coloring pigment”).
　これらの顔料の化学構造は特に限定されないが、アゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、イソインドリノン系、ジオキサジン系、インダンスレン系、ペリレン系等の有機顔料が利用可能である。以下、使用できる有機顔料の具体例をピグメントナンバーで示す。以下に挙げる「Ｃ．Ｉ．ピグメントレッド２」等の用語は、カラーインデックス（Ｃ．Ｉ．）を意味する。 The chemical structure of these pigments is not particularly limited, but organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene can be used. . Hereinafter, 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).
　赤色顔料としては、Ｃ．Ｉ．ピグメントレッド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、１７９、１８１、１８４、１８５、１８７、１８８、１９０、１９３、１９４、２００、２０２、２０６、２０７、２０８、２０９、２１０、２１４、２１６、２２０、２２１、２２４、２３０、２３１、２３２、２３３、２３５、２３６、２３７、２３８、２３９、２４２、２４３、２４５、２４７、２４９、２５０、２５１、２５３、２５４、２５５、２５６、２５７、２５８、２５９、２６０、２６２、２６３、２６４、２６５、２６６、２６７、２６８、２６９、２７０、２７１、２７２、２７３、２７４、２７５、２７６を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントレッド４８：１、１２２、１４９、１６８、１７７、１７９、１９４、２０２、２０６、２０７、２０９、２２４、２４２、２５４、更に好ましくはＣ．Ｉ．ピグメントレッド１７７、２０９、２２４、２５４を挙げることができる。
　なお、分散性や遮光性の点で、Ｃ．Ｉ．ピグメントレッド１７７、２５４、２７２を用いることが好ましく、本発明の着色感光性樹脂組成物を紫外線で硬化させる場合には、赤色顔料としては紫外線吸収率の低いものを使用することが好ましく、係る観点からはＣ．Ｉ．ピグメントレッド２５４、２７２を用いることがより好ましい。 Examples of red pigments 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, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, 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.
In terms of dispersibility and light shielding properties, C.I. I. Pigment Red 177, 254, and 272 are preferably used. When the colored photosensitive resin composition of the present invention is cured with ultraviolet rays, it is preferable to use a red pigment having a low ultraviolet absorption rate. From C.I. I. More preferably, CI pigment red 254 and 272 are used.
　橙色（オレンジ）顔料としては、Ｃ．Ｉ．ピグメントオレンジ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を挙げることができる。この中でも、分散性や遮光性の点で、Ｃ．Ｉ．ピグメントオレンジ１３、４３、６４、７２を用いることが好ましく、本発明の着色感光性樹脂組成物を紫外線で硬化させる場合には、橙色顔料としては紫外線吸収率の低いものを使用することが好ましく、係る観点からはＣ．Ｉ．ピグメントオレンジ６４、７２を用いることがより好ましく、Ｃ．Ｉ．ピグメントオレンジ６４が特に好ましい。 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. Of these, 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.
　青色顔料としては、Ｃ．Ｉ．ピグメントブルー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を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：６、更に好ましくはＣ．Ｉ．ピグメントブルー１５：６を挙げることができる。
　なお、分散性や遮光性の点で、Ｃ．Ｉ．ピグメントブルー１５：６、１６、６０を用いることが好ましく、本発明の着色感光性樹脂組成物を紫外線で硬化させる場合には、青色顔料としては紫外線吸収率の低いものを使用することが好ましく、係る観点からはＣ．Ｉ．ピグメントブルー６０を用いることがより好ましい。 Examples of blue pigments 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. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6.
In terms of dispersibility and light shielding properties, C.I. I. Pigment Blue 15: 6, 16, and 60 are preferably used. When 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.
　紫色顔料としては、Ｃ．Ｉ．ピグメントバイオレット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を挙げることができる。この中でも、遮光性の点では、Ｃ．Ｉ．ピグメントバイオレット１９、２３を用いることが好ましく、Ｃ．Ｉ．ピグメントバイオレット２３を用いることがより好ましい。
　なお、分散性や遮光性の点で、Ｃ．Ｉ．ピグメントバイオレット２３、２９を用いることが好ましく、本発明の着色感光性樹脂組成物を紫外線で硬化させる場合には、紫色顔料としては紫外線吸収率の低いものを使用することが好ましく、係る観点からはＣ．Ｉ．ピグメントバイオレット２９を用いることがより好ましい。 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. Among these, C.C. I. Pigment Violet 19 and 23 are preferably used. I. More preferably, CI Pigment Violet 23 is used.
In terms of dispersibility and light shielding properties, 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.
　赤色顔料、橙色顔料、青色顔料、紫色顔料の他に用いることができる有機着色顔料としては例えば、緑色顔料、黄色顔料などを挙げることができる。
　緑色顔料としては、Ｃ．Ｉ．ピグメントグリーン１、２、４、７、８、１０、１３、１４、１５、１７、１８、１９、２６、３６、４５、４８、５０、５１、５４、５５、５８を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントグリーン７、３６を挙げることができる。
　黄色顔料としては、Ｃ．Ｉ．ピグメントイエロー１、１：１、２、３、４、５、６、９、１０、１２、１３、１４、１６、１７、２４、３１、３２、３４、３５、３５：１、３６、３６：１、３７、３７：１、４０、４１、４２、４３、４８、５３、５５、６１、６２、６２：１、６３、６５、７３、７４、７５、８１、８３、８７、９３、９４、９５、９７、１００、１０１、１０４、１０５、１０８、１０９、１１０、１１１、１１６、１１７、１１９、１２０、１２６、１２７、１２７：１、１２８、１２９、１３３、１３４、１３６、１３８、１３９、１４２、１４７、１４８、１５０、１５１、１５３、１５４、１５５、１５７、１５８、１５９、１６０、１６１、１６２、１６３、１６４、１６５、１６６、１６７、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１８０、１８１、１８２、１８３、１８４、１８５、１８８、１８９、１９０、１９１、１９１：１、１９２、１９３、１９４、１９５、１９６、１９７、１９８、１９９、２００、２０２、２０３、２０４、２０５、２０６、２０７、２０８を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントイエロー８３、１１７、１２９、１３８、１３９、１５０、１５４、１５５、１８０、１８５、更に好ましくはＣ．Ｉ．ピグメントイエロー８３、１３８、１３９、１５０、１８０を挙げることができる。 Examples of 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.
Examples of 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.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, 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.
　これらの顔料の中でも、赤色顔料及び橙色顔料からなる群から選ばれる少なくとも１種と、青色顔料及び紫色顔料からなる群から選ばれる少なくとも１種との組み合わせを用いることが好ましい。このように、特定の顔料の組み合わせを用いることで、高遮光性を達成することができる傾向がある。 Among these 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. Thus, there exists a tendency which can achieve high light-shielding property by using the combination of a specific pigment.
　これらの中でも、遮光性や色調の観点からは、以下の顔料のうち少なくとも１種以上を含有するものとすることが好ましい。
　赤色顔料：Ｃ．Ｉ．ピグメントレッド１７７、２５４、２７２
　橙色顔料：Ｃ．Ｉ．ピグメントオレンジ４３、６４、７２
　青色顔料：Ｃ．Ｉ．ピグメントブルー１５：６、６０
　紫色顔料：Ｃ．Ｉ．ピグメントバイオレット２３、２９ Among these, from the viewpoint of light shielding properties and color tone, it is preferable to contain at least one of the following pigments.
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
　なお、色の組み合わせについては特に限定されないが、遮光性の観点からは例えば、赤色顔料と青色顔料の組み合わせ、青色顔料と橙色顔料の組み合わせ、青色顔料と橙色顔料と紫色顔料の組み合わせなどが挙げられる。 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. .
　さらに、その他の着色剤としては、これらの有機着色顔料以外に、その他の黒色着色剤を用いることができる。
　黒色着色剤の中でも、遮光性や色調の観点からは、前記一般式（Ｉ）で表される以外の、その他の有機黒色顔料を用いてもよい。その他の有機黒色顔料としては、アニリンブラック、ペリレンブラック、シアニンブラックなどが挙げられる。 In addition to these organic color pigments, other black colorants can be used as other colorants.
Among the black 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.
　また、本発明では、無機黒色顔料を用いることができる。無機黒色顔料としては、カーボンブラック、アセチレンブラック、ランプブラック、ボーンブラック、黒鉛、鉄黒、チタンブラック、等が挙げられる。これらの中でも、遮光性、画像特性の観点からカーボンブラック（以下「（Ａ３）カーボンブラック」と称する場合がある。）を好ましく用いることができる。カーボンブラックの例としては、以下のようなカーボンブラックが挙げられる。 In the present invention, an inorganic black pigment can be used. Examples of the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, titanium black, and the like. Among these, 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.
　三菱ケミカル社製：ＭＡ７、ＭＡ８、ＭＡ１１、ＭＡ７７、ＭＡ１００、ＭＡ１００Ｒ、ＭＡ１００Ｓ、ＭＡ２２０、ＭＡ２３０、ＭＡ６００、ＭＣＦ８８、＃５、＃１０、＃２０、＃２５、＃３０、＃３２、＃３３、＃４０、＃４４、＃４５、＃４７、＃５０、＃５２、＃５５、＃６５０、＃７５０、＃８５０、＃９００、＃９５０、＃９６０、＃９７０、＃９８０、＃９９０、＃１０００、＃２２００、＃２３００、＃２３５０、＃２４００、＃２６００、＃２６５０、＃３０３０、＃３０５０、＃３１５０、＃３２５０、＃３４００、＃３６００、＃３７５０、＃３９５０、＃４０００、＃４０１０、ＯＩＬ７Ｂ、ＯＩＬ９Ｂ、ＯＩＬ１１Ｂ、ＯＩＬ３０Ｂ、ＯＩＬ３１Ｂ
　デグサ社製：Ｐｒｉｎｔｅｘ（登録商標。以下同じ。）３、Ｐｒｉｎｔｅｘ３ＯＰ、Ｐｒｉｎｔｅｘ３０、Ｐｒｉｎｔｅｘ３０ＯＰ、Ｐｒｉｎｔｅｘ４０、Ｐｒｉｎｔｅｘ４５、Ｐｒｉｎｔｅｘ５５、Ｐｒｉｎｔｅｘ６０、Ｐｒｉｎｔｅｘ７５、Ｐｒｉｎｔｅｘ８０、Ｐｒｉｎｔｅｘ８５、Ｐｒｉｎｔｅｘ９０、Ｐｒｉｎｔｅｘ　Ａ、Ｐｒｉｎｔｅｘ　Ｌ、Ｐｒｉｎｔｅｘ　Ｇ、Ｐｒｉｎｔｅｘ　Ｐ、Ｐｒｉｎｔｅｘ　Ｕ、Ｐｒｉｎｔｅｘ　Ｖ、ＳｐｅｃｉａｌＢｌａｃｋ５５０、ＳｐｅｃｉａｌＢｌａｃｋ３５０、ＳｐｅｃｉａｌＢｌａｃｋ２５０、ＳｐｅｃｉａｌＢｌａｃｋ１００、ＳｐｅｃｉａｌＢｌａｃｋ６、ＳｐｅｃｉａｌＢｌａｃｋ５、ＳｐｅｃｉａｌＢｌａｃｋ４、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ１、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ２、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ２Ｖ、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ１８、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ２００、Ｃｏｌｏｒ　Ｂｌａｃｋ　Ｓ１６０、Ｃｏｌｏｒ　Ｂｌａｃｋ　Ｓ１７０
　キャボット社製：Ｍｏｎａｒｃｈ（登録商標。以下同じ。）１２０、Ｍｏｎａｒｃｈ２８０、Ｍｏｎａｒｃｈ４６０、Ｍｏｎａｒｃｈ８００、Ｍｏｎａｒｃｈ８８０、Ｍｏｎａｒｃｈ９００、Ｍｏｎａｒｃｈ１０００、Ｍｏｎａｒｃｈ１１００、Ｍｏｎａｒｃｈ１３００、Ｍｏｎａｒｃｈ１４００、Ｍｏｎａｒｃｈ４６３０、ＲＥＧＡＬ（登録商標。以下同じ。）９９、ＲＥＧＡＬ９９Ｒ、ＲＥＧＡＬ４１５、ＲＥＧＡＬ４１５Ｒ、ＲＥＧＡＬ２５０、ＲＥＧＡＬ２５０Ｒ、ＲＥＧＡＬ３３０、ＲＥＧＡＬ４００Ｒ、ＲＥＧＡＬ５５Ｒ０、ＲＥＧＡＬ６６０Ｒ、ＢＬＡＣＫ　ＰＥＡＲＬＳ４８０、ＰＥＡＲＬＳ１３０、ＶＵＬＣＡＮ（登録商標。以下同じ。）　ＸＣ７２Ｒ、ＥＬＦＴＥＸ（登録商標）－８
　ビルラー社製：ＲＡＶＥＮ（登録商標。以下同じ。）１１、ＲＡＶＥＮ１４、ＲＡＶＥＮ１５、ＲＡＶＥＮ１６、ＲＡＶＥＮ２２ＲＡＶＥＮ３０、ＲＡＶＥＮ３５、ＲＡＶＥＮ４０、ＲＡＶＥＮ４１０、ＲＡＶＥＮ４２０、ＲＡＶＥＮ４５０、ＲＡＶＥＮ５００、ＲＡＶＥＮ７８０、ＲＡＶＥＮ８５０、ＲＡＶＥＮ８９０Ｈ、ＲＡＶＥＮ１０００、ＲＡＶＥＮ１０２０、ＲＡＶＥＮ１０４０、ＲＡＶＥＮ１０６０Ｕ、ＲＡＶＥＮ１０８０Ｕ、ＲＡＶＥＮ１１７０、ＲＡＶＥＮ１１９０Ｕ、ＲＡＶＥＮ１２５０、ＲＡＶＥＮ１５００、ＲＡＶＥＮ２０００、ＲＡＶＥＮ２５００Ｕ、ＲＡＶＥＮ３５００、ＲＡＶＥＮ５０００、ＲＡＶＥＮ５２５０、ＲＡＶＥＮ５７５０、ＲＡＶＥＮ７０００ Made by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40 # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 900, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 2650, # 3030, # 3050, # 3150, # 3250, # 3400, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B
Made by Degussa: Printex (registered trademark, the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, PrintP85, PrintP85, PrintP85 U, Printex V, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black5, Special Black4, Color Black, Color Black, Color Black lor Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Manufactured by Cabot Corporation: Monarch (registered trademark; the same shall apply hereinafter) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (99, REGAL 99) REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark; the same shall apply hereinafter) XC72R, ELFTEX (registered trademark) -8
Made by Birler: RAVEN (registered trademark; the same shall apply hereinafter) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN10RA, RAVEN10U, RAVEN890H, RAVEN890H, RAVEN890H, RAVEN890H , RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
　カーボンブラックは、樹脂で被覆されたものを使用しても構わない。樹脂で被覆されたカーボンブラックを使用すると、ガラス基板への密着性や体積抵抗値を向上させる効果がある。樹脂で被覆されたカーボンブラックとしては、例えば日本国特開平０９－７１７３３号公報に記載されているカーボンブラック等が好適に使用できる。体積抵抗や誘電率の点で、樹脂被覆カーボンブラックが好適に用いられる。 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. As the 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.
　樹脂による被覆処理に供するカーボンブラックとしては、ＮａとＣａの合計含有量が１００ｐｐｍ以下であることが好ましい。カーボンブラックは、通常、製造時の原料油や燃焼油（又はガス）、反応停止水や造粒水、更には反応炉の炉材等から混入したＮａや、Ｃａ，Ｋ，Ｍｇ，Ａｌ，Ｆｅ等を組成とする灰分がパーセントのオーダーで含有されている。この内、ＮａやＣａは、各々数百ｐｐｍ以上含有されているのが一般的であるが、これらを少なくすることで、透明電極（ＩＴＯ）やその他の電極への浸透を抑制して、電気的短絡を防止できる傾向がある。 As carbon black to be subjected to coating treatment with resin, 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. Of these, 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.
　これらのＮａやＣａを含む灰分の含有量を低減する方法としては、カーボンブラックを製造する際の原料油や燃料油（又はガス）並びに反応停止水として、これらの含有量が極力少ない物を厳選すること及びストラクチャーを調整するアルカリ物質の添加量を極力少なくすることにより可能である。他の方法としては、炉から製出したカーボンブラックを水や塩酸等で洗いＮａやＣａを溶解し除去する方法が挙げられる。 As a method for reducing the content of ash containing these Na and Ca, carefully select those with as little content as possible as raw oil, fuel oil (or gas) and reaction stop water when producing carbon black. This is possible by reducing the addition amount of the alkaline substance for adjusting the structure as much as possible. As another method, carbon black produced from the furnace is washed with water, hydrochloric acid or the like, and Na or Ca is dissolved and removed.
　具体的にはカーボンブラックを水、塩酸、又は過酸化水素水に混合分散させた後、水に難溶の溶媒を添加していくとカーボンブラックは溶媒側に移行し、水と完全に分離すると共にカーボンブラック中に存在した殆どのＮａやＣａは、水や酸に溶解、除去される。ＮａとＣａの合計量を１００ｐｐｍ以下に低減するためには、原材料を厳選したカーボンブラック製造過程単独或は水や酸溶解方式単独でも可能な場合もあるが、この両方式を併用することにより更に容易にＮａとＣａの合計量を１００ｐｐｍ以下とすることができる。 Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide, carbon black moves to the solvent side and is completely separated from water when a solvent that is hardly soluble in water is added. At the same time, most of Na and Ca present in the carbon black are dissolved and removed in water and acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, there may be a case where a carbon black production process alone or a water or acid dissolution method alone with carefully selected raw materials may be possible. The total amount of Na and Ca can be easily made 100 ppm or less.
　また樹脂被覆カーボンブラックは、ｐＨ６以下のいわゆる酸性カーボンブラックであることが好ましい。水中での分散径（アグロメレート径）が小さくなるので、微細ユニットまでの被覆が可能となり好適である。さらに平均粒子径４０ｎｍ以下、ジブチルフタレート（ＤＢＰ）吸収量１４０ｍＬ／１００ｇ以下であることが好ましい。前記範囲内とすることで、遮光性の良好な塗膜が得られる傾向がある。平均粒子径は数平均粒子径を意味し、電子顕微鏡観察により数万倍の倍率で数視野分撮影し、得られた写真中のカーボンブラック粒子を画像処理装置により２０００～３０００個程度計測する粒子画像解析により求められる円相当径を意味する。 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.
　樹脂で被覆されたカーボンブラックを調製する方法には特に限定されないが、例えば、カーボンブラック及び樹脂の配合量を適宜調整した後、１．樹脂とシクロヘキサノン、トルエン、キシレンなどの溶剤とを混合して加熱溶解させた樹脂溶液と、カーボンブラック及び水を混合した懸濁液とを混合撹拌し、カーボンブラックと水とを分離させた後、水を除去して加熱混練して得られた組成物をシート状に成形し、粉砕した後、乾燥させる方法；２．前記と同様にして調製した樹脂溶液と懸濁液とを混合撹拌してカーボンブラック及び樹脂を粒状化した後、得られた粒状物を分離、加熱して残存する溶剤及び水を除去する方法；３．溶剤にマレイン酸、フマル酸などのカルボン酸を溶解させ、カーボンブラックを添加、混合して乾燥させ、溶剤を除去してカルボン酸添着カーボンブラックを得た後、これに樹脂を添加してドライブレンドする方法；４．被覆させる樹脂を構成する反応性基含有モノマー成分と水とを高速撹拌して懸濁液を調製し、重合後冷却して重合体懸濁液から反応性基含有樹脂を得た後、これにカーボンブラックを添加して混練し、カーボンブラックと反応性基とを反応させ（カーボンブラックをグラフトさせ）、冷却及び粉砕する方法などを採用することができる。 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 How to: 4 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.
　被覆処理する樹脂の種類も特に限定されるものではないが、合成樹脂が一般的であり、さらに、構造の中にベンゼン環を有する樹脂の方が両性系界面活性剤的な働きがより強いため、分散性及び分散安定性の点から好ましい。
　具体的な合成樹脂としては、フェノール樹脂、メラミン樹脂、キシレン樹脂、ジアリルフタレート樹脂、グリプタル樹脂、エポキシ樹脂、アルキルベンゼン樹脂等の熱硬化性樹脂や、ポリスチレン、ポリカーボネート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、変性ポリフェニレンオキサイド、ポリスルフォン、ポリパラフェニレンテレフタルアミド、ポリアミドイミド、ポリイミド、ポリアミノビスマレイミド、ポリエーテルスルフォポリフェニレンスルフォン、ポリアリレート、ポリエーテルエーテルケトン、等の熱可塑性樹脂が使用できる。被覆樹脂の量は、カーボンブラックと被覆樹脂の合計量に対し１～３０質量％が好ましい。前記下限値以上とすることで被覆を十分なものとすることができる傾向がある。一方で、前記上限値以下とすることで、樹脂同士の粘着を防ぎ、分散性が良好なものとすることができる傾向がある。 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 | cover sufficient by setting it as the said lower limit or more. On the other hand, by setting it to the upper limit value or less, there is a tendency that adhesion between resins can be prevented and dispersibility can be improved.
　このようにして樹脂で被覆処理してなるカーボンブラックは、常法に従い、隔壁、着色スペーサー等の遮光材として用いることができ、この隔壁、着色スペーサーを構成要素とする有機発光素子、カラーフィルターを常法により作成することができる。このようなカーボンブラックを用いると、高遮光率でかつ低コストにできる傾向がある。また、カーボンブラック表面を樹脂で被覆したことにより、高抵抗、低誘電率の隔壁、着色スペーサー等の遮光材を作成することができる。 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.
　また、その他の着色剤として、上述の有機着色顔料、黒色着色剤の他に、染料を使用してもよい。着色剤として使用できる染料としては、アゾ系染料、アントラキノン系染料、フタロシアニン系染料、キノンイミン系染料、キノリン系染料、ニトロ系染料、カルボニル系染料、メチン系染料等が挙げられる。
　アゾ系染料としては、例えば、Ｃ．Ｉ．アシッドイエロー１１、Ｃ．Ｉ．アシッドオレンジ７、Ｃ．Ｉ．アシッドレッド３７、Ｃ．Ｉ．アシッドレッド１８０、Ｃ．Ｉ．アシッドブルー２９、Ｃ．Ｉ．ダイレクトレッド２８、Ｃ．Ｉ．ダイレクトレッド８３、Ｃ．Ｉ．ダイレクトイエロー１２、Ｃ．Ｉ．ダイレクトオレンジ２６、Ｃ．Ｉ．ダイレクトグリーン２８、Ｃ．Ｉ．ダイレクトグリーン５９、Ｃ．Ｉ．リアクティブイエロー２、Ｃ．Ｉ．リアクティブレッド１７、Ｃ．Ｉ．リアクティブレッド１２０、Ｃ．Ｉ．リアクティブブラック５、Ｃ．Ｉ．ディスパースオレンジ５、Ｃ．Ｉ．ディスパースレッド５８、Ｃ．Ｉ．ディスパースブルー１６５、Ｃ．Ｉ．ベーシックブルー４１、Ｃ．Ｉ．ベーシックレッド１８、Ｃ．Ｉ．モルダントレッド７、Ｃ．Ｉ．モルダントイエロー５、Ｃ．Ｉ．モルダントブラック７等が挙げられる。 In addition to the organic color pigments and black colorants described above, dyes may be used as other colorants. Examples of 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.
Examples of 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. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.
　アントラキノン系染料としては、例えば、Ｃ．Ｉ．バットブルー４、Ｃ．Ｉ．アシッドブルー４０、Ｃ．Ｉ．アシッドグリーン２５、Ｃ．Ｉ．リアクティブブルー１９、Ｃ．Ｉ．リアクティブブルー４９、Ｃ．Ｉ．ディスパースレッド６０、Ｃ．Ｉ．ディスパースブルー５６、Ｃ．Ｉ．ディスパースブルー６０等が挙げられる。
　この他、フタロシアニン系染料として、例えば、Ｃ．Ｉ．パッドブルー５等が、キノンイミン系染料として、例えば、Ｃ．Ｉ．ベーシックブルー３、Ｃ．Ｉ．ベーシックブルー９等が、キノリン系染料として、例えば、Ｃ．Ｉ．ソルベントイエロー３３、Ｃ．Ｉ．アシッドイエロー３、Ｃ．Ｉ．ディスパースイエロー６４等が、ニトロ系染料として、例えば、Ｃ．Ｉ．アシッドイエロー１、Ｃ．Ｉ．アシッドオレンジ３、Ｃ．Ｉ．ディスパースイエロー４２等が挙げられる。 Examples of anthraquinone dyes 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.
　これらの（Ａ１）有機黒色顔料、（Ａ２）有機着色顔料、黒色着色剤等の顔料は、平均粒子径が通常１μｍ以下、好ましくは０．５μｍ以下、更に好ましくは０．２５μｍ以下となるよう、分散して用いることが好ましい。ここで平均粒子径の基準は顔料粒子の数である。
　なお、この顔料の平均粒子径は、動的光散乱（ＤＬＳ）により測定された顔料粒子径から求めた値である。粒子径測定は、十分に希釈された着色感光性樹脂組成物（通常は希釈して、顔料含有割合０．００５～０．２質量％程度に調製。但し測定機器により推奨された濃度があれば、その濃度に従う。）に対して行い、２５℃にて測定する。 These (A1) organic black pigment, (A2) organic color pigment, black colorant and other pigments have an average particle size of usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less. It is preferable to use in a dispersed manner. Here, the standard of the average particle diameter is the number of pigment particles.
In addition, 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.
［１－２］（Ｂ）分散剤
　本発明の着色感光性樹脂組成物及び顔料分散液においては、（Ａ）着色剤を微細に分散させ、且つその分散状態を安定化させることが品質の安定性確保には重要なため、（Ｂ）分散剤を含む。 [1-2] (B) Dispersant In the colored photosensitive resin composition and pigment dispersion of the present invention, (A) the colorant is finely dispersed and the dispersion state is stabilized to stabilize the quality. (B) A dispersant is included because it is important for securing the property.
　本発明の第１の態様に係る着色感光性樹脂組成物、及び本発明の第３の態様に係る顔料分散液においては、（Ｂ）分散剤が、アクリル系分散剤を含む。アクリル系分散剤は、直鎖状の分子構造の柔軟な主骨格を有するため、吸着基の多くが着色剤に吸着することで着色感光性樹脂組成物及び顔料分散液中に着色剤が均一に分散されると考えられる。塗布膜中に着色剤が均一に配置されることで、該塗布膜が緻密な膜となり、さらに、アルカリ現像液に不溶な成分である着色剤が塗布膜中に均一に配置されることにより、現像処理時に塗布膜内部への現像液の浸透が抑えられてパターン密着性が良好になる、特に微細パターンであっても密着性が良好になると考えられる。 In the colored photosensitive resin composition according to the first aspect of the present invention and the pigment dispersion according to the third aspect of the present invention, (B) 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. By uniformly arranging the colorant in the coating film, 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.
　またアクリル系分散剤としては、官能基を有する高分子分散剤が好ましい。また分散安定性の面からカルボキシル基；リン酸基；スルホン酸基；又はこれらの塩基；窒素原子を含有するアクリル系分散剤が好ましく、中でも窒素原子を含有するアクリル系分散剤が好ましい。さらには１級、２級又は３級アミノ基；４級アンモニウム塩基；ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の塩基性官能基を有する高分子分散剤が、顔料等の着色剤を分散する際に少量の分散剤で分散することができるとの観点から特に好ましい。これらの官能基は、着色剤に吸着する吸着基として作用する。
　市販されているアクリル系分散剤としては、例えばＤＩＳＰＥＲＢＹＫ－２０００、ＤＩＳＰＥＲＢＹＫ－２００１、ＢＹＫ－ＬＰＮ２１１１６、ＢＹＫ－ＬＰＮ６９１９等（以上すべてビックケミー社製）が挙げられる。 As the acrylic dispersant, 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. This is particularly preferable from the viewpoint that the colorant can be dispersed with a small amount of a dispersant. These functional groups act as adsorbing groups that adsorb to the colorant.
Examples of commercially available acrylic dispersants include DISPERBYK-2000, DISPERBYK-2001, BYK-LPN21116, BYK-LPN6919, and the like (all manufactured by BYK Chemie).
　窒素原子を含有するアクリル系分散剤としては、官能基（ここでいう官能基とは、高分子分散剤に含有される官能基として前述した官能基である。）を有する不飽和基含有単量体と、官能基を有さない不飽和基含有単量体とのランダム共重合体、グラフト共重合体、ブロック共重合体を使用することが好ましい。これらの共重合体は公知の方法で製造することができる。 As an acrylic dispersant containing a nitrogen atom, 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.
　官能基を有する不飽和基含有単量体としては、（メタ）アクリル酸、２－（メタ）アクリロイルオキシエチルコハク酸、２－（メタ）アクリロイルオキシエチルフタル酸、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸、アクリル酸ダイマー等のカルボキシル基を有する不飽和単量体；ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート及びこれらの４級化物などの３級アミノ基、４級アンモニウム塩基を有する不飽和単量体が具体例として挙げられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 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.
　官能基を有さない不飽和基含有単量体としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシメチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、トリシクロデカン（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、Ｎ－ビニルピロリドン、スチレン及びその誘導体、α－メチルスチレン、Ｎ－シクロヘキシルマレイミド、Ｎ－フェニルマレイミド、Ｎ－ベンジルマレイミドなどのＮ－置換マレイミド、アクリロニトリル、酢酸ビニル及びポリメチル（メタ）アクリレートマクロモノマー、ポリスチレンマクロモノマー、ポリ２－ヒドロキシエチル（メタ）アクリレートマクロモノマー、ポリエチレングリコールマクロモノマー、ポリプロピレングリコールマクロモノマー、ポリカプロラクトンマクロモノマーなどのマクロモノマー等が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。これらの単量体の側鎖は、溶剤に相溶する溶媒親和部として作用する。 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, α-methylstyrene, N-cyclo N-substituted maleimides such as xylmaleimide, N-phenylmaleimide, N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly-2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol Examples thereof include macromonomers, polypropylene glycol macromonomers, and macromonomers such as polycaprolactone macromonomers. These may be used alone or in combination of two or more. The side chain of these monomers acts as a solvent affinity part that is compatible with the solvent.
　アクリル系分散剤は、分散性の観点から、好ましくは官能基を有するＡブロックと官能基を有さないＢブロックから構成されるＡ－Ｂ又はＢ－Ａ－Ｂブロック共重合体である。この場合、Ａブロック中には上記官能基を含む不飽和基含有単量体由来の部分構造の他に、上記官能基を含まない不飽和基含有単量体由来の部分構造が含まれていてもよく、これらが該Ａブロック中においてランダム共重合又はブロック共重合のいずれの態様で含有されていてもよい。また、官能基を含まない部分構造の、Ａブロック中の含有割合は、通常８０質量％以下であり、好ましくは５０質量％以下、より好ましくは３０質量％以下、さらに好ましくは１０質量％以下、最も好ましくは０質量％である。 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. In this case, 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. Moreover, 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%.
　分散性の観点から、Ｂブロックは上記官能基を含まない不飽和基含有単量体由来の部分構造のみから構成されるものであることが好ましく、１つのＢブロック中に２種以上の単量体由来の部分構造が含有されていてもよく、これらは、該Ｂブロック中においてランダム共重合又はブロック共重合のいずれの態様で含有されていてもよい。
　該Ａ－Ｂ又はＢ－Ａ－Ｂブロック共重合体は、例えば、以下に示すリビング重合法にて調製される。
　リビング重合法には、アニオンリビング重合法、カチオンリビング重合法、ラジカルリビング重合法があり、このうち、アニオンリビング重合法は、重合活性種がアニオンであり、例えば下記スキームで表される。 From the viewpoint of dispersibility, 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. Among these, the anion living polymerization method has a polymerization active species as an anion, and is represented by the following scheme, for example.
Figure JPOXMLDOC01-appb-C000022
  
Figure JPOXMLDOC01-appb-C000022
  
　上記スキーム中、Ａｒ1は１価の有機基であり、Ａｒ2はＡｒ1とは異なる１価の有機基であり、Ｍは金属原子であり、ｓ及びｔはそれぞれ１以上の整数である。 In the above scheme, Ar 1 is a monovalent organic group, Ar 2 is a monovalent organic group different from Ar 1 , M is a metal atom, and s and t are each an integer of 1 or more.
　ラジカルリビング重合法は重合活性種がラジカルであり、例えば下記スキームで示される。 In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.
Figure JPOXMLDOC01-appb-C000023
  
Figure JPOXMLDOC01-appb-C000023
  
　上記スキーム中、Ａｒ1は１価の有機基であり、Ａｒ2はＡｒ1とは異なる１価の有機基であり、ｊ及びｋはそれぞれ１以上の整数であり、Ｒaは水素原子又は１価の有機基であり、ＲbはＲaとは異なる水素原子又は１価の有機基である。 In the above scheme, 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, and R a is a hydrogen atom or 1 R b is a hydrogen atom different from R a or a monovalent organic group.
　このアクリル系分散剤を合成するに際しては、日本国特開平９－６２００２号公報や、Ｐ．Ｌｕｔｚ，　Ｐ．Ｍａｓｓｏｎ　ｅｔ　ａｌ，　Ｐｏｌｙｍ．　Ｂｕｌｌ．　１２，　７９　（１９８４），　Ｂ．Ｃ．Ａｎｄｅｒｓｏｎ，　Ｇ．Ｄ．Ａｎｄｒｅｗｓ　ｅｔａｌ，　Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，　１４，　１６０１（１９８１），　Ｋ．Ｈａｔａｄａ，　Ｋ．Ｕｔｅ，ｅｔ　ａｌ，　Ｐｏｌｙｍ．　Ｊ．　１７，　９７７（１９８５），　１８，　１０３７（１９８６），　右手浩一、畑田耕一、高分子加工、３６，３６６（１９８７），東村敏延、沢本光男、高分子論文集、４６，　１８９（１９８９），　Ｍ．Ｋｕｒｏｋｉ，　Ｔ．Ａｉｄａ，　Ｊ．　Ａｍ．　Ｃｈｅｍ．　Ｓｉｃ，　１０９，　４７３７（１９８７）、相田卓三、井上祥平、有機合成化学、４３，　３００（１９８５），　Ｄ．Ｙ．Ｓｏｇｏｈ，　Ｗ．Ｒ．Ｈｅｒｔｌｅｒ　ｅｔ　ａｌ，　Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，　２０，　１４７３（１９８７）などに記載の公知の方法を採用することができる。 In synthesizing this acrylic dispersant, Japanese Patent Application Laid-Open No. 9-62002 and P.I. Lutz, P.M. Masson et al, Polym. Bull. 12, 79 (1984), B.R. C. Anderson, G. D. Andrews etal, Macromolecules, 14, 1601 (1981), K.K. Hatada, K.A. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Right hand, Koichi Hatada, polymer processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Thesis, 46, 189 (1989), M.M. Kuroki, T.A. Aida, J.A. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.C. Y. Sogoh, W.H. R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) can be employed.
　前述のとおり、本発明で用いることができるアクリル系分散剤はＡ－Ｂブロック共重合体であっても、Ｂ－Ａ－Ｂブロック共重合体であってもよく、その共重合体を構成するＡブロック／Ｂブロック比も特に限定されず、１／９９～８０／２０（質量比）であることが好ましく、５／９５～６０／４０（質量比）であることがより好ましい。この範囲内にすることで分散性と保存安定性のバランスの確保がとりやすい傾向がある。
　また、本発明で用いることができるＡ－Ｂブロック共重合体、Ｂ－Ａ－Ｂブロック共重合体１ｇ中の４級アンモニウム塩基の量は、通常０．１～１０ｍｍｏｌであることが好ましい。この範囲内にすることで良好な分散性を確保しやすい傾向がある。 As described above, 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.
In addition, 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.
　一方で、このようなアクリル系分散剤中には、アミノ基が含有されていてもよい。アクリル系分散剤のアミン価は通常１～１３０ｍｇＫＯＨ／ｇ程度である。１０ｍｇＫＯＨ／ｇ以上が好ましく、３０ｍｇＫＯＨ／ｇ以上がより好ましく、５０ｍｇＫＯＨ／ｇ以上がさらに好ましく、６０ｍｇＫＯＨ／ｇ以上が特に好ましく、また、１２０ｍｇＫＯＨ／ｇ以下が好ましく、１００ｍｇＫＯＨ／ｇ以下がより好ましく、９０ｍｇＫＯＨ／ｇ以下がさらに好ましく、８０ｍｇＫＯＨ／ｇ以下が特に好ましい。前記下限値以上とすることで分散性が良好となる傾向があり、また、前記上限値以下とすることで分散後の保存性が良好となる傾向がある。上限と下限の組み合わせとしては、１０～１２０ｍｇＫＯＨ／ｇが好ましく、３０～１００ｍｇＫＯＨ／ｇがより好ましく、５０～９０ｍｇＫＯＨ／ｇがさらに好ましく、６０～８０ｍｇＫＯＨ／ｇが特に好ましく挙げられる。
　ここで、アクリル系分散剤のアミン価は、分散剤試料中の溶剤を除いた固形分１ｇあたりの塩基量と当量のＫＯＨの質量で表し、次の方法により測定する。
　１００ｍＬのビーカーに分散剤試料の０．５～１．５ｇを精秤し、５０ｍＬの酢酸で溶解する。ｐＨ電極を備えた自動滴定装置を使って、この溶液を０．１ｍｏｌ／ＬのＨＣｌＯ4の酢酸溶液にて中和滴定する。滴定ｐＨ曲線の変曲点を滴定終点とし次式によりアミン価を求める。 On the other hand, 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. When the amount is not less than the lower limit value, the dispersibility tends to be good, and when the value is not more than the upper limit value, the preservability after dispersion tends to be good. 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.
Here, 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.
Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with an 0.1 mol / L HClO 4 acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.
　アミン価［ｍｇＫＯＨ／ｇ］＝（５６１×Ｖ）／（Ｗ×Ｓ）
〔但し、Ｗ：分散剤試料秤取量［ｇ］、Ｖ：滴定終点での滴定量［ｍＬ］、Ｓ：分散剤試料の固形分濃度［質量％］を表す。〕 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. ]
　アクリル系分散剤の重量平均分子量（Ｍｗ）は特に限定されないが、１０００以上が好ましく、３０００以上がより好ましく、４０００以上がさらに好ましく、５０００以上が特に好ましく、また、５００００以下が好ましく、２００００以下がより好ましく、１５０００以下がさらに好ましい。前記下限値以上とすることで分散性が良好となる傾向があり、また、前記上限値以下とすることで粘度変化が起こりにくい傾向がある。上限と下限の組み合わせとしては、１０００～５００００が好ましく、３０００～２００００がより好ましく、４０００～１５０００がさらに好ましく、５０００～１５０００が特に好ましく挙げられる。 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. When the amount is not less than the lower limit value, the dispersibility tends to be good, and when the value is not more than the upper limit value, the viscosity does not easily change. 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.
　アクリル系分散剤が４級アンモニウム塩基を官能基として有する場合、４級アンモニウム塩基を含む繰り返し単位の化学構造は特に限定されないが、分散性の観点からは、アクリル系分散剤が下記一般式（Ｖ）で表される繰り返し単位（以下、「繰り返し単位（Ｖ）」ということがある。）を有することが好ましい。 When 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)”).
Figure JPOXMLDOC01-appb-C000024
  
Figure JPOXMLDOC01-appb-C000024
  
　上記式（Ｖ）中、Ｒ31～Ｒ33は各々独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基であり、Ｒ31～Ｒ33のうち２つ以上が互いに結合して環状構造を形成してもよく；
Ｒ34は水素原子又はメチル基であり；
Ｘは２価の連結基であり；
Ｙ-は対アニオンである。 In the above formula (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. An aralkyl group that may be present, and two or more of R 31 to R 33 may be bonded to each other to form a cyclic structure;
R 34 is a hydrogen atom or a methyl group;
X is a divalent linking group;
Y − is a counter anion.
　上記式（Ｖ）のＲ31～Ｒ33における、置換基を有していてもよいアルキル基の炭素数は特に限定されないが、通常１以上であり、また、１０以下であることが好ましく、６以下であることがより好ましく、４以下であることがさらに好ましく、２以下であることが特に好ましい。アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基などが挙げられ、これらの中でも、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、又はヘキシル基であることが好ましく、メチル基、エチル基、プロピル基、又はブチル基であることがより好ましく、メチル基又はエチル基であることがさらに好ましい。また、直鎖状、分岐鎖状のいずれであってもよい。また、シクロヘキシル基、シクロヘキシルメチル基などの環状構造を含むものでもよい。 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.
　上記式（Ｖ）のＲ31～Ｒ33における、置換基を有していてもよいアリール基の炭素数は特に限定されないが、通常６以上であり、また、１６以下であることが好ましく、１２以下であることがより好ましい。アリール基の具体例としては、フェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、ジエチルフェニル基、ナフチル基、アントラセニル基などが挙げられ、これらの中でもフェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、又はジエチルフェニル基であることが好ましく、フェニル基、メチルフェニル基、又はエチルフェニル基であることがより好ましい。 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. Among these, 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.
　上記式（Ｖ）のＲ31～Ｒ33における、置換基を有していてもよいアラルキル基の炭素数は特に限定されないが、通常７以上であり、また、１６以下であることが好ましく、１２以下であることがより好ましく、１０以下であることがさらに好ましく、８以下であることが特に好ましい。アラルキル基の具体例としては、フェニルメチル基（ベンジル基）、フェニルエチル基（フェネチル基）、フェニルプロピル基、フェニルブチル基、フェニルイソプロピル基などが挙げられ、これらの中でも、フェニルメチル基、フェニルエチル基、フェニルプロピル基、又はフェニルブチル基であることが好ましく、フェニルメチル基、又はフェニルエチル基であることがより好ましい。 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. Among these, 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.
　これらの中でも、分散性の観点から、Ｒ31～Ｒ33が各々独立にアルキル基、又はアラルキル基であることが好ましく、具体的には、Ｒ31及びＲ33が各々独立にメチル基、又はエチル基であり、かつ、Ｒ32がフェニルメチル基、又はフェニルエチル基であることが好ましく、Ｒ31及びＲ33がメチル基であり、かつ、Ｒ32がフェニルメチル基であることがさらに好ましい。 Among these, from the viewpoint of dispersibility, 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.
　また、前記高分子分散剤が官能基として３級アミンを有する場合、分散性の観点からは、下記一般式（ＶＩ）で表される繰り返し単位（以下、「繰り返し単位（ＶＩ）」ということがある。）を有することが好ましい。 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.
Figure JPOXMLDOC01-appb-C000025
  
Figure JPOXMLDOC01-appb-C000025
  
　上記式（ＶＩ）中、Ｒ35及びＲ36は各々独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基であり、Ｒ35及びＲ36が互いに結合して環状構造を形成してもよく；
Ｒ37は水素原子又はメチル基であり；
Ｚは２価の連結基である。 In the above formula (VI), 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.
　また、上記式（ＶＩ）のＲ35及びＲ36における、置換基を有していてもよいアルキル基としては、上記式（Ｖ）のＲ31～Ｒ33として例示したものを好ましく採用することができる。
　同様に、上記式（ＶＩ）のＲ35及びＲ36における、置換基を有していてもよいアリール基としては、上記式（Ｖ）のＲ31～Ｒ33として例示したものを好ましく採用することができる。また、上記式（ＶＩ）のＲ35及びＲ36における、置換基を有していてもよいアラルキル基としては、上記式（Ｖ）のＲ31～Ｒ33として例示したものを好ましく採用することができる。 In addition, as the 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.
Similarly, as the 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. In addition, as 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.
　これらの中でも、分散性の観点から、Ｒ35及びＲ36が各々独立に、置換基を有していてもよいアルキル基であることが好ましく、メチル基、又はエチル基であることがより好ましい。 Among these, from the viewpoint of dispersibility, independently 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.
　上記式（Ｖ）のＲ31～Ｒ33及び上記式（ＶＩ）のＲ35及びＲ36におけるアルキル基、アラルキル基又はアリール基が有していてもよい置換基としては、ハロゲン原子、アルコキシ基、ベンゾイル基、水酸基などが挙げられる。 Examples of the substituent that the 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.
　上記式（Ｖ）及び（ＶＩ）において、２価の連結基Ｘ及びＺとしては、例えば、炭素数１～１０のアルキレン基、炭素数６～１２のアリーレン基、－ＣＯＮＨ－Ｒ43－基、－ＣＯＯＲ44－基〔但し、Ｒ43及びＲ44は単結合、炭素数１～１０のアルキレン基、又は炭素数２～１０のエーテル基（アルキルオキシアルキル基）である〕等が挙げられ、好ましくは－ＣＯＯ－Ｒ44－基、より好ましくは－ＣＯＯ－Ｃ２Ｈ４－基である。
　また、上記式（Ｖ）において、対アニオンのＹ-としては、Ｃｌ-、Ｂｒ-、Ｉ-、ＣｌＯ4 -、ＢＦ4 -、ＣＨ3ＣＯＯ-、ＰＦ6 -等が挙げられる。 In the above formulas (V) and (VI), 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.
In the formula (V), examples of Y − of the counter anion include Cl − , Br − , I − , ClO 4 − , BF 4 − , CH 3 COO − , PF 6 − and the like.
　前記式（Ｖ）で表される繰り返し単位の含有割合は特に限定されないが、分散性の観点から、前記式（Ｖ）で表される繰り返し単位の含有割合と前記式（ＶＩ）で表される繰り返し単位の含有割合の合計に対して好ましくは６０モル％以下であり、より好ましくは５０モル％以下であり、さらに好ましくは４０モル％以下であり、特に好ましくは３５モル％以下であり、また、好ましくは５モル％以上であり、より好ましくは１０モル％以上であり、さらに好ましくは２０モル％以上であり、特に好ましくは３０モル％以上である。上限と下限の組み合わせとしては、５～６０モル％が好ましく、１０～５０モル％がより好ましく、２０～４０モル％がさらに好ましく、３０～３５モル％が特に好ましく挙げられる。 Although 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). Preferably 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%.
　また、分散剤の全繰り返し単位に占める前記式（Ｖ）で表される繰り返し単位の含有割合は特に限定されないが、分散性の観点から、１モル％以上であることが好ましく、５モル％以上であることがより好ましく、８モル％以上であることがさらに好ましく、１０モル％以上であることが特に好ましく、また、５０モル％以下であることが好ましく、３０モル％以下であることがより好ましく、２０モル％以下であることがさらに好ましく、１５モル％以下であることが特に好ましい。上限と下限の組み合わせとしては、１～５０モル％が好ましく、５～３０モル％がより好ましく、８～２０モル％がさらに好ましく、１０～１５モル％が特に好ましく挙げられる。 Further, 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%.
　前記式（ＶＩ）で表される繰り返し単位の含有割合は特に限定されないが、分散性の観点から、前記式（Ｖ）で表される繰り返し単位の含有割合と前記式（ＶＩ）で表される繰り返し単位の含有割合の合計に対して好ましくは１００モル％以下であり、より好ましくは９０モル％以下であり、さらに好ましくは８０モル％以下であり、特に好ましくは７０モル％以下であり、また、好ましくは１０モル％以上であり、より好ましくは３０モル％以上であり、さらに好ましくは５０モル％以上であり、特に好ましくは６０モル％以上である。上限と下限の組み合わせとしては、１０～１００モル％が好ましく、３０～９０モル％がより好ましく、５０～８０モル％がさらに好ましく、６０～７０モル％が特に好ましく挙げられる。 Although 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). Preferably 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%.
　また、分散剤の全繰り返し単位に占める前記式（ＶＩ）で表される繰り返し単位の含有割合は特に限定されないが、分散性の観点から、５モル％以上であることが好ましく、１０モル％以上であることがより好ましく、１５モル％以上であることがさらに好ましく、２０モル％以上であることが特に好ましく、また、６０モル％以下であることが好ましく、４０モル％以下であることがより好ましく、３０モル％以下であることがさらに好ましく、２５モル％以下であることが特に好ましい。上限と下限の組み合わせとしては、５～６００モル％が好ましく、１０～４０モル％がより好ましく、１５～３０モル％がさらに好ましく、２０～２５モル％が特に好ましく挙げられる。 Further, 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%.
　また、アクリル系分散剤は、溶媒等のバインダー成分に対する相溶性を高め、分散安定性を向上させるとの観点から、下記一般式（ＶＩＩ）で表される繰り返し単位（以下、「繰り返し単位（ＶＩＩ）」ということがある。）を有することが好ましい。 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. ) ").).
Figure JPOXMLDOC01-appb-C000026
  
Figure JPOXMLDOC01-appb-C000026
  
　上記式（ＶＩＩ）中、Ｒ40はエチレン基又はプロピレン基であり；
Ｒ41は置換基を有していてもよいアルキル基であり；
Ｒ42は水素原子又はメチル基であり；
ｎは１～２０の整数である。 In the above formula (VII), 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.
　上記式（ＶＩＩ）のＲ41における、置換基を有していてもよいアルキル基の炭素数は特に限定されないが、通常１以上であり、２以上であることが好ましく、また、１０以下であることが好ましく、６以下であることがより好ましく、４以下であることがさらに好ましい。アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基などが挙げられ、これらの中でも、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、又はヘキシル基であることが好ましく、メチル基、エチル基、プロピル基、又はブチル基であることがより好ましい。また、直鎖状、分岐鎖状のいずれであってもよい。また、シクロヘキシル基、シクロヘキシルメチル基などの環状構造を含んでもよい。 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.
　また、上記式（ＶＩＩ）におけるｎは溶媒等バインダー成分に対する相溶性と分散性の観点から、１以上であることが好ましく、２以上であることがより好ましく、また、１０以下であることが好ましく、５以下であることがより好ましい。上限と下限の組み合わせとしては、１～１０の整数が好ましく、２～５の整数がより好ましく挙げられる。 Further, 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.
　また、分散剤の全繰り返し単位に占める前記式（ＶＩＩ）で表される繰り返し単位の含有割合は特に限定されないが、１モル％以上であることが好ましく、２モル％以上であることがより好ましく、４モル％以上であることがさらに好ましく、また、３０モル％以下であることが好ましく、２０モル％以下であることがより好ましく、１０モル％以下であることがさらに好ましい。前記範囲内の場合には溶媒等バインダー成分に対する相溶性と分散安定性の両立がしやすい傾向がある。上限と下限の組み合わせとしては、１～３０モル％が好ましく、２～２０モル％がより好ましく、４～１０モル％がさらに好ましく挙げられる。 Further, 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.
　また、アクリル系分散剤は、分散剤の溶媒等バインダー成分に対する相溶性を高め、分散安定性を向上させるという観点から、１種以上の下記一般式（ＶＩＩＩ）で表される繰り返し単位（以下、「繰り返し単位（ＶＩＩＩ）」ということがある。）を有することが好ましい。 In addition, 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)”.
Figure JPOXMLDOC01-appb-C000027
  
Figure JPOXMLDOC01-appb-C000027
  
　上記式（ＶＩＩＩ）中、Ｒ38は置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基であり；
Ｒ39は水素原子又はメチル基である。 In the above formula (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.
　上記式（ＶＩＩＩ）のＲ38における、置換基を有していてもよいアルキル基の炭素数は特に限定されないが、通常１以上であり、２以上であることが好ましく、４以上であることがより好ましく、また、１０以下であることが好ましく、８以下であることがより好ましい。アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、２－エチルヘキシル基などが挙げられ、これらの中でも、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、又は２－エチルヘキシル基であることが好ましく、メチル基、エチル基、プロピル基、ブチル基、又は２－エチルヘキシル基であることがより好ましい。また、直鎖状、分岐鎖状のいずれであってもよい。また、シクロヘキシル基、シクロヘキシルメチル基などの環状構造を含んでもよい。 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. Among these, 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. Further, it may be either linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
　上記式（ＶＩＩＩ）のＲ38における、置換基を有していてもよいアリール基の炭素数は特に限定されないが、通常６以上であり、また、１６以下であることが好ましく、１２以下であることがより好ましく、８以下であることがさらに好ましい。アリール基の具体例としては、フェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、ジエチルフェニル基、ナフチル基、アントラセニル基などが挙げられ、これらの中でもフェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、又はジエチルフェニル基であることが好ましく、フェニル基、メチルフェニル基、又はエチルフェニル基であることがより好ましい。 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. Among these, 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.
　上記式（ＶＩＩＩ）のＲ38における、置換基を有していてもよいアラルキル基の炭素数は特に限定されないが、通常７以上であり、また、１６以下であることが好ましく、１２以下であることがより好ましく、１０以下であることがさらに好ましい。アラルキル基の具体例としては、フェニルメチル基（ベンジル基）、フェニルエチル基（フェネチル基）、フェニルプロピル基、フェニルブチル基、フェニルイソプロピル基などが挙げられ、これらの中でも、フェニルメチル基、フェニルエチル基、フェニルプロピル基、又はフェニルブチル基であることが好ましく、フェニルメチル基、又はフェニルエチル基であることがより好ましい。 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. Among these, 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.
　これらの中でも、溶剤相溶性と分散安定性の観点から、Ｒ38がアルキル基、又はアラルキル基であることが好ましく、メチル基、エチル基、ブチル基、２－エチルヘキシル基又はフェニルメチル基であることがより好ましい。
　Ｒ38における、アルキル基が有していてもよい置換基としては、ハロゲン原子、アルコキシ基等が挙げられる。また、アリール基又はアラルキル基が有していてもよい置換基としては、鎖状のアルキル基、ハロゲン原子、アルコキシ基等が挙げられる。また、Ｒ38で示される鎖状のアルキル基には、直鎖状及び分岐鎖状のいずれも含まれる。 Among these, from the viewpoint of solvent compatibility and dispersion stability, 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.
Examples of the substituent that the alkyl group may have in R 38 include a halogen atom and an alkoxy group. Examples of the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group. Further, the linear alkyl group represented by R 38 includes both linear and branched chains.
　また、分散剤の全繰り返し単位に占める前記式（ＶＩＩＩ）で表される繰り返し単位の含有割合（２種以上の前記式（ＶＩＩＩ）で表される繰り返し単位を含む場合はその合計の含有割合）は、分散性の観点から、３０モル％以上であることが好ましく、４０モル％以上であることがより好ましく、５０モル％以上であることがさらに好ましく、また、８０モル％以下であることが好ましく、７０モル％以下であることがより好ましい。上限と下限の組み合わせとしては、３０～８０モル％が好ましく、４０～７０モル％がより好ましく、５０～７０モル％がさらに好ましく挙げられる。 Moreover, 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%.
　アクリル系分散剤は、繰り返し単位（Ｖ）、繰り返し単位（ＶＩ）、繰り返し単位（ＶＩＩ）及び繰り返し単位（ＶＩＩＩ）以外の繰り返し単位を有していてもよい。そのような繰り返し単位の例としては、スチレン、α－メチルスチレンなどのスチレン系単量体；（メタ）アクリル酸クロリドなどの（メタ）アクリル酸塩系単量体；（メタ）アクリルアミド、Ｎ－メチロールアクリルアミドなどの（メタ）アクリルアミド系単量体；酢酸ビニル；アクリロニトリル；アリルグリシジルエーテル、クロトン酸グリシジルエーテル；Ｎ－メタクリロイルモルホリン等の単量体に由来する繰り返し単位が挙げられる。 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). Examples of such repeating units include styrene monomers such as styrene and α-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.
　アクリル系分散剤は、分散性をより高めるとの観点から、繰り返し単位（Ｖ）及び繰り返し単位（ＶＩ）を有するＡブロックと、繰り返し単位（Ｖ）及び繰り返し単位（ＶＩ）を有さないＢブロックとを有する、ブロック共重合体であることが好ましい。該ブロック共重合体は、Ａ－Ｂブロック共重合体又はＢ－Ａ－Ｂブロック共重合体であることが好ましい。Ａブロックに４級アンモニウム塩基だけでなく３級アミノ基も導入することにより、意外にも、分散剤の分散能力が著しく向上する傾向がある。また、Ｂブロックが繰り返し単位（ＶＩＩ）を有することが好ましく、更に繰り返し単位（ＶＩＩＩ）を有することがより好ましい。 From the viewpoint of further improving dispersibility, 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).
　Ａブロック中において、繰り返し単位（Ｖ）及び繰り返し単位（ＶＩ）は、ランダム共重合、ブロック共重合のいずれの態様で含有されていてもよい。また、繰り返し単位（Ｖ）及び繰り返し単位（ＶＩ）は、１つのＡブロック中に各々２種以上含有されていてもよく、その場合、各々の繰り返し単位は、該Ａブロック中においてランダム共重合、ブロック共重合のいずれの態様で含有されていてもよい。 In the A block, 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.
　また、繰り返し単位（Ｖ）及び繰り返し単位（ＶＩ）以外の繰り返し単位が、Ａブロック中に含有されていてもよく、そのような繰り返し単位の例としては、前述の（メタ）アクリル酸エステル系単量体由来の繰り返し単位等が挙げられる。繰り返し単位（Ｖ）及び繰り返し単位（ＶＩ）以外の繰り返し単位の、Ａブロック中の含有量は、好ましくは０～５０モル％、より好ましくは０～２０モル％であるが、係る繰り返し単位はＡブロック中に含有されないことが最も好ましい。 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.
　繰り返し単位（ＶＩＩ）及び（ＶＩＩＩ）以外の繰り返し単位がＢブロック中に含有されていてもよく、そのような繰り返し単位の例としては、スチレン、α－メチルスチレンなどのスチレン系単量体；（メタ）アクリル酸クロリドなどの（メタ）アクリル酸塩系単量体；（メタ）アクリルアミド、Ｎ－メチロールアクリルアミドなどの（メタ）アクリルアミド系単量体；酢酸ビニル；アクリロニトリル；アリルグリシジルエーテル、クロトン酸グリシジルエーテル；Ｎ－メタクリロイルモルホリン等の単量体に由来する繰り返し単位が挙げられる。繰り返し単位（ＶＩＩ）及び繰り返し単位（ＶＩＩＩ）以外の繰り返し単位の、Ｂブロック中の含有割合は、好ましくは０～５０モル％、より好ましくは０～２０モル％であるが、かかる繰り返し単位はＢブロック中に含有されないことが最も好ましい。
　これらのアクリル系分散剤は１種を単独で使用してもよく、又は２種以上を併用してもよい。
　また、本発明の第１の態様に係る着色感光性樹脂組成物、及び本発明の第３の態様に係る顔料分散液において、（Ｂ）分散剤は前述のアクリル系分散剤以外に、以下に示すその他の高分子分散剤を含んでいてもよい。 Repeating units other than the repeating units (VII) and (VIII) may be contained in the B block. Examples of such repeating units include styrene monomers such as styrene and α-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.
Further, in the colored photosensitive resin composition according to the first aspect of the present invention and the pigment dispersion according to the third aspect of the present invention, (B) the dispersant is the following in addition to the acrylic dispersant described above. Other polymer dispersants shown may be included.
　その他の高分子分散剤としては、例えばウレタン系分散剤、ポリエチレンイミン系分散剤、ポリアリルアミン系分散剤、アミノ基を持つモノマーとマクロモノマーからなる分散剤、ポリオキシエチレンアルキルエーテル系分散剤、ポリオキシエチレンジエステル系分散剤、ポリエーテルリン酸系分散剤、ポリエステルリン酸系分散剤、ソルビタン脂肪族エステル系分散剤、脂肪族変性ポリエステル系分散剤等を挙げることができる。 Other 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.
　このような分散剤の具体例としては、商品名で、ＥＦＫＡ（登録商標。ＢＡＳＦ社製。）、ＤＩＳＰＥＲＢＹＫ（登録商標。ビックケミー社製。）、ディスパロン（登録商標。楠本化成社製。）、ＳＯＬＳＰＥＲＳＥ（登録商標。ルーブリゾール社製。）、ＫＰ（信越化学工業社製）、ポリフロー（共栄社化学社製）、アジスパー（登録商標。味の素社製。）等を挙げることができる。 Specific examples of such a dispersant are 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.
　その他の高分子分散剤の重量平均分子量（Ｍｗ）は通常７００以上、好ましくは１０００以上であり、また通常１０００００以下、好ましくは５００００以下である。
　その他の高分子分散剤の中でも、顔料の分散性の観点からは、ウレタン系高分子分散剤が好ましく挙げられる。
　またウレタン系高分子分散剤の中でも、分散性、保存性の面から、塩基性官能基を有し、ポリエステル結合及び／又はポリエーテル結合を有する高分子分散剤が好ましい。 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.
Among other polymer dispersants, urethane polymer dispersants are preferable from the viewpoint of pigment dispersibility.
Among urethane-based polymer dispersants, 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.
　ウレタン系高分子分散剤としては、例えばＤＩＳＰＥＲＢＹＫ１６０～１６７、１８２シリーズが挙げられる。
　ウレタン系高分子分散剤として好ましい化学構造を具体的に例示するならば、例えば、ポリイソシアネート化合物と、分子内に水酸基を１個又は２個有する数平均分子量３００～１００００の化合物と、同一分子内に活性水素と３級アミノ基を有する化合物とを反応させることによって得られる、重量平均分子量１０００～２０００００の分散樹脂等が挙げられる。これらをベンジルクロリド等の四級化剤で処理することで、３級アミノ基の全部又は一部を４級アンモニウム塩基にすることができる。 Examples of urethane polymer dispersants 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. And 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. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino group can be converted to a quaternary ammonium base.
　上記のポリイソシアネート化合物の例としては、パラフェニレンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、４，４′－ジフェニルメタンジイソシアネート、ナフタレン－１，５－ジイソシアネート、トリジンジイソシアネート等の芳香族ジイソシアネート、ヘキサメチレンジイソシアネート、リジンメチルエステルジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、ダイマー酸ジイソシアネート等の脂肪族ジイソシアネート、イソホロンジイソシアネート、４，４′－メチレンビス（シクロヘキシルイソシアネート）、ω，ω′－ジイソシネートジメチルシクロヘキサン等の脂環族ジイソシアネート、キシリレンジイソシアネート、α，α，α’，α’－テトラメチルキシリレンジイソシアネート等の芳香環を有する脂肪族ジイソシアネート、リジンエステルトリイソシアネート、１，６，１１－ウンデカントリイソシアネート、１，８－ジイソシアネート－４－イソシアネートメチルオクタン、１，３，６－ヘキサメチレントリイソシアネート、ビシクロヘプタントリイソシアネート、トリス（イソシアネートフェニルメタン）、トリス（イソシアネートフェニル）チオホスフェート等のトリイソシアネート、及びこれらの三量体、水付加物、及びこれらのポリオール付加物等が挙げられる。ポリイソシアネートとして好ましいのは有機ジイソシアネートの三量体で、最も好ましいのはトリレンジイソシアネートの三量体とイソホロンジイソシアネートの三量体である。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the above polyisocyanate compounds 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), ω, ω Alicyclic diisocyanates such as ′ -diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α ′, α′-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 triisocyanates such as isocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, trimers thereof, water adducts, and polyol adducts thereof. Preferred as the 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.
　イソシアネートの三量体の製造方法としては、前記ポリイソシアネート類を適当な三量化触媒、例えば第３級アミン類、ホスフィン類、アルコキシド類、金属酸化物、カルボン酸塩類等を用いてイソシアネート基の部分的な三量化を行い、触媒毒の添加により三量化を停止させた後、未反応のポリイソシアネートを溶剤抽出、薄膜蒸留により除去して目的のイソシアヌレート基含有ポリイソシアネートを得る方法が挙げられる。 As a method for producing an isocyanate trimer, 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.
　同一分子内に水酸基を１個又は２個有する数平均分子量３００～１００００の化合物としては、ポリエーテルグリコール、ポリエステルグリコール、ポリカーボネートグリコール、ポリオレフィングリコール等、及びこれらの化合物の片末端水酸基が炭素数１～２５のアルキル基でアルコキシ化されたもの及びこれら２種類以上の混合物が挙げられる。
　ポリエーテルグリコールとしては、ポリエーテルジオール、ポリエーテルエステルジオール、及びこれら２種類以上の混合物が挙げられる。ポリエーテルジオールとしては、アルキレンオキシドを単独又は共重合させて得られるもの、例えばポリエチレングリコール、ポリプロピレングリコール、ポリエチレン－プロピレングリコール、ポリオキシテトラメチレングリコール、ポリオキシヘキサメチレングリコール、ポリオキシオクタメチレングリコール及びそれらの２種以上の混合物が挙げられる。 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. Examples of 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.
　ポリエーテルエステルジオールとしては、エーテル基含有ジオールもしくは他のグリコールとの混合物をジカルボン酸又はそれらの無水物と反応させるか、又はポリエステルグリコールにアルキレンオキシドを反応させることによって得られるもの、例えばポリ（ポリオキシテトラメチレン）アジペート等が挙げられる。ポリエーテルグリコールとして最も好ましいのはポリエチレングリコール、ポリプロピレングリコール、ポリオキシテトラメチレングリコール又はこれらの化合物の片末端水酸基が炭素数１～２５のアルキル基でアルコキシ化された化合物である。 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. Most preferred as 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.
　ポリエステルグリコールとしては、ジカルボン酸（コハク酸、グルタル酸、アジピン酸、セバシン酸、フマル酸、マレイン酸、フタル酸等）又はそれらの無水物とグリコール（エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２，３－ブタンジオール、３－メチル－１，５－ペンタンジオール、ネオペンチルグリコール、２－メチル－１，３－プロパンジオール、２－メチル－２－プロピル－１，３－プロパンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、２－メチル－２，４－ペンタンジオール、２，２，４－トリメチル－１，３－ペンタンジオール、２－エチル－１，３－ヘキサンジオール、２，５－ジメチル－２，５－ヘキサンジオール、１，８－オクタメチレングリコール、２－メチル－１，８－オクタメチレングリコール、１，９－ノナンジオール等の脂肪族グリコール、ビスヒドロキシメチルシクロヘキサン等の脂環族グリコール、キシリレングリコール、ビスヒドロキシエトキシベンゼン等の芳香族グリコール、Ｎ－メチルジエタノールアミン等のＮ－アルキルジアルカノールアミン等）とを重縮合させて得られたもの、例えばポリエチレンアジペート、ポリブチレンアジペート、ポリヘキサメチレンアジペート、ポリエチレン／プロピレンアジペート等、又は前記ジオール類又は炭素数１～２５の１価アルコールを開始剤として用いて得られるポリラクトンジオール又はポリラクトンモノオール、例えばポリカプロラクトングリコール、ポリメチルバレロラクトン及びこれらの２種以上の混合物が挙げられる。ポリエステルグリコールとして最も好ましいのはポリカプロラクトングリコール又は炭素数１～２５のアルコールを開始剤としたポリカプロラクトンである。 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, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N Obtained by polycondensation with N-alkyl dialkanolamine such as methyldiethanolamine), such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diols or carbon number 1-25 1 Alcohol polylactone diol obtained by using as an initiator or polylactone monool, for example polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone initiated with an alcohol having 1 to 25 carbon atoms.
　ポリカーボネートグリコールとしては、ポリ（１，６－ヘキシレン）カーボネート、ポリ（３－メチル－１，５－ペンチレン）カーボネート等、ポリオレフィングリコールとしてはポリブタジエングリコール、水素添加型ポリブタジエングリコール、水素添加型ポリイソプレングリコール等が挙げられる。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 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.
　同一分子内に水酸基を１個又は２個有する化合物の数平均分子量は、通常３００～１００００、好ましくは５００～６０００、更に好ましくは１０００～４０００である。 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.
　本発明に用いられる同一分子内に活性水素と３級アミノ基を有する化合物を説明する。
　活性水素、即ち、酸素原子、窒素原子又は硫黄原子に直接結合している水素原子としては、水酸基、アミノ基、チオール基等の官能基中の水素原子が挙げられ、中でもアミノ基、特に１級のアミノ基の水素原子が好ましい。 A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described.
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.
　３級アミノ基は、特に限定されないが、例えば炭素数１～４のアルキル基を有するアミノ基、又はヘテロ環構造、より具体的にはイミダゾール環又はトリアゾール環、などが挙げられる。
　このような同一分子内に活性水素と３級アミノ基を有する化合物を例示するならば、Ｎ，Ｎ－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジエチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジプロピル－１，３－プロパンジアミン、Ｎ，Ｎ－ジブチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジメチルエチレンジアミン、Ｎ，Ｎ－ジエチルエチレンジアミン、Ｎ，Ｎ－ジプロピルエチレンジアミン、Ｎ，Ｎ－ジブチルエチレンジアミン、Ｎ，Ｎ－ジメチル－１，４－ブタンジアミン、Ｎ，Ｎ－ジエチル－１，４－ブタンジアミン、Ｎ，Ｎ－ジプロピル－１，４－ブタンジアミン、Ｎ，Ｎ－ジブチル－１，４－ブタンジアミン等が挙げられる。 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-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.
　また、３級アミノ基が含窒素ヘテロ環構造である場合の該含窒素ヘテロ環としては、ピラゾール環、イミダゾール環、トリアゾール環、テトラゾール環、インドール環、カルバゾール環、インダゾール環、ベンズイミダゾール環、ベンゾトリアゾール環、ベンゾオキサゾール環、ベンゾチアゾール環、ベンゾチアジアゾール環等の含窒素ヘテロ５員環、ピリジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、アクリジン環、イソキノリン環等の含窒素ヘテロ６員環が挙げられる。これらの含窒素ヘテロ環のうち好ましいものはイミダゾール環又はトリアゾール環である。 In addition, when the tertiary amino group is a nitrogen-containing heterocyclic structure, 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. Among these nitrogen-containing heterocycles, preferred are an imidazole ring or a triazole ring.
　これらのイミダゾール環とアミノ基を有する化合物を具体的に例示するならば、１－（３－アミノプロピル）イミダゾール、ヒスチジン、２－アミノイミダゾール、１－（２－アミノエチル）イミダゾール等が挙げられる。また、トリアゾール環とアミノ基を有する化合物を具体的に例示するならば、３－アミノ－１，２，４－トリアゾール、５－（２－アミノ－５－クロロフェニル）－３－フェニル－１Ｈ－１，２，４－トリアゾール、４－アミノ－４Ｈ－１，２，４－トリアゾール－３，５－ジオール、３－アミノ－５－フェニル－１Ｈ－１，３，４－トリアゾール、５－アミノ－１，４－ジフェニル－１，２，３－トリアゾール、３－アミノ－１－ベンジル－１Ｈ－２，４－トリアゾール等が挙げられる。中でも、Ｎ，Ｎ－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジエチル－１，３－プロパンジアミン、１－（３－アミノプロピル）イミダゾール、３－アミノ－１，２，４－トリアゾールが好ましい。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Specific examples of 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. Further, 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. Among these, 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.
　ウレタン系高分子分散剤を製造する際の原料の好ましい配合比率はポリイソシアネート化合物１００質量部に対し、同一分子内に水酸基を１個又は２個有する数平均分子量３００～１００００の化合物が１０～２００質量部、好ましくは２０～１９０質量部、更に好ましくは３０～１８０質量部、同一分子内に活性水素と３級アミノ基を有する化合物が０．２～２５質量部、好ましくは０．３～２４質量部である。 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.
　ウレタン系高分子分散剤の製造は、公知のポリウレタン樹脂製造方法に従って行うことができる。製造する際の溶媒としては、通常、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン、イソホロン等のケトン類、酢酸エチル、酢酸ブチル、酢酸セロソルブ等のエステル類、ベンゼン、トルエン、キシレン、ヘキサン等の炭化水素類、ダイアセトンアルコール、イソプロパノール、第二ブタノール、第三ブタノール等一部のアルコール類、塩化メチレン、クロロホルム等の塩化物、テトラヒドロフラン、ジエチルエーテル等のエーテル類、ジメチルホルムアミド、Ｎ－メチルピロリドン、ジメチルスルホキサイド等の非プロトン性極性溶媒等が用いられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 The production of the urethane-based polymer dispersant can be performed according to a known polyurethane resin production method. As 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 more.
　上記製造に際して、通常、ウレタン化反応触媒が用いられる。この触媒としては、例えば、ジブチルチンジラウレート、ジオクチルチンジラウレート、ジブチルチンジオクトエート、スタナスオクトエート等の錫系、鉄アセチルアセトナート、塩化第二鉄等の鉄系、トリエチルアミン、トリエチレンジアミン等の３級アミン系等が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用して用いてもよい。 In the above production, a urethanization reaction catalyst is usually used. Examples of 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.
　同一分子内に活性水素と３級アミノ基を有する化合物の導入量は反応後のアミン価で１～１００ｍｇＫＯＨ／ｇの範囲に制御するのが好ましい。より好ましくは５～９５ｍｇＫＯＨ／ｇの範囲である。アミン価は、塩基性アミノ基を酸により中和滴定し、酸価に対応させてＫＯＨのｍｇ数で表した値である。前記下限値以上とすることで分散能力が向上する傾向があり、また、前記上限値以下とすることで現像性が良好になる傾向がある。 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.
　なお、以上の反応で高分子分散剤にイソシアネート基が残存する場合には更に、アルコールやアミノ化合物でイソシアネート基を潰すと生成物の経時安定性が高くなるので好ましい。
　ウレタン系高分子分散剤の重量平均分子量（Ｍｗ）は通常１０００～２０００００、好ましくは２０００～１０００００、より好ましくは３０００～５００００の範囲である。前記下限値以上とすることで分散性及び分散安定性が良好となる傾向があり、前記上限値以下とすることで溶解性が向上し分散性が良好となり、反応の制御も容易となる傾向がある。 In addition, when an isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time is increased.
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.
　また分散安定性向上の点から、（Ｂ）分散剤は、後述する顔料誘導体と併用することが好ましい。 Further, from the viewpoint of improving dispersion stability, (B) the dispersant is preferably used in combination with a pigment derivative described later.
　一方で、本発明の第２の態様に係る着色感光性樹脂組成物における（Ｂ）分散剤は、（Ａ）着色剤を分散できるものであれば何ら限定されない。具体的には、上述のアクリル系分散剤でもよく、上述のその他の高分子分散剤でもよい。これらの中でも、分散性の観点からはアクリル系分散剤、又はウレタン系高分子分散剤を含むことが好ましい。 On the other hand, 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. Specifically, the above-mentioned acrylic dispersant may be used, and the other polymer dispersants described above may be used. Among these, it is preferable that an acrylic type dispersing agent or a urethane type polymer dispersing agent is included from a dispersible viewpoint.
［１－３］（Ｃ）バインダー樹脂
　本発明の着色感光性樹脂組成物及び顔料分散液は、（Ｃ）バインダー樹脂を含む。（Ｃ）バインダー樹脂を含むことで、均質な膜を得ることが可能になる。（Ｃ）バインダー樹脂は均質な膜が得られるものであれば特に限定されないが、アルカリ現像液に対する溶解性の観点から、アルカリ可溶性樹脂であることが好ましい。
　本発明の着色感光性樹脂組成物及び顔料分散液において、（Ｃ）バインダー樹脂は、アウトガス低減の観点から（Ｃ１）エポキシ（メタ）アクリレート樹脂を含むことを特徴とする。（Ｃ１）エポキシ（メタ）アクリレート樹脂は剛直な骨格を有しており、耐熱性が高く熱分解しにくく、また、骨格が剛直なため硬化時に配列構造をとって架橋性の高い膜が形成されることから、硬化物形成後に発生するアウトガス量が少なくなると考えられる。
　またアルカリ現像液に対する溶解性の観点から、（Ｃ１）エポキシ（メタ）アクリレート樹脂は、カルボキシル基又は水酸基を含むものであることが好ましい。 [1-3] (C) Binder Resin The colored photosensitive resin composition and the pigment dispersion of the present invention contain (C) a binder resin. (C) By containing a binder resin, it becomes possible to obtain a homogeneous film. (C) 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.
In the colored photosensitive resin composition and the pigment dispersion of the present invention, 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.
Moreover, from the viewpoint of solubility in an alkali developer, the (C1) epoxy (meth) acrylate resin preferably contains a carboxyl group or a hydroxyl group.
　（Ｃ１）エポキシ（メタ）アクリレート樹脂は、エポキシ樹脂にエチレン性不飽和結合を有する酸又はエステル化合物を付加し、更に多塩基酸又はその無水物を反応させた樹脂であることが好ましい。例えば、エポキシ樹脂のエポキシ基に、エチレン性不飽和結合を有する酸のカルボキシル基が開環付加されることにより、エポキシ化合物にエステル結合（－ＣＯＯ－）を介してエチレン性不飽和結合が付加されると共に、その際生じた水酸基に、多塩基酸無水物の一方のカルボキシル基が付加されたものが挙げられる。また多塩基酸無水物を付加するときに、多価アルコールを同時に添加して付加されたものも挙げられる。
　また上記反応で得られた樹脂のカルボキシル基に、さらに反応し得る官能基を有する化合物を反応させて得られる樹脂も、上記（Ｃ１）エポキシ（メタ）アクリレート樹脂に含まれる。
　このように、エポキシ（メタ）アクリレート樹脂は化学構造上、実質的にエポキシ基を有さず、かつ「（メタ）アクリレート」に限定されるものではないが、エポキシ化合物（エポキシ樹脂）が原料であり、かつ、「（メタ）アクリレート」が代表例であるので慣用に従いこのように命名されている。 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. For example, 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. In addition, one in which one carboxyl group of the polybasic acid anhydride is added to the hydroxyl group generated at that time. Moreover, when adding a polybasic acid anhydride, what was added by adding a polyhydric alcohol simultaneously is also mentioned.
Moreover, 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.
As described above, 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. In addition, since “(meth) acrylate” is a representative example, it is named in accordance with conventional usage.
　ここで、エポキシ樹脂とは、熱硬化により樹脂を形成する以前の原料化合物をも含めて言うこととし、そのエポキシ樹脂としては、公知のエポキシ樹脂の中から適宜選択して用いることができる。
　また、エポキシ樹脂は、フェノール性化合物とエピハロヒドリンとを反応させて得られる化合物を用いることができる。フェノール性化合物としては、２価もしくは３価以上のフェノール性水酸基を有する化合物が好ましく、単量体でも重合体でもよい。
　具体的には、例えば、ビスフェノールＡエポキシ樹脂、ビスフェノールＦエポキシ樹脂、ビスフェノールＳエポキシ樹脂、フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、ビフェニルノボラックエポキシ樹脂、トリスフェノールエポキシ樹脂、フェノールとジシクロペンタンとの重合エポキシ樹脂、ジハイドロオキシルフルオレン型エポキシ樹脂、ジハイドロオキシルアルキレンオキシルフルオレン型エポキシ樹脂、９，９－ビス（４’－ヒドロキシフェニル）フルオレンのジグリシジルエーテル化物、１，１－ビス（４’－ヒドロキシフェニル）アダマンタンのジグリシジルエーテル化物、などが挙げられ、このように主鎖に芳香族環を有するものを好適に用いることができる。 Here, 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.
Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, 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.
　中でも、高い硬化膜強度の観点から、ビスフェノールＡエポキシ樹脂、フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、フェノールとジシクロペンタジエンとの重合体のエポキシ化物、９，９－ビス（４’－ヒドロキシフェニル）フルオレンのエポキシ化物（ジグリシジルエーテル化物）、アダマンチル基を有するエポキシ樹脂などが好ましく、フェノールとジシクロペンタジエンとの重合体のエポキシ化物、９，９－ビス（４’－ヒドロキシフェニル）フルオレンのエポキシ化物、アダマンチル基を有するエポキシ樹脂が更に好ましい。 Among them, from the viewpoint of high cured film strength, 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.
　エチレン性不飽和結合を有する酸の中でもエチレン性不飽和モノカルボン酸が好ましい。エチレン性不飽和結合を有する酸としては、例えば、（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸、ペンタエリスリトールトリ（メタ）アクリレート無水コハク酸付加物、ペンタエリスリトールトリ（メタ）アクリレートテトラヒドロ無水フタル酸付加物、ジペンタエリスリトールペンタ（メタ）アクリレート無水コハク酸付加物、ジペンタエリスリトールペンタ（メタ）アクリレート無水フタル酸付加物、ジペンタエリスリトールペンタ（メタ）アクリレートテトラヒドロ無水フタル酸付加物、（メタ）アクリル酸とε－カプロラクトンとの反応生成物などが挙げられる。中でも、感度の観点から、（メタ）アクリル酸が好ましい。 Among the acids having an ethylenically unsaturated bond, ethylenically unsaturated monocarboxylic acid is preferable. Examples of 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. (Meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride Examples include acid addition products, reaction products of (meth) acrylic acid and ε-caprolactone. Among these, (meth) acrylic acid is preferable from the viewpoint of sensitivity.
　多塩基酸（無水物）としては、例えば、コハク酸、マレイン酸、イタコン酸、フタル酸、テトラヒドロフタル酸、３－メチルテトラヒドロフタル酸、４－メチルテトラヒドロフタル酸、３－エチルテトラヒドロフタル酸、４－エチルテトラヒドロフタル酸、ヘキサヒドロフタル酸、３－メチルヘキサヒドロフタル酸、４－メチルヘキサヒドロフタル酸、３－エチルヘキサヒドロフタル酸、４－エチルヘキサヒドロフタル酸、トリメリット酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸、ビフェニルテトラカルボン酸、及びそれらの無水物などが挙げられる。中でも、アウトガス低減の観点から、コハク酸無水物、マレイン酸無水物、テトラヒドロフタル酸無水物、又はヘキサヒドロフタル酸無水物が好ましく、コハク酸無水物又はテトラヒドロフタル酸無水物がより好ましく、テトラヒドロフタル酸無水物が更に好ましい。 Examples of the polybasic acid (anhydride) include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4 -Ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid , Benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and anhydrides thereof. Among these, from the viewpoint of reducing outgas, 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.
　多価アルコールを用いることで、（Ｃ１）エポキシ（メタ）アクリレート樹脂の分子量を増大させ、分子中に分岐を導入することが出来、分子量と粘度のバランスをとることができる傾向がある。また、分子中への酸基の導入率を増やすことができ、感度や密着性等のバランスがとれやすい傾向がある。
　多価アルコールとしては、例えばトリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリメチロールエタン、１，２，３－プロパントリオールの中から選ばれる１種又は２種以上の多価アルコールであることが好ましい。 By using a polyhydric alcohol, the molecular weight of the (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. In addition, 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.
Examples of the polyhydric alcohol include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. Preferably there is.
　（Ｃ１）エポキシ（メタ）アクリレート樹脂の酸価は特に限定されないが、１０ｍｇＫＯＨ／ｇ以上が好ましく、２０ｍｇＫＯＨ／ｇ以上がより好ましく、４０ｍｇＫＯＨ／ｇ以上がさらに好ましく、６０ｍｇＫＯＨ／ｇ以上がよりさらに好ましく、８０ｍｇＫＯＨ／ｇ以上が特に好ましく、また、２００ｍｇＫＯＨ／ｇ以下が好ましく、１８０ｍｇＫＯＨ／ｇ以下がより好ましく、１５０ｍｇＫＯＨ／ｇ以下がさらに好ましく、１３０ｍｇＫＯＨ／ｇ以下がよりさらに好ましく、１２０ｍｇＫＯＨ／ｇ以下が特に好ましい。前記下限値以上とすることで未露光部の現像性が良化する傾向があり、また、前記上限値以下とすることで膜減り等を抑制できる傾向がある。上限と下限の組み合わせとしては、１０～２００ｍｇＫＯＨ／ｇが好ましく、２０～１８０ｍｇＫＯＨ／ｇがより好ましく、４０～１５０ｍｇＫＯＨ／ｇがさらに好ましく、６０～１３０ｍｇＫＯＨ／ｇがよりさらに好ましく、８０～１２０ｍｇＫＯＨ／ｇが特に好ましく挙げられる。 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. When the amount is not less than the lower limit, the developability of the unexposed portion tends to be improved, and when the amount is not more than the upper limit, there is a tendency that film reduction or the like can be suppressed. 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.
　（Ｃ１）エポキシ（メタ）アクリレート樹脂の重量平均分子量（Ｍｗ）は特に限定されないが、通常１０００以上、好ましくは２０００以上、より好ましくは３０００以上、さらに好ましくは４０００以上、特に好ましくは５０００以上、また、通常３００００以下、好ましくは２００００以下、より好ましくは１５０００以下、さらに好ましくは１００００以下、特に好ましくは８０００以下である。前記下限値以上とすることで膜減り等を抑制できる傾向があり、また、前記上限値以下とすることで未露光部の現像性が良化する傾向がある。上限と下限の組み合わせとしては、１０００～３００００が好ましく、２０００～２００００がより好ましく、３０００～１５０００がさらに好ましく、４０００～１００００がさらに好ましく、５０００～８０００が特に好ましく挙げられる。 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. When the amount is not less than the lower limit, there is a tendency that film loss can be suppressed, and when the amount is not more than the upper limit, the developability of the unexposed area tends to be improved. 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.
　（Ｃ１）エポキシ（メタ）アクリレート樹脂は、従来公知の方法により合成することができる。具体的には、前記エポキシ樹脂を有機溶剤に溶解させ、触媒と熱重合禁止剤の共存下、前記エチレン性不飽和結合を有する酸又はエステル化合物を加えて付加反応させ、更に多塩基酸又はその無水物を加えて反応を続ける方法を用いることができる。 (C1) 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.
　ここで、反応に用いる有機溶剤としては、メチルエチルケトン、シクロヘキサノン、ジエチレングリコールエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテートなどの有機溶剤の１種又は２種以上が挙げられる。また、上記触媒としては、トリエチルアミン、ベンジルジメチルアミン、トリベンジルアミン等の第３級アミン類、テトラメチルアンモニウムクロライド、メチルトリエチルアンモニウムクロライド、テトラエチルアンモニウムクロライド、テトラブチルアンモニウムクロライド、トリメチルベンジルアンモニウムクロライドなどの第４級アンモニウム塩類、トリフェニルホスフィンなどの燐化合物、トリフェニルスチビンなどのスチビン類などの１種又は２種以上が挙げられる。更に、熱重合禁止剤としては、ハイドロキノン、ハイドロキノンモノメチルエーテル、メチルハイドロキノンなどの１種又は２種以上が挙げられる。 Here, 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. 1 type or 2 types or more, such as quaternary ammonium salts, phosphorus compounds, such as a triphenylphosphine, and stibines, such as a triphenylstibine, are mentioned. Further, examples of the thermal polymerization inhibitor include one or more of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone and the like.
　また、エチレン性不飽和結合を有する酸又はエステル化合物としては、エポキシ樹脂のエポキシ基の１化学当量に対して通常０．７～１．３化学当量、好ましくは０．９～１．１化学当量となる量とすることができる。また、付加反応時の温度としては、通常６０～１５０℃、好ましくは８０～１２０℃の温度とすることができる。更に、多塩基酸（無水物）の使用量としては、前記付加反応で生じた水酸基の１化学当量に対して、通常０．１～１．２化学当量、好ましくは０．２～１．１化学当量となる量とすることができる。 The acid or ester compound having an ethylenically unsaturated bond is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, 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. Further, 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.
　（Ｃ１）エポキシ（メタ）アクリレート樹脂の化学構造は特に限定されないが、アウトガス低減の観点から、下記一般式（ＩＩ）で表される繰り返し単位構造を有するエポキシ（メタ）アクリレート樹脂及び／又は下記一般式（ＩＩＩ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂を含有することが好ましい。エポキシ（メタ）アクリレート樹脂は高感度であることからパターニング性能が良好であり、また疎水骨格を有し、溶解速度がマイルドであることから基板密着性が良好である。さらに、アクリル樹脂と違って剛直な骨格を有し、また硬化時に配列構造をとって密に架橋されることから、アウトガスの発生を抑制できると考えられる。
　特に、下記一般式（ＩＩ）で表される繰り返し単位構造を有するエポキシ（メタ）アクリレート樹脂及び／又は下記一般式（ＩＩＩ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂は、中央部に嵩高く剛直な骨格を持つため、（メタ）アクリロイル基等の親水部位が外側に展開される形となり、現像性が良好となると考えられる。 (C1) 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. Further, 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.
In particular, 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.
Figure JPOXMLDOC01-appb-C000028
  
Figure JPOXMLDOC01-appb-C000028
  
　式（ＩＩ）中、Ｒ11は水素原子又はメチル基を表し；
Ｒ12は置換基を有していてもよい２価の炭化水素基を表し；
式（ＩＩ）中のベンゼン環は、更に任意の置換基により置換されていてもよく；
＊は結合手を表す。 In formula (II), 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;
* Represents a bond.
Figure JPOXMLDOC01-appb-C000029
  
Figure JPOXMLDOC01-appb-C000029
  
　式（ＩＩＩ）中、Ｒ13は各々独立に、水素原子又はメチル基を表し；
Ｒ14は、環状炭化水素基を側鎖として有する２価の炭化水素基を表し；
Ｒ15及びＲ16は各々独立に、置換基を有していてもよい２価の脂肪族基を表し；
ｍ及びｎは各々独立に０～２の整数を表し；
＊は結合手を表す。 In formula (III), 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;
* Represents a bond.
　［（Ｃ１－１）エポキシ（メタ）アクリレート樹脂］
　次に、前記一般式（ＩＩ）で表される繰り返し単位構造を有するエポキシ（メタ）アクリレート樹脂（以下、「（Ｃ１－１）エポキシ（メタ）アクリレート樹脂」と略記する。）について詳述する。 [(C1-1) Epoxy (meth) acrylate resin]
Next, an epoxy (meth) acrylate resin having a repeating unit structure represented by the general formula (II) (hereinafter abbreviated as “(C1-1) epoxy (meth) acrylate resin”) will be described in detail.
Figure JPOXMLDOC01-appb-C000030
  
Figure JPOXMLDOC01-appb-C000030
  
　式（ＩＩ）中、Ｒ11は水素原子又はメチル基を表し；
Ｒ12は置換基を有していてもよい２価の炭化水素基を表し；
式（ＩＩ）中のベンゼン環は、更に任意の置換基により置換されていてもよく；
＊は結合手を表す。 In formula (II), 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;
* Represents a bond.
　（Ｒ12）
　前記式（ＩＩ）において、Ｒ12は置換基を有していてもよい２価の炭化水素基を表す。
　２価の炭化水素基としては、２価の脂肪族基、２価の芳香族環基、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基が挙げられる。 (R 12)
In the formula (II), R 12 represents a divalent hydrocarbon group which may have a substituent.
Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups. Can be mentioned.
　２価の脂肪族基は、直鎖状、分岐鎖状、環状のものが挙げられる。これらの中でも現像溶解性の観点からは直鎖状のものが好ましく、一方で露光部への現像液の浸透低減の観点からは環状のものが好ましい。その炭素数は通常１以上であり、３以上が好ましく、６以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくく、基板への密着性が良好となる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。上限と下限の組み合わせとしては、１～２０が好ましく、３～１５がより好ましく、６～１０がさらに好ましく挙げられる。 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. When 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 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.
　２価の直鎖状脂肪族基の具体例としては、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ヘキシレン基、ｎ－ヘプチレン基等が挙げられる。これらの中でも骨格の剛直性の観点から、メチレン基が好ましい。
　２価の分岐鎖状脂肪族基の具体例としては、ｉｓｏ－プロピル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｉｓｏ－アミル基等が挙げられる。
　２価の環状の脂肪族基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、通常１２以下、１０以下が好ましい。前記下限値以上とすることで強固な膜となり、基板密着性が良好となる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。２価の環状の脂肪族基の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、トリシクロデカン環、アダマンタン環、シクロドデカン環、ジシクロペンタジエン等の環から水素原子を２つ除した基が挙げられる。これらの中でも骨格の剛直性の観点から、トリシクロデカン環、アダマンタン環から水素原子を２つ除した基が好ましい。 Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
Specific examples of the divalent branched aliphatic group 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. When 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. When 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. Specific examples of 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. And a group obtained by removing two hydrogen atoms from the ring. Among these, a group obtained by removing two hydrogen atoms from a tricyclodecane ring or an adamantane ring is preferable from the viewpoint of the rigidity of the skeleton.
　２価の脂肪族基が有していてもよい置換基としては、メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成容易性の観点から、無置換であることが好ましい。 Examples of the substituent 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.
　また、２価の芳香族環基としては、２価の芳香族炭化水素環基及び２価の芳香族複素環基が挙げられる。その炭素数は通常４以上であり、５以上が好ましく、６以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくく、基板への密着性が良好となる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。 In addition, 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. When 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.
　２価の芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。２価の芳香族炭化水素環基としては、例えば、２個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。 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.
　また、２価の芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。２価の芳香族複素環基としては、例えば、２個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
　これらの中でもパターニング特性の観点から、２個の遊離原子価を有する、ベンゼン環又はナフタレン環が好ましく、２個の遊離原子価を有するベンゼン環がより好ましい。 In addition, the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of 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. Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, 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. That.
Among these, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.
　２価の芳香族環基が有していてもよい置換基としては、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基、グリシジルエーテル基等が挙げられる。これらの中でも現像溶解性、耐吸湿性の観点から、無置換が好ましい。 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. Among these, unsubstituted is preferable from the viewpoints of development solubility and moisture absorption resistance.
　また、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基としては、前述の２価の脂肪族基を１以上と、前述の２価の芳香族環基を１以上とを連結した基が挙げられる。
　２価の脂肪族基の数は特に限定されないが、通常１以上、２以上が好ましく、通常１０以下、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくく、基板への密着性が良好となる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。
　２価の芳香族環基の数は特に限定されないが、通常１以上、２以上が好ましく、通常１０以下、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくく、基板への密着性が良好となる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。 In addition, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above divalent aliphatic groups and the above divalent aromatic group are used. And a group in which one or more cyclic groups are linked.
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. When 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. When 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.
　１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基の具体例としては、下記式（ＩＩ－Ａ）～（ＩＩ－Ｆ）で表される基等が挙げられる。これらの中でも骨格の剛直性と膜の疎水化の観点から、下記式（ＩＩ－Ａ）で表される基が好ましい。化学式中の＊は結合手を表す。 Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the following formulas (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.
Figure JPOXMLDOC01-appb-C000031
  
Figure JPOXMLDOC01-appb-C000031
  
　前記のとおり、式（ＩＩ）中のベンゼン環は、更に任意の置換基により置換されていてもよい。該置換基としては、例えば、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基等が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。
　これらの中でもパターニング特性の観点から、無置換であることが好ましい。 As described above, the benzene ring in formula (II) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, either one or two or more.
Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.
　また、前記式（ＩＩ）で表される繰り返し単位構造は、合成の簡易性の観点から、下記式（ＩＩ－１）で表される繰り返し単位構造であることが好ましい。 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.
Figure JPOXMLDOC01-appb-C000032
  
Figure JPOXMLDOC01-appb-C000032
  
　式（ＩＩ－１）中、Ｒ11及びＲ12は、前記式（ＩＩ）のものと同義であり；
ＲXは水素原子又は多塩基酸残基を表し；
＊は結合手を表し；
式（ＩＩ－１）中のベンゼン環は、更に任意の置換基により置換されていてもよい。 In formula (II-1), 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.
　多塩基酸残基とは、多塩基酸又はその無水物からＯＨ基を１つ除した１価の基を意味する。多塩基酸としては、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸から選ばれた１種又は２種以上が挙げられる。
　これらの中でもパターニング特性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸であり、さらに好ましくはテトラヒドロフタル酸無水物である。 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.
Among these, from the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable. Are tetrahydrophthalic acid and biphenyltetracarboxylic acid, more preferably tetrahydrophthalic anhydride.
　（Ｃ１－１）エポキシ（メタ）アクリレート樹脂１分子中に含まれる、前記式（ＩＩ－１）で表される繰り返し単位構造は、１種でも２種以上でもよく、例えば、ＲXが水素原子のものと、ＲXが多塩基酸残基のものが混在していてもよい。 (C1-1) 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. For example, R X is a hydrogen atom. And those in which R X is a polybasic acid residue may be mixed.
　また、（Ｃ１－１）エポキシ（メタ）アクリレート樹脂１分子中に含まれる、前記式（ＩＩ）で表される繰り返し単位構造の数は特に限定されないが、１以上が好ましく、３以上がより好ましく、また、２０以下が好ましく、１５以下がさらに好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。 Further, 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.
　（Ｃ１－１）エポキシ（メタ）アクリレート樹脂の、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定したポリスチレン換算の重量平均分子量（Ｍｗ）は特に限定されないが、１０００以上が好ましく、１５００以上がより好ましく、２０００以上がさらに好ましく、３０００以上が特に好ましく、また、３００００以下が好ましく、２００００以下がより好ましく、１００００以下がさらに好ましく、８０００以下が特に好ましい。前記下限値以上とすることで着色感光性樹脂組成物の残膜率が良好となる傾向があり、また、前記上限値以下とすることで解像性が良好となる傾向がある。上限と下限の組み合わせとしては、１０００～３００００が好ましく、１５００～２００００がより好ましく、２０００～１００００がさらに好ましく、３０００～８０００が特に好ましく挙げられる。 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. There exists a tendency for the residual film rate of a coloring photosensitive resin composition to become favorable by setting it as the said lower limit or more, and there exists a tendency for resolution 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 1000 to 30000, more preferably 1500 to 20000, still more preferably 2000 to 10000, and particularly preferably 3000 to 8000.
　（Ｃ１－１）エポキシ（メタ）アクリレート樹脂の、酸価は特に限定されないが、１０ｍｇＫＯＨ／ｇ以上が好ましく、２０ｍｇＫＯＨ／ｇ以上がより好ましく、４０ｍｇＫＯＨ／ｇ以上がさらに好ましく、５０ｍｇＫＯＨ／ｇ以上がよりさらに好ましく、８０ｍｇＫＯＨ／ｇ以上が特に好ましく、また、２００ｍｇＫＯＨ／ｇ以下が好ましく、１５０ｍｇＫＯＨ／ｇ以下がより好ましく、１３０ｍｇＫＯＨ／ｇ以下がよりさらに好ましく、１００ｍｇＫＯＨ／ｇ以下が特に好ましい。前記下限値以上とすることで現像溶解性が向上し、解像性が良好となる傾向があり、また、前記上限値以下とすることで着色感光性樹脂組成物の残膜率が良好となる傾向がある。上限と下限の組み合わせとしては、１０～２００ｍｇＫＯＨ／ｇが好ましく、２０～１５０ｍｇＫＯＨ／ｇがより好ましく、４０～１３０ｍｇＫＯＨ／ｇがさらに好ましく、５０～１００ｍｇＫＯＨ／ｇがよりさらに好ましく、８０～１００ｍｇＫＯＨ／ｇが特に好ましく挙げられる。 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. When the amount is not less than the above lower limit, the development solubility is improved and the resolution tends to be good, and when the amount is not more than the above upper limit, the remaining film ratio of the colored photosensitive resin composition becomes good. Tend. 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.
　以下に（Ｃ１－１）エポキシ（メタ）アクリレート樹脂の具体例を挙げる。 Specific examples of the (C1-1) epoxy (meth) acrylate resin are given below.
Figure JPOXMLDOC01-appb-C000033
  
Figure JPOXMLDOC01-appb-C000033
  
Figure JPOXMLDOC01-appb-C000034
  
Figure JPOXMLDOC01-appb-C000034
  
Figure JPOXMLDOC01-appb-C000035
  
Figure JPOXMLDOC01-appb-C000035
  
Figure JPOXMLDOC01-appb-C000036
  
Figure JPOXMLDOC01-appb-C000036
  
　［（Ｃ１－２）エポキシ（メタ）アクリレート樹脂］
　次に、前記一般式（ＩＩＩ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂（以下、「（Ｃ１－２）エポキシ（メタ）アクリレート樹脂」と略記する。）について詳述する。 [(C1-2) Epoxy (meth) acrylate resin]
Next, an epoxy (meth) acrylate resin having a partial structure represented by the general formula (III) (hereinafter abbreviated as “(C1-2) epoxy (meth) acrylate resin”) will be described in detail.
Figure JPOXMLDOC01-appb-C000037
  
Figure JPOXMLDOC01-appb-C000037
  
　式（ＩＩＩ）中、Ｒ13は各々独立に、水素原子又はメチル基を表し；
Ｒ14は、環状炭化水素基を側鎖として有する２価の炭化水素基を表し；
Ｒ15及びＲ16は各々独立に、置換基を有していてもよい２価の脂肪族基を表し；
ｍ及びｎは各々独立に０～２の整数を表し；
＊は結合手を表す。 In formula (III), 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;
* Represents a bond.
　（Ｒ14）
　前記一般式（ＩＩＩ）において、Ｒ14は、環状炭化水素基を側鎖として有する２価の炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 (R 14 )
In the general formula (III), R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
　脂肪族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、通常１０以下、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。上限と下限の組み合わせとしては、１～１０が好ましく、２～５がより好ましく、２～３がさらに好ましく挙げられる。
　また、脂肪族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上するとなる傾向がある。上限と下限の組み合わせとしては、４～４０が好ましく、６～３０がより好ましく、８～２０がさらに好ましく、８～１５が特に好ましく挙げられる。
　脂肪族環基における脂肪族環の具体例としてはシクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等が挙げられる。これらの中でも着色感光性樹脂組成物の残膜率と解像性の観点から、アダマンタン環が好ましい。 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.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of the remaining film ratio and resolution of the colored photosensitive resin composition.
　一方で、芳香族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、３以上がより好ましく、また、通常１０以下、５以下が好ましく、４以下がより好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上するとなる傾向がある。上限と下限の組み合わせとしては、１～１０が好ましく、２～５がより好ましく、３～４がさらに好ましく挙げられる。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、１０以上がよりさらに好ましく、１２以上が特に好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることでパターニング特性が良好となる傾向がある。上限と下限の組み合わせとしては、４～４０が好ましく、６～３０がより好ましく、８～２０がさらに好ましく、１０～１５がよりさらに好ましく、１２～１５が特に好ましく挙げられる。
　芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環等が挙げられる。これらの中でもパターニング特性の観点から、フルオレン環が好ましい。 On the other hand, the number of rings 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.
Examples of 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. 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 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.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, Examples include fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of patterning characteristics.
　また、環状炭化水素基を側鎖として有する２価の炭化水素基における、２価の炭化水素基は特に限定されないが、例えば、２価の脂肪族基、２価の芳香族環基、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基が挙げられる。 Further, the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited. For example, a divalent aliphatic group, a divalent aromatic ring group, one or more And a group in which one or more divalent aromatic ring groups are linked to each other.
　２価の脂肪族基は、直鎖状、分岐鎖状、環状のものが挙げられる。これらの中でも現像溶解性の観点からは直鎖状のものが好ましく、一方で露光部への現像液の浸透低減の観点からは環状のものが好ましい。その炭素数は通常１以上であり、３以上が好ましく、６以上がより好ましく、また、２５以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくく、基板への密着性が良好となる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。 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. When 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.
　２価の直鎖状脂肪族基の具体例としては、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ヘキシレン基、ｎ－ヘプチレン基等が挙げられる。これらの中でも骨格の剛直性の観点から、メチレン基が好ましい。
　２価の分岐鎖状脂肪族基の具体例としては、前述の２価の直鎖状脂肪族基に、側鎖としてメチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｉｓｏ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等を有する構造が挙げられる。
　２価の環状の脂肪族基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、通常１０以下、５以下、さらに好ましくは３以下が好ましい。前記下限値以上とすることで強固な膜となり、基板密着性が良好となる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。２価の環状の脂肪族基の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等の環から水素原子を２つ除した基が挙げられる。これらの中でも骨格の剛直性の観点から、アダマンタン環から水素原子を２つ除した基が好ましい。 Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
Specific examples of the divalent branched aliphatic group 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. And structures having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group, and the like.
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. When 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. When 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. Specific examples of the divalent aliphatic group 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. Group. Among these, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of the rigidity of the skeleton.
　２価の脂肪族基が有していてもよい置換基としては、メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成容易性の観点から、無置換であることが好ましい。 Examples of the substituent 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.
　また、２価の芳香族環基としては、２価の芳香族炭化水素環基及び２価の芳香族複素環基が挙げられる。その炭素数は通常４以上であり、５以上が好ましく、６以上がより好ましく、また、３０以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくく、基板への密着性が良好となる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。 In addition, 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. When 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.
　２価の芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。２価の芳香族炭化水素環基としては、例えば、２個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの基が挙げられる。 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.
　また、２価の芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。２価の芳香族複素環基としては、例えば、２個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。これらの中でもパターニング特性の観点から、２個の遊離原子価を有する、ベンゼン環又はナフタレン環が好ましく、２個の遊離原子価を有するフルオレン環がより好ましい。 In addition, the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of 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. Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, 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. That. Among these, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring having two free valences is preferable, and a fluorene ring having two free valences is more preferable.
　２価の芳香族環基が有していてもよい置換基としては、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基等が挙げられる。これらの中でも現像溶解性の観点から、無置換が好ましい。 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.
　また、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基としては、前述の２価の脂肪族基を１以上と、前述の２価の芳香族環基を１以上とを連結した基が挙げられる。
　２価の脂肪族基の数は特に限定されないが、通常１以上、２以上が好ましく、通常１０以下、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくく、基板への密着性が良好となる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。
　２価の芳香族環基の数は特に限定されないが、通常１以上、２以上が好ましく、通常１０以下、５以下が好ましく、３以下がより好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくく、基板への密着性が良好となる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。 In addition, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above divalent aliphatic groups and the above divalent aromatic group are used. And a group in which one or more cyclic groups are linked.
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. When 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. When 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.
　１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基の具体例としては、前記式（ＩＩ－Ａ）～（ＩＩ－Ｆ）で表される基等が挙げられる。これらの中でも骨格の剛直性と膜の疎水化の観点から、前記式（ＩＩ－Ｃ）で表される基又は前記式（ＩＩ－Ｄ）で表される基が好ましい。 Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the above formulas (II-A) to (II-F) Is mentioned. Among these, 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.
　これらの２価の炭化水素基に対して、側鎖である環状炭化水素基の結合態様は特に限定されないが、例えば、脂肪族基や芳香族環基の水素原子１つを該側鎖で置換した態様や、脂肪族基の炭素原子の１つを含めて側鎖である環状炭化水素基を構成した態様が挙げられる。 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.
　（Ｒ15、Ｒ16）
　前記一般式（ＩＩＩ）において、Ｒ15及びＲ16は各々独立に、置換基を有していてもよい２価の脂肪族基を表す。 (R 15, R 16)
In the general formula (III), R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent.
　２価の脂肪族基は、直鎖状、分岐鎖状、環状のものが挙げられる。これらの中でも現像溶解性の観点からは直鎖状のものが好ましく、一方で露光部への現像液の浸透低減の観点からは環状のものが好ましい。その炭素数は通常１以上であり、３以上が好ましく、６以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくく、基板への密着性が良好となる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。 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. When 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.
　２価の直鎖状脂肪族基の具体例としては、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ヘキシレン基、ｎ－ヘプチレン基等が挙げられる。これらの中でも骨格の剛直性の観点から、メチレン基が好ましい。
　２価の分岐鎖状脂肪族基の具体例としては、前述の２価の直鎖状脂肪族基に、側鎖としてメチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｉｓｏ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等を有する構造が挙げられる。
　２価の環状の脂肪族基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、通常１２以下、１０以下が好ましい。前記下限値以上とすることで強固な膜となり、基板密着性が良好となる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。２価の環状の脂肪族基の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環、ジシクロペンタジエン等の環から水素原子を２つ除した基が挙げられる。これらの中でも骨格の剛直性の観点から、ジシクロペンタジエン環、アダマンタン環から水素原子を２つ除した基が好ましい。 Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
Specific examples of the divalent branched aliphatic group 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. And structures having a group, an iso-butyl group, a sec-butyl group, a tert-butyl 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. When 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. When 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. Specific examples of the divalent cyclic aliphatic group 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. And 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.
　２価の脂肪族基が有していてもよい置換基としては、メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成容易性の観点から、無置換であることが好ましい。 Examples of the substituent 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、ｎ）
　前記一般式（ＩＩＩ）において、ｍ及びｎは各々独立に０～２の整数を表す。前記下限値以上とすることでパターニング適正が良好となり、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることで現像性が良好となる傾向がある。現像性の観点からｍ及びｎが０であることが好ましく、一方で、パターニング適正、表面荒れの観点からｍ及びｎが各々独立に１以上であることが好ましい。 (M, n)
In the general formula (III), m and n each independently represents an integer of 0 to 2. When it is at least the lower limit, patterning suitability is good and surface roughness tends to be less likely to occur, and when it is at most the upper limit, developability tends to be good. From the viewpoint of developability, m and n are preferably 0. On the other hand, it is preferable that m and n are each independently 1 or more from the viewpoint of patterning suitability and surface roughness.
　また、前記一般式（ＩＩＩ）で表される部分構造は、基板への密着性の観点から、下記一般式（ＩＩＩ－１）で表される部分構造であることが好ましい。 The partial structure represented by the general formula (III) is preferably a partial structure represented by the following general formula (III-1) from the viewpoint of adhesion to the substrate.
Figure JPOXMLDOC01-appb-C000038
  
Figure JPOXMLDOC01-appb-C000038
  
　式（ＩＩＩ－１）中、Ｒ13、Ｒ１5、Ｒ１6、ｍ及びｎは前記式（ＩＩＩ）と同義であり；
Ｒαは、置換基を有していてもよい１価の環状炭化水素基を表し；
ｐは１以上の整数であり；
式（ＩＩＩ－１）中のベンゼン環は、更に任意の置換基により置換されていてもよく；
＊は結合手を表す。 In the formula (III-1), 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.
　（Ｒα）
　前記一般式（ＩＩＩ－１）において、Ｒαは、１価の環状炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 (R α )
In the general formula (III-1), R α represents a monovalent cyclic hydrocarbon group.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
　脂肪族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、通常６以下、４以下が好ましく、３以下がより好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることでパターニング特性が良好となる傾向がある。上限と下限の組み合わせとしては、１～６が好ましく、２～４がより好ましく、２～３がさらに好ましく挙げられる。
　また、脂肪族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることでパターニング特性が良好となる傾向がある。上限と下限の組み合わせとしては、４～４０が好ましく、６～３０がより好ましく、８～２０がさらに好ましく、８～１５が特に好ましく挙げられる。
　脂肪族環基における脂肪族環の具体例としてはシクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等が挙げられる。これらの中でも強固な膜特性の観点から、アダマンタン環が好ましい。 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. 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 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. 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 4 to 40, more preferably 6 to 30, further preferably 8 to 20, and particularly preferably 8 to 15.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of strong film characteristics.
　一方で、芳香族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、３以上がより好ましく、また、通常１０以下、５以下が好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることでパターニング特性が良好となる傾向がある。上限と下限の組み合わせとしては、１～１０が好ましく、２～５がより好ましく、３～５がさらに好ましく挙げられる。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられるまた、芳香族環基の炭素数は通常４以上であり、５以上が好ましく、６以上がより好ましく、また、３０以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることでパターニング特性が良好となる傾向がある。上限と下限の組み合わせとしては、４～３０が好ましく、５～２０がより好ましく、６～１５がさらに好ましく挙げられる。
　芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環等が挙げられる。これらの中でも現像溶解性の観点から、フルオレン環が好ましい。 On the other hand, the number of rings 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. 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.
Examples of 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. 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 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.
　環状炭化水素基が有していてもよい置換基としては、ヒドロキシル基、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、アミル基、ｉｓｏ－アミル基等の炭素数１～５のアルキル基；メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成の容易性の観点から、無置換が好ましい。 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は１以上の整数を表すが、２以上が好ましく、また、３以下が好ましい。前記下限値以上とすることで膜硬化度と残膜率が良好となる傾向があり、また、前記上限値以下とすることで現像性が良好となる傾向がある。上限と下限の組み合わせとしては、１～３が好ましく、２～３がより好ましく挙げられる。 P represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less. By setting it as the said lower limit or more, there exists a tendency for a film hardening degree and a residual film rate to become favorable, and there exists a tendency for developability 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 1 to 3, and more preferably 2 to 3.
　これらの中でも、強固な膜硬化度の観点から、Ｒαが１価の脂肪族環基であることが好ましく、アダマンチル基であることがより好ましい。 Among these, from the viewpoint of a strong film curing degree, R α is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.
　前記のとおり、式（ＩＩＩ－１）中のベンゼン環は、更に任意の置換基により置換されていてもよい。該置換基としては、例えば、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基等が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。
　これらの中でもパターニング特性の観点から、無置換であることが好ましい。 As described above, the benzene ring in formula (III-1) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, either one or two or more.
Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.
　以下に前記式（ＩＩＩ－１）で表される部分構造の具体例を挙げる。 Specific examples of the partial structure represented by the formula (III-1) are given below.
Figure JPOXMLDOC01-appb-C000039
  
Figure JPOXMLDOC01-appb-C000039
  
Figure JPOXMLDOC01-appb-C000040
  
Figure JPOXMLDOC01-appb-C000040
  
Figure JPOXMLDOC01-appb-C000041
  
Figure JPOXMLDOC01-appb-C000041
  
Figure JPOXMLDOC01-appb-C000042
  
Figure JPOXMLDOC01-appb-C000042
  
Figure JPOXMLDOC01-appb-C000043
  
Figure JPOXMLDOC01-appb-C000043
  
　また、前記一般式（ＩＩＩ）で表される部分構造は、骨格の剛直性、及び膜疎水化の観点から、下記一般式（ＩＩＩ－２）で表される部分構造であることが好ましい。 In addition, 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.
Figure JPOXMLDOC01-appb-C000044
  
Figure JPOXMLDOC01-appb-C000044
  
　式（ＩＩＩ－２）中、Ｒ13、Ｒ15、Ｒ16、ｍ及びｎは前記式（ＩＩＩ）と同義であり；
Ｒβは、置換基を有していてもよい２価の環状炭化水素基を表し；
式（ＩＩＩ－２）中のベンゼン環は、更に任意の置換基により置換されていてもよく；
＊は結合手を表す。 In the formula (III-2), R 13 , R 15 , R 16 , m and n are as defined in the formula (III);
R β 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.
　（Ｒβ）
　前記式（ＩＩＩ－２）において、Ｒβは、２価の環状炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 (R β )
In the above formula (III-2), R β represents a divalent cyclic hydrocarbon group.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
　脂肪族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、通常１０以下、５以下が好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。上限と下限の組み合わせとしては、１～１０が好ましく、２～５がより好ましく挙げられる。
　また、脂肪族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、また、４０以下が好ましく、３５以下がより好ましく、３０以下がさらに好ましい。前記下限値以上とすることで現像時の膜あれの抑制する傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上するとなる傾向がある。上限と下限の組み合わせとしては、４～４０が好ましく、６～３５がより好ましく、８～３０がさらに好ましく挙げられる。
　脂肪族環基における脂肪族環の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等が挙げられる。これらの中でも保存安定性の観点から、アダマンタン環が好ましい。 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.
Moreover, 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. When the amount is not less than the above lower limit value, there is a tendency to suppress film deterioration during development, and when the amount is not more than the above upper limit value, it is easy to suppress the surface smoothness and sensitivity of the film, and the resolution is improved. Tend to be. 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.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of storage stability.
　一方で、芳香族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、３以上がより好ましく、また、通常１０以下、５以下が好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。上限と下限の組み合わせとしては、１～１０が好ましく、２～５がより好ましく、３～５がさらに好ましく挙げられる。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられるまた、芳香族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、１０以上がさらに好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。上限と下限の組み合わせとしては、４～４０が好ましく、６～３０がより好ましく、８～２０がさらに好ましく、１０～１５が特に好ましく挙げられる。
　芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環等が挙げられる。これらの中でも現像性の観点から、フルオレン環が好ましい。 On the other hand, the number of rings 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.
Examples of 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.
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 developability.
　環状炭化水素基が有していてもよい置換基としては、ヒドロキシル基、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、アミル基、ｉｓｏ－アミル基等の炭素数１～５のアルキル基；メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシル基等が挙げられる。これらの中でも合成の簡易性の観点から、無置換が好ましい。 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.
　これらの中でも、保存安定性及び電気特性の観点から、Ｒβが２価の脂肪族環基であることが好ましく、２価のアダマンタン環基であることがより好ましい。
　一方で、塗膜の低吸湿性及びパターニング特性の観点から、Ｒβが２価の芳香族環基であることが好ましく、２価のフルオレン環基であることがより好ましい。 Among these, from the viewpoint of storage stability and electrical properties, it is preferred that R beta is a divalent aliphatic cyclic group, and more preferably a divalent adamantane ring group.
On the other hand, from the viewpoint of low hygroscopicity and patterning properties of the coating film, it is preferred that R beta is a divalent aromatic ring group, and more preferably a divalent fluorene ring group.
　前記のとおり、式（ＩＩＩ－２）中のベンゼン環は、更に任意の置換基により置換されていてもよい。該置換基としては、例えば、ヒドロキシル基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基等が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。また、これらの置換基を介して、式（ＩＩＩ－２）中の２つのベンゼン環が連結されていてもよい。
　これらの中でもパターニング特性の観点から、無置換であることが好ましい。また、膜減り等を生じにくくする観点から、メチル基置換であることが好ましい。 As described above, the benzene ring in formula (III-2) may be further substituted with an arbitrary substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, either one or two or more. In addition, 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.
　以下に前記式（ＩＩＩ－２）で表される部分構造の具体例を挙げる。 Specific examples of the partial structure represented by the formula (III-2) are given below.
   
Figure JPOXMLDOC01-appb-C000046
  
Figure JPOXMLDOC01-appb-C000046
  
Figure JPOXMLDOC01-appb-C000047
  
Figure JPOXMLDOC01-appb-C000047
  
Figure JPOXMLDOC01-appb-C000048
  
Figure JPOXMLDOC01-appb-C000048
  
　一方で、前記式（ＩＩＩ）で表される部分構造は、塗膜残膜率とパターニング特性の観点から、下記式（ＩＩＩ－３）で表される部分構造であることが好ましい。 On the other hand, the partial structure represented by the formula (III) is preferably a partial structure represented by the following formula (III-3) from the viewpoint of the remaining film ratio and patterning characteristics.
Figure JPOXMLDOC01-appb-C000049
  
Figure JPOXMLDOC01-appb-C000049
  
　式（ＩＩＩ－３）中、Ｒ13、Ｒ14、Ｒ15、Ｒ16、ｍ及びｎは前記式（ＩＩＩ）と同義であり；
ＲZは水素原子又は多塩基酸残基を表す。 In the formula (III-3), 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.
　多塩基酸残基とは、多塩基酸又はその無水物からＯＨ基を１つ除した１価の基を意味する。なお、さらにもう１つのＯＨ基が除され、式（ＩＩＩ－３）で表される他の分子におけるＲZと共用されていてもよく、つまり、ＲZを介して複数の式（ＩＩＩ－３）が連結していてもよい。
　多塩基酸としては、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸から選ばれた１種又は２種以上が挙げられる。
　これらの中でもパターニング特性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸である。 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.
Among these, from the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable. Are tetrahydrophthalic acid and biphenyltetracarboxylic acid.
　（Ｃ１－２）エポキシ（メタ）アクリレート樹脂１分子中に含まれる、前記式（ＩＩＩ－３）で表される部分構造は、１種でも２種以上でもよく、例えば、ＲZが水素原子のものと、ＲZが多塩基酸残基のものが混在していてもよい。 (C1-2) 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. For example, R Z is a hydrogen atom. And those in which R Z is a polybasic acid residue may be mixed.
　また、（Ｃ１－２）エポキシ（メタ）アクリレート樹脂１分子中に含まれる、前記式（ＩＩＩ）で表される部分構造の数は特に限定されないが、１以上が好ましく、３以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくく、電気特性が良好となる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすく、解像性が向上する傾向がある。 Further, 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. By setting 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.
　（Ｃ１－２）エポキシ（メタ）アクリレート樹脂の、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定したポリスチレン換算の重量平均分子量（Ｍｗ）は特に限定されないが、１０００以上が好ましく、２０００以上がより好ましく、３０００以上がさらに好ましく、３５００以上が特に好ましく、また、３００００以下が好ましく、２００００以下がより好ましく、１００００以下がさらに好ましく、７０００以下がよりさらに好ましく、５０００以下が特に好ましい。前記下限値以上とすることでパターニング特性が良好となる傾向があり、また、前記上限値以下とすることで強固な膜が得られやすく、表面荒れが生じにくい傾向がある。上限と下限の組み合わせとしては、１０００～３００００が好ましく、２０００～２００００がより好ましく、３０００～１００００がさらに好ましく、３５００～７０００がよりさらに好ましく、３５００～５０００が特に好ましく挙げられる。 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. When it is at least the lower limit value, the patterning characteristics tend to be good, and when it is at most the upper limit value, a strong film is likely to be obtained and surface roughness tends not to occur. 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.
　（Ｃ１－２）エポキシ（メタ）アクリレート樹脂の酸価は特に限定されないが、１０ｍｇＫＯＨ／ｇ以上が好ましく、２０ｍｇＫＯＨ／ｇ以上がより好ましく、４０ｍｇＫＯＨ／ｇ以上がさらに好ましく、６０ｍｇＫＯＨ／ｇ以上がよりさらに好ましく、８０ｍｇＫＯＨ／ｇ以上が特に好ましく、また、２００ｍｇＫＯＨ／ｇ以下が好ましく、１５０ｍｇＫＯＨ／ｇ以下がより好ましく、１２０ｍｇＫＯＨ／ｇ以下がさらに好ましい。前記下限値以上とすることで強固な膜が得られやすくなる傾向があり、また、前記上限値以下とすることで現像溶解性が向上し、解像性が良好となる傾向がある。上限と下限の組み合わせとしては、１０～２００ｍｇＫＯＨ／ｇが好ましく、２０～１５０ｍｇＫＯＨ／ｇがより好ましく、４０～１５０ｍｇＫＯＨ／ｇがさらに好ましく、６０～１２０ｍｇＫＯＨ／ｇがよりさらに好ましく、８０～１２０ｍｇＫＯＨ／ｇが特に好ましく挙げられる。 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. Preferably, 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. When the amount is not less than the lower limit, a strong film tends to be easily obtained, and when the amount is not more than the upper limit, the development solubility is improved and the resolution tends to be good. 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.
　本発明の着色感光性樹脂組成物及び顔料分散液に含まれる（Ｃ）バインダー樹脂は、（Ｃ１）エポキシ（メタ）アクリレート樹脂以外のバインダー樹脂（以下、「（Ｃ２）その他のバインダー樹脂」と略記する。）を含んでいてもよい。
　（Ｃ２）その他のバインダー樹脂としては、例えば、アクリル系樹脂、カルボキシル基含有エポキシ樹脂、カルボシキル基含有ウレタン樹脂、ノボラック系樹脂、ポリビニルフェノール系樹脂等が挙げられ、これらは１種を単独で用いてもよく、複数種を混合して使用してもよい。 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.
　本発明の着色感光性樹脂組成物において、（Ｃ）バインダー樹脂は、（Ｃ１）エポキシ（メタ）アクリレート樹脂を７５質量％以上含む。（Ｃ）バインダー樹脂中に（Ｃ１）エポキシ（メタ）アクリレート樹脂を７５質量％以上含ませることによって、硬化物の耐熱性も向上し、硬化物形成後に発生するアウトガス量を少なくできると考えられる。
　（Ｃ）バインダー樹脂に対する（Ｃ１）エポキシ（メタ）アクリレート樹脂の含有割合は７５質量％以上であれば特に限定されず、８０重量％以上が好ましく、８５重量％以上がより好ましく、９０重量％以上がさらに好ましく、９５質量％以上が特に好ましい。また、通常１００質量％以下である。前記下限値以上とすることでアウトガスが抑えられる傾向がある。上限と下限の組み合わせとしては、７５～１００質量％が好ましく、８０～１００質量％がより好ましく、８５～１００質量％がさらに好ましく、９０～１００質量％がよりさらに好ましく、９５～１００質量％が特に好ましく挙げられる。 In the colored photosensitive resin composition of the present invention, 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 | cured material can also be improved by containing 75 mass% or more of (C1) epoxy (meth) acrylate resin in binder resin, and the amount of outgas generated after hardened | cured material formation can be decreased.
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. Moreover, it is 100 mass% or less normally. There exists a tendency for outgassing to be suppressed by setting it as the above-mentioned 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.
［１－４］（Ｄ）光重合性モノマー
　本発明の着色感光性樹脂組成物は、（Ｄ）光重合性モノマーを含む。（Ｄ）光重合性モノマーを含むことで、感度が向上する。
　本発明に用いられる（Ｄ）光重合性モノマーは、分子内にエチレン性不飽和基を少なくとも１個有する化合物である。具体的には、例えば（メタ）アクリル酸、（メタ）アクリル酸アルキルエステル、アクリロニトリル、スチレン、及びエチレン性不飽和結合を１個有するカルボン酸と、多価又は１価アルコールのエステル、等が挙げられる。 [1-4] (D) Photopolymerizable monomer The colored photosensitive resin composition of the present invention contains (D) a photopolymerizable monomer. (D) A sensitivity improves by including 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.
　本発明においては、特に、１分子中にエチレン性不飽和基を２個以上有する多官能エチレン性単量体を使用することが望ましい。多官能エチレン性単量体が有するエチレン性不飽和基の数は特に限定されないが、通常２個以上であり、好ましくは４個以上であり、より好ましくは５個以上であり、また、好ましくは８個以下であり、より好ましくは７個以下である。前記下限値以上とすることで高感度となる傾向があり、前記上限値以下とすることで溶媒への溶解性が向上する傾向がある。上限と下限の組み合わせとしては、２～８個が好ましく、４～８個がより好ましく、５～７個がさらに好ましく挙げられる。
　多官能エチレン性単量体の例としては、例えば脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と、不飽和カルボン酸及び多塩基性カルボン酸とのエステル化反応により得られるエステルなどが挙げられる。 In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. 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. There exists a tendency for it to become high sensitivity by setting it as the said lower limit or more, and there exists a tendency for the solubility to a solvent to improve by setting it as the said upper limit 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.
Examples of the polyfunctional ethylenic monomer 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. Examples thereof include 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.
　前記脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールエタントリアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、グリセロールアクリレート等の脂肪族ポリヒドロキシ化合物のアクリル酸エステル、これら例示化合物のアクリレートをメタクリレートに代えたメタクリル酸エステル、同様にイタコネートに代えたイタコン酸エステル、クロネートに代えたクロトン酸エステルもしくはマレエートに代えたマレイン酸エステル等が挙げられる。 Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. In the same way, itaconic acid ester replaced by itaconate, Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to bets and the like.
　芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、ハイドロキノンジアクリレート、ハイドロキノンジメタクリレート、レゾルシンジアクリレート、レゾルシンジメタクリレート、ピロガロールトリアクリレート等の芳香族ポリヒドロキシ化合物のアクリル酸エステル及びメタクリル酸エステル等が挙げられる。
　多塩基性カルボン酸及び不飽和カルボン酸と、多価ヒドロキシ化合物のエステル化反応により得られるエステルとしては必ずしも単一物ではないが、代表的な具体例を挙げれば、アクリル酸、フタル酸、及びエチレングリコールの縮合物、アクリル酸、マレイン酸、及びジエチレングリコールの縮合物、メタクリル酸、テレフタル酸及びペンタエリスリトールの縮合物、アクリル酸、アジピン酸、ブタンジオール及びグリセリンの縮合物等が挙げられる。 Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid 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.
　その他、本発明に用いられる多官能エチレン性単量体の例としては、ポリイソシアネート化合物と水酸基含有（メタ）アクリル酸エステル又はポリイソシアネート化合物とポリオール及び水酸基含有（メタ）アクリル酸エステルを反応させて得られるようなウレタン（メタ）アクリレート類；多価エポキシ化合物とヒドロキシ（メタ）アクリレート又は（メタ）アクリル酸との付加反応物のようなエポキシアクリレート類；エチレンビスアクリルアミド等のアクリルアミド類；フタル酸ジアリル等のアリルエステル類；ジビニルフタレート等のビニル基含有化合物等が有用である。
　上記ウレタン（メタ）アクリレート類としては、例えば、ＤＰＨＡ－４０Ｈ、ＵＸ－５０００、ＵＸ－５００２Ｄ－Ｐ２０、ＵＸ－５００３Ｄ、ＵＸ－５００５（日本化薬社製）、Ｕ－２ＰＰＡ、Ｕ－６ＬＰＡ、Ｕ－１０ＰＡ、Ｕ－３３Ｈ、ＵＡ－５３Ｈ、ＵＡ－３２Ｐ、ＵＡ－１１００Ｈ（新中村化学工業社製）、ＵＡ－３０６Ｈ、ＵＡ－５１０Ｈ、ＵＦ－８００１Ｇ（協栄社化学社製）、ＵＶ－１７００Ｂ、ＵＶ－７６００Ｂ、ＵＶ－７６０５Ｂ、ＵＶ－７６３０Ｂ、ＵＶ７６４０Ｂ（日本合成化学工業社製）等が挙げられる。 In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, 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 as obtained; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate Allyl esters such as: vinyl group-containing compounds such as divinyl phthalate are useful.
Examples of the urethane (meth) acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-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.
　これらの中でも、硬化性の観点から（Ｄ）光重合性モノマーとして、（メタ）アクリル酸アルキルエステルを用いることが好ましく、ジペンタエリスリトールヘキサアクリレートを用いることがより好ましい。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Among these, from the viewpoint of curability, (D) 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.
［１－５］（Ｅ）光重合開始剤
　本発明の着色感光性樹脂組成物は（Ｅ）光重合開始剤を含有する。（Ｅ）光重合開始剤は、光を直接吸収し、分解反応又は水素引き抜き反応を起こし、重合活性ラジカルを発生する機能を有する成分である。必要に応じて重合促進剤（連鎖移動剤）、増感色素等の付加剤を添加して使用してもよい。
　光重合開始剤としては、例えば、日本国特開昭５９－１５２３９６号公報、日本国特開昭６１－１５１１９７号各公報に記載のチタノセン化合物を含むメタロセン化合物；日本国特開２０００－５６１１８号公報に記載のヘキサアリールビイミダゾール誘導体；日本国特開平１０－３９５０３号公報記載のハロメチル化オキサジアゾール誘導体、ハロメチル－ｓ－トリアジン誘導体、Ｎ－フェニルグリシン等のＮ－アリール－α－アミノ酸類、Ｎ－アリール－α－アミノ酸塩類、Ｎ－アリール－α－アミノ酸エステル類等のラジカル活性剤、α－アミノアルキルフェノン誘導体；日本国特開２０００－８００６８号公報、日本国特開２００６－３６７５０号公報等に記載されているオキシムエステル誘導体等が挙げられる。 [1-5] (E) Photopolymerization initiator The colored photosensitive resin composition of the present invention contains (E) a photopolymerization initiator. (E) 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-α-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-α-amino acid salts and N-aryl-α-amino acid esters, α-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.
　具体的には、例えば、チタノセン誘導体類としては、ジシクロペンタジエニルチタニウムジクロリド、ジシクロペンタジエニルチタニウムビスフェニル、ジシクロペンタジエニルチタニウムビス（２，３，４，５，６－ペンタフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムビス（２，３，５，６－テトラフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムビス（２，４，６－トリフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムジ（２，６－ジフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムジ（２，４－ジフルオロフェニ－１－イル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，３，４，５，６－ペンタフルオロフェニ－１－イル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，６－ジフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウム〔２，６－ジ－フルオロ－３－（ピロ－１－イル）－フェニ－１－イル〕等が挙げられる。 Specifically, for example, 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), dicyclopentadienyltitanium [2,6-di-fluoro-3- (pyro-1-yl) -phen-1-yl] and the like Can be mentioned.
　また、ビイミダゾール誘導体類としては、２－（２’－クロロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（２’－クロロフェニル）－４，５－ビス（３’－メトキシフェニル）イミダゾール２量体、２－（２’－フルオロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（２’－メトキシフェニル）－４，５－ジフェニルイミダゾール２量体、（４’－メトキシフェニル）－４，５－ジフェニルイミダゾール２量体等が挙げられる。 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.
　また、ハロメチル化オキサジアゾール誘導体類としては、２－トリクロロメチル－５－（２’－ベンゾフリル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２’－ベンゾフリル）ビニル〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２’－（６’’－ベンゾフリル）ビニル）〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５－フリル－１，３，４－オキサジアゾール等が挙げられる。 Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, And 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
　また、ハロメチル－ｓ－トリアジン誘導体類としては、２－（４－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシカルボニルナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン等が挙げられる。 Examples of halomethyl-s-triazine derivatives 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.
　また、α－アミノアルキルフェノン誘導体類としては、２－メチル－１〔４－（メチルチオ）フェニル〕－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタン－１－オン、４－ジメチルアミノエチルベンゾエ－ト、４－ジメチルアミノイソアミルベンゾエ－ト、４－ジエチルアミノアセトフェノン、４－ジメチルアミノプロピオフェノン、２－エチルヘキシル－１，４－ジメチルアミノベンゾエート、２，５－ビス（４－ジエチルアミノベンザル）シクロヘキサノン、７－ジエチルアミノ－３－（４－ジエチルアミノベンゾイル）クマリン、４－（ジエチルアミノ）カルコン等が挙げられる。 Further, α-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 below.
　光重合開始剤としては、特に、感度や製版性の点でオキシムエステル誘導体類（オキシムエステル系化合物及びケトオキシムエステル系化合物）が有効であり、フェノール性水酸基を含むアルカリ可溶性樹脂を用いる場合などは、感度の点で不利になるため、特にこのような感度に優れたオキシムエステル誘導体類（オキシムエステル系化合物及びケトオキシムエステル系化合物）が有用である。
　オキシムエステル系化合物としては、下記一般式（ＩＸ）で示される部分構造を含む化合物が挙げられ、好ましくは、下記一般式（ＩＸ－Ａ）で示されるオキシムエステル系化合物が挙げられる。 As photopolymerization initiators, oxime ester derivatives (oxime ester compounds and ketoxime ester compounds) 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.
Examples of 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).
Figure JPOXMLDOC01-appb-C000050
  
Figure JPOXMLDOC01-appb-C000050
  
　式（ＩＸ）中、Ｒ22は、それぞれ置換されていてもよい、炭素数２～１２のアルカノイル基、炭素数１～２０のヘテロアリールアルカノイル基、炭素数３～２５のアルケノイル基、炭素数３～８のシクロアルカノイル基、炭素数３～２０のアルコキシカルボニルアルカノイル基、炭素数８～２０のフェノキシカルボニルアルカノイル基、炭素数３～２０のヘテロアリ－ルオキシカルボニルアルカノイル基、炭素数２～１０のアミノアルキルカルボニル基、炭素数７～２０のアリーロイル基、炭素数１～２０のヘテロアリーロイル基、炭素数２～１０のアルコキシカルボニル基、又は炭素数７～２０のアリールオキシカルボニル基を示す。 In the formula (IX), 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. A cycloalkanoyl group having 8 to 8 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkanoyl group having 3 to 20 carbon atoms, and an amino group having 2 to 10 carbon atoms An alkylcarbonyl group, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms;
Figure JPOXMLDOC01-appb-C000051
  
Figure JPOXMLDOC01-appb-C000051
  
　式（ＩＸ－Ａ）中、Ｒ21aは、水素原子、又はそれぞれ置換されていてもよい、炭素数１～２０のアルキル基、炭素数２～２５のアルケニル基、炭素数１～２０のヘテロアリールアルキル基、炭素数３～２０のアルコキシカルボニルアルキル基、炭素数８～２０のフェノキシカルボニルアルキル基、炭素数１～２０のヘテロアリールオキシカルボニルアルキル基もしくはヘテロアリールチオアルキル基、炭素数１～２０のアミノアルキル基、炭素数２～１２のアルカノイル基、炭素数３～２５のアルケノイル基、炭素数３～８のシクロアルカノイル基、炭素数７～２０のアリーロイル基、炭素数１～２０のヘテロアリーロイル基、炭素数２～１０のアルコキシカルボニル基、炭素数７～２０のアリールオキシカルボニル基、又は炭素数１～１０のシクロアルキルアルキル基を示し；
Ｒ21bは芳香族炭化水素環又は芳香族複素環（ヘテロ芳香環）を含む任意の置換基を示す。
　なお、Ｒ21aはＲ21bと連結して環を形成してもよく、その連結基は、それぞれ置換基を有していてもよい炭素数１～１０のアルキレン基、ポリエチレン基（－（ＣＨ＝ＣＨ）r－）、ポリエチニレン基（－（Ｃ≡Ｃ）r－）あるいはこれらを組み合わせてなる基が挙げられる（なお、ｒは０～３の整数である。）。 In the formula (IX-A), 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. An alkyl group, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms, or an alkyl group 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).
　式（ＩＸ－Ａ）中、Ｒ22aは、それぞれ置換されていてもよい、炭素数２～１２のアルカノイル基、炭素数１～２０のヘテロアリールアルカノイル基、炭素数３～２５のアルケノイル基、炭素数３～８のシクロアルカノイル基、炭素数３～２０のアルコキシカルボニルアルカノイル基、炭素数８～２０のフェノキシカルボニルアルカノイル基、炭素数３～２０のヘテロアリ－ルオキシキシカルボニルアルカノイル基、炭素数２～１０のアミノカルボニル基、炭素数７～２０のアリーロイル基、炭素数１～２０のヘテロアリーロイル基、炭素数２～１０のアルコキシカルボニル基又は炭素数７～２０のアリールオキシカルボニル基を示す。 In the formula (IX-A), 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 An aminocarbonyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms.
　上記一般式（ＩＸ）におけるＲ22及び上記一般式（ＩＸ－Ａ）におけるＲ22aとしては、好ましくは、炭素数２～１２のアルカノイル基、炭素数１～２０のヘテロアリールアルカノイル基、炭素数３～８のシクロアルカノイル基が挙げられる。
　上記一般式（ＩＸ－Ａ）におけるＲ21aとしては、好ましくは無置換のメチル基、エチル基、プロピル基や、Ｎ－アセチル－Ｎ－アセトキシアミノ基で置換されたプロピル基が挙げられる。
　また、上記一般式（ＩＸ－Ａ）におけるＲ21bとしては、好ましくは置換されていてもよいカルバゾイル基、置換されていてもよいフルオレニル基、置換されていてもよいチオキサントニル基、置換されていてもよいフェニルスルフィド基が挙げられる。 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.
In the general formula (IX-A), 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.
　また、上記一般式（ＩＸ）及び（ＩＸ－Ａ）における任意の置換基としては、アルキル基、芳香族炭化水素環基（アリール基）、脂肪族環基、芳香族複素環基、ハロゲン基、水酸基、カルボキシル基、アミノ基、アミド基等が挙げられる。
　本発明に好適なオキシムエステル系化合物として具体的には、以下に例示されるような化合物が挙げられるが、何らこれらの化合物に限定されるものではない。 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.
Figure JPOXMLDOC01-appb-C000052
  
Figure JPOXMLDOC01-appb-C000052
  
Figure JPOXMLDOC01-appb-C000053
  
Figure JPOXMLDOC01-appb-C000053
  
　ケトオキシムエステル系化合物としては、下記一般式（Ｘ）で示される部分構造を含む化合物が挙げられ、好ましくは、下記一般式（Ｘ－Ａ）で示されるケトオキシムエステル系化合物が挙げられる。 Examples of the ketoxime ester compound 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).
Figure JPOXMLDOC01-appb-C000054
  
Figure JPOXMLDOC01-appb-C000054
  
　上記一般式（Ｘ）において、Ｒ24は、前記一般式（ＩＸ）におけるＲ22と同義である。 In the general formula (X), R 24 has the same meaning as R 22 in the general formula (IX).
Figure JPOXMLDOC01-appb-C000055
  
Figure JPOXMLDOC01-appb-C000055
  
　上記一般式（Ｘ－Ａ）において、Ｒ23aは、それぞれ置換されていてもよい、フェニル基、炭素数１～２０のアルキル基、炭素数２～２５のアルケニル基、炭素数１～２０のヘテロアリールアルキル基、炭素数３～２０のアルコキシカルボニルアルキル基、炭素数８～２０のフェノキシカルボニルアルキル基、炭素数２～２０のアルキルチオアルキル基、炭素数１～２０のヘテロアリールオキシカルボニルアルキル基もしくはヘテロアリールチオアルキル基、炭素数１～２０のアミノアルキル基、炭素数２～１２のアルカノイル基、炭素数３～２５のアルケノイル基、炭素数３～８のシクロアルカノイル基、炭素数７～２０のアリーロイル基、炭素数１～２０のヘテロアリーロイル基、炭素数２～１０のアルコキシカルボニル基、炭素数７～２０のアリールオキシカルボニル基、又は炭素数１～１０のシクロアルキルアルキル基を示し；
Ｒ23bは芳香族炭化水素環又は芳香族複素環（ヘテロ芳香環）を含む任意の置換基を示す。
　なお、Ｒ23aはＲ23bと連結して環を形成してもよく、その連結基は、それぞれ置換基を有していてもよい炭素数１～１０のアルキレン基、ポリエチレン基（－（ＣＨ＝ＣＨ）r－）、ポリエチニレン基（－（Ｃ≡Ｃ）r－）あるいはこれらを組み合わせてなる基が挙げられる（なお、ｒは０～３の整数である。）。 In the above general formula ( XA ), 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. An arylalkyl group, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms, or hetero Arylthioalkyl group, aminoalkyl group having 1 to 20 carbon atoms, alkanoyl group having 2 to 12 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, cycloalkanoyl group having 3 to 8 carbon atoms, and aryloyl having 7 to 20 carbon atoms Group, heteroaryloyl group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, 7 to 2 carbon atoms 0 aryloxycarbonyl group or a cycloalkylalkyl group having 1 to 10 carbon atoms;
R 23b represents an arbitrary substituent containing an aromatic hydrocarbon ring or an aromatic heterocyclic ring (heteroaromatic ring).
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).
　一般式（Ｘ－Ａ）中、Ｒ24aは、それぞれ置換されていてもよい、炭素数２～１２のアルカノイル基、炭素数３～２５のアルケノイル基、炭素数４～８のシクロアルカノイル基、炭素数７～２０のベンゾイル基、炭素数３～２０のヘテロアリーロイル基、炭素数２～１０のアルコキシカルボニル基、炭素数７～２０のアリールオキシカルボニル基、炭素数２～２０のヘテロアリール基、又は炭素数２～２０のアルキルアミノカルボニル基を表す。 In the general formula ( XA ), 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.
　上記一般式（Ｘ）におけるＲ24及び上記一般式（Ｘ－Ａ）におけるＲ24aとしては、好ましくは、炭素数２～１２のアルカノイル基、炭素数１～２０のヘテロアリールアルカノイル基、炭素数３～８のシクロアルカノイル基、炭素数７～２０のアリーロイル基が挙げられる。
　上記一般式（Ｘ－Ａ）におけるＲ23aとしては、好ましくは無置換のエチル基、プロピル基、ブチル基や、メトキシカルボニル基で置換されたエチル基又はプロピル基が挙げられる。
　また、上記一般式（Ｘ－Ａ）におけるＲ23bとしては、好ましくは置換されていてもよいカルバゾイル基、置換されていてもよいフルオレニル基、置換されていてもよいフェニルスルフィド基が挙げられる。 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.
In addition, 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.
　また、上記一般式（Ｘ）及び（Ｘ－Ａ）における任意の置換基としては、アルキル基、芳香族炭化水素環基（アリール基）、脂肪族環基、芳香族複素環基、ハロゲン基、水酸基、カルボキシル基、アミノ基、アミド基等が挙げられる。
　本発明に好適なケトオキシムエステル系化合物として具体的には、以下に例示されるような化合物が挙げられるが、何らこれらの化合物に限定されるものではない。 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.
Figure JPOXMLDOC01-appb-C000056
  
Figure JPOXMLDOC01-appb-C000056
  
Figure JPOXMLDOC01-appb-C000057
  
Figure JPOXMLDOC01-appb-C000057
  
　これらのオキシムエステル系化合物及びケトオキシムエステル系化合物は、それ自体公知の化合物であり、例えば、日本国特開２０００－８００６８号公報や、日本国特開２００６－３６７５０号公報に記載されている一連の化合物の一種である。感度の観点から本発明では、（Ｅ）光重合開始剤が、オキシムエステル系化合物及び／又はケトオキシムエステル系化合物であることが好ましい。
　上記光重合開始剤は１種を単独で用いてもよく、２種以上を併用してもよい。 These 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.
　（Ｅ）光重合開始剤としては、上述のものの他に、ベンゾインメチルエーテル、ベンゾインフェニルエーテル、ベンゾインイソブチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインアルキルエーテル類；２－メチルアントラキノン、２－エチルアントラキノン、２－ｔ－ブチルアントラキノン、１－クロロアントラキノン等のアントラキノン誘導体類；ベンゾフェノン、ミヒラーズケトン、２－メチルベンゾフェノン、３－メチルベンゾフェノン、４－メチルベンゾフェノン、２－クロロベンゾフェノン、４－ブロモベンゾフェノン、２－カルボキシベンゾフェノン等のベンゾフェノン誘導体類；２，２－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシアセトフェノン、１－ヒドロキシシクロへキシルフェニルケトン、α－ヒドロキシ－２－メチルフェニルプロパノン、１－ヒドロキシ－１－メチルエチル－（ｐ－イソプロピルフェニル）ケトン、１－ヒドロキシ－１－（ｐ－ドデシルフェニル）ケトン、２－メチル－（４’－メチルチオフェニル）－２－モルホリノ－１－プロパノン、１，１，１－トリクロロメチル－（ｐ－ブチルフェニル）ケトン等のアセトフェノン誘導体類；チオキサントン、２－エチルチオキサントン、２－イソプロピルチオキサントン、２－クロロチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジイソプロピルチオキサントン等のチオキサントン誘導体類；ｐ－ジメチルアミノ安息香酸エチル、ｐ－ジエチルアミノ安息香酸エチル等の安息香酸エステル誘導体類；９－フェニルアクリジン、９－（ｐ－メトキシフェニル）アクリジン等のアクリジン誘導体類；９，１０－ジメチルベンズフェナジン等のフェナジン誘導体類；ベンズアンスロン等のアンスロン誘導体類等も挙げられる。 (E) As the photopolymerization initiator, in addition to the above, 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, α-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-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate ; 9-F Examples also include acridine derivatives such as phenylacridine and 9- (p-methoxyphenyl) acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; and anthrone derivatives such as benzanthrone.
　これらの光重合開始剤の中では、感度、溶剤への溶解性、現像時のパターン密着性の観点から、オキシムエステル誘導体類の中でも、前記一般式（ＩＸ）で示される部分構造を含む化合物である以下の化合物、 Among these photopolymerization initiators, from the viewpoints of sensitivity, solubility in a solvent, and pattern adhesion during development, among oxime ester derivatives, a compound having a partial structure represented by the general formula (IX). The following compounds,
Figure JPOXMLDOC01-appb-C000058
  
Figure JPOXMLDOC01-appb-C000058
  
Figure JPOXMLDOC01-appb-C000059
  
Figure JPOXMLDOC01-appb-C000059
  
　又は、前記一般式（Ｘ）で示される部分構造を含む化合物である以下の化合物がさらに好ましい。 Alternatively, the following compounds that are compounds including the partial structure represented by the general formula (X) are more preferable.
Figure JPOXMLDOC01-appb-C000060
  
Figure JPOXMLDOC01-appb-C000060
  
Figure JPOXMLDOC01-appb-C000061
  
Figure JPOXMLDOC01-appb-C000061
  
Figure JPOXMLDOC01-appb-C000062
  
Figure JPOXMLDOC01-appb-C000062
  
　（Ｅ）光重合開始剤は、１種類を単独で用いても、２種類以上を組み合わせて使用してもよい。
　（Ｅ）光重合開始剤には、必要に応じて、感応感度を高める目的で、画像露光光源の波長に応じた増感色素、重合促進剤を配合させることができる。増感色素としては、日本国特開平４－２２１９５８号、日本国特開平４－２１９７５６号公報に記載のキサンテン色素、日本国特開平３－２３９７０３号、日本国特開平５－２８９３３５号公報に記載の複素環を有するクマリン色素、日本国特開平３－２３９７０３号、日本国特開平５－２８９３３５号に記載の３－ケトクマリン化合物、日本国特開平６－１９２４０号公報に記載のピロメテン色素、その他、日本国特開昭４７－２５２８号、日本国特開昭５４－１５５２９２号、日本国特公昭４５－３７３７７号、日本国特開昭４８－８４１８３号、日本国特開昭５２－１１２６８１号、日本国特開昭５８－１５５０３号、日本国特開昭６０－８８００５号、日本国特開昭５９－５６４０３号、日本国特開平２－６９号、日本国特開昭５７－１６８０８８号、日本国特開平５－１０７７６１号、日本国特開平５－２１０２４０号、日本国特開平４－２８８８１８号公報に記載のジアルキルアミノベンゼン骨格を有する色素等を挙げることができる。 (E) A photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more types.
(E) 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. As 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. A coumarin dye having a heterocyclic ring, a 3-ketocoumarin compound described in JP-A-3-239703, JP-A-5-289335, a pyromethene dye described in JP-A-6-19240, Japanese Unexamined Patent Publication No. 47-2528, Japanese Unexamined Patent Publication No. 54-155292, Japanese Special Publication No. 45-37377, Japanese Unexamined Patent Publication No. 48-84183, Japanese Unexamined Patent Publication No. 52-112682, Japan JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57 No. 168,088, Japanese Patent Laid-Open No. 5-107761, Japanese Patent Laid-Open No. 5-210240, may be mentioned dyes having a dialkyl aminobenzene skeleton described in JP Japanese Patent Laid-Open No. 4-288818.
　これらの増感色素のうち好ましいものは、アミノ基含有増感色素であり、更に好ましいものは、アミノ基及びフェニル基を同一分子内に有する化合物である。特に、好ましいのは、例えば、４，４’－ジメチルアミノベンゾフェノン、４，４’－ジエチルアミノベンゾフェノン、２－アミノベンゾフェノン、４－アミノベンゾフェノン、４，４’－ジアミノベンゾフェノン、３，３’－ジアミノベンゾフェノン、３，４－ジアミノベンゾフェノン等のベンゾフェノン系化合物；２－（ｐ－ジメチルアミノフェニル）ベンゾオキサゾール、２－（ｐ－ジエチルアミノフェニル）ベンゾオキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾ［４，５］ベンゾオキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾ［６，７］ベンゾオキサゾール、２，５－ビス（ｐ－ジエチルアミノフェニル）－１，３，４－オキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾチアゾール、２－（ｐ－ジエチルアミノフェニル）ベンゾチアゾール、２－（ｐ－ジメチルアミノフェニル）ベンズイミダゾール、２－（ｐ－ジエチルアミノフェニル）ベンズイミダゾール、２，５－ビス（ｐ－ジエチルアミノフェニル）－１，３，４－チアジアゾール、（ｐ－ジメチルアミノフェニル）ピリジン、（ｐ－ジエチルアミノフェニル）ピリジン、（ｐ－ジメチルアミノフェニル）キノリン、（ｐ－ジエチルアミノフェニル）キノリン、（ｐ－ジメチルアミノフェニル）ピリミジン、（ｐ－ジエチルアミノフェニル）ピリミジン等のｐ－ジアルキルアミノフェニル基含有化合物等である。このうち最も好ましいものは、４，４’－ジアルキルアミノベンゾフェノンである。
　増感色素もまた１種類を単独で用いてもよく、２種類以上を併用してもよい。 Among these 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-thiadiazole, (P-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine P-dialkylaminophenyl group-containing compounds such as Of these, 4,4′-dialkylaminobenzophenone is most preferred.
A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.
　重合促進剤としては、例えば、ｐ－ジメチルアミノ安息香酸エチル、安息香酸２－ジメチルアミノエチル等の芳香族アミン、ｎ－ブチルアミン、Ｎ－メチルジエタノールアミン等の脂肪族アミン、後述するメルカプト化合物等が用いられる。重合促進剤は、１種類を単独で用いても、２種類以上を組み合わせて使用してもよい。 Examples of the polymerization accelerator 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.
［１－６］着色感光性樹脂組成物のその他の配合成分
　本発明の着色感光性樹脂組成物には、上述の成分の他、シランカップリング剤等の密着向上剤、塗布性向上剤、現像改良剤、紫外線吸収剤、酸化防止剤、界面活性剤、顔料誘導体等を適宜配合することができる。 [1-6] Other Compounding Components of Colored Photosensitive Resin Composition In addition to the above-described components, 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.
［１－６－１］密着向上剤
　本発明の着色感光性樹脂組成物には、基板との密着性を改善するため、密着向上剤を含有させてもよい。密着向上剤としては、シランカップリング剤、燐酸基含有化合物等が好ましい。
　シランカップリング剤の種類としては、エポキシ系、（メタ）アクリル系、アミノ系等種々のものを１種単独で、或いは２種以上を混合して使用できる。 [1-6-1] Adhesion improver The colored photosensitive resin composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate. As the adhesion improver, a silane coupling agent, a phosphoric acid group-containing compound and the like are preferable.
As 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.
　好ましいシランカップリング剤として、例えば、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン等の（メタ）アクリロキシシラン類、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン等のエポキシシラン類、３－ウレイドプロピルトリエトキシシラン等のウレイドシラン類、３－イソシアネートプロピルトリエトキシシラン等のイソシアネートシラン類が挙げられるが、特に好ましくは、エポキシシラン類のシランカップリング剤である。
　燐酸基含有化合物としては、（メタ）アクリロイル基含有ホスフェート類が好ましく、下記一般式（ＸＩ－Ａ）、（ＸＩ－Ｂ）又は（ＸＩ－Ｃ）で表されるものが好ましい。 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.
As 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.
Figure JPOXMLDOC01-appb-C000063
  
Figure JPOXMLDOC01-appb-C000063
  
　上記一般式（ＸＩ－Ａ）、（ＸＩ－Ｂ）及び（ＸＩ－Ｃ）において、Ｒ51は水素原子又はメチル基を表し；
ｌ及びｌ’は１～１０の整数を表し；
ｍは１、２又は３を表す。
　これらの燐酸基含有化合物も１種類を単独で用いても、２種以上を組み合わせて使用してもよい。 In the above general formulas (XI-A), (XI-B) and (XI-C), 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.
［１－６－２］顔料誘導体
　本発明の着色感光性樹脂組成物には、分散性、保存性向上のため、分散助剤として顔料誘導体を含有させてもよい。
　顔料誘導体としてはアゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、キノフタロン系、イソインドリノン系、ジオキサジン系、アントラキノン系、インダンスレン系、ペリレン系、ペリノン系、ジケトピロロピロール系、ジオキサジン系等の誘導体が挙げられるが、中でもフタロシアニン系、キノフタロン系が好ましい。
　顔料誘導体の置換基としてはスルホン酸基、スルホンアミド基及びその４級塩、フタルイミドメチル基、ジアルキルアミノアルキル基、水酸基、カルボキシル基、アミド基等が顔料骨格に直接又はアルキル基、アリール基、複素環基等を介して結合したものが挙げられ、好ましくはスルホン酸基である。またこれら置換基は一つの顔料骨格に複数置換していてもよい。 [1-6-2] Pigment Derivative 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.
As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Among them, 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.
　顔料誘導体の具体例としてはフタロシアニンのスルホン酸誘導体、キノフタロンのスルホン酸誘導体、アントラキノンのスルホン酸誘導体、キナクリドンのスルホン酸誘導体、ジケトピロロピロールのスルホン酸誘導体、ジオキサジンのスルホン酸誘導体等が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Specific examples of 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.
［１－６－３］光酸発生剤
　光酸発生剤とは、紫外線により酸を発生することができる化合物であり、露光を行った際に発生する酸の作用により、例えばメラミン化合物等架橋剤があることで架橋反応を進行させることとなる。係る光酸発生剤の中でも、溶剤に対する溶解性、特に感光性着色組成物に使われる溶剤に対する溶解性が大きいものが好ましいものであり、例えば、ジフェニルヨードニウム、ジトリルヨードニウム、フェニル（ｐ－アニシル）ヨードニウム、ビス（ｍ－ニトロフェニル）ヨードニウム、ビス（ｐ－ｔｅｒｔ－ブチルフェニル）ヨードニウム、ビス（ｐ－クロロフェニル）ヨードニウム、ビス（ｎ－ドデシル）ヨードニウム、ｐ－イソブチルフェニル（ｐ－トリル）ヨードニウム、ｐ－イソプロピルフェニル（ｐ－トリル）ヨードニウムなどのジアリールヨードニウム、あるいはトリフェニルスルホニウムなどのトリアリールスルホニウムのクロリド、ブロミド、あるいはホウフッ化塩、ヘキサフルオロフォスフェート塩、ヘキサフルオロアルセネート塩、芳香族スルホン酸塩、テトラキス（ペンタフルオロフェニル）ボレート塩等や、ジフェニルフェナシルスルホニウム（ｎ－ブチル）トリフェニルボレート等のスルホニウム有機ホウ素錯体類、あるいは、２－メチル－４，６－ビストリクロロメチルトリアジン、２－（４－メトキシフェニル）－４，６－ビストリクロロメチルトリアジンなどのトリアジン化合物等を挙げることができるがこの限りではない。 [1-6-3] Photoacid generator The photoacid generator is a compound capable of generating an acid by ultraviolet rays. By the action of the acid generated upon exposure, for example, a crosslinking agent such as a melamine compound. If there is, it will advance a crosslinking reaction. Among such 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) triphenylborate, or 2-methyl-4,6- Examples thereof include, but are not limited to, triazine compounds such as bistrichloromethyltriazine and 2- (4-methoxyphenyl) -4,6-bistrichloromethyltriazine.
［１－６－４］架橋剤
　本発明の着色感光性樹脂組成物には、さらに架橋剤を加えることができ、例えばメラミン又はグアナミン系の化合物を用いることができる。これら架橋剤としては、例えば、下記一般式（ＸＩＩ）で示されるメラミン又はグアナミン系の化合物を挙げることができる。 [1-6-4] Crosslinking Agent A crosslinked agent can be further added to the colored photosensitive resin composition of the present invention. For example, a melamine or guanamine compound can be used. Examples of these crosslinking agents include melamine or guanamine compounds represented by the following general formula (XII).
Figure JPOXMLDOC01-appb-C000064
  
Figure JPOXMLDOC01-appb-C000064
  
　式（ＸＩＩ）中、Ｒ61は－ＮＲ66Ｒ67基又は炭素数６～１２のアリール基を表し；
Ｒ61が－ＮＲ66Ｒ67基の場合はＲ62、Ｒ63、Ｒ64、Ｒ65、Ｒ66及びＲ67の一つ、そしてＲ61が炭素数６～１２のアリール基の場合はＲ62、Ｒ63、Ｒ64及びＲ65の一つが－ＣＨ2ＯＲ68基を表し；
Ｒ62、Ｒ63、Ｒ64、Ｒ65、Ｒ66及びＲ67の残りは各々独立に、水素原子又は－ＣＨ2ＯＲ68基を表し；
Ｒ68は水素原子又は炭素数１～４のアルキル基を表す。
　ここで、炭素数６～１２のアリール基は典型的にはフェニル基、１－ナフチル基又は２－ナフチル基であり、これらのフェニル基やナフチル基には、アルキル基、アルコキシ基、ハロゲン原子などの置換基が結合していてもよい。アルキル基及びアルコキシ基は、それぞれ炭素数１～６程度であることができる。Ｒ68で表されるアルキル基は、上記の中でも、メチル基又はエチル基が好ましく、メチル基がより好ましい。 In the formula (XII), R 61 represents a —NR 66 R 67 group or an aryl group having 6 to 12 carbon atoms;
When 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.
Here, 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.
　一般式（ＸＩＩ）に相当するメラミン系化合物、すなわち下記一般式（ＸＩＩ－Ａ）の化合物には、ヘキサメチロールメラミン、ペンタメチロールメラミン、テトラメチロールメラミン、ヘキサメトキシメチルメラミン、ペンタメトキシメチルメラミン、テトラメトキシメチルメラミン、ヘキサエトキシメチルメラミンなどが包含される。 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.
Figure JPOXMLDOC01-appb-C000065
  
Figure JPOXMLDOC01-appb-C000065
  
　式（ＸＩＩ－Ａ）中、Ｒ62、Ｒ63、Ｒ64、Ｒ65、Ｒ66及びＲ67の一つがアリール基の場合はＲ62、Ｒ63、Ｒ64及びＲ65の一つが－ＣＨ2ＯＲ68基を表し；
Ｒ62、Ｒ63、Ｒ64、Ｒ65、Ｒ66及びＲ67の残りは各々独立に、水素原子又は－ＣＨ2ＯＲ68基を表し；
Ｒ68は水素原子又はアルキル基を表す。 In the formula (XII-A), 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.
　また、一般式（ＸＩＩ）に相当するグアナミン系化合物、すなわち一般式（ＸＩＩ）中のＲ61がアリールである化合物には、テトラメチロールベンゾグアナミン、テトラメトキシメチルベンゾグアナミン、トリメトキシメチルベンゾグアナミン、テトラエトキシメチルベンゾグアナミンなどが包含される。 Further, 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.
　さらに、メチロール基又はメチロールアルキルエーテル基を有する架橋剤を用いることもできる。以下にその例を挙げる。
　２，６－ビス（ヒドロキシメチル）－４－メチルフェノール、４－ｔｅｒｔ－ブチル－２，６－ビス（ヒドロキシメチル）フェノール、５－エチル－１，３－ビス（ヒドロキシメチル）ペルヒドロ－１，３，５－トリアジン－２－オン（通称Ｎ－エチルジメチロールトリアゾン）又はそのジメチルエーテル体、ジメチロールトリメチレン尿素又はそのジメチルエーテル体、３，５－ビス（ヒドロキシメチル）ペルヒドロ－１，３，５－オキサジアジン－４－オン（通称ジメチロールウロン）又はそのジメチルエーテル体、テトラメチロールグリオキザールジウレイン又はそのテトラメチルエーテル体。 Furthermore, 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.
　なお、これら架橋剤は１種を単独で用いても、２種以上を組み合わせて使用してもよい。架橋剤を用いる際の量は、感光性着色組成物の全固形分に対して０．１～１５質量％が好ましく、特に好ましくは０．５～１０質量％である。 In addition, these 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.
［１－６－５］メルカプト化合物
　重合促進剤として、また、基板への密着性の向上のため、メルカプト化合物を添加することも可能である。 [1-6-5] Mercapto Compound It is also possible to add a mercapto compound as a polymerization accelerator and to improve adhesion to the substrate.
　メルカプト化合物の種類としては、２－メルカプトベンゾチアゾール、２－メルカプトベンゾオキサゾール、２－メルカプトベンゾイミダゾール、ヘキサンジチオール、デカンジチオール、１，４－ジメチルメルカプトベンゼン、ブタンジオールビスチオプロピオネート、ブタンジオールビスチオグリコレート、エチレングリコールビスチオグリコレート、トリメチロールプロパントリスチオグリコレート、ブタンジオールビスチオプロピオネート、トリメチロールプロパントリスチオプロピオネート、トリメチロールプロパントリスチオグリコレート、ペンタエリスリトールテトラキスチオプロピオネート、ペンタエリスリトールテトラキスチオグリコレート、トリスヒドロキシエチルトリスチオプロピオネート、エチレングリコールビス（３－メルカプトブチレート）、ブタンジオールビス（３－メルカプトブチレート）、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、トリメチロールプロパントリス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、ペンタエリスリトールトリス（３－メルカプトブチレート）、エチレングリコールビス（３－メルカプトイソブチレート）、ブタンジオールビス（３－メルカプトイソブチレート）、トリメチロールプロパントリス（３－メルカプトイソブチレート）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン等の複素環を有するメルカプト化合物又は脂肪族多官能メルカプト化合物等が挙げられる。これらは種々のものを１種類単独で、或いは２種類以上を混合して使用できる。 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-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis ( 3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercapto) Mercapto having a heterocyclic ring such as isobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione Compounds or aliphatic polyfunctional mercapto compounds, etc. It is below. These can be used alone or in combination of two or more.
［１－６－６］界面活性剤
　本発明の着色感光性樹脂組成物には、塗布性向上ため、界面活性剤を含有させてもよい。 [1-6-6] Surfactant The colored photosensitive resin composition of the present invention may contain a surfactant in order to improve coatability.
　界面活性剤としては、例えば、アニオン系界面活性剤、カチオン系界面活性剤、非イオン系界面活性剤、両性界面活性剤等の各種のものを用いることができる。中でも、諸特性に悪影響を及ぼす可能性が低い点で、非イオン系界面活性剤を用いるのが好ましく、中でもフッ素系やシリコーン系の界面活性剤が塗布性の面で効果的である。
　これらの市販品としては、例えば、ＢＭ　Ｃｈｅｍｉｅ社製「ＢＭ－１０００」、「ＢＭ－１１００」、ＤＩＣ社製「メガファックＦ－１４２Ｄ」、「メガファックＦ－１７２」、「メガファックＦ－１７３」、「メガファックＦ－１８３」、「メガファックＦ－４７０」、「メガファックＦ－４７５」、「メガファックＦ－４７８」、「メガファックＦ－５５４」、「メガファックＦ－５５９」、スリーエムジャパン社製「ＦＣ４３０」、ネオス社製「ＤＦＸ－１８」などを挙げることができる。 As the surfactant, for example, various types such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used. Among these, 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.
Examples of 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. ”,“ Megafuck F-183 ”,“ Megafuck F-470 ”,“ Megafuck F-475 ”,“ Megafuck F-478 ”,“ Megafuck F-554 ”,“ Megafuck F-559 ”, Examples thereof include “FC430” manufactured by 3M Japan, “DFX-18” manufactured by Neos, and the like.
　また、シリコーン系界面活性剤としては、例えば、東レ・ダウコーニング社製「ＤＣ３ＰＡ」、「ＳＨ７ＰＡ」、「ＤＣ１１ＰＡ」、「ＳＨ２１ＰＡ」、「ＳＨ２８ＰＡ」、「ＳＨ２９ＰＡ」、「８０３２Ａｄｄｉｔｉｖｅ」、「ＳＨ８４００」、ビックケミー社製「ＢＹＫ３００」、「ＢＹＫ３２３」、「ＢＹＫ３２５」、「ＢＹＫ３３０」、信越シリコーン社製「ＫＰ３４０」などの市販品を挙げることができる。
　界面活性剤として、フッ素系界面活性剤及びシリコーン系界面活性剤以外のものを含んでいてもよく、その他の界面活性剤としては、非イオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤などが挙げられる。
　なお、界面活性剤は、１種類を単独で用いてもよく、２種類以上を任意の組み合わせ及び比率で併用してもよい。中でも、シリコーン系界面活性剤／フッ素系界面活性剤の組み合わせが好ましい。このシリコーン系界面活性剤／フッ素系界面活性剤の組み合わせでは、例えば、ビックケミー社製「ＢＹＫ－３００」又は「ＢＹＫ－３３０」／ＤＩＣ社製「Ｆ－４７５」「Ｆ－４７８」「Ｆ－５５４」又は「Ｆ－５５９」などが挙げられる。 Examples of the silicone surfactant 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.
In addition, surfactant may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. Of these, a combination of silicone surfactant / fluorine surfactant is preferable. In 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”.
［１－６－７］撥液剤
　本発明の着色感光性樹脂組成物は、撥液剤を含有していてもよい。特に本発明の着色感光性樹脂組成物を用いて隔壁を作成し、インクジェット法で有機電界発光素子を作成する場合には、撥液剤を含有することが好ましい。撥液剤を含有することでそれが隔壁の表面に撥液性を付与できることから、得られる隔壁を有機層の画素ごとの混色を防ぐものとすることができる。
　撥液剤としては、シリコーン含有化合物やフッ素系化合物が挙げられ、好ましくは、架橋基を有する撥液剤（以下、「架橋基含有撥液剤」と称す場合がある。）が挙げられる。架橋基としては、エポキシ基又はエチレン性不飽和基が挙げられ、現像液の撥液成分の流出抑制の観点から、好ましくはエチレン性不飽和基である。
　架橋基含有撥液剤を用いる場合には、形成した塗布膜を露光する際にその表面での架橋反応を加速することができ、撥液剤が現像処理で流出しにくくなり、その結果、得られる隔壁を高い撥液性を示すものとすることができると考えられる。 [1-6-7] Liquid repellent agent The colored photosensitive resin composition of the present invention may contain a liquid repellent agent. In particular, when a partition is formed using the colored photosensitive resin composition of the present invention and an organic electroluminescent element is formed by an inkjet method, it is preferable to contain 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.
Examples of 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”). Examples of the crosslinking group 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.
When the crosslinkable group-containing liquid repellent is 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.
　撥液剤としてフッ素系化合物を用いた場合には、当該フッ素系化合物が隔壁の表面に配向して、インキのにじみや混色を防止する働きをする傾向がある。さらに詳しくは、フッ素原子を有する基が、インキをはじき、インキが隔壁を越えて隣接する領域に進入することによるインキのにじみや混色を防ぐ働きをする傾向がある。 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.
　架橋基含有撥液剤、特にエチレン性不飽和基含有フッ素系化合物の具体例としては、例えばパーフルオロアルキルスルホン酸、パーフルオロアルキルカルボン酸、パーフルオロアルキルアルキレンオキシド付加物、パーフルオロアルキルトリアルキルアンモニウム塩、パーフルオロアルキル基と親水基を含むオリゴマー、パーフルオロアルキル基と親油基を含むオリゴマー、パーフルオロアルキル基と親水基と親油基を含むオリゴマー、パーフルオロアルキルと親水基を含むウレタン、パーフルオロアルキルエステル、パーフルオロアルキル燐酸エステルなどのフッ素含有有機化合物を挙げることができる。 Specific examples of the crosslinkable group-containing liquid repellent, particularly the ethylenically unsaturated group-containing fluorine-based compound include, for example, 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.
　これらのフッ素含有化合物の市販品としては、ＤＩＣ社製「ＤＥＦＥＮＳＡＭＣＦ－３００」、「ＤＥＦＥＮＳＡＭＣＦ－３１０」、「ＤＥＦＥＮＳＡＭＣＦ－３１２」、「ＤＥＦＥＮＳＡＭＣＦ－３２３」、「メガファックＲＳ－７２－Ｋ」、スリーエムジャパン社製「フロラードＦＣ－４３１」、「フロラードＦＣ－４４３０」、「フロラードＦＣ－４４３２」、旭硝子社製「アサヒガードＡＧ７１０」、「サーフロンＳ－３８２」、「サーフロンＳＣ－１０１」、「サーフロンＳＣ－１０２」、「サーフロンＳＣ－１０３」、「サーフロンＳＣ－１０４」、「サーフロンＳＣ－１０５」、「サーフロンＳＣ－１０６」、ダイキン工業社製「オプツールＤＡＣ―ＨＰ」、「ＨＰ－６５０」などの商品名で市販されているフッ素含有化合物を使用することができる。 Commercially available products of these 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. “Asahi Guard AG710”, “Surflon S-382”, “Surflon SC-101”, “Surflon SC-” Products such as “102”, “Surflon SC-103”, “Surflon SC-104”, “Surflon SC-105”, “Surflon SC-106”, “Optool DAC-HP”, “HP-650” manufactured by Daikin Industries, Ltd. Fluorine-containing compounds marketed by name It can be used.
　このように、撥液剤としてフッ素系化合物を用いる場合において、撥液剤中のフッ素原子含有割合は特に制限されないが、好ましくはフッ素原子含有割合が１質量％以上が好ましく、５質量％以上がより好ましく、また、５０質量％以下が好ましく、２５質量％以下がより好ましい。前記下限値以上とすることで高い接触角を示す傾向があり、また、前記上限値以下とすることで画素部への流出を抑制できる傾向がある。 Thus, in the case of using a fluorine-based compound as the liquid repellent, 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.
　撥液剤の分子量は特に制限されず、低分子量の化合物でも、高分子量体であってもよい。高分子量体の撥液剤の方が、焼成による撥液剤の流動性が抑えられるため、隔壁外に撥液剤が流出するのを抑制できる傾向があるため好ましく、係る観点から撥液剤の数平均分子量は、１００以上が好ましく、５００以上がより好ましく、１０００００以下が好ましく、１００００以下がより好ましい。 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. From this viewpoint, 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.
　本発明の着色感光性樹脂組成物中の撥液剤の含有割合は、全固形分に対して通常０．０１質量％以上、好ましくは０．０５質量％以上、より好ましくは０．１質量％以上、通常１質量％以下、好ましくは０．５質量％以下、より好ましくは０．３質量％以下である。前記下限値以上とすることで高い撥液性を示す傾向があり、また、前記上限値以下とすることで撥液剤の画素部への流出を抑制できる傾向がある。 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. When it is at least the lower limit, there is a tendency to exhibit high liquid repellency, and when it is at most the upper limit, there is a tendency that outflow of the liquid repellent to the pixel portion can be suppressed.
［１－６－８］紫外線吸収剤
　本発明の着色感光性樹脂組成物は、紫外線吸収剤を含有してもよい。紫外線吸収剤は、露光に用いられる光源の特定の波長を紫外線吸収剤によって吸収させることにより、光硬化分布を制御する目的で添加されるものである。紫外線吸収剤の添加により、現像後のテーパ角度及び形状を改善したり、現像後に非露光部に残る残渣をなくしたりするなどの効果が得られる傾向がある。紫外線吸収剤としては、開始剤の光吸収の阻害の観点から、例えば、波長２５０ｎｍから４００ｎｍの間に吸収極大を有する化合物を用いることができる。
　紫外線吸収剤としては、ベンゾトリアゾール系化合物及び／又はトリアジン系化合物が望ましい。ベンゾトリアゾール系化合物及び／又はトリアジン系化合物を含むことで開始剤の膜底部での光吸収率が減少し、膜表層と膜底部の硬化面積の差が小さくなることによりテーパ角度の増大効果が得られると考えられる。 [1-6-8] Ultraviolet Absorber 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. As 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.
As the ultraviolet absorber, a benzotriazole compound and / or a triazine compound is desirable. Inclusion of a benzotriazole compound and / or a triazine compound reduces the light absorption rate at the film bottom of the initiator, and reduces the difference in the cured area between the film surface layer and the film bottom, thereby increasing the taper angle. It is thought that.
　ベンゾトリアゾール系化合物としては、２－（５メチル－２－ヒドロキシフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）－２Ｈ－ベンゾトリアゾール、オクチル－３［３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－（５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル）フェニル］プロピオネートと２－エチルヘキシル－３－［３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－（５－クロロ－２Ｈ－ベンゾトリアゾール－２－イル）フェニル］プロピオネートの混合物、２－［２－ヒドロキシ－３，５－ビス（α，α－ジメチルベンジル）フェニル］－２Ｈ－ベンゾトリアゾール、２－（３－ｔｅｒｔ－ブチル－５－メチル－２－ヒドロキシフェニル）－５－クロロベンゾトリアゾール、２－（３，５－ジ－ｔｅｒｔ－アミル－２－ヒドロキシフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－５’－ｔｅｒｔ－オクチルフェニル）ベンゾトリアゾール、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ビス（１－メチル－１－フェニルエチル）フェノール、２－（２Ｈ－ベンゾトリアゾール－２－イル）－６－（１－メチル－１－フェニルエチル）－４－（１，１，３，３－テトラメチルブチル）フェノール、ベンゼンプロパン酸、３－（２Ｈ－ベンゾトリアゾール－２－イル）－５－（１，１－ジメチルエチル）－４－ヒドロキシ、Ｃ７－９側鎖及び直鎖アルキルエステルが挙げられる。 Examples of the benzotriazole compounds include 2- (5 methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, and octyl-3 [3-tert-butyl. -4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H -Benzotriazol-2-yl) phenyl] propionate, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-tert-butyl -5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3 3-tetramethylbutyl) phenol, benzenepropanoic acid, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester Is mentioned.
　市販されているベンゾトリアゾール系化合物としては例えば、スミソーブ２００、スミソーブ２５０、スミソーブ３００、スミソーブ３４０、スミソーブ３５０（住友化学社製）、ＪＦ７７、ＪＦ７８、ＪＦ７９、ＪＦ８０、ＪＦ８３（城北化学工業社製）、ＴＩＮＵＶＩＮ　ＰＳ、ＴＩＮＵＶＩＮ９９－２、ＴＩＮＵＶＩＮ１０９、ＴＩＮＵＶＩＮ３８４－２、ＴＩＮＵＶＩＮ　３２６、ＴＩＮＵＶＩＮ９００、ＴＩＮＵＶＩＮ　９２８、ＴＩＮＵＶＩＮ９２８、ＴＩＮＵＶＩＮ１１３０（ＢＡＳＦ社製）、ＥＶＥＲＳＯＲＢ７０、ＥＶＥＲＳＯＲＢ７１、ＥＶＥＲＳＯＲＢ７２、ＥＶＥＲＳＯＲＢ７３、ＥＶＥＲＳＯＲＢ７４、ＥＶＥＲＳＯＲＢ７５、ＥＶＥＲＳＯＲＢ７６、ＥＶＥＲＳＯＲＢ２３４、ＥＶＥＲＳＯＲＢ７７、ＥＶＥＲＳＯＲＢ７８、ＥＶＥＲＳＯＲＢ８０、ＥＶＥＲＳＯＲＢ８１（台湾永光化学工業社製）、トミソーブ１００、トミソーブ６００（エーピーアイコーポレーション社製）、ＳＥＥＳＯＲＢ７０１、ＳＥＥＳＯＲＢ７０２、ＳＥＥＳＯＲＢ７０３、ＳＥＥＳＯＲＢ７０４、ＳＥＥＳＯＲＢ７０６、ＳＥＥＳＯＲＢ７０７、ＳＥＥＳＯＲＢ７０９（シプロ化成社製）、ＲＵＶＡ－９３（大塚化学社製）などが挙げられる。
　トリアジン系化合物としては、２－［４，６－ジ（２，４－キシリル）－１，３，５－トリアジン－２－イル］－５－オクチルオキシフェノール、２‐［４，６‐ビス（２，４‐ジメチルフェニル）‐１，３，５‐トリアジン‐２‐イル］‐５‐［３‐（ドデシルオキシ）‐２‐ヒドロキシプロポキシ］フェノール、２－（２，４－ジヒドロキシフェニル）－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジンと（２－エチルヘキシル－グリシド酸エステルの反応生成物、２，４－ビス「２－ヒドロキシ－４－ブトキシフェニル」－６－（２，４－ジブトキシフェニル）－１，３－５－トリアジン等が挙げられる。これらの中でも、テーパ角度と露光感度の観点から、ヒドロキシフェニルトリアジン化合物が好ましい。
　市販されているトリアジン系化合物としては例えば、ＴＩＮＵＶＩＮ４００、ＴＩＮＵＶＩＮ４０５、ＴＩＮＵＶＩＮ４６０、ＴＩＮＵＶＩＮ４７７、ＴＩＮＵＶＩＮ４７９（ＢＡＳＦ製）などを挙げることができる。 Examples of commercially available benzotriazole-based compounds 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.), Tomisorb 100, Tomisorb 600 (manufactured by API Corporation), SEESORB701, SEESORB702, SEESORB703, SEESORB706, SEESORB707, SEESORB707, SEESORB707, SEESORB707 (Otsuka Chemical Co., Ltd.).
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. Among these, 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).
［１－６－９］重合禁止剤
　本発明の着色感光性樹脂組成物は、重合禁止剤を含有してもよい。重合禁止剤を含有することでそれがラジカル重合を阻害することから、得られる硬化物のテーパ角度を大きくすることができる傾向がある。
　重合禁止剤としては、ハイドロキノン、ハイドロキノンモノメチルエーテル、メチルハイドロキノン、メトキシフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－クレゾール（ＢＨＴ）などが挙げられる。これらの中でも重合禁止能力の観点から、２，６－ジ－ｔｅｒｔ－ブチル－４－クレゾール、ハイドロキノン又はメトキシフェノールが好ましい。 [1-6-9] Polymerization inhibitor 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.
Examples of 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.
　重合禁止剤は、１種又は２種以上を含有することが好ましい。通常、（Ｃ）バインダー樹脂を製造する際に、当該樹脂中に重合禁止剤が含まれることがあり、樹脂中に含まれる重合禁止剤の他に、それと同一、又は異なる重合禁止剤を感光性樹脂組成物製造時に添加してもよい。 The polymerization inhibitor preferably contains one or more kinds. Usually, when the (C) binder resin is produced, 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.
　着色感光性樹脂組成物中の重合禁止剤の含有割合は、着色感光性樹脂組成物の全固形分に対して、通常０．０００５質量％以上、好ましくは０．００１質量％以上、より好ましくは０．０１質量％以上であり、また通常０．１質量％以下、好ましくは０．０８質量％以下、より好ましくは０．０５質量％以下である。前記下限値以上とすることでテーパ角度を高くすることができる傾向があり、また、前記上限値以下とすることで高感度を保つことができる傾向がある。 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.
［１－６－１０］無機充填剤
　また、本発明の着色感光性樹脂組成物は、さらに、硬化物の強度の向上や、（Ｃ）バインダー樹脂との適度な相互作用（マトリックス構造の形成）による塗布膜の平坦性とテーパ角の向上等を目的として、無機充填剤を含有していてもよい。そのような無機充填剤としては、例えば、タルク、シリカ、アルミナ、硫酸バリウム、酸化マグネシウム、或いは、これらを各種シランカップリング剤により表面処理したものなどが挙げられる。 [1-6-10] Inorganic filler In addition, 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). For the purpose of improving the flatness of the coating film and the taper angle, etc., 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.
　これら無機充填剤の平均粒子径としては、通常０．００５～２０μｍ、好ましくは０．０１～１０μｍである。ここで本実施の形態にいう平均粒子径とは、ベックマン・コールター社製などのレーザ回折散乱粒度分布測定装置にて測定した値である。これらの無機充填剤のうち、特に、シリカゾル及びシリカゾル変性物は、分散安定性と共にテーパ角度の向上効果に優れる傾向があるため、好ましく配合される。本発明の着色感光性樹脂組成物がこれらの無機充填剤を含む場合、その含有割合としては、感度の観点から、全固形分に対して、通常５質量％以上、好ましくは１０質量％以上であり、通常８０質量％以下、好ましくは７０質量％以下である。 The average particle size of these inorganic fillers is usually 0.005 to 20 μm, preferably 0.01 to 10 μm. Here, the average particle 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. Among these inorganic fillers, 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. When the colored photosensitive resin composition of the present invention contains these inorganic fillers, 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.
［１－７］溶剤
　本発明の着色感光性樹脂組成物及び顔料分散液は、通常、溶剤を含む。溶剤を含むことで、顔料等の着色剤を溶剤中に分散でき、また、塗布が容易となる。
　本発明の着色感光性樹脂組成物は、通常、（Ａ）着色剤、（Ｂ）分散剤、（Ｃ）バインダー樹脂、（Ｄ）光重合性モノマー、（Ｅ）光重合開始剤及び必要に応じて使用されるその他の各種材料が、溶剤に溶解又は分散した状態で使用される。同様に、本発明の顔料分散液は、通常、（Ａ）着色剤、（Ｂ）分散剤、（Ｃ）バインダー樹脂及び必要に応じて使用されるその他の各種材料が、溶剤に溶解又は分散した状態で使用される。溶剤の中でも、分散性や塗布性の観点から有機溶剤が好ましい。 [1-7] Solvent 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. Similarly, in the pigment dispersion of the present invention, (A) 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. Among the solvents, organic solvents are preferable from the viewpoints of dispersibility and coatability.
　有機溶剤の中でも、塗布性の観点から沸点が１００～３００℃（圧力１０１３．２５ｈＰａ条件下。以下、沸点に関しては全て同様。）の範囲のものを選択するのが好ましく、沸点が１２０～２８０℃の範囲のものを選択するのがより好ましい。 Among 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.
　このような有機溶剤としては、例えば、次のようなものが挙げられる。
　エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ－ｎ－ブチルエーテル、プロピレングリコール－ｔ－ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ－ｎ－ブチルエーテル、メトキシメチルペンタノール、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、３－メトキシブタノール、３－メチル－３－メトキシブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリプロピレングリコールメチルエーテルのようなグリコールモノアルキルエーテル類；
　エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジメチルエーテルのようなグリコールジアルキルエーテル類； Examples of such 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 dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
　エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ－ｎ－ブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、メトキシブチルアセテート、３－メトキシブチルアセテート、メトキシペンチルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノ－ｎ－ブチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノエチルエーテルアセテート、３－メチル－３－メトキシブチルアセテートのようなグリコールアルキルエーテルアセテート類；
　エチレングリコールジアセテート、１，３－ブチレングリコールジアセテート、１，６－ヘキサノールジアセテートなどのグリコールジアセテート類；
　シクロヘキサノールアセテートなどのアルキルアセテート類；
　アミルエーテル、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジアミルエーテル、エチルイソブチルエーテル、ジヘキシルエーテルのようなエーテル類； Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
　アセトン、メチルエチルケトン、メチルアミルケトン、メチルイソプロピルケトン、メチルイソアミルケトン、ジイソプロピルケトン、ジイソブチルケトン、メチルイソブチルケトン、シクロヘキサノン、エチルアミルケトン、メチルブチルケトン、メチルヘキシルケトン、メチルノニルケトン、メトキシメチルペンタノンのようなケトン類；
　エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、メトキシメチルペンタノール、グリセリン、ベンジルアルコールのような１価又は多価アルコール類；
　ｎ－ペンタン、ｎ－オクタン、ジイソブチレン、ｎ－ヘキサン、ヘキセン、イソプレン、ジペンテン、ドデカンのような脂肪族炭化水素類；
　シクロヘキサン、メチルシクロヘキサン、メチルシクロヘキセン、ビシクロヘキシルのような脂環式炭化水素類； 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-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
　ベンゼン、トルエン、キシレン、クメンのような芳香族炭化水素類；
　アミルホルメート、エチルホルメート、酢酸エチル、酢酸ブチル、酢酸プロピル、酢酸アミル、メチルイソブチレート、エチレングリコールアセテート、エチルプロピオネート、プロピルプロピオネート、酪酸ブチル、酪酸イソブチル、イソ酪酸メチル、エチルカプリレート、ブチルステアレート、エチルベンゾエート、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、γ－ブチロラクトンのような鎖状又は環状エステル類；
　３－メトキシプロピオン酸、３－エトキシプロピオン酸のようなアルコキシカルボン酸類；
　ブチルクロリド、アミルクロリドのようなハロゲン化炭化水素類；
　メトキシメチルペンタノンのようなエーテルケトン類；
　アセトニトリル、ベンゾニトリルのようなニトリル類等。 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, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile.
　上記に該当する市販の有機溶剤としては、ミネラルスピリット、バルソル＃２、アプコ＃１８ソルベント、アプコシンナー、ソーカルソルベントＮｏ．１及びＮｏ．２、ソルベッソ＃１５０、シェルＴＳ２８　ソルベント、カルビトール、エチルカルビトール、ブチルカルビトール、メチルセロソルブ（「セロソルブ」は登録商標。以下同じ。）、エチルセロソルブ、エチルセロソルブアセテート、メチルセロソルブアセテート、ジグライム（いずれも商品名）などが挙げられる。
　これらの有機溶剤は、単独で用いてもよく、２種以上を併用してもよい。 Commercially available 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.
　フォトリソグラフィー法にて隔壁、着色スペーサーを形成する場合、有機溶剤としては沸点が１００～２００℃の範囲のものを選択するのが好ましい。より好ましくは１２０～１７０℃の沸点を持つものである。 When the partition walls and the colored spacers are formed by photolithography, it is preferable to select 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.
　上記有機溶剤のうち、塗布性、表面張力などのバランスが良く、組成物中の構成成分の溶解度が比較的高い点からは、グリコールアルキルエーテルアセテート類が好ましい。
　また、グリコールアルキルエーテルアセテート類は、単独で使用してもよいが、他の有機溶剤を併用してもよい。併用する有機溶剤として、特に好ましいのはグリコールモノアルキルエーテル類である。中でも、特に組成物中の構成成分の溶解性からプロピレングリコールモノメチルエーテルが好ましい。なお、グリコールモノアルキルエーテル類は極性が高く、添加量が多すぎると顔料が凝集しやすく、後に得られる着色感光性樹脂組成物の粘度が上がっていくなどの保存安定性が低下する傾向があるので、溶剤中のグリコールモノアルキルエーテル類の割合は５質量％～３０質量％が好ましく、５質量％～２０質量％がより好ましい。 Of the above organic solvents, 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.
In addition, glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. In addition, 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.
　また、１５０℃以上の沸点をもつ有機溶剤（以下「高沸点溶剤」と称す場合がある。）を併用することも好ましい。このような高沸点溶剤を併用することにより、着色感光性樹脂組成物は乾きにくくなるが、組成物中における顔料の均一な分散状態が、急激な乾燥により破壊されることを防止する効果がある。すなわち、例えばスリットノズル先端における、着色剤などの析出・固化による異物欠陥の発生を防止する効果がある。このような効果が高い点から、上述の各種溶剤の中でも、特にジエチレングリコールモノ－ｎ－ブチルエーテル、ジエチレングリコールモノ－ｎ－ブチルエーテルアセテート、及びジエチレングリコールモノエチルエーテルアセテートが好ましい。 It is also preferable to use an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”). By using such a high boiling point solvent in combination, 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. Of these various solvents, 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.
　有機溶剤中の高沸点溶剤の含有割合は、３質量％～５０質量％が好ましく、５質量％～４０質量％がより好ましく、５質量％～３０質量％が特に好ましい。前記下限値以上とすることで、例えばスリットノズル先端で着色材などが析出・固化して異物欠陥を惹き起こすのを抑制できる傾向があり、また前記上限値以下とすることで組成物の乾燥温度が遅くなるのを抑制し、減圧乾燥プロセスのタクト不良や、プリベークのピン跡といった問題を抑制できる傾向がある 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. By setting it to the lower limit value or more, for example, there is a tendency to suppress the occurrence of foreign matter defects due to precipitation and solidification of coloring materials at the tip of the slit nozzle, and by setting the lower limit value or less, 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
　なお、沸点１５０℃以上の高沸点溶剤が、グリコールアルキルエーテルアセテート類であってもよく、またグリコールアルキルエーテル類であってもよく、この場合は、沸点１５０℃以上の高沸点溶剤を別途含有させなくてもかまわない。
　好ましい高沸点溶剤として、例えば前述の各種溶剤の中ではジエチレングリコールモノ－ｎ－ブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジプロピレングリコールメチルエーテルアセテート、１，３－ブチレングリコールジアセテート、１，６－ヘキサノールジアセテート、トリアセチンなどが挙げられる。 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.
＜着色感光性樹脂組成物中の成分配合量＞
　本発明の着色感光性樹脂組成物において、（Ａ）着色剤の含有割合は、着色感光性樹脂組成物中の全固形分量に対して通常２０質量％以上、２５質量％以上であることが好ましく、３０質量％以上であることがより好ましくまた、６０質量％以下であることが好ましく、５０質量％以下であることがより好ましく、４５質量％以下であることがさらに好ましく、４０質量％以下であることがよりさらに好ましい。前記下限値以上とすることで十分な光学濃度（ＯＤ）が得られやすくなる傾向があり、また、前記上限値以下とすることで十分な画像形成性が確保しやすくなる傾向がある。上限と下限の組み合わせとしては、２０～６０質量％が好ましく、２５～５０質量％がより好ましく、３０～４５質量％がさらに好ましく、３０～４０質量％が特に好ましく挙げられる。 <Ingredient compounding amount in colored photosensitive resin composition>
In the colored photosensitive resin composition of the present invention, 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. When it is at least the lower limit, 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.
　また、本発明の着色感光性樹脂組成物及び顔料分散液において、（Ａ）着色剤に対する（Ａ１）有機黒色顔料の含有割合は、通常１０質量％以上、好ましくは３０質量％以上、より好ましくは５０質量％以上、さらに好ましくは７０質量％以上、よりさらに好ましくは８０質量％以上、特に好ましくは９０質量％以上であり、また、通常１００質量％以下である。（Ａ）着色剤中の（Ａ１）有機黒色顔料の含有割合を前記下限値以上とすることでより所望の黒い色調の塗膜が得られ、また、強度の高い塗膜が得られる傾向がある。上限と下限の組み合わせとしては、１０～１００質量％が好ましく、３０～１００質量％がより好ましく、５０～１００質量％がさらに好ましく、７０～１００質量％がよりさらに好ましく、８０～１００質量％が特に好ましく、９０～１００質量％が最も好ましく挙げられる。 In the colored photosensitive resin composition and pigment dispersion of the present invention, 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. (A) By setting the content ratio of (A1) organic black pigment in the colorant to be equal to or higher than the lower limit value, a coating film having a desired black color tone is obtained, and a coating film having high strength tends to be obtained. . 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.
　本発明の着色感光性樹脂組成物及び顔料分散液において、（Ａ）着色剤中に、（Ａ１）有機黒色顔料と共に（Ａ２）有機着色顔料を含有する場合もある。その場合、（Ａ）着色剤に対する（Ａ１）有機黒色顔料の含有割合は、通常１０質量％以上、好ましくは２０質量％以上、より好ましくは３０質量％以上、また通常９０質量％以下、好ましくは８０質量％以下である、より好ましくは６０質量％以下である。また、（Ａ２）有機着色顔料の含有割合は、通常１０質量％以上、好ましくは２０質量％以上、より好ましくは４０質量％以上であり、また通常９０質量％以下、好ましくは８０質量％以下、より好ましくは７０質量％以下である。前記下限値以上とすることでテーパ角度が低くなる傾向があり、また、前記上限値以下とすることでより黒い色調の塗膜が得られる傾向がある。
　また、（Ａ２）有機着色顔料１００質量部に対する（Ａ１）有機黒色顔料の含有割合は、通常１５質量部以上、好ましくは２０質量部以上、通常９００質量部以下、好ましくは８００質量部以下、より好ましくは５００質量部以下、さらに好ましくは２００質量部以下である。 In the colored photosensitive resin composition and the pigment dispersion of the present invention, the (A) colorant may contain (A2) an organic color pigment together with (A1) the organic black pigment. In that case, 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. In addition, 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.
　本発明の着色感光性樹脂組成物及び顔料分散液において、（Ａ）着色剤中に、（Ａ１）有機黒色顔料と共に（Ａ３）カーボンブラックを含有する場合もある。その場合、（Ａ）着色剤に対する（Ａ１）有機黒色顔料の含有割合は、通常５０質量％以上、好ましくは６０質量％以上、また、通常９５質量％以下、好ましくは９０質量％以下である。また、（Ａ３）カーボンブラックの含有割合は、通常５質量％以上、好ましくは１０質量％以上、また通常５０質量％以下、好ましくは４０質量％以下である。前記下限値以上とすることで十分な光学濃度（ＯＤ）が得られる傾向があり、また、前記上限値以下とすることで高い体積抵抗値や低い比誘電率が得られ、またキュア時のシワ等が発生しにくくなる傾向がある。また、（Ａ３）カーボンブラック１００質量部に対する（Ａ１）有機黒色顔料の含有割合は、通常１００質量部以上、好ましくは１５０質量部以上、通常２０００質量部以下、好ましくは１０００質量部以下である。 In the colored photosensitive resin composition and the pigment dispersion of the present invention, (A) the colorant may contain (A3) carbon black together with (A1) the organic black pigment. In that case, 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. There is a tendency that a sufficient optical density (OD) can be obtained by setting it to the lower limit value or more, and by setting the upper limit value or less, a high volume resistance value and a low relative dielectric constant can be obtained. Etc. tend to be less likely to occur. Further, 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.
　また、本発明の着色感光性樹脂組成物及び顔料分散液において、（Ａ）着色剤中に、（Ａ１）有機黒色顔料と共に（Ａ２）有機着色顔料及び（Ａ３）カーボンブラックを含有する場合もある。その場合、（Ａ）着色剤に対する（Ａ１）有機黒色顔料の含有割合は、通常１０質量％以上、好ましくは２０質量％以上、また通常８０質量％以下、好ましくは７０質量％以下である。また、（Ａ２）有機着色顔料の含有割合は、通常１０質量％以上、好ましくは２０質量％以上、また通常６０質量％以下、好ましくは５０質量％以下である。さらに（Ａ３）カーボンブラックの含有割合は、通常５質量％以上、好ましくは１０質量％以上、また通常５０質量％以下、好ましくは４０質量％以下である。この場合、（Ａ２）有機着色顔料１００質量部に対する（Ａ１）有機黒色顔料の含有割合は、通常１５質量部以上、好ましくは２０質量部以上、通常８００質量部以下、好ましくは７００質量部以下である。また、（Ａ３）カーボンブラック１００質量部に対する（Ａ１）有機黒色顔料の含有割合は、通常４０質量部以上、好ましくは５０質量部以上、通常１０００質量部以下、好ましくは９００質量部以下である。 In the colored photosensitive resin composition and the pigment dispersion of the present invention, (A) the colorant may contain (A2) an organic color pigment and (A3) carbon black together with (A1) the organic black pigment. . In that case, 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. Moreover, 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. Furthermore, 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. In this case, 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. Further, 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.
　（Ｂ）分散剤の含有割合は、着色感光性樹脂組成物の固形分中、通常１質量％以上であり、３質量％以上が好ましく、５質量％以上がより好ましく、また通常３０質量％以下、２０質量％以下が好ましく、１５質量％以下がより好ましく、１０質量％以下がさらに好ましい。前記下限値以上とすることで分散性が良好となる傾向があり、また、前記上限値以下とすることで余剰な分散剤を減らすことができ、現像性が良好となる傾向がある。上限と下限の組み合わせとしては、１～３０質量％が好ましく、３～２０質量％がより好ましく、５～１５質量％がさらに好ましく、５～１０質量％が特に好ましく挙げられる。 (B) 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. When 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.
　また、（Ａ）着色剤１００質量部に対する（Ｂ）分散剤の含有割合は、通常５質量部以上、１０質量部以上が好ましく、通常５０質量部以下、３０質量部以下が好ましい。前記下限値以上とすることで分散性が良好となる傾向があり、また、前記上限値以下とすることで余剰な分散剤を減らすことができ、現像性が良好となる傾向がある。上限と下限の組み合わせとしては、５～５０質量部が好ましく、１０～３０質量部がより好ましく挙げられる。 In addition, 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. When 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.
　本発明の第１の態様に係る着色感光性樹脂組成物において、アクリル系分散剤の含有割合は特に限定されないが、着色感光性樹脂組成物の固形分中、通常１質量％以上であり、３質量％以上が好ましく、５質量％以上がより好ましく、また通常３０質量％以下、２０質量％以下が好ましく、１５質量％以下がより好ましく、１０質量％以下がさらに好ましい。前記下限値以上とすることで分散性が良好となる傾向があり、また、前記上限値以下とすることで余剰な分散剤を減らすことができ、現像性が良好となる傾向がある。上限と下限の組み合わせとしては、１～３０質量％が好ましく、３～２０質量％がより好ましく、５～１５質量％がさらに好ましく、５～１０質量％が特に好ましく挙げられる。
　また、本発明の第１の態様に係る着色感光性樹脂組成物及び本発明の第３の態様に係る顔料分散液において、（Ａ）着色剤１００質量部に対するアクリル系分散剤の含有割合は、通常５質量部以上、１０質量部以上が好ましく、通常５０質量部以下、３０質量部以下が好ましい。前記下限値以上とすることで分散性が良好となる傾向があり、また、前記上限値以下とすることで余剰な分散剤を減らすことができ、現像性が良好となる傾向がある。上限と下限の組み合わせとしては、５～５０質量部が好ましく、１０～３０質量部がより好ましく挙げられる。 In the colored photosensitive resin composition according to the first aspect of the present invention, 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. When 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.
In the colored photosensitive resin composition according to the first aspect of the present invention and the pigment dispersion according to the third aspect of the present invention, (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. When 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.
　（Ｃ）バインダー樹脂の含有割合は特に限定されないが、本発明の着色感光性樹脂組成物の全固形分に対して、通常５質量％以上、好ましくは１０質量％以上、より好ましくは２０質量％以上、さらに好ましくは３０質量％以上、特に好ましくは４０質量％以上であり、通常８０質量％以下、好ましくは７０質量％以下、より好ましくは６０質量％以下、さらに好ましくは５０質量％以下である。前記下限値以上とすることで強固な膜が得られやすくなる傾向があり、また、前記上限値以下とすることで露光部への現像液の浸透を低く抑え、膜の表面平滑性や感度の悪化を抑制しやすくなる傾向がある。上限と下限の組み合わせとしては、５～８０質量％が好ましく、１０～７０質量％がより好ましく、２０～６０質量％がさらに好ましく、３０～５０質量％がよりさらに好ましく、４０～５０質量％が特に好ましく挙げられる。 (C) Although 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. . When 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. There is a tendency to suppress deterioration. 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.
　（Ｃ１）エポキシ（メタ）アクリレート樹脂の含有割合は、本発明の着色感光性樹脂組成物の全固形分に対して、通常５質量％以上、好ましくは１０質量％以上、より好ましくは２０質量％以上、さらに好ましくは３０質量％以上、よりさらに好ましくは３５質量％以上、特に好ましくは４０質量％以上であり、通常８０質量％以下、好ましくは７０質量％以下、より好ましくは６０質量％以下、さらに好ましくは５０質量％以下である。前記下限値以上とすることで強固な膜が得られやすくなる傾向があり、また、前記上限値以下とすることで膜の表面平滑性や感度の悪化を抑制しやすくなる傾向がある。上限と下限の組み合わせとしては、５～８０質量％が好ましく、１０～７０質量％がより好ましく、２０～６０質量％がさらに好ましく、３０～６０質量％がよりさらに好ましく、３５～６０質量％が特に好ましく、４０～５０質量％が最も好ましく挙げられる。 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. By setting the lower limit value or more, a strong film tends to be easily obtained, and by setting the upper limit value or less, it tends to suppress deterioration of the surface smoothness and sensitivity of the film. 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.
　本発明において（Ｃ）バインダー樹脂に占める前記一般式（ＩＩ）で表される繰り返し単位構造を有するエポキシ（メタ）アクリレート樹脂及び／又は前記一般式（ＩＩＩ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂の含有割合（両方を含む場合はその合計の含有割合）は特に限定されないが、７５質量％以上であることが好ましく、８０質量％以上であることがより好ましく、８５質量％以上であることがさらに好ましく、９０質量％以上であることがよりさらに好ましく、９５質量％以上であることが特に好ましい。また、通常１００質量％以下である。前記下限値以上とすることでアウトガス適性が良好となる傾向がある。上限と下限の組み合わせとしては、７５～１００質量％が好ましく、８０～１００質量％がより好ましく、８５～１００質量％がさらに好ましく、９０～１００質量％がよりさらに好ましく、９５～１００質量％が特に好ましく挙げられる。 In the present invention, (C) an epoxy (meth) acrylate resin having a repeating unit structure represented by the general formula (II) in the binder resin and / or an epoxy having a partial structure represented by the general formula (III) ( The content ratio of the meth) acrylate resin (the total content ratio when both are included) 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.
　（Ｄ）光重合性モノマーの含有割合は、着色感光性樹脂組成物の全固形分に対して、通常１質量％以上、好ましくは５質量％以上、より好ましくは８質量％以上であり、また、通常３０質量％以下、好ましくは２０質量％以下、より好ましくは１５質量％以下である。前記下限値以上とすることで高感度となる傾向があり、また、前記上限値以下とすることで現像性が良好となる傾向がある。上限と下限の組み合わせとしては、１～３０質量％が好ましく、５～２０質量％がより好ましく、８～１５質量％がさらに好ましく挙げられる。 (D) 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.
　（Ｅ）光重合開始剤の含有割合は、本発明の着色感光性樹脂組成物の全固形分に対して、通常０．１質量％以上、好ましくは０．５質量％以上、より好ましくは１質量％以上、さらに好ましくは２質量％以上、特に好ましくは３質量％以上であり、通常１５質量％以下、好ましくは１０質量％以下、より好ましくは８質量％以下、さらに好ましくは５質量％以下である。前記下限値以上とすることで良好な感度が得られる傾向があり、また、前記上限値以下とすることで現像に適性なバインダー樹脂、光重合性モノマーの量を確保できる傾向がある。上限と下限の組み合わせとしては、０．１～１５質量％が好ましく、０．５～１０質量％がより好ましく、１～８質量％がさらに好ましく、２～５質量％がよりさらに好ましく、３～５質量％が特に好ましく挙げられる。 (E) 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.
　（Ｅ）光重合開始剤と共に重合促進剤を用いる場合、重合促進剤の含有割合は、本発明の着色感光性樹脂組成物の全固形分に対して、好ましくは０．０５質量％以上であり、通常１０質量％以下、好ましくは５質量％以下である。また、重合促進剤は（Ｄ）光重合開始剤１００質量部に対して、通常０．１質量部以上、好ましくは０．２質量部以上であり、通常１００質量部以下、好ましくは５０重量部以下である。 (E) When using a polymerization accelerator together with a photopolymerization initiator, 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. Further, 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.
　重合促進剤の含有割合を前記下限値以上とすることで良好な感度が得られる傾向があり、また上限値以下とすることで未露光部分の現像液に対する溶解性が良好となる傾向がある。
　また、本発明の着色感光性樹脂組成物中に占める増感色素の配合割合は、感度の観点から、着色感光性樹脂組成物中の全固形分中、通常０．５質量％以上、好ましくは１質量％以下であり、通常２０質量％以下、好ましくは１５質量％以下、更に好ましくは１０質量％以下である。 There exists a tendency for a favorable sensitivity to be obtained by making the content rate of a polymerization accelerator more than the said lower limit, and there exists a tendency for the solubility with respect to the developing solution of an unexposed part to become favorable by making it into an upper limit or less.
In addition, 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.
　密着向上剤を用いる場合、その含有割合は、着色感光性樹脂組成物中の全固形分に対して通常０．１～５質量％、好ましくは０．２～３質量％、さらに好ましくは０．４～２質量％である。密着向上剤の含有割合を前記下限値以上とすることで、密着性を向上する傾向があり、また上限値以下とすることで、良好な感度が得られ、また現像後の残渣が発生しにくい傾向がある。 When the adhesion improver is used, 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. By setting the content ratio of the adhesion improver to the above lower limit value or more, there is a tendency to improve adhesion, and by setting the content ratio to the upper limit value or less, good sensitivity can be obtained, and residues after development are hardly generated. Tend.
　また、界面活性剤を用いる場合、その含有割合は、着色感光性樹脂組成物中の全固形分に対して通常０．００１～１０質量％、好ましくは０．００５～１質量％、さらに好ましくは０．０１～０．５質量％、最も好ましくは０．０３～０．３質量％である。界面活性剤の含有割合は前記下限値以上とすることで、塗布膜の平滑性、均一性が得られる傾向があり、また上限値以下とすることで、ムラ等の発生を抑えられる傾向がある。
　なお、本発明の着色感光性樹脂組成物は、前述の有機溶剤を使用して、その固形分濃度が通常５～５０質量％、好ましくは１０～３０質量％となるように調液される。 In the case of using a surfactant, 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. When 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.
　＜着色感光性樹脂組成物の物性＞
　本発明の着色感光性樹脂組成物は、隔壁、着色スペーサー以外にもブラックマトリクス形成用に好適に使用することができ、係る観点から黒色を呈していることが好ましく、その塗膜の膜厚１μｍ当たりの光学濃度（ＯＤ）が０．５以上であることが好ましく、０．８以上であることがより好ましく、１．０以上であることがさらに好ましく、１．３以上であることが特に好ましい。 <Physical properties of colored photosensitive resin composition>
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 μm. 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. .
　また、有機電界発光素子の隔壁等のように、画像表示装置の画像表示領域に占める面積割合が高い部材に適用する場合には、色調がより黒色に近いことが好ましい。係る観点から、硬化させた際の色度のｘが０．２０以上であることが好ましく、０．２５以上であることがより好ましく、０．３０以上であることがさらに好ましく、また、０．５０以下であることが好ましく、０．４５以下であることがより好ましく、０．４０以下であることがさらに好ましい。また、色度のｙが０．２０以上であることが好ましく、０．２５以上であることがより好ましく、０．３０以上であることがさらに好ましく、また、０．５０以下であることが好ましく、０．４５以下であることがより好ましく、０．４０以下であることがさらに好ましい。 Further, 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. From such a viewpoint, 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.
［２］顔料分散液の成分及び組成
　本発明の顔料分散液を構成する成分及びその組成について説明する。
　本発明の顔料分散液（以下、単に「顔料分散液」という場合がある）は、（Ａ）着色剤、（Ｂ）分散剤及び（Ｃ）バインダー樹脂を含有する。通常は、さらに溶剤も含有する。また、本発明の顔料分散液は、後述のとおり、着色感光性樹脂組成物を製造する際に用いる原料の１つとして好適に使用することができる。 [2] Components and Composition of Pigment Dispersion Liquid The components and composition of the pigment dispersion liquid of the present invention will be described.
The pigment dispersion of the present invention (hereinafter sometimes simply referred to as “pigment dispersion”) 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.
　顔料分散液に使用する（Ａ）着色剤、（Ｂ）分散剤、（Ｃ）バインダー樹脂及び溶剤としては、着色感光性樹脂組成物に使用するものとして挙げたものを好適に使用することができる。 As (A) the colorant, (B) the dispersant, (C) the binder resin and the solvent used in the pigment dispersion, those mentioned for use in the colored photosensitive resin composition can be suitably used. .
　本発明の顔料分散液において、（Ａ）着色剤は、前述の（Ａ１）有機黒色顔料を含む。（Ａ１）有機黒色顔料を含む顔料分散液を用いて製造した着色感光性樹脂組成物を塗布して得られた塗膜が、高抵抗、低誘電率かつ高遮光率を実現でき、より黒色に近い色調の硬化物となる傾向がある。
　また、（Ｂ）分散剤は、アクリル系分散剤を含む。アクリル系分散剤を含む顔料分散液を用いて着色感光性樹脂組成物を製造することで、現像時のパターン密着性が良好になる傾向がある。
　また、（Ｃ）バインダー樹脂は、（Ｃ１）エポキシ（メタ）アクリレート樹脂を含む。（Ｃ１）エポキシ（メタ）アクリレート樹脂を含む顔料分散液を用いて着色感光性樹脂組成物を製造することで、硬化物形成後に発生するアウトガス量が少なくなる傾向がある。 In the pigment dispersion of the present invention, (A) the colorant contains the aforementioned (A1) organic black pigment. (A1) 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.
Moreover, (B) 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.
Moreover, (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.
＜顔料分散液中の成分配合量＞
　本発明の顔料分散液において、（Ａ）着色剤の含有割合は、顔料分散液中の全固形分に対して通常１０質量％以上、好ましくは２０質量％以上、より好ましくは３０質量％以上、さらに好ましくは４０質量％以上、よりさらに好ましくは５０質量％以上、特に好ましくは５５質量％以上、また、通常１００質量％以下、好ましくは８０質量％以下、より好ましくは７０質量％以下、さらに好ましくは６０質量％以下である。前記下限値以上とすることで着色感光性樹脂組成物を適性な固形分濃度にて製造することができ、また、前記上限値以下とすることで分散性が良好となる傾向がある。上限と下限の組み合わせとしては、１０～８０質量％が好ましく、２０～８０質量％がより好ましく、３０～７０質量％がさらに好ましく、４０～７０質量％がよりさらに好ましく、５０～６０質量％が特に好ましく、５５～６０質量が最も好ましく挙げられる。 <Component content in pigment dispersion>
In the pigment dispersion of the present invention, 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. By setting it as the said lower limit or more, 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.
　本発明の顔料分散液において、（Ｂ）分散剤の含有割合は、顔料分散液中の全固形分に対して通常２質量％以上、好ましくは５質量％以上、より好ましくは１０質量％以上、また、通常５０質量％以下、好ましくは４０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２０質量％以下、特に好ましくは１５質量％以下である。前記下限値以上とすることで分散性が良好となる傾向があり、また、前記上限値以下とすることで余剰な分散剤を減らせ、得られる着色感光性樹脂組成物の現像性が良好となる傾向がある。上限と下限の組み合わせとしては、２～５０質量％が好ましく、５～４０質量％がより好ましく、５～３０質量％がさらに好ましく、５～２０質量％がよりさらに好ましく、１０～１５質量％が特に好ましく挙げられる。 In the pigment dispersion of the present invention, 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. Tend. 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.
　本発明の顔料分散液において、アクリル系分散剤の含有割合は、顔料分散液中の全固形分に対して通常２質量％以上、好ましくは５質量％以上、より好ましくは１０質量％以上、また、通常５０質量％以下、好ましくは４０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２０質量％以下、特に好ましくは１５質量％以下である。前記下限値以上とすることで分散性が良好となるとともに硬化物の現像時にパターン密着性が良好となる傾向があり、また、前記上限値以下とすることで得られる着色感光性樹脂組成物の現像性が良好となる傾向がある。上限と下限の組み合わせとしては、２～５０質量％が好ましく、５～４０質量％がより好ましく、５～３０質量％がさらに好ましく、５～２０質量％がよりさらに好ましく、１０～１５質量％が特に好ましく挙げられる。 In the pigment dispersion of the present invention, 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. There is a tendency that 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. There exists a tendency for developability to become favorable. 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.
　本発明の顔料分散液において、（Ｃ）バインダー樹脂の含有割合は、顔料分散液中の全固形分に対して通常５質量％以上、好ましくは１０質量％以上、より好ましくは１５質量％以上、さらに好ましくは２０質量％以上、特に好ましくは２５質量％以上、また、通常５０質量％以下、好ましくは４０質量％以下、より好ましくは３５質量％以下、さらに好ましくは３０質量％以下である。前記下限値以上とすることで分散性が良好となる傾向があり、また、前記上限値以下とすることで得られる着色感光性樹脂組成物中の着色剤量を適正化でき、十分な遮光性が確保できる傾向がある。上限と下限の組み合わせとしては、５～５０質量％が好ましく、１０～４０質量％がより好ましく、１５～３５質量％がさらに好ましく、２０～３５質量％がよりさらに好ましく、２５～３０質量％が特に好ましく挙げられる。 In the pigment dispersion of the present invention, 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.
　本発明の顔料分散液において、（Ｃ１）エポキシ（メタ）アクリレート樹脂の含有割合は、顔料分散液中の全固形分に対して通常５質量％以上、好ましくは１０質量％以上、より好ましくは１５質量％以上、さらに好ましくは２０質量％以上、特に好ましくは２５質量％以上、また、通常５０質量％以下、好ましくは４０質量％以下、より好ましくは３５質量％以下、さらに好ましくは３０質量％以下である。前記下限値以上とすることで硬化物のアウトガス適性が良好となる傾向があり、また、前記上限値以下とすることで得られる着色感光性樹脂組成物中の着色剤量を適正化でき、十分な遮光性が確保できる傾向がある。上限と下限の組み合わせとしては、５～５０質量％が好ましく、１０～４０質量％がより好ましく、１５～３５質量％がさらに好ましく、２０～３５質量％がよりさらに好ましく、２５～３０質量％が特に好ましく挙げられる。 In the pigment dispersion of the present invention, 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. There is a tendency to ensure a good light shielding property. 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.
　なお、本発明の顔料分散液は、前述の有機溶剤を使用して、その固形分濃度が通常５～５０質量％、好ましくは１０～３０質量％となるように調液される。 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.
［３］着色感光性樹脂組成物の製造方法
　本発明の着色感光性樹脂組成物（以下、「レジスト」と称することがある。）は、常法に従って製造される。
　通常、（Ａ）着色剤は、予めペイントコンディショナー、サンドグラインダー、ボールミル、ロールミル、ストーンミル、ジェットミル、ホモジナイザー等を用いて分散処理するのが好ましい。分散処理により（Ａ）着色剤が微粒子化されるため、レジストの塗布特性が向上する。 [3] Method for producing colored photosensitive resin composition 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.
　分散処理は、通常、（Ａ）着色剤、有機溶剤、及び（Ｂ）分散剤、並びに（Ｃ）バインダー樹脂の一部又は全部を併用した系にて行うことが好ましい（以下、分散処理に供する混合物、及び該処理にて得られた組成物を「インク」又は「顔料分散液」と称することがある）。特に（Ｂ）分散剤として高分子分散剤を用いると、得られたインク及びレジストの経時の増粘が抑制される（分散安定性に優れる）ので好ましい。
　このように、レジストを製造する工程において、（Ａ）着色剤、有機溶剤、及び（Ｂ）分散剤を少なくとも含有する顔料分散液を製造することが好ましい。 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”). In particular, it is preferable to use a polymer dispersant as the dispersant (B) because the resulting ink and resist are prevented from thickening with time (excellent in dispersion stability).
Thus, in the process of producing a resist, it is preferable to produce a pigment dispersion containing at least (A) a colorant, an organic solvent, and (B) a dispersant.
　なお、着色感光性樹脂組成物に配合する全成分を含有する液に対して分散処理を行った場合、分散処理時に生じる発熱のため、高反応性の成分が変性する可能性がある。従って、高分子分散剤を含む系にて分散処理を行うことが好ましい。
　サンドグラインダーで（Ａ）着色剤を分散させる場合には、０．１～８ｍｍ程度の径のガラスビーズ又はジルコニアビーズが好ましく用いられる。分散処理条件は、温度は通常０℃から１００℃であり、好ましくは室温から８０℃の範囲である。分散時間は液の組成及び分散処理装置のサイズ等により適正時間が異なるため適宜調節すればよい。レジストの２０度鏡面光沢度（ＪＩＳ　Ｚ８７４１）が５０～３００の範囲となるように、インクの光沢を制御するのが分散の目安である。レジストの光沢度を前記下限値以上とすることで、分散処理が十分でなく粗い顔料（着色剤）粒子の残存を抑制でき、現像性、密着性、解像性等を十分にしやすい傾向がある。また、光沢値を前記上限値以下とすることで、顔料が破砕して超微粒子が多数生じるのを回避でき、分散安定性を維持しやすい傾向がある。 In addition, when a dispersion treatment is performed on a liquid containing all the components blended in the colored photosensitive resin composition, 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.
When 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. In the dispersion treatment conditions, 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. 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. . Further, by setting 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.
　また、インク中に分散した顔料の分散粒径は通常０．０３～０．３μｍであり、動的光散乱法等により測定される。次に、上記分散処理により得られたインクと、レジスト中に含まれる、上記の他の成分を混合し、均一な溶液とする。レジストの製造工程においては、微細なゴミが液中に混じることが多いため、得られたレジストはフィルター等により濾過処理するのが望ましい。 Further, the dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, and is measured by a dynamic light scattering method or the like. Next, the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution. In the resist manufacturing process, fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered by a filter or the like.
［４］硬化物及びその形成方法
［４－１］硬化物
　本発明の着色感光性樹脂組成物を硬化させることで、硬化物を得ることができる。着色感光性樹脂組成物で構成される硬化物は、隔壁、着色スペーサーとして好適に用いることができる。 [4] Cured product and formation method thereof [4-1] 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.
［４－１－１］隔壁
　本発明の着色感光性樹脂組成物は隔壁、特に有機電界発光素子の有機層を区画するための隔壁を形成するために好適に用いることができる。有機電界発光素子に用いる有機層としては、例えば日本国特開２０１６－１６５３９６号公報に記載されているような、正孔注入層、正孔輸送層あるいは正孔注入層上の正孔輸送層に用いる有機層が挙げられる。 [4-1-1] Partition Wall 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. Examples of 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.
［４－１－２］着色スペーサー
　また、本発明の着色感光性樹脂組成物は、隔壁以外に着色スペーサー用のレジストとして好適に用いることができる。スペーサーをＴＦＴ型ＬＣＤに使用する場合、ＴＦＴに入射する光によりスイッチング素子としてＴＦＴが誤作動を起こすことがあり、着色スペーサーはこれを防止するために用いられる（例えば、日本国特開平８－２３４２１２号公報参照）。 [4-1-2] Colored spacer The colored photosensitive resin composition of the present invention can be suitably used as a resist for colored spacers other than the partition walls. When a spacer is used in a TFT type LCD, 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).
［４－２］形成方法
　次に本発明の着色感光性樹脂組成物を用いた隔壁、着色スペーサーについて、その製造方法に従って説明する。またブラックマトリクスやそれ以外の硬化物も同様の方法で形成することができる。 [4-2] Forming Method Next, the partition and the colored spacer using the colored photosensitive resin composition of the present invention will be described according to the production method thereof. A black matrix and other cured products can be formed by the same method.
［４－２－１］支持体
　隔壁、着色スペーサーを形成するための支持体としては、適度の強度があれば、その材質は特に限定されるものではない。おもに透明基板が使用されるが、材質としては、例えば、ポリエチレンテレフタレートなどのポリエステル系樹脂、ポリプロピレン、ポリエチレンなどのポリオレフィン系樹脂、ポリカーボネート、ポリメチルメタクリレート、ポリスルフォンなどの熱可塑性樹脂製シート、エポキシ樹脂、不飽和ポリエステル樹脂、ポリ（メタ）アクリル系樹脂などの熱硬化性樹脂シート、又は各種ガラスなどが挙げられる。この中でも、耐熱性の観点からガラス、耐熱性樹脂が好ましい。また、基板の表面にＩＴＯ、ＩＺＯ等の透明電極が成膜されている場合もある。透明基板以外では、ＴＦＴアレイ上に形成することも可能である。 [4-2-1] Support 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. In some cases, 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.
　支持体には、接着性などの表面物性の改良のため、必要に応じ、コロナ放電処理、オゾン処理、シランカップリング剤や、ウレタン系樹脂などの各種樹脂の薄膜形成処理などを行ってもよい。
　透明基板の厚さは、通常０．０５～１０ｍｍ、好ましくは０．１～７ｍｍの範囲とされる。また各種樹脂の薄膜形成処理を行う場合、その膜厚は、通常０．０１～１０μｍ、好ましくは０．０５～５μｍの範囲である。 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 μm, preferably 0.05 to 5 μm.
［４－２－２］着色感光性樹脂組成物の塗布
　着色感光性樹脂組成物の基板上への塗布は、スピナー法、ワイヤーバー法、フローコート法、ダイコート法、ロールコート法、又はスプレーコート法などによって行うことができる。中でも、ダイコート法によれば、塗布液使用量が大幅に削減され、かつ、スピンコート法によった際に付着するミストなどの影響が全くなく、異物発生が抑制されるなど、総合的な観点から好ましい。 [4-2-2] Application of colored photosensitive resin composition 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. In particular, 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.
　塗膜の厚さは、厚すぎると、パターン現像が困難となることがあり、薄すぎると顔料濃度を高めることが困難となり所望の色発現が不可能となることがある。塗膜の厚さは、乾燥後の膜厚として、通常０．２～１０μｍの範囲とするのが好ましく、より好ましいのは０．５～６μｍの範囲、更に好ましいのは１～４μｍの範囲である。 If the thickness of the coating film is too thick, pattern development may be difficult, and if it is too thin, it may be difficult to increase the pigment concentration and the desired color expression may be impossible. The thickness of the coating film is usually preferably in the range of 0.2 to 10 μm, more preferably in the range of 0.5 to 6 μm, and still more preferably in the range of 1 to 4 μm, as the film thickness after drying. is there.
［４－２－３］塗膜の乾燥
　基板に着色感光性樹脂組成物を塗布した後の塗膜の乾燥は、ホットプレート、ＩＲオーブン、又はコンベクションオーブンを使用した乾燥法により行うのが好ましい。乾燥の条件は、前記溶剤成分の種類、使用する乾燥機の性能などに応じて適宜選択することができる。乾燥時間は、溶剤成分の種類、使用する乾燥機の性能などに応じて、通常は、４０～２００℃の温度で１５秒～５分間の範囲で選ばれ、好ましくは５０～１３０℃の温度で３０秒～３分間の範囲で選ばれる。
　乾燥温度は、高いほど透明基板に対する塗膜の接着性が向上するが、高すぎると（Ｃ）バインダー樹脂が分解し、熱重合を誘発して現像不良を生ずる場合がある。なお、この塗膜の乾燥工程は、温度を高めず、減圧チャンバー内で乾燥を行う、減圧乾燥法であってもよい。 [4-2-3] Drying of Coating Film 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. However, if the drying temperature is too high, the (C) binder resin may be decomposed to induce thermal polymerization, resulting in poor development. In addition, 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.
［４－２－４］露光
　画像露光は、着色感光性樹脂組成物の塗膜上に、ネガのマスクパターンを重ね、このマスクパターンを介し、紫外線又は可視光線の光源を照射して行う。この際、必要に応じ、酸素による光重合性層の感度の低下を防ぐため、光重合性の塗膜上にポリビニルアルコール層などの酸素遮断層を形成した後に露光を行ってもよい。上記の画像露光に使用される光源は、特に限定されるものではない。光源としては、例えば、キセノンランプ、ハロゲンランプ、タングステンランプ、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、中圧水銀灯、低圧水銀灯、カーボンアーク、蛍光ランプなどのランプ光源や、アルゴンイオンレーザー、ＹＡＧレーザー、エキシマレーザー、窒素レーザー、ヘリウムカドミニウムレーザー、半導体レーザーなどのレーザー光源などが挙げられる。特定の波長の光を照射して使用する場合には、光学フィルタを利用することもできる。 [4-2-4] 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. As the light source, 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 when used by irradiating light of a specific wavelength.
［４－２－５］現像
　本発明に係る隔壁、着色スペーサーは、着色感光性樹脂組成物による塗膜を、上記の光源によって画像露光を行った後、有機溶剤、又は、界面活性剤とアルカリ性化合物とを含む水溶液を用いる現像によって、基板上に画像を形成して作製することができる。この水溶液には、更に有機溶剤、緩衝剤、錯化剤、染料又は顔料を含ませることができる。 [4-2-5] Development 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.
　アルカリ性化合物としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、ケイ酸ナトリウム、ケイ酸カリウム、メタケイ酸ナトリウム、リン酸ナトリウム、リン酸カリウム、リン酸水素ナトリウム、リン酸水素カリウム、リン酸二水素ナトリウム、リン酸二水素カリウム、水酸化アンモニウムなどの無機アルカリ性化合物や、モノ－・ジ－又はトリエタノールアミン、モノ－・ジ－又はトリメチルアミン、モノ－・ジ－又はトリエチルアミン、モノ－又はジイソプロピルアミン、ｎ－ブチルアミン、モノ－・ジ－又はトリイソプロパノールアミン、エチレンイミン、エチレンジイミン、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、コリンなどの有機アルカリ性化合物が挙げられる。これらのアルカリ性化合物は、２種以上の混合物であってもよい。 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.
　界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレンアルキルエステル類、ソルビタンアルキルエステル類、モノグリセリドアルキルエステル類などのノニオン系界面活性剤、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキル硫酸塩類、アルキルスルホン酸塩類、スルホコハク酸エステル塩類などのアニオン性界面活性剤、アルキルベタイン類、アミノ酸類などの両性界面活性剤が挙げられる。 Examples of the surfactant 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. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.
　有機溶剤としては、例えば、イソプロピルアルコール、ベンジルアルコール、エチルセロソルブ、ブチルセロソルブ、フェニルセロソルブ、プロピレングリコール、ジアセトンアルコールなどが挙げられる。有機溶剤は、単独で用いてもよく、また、水溶液と併用してもよい。 Examples of the organic solvent 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.
　現像処理の条件は特に制限はなく、通常、現像温度は１０～５０℃の範囲、中でも１５～４５℃、特に好ましくは２０～４０℃で、現像方法は、浸漬現像法、スプレー現像法、ブラシ現像法、超音波現像法などのいずれかの方法によることができる。 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.
［４－２－６］熱硬化処理
　現像の後の基板には、熱硬化処理又は光硬化処理、好ましくは熱硬化処理を施す。この際の熱硬化処理条件は、温度は１００～２８０℃の範囲、好ましくは１５０～２５０℃の範囲で選ばれ、時間は５～６０分間の範囲で選ばれる。 [4-2-6] 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.
［５］有機電界発光素子、画像表示装置及び照明
［５－１］有機電界発光素子
　本発明の有機電界発光素子は、前述の着色感光性樹脂組成物で構成される硬化物、例えば隔壁を備える。
　例えば、以上説明した方法により製造された隔壁パターンを備える基板を用いて、種々の有機電界発光素子が製造される。有機電界発光素子を形成する方法は特に限定されないが、好ましくは、上記方法により基板上に隔壁のパターンを形成した後に、機能材料を真空状態で昇華させ、基板上の隔壁により囲まれた領域内に付着させて成膜する蒸着法や、キャスト法、スピンコート法、インクジェット印刷法といったウェットプロセスにて画素等の有機層を形成することによって、有機電界発光素子が製造される。 [5] Organic electroluminescent device, image display device and illumination [5-1] Organic electroluminescent device The organic electroluminescent device of the present invention includes a cured product composed of the above-mentioned colored photosensitive resin composition, for example, a partition. .
For example, 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.
　有機電界発光素子を画像表示装置の画素として使用する場合には、ある画素の発光層の光が他の画素に漏れることを防止する必要があり、さらに、電極等が金属である場合には外光の反射に伴う画像品質の低下を防止する必要があるため、有機電界発光素子を構成する隔壁に遮光性を付与することが好ましい。
　また、有機電界発光素子においては、隔壁の上面及び下面に電極を付与することが必要であるため、絶縁性の観点から、隔壁は高抵抗、低誘電率であることが好ましい。そのため、隔壁に遮光性を付与するために着色剤を使用する場合には、高抵抗かつ低誘電率である前記（Ａ１）有機黒色顔料を用いることが好ましい。 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.
［５－２］画像表示装置
　本発明の画像表示装置としては、画像や映像を表示する装置であれば特に限定は受けないが、液晶表示装置や有機ＥＬ表示装置等が挙げられる。例えば、前述の着色スペーサーを含む液晶表示装置や、前述の有機電界発光素子を含む有機ＥＬ表示装置等が挙げられる。 [5-2] Image Display Device 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. For example, the 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.
［５－２－１］液晶表示装置
　液晶表示装置は、前述の着色スペーサーを含むものであれば型式や構造については特に制限はない。例えば、ＴＦＴ素子基板上に、本発明のブラックマトリクスを設け、赤色、緑色、青色の画素を形成し、必要に応じてオーバーコート層を形成した後に、更にその上に、画像上にＩＴＯ、ＩＺＯ等の透明電極を形成して、カラーディスプレー、液晶表示装置などの部品の一部として使用される。また一部、平面配向型駆動方式（ＩＰＳモード）などの用途においては、透明電極を形成しないこともある。 [5-2-1] Liquid crystal display device The liquid crystal display device is not particularly limited in type and structure as long as it includes the above-described colored spacer. For example, 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. Are used as part of components such as a color display and a liquid crystal display device. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.
　通常、カラーフィルター上に配向膜を形成し、この配向膜上にフォトスペーサーを形成した後、対向基板と貼り合わせて液晶セルを形成し、形成した液晶セルに液晶を注入し、対向電極に結線して完成する。配向膜としては、ポリイミド等の樹脂膜が好適である。配向膜の形成には、通常、グラビア印刷法及び／又はフレキソ印刷法が採用され、配向膜の厚さは数１０ｎｍとされる。熱焼成によって配向膜の硬化処理を行った後、紫外線の照射やラビング布による処理によって表面処理し、液晶の傾きを調整しうる表面状態に加工される。 Usually, 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. As the alignment film, a resin film such as polyimide is suitable. For the formation of the alignment film, 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. After 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.
［５－２－２］有機ＥＬ表示装置
　有機ＥＬ表示装置は、前述の有機電界発光素子を含むものであれば画像表示装置の型式や構造については特に制限はなく、例えばアクティブ駆動型有機電界発光素子を用いて常法に従って組み立てることができる。例えば、「有機ＥＬディスプレイ」（オーム社、平成１６年８月２０日発行、時任静士、安達千波矢、村田英幸著）に記載されているような方法で、本発明の画像表示装置を形成することができる。例えば、白色光を発光する有機電界発光素子とカラーフィルターとを組み合わせて画像表示させてもよいし、ＲＧＢ等の発光色の異なる有機電界発光素子を組み合わせて画像表示させてもよい。 [5-2-2] 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. For example, 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. For example, 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.
［５－３］照明
　本発明の照明は、前述の有機電界発光素子を含むものである。型式や構造については特に制限はなく、本発明の有機電界発光素子を用いて常法に従って組み立てることができる。有機電界発光素子としては、単純マトリックス駆動方式としてもよいし、アクティブマトリックス駆動方式としてもよい。
　本発明の照明が白色光を発光するものとするために、白色光を発光する有機電界発光素子を用いてもよい。また、発光色の異なる有機電界発光素子を組み合わせて、各色が混色して白色となるよう構成してもよいし、混色比率を調整できるように構成して調色機能を付与してもよい。 [5-3] Illumination The illumination of the present invention includes the organic electroluminescent element described above. There is no restriction | limiting in particular about a model or a structure, It can assemble in accordance with a conventional method using the organic electroluminescent element of this invention. The organic electroluminescence element may be a simple matrix driving method or an active matrix driving method.
In order for the illumination of the present invention to emit white light, an organic electroluminescent element that emits white light may be used. In addition, 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.
　次に、実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。
　以下の実施例及び比較例で用いた着色感光性樹脂組成物の構成成分は次の通りである。 EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
The components of the colored photosensitive resin composition used in the following examples and comparative examples are as follows.
＜バインダー樹脂－Ｉ＞
　日本化薬社製「ＺＣＲ－１６４２Ｈ」（重量平均分子量（Ｍｗ）６５００、酸価９８ｍｇＫＯＨ／ｇ、カルボキシル基含有エポキシ（メタ）アクリレート樹脂）。この樹脂は（Ｃ１－１）に該当し、化学式（ＩＩ－１）で表される繰り返し単位構造を有し、そのＲ１１はメチル基であり、Ｒ１２は前記式（ＩＩ－Ａ）で表される基であり、ＲＸはテトラヒドロフタル酸残基である。 <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.
＜バインダー樹脂－ＩＩ＞ <Binder resin-II>
Figure JPOXMLDOC01-appb-C000066
  
Figure JPOXMLDOC01-appb-C000066
  
　上記構造のエポキシ化合物（エポキシ当量２６４）５０質量部、アクリル酸１３．６５質量部、３－メトキシブチルアセテート６０．５質量部、トリフェニルホスフィン０．９３６質量部、及びパラメトキシフェノール０．０３２質量部を、温度計、攪拌機、冷却管を取り付けたフラスコに入れ、攪拌しながら９０℃で酸価が５ｍｇＫＯＨ／ｇ以下になるまで反応させた。反応には１２時間を要し、エポキシアクリレート溶液を得た。
　上記エポキシアクリレート溶液２５質量部及び、トリメチロールプロパン（ＴＭＰ）０．７４質量部、ビフェニルテトラカルボン酸２無水物（ＢＰＤＡ）３．９５質量部、テトラヒドロフタル酸無水物（ＴＨＰＡ）２．７質量部を、温度計、攪拌機、冷却管を取り付けたフラスコに入れ、攪拌しながら１０５℃までゆっくり昇温し反応させた。
　樹脂溶液が透明になったところで、３－メトキシブチルアセテートで希釈し、固形分５０質量％となるよう調製し、酸価１１２ｍｇＫＯＨ／ｇ、重量平均分子量（Ｍｗ）４１００のカルボキシル基含有エポキシ（メタ）アクリレート樹脂を得た。この樹脂は（Ｃ１－２）に該当する。 50 parts by mass of the epoxy compound having the above structure (epoxy equivalent 264), 13.65 parts by mass of acrylic acid, 60.5 parts by mass of 3-methoxybutyl acetate, 0.936 parts by mass of triphenylphosphine, and 0.032 parts by mass of paramethoxyphenol Was placed in a flask equipped with a thermometer, a stirrer, and a condenser and allowed to react at 90 ° C. with stirring until the acid value was 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by mass of the above epoxy acrylate solution, 0.74 parts by mass of trimethylolpropane (TMP), 3.95 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), 2.7 parts by mass of tetrahydrophthalic anhydride (THPA) Was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution becomes transparent, it is diluted with 3-methoxybutyl acetate and prepared to have a solid content of 50% by mass. The carboxyl group-containing epoxy (meth) having an acid value of 112 mgKOH / g and a weight average molecular weight (Mw) of 4100 An acrylate resin was obtained. This resin corresponds to (C1-2).
＜バインダー樹脂－ＩＩＩ＞ <Binder resin-III>
Figure JPOXMLDOC01-appb-C000067
  
Figure JPOXMLDOC01-appb-C000067
  
　上記構造式で表されるエポキシ化合物（ＤＩＣ社製ＥＰＩＣＬＯＮ　ＨＰ７２００ＨＨ、ジシクロペンタジエン・フェノール重合物のポリグリシジルエーテル、重量平均分子量１０００、エポキシ当量２７０）１５５質量部、アクリル酸４１質量部、ｐ－メトキシフェノール０．１質量部、トリフェニルホスフィン２．５質量部、プロピレングリコールモノメチルエーテルアセテート１３０質量部を反応容器に仕込み、１００℃で酸価が３．０ｍｇＫＯＨ／ｇ以下になるまで加熱撹拌をした。酸価が目標に達するまで９時間を要した（酸価２．９ｍｇＫＯＨ／ｇ）。次いで更にテトラヒドロ無水フタル酸７４質量部を添加し、１２０℃で４時間反応させ、酸価９８ｍｇＫＯＨ／ｇ、重量平均分子量（Ｍｗ）３５００のバインダー樹脂－ＩＩＩ溶液を得た。この樹脂は（Ｃ１－１）に該当する。 155 parts by mass of epoxy compound represented by the above structural formula (EPICLON HP7200HH manufactured by DIC, polyglycidyl ether of dicyclopentadiene / phenol polymer, weight average molecular weight 1000, epoxy equivalent 270), 41 parts by mass of acrylic acid, p-methoxy A reaction vessel was charged with 0.1 parts by mass of phenol, 2.5 parts by mass of triphenylphosphine, and 130 parts by mass of propylene glycol monomethyl ether acetate, and the mixture was heated and stirred at 100 ° C. until the acid value became 3.0 mgKOH / g or less. It took 9 hours for the acid value to reach the target (acid value 2.9 mgKOH / g). Subsequently, 74 parts by mass of tetrahydrophthalic anhydride was further added and reacted at 120 ° C. for 4 hours to obtain a binder resin-III solution having an acid value of 98 mg KOH / g and a weight average molecular weight (Mw) of 3500. This resin corresponds to (C1-1).
＜バインダー樹脂－ＩＶ＞ <Binder resin-IV>
Figure JPOXMLDOC01-appb-C000068
  
Figure JPOXMLDOC01-appb-C000068
  
　上記構造式で表されるエポキシ化合物（エポキシ当量２４５）９８．０質量部、アクリル酸２８．８質量部、３－メトキシブチルアセテート１１３．０質量部、トリフェニルホスフィン１．１質量部、及びパラメトキシフェノール０．０２質量部を、温度計、攪拌機、冷却管を取り付けたフラスコに入れ、攪拌しながら９０℃で酸価が５ｍｇＫＯＨ／ｇ以下になるまで反応させた。反応には１５時間を要し、エポキシアクリレート溶液を得た。 98.0 parts by mass of an epoxy compound represented by the above structural formula (epoxy equivalent 245), 28.8 parts by mass of acrylic acid, 113.0 parts by mass of 3-methoxybutyl acetate, 1.1 parts by mass of triphenylphosphine, and para 0.02 part by mass of methoxyphenol was placed in a flask equipped with a thermometer, a stirrer, and a condenser, and reacted at 90 ° C. with stirring until the acid value reached 5 mgKOH / g or less. The reaction took 15 hours to obtain an epoxy acrylate solution.
　上記エポキシアクリレート溶液１８９．１質量部に、ビフェニルテトラカルボン酸２無水物（ＢＰＤＡ）１１．８質量部、及びテトラヒドロフタル酸無水物（ＴＨＰＡ）３０．４質量部を入れ、攪拌しながら１０５℃までゆっくり昇温し反応させた。
　樹脂溶液が透明になったところで３－メトキシブチルアセテートで希釈し、固形分５５質量％となるよう調製し、酸価１１０ｍｇＫＯＨ／ｇ、重量平均分子量（Ｍｗ）２８００のバインダー樹脂－ＩＶを得た。この樹脂は（Ｃ１－２）に該当する。 Into 189.1 parts by mass of the above-mentioned epoxy acrylate solution, 11.8 parts by mass of biphenyltetracarboxylic dianhydride (BPDA) and 30.4 parts by mass of tetrahydrophthalic anhydride (THPA) are added and stirred to 105 ° C. The temperature was raised slowly to react.
When the resin solution became transparent, it was diluted with 3-methoxybutyl acetate and prepared to have a solid content of 55% by mass to obtain 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).
＜バインダー樹脂－Ｖ＞
　プロピレングリコールモノメチルエーテルアセテート１４５質量部を窒素置換しながら攪拌し、１２０℃に昇温した。ここにスチレン１０質量部、グリシジルメタクリレート８５．２質量部及びトリシクロデカン骨格を有するモノメタクリレート（日立化成社製ＦＡ－５１３Ｍ）６６質量部を滴下し、及び２，２’－アゾビス－２－メチルブチロニトリル８．４７質量部を３時間かけて滴下し、更に９０℃で２時間攪拌し続けた。次に反応容器内を空気置換に変え、アクリル酸４３．２質量部にトリスジメチルアミノメチルフェノール０．７質量部及びハイドロキノン０．１２質量部を投入し、１００℃で１２時間反応を続けた。その後、テトラヒドロ無水フタル酸（ＴＨＰＡ）５６．２質量部、トリエチルアミン０．７質量部を加え、１００℃３．５時間反応させた。こうして得られたバインダー樹脂－Ｖの重量平均分子量（Ｍｗ）は約８４００、酸価は８０ｍｇＫＯＨ／ｇ、二重結合当量は４８０ｇ／ｍｏｌであった。 <Binder resin-V>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate and 66 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2,2′-azobis-2-methyl was added. 8.47 parts by mass of butyronitrile was added dropwise over 3 hours, and stirring was further continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 100 ° C. for 3.5 hours. 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.
＜着色剤－Ｉ＞
　ＢＡＳＦ社製、Ｉｒｇａｐｈｏｒ（登録商標）　Ｂｌａｃｋ　Ｓ　０１００　ＣＦ（下記式（Ｉ－１）で表される化学構造を有する） <Colorant-I>
Irgaphor (registered trademark) Black S 0100 CF (having a chemical structure represented by the following formula (I-1)) manufactured by BASF
Figure JPOXMLDOC01-appb-C000069
  
Figure JPOXMLDOC01-appb-C000069
  
＜分散剤－Ｉ＞
　ビックケミー社製　ＢＹＫ－ＬＰＮ２１１１６（側鎖に４級アンモニウム塩基及び３級アミノ基を有するＡブロックと、４級アンモニウム塩基及び３級アミノ基を有さないＢブロックからなる、アクリル系Ａ－Ｂブロック共重合体。アミン価は７０ｍｇＫＯＨ／ｇ。酸価は１ｍｇＫＯＨ／ｇ以下。）
　分散剤－ＩのＡブロック中には、下記式（１ａ）及び（２ａ）の繰り返し単位が含まれ、Ｂブロック中には下記式（３ａ）の繰り返し単位が含まれる。分散剤－Ｉの全繰り返し単位に占める下記式（１ａ）、（２ａ）、及び（３ａ）の繰り返し単位の含有割合はそれぞれ１１．１モル％、２２．２モル％、６．７モル％である。 <Dispersant-I>
BYK-LPN21116 manufactured by BYK Chemie Co., Ltd. (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.
Figure JPOXMLDOC01-appb-C000070
  
Figure JPOXMLDOC01-appb-C000070
  
＜分散剤－ＩＩ＞
　ビックケミー社製　ＤＩＳＰＥＲＢＹＫ－１６７（ウレタン系高分子分散剤）
＜溶剤－Ｉ＞
　ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
＜溶剤－ＩＩ＞
　ＭＢ：３－メトキシ－１－ブタノール
＜溶剤－ＩＩＩ＞
　ＭＢＡ：３－メトキシブチルアセテート <Dispersant-II>
DISPERBYK-167 (urethane polymer dispersant) manufactured by Big Chemie
<Solvent-I>
PGMEA: Propylene glycol monomethyl ether acetate <Solvent-II>
MB: 3-methoxy-1-butanol <solvent-III>
MBA: 3-methoxybutyl acetate
＜光重合開始剤－Ｉ＞
　＜ジケトン体＞
　エチルカルバゾール（５ｇ、２５．６１ｍｍｏｌ）とｏ－ナフトイルクロリド（５．１３ｇ、２６．８９ｍｍｏｌ）を３０ｍＬのジクロロメタンに溶解し、氷水バスにて２℃に冷却して攪拌し、ＡｌＣｌ3（３．４１ｇ、２５．６１ｍｍｏｌ）を添加した。さらに室温にて３時間攪拌後、反応液にクロトノイルクロリド（２．８１ｇ、２６．８９ｍｍｏｌ）の１５ｍＬジクロロメタン溶液を加え、ＡｌＣｌ3（４．１ｇ、３０．７３ｍｍｏｌ）を添加し、さらに１時間３０分攪拌した。反応液を氷水２００ｍＬにあけ、ジクロロメタン２００ｍＬを添加し有機層を分液した。回収した有機層を無水硫酸マグネシウムで乾燥した後、減圧下濃縮し、白色固体のジケトン体（１０ｇ）を得た。 <Photopolymerization initiator-I>
<Diketone body>
Ethylcarbazole (5 g, 25.61 mmol) and o-naphthoyl chloride (5.13 g, 26.89 mmol) are dissolved in 30 mL of dichloromethane, cooled to 2 ° C. with an ice-water bath and stirred, and then AlCl 3 (3. 41 g, 25.61 mmol) was added. After further stirring at room temperature for 3 hours, a 15 mL dichloromethane solution of crotonoyl chloride (2.81 g, 26.89 mmol) was added to the reaction solution, then AlCl 3 (4.1 g, 30.73 mmol) was added, and another 1 hour 30 hours. Stir for minutes. The reaction solution was poured into 200 mL of ice water, 200 mL of dichloromethane was added, and the organic layer was separated. The collected organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a white solid diketone body (10 g).
　＜オキシム体＞
　ジケトン体（３．００ｇ、７．１９ｍｍｏｌ）、ＮＨ2ＯＨ・ＨＣｌ（１．０９ｇ、１５．８１ｍｍｏｌ）、及び酢酸ナトリウム（１．２３ｇ、１５．０８ｍｍｏｌ）をイソプロパノール３０ｍＬに混合し、３時間還流した。
　反応終了後、反応液を濃縮し、得られた残渣に酢酸エチル３０ｍＬを加え、飽和炭酸水素ナトリウム水溶液３０ｍＬ、飽和食塩水３０ｍＬで洗浄し、無水硫酸マグネシウムで乾燥した。ろ過した後、有機層を減圧下濃縮し、固体３．０１ｇを得た。これをカラムクロマトグラフィーで精製し、淡黄色固体のオキシム体２．２２ｇを得た。 <Oxime body>
Diketone (3.00 g, 7.19 mmol), NH 2 OH · HCl (1.09 g, 15.81 mmol), and sodium acetate (1.23 g, 15.08 mmol) were mixed with 30 mL of isopropanol and refluxed for 3 hours. .
After completion of the reaction, the reaction mixture was concentrated, 30 mL of ethyl acetate was added to the resulting residue, washed with 30 mL of saturated aqueous sodium hydrogen carbonate solution and 30 mL of saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure to obtain 3.01 g of a solid. This was purified by column chromatography to obtain 2.22 g of an oxime compound as a pale yellow solid.
　＜オキシムエステル体＞
　オキシム体（２．２２ｇ、４．７７ｍｍｏｌ）とアセチルクロリド（１．３４ｇ、１７．０ｍｍｏｌ）をジクロロメタン２０ｍＬに加えて氷冷し、トリエチルアミン（１．７７ｇ、１７．５ｍｍｏｌ）を滴下して、そのまま１時間反応した。薄層クロマトグラフィーにより原料の消失を確認した後、水を加えて反応を停止した。反応液を飽和炭酸水素ナトリウム水溶液５ｍＬで２回洗浄し、飽和食塩水５ｍＬで２回洗浄し、無水硫酸ナトリウムで乾燥した。ろ過した後、有機層を減圧下で濃縮し、得られた残渣をカラムクロマトグラフィー（酢酸エチル／ヘキサン＝体積比２／１）で精製して、０．７９ｇの淡黄色固体の光重合開始剤－Ｉ（以下の化学構造の化合物）を得た。光重合開始剤－Ｉのケミカルシフトを以下に示す。 <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. After filtration, the organic layer was concentrated under reduced pressure, and the resulting residue was purified by column chromatography (ethyl acetate / hexane = volume ratio 2/1) to give 0.79 g of a light yellow solid photopolymerization initiator. -I (compound with the following chemical structure) was obtained. The chemical shift of Photopolymerization Initiator-I is shown below.
1Ｈ　ＮＭＲ（ＣＤＣｌ３）：δ１．１７（ｄ，３Ｈ），１．４８（ｔ，３Ｈ），１．８１（ｓ，３Ｈ），２．１６（ｓ，３Ｈ），２．３０（ｓ，３Ｈ），３．１７－３．３２（ｍ，２Ｈ），４．４２（ｑ，２Ｈ），４．７８－４．９４（ｂｒ，１Ｈ），７．４５－７．５９（ｍ，５Ｈ），７．６５（ｄｄ，１Ｈ），７．９５（ｍ，２Ｈ），８．０４（ｍ，２Ｈ），８．１４（ｄｄ，１Ｈ），８．４２（ｄ，１Ｈ），８．６４（ｄ，１Ｈ） 1 H NMR (CDCl 3 ): δ 1.17 (d, 3H), 1.48 (t, 3H), 1.81 (s, 3H), 2.16 (s, 3H), 2.30 (s, 3H), 3.17-3.32 (m, 2H), 4.42 (q, 2H), 4.78-4.94 (br, 1H), 7.45-7.59 (m, 5H) , 7.65 (dd, 1H), 7.95 (m, 2H), 8.04 (m, 2H), 8.14 (dd, 1H), 8.42 (d, 1H), 8.64 ( d, 1H)
Figure JPOXMLDOC01-appb-C000071
  
Figure JPOXMLDOC01-appb-C000071
  
＜光重合性モノマー＞
　ＤＰＨＡ：日本化薬社製　ジペンタエリスリトールヘキサアクリレート
＜界面活性剤＞
　ＤＩＣ社製　メガファック　Ｆ－５５９
＜添加剤＞
　日本化薬社製　ＫＡＹＡＭＥＲ　ＰＭ－２１（メタクリロイル基含有ホスフェート） <Photopolymerizable monomer>
DPHA: Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate <surfactant>
DIC Mega Fuck F-559
<Additives>
KAYAMER PM-21 (phosphate containing methacryloyl group) manufactured by Nippon Kayaku Co., Ltd.
＜顔料分散液１～６の調製＞
　着色剤（顔料）、分散剤、バインダー樹脂を、その固形分中の比率が表１記載の配合割合となるように加え、さらに溶剤が表１記載の質量比となるように混合した。この溶液をペイントシェーカーにより２５～４５℃の範囲で３時間分散処理を行った。ビーズとしては、０．５ｍｍφのジルコニアビーズを用い、分散液の２．５倍の質量を加えた。分散終了後、フィルターによりビーズと分散液を分離して、顔料分散液１～６を調製した。 <Preparation of pigment dispersions 1 to 6>
A colorant (pigment), a dispersant, and a binder resin were added so that the ratio in the solid content was a mixing ratio shown in Table 1, and the solvent was further mixed so as to have a mass ratio shown in Table 1. This solution was subjected to a dispersion treatment in the range of 25 to 45 ° C. for 3 hours using a paint shaker. As the beads, 0.5 mmφ 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.
Figure JPOXMLDOC01-appb-T000072
  
Figure JPOXMLDOC01-appb-T000072
  
［実施例１～６、参考例１、及び比較例１］
　上記調製した顔料分散液１～６を用いて、固形分中の比率が表２の配合割合となるように各成分を加え、さらに全固形分の含有割合が２２質量％となるようにＰＧＭＥＡを加え、攪拌、溶解させて、着色感光性樹脂組成物を調製した。得られた着色感光性樹脂組成物を用いて、後述する方法でパターンを作成し評価を行った。 [Examples 1 to 6, Reference Example 1, and Comparative Example 1]
Using the pigment dispersions 1 to 6 prepared above, 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. In addition, the mixture was stirred and dissolved to prepare a colored photosensitive resin composition. Using the obtained colored photosensitive resin composition, a pattern was prepared by the method described later and evaluated.
Figure JPOXMLDOC01-appb-T000073
  
Figure JPOXMLDOC01-appb-T000073
  
＜隔壁基板の作成方法＞
　ＩＴＯ基板（膜厚１５００ÅのＩＴＯを蒸着したガラス基板）上にスピナーを用いて各着色感光性樹脂組成物を塗布した。次いで、１００℃にて８０秒間、ホットプレート上で加熱乾燥して塗布膜を形成した。
　得られた塗布膜に対し、開口幅５～５０μｍ（５～２０μｍ：１μｍおき、２５～５０μｍ：５μｍおき）の各種幅のライン状の開口部を有する露光マスクを用いて露光処理を施した。露光ギャップ（露光マスクと塗布面間の距離）は、５μｍであった。照射光としては、波長３６５ｎｍでの強度が３２ｍＷ／ｃｍ2である紫外線を用い、露光量は６０ｍＪ／ｃｍ2とした。また、紫外線照射は空気下で行った。 <Method for making partition wall substrate>
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 μm (5 to 20 μm: every 1 μm, 25 to 50 μm: every 5 μm). The exposure gap (distance between the exposure mask and the coated surface) was 5 μm. 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.
　続いて、２．３８質量％のＴＭＡＨ（水酸化テトラメチルアンモニウム）水溶液よりなる現像液を用い、２５℃において水圧０．０５ＭＰａのシャワー現像を施した後、純水にて現像を停止し、水洗スプレーにて洗浄した。シャワー現像時間は１０～１２０秒間の間で調整し、未露光部の塗膜が溶解除去される時間の１．２倍とした。
　これらの操作により、不要部分を除去したパターンを得た。当該パターンの形成された基板をオーブン中、２３０℃で４５分間加熱してパターンを硬化させ、膜厚が２．５μｍのライン状パターン（パターン１）を得た。また、露光マスクを使わなかった以外は同様の手順で膜厚が２．５μｍの全面被覆パターン（パターン２）も作製した。 Subsequently, using a developer composed of a 2.38% by mass aqueous solution of TMAH (tetramethylammonium hydroxide), shower development was performed at 25 ° C. with a water pressure of 0.05 MPa, and then development was stopped with pure water, followed by washing with water. Washed with spray. The shower development time was adjusted between 10 and 120 seconds, and was 1.2 times the time during which the unexposed film was dissolved and removed.
By these operations, a pattern from which unnecessary portions were removed was obtained. The board | substrate with which the said pattern was formed was heated for 45 minutes at 230 degreeC in oven, the pattern was hardened, and the linear pattern (pattern 1) with a film thickness of 2.5 micrometers was obtained. Further, an entire surface covering pattern (pattern 2) having a film thickness of 2.5 μm was also produced in the same procedure except that no exposure mask was used.
＜基板密着性の評価＞
　５～５０μｍのライン状開口部に対応するパターンにおいて、解像性良くパターンが基板上に残っているもののうち、幅が最小のもののマスク開口幅（μｍ）の値を最小密着として表２に示した。この値が小さいほど基板密着性に優れ、最小密着が２０μｍ以下であれば現像に対する現像密着性が実用上十分であり、特に１０μｍ以下であれば現像に対する現像密着性が優れると言える。 <Evaluation of substrate adhesion>
Among the patterns corresponding to 5 to 50 μm line openings, the mask opening width (μm) of the smallest width among the patterns remaining on the substrate with good resolution is shown in Table 2 as the minimum adhesion. It was. The smaller this value, the better the substrate adhesion, and if the minimum adhesion is 20 μm or less, the development adhesion to development is practically sufficient, and if it is 10 μm or less, the development adhesion to development is excellent.
＜アウトガスの評価方法＞
　パターン２の基板から、塗膜を約３ｍｇ削り出してアウトガス測定用の試料を得た。
　ＴＧ－ＤＴＡ６３００（日立ハイテクサイエンス社製）を用いて、試料を空気雰囲気下（Ｆｌｏｗ　２００ｍｌ／ｍｉｎ）、室温から５００℃まで１０℃／ｍｉｎで昇温し、その時の重量減少を測定した。各着色感光性樹脂組成物に含まれる全バインダー樹脂量に対する、室温から４００℃まで上昇した際の重量減少量（質量％）を表２に示した。なお、各着色感光性樹脂組成物の全固形分に対する、室温から４００℃まで上昇した際の重量減少量（質量％）は、実施例１：２６．８、実施例２：３０．２、実施例３：２９．７、実施例４：２７．９、実施例５：３０．８、実施例６：３１．９、参考例１：２５．６、比較例１：３３．７であった。 <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. In addition, the 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. Example 3: 29.7, Example 4: 27.9, Example 5: 30.8, Example 6: 31.9, Reference Example 1: 25.6, and Comparative Example 1: 33.7.
＜色度＞
　実施例１のパターン２の基板を用いて、分光光度計ＵＶ－３１００（島津製作所社製）にて、アルミ蒸着板を基準板とし、波長３８０～７８０ｎｍでの５度の鏡面反射率を塗膜側から測定し、ＸＹＺ表色系における色度（Ｄ６５光源）を算出した。
　実施例１の基板はｓｘ＝０．３２３、ｓｙ＝０．３２９であった。 <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 substrate of Example 1 was sx = 0.323 and sy = 0.329.
　実施例１～６及び参考例１の着色感光性樹脂組成物を用いた塗布基板は、アウトガス特性に優れることが確認された。
これに対して、比較例１の着色感光性樹脂組成物を用いた塗布基板は、アウトガス特性が悪いことが確認された。
　比較例１の着色感光性樹脂組成物に比べて、実施例１～６及び参考例１の着色感光性樹脂組成物はバインダー樹脂中のエポキシ（メタ）アクリレート樹脂の含有割合が高い。エポキシ（メタ）アクリレート樹脂は剛直な骨格を有するため熱分解しにくく、また、骨格が剛直なため硬化時に配列構造をとって架橋性の高い膜が形成されるため、バインダー樹脂中のエポキシ（メタ）アクリレート樹脂の含有割合を高くすることによって、アウトガス特性が良好になったと考えられる。 It was confirmed that the coated substrates using the colored photosensitive resin compositions of Examples 1 to 6 and Reference Example 1 were excellent in outgas characteristics.
On the other hand, it was confirmed that the coated substrate using the colored photosensitive resin composition of Comparative Example 1 has poor outgas characteristics.
Compared to the colored photosensitive resin composition of Comparative Example 1, 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.
　一方で、参考例１の着色感光性樹脂組成物を用いた塗布基板に比べて、実施例１～６の着色感光性樹脂組成物を用いた塗布基板のほうが細線パターンの現像密着性に優れることが確認された。参考例１の着色感光性樹脂組成物であっても一般的な解像度の有機電界発光素子の隔壁としては十分に適用できるが、実施例１～６の着色感光性樹脂組成物であれば高解像度の有機電界発光素子の隔壁にも適用できることが示唆された。
　参考例１の着色感光性樹脂組成物に含まれる分散剤はアクリル系分散剤でないため、現像時に膜内へ現像液が浸透しやすく、細線パターンが基板上に残りにくかったと考えられる。
　これに対して実施例１～６の着色感光性樹脂組成物に含まれる分散剤はアクリル系分散剤であるので、直鎖状の分子構造の柔軟な主骨格を有するため、吸着基の多くが着色剤に吸着することで着色感光性樹脂組成物中に着色剤が均一に分散されて、得られる塗布膜中においても現像液不溶成分である着色剤が均一に配置されて緻密な膜となり、現像時に膜内への現像液の浸透が抑制され、細線パターンであっても基板上に形成できたと考えられる。 On the other hand, compared to the coated substrate using the colored photosensitive resin composition of Reference Example 1, the coated substrate using the colored photosensitive resin composition of Examples 1 to 6 has better development adhesion of the fine line pattern. Was confirmed. Even 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. However, 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.
On the other hand, since 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. By adsorbing to the colorant, 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.
　また、実施例１～６の着色感光性樹脂組成物においては、バインダー樹脂としてエポキシ（メタ）アクリレート樹脂を含む顔料分散液１～５を用いて調製したことで、得られた着色感光性樹脂組成物に含まれるエポキシ（メタ）アクリレート樹脂の含有割合を高めることができた。 In 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.

Claims (23)

  1. 　（Ａ）着色剤、（Ｂ）分散剤、（Ｃ）バインダー樹脂、（Ｄ）光重合性モノマー及び（Ｅ）光重合開始剤を含有する着色感光性樹脂組成物であって、
    　前記（Ａ）着色剤が、下記一般式（Ｉ）で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも１種を含有する（Ａ１）有機黒色顔料を含み、
    　前記（Ｂ）分散剤が、アクリル系分散剤を含み、
    　前記（Ｃ）バインダー樹脂が、（Ｃ１）エポキシ（メタ）アクリレート樹脂を７５質量％以上含むことを特徴とする着色感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
      
    （式（Ｉ）中、Ｒａ1及びＲａ6は各々独立に、水素原子、ＣＨ3、ＣＦ3、フッ素原子又は塩素原子を表し；
    Ｒａ2、Ｒａ3、Ｒａ4、Ｒａ5、Ｒａ7、Ｒａ8、Ｒａ9及びＲａ10は各々独立に、水素原子、ハロゲン原子、Ｒａ11、ＣＯＯＨ、ＣＯＯＲａ11、ＣＯＯ-、ＣＯＮＨ2、ＣＯＮＨＲａ11、ＣＯＮＲａ11Ｒａ12、ＣＮ、ＯＨ、ＯＲａ11、ＣＯＣＲａ11、ＯＯＣＮＨ2、ＯＯＣＮＨＲａ11、ＯＯＣＮＲａ11Ｒａ12、ＮＯ2、ＮＨ2、ＮＨＲａ11、ＮＲａ11Ｒａ12、ＮＨＣＯＲａ12、ＮＲａ11ＣＯＲａ12、Ｎ＝ＣＨ2、Ｎ＝ＣＨＲａ11、Ｎ＝ＣＲａ11Ｒａ12、ＳＨ、ＳＲａ11、ＳＯＲａ11、ＳＯ2Ｒａ11、ＳＯ3Ｒａ11、ＳＯ3Ｈ、ＳＯ3 -、ＳＯ2ＮＨ2、ＳＯ2ＮＨＲａ11又はＳＯ2ＮＲａ11Ｒａ12を表し；
    且つ、Ｒａ2とＲａ3、Ｒａ3とＲａ4、Ｒａ4とＲａ5、Ｒａ7とＲａ8、Ｒａ8とＲａ9、及びＲａ9とＲａ10からなる群から選ばれる少なくとも１つの組み合わせは、互いに直接結合してもよく、又は酸素原子、硫黄原子、ＮＨ若しくはＮＲａ11ブリッジによって互いに結合してもよく；
    Ｒａ11及びＲａ12は各々独立に、炭素数１～１２のアルキル基、炭素数３～１２のシクロアルキル基、炭素数２～１２のアルケニル基、炭素数３～１２のシクロアルケニル基又は炭素数２～１２のアルキニル基を表す。）     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,
    The colored photosensitive resin composition, wherein the (C) binder resin contains 75% by mass or more of (C1) epoxy (meth) acrylate resin.
    Figure JPOXMLDOC01-appb-C000001
    (In formula (I), R a1 and R a6 each independently represents a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
    R a2 , R a3 , R a4 , R a5 , R a7 , R a8 , R a9 and R a10 are each independently a hydrogen atom, a halogen atom, R a11 , COOH, COOR a11 , COO − , CONH 2 , CONHR a11 , CONR a11 R a12, CN, OH, OR a11, COCR a11, OOCNH 2, OOCNHR a11, OOCNR a11 R a12, NO 2, NH 2, NHR a11, NR a11 R a12, NHCOR a12, NR a11 COR a12, N = CH 2 , N = CHR a11 , N = CR a11 R a12 , SH, SR a11 , SOR a11 , SO 2 R a11 , SO 3 R a11 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR represents a11 or SO 2 NR a11 R a12 ;
    And at least one combination selected from the group consisting of R a2 and R a3 , R a3 and R a4 , R a4 and R a5 , R a7 and R a8 , R a8 and R a9 , and R a9 and R a10 , May be bonded directly to each other, or may be bonded to each other by oxygen, sulfur, NH or NR a11 bridges;
    R a11 and R a12 each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a carbon number Represents 2 to 12 alkynyl groups. )
  2. 　前記（Ｃ）バインダー樹脂における前記（Ｃ１）エポキシ（メタ）アクリレート樹脂の含有割合が８５質量％以上である、請求項１に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to claim 1, wherein the content ratio of the (C1) epoxy (meth) acrylate resin in the (C) binder resin is 85% by mass or more.
  3. 　前記（Ｃ１）エポキシ（メタ）アクリレート樹脂が、下記一般式（ＩＩ）で表される繰り返し単位構造を有するエポキシ（メタ）アクリレート樹脂及び下記一般式（ＩＩＩ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂の一方又は両方を含む、請求項１又は２に記載の着色感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000002
      
    （式（ＩＩ）中、Ｒ11は水素原子又はメチル基を表し；
    Ｒ12は置換基を有していてもよい２価の炭化水素基を表し；
    式（ＩＩ）中のベンゼン環は、更に任意の置換基により置換されていてもよく；
    ＊は結合手を表す。）
    Figure JPOXMLDOC01-appb-C000003
      
    （式（ＩＩＩ）中、Ｒ13は各々独立に、水素原子又はメチル基を表し；
    Ｒ14は、環状炭化水素基を側鎖として有する２価の炭化水素基を表し；
    Ｒ15及びＲ16は各々独立に、置換基を有していてもよい２価の脂肪族基を表し；
    ｍ及びｎは各々独立に０～２の整数を表し；
    ＊は結合手を表す。）     The (C1) epoxy (meth) acrylate resin is an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and an epoxy having a partial structure represented by the following general formula (III) ( The colored photosensitive resin composition according to claim 1 or 2, comprising one or both of a (meth) acrylate resin.
    Figure JPOXMLDOC01-appb-C000002
    (In formula (II), 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;
    * Represents a bond. )
    Figure JPOXMLDOC01-appb-C000003
    (In formula (III), 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;
    * Represents a bond. )
  4. 　前記アクリル系分散剤が、窒素原子を含有するアクリル系分散剤である、請求項１～３のいずれか１項に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 1 to 3, wherein the acrylic dispersant is an acrylic dispersant containing a nitrogen atom.
  5. 　前記（Ａ）着色剤の含有割合が、前記着色感光性樹脂組成物の全固形分あたり６０質量％以下である、請求項１～４のいずれか１項に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 1 to 4, wherein a content ratio of the (A) colorant is 60% by mass or less based on a total solid content of the colored photosensitive resin composition.
  6. 　前記（Ａ）着色剤が、さらに（Ａ２）有機着色顔料及び（Ａ３）カーボンブラックの一方又は両方を含む、請求項１～５のいずれか１項に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 1 to 5, wherein the (A) colorant further contains one or both of (A2) an organic color pigment and (A3) carbon black.
  7. 　前記（Ａ）着色剤における（Ａ１）有機黒色顔料の含有割合が１０質量％以上である、請求項１～６のいずれか１項に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 1 to 6, wherein a content ratio of the (A1) organic black pigment in the (A) colorant is 10% by mass or more.
  8. 　有機電界発光素子の隔壁を形成するために用いられる、請求項１～７のいずれか１項に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 1 to 7, which is used for forming partition walls of an organic electroluminescence device.
  9. 　（Ａ）着色剤、（Ｂ）分散剤、（Ｃ）バインダー樹脂、（Ｄ）光重合性モノマー及び（Ｅ）光重合開始剤を含有する、有機電界発光素子の隔壁を形成するための着色感光性樹脂組成物であって、
    　前記（Ａ）着色剤が、下記一般式（Ｉ）で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも１種を含有する（Ａ１）有機黒色顔料を含み、
    　前記（Ｃ）バインダー樹脂が、（Ｃ１）エポキシ（メタ）アクリレート樹脂を７５質量％以上含むことを特徴とする着色感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000004
      
    （式（Ｉ）中、Ｒａ1及びＲａ6は各々独立に、水素原子、ＣＨ3、ＣＦ3、フッ素原子又は塩素原子を表し；
    Ｒａ2、Ｒａ3、Ｒａ4、Ｒａ5、Ｒａ7、Ｒａ8、Ｒａ9及びＲａ10は各々独立に、水素原子、ハロゲン原子、Ｒａ11、ＣＯＯＨ、ＣＯＯＲａ11、ＣＯＯ-、ＣＯＮＨ2、ＣＯＮＨＲａ11、ＣＯＮＲａ11Ｒａ12、ＣＮ、ＯＨ、ＯＲａ11、ＣＯＣＲａ11、ＯＯＣＮＨ2、ＯＯＣＮＨＲａ11、ＯＯＣＮＲａ11Ｒａ12、ＮＯ2、ＮＨ2、ＮＨＲａ11、ＮＲａ11Ｒａ12、ＮＨＣＯＲａ12、ＮＲａ11ＣＯＲａ12、Ｎ＝ＣＨ2、Ｎ＝ＣＨＲａ11、Ｎ＝ＣＲａ11Ｒａ12、ＳＨ、ＳＲａ11、ＳＯＲａ11、ＳＯ2Ｒａ11、ＳＯ3Ｒａ11、ＳＯ3Ｈ、ＳＯ3 -、ＳＯ2ＮＨ2、ＳＯ2ＮＨＲａ11又はＳＯ2ＮＲａ11Ｒａ12を表し；
    且つ、Ｒａ2とＲａ3、Ｒａ3とＲａ4、Ｒａ4とＲａ5、Ｒａ7とＲａ8、Ｒａ8とＲａ9、及びＲａ9とＲａ10からなる群から選ばれる少なくとも１つの組み合わせは、互いに直接結合してもよく、又は酸素原子、硫黄原子、ＮＨ若しくはＮＲａ11ブリッジによって互いに結合してもよく；
    Ｒａ11及びＲａ12は各々独立に、炭素数１～１２のアルキル基、炭素数３～１２のシクロアルキル基、炭素数２～１２のアルケニル基、炭素数３～１２のシクロアルケニル基又は炭素数２～１２のアルキニル基を表す。）     Colored photosensitivity for forming a partition of an organic electroluminescent device, comprising (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, and (E) a photopolymerization initiator. A functional 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.
    Figure JPOXMLDOC01-appb-C000004
    (In formula (I), R a1 and R a6 each independently represents a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
    R a2 , R a3 , R a4 , R a5 , R a7 , R a8 , R a9 and R a10 are each independently a hydrogen atom, a halogen atom, R a11 , COOH, COOR a11 , COO − , CONH 2 , CONHR a11 , CONR a11 R a12, CN, OH, OR a11, COCR a11, OOCNH 2, OOCNHR a11, OOCNR a11 R a12, NO 2, NH 2, NHR a11, NR a11 R a12, NHCOR a12, NR a11 COR a12, N = CH 2 , N = CHR a11 , N = CR a11 R a12 , SH, SR a11 , SOR a11 , SO 2 R a11 , SO 3 R a11 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR represents a11 or SO 2 NR a11 R a12 ;
    And at least one combination selected from the group consisting of R a2 and R a3 , R a3 and R a4 , R a4 and R a5 , R a7 and R a8 , R a8 and R a9 , and R a9 and R a10 , May be bonded directly to each other, or may be bonded to each other by oxygen, sulfur, NH or NR a11 bridges;
    R a11 and R a12 each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a carbon number Represents 2 to 12 alkynyl groups. )
  10. 　前記（Ｃ）バインダー樹脂における前記（Ｃ１）エポキシ（メタ）アクリレート樹脂の含有割合が８５質量％以上である、請求項９に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to claim 9, wherein a content ratio of the (C1) epoxy (meth) acrylate resin in the (C) binder resin is 85% by mass or more.
  11. 　前記（Ｃ１）エポキシ（メタ）アクリレート樹脂が、下記一般式（ＩＩ）で表される繰り返し単位構造を有するエポキシ（メタ）アクリレート樹脂及び下記一般式（ＩＩＩ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂の一方又は両方を含む、請求項９又は１０に記載の着色感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000005
      
    （式（ＩＩ）中、Ｒ11は水素原子又はメチル基を表し；
    Ｒ12は置換基を有していてもよい２価の炭化水素基を表し；
    式（ＩＩ）中のベンゼン環は、更に任意の置換基により置換されていてもよく；
    ＊は結合手を表す。）
    Figure JPOXMLDOC01-appb-C000006
      
    （式（ＩＩＩ）中、Ｒ13は各々独立に、水素原子又はメチル基を表し；
    Ｒ14は、環状炭化水素基を側鎖として有する２価の炭化水素基を表し；
    Ｒ15及びＲ16は各々独立に、置換基を有していてもよい２価の脂肪族基を表し；
    ｍ及びｎは各々独立に０～２の整数を表し；
    ＊は結合手を表す。）     The (C1) epoxy (meth) acrylate resin is an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and an epoxy having a partial structure represented by the following general formula (III) ( The colored photosensitive resin composition according to claim 9 or 10, comprising one or both of a (meth) acrylate resin.
    Figure JPOXMLDOC01-appb-C000005
    (In formula (II), 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;
    * Represents a bond. )
    Figure JPOXMLDOC01-appb-C000006
    (In formula (III), 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;
    * Represents a bond. )
  12. 　前記（Ａ）着色剤の含有割合が、前記着色感光性樹脂組成物の全固形分あたり６０質量％以下である、請求項９～１１のいずれか１項に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 9 to 11, wherein a content ratio of the (A) colorant is 60% by mass or less based on a total solid content of the colored photosensitive resin composition.
  13. 　前記（Ａ）着色剤が、さらに（Ａ２）有機着色顔料及び（Ａ３）カーボンブラックの一方又は両方を含む、請求項９～１２のいずれか１項に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 9 to 12, wherein the (A) colorant further comprises one or both of (A2) an organic color pigment and (A3) carbon black.
  14. 　前記（Ａ）着色剤における（Ａ１）有機黒色顔料の含有割合が１０質量％以上である、請求項９～１３のいずれか１項に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 9 to 13, wherein a content ratio of the (A1) organic black pigment in the (A) colorant is 10% by mass or more.
  15. 　請求項１～１４のいずれか１項に記載の着色感光性樹脂組成物で構成される隔壁。 A partition comprising the colored photosensitive resin composition according to any one of claims 1 to 14.
  16. 　請求項１５に記載の隔壁を備える有機電界発光素子。 An organic electroluminescent element comprising the partition wall according to claim 15.
  17. 　請求項１６に記載の有機電界発光素子を含む画像表示装置。 An image display device comprising the organic electroluminescent element according to claim 16.
  18. 　請求項１６に記載の有機電界発光素子を含む照明。 Lighting including the organic electroluminescent element according to claim 16.
  19. 　（Ａ）着色剤、（Ｂ）分散剤及び（Ｃ）バインダー樹脂を含有する顔料分散液であって、
    　前記（Ａ）着色剤が、下記一般式（Ｉ）で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも１種を含有する（Ａ１）有機黒色顔料を含み、
    　前記（Ｂ）分散剤が、アクリル系分散剤を含み、
    　前記（Ｃ）バインダー樹脂が、（Ｃ１）エポキシ（メタ）アクリレート樹脂を含むことを特徴とする顔料分散液。
    Figure JPOXMLDOC01-appb-C000007
      
    （式（Ｉ）中、Ｒａ1及びＲａ6は各々独立に、水素原子、ＣＨ3、ＣＦ3、フッ素原子又は塩素原子を表し；
    Ｒａ2、Ｒａ3、Ｒａ4、Ｒａ5、Ｒａ7、Ｒａ8、Ｒａ9及びＲａ10は各々独立に、水素原子、ハロゲン原子、Ｒ11、ＣＯＯＨ、ＣＯＯＲａ11、ＣＯＯ-、ＣＯＮＨ2、ＣＯＮＨＲａ11、ＣＯＮＲａ11Ｒａ12、ＣＮ、ＯＨ、ＯＲａ11、ＣＯＣＲａ11、ＯＯＣＮＨ2、ＯＯＣＮＨＲａ11、ＯＯＣＮＲａ11Ｒａ12、ＮＯ2、ＮＨ2、ＮＨＲａ11、ＮＲａ11Ｒａ12、ＮＨＣＯＲａ12、ＮＲａ11ＣＯＲａ12、Ｎ＝ＣＨ2、Ｎ＝ＣＨＲａ11、Ｎ＝ＣＲａ11Ｒａ12、ＳＨ、ＳＲａ11、ＳＯＲａ11、ＳＯ2Ｒａ11、ＳＯ3Ｒａ11、ＳＯ3Ｈ、ＳＯ3 -、ＳＯ2ＮＨ2、ＳＯ2ＮＨＲａ11又はＳＯ2ＮＲａ11Ｒａ12を表し；
    且つ、Ｒａ2とＲａ3、Ｒａ3とＲａ4、Ｒａ4とＲａ5、Ｒａ7とＲａ8、Ｒａ8とＲａ9、及びＲａ9とＲａ10からなる群から選ばれる少なくとも１つの組み合わせは、互いに直接結合してもよく、又は酸素原子、硫黄原子、ＮＨ若しくはＮＲａ11ブリッジによって互いに結合してもよく；
    Ｒａ11及びＲａ12は各々独立に、炭素数１～１２のアルキル基、炭素数３～１２のシクロアルキル基、炭素数２～１２のアルケニル基、炭素数３～１２のシクロアルケニル基又は炭素数２～１２のアルキニル基を表す。）     A pigment dispersion containing (A) a colorant, (B) a dispersant and (C) a binder resin,
    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,
    The pigment dispersion, wherein the (C) binder resin contains (C1) an epoxy (meth) acrylate resin.
    Figure JPOXMLDOC01-appb-C000007
    (In formula (I), R a1 and R a6 each independently represents a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
    R a2 , R a3 , R a4 , R a5 , R a7 , R a8 , R a9 and R a10 are each independently a hydrogen atom, a halogen atom, R 11 , COOH, COOR a11 , COO − , CONH 2 , CONHR a11 , CONR a11 R a12, CN, OH, OR a11, COCR a11, OOCNH 2, OOCNHR a11, OOCNR a11 R a12, NO 2, NH 2, NHR a11, NR a11 R a12, NHCOR a12, NR a11 COR a12, N = CH 2 , N = CHR a11 , N = CR a11 R a12 , SH, SR a11 , SOR a11 , SO 2 R a11 , SO 3 R a11 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR represents a11 or SO 2 NR a11 R a12 ;
    And at least one combination selected from the group consisting of R a2 and R a3 , R a3 and R a4 , R a4 and R a5 , R a7 and R a8 , R a8 and R a9 , and R a9 and R a10 , May be bonded directly to each other, or may be bonded to each other by oxygen, sulfur, NH or NR a11 bridges;
    R a11 and R a12 each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a carbon number Represents 2 to 12 alkynyl groups. )
  20. 　前記（Ｂ）分散剤の含有割合が、（Ａ）着色剤１００質量部に対して１０質量部以上である、請求項１９に記載の顔料分散液。 The pigment dispersion according to claim 19, wherein the content ratio of the (B) dispersant is 10 parts by mass or more with respect to 100 parts by mass of the (A) colorant.
  21. 　前記（Ｃ１）エポキシ（メタ）アクリレート樹脂が、下記一般式（ＩＩ）で表される繰り返し単位構造を有するエポキシ（メタ）アクリレート樹脂及び下記一般式（ＩＩＩ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂の一方又は両方を含む、請求項１９又は２０に記載の顔料分散液。
    Figure JPOXMLDOC01-appb-C000008
      
    （式（ＩＩ）中、Ｒ11は水素原子又はメチル基を表し；
    Ｒ12は置換基を有していてもよい２価の炭化水素基を表し；
    式（ＩＩ）中のベンゼン環は、更に任意の置換基により置換されていてもよく；
    ＊は結合手を表す。）
    Figure JPOXMLDOC01-appb-C000009
      
    （式（ＩＩＩ）中、Ｒ13は各々独立に、水素原子又はメチル基を表し；
    Ｒ14は、環状炭化水素基を側鎖として有する２価の炭化水素基を表し；
    Ｒ15及びＲ16は各々独立に、置換基を有していてもよい２価の脂肪族基を表し；
    ｍ及びｎは各々独立に０～２の整数を表し；
    ＊は結合手を表す。）     The (C1) epoxy (meth) acrylate resin is an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and an epoxy having a partial structure represented by the following general formula (III) ( The pigment dispersion according to claim 19 or 20, comprising one or both of a (meth) acrylate resin.
    Figure JPOXMLDOC01-appb-C000008
    (In formula (II), 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;
    * Represents a bond. )
    Figure JPOXMLDOC01-appb-C000009
    (In formula (III), 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;
    * Represents a bond. )
  22. 　前記アクリル系分散剤が、窒素原子を含有するアクリル系分散剤である、請求項１９～２１のいずれか１項に記載の顔料分散液。 The pigment dispersion according to any one of claims 19 to 21, wherein the acrylic dispersant is an acrylic dispersant containing a nitrogen atom.
  23. 　着色感光性樹脂組成物を製造するために用いられる、請求項１９～２２のいずれか１項に記載の顔料分散液。 The pigment dispersion according to any one of claims 19 to 22, which is used for producing a colored photosensitive resin composition.
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