WO2022065490A1 - Photosensitive coloring composition, cured product, organic electroluminescent element, and image display device - Google Patents

Photosensitive coloring composition, cured product, organic electroluminescent element, and image display device Download PDF

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Publication number
WO2022065490A1
WO2022065490A1 PCT/JP2021/035403 JP2021035403W WO2022065490A1 WO 2022065490 A1 WO2022065490 A1 WO 2022065490A1 JP 2021035403 W JP2021035403 W JP 2021035403W WO 2022065490 A1 WO2022065490 A1 WO 2022065490A1
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group
preferable
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coloring composition
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PCT/JP2021/035403
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French (fr)
Japanese (ja)
Inventor
良尚 沢井
信夫 力武
康太郎 三島
賀子 宮下
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三菱ケミカル株式会社
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Priority to CN202180064110.2A priority Critical patent/CN116323716A/en
Priority to KR1020237009602A priority patent/KR20230076816A/en
Priority to JP2022552105A priority patent/JPWO2022065490A1/ja
Publication of WO2022065490A1 publication Critical patent/WO2022065490A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • 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
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/02—Coumarine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

  • the present invention relates to a photosensitive coloring composition, a cured product, an organic electroluminescent device, and an image display device.
  • This application claims priority under Japanese Patent Application No. 2020-162460 filed in Japan on September 28, 2020 and Japanese Patent Application No. 2021-204490 filed in Japan on February 18, 2021. Incorporate the content here.
  • the liquid crystal display utilizes the property that the arrangement of liquid crystal molecules is switched by turning the voltage on and off the liquid crystal.
  • Each member constituting the cell of the LCD is often formed by a method using a photosensitive composition represented by a photolithography method.
  • the range of application of this photosensitive composition is further expanded because it is easy to form a fine structure and it is easy to process a substrate for a large screen.
  • An image display device including an organic electroluminescent element (also referred to as organic electroluminescence or organic EL) has excellent visibility and responsiveness such as contrast and viewing angle, and is low in power consumption, thin and lightweight, and a display body. It is attracting attention as a next-generation flat panel display (FPD) because it can be made flexible.
  • the organic electroluminescent device has a structure in which an organic layer including a light emitting layer or various functional layers is sandwiched between a pair of electrodes having at least one translucent property.
  • 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 device has been manufactured by forming a partition wall (bank) on a substrate and then laminating a light emitting layer or various functional layers in a region surrounded by the partition wall.
  • a vapor deposition method in which a material is sublimated in a vacuum state and adhered to a substrate to form a film is mainly applied.
  • a method of forming a film by a wet process such as a casting method, a spin coating method, and an inkjet printing method has attracted attention.
  • the inkjet printing method can reduce film thickness unevenness when a large area is used, and can improve the definition of the display by painting separately at the time of coating, reduce the amount of material used, and improve the yield. Since it is possible, it is suitable as a method for forming an organic layer in a large panel.
  • a method for easily forming a partition wall a method of forming by a photolithography method using a photosensitive composition is known. Further, as a method of imparting a light-shielding property to a partition wall and suppressing light leakage between pixels, a method of incorporating a colorant in a photosensitive composition is known.
  • Patent Document 1 describes a colored photosensitive resin composition that suppresses the generation of outgas by using a specific organic black pigment and an alkali-soluble resin.
  • top emission type and bottom emission type panel forms for organic electroluminescent devices.
  • a reflective electrode such as silver is used as an electrode to form a cured product such as a partition wall on it, but the components in the photosensitive composition act during the heat treatment to corrode or migrate the metal electrode. May cause. If the surface of the electrode is uneven (hereinafter, also referred to as surface roughness), it is not possible to form a light emitting layer uniformly on that part, and when an organic electroluminescent element is created, it is displayed due to a short circuit or the like. May cause defects.
  • the present invention has been made in view of the above circumstances, and provides a photosensitive coloring composition that does not cause surface roughness of an electrode after heat treatment, and provides a highly reliable organic light emitting device and an image without display defects. It is an object of the present invention to provide a display device.
  • the gist of the present invention is as follows.
  • Photosensitive coloring containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. It ’s a composition,
  • 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.
  • the photosensitive coloring composition is characterized in that the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less with respect to the total solid content of the photosensitive coloring composition.
  • R 1 and R 6 are independent hydrogen atoms, CH 3 , CF 3 , fluorine atoms or chlorine atoms;
  • R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 and R 10 are independent of each other from hydrogen atom, halogen atom, R 11 , COOH, COOR 11 , COO- , CONH.
  • R 11 and R 12 are independent of each other, 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 carbon. It is an alkynyl group of the number 2-12.
  • R 31 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 32 is a hydrogen atom or a methyl group. * Represents a bond.
  • R 33 is a methylene group, an ethylene group or a propylene group
  • R 34 is an alkyl group which may have a substituent
  • R 35 is a hydrogen atom or a methyl group.
  • n is an integer from 1 to 20. * Represents a bond.
  • R 36 and R 37 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. It is an aralkyl group which may be present, and R 36 and R 37 may be bonded to each other to form a cyclic structure.
  • R 38 is a hydrogen atom or a methyl group.
  • Z is a divalent linking group. * Represents a bond.
  • Photosensitive coloring containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. It ’s a composition, The optical density per 1 ⁇ m of the cured coating film is 0.5 or more.
  • R 31 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 32 is a hydrogen atom or a methyl group. * Represents a bond.
  • R 33 is a methylene group, an ethylene group or a propylene group
  • R 34 is an alkyl group which may have a substituent
  • R 35 is a hydrogen atom or a methyl group.
  • n is an integer from 1 to 20. * Represents a bond.
  • R 36 and R 37 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. It is an aralkyl group which may be present, and R 36 and R 37 may be bonded to each other to form a cyclic structure.
  • R 38 is a hydrogen atom or a methyl group.
  • Z is a divalent linking group. * Represents a bond.
  • (meth) acrylic means “acrylic and / or methacrylic", and the same applies to "(meth) acrylate” and "(meth) acryloyl”.
  • the "(co) polymer” means that both a monopolymer (homopolymer) and a copolymer (copolymer) are contained, and "acid (anhydrous)” and “(anhydrous) ... acid” are used. , Means to contain both acids and their anhydrides.
  • the "acrylic resin” means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylic acid ester having a carboxy group.
  • the term "monomer” is a term relative to a so-called polymer substance (polymer), and means that a dimer, a trimer, and an oligomer are included in addition to a monomer (monomer) in a narrow sense.
  • the “total solid content” means the total amount of components other than the solvent contained in the photosensitive coloring composition or the pigment dispersion liquid. Even if the components other than the solvent are liquid at room temperature, the components are not included in the solvent and are included in the total solid content.
  • the "weight average molecular weight” means the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
  • the "amine value” represents an amine value in terms of effective solid content, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the equivalent mass of KOH, unless otherwise specified. .. The measurement method will be described later. Unless otherwise specified, the “acid value” represents the acid value in terms of effective solid content and is calculated by neutralization titration.
  • CI means a color index
  • the photosensitive coloring composition of the present invention is (A) Colorant (b) Alkali-soluble resin (c) Photopolymerization initiator (d) Ethylene unsaturated compound (e) Solvent (f) Dispersant is contained as an essential component.
  • A) Colorant b) Alkali-soluble resin
  • c) Photopolymerization initiator d) Ethylene unsaturated compound
  • e) Solvent f) Dispersant is contained as an essential component.
  • a colorant a compound represented by the general formula (I), a geometric isomer of the compound represented by the general formula (I), and a compound represented by the general formula (I). It contains at least one selected from the group consisting of a salt or a salt of a geometric isomer of a compound represented by the general formula (I).
  • the optical density per 1 ⁇ m of the film thickness of the coating film obtained by curing the photosensitive coloring composition of the present invention is 0.5 or more. Further, if necessary, it further contains other compounding components such as an adhesion improver such as a silane coupling agent, a surfactant, a pigment derivative, a photoacid generator, a cross-linking agent, a mercapto compound, and a polymerization inhibitor. Usually, each compounding component is used in a state of being dissolved or dispersed in a solvent.
  • the photosensitive coloring composition of the present invention contains (a) a colorant.
  • (A) By containing a colorant, it is possible to obtain an appropriate light absorption property, particularly an appropriate light shielding property when used for forming a light shielding member such as a partition wall.
  • the colorant (a) the compound represented by the general formula (I), the geometric isomer of the compound represented by the general formula (I), and the compound represented by the general formula (I). It contains at least one selected from the group consisting of salts and salts of geometric isomers of compounds represented by the general formula (I).
  • the compound represented by the general formula (I) (hereinafter, also referred to as “compound (I)”) is an organic black pigment.
  • R 11 and R 16 each independently represent a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
  • R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 are independent of each other, hydrogen atom, halogen atom, R 21 , COOH, COOR 21 , COO- , CONH 2 , CONHR 21 .
  • R 21 and R 22 independently has 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 cycloalkenyl group having 3 to 12 carbon atoms. Represents 2-12 alkynyl groups.
  • compound (I) When compound (I) is anionic, its charge can be charged to any known suitable cation such as metal, organic, inorganic or metallic organic cation, specifically alkali metal, alkaline earth metal, transition metal, primary ammonium. , Secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or salts supplemented with an organic metal complex are preferred. When the geometric isomer of compound (I) is anionic, it is preferably a similar salt.
  • suitable cation such as metal, organic, inorganic or metallic organic cation, specifically alkali metal, alkaline earth metal, transition metal, primary ammonium. , Secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or salts supplemented with an organic metal complex are preferred.
  • R 12 , R 14 , R 15 , R 17 , R 19 and R 20 are each independently, preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.
  • R 13 and R 18 are independent of each other, preferably 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).
  • R 11 and R 16 is independently, preferably a hydrogen atom, CH 3 or CF 3 , and more preferably a hydrogen atom.
  • at least one combination selected from the group consisting of R 11 and R 16 , R 12 and R 17 , R 13 and R 18 , R 14 and R 19 , and R 15 and R 20 is the same, more preferably.
  • R 11 is the same as R 16
  • R 12 is the same as R 17
  • R 13 is the same as R 18
  • R 14 is the same as R 19
  • R 15 is R 20 . It is the same.
  • the alkyl group having 1 to 12 carbon atoms is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a 2-methylbutyl group, or n-.
  • Pentyl group 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2 -Ethylhexyl group, nonyl group, decyl group, undecyl group or dodecyl group.
  • the cycloalkyl group having 3 to 12 carbon atoms is, for example, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a trimethylcyclohexyl group, a tudyl group, a norbornyl group, a boronyl group, or a norcaryl group.
  • the alkenyl group having 2 to 12 carbon atoms is, for example, a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-butene-1-yl group, a 3-buten-1-yl group, or a 1,3-butadiene.
  • -2-yl group 2-penten-1-yl group, 3-penten-2-yl group, 2-methyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, It is a 3-methyl-2-buten-1-yl group, a 1,4-pentadiene-3-yl group, a hexenyl group, an octenyl group, a nonenyl group, a decenyl group or a dodecenyl group.
  • the cycloalkenyl group having 3 to 12 carbon atoms is, for example, 2-cyclobutene-1-yl group, 2-cyclopentene-1-yl group, 2-cyclohexene-1-yl group, 3-cyclohexene-1-yl group, 2 , 4-Cyclohexadiene-1-yl group, 1-p-menten-8-yl group, 4 (10) -Tsgen-10-yl group, 2-norbornene-1-yl group, 2,5-norbornadiene-1 -Il group, 7,7-dimethyl-2,4-norborneadiene-3-yl group or canphenyl group.
  • the alkynyl group having 2 to 12 carbon atoms is, for example, 1-propin-3-yl group, 1-butin-4-yl group, 1-pentin-5-yl group, 2-methyl-3-butin-2-yl.
  • the halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • the compound represented by the general formula (I) is preferably from the compound represented by the following general formula (II) (hereinafter, also referred to as “compound (II)”) and the geometric isomer of the compound (II). It is a compound containing at least one selected from the group.
  • Examples of such a compound include, in the trade name, Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).
  • This organic black pigment is preferably dispersed and used by the method described later. Further, at the time of dispersion, the sulfonic acid derivative of the compound (I) or the sulfonic acid derivative of the geometric isomer of the compound (I), particularly the sulfonic acid derivative of the compound (II) or the sulfon of the geometric isomer of the compound (II).
  • the presence of an acid derivative may improve dispersibility and storage stability.
  • the colorant (A) may contain other colorants in addition to the compound of the general formula (I).
  • a pigment is preferable, and the pigment may be an organic pigment or an inorganic pigment. From the viewpoint of high resistance and low dielectric constant, organic pigments are more preferable, and organic coloring pigments described later are particularly preferable.
  • the organic coloring pigments it is preferable to use the compound (I) and the blue pigment from the viewpoint of making the transmittance in the high wavelength region of the visible light region uniform.
  • Pigment Blue B60, 15: 6, 16 is preferable, and Pigment Blue B60 is more preferable.
  • At least one selected from the group consisting of a red pigment and an orange pigment and a group consisting of a blue pigment and a purple pigment are selected in addition to the compound (I). It is preferable to use at least one kind.
  • the photosensitive coloring composition of the present invention has an optical density per 1 ⁇ m of a cured coating film (hereinafter, may be referred to as “OD per unit film thickness”) of 0.5. That is all.
  • OD per unit film thickness an optical density per 1 ⁇ m of a cured coating film
  • the OD per unit film thickness can be calculated by measuring the optical density and the film thickness of the coating film obtained by curing the photosensitive coloring composition and dividing the optical density by the film thickness.
  • the conditions for producing the coating film are not particularly limited, but for example, the conditions described in Examples described later can be adopted. In order to make the OD per unit film thickness equal to or higher than the lower limit, for example, (a) the type of the colorant and the content ratio in the total solid content may be appropriately adjusted.
  • the type of (a) colorant that can be used in the photosensitive coloring composition is not particularly limited, and a pigment or a dye may be used. Among these, it is preferable to use a pigment from the viewpoint of durability.
  • the pigment contained in the colorant may be one kind alone or two or more kinds. In particular, from the viewpoint of achieving both uniform light shielding in the visible region and OD per unit film thickness, two or more types are preferable.
  • the type of pigment that can be used as the colorant is not particularly limited, and examples thereof include organic color pigments and black pigments.
  • the organic coloring pigment means an organic pigment exhibiting a color other than black, and examples thereof include a red pigment, an orange pigment, a blue pigment, a purple pigment, a green pigment, and a yellow pigment.
  • pigments it is preferable to use an organic coloring pigment from the viewpoint of high resistance and low dielectric constant. Further, from the viewpoint of light-shielding property, it is preferable to use compound (I) or another black pigment.
  • organic coloring pigment one type may be used alone, or two or more types may be used in combination.
  • the organic coloring pigments having different colors it is more preferable to use a combination of organic coloring pigments having different colors, and it is preferable to use a combination of organic coloring pigments having a color close to black. More preferred.
  • organic coloring pigments are not particularly limited, and examples thereof include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindoleinone-based, dioxazine-based, indanthrone-based, and perylene-based.
  • specific examples of pigments that can be used are shown by pigment numbers.
  • "CI” in "CI Pigment Red 2" and the like listed below means a color index.
  • 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 can be mentioned.
  • C.I. I. Pigment Red 177, 254, 272 are preferable, and when the photosensitive coloring composition is cured with ultraviolet rays, a red pigment having a low ultraviolet absorption rate is preferable, and from this viewpoint, C.I. I. Pigment Red 254 and 272 are more preferred.
  • 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 can be mentioned.
  • C.I. I. Pigments Orange 13, 43, 64, 72 are preferable, and when the photosensitive coloring composition is cured with ultraviolet rays, the orange pigment having a low ultraviolet absorption rate is preferable, and from this viewpoint, C.I. I. Pigment Oranges 64 and 72 are more preferred.
  • C.I. I. Pigment Blue 1 As a blue pigment, 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 can be mentioned. From the viewpoint of light-shielding property, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 60, more preferably C.I. I. Pigment Blue 15: 6 can be mentioned. In terms of dispersibility and light blocking effect, C.I. I. Pigment Blue 15: 6, 16, 60 is preferable, and when the photosensitive coloring composition is cured with ultraviolet rays, a blue pigment having a low ultraviolet absorption rate is preferable, and from this viewpoint, C.I. I. Pigment Blue 60 is more preferred.
  • C.I. I. Pigment Violet 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 can be mentioned.
  • C.I. I. Pigment Violet 19 23, 29, more preferably C.I. I. Pigment Violet 23 can be mentioned.
  • C.I. I. Pigments Violet 23 and 29 are preferable, and when the photosensitive coloring composition is cured with ultraviolet rays, the purple pigment having a low ultraviolet absorption rate is preferable, and from this viewpoint, C.I. I. Pigment Violet 29 is more preferred.
  • C.I. I. Pigment Greens 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59 can be mentioned. ..
  • C.I. I. Pigment Greens 7 and 36 can be mentioned.
  • 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 can be mentioned.
  • At least one selected from the group consisting of red pigment, orange pigment, blue pigment and purple pigment is preferable.
  • 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 organic coloring pigments is not particularly limited, but from the viewpoint of light-shielding property, at least one selected from the group consisting of red pigments and orange pigments, and blue pigments and purples. It is preferable to use at least one selected from the group consisting of pigments in combination.
  • the color combination is not particularly limited, and examples thereof include a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment, an orange pigment, and a purple pigment from the viewpoint of light-shielding property.
  • Organic black pigments other than organic color pigments and organic black pigments represented by the general formula (I), and inorganic black pigments can be used.
  • examples of the organic black pigment other than the organic black pigment represented by the general formula (I) include aniline black and perylene black.
  • inorganic black pigment examples include the inorganic black pigment described in International Publication No. 2018/101314.
  • the colorant when using these colorants, if the colorant contains chlorine atoms, it can be used by adjusting the amount of chlorine added so that the amount of chlorine does not increase too much.
  • the average particle size of the pigment is usually 1 ⁇ m or less, preferably 0.5 ⁇ m or less, and more preferably 0.25 ⁇ m or less.
  • the standard of the average particle size is the number of pigment particles.
  • the average particle size of the pigment is a value obtained from the pigment particle size measured by dynamic light scattering (DLS).
  • the particle size is measured by a sufficiently diluted photosensitive coloring composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring device, Follow the concentration) and measure at 25 ° C.
  • one kind of coloring agent such as an organic coloring pigment or a black pigment may be used alone, or two or more kinds may be used in combination.
  • Dyes may be used in addition to the above-mentioned organic coloring pigments and black pigments.
  • examples of the dye that can be used as a colorant include the dyes described in International Publication No. 2018/101314.
  • the (b) alkali-soluble resin used in the present invention is not particularly limited as long as it is a resin containing a carboxy group or a hydroxyl group, and is, for example, an epoxy (meth) acrylate resin, an acrylic resin, a carboxy group-containing epoxy resin, or a carboxy group. Examples thereof include a contained urethane resin, a novolak resin, and a polyvinylphenol resin. Above all (B1) Epoxy (meth) acrylate-based resin (b2) Acrylic copolymer resin is preferably used from the viewpoint of excellent plate-making property. These can be used alone or in combination of two or more.
  • Epoxy (meth) acrylate resin comprises an epoxy compound (epoxy resin) and an ⁇ , ⁇ -unsaturated monocarboxylic acid and / or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group at the ester moiety. It is a resin obtained by further reacting a hydroxyl group generated by the reaction with a compound having two or more substituents capable of reacting with a hydroxyl group such as a polybasic acid and / or an anhydride thereof.
  • the resin to be obtained is also included in the above (b1) epoxy (meth) acrylate-based resin.
  • the resin obtained by reacting the carboxy group of the resin obtained by the above reaction with a compound having a functional group capable of further reacting is also included in the (b1) epoxy (meth) acrylate-based resin.
  • the epoxy (meth) acrylate-based resin has substantially no epoxy group due to its chemical structure and is not limited to "(meth) acrylate", but the epoxy compound (epoxy resin) is used as a raw material.
  • (meth) acrylate is a typical example, it is named in this way according to the convention.
  • Examples of the (b1) epoxy (meth) acrylate-based resin used in the present invention include the following epoxy (meth) acrylate-based resin (b1-1) and / or epoxy (meth) acrylate-based resin (b1-2) (hereinafter, “carboxy).
  • Group-containing epoxy (meth) acrylate-based resin ” may be referred to as“ group-containing epoxy (meth) acrylate resin ”), which is preferably used from the viewpoint of developability and reliability.
  • the (b1) epoxy (meth) acrylate-based resin those having an aromatic ring in the main chain can be more preferably used from the viewpoint of outgas.
  • the epoxy resin includes a raw material compound before forming the resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins and used. Further, as the epoxy resin, a compound obtained by reacting a phenolic compound with epihalohydrin can be used.
  • the phenolic compound is preferably a compound having a divalent or divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
  • the types of epoxy resins used as raw materials include, for example, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, biphenyl novolac type epoxy resin, and naphthalene.
  • Novolak type epoxy resin epoxy resin which is a reaction product of dicyclopentadiene and phenol or cresol and epihalohydrin, adamantyl group-containing epoxy resin, and fluorene type epoxy resin can be preferably used. Among them, those having an aromatic ring in the main chain can be more preferably used.
  • epoxy resin examples include bisphenol A type epoxy resin (for example, "jER (registered trademark, the same shall apply hereinafter) 828", “jER1001", “jER1002", “jER1004", etc.) manufactured by Mitsubishi Chemical Corporation, and bisphenol A type.
  • Epoxy resin obtained by the reaction of the alcoholic hydroxyl group of the epoxy resin with epichlorohydrin for example, "NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin (for example, Mitsubishi Chemical).
  • NER-1302 epoxy equivalent 323, softening point 76 ° C.
  • Cresol novolac type epoxy resin for example, "EOCN (registered trademark, the same shall apply hereinafter) -102S", “EOCN-1020", “EOCN-104S" manufactured by Nippon Kayaku Co., Ltd., triglycidyl isocyanurate (for example, “TEPIC (registered trademark)” manufactured by Nissan Chemical Corporation), Trisphenol methane type epoxy resin (for example, “EPPN (registered trademark, the same shall apply hereinafter) -501", “EPPN-502", “EPPN-502” manufactured by Nippon Kayaku Co., Ltd.
  • EPPN-503 alicyclic epoxy resin
  • a resin for example, "EXA-7200” manufactured by DIC, “NC-7300” manufactured by Nippon Kayaku Co., Ltd.
  • an epoxy resin represented by the following general formulas (B1) to (B4) can be preferably used.
  • B1 XD-1000
  • Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (B1)
  • Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (B2).
  • NC-3000 "E-201” manufactured by Osaka Organic Chemical Industry Co., Ltd. as an epoxy resin represented by the following general formula (B3), Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (B4) "ESF-300" manufactured by the company can be mentioned.
  • a is an average value and represents a number of 0 to 10
  • R 111 is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, and 3 to 10 carbon atoms, respectively.
  • the plurality of R 111s existing in one molecule may be the same or different from each other.
  • b1 and b2 are independently average values and represent numbers of 0 to 10
  • R 121 is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, and carbon. Represents a cycloalkyl group, a phenyl group, a naphthyl group, or a biphenyl group having a number of 3 to 10.
  • the plurality of R 121s existing in one molecule may be the same or different from each other.
  • X represents a linking group represented by the following general formula (B3-1) or (B3-2).
  • the molecular structure contains one or more adamantane structures.
  • c represents 2 or 3.
  • R 131 to R 134 and R 135 to R 137 each independently may have a substituent, an adamantyl group, a hydrogen atom, or a substituent.
  • p and q each independently represent an integer of 0 to 4
  • R 141 and R 142 independently represent an alkyl group or a halogen atom having 1 to 4 carbon atoms, respectively
  • R 143 and R 144 independently represent an alkylene group having 1 to 4 carbon atoms
  • x and y each independently represent an integer of 0 or more.
  • an epoxy resin represented by any of the general formulas (B1) to (B4) it is preferable to use an epoxy resin represented by any of the general formulas (B1) to (B4).
  • Examples of the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having an ⁇ , ⁇ -unsaturated monocarboxylic acid or a carboxy group include (meth) acrylic acid, crotonic acid, o-, m- or p-vinyl benzoic acid, and (meth).
  • Monocarboxylic acid such as ⁇ -position haloalkyl, alkoxyl, halogen, nitro, cyano-substituted acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( Meta) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- ( Meta) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) ) Acryl
  • a known method can be used as a method for adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group to the epoxy resin.
  • an esterification catalyst an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group can be reacted with an epoxy resin at a temperature of 50 to 150 ° C. can.
  • esterification catalyst used here tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride can be used. ..
  • each component of the epoxy resin ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group, and the esterification catalyst
  • each component may be selected and used one by one. Two or more types may be used in combination.
  • the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group is preferably in the range of 0.5 to 1.2 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. , More preferably in the range of 0.7 to 1.1 equivalents.
  • polybasic acid and / or its anhydrate examples include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid and methylhexa.
  • examples thereof include hydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
  • maleic acid succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof.
  • Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.
  • the addition reaction of the polybasic acid and / or its anhydride can be carried out using a known method and is an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid having a carboxy group on an epoxy resin.
  • the desired product can be obtained by continuing the reaction under the same conditions as the addition reaction of the carboxylic acid ester.
  • the addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the carboxy group-containing epoxy (meth) acrylate-based resin to be produced is in the range of 10 to 150 mgKOH / g, and further. It is preferably in the range of 20 to 140 mgKOH / g. When the value is equal to or higher than the lower limit, the alkali developability tends to be good. When the value is not more than the upper limit, the curing performance tends to be good.
  • Polyfunctional alcohols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3-propanetriol during the addition reaction of polybasic acid and / or its anhydride.
  • polyhydric alcohols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3-propanetriol during the addition reaction of polybasic acid and / or its anhydride.
  • the mixing order of the polybasic acid and / or its anhydride and the polyfunctional alcohol is not particularly limited.
  • Any hydroxyl group present in the mixture of the reaction product of the epoxy resin with the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group and the polyfunctional alcohol by heating.
  • a polybasic acid and / or its anhydride undergoes an addition reaction with respect to.
  • the molecular weight of the (b1) epoxy (meth) acrylate resin can be increased, branches 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 for the sensitivity, adhesion, and the like to be easily balanced.
  • Examples of the carboxy group-containing epoxy (meth) acrylate-based resin include those described in Korean Patent Publication No. 10-2013-0022955, in addition to the above-mentioned ones.
  • the polystyrene-equivalent weight average molecular weight (Mw) of the carboxy group-containing epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, and more preferably. Is 3000 or more, more preferably 4000 or more, particularly preferably 5000 or more, usually 30,000 or less, preferably 20,000 or less, and more preferably 15,000 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1000 to 30000 is preferable, 1500 to 20000 is more preferable, 1500 to 15000 is even more preferable, and 2000 to 15000 is even more preferable.
  • the acid value of the carboxy group-containing epoxy (meth) acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, still more preferably 80 mgKOH / g or more. , 100 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 further preferable, and 120 mgKOH / g or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • 20 mgKOH / g to 200 mgKOH / g is preferable, 60 mgKOH / g to 150 mgKOH / g is more preferable, 80 mgKOH / g to 130 mgKOH / g is further preferable, and 100 mgKOH / g to 130 mgKOH / g is even more preferable.
  • the value By setting the value to the lower limit or more, the develop solubility tends to be improved and the resolution tends to be good.
  • the value is not more than the upper limit, the residual film ratio of the photosensitive coloring composition tends to be good.
  • the chemical structure of the epoxy (meth) acrylate-based resin is not particularly limited, but from the viewpoint of developability and reliability, an epoxy (meth) acrylate-based resin having a partial structure represented by the following general formula (b1-I) (hereinafter referred to as “meth) acrylate-based resin”. , "(B1-I) Epoxy (meth) acrylate-based resin”) and / or an epoxy (meth) acrylate-based resin having a partial structure represented by the following general formula (b1-II).
  • (b1-II) epoxy (meth) acrylate-based resin” it may be abbreviated as "(b1-II) epoxy (meth) acrylate-based resin”).
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 represents a divalent hydrocarbon group which may have a substituent
  • k represents 1 or 2
  • * represents. Represents a bond.
  • the benzene ring in the formula (b1-I) may be further substituted with any substituent.
  • 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 represent an integer of 0 to 2
  • * represents a bond.
  • R 11 represents a hydrogen atom or a methyl group
  • R 12 represents a divalent hydrocarbon group which may have a substituent
  • k represents 1 or 2
  • * represents. Represents a bond.
  • the benzene ring in the formula (b1-I) may be further substituted with any substituent.
  • R 12 represents a divalent hydrocarbon group which may have a substituent.
  • a divalent hydrocarbon group a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked is used. Can be mentioned.
  • Examples of the divalent aliphatic group include linear, branched and cyclic aliphatic groups. Among these, a linear aliphatic group is preferable from the viewpoint of development solubility. On the other hand, cyclic aliphatic groups are preferable from the viewpoint of reducing the penetration of the developer into the exposed area.
  • the carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 20 is preferable, 1 to 15 is more preferable, and 1 to 10 is even more preferable.
  • the value By setting the value to the lower limit or more, a strong film is likely to be obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be good.
  • the value By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, 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-pentylene group, an n-hexylene group and an n-heptylene group.
  • a methylene group is preferable from the viewpoint of skeletal rigidity.
  • the divalent branched chain aliphatic group includes the above-mentioned divalent linear aliphatic group, and the side chains include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl.
  • Examples thereof include a structure having a group, an isobutyl group, a sec-butyl group and a tert-butyl group.
  • the number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 12 is preferable, 1 to 10 is more preferable, and 2 to 10 is even more preferable.
  • 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 dicyclopentane ring.
  • a group obtained by dividing two hydrogen atoms from the above can be mentioned. Among these, from the viewpoint of skeletal rigidity, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring, a dicyclopentane ring, and an adamantane ring is preferable.
  • 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; and a carboxy group.
  • unsubstituted is preferable from the viewpoint of easiness of synthesis.
  • divalent aromatic ring group examples 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, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 4 to 20 is preferable, 5 to 15 is more preferable, and 6 to 10 is even more preferable.
  • By setting the value to the lower limit or more a strong film is likely to be obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be good.
  • By setting the value to the upper limit or less it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring.
  • the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have two free atomic valences.
  • Examples include an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
  • the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring.
  • the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having two free atomic valences.
  • Examples of the substituent that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Of these, no substitution is preferable from the viewpoint of development solubility.
  • the above-mentioned divalent aliphatic group is 1 or more, and the above-mentioned divalent aromatic ring group is described. Can be mentioned as a group in which 1 or more are linked.
  • the number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is further preferable, and 2 to 3 is particularly preferable.
  • the number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is further preferable, and 2 to 3 is particularly preferable.
  • the value By setting the value to the lower limit or more, a strong film is likely to be obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be good.
  • the value By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
  • Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked are represented by the following formulas (b1-IA) to (b1-IF). Group is mentioned. Among these, the group represented by the following formula (b1-IA) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobicity of the membrane.
  • k represents 1 or 2. From the viewpoint of adhesion and patterning, k is preferably 1. From the viewpoint of NMP resistance, k is preferably 2.
  • the epoxy (meth) acrylate may contain both a partial structure having a k of 1 and a partial structure having a k of 2.
  • the benzene ring in the formula (b1-I) may be further substituted with any substituent.
  • substituent allowed on the benzene ring in the formula (b1-I) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group.
  • the number of the substituents is not particularly limited and may be one or two or more. From the viewpoint of patterning properties, it is preferable that the benzene ring in the formula (b1-I) is unsubstituted.
  • the partial structure represented by the formula (b1-I) is preferably a partial structure represented by the following formula (b1-I-1) from the viewpoint of simplicity of synthesis.
  • R 11 , R 12 and k are synonymous with those of the above formula ( b1 -I)
  • RX represents a hydrogen atom or a polybasic acid residue
  • * represents a bond. Represent a hand.
  • the benzene ring in the formula (b1-I-1) may be further substituted with any substituent.
  • the polybasic acid residue means a monovalent group obtained by subtracting one OH group from the polybasic acid or its anhydride.
  • the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid and endomethylene.
  • examples thereof include tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid and biphenyltetracarboxylic acid are preferable, and tetrahydro is more preferable.
  • the benzene ring in the formula (b1-I-1) may be further substituted with any substituent.
  • substituent those mentioned for the benzene ring in the formula (b1-I) can be preferably adopted.
  • the partial structure represented by the above formula (b1-I-1) contained in one molecule of the (b1-I) epoxy (meth) acrylate-based resin may be one kind or two or more kinds, for example, RX .
  • a hydrogen atom and a polybasic acid residue of RX may be mixed.
  • the number of partial structures represented by the above formula (b1-I) contained in one molecule of the (b1-I) epoxy (meth) acrylate resin is not particularly limited, but 1 or more is preferable, and 3 or more is preferable. More preferably, 20 or less is preferable, and 15 or less is further preferable. 1 to 20 is preferable, 1 to 15 is more preferable, and 3 to 15 is even more preferable.
  • the polystyrene-equivalent weight average molecular weight (Mw) of the (b1-I) epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more. , 2000 or more is more preferable, 3000 or more is more preferable, 4000 or more is particularly preferable, 5000 or more is most preferable, usually 30,000 or less, 20,000 or less is preferable, and 15,000 or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1000 to 30000 is preferable, 1500 to 2000 is more preferable, 1500 to 15000 is further preferable, and 2000 to 1500 is even more preferable.
  • the value to the lower limit or more the residual film ratio of the photosensitive coloring composition tends to be good. When the value is not more than the upper limit, the solubility in a developing solution tends to be good.
  • the acid value of the (b1-I) epoxy (meth) acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, and 80 mgKOH / g or more. More preferably, 100 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 even more preferable, and 120 mgKOH / g or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • 20 mgKOH / g to 200 mgKOH / g is preferable, 60 mgKOH / g to 150 mgKOH / g is more preferable, 80 mgKOH / g to 130 mgKOH / g is further preferable, and 100 mgKOH / g to 130 mgKOH / g is even more preferable.
  • the value By setting the value to the lower limit or more, the develop solubility tends to be improved and the resolution tends to be good.
  • the value is not more than the upper limit, the residual film ratio of the photosensitive coloring composition tends to be good.
  • 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 represent an integer of 0 to 2
  • * represents a bond.
  • 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 contained in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is further preferable, and 2 to 3 is particularly preferable.
  • the number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less.
  • the above upper and lower limits can be combined arbitrarily.
  • 4 to 40 is preferable, 4 to 30 is more preferable, 6 to 20 is more preferable, and 8 to 15 is particularly preferable.
  • By setting the value to the lower limit or more a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur.
  • By setting the value to the upper limit or less it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
  • 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.
  • the adamantane ring is preferable from the viewpoint of the residual film ratio and the resolution of the photosensitive coloring composition.
  • the number of rings contained in 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, preferably 5 or less, and more preferably 4 or less. ..
  • the above upper and lower limits can be combined arbitrarily.
  • 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 4 is further preferable, 2 to 4 is more preferable, and 3 to 4 is particularly preferable.
  • the aromatic ring group examples 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, still more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, preferably 30 or less. More preferably, 20 or less is further preferable, and 15 or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferable, 6 to 40 is more preferable, 8 to 30 is further preferable, 10 to 20 is more preferable, and 12 to 15 is particularly preferable.
  • the value By setting the value to the lower limit or more, a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur.
  • the value When the value is not more than the upper limit, the patterning characteristics tend to be good.
  • the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. Ring is mentioned. Among these, the 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, but for example, a divalent aliphatic group, a divalent aromatic ring group, 1 or more 2 Examples thereof include a group in which a valent aliphatic group and one or more divalent aromatic ring groups are linked.
  • Examples of the divalent aliphatic group include linear, branched and cyclic aliphatic groups. Among these, a linear aliphatic group is preferable from the viewpoint of development solubility, while a cyclic aliphatic group is preferable from the viewpoint of reducing the penetration of the developer into the exposed portion.
  • the carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, preferably 25 or less, more preferably 20 or less, still more preferably 15 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 25 is preferable, 3 to 20 is more preferable, and 6 to 15 is even more preferable.
  • the value By setting the value to the lower limit or more, a strong film is likely to be obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be good.
  • the value By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
  • Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of skeletal rigidity.
  • Examples of the divalent branched chain aliphatic group include the above-mentioned divalent linear aliphatic group and the side chains of a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group.
  • the number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and even more preferably 3 or less.
  • 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is further preferable, and 2 to 3 is particularly preferable.
  • Examples of the divalent cyclic aliphatic group include a group obtained by removing two hydrogen atoms from the cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. Can be mentioned. Among these, from the viewpoint of skeletal rigidity, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable.
  • 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; and a carboxy group.
  • unsubstituted is preferable from the viewpoint of easiness of synthesis.
  • divalent aromatic ring group examples 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, preferably 30 or less, more preferably 20 or less, still more preferably 15 or less.
  • 4 to 30 is preferable, 5 to 20 is more preferable, and 6 to 15 is even more preferable.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring.
  • the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have two free atomic valences.
  • Examples include an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
  • the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring.
  • the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having two free atomic valences.
  • Examples of the substituent that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Of these, no substitution is preferable from the viewpoint of development solubility.
  • the above-mentioned divalent aliphatic group is 1 or more, and the above-mentioned divalent aromatic ring group is described. Can be mentioned as a group in which 1 or more are linked.
  • the number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is further preferable, and 2 to 3 is particularly preferable.
  • the number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is further preferable, and 2 to 3 is particularly preferable.
  • the value By setting the value to the lower limit or more, a strong film is likely to be obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be good.
  • the value By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
  • Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked are represented by the above formulas (b1-IA) to (b1-IF). Group is mentioned. Among these, the group represented by the above formula (b1-IC) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobicity of the membrane.
  • the bonding mode of the cyclic hydrocarbon group which is a side chain, is not particularly limited with respect to these divalent hydrocarbon groups, but for example, one hydrogen atom of an aliphatic group or an aromatic ring group is cyclic as a side chain.
  • Examples thereof include an embodiment substituted with a hydrocarbon group and an embodiment in which a cyclic hydrocarbon group as a side chain is formed including one of the carbon atoms of the aliphatic group.
  • R 15 and R 16 each independently represent a divalent aliphatic group which may have a substituent.
  • Examples of the divalent aliphatic group include linear, branched and cyclic aliphatic groups. Among these, a linear aliphatic group is preferable from the viewpoint of development solubility, while a cyclic aliphatic group is preferable from the viewpoint of reducing the penetration of the developer into the exposed portion.
  • the carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less. For example, 1 to 20 is preferable, 3 to 15 is more preferable, and 6 to 10 is even more preferable.
  • the value By setting the value to the lower limit or more, a strong film is likely to be obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be good.
  • the value By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, 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-pentylene group, an n-hexylene group and an n-heptylene group.
  • a methylene group is preferable from the viewpoint of skeletal rigidity.
  • the divalent branched chain aliphatic group includes the above-mentioned divalent linear aliphatic group, and the side chains include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl.
  • Examples thereof include a structure having a group, an isobutyl group, a sec-butyl group and a tert-butyl group.
  • the number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. For example, 1 to 12 is preferable, and 2 to 10 is more preferable.
  • Examples of the divalent cyclic aliphatic group include two hydrogen atoms from 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 a dicyclopentadiene ring.
  • the group to be removed is mentioned. Among these, from the viewpoint of skeletal rigidity, a group obtained by removing two hydrogen atoms from the dicyclopentadiene ring and the adamantane ring is preferable.
  • 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; and a carboxy group.
  • unsubstituted is preferable from the viewpoint of easiness of synthesis.
  • m and n each independently represent an integer of 0 to 2.
  • the patterning suitability is improved and surface roughness which occurs during development tends to be less likely to occur, and when it is set to the upper limit value or less, the developability tends to be good.
  • m and n are preferably 0.
  • the partial structure represented by the general formula (b1-II) is preferably a partial structure represented by the following general formula (b1-II-1) from the viewpoint of adhesion to the substrate.
  • R 13 , R 15 , R 16 , m and n are synonymous with formula (b1-II) and R ⁇ is a monovalent which may have a substituent. It represents a cyclic hydrocarbon group, p represents an integer of 1 or more, and * represents a bond.
  • the benzene ring in the formula (b1-II-1) may be further substituted with any substituent.
  • R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings contained in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less.
  • 1 to 6 is preferable
  • 1 to 4 is more preferable
  • 1 to 3 is further preferable
  • 2 to 3 is particularly preferable.
  • the number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less.
  • the above upper and lower limits can be combined arbitrarily.
  • 4 to 40 is preferable, 4 to 30 is more preferable, 6 to 20 is more preferable, and 8 to 15 is particularly preferable.
  • 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.
  • the adamantane ring is preferable from the viewpoint of strong film characteristics.
  • the number of rings contained in 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, preferably 5 or less.
  • the above upper and lower limits can be combined arbitrarily.
  • 1 to 10 is preferable, 1 to 5 is more preferable, 2 to 5 is further preferable, and 3 to 5 is particularly preferable.
  • the value By setting the value to the lower limit or more, a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur. When the value is not more than the upper limit, the patterning characteristics tend to be good.
  • 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, preferably 30 or less, more preferably 20 or less, still more preferably 15 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 4 to 30 is preferable, 5 to 20 is more preferable, and 6 to 15 is even more preferable.
  • 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.
  • the fluorene ring is preferable from the viewpoint of development solubility.
  • Examples of the substituent that the cyclic hydrocarbon group may have include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and an amyl group.
  • Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an isoamyl group; 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; and a carboxy group. Of these, no substitution is preferable from the viewpoint of ease of synthesis.
  • P represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. For example, 1 to 3 is preferable, and 2 to 3 is more preferable.
  • the value is equal to or higher than the lower limit, the degree of film hardening and the residual film ratio tend to be good.
  • the value is not more than the upper limit, the developability tends to be good.
  • R ⁇ is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.
  • the benzene ring in the formula (b1-II-1) may be further substituted with any substituent.
  • substituent allowed on the benzene ring in the formula (b1-II-1) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group.
  • the number of the substituents is not particularly limited and may be one or two or more. From the viewpoint of patterning properties, the benzene ring in the formula (b1-II-1) is preferably unsubstituted.
  • the partial structure represented by the general formula (b1-II) is preferably the partial structure represented by the following general formula (b1-II-2) from the viewpoint of skeletal rigidity and membrane hydrophobicity.
  • R 13 , R 15 , R 16 , m and n are synonymous with formula (b1-II), and R ⁇ is a divalent group which may have a substituent. It represents a cyclic hydrocarbon group, and * represents a bond.
  • the benzene ring in the formula (b1-II-2) may be further substituted with any substituent.
  • R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings contained in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. For example, 1 to 10 is preferable, and 2 to 5 is more preferable.
  • the value By setting the value to the lower limit or more, a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur.
  • the value By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
  • the number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 35 or less, still more preferably 30 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferable, 6 to 35 is more preferable, and 8 to 30 is even more preferable.
  • By setting the value to the lower limit or higher there is a tendency to suppress film roughness during development.
  • By setting the value to the upper limit or less it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
  • 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.
  • the adamantane ring is preferable from the viewpoint of film reduction during development and resolution.
  • the number of rings contained in 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, preferably 5 or less.
  • the above upper and lower limits can be combined arbitrarily.
  • 1 to 10 is preferable, 1 to 5 is more preferable, 2 to 5 is further preferable, and 3 to 5 is particularly preferable.
  • the aromatic ring group examples 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, further preferably 10 or more, preferably 40 or less, more preferably 30 or less, and further preferably 20 or less. It is preferable, and 15 or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferable, 6 to 30 is more preferable, 8 to 20 is more preferable, and 10 to 15 is particularly preferable.
  • the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthren ring, and a fluorene ring.
  • the fluorene ring is preferable from the viewpoint of developability.
  • Examples of the substituent that the cyclic hydrocarbon group may have include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and an amyl group.
  • Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an isoamyl group; 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; and a carboxy group. Of these, no substitution is preferable from the viewpoint of simplicity of synthesis.
  • R ⁇ is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group.
  • R ⁇ is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.
  • the benzene ring in the formula (b1-II-2) may be further substituted with any substituent.
  • substituent allowed on the benzene ring in the formula (b1-II-2) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group.
  • the number of the substituents is not particularly limited and may be one or two or more. Further, two benzene rings may be linked via a substituent.
  • the substituent in this case examples include divalent groups such as -O-, -S-, -NH-, and -CH 2- .
  • the benzene ring in the formula (b1-II-2) is preferably unsubstituted. Further, from the viewpoint of making it difficult for film loss and the like to occur, it is preferable that the benzene ring in the formula (b1-II-2) is substituted with a methyl group.
  • the partial structure represented by the formula (b1-II) is preferably a partial structure represented by the following formula (b1-II-3) from the viewpoint of the coating film residual film ratio and the patterning characteristics.
  • R 13 , R 14 , R 15 , R 16 , m and n are synonymous with formula (b1-II), and R Z represents a hydrogen atom or a polybasic acid residue. ..
  • the polybasic acid residue means a monovalent group obtained by subtracting one OH group from the polybasic acid. Further, another OH group may be removed and shared with R Z in another molecule represented by the formula (b1-II-3), that is, a plurality of formulas (b1) may be shared via R Z. -II-3) may be linked.
  • the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid and endomethylene.
  • Examples thereof include tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid and biphenyltetracarboxylic acid are preferable.
  • the partial structure represented by the formula (b1-II-3) contained in one molecule of the (b1-II) epoxy (meth) acrylate-based resin may be one kind or two or more kinds, for example, R Z is hydrogen. Atomic ones and those having R Z as a polybasic acid residue may be mixed.
  • the number of partial structures represented by the formula (b1-II) contained in one molecule of the (b1-II) epoxy (meth) acrylate resin is not particularly limited, but 1 or more is preferable, and 3 or more is more preferable. Further, 20 or less is preferable, 15 or less is more preferable, and 10 or less is further preferable. For example, 1 to 20 is preferable, 1 to 15 is more preferable, and 3 to 10 is even more preferable.
  • the polystyrene-equivalent weight average molecular weight (Mw) of the (b1-II) epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more. , 2000 or more is more preferable, 3000 or more is more preferable, 4000 or more is particularly preferable, 5000 or more is most preferable, usually 10000 or less, 8000 or less is preferable, and 7000 or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • 1000 to 10000 is preferable, 1500 to 10000 is more preferable, 1500 to 8000 is further preferable, 2000 to 8000 is further preferable, and 2000 to 7000 is particularly preferable.
  • the value By setting the value to the lower limit or more, the residual film ratio of the photosensitive coloring composition tends to be good.
  • the value is not more than the upper limit, the solubility in a developing solution tends to be good.
  • the acid value of the (b1-II) epoxy (meth) acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, and more preferably 80 mgKOH / g or more. More preferably, 100 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 even more preferable, and 120 mgKOH / g or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • 20 mgKOH / g to 200 mgKOH / g is preferable, 60 mgKOH / g to 150 mgKOH / g is more preferable, 80 mgKOH / g to 130 mgKOH / g is further preferable, and 100 mgKOH / g to 130 mgKOH / g is even more preferable.
  • the value By setting the value to the lower limit or more, the develop solubility tends to be improved and the resolution tends to be good.
  • the value is not more than the upper limit, the residual film ratio of the photosensitive coloring composition tends to be good.
  • the carboxy group-containing epoxy (meth) acrylate-based resin one type may be used alone, or two or more types of resins may be mixed and used. A part of the carboxy group-containing epoxy (meth) acrylate resin may be replaced with another binder resin and used. That is, a carboxy group-containing epoxy (meth) acrylate resin and another binder resin may be used in combination.
  • the ratio of the carboxy group-containing epoxy (meth) acrylate-based resin in the alkali-soluble resin is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. It is more preferably 80% by mass or more, and usually 100% by mass or less.
  • (B) As the alkali-soluble resin it is preferable to use (b2) an acrylic copolymer resin from the viewpoint of compatibility with pigments, dispersants and the like, and the acrylic copolymer resin described in Japanese Patent Application Laid-Open No. 2014-137466. Can be preferably used.
  • acrylic copolymer resin examples include an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter referred to as “unsaturated monomer (b2-1)”) and other copolymerizable ethylene. Examples thereof include a copolymer with a sex-unsaturated monomer (hereinafter referred to as “unsaturated monomer (b2-2)"). Examples of the unsaturated monomer (b2-1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, ⁇ -chloracrylic acid, and dermal acid; maleic acid, maleic anhydride, and fumaric acid.
  • unsaturated monomer (b2-1) examples include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, ⁇ -chloracrylic acid, and dermal acid; maleic acid, maleic anhydride, and fumaric acid.
  • Citraconic acid anhydrous citraconic acid, unsaturated dicarboxylic acid such as mesaconic acid or its anhydride
  • mono-succinic acid [2- (meth) acryloyloxyethyl]
  • mono-phthalic acid [2- (meth) acryloyloxyethyl]
  • Ester p-vinylbenzoic acid can be mentioned.
  • These unsaturated monomers (b2-1) can be used alone or in admixture of two or more.
  • Examples of the unsaturated monomer (b2-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; Aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-hydroxystyrene, p-hydroxy- ⁇ -methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;
  • N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide
  • Aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-hydroxystyrene, p-hydroxy- ⁇ -methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;
  • Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 2,6 ] decane-8-ylvinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
  • Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
  • These unsaturated monomers (b2-2) can be used alone or in admixture of two or more.
  • the copolymerization ratio of the unsaturated monomer (b2-1) is preferably 5 to 50% by mass. , More preferably 10 to 40% by mass.
  • Examples of the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) include Japanese Patent Application Laid-Open No. 7-140654 and Japanese Patent Application Laid-Open No. 8-259876.
  • Japanese Patent Application Laid-Open No. 10-313008 Japanese Patent Application Laid-Open No. 10-300922
  • Japanese Patent Application Laid-Open No. 11-174224 Japanese Patent Application Laid-Open No. 11-258415
  • Japanese Patent Application Laid-Open No. 2000-56118 Examples thereof include the copolymer disclosed in Japanese Patent Application Laid-Open No. 2004-101728.
  • the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) can be produced by a known method, and for example, Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2003-222717.
  • the structure, Mw, and Mw / Mn can also be controlled by the methods disclosed in Japanese Patent Laid-Open No. 2006-259680 and International Publication No. 2007/029871.
  • 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.
  • a polymerization accelerator chain transfer agent
  • a sensitizing dye may be added and used.
  • the photopolymerization initiator for example, a metallocene compound containing a titanosen compound described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Laid-Open No.
  • metallocene compound examples include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis (2,3,4,5,6-pentafluorophenyl) and dicyclopenta.
  • hexaarylbiimidazole derivatives examples include 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer and 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 can be mentioned.
  • halomethylated oxadiazole derivatives examples include 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole and 2-trichloromethyl-5-[ ⁇ - (2'-).
  • Benzofuryl) vinyl] -1,3,4-oxadiazole 2-trichloromethyl-5-[ ⁇ - (2'-(6''-benzofuryl) vinyl)]-1,3,4-oxadiazole
  • Examples thereof include 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
  • halomethyl-s-triazine derivatives examples include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and 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 is mentioned.
  • Examples of ⁇ -aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-). Morphorinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-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 can
  • an oxime ester compound is particularly effective in terms of sensitivity and plate-making property.
  • an alkali-soluble resin containing a phenolic hydroxyl group is used, an oxime ester having such excellent sensitivity is particularly effective.
  • Esters are useful. Since the oxime ester compound has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in its structure, it is highly sensitive to a small amount and stable to a thermal reaction. Therefore, it is possible to obtain a highly sensitive photosensitive coloring composition in a small amount.
  • Examples of the oxime ester compound include compounds represented by the following general formula (IV).
  • R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
  • R 21b represents any substituent including an aromatic ring.
  • R 22a indicates an alkanoyl group which may have a substituent or an allyloyl group which may have a substituent.
  • n represents an integer of 0 or 1.
  • the number of carbon atoms of the alkyl group in R 21a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. Is. For example, it is, for example, 1 to 20, preferably 1 to 15, and more preferably 2 to 10.
  • the alkyl group include a methyl group, an ethyl group, a propyl group and a cyclopentylethyl group.
  • alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and 4- (2-methoxy-1-methyl) ethoxy-2-.
  • substituents that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and 4- (2-methoxy-1-methyl) ethoxy-2-.
  • substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and 4- (2-methoxy-1-methyl) ethoxy-2-.
  • substituents that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and 4- (2-methoxy-1
  • Examples of the aromatic ring group in R 21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and further preferably 12 or less. For example, it is 5 to 30, preferably 5 to 20, and more preferably 5 to 12 or less.
  • Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a frill group. Among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable, from the viewpoint of developability.
  • Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group in which these substituents are linked.
  • R 21a is preferably an aromatic ring group which may have a substituent, and further preferably an aromatic ring group having a linked alkoxy group as a substituent. preferable.
  • R 21b examples include a carbazolyl group which may be substituted, a thioxanthonyl group which may be substituted, and a diphenylsulfide group which may be substituted.
  • a carbazolyl group which may be substituted is preferable from the viewpoint of sensitivity.
  • a diphenyl sulfide group which may be substituted is preferable.
  • the carbon number of the alkanoyl group in R 22a is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably, from the viewpoint of solubility in a solvent and sensitivity. It is 10 or less, more preferably 5 or less. For example, it is, for example, 2 to 20, preferably 2 to 15, more preferably 3 to 10, and even more preferably 3 to 5.
  • Examples of the alkanoyl group include an acetyl group, a propanoyl group and a butanoyl group.
  • alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group and an amide group, which are unsubstituted from the viewpoint of ease of synthesis. Is preferable.
  • the carbon number of the allylloyl group in R 22a is not particularly limited, but is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably, from the viewpoint of solubility in a solvent and sensitivity. It is 10 or less. For example, it is 7 to 20, preferably 7 to 15, and more preferably 8 to 10.
  • the allylloyl group include a benzoyl group and a naphthoyl group.
  • the substituent that the allylloyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group and an alkyl group, and from the viewpoint of ease of synthesis, no substitution is preferable.
  • R 22a is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.
  • the initiator described in Japanese Patent Application Laid-Open No. 2016-133574 is also preferably used from the viewpoint of reducing contamination of the liquid crystal layer by the colorant.
  • One type of photopolymerization initiator may be used alone, or two or more types may be used in combination. If necessary, the photopolymerization initiator may be blended with a sensitizing dye and a polymerization accelerator according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity.
  • the sensitizing dye include the xanthene dye 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.
  • sensitizing dyes amino group-containing sensitizing dyes are preferable, and compounds having an amino group and a phenyl group in the same molecule are more preferable.
  • Preferred sensitizing dyes include, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone.
  • polymerization accelerator for example, 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 are used. ..
  • aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate
  • aliphatic amines such as n-butylamine and N-methyldiethanolamine
  • mercapto compounds described later are used. ..
  • the polymerization accelerator may be used alone or in combination of two or more.
  • the photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound.
  • (D) The sensitivity is improved by containing the ethylenically unsaturated compound.
  • the ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specific examples thereof include (meth) acrylic acid, (meth) acrylic acid alkyl esters, acrylonitrile, styrene, carboxylic acids having one ethylenically unsaturated bond, and monoesters of polyvalent or monovalent alcohols.
  • a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule is particularly desirable.
  • the number of ethylenically unsaturated groups contained in the polyfunctional ethylenically monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 5 or more.
  • the number is 8 or less, more preferably 7 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 2 to 8 pieces are preferable, 2 to 7 pieces are more preferable, 4 to 7 pieces are further preferable, and 5 to 7 pieces are particularly preferable. When the value is equal to or higher than the lower limit, the sensitivity tends to be high.
  • polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatics.
  • esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include, for example, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatics.
  • examples thereof include an ester obtained by an esterification reaction between a polyvalent hydroxy compound such as a polyhydroxy compound and 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, trimethylol ethanetriacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate.
  • Pentaerythritol tetraacrylate dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate
  • acrylic acid ester of aliphatic polyhydroxy compounds such as glycerol acrylate, methacrylic acid ester in which these acrylates are replaced with methacrylate, itaconate. Examples thereof include an itaconic acid ester replaced with, a crotonic acid ester replaced with clonate, and a maleic acid ester replaced with maleate.
  • ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid examples include acrylic acid esters and methacrylic acids of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcindiacrylate, resorcindimethacrylate, and pyrogallol triacrylate. Acid esters can be mentioned.
  • the ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single ester, but for example, a condensate of acrylic acid, phthalic acid, and ethylene glycol.
  • a condensate of acrylic acid, phthalic acid, and ethylene glycol examples thereof include condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, and condensates of acrylic acid, adipic acid, butanediol and glycerin.
  • polyfunctional ethylenic monomer used in the present invention for example, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylic acid ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylic acid ester are reacted.
  • urethane (meth) acrylates examples include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U- 10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV- Examples thereof include 7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation).
  • urethane (meth) acrylates obtained by reacting an acrylic acid ester or polyisocyanate compound with a polyol and a hydroxyl group-containing (meth) acrylic acid ester, and it is more preferable to use a (meth) acrylic acid alkyl ester.
  • dipentaerythritol hexaacrylate and it is more preferable to use it.
  • the photosensitive coloring composition of the present invention contains (e) a solvent.
  • a solvent By including (e) a solvent, (a) the colorant can be dispersed or dissolved in the solvent, and application becomes easy.
  • the photosensitive coloring composition of the present invention usually comprises (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and necessary.
  • Various other materials used according to the above are used in a state of being dissolved or dispersed in a solvent.
  • an organic solvent is preferable from the viewpoint of dispersibility and coatability.
  • the organic solvents those having a boiling point of 100 to 300 ° C. are preferably selected, and those having a boiling point of 120 to 280 ° C. are more preferable.
  • the boiling point here means the boiling point at a pressure of 1013.25 hPa, and the following boiling points are all the same.
  • Examples of such an organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-butyl ether.
  • Propropylene 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
  • Glycol monoalkyl ethers such as -3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether;
  • Glycoldialkyl 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;
  • acetone methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methylnonyl ketone, methoxymethylpentanone.
  • Ketones Monohydric 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; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
  • Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; Amilformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Chain or cyclic esters such as butyl, ⁇ -butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropi
  • organic solvents examples include mineral spirit, valsol # 2, apco # 18 solvent, apco thinner, and socal solvent No. 1 and No. 2.
  • Solvento # 150 Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve (“Cellosolve” is a registered trademark; the same shall apply hereinafter), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglime (any of them). Also trade name) can be used.
  • These organic solvents may be used alone or in combination of two or more.
  • an organic solvent having a boiling point of 100 to 240 ° C., more preferably 120 to 200 ° C., and even more preferably 120 ° C. to 170 ° C. ..
  • glycol alkyl ether acetates are preferable because they have a good balance of coatability, surface tension and the like, and the solubility of the constituent components in the composition is relatively high.
  • Glycol alkyl ether acetates may be used alone or in combination with other organic solvents.
  • Glycol monoalkyl ethers are particularly preferable as the organic solvent to be used in combination.
  • Propylene glycol monomethyl ether is preferable because of the solubility of the constituents in the composition.
  • Glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate, and the storage stability of the photosensitive coloring composition obtained later tends to increase and the storage stability tends to decrease.
  • the proportion of glycol monoalkyl ethers in the mixture is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.
  • an organic solvent having a boiling point of 150 ° C. or higher (hereinafter, may be referred to as "high boiling point solvent”) in combination.
  • high boiling point solvent an organic solvent having a boiling point of 150 ° C. or higher
  • the photosensitive coloring composition becomes difficult to dry, but there is an effect of preventing the uniformly dispersed state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the generation of foreign matter defects due to precipitation and solidification of colorants and the like at the tip of the slit nozzle.
  • diethylene glycol mono-n-butyl ether diethylene glycol mono-n-butyl ether acetate
  • diethylene glycol monoethyl ether acetate diethylene glycol monoethyl ether acetate are particularly preferable because of such a high effect.
  • the content ratio 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. preferable.
  • the drying temperature of the composition By setting it to the above lower limit value or more, for example, it tends to be possible to suppress precipitation and solidification of coloring materials and the like at the tip of the slit nozzle to cause foreign matter defects, and by setting it to the above upper limit value or less, the drying temperature of the composition. There is a tendency to suppress the slowdown of the temperature, and to suppress problems such as poor tact in the vacuum drying process and pin marks of prebake.
  • 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, it is not necessary to separately contain a high boiling point solvent having a boiling point of 150 ° C. or higher.
  • various solvents for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6- Hexanol diacetate and triacetin can be mentioned.
  • the photosensitive coloring composition of the present invention contains (f) a dispersant.
  • a dispersant By containing (f) a dispersant, (a) the colorant can be stably dispersed.
  • the (f) dispersant in the photosensitive coloring composition of the present invention is an acrylic copolymer (f1) having a repeating unit represented by the following general formulas (1) to (3) (hereinafter, “dispersant (f1)). It does not have a repeating unit containing a quaternary ammonium group.
  • R 31 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 32 is a hydrogen atom or a methyl group. * Represents a bond.
  • R 33 is a methylene group, an ethylene group or a propylene group
  • R 34 is an alkyl group which may have a substituent
  • R 35 is a hydrogen atom or a methyl group.
  • n is an integer from 1 to 20. * Represents a bond.
  • R 36 and R 37 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. It is an aralkyl group which may be present, and R 36 and R 37 may be bonded to each other to form a cyclic structure.
  • R 38 is a hydrogen atom or a methyl group.
  • Z is a divalent linking group. * Represents a bond.
  • the dispersant (f1) has a repeating unit represented by the following general formula (1) from the viewpoint of increasing compatibility with a solvent or an alkali-soluble resin and improving dispersion stability.
  • R 31 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 32 is a hydrogen atom or a methyl group. * Represents a bond.
  • examples of the alkyl group in R 31 include linear, branched, or cyclic alkyl groups, which are linear from the viewpoint of compatibility with a solvent or an alkali-soluble resin. Is preferable, and it is preferable that the chain is branched from the viewpoint of affinity for the pigment.
  • the number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, preferably 10 or less, more preferably 8 or less, still more preferably 6 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferable, 2 to 8 is more preferable, and 4 to 6 is further preferable.
  • the alkyl group includes 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 an ethylhexyl group, and from the viewpoint of compatibility with a solvent or an alkali-soluble resin, the alkyl group includes.
  • a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
  • the substituent that the alkyl group may have include an alkoxy group such as a methoxy group and an ethoxy group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; and an aryl group such as a phenyl group and a naphthyl group. Therefore, it is preferably unsubstituted from the viewpoint of compatibility with a solvent or an alkali-soluble resin, and preferably a phenyl group from the viewpoint of affinity with a pigment.
  • Examples of the aryl group in R 31 include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.
  • the number of carbon atoms of the aryl group is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, still more preferably 10 or less. By setting the value to the upper limit or less, there is a tendency to increase the affinity for the pigment.
  • Examples of the aryl group include a phenyl group, a naphthyl group and an anthrasenyl group. From the viewpoint of dispersibility, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
  • the substituent that the aryl group may have include an alkyl group such as a methyl group and an ethyl group; an alkoxy group such as a methoxy group and an ethoxy group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; and a phenyl.
  • An aryl group such as a group or a naphthyl group; an aralkyl group such as a benzyl group or a phenethyl group may be mentioned, and an unsubstituted group is preferable from the viewpoint of dispersibility.
  • R 31 is preferably an alkyl group which may have a substituent, and more preferably a methyl group, a butyl group, an ethylhexyl group or a benzyl group.
  • the dispersant (f1) has a repeating unit represented by the following general formula (2) from the viewpoint of compatibility with a solvent or an alkali-soluble resin.
  • R 33 is a methylene group, an ethylene group or a propylene group
  • R 34 is an alkyl group which may have a substituent
  • R 35 is a hydrogen atom or a methyl group.
  • n is an integer from 1 to 20. * Represents a bond.
  • R 33 is a methylene group, an ethylene group, or a propylene group, but an ethylene group is preferable from the viewpoint of compatibility with a solvent or an alkali-soluble resin.
  • R 34 is an alkyl group which may have a substituent, but a methyl group or an ethyl group is preferable from the viewpoint of compatibility with a solvent or an alkali-soluble resin.
  • n is an integer of 1 to 20, but 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, and 5 or less is more preferable.
  • 1 to 10 is preferable, 1 to 5 is more preferable, and 2 to 5 is even more preferable.
  • the dispersant (f1) has a repeating unit represented by the general formula (3). It is preferably used from the viewpoint of surface roughness of the electrode.
  • R 36 and R 37 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. It is an aralkyl group which may be present, and R 36 and R 37 may be bonded to each other to form a cyclic structure.
  • R 38 is a hydrogen atom or a methyl group.
  • Z is a divalent linking group. * Represents a bond.
  • R 36 and R 37 each independently have a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, or a substituent. It is an aralkyl group that may be used.
  • the alkyl group which may have a substituent and the aryl group which may have a substituent those listed as R 31 in the above formula (1) can be preferably adopted.
  • R 36 and R 37 may be combined with each other to form a cyclic structure.
  • the cyclic structure include a nitrogen-containing heterocyclic monocycle having a 5- to 7-membered ring or a fused ring formed by condensing two of them.
  • the nitrogen-containing heterocycle is preferably one that does not have aromaticity, and a saturated ring is more preferable. Specifically, the following can be mentioned.
  • Z is a divalent linking group.
  • the divalent linking group include a single bond, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a -CONH-R 39- group, and a -COOR 40- group (however, R 39 and).
  • R 40 is independently a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group)), and is ⁇ COOR from the viewpoint of dispersibility. 7 -groups are preferred.
  • an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is further preferable, from the viewpoint of the stability of the dispersion with time.
  • the content ratio of the repeating unit represented by the general formula (1) (hereinafter, may be referred to as “repeating unit (1)”) in the dispersant (f1) is not particularly limited, but 20 in all the repeating units. More than mol% is preferable, 30 mol% or more is more preferable, 40 mol% or more is further preferable, 50 mol% or more is further preferable, 60 mol% or more is particularly preferable, and 90 mol% or less is more preferable, 85 mol. % Or less is more preferable, 80 mol% or less is further preferable, and 75 mol% or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • 20 mol% to 90 mol% is preferable, 30 mol% to 90 mol% is more preferable, 40 mol% to 80 mol% is further preferable, 50 mol% to 80 mol% is more preferable, and 60 mol% to 60 mol% is preferable. 80 mol% is particularly preferred.
  • the affinity for the pigment tends to be enhanced.
  • the compatibility with the solvent or the alkali-soluble resin tends to be improved.
  • the content ratio of the repeating unit represented by the general formula (2) (hereinafter, may be referred to as “repeating unit (2)”) in the dispersant (f1) is not particularly limited, but is included in all the repeating units. 1 mol% or more is preferable, 2 mol% or more is more preferable, 2.5 mol% or more is further preferable, 3 mol% or more is particularly preferable, 30 mol% or less is preferable, and 20 mol% or less is more preferable. It is more preferably 15 mol% or less, still more preferably 10 mol% or less, and particularly preferably 8 mol% or less. The above upper and lower limits can be combined arbitrarily.
  • 1 mol% to 30 mol% is preferable, 1 mol% to 20 mol% is more preferable, 1 mol% to 15 mol% is more preferable, 1 mol% to 10 mol% is more preferable, and 2 mol% to 2 mol% to 10 mol% is particularly preferred.
  • the value to the lower limit or higher the compatibility with the solvent or the alkali-soluble resin tends to be improved.
  • the value to the upper limit or less the affinity for the pigment tends to be enhanced.
  • the content ratio of the repeating unit represented by the general formula (3) (hereinafter, may be referred to as “repeating unit (3)”) in the dispersant (f1) is not particularly limited, but is included in all the repeating units. 10 mol% or more is preferable, 20 mol% or more is more preferable, 25 mol% or more is further preferable, 30 mol% or more is particularly preferable, 50 mol% or less is preferable, 45 mol% or less is more preferable, and 40 mol is more preferable. % Or less is more preferable, and 35 mol% or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • 10 mol% to 50 mol% is preferable, 20 mol% to 40 mol% is more preferable, 25 mol% to 35 mol% is further preferable, and 30 mol% to 35 mol% is particularly preferable.
  • the value is equal to or higher than the lower limit, the dispersibility tends to be good.
  • the value is not more than the upper limit, the stability of the dispersion with time tends to be good.
  • the dispersant (f1) may be contained in either a random copolymer or a block copolymer, but from the viewpoint of dispersibility, it is preferably a block copolymer, and the block copolymer is a parent solvent. It is preferable to include an A block containing a repeating unit having a group and a B block containing a repeating unit having a pigment adsorbing group.
  • the dispersant (f1) is preferably contained in the repeating unit (1) and the repeating unit (2) is contained in the A block, and may be contained in any aspect of random copolymerization or block copolymerization. Further, the repeating unit (1) and the repeating unit (2) may each be contained in two or more kinds in the A block, and in that case, each repeating unit is a random copolymerization or a block copolymerization in the A block. It may be contained in any of the above embodiments.
  • Repeating units other than the repeating units (1) and (2) may be contained in the A block, and such repeating units include styrene-based monomers such as styrene and ⁇ -methylstyrene; (meth). (Meta) acrylate-based monomers such as acrylic acid chloride; (meth) acrylamide-based monomers such as (meth) acrylamide and N-methylol acrylamide; vinyl acetate; acrylonitrile; allylglycidyl ether, glycidyl crotonate ether; Repeat units derived from N-methacryloylmorpholine can be mentioned.
  • the block copolymer having the A block having the repeating unit (1) and the repeating unit (2) and the B block having the repeating unit (3) is an AB block copolymer or AB.
  • -A block copolymer is more preferable.
  • the amine value of the dispersant (f1) is not particularly limited, but is preferably 50 mgKOH / g or more, more preferably 80 mgKOH / g or more, further preferably 90 mgKOH / g or more, particularly preferably 100 mgKOH / g or more, and 200 mgKOH / g.
  • the following is preferable, 160 mgKOH / g or less is more preferable, 140 mgKOH / g or less is further preferable, and 130 mgKOH / g or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • 50 mgKOH / g to 200 mgKOH / g is preferable, 80 mgKOH / g to 160 mgKOH / g is more preferable, 100 mgKOH / g to 140 mgKOH / g is further preferable, and 100 mgKOH / g to 130 mgKOH / g is particularly preferable.
  • the value is set to the lower limit or higher, the surface roughness of the electrode tends to be suppressed.
  • the stability of the dispersion with time tends to be improved.
  • the amine value is expressed by the amount of base per 1 g of the solid content of the dispersant (f1) and the mass of equivalent KOH.
  • the acid value of the dispersant (f1) is not particularly limited, but from the viewpoint of dispersibility, it is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, further preferably 1 mgKOH / g, and particularly preferably 0 mgKOH / g.
  • the weight average molecular weight of the dispersant (f1) is not particularly limited, but is preferably 3000 or more, more preferably 5000 or more, further preferably 7,000 or more, preferably 100,000 or less, more preferably 50,000 or less, still more preferably 10,000 or less. ..
  • the above upper and lower limits can be combined arbitrarily. For example, 3000 to 100,000 is preferable, 5000 to 50000 is more preferable, and 7000 to 10000 is even more preferable.
  • the value is equal to or higher than the lower limit, the dispersibility tends to be improved.
  • the stability of the dispersion with time tends to be improved.
  • the content of chlorine atoms in the dispersant (f1) is not particularly limited, but is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, and substantially. It is particularly preferable that it does not contain chlorine atoms, that is, it is 0.1% by mass or less. When the value is not more than the upper limit, surface roughness tends to be suppressed.
  • the method for producing the dispersant (f1) is not particularly limited, and a known method can be adopted.
  • Japanese Patent Application Laid-Open No. 01-299014 Japanese Patent Application Laid-Open No. 2017-019937
  • Japanese Patent Application Laid-Open No. 2018-172530 Japanese Patent Application Laid-Open No. 2018-203795
  • the (f) dispersant in the photosensitive coloring composition of the present invention may contain a dispersant other than the dispersant (f1) (hereinafter, may be referred to as “other dispersants”).
  • dispersants include, for example, a carboxy group as a functional group; or a base thereof; a primary, secondary or tertiary amino group; a quaternary ammonium base; pyridine, pyrimidine, pyrazine and the like from the viewpoint of dispersion stability.
  • Dispersants having a group derived from the nitrogen heterocycle are preferred.
  • a dispersant having a basic functional group for example, a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is more preferable.
  • a polymer dispersant is preferable from the viewpoint that the pigment can be dispersed with a small amount of the dispersant.
  • polymer dispersant examples include an acrylic dispersant other than the dispersant (f1), a urethane dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, and a dispersant consisting of a monomer having an amino group and a macromonomer.
  • an acrylic dispersant other than the dispersant (f1) a urethane dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, and a dispersant consisting of a monomer having an amino group and a macromonomer.
  • Polyoxyethylene alkyl ether dispersant, polyoxyethylene diester dispersant, polyether phosphoric acid dispersant, polyester phosphate dispersant, sorbitan aliphatic ester dispersant, aliphatic modified polyester dispersant be able to.
  • polymer dispersants examples include EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by Big Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei), and the like.
  • SOLPERSE registered trademark, manufactured by Lubrizol
  • KP manufactured by Shinetsu Chemical Industry Co., Ltd.
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • Azisper registered trademark, manufactured by Ajinomoto Co., Ltd.
  • urethane-based and acrylic-based polymer dispersants examples include DISPERBYK 160 to 166, 182 series (all urethane-based), DISPERBYK2000, 2001, BYK-LPN21116 (all acrylic-based) (all manufactured by Big Chemie). ..
  • One type of other dispersant may be used, or two or more types may be used in combination.
  • the photosensitive coloring composition of the present invention includes adhesion improvers such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, cross-linking agents, mercapto compounds, polymerization inhibitors and the like. Additives can be added as appropriate.
  • the photosensitive coloring 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 and a phosphoric acid group-containing compound are preferable.
  • type of silane coupling agent various types such as epoxy type, (meth) acrylic type, and amino type can be used alone or in combination of two or more.
  • silane coupling agent examples include (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • Epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, Examples thereof include isocyanate silanes such as 3-isocyanate propyltriethoxysilane. Silane coupling agents of epoxy silanes are particularly preferred.
  • the phosphoric acid group-containing compound (meth) acryloyl group-containing phosphates are preferable, and those represented by the following general formulas (g1), (g2) or (g3) are preferable.
  • R 51 represents a hydrogen atom or a methyl group
  • m is 1, 2 or 3.
  • These phosphoric acid group-containing compounds may be used alone or in combination of two or more.
  • the photosensitive coloring composition of the present invention may contain a surfactant in order to improve coatability.
  • surfactant for example, various kinds such as anionic type, cationic type, nonionic type and amphoteric surfactant can be used. Of these, nonionic surfactants are preferable because they are less likely to adversely affect various properties, and fluorine-based and silicon-based surfactants are particularly effective in terms of coatability. Examples of such a surfactant include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by Big Chemie), and KP340.
  • anionic type cationic type
  • nonionic type and amphoteric surfactant are preferable because they are less likely to adversely affect various properties
  • fluorine-based and silicon-based surfactants are particularly effective in terms of coatability.
  • examples of such a surfactant include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos),
  • surfactant one type may be used, or two or more types may be used in combination in any combination and ratio.
  • the photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersion aid in order to improve dispersibility and storage stability.
  • Pigment derivatives include, for example, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindoleinone-based, dioxazine-based, anthraquinone-based, indanthrone-based, perylene-based, perinone-based, and diketopyrrolopyrrole.
  • Examples thereof include phthalocyanine-based and dioxazine-based derivatives, and among them, phthalocyanine-based and quinophthalone-based derivatives are preferable.
  • a substituent of the pigment derivative for example, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxy group, an amide group and the like are directly on the pigment skeleton or an alkyl group or aryl. Examples thereof include those bonded via a group, a heterocyclic group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted into one pigment skeleton.
  • pigment derivative examples include phthalocyanine sulfonic acid derivative, quinophthalone sulfonic acid derivative, anthraquinone sulfonic acid derivative, quinacridone sulfonic acid derivative, diketopyrrolopyrrole sulfonic acid derivative, and dioxazine sulfonic acid derivative. These may be used alone or in combination of two or more.
  • Examples of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate and butanediol bis.
  • Thioglycolate ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropio Nate, Pentaerythritol Tetrakissthioglycolate, Trishydroxyethyl Tristhiopropionate, Ethylene Glycolbis (3-Mercaptobutyrate), Butanediolbis (3-Mercaptobutyrate), 1,4-Bis (3-Mercaptobutyrate) Liloxy) butane, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobuty
  • the photosensitive coloring composition of the present invention may contain a polymerization inhibitor from the viewpoint of controlling the shape of the cured product. It is considered that the taper angle (the angle formed by the support and the cured product in the cross section of the cured product) can be controlled because the inclusion of the polymerization inhibitor inhibits the radical polymerization of the lower layer of the coating film.
  • the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, 2,6-di-tert-butyl-4-cresol is preferable from the viewpoint of shape control.
  • hydroquinone monomethyl ether and methylhydroquinone are preferable from the viewpoint of particularly excellent safety to the human body.
  • the polymerization inhibitor can be used alone or in combination of two or more.
  • a polymerization inhibitor may be contained in the resin, which may be used as the polymerization inhibitor of the present invention, or the resin may contain a polymerization inhibitor in addition to the polymerization inhibitor. The same or different polymerization inhibitor may be added at the time of producing the photosensitive coloring composition.
  • the content thereof is not particularly limited, but is usually 0.0005% by mass or more, preferably 0.001% by mass or more, based on the total solid content of the photosensitive coloring composition. , More preferably 0.01% by mass or more, and usually 0.3% by mass or less, preferably 0.2% by mass or less, more preferably 0.1% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.0005% by mass to 0.3% by mass is preferable, 0.001% by mass to 0.2% by mass is more preferable, and 0.01% by mass to 0.1% by mass is further preferable.
  • the content ratio of the (a) colorant in the photosensitive coloring composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more with respect to the total solid content. It is preferable that 20% by mass or more is more preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, 30% by mass or less is further preferable, and 25% by mass or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • 5% by mass to 50% by mass is preferable, 10% by mass to 40% by mass is more preferable, 15% by mass to 40% by mass is further preferable, 15% by mass to 30% by mass is more preferable, and 15% by mass to 15% by mass. 25% by mass is particularly preferable.
  • the value to the lower limit or more there is a tendency that the light blocking effect can be ensured.
  • the value to the upper limit or less the amount of the dispersant can be reduced, and the surface roughness tends to be suppressed.
  • the content ratio of the compound (I) in the photosensitive coloring composition is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 15% by mass, based on the total solid content of the photosensitive coloring composition. It is more preferably mass% or more, particularly preferably 20% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 5% by mass to 70% by mass is preferable, 20% by mass to 70% by mass is more preferable, 20% by mass to 60% by mass is further preferable, and 20% by mass to 50% by mass is particularly preferable.
  • the value to the lower limit or more By setting the value to the lower limit or more, the light-shielding property tends to be improved while suppressing the loss of ultraviolet light required for curing.
  • the value to the upper limit or less By setting the value to the upper limit or less, the amount of the dispersant can be reduced, and the surface roughness tends to be suppressed.
  • the total content ratio thereof is not particularly limited, but (a) the content ratio of the compound (I) in the colorant.
  • 10% by mass or more is preferable, 20% by mass or more is more preferable, 30% by mass or more is further preferable, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 10% by mass to 90% by mass is preferable, 20% by mass to 80% by mass is more preferable, and 30% by mass to 70% by mass is further preferable.
  • the value By setting the value to the lower limit or higher, the light-shielding property is enhanced, and the color tone tends to be close to black.
  • the value By setting the value to the upper limit or less, the residue during development tends to be small, and the reliability at the time of producing the element tends to be good.
  • the total content ratio thereof is not particularly limited, but (a) the content ratio of the compound (I) in the colorant.
  • 10% by mass or more is preferable, 20% by mass or more is more preferable, 30% by mass or more is further preferable, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 10% by mass to 90% by mass is preferable, 20% by mass to 80% by mass is more preferable, and 30% by mass to 70% by mass is further preferable.
  • the value By setting the value to the lower limit or higher, the light-shielding property is enhanced, and the color tone tends to be close to black.
  • the value By setting the value to the upper limit or less, the residue during development tends to be small, and the reliability at the time of producing the element tends to be good.
  • the content ratio thereof is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content of the photosensitive coloring composition. 15% by mass or more is further preferable, 20% by mass or more is particularly preferable, and usually 50% by mass or less, 40% by mass or less is preferable, 30% by mass or less is more preferable, and 25% by mass or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 5% by mass to 70% by mass is preferable, 20% by mass to 70% by mass is more preferable, 20% by mass to 60% by mass is further preferable, and 20% by mass to 50% by mass is particularly preferable.
  • the value is equal to or higher than the lower limit, the light blocking effect tends to be improved. By setting the value to the upper limit or less, the amount of the dispersant can be reduced, and the surface roughness tends to be suppressed.
  • the total content of the red pigment and the orange pigment is not particularly limited, but (a) 5% by mass or more is preferable in the colorant, and 8% by mass is preferable.
  • the above is more preferable, 10% by mass or more is further preferable, 12% by mass or more is particularly preferable, 40% by mass or less is preferable, 30% by mass or less is more preferable, and 20% by mass or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 5% by mass to 40% by mass is preferable, 8% by mass to 40% by mass is more preferable, 10% by mass to 30% by mass is further preferable, and 12% by mass to 20% by mass is particularly preferable.
  • the total content of the blue pigment and the purple pigment is not particularly limited, but (a) 30% by mass or more is preferable in the colorant, and 50% by mass is preferable.
  • the above is more preferable, 70% by mass or more is further preferable, 80% by mass or more is particularly preferable, 95% by mass or less is preferable, 92% by mass or less is more preferable, and 90% by mass or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 30% by mass to 95% by mass is preferable, 50% by mass to 95% by mass is more preferable, 70% by mass to 92% by mass is further preferable, and 80% by mass to 90% by mass is particularly preferable.
  • the content ratio of the red pigment and / or the orange pigment is the content of the blue pigment and / or the purple pigment.
  • 1% by mass or more is preferable, 3% by mass or more is more preferable, 5% by mass or more is further preferable, 8% by mass or more is particularly preferable, and 300% by mass or less is particularly preferable. More preferably, it is more preferably mass% or less, and particularly preferably 50% by mass or less.
  • the above upper and lower limits can be combined arbitrarily.
  • 1% by mass to 300% by mass is preferable, 3% by mass to 100% by mass is more preferable, 5% by mass to 100% by mass is further preferable, and 8% by mass to 50% by mass is particularly preferable.
  • the value to the lower limit or more the transmission of blue light tends to be suppressed and the light-shielding property tends to be improved.
  • the value to the upper limit or less the color tone tends to be close to black.
  • the content ratio thereof is not particularly limited, but is preferably 3% by mass or more, more preferably 5% by mass or more, and 10% by mass, based on the total solid content of the photosensitive coloring composition. More preferably, it is more preferably mass% or more, 20% by mass or more, particularly preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 3% by mass to 60% by mass is preferable, 5% by mass to 60% by mass is more preferable, 10% by mass to 50% by mass is further preferable, and 20% by mass to 40% by mass is particularly preferable.
  • the value is equal to or higher than the lower limit, the light blocking effect tends to be improved.
  • the amount of the dispersant can be reduced to the upper limit or less, and the surface roughness tends to be suppressed.
  • the photosensitive coloring composition contains carbon black as an inorganic black pigment
  • the content thereof is not particularly limited, but it is preferably 1% by mass or more, more preferably 3% by mass or more, based on the total solid content of the photosensitive coloring composition. It is preferable, 5% by mass or more is further preferable, 30% by mass or less is preferable, 20% by mass or less is more preferable, and 10% by mass or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1% by mass to 30% by mass is preferable, 3% by mass to 20% by mass is more preferable, and 3% by mass to 10% by mass is further preferable.
  • the value is equal to or higher than the lower limit, the light blocking effect tends to be improved. By setting the value to the upper limit or less, there is a tendency that a cured product having high resistance and low dielectric constant can be formed.
  • the total content thereof is not particularly limited, but (a) the content ratio of the black pigment in the colorant is preferably 10% by mass or more, preferably 20% by mass. % Or more is more preferable, 30% by mass or more is further preferable, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 10% by mass to 90% by mass is preferable, 20% by mass to 80% by mass is more preferable, and 30% by mass to 70% by mass is further preferable.
  • the value By setting the value to the lower limit or higher, the light-shielding property is enhanced, and the color tone tends to be close to black.
  • the value By setting the value to the upper limit or less, the residue during development tends to be small, and the reliability at the time of producing the element tends to be good.
  • the content ratio of the alkali-soluble resin is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, based on the total solid content of the photosensitive coloring composition of the present invention. More preferably 30% by mass or more, particularly preferably 40% by mass or more, usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, still more. It is preferably 55% by mass or less.
  • the above upper and lower limits can be combined arbitrarily.
  • 5% by mass to 80% by mass is preferable, 10% by mass to 70% by mass is more preferable, 20% by mass to 60% by mass is further preferable, 30% by mass to 60% by mass is further preferable, and 30% by mass to 30% by mass. 55% by mass is particularly preferable, and 40% by mass to 55% by mass is particularly preferable.
  • the content ratio of the epoxy (meth) acrylate-based resin is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 10% by mass or more, based on the total solid content of the photosensitive coloring composition of the present invention. It is 15% by mass or more, more preferably 20% by mass or more, further 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. It is 60% by mass or less, particularly preferably 55% by mass or less. The above upper and lower limits can be combined arbitrarily.
  • 5% by mass to 80% by mass is preferable, 10% by mass to 70% by mass is more preferable, 20% by mass to 60% by mass is further preferable, 30% by mass to 60% by mass is further preferable, and 30% by mass to 30% by mass. 55% by mass is particularly preferable, and 40% by mass to 55% by mass is particularly preferable.
  • the content of the (b1) epoxy (meth) acrylate-based resin contained in the (b) alkali-soluble resin is not particularly limited, but is usually 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more. It is usually 100% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 20% by mass to 90% by mass is preferable, 30% by mass to 80% by mass is more preferable, and 40% by mass to 80% by mass is further preferable.
  • By setting the value to the lower limit or more there is a tendency that the solubility of the unexposed portion in the developing solution can be ensured.
  • By setting the value to the upper limit or less it tends to be possible to maintain appropriate sensitivity, suppress dissolution of the exposed portion by the developing solution, and suppress deterioration of pattern sharpness and adhesion.
  • the content ratio of the photopolymerization initiator is not particularly limited, but is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably, with respect to the total solid content of the photosensitive coloring composition of the present invention. Is 1% by mass or more, more preferably 2% by mass or more, still more 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, still more preferably 6. It is less than mass%.
  • the above upper and lower limits can be combined arbitrarily.
  • 0.1% by mass to 15% by mass is preferable, 0.5% by mass to 15% by mass is more preferable, 1% by mass to 10% by mass is further preferable, and 2% by mass to 8% by mass is further preferable. 3% by mass to 6% by mass is particularly preferable.
  • the content ratio of the polymerization accelerator is not particularly limited, but is preferably 0.05% by mass or more with respect to the total solid content of the photosensitive coloring composition of the present invention. , Usually 10% by mass or less, preferably 5% by mass or less. Further, it is preferable to use the polymerization accelerator in a ratio of usually 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass with respect to 100 parts by mass of the (c) photopolymerization initiator. By setting the content ratio of the polymerization accelerator to the lower limit value or more, there is a tendency that the decrease in sensitivity to the exposed light can be suppressed.
  • the content ratio thereof is not particularly limited, but from the viewpoint of sensitivity, it is usually 20% by mass or less, preferably 15 by mass or less, based on the total solid content in the photosensitive coloring composition. It is mass% or less, more preferably 10 mass% or less.
  • the content of the ethylenically unsaturated compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass, based on the total solid content of the photosensitive coloring composition of the present invention. % Or more, more preferably 15% by mass or more, and usually 30% by mass or less, preferably 25% by mass or less, and more preferably 20% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1% by mass to 30% by mass is preferable, 5% by mass to 20% by mass is more preferable, and 10% by mass to 20% by mass is further preferable.
  • the value By setting the value to the lower limit or more, it tends to be possible to maintain appropriate sensitivity, suppress dissolution of the exposed portion by the developing solution, and suppress deterioration of pattern sharpness and adhesion.
  • the value By setting the value to the upper limit or less, it tends to prevent the developer from increasing the permeability to the exposed portion, and it tends to be easy to obtain a good image.
  • the content ratio of the total solid content is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more.
  • the liquid is adjusted so as to be preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the liquid is preferably adjusted to be 5% by mass to 50% by mass, more preferably 10% by mass to 30% by mass, and further preferably 15% by mass to 25% by mass.
  • the content ratio of the dispersant is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and more preferably 3% by mass or more, based on the total solid content of the photosensitive coloring composition. Usually, 20% by mass or less, 15% by mass or less is preferable, 10% by mass or less is more preferable, and 7% by mass or less is further preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1% by mass to 20% by mass is preferable, 2% by mass to 15% by mass is more preferable, 3% by mass to 10% by mass is further preferable, and 3% by mass to 7% by mass is particularly preferable.
  • the content ratio of the dispersant (f1) is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and more preferably 3% by mass or more, based on the total solid content of the photosensitive coloring composition. Usually, 20% by mass or less, 15% by mass or less is preferable, 10% by mass or less is more preferable, and 7% by mass or less is further preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1% by mass to 20% by mass is preferable, 2% by mass to 15% by mass is more preferable, 3% by mass to 10% by mass is further preferable, and 3% by mass to 7% by mass is particularly preferable.
  • the content ratio of the dispersant (f1) is not particularly limited, but (f) is usually 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, and further preferably 80% by mass or more in the dispersant. It is preferable, and usually it is 100% by mass or less. By setting the value to the lower limit or higher, the surface roughness of the electrode surface tends to be suppressed.
  • the content ratio of the (f) dispersant to 100 parts by mass of the colorant is not particularly limited, but is usually 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and usually 50 parts by mass or less. In particular, it is preferably 30 parts by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 5 parts by mass to 50 parts by mass is preferable, 10 parts by mass to 50 parts by mass is more preferable, and 15 parts by mass to 30 parts by mass is further preferable.
  • By setting the value to the lower limit or more it tends to be easy to obtain sufficient dispersibility.
  • the value to the upper limit or less the surface roughness of the electrode surface tends to be suppressed.
  • the content ratio of (b) alkali-soluble resin to 100 parts by mass of (d) ethylenically unsaturated compound is not particularly limited, but is usually preferably 100 parts by mass or more, 200 parts by mass or more, more preferably 250 parts by mass or more, and 300 parts by mass. More than parts are more preferable, 350 parts by mass or more are particularly preferable, and usually 700 parts by mass or less, 500 parts by mass or less are preferable, 450 parts by mass or less are more preferable, and 400 parts by mass or less are further preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • 100 parts by mass to 700 parts by mass is preferable, 200 parts by mass to 700 parts by mass is more preferable, 250 parts by mass to 500 parts by mass is further preferable, 250 parts by mass to 450 parts by mass is more preferable, and 250 parts by mass to 250 parts by mass. 400 parts by mass is particularly preferable.
  • the value to the lower limit or more there is a tendency that an appropriate dissolution and development state without peeling or the like is obtained.
  • the value to the upper limit or less it tends to be possible to obtain an appropriate dissolution time for the developing solution.
  • the adhesion improver When the adhesion improver is used, its content is not particularly limited, but it is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0.2 to 3% by mass, based on the total solid content of the photosensitive coloring composition. It is 0.4 to 2% by mass.
  • the value By setting the value to the lower limit or more, there is a tendency that the effect of improving the adhesion can be sufficiently obtained.
  • the value to the upper limit or less By setting the value to the upper limit or less, there is a tendency that the sensitivity is lowered and that the residue remains after development and becomes a defect.
  • a surfactant When a surfactant is used, its content is not particularly limited, but it is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.001 to 1% by mass, based on the total solid content of the photosensitive coloring composition. It is 0.01 to 0.5% by mass, most preferably 0.03 to 0.3% by mass.
  • the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less with respect to the total solid content of the photosensitive coloring composition.
  • the partition wall is prepared by performing a heat treatment as described later to cure the photosensitive coloring composition. At that time, surface roughness may occur on the electrode surface. Surface roughness can be observed with an optical microscope, and the surface roughness is also high. When the surface of the electrode is roughened, the light emitting layer cannot be uniformly formed on the portion thereof, which may cause display failure due to a short circuit or the like when an organic electroluminescent element is manufactured.
  • chlorine atoms in the photosensitive coloring composition decompose, volatilize, or sublimate during heat treatment, especially during firing, and act on metal electrodes such as silver, causing corrosion or etching.
  • metal electrodes such as silver, causing corrosion or etching.
  • Chlorine atoms in the photosensitive coloring composition are mainly contained in constituent materials such as (a) a colorant, (b) an alkali-soluble resin, and (f) a dispersant, but may also be contained in other materials. be.
  • constituent materials such as (a) a colorant, (b) an alkali-soluble resin, and (f) a dispersant, but may also be contained in other materials.
  • the chlorine content of one constituent material may be reduced, or the chlorine content of each material may be reduced to enter the specified numerical range. It may be designed as follows.
  • the content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is 0.05% by mass or less, preferably 0.04% by mass or less, and 0, based on the total solid content of the photosensitive coloring composition. 3.03% by mass or less is more preferable, and 0.01% by mass or less is further preferable. By setting the value to the upper limit or less, the surface roughness of the electrode tends to be suppressed.
  • the content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is usually 0.0005% by mass or more, preferably 0.001% by mass or more, and more preferably 0.002% by mass. By setting the value to the lower limit or more, it is effective in that purification can be relaxed during the production of each constituent material.
  • the above upper and lower limits can be combined arbitrarily.
  • 0.0005 to 0.05% by mass is preferable, 0.0005 to 0.04% by mass is more preferable, 0.001 to 0.03% by mass is further preferable, and 0.002 to 0.01% by mass is more preferable.
  • 0.0005 to 0.05% by mass is preferable, 0.0005 to 0.04% by mass is more preferable, 0.001 to 0.03% by mass is further preferable, and 0.002 to 0.01% by mass is more preferable.
  • 0.001 to 0.03% by mass is further preferable
  • 0.002 to 0.01% by mass is more preferable.
  • Especially preferable Especially preferable.
  • the content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is preferably 100 ⁇ g / g or less, more preferably 80 ⁇ g / g or less, based on the total mass of the photosensitive coloring composition including the solvent. 50 ⁇ g / g or less is further preferable, 30 ⁇ g / g or less is further preferable, and 10 ⁇ g / g or less is particularly preferable. By setting the value to the upper limit or less, the surface roughness of the electrode tends to be suppressed from being good.
  • the content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is usually 0.5 ⁇ g / g or more, preferably 1.0 ⁇ g / g or more, and more preferably 2.0 ⁇ g / g or more.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.5 to 100 ⁇ g / g is preferable, 0.5 to 80 ⁇ g / g is more preferable, 1.0 to 50 ⁇ g / g is further preferable, 1.0 to 30 ⁇ g / g is more preferable, and 2.0 to 20 to 10 ⁇ g / g is particularly preferable.
  • the content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is preferably 0.20% by mass or less, preferably 0.20% by mass or less, based on 100% by mass of the (a) colorant content of the photosensitive coloring composition. It is more preferably .15% by mass or less, further preferably 0.10% by mass or less, further preferably 0.05% by mass or less, and particularly preferably 0.03% by mass or less. By setting the value to the upper limit or less, the surface roughness of the electrode tends to be suppressed.
  • the content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is usually 0.001% by mass or more, preferably 0.005% by mass or more, and more preferably 0.010% by mass.
  • the value By setting the value to the lower limit or higher, it is effective in that purification can be relaxed during the production of each constituent material.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.001 to 0.20% by mass is preferable, 0.001 to 0.15% by mass is more preferable, and 0. 005 to 0.10% by mass is further preferable, 0.005 to 0.05% by mass is further preferable, and 0.010 to 0.03% by mass is particularly preferable.
  • the content of chlorine atoms in the photosensitive coloring composition can be measured by, for example, a combustion ion chromatograph method (Combustion ion chromatography).
  • the optical density (OD) per 1 ⁇ m of the film thickness of the coating film is not particularly limited in the first aspect, but is preferably 0.5 or more.
  • it is 0.5 or more.
  • 0.7 or more is more preferable, 1.0 or more is further preferable, 1.3 or more is more preferable, 1.5 or more is particularly preferable, usually 4.0 or less, 3.0 or less is preferable, and 2. 0 or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • 0.5 to 4.0 is preferable
  • 0.7 to 4.0 is more preferable
  • 1.0 to 3.0 is further preferable, and 1.
  • 3 to 3.0 is more preferable, and 1.5 to 2.0 is particularly preferable.
  • the value By setting the value to the lower limit or higher, sufficient light-shielding property tends to be obtained.
  • the value is not more than the upper limit, the surface roughness of the electrode tends to be good.
  • the optical density (OD) per 1 ⁇ m of the film thickness of the coating film may be measured by using a coating film obtained by curing the photosensitive coloring composition of the present invention, and using a coating film heat-cured at 230 ° C. for 20 minutes. Can be measured.
  • the optical density means a transmission optical density in which the spectral sensitivity characteristic of the light receiving portion is indicated by ISO visual density in the ISO 5-3 standard.
  • the light source the A light source specified by the CIE (Commission Internationale de l'Eclairage) is used.
  • X-Rite 361T (V) manufactured by Sakata Inx Corporation can be mentioned.
  • the photosensitive coloring composition of the present invention is produced according to a conventional method.
  • the colorant is preferably dispersed 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 (a) colorant is made into fine particles 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, (e) a solvent, and (f) a dispersant, and (b) a part or all of an alkali-soluble resin are used in combination (hereinafter, dispersion).
  • the mixture to be subjected to the treatment and the composition obtained by the dispersion treatment may be referred to as "pigment dispersion liquid").
  • a polymer dispersant as the dispersant (f) because the thickening of the obtained pigment dispersion and the photosensitive coloring composition over time is suppressed, that is, the dispersion stability is excellent.
  • a pigment dispersion liquid containing at least (a) a colorant, (e) a solvent, and (f) a dispersant.
  • a colorant, (e) solvent, and (f) dispersant that can be used in the pigment dispersion those described as being usable in the photosensitive coloring composition are preferably used.
  • the content ratio of each colorant of (a) the colorant in the pigment dispersion liquid those described as the content ratio in the photosensitive coloring composition can be preferably adopted.
  • the highly reactive components may be denatured due to the heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
  • a liquid containing all the components to be blended in the photosensitive coloring composition is subjected to the dispersion treatment, the highly reactive components may be denatured due to the heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
  • the colorant is dispersed by a sand grinder, glass beads or zirconia beads having a particle size of about 0.1 to 8 mm are preferably used.
  • the dispersion treatment conditions are such that the temperature is usually 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C.
  • the dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment device, etc., and is appropriately adjusted.
  • the guideline for dispersion is to control the gloss of the pigment dispersion so that the 20-degree mirror gloss (JIS Z8741) of the photosensitive coloring composition is in the range of 50 to 300.
  • the glossiness of the photosensitive coloring composition is low, the dispersion treatment is not sufficient and rough pigment (coloring material) particles often remain, resulting in insufficient developability, adhesion, resolution and the like. there is a possibility.
  • the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.
  • the dispersed particle size of the pigment dispersed in the pigment dispersion is usually 0.03 to 0.3 ⁇ m, and can be measured by a dynamic light scattering method.
  • the pigment dispersion obtained by the dispersion treatment and the other components contained in the photosensitive coloring composition are mixed to obtain a uniform solution or dispersion.
  • fine dust may be mixed in the liquid, so that it is desirable to filter the obtained photosensitive coloring composition with a filter or the like.
  • the cured product of the present invention By curing the photosensitive coloring composition of the present invention, the cured product of the present invention can be obtained.
  • the cured product obtained by curing the photosensitive coloring composition of the present invention can be suitably used as a partition wall.
  • the photosensitive coloring 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 electroluminescent device.
  • the organic layer used for the organic electroluminescent device include a hole injection layer, a hole transport layer, or a hole transport layer on a hole injection layer as described in Japanese Patent Application Laid-Open No. 2016-165396. Examples include the organic layer used.
  • the material of the support for forming the partition wall is not particularly limited as long as it has an appropriate strength.
  • Substrates are mainly used, but as materials, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethylmethacrylate and polysulphon, and epoxy resins.
  • Thermo-curable resin sheets such as unsaturated polyester resin and poly (meth) acrylic resin, and various types of glass. Among them, glass and heat-resistant resin are preferable from the viewpoint of heat resistance.
  • a transparent electrode such as ITO or IZO or a metal electrode such as silver, gold, platinum, aluminum or magnesium may be formed on the surface of the substrate.
  • a transparent electrode such as ITO or IZO or a metal electrode such as silver, gold, platinum, aluminum or magnesium may be formed on the surface of the substrate.
  • it can also be formed on a TFT array.
  • the support may be subjected to, for example, corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agent and urethane resin, if necessary, in order to improve surface physical properties such as adhesiveness. ..
  • the thickness of the substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm.
  • the film thickness is usually in the range of 0.01 to 10 ⁇ m, preferably 0.05 to 5 ⁇ m.
  • photosensitive partition wall The photosensitive coloring composition of the present invention is used for the same purposes as the known photosensitive coloring composition for color filters, but hereinafter, when used as a partition wall, the photosensitive coloring composition of the present invention is used. A specific example of a method for forming a partition wall using a composition will be described.
  • the photosensitive coloring composition is supplied in the form of a film or a pattern on a substrate on which a partition wall should be provided by a method such as coating, and the solvent is dried. Subsequently, pattern formation is performed by a method such as a photolithography method that performs exposure-development. After that, a partition wall is formed on the substrate by performing additional exposure and thermosetting treatment as necessary.
  • the photosensitive coloring composition of the present invention is usually supplied onto a substrate in a state of being dissolved or dispersed in a solvent.
  • a conventionally known method for example, a spinner method, a wire bar method, a flow coat method, a die coat method, a roll coat method, or a spray coat method can be used. Further, for example, it may be supplied in a pattern by an inkjet method or a printing method.
  • the die coating method the amount of the coating liquid used is significantly reduced, and there is no influence of mist or the like adhering when the spin coating method is used, and the generation of foreign substances is suppressed. Preferred from the point of view.
  • the coating amount varies depending on the application, but in the case of a partition wall, for example, the dry film thickness is usually 0.5 ⁇ m to 10 ⁇ m, preferably 1 ⁇ m to 9 ⁇ m, and particularly preferably 1 ⁇ m to 7 ⁇ m. It is important that the dry film thickness or the height of the finally formed bulkhead is uniform over the entire substrate. By reducing the variation, the light emitting layer can be uniformly created, and display defects during light emission can be suppressed.
  • the photosensitive coloring composition of the present invention When used to collectively form partition walls having different heights by a photolithography method, the heights of the finally formed partition walls are different.
  • the substrate a known substrate such as a glass substrate or an array substrate can be used. It is preferable that the surface of the substrate is flat.
  • Drying after supplying the photosensitive coloring composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven.
  • a vacuum drying method may be combined in which drying is performed in a vacuum chamber without increasing the temperature.
  • the drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer used, and the like.
  • the drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 ° C. to 130 ° C., preferably 50 ° C. to 110 ° C., depending on the type of solvent component, the performance of the dryer used, and the like.
  • the temperature is selected in the range of 30 seconds to 3 minutes.
  • Exposure is performed by superimposing a negative mask pattern on a coating film of a photosensitive coloring composition and irradiating a light source of ultraviolet rays or visible light through the mask pattern.
  • the exposure mask may be placed close to the coating film of the photosensitive coloring composition, or the exposure mask may be placed away from the coating film of the photosensitive coloring composition. It may also be a method of projecting the exposure light through. A scanning exposure method using a laser beam that does not use a mask pattern may be used.
  • the photopolymerizable layer may be performed in a deoxidizing atmosphere, or it may be exposed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. May be good.
  • a light-shielding portion (light transmittance 0%) and a plurality of openings having the highest average light transmittance.
  • An exposure mask having an opening (intermediate transmittance opening) having a small average light transmittance with respect to the portion (completely transmitted opening) is used.
  • the difference in the average light transmittance between the intermediate transmission opening and the complete transmission opening that is, the difference in the exposure amount causes a difference in the residual film ratio.
  • a method is known in which the intermediate transmission opening is created by, for example, a matrix-like light-shielding pattern having a minute polygonal light-shielding unit.
  • an absorber for example, a method of controlling the light transmittance by a film of a chromium-based, molybdenum-based, tungsten-based, or silicon-based material is known.
  • the light source used for the above exposure is not particularly limited.
  • the light source include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, etc.
  • lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, etc.
  • laser light sources such as an excima laser, a nitrogen laser, a helium cadmium laser, a blue-violet semiconductor laser, and a near-infrared semiconductor laser.
  • An optical filter can also be used when irradiating light of a specific wavelength for use.
  • the optical filter may be, for example, a type that can control the light transmittance at the exposure wavelength with a thin film, and the material in that case is, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.). , MoSi, Si, W, Al.
  • the exposure amount is not particularly limited, but is usually 1 mJ / cm 2 or more, preferably 5 mJ / cm 2 or more, more preferably 10 mJ / cm 2 or more, and usually 300 mJ / cm 2 or less, preferably 200 mJ / cm 2 . Below, it is more preferably 150 mJ / cm 2 or less.
  • the distance between the exposure target and the mask pattern is not particularly limited, but is usually 10 ⁇ m or more, preferably 50 ⁇ m or more, more preferably 75 ⁇ m or more, and usually 500 ⁇ m or less, preferably 400 ⁇ m or less. It is more preferably 300 ⁇ m or less.
  • an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent.
  • the aqueous solution of the alkaline compound may further contain, for example, a surfactant, an organic solvent, a buffer, a complexing agent, a dye or a pigment.
  • alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and 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, Organic alkaline compounds such as mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline. Can be mentioned. These alkaline compounds may be a mixture of two or more kinds.
  • surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; alkylbenzene sulfonic acids.
  • Anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; and amphoteric surfactants such as alkyl betaines and amino acids.
  • organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Two or more of these organic solvents may be used in combination. Further, the organic solvent may be used alone or in combination with water or an aqueous solution of an alkaline compound.
  • the conditions of the development treatment are not particularly limited, and the development temperature is usually 10 to 50 ° C, preferably 15 to 45 ° C, and more preferably 20 to 40 ° C.
  • the developing method can be, for example, a dipping developing method, a spray developing method, a brush developing method, or an ultrasonic developing method.
  • thermosetting treatment also referred to as firing
  • the thermosetting treatment conditions are such that the temperature is preferably 100 ° C. to 280 ° C., more preferably 150 ° C. to 250 ° C., and the time is 5 minutes to 60 minutes.
  • the size, shape, and the like when the photosensitive coloring composition of the present invention is used as a partition wall are appropriately adjusted according to the specifications of the organic electroluminescent element to which the photosensitive coloring composition is applied, but are formed from the photosensitive coloring composition of the present invention.
  • the height of the partition wall is usually about 0.5 to 10 ⁇ m.
  • the optical density (OD) per 1 ⁇ m as the partition wall of the present invention is preferably 0.7 or more, more preferably 1.2 or more, still more preferably 1.5 or more, and 1.8 or more, from the viewpoint of light-shielding property.
  • the above is particularly preferable. Further, it is preferably 4.0 or less, and more preferably 3.0 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.7 to 4.0 is preferable, 1.2 to 4.0 is more preferable, 1.5 to 3.0 is further preferable, and 1.8 to 3.0 is particularly preferable.
  • the optical density (OD) is a value measured by a method described later.
  • the organic electroluminescent device of the present invention comprises a cured product of the present invention, for example, a partition wall.
  • various organic electroluminescent devices are manufactured using a substrate having a partition wall pattern manufactured by the above method.
  • the method for forming the organic electroluminescent device is not particularly limited, but preferably, after forming the pattern of the partition wall on the substrate by the above-mentioned method, the functional material is sublimated in a vacuum state and the region surrounded by the partition wall on the substrate.
  • An organic electroluminescent device is manufactured by forming an organic layer such as a pixel by a wet process such as a vapor deposition method of adhering to the inside to form a film, a casting method, a spin coating method, or an inkjet printing method.
  • a wet process such as a vapor deposition method of adhering to the inside to form a film, a casting method, a spin coating method, or an inkjet printing method.
  • Examples of the type of the organic electroluminescent element include a bottom emission type and a top emission type.
  • a partition wall is formed on a glass substrate on which transparent electrodes are laminated, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the partition wall.
  • a partition wall is formed on a glass substrate on which a metal electrode layer is laminated as a reflection layer, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are formed in an opening surrounded by the partition wall. Is created by stacking.
  • Examples of the light emitting layer include an organic electroluminescent layer as described in Japanese Patent Application Laid-Open No. 2009-146691 and Japanese Patent No. 5734681. Further, quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.
  • each layer of the hole transport layer and the electron transport layer may have a laminated structure consisting of two or more layers from the viewpoint of luminous efficiency.
  • the thickness of each layer is not particularly limited, but is usually 1 to 500 nm from the viewpoint of luminous efficiency and brightness.
  • the organic electroluminescent element may be formed by separating each RGB color for each opening, or two or more colors may be laminated in one opening.
  • the organic electroluminescent device may be provided with a sealing layer from the viewpoint of improving reliability.
  • the sealing layer has a function of preventing moisture in the air from adsorbing to the organic electroluminescent element and lowering the luminous efficiency.
  • the organic electroluminescent device may be provided with a low reflection film at the interface with air from the viewpoint of improving the light extraction efficiency. By arranging the low-reflection film at the interface between the air and the element, it can be expected that the gap in the refractive index is reduced and the reflection at the interface is suppressed. For such a low-reflection film, for example, a technique of a moth-eye structure or a super-multilayer film can be applied.
  • an organic electroluminescent element When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent the light of the light emitting layer of one pixel from leaking to another pixel, and further, when the electrode or the like is made of metal, it is outside. Since it is necessary to prevent deterioration of image quality due to light reflection, it is preferable to impart light-shielding property to the partition wall constituting the organic electroluminescent element. Further, in the organic electroluminescent device, since it is necessary to provide electrodes on the upper surface and the lower surface of the partition wall, it is preferable that the partition wall has high resistance and low dielectric constant from the viewpoint of insulating property. Therefore, when a colorant is used to impart light-shielding properties to the partition wall, it is preferable to use the organic pigment having high resistance and low dielectric constant.
  • Examples of the image display device of the present invention include an organic EL display device having a partition wall containing the cured product of the present invention and the organic electroluminescent element of the present invention.
  • the organic EL display device is not particularly limited in terms of the model and structure of the image display device as long as it includes the above-mentioned organic electroluminescent element.
  • the organic EL display device can be assembled according to a conventional method using an active drive type organic electroluminescent element. can.
  • it can be formed by the method described in "Organic EL Display” (Ohmsha, published on August 20, 2004, by Shizushi Tokito, Chihaya Adachi, Hideyuki Murata).
  • an organic electroluminescent element that emits white light and a color filter may be combined to display an image, or an organic electroluminescent element having a different emission color such as RGB may be combined to display an image.
  • the organic electroluminescent device containing the cured product of the present invention can be used for lighting. There are no particular restrictions on the type and structure of the lighting, and it can be assembled according to a conventional method using the organic electroluminescent device containing the cured product of the present invention.
  • the organic electroluminescent device may be a simple matrix drive system or an active matrix drive system. In order for the illumination to emit white light, an organic electroluminescent device that emits white light may be used. Further, organic electroluminescent elements having different emission colors may be combined so that the colors are mixed to be white, or the color mixing ratio may be adjusted to provide a toning function.
  • the weight average molecular weight Mw of the alkali-soluble resin-I thus obtained measured by GPC was 2600, and the acid value was 106 mgKOH / g.
  • a methacrylic AB diblock copolymer comprising an A block containing a repeating unit having a parent solvent group and a B block containing a repeating unit having a pigment adsorbing group. It has a repeating unit of the following formulas (a) to (f).
  • the amine value is 120 mgKOH / g.
  • the weight average molecular weight is 9000.
  • the dispersant contains substantially no chlorine atom.
  • the content ratios of the repeating units of the following formulas (a) to (f) in all the repeating units are (a) 33.3 mol%, (b) 13.3 mol%, and (c) 6.7 mol%, respectively.
  • (D) is 6.7 mol%
  • (e) is 6.7 mol%
  • (f) is 33.3 mol%.
  • a methacrylic AB diblock copolymer comprising an A block containing a repeating unit having a parent solvent group and a B block containing a repeating unit having a pigment adsorbing group. It has a repeating unit of the following formulas (h) to (n).
  • the amine value is 70 mgKOH / g.
  • the weight average molecular weight before quaternizing the amino group is 9000.
  • the content of chlorine atoms in the dispersant is 2.1% by mass.
  • the content ratios of the repeating units of the following formulas (h) to (n) in all the repeating units are (h) 33.3 mol%, (i) 13.3 mol%, (j) 6.7 mol%, respectively.
  • (K) is 6.7 mol%
  • (l) is 6.7 mol%
  • (m) is 24.0 mol%
  • (n) is 9.3 mol%.
  • the optical density per unit film thickness was measured by the following procedure. First, the prepared photosensitive coloring composition is applied to a glass substrate with a spin coater so that the film thickness after firing is 1.5 ⁇ m, dried under reduced pressure for 1 minute, and then dried on a hot plate at 100 ° C. for 120 seconds. It was dry. The obtained coating film was exposed without using an exposure mask. As the irradiation light source, a high-pressure mercury lamp having an intensity of 40 mW / cm 2 at a wavelength of 365 nm was used, and the exposure amount was 50 mJ / cm 2 .
  • the resist-coated substrate 1 was obtained by heating and curing at 230 ° C. for 30 minutes.
  • the optical density (OD value) of the obtained resist coated substrate 1 is measured by a 361T (V) transmission densitometer manufactured by X-Rite (color temperature of an illumination light source: about 2850K (equivalent to CIE standard light source A), spectral sensitivity of a light receiving portion).
  • Each photosensitive coloring composition was applied to an electrode substrate on which a silver thin film having a thickness of 60 nm was vapor-deposited on the entire surface of the glass substrate with a spin coater so that the thickness after firing was 1.5 ⁇ m. After drying under reduced pressure for 1 minute, it was dried on a hot plate at 100 ° C. for 120 seconds. Next, using a photomask capable of forming a square aperture pattern with a side of 50 ⁇ m on the obtained coating film substrate, a wavelength of 330 nm or less was cut with a high-pressure mercury lamp, and an exposure gap of 5 ⁇ m was 50 mJ / cm 2 . UV exposure was performed.
  • the light intensity at a wavelength of 365 nm was 40 mW / cm 2 .
  • TMAH tetramethylammonium hydroxide
  • shower development at 25 ° C. and a developer water pressure of 0.05 MPa was performed for 60 seconds, and then the developing solution was poured with pure water. Development was stopped and washed with a washing spray for 60 seconds.
  • the opening portion was developed and removed to obtain an electrode substrate having a patterned partition wall.
  • the substrate on which the pattern was formed was heated (baked) at 230 ° C. for 30 minutes in an oven to cure the pattern.
  • the obtained electrode substrate on which the 50 ⁇ m aperture pattern was formed was observed with an optical microscope at a magnification of 200, and the presence or absence of a shape change (surface roughness) of the electrode surface in the aperture pattern was confirmed.
  • the surface roughness is good in the order of A, B, and C, indicating that A is the best.
  • C After heat curing, unevenness is visible on the electrode surface and surface roughness is generated, which is practically problematic and unacceptable.
  • Each photosensitive coloring composition is obtained by depositing an indium tin oxide (ITO) transparent conductive film to a thickness of 70 nm on glass and forming an anode on a substrate using ordinary photolithography technology and hydrochloric acid etching.
  • ITO indium tin oxide
  • a wavelength of 330 nm or less was cut by using an exposure mask (a rectangular covering portion (length 40 ⁇ m ⁇ width 80 ⁇ m) having a plurality of pieces at a pitch of 60 ⁇ m in length and 100 ⁇ m in width) on the obtained coating film substrate.
  • Ultraviolet exposure of 50 mJ / cm 2 was performed with a high-pressure mercury lamp with an exposure gap of 5 ⁇ m. At this time, the light intensity at a wavelength of 365 nm was 40 mW / cm 2 . Subsequently, using a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution as a developing solution, shower development at 25 ° C. and a developer water pressure of 0.05 MPa was performed for 60 to 120 seconds, and then the developing solution was prepared with pure water. The development was stopped by flushing, and the mixture was washed with a washing spray for 60 seconds.
  • TMAH tetramethylammonium hydroxide
  • the shower development time was set to 1.2 times or more the time for dissolving and removing the unexposed portion of the coating film. By these operations, the opening portion was developed and removed to obtain an electrode substrate having a patterned partition wall.
  • the substrate on which the pattern was formed was heated (baked) at 230 ° C. for 30 minutes in an oven to cure the pattern.
  • molybdenum oxide was applied as a hole injection layer with a thickness of 10 nm, and N- ([1,1'-biphenyl] -4-yl) -9,9 as a hole transport layer.
  • N- ([1,1'-biphenyl] -4-yl) -9,9 as a hole transport layer.
  • An organic electroluminescent element was prepared by sequentially laminating 8-hydroxyquinolinolato-lithium as an electron injection layer having a film thickness of 60 nm and aluminum as a cathode having a film thickness of 80 nm by a vacuum vapor deposition method. Next, a desiccant was attached to the recess of the sealing glass having a recess in the center, and the UV curable resin was applied to the frame portion around the recess. The concave portion of the sealing glass is arranged so as to cover all the organic electroluminescent elements on the electrode substrate, the sealing glass is attached to the electrode substrate, the UV curable resin is irradiated with UV and cured, and the hollow structure is sealed. A device for evaluating an organic electroluminescent element was manufactured.
  • Examples 1 and 2 Comparative Example 1
  • Add each component so that the solid content ratio of each component in the total solid content is as shown in Table 2, and further add PGMEA / MB / MBA 72/20/8, and the content ratio of the total solid content is A solvent was added so as to be 17% by mass, and the mixture was stirred and dissolved to prepare the photosensitive coloring compositions of Examples 1 and 2 and Comparative Example 1.
  • Tables 2 and 3 show the chlorine atom content measured by the above method, the unit OD value, and the evaluation results of the surface roughness of the electrode.
  • the substrate using the photosensitive coloring composition of Comparative Example 1 had irregularities on the silver (electrode) surface and was rough. Since the amount of chlorine atom contained in the dispersant-II is large, it is also contained in a large amount in the photosensitive coloring composition, and chlorine-containing gas is generated at the time of firing and reacts with the silver (electrode) surface to be on the surface. It is probable that unevenness was formed. On the other hand, in the substrate using the photosensitive coloring composition of Example 1, it was not observed that the surface of silver (electrode) was uneven.
  • Example 1 has a longer life than Comparative Example 1. It is considered that this is because the amount of chlorine is small and the deterioration of the light emitting element with time is suppressed.
  • Example 2 Even in the substrate using the photosensitive coloring composition of Example 2, the unevenness of the silver (electrode) surface was at a level where there was virtually no problem. The reason why the silver (electrode) surface roughness was better in Example 1 than in Example 2 is that even a small amount of chlorine atoms are released to the outside of the film because the pigment-I has a rigid skeleton consisting of an aromatic ring. It is probable that it was not.
  • Example 2 In the light emitting characteristics of the organic electroluminescent device, the initial drive voltage of Example 2 was low, which was good. It was also better than Example 1.

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Abstract

Provided is a photosensitive coloring composition that causes little roughness of the surface of an electrode following a heat treatment. This photosensitive coloring composition is characterized: by containing (a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent and (f) a dispersing agent; in that the coloring agent (a) contains a compound represented by a specific general formula (I), a geometric isomer of the compound, a salt of the compound or a salt of a geometric isomer of the compound; in that the dispersing agent (f) contains an acrylic copolymer (f1) which contains repeating units represented by specific general formulae (1), (2) and (3) and does not contain a repeating unit having a quaternary ammonium group; and in that the content of chlorine atoms in the photosensitive coloring composition is 0.05 mass% or less relative to the total solids content in the photosensitive coloring composition.

Description

感光性着色組成物、硬化物、有機電界発光素子及び画像表示装置Photosensitive coloring composition, cured product, organic electroluminescent device and image display device
　本発明は、感光性着色組成物、硬化物、有機電界発光素子及び画像表示装置に関する。
　本願は、２０２０年９月２８日に日本に出願された特願２０２０－１６２４６０号、及び２０２１年２月１８日に日本に出願された特願２０２１－０２４４９０号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a photosensitive coloring composition, a cured product, an organic electroluminescent device, and an image display device.
This application claims priority under Japanese Patent Application No. 2020-162460 filed in Japan on September 28, 2020 and Japanese Patent Application No. 2021-204490 filed in Japan on February 18, 2021. Incorporate the content here.
　液晶ディスプレイ（ＬＣＤ）は液晶への電圧のオン・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。ＬＣＤのセルを構成する各部材は、フォトリソグラフィー法に代表される、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く、大画面用の基板に対しての処理もし易いといった理由から、さらにその適用範囲は広がっている。 The liquid crystal display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by turning the voltage on and off the liquid crystal. Each member constituting the cell of the LCD is often formed by a method using a photosensitive composition represented by a photolithography method. The range of application of this photosensitive composition is further expanded because it is easy to form a fine structure and it is easy to process a substrate for a large screen.
　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。 An image display device including an organic electroluminescent element (also referred to as organic electroluminescence or organic EL) has excellent visibility and responsiveness such as contrast and viewing angle, and is low in power consumption, thin and lightweight, and a display body. It is attracting attention as a next-generation flat panel display (FPD) because it can be made flexible.
The organic electroluminescent device has a structure in which an organic layer including a light emitting layer or various functional layers is sandwiched between a pair of electrodes having at least one translucent property. 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 device has been manufactured by forming a partition wall (bank) on a substrate and then laminating a light emitting layer or various functional layers in a region surrounded by the partition wall.
　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 adhered to a substrate to form a film is mainly applied.
Further, in recent years, a method of forming a film by a wet process such as a casting method, a spin coating method, and an inkjet printing method has attracted attention. In particular, the inkjet printing method can reduce film thickness unevenness when a large area is used, and can improve the definition of the display by painting separately at the time of coating, reduce the amount of material used, and improve the yield. Since it is possible, it is suitable as a method for forming an organic layer in a large panel.
　隔壁を容易に形成する方法としては、感光性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。また、隔壁に遮光性を付与し画素間の光漏れを抑制する方法として、感光性組成物中に着色剤を含有させる方法が知られている。 As a method for easily forming a partition wall, a method of forming by a photolithography method using a photosensitive composition is known. Further, as a method of imparting a light-shielding property to a partition wall and suppressing light leakage between pixels, a method of incorporating a colorant in a photosensitive composition is known.
　特許文献１には、特定の有機黒色顔料とアルカリ可溶性樹脂を用いることにより、アウトガスの発生を抑制する着色感光性樹脂組成物について記載されている。 Patent Document 1 describes a colored photosensitive resin composition that suppresses the generation of outgas by using a specific organic black pigment and an alkali-soluble resin.
国際公開第２０１８／１０１３１４号International Publication No. 2018/101314
　有機電界発光素子においてはトップエミッション型とボトムエミッション型のパネル形態がある。トップエミッションの場合、電極として銀などの反射電極を用いてその上に隔壁等の硬化物を作成するが、加熱処理時に感光性組成物中の成分が作用して、金属電極の腐食あるいはマイグレーション等を引き起こすことがある。電極表面に凹凸が生じた（以降、表面荒れ、とも表記する）場合には、その部分に均一に発光層を形成することができず、有機電界発光素子を作成したときに、短絡等による表示不良を引き起こす可能性がある。 There are top emission type and bottom emission type panel forms for organic electroluminescent devices. In the case of top emission, a reflective electrode such as silver is used as an electrode to form a cured product such as a partition wall on it, but the components in the photosensitive composition act during the heat treatment to corrode or migrate the metal electrode. May cause. If the surface of the electrode is uneven (hereinafter, also referred to as surface roughness), it is not possible to form a light emitting layer uniformly on that part, and when an organic electroluminescent element is created, it is displayed due to a short circuit or the like. May cause defects.
　本発明者らが検討したところ、特許文献１に記載の着色感光性樹脂組成物では、電極の表面荒れが発生し、実用上問題があることが見出された。 As a result of examination by the present inventors, it was found that the colored photosensitive resin composition described in Patent Document 1 causes surface roughness of the electrode, which causes a practical problem.
　本発明は、上記事情に鑑みてなされたものであり、加熱処理後に電極の表面荒れを生じることの少ない感光性着色組成物を提供し、表示不良のない、信頼性の高い有機発光素子、画像表示装置を提供することを目的とする。 The present invention has been made in view of the above circumstances, and provides a photosensitive coloring composition that does not cause surface roughness of an electrode after heat treatment, and provides a highly reliable organic light emitting device and an image without display defects. It is an object of the present invention to provide a display device.
　本発明者が鋭意検討を行った結果、特定の分散剤と着色剤を用いることで、上記課題を解決しうることを見出し、本発明を完成するに至った。
　即ち本発明の要旨は以下のとおりである。 As a result of diligent studies by the present inventor, it has been found that the above problems can be solved by using a specific dispersant and a colorant, and the present invention has been completed.
That is, the gist of the present invention is as follows.
［１］　（ａ）着色剤、（ｂ）アルカリ可溶性樹脂、（ｃ）光重合開始剤、（ｄ）エチレン性不飽和化合物、（ｅ）溶剤、及び（ｆ）分散剤を含有する感光性着色組成物であって、
　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より選ばれる少なくとも１種を含有し、
　前記（ｆ）分散剤が、少なくとも下記一般式（１）、（２）及び（３）で表される繰り返し単位を含有し、４級アンモニウム基を含む繰り返し単位を有しないアクリル共重合体（ｆ１）を含有し、
　かつ、感光性着色組成物中の塩素原子の含有量が、感光性着色組成物の全固形分量に対して０．０５質量％以下であることを特徴とする感光性着色組成物。 [1] Photosensitive coloring containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. It ’s a composition,
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. Contains,
The acrylic copolymer (f1) in which the dispersant (f) contains at least the repeating units represented by the following general formulas (1), (2) and (3) and does not have the repeating unit containing the quaternary ammonium group. ) Containing,
Moreover, the photosensitive coloring composition is characterized in that the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less with respect to the total solid content of the photosensitive coloring composition.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
（式（Ｉ）中、Ｒ１及びＲ６は互いに独立して水素原子、ＣＨ３、ＣＦ３、フッ素原子又は塩素原子である；
　Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ７、Ｒ８、Ｒ９及びＲ１０は他の全てから互いに独立して水素原子、ハロゲン原子、Ｒ１１、ＣＯＯＨ、ＣＯＯＲ１１、ＣＯＯ－、ＣＯＮＨ２、ＣＯＮＨＲ１１、ＣＯＮＲ１１Ｒ１２、ＣＮ、ＯＨ、ＯＲ１１、ＣＯＣＲ１１、ＯＯＣＮＨ２、ＯＯＣＮＨＲ１１、ＯＯＣＮＲ１１Ｒ１２、ＮＯ２、ＮＨ２、ＮＨＲ１１、ＮＲ１１Ｒ１２、ＮＨＣＯＲ１２、ＮＲ１１ＣＯＲ１２、Ｎ＝ＣＨ２、Ｎ＝ＣＨＲ１１、Ｎ＝ＣＲ１１Ｒ１２、ＳＨ、ＳＲ１１、ＳＯＲ１１、ＳＯ２Ｒ１１、ＳＯ３Ｒ１１、ＳＯ３Ｈ、ＳＯ３ －、ＳＯ２ＮＨ２、ＳＯ２ＮＨＲ１１又はＳＯ２ＮＲ１１Ｒ１２である；
　Ｒ２とＲ３、Ｒ３とＲ４、Ｒ４とＲ５、Ｒ７とＲ８、Ｒ８とＲ９、及びＲ９とＲ１０からなる群から選ばれる少なくとも１つの組み合わせは、互いに直接結合し、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することもできる；
　Ｒ１１及びＲ１２は互いに独立して、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のアルキニル基である。） (In formula (I), R 1 and R 6 are independent hydrogen atoms, CH 3 , CF 3 , fluorine atoms or chlorine atoms;
R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 and R 10 are independent of each other from hydrogen atom, halogen atom, R 11 , COOH, COOR 11 , COO- , CONH. 2 , CONHR 11 , CONR 11 R 12 , CN, OH, OR 11 , COCR 11 , OOCNH 2 , OOCNHR 11 , OOCNR 11 R 12 , NO 2 , NH 2 , NHR 11 , NR 11 R 12 , NHCOR 12 , NR 11 COR 12 , N = CH 2 , N = CHR 11 , N = CR 11 R 12 , SH, SR 11 , SOR 11 , SO 2 R 11 , SO 3 R 11 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR 11 or SO 2 NR 11 R 12 ;
At least one combination selected from the group consisting of R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 7 and R 8 , R 8 and R 9 , and R 9 and R 10 is direct to each other. They can also be bonded or bonded to each other by oxygen, sulfur, NH or NR 11 bridges;
R 11 and R 12 are independent of each other, 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 carbon. It is an alkynyl group of the number 2-12. )
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　（式（１）中、Ｒ３１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る。
　Ｒ３２は水素原子又はメチル基である。
　＊は結合手を表す。） (In the formula (1), R 31 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 32 is a hydrogen atom or a methyl group.
* Represents a bond. )
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　（式（２）中、Ｒ３３はメチレン基、エチレン基又はプロピレン基であり、Ｒ３４は置換基を有していてもよいアルキル基であり、Ｒ３５は水素原子又はメチル基である。
　ｎは１～２０の整数である。
　＊は結合手を表す。） (In the formula (2), R 33 is a methylene group, an ethylene group or a propylene group, R 34 is an alkyl group which may have a substituent, and R 35 is a hydrogen atom or a methyl group.
n is an integer from 1 to 20.
* Represents a bond. )
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　（式（３）中、Ｒ３６及びＲ３７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、Ｒ３６及びＲ３７が互いに結合して環状構造を形成してもよい。
　Ｒ３８は水素原子又はメチル基である。
　Ｚは２価の連結基である。
　＊は結合手を表す。）
［２］　前記（ａ）着色剤が、有機着色顔料を含む、［１］に記載の感光性着色組成物。
［３］　（ａ）着色剤、（ｂ）アルカリ可溶性樹脂、（ｃ）光重合開始剤、（ｄ）エチレン性不飽和化合物、（ｅ）溶剤、及び（ｆ）分散剤を含有する感光性着色組成物であって、
　硬化した塗膜の膜厚１μｍあたりの光学濃度が０．５以上であり、
　前記（ｆ）分散剤が、少なくとも下記一般式（１）、（２）及び（３）で表される繰り返し単位を含有し、４級アンモニウム基を含む繰り返し単位を有しないアクリル共重合体（ｆ１）を含有し、
　かつ、感光性着色組成物中の塩素原子の含有量が、感光性着色組成物の全固形分量に対して０．０５質量％以下であることを特徴とする感光性着色組成物。 (In the formula (3), R 36 and R 37 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. It is an aralkyl group which may be present, and R 36 and R 37 may be bonded to each other to form a cyclic structure.
R 38 is a hydrogen atom or a methyl group.
Z is a divalent linking group.
* Represents a bond. )
[2] The photosensitive coloring composition according to [1], wherein the (a) colorant contains an organic coloring pigment.
[3] Photosensitive coloring containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. It ’s a composition,
The optical density per 1 μm of the cured coating film is 0.5 or more.
The acrylic copolymer (f1) in which the dispersant (f) contains at least the repeating units represented by the following general formulas (1), (2) and (3) and does not have the repeating unit containing the quaternary ammonium group. ) Containing,
Moreover, the photosensitive coloring composition is characterized in that the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less with respect to the total solid content of the photosensitive coloring composition.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　（式（１）中、Ｒ３１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る。
　Ｒ３２は水素原子又はメチル基である。
　＊は結合手を表す。） (In the formula (1), R 31 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 32 is a hydrogen atom or a methyl group.
* Represents a bond. )
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　（式（２）中、Ｒ３３はメチレン基、エチレン基又はプロピレン基であり、Ｒ３４は置換基を有していてもよいアルキル基であり、Ｒ３５は水素原子又はメチル基である。
　ｎは１～２０の整数である。
　＊は結合手を表す。） (In the formula (2), R 33 is a methylene group, an ethylene group or a propylene group, R 34 is an alkyl group which may have a substituent, and R 35 is a hydrogen atom or a methyl group.
n is an integer from 1 to 20.
* Represents a bond. )
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　（式（３）中、Ｒ３６及びＲ３７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、Ｒ３６及びＲ３７が互いに結合して環状構造を形成してもよい。
　Ｒ３８は水素原子又はメチル基である。
　Ｚは２価の連結基である。
　＊は結合手を表す。）
［４］　前記（ａ）着色剤が、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種を含む、［３］に記載の感光性着色組成物。
［５］　前記アクリル共重合体（ｆ１）がブロック共重合体である、［１］～［４］のいずれかに記載の感光性着色組成物。
［６］　前記アクリル共重合体（ｆ１）のアミン価が、９０ｍｇＫＯＨ／ｇ以上である、［１］～［５］のいずれかに記載の感光性着色組成物。
［７］　前記（ａ）着色剤が、感光性着色組成物の全固形分量に対して１０質量％以上含む、［１］～［６］のいずれかに記載の感光性着色組成物。
［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］のいずれかに記載の感光性着色組成物。
［９］　［１］～［８］のいずれかに記載の感光性着色組成物を硬化させた硬化物。
［１０］　［９］に記載の硬化物を含む有機電界発光素子。
［１１］　［１０］に記載の有機電界発光素子を含む画像表示装置。 (In the formula (3), R 36 and R 37 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. It is an aralkyl group which may be present, and R 36 and R 37 may be bonded to each other to form a cyclic structure.
R 38 is a hydrogen atom or a methyl group.
Z is a divalent linking group.
* Represents a bond. )
[4] The colorant according to [3], wherein the (a) colorant contains 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. Photosensitive coloring composition.
[5] The photosensitive coloring composition according to any one of [1] to [4], wherein the acrylic copolymer (f1) is a block copolymer.
[6] The photosensitive coloring composition according to any one of [1] to [5], wherein the acrylic copolymer (f1) has an amine value of 90 mgKOH / g or more.
[7] The photosensitive coloring composition according to any one of [1] to [6], wherein the (a) colorant contains 10% by mass or more with respect to the total solid content of the photosensitive coloring composition.
[8] The photosensitive coloring composition according to any one of [1] to [7], which is used for forming a partition wall of an organic electroluminescent device.
[9] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [8].
[10] An organic electroluminescent device containing the cured product according to [9].
[11] An image display device including the organic electroluminescent element according to [10].
　本発明によれば、加熱処理後に電極に表面荒れを生じることの少ない感光性着色組成物を提供することができる。 According to the present invention, it is possible to provide a photosensitive coloring composition that does not cause surface roughness on the electrode after heat treatment.
　以下、本発明の実施の形態を具体的に説明するが、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々に変更して実施することができる。
　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」を意味し、「（メタ）アクリレート」、「（メタ）アクリロイル」についても同様である。 Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
In the present invention, "(meth) acrylic" means "acrylic and / or methacrylic", and the same applies to "(meth) acrylate" and "(meth) acryloyl".
　「（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、「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「アクリル系樹脂」とは、（メタ）アクリル酸を含む（共）重合体、カルボキシ基を有する（メタ）アクリル酸エステルを含む（共）重合体を意味する。 The "(co) polymer" means that both a monopolymer (homopolymer) and a copolymer (copolymer) are contained, and "acid (anhydrous)" and "(anhydrous) ... acid" are used. , Means to contain both acids and their anhydrides.
In the present invention, the "acrylic resin" means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylic acid ester having a carboxy group.
　本発明において「モノマー」とは、いわゆる高分子物質（ポリマー）に相対する用語であり、狭義の単量体（モノマー）の他に、二量体、三量体、オリゴマーも含む意味である。
　本発明において「全固形分量」とは、感光性着色組成物中又は顔料分散液中に含まれる、溶剤以外の全成分量を意味する。溶剤以外の成分が常温で液体であっても、その成分は溶剤には含めず、全固形分量に含める。
　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）を意味する。
　本発明において、「アミン価」とは、特に断りのない限り、有効固形分換算のアミン価を表し、分散剤の固形分１ｇあたりの塩基量と当量のＫＯＨの質量で表される値である。なお、測定方法については後述する。「酸価」とは、特に断りのない限り、有効固形分換算の酸価を表し、中和滴定により算出される。 In the present invention, the term "monomer" is a term relative to a so-called polymer substance (polymer), and means that a dimer, a trimer, and an oligomer are included in addition to a monomer (monomer) in a narrow sense.
In the present invention, the "total solid content" means the total amount of components other than the solvent contained in the photosensitive coloring composition or the pigment dispersion liquid. Even if the components other than the solvent are liquid at room temperature, the components are not included in the solvent and are included in the total solid content.
In the present invention, the "weight average molecular weight" means the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
In the present invention, the "amine value" represents an amine value in terms of effective solid content, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the equivalent mass of KOH, unless otherwise specified. .. The measurement method will be described later. Unless otherwise specified, the "acid value" represents the acid value in terms of effective solid content and is calculated by neutralization titration.
　顔料に関し、「Ｃ．Ｉ．」とはカラーインデックスを意味する。 Regarding pigments, "CI" means a color index.
　本明細書において、「質量」で表される百分率や部は「重量」で表される百分率や部と同義である。 In the present specification, the percentage or part represented by "mass" is synonymous with the percentage or part represented by "weight".
［感光性着色組成物］
　本発明の感光性着色組成物は、
（ａ）着色剤
（ｂ）アルカリ可溶性樹脂
（ｃ）光重合開始剤
（ｄ）エチレン性不飽和化合物
（ｅ）溶剤
（ｆ）分散剤
を必須成分として含有する。
　第一の態様として、（ａ）着色剤として、一般式（Ｉ）で表される化合物、一般式（Ｉ）で表される化合物の幾何異性体、一般式（Ｉ）で表される化合物の塩、又は一般式（Ｉ）で表される化合物の幾何異性体の塩をからなる群から選ばれる少なくとも１種を含有する。
　第二の態様として、本発明の感光性着色組成物を硬化した塗膜の膜厚１μｍあたりの光学濃度が０．５以上である。
　また必要に応じて、さらにシランカップリング剤等の密着向上剤、界面活性剤、顔料誘導体、光酸発生剤、架橋剤、メルカプト化合物、重合禁止剤等のその他の配合成分を含むものであり、通常、各配合成分が、溶剤に溶解又は分散した状態で使用される。 [Photosensitive coloring composition]
The photosensitive coloring composition of the present invention is
(A) Colorant (b) Alkali-soluble resin (c) Photopolymerization initiator (d) Ethylene unsaturated compound (e) Solvent (f) Dispersant is contained as an essential component.
As a first aspect, (a) as a colorant, a compound represented by the general formula (I), a geometric isomer of the compound represented by the general formula (I), and a compound represented by the general formula (I). It contains at least one selected from the group consisting of a salt or a salt of a geometric isomer of a compound represented by the general formula (I).
As a second aspect, the optical density per 1 μm of the film thickness of the coating film obtained by curing the photosensitive coloring composition of the present invention is 0.5 or more.
Further, if necessary, it further contains other compounding components such as an adhesion improver such as a silane coupling agent, a surfactant, a pigment derivative, a photoacid generator, a cross-linking agent, a mercapto compound, and a polymerization inhibitor. Usually, each compounding component is used in a state of being dissolved or dispersed in a solvent.
＜（ａ）着色剤＞
　本発明の感光性着色組成物は、（ａ）着色剤を含有する。（ａ）着色剤を含有することで、適度な光吸収性、特に隔壁等の遮光部材を形成する用途に用いる場合には適度な遮光性を得ることができる。
　第一の態様において、（ａ）着色剤として、一般式（Ｉ）で表される化合物、一般式（Ｉ）で表される化合物の幾何異性体、一般式（Ｉ）で表される化合物の塩、及び一般式（Ｉ）で表される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。
　一般式（Ｉ）で表される化合物（以下、「化合物（Ｉ）」ともいう。）は、有機黒色顔料である。芳香環を有する剛直な骨格を有することで、加熱処理時に発生した塩素を含有するガスが塗膜中を浸透しにくいと推定される。また紫外線の透過率が高いため塗布された感光性組成物が光硬化しやすくなり、これらの点で有用である。 <(A) Colorant>
The photosensitive coloring composition of the present invention contains (a) a colorant. (A) By containing a colorant, it is possible to obtain an appropriate light absorption property, particularly an appropriate light shielding property when used for forming a light shielding member such as a partition wall.
In the first aspect, as the colorant (a), the compound represented by the general formula (I), the geometric isomer of the compound represented by the general formula (I), and the compound represented by the general formula (I). It contains at least one selected from the group consisting of salts and salts of geometric isomers of compounds represented by the general formula (I).
The compound represented by the general formula (I) (hereinafter, also referred to as “compound (I)”) is an organic black pigment. It is presumed that the chlorine-containing gas generated during the heat treatment does not easily permeate into the coating film due to having a rigid skeleton having an aromatic ring. Further, since the transmittance of ultraviolet rays is high, the applied photosensitive composition is easily photocured, which is useful in these respects.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　式（Ｉ）中、Ｒ１１及びＲ１６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；
　Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１７、Ｒ１８、Ｒ１９及びＲ２０は各々独立に、水素原子、ハロゲン原子、Ｒ２１、ＣＯＯＨ、ＣＯＯＲ２１、ＣＯＯ－、ＣＯＮＨ２、ＣＯＮＨＲ２１、ＣＯＮＲ２１Ｒ２２、ＣＮ、ＯＨ、ＯＲ２１、ＣＯＣＲ２１、ＯＯＣＮＨ２、ＯＯＣＮＨＲ２１、ＯＯＣＮＲ２１Ｒ２２、ＮＯ２、ＮＨ２、ＮＨＲ２１、ＮＲ２１Ｒ２２、ＮＨＣＯＲ２２、ＮＲ２１ＣＯＲ２２、Ｎ＝ＣＨ２、Ｎ＝ＣＨＲ２１、Ｎ＝ＣＲ２１Ｒ２２、ＳＨ、ＳＲ２１、ＳＯＲ２１、ＳＯ２Ｒ２１、ＳＯ３Ｒ２１、ＳＯ３Ｈ、ＳＯ３ －、ＳＯ２ＮＨ２、ＳＯ２ＮＨＲ２１又はＳＯ２ＮＲ２１Ｒ２２を表し；
　Ｒ１２とＲ１３、Ｒ１３とＲ１４、Ｒ１４とＲ１５、Ｒ１７とＲ１８、Ｒ１８とＲ１９、及びＲ１９とＲ２０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ＮＲ２１ブリッジによって互いに結合してもよく；
　Ｒ２１及びＲ２２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 11 and R 16 each independently represent a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
R 12 , R 13 , R 14 , R 15 , R 17 , R 18 , R 19 and R 20 are independent of each other, hydrogen atom, halogen atom, R 21 , COOH, COOR 21 , COO- , CONH 2 , CONHR 21 . , CONR 21 R 22 , CN, OH, OR 21 , COCR 21 , OOCNH 2 , OOCNHR 21 , NO2, NH 2 , NHR 21 , NR 21 R 22 , NHCOR 22 , NR 21 COR 22 = CH 2 , N = CHR 21 , N = CR 21 R 22 , SH, SR 21 , SOR 21 , SO 2 R 21 , SO 3 R 21 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR Represents 21 or SO 2 NR 21 R 22 ;
At least one combination selected from the group consisting of R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 17 and R 18 , R 18 and R 19 , and R 19 and R 20 is directly attached to each other. They may be bonded or bonded to each other by oxygen, sulfur, NH or NR 21 bridges;
Each of R 21 and R 22 independently has 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 cycloalkenyl group having 3 to 12 carbon atoms. Represents 2-12 alkynyl groups.
　化合物（Ｉ）及び化合物（Ｉ）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 isomers of compound (I) and compound (I) have 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-C000016
Figure JPOXMLDOC01-appb-C000016
　化合物（Ｉ）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等の三級アンモニウム、テトラアルキルアンモニウム等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、化合物（Ｉ）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 compound (I) is anionic, its charge can be charged to any known suitable cation such as metal, organic, inorganic or metallic organic cation, specifically alkali metal, alkaline earth metal, transition metal, primary ammonium. , Secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or salts supplemented with an organic metal complex are preferred. When the geometric isomer of compound (I) is anionic, it is preferably a similar salt.
　一般式（Ｉ）の置換基及びそれらの定義においては、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。
　Ｒ１２、Ｒ１４、Ｒ１５、Ｒ１７、Ｒ１９及びＲ２０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。
　Ｒ１３及びＲ１８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であり、特に好ましくは水素原子である。 In the substituents of the general formula (I) and their definitions, the following are preferable because the shielding rate tends to be high. This is because the following substituents are considered to be non-absorbent and do not affect the hue of the pigment.
R 12 , R 14 , R 15 , R 17 , R 19 and R 20 are each independently, preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.
R 13 and R 18 are independent of each other, preferably 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 hydrogen atom or SO 3 H, particularly preferred. Is a hydrogen atom.
　Ｒ１１及びＲ１６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、Ｒ１１とＲ１６、Ｒ１２とＲ１７、Ｒ１３とＲ１８、Ｒ１４とＲ１９、及びＲ１５とＲ２０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、Ｒ１１はＲ１６と同一であり、Ｒ１２はＲ１７と同一であり、Ｒ１３はＲ１８と同一であり、Ｒ１４はＲ１９と同一であり、かつ、Ｒ１５はＲ２０と同一である。 Each of R 11 and R 16 is independently, preferably a hydrogen atom, CH 3 or CF 3 , and more preferably a hydrogen atom.
Preferably, at least one combination selected from the group consisting of R 11 and R 16 , R 12 and R 17 , R 13 and R 18 , R 14 and R 19 , and R 15 and R 20 is the same, more preferably. R 11 is the same as R 16 , R 12 is the same as R 17 , R 13 is the same as R 18 , R 14 is the same as R 19 , and R 15 is R 20 . It is 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、ｎ－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。 The alkyl group having 1 to 12 carbon atoms is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a 2-methylbutyl group, or n-. Pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-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、メチルシクロヘキシル基、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、アダマンタン－１－イル基又はアダマンタン－２－イル基である。 The cycloalkyl group having 3 to 12 carbon atoms is, for example, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a trimethylcyclohexyl group, a tudyl group, a norbornyl group, a boronyl group, or a norcaryl group. , Caryl group, mentyl group, norpinyl group, pinyl group, adamantan-1-yl group or adamantan-2-yl 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。 The alkenyl group having 2 to 12 carbon atoms is, for example, a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-butene-1-yl group, a 3-buten-1-yl group, or a 1,3-butadiene. -2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-methyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, It is a 3-methyl-2-buten-1-yl group, a 1,4-pentadiene-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。 The cycloalkenyl group having 3 to 12 carbon atoms is, for example, 2-cyclobutene-1-yl group, 2-cyclopentene-1-yl group, 2-cyclohexene-1-yl group, 3-cyclohexene-1-yl group, 2 , 4-Cyclohexadiene-1-yl group, 1-p-menten-8-yl group, 4 (10) -Tsgen-10-yl group, 2-norbornene-1-yl group, 2,5-norbornadiene-1 -Il group, 7,7-dimethyl-2,4-norborneadiene-3-yl group or canphenyl 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。 The alkynyl group having 2 to 12 carbon atoms is, for example, 1-propin-3-yl group, 1-butin-4-yl group, 1-pentin-5-yl group, 2-methyl-3-butin-2-yl. Group, 1,4-pentaziin-3-yl group, 1,3-pentadiin-5-yl group, 1-hexin-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, It is a 1-decine-10-yl group or a 1-dodecine-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.
　前記一般式（Ｉ）で表される化合物は、好ましくは下記一般式（ＩＩ）で表される化合物（以下、「化合物（ＩＩ）」ともいう。）、及び化合物（ＩＩ）の幾何異性体からなる群から選ばれる少なくとも１種を含む化合物である。 The compound represented by the general formula (I) is preferably from the compound represented by the following general formula (II) (hereinafter, also referred to as “compound (II)”) and the geometric isomer of the compound (II). It is a compound containing at least one selected from the group.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　このような化合物としては、例えば、商品名で、Ｉｒｇａｐｈｏｒ（登録商標）　Ｂｌａｃｋ　Ｓ　０１００　ＣＦ（ＢＡＳＦ社製）が挙げられる。 Examples of such a compound include, in the trade name, Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).
　この有機黒色顔料は、好ましくは後述される方法によって分散して使用される。また、分散の際に化合物（Ｉ）のスルホン酸誘導体、又は化合物（Ｉ）の幾何異性体のスルホン酸誘導体、特に化合物（ＩＩ）のスルホン酸誘導体、又は化合物（ＩＩ）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。 This organic black pigment is preferably dispersed and used by the method described later. Further, at the time of dispersion, the sulfonic acid derivative of the compound (I) or the sulfonic acid derivative of the geometric isomer of the compound (I), particularly the sulfonic acid derivative of the compound (II) or the sulfon of the geometric isomer of the compound (II). The presence of an acid derivative may improve dispersibility and storage stability.
　本発明の第一の態様において、（Ａ）着色剤は、一般式（Ｉ）の化合物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。高抵抗、低誘電率の観点からは、有機顔料がより好ましく、特に後述の有機着色顔料がさらに好ましい。
　有機着色顔料の中でも、可視光領域の高波長域の透過率を均一にする観点から、化合物（Ｉ）と青色顔料を用いることが好ましい。ピグメントブルーＢ６０、１５：６、１６が好ましく、ピグメントブルーＢ６０がより好ましい。
　一方、可視光領域全体の透過率を均一にする観点から、化合物（Ｉ）以外に、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種とを用いることが好ましい。 In the first aspect of the present invention, the colorant (A) may contain other colorants in addition to the compound of the general formula (I). As the other colorant, a pigment is preferable, and the pigment may be an organic pigment or an inorganic pigment. From the viewpoint of high resistance and low dielectric constant, organic pigments are more preferable, and organic coloring pigments described later are particularly preferable.
Among the organic coloring pigments, it is preferable to use the compound (I) and the blue pigment from the viewpoint of making the transmittance in the high wavelength region of the visible light region uniform. Pigment Blue B60, 15: 6, 16 is preferable, and Pigment Blue B60 is more preferable.
On the other hand, from the viewpoint of making the transmittance of the entire visible light region uniform, at least one selected from the group consisting of a red pigment and an orange pigment and a group consisting of a blue pigment and a purple pigment are selected in addition to the compound (I). It is preferable to use at least one kind.
　第二の態様において、本発明の感光性着色組成物は、硬化した塗膜の膜厚１μｍあたりの光学濃度（以下、「単位膜厚あたりのＯＤ」と称する場合がある。）が０．５以上である。（ａ）着色剤を含有し、かつ、単位膜厚あたりのＯＤを前記下限値以上とすることにより、得られる硬化物、特に隔壁の遮光性が高くなる。 In the second aspect, the photosensitive coloring composition of the present invention has an optical density per 1 μm of a cured coating film (hereinafter, may be referred to as “OD per unit film thickness”) of 0.5. That is all. (A) By containing a colorant and setting the OD per unit film thickness to the above lower limit value or more, the light-shielding property of the obtained cured product, particularly the partition wall, is enhanced.
　単位膜厚あたりのＯＤは、感光性着色組成物を硬化させた塗膜の光学濃度と膜厚を測定し、光学濃度を膜厚で除することで算出することができる。塗膜の作成条件は特に限定されないが、例えば後述の実施例に記載の条件を採用することができる。
　単位膜厚あたりのＯＤを前記下限値以上にするには、例えば（ａ）着色剤の種類や、全固形分量中の含有割合を適宜調整すればよい。 The OD per unit film thickness can be calculated by measuring the optical density and the film thickness of the coating film obtained by curing the photosensitive coloring composition and dividing the optical density by the film thickness. The conditions for producing the coating film are not particularly limited, but for example, the conditions described in Examples described later can be adopted.
In order to make the OD per unit film thickness equal to or higher than the lower limit, for example, (a) the type of the colorant and the content ratio in the total solid content may be appropriately adjusted.
　本発明の第二の態様において、感光性着色組成物に用いることのできる（ａ）着色剤の種類は特に限定されず、顔料を用いてもよいし、染料を用いてもよい。これらの中でも、耐久性の観点から、顔料を用いることが好ましい。 In the second aspect of the present invention, the type of (a) colorant that can be used in the photosensitive coloring composition is not particularly limited, and a pigment or a dye may be used. Among these, it is preferable to use a pigment from the viewpoint of durability.
　（ａ）着色剤に含まれる顔料は、１種単独でもよいし、２種以上であってもよい。特に、可視領域において均一に遮光することと、単位膜厚あたりのＯＤを両立させるとの観点からは、２種以上であることが好ましい。
　（ａ）着色剤として用いることができる顔料の種類は特に限定されないが、例えば、有機着色顔料や黒色顔料が挙げられる。ここで、有機着色顔料とは、黒色以外の色を呈する有機顔料のことを意味し、例えば、赤色顔料、橙色顔料、青色顔料、紫色顔料、緑色顔料、黄色顔料が挙げられる。 (A) The pigment contained in the colorant may be one kind alone or two or more kinds. In particular, from the viewpoint of achieving both uniform light shielding in the visible region and OD per unit film thickness, two or more types are preferable.
(A) The type of pigment that can be used as the colorant is not particularly limited, and examples thereof include organic color pigments and black pigments. Here, the organic coloring pigment means an organic pigment exhibiting a color other than black, and examples thereof include a red pigment, an orange pigment, a blue pigment, a purple pigment, a green pigment, and a yellow pigment.
　顔料の中でも、高抵抗、低誘電率の観点から、有機着色顔料を用いることが好ましい。また、遮光性の観点からは、化合物（Ｉ）あるいは他の黒色顔料を用いることが好ましい。 Among the pigments, it is preferable to use an organic coloring pigment from the viewpoint of high resistance and low dielectric constant. Further, from the viewpoint of light-shielding property, it is preferable to use compound (I) or another black pigment.
　有機着色顔料は、１種を単独で使用してもよいが、２種以上を併用してもよい。特に、単位膜厚あたりのＯＤを０．５以上にするとの観点からは、色の異なる有機着色顔料を組み合わせて用いることがより好ましく、黒に近い色を呈する有機着色顔料の組み合わせを用いることがさらに好ましい。 As the organic coloring pigment, one type may be used alone, or two or more types may be used in combination. In particular, from the viewpoint of setting the OD per unit film thickness to 0.5 or more, it is more preferable to use a combination of organic coloring pigments having different colors, and it is preferable to use a combination of organic coloring pigments having a color close to black. More preferred.
　これらの有機着色顔料の化学構造は特に限定されないが、例えば、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、ペリレン系が挙げられる。以下、使用できる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」等における「Ｃ．Ｉ．」は、カラーインデックスを意味する。 The chemical structure of these organic coloring pigments is not particularly limited, and examples thereof include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindoleinone-based, dioxazine-based, indanthrone-based, and perylene-based. Hereinafter, specific examples of pigments that can be used are shown by pigment numbers. "CI" in "CI Pigment Red 2" and the like listed below means a color index.
　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。遮光性、分散性の観点から好ましくは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、さらに好ましくはＣ．Ｉ．ピグメントレッド１７７、２０９、２２４、２５４を挙げることができる。分散性や遮光性の点で、Ｃ．Ｉ．ピグメントレッド１７７、２５４、２７２が好ましく、感光性着色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が好ましく、係る観点からはＣ．Ｉ．ピグメントレッド２５４、２７２がより好ましい。 As a red pigment, 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, 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 can be mentioned. From the viewpoint of light-shielding property and dispersibility, 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 can be mentioned. In terms of dispersibility and light blocking effect, C.I. I. Pigment Red 177, 254, 272 are preferable, and when the photosensitive coloring composition is cured with ultraviolet rays, a red pigment having a low ultraviolet absorption rate is preferable, and from this viewpoint, C.I. I. Pigment Red 254 and 272 are more preferred.
　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。分散性や遮光性の観点から、Ｃ．Ｉ．ピグメントオレンジ１３、４３、６４、７２が好ましく、感光性着色組成物を紫外線で硬化させる場合には、オレンジ顔料としては紫外線吸収率の低いものが好ましく、係る観点からはＣ．Ｉ．ピグメントオレンジ６４、７２がより好ましい。 As an orange pigment, 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 can be mentioned. From the viewpoint of dispersibility and light-shielding property, C.I. I. Pigments Orange 13, 43, 64, 72 are preferable, and when the photosensitive coloring composition is cured with ultraviolet rays, the orange pigment having a low ultraviolet absorption rate is preferable, and from this viewpoint, C.I. I. Pigment Oranges 64 and 72 are more preferred.
　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。遮光性の観点から、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、６０、さらに好ましくはＣ．Ｉ．ピグメントブルー１５：６を挙げることができる。分散性や遮光性の点で、Ｃ．Ｉ．ピグメントブルー１５：６、１６、６０が好ましく、感光性着色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が好ましく、かかる観点からはＣ．Ｉ．ピグメントブルー６０がより好ましい。 As a blue pigment, 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 can be mentioned. From the viewpoint of light-shielding property, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 60, more preferably C.I. I. Pigment Blue 15: 6 can be mentioned. In terms of dispersibility and light blocking effect, C.I. I. Pigment Blue 15: 6, 16, 60 is preferable, and when the photosensitive coloring composition is cured with ultraviolet rays, a blue pigment having a low ultraviolet absorption rate is preferable, and from this viewpoint, C.I. I. Pigment Blue 60 is more preferred.
　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。遮光性の観点から、好ましくはＣ．Ｉ．ピグメントバイオレット１９、２３、２９、さらに好ましくはＣ．Ｉ．ピグメントバイオレット２３を挙げることができる。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が好ましく、感光性着色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がより好ましい。 As a purple pigment, 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 can be mentioned. From the viewpoint of light-shielding property, C.I. I. Pigment Violet 19, 23, 29, more preferably C.I. I. Pigment Violet 23 can be mentioned. In terms of dispersibility and light blocking effect, C.I. I. Pigments Violet 23 and 29 are preferable, and when the photosensitive coloring composition is cured with ultraviolet rays, the purple pigment having a low ultraviolet absorption rate is preferable, and from this viewpoint, C.I. I. Pigment Violet 29 is more preferred.
　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、５９を挙げることができる。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。 As a green pigment, C.I. I. Pigment Greens 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59 can be mentioned. .. Preferably C.I. I. Pigment Greens 7 and 36 can be mentioned.
　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。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、さらに好ましくは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。 As a yellow pigment, 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, 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 can be mentioned. Preferably 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 can be mentioned.
　硬化物の遮光性や、形状及び段差のコントロールの観点から、赤色顔料、橙色顔料、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種が好ましい。 From the viewpoint of light-shielding property of the cured product and control of shape and step, at least one selected from the group consisting of red pigment, orange pigment, blue pigment and purple pigment is preferable.
　硬化物の遮光性や、形状及び段差のコントロールの観点からは、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 From the viewpoint of light-shielding property of the cured product and control of shape and step, 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
　有機着色顔料を２種以上併用する場合の、有機着色顔料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、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種とを併用することが好ましい。
　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が挙げられる。 When two or more kinds of organic coloring pigments are used in combination, the combination of organic coloring pigments is not particularly limited, but from the viewpoint of light-shielding property, at least one selected from the group consisting of red pigments and orange pigments, and blue pigments and purples. It is preferable to use at least one selected from the group consisting of pigments in combination.
The color combination is not particularly limited, and examples thereof include a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment, an orange pigment, and a purple pigment from the viewpoint of light-shielding property.
　有機着色顔料、一般式（Ｉ）で表される有機黒色顔料以外の有機黒色顔料や、無機黒色顔料を用いることができる。
　一般式（Ｉ）で表される有機黒色顔料以外の有機黒色顔料としては、例えば、アニリンブラックやペリレンブラックが挙げられる。 Organic black pigments other than organic color pigments and organic black pigments represented by the general formula (I), and inorganic black pigments can be used.
Examples of the organic black pigment other than the organic black pigment represented by the general formula (I) include aniline black and perylene black.
　無機黒色顔料としては、例えば国際公開第２０１８／１０１３１４号に記載されている無機黒色顔料が挙げられる。 Examples of the inorganic black pigment include the inorganic black pigment described in International Publication No. 2018/101314.
　これらの着色剤を用いるにあたり、着色剤中に塩素原子を含有する場合は、塩素量が増えすぎないように添加量を調整することで、使用が可能である。 When using these colorants, if the colorant contains chlorine atoms, it can be used by adjusting the amount of chlorine added so that the amount of chlorine does not increase too much.
　これらの顔料は、平均粒子径が通常１μｍ以下、好ましくは０．５μｍ以下、さらに好ましくは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、本発明の感光性着色組成物において、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、十分に希釈された感光性着色組成物（通常は希釈して、顔料濃度０．００５～０．２質量％程度に調製する。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 pigments are preferably dispersed and used so that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the standard of the average particle size is the number of pigment particles.
In the photosensitive coloring composition of the present invention, the average particle size of the pigment is a value obtained from the pigment particle size measured by dynamic light scattering (DLS). The particle size is measured by a sufficiently diluted photosensitive coloring composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring device, Follow the concentration) and measure at 25 ° C.
　本発明の第二の態様の感光性着色組成物において、有機着色顔料、黒色顔料等の着色剤を１種類単独で使用してもよく、２種類以上を併用してもよい。 In the photosensitive coloring composition of the second aspect of the present invention, one kind of coloring agent such as an organic coloring pigment or a black pigment may be used alone, or two or more kinds may be used in combination.
　上述の有機着色顔料、黒色顔料の他に、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、例えば、国際公開第２０１８／１０１３１４号に記載されている染料が挙げられる。 Dyes may be used in addition to the above-mentioned organic coloring pigments and black pigments. Examples of the dye that can be used as a colorant include the dyes described in International Publication No. 2018/101314.
＜（ｂ）アルカリ可溶性樹脂＞
　本発明で用いる（ｂ）アルカリ可溶性樹脂としては、カルボキシ基又は水酸基を含む樹脂であれば特に限定はなく、例えば、エポキシ（メタ）アクリレート系樹脂、アクリル系樹脂、カルボキシ基含有エポキシ樹脂、カルボキシ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が挙げられる。中でも、
（ｂ１）エポキシ（メタ）アクリレート系樹脂
（ｂ２）アクリル共重合樹脂
が優れた製版性の観点から好適に用いられる。これらは１種を単独で、あるいは２種以上を併用することができる。 <(B) Alkali-soluble resin>
The (b) alkali-soluble resin used in the present invention is not particularly limited as long as it is a resin containing a carboxy group or a hydroxyl group, and is, for example, an epoxy (meth) acrylate resin, an acrylic resin, a carboxy group-containing epoxy resin, or a carboxy group. Examples thereof include a contained urethane resin, a novolak resin, and a polyvinylphenol resin. Above all
(B1) Epoxy (meth) acrylate-based resin (b2) Acrylic copolymer resin is preferably used from the viewpoint of excellent plate-making property. These can be used alone or in combination of two or more.
　＜（ｂ１）エポキシ（メタ）アクリレート系樹脂＞
　（ｂ１）エポキシ（メタ）アクリレート系樹脂は、エポキシ化合物（エポキシ樹脂）とα，β－不飽和モノカルボン酸及び／又はエステル部分にカルボキシ基を有するα，β－不飽和モノカルボン酸エステルとの反応により生成した水酸基を、さらに多塩基酸及び／又はその無水物等の水酸基と反応し得る置換基を２個以上有する化合物と反応させて得られる樹脂である。
　多塩基酸及び／又はその無水物を水酸基と反応させる前に、水酸基と反応し得る置換基を２個以上有する化合物を反応させた後、多塩基酸及び／又はその無水物を反応させて得られる樹脂も、上記（ｂ１）エポキシ（メタ）アクリレート系樹脂に含まれる。 <(B1) Epoxy (meth) acrylate resin>
(B1) The epoxy (meth) acrylate-based resin comprises an epoxy compound (epoxy resin) and an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxy group at the ester moiety. It is a resin obtained by further reacting a hydroxyl group generated by the reaction with a compound having two or more substituents capable of reacting with a hydroxyl group such as a polybasic acid and / or an anhydride thereof.
Obtained by reacting a compound having two or more substituents capable of reacting with a hydroxyl group before reacting the polybasic acid and / or its anhydride with a hydroxyl group, and then reacting with the polybasic acid and / or its anhydride. The resin to be obtained is also included in the above (b1) epoxy (meth) acrylate-based resin.
　上記反応で得られた樹脂のカルボキシ基に、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（ｂ１）エポキシ（メタ）アクリレート系樹脂に含まれる。
　このように、エポキシ（メタ）アクリレート系樹脂は化学構造上、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 resin obtained by reacting the carboxy group of the resin obtained by the above reaction with a compound having a functional group capable of further reacting is also included in the (b1) epoxy (meth) acrylate-based resin.
As described above, the epoxy (meth) acrylate-based resin has substantially no epoxy group due to its chemical structure and is not limited to "(meth) acrylate", but the epoxy compound (epoxy resin) is used as a raw material. Moreover, since "(meth) acrylate" is a typical example, it is named in this way according to the convention.
　本発明で用いる（ｂ１）エポキシ（メタ）アクリレート系樹脂としては、特に下記エポキシ（メタ）アクリレート系樹脂（ｂ１－１）及び／又はエポキシ（メタ）アクリレート系樹脂（ｂ１－２）（以下「カルボキシ基含有エポキシ（メタ）アクリレート系樹脂」と称す場合がある。）が現像性、信頼性の観点から好適に用いられる。
　また、（ｂ１）エポキシ（メタ）アクリレート系樹脂としては、アウトガスの観点から、主鎖に芳香族環を有するものをより好適に用いることができる。 Examples of the (b1) epoxy (meth) acrylate-based resin used in the present invention include the following epoxy (meth) acrylate-based resin (b1-1) and / or epoxy (meth) acrylate-based resin (b1-2) (hereinafter, “carboxy). Group-containing epoxy (meth) acrylate-based resin ”may be referred to as“ group-containing epoxy (meth) acrylate resin ”), which is preferably used from the viewpoint of developability and reliability.
Further, as the (b1) epoxy (meth) acrylate-based resin, those having an aromatic ring in the main chain can be more preferably used from the viewpoint of outgas.
　＜エポキシ（メタ）アクリレート系樹脂（ｂ１－１）＞
　エポキシ樹脂にα，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルを付加させ、任意でイソシアネート基含有化合物を反応させた後、さらに、多塩基酸及び／又はその無水物を反応させることによって得られたアルカリ可溶性樹脂。
　＜エポキシ（メタ）アクリレート系樹脂（ｂ１－２）＞
　エポキシ樹脂にα，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルを付加させ、任意でイソシアネート基含有化合物を反応させた後、さらに、多価アルコール、及び多塩基酸及び／又はその無水物と反応させることによって得られたアルカリ可溶性樹脂。 <Epoxy (meth) acrylate resin (b1-1)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxy group is added to the epoxy resin, and an isocyanate group-containing compound is optionally reacted. Or an alkali-soluble resin obtained by reacting the anhydride thereof.
<Epoxy (meth) acrylate resin (b1-2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxy group is added to the epoxy resin, and an isocyanate group-containing compound is optionally reacted. An alkali-soluble resin obtained by reacting with a polybasic acid and / or an anhydride thereof.
　ここで、エポキシ樹脂とは、熱硬化により樹脂を形成する以前の原料化合物をも含めて言うこととし、そのエポキシ樹脂としては、公知のエポキシ樹脂の中から適宜選択して用いることができる。また、エポキシ樹脂は、フェノール性化合物とエピハロヒドリンとを反応させて得られる化合物を用いることができる。フェノール性化合物としては、２価もしくは２価以上のフェノール性水酸基を有する化合物が好ましく、単量体でも重合体でもよい。
　原料となるエポキシ樹脂の種類としては、例えば、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフタレンノボラック型エポキシ樹脂、ジシクロペンタジエンとフェノール又はクレゾールとの重付加反応物とエピハロヒドリンとの反応生成物であるエポキシ樹脂、アダマンチル基含有エポキシ樹脂、フルオレン型エポキシ樹脂を好適に用いることができ、これらの中でも、主鎖に芳香族環を有するものをより好適に用いることができる。 Here, the epoxy resin includes a raw material compound before forming the resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins and used. Further, as the epoxy resin, a compound obtained by reacting a phenolic compound with epihalohydrin can be used. The phenolic compound is preferably a compound having a divalent or divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
The types of epoxy resins used as raw materials include, for example, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, biphenyl novolac type epoxy resin, and naphthalene. Novolak type epoxy resin, epoxy resin which is a reaction product of dicyclopentadiene and phenol or cresol and epihalohydrin, adamantyl group-containing epoxy resin, and fluorene type epoxy resin can be preferably used. Among them, those having an aromatic ring in the main chain can be more preferably used.
　エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂（例えば、三菱ケミカル社製の「ｊＥＲ（登録商標、以下同じ。）８２８」、「ｊＥＲ１００１」、「ｊＥＲ１００２」、「ｊＥＲ１００４」等）、ビスフェノールＡ型エポキシ樹脂のアルコール性水酸基とエピクロルヒドリンの反応により得られるエポキシ樹脂（例えば、日本化薬社製の「ＮＥＲ－１３０２」（エポキシ当量３２３，軟化点７６℃））、ビスフェノールＦ型樹脂（例えば、三菱ケミカル社製の「ｊＥＲ８０７」、「ＥＰ－４００１」、「ＥＰ－４００２」、「ＥＰ－４００４」等）、ビスフェノールＦ型エポキシ樹脂のアルコール性水酸基とエピクロルヒドリンの反応により得られるエポキシ樹脂（例えば、日本化薬社製の「ＮＥＲ－７４０６」（エポキシ当量３５０，軟化点６６℃））、ビスフェノールＳ型エポキシ樹脂、ビフェニルグリシジルエーテル（例えば、三菱ケミカル社製の「ＹＸ－４０００」）、フェノールノボラック型エポキシ樹脂（例えば、日本化薬社製の「ＥＰＰＮ－２０１」、三菱ケミカル社製の「ＥＰ－１５２」、「ＥＰ－１５４」、ダウケミカル社製の「ＤＥＮ－４３８」）、（ｏ，ｍ，ｐ－）クレゾールノボラック型エポキシ樹脂（例えば、日本化薬社製の「ＥＯＣＮ（登録商標、以下同じ。）－１０２Ｓ」、「ＥＯＣＮ－１０２０」、「ＥＯＣＮ－１０４Ｓ」）、トリグリシジルイソシアヌレート（例えば、日産化学社製の「ＴＥＰＩＣ（登録商標）」）、トリスフェノールメタン型エポキシ樹脂（例えば、日本化薬社製の「ＥＰＰＮ（登録商標、以下同じ。）－５０１」、「ＥＰＰＮ－５０２」、「ＥＰＰＮ－５０３」）、脂環式エポキシ樹脂（ダイセル社製の「セロキサイド（登録商標、以下同じ。）２０２１Ｐ」、「セロキサイドＥＨＰＥ」）、ジシクロペンタジエンとフェノールの反応によるフェノール樹脂をグリシジル化したエポキシ樹脂（例えば、ＤＩＣ社製の「ＥＸＡ－７２００」、日本化薬社製の「ＮＣ－７３００」）、下記一般式（Ｂ１）～（Ｂ４）で表されるエポキシ樹脂、を好適に用いることができる。具体的には、例えば、下記一般式（Ｂ１）で表されるエポキシ樹脂として日本化薬社製の「ＸＤ－１０００」、下記一般式（Ｂ２）で表されるエポキシ樹脂として日本化薬社製の「ＮＣ－３０００」、下記一般式（Ｂ３）で表されるエポキシ樹脂として大阪有機化学工業社製の「Ｅ－２０１」、下記一般式（Ｂ４）で表されるエポキシ樹脂として新日鉄住金化学社製の「ＥＳＦ－３００」が挙げられる。 Examples of the epoxy resin include bisphenol A type epoxy resin (for example, "jER (registered trademark, the same shall apply hereinafter) 828", "jER1001", "jER1002", "jER1004", etc.) manufactured by Mitsubishi Chemical Corporation, and bisphenol A type. Epoxy resin obtained by the reaction of the alcoholic hydroxyl group of the epoxy resin with epichlorohydrin (for example, "NER-1302" (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin (for example, Mitsubishi Chemical). "JER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Mitsubishi Chemical Corporation), an epoxy resin obtained by the reaction of an alcoholic hydroxyl group of a bisphenol F type epoxy resin with epichlorohydrin (for example, Japan) "NER-7406" manufactured by Yakusha (epoxy equivalent 350, softening point 66 ° C), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (For example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Corporation), (o, m, p. -) Cresol novolac type epoxy resin (for example, "EOCN (registered trademark, the same shall apply hereinafter) -102S", "EOCN-1020", "EOCN-104S") manufactured by Nippon Kayaku Co., Ltd., triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Corporation), Trisphenol methane type epoxy resin (for example, "EPPN (registered trademark, the same shall apply hereinafter) -501", "EPPN-502", "EPPN-502" manufactured by Nippon Kayaku Co., Ltd. EPPN-503 "), alicyclic epoxy resin ("Seroxide (registered trademark, the same shall apply hereinafter) 2021P "manufactured by Daicel Co., Ltd." A resin (for example, "EXA-7200" manufactured by DIC, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.) and an epoxy resin represented by the following general formulas (B1) to (B4) can be preferably used. can. Specifically, for example, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (B1), and Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (B2). "NC-3000", "E-201" manufactured by Osaka Organic Chemical Industry Co., Ltd. as an epoxy resin represented by the following general formula (B3), Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (B4) "ESF-300" manufactured by the company can be mentioned.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　上記一般式（Ｂ１）において、ａは平均値であり、０～１０の数を表し、Ｒ１１１は各々独立に水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ１１１は、それぞれ同じであっても異なっていてもよい。 In the above general formula (B1), a is an average value and represents a number of 0 to 10, and R 111 is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, and 3 to 10 carbon atoms, respectively. Represents a cycloalkyl group, a phenyl group, a naphthyl group, or a biphenyl group. The plurality of R 111s existing in one molecule may be the same or different from each other.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　上記一般式（Ｂ２）において、ｂ１及びｂ２は各々独立に平均値であり、０～１０の数を表し、Ｒ１２１は各々独立に水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ１２１は、それぞれ同じであっても異なっていてもよい。 In the above general formula (B2), b1 and b2 are independently average values and represent numbers of 0 to 10, and R 121 is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, and carbon. Represents a cycloalkyl group, a phenyl group, a naphthyl group, or a biphenyl group having a number of 3 to 10. The plurality of R 121s existing in one molecule may be the same or different from each other.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　上記一般式（Ｂ３）において、Ｘは下記一般式（Ｂ３－１）又は（Ｂ３－２）で表される連結基を表す。但し、分子構造中に１つ以上のアダマンタン構造を含む。ｃは２又は３を表す。 In the above general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2). However, the molecular structure contains one or more adamantane structures. c represents 2 or 3.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　上記一般式（Ｂ３－１）及び（Ｂ３－２）において、Ｒ１３１～Ｒ１３４及びＲ１３５～Ｒ１３７は、各々独立に、置換基を有していてもよいアダマンチル基、水素原子、置換基を有していてもよい炭素数１～１２のアルキル基、又は置換基を有していてもよいフェニル基を表し、＊は結合手を表す。 In the above general formulas (B3-1) and (B3-2), R 131 to R 134 and R 135 to R 137 each independently may have a substituent, an adamantyl group, a hydrogen atom, or a substituent. Represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, and * represents a bond.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　上記一般式（Ｂ４）において、ｐ及びｑは各々独立に０～４の整数を表し、Ｒ１４１及びＲ１４２は各々独立に炭素数１～４のアルキル基又はハロゲン原子を表し、Ｒ１４３及びＲ１４４は各々独立に炭素数１～４のアルキレン基を表し、ｘ及びｙは各々独立に０以上の整数を表す。 In the above general formula (B4), p and q each independently represent an integer of 0 to 4, and R 141 and R 142 independently represent an alkyl group or a halogen atom having 1 to 4 carbon atoms, respectively, and R 143 and R 144 independently represent an alkylene group having 1 to 4 carbon atoms, and x and y each independently represent an integer of 0 or more.
　これらの中で、一般式（Ｂ１）～（Ｂ４）のいずれかで表されるエポキシ樹脂を用いるのが好ましい。 Among these, it is preferable to use an epoxy resin represented by any of the general formulas (B1) to (B4).
　α，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルとしては、（メタ）アクリル酸、クロトン酸、ｏ－、ｍ－又はｐ－ビニル安息香酸、（メタ）アクリル酸のα位ハロアルキル、アルコキシル、ハロゲン、ニトロ、シアノ置換体等のモノカルボン酸、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルアジピン酸、２－（メタ）アクリロイロキシエチルフタル酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチルマレイン酸、２－（メタ）アクリロイロキシプロピルコハク酸、２－（メタ）アクリロイロキシプロピルアジピン酸、２－（メタ）アクリロイロキシプロピルテトラヒドロフタル酸、２－（メタ）アクリロイロキシプロピルフタル酸、２－（メタ）アクリロイロキシプロピルマレイン酸、２－（メタ）アクリロイロキシブチルコハク酸、２－（メタ）アクリロイロキシブチルアジピン酸、２－（メタ）アクリロイロキシブチルヒドロフタル酸、２－（メタ）アクリロイロキシブチルフタル酸、２－（メタ）アクリロイロキシブチルマレイン酸（メタ）、アクリル酸にε－カプロラクトン、β－プロピオラクトン、γ－ブチロラクトン、δ－バレロラクトン等のラクトン類を付加させたものである単量体、あるいはヒドロキシアルキル（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートに（無水）コハク酸、（無水）フタル酸、（無水）マレイン酸等の酸（無水物）を付加させた単量体、（メタ）アクリル酸ダイマー等が挙げられる。
　これらのうち、感度の点から、特に好ましいものは（メタ）アクリル酸である。 Examples of the α, β-unsaturated monocarboxylic acid ester having an α, β-unsaturated monocarboxylic acid or a carboxy group include (meth) acrylic acid, crotonic acid, o-, m- or p-vinyl benzoic acid, and (meth). ) Monocarboxylic acid such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano-substituted acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( Meta) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- ( Meta) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) ) Acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) Acryloyloxybutylmaleic acid (meth), a monomer obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to acrylic acid, or hydroxyalkyl ( A monomer obtained by adding an acid (anhydrous) such as (anhydrous) succinic acid, (anhydrous) phthalic acid, and (anhydrous) maleic acid to meta) acrylate and pentaerythritol tri (meth) acrylate, (meth) acrylic acid dimer. And so on.
Of these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.
　エポキシ樹脂にα，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルを付加させる方法としては、公知の手法を用いることができる。例えば、エステル化触媒の存在下、５０～１５０℃の温度で、α，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルとエポキシ樹脂とを反応させることができる。ここで用いるエステル化触媒としては、トリエチルアミン、トリメチルアミン、ベンジルジメチルアミン、ベンジルジエチルアミン等の３級アミン、テトラメチルアンモニウムクロリド、テトラエチルアンモニウムクロリド、ドデシルトリメチルアンモニウムクロリド等の４級アンモニウム塩等を用いることができる。 A known method can be used as a method for adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxy group to the epoxy resin. For example, in the presence of an esterification catalyst, an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxy group can be reacted with an epoxy resin at a temperature of 50 to 150 ° C. can. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride can be used. ..
　エポキシ樹脂、α，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステル、及びエステル化触媒の各成分は、各成分を１種ずつ選択して用いてもよく、２種以上を併用してもよい。
　α，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルの使用量は、エポキシ樹脂のエポキシ基１当量に対し０．５～１．２当量の範囲が好ましく、さらに好ましくは０．７～１．１当量の範囲である。α，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルの使用量を前記下限値以上とすることで不飽和基の導入量の不足が抑制でき、引き続く多塩基酸及び／又はその無水物との反応も十分なものとしやすい傾向がある。一方、前記上限値以下とすることでα，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルの未反応物の残存を抑制でき、硬化特性を良好なものとしやすい傾向が認められる。 As each component of the epoxy resin, α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxy group, and the esterification catalyst, each component may be selected and used one by one. Two or more types may be used in combination.
The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxy group is preferably in the range of 0.5 to 1.2 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. , More preferably in the range of 0.7 to 1.1 equivalents. By setting the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxy group to the above lower limit or more, it is possible to suppress the shortage of the amount of unsaturated group introduced, and the number continues to increase. Reactions with basic acids and / or their anhydrides also tend to be sufficient. On the other hand, when the value is not more than the above upper limit, the residual unreacted substance of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxy group can be suppressed, and the curing characteristics are good. There is a tendency for it to be easy to do.
　多塩基酸及び／又はその無水物としては、例えば、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、及びこれらの無水物が挙げられる。 Examples of the polybasic acid and / or its anhydrate include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid and methylhexa. Examples thereof include hydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
　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、又はこれらの無水物である。特に好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸、無水テトラヒドロフタル酸、又はビフェニルテトラカルボン酸二無水物である。 Preferably maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.
　多塩基酸及び／又はその無水物の付加反応は、公知の手法を用いて行うことができ、エポキシ樹脂へのα，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルの付加反応と同様な条件下で、継続反応させて目的物を得ることができる。多塩基酸及び／又はその無水物成分の付加量は、生成するカルボキシ基含有エポキシ（メタ）アクリレート系樹脂の酸価が１０～１５０ｍｇＫＯＨ／ｇの範囲となるような程度であることが好ましく、さらに２０～１４０ｍｇＫＯＨ／ｇの範囲となるような程度であることが好ましい。前記下限値以上とすることでアルカリ現像性が良好となる傾向がある。前記上限値以下とすることで硬化性能が良好となる傾向がある。 The addition reaction of the polybasic acid and / or its anhydride can be carried out using a known method and is an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid having a carboxy group on an epoxy resin. The desired product can be obtained by continuing the reaction under the same conditions as the addition reaction of the carboxylic acid ester. The addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the carboxy group-containing epoxy (meth) acrylate-based resin to be produced is in the range of 10 to 150 mgKOH / g, and further. It is preferably in the range of 20 to 140 mgKOH / g. When the value is equal to or higher than the lower limit, the alkali developability tends to be good. When the value is not more than the upper limit, the curing performance tends to be good.
　多塩基酸及び／又はその無水物の付加反応時に、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等の多官能アルコール（多価アルコール）を添加し、多分岐構造を導入したものとしてもよい。この場合、多塩基酸及び／又はその無水物と多官能アルコールの混合順序に、特に制限はない。加温により、エポキシ樹脂とα，β－不飽和モノカルボン酸又はカルボキシ基を有するα，β－不飽和モノカルボン酸エステルとの反応物と多官能アルコールとの混合物中に存在するいずれかの水酸基に対して多塩基酸及び／又はその無水物が付加反応する。 Polyfunctional alcohols (polyhydric alcohols) such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3-propanetriol during the addition reaction of polybasic acid and / or its anhydride. ) May be added to introduce a multi-branched structure. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyfunctional alcohol is not particularly limited. Any hydroxyl group present in the mixture of the reaction product of the epoxy resin with the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxy group and the polyfunctional alcohol by heating. A polybasic acid and / or its anhydride undergoes an addition reaction with respect to.
　多価アルコールを用いることで、（ｂ１）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。 By using a polyhydric alcohol, the molecular weight of the (b1) epoxy (meth) acrylate resin can be increased, branches 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 for the sensitivity, adhesion, and the like to be easily balanced.
　カルボキシ基含有エポキシ（メタ）アクリレート系樹脂としては、前述のもの以外に、例えば、大韓民国公開特許第１０－２０１３－００２２９５５号公報に記載のものが挙げられる。 Examples of the carboxy group-containing epoxy (meth) acrylate-based resin include those described in Korean Patent Publication No. 10-2013-0022955, in addition to the above-mentioned ones.
　カルボキシ基含有エポキシ（メタ）アクリレート系樹脂の、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）は通常１０００以上、好ましくは１５００以上、より好ましくは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以上であり、通常３００００以下、好ましくは２００００以下、より好ましくは１５０００以下である。上記の上限及び下限は任意に組み合わせることができる。例えば、１０００～３００００が好ましく、１５００～２００００がより好ましく、１５００～１５０００がさらに好ましく、２０００～１５０００がよりさらに好ましい。前記下限値以上とすることで現像液に対する溶解性が高くなりすぎるのを抑制できる傾向がある。前記上限値以下とすることで現像液に対する溶解性が良好なものとしやすい傾向がある。 The polystyrene-equivalent weight average molecular weight (Mw) of the carboxy group-containing epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, and more preferably. Is 3000 or more, more preferably 4000 or more, particularly preferably 5000 or more, usually 30,000 or less, preferably 20,000 or less, and more preferably 15,000 or less. The above upper and lower limits can be combined arbitrarily. For example, 1000 to 30000 is preferable, 1500 to 20000 is more preferable, 1500 to 15000 is even more preferable, and 2000 to 15000 is even more preferable. By setting the value to the lower limit or higher, it tends to be possible to prevent the solubility in the developing solution from becoming too high. By setting the value to the upper limit or less, the solubility in a developing solution tends to be good.
　カルボキシ基含有エポキシ（メタ）アクリレート系樹脂の酸価は特に限定されないが、２０ｍｇＫＯＨ／ｇ以上が好ましく、４０ｍｇＫＯＨ／ｇ以上がより好ましく、６０ｍｇＫＯＨ／ｇ以上がさらに好ましく、８０ｍｇＫＯＨ／ｇ以上がよりさらに好ましく、１００ｍｇＫＯＨ／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以下がさらに好ましく、１２０ｍｇＫＯＨ／ｇ以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、２０ｍｇＫＯＨ／ｇ～２００ｍｇＫＯＨ／ｇが好ましく、６０ｍｇＫＯＨ／ｇ～１５０ｍｇＫＯＨ／ｇがより好ましく、８０ｍｇＫＯＨ／ｇ～１３０ｍｇＫＯＨ／ｇがさらに好ましく、１００ｍｇＫＯＨ／ｇ～１３０ｍｇＫＯＨ／ｇがよりさらに好ましい。前記下限値以上とすることで現像溶解性が向上し、解像性が良好となる傾向がある。前記上限値以下とすることで感光性着色組成物の残膜率が良好となる傾向がある。 The acid value of the carboxy group-containing epoxy (meth) acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, still more preferably 80 mgKOH / g or more. , 100 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 further preferable, and 120 mgKOH / g or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 20 mgKOH / g to 200 mgKOH / g is preferable, 60 mgKOH / g to 150 mgKOH / g is more preferable, 80 mgKOH / g to 130 mgKOH / g is further preferable, and 100 mgKOH / g to 130 mgKOH / g is even more preferable. By setting the value to the lower limit or more, the develop solubility tends to be improved and the resolution tends to be good. When the value is not more than the upper limit, the residual film ratio of the photosensitive coloring composition tends to be good.
　エポキシ（メタ）アクリレート系樹脂の化学構造は特に限定されないが、現像性、信頼性の観点から、下記一般式（ｂ１－Ｉ）で表される部分構造を有するエポキシ（メタ）アクリレート系樹脂（以下、「（ｂ１－Ｉ）エポキシ（メタ）アクリレート系樹脂」と略記する場合がある。）及び／又は下記一般式（ｂ１－ＩＩ）で表される部分構造を有するエポキシ（メタ）アクリレート系樹脂（以下、「（ｂ１－ＩＩ）エポキシ（メタ）アクリレート系樹脂」と略記する場合がある。）を含有することが好ましい。 The chemical structure of the epoxy (meth) acrylate-based resin is not particularly limited, but from the viewpoint of developability and reliability, an epoxy (meth) acrylate-based resin having a partial structure represented by the following general formula (b1-I) (hereinafter referred to as “meth) acrylate-based resin”. , "(B1-I) Epoxy (meth) acrylate-based resin") and / or an epoxy (meth) acrylate-based resin having a partial structure represented by the following general formula (b1-II). Hereinafter, it may be abbreviated as "(b1-II) epoxy (meth) acrylate-based resin").
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（ｂ１－Ｉ）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、ｋは１又は２を表し、＊は結合手を表す。
式（ｂ１－Ｉ）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。 In formula (b1-I), R 11 represents a hydrogen atom or a methyl group, R 12 represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents. Represents a bond.
The benzene ring in the formula (b1-I) may be further substituted with any substituent.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　式（ｂ１－ＩＩ）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 (b1-II), R 13 independently represents a hydrogen atom or a methyl group, and 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 represent an integer of 0 to 2, and * represents a bond.
　＜（ｂ１－Ｉ）エポキシ（メタ）アクリレート系樹脂＞
　まず、前記一般式（ｂ１－Ｉ）で表される部分構造を有するエポキシ（メタ）アクリレート系樹脂について詳述する。 <(B1-I) Epoxy (meth) acrylate resin>
First, an epoxy (meth) acrylate-based resin having a partial structure represented by the general formula (b1-I) will be described in detail.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　式（ｂ１－Ｉ）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、ｋは１又は２を表し、＊は結合手を表す。
式（ｂ１－Ｉ）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。 In formula (b1-I), R 11 represents a hydrogen atom or a methyl group, R 12 represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents. Represents a bond.
The benzene ring in the formula (b1-I) may be further substituted with any substituent.
　（Ｒ１２）
　前記式（ｂ１－Ｉ）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 (b1-I), R 12 represents a divalent hydrocarbon group which may have a substituent.
As the divalent hydrocarbon group, a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked is used. Can be mentioned.
　２価の脂肪族基は、直鎖状、分岐鎖状、環状の脂肪族基が挙げられる。これらの中でも現像溶解性の観点からは直鎖状の脂肪族基が好ましい。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脂肪族基が好ましい。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。上記の上限及び下限は任意に組み合わせることができる。例えば、１～２０が好ましく、１～１５がより好ましく、１～１０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、現像時に生じる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る。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。 Examples of the divalent aliphatic group include linear, branched and cyclic aliphatic groups. Among these, a linear aliphatic group is preferable from the viewpoint of development solubility. On the other hand, cyclic aliphatic groups are preferable from the viewpoint of reducing the penetration of the developer into the exposed area. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 20 is preferable, 1 to 15 is more preferable, and 1 to 10 is even more preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
　２価の直鎖状の脂肪族基としては、例えば、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ペンチレン基、ｎ－ヘキシレン基、ｎ－ヘプチレン基が挙げられる。これらの中でも骨格の剛直性の観点から、メチレン基が好ましい。
　２価の分岐鎖状の脂肪族基としては、前述の２価の直鎖状の脂肪族基に、側鎖として、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、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基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以上であり、２以上が好ましく、また、通常１２以下であり、１０以下が好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１～１２が好ましく、１～１０がより好ましく、２～１０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となり、基板密着性が良好となる傾向がある。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。
　２価の環状の脂肪族基としては、例えば、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、ジシクロペンタ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、ジシクロペンタン環、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。 Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of skeletal rigidity.
The divalent branched chain aliphatic group includes the above-mentioned divalent linear aliphatic group, and the side chains include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl. Examples thereof include a structure having a group, an isobutyl group, a sec-butyl group and a tert-butyl group.
The number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 12 is preferable, 1 to 10 is more preferable, and 2 to 10 is even more preferable. By setting the value to the lower limit or higher, the film becomes strong and the substrate adhesion tends to be good. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
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 dicyclopentane ring. A group obtained by dividing two hydrogen atoms from the above can be mentioned. Among these, from the viewpoint of skeletal rigidity, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring, a dicyclopentane ring, and an adamantane ring is preferable.
　２価の脂肪族基が有していてもよい置換基としては、例えば、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；カルボキシ基が挙げられる。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; and a carboxy group. Among these, unsubstituted is preferable from the viewpoint of easiness of synthesis.
　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。上記の上限及び下限は任意に組み合わせることができる。例えば、４～２０が好ましく、５～１５がより好ましく、６～１０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、現像時に生じる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る。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。 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, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, 4 to 20 is preferable, 5 to 15 is more preferable, and 6 to 10 is even more preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, 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。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、フルオレン環が挙げられる。
　また、芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。芳香族複素環基としては、例えば、２個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環が挙げられる。
　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。 The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have two free atomic valences. Examples include an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having two free atomic valences. Rings, pyrrolobymidazole rings, pyrrolopyrazole rings, pyrolopyrrole rings, thienopyrol rings, thienothiophene rings, flopyrol rings, floran rings, thienofran rings, benzoisoxazole rings, benzoisothiazole rings, benzoimidazole rings, pyridine rings, pyrazine rings, Examples thereof include a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxalin ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.
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、例えば、ヒドロキシ基、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 hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Of these, no substitution is preferable from the viewpoint of development solubility.
　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以上であり、２以上が好ましく、通常１０以下であり、５以下が好ましく、３以下がより好ましい。例えば、１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましく、２～３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、現像時に生じる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る。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、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以上であり、２以上が好ましく、通常１０以下であり、５以下が好ましく、３以下がより好ましい。例えば、１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましく、２～３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、現像時に生じる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る。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。 As a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, the above-mentioned divalent aliphatic group is 1 or more, and the above-mentioned divalent aromatic ring group is described. Can be mentioned as a group in which 1 or more are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is further preferable, and 2 to 3 is particularly preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is further preferable, and 2 to 3 is particularly preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, 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としては、例えば、下記式（ｂ１－Ｉ－Ａ）～（ｂ１－Ｉ－Ｆ）で表される基が挙げられる。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（ｂ１－Ｉ－Ａ）で表される基が好ましい。 Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked are represented by the following formulas (b1-IA) to (b1-IF). Group is mentioned. Among these, the group represented by the following formula (b1-IA) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobicity of the membrane.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　前記式（ｂ１－Ｉ）において、ｋは１又は２を表す。密着性、パターニング性の観点からｋは１が好ましい。ＮＭＰ耐性の観点からｋは２が好ましい。（ｂ１－Ｉ）エポキシ（メタ）アクリレート中にｋが１の部分構造と、ｋが２の部分構造の両方が含有されていてもよい。 In the above formula (b1-I), k represents 1 or 2. From the viewpoint of adhesion and patterning, k is preferably 1. From the viewpoint of NMP resistance, k is preferably 2. (B1-I) The epoxy (meth) acrylate may contain both a partial structure having a k of 1 and a partial structure having a k of 2.
　式（ｂ１－Ｉ）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。式（ｂ１－Ｉ）中のベンゼン環に許容される置換基としては、例えば、ヒドロキシ基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基が挙げられる。式（ｂ１－Ｉ）中のベンゼン環が置換基を有する場合、その置換基の数は特に限定されず、１つでもよいし、２つ以上でもよい。
　パターニング特性の観点から、式（ｂ１－Ｉ）中のベンゼン環は無置換であることが好ましい。 The benzene ring in the formula (b1-I) may be further substituted with any substituent. Examples of the substituent allowed on the benzene ring in the formula (b1-I) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. When the benzene ring in the formula (b1-I) has a substituent, the number of the substituents is not particularly limited and may be one or two or more.
From the viewpoint of patterning properties, it is preferable that the benzene ring in the formula (b1-I) is unsubstituted.
　式（ｂ１－Ｉ）で表される部分構造は、合成の簡易性の観点から、下記式（ｂ１－Ｉ－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 formula (b1-I) is preferably a partial structure represented by the following formula (b1-I-1) from the viewpoint of simplicity of synthesis.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　式（ｂ１－Ｉ－１）中、Ｒ１１、Ｒ１２及びｋは、前記式（ｂ１－Ｉ）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、＊は結合手を表す。
式（ｂ１－Ｉ－１）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。 In the formula (b1-I-1), R 11 , R 12 and k are synonymous with those of the above formula ( b1 -I), RX represents a hydrogen atom or a polybasic acid residue, and * represents a bond. Represent a hand.
The benzene ring in the formula (b1-I-1) may be further substituted with any 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、例えば、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が挙げられる。
　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、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 subtracting one OH group from the polybasic acid or its anhydride. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid and endomethylene. Examples thereof include tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid and biphenyltetracarboxylic acid.
From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid and biphenyltetracarboxylic acid are preferable, and tetrahydro is more preferable. Phthalic acid, biphenyltetracarboxylic acid, biphenyltetracarboxylic acid.
　式（ｂ１－Ｉ－１）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。置換基としては、式（ｂ１－Ｉ）中のベンゼン環について挙げたものを好ましく採用することができる。 The benzene ring in the formula (b1-I-1) may be further substituted with any substituent. As the substituent, those mentioned for the benzene ring in the formula (b1-I) can be preferably adopted.
　（ｂ１－Ｉ）エポキシ（メタ）アクリレート系樹脂１分子中に含まれる、前記式（ｂ１－Ｉ－１）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、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。 The partial structure represented by the above formula (b1-I-1) contained in one molecule of the (b1-I) epoxy (meth) acrylate-based resin may be one kind or two or more kinds, for example, RX . A hydrogen atom and a polybasic acid residue of RX may be mixed.
　また、（ｂ１－Ｉ）エポキシ（メタ）アクリレート系樹脂１分子中に含まれる、前記式（ｂ１－Ｉ）で表される部分構造の数は特に限定されないが、１以上が好ましく、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。１～２０が好ましく、１～１５がより好ましく、３～１５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、現像時に生じる表面荒れが生じにくくなる傾向がある。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。 Further, the number of partial structures represented by the above formula (b1-I) contained in one molecule of the (b1-I) epoxy (meth) acrylate resin is not particularly limited, but 1 or more is preferable, and 3 or more is preferable. More preferably, 20 or less is preferable, and 15 or less is further preferable. 1 to 20 is preferable, 1 to 15 is more preferable, and 3 to 15 is even more preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
　（ｂ１－Ｉ）エポキシ（メタ）アクリレート系樹脂の、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以上がよりさらに好ましく、４０００以上が特に好ましく、５０００以上が最も好ましく、通常３００００以下であり、２００００以下が好ましく、１５０００以下がより好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１０００～３００００が好ましく、１５００～２０００がより好ましく、１５００～１５０００がさらに好ましく、２０００～１５００がよりさらに好ましい。前記下限値以上とすることで感光性着色組成物の残膜率が良好となる傾向がある。前記上限値以下とすることで現像液に対する溶解性が良好となる傾向がある。 The polystyrene-equivalent weight average molecular weight (Mw) of the (b1-I) epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more. , 2000 or more is more preferable, 3000 or more is more preferable, 4000 or more is particularly preferable, 5000 or more is most preferable, usually 30,000 or less, 20,000 or less is preferable, and 15,000 or less is more preferable. The above upper and lower limits can be combined arbitrarily. For example, 1000 to 30000 is preferable, 1500 to 2000 is more preferable, 1500 to 15000 is further preferable, and 2000 to 1500 is even more preferable. By setting the value to the lower limit or more, the residual film ratio of the photosensitive coloring composition tends to be good. When the value is not more than the upper limit, the solubility in a developing solution tends to be good.
　（ｂ１－Ｉ）エポキシ（メタ）アクリレート系樹脂の、酸価は特に限定されないが、２０ｍｇＫＯＨ／ｇ以上が好ましく、４０ｍｇＫＯＨ／ｇ以上がより好ましく、６０ｍｇＫＯＨ／ｇ以上がさらに好ましく、８０ｍｇＫＯＨ／ｇ以上がよりさらに好ましく、１００ｍｇＫＯＨ／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、１２０ｍｇＫＯＨ／ｇ以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、２０ｍｇＫＯＨ／ｇ～２００ｍｇＫＯＨ／ｇが好ましく、６０ｍｇＫＯＨ／ｇ～１５０ｍｇＫＯＨ／ｇがより好ましく、８０ｍｇＫＯＨ／ｇ～１３０ｍｇＫＯＨ／ｇがさらに好ましく、１００ｍｇＫＯＨ／ｇ～１３０ｍｇＫＯＨ／ｇがよりさらに好ましい。前記下限値以上とすることで現像溶解性が向上し、解像性が良好となる傾向がある。前記上限値以下とすることで感光性着色組成物の残膜率が良好となる傾向がある。 The acid value of the (b1-I) epoxy (meth) acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, and 80 mgKOH / g or more. More preferably, 100 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 even more preferable, and 120 mgKOH / g or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 20 mgKOH / g to 200 mgKOH / g is preferable, 60 mgKOH / g to 150 mgKOH / g is more preferable, 80 mgKOH / g to 130 mgKOH / g is further preferable, and 100 mgKOH / g to 130 mgKOH / g is even more preferable. By setting the value to the lower limit or more, the develop solubility tends to be improved and the resolution tends to be good. When the value is not more than the upper limit, the residual film ratio of the photosensitive coloring composition tends to be good.
　以下に（ｂ１－Ｉ）エポキシ（メタ）アクリレート系樹脂の具体例を挙げる。なお、例中の＊は結合手を示す。 Specific examples of the (b1-I) epoxy (meth) acrylate-based resin are given below. In addition, * in the example indicates a bond.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　＜（ｂ１－ＩＩ）エポキシ（メタ）アクリレート系樹脂＞
　前記一般式（ｂ１－ＩＩ）で表される部分構造を有するエポキシ（メタ）アクリレート系樹脂について詳述する。 <(B1-II) Epoxy (meth) acrylate resin>
The epoxy (meth) acrylate-based resin having a partial structure represented by the general formula (b1-II) will be described in detail.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
　式（ｂ１－ＩＩ）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 (b1-II), R 13 independently represents a hydrogen atom or a methyl group, and 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 represent an integer of 0 to 2, and * represents a bond.
　（Ｒ１４）
　前記一般式（ｂ１－ＩＩ）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 (b1-II), 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以上であり、２以上が好ましく、また、通常１０以下であり、５以下が好ましく、３以下がより好ましい。例えば、１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましく、２～３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、現像時に生じる表面荒れが生じにくくなる傾向がある。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。
　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。上記の上限及び下限は任意に組み合わせることができる。例えば、４～４０が好ましく、４～３０がより好ましく、６～２０がさらに好ましく、８～１５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、現像時に生じる表面荒れが生じにくくなる傾向がある。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。
　脂肪族環基における脂肪族環としては、例えば、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、シクロドデカン環が挙げられる。これらの中でも感光性着色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 contained in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is further preferable, and 2 to 3 is particularly preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
The number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferable, 4 to 30 is more preferable, 6 to 20 is more preferable, and 8 to 15 is particularly preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
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, the adamantane ring is preferable from the viewpoint of the residual film ratio and the resolution of the photosensitive coloring composition.
　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以上であり、２以上が好ましく、３以上がより好ましく、また、通常１０以下であり、５以下が好ましく、４以下がより好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、１～５がより好ましく、１～４がさらに好ましく、２～４がよりさらに好ましく、３～４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、現像時に生じる表面荒れが生じにくくなる傾向がある。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、１０以上がよりさらに好ましく、１２以上が特に好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、４～４０が好ましく、６～４０がより好ましく、８～３０がさらに好ましく、１０～２０がよりさらに好ましく、１２～１５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、現像時に生じる表面荒れが生じにくくなる傾向がある。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。
　芳香族環基における芳香族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環が挙げられる。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。 The number of rings contained in 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, preferably 5 or less, and more preferably 4 or less. .. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 4 is further preferable, 2 to 4 is more preferable, and 3 to 4 is particularly preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
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, still more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, preferably 30 or less. More preferably, 20 or less is further preferable, and 15 or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferable, 6 to 40 is more preferable, 8 to 30 is further preferable, 10 to 20 is more preferable, and 12 to 15 is particularly preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur. When the value is not more than the upper limit, the patterning characteristics tend to be good.
Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. Ring is mentioned. Among these, the fluorene ring is preferable from the viewpoint of patterning characteristics.
　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。 The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, but for example, a divalent aliphatic group, a divalent aromatic ring group, 1 or more 2 Examples thereof include a group in which a valent aliphatic group and one or more divalent aromatic ring groups are linked.
　２価の脂肪族基は、直鎖状、分岐鎖状、環状の脂肪族基が挙げられる。これらの中でも現像溶解性の観点からは直鎖状の脂肪族基が好ましく、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脂肪族基が好ましい。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。上記の上限及び下限は任意に組み合わせることができる。例えば、１～２５が好ましく、３～２０がより好ましく、６～１５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、現像時に生じる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る。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。 Examples of the divalent aliphatic group include linear, branched and cyclic aliphatic groups. Among these, a linear aliphatic group is preferable from the viewpoint of development solubility, while a cyclic aliphatic group is preferable from the viewpoint of reducing the penetration of the developer into the exposed portion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, preferably 25 or less, more preferably 20 or less, still more preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 25 is preferable, 3 to 20 is more preferable, and 6 to 15 is even more preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
　２価の直鎖状の脂肪族基としては、例えば、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ペンチレン基、ｎ－ヘキシレン基、ｎ－ヘプチレン基が挙げられる。これらの中でも骨格の剛直性の観点から、メチレン基が好ましい。
　２価の分岐鎖状の脂肪族基としては、例えば、前述の２価の直鎖状の脂肪族基に、側鎖としてメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基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以上であり、２以上が好ましく、また、通常１０以下であり、５以下が好ましく、３以下がさらに好ましい。例えば、１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましく、２～３が特に好ましい。前記下限値以上とすることで強固な膜となり、基板密着性と良好となる傾向がある。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。
　２価の環状の脂肪族基としては、例えば、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。 Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of skeletal rigidity.
Examples of the divalent branched chain aliphatic group include the above-mentioned divalent linear aliphatic group and the side chains of a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. , Isobutyl group, sec-butyl group, tert-butyl group.
The number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and even more preferably 3 or less. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is further preferable, and 2 to 3 is particularly preferable. By setting the value to the lower limit or higher, the film becomes strong and tends to have good substrate adhesion. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
Examples of the divalent cyclic aliphatic group include a group obtained by removing two hydrogen atoms from the cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. Can be mentioned. Among these, from the viewpoint of skeletal rigidity, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable.
　２価の脂肪族基が有していてもよい置換基としては、例えば、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；カルボキシ基が挙げられる。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; and a carboxy group. Among these, unsubstituted is preferable from the viewpoint of easiness of synthesis.
　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。例えば、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、現像時に生じる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る。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。 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, preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. For example, 4 to 30 is preferable, 5 to 20 is more preferable, and 6 to 15 is even more preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, 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。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、フルオレン環が挙げられる。
　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。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。 The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring, which have two free atomic valences. Examples include an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having two free atomic valences. Ring, Pyrolobymidazole ring, Pyrrolopyrazole ring, Pyrrolopyrrole ring, Thienopyrrole ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Thienofranc ring, Benzoisoxazole ring, Benzoisothiazole ring, Benzimidazole ring, Ppyridine ring, Pyrazine ring, Examples thereof include a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxalin ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. 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、例えば、ヒドロキシ基、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 hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Of these, no substitution is preferable from the viewpoint of development solubility.
　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以上であり、２以上が好ましく、通常１０以下であり、５以下が好ましく、３以下がより好ましい。例えば、１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましく、２～３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、現像時に生じる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る。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、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以上であり、２以上が好ましく、通常１０以下であり、５以下が好ましく、３以下がより好ましい。例えば、１～１０が好ましく、１～５がより好ましく、１～３がさらに好ましく、２～３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、現像時に生じる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る。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。 As a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, the above-mentioned divalent aliphatic group is 1 or more, and the above-mentioned divalent aromatic ring group is described. Can be mentioned as a group in which 1 or more are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is further preferable, and 2 to 3 is particularly preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 1 to 3 is further preferable, and 2 to 3 is particularly preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, 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としては、例えば、前記式（ｂ１－Ｉ－Ａ）～（ｂ１－Ｉ－Ｆ）で表される基が挙げられる。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（ｂ１－Ｉ－Ｃ）で表される基が好ましい。 Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked are represented by the above formulas (b1-IA) to (b1-IF). Group is mentioned. Among these, the group represented by the above formula (b1-IC) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobicity of the membrane.
　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つを側鎖である環状炭化水素基で置換した態様や、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, is not particularly limited with respect to these divalent hydrocarbon groups, but for example, one hydrogen atom of an aliphatic group or an aromatic ring group is cyclic as a side chain. Examples thereof include an embodiment substituted with a hydrocarbon group and an embodiment in which a cyclic hydrocarbon group as a side chain is formed including one of the carbon atoms of the aliphatic group.
　（Ｒ１５、Ｒ１６）
　一般式（ｂ１－ＩＩ）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 and R 16 )
In the general formula (b1-II), R 15 and R 16 each independently represent a divalent aliphatic group which may have a substituent.
　２価の脂肪族基は、直鎖状、分岐鎖状、環状の脂肪族基が挙げられる。これらの中でも現像溶解性の観点からは直鎖状の脂肪族基が好ましく、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脂肪族基が好ましい。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。例えば、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、現像時に生じる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る。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。 Examples of the divalent aliphatic group include linear, branched and cyclic aliphatic groups. Among these, a linear aliphatic group is preferable from the viewpoint of development solubility, while a cyclic aliphatic group is preferable from the viewpoint of reducing the penetration of the developer into the exposed portion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less. For example, 1 to 20 is preferable, 3 to 15 is more preferable, and 6 to 10 is even more preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, surface roughness that occurs during development is less likely to occur, and adhesion to the substrate tends to be good. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
　２価の直鎖状の脂肪族基としては、例えば、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ペンチレン基、ｎ－ヘキシレン基、ｎ－ヘプチレン基が挙げられる。これらの中でも骨格の剛直性の観点から、メチレン基が好ましい。
　２価の分岐鎖状の脂肪族基としては、前述の２価の直鎖状の脂肪族基に、側鎖として、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、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基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以上であり、２以上が好ましく、また、通常１２以下であり、１０以下が好ましい。例えば、１～１２が好ましく、２～１０がより好ましい。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る。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。
　２価の環状の脂肪族基としては、例えば、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。 Examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of skeletal rigidity.
The divalent branched chain aliphatic group includes the above-mentioned divalent linear aliphatic group, and the side chains include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl. Examples thereof include a structure having a group, an isobutyl group, a sec-butyl group and a tert-butyl group.
The number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. For example, 1 to 12 is preferable, and 2 to 10 is more preferable. By setting the value to the lower limit or higher, the film becomes strong and the substrate adhesion tends to be good. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
Examples of the divalent cyclic aliphatic group include two hydrogen atoms from 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 a dicyclopentadiene ring. The group to be removed is mentioned. Among these, from the viewpoint of skeletal rigidity, a group obtained by removing two hydrogen atoms from the dicyclopentadiene ring and the adamantane ring is preferable.
　２価の脂肪族基が有していてもよい置換基としては、例えば、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；カルボキシ基が挙げられる。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; and a carboxy group. Among these, unsubstituted is preferable from the viewpoint of easiness of synthesis.
　（ｍ、ｎ）
　一般式（ｂ１－ＩＩ）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、現像時に生じる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い。一方で、パターニング適正、現像時に生じる表面荒れの観点からｍ及びｎが１以上であることが好ましい。 (M, n)
In the general formula (b1-II), m and n each independently represent an integer of 0 to 2. When it is set to the lower limit value or more, the patterning suitability is improved and surface roughness which occurs during development tends to be less likely to occur, and when it is set to the upper limit value or less, the 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 1 or more from the viewpoint of proper patterning and surface roughness generated during development.
　一般式（ｂ１－ＩＩ）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（ｂ１－ＩＩ－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 (b1-II) is preferably a partial structure represented by the following general formula (b1-II-1) from the viewpoint of adhesion to the substrate.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　式（ｂ１－ＩＩ－１）中、Ｒ１３、Ｒ１５、Ｒ１６、ｍ及びｎは式（ｂ１－ＩＩ）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以上の整数を表し、＊は結合手を表す。式（ｂ１－ＩＩ－１）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。 In formula (b1-II-1), R 13 , R 15 , R 16 , m and n are synonymous with formula (b1-II) and R α is a monovalent which may have a substituent. It represents a cyclic hydrocarbon group, p represents an integer of 1 or more, and * represents a bond. The benzene ring in the formula (b1-II-1) may be further substituted with any substituent.
　（Ｒα）
　一般式（ｂ１－ＩＩ－１）において、Ｒαは、置換基を有していてもよい１価の環状炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 (R α )
In the general formula (b1-II-1), R α represents a monovalent cyclic hydrocarbon group which may have a substituent.
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以上であり、２以上が好ましく、また、通常６以下であり、４以下が好ましく、３以下がより好ましい。例えば、１～６が好ましく、１～４がより好ましく、１～３がさらに好ましく、２～３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、現像時に生じる表面荒れが生じにくくなる傾向がある。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。
　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。上記の上限及び下限は任意に組み合わせることができる。例えば、４～４０が好ましく、４～３０がより好ましく、６～２０がさらに好ましく、８～１５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、現像時に生じる表面荒れが生じにくくなる傾向がある。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。
　脂肪族環基における脂肪族環としては、例えば、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 contained in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. For example, 1 to 6 is preferable, 1 to 4 is more preferable, 1 to 3 is further preferable, and 2 to 3 is particularly preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur. When the value is not more than the upper limit, the patterning characteristics tend to be good.
The number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferable, 4 to 30 is more preferable, 6 to 20 is more preferable, and 8 to 15 is particularly preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur. When the value is not more than the upper limit, the patterning characteristics tend to be good.
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, the adamantane ring is preferable from the viewpoint of strong film characteristics.
　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以上であり、２以上が好ましく、３以上がより好ましく、また、通常１０以下であり、５以下が好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、１～５がより好ましく、２～５がさらに好ましく、３～５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、現像時に生じる表面荒れが生じにくくなる傾向がある。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。
　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。上記の上限及び下限は任意に組み合わせることができる。例えば、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、現像時に生じる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。
　芳香族環基における芳香族環としては、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。 The number of rings contained in 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, preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 2 to 5 is further preferable, and 3 to 5 is particularly preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur. When the value is not more than the upper limit, the patterning characteristics tend to be good.
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, preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. The above upper and lower limits can be combined arbitrarily. For example, 4 to 30 is preferable, 5 to 20 is more preferable, and 6 to 15 is even more preferable. When it is set to the lower limit value or more, a strong film is likely to be obtained, surface roughness which occurs during development tends to be less likely to occur, and when it is set to the upper limit value or less, the patterning property tends to be improved.
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, the 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、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、ｔｅｒｔ－ブチル基、アミル基、イソ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；カルボキシ基が挙げられる。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 methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and an amyl group. Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an isoamyl group; 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; and a carboxy group. Of these, no substitution 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。例えば、１～３が好ましく、２～３がより好ましい。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る。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。 P represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. For example, 1 to 3 is preferable, and 2 to 3 is more preferable. When the value is equal to or higher than the lower limit, the degree of film hardening and the residual film ratio tend to be good. When the value is not more than the upper limit, the developability tends to be good.
　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 strong film hardening degree, R α is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.
　式（ｂ１－ＩＩ－１）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。式（ｂ１－ＩＩ－１）中のベンゼン環に許容される置換基としては、例えば、ヒドロキシ基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基が挙げられる。式（ｂ１－ＩＩ－１）中のベンゼン環が置換基を有する場合、置換基の数は特に限定されず、１つでもよいし、２つ以上でもよい。
　パターニング特性の観点から、式（ｂ１－ＩＩ－１）中のベンゼン環は無置換であることが好ましい。 The benzene ring in the formula (b1-II-1) may be further substituted with any substituent. Examples of the substituent allowed on the benzene ring in the formula (b1-II-1) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. When the benzene ring in the formula (b1-II-1) has a substituent, the number of the substituents is not particularly limited and may be one or two or more.
From the viewpoint of patterning properties, the benzene ring in the formula (b1-II-1) is preferably unsubstituted.
　以下に式（ｂ１－ＩＩ－１）で表される部分構造の具体例を挙げる。 The following is a specific example of the partial structure represented by the formula (b1-II-1).
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　一般式（ｂ１－ＩＩ）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（ｂ１－ＩＩ－２）で表される部分構造であることが好ましい。 The partial structure represented by the general formula (b1-II) is preferably the partial structure represented by the following general formula (b1-II-2) from the viewpoint of skeletal rigidity and membrane hydrophobicity.
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　式（ｂ１－ＩＩ－２）中、Ｒ１３、Ｒ１５、Ｒ１６、ｍ及びｎは式（ｂ１－ＩＩ）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、＊は結合手を表す。
　式（ｂ１－ＩＩ－２）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。 In formula (b1-II-2), R 13 , R 15 , R 16 , m and n are synonymous with formula (b1-II), and R β is a divalent group which may have a substituent. It represents a cyclic hydrocarbon group, and * represents a bond.
The benzene ring in the formula (b1-II-2) may be further substituted with any substituent.
　（Ｒβ）
　式（ｂ１－ＩＩ－２）において、Ｒβは、置換基を有していてもよい２価の環状炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 (R β )
In formula (b1-II-2), R β represents a divalent cyclic hydrocarbon group which may have a substituent.
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以上であり、２以上が好ましく、また、通常１０以下であり、５以下が好ましい。例えば、１～１０が好ましく、２～５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、現像時に生じる表面荒れが生じにくくなる傾向がある。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。
　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。上記の上限及び下限は任意に組み合わせることができる。例えば、４～４０が好ましく、６～３５がより好ましく、８～３０がさらに好ましい。前記下限値以上とすることで現像時の膜あれを抑制する傾向がある。前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。
　脂肪族環基における脂肪族環としては、例えば、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、シクロドデカン環が挙げられる。これらの中でも現像時の膜減り、解像性の観点から、アダマンタン環が好ましい。 The number of rings contained in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. For example, 1 to 10 is preferable, and 2 to 5 is more preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
The number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. The above upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferable, 6 to 35 is more preferable, and 8 to 30 is even more preferable. By setting the value to the lower limit or higher, there is a tendency to suppress film roughness during development. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss during development, and the resolution tends to be improved.
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, the adamantane ring is preferable from the viewpoint of film reduction during development and resolution.
　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以上であり、２以上が好ましく、３以上がより好ましく、また、通常１０以下であり、５以下が好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、１～５がより好ましく、２～５がさらに好ましく、３～５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、現像時に生じる表面荒れが生じにくくなる傾向がある。前記上限値以下とすることで感度の悪化や膜減りを抑制しやすく、解像性が向上する傾向がある。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、１０以上がさらに好ましく、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。上記の上限及び下限は任意に組み合わせることができる。例えば、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、現像時に生じる表面荒れが生じにくくなる傾向がある。前記上限値以下とすることで感度の悪化や膜減りを抑制しやすく、解像性が向上する傾向がある。
　芳香族環基における芳香族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環が挙げられる。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 contained in 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, preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferable, 1 to 5 is more preferable, 2 to 5 is further preferable, and 3 to 5 is particularly preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss, and the resolution tends to be improved.
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, further preferably 10 or more, preferably 40 or less, more preferably 30 or less, and further preferably 20 or less. It is preferable, and 15 or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 4 to 40 is preferable, 6 to 30 is more preferable, 8 to 20 is more preferable, and 10 to 15 is particularly preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss, and the resolution tends to be improved.
Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthren ring, and a fluorene ring. Among these, the 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、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、ｔｅｒｔ－ブチル基、アミル基、イソ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；カルボキシ基が挙げられる。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 methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and an amyl group. Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an isoamyl group; 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; and a carboxy group. Of these, no substitution is preferable from the viewpoint of simplicity of synthesis.
　これらの中でも、膜減りの抑制、解像性の観点から、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、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 suppression of membrane loss and resolution, Rβ is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group.
On the other hand, from the viewpoint of patterning characteristics, R β is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.
　式（ｂ１－ＩＩ－２）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。式（ｂ１－ＩＩ－２）中のベンゼン環に許容される置換基としては、例えば、ヒドロキシ基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基が挙げられる。式（ｂ１－ＩＩ－２）中のベンゼン環が置換基を有する場合、置換基の数は特に限定されず、１つでもよいし、２つ以上でもよい。
　また、置換基を介して２つのベンゼン環が連結していてもよい。この場合の置換基としては、－Ｏ－、－Ｓ－、－ＮＨ－、－ＣＨ２－等の２価の基が挙げられる。
　パターニング特性の観点から、式（ｂ１－ＩＩ－２）中のベンゼン環は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、式（ｂ１－ＩＩ－２）中のベンゼン環はメチル基で置換されていることが好ましい。 The benzene ring in the formula (b1-II-2) may be further substituted with any substituent. Examples of the substituent allowed on the benzene ring in the formula (b1-II-2) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. When the benzene ring in the formula (b1-II-2) has a substituent, the number of the substituents is not particularly limited and may be one or two or more.
Further, two benzene rings may be linked via a substituent. Examples of the substituent in this case include divalent groups such as -O-, -S-, -NH-, and -CH 2- .
From the viewpoint of patterning properties, the benzene ring in the formula (b1-II-2) is preferably unsubstituted. Further, from the viewpoint of making it difficult for film loss and the like to occur, it is preferable that the benzene ring in the formula (b1-II-2) is substituted with a methyl group.
　以下に前記式（ｂ１－ＩＩ－２）で表される部分構造の具体例を挙げる。なお、例中の＊は結合手を示す。 The following is a specific example of the partial structure represented by the above formula (b1-II-2). In addition, * in the example indicates a bond.
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
　式（ｂ１－ＩＩ）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（ｂ１－ＩＩ－３）で表される部分構造であることが好ましい。 The partial structure represented by the formula (b1-II) is preferably a partial structure represented by the following formula (b1-II-3) from the viewpoint of the coating film residual film ratio and the patterning characteristics.
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
　式（ｂ１－ＩＩ－３）中、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６、ｍ及びｎは式（ｂ１－ＩＩ）と同義であり、ＲＺは水素原子又は多塩基酸残基を表す。 In formula (b1-II-3), R 13 , R 14 , R 15 , R 16 , m and n are synonymous with formula (b1-II), and R Z represents a hydrogen atom or a polybasic acid residue. ..
　多塩基酸残基とは、多塩基酸から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（ｂ１－ＩＩ－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（ｂ１－ＩＩ－３）が連結していてもよい。
　多塩基酸としては、例えば、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、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 subtracting one OH group from the polybasic acid. Further, another OH group may be removed and shared with R Z in another molecule represented by the formula (b1-II-3), that is, a plurality of formulas (b1) may be shared via R Z. -II-3) may be linked.
Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid and endomethylene. Examples thereof include tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid and biphenyltetracarboxylic acid.
Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid and biphenyltetracarboxylic acid are preferable. Is tetrahydrophthalic acid, biphenyltetracarboxylic acid, biphenyltetracarboxylic acid.
　（ｂ１－ＩＩ）エポキシ（メタ）アクリレート系樹脂１分子中に含まれる、式（ｂ１－ＩＩ－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。 The partial structure represented by the formula (b1-II-3) contained in one molecule of the (b1-II) epoxy (meth) acrylate-based resin may be one kind or two or more kinds, for example, R Z is hydrogen. Atomic ones and those having R Z as a polybasic acid residue may be mixed.
　（ｂ１－ＩＩ）エポキシ（メタ）アクリレート系樹脂１分子中に含まれる、式（ｂ１－ＩＩ）で表される部分構造の数は特に限定されないが、１以上が好ましく、３以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。例えば、１～２０が好ましく、１～１５がより好ましく、３～１０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、現像時に生じる表面荒れが生じにくくなる傾向がある。前記上限値以下とすることで感度の悪化や膜減りを抑制しやすく、解像性が向上する傾向がある。 The number of partial structures represented by the formula (b1-II) contained in one molecule of the (b1-II) epoxy (meth) acrylate resin is not particularly limited, but 1 or more is preferable, and 3 or more is more preferable. Further, 20 or less is preferable, 15 or less is more preferable, and 10 or less is further preferable. For example, 1 to 20 is preferable, 1 to 15 is more preferable, and 3 to 10 is even more preferable. By setting the value to the lower limit or more, a strong film is likely to be obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting the value to the upper limit or less, it is easy to suppress deterioration of sensitivity and film loss, and the resolution tends to be improved.
　（ｂ１－ＩＩ）エポキシ（メタ）アクリレート系樹脂の、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以上がよりさらに好ましく、４０００以上が特に好ましく、５０００以上が最も好ましく、通常１００００以下であり、８０００以下が好ましく、７０００以下がより好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１０００～１００００が好ましく、１５００～１００００がより好ましく、１５００～８０００がさらに好ましく、２０００～８０００がよりさらに好ましく、２０００～７０００が特に好ましい。前記下限値以上とすることで感光性着色組成物の残膜率が良好となる傾向がある。前記上限値以下とすることで現像液に対する溶解性が良好となる傾向がある。 The polystyrene-equivalent weight average molecular weight (Mw) of the (b1-II) epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more. , 2000 or more is more preferable, 3000 or more is more preferable, 4000 or more is particularly preferable, 5000 or more is most preferable, usually 10000 or less, 8000 or less is preferable, and 7000 or less is more preferable. The above upper and lower limits can be combined arbitrarily. For example, 1000 to 10000 is preferable, 1500 to 10000 is more preferable, 1500 to 8000 is further preferable, 2000 to 8000 is further preferable, and 2000 to 7000 is particularly preferable. By setting the value to the lower limit or more, the residual film ratio of the photosensitive coloring composition tends to be good. When the value is not more than the upper limit, the solubility in a developing solution tends to be good.
　（ｂ１－ＩＩ）エポキシ（メタ）アクリレート系樹脂の酸価は特に限定されないが、２０ｍｇＫＯＨ／ｇ以上が好ましく、４０ｍｇＫＯＨ／ｇ以上がより好ましく、６０ｍｇＫＯＨ／ｇ以上がさらに好ましく、８０ｍｇＫＯＨ／ｇ以上がよりさらに好ましく、１００ｍｇＫＯＨ／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、１２０ｍｇＫＯＨ／ｇ以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、２０ｍｇＫＯＨ／ｇ～２００ｍｇＫＯＨ／ｇが好ましく、６０ｍｇＫＯＨ／ｇ～１５０ｍｇＫＯＨ／ｇがより好ましく、８０ｍｇＫＯＨ／ｇ～１３０ｍｇＫＯＨ／ｇがさらに好ましく、１００ｍｇＫＯＨ／ｇ～１３０ｍｇＫＯＨ／ｇがよりさらに好ましい。前記下限値以上とすることで現像溶解性が向上し、解像性が良好となる傾向がある。前記上限値以下とすることで感光性着色組成物の残膜率が良好となる傾向がある。 The acid value of the (b1-II) epoxy (meth) acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 60 mgKOH / g or more, and more preferably 80 mgKOH / g or more. More preferably, 100 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 even more preferable, and 120 mgKOH / g or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 20 mgKOH / g to 200 mgKOH / g is preferable, 60 mgKOH / g to 150 mgKOH / g is more preferable, 80 mgKOH / g to 130 mgKOH / g is further preferable, and 100 mgKOH / g to 130 mgKOH / g is even more preferable. By setting the value to the lower limit or more, the develop solubility tends to be improved and the resolution tends to be good. When the value is not more than the upper limit, the residual film ratio of the photosensitive coloring composition tends to be good.
　カルボキシ基含有エポキシ（メタ）アクリレート系樹脂は、１種を単独で用いても、２種以上の樹脂を混合して用いてもよい。
　カルボキシ基含有エポキシ（メタ）アクリレート系樹脂の一部を、他のバインダー樹脂に置き換えて用いてもよい。即ち、カルボキシ基含有エポキシ（メタ）アクリレート系樹脂と他のバインダー樹脂を併用してもよい。この場合において、（ｂ）アルカリ可溶性樹脂におけるカルボキシ基含有エポキシ（メタ）アクリレート系樹脂の割合を、５０質量％以上とすることが好ましく、６０質量％以上とすることがより好ましく、７０質量％以上とすることがさらに好ましく、８０質量％以上とすることが特に好ましく、通常１００質量％以下である。 As the carboxy group-containing epoxy (meth) acrylate-based resin, one type may be used alone, or two or more types of resins may be mixed and used.
A part of the carboxy group-containing epoxy (meth) acrylate resin may be replaced with another binder resin and used. That is, a carboxy group-containing epoxy (meth) acrylate resin and another binder resin may be used in combination. In this case, (b) the ratio of the carboxy group-containing epoxy (meth) acrylate-based resin in the alkali-soluble resin is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. It is more preferably 80% by mass or more, and usually 100% by mass or less.
　（ｂ）アルカリ可溶性樹脂として、顔料や分散剤等との相溶性の観点から、（ｂ２）アクリル共重合樹脂を用いることが好ましく、日本国特開２０１４－１３７４６６号公報に記載のアクリル共重合樹脂を好ましく用いることができる。 (B) As the alkali-soluble resin, it is preferable to use (b2) an acrylic copolymer resin from the viewpoint of compatibility with pigments, dispersants and the like, and the acrylic copolymer resin described in Japanese Patent Application Laid-Open No. 2014-137466. Can be preferably used.
　アクリル共重合樹脂としては、例えば、１個以上のカルボキシ基を有するエチレン性不飽和単量体（以下、「不飽和単量体（ｂ２－１）」という。）と他の共重合可能なエチレン性不飽和単量体（以下、「不飽和単量体（ｂ２－２）」という。）との共重合体を挙げることができる。
　不飽和単量体（ｂ２－１）としては、例えば、（メタ）アクリル酸、クロトン酸、α－クロルアクリル酸、けい皮酸等の不飽和モノカルボン酸；マレイン酸、無水マレイン酸、フマル酸、シトラコン酸、無水シトラコン酸、メサコン酸等の不飽和ジカルボン酸又はその無水物；こはく酸モノ〔２－（メタ）アクリロイロキシエチル〕、フタル酸モノ〔２－（メタ）アクリロイロキシエチル〕等の２価以上の多価カルボン酸のモノ〔（メタ）アクリロイロキシアルキル〕エステル；ω－カルボキシポリカプロラクトンモノ（メタ）アクリレート等の両末端にカルボキシ基と水酸基とを有するポリマーのモノ（メタ）アクリレート；ｐ－ビニル安息香酸を挙げることができる。
　これらの不飽和単量体（ｂ２－１）は、単独で又は２種以上を混合して使用することができる。 Examples of the acrylic copolymer resin include an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter referred to as “unsaturated monomer (b2-1)”) and other copolymerizable ethylene. Examples thereof include a copolymer with a sex-unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2-2)").
Examples of the unsaturated monomer (b2-1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloracrylic acid, and dermal acid; maleic acid, maleic anhydride, and fumaric acid. , Citraconic acid, anhydrous citraconic acid, unsaturated dicarboxylic acid such as mesaconic acid or its anhydride; mono-succinic acid [2- (meth) acryloyloxyethyl], mono-phthalic acid [2- (meth) acryloyloxyethyl] Mono [(meth) acryloyloxyalkyl] ester of a polyvalent carboxylic acid having a valence of 2 or more; ) Ester; p-vinylbenzoic acid can be mentioned.
These unsaturated monomers (b2-1) can be used alone or in admixture of two or more.
　不飽和単量体（ｂ２－２）としては、例えば、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等のＮ－置換マレイミド；
　スチレン、α－メチルスチレン、ｐ－ヒドロキシスチレン、ｐ－ヒドロキシ－α－メチルスチレン、ｐ－ビニルベンジルグリシジルエーテル、アセナフチレン等の芳香族ビニル化合物； Examples of the unsaturated monomer (b2-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;
　メチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、アリル（メタ）アクリレート、ベンジル（メタ）アクリレート、ポリエチレングルコール（重合度２～１０）メチルエーテル（メタ）アクリレート、ポリプロピレングルコール（重合度２～１０）メチルエーテル（メタ）アクリレート、ポリエチレングリコール（重合度２～１０）モノ（メタ）アクリレート、ポリプロピレングリコール（重合度２～１０）モノ（メタ）アクリレート、シクロヘキシル（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［５．２．１．０２，６］デカン－８－イル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、４－ヒドロキシフェニル（メタ）アクリレート、パラクミルフェノールのエチレンオキサイド変性（メタ）アクリレート、グリシジル（メタ）アクリレート、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、３－〔（メタ）アクリロイルオキシメチル〕オキセタン、３－〔（メタ）アクリロイルオキシメチル〕－３－エチルオキセタン等の（メタ）アクリル酸エステル； Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glucol (degree of polymerization 2) ~ 10) Methyl ether (meth) acrylate, polypropylene glucol (polymerization degree 2 to 10) Methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) ) Mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decane-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, Gglycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(( (Meta) Acryloyloxymethyl] Oxetane, 3-[(Meta) Acryloyloxymethyl] -3-ethyl Oxetane and other (meth) acrylic acid esters;
　シクロヘキシルビニルエーテル、イソボルニルビニルエーテル、トリシクロ［５．２．１．０２，６］デカン－８－イルビニルエーテル、ペンタシクロペンタデカニルビニルエーテル、３－（ビニルオキシメチル）－３－エチルオキセタン等のビニルエーテル；
　ポリスチレン、ポリメチル（メタ）アクリレート、ポリ－ｎ－ブチル（メタ）アクリレート、ポリシロキサン等の重合体分子鎖の末端にモノ（メタ）アクリロイル基を有するマクロモノマーを挙げることができる。
　これらの不飽和単量体（ｂ２－２）は、単独で又は２種以上を混合して使用することができる。 Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 2,6 ] decane-8-ylvinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (b2-2) can be used alone or in admixture of two or more.
　不飽和単量体（ｂ２－１）と不飽和単量体（ｂ２－２）の共重合体において、不飽和単量体（ｂ２－１）の共重合割合は、好ましくは５～５０質量％、さらに好ましくは１０～４０質量％である。このような範囲で不飽和単量体（ｂ２－１）を共重合させることにより、アルカリ現像性及び保存安定性に優れた感光性着色組成物を得ることができる傾向がある。 In the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2), the copolymerization ratio of the unsaturated monomer (b2-1) is preferably 5 to 50% by mass. , More preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b2-1) in such a range, it tends to be possible to obtain a photosensitive coloring composition having excellent alkali developability and storage stability.
　不飽和単量体（ｂ２－１）と不飽和単量体（ｂ２－２）の共重合体としては、例えば、日本国特開平７－１４０６５４号公報、日本国特開平８－２５９８７６号公報、日本国特開平１０－３１３０８号公報、日本国特開平１０－３００９２２号公報、日本国特開平１１－１７４２２４号公報、日本国特開平１１－２５８４１５号公報、日本国特開２０００－５６１１８号公報、日本国特開２００４－１０１７２８号公報に開示されている共重合体を挙げることができる。
　不飽和単量体（ｂ２－１）と不飽和単量体（ｂ２－２）の共重合体は、公知の方法により製造することができるが、例えば、日本国特開２００３－２２２７１７号公報、日本国特開２００６－２５９６８０号公報、国際公開第２００７／０２９８７１号公報に開示されている方法により、その構造やＭｗ、Ｍｗ／Ｍｎを制御することもできる。 Examples of the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) include Japanese Patent Application Laid-Open No. 7-140654 and Japanese Patent Application Laid-Open No. 8-259876. Japanese Patent Application Laid-Open No. 10-31308, Japanese Patent Application Laid-Open No. 10-300922, Japanese Patent Application Laid-Open No. 11-174224, Japanese Patent Application Laid-Open No. 11-258415, Japanese Patent Application Laid-Open No. 2000-56118, Examples thereof include the copolymer disclosed in Japanese Patent Application Laid-Open No. 2004-101728.
The copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) can be produced by a known method, and for example, Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2003-222717. The structure, Mw, and Mw / Mn can also be controlled by the methods disclosed in Japanese Patent Laid-Open No. 2006-259680 and International Publication No. 2007/029871.
　そのほか、国際公開第２０１６／１９４６１９号、国際公開第２０１７／１５４４３９号に記載の樹脂を用いてもよい。 In addition, the resins described in International Publication No. 2016/194619 and International Publication No. 2017/154439 may be used.
＜（ｃ）光重合開始剤＞
　（ｃ）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類；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類、ハロメチル－ｓ－トリアジン誘導体類；α－アミノアルキルフェノン誘導体類；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系化合物が挙げられる。 <(C) Photopolymerization Initiator>
(C) 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.
As the photopolymerization initiator, for example, a metallocene compound containing a titanosen compound described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Laid-Open No. 61-151197; Hexaaryl imidazole derivatives described; halomethylated oxadiazole derivatives and halomethyl-s-triazine derivatives described in Japanese Patent Application Laid-Open No. 10-39503; α-aminoalkylphenone derivatives; Japanese Patent Application Laid-Open No. 2000- Examples thereof include oxime ester compounds described in Japanese Patent Application Laid-Open No. 80068, Japanese Patent Application Laid-Open No. 2006-36750 and the like.
　メタロセン化合物としては、例えば、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－（ピロール－１－イル）フェニル〕が挙げられる。 Examples of the metallocene compound include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis (2,3,4,5,6-pentafluorophenyl) and dicyclopenta. Dienyltitanium bis (2,3,5,6-tetrafluorophenyl), dicyclopentadienyltitanium bis (2,4,6-trifluorophenyl), dicyclopentadienyltitanium di (2,6-difluorophenyl) Phenyl), dicyclopentadienyl titanium di (2,4-difluorophenyl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl), di (methylcyclopenta) Dienyl) Titanium bis (2,6-difluorophenyl), dicyclopentadienyltitanium [2,6-di-fluoro-3- (pyrrole-1-yl) phenyl] can be mentioned.
　ヘキサアリールビイミダゾール誘導体類としては、例えば、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量体が挙げられる。 Examples of hexaarylbiimidazole derivatives include 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer and 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 can be mentioned.
　ハロメチル化オキサジアゾール誘導体類としては、例えば、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－オキサジアゾールが挙げられる。 Examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole and 2-trichloromethyl-5-[β- (2'-). Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5-[β- (2'-(6''-benzofuryl) vinyl)]-1,3,4-oxadiazole, Examples thereof include 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
　ハロメチル－ｓ－トリアジン誘導体類としては、例えば、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－トリアジンが挙げられる。 Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and 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 is mentioned.
　α－アミノアルキルフェノン誘導体類としては、例えば、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）カルコンが挙げられる。 Examples of α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-). Morphorinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-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 can be mentioned.
　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系化合物が有効であり、例えば、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は、特にこのような感度に優れた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は、その構造の中に紫外線を吸収する構造と光エネルギーを伝達する構造とラジカルを発生する構造を併せ持っているために、少量で感度が高く、かつ、熱反応に対して安定であり、少量で高感度な感光性着色組成物を得ることが可能である。 As the photopolymerization initiator, an oxime ester compound is particularly effective in terms of sensitivity and plate-making property. For example, when an alkali-soluble resin containing a phenolic hydroxyl group is used, an oxime ester having such excellent sensitivity is particularly effective. Esters are useful. Since the oxime ester compound has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in its structure, it is highly sensitive to a small amount and stable to a thermal reaction. Therefore, it is possible to obtain a highly sensitive photosensitive coloring composition in a small amount.
　オキシムエステル系化合物としては、例えば、下記一般式（ＩＶ）で表される化合物が挙げられる。 Examples of the oxime ester compound include compounds represented by the following general formula (IV).
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
　上記式（ＩＶ）中、Ｒ２１ａは、水素原子、置換基を有していてもよいアルキル基、又は、置換基を有していてもよい芳香族環基を示す。
　Ｒ２１ｂは芳香環を含む任意の置換基を示す。
　Ｒ２２ａは、置換基を有していてもよいアルカノイル基、又は、置換基を有していてもよいアリーロイル基を示す。
　ｎは０又は１の整数を示す。 In the above formula (IV), R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R 21b represents any substituent including an aromatic ring.
R 22a indicates an alkanoyl group which may have a substituent or an allyloyl group which may have a substituent.
n represents an integer of 0 or 1.
　Ｒ２１ａにおけるアルキル基の炭素数は特に限定されないが、溶媒への溶解性や感度の観点から、通常１以上、好ましくは２以上、また、通常２０以下、好ましくは１５以下、より好ましくは１０以下である。例えば、例えば、１～２０、好ましくは１～１５、より好ましくは２～１０である。アルキル基としては、メチル基、エチル基、プロピル基、シクロペンチルエチル基が挙げられる。
　アルキル基が有していてもよい置換基としては、例えば、芳香族環基、水酸基、カルボキシ基、ハロゲン原子、アミノ基、アミド基、４－（２－メトキシ－１－メチル）エトキシ－２－メチルフェニル基又はＮ－アセチル－Ｎ－アセトキシアミノ基が挙げられ、合成容易性の観点からは、無置換であることが好ましい。 The number of carbon atoms of the alkyl group in R 21a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. Is. For example, it is, for example, 1 to 20, preferably 1 to 15, and more preferably 2 to 10. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group and a cyclopentylethyl group.
Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and 4- (2-methoxy-1-methyl) ethoxy-2-. Examples thereof include a methylphenyl group and an N-acetyl-N-acetoxyamino group, which are preferably unsubstituted from the viewpoint of ease of synthesis.
　Ｒ２１ａにおける芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。芳香族環基の炭素数は特に限定されないが、感光性着色組成物への溶解性の観点から５以上であることが好ましい。また、現像性の観点から３０以下であることが好ましく、２０以下であることがより好ましく、１２以下であることがさらに好ましい。例えば、５～３０、好ましくは５～２０、より好ましくは５～１２以下である。 Examples of the aromatic ring group in R 21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and further preferably 12 or less. For example, it is 5 to 30, preferably 5 to 20, and more preferably 5 to 12 or less.
　芳香族環基としては、例えば、フェニル基、ナフチル基、ピリジル基、フリル基が挙げられ、これらの中でも現像性の観点から、フェニル基又はナフチル基が好ましく、フェニル基がより好ましい。
　芳香族環基が有していてもよい置換基としては、例えば、水酸基、カルボキシ基、ハロゲン原子、アミノ基、アミド基、アルキル基、アルコキシ基、これらの置換基が連結した基が挙げられ、現像性の観点からアルキル基、アルコキシ基、これらを連結した基が好ましく、連結したアルコキシ基がより好ましい。
　これらの中でも、現像性の観点から、Ｒ２１ａが置換基を有していてもよい芳香族環基であることが好ましく、連結したアルコキシ基を置換基に有する芳香族環基であることがさらに好ましい。 Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a frill group. Among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable, from the viewpoint of developability.
Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group in which these substituents are linked. From the viewpoint of developability, an alkyl group, an alkoxy group, and a group in which these are linked are preferable, and a linked alkoxy group is more preferable.
Among these, from the viewpoint of developability, R 21a is preferably an aromatic ring group which may have a substituent, and further preferably an aromatic ring group having a linked alkoxy group as a substituent. preferable.
　また、Ｒ２１ｂとしては、置換されていてもよいカルバゾリル基、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ジフェニルスルフィド基が挙げられる。これらの中でも、感度の観点からは、置換されていてもよいカルバゾリル基が好ましい。電気信頼性の観点からは、置換されていてもよいジフェニルスルフィド基が好ましい。 Examples of R 21b include a carbazolyl group which may be substituted, a thioxanthonyl group which may be substituted, and a diphenylsulfide group which may be substituted. Among these, a carbazolyl group which may be substituted is preferable from the viewpoint of sensitivity. From the viewpoint of electrical reliability, a diphenyl sulfide group which may be substituted is preferable.
　また、Ｒ２２ａにおけるアルカノイル基の炭素数は特に限定されないが、溶媒への溶解性や感度の観点から、通常２以上、好ましくは３以上、また、通常２０以下、好ましくは１５以下、より好ましくは１０以下、さらに好ましくは５以下である。例えば、例えば、２～２０、好ましくは２～１５、より好ましくは３～１０、さらに好ましくは３～５である。アルカノイル基としては、アセチル基、プロパノイル基、ブタノイル基が挙げられる。
　アルカノイル基が有していてもよい置換基としては、例えば、芳香族環基、水酸基、カルボキシ基、ハロゲン原子、アミノ基、アミド基が挙げられ、合成容易性の観点からは、無置換であることが好ましい。 The carbon number of the alkanoyl group in R 22a is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably, from the viewpoint of solubility in a solvent and sensitivity. It is 10 or less, more preferably 5 or less. For example, it is, for example, 2 to 20, preferably 2 to 15, more preferably 3 to 10, and even more preferably 3 to 5. Examples of the alkanoyl group include an acetyl group, a propanoyl group and a butanoyl group.
Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group and an amide group, which are unsubstituted from the viewpoint of ease of synthesis. Is preferable.
　また、Ｒ２２ａにおけるアリーロイル基の炭素数は特に限定されないが、溶媒への溶解性や感度の観点から、通常７以上、好ましくは８以上、また、通常２０以下、好ましくは１５以下、より好ましくは１０以下である。例えば、７～２０、好ましくは７～１５、より好ましくは８～１０である。アリーロイル基としては、ベンゾイル基、ナフトイル基が挙げられる。
　アリーロイル基が有していてもよい置換基としては、例えば、水酸基、カルボキシ基、ハロゲン原子、アミノ基、アミド基、アルキル基が挙げられ、合成容易性の観点からは、無置換が好ましい。
　これらの中でも、感度の観点から、Ｒ２２ａが置換基を有していてもよいアルカノイル基であることが好ましく、無置換のアルカノイル基がより好ましく、アセチル基がさらに好ましい。 The carbon number of the allylloyl group in R 22a is not particularly limited, but is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably, from the viewpoint of solubility in a solvent and sensitivity. It is 10 or less. For example, it is 7 to 20, preferably 7 to 15, and more preferably 8 to 10. Examples of the allylloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the allylloyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group and an alkyl group, and from the viewpoint of ease of synthesis, no substitution is preferable.
Among these, from the viewpoint of sensitivity, R 22a is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.
　日本国特開２０１６－１３３５７４号公報に記載される開始剤も、着色剤による液晶層の汚染が低減されるという点から好適に用いられる。 The initiator described in Japanese Patent Application Laid-Open No. 2016-133574 is also preferably used from the viewpoint of reducing contamination of the liquid crystal layer by the colorant.
　光重合開始剤は、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。
　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、例えば、日本国特開平４－２２１９５８号公報、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号公報、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号公報、日本国特開平５－２８９３３５号公報に記載の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、日本国特開昭４７－２５２８号公報、日本国特開昭５４－１５５２９２号公報、日本国特公昭４５－３７３７７号公報、日本国特開昭４８－８４１８３号公報、日本国特開昭５２－１１２６８１号公報、日本国特開昭５８－１５５０３号公報、日本国特開昭６０－８８００５号公報、日本国特開昭５９－５６４０３号公報、日本国特開平２－６９号公報、日本国特開昭５７－１６８０８８号公報、日本国特開平５－１０７７６１号公報、日本国特開平５－２１０２４０号公報、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を挙げることができる。 One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.
If necessary, the photopolymerization initiator may be blended with a sensitizing dye and a polymerization accelerator according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. Examples of the sensitizing dye include the xanthene dye 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. A coumarin dye having a heterocycle described in Japanese Patent Application Laid-Open No. 3-239703, a 3-ketocoumarin compound described in Japanese Patent Application Laid-Open No. 5-289335, and Japanese Patent Application Laid-Open No. 6-19240. Pyromethene dye, Japanese Patent Application Laid-Open No. 47-2528, Japanese Patent Application Laid-Open No. 54-155292, Japanese Patent Application Laid-Open No. 45-373777, Japanese Patent Application Laid-Open No. 48-84183, Japanese Patent Laid-Open No. Japanese Patent Application Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88805, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69 The dialkylaminobenzene skeleton described in Japanese Patent Application Laid-Open No. 57-168888, Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, and Japanese Patent Application Laid-Open No. 4-288818. Pigments can be mentioned.
　これらの増感色素のうち、アミノ基含有増感色素が好ましく、アミノ基及びフェニル基を同一分子内に有する化合物がより好ましい。好ましい増感色素として、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が挙げられる。これらのうち、４，４’－ジアルキルアミノベンゾフェノンが特に好ましい。
　増感色素は、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 sensitizing dyes, amino group-containing sensitizing dyes are preferable, and compounds having an amino group and a phenyl group in the same molecule are more preferable. Preferred sensitizing dyes include, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone. , 3,4-Diaminobenzophenone and other benzophenone compounds; 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-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl)- 1,3,4-Thiadiazol, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine , P-dialkylaminophenyl group-containing compounds such as (p-diethylaminophenyl) pyrimidine. Of these, 4,4'-dialkylaminobenzophenone is particularly preferred.
As the sensitizing dye, one type may be used alone, or two or more types may be used in combination.
　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が用いられる。重合促進剤は、１種を単独で用いても、２種以上を併用してもよい。 As the polymerization accelerator, for example, 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 are used. .. The polymerization accelerator may be used alone or in combination of two or more.
＜（ｄ）エチレン性不飽和化合物＞
　本発明の感光性着色組成物は、（ｄ）エチレン性不飽和化合物を含む。（ｄ）エチレン性不飽和化合物を含むことで、感度が向上する。
　本発明に用いられるエチレン性不飽和化合物は、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、エチレン性不飽和結合を１個有するカルボン酸、多価又は１価アルコールのモノエステルが挙げられる。 <(D) Ethylene unsaturated compound>
The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound. (D) The sensitivity is improved by containing the ethylenically unsaturated compound.
The ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specific examples thereof include (meth) acrylic acid, (meth) acrylic acid alkyl esters, acrylonitrile, styrene, carboxylic acids having one ethylenically unsaturated bond, and monoesters of polyvalent or monovalent alcohols.
　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。上記の上限及び下限は任意に組み合わせることができる。例えば、２～８個が好ましく、２～７個がより好ましく、４～７個がさらに好ましく、５～７個が特に好ましい。前記下限値以上とすることで高感度となる傾向がある。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。
　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 contained in the polyfunctional ethylenically monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 5 or more. The number is 8 or less, more preferably 7 or less. The above upper and lower limits can be combined arbitrarily. For example, 2 to 8 pieces are preferable, 2 to 7 pieces are more preferable, 4 to 7 pieces are further preferable, and 5 to 7 pieces are particularly preferable. When the value is equal to or higher than the lower limit, the sensitivity tends to be high. When the value is not more than the upper limit, the solubility in a solvent tends to be improved.
Examples of polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatics. Examples thereof include an ester obtained by an esterification reaction between a polyvalent hydroxy compound such as a polyhydroxy compound and an unsaturated carboxylic acid and a polybasic carboxylic acid.
　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、例えば、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、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、マレエートに代えたマレイン酸エステルが挙げられる。 Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethanetriacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. , Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, acrylic acid ester of aliphatic polyhydroxy compounds such as glycerol acrylate, methacrylic acid ester in which these acrylates are replaced with methacrylate, itaconate. Examples thereof include an itaconic acid ester replaced with, a crotonic acid ester replaced with clonate, and a maleic acid ester replaced with maleate.
　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、例えば、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が挙げられる。 Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include acrylic acid esters and methacrylic acids of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcindiacrylate, resorcindimethacrylate, and pyrogallol triacrylate. Acid esters can be mentioned.
　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、例えば、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が挙げられる。 The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single ester, but for example, a condensate of acrylic acid, phthalic acid, and ethylene glycol. Examples thereof include condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, and 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としては、例えば、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が有用である。 In addition, as the polyfunctional ethylenic monomer used in the present invention, for example, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylic acid ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylic acid ester are reacted. Urethane (meth) acrylates as obtained; epoxy acrylates such as an addition reaction product of a 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 divinylphthalate are useful.
　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（共栄社化学社製）、ＵＶ－１７００Ｂ、ＵＶ－７６００Ｂ、ＵＶ－７６０５Ｂ、ＵＶ－７６３０Ｂ、ＵＶ７６４０Ｂ（三菱ケミカル社製）が挙げられる。 Examples of urethane (meth) acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U- 10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV- Examples thereof include 7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation).
　これらの中でも、硬化性の観点から（ｄ）エチレン性不飽和化合物として、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類又はウレタン（メタ）アクリレート類、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）アクリレート類を用いることが好ましく、（メタ）アクリル酸アルキルエステルを用いることがより好ましく、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さらに好ましい。
　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) as ethylenically unsaturated compounds, esters or urethane (meth) acrylates of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, polyisocyanate compounds and a hydroxyl group-containing (meth). It is preferable to use urethane (meth) acrylates obtained by reacting an acrylic acid ester or polyisocyanate compound with a polyol and a hydroxyl group-containing (meth) acrylic acid ester, and it is more preferable to use a (meth) acrylic acid alkyl ester. It is preferable to use dipentaerythritol hexaacrylate, and it is more preferable to use it.
These may be used alone or in combination of two or more.
＜（ｅ）溶剤＞
　本発明の感光性着色組成物は、（ｅ）溶剤を含む。（ｅ）溶剤を含むことで、（ａ）着色剤を溶剤中に分散又は溶解でき、また、塗布が容易となる。
　本発明の感光性着色組成物は、通常、（ａ）着色剤、（ｂ）アルカリ可溶性樹脂、（ｃ）光重合開始剤、（ｄ）エチレン性不飽和化合物、（ｆ）分散剤、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。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。 <(E) Solvent>
The photosensitive coloring composition of the present invention contains (e) a solvent. By including (e) a solvent, (a) the colorant can be dispersed or dissolved in the solvent, and application becomes easy.
The photosensitive coloring composition of the present invention usually comprises (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and necessary. Various other materials used according to the above are used in a state of being dissolved or dispersed in a solvent. Among the solvents, an organic solvent is preferable from the viewpoint 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℃のものを選択するのが好ましく、１２０～２８０℃のものがより好ましい。なお、ここでいう沸点は、圧力１０１３．２５ｈＰａにおける沸点を意味し、以下沸点に関しては全て同様である。 Among the organic solvents, those having a boiling point of 100 to 300 ° C. are preferably selected, and those having a boiling point of 120 to 280 ° C. are more preferable. The boiling point here means the boiling point at a pressure of 1013.25 hPa, and the following boiling points are all the same.
　このような有機溶剤としては、例えば、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 an organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-butyl ether. , Propropylene 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 Glycol monoalkyl ethers such as -3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether;
Glycoldialkyl 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等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等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 monomethyl ether acetate, triethylene glycol monoethyl Glycolalkyl ether acetates such as ether acetate, 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, diamil ether, ethylisobutyl 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, methylhexyl ketone, methylnonyl ketone, methoxymethylpentanone. Ketones;
Monohydric 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;
Alicyclic 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；が挙げられる。 Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amilformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Chain or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amilkloride;
Etheretones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile;
　市販の有機溶剤としては、例えば、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）を使用し得る。
　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。 Examples of commercially available organic solvents include mineral spirit, valsol # 2, apco # 18 solvent, apco thinner, and socal solvent No. 1 and No. 2. Solvento # 150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve (“Cellosolve” is a registered trademark; the same shall apply hereinafter), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglime (any of them). Also trade name) can be used.
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を形成する場合、有機溶剤としては沸点が１００～２４０℃のものを選択するのが好ましく、１２０～２００℃のものがより好ましく、１２０℃～１７０℃のものがさらに好ましい。 When forming a partition wall by a photolithography method, it is preferable to select an organic solvent having a boiling point of 100 to 240 ° C., more preferably 120 to 200 ° C., and even more preferably 120 ° C. to 170 ° C. ..
　上記有機溶剤のうち、塗布性、表面張力等のバランスがよく、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。
　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。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。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、後に得られる感光性着色組成物の粘度が上がっていく等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 preferable because they have a good balance of coatability, surface tension and the like, and the solubility of the constituent components in the composition is relatively high.
Glycol alkyl ether acetates may be used alone or in combination with other organic solvents. Glycol monoalkyl ethers are particularly preferable as the organic solvent to be used in combination. Propylene glycol monomethyl ether is preferable because of the solubility of the constituents in the composition. Glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate, and the storage stability of the photosensitive coloring composition obtained later tends to increase and the storage stability tends to decrease. The proportion of glycol monoalkyl ethers in the mixture is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.
　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。高沸点溶剤を併用することにより、感光性着色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、着色剤等の析出・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, may be referred to as "high boiling point solvent") in combination. By using a high boiling point solvent in combination, the photosensitive coloring composition becomes difficult to dry, but there is an effect of preventing the uniformly dispersed state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the generation of foreign matter defects due to precipitation and solidification of colorants and the like at the tip of the slit nozzle. Among the above-mentioned various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable because of such a high effect.
　高沸点溶剤を併用する場合、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色材等が析出・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。 When a high boiling point solvent is used in combination, the content ratio 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. preferable. By setting it to the above lower limit value or more, for example, it tends to be possible to suppress precipitation and solidification of coloring materials and the like at the tip of the slit nozzle to cause foreign matter defects, and by setting it to the above upper limit value or less, the drying temperature of the composition. There is a tendency to suppress the slowdown of the temperature, and to suppress problems such as poor tact in the vacuum drying process and pin marks of prebake.
　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い。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、前述の各種溶剤の中では、例えば、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, it is not necessary to separately contain a high boiling point solvent having a boiling point of 150 ° C. or higher.
Among the above-mentioned various solvents, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6- Hexanol diacetate and triacetin can be mentioned.
＜（ｆ）分散剤＞
　本発明の感光性着色組成物は、（ｆ）分散剤を含有する。（ｆ）分散剤を含有することで、（ａ）着色剤を安定に分散させることができる。
　本発明の感光性着色組成物における（ｆ）分散剤は、下記一般式（１）～（３）で表される繰り返し単位を有するアクリル共重合体（ｆ１）（以下、「分散剤（ｆ１）」と称する場合がある。）を含有し、４級アンモニウム基を含む繰り返し単位を有しない。 <(F) Dispersant>
The photosensitive coloring composition of the present invention contains (f) a dispersant. By containing (f) a dispersant, (a) the colorant can be stably dispersed.
The (f) dispersant in the photosensitive coloring composition of the present invention is an acrylic copolymer (f1) having a repeating unit represented by the following general formulas (1) to (3) (hereinafter, “dispersant (f1)). It does not have a repeating unit containing a quaternary ammonium group.
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
　（式（１）中、Ｒ３１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る。
　Ｒ３２は水素原子又はメチル基である。
　＊は結合手を表す。） (In the formula (1), R 31 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 32 is a hydrogen atom or a methyl group.
* Represents a bond. )
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
　（式（２）中、Ｒ３３はメチレン基、エチレン基又はプロピレン基であり、Ｒ３４は置換基を有していてもよいアルキル基であり、Ｒ３５は水素原子又はメチル基である。
　ｎは１～２０の整数である。
　＊は結合手を表す。） (In the formula (2), R 33 is a methylene group, an ethylene group or a propylene group, R 34 is an alkyl group which may have a substituent, and R 35 is a hydrogen atom or a methyl group.
n is an integer from 1 to 20.
* Represents a bond. )
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
　（式（３）中、Ｒ３６及びＲ３７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、Ｒ３６及びＲ３７が互いに結合して環状構造を形成してもよい。
　Ｒ３８は水素原子又はメチル基である。
　Ｚは２価の連結基である。
　＊は結合手を表す。） (In the formula (3), R 36 and R 37 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. It is an aralkyl group which may be present, and R 36 and R 37 may be bonded to each other to form a cyclic structure.
R 38 is a hydrogen atom or a methyl group.
Z is a divalent linking group.
* Represents a bond. )
　分散剤（ｆ１）は、溶剤やアルカリ可溶性樹脂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（１）で表される繰り返し単位を有する。 The dispersant (f1) has a repeating unit represented by the following general formula (1) from the viewpoint of increasing compatibility with a solvent or an alkali-soluble resin and improving dispersion stability.
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
　（式（１）中、Ｒ３１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る。
　Ｒ３２は水素原子又はメチル基である。
　＊は結合手を表す。） (In the formula (1), R 31 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 32 is a hydrogen atom or a methyl group.
* Represents a bond. )
（Ｒ３１）
　前記式（１）において、Ｒ３１におけるアルキル基としては、直鎖状、分岐鎖状、又は環状のアルキル基が挙げられ、溶剤やアルカリ可溶性樹脂に対する相溶性の観点から、直鎖状であることが好ましく、また、顔料に対する親和性の観点から分岐鎖状であることが好ましい。
　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以上が好ましく、４以上がより好ましく、また１０以下が好ましく、８以下がより好ましく、６以下がさらに好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、２～８がより好ましく、４～６がさらに好ましい。前記下限値以上とすることで顔料に対する親和性を高める傾向がある。前記上限値以下とすることで溶剤やアルカリ可溶性樹脂に対する相溶性を高め分散性を良化する傾向がある。
　アルキル基としては、例えば、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、へプチル基、オクチル基、エチルヘキシル基が挙げられ、溶剤やアルカリ可溶性樹脂に対する相溶性の観点から、メチル基、エチル基が好ましく、メチル基がより好ましい。
　アルキル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基等のアルコキシ基；フッ素原子、塩素原子、臭素原子等のハロゲン原子；フェニル基、ナフチル基等のアリール基が挙げられ、溶剤やアルカリ可溶性樹脂に対する相溶性の観点から無置換であることが好ましく、顔料に対する親和性の観点からフェニル基であることが好ましい。 (R 31 )
In the above formula (1), examples of the alkyl group in R 31 include linear, branched, or cyclic alkyl groups, which are linear from the viewpoint of compatibility with a solvent or an alkali-soluble resin. Is preferable, and it is preferable that the chain is branched from the viewpoint of affinity for the pigment.
The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, preferably 10 or less, more preferably 8 or less, still more preferably 6 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 is preferable, 2 to 8 is more preferable, and 4 to 6 is further preferable. By setting the value to the lower limit or higher, the affinity for the pigment tends to be enhanced. By setting the value to the upper limit or less, the compatibility with the solvent or the alkali-soluble resin tends to be enhanced and the dispersibility tends to be improved.
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 an ethylhexyl group, and from the viewpoint of compatibility with a solvent or an alkali-soluble resin, the alkyl group includes. A methyl group and an ethyl group are preferable, and a methyl group is more preferable.
Examples of the substituent that the alkyl group may have include an alkoxy group such as a methoxy group and an ethoxy group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; and an aryl group such as a phenyl group and a naphthyl group. Therefore, it is preferably unsubstituted from the viewpoint of compatibility with a solvent or an alkali-soluble resin, and preferably a phenyl group from the viewpoint of affinity with a pigment.
　Ｒ３１におけるアリール基としては、１価の芳香族炭化水素環基、１価の芳香族複素環基が挙げられる。
　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以下が好ましく、１２以下がより好ましく、１０以下がさらに好ましい。前記上限値以下とすることで顔料に対する親和性を高める傾向がある。アリール基としては、例えば、フェニル基、ナフチル基、アントラセニル基が挙げられ、分散性の観点から、フェニル基、ナフチル基が好ましく、フェニル基がより好ましい。
　アリール基が有していてもよい置換基としては、例えば、メチル基、エチル基等のアルキル基；メトキシ基、エトキシ基等のアルコキシ基；フッ素原子、塩素原子、臭素原子等のハロゲン原子；フェニル基、ナフチル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基が挙げられ、分散性の観点から無置換であることが好ましい。 Examples of the aryl group in R 31 include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.
The number of carbon atoms of the aryl group is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, still more preferably 10 or less. By setting the value to the upper limit or less, there is a tendency to increase the affinity for the pigment. Examples of the aryl group include a phenyl group, a naphthyl group and an anthrasenyl group. From the viewpoint of dispersibility, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
Examples of the substituent that the aryl group may have include an alkyl group such as a methyl group and an ethyl group; an alkoxy group such as a methoxy group and an ethoxy group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; and a phenyl. An aryl group such as a group or a naphthyl group; an aralkyl group such as a benzyl group or a phenethyl group may be mentioned, and an unsubstituted group is preferable from the viewpoint of dispersibility.
　これらの中でも、溶剤やアルカリ可溶性樹脂に対する相溶性の観点から、Ｒ３１としては置換基を有していてもよいアルキル基が好ましく、メチル基、ブチル着、エチルヘキシル基、又はベンジル基がより好ましい。 Among these, from the viewpoint of compatibility with a solvent or an alkali-soluble resin, R 31 is preferably an alkyl group which may have a substituent, and more preferably a methyl group, a butyl group, an ethylhexyl group or a benzyl group.
　分散剤（ｆ１）は、溶剤やアルカリ可溶性樹脂に対する相溶性の観点から、下記一般式（２）で表される繰り返し単位を有する。 The dispersant (f1) has a repeating unit represented by the following general formula (2) from the viewpoint of compatibility with a solvent or an alkali-soluble resin.
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
　（式（２）中、Ｒ３３はメチレン基、エチレン基又はプロピレン基であり、Ｒ３４は置換基を有していてもよいアルキル基であり、Ｒ３５は水素原子又はメチル基である。
　ｎは１～２０の整数である。
　＊は結合手を表す。） (In the formula (2), R 33 is a methylene group, an ethylene group or a propylene group, R 34 is an alkyl group which may have a substituent, and R 35 is a hydrogen atom or a methyl group.
n is an integer from 1 to 20.
* Represents a bond. )
　前記式（２）において、Ｒ３３はメチレン基、エチレン基、又はプロピレン基であるが、溶剤やアルカリ可溶性樹脂に対する相溶性の観点から、エチレン基が好ましい。
　前記式（２）において、Ｒ３４は置換基を有していてもよいアルキル基であるが、溶剤やアルカリ可溶性樹脂に対する相溶性の観点から、メチル基又はエチル基が好ましい。 In the above formula (2), R 33 is a methylene group, an ethylene group, or a propylene group, but an ethylene group is preferable from the viewpoint of compatibility with a solvent or an alkali-soluble resin.
In the above formula (2), R 34 is an alkyl group which may have a substituent, but a methyl group or an ethyl group is preferable from the viewpoint of compatibility with a solvent or an alkali-soluble resin.
　前記式（２）において、ｎは１～２０の整数であるが、１以上が好ましく、２以上がより好ましく、また、１０以下が好ましく、５以下がより好ましい。例えば、１～１０が好ましく、１～５がより好ましく、２～５がさらに好ましい。前記下限値以上とすることで溶剤やアルカリ可溶性樹脂に対する相溶性が良化する傾向がある。前記上限値以下とすることで顔料に対する親和性を高め分散性を良化する傾向がある。 In the above formula (2), n is an integer of 1 to 20, but 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, and 5 or less is more preferable. For example, 1 to 10 is preferable, 1 to 5 is more preferable, and 2 to 5 is even more preferable. By setting the value to the lower limit or higher, the compatibility with the solvent or the alkali-soluble resin tends to be improved. By setting the value to the upper limit or less, there is a tendency to increase the affinity for the pigment and improve the dispersibility.
　分散剤（ｆ１）は、前記一般式（３）で表される繰り返し単位を有する。電極の表面荒れの観点から、好適に用いられる。 The dispersant (f1) has a repeating unit represented by the general formula (3). It is preferably used from the viewpoint of surface roughness of the electrode.
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
　（式（３）中、Ｒ３６及びＲ３７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、Ｒ３６及びＲ３７が互いに結合して環状構造を形成してもよい。
　Ｒ３８は水素原子又はメチル基である。
　Ｚは２価の連結基である。
　＊は結合手を表す。） (In the formula (3), R 36 and R 37 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. It is an aralkyl group which may be present, and R 36 and R 37 may be bonded to each other to form a cyclic structure.
R 38 is a hydrogen atom or a methyl group.
Z is a divalent linking group.
* Represents a bond. )
　前記式（３）において、Ｒ３６及びＲ３７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、又は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る。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としては、前記式（１）におけるＲ３１として挙げたものを好ましく採用することができる。 In the above formula (3), R 36 and R 37 each independently have a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, or a substituent. It is an aralkyl group that may be used. As the alkyl group which may have a substituent and the aryl group which may have a substituent, those listed as R 31 in the above formula (1) can be preferably adopted.
　前記式（３）において、Ｒ３６及びＲ３７が互いに結合して環状構造を形成してもよい。環状構造としては、例えば５～７員環の含窒素複素環単環又はこれらが２個縮合してなる縮合環が挙げられる。含窒素複素環は芳香族性を有さないものが好ましく、飽和環がより好ましい。具体的には、以下のものが挙げられる。 In the formula (3), R 36 and R 37 may be combined with each other to form a cyclic structure. Examples of the cyclic structure include a nitrogen-containing heterocyclic monocycle having a 5- to 7-membered ring or a fused ring formed by condensing two of them. The nitrogen-containing heterocycle is preferably one that does not have aromaticity, and a saturated ring is more preferable. Specifically, the following can be mentioned.
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
（これらの環状構造は、さらに置換基を有していてもよい。
＊は結合手を表す。） (These cyclic structures may further have substituents.
* Represents a bond. )
（Ｚ）
　前記式（３）において、Ｚは２価の連結基である。
　２価の連結基としては、例えば、単結合、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－Ｒ３９－基、－ＣＯＯＲ４０－基（但し、Ｒ３９及びＲ４０は、各々独立に、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。）が挙げられ、分散性の観点から－ＣＯＯＲ７－基が好ましい。Ｒ４０の中でも、分散液の経時安定性の観点から、炭素数１～１０のアルキレン基が好ましく、炭素数１～５のアルキレン基がより好ましく、炭素数１～３のアルキレン基がさらに好ましい。 (Z)
In the formula (3), Z is a divalent linking group.
Examples of the divalent linking group include a single bond, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a -CONH-R 39- group, and a -COOR 40- group (however, R 39 and). Each of R 40 is independently a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group)), and is −COOR from the viewpoint of dispersibility. 7 -groups are preferred. Among R 40 , an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is further preferable, from the viewpoint of the stability of the dispersion with time.
　分散剤（ｆ１）における、一般式（１）で表される繰り返し単位（以下、「繰り返し単位（１）」と称する場合がある。）の含有割合は特に限定されないが、全繰り返し単位中に２０モル％以上が好ましく、３０モル％以上がより好ましく、４０モル％以上がさらに好ましく、５０モル％以上がよりさらに好ましく、６０モル％以上が特に好ましく、また、９０モル％以下が好ましく、８５モル％以下がより好ましく、８０モル％以下がさらに好ましく、７５モル％以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、２０モル％～９０モル％が好ましく、３０モル％～９０モル％がより好ましく、４０モル％～８０モル％がさらに好ましく、５０モル％～８０モル％がよりさらに好ましく、６０モル％～８０モル％が特に好ましい。前記下限値以上とすることで顔料に対する親和性を高める傾向がある。前記上限値以下とすることで溶剤やアルカリ可溶性樹脂に対する相溶性を高める傾向がある。 The content ratio of the repeating unit represented by the general formula (1) (hereinafter, may be referred to as “repeating unit (1)”) in the dispersant (f1) is not particularly limited, but 20 in all the repeating units. More than mol% is preferable, 30 mol% or more is more preferable, 40 mol% or more is further preferable, 50 mol% or more is further preferable, 60 mol% or more is particularly preferable, and 90 mol% or less is more preferable, 85 mol. % Or less is more preferable, 80 mol% or less is further preferable, and 75 mol% or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 20 mol% to 90 mol% is preferable, 30 mol% to 90 mol% is more preferable, 40 mol% to 80 mol% is further preferable, 50 mol% to 80 mol% is more preferable, and 60 mol% to 60 mol% is preferable. 80 mol% is particularly preferred. By setting the value to the lower limit or higher, the affinity for the pigment tends to be enhanced. By setting the value to the upper limit or less, the compatibility with the solvent or the alkali-soluble resin tends to be improved.
　分散剤（ｆ１）における、前記一般式（２）で表される繰り返し単位（以下、「繰り返し単位（２）」と称する場合がある。）の含有割合は特に限定されないが、全繰り返し単位中に１モル％以上が好ましく、２モル％以上がより好ましく、２．５モル％以上がさらに好ましく、３モル％以上が特に好ましく、また、３０モル％以下が好ましく、２０モル％以下がより好ましく、１５モル％以下がさらに好ましく、１０モル％以下がよりさらに好ましく、８モル％以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１モル％～３０モル％が好ましく、１モル％～２０モル％がより好ましく、１モル％～１５モル％がさらに好ましく、１モル％～１０モル％がよりさらに好ましく、２モル％～１０モル％が特に好ましい。前記下限値以上とすることで溶剤やアルカリ可溶性樹脂に対する相溶性を高める傾向がある。前記上限値以下とすることで顔料に対する親和性を高める傾向がある。 The content ratio of the repeating unit represented by the general formula (2) (hereinafter, may be referred to as “repeating unit (2)”) in the dispersant (f1) is not particularly limited, but is included in all the repeating units. 1 mol% or more is preferable, 2 mol% or more is more preferable, 2.5 mol% or more is further preferable, 3 mol% or more is particularly preferable, 30 mol% or less is preferable, and 20 mol% or less is more preferable. It is more preferably 15 mol% or less, still more preferably 10 mol% or less, and particularly preferably 8 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, 1 mol% to 30 mol% is preferable, 1 mol% to 20 mol% is more preferable, 1 mol% to 15 mol% is more preferable, 1 mol% to 10 mol% is more preferable, and 2 mol% to 2 mol% to 10 mol% is particularly preferred. By setting the value to the lower limit or higher, the compatibility with the solvent or the alkali-soluble resin tends to be improved. By setting the value to the upper limit or less, the affinity for the pigment tends to be enhanced.
　分散剤（ｆ１）における、前記一般式（３）で表される繰り返し単位（以下、「繰り返し単位（３）」と称する場合がある。）の含有割合は特に限定されないが、全繰り返し単位中に１０モル％以上が好ましく、２０モル％以上がより好ましく、２５モル％以上がさらに好ましく、３０モル％以上が特に好ましく、また、５０モル％以下が好ましく、４５モル％以下がより好ましく、４０モル％以下がさらに好ましく、３５モル％以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１０モル％～５０モル％が好ましく、２０モル％～４０モル％がより好ましく、２５モル％～３５モル％がさらに好ましく、３０モル％～３５モル％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る。前記上限値以下とすることで分散液の経時安定性が良好となる傾向がある。 The content ratio of the repeating unit represented by the general formula (3) (hereinafter, may be referred to as “repeating unit (3)”) in the dispersant (f1) is not particularly limited, but is included in all the repeating units. 10 mol% or more is preferable, 20 mol% or more is more preferable, 25 mol% or more is further preferable, 30 mol% or more is particularly preferable, 50 mol% or less is preferable, 45 mol% or less is more preferable, and 40 mol is more preferable. % Or less is more preferable, and 35 mol% or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 10 mol% to 50 mol% is preferable, 20 mol% to 40 mol% is more preferable, 25 mol% to 35 mol% is further preferable, and 30 mol% to 35 mol% is particularly preferable. When the value is equal to or higher than the lower limit, the dispersibility tends to be good. When the value is not more than the upper limit, the stability of the dispersion with time tends to be good.
　分散剤（ｆ１）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が、分散性の観点から、ブロック共重合体であることが好ましく、ブロック共重合体は、親溶媒基を有する繰り返し単位を含むＡブロックと、顔料吸着基を有する繰り返し単位を含むＢブロックを含むことが好ましい。 The dispersant (f1) may be contained in either a random copolymer or a block copolymer, but from the viewpoint of dispersibility, it is preferably a block copolymer, and the block copolymer is a parent solvent. It is preferable to include an A block containing a repeating unit having a group and a B block containing a repeating unit having a pigment adsorbing group.
　分散剤（ｆ１）が繰り返し単位（１）、繰り返し単位（２）はＡブロック中に含有されることが好ましく、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（１）や繰り返し単位（２）は、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、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。 The dispersant (f1) is preferably contained in the repeating unit (1) and the repeating unit (2) is contained in the A block, and may be contained in any aspect of random copolymerization or block copolymerization. Further, the repeating unit (1) and the repeating unit (2) may each be contained in two or more kinds in the A block, and in that case, each repeating unit is a random copolymerization or a block copolymerization in the A block. It may be contained in any of the above embodiments.
　繰り返し単位（１）及び（２）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としては、スチレン、α－メチルスチレン等のスチレン系単量体；（メタ）アクリル酸クロリド等の（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等の（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に由来する繰り返し単位が挙げられる。 Repeating units other than the repeating units (1) and (2) may be contained in the A block, and such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (meth). (Meta) acrylate-based monomers such as acrylic acid chloride; (meth) acrylamide-based monomers such as (meth) acrylamide and N-methylol acrylamide; vinyl acetate; acrylonitrile; allylglycidyl ether, glycidyl crotonate ether; Repeat units derived from N-methacryloylmorpholine can be mentioned.
　これらの中でも、繰り返し単位（１）、繰り返し単位（２）を有するＡブロックと、繰り返し単位（３）を有するＢブロックと、を有するブロック共重合体はＡ－Ｂブロック共重合体又はＡ－Ｂ－Ａブロック共重合体であることがより好ましい。 Among these, the block copolymer having the A block having the repeating unit (1) and the repeating unit (2) and the B block having the repeating unit (3) is an AB block copolymer or AB. -A block copolymer is more preferable.
　分散剤（ｆ１）のアミン価は特に限定されないが、５０ｍｇＫＯＨ／ｇ以上が好ましく、８０ｍｇＫＯＨ／ｇ以上がより好ましく、９０ｍｇＫＯＨ／ｇ以上がさらに好ましく、１００ｍｇＫＯＨ／ｇ以上が特に好ましく、また、２００ｍｇＫＯＨ／ｇ以下が好ましく、１６０ｍｇＫＯＨ／ｇ以下がより好ましく、１４０ｍｇＫＯＨ／ｇ以下がさらに好ましく、１３０ｍｇＫＯＨ／ｇ以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、５０ｍｇＫＯＨ／ｇ～２００ｍｇＫＯＨ／ｇが好ましく、８０ｍｇＫＯＨ／ｇ～１６０ｍｇＫＯＨ／ｇがより好ましく、１００ｍｇＫＯＨ／ｇ～１４０ｍｇＫＯＨ／ｇがさらに好ましく、１００ｍｇＫＯＨ／ｇ～１３０ｍｇＫＯＨ／ｇが特に好ましい。前記下限値以上とすることで電極の表面荒れを抑止できる傾向がある。前記上限値以下とすることで分散液の経時安定性が良化する傾向がある。アミン価は、分散剤（ｆ１）の固形分１ｇあたりの塩基量と当量のＫＯＨの質量で表される。 The amine value of the dispersant (f1) is not particularly limited, but is preferably 50 mgKOH / g or more, more preferably 80 mgKOH / g or more, further preferably 90 mgKOH / g or more, particularly preferably 100 mgKOH / g or more, and 200 mgKOH / g. The following is preferable, 160 mgKOH / g or less is more preferable, 140 mgKOH / g or less is further preferable, and 130 mgKOH / g or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 50 mgKOH / g to 200 mgKOH / g is preferable, 80 mgKOH / g to 160 mgKOH / g is more preferable, 100 mgKOH / g to 140 mgKOH / g is further preferable, and 100 mgKOH / g to 130 mgKOH / g is particularly preferable. By setting the value to the lower limit or higher, the surface roughness of the electrode tends to be suppressed. When the value is not more than the upper limit, the stability of the dispersion with time tends to be improved. The amine value is expressed by the amount of base per 1 g of the solid content of the dispersant (f1) and the mass of equivalent KOH.
　分散剤（ｆ１）の酸価は特に限定されないが、分散性の観点から、１０ｍｇＫＯＨ／ｇ以下が好ましく、５ｍｇＫＯＨ／ｇ以下がより好ましく、１ｍｇＫＯＨ／ｇがさらに好ましく、０ｍｇＫＯＨ／ｇが特に好ましい。 The acid value of the dispersant (f1) is not particularly limited, but from the viewpoint of dispersibility, it is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, further preferably 1 mgKOH / g, and particularly preferably 0 mgKOH / g.
　分散剤（ｆ１）の重量平均分子量は特に限定されないが、３０００以上が好ましく、５０００以上がより好ましく、７０００以上がさらに好ましく、また、１０００００以下が好ましく、５００００以下がより好ましく、１００００以下がさらに好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、３０００～１０００００が好ましく、５０００～５００００がより好ましく、７０００～１００００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化する傾向がある。前記上限値以下とすることで分散液の経時安定性が良化する傾向がある。 The weight average molecular weight of the dispersant (f1) is not particularly limited, but is preferably 3000 or more, more preferably 5000 or more, further preferably 7,000 or more, preferably 100,000 or less, more preferably 50,000 or less, still more preferably 10,000 or less. .. The above upper and lower limits can be combined arbitrarily. For example, 3000 to 100,000 is preferable, 5000 to 50000 is more preferable, and 7000 to 10000 is even more preferable. When the value is equal to or higher than the lower limit, the dispersibility tends to be improved. When the value is not more than the upper limit, the stability of the dispersion with time tends to be improved.
　分散剤（ｆ１）中の塩素原子の含有量は、特に限定されないが、１．０質量％以下が好ましく、０．５質量％以下がより好ましく、０．２質量％以下がさらに好ましく、実質的に塩素原子を含有しない、すなわち０．１質量％以下であることが特に好ましい。前記上限値以下とすることで表面荒れが抑制される傾向がある。 The content of chlorine atoms in the dispersant (f1) is not particularly limited, but is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, and substantially. It is particularly preferable that it does not contain chlorine atoms, that is, it is 0.1% by mass or less. When the value is not more than the upper limit, surface roughness tends to be suppressed.
　分散剤（ｆ１）の製造方法は特に限定されず、公知の方法を採用することができる。例えば、日本国特開平０１－２９９０１４号公報、日本国特開２０１７－０１９９３７号公報、日本国特開２０１８－１７２５３０号公報、日本国特開２０１８－２０３７９５号公報、日本国特開２０１９－０９９８０１号公報、国際公開第２０１９／０７９６５９号公報に記載される方法が挙げられる。 The method for producing the dispersant (f1) is not particularly limited, and a known method can be adopted. For example, Japanese Patent Application Laid-Open No. 01-299014, Japanese Patent Application Laid-Open No. 2017-019937, Japanese Patent Application Laid-Open No. 2018-172530, Japanese Patent Application Laid-Open No. 2018-203795, Japanese Patent Application Laid-Open No. 2019-099801. Examples thereof include the methods described in Japanese Patent Publication No. 2019/079659.
　本発明の感光性着色組成物における（ｆ）分散剤は、分散剤（ｆ１）以外の分散剤（以下、「その他の分散剤」と称する場合がある。）を含有していてもよい。 The (f) dispersant in the photosensitive coloring composition of the present invention may contain a dispersant other than the dispersant (f1) (hereinafter, may be referred to as “other dispersants”).
　その他の分散剤としては、分散安定性の面から、例えば、官能基としてカルボキシ基；又はこれらの塩基；一級、二級又は三級アミノ基；四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を有する分散剤が好ましい。中でも、塩基性官能基、例えば、一級、二級又は三級アミノ基；四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を有する分散剤がより好ましい。
　また顔料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、高分子分散剤が好ましい。 Other dispersants include, for example, a carboxy group as a functional group; or a base thereof; a primary, secondary or tertiary amino group; a quaternary ammonium base; pyridine, pyrimidine, pyrazine and the like from the viewpoint of dispersion stability. Dispersants having a group derived from the nitrogen heterocycle are preferred. Among them, a dispersant having a basic functional group, for example, a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is more preferable.
Further, a polymer dispersant is preferable from the viewpoint that the pigment can be dispersed with a small amount of the dispersant.
　高分子分散剤としては、例えば、分散剤（ｆ１）以外のアクリル系分散剤、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を挙げることができる。 Examples of the polymer dispersant include an acrylic dispersant other than the dispersant (f1), a urethane dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, and a dispersant consisting of a monomer having an amino group and a macromonomer. , Polyoxyethylene alkyl ether dispersant, polyoxyethylene diester dispersant, polyether phosphoric acid dispersant, polyester phosphate dispersant, sorbitan aliphatic ester dispersant, aliphatic modified polyester dispersant. be able to.
　このような高分子分散剤としては、例えば、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。）を挙げることができる。 Examples of such polymer dispersants include EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by Big Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei), and the like. Examples include SOLPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shinetsu Chemical Industry Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Azisper (registered trademark, manufactured by Ajinomoto Co., Ltd.).
　ウレタン系及びアクリル系高分子分散剤としては、例えば、ＤＩＳＰＥＲＢＹＫ１６０～１６６、１８２シリーズ（いずれもウレタン系）、ＤＩＳＰＥＲＢＹＫ２０００、２００１、ＢＹＫ－ＬＰＮ２１１１６（いずれもアクリル系）（以上すべてビックケミー社製）が挙げられる。 Examples of the urethane-based and acrylic-based polymer dispersants include DISPERBYK 160 to 166, 182 series (all urethane-based), DISPERBYK2000, 2001, BYK-LPN21116 (all acrylic-based) (all manufactured by Big Chemie). ..
　その他の分散剤は１種を用いてもよく、２種以上を併用してもよい。 One type of other dispersant may be used, or two or more types may be used in combination.
＜感光性着色組成物のその他の配合成分＞
　本発明の感光性着色組成物には、上述の成分の他、シランカップリング剤等の密着向上剤、界面活性剤、顔料誘導体、光酸発生剤、架橋剤、メルカプト化合物、重合禁止剤等の添加剤を適宜配合することができる。 <Other ingredients of the photosensitive coloring composition>
In addition to the above-mentioned components, the photosensitive coloring composition of the present invention includes adhesion improvers such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, cross-linking agents, mercapto compounds, polymerization inhibitors and the like. Additives can be added as appropriate.
　（１）密着向上剤
　本発明の感光性着色組成物には、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、あるいは２種以上を混合して使用できる。 (1) Adhesion Improver The photosensitive coloring 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 and a phosphoric acid group-containing compound are preferable.
As the type of silane coupling agent, various types such as epoxy type, (meth) acrylic type, and amino type can be used alone or in combination of two or more.
　シランカップリング剤としては、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。エポキシシラン類のシランカップリング剤が特に好ましい。
　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（ｇ１）、（ｇ２）又は（ｇ３）で表されるものが好ましい。 Examples of the silane coupling agent include (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. , Epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, Examples thereof include isocyanate silanes such as 3-isocyanate propyltriethoxysilane. Silane coupling agents of epoxy silanes are particularly preferred.
As the phosphoric acid group-containing compound, (meth) acryloyl group-containing phosphates are preferable, and those represented by the following general formulas (g1), (g2) or (g3) are preferable.
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
　上記一般式（ｇ１）、（ｇ２）及び（ｇ３）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の整数であり、ｍは１、２又は３である。
　これらの燐酸基含有化合物は、１種単独で用いても、２種以上を併用してもよい。 In the above general formulas (g1), (g2) and (g3), R 51 represents a hydrogen atom or a methyl group, l and l'are integers of 1 to 10, and m is 1, 2 or 3.
These phosphoric acid group-containing compounds may be used alone or in combination of two or more.
　（２）界面活性剤
　本発明の感光性着色組成物は、塗布性向上ため、界面活性剤を含有してもよい。 (2) Surfactant The photosensitive coloring 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、カチオン系、非イオン系、両性界面活性剤等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ン系の界面活性剤が塗布性の面で効果的である。
　このような界面活性剤としては、例えば、ＴＳＦ４４６０（モメンティブ・パフォーマンス・マテリアルズ社製）、ＤＦＸ－１８（ネオス社製）、ＢＹＫ－３００、ＢＹＫ－３２５、ＢＹＫ－３３０（ビックケミー社製）、ＫＰ３４０（信越シリコーン社製）、Ｆ－４７０、Ｆ－４７５、Ｆ－４７８、Ｆ－５５４、Ｆ－５５９（ＤＩＣ社製）、ＳＨ７ＰＡ（東レ・ダウコーニング社製）、ＤＳ－４０１（ダイキン社製）、Ｌ－７７（日本ユニカー社製）、ＦＣ４４３０（３Ｍ社製）が挙げられる。
　界面活性剤は、１種を用いてもよく、２種以上を任意の組み合わせ及び比率で併用してもよい。 As the surfactant, for example, various kinds such as anionic type, cationic type, nonionic type and amphoteric surfactant can be used. Of these, nonionic surfactants are preferable because they are less likely to adversely affect various properties, and fluorine-based and silicon-based surfactants are particularly effective in terms of coatability.
Examples of such a surfactant include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by Big Chemie), and KP340. (Manufactured by Shinetsu Silicone), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Toray Dow Corning), DS-401 (manufactured by Daikin) , L-77 (manufactured by Nippon Unicar), FC4430 (manufactured by 3M).
As the surfactant, one type may be used, or two or more types may be used in combination in any combination and ratio.
　（３）顔料誘導体
　本発明の感光性着色組成物には、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、例えば、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、例えば、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。 (3) Pigment Derivative The photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersion aid in order to improve dispersibility and storage stability.
Pigment derivatives include, for example, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindoleinone-based, dioxazine-based, anthraquinone-based, indanthrone-based, perylene-based, perinone-based, and diketopyrrolopyrrole. Examples thereof include phthalocyanine-based and dioxazine-based derivatives, and among them, phthalocyanine-based and quinophthalone-based derivatives are preferable.
As the substituent of the pigment derivative, for example, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxy group, an amide group and the like are directly on the pigment skeleton or an alkyl group or aryl. Examples thereof include those bonded via a group, a heterocyclic group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted into one pigment skeleton.
　顔料誘導体としては、例えば、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。 Examples of the pigment derivative include phthalocyanine sulfonic acid derivative, quinophthalone sulfonic acid derivative, anthraquinone sulfonic acid derivative, quinacridone sulfonic acid derivative, diketopyrrolopyrrole sulfonic acid derivative, and dioxazine sulfonic acid derivative. These may be used alone or in combination of two or more.
　（４）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。 (4) Mercapto compound It is also possible to add a mercapto compound as a polymerization accelerator and for improving the adhesion to the substrate.
　メルカプト化合物としては、例えば、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、脂肪族多官能メルカプト化合物が挙げられる。これらは種々のものを１種単独で、あるいは２種以上を混合して使用できる。 Examples of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate and butanediol bis. Thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropio Nate, Pentaerythritol Tetrakissthioglycolate, Trishydroxyethyl Tristhiopropionate, Ethylene Glycolbis (3-Mercaptobutyrate), Butanediolbis (3-Mercaptobutyrate), 1,4-Bis (3-Mercaptobutyrate) Liloxy) butane, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate) , Butanediolbis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine- Examples thereof include mercapto compounds having a heterocycle such as 2,4,6 (1H, 3H, 5H) -trione, and aliphatic polyfunctional mercapto compounds. These can be used alone or in admixture of two or more.
　（５）重合禁止剤
　本発明の感光性着色組成物には、硬化物の形状制御の観点から、重合禁止剤を含有させてもよい。重合禁止剤を含有することでそれが塗布膜下層のラジカル重合を阻害することから、テーパー角（硬化物断面に於ける支持体と硬化物のなす角度）を制御できると考えられる。
　重合禁止剤としては、例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、メチルヒドロキノン、メトキシフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－クレゾール（ＢＨＴ）が挙げられる。これらの中でも形状制御の観点から、２，６－ジ－ｔｅｒｔ－ブチル－４－クレゾールが好ましい。また人体への安全性が特に優れるとの観点から、ハイドロキノンモノメチルエーテル、メチルヒドロキノンが好ましい。
　重合禁止剤は、１種単独で、あるいは２種以上を混合して使用できる。
　（ｂ）アルカリ可溶性樹脂を製造する際に、樹脂中に重合禁止剤が含まれることがあり、それを本発明の重合禁止剤として用いてもよいし、樹脂中に重合禁止剤の他に、それと同一、又は異なる重合禁止剤を感光性着色組成物製造時に添加してもよい。 (5) Polymerization inhibitor The photosensitive coloring composition of the present invention may contain a polymerization inhibitor from the viewpoint of controlling the shape of the cured product. It is considered that the taper angle (the angle formed by the support and the cured product in the cross section of the cured product) can be controlled because the inclusion of the polymerization inhibitor inhibits the radical polymerization of the lower layer of the coating film.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, 2,6-di-tert-butyl-4-cresol is preferable from the viewpoint of shape control. Further, hydroquinone monomethyl ether and methylhydroquinone are preferable from the viewpoint of particularly excellent safety to the human body.
The polymerization inhibitor can be used alone or in combination of two or more.
(B) When producing an alkali-soluble resin, a polymerization inhibitor may be contained in the resin, which may be used as the polymerization inhibitor of the present invention, or the resin may contain a polymerization inhibitor in addition to the polymerization inhibitor. The same or different polymerization inhibitor may be added at the time of producing the photosensitive coloring composition.
　感光性着色組成物が重合禁止剤を含む場合、その含有割合は特に限定されないが、感光性着色組成物の全固形分量に対して通常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０．３質量％以下、好ましくは０．２質量％以下、より好ましくは０．１質量％以下である。上記の上限及び下限は任意に組み合わせることができる。例えば、０．０００５質量％～０．３質量％が好ましく、０．００１質量％～０．２質量％がより好ましく、０．０１質量％～０．１質量％がさらに好ましい。前記下限値以上とすることで硬化物の形状制御できる傾向がある。前記上限値以下とすることで必要な感度を維持できる傾向がある。 When the photosensitive coloring composition contains a polymerization inhibitor, the content thereof is not particularly limited, but is usually 0.0005% by mass or more, preferably 0.001% by mass or more, based on the total solid content of the photosensitive coloring composition. , More preferably 0.01% by mass or more, and usually 0.3% by mass or less, preferably 0.2% by mass or less, more preferably 0.1% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 0.0005% by mass to 0.3% by mass is preferable, 0.001% by mass to 0.2% by mass is more preferable, and 0.01% by mass to 0.1% by mass is further preferable. By setting the value to the lower limit or higher, the shape of the cured product tends to be controlled. By setting the value to the upper limit or less, the required sensitivity tends to be maintained.
＜感光性着色組成物中の各成分の含有割合＞
　本発明の感光性着色組成物における（ａ）着色剤の含有割合は特に限定されないが、全固形分量に対して５質量％以上が好ましく、１０質量％以上がより好ましく、１５質量％以上がさらに好ましく、２０質量％以上がよりさらに好ましく、また、５０質量％以下が好ましく、４０質量％以下がより好ましく、３０質量％以下がさらに好ましく、２５質量％以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、５質量％～５０質量％が好ましく、１０質量％～４０質量％がより好ましく、１５質量％～４０質量％がさらに好ましく、１５質量％～３０質量％がよりさらに好ましく、１５質量％～２５質量％が特に好ましい。前記下限値以上とすることで遮光性を確保出来る傾向がある。前記上限値以下とすることで分散剤量を減らすことができ、表面荒れを抑止できる傾向がある。 <Content ratio of each component in the photosensitive coloring composition>
The content ratio of the (a) colorant in the photosensitive coloring composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more with respect to the total solid content. It is preferable that 20% by mass or more is more preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, 30% by mass or less is further preferable, and 25% by mass or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 5% by mass to 50% by mass is preferable, 10% by mass to 40% by mass is more preferable, 15% by mass to 40% by mass is further preferable, 15% by mass to 30% by mass is more preferable, and 15% by mass to 15% by mass. 25% by mass is particularly preferable. By setting the value to the lower limit or more, there is a tendency that the light blocking effect can be ensured. By setting the value to the upper limit or less, the amount of the dispersant can be reduced, and the surface roughness tends to be suppressed.
　第一の態様において、感光性着色組成物中の化合物（Ｉ）の含有割合は、感光性着色組成物の全固形分量に対して５質量％以上が好ましく、１０質量％以上がより好ましく、１５質量％以上がさらに好ましく、２０質量％以上が特に好ましく、また、通常５０質量％以下であり、４０質量％以下が好ましく、３０質量％以下がより好ましく、２５質量％以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、５質量％～７０質量％が好ましく、２０質量％～７０質量％がより好ましく、２０質量％～６０質量％がさらに好ましく、２０質量％～５０質量％が特に好ましい。前記下限値以上とすることで硬化に必要な紫外線光の損失を抑えつつ遮光性が高くなる傾向がある。前記上限値以下とすることで分散剤量を減らすことができ、表面荒れを抑止できる傾向がある。 In the first aspect, the content ratio of the compound (I) in the photosensitive coloring composition is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 15% by mass, based on the total solid content of the photosensitive coloring composition. It is more preferably mass% or more, particularly preferably 20% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 5% by mass to 70% by mass is preferable, 20% by mass to 70% by mass is more preferable, 20% by mass to 60% by mass is further preferable, and 20% by mass to 50% by mass is particularly preferable. By setting the value to the lower limit or more, the light-shielding property tends to be improved while suppressing the loss of ultraviolet light required for curing. By setting the value to the upper limit or less, the amount of the dispersant can be reduced, and the surface roughness tends to be suppressed.
　第一の態様にて、（ａ）着色剤が化合物（Ｉ）及び他の顔料を含む場合、その含有割合の合計は特に限定されないが、（ａ）着色剤中の化合物（Ｉ）の含有割合が、１０質量％以上が好ましく、２０質量％以上がより好ましく、３０質量％以上がさらに好ましく、また、９０質量％以下が好ましく、８０質量％以下がより好ましく、７０質量％以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１０質量％～９０質量％が好ましく、２０質量％～８０質量％がより好ましく、３０質量％～７０質量％がさらに好ましい。前記下限値以上とすることで遮光性が高くなり、黒色に近い色調にできる傾向がある。前記上限値以下とすることで現像時の残渣が少なくなり、素子作成時の信頼性が良好となる傾向がある。 In the first aspect, when (a) the colorant contains the compound (I) and other pigments, the total content ratio thereof is not particularly limited, but (a) the content ratio of the compound (I) in the colorant. However, 10% by mass or more is preferable, 20% by mass or more is more preferable, 30% by mass or more is further preferable, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 10% by mass to 90% by mass is preferable, 20% by mass to 80% by mass is more preferable, and 30% by mass to 70% by mass is further preferable. By setting the value to the lower limit or higher, the light-shielding property is enhanced, and the color tone tends to be close to black. By setting the value to the upper limit or less, the residue during development tends to be small, and the reliability at the time of producing the element tends to be good.
　第一の態様にて、（ａ）着色剤が化合物（Ｉ）及び有機着色顔料を含む場合、その含有割合の合計は特に限定されないが、（ａ）着色剤中の化合物（Ｉ）の含有割合が、１０質量％以上が好ましく、２０質量％以上がより好ましく、３０質量％以上がさらに好ましく、また、９０質量％以下が好ましく、８０質量％以下がより好ましく、７０質量％以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１０質量％～９０質量％が好ましく、２０質量％～８０質量％がより好ましく、３０質量％～７０質量％がさらに好ましい。前記下限値以上とすることで遮光性が高くなり、黒色に近い色調にできる傾向がある。前記上限値以下とすることで現像時の残渣が少なくなり、素子作成時の信頼性が良好となる傾向がある。 In the first aspect, when (a) the colorant contains the compound (I) and the organic coloring pigment, the total content ratio thereof is not particularly limited, but (a) the content ratio of the compound (I) in the colorant. However, 10% by mass or more is preferable, 20% by mass or more is more preferable, 30% by mass or more is further preferable, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 10% by mass to 90% by mass is preferable, 20% by mass to 80% by mass is more preferable, and 30% by mass to 70% by mass is further preferable. By setting the value to the lower limit or higher, the light-shielding property is enhanced, and the color tone tends to be close to black. By setting the value to the upper limit or less, the residue during development tends to be small, and the reliability at the time of producing the element tends to be good.
　感光性着色組成物が、有機着色顔料を含む場合、その含有割合は特に限定されないが、感光性着色組成物の全固形分量に対して５質量％以上が好ましく、１０質量％以上がより好ましく、１５質量％以上がさらに好ましく、２０質量％以上が特に好ましく、また、通常５０質量％以下であり、４０質量％以下が好ましく、３０質量％以下がより好ましく、２５質量％以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、５質量％～７０質量％が好ましく、２０質量％～７０質量％がより好ましく、２０質量％～６０質量％がさらに好ましく、２０質量％～５０質量％が特に好ましい。前記下限値以上とすることで遮光性が高くなる傾向がある。前記上限値以下とすることで分散剤量を減らすことができ、表面荒れを抑止できる傾向がある。 When the photosensitive coloring composition contains an organic coloring pigment, the content ratio thereof is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content of the photosensitive coloring composition. 15% by mass or more is further preferable, 20% by mass or more is particularly preferable, and usually 50% by mass or less, 40% by mass or less is preferable, 30% by mass or less is more preferable, and 25% by mass or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 5% by mass to 70% by mass is preferable, 20% by mass to 70% by mass is more preferable, 20% by mass to 60% by mass is further preferable, and 20% by mass to 50% by mass is particularly preferable. When the value is equal to or higher than the lower limit, the light blocking effect tends to be improved. By setting the value to the upper limit or less, the amount of the dispersant can be reduced, and the surface roughness tends to be suppressed.
　（ａ）着色剤が赤色顔料及び／又は橙色顔料を含む場合、赤色顔料及び橙色顔料の含有割合の合計は特に限定されないが、（ａ）着色剤中に５質量％以上が好ましく、８質量％以上がより好ましく、１０質量％以上がさらに好ましく、１２質量％以上が特に好ましく、また、４０質量％以下が好ましく、３０質量％以下がより好ましく、２０質量％以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、５質量％～４０質量％が好ましく、８質量％～４０質量％がより好ましく、１０質量％～３０質量％がさらに好ましく、１２質量％～２０質量％が特に好ましい。前記下限値以上とすることで黒色に近い色調にできる傾向がある。前記上限値以下とすることで高感度となる傾向がある。 (A) When the colorant contains a red pigment and / or an orange pigment, the total content of the red pigment and the orange pigment is not particularly limited, but (a) 5% by mass or more is preferable in the colorant, and 8% by mass is preferable. The above is more preferable, 10% by mass or more is further preferable, 12% by mass or more is particularly preferable, 40% by mass or less is preferable, 30% by mass or less is more preferable, and 20% by mass or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 5% by mass to 40% by mass is preferable, 8% by mass to 40% by mass is more preferable, 10% by mass to 30% by mass is further preferable, and 12% by mass to 20% by mass is particularly preferable. By setting the value to the lower limit or higher, the color tone tends to be close to black. When it is set to the upper limit or less, the sensitivity tends to be high.
　（ａ）着色剤が青色顔料及び／又は紫色顔料を含む場合、青色顔料及び紫色顔料の含有割合の合計は特に限定されないが、（ａ）着色剤中に３０質量％以上が好ましく、５０質量％以上がより好ましく、７０質量％以上がさらに好ましく、８０質量％以上が特に好ましく、また、９５質量％以下が好ましく、９２質量％以下がより好ましく、９０質量％以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、３０質量％～９５質量％が好ましく、５０質量％～９５質量％がより好ましく、７０質量％～９２質量％がさらに好ましく、８０質量％～９０質量％が特に好ましい。前記下限値以上とすることで黒色に近い色調にできる傾向がある。前記上限値以下とすることで感度、遮光性が良好となる傾向がある。 (A) When the colorant contains a blue pigment and / or a purple pigment, the total content of the blue pigment and the purple pigment is not particularly limited, but (a) 30% by mass or more is preferable in the colorant, and 50% by mass is preferable. The above is more preferable, 70% by mass or more is further preferable, 80% by mass or more is particularly preferable, 95% by mass or less is preferable, 92% by mass or less is more preferable, and 90% by mass or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 30% by mass to 95% by mass is preferable, 50% by mass to 95% by mass is more preferable, 70% by mass to 92% by mass is further preferable, and 80% by mass to 90% by mass is particularly preferable. By setting the value to the lower limit or higher, the color tone tends to be close to black. When it is set to the upper limit or less, the sensitivity and the light-shielding property tend to be good.
　（ａ）着色剤が赤色顔料及び／又は橙色顔料と、青色顔料及び／又は紫色顔料の両方を含む場合、赤色顔料及び／又は橙色顔料の含有割合は、青色顔料及び／又は紫色顔料の含有量に対し、特に限定はないが、１質量％以上が好ましく、３質量％以上がより好ましく、５質量％以上がさらに好ましく、８質量％以上が特に好ましく、また、３００質量％以下が好ましく、１００質量％以下がより好ましく、５０質量％以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１質量％～３００質量％が好ましく、３質量％～１００質量％がより好ましく、５質量％～１００質量％がさらに好ましく、８質量％～５０質量％が特に好ましい。前記下限値以上とすることで青色光の透過を抑え、遮光性が高くなる傾向がある。前記上限値以下とすることで黒色に近い色調にできる傾向がある。 (A) When the colorant contains both a red pigment and / or an orange pigment and both a blue pigment and / or a purple pigment, the content ratio of the red pigment and / or the orange pigment is the content of the blue pigment and / or the purple pigment. However, there is no particular limitation, but 1% by mass or more is preferable, 3% by mass or more is more preferable, 5% by mass or more is further preferable, 8% by mass or more is particularly preferable, and 300% by mass or less is particularly preferable. More preferably, it is more preferably mass% or less, and particularly preferably 50% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 1% by mass to 300% by mass is preferable, 3% by mass to 100% by mass is more preferable, 5% by mass to 100% by mass is further preferable, and 8% by mass to 50% by mass is particularly preferable. By setting the value to the lower limit or more, the transmission of blue light tends to be suppressed and the light-shielding property tends to be improved. By setting the value to the upper limit or less, the color tone tends to be close to black.
　感光性着色組成物が有機黒色顔料を含む場合、その含有割合は特に限定されないが、感光性着色組成物の全固形分量に対して３質量％以上が好ましく、５質量％以上がより好ましく、１０質量％以上がさらに好ましく、２０質量％以上が特に好ましく、また、６０質量％以下が好ましく、５０質量％以下がより好ましく、４０質量％以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、３質量％～６０質量％が好ましく、５質量％～６０質量％がより好ましく、１０質量％～５０質量％がさらに好ましく、２０質量％～４０質量％が特に好ましい。前記下限値以上とすることで遮光性が高くなる傾向がある。前記上限値以下と分散剤量を減らすことができ、表面荒れを抑止できる傾向がある。 When the photosensitive coloring composition contains an organic black pigment, the content ratio thereof is not particularly limited, but is preferably 3% by mass or more, more preferably 5% by mass or more, and 10% by mass, based on the total solid content of the photosensitive coloring composition. More preferably, it is more preferably mass% or more, 20% by mass or more, particularly preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 3% by mass to 60% by mass is preferable, 5% by mass to 60% by mass is more preferable, 10% by mass to 50% by mass is further preferable, and 20% by mass to 40% by mass is particularly preferable. When the value is equal to or higher than the lower limit, the light blocking effect tends to be improved. The amount of the dispersant can be reduced to the upper limit or less, and the surface roughness tends to be suppressed.
　感光性着色組成物が無機黒色顔料としてカーボンブラックを含む場合、その含有割合は特に限定されないが、感光性着色組成物の全固形分量に対して１質量％以上が好ましく、３質量％以上がより好ましく、５質量％以上がさらに好ましく、また、３０質量％以下が好ましく、２０質量％以下がより好ましく、１０質量％以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１質量％～３０質量％が好ましく、３質量％～２０質量％がより好ましく、３質量％～１０質量％がさらに好ましい。前記下限値以上とすることで遮光性が高くなる傾向がある。前記上限値以下とすることで高抵抗、低誘電率の硬化物を形成できる傾向がある。 When the photosensitive coloring composition contains carbon black as an inorganic black pigment, the content thereof is not particularly limited, but it is preferably 1% by mass or more, more preferably 3% by mass or more, based on the total solid content of the photosensitive coloring composition. It is preferable, 5% by mass or more is further preferable, 30% by mass or less is preferable, 20% by mass or less is more preferable, and 10% by mass or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 1% by mass to 30% by mass is preferable, 3% by mass to 20% by mass is more preferable, and 3% by mass to 10% by mass is further preferable. When the value is equal to or higher than the lower limit, the light blocking effect tends to be improved. By setting the value to the upper limit or less, there is a tendency that a cured product having high resistance and low dielectric constant can be formed.
　（ａ）着色剤が黒色顔料及び有機着色顔料を含む場合、その含有割合の合計は特に限定されないが、（ａ）着色剤中の黒色顔料の含有割合が、１０質量％以上が好ましく、２０質量％以上がより好ましく、３０質量％以上がさらに好ましく、また、９０質量％以下が好ましく、８０質量％以下がより好ましく、７０質量％以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１０質量％～９０質量％が好ましく、２０質量％～８０質量％がより好ましく、３０質量％～７０質量％がさらに好ましい。前記下限値以上とすることで遮光性が高くなり、黒色に近い色調にできる傾向がある。前記上限値以下とすることで現像時の残渣が少なくなり、素子作成時の信頼性が良好となる傾向がある。 When the (a) colorant contains a black pigment and an organic color pigment, the total content thereof is not particularly limited, but (a) the content ratio of the black pigment in the colorant is preferably 10% by mass or more, preferably 20% by mass. % Or more is more preferable, 30% by mass or more is further preferable, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 10% by mass to 90% by mass is preferable, 20% by mass to 80% by mass is more preferable, and 30% by mass to 70% by mass is further preferable. By setting the value to the lower limit or higher, the light-shielding property is enhanced, and the color tone tends to be close to black. By setting the value to the upper limit or less, the residue during development tends to be small, and the reliability at the time of producing the element tends to be good.
　（ｂ）アルカリ可溶性樹脂の含有割合は特に限定されないが、本発明の感光性着色組成物の全固形分量に対して通常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８５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、よりさらに好ましくは５５質量％以下である。上記の上限及び下限は任意に組み合わせることができる。例えば、５質量％～８０質量％が好ましく、１０質量％～７０質量％がより好ましく、２０質量％～６０質量％がさらに好ましく、３０質量％～６０質量％がよりさらに好ましく、３０質量％～５５質量％がことさら好ましく、４０質量％～５５質量％が特に好ましい。前記下限値以上とすることで未露光部分の現像液に対する溶解性の低下を抑制し、現像不良を抑制できる傾向がある。前記上限値以下とすることで、適正な感度を維持し、露光部の現像液による溶解を抑制でき、またパターンのシャープ性や密着性の低下を抑制できる傾向がある。 (B) The content ratio of the alkali-soluble resin is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, based on the total solid content of the photosensitive coloring composition of the present invention. More preferably 30% by mass or more, particularly preferably 40% by mass or more, usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, still more. It is preferably 55% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 5% by mass to 80% by mass is preferable, 10% by mass to 70% by mass is more preferable, 20% by mass to 60% by mass is further preferable, 30% by mass to 60% by mass is further preferable, and 30% by mass to 30% by mass. 55% by mass is particularly preferable, and 40% by mass to 55% by mass is particularly preferable. By setting the value to the lower limit or more, it tends to be possible to suppress a decrease in solubility of the unexposed portion in a developing solution and suppress development defects. By setting the value to the upper limit or less, it tends to be possible to maintain appropriate sensitivity, suppress dissolution of the exposed portion by the developing solution, and suppress deterioration of pattern sharpness and adhesion.
　（ｂ１）エポキシ（メタ）アクリレート系樹脂の含有割合は特に限定されないが、本発明の感光性着色組成物の全固形分量に対して通常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、ことさらに好ましくは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、特に好ましくは５５質量％以下である。上記の上限及び下限は任意に組み合わせることができる。例えば、５質量％～８０質量％が好ましく、１０質量％～７０質量％がより好ましく、２０質量％～６０質量％がさらに好ましく、３０質量％～６０質量％がよりさらに好ましく、３０質量％～５５質量％がことさら好ましく、４０質量％～５５質量％が特に好ましい。前記下限値以上とすることで未露光部分の現像液に対する溶解性を確保できる傾向がある。前記上限値以下とすることで適正な感度を維持し、露光部の現像液による溶解を抑制でき、またパターンのシャープ性や密着性の低下を抑制できる傾向がある。 (B1) The content ratio of the epoxy (meth) acrylate-based resin is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 10% by mass or more, based on the total solid content of the photosensitive coloring composition of the present invention. It is 15% by mass or more, more preferably 20% by mass or more, further 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. It is 60% by mass or less, particularly preferably 55% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 5% by mass to 80% by mass is preferable, 10% by mass to 70% by mass is more preferable, 20% by mass to 60% by mass is further preferable, 30% by mass to 60% by mass is further preferable, and 30% by mass to 30% by mass. 55% by mass is particularly preferable, and 40% by mass to 55% by mass is particularly preferable. By setting the value to the lower limit or more, there is a tendency that the solubility of the unexposed portion in the developing solution can be ensured. By setting the value to the upper limit or less, it tends to be possible to maintain appropriate sensitivity, suppress dissolution of the exposed portion by the developing solution, and suppress deterioration of pattern sharpness and adhesion.
　（ｂ）アルカリ可溶性樹脂中に含まれる（ｂ１）エポキシ（メタ）アクリレート系樹脂の含有割合は特に限定されないが、通常２０質量％以上、好ましくは３０質量％以上、より好ましくは４０質量％以上であり、通常１００質量％以下、好ましくは９０質量％以下、より好ましくは８０質量％以下である。上記の上限及び下限は任意に組み合わせることができる。例えば、２０質量％～９０質量％が好ましく、３０質量％～８０質量％がより好ましく、４０質量％～８０質量％がさらに好ましい。前記下限値以上とすることで未露光部分の現像液に対する溶解性を確保できる傾向がある。前記上限値以下とすることで適正な感度を維持し、露光部の現像液による溶解を抑制でき、またパターンのシャープ性や密着性の低下を抑制できる傾向がある。 The content of the (b1) epoxy (meth) acrylate-based resin contained in the (b) alkali-soluble resin is not particularly limited, but is usually 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more. It is usually 100% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 20% by mass to 90% by mass is preferable, 30% by mass to 80% by mass is more preferable, and 40% by mass to 80% by mass is further preferable. By setting the value to the lower limit or more, there is a tendency that the solubility of the unexposed portion in the developing solution can be ensured. By setting the value to the upper limit or less, it tends to be possible to maintain appropriate sensitivity, suppress dissolution of the exposed portion by the developing solution, and suppress deterioration of pattern sharpness and adhesion.
　（ｃ）光重合開始剤の含有割合は特に限定されないが、本発明の感光性着色組成物の全固形分量に対して通常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、よりさらに好ましくは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６質量％以下である。上記の上限及び下限は任意に組み合わせることができる。例えば、０．１質量％～１５質量％が好ましく、０．５質量％～１５質量％がより好ましく、１質量％～１０質量％がさらに好ましく、２質量％～８質量％がよりさらに好ましく、３質量％～６質量％が特に好ましい。前記下限値以上とすることで感度低下を抑制できる傾向がある。前記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の低下を抑制し、現像不良を抑制できる傾向がある。 (C) The content ratio of the photopolymerization initiator is not particularly limited, but is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably, with respect to the total solid content of the photosensitive coloring composition of the present invention. Is 1% by mass or more, more preferably 2% by mass or more, still more 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, still more preferably 6. It is less than mass%. The above upper and lower limits can be combined arbitrarily. For example, 0.1% by mass to 15% by mass is preferable, 0.5% by mass to 15% by mass is more preferable, 1% by mass to 10% by mass is further preferable, and 2% by mass to 8% by mass is further preferable. 3% by mass to 6% by mass is particularly preferable. By setting the value to the lower limit or more, there is a tendency that the decrease in sensitivity can be suppressed. By setting the value to the upper limit or less, it tends to be possible to suppress a decrease in solubility of the unexposed portion in a developing solution and suppress development defects.
　（ｃ）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特に限定されないが、本発明の感光性着色組成物の全固形分量に対して好ましくは０．０５質量％以上、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、（ｃ）光重合開始剤１００質量部に対して通常０．１～５０質量部、特に０．１～２０質量部の割合で用いることが好ましい。重合促進剤の含有割合を前記下限値以上とすることで、露光光線に対する感度の低下を抑制できる傾向がある。前記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の低下を抑制し、現像不良を抑制できる傾向がある。
　（ｃ）光重合開始剤と共に増感色素を用いる場合、その含有割合は特に限定されないが、感度の観点から感光性着色組成物中の全固形分量に対して通常２０質量％以下、好ましくは１５質量％以下、より好ましくは１０質量％以下である。 (C) When a polymerization accelerator is used together with the photopolymerization initiator, the content ratio of the polymerization accelerator is not particularly limited, but is preferably 0.05% by mass or more with respect to the total solid content of the photosensitive coloring composition of the present invention. , Usually 10% by mass or less, preferably 5% by mass or less. Further, it is preferable to use the polymerization accelerator in a ratio of usually 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass with respect to 100 parts by mass of the (c) photopolymerization initiator. By setting the content ratio of the polymerization accelerator to the lower limit value or more, there is a tendency that the decrease in sensitivity to the exposed light can be suppressed. By setting the value to the upper limit or less, it tends to be possible to suppress a decrease in solubility of the unexposed portion in a developing solution and suppress development defects.
(C) When a sensitizing dye is used together with the photopolymerization initiator, the content ratio thereof is not particularly limited, but from the viewpoint of sensitivity, it is usually 20% by mass or less, preferably 15 by mass or less, based on the total solid content in the photosensitive coloring composition. It is mass% or less, more preferably 10 mass% or less.
　（ｄ）エチレン性不飽和化合物の含有割合は特に限定されないが、本発明の感光性着色組成物の全固形分量に対して通常１質量％以上、好ましくは５質量％以上、より好ましくは１０質量％以上であり、さらに好ましくは１５質量％以上であり、また、通常３０質量％以下、好ましくは２５質量％以下、より好ましくは２０質量％以下である。上記の上限及び下限は任意に組み合わせることができる。例えば、１質量％～３０質量％が好ましく、５質量％～２０質量％がより好ましく、１０質量％～２０質量％がさらに好ましい。前記下限値以上とすることで適正な感度を維持し、露光部の現像液による溶解を抑制でき、またパターンのシャープ性や密着性の低下を抑制できる傾向がある。前記上限値以下とすることで、露光部への現像液の浸透性が高くなるのを抑制し、良好な画像を得ることが容易となる傾向がある。 (D) The content of the ethylenically unsaturated compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass, based on the total solid content of the photosensitive coloring composition of the present invention. % Or more, more preferably 15% by mass or more, and usually 30% by mass or less, preferably 25% by mass or less, and more preferably 20% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 1% by mass to 30% by mass is preferable, 5% by mass to 20% by mass is more preferable, and 10% by mass to 20% by mass is further preferable. By setting the value to the lower limit or more, it tends to be possible to maintain appropriate sensitivity, suppress dissolution of the exposed portion by the developing solution, and suppress deterioration of pattern sharpness and adhesion. By setting the value to the upper limit or less, it tends to prevent the developer from increasing the permeability to the exposed portion, and it tends to be easy to obtain a good image.
　本発明の感光性着色組成物は、（ｅ）溶剤を使用することで、全固形分量の含有割合が好ましくは５質量％以上、より好ましくは１０質量％以上、さらに好ましくは１５質量％以上、また、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２５質量％以下となるように調液される。上記の上限及び下限は任意に組み合わせることができる。例えば、好ましくは５質量％～５０質量％、より好ましくは１０質量％～３０質量％、さらに好ましくは１５質量％～２５質量％となるように調液される。 In the photosensitive coloring composition of the present invention, by using the solvent (e), the content ratio of the total solid content is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more. Further, the liquid is adjusted so as to be preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the liquid is preferably adjusted to be 5% by mass to 50% by mass, more preferably 10% by mass to 30% by mass, and further preferably 15% by mass to 25% by mass.
　（ｆ）分散剤の含有割合は特に限定されないが、感光性着色組成物の全固形分量に対して通常１質量％以上であり、２質量％以上が好ましく、３質量％以上がより好ましく、また通常２０質量％以下、１５質量％以下が好ましく、１０質量％以下がより好ましく、７質量％以下がさらに好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１質量％～２０質量％が好ましく、２質量％～１５質量％がより好ましく、３質量％～１０質量％がさらに好ましく、３質量％～７質量％が特に好ましい。前記下限値以上とすることで、十分な分散性が得られやすい傾向がある。前記上限値以下とすることで電極表面の表面荒れを抑制できる傾向がある。 (F) The content ratio of the dispersant is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and more preferably 3% by mass or more, based on the total solid content of the photosensitive coloring composition. Usually, 20% by mass or less, 15% by mass or less is preferable, 10% by mass or less is more preferable, and 7% by mass or less is further preferable. The above upper and lower limits can be combined arbitrarily. For example, 1% by mass to 20% by mass is preferable, 2% by mass to 15% by mass is more preferable, 3% by mass to 10% by mass is further preferable, and 3% by mass to 7% by mass is particularly preferable. By setting the value to the lower limit or more, it tends to be easy to obtain sufficient dispersibility. By setting the value to the upper limit or less, the surface roughness of the electrode surface tends to be suppressed.
　分散剤（ｆ１）の含有割合は特に限定されないが、感光性着色組成物の全固形分量に対して通常１質量％以上であり、２質量％以上が好ましく、３質量％以上がより好ましく、また通常２０質量％以下、１５質量％以下が好ましく、１０質量％以下がより好ましく、７質量％以下がさらに好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１質量％～２０質量％が好ましく、２質量％～１５質量％がより好ましく、３質量％～１０質量％がさらに好ましく、３質量％～７質量％が特に好ましい。前記下限値以上とすることで、十分な分散性が得られやすい傾向がある。前記上限値以下とすることで電極表面の表面荒れを抑制できる傾向がある。 The content ratio of the dispersant (f1) is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and more preferably 3% by mass or more, based on the total solid content of the photosensitive coloring composition. Usually, 20% by mass or less, 15% by mass or less is preferable, 10% by mass or less is more preferable, and 7% by mass or less is further preferable. The above upper and lower limits can be combined arbitrarily. For example, 1% by mass to 20% by mass is preferable, 2% by mass to 15% by mass is more preferable, 3% by mass to 10% by mass is further preferable, and 3% by mass to 7% by mass is particularly preferable. By setting the value to the lower limit or more, it tends to be easy to obtain sufficient dispersibility. By setting the value to the upper limit or less, the surface roughness of the electrode surface tends to be suppressed.
　分散剤（ｆ１）の含有割合は特に限定されないが、（ｆ）分散剤中に通常２０質量％以上であり、４０質量％以上が好ましく、６０質量％以上がより好ましく、８０質量％以上がさらに好ましく、また通常１００質量％以下である。前記下限値以上とすることで、電極表面の表面荒れを抑制できる傾向がある。 The content ratio of the dispersant (f1) is not particularly limited, but (f) is usually 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, and further preferably 80% by mass or more in the dispersant. It is preferable, and usually it is 100% by mass or less. By setting the value to the lower limit or higher, the surface roughness of the electrode surface tends to be suppressed.
　（ａ）着色剤１００質量部に対する（ｆ）分散剤の含有割合は特に限定されないが、通常５質量部以上、１０質量部以上がより好ましく、１５質量部以上がさらに好ましく、通常５０質量部以下、特に３０質量部以下であることが好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、５質量部～５０質量部が好ましく、１０質量部～５０質量部がより好ましく、１５質量部～３０質量部がさらに好ましい。前記下限値以上とすることで、十分な分散性が得られやすい傾向がある。前記上限値以下とすることで電極表面の表面荒れを抑制できる傾向がある。 (A) The content ratio of the (f) dispersant to 100 parts by mass of the colorant is not particularly limited, but is usually 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and usually 50 parts by mass or less. In particular, it is preferably 30 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 5 parts by mass to 50 parts by mass is preferable, 10 parts by mass to 50 parts by mass is more preferable, and 15 parts by mass to 30 parts by mass is further preferable. By setting the value to the lower limit or more, it tends to be easy to obtain sufficient dispersibility. By setting the value to the upper limit or less, the surface roughness of the electrode surface tends to be suppressed.
　（ｄ）エチレン性不飽和化合物１００質量部に対する（ｂ）アルカリ可溶性樹脂の含有割合は特に限定されないが、通常１００質量部以上、２００質量部以上が好ましく、２５０質量部以上がより好ましく、３００質量部以上がさらに好ましく、３５０質量部以上が特に好ましく、また、通常７００質量部以下、５００質量部以下が好ましく、４５０質量部以下がより好ましく、４００質量部以下がさらに好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、１００質量部～７００質量部が好ましく、２００質量部～７００質量部がより好ましく、２５０質量部～５００質量部がさらに好ましく、２５０質量部～４５０質量部がよりさらに好ましく、２５０質量部～４００質量部が特に好ましい。前記下限値以上とすることで剥離等のない適正な溶解現像状態となる傾向がある。前記上限値以下とすることで現像液に対して適切な溶解時間を得ることができる傾向がある。 The content ratio of (b) alkali-soluble resin to 100 parts by mass of (d) ethylenically unsaturated compound is not particularly limited, but is usually preferably 100 parts by mass or more, 200 parts by mass or more, more preferably 250 parts by mass or more, and 300 parts by mass. More than parts are more preferable, 350 parts by mass or more are particularly preferable, and usually 700 parts by mass or less, 500 parts by mass or less are preferable, 450 parts by mass or less are more preferable, and 400 parts by mass or less are further preferable. The above upper and lower limits can be combined arbitrarily. For example, 100 parts by mass to 700 parts by mass is preferable, 200 parts by mass to 700 parts by mass is more preferable, 250 parts by mass to 500 parts by mass is further preferable, 250 parts by mass to 450 parts by mass is more preferable, and 250 parts by mass to 250 parts by mass. 400 parts by mass is particularly preferable. By setting the value to the lower limit or more, there is a tendency that an appropriate dissolution and development state without peeling or the like is obtained. By setting the value to the upper limit or less, it tends to be possible to obtain an appropriate dissolution time for the developing solution.
　密着向上剤を用いる場合、その含有割合は特に限定されないが、感光性着色組成物の全固形分量に対して通常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。前記下限値以上とすることで密着性の向上効果を十分に得ることができる傾向がある。前記上限値以下とすることで感度が低下したり、現像後に残渣が残り欠陥となったりするのを抑制できる傾向がある。 When the adhesion improver is used, its content is not particularly limited, but it is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0.2 to 3% by mass, based on the total solid content of the photosensitive coloring composition. It is 0.4 to 2% by mass. By setting the value to the lower limit or more, there is a tendency that the effect of improving the adhesion can be sufficiently obtained. By setting the value to the upper limit or less, there is a tendency that the sensitivity is lowered and that the residue remains after development and becomes a defect.
　界面活性剤を用いる場合、その含有割合は特に限定されないが、感光性着色組成物の全固形分量に対して通常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。前記下限値以上とすることで塗布膜の平滑性、均一性が発現しやすい傾向がある。前記上限値以下とすることで塗布膜の平滑性、均一性が発現しやすく、他の特性の悪化も抑制できる傾向がある。 When a surfactant is used, its content is not particularly limited, but it is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.001 to 1% by mass, based on the total solid content of the photosensitive coloring composition. It is 0.01 to 0.5% by mass, most preferably 0.03 to 0.3% by mass. By setting the value to the lower limit or higher, the smoothness and uniformity of the coating film tend to be easily developed. By setting the value to the upper limit or less, the smoothness and uniformity of the coating film are likely to be exhibited, and deterioration of other characteristics tends to be suppressed.
＜感光性着色組成物中の塩素原子含有量＞
　本発明の感光性着色組成物は、感光性着色組成物中の塩素原子の含有量が、感光性着色組成物の全固形分量に対して０．０５質量％以下である。
　隔壁を作成するにおいては、後述するような、加熱処理を行い、感光性着色組成物を硬化させる工程を伴う。その時、電極表面に表面荒れが発生する場合がある。表面荒れは光学顕微鏡で観察でき、また表面粗度も高くなる。電極表面に表面荒れが生じた場合には、その部分に発光層を均一に形成することができず、有機電界発光素子を作成したときに、短絡等による表示不良を引き起こす可能性がある。これは、加熱処理時に、特に焼成時に、感光性着色組成物中の塩素原子が分解、揮発、あるいは昇華し、銀などの金属電極に対し作用し、腐食あるいはエッチング等を起こすためと推定され、塩素原子の含有量を一定値以下にすることで、表面荒れを抑制できる。 <Chlorine atom content in photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less with respect to the total solid content of the photosensitive coloring composition.
The partition wall is prepared by performing a heat treatment as described later to cure the photosensitive coloring composition. At that time, surface roughness may occur on the electrode surface. Surface roughness can be observed with an optical microscope, and the surface roughness is also high. When the surface of the electrode is roughened, the light emitting layer cannot be uniformly formed on the portion thereof, which may cause display failure due to a short circuit or the like when an organic electroluminescent element is manufactured. It is presumed that this is because chlorine atoms in the photosensitive coloring composition decompose, volatilize, or sublimate during heat treatment, especially during firing, and act on metal electrodes such as silver, causing corrosion or etching. By setting the chlorine atom content to a certain value or less, surface roughness can be suppressed.
　感光性着色組成物中の塩素原子は、主に（ａ）着色剤、（ｂ）アルカリ可溶性樹脂、（ｆ）分散剤といった構成材料に含有されるが、他の材料にも含有される場合がある。塩素原子の含有量を本発明の規定する数値範囲に入れるためには、一つの構成材料の塩素含有量を減らしてもよく、あるいは各々の材料における塩素含有量を減らし、規定の数値範囲に入るように設計してもよい。 Chlorine atoms in the photosensitive coloring composition are mainly contained in constituent materials such as (a) a colorant, (b) an alkali-soluble resin, and (f) a dispersant, but may also be contained in other materials. be. In order to bring the chlorine atom content into the specified numerical range of the present invention, the chlorine content of one constituent material may be reduced, or the chlorine content of each material may be reduced to enter the specified numerical range. It may be designed as follows.
　感光性着色組成物中の塩素原子の含有量は、特に限定されないが、感光性着色組成物の全固形分量に対して０．０５質量％以下であり、０．０４質量％以下が好ましく、０．０３質量％以下がよりに好ましく、０．０１質量％以下がさらに好ましい。前記上限値以下にすることで、電極の表面荒れを抑制できる傾向がある。
　感光性着色組成物中の塩素原子の含有量は、特に限定されないが、通常０．０００５質量％以上であり、０．００１質量％以上が好ましく、０．００２質量％がより好ましい。前記下限値以上とすることで、各構成材料の製造時に精製を緩和化できる点で有効である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．０００５～０．０５質量％が好ましく、０．０００５～０．０４質量％がより好ましく、０．００１～０．０３質量％がさらに好ましく、０．００２～０．０１質量％が特に好ましい。 The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is 0.05% by mass or less, preferably 0.04% by mass or less, and 0, based on the total solid content of the photosensitive coloring composition. 3.03% by mass or less is more preferable, and 0.01% by mass or less is further preferable. By setting the value to the upper limit or less, the surface roughness of the electrode tends to be suppressed.
The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is usually 0.0005% by mass or more, preferably 0.001% by mass or more, and more preferably 0.002% by mass. By setting the value to the lower limit or more, it is effective in that purification can be relaxed during the production of each constituent material.
The above upper and lower limits can be combined arbitrarily. For example, 0.0005 to 0.05% by mass is preferable, 0.0005 to 0.04% by mass is more preferable, 0.001 to 0.03% by mass is further preferable, and 0.002 to 0.01% by mass is more preferable. Especially preferable.
　感光性着色組成物中の塩素原子の含有量は、特に限定されないが、溶剤を含めた感光性着色組成物の全質量に対して、１００μｇ／ｇ以下が好ましく、８０μｇ／ｇ以下がより好ましく、５０μｇ／ｇ以下がさらに好ましく、３０μｇ／ｇ以下がよりさらに好ましく、１０μｇ／ｇ以下が特に好ましい。前記上限値以下にすることで、電極の表面荒れが良好を抑制できる傾向がある。
　感光性着色組成物中の塩素原子の含有量は、特に限定されないが、通常０．５μｇ／ｇ以上であり、１．０μｇ／ｇ以上が好ましく、２．０μｇ／ｇ以上がより好ましい。下限値以上とすることで、各構成材料の製造時に精製を緩和化できる点で有効である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．５～１００μｇ／ｇが好ましく、０．５～８０μｇ／ｇがより好ましく、１．０～５０μｇ／ｇがさらに好ましく、１．０～３０μｇ／ｇがよりさらに好ましく、２．０～１０μｇ／ｇが特に好ましい。 The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is preferably 100 μg / g or less, more preferably 80 μg / g or less, based on the total mass of the photosensitive coloring composition including the solvent. 50 μg / g or less is further preferable, 30 μg / g or less is further preferable, and 10 μg / g or less is particularly preferable. By setting the value to the upper limit or less, the surface roughness of the electrode tends to be suppressed from being good.
The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is usually 0.5 μg / g or more, preferably 1.0 μg / g or more, and more preferably 2.0 μg / g or more. By setting the value to the lower limit or higher, it is effective in that purification can be relaxed during the production of each constituent material.
The above upper and lower limits can be combined arbitrarily. For example, 0.5 to 100 μg / g is preferable, 0.5 to 80 μg / g is more preferable, 1.0 to 50 μg / g is further preferable, 1.0 to 30 μg / g is more preferable, and 2.0 to 20 to 10 μg / g is particularly preferable.
　感光性着色組成物中の塩素原子の含有量は、特に限定されないが、感光性着色組成物の（ａ）着色剤の含有量１００質量％に対して、０．２０質量％以下が好ましく、０．１５質量％以下がより好ましく、０．１０質量％以下がさらに好ましく、０．０５質量％以下がよりさらに好ましく、０．０３質量％以下が特に好ましい。前記上限値以下にすることで、電極の表面荒れを抑制できる傾向がある。
　感光性着色組成物中の塩素原子の含有量は、特に限定されないが、通常０．００１質量％以上であり、０．００５質量％以上が好ましく、０．０１０質量％がより好ましい。下限値以上とすることで、各構成材料の製造時に精製を緩和化できる点で有効である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、感光性着色組成物の（ａ）着色剤の含有量１００質量％に対して、０．００１～０．２０質量％が好ましく、０．００１～０．１５質量％がより好ましく、０．００５～０．１０質量％がさらに好ましく、０．００５～０．０５質量％がよりさらに好ましく、０．０１０～０．０３質量％が特に好ましい。 The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is preferably 0.20% by mass or less, preferably 0.20% by mass or less, based on 100% by mass of the (a) colorant content of the photosensitive coloring composition. It is more preferably .15% by mass or less, further preferably 0.10% by mass or less, further preferably 0.05% by mass or less, and particularly preferably 0.03% by mass or less. By setting the value to the upper limit or less, the surface roughness of the electrode tends to be suppressed.
The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is usually 0.001% by mass or more, preferably 0.005% by mass or more, and more preferably 0.010% by mass. By setting the value to the lower limit or higher, it is effective in that purification can be relaxed during the production of each constituent material.
The above upper and lower limits can be combined arbitrarily. For example, 0.001 to 0.20% by mass is preferable, 0.001 to 0.15% by mass is more preferable, and 0. 005 to 0.10% by mass is further preferable, 0.005 to 0.05% by mass is further preferable, and 0.010 to 0.03% by mass is particularly preferable.
　感光性着色組成物中の塩素原子の含有量は、例えば、燃焼イオンクロマトグラフ法（Ｃｏｍｂｕｓｔｉｏｎ　ｉｏｎ　ｃｈｒｏｍａｔｏｇｒａｐｈｙ）などで測定することができる。 The content of chlorine atoms in the photosensitive coloring composition can be measured by, for example, a combustion ion chromatograph method (Combustion ion chromatography).
＜感光性着色組成物の物性＞
　本発明の感光性着色組成物は、その塗膜の膜厚１μｍ当たりの光学濃度（ＯＤ）が第一の態様においては特に限定されないが、０．５以上が好ましい。第二の態様においては、０．５以上である。０．７以上がより好ましく、１．０以上がさらに好ましく、１．３以上がよりさらに好ましく、１．５以上が特に好ましく、通常４．０以下であり、３．０以下が好ましく、２．０以下がより好ましい。上記の上限及び下限は任意に組み合わせることができる。第一の態様及び第二の態様のいずれにおいても、例えば、０．５～４．０が好ましく、０．７～４．０がより好ましく、１．０～３．０がさらに好ましく、１．３～３．０がよりさらに好ましく、１．５～２．０が特に好ましい。前記下限値以上とすることで、十分な遮光性が得られる傾向がある。前記上限値以下とすることで電極の表面荒れが良好となる傾向がある。 <Physical characteristics of the photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, the optical density (OD) per 1 μm of the film thickness of the coating film is not particularly limited in the first aspect, but is preferably 0.5 or more. In the second aspect, it is 0.5 or more. 0.7 or more is more preferable, 1.0 or more is further preferable, 1.3 or more is more preferable, 1.5 or more is particularly preferable, usually 4.0 or less, 3.0 or less is preferable, and 2. 0 or less is more preferable. The above upper and lower limits can be combined arbitrarily. In both the first aspect and the second aspect, for example, 0.5 to 4.0 is preferable, 0.7 to 4.0 is more preferable, 1.0 to 3.0 is further preferable, and 1. 3 to 3.0 is more preferable, and 1.5 to 2.0 is particularly preferable. By setting the value to the lower limit or higher, sufficient light-shielding property tends to be obtained. When the value is not more than the upper limit, the surface roughness of the electrode tends to be good.
　塗膜の膜厚１μｍ当たりの光学濃度（ＯＤ）は、本発明の感光性着色組成物を硬化した塗膜を用いて測定すればよく、２３０℃で２０分間加熱硬化させた塗膜を用いて測定することができる。
　光学濃度とは、受光部の分光感度特性がＩＳＯ　５－３規格におけるＩＳＯ　ｖｉｓｕａｌ　ｄｅｎｓｉｔｙで示される透過光学濃度をいう。通常、光源としては、ＣＩＥ（国際照明委員会）が規定するＡ光源が用いられる。透過光学濃度の測定に用いることができる測定器としては、例えば、サカタインクスエンジニアリング社のＸ－Ｒｉｔｅ　３６１Ｔ（Ｖ）を挙げることができる。 The optical density (OD) per 1 μm of the film thickness of the coating film may be measured by using a coating film obtained by curing the photosensitive coloring composition of the present invention, and using a coating film heat-cured at 230 ° C. for 20 minutes. Can be measured.
The optical density means a transmission optical density in which the spectral sensitivity characteristic of the light receiving portion is indicated by ISO visual density in the ISO 5-3 standard. Usually, as the light source, the A light source specified by the CIE (Commission Internationale de l'Eclairage) is used. As a measuring instrument that can be used for measuring the transmitted optical density, for example, X-Rite 361T (V) manufactured by Sakata Inx Corporation can be mentioned.
＜感光性着色組成物の製造方法＞
　本発明の感光性着色組成物は、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されるのが好ましい。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。 <Manufacturing method of photosensitive coloring composition>
The photosensitive coloring composition of the present invention is produced according to a conventional method.
Usually, (a) the colorant is preferably dispersed 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 (a) colorant is made into fine particles by the dispersion treatment, the coating characteristics of the resist are improved.
　分散処理は、通常、（ａ）着色剤、（ｅ）溶剤、及び（ｆ）分散剤、並びに（ｂ）アルカリ可溶性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、及び分散処理にて得られた組成物を「顔料分散液」と称することがある）。特に（ｆ）分散剤として高分子分散剤を用いると、得られた顔料分散液及び感光性着色組成物の経時の増粘が抑制される、すなわち分散安定性に優れるので好ましい。
　このように、感光性着色組成物を製造する工程において、（ａ）着色剤、（ｅ）溶剤、及び（ｆ）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。
　顔料分散液に用いることができる（ａ）着色剤、（ｅ）溶剤、及び（ｆ）分散剤としては、それぞれ感光性着色組成物に用いることができるものとして記載したものを好ましく採用することができる。また、顔料分散液における（ａ）着色剤の各着色剤の含有割合としても、感光性着色組成物における含有割合として記載したものを好ましく採用することができる。 The dispersion treatment is usually preferably carried out in a system in which (a) a colorant, (e) a solvent, and (f) a dispersant, and (b) a part or all of an alkali-soluble resin are used in combination (hereinafter, dispersion). The mixture to be subjected to the treatment and the composition obtained by the dispersion treatment may be referred to as "pigment dispersion liquid"). In particular, it is preferable to use a polymer dispersant as the dispersant (f) because the thickening of the obtained pigment dispersion and the photosensitive coloring composition over time is suppressed, that is, the dispersion stability is excellent.
As described above, in the step of producing the photosensitive coloring composition, it is preferable to produce a pigment dispersion liquid containing at least (a) a colorant, (e) a solvent, and (f) a dispersant.
As the (a) colorant, (e) solvent, and (f) dispersant that can be used in the pigment dispersion, those described as being usable in the photosensitive coloring composition are preferably used. can. Further, as the content ratio of each colorant of (a) the colorant in the pigment dispersion liquid, those described as the content ratio in the photosensitive coloring composition can be preferably adopted.
　感光性着色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程度の粒子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る。感光性着色組成物の２０度鏡面光沢度（ＪＩＳ　Ｚ８７４１）が５０～３００の範囲となるように、顔料分散液の光沢を制御するのが分散の目安である。感光性着色組成物の光沢度が低い場合には、分散処理が十分でなく荒い顔料（色材）粒子が残っていることが多く、現像性、密着性、解像性等が不十分となる可能性がある。光沢値が上記範囲を超えるまで分散処理を行うと、顔料が破砕して超微粒子が多数生じるため、却って分散安定性が損なわれる傾向がある。
　顔料分散液中に分散した顔料の分散粒径は通常０．０３～０．３μｍであり、動的光散乱法により測定されうる。 When a liquid containing all the components to be blended in the photosensitive coloring composition is subjected to the dispersion treatment, the highly reactive components may be denatured due to the heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
When (a) the colorant is dispersed by a sand grinder, glass beads or zirconia beads having a particle size of about 0.1 to 8 mm are preferably used. The dispersion treatment conditions are such that the temperature is usually 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. The dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment device, etc., and is appropriately adjusted. The guideline for dispersion is to control the gloss of the pigment dispersion so that the 20-degree mirror gloss (JIS Z8741) of the photosensitive coloring composition is in the range of 50 to 300. When the glossiness of the photosensitive coloring composition is low, the dispersion treatment is not sufficient and rough pigment (coloring material) particles often remain, resulting in insufficient developability, adhesion, resolution and the like. there is a possibility. When the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.
The dispersed particle size of the pigment dispersed in the pigment dispersion is usually 0.03 to 0.3 μm, and can be measured by a dynamic light scattering method.
　次に、上記分散処理により得られた顔料分散液と、感光性着色組成物中に含まれる、上記の他の成分を混合し、均一な溶液若しくは分散液とする。感光性着色組成物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あるため、得られた感光性着色組成物はフィルター等により濾過処理するのが望ましい。 Next, the pigment dispersion obtained by the dispersion treatment and the other components contained in the photosensitive coloring composition are mixed to obtain a uniform solution or dispersion. In the manufacturing process of the photosensitive coloring composition, fine dust may be mixed in the liquid, so that it is desirable to filter the obtained photosensitive coloring composition with a filter or the like.
［硬化物］
　本発明の感光性着色組成物を硬化させることで、本発明の硬化物を得ることができる。本発明の感光性着色組成物を硬化してなる硬化物は、隔壁として好適に用いることができる。 [Cursed product]
By curing the photosensitive coloring composition of the present invention, the cured product of the present invention can be obtained. The cured product obtained by curing the photosensitive coloring composition of the present invention can be suitably used as a partition wall.
［隔壁］
　本発明の感光性着色組成物は隔壁、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。 [Septum]
The photosensitive coloring 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 electroluminescent device. Examples of the organic layer used for the organic electroluminescent device include a hole injection layer, a hole transport layer, or a hole transport layer on a hole injection layer as described in Japanese Patent Application Laid-Open No. 2016-165396. Examples include the organic layer used.
　次に、本発明の感光性着色組成物を用いた隔壁について、その製造方法に従って説明する。 Next, the partition wall using the photosensitive coloring composition of the present invention will be described according to the manufacturing method thereof.
　（１）支持体
　隔壁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。主に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等のポリエステル系樹脂、ポリプロピレン、ポリエチレン等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、ポリスルフォン等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）アクリル樹脂等の熱硬化性樹脂シート、各種ガラスが挙げられる。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、あるいは銀、金、白金、アルミニウム、マグネシウムのような金属電極が成膜されている場合もある。上述の基板以外では、ＴＦＴアレイ上に形成することも可能である。 (1) Support The material of the support for forming the partition wall is not particularly limited as long as it has an appropriate strength. Substrates are mainly used, but as materials, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethylmethacrylate and polysulphon, and epoxy resins. , Thermo-curable resin sheets such as unsaturated polyester resin and poly (meth) acrylic resin, and various types of glass. Among them, glass and heat-resistant resin are preferable from the viewpoint of heat resistance. Further, a transparent electrode such as ITO or IZO or a metal electrode such as silver, gold, platinum, aluminum or magnesium may be formed on the surface of the substrate. Other than the above-mentioned substrate, it can also be formed on a TFT array.
　支持体には、接着性等の表面物性の改良のため、必要に応じ、例えば、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等の各種樹脂の薄膜形成処理を行ってもよい。
　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, for example, corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agent and urethane resin, if necessary, in order to improve surface physical properties such as adhesiveness. ..
The thickness of the substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When the thin film forming treatment of various resins is performed, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.
　（２）隔壁
　本発明の感光性着色組成物は、公知のカラーフィルター用感光性着色組成物と同様の用途に使用されるが、以下、隔壁として使用される場合について、本発明の感光性着色組成物を用いた隔壁の形成方法の具体例に従って説明する。 (2) Photosensitive partition wall The photosensitive coloring composition of the present invention is used for the same purposes as the known photosensitive coloring composition for color filters, but hereinafter, when used as a partition wall, the photosensitive coloring composition of the present invention is used. A specific example of a method for forming a partition wall using a composition will be described.
　通常、隔壁が設けられるべき基板上に、感光性着色組成物を、塗布等の方法により膜状あるいはパターン状に供給し、溶剤を乾燥させる。続いて、露光－現像を行うフォトリソグラフィー法等の方法によりパターン形成を行う。その後、必要により追露光や熱硬化処理を行うことにより、基板上に隔壁が形成される。 Normally, the photosensitive coloring composition is supplied in the form of a film or a pattern on a substrate on which a partition wall should be provided by a method such as coating, and the solvent is dried. Subsequently, pattern formation is performed by a method such as a photolithography method that performs exposure-development. After that, a partition wall is formed on the substrate by performing additional exposure and thermosetting treatment as necessary.
　（３）隔壁の形成
［１］基板への供給方法
　本発明の感光性着色組成物は、通常、溶剤に溶解あるいは分散された状態で、基板上へ供給される。その供給方法としては、従来公知の方法、例えば、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、スプレーコート法によって行うことができる。また、例えば、インクジェット法や印刷法により、パターン状に供給されてもよい。中でも、ダイコート法によれば、塗布液の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等の影響が全くない、異物発生が抑制される等、総合的な観点から好ましい。 (3) Formation of partition wall [1] Method of supplying to a substrate The photosensitive coloring composition of the present invention is usually supplied onto a substrate in a state of being dissolved or dispersed in a solvent. As the supply method, a conventionally known method, for example, a spinner method, a wire bar method, a flow coat method, a die coat method, a roll coat method, or a spray coat method can be used. Further, for example, it may be supplied in a pattern by an inkjet method or a printing method. Above all, according to the die coating method, the amount of the coating liquid used is significantly reduced, and there is no influence of mist or the like adhering when the spin coating method is used, and the generation of foreign substances is suppressed. Preferred from the point of view.
　塗布量は用途により異なるが、例えば隔壁の場合には、乾燥膜厚として、通常０．５μｍ～１０μｍ、好ましくは１μｍ～９μｍ、特に好ましくは１μｍ～７μｍとなるように塗布される。乾燥膜厚あるいは最終的に形成された隔壁の高さが、基板全域に渡って均一であることが重要である。ばらつきが小さくすることで、発光層を均一に作成でき、発光時の表示不良を抑制することができる。 The coating amount varies depending on the application, but in the case of a partition wall, for example, the dry film thickness is usually 0.5 μm to 10 μm, preferably 1 μm to 9 μm, and particularly preferably 1 μm to 7 μm. It is important that the dry film thickness or the height of the finally formed bulkhead is uniform over the entire substrate. By reducing the variation, the light emitting layer can be uniformly created, and display defects during light emission can be suppressed.
　本発明の感光性着色組成物を用いて、フォトリソグラフィー法により高さの異なる隔壁を一括形成する場合は、最終的に形成された隔壁の高さは異なるものとなる。 When the photosensitive coloring composition of the present invention is used to collectively form partition walls having different heights by a photolithography method, the heights of the finally formed partition walls are different.
　なお、基板としてはガラス基板、アレイ基板等、公知の基板を使用することができる。基板表面は平面であることが好適である。 As the substrate, a known substrate such as a glass substrate or an array substrate can be used. It is preferable that the surface of the substrate is flat.
［２］乾燥方法
　基板上に感光性着色組成物を供給した後の乾燥は、ホットプレート、ＩＲオーブン、コンベクションオーブンを使用した乾燥方法によるのが好ましい。温度を高めず、減圧チャンバー内で乾燥を行う、減圧乾燥法を組み合わせてもよい。 [2] Drying Method Drying after supplying the photosensitive coloring composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. A vacuum drying method may be combined in which drying is performed in a vacuum chamber without increasing the temperature.
　乾燥の条件は、溶剤成分の種類、使用する乾燥機の性能等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等に応じて、通常は、４０℃～１３０℃の温度で１５秒～５分間の範囲で選ばれ、好ましくは５０℃～１１０℃の温度で３０秒～３分間の範囲で選ばれる。 The drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 ° C. to 130 ° C., preferably 50 ° C. to 110 ° C., depending on the type of solvent component, the performance of the dryer used, and the like. The temperature is selected in the range of 30 seconds to 3 minutes.
［３］露光方法
　露光は、感光性着色組成物の塗布膜上に、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。露光マスクを用いて露光を行う場合には、露光マスクを感光性着色組成物の塗布膜に近接させる方法や、露光マスクを感光性着色組成物の塗布膜から離れた位置に配置し、露光マスクを介した露光光を投影する方法によってもよい。マスクパターンを用いないレーザー光による走査露光方式によってもよい。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、脱酸素雰囲気下で行ったり、光重合性層上にポリビニルアルコール層等の酸素遮断層を形成した後に露光を行ったりしてもよい。 [3] Exposure Method Exposure is performed by superimposing a negative mask pattern on a coating film of a photosensitive coloring composition and irradiating a light source of ultraviolet rays or visible light through the mask pattern. When exposure is performed using an exposure mask, the exposure mask may be placed close to the coating film of the photosensitive coloring composition, or the exposure mask may be placed away from the coating film of the photosensitive coloring composition. It may also be a method of projecting the exposure light through. A scanning exposure method using a laser beam that does not use a mask pattern may be used. If necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, it may be performed in a deoxidizing atmosphere, or it may be exposed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. May be good.
　本発明の好ましい態様として、フォトリソグラフィー法により高さの異なる隔壁を同時に形成する場合は、例えば、遮光部（光透過率０％）と、複数の開口部として、平均光透過率の最も高い開口部（完全透過開口部）に対して平均光透過率の小さい開口部（中間透過開口部）を有する露光マスクを用いる。この方法により、中間透過開口部と完全透過開口部の平均光透過率の差、即ち露光量の差により、残膜率の差異を生じさせる。
　中間透過開口部は、例えば、微小な多角形の遮光ユニットを有するマトリックス状遮光パターンによって作成する方法が知られている。また吸収体として、例えば、クロム系、モリブデン系、タングステン系、シリコン系材料の膜によって、光透過率を制御し作成する方法が知られている。 As a preferred embodiment of the present invention, when partition walls having different heights are simultaneously formed by a photolithography method, for example, a light-shielding portion (light transmittance 0%) and a plurality of openings having the highest average light transmittance. An exposure mask having an opening (intermediate transmittance opening) having a small average light transmittance with respect to the portion (completely transmitted opening) is used. By this method, the difference in the average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in the exposure amount causes a difference in the residual film ratio.
A method is known in which the intermediate transmission opening is created by, for example, a matrix-like light-shielding pattern having a minute polygonal light-shielding unit. Further, as an absorber, for example, a method of controlling the light transmittance by a film of a chromium-based, molybdenum-based, tungsten-based, or silicon-based material is known.
　上記の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、蛍光ランプ等のランプ光源や、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、青紫色半導体レーザー、近赤外半導体レーザー等のレーザー光源が挙げられる。特定の波長の光を照射して使用する場合には、光学フィルターを利用することもできる。 The light source used for the above exposure is not particularly limited. Examples of the light source include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, etc. Examples thereof include laser light sources such as an excima laser, a nitrogen laser, a helium cadmium laser, a blue-violet semiconductor laser, and a near-infrared semiconductor laser. An optical filter can also be used when irradiating light of a specific wavelength for use.
　光学フィルターとしては、例えば薄膜で露光波長における光透過率を制御可能なタイプでもよく、その場合の材質としては、例えば、Ｃｒ化合物（Ｃｒの酸化物、窒化物、酸窒化物、フッ化物等）、ＭｏＳｉ、Ｓｉ、Ｗ、Ａｌが挙げられる。 The optical filter may be, for example, a type that can control the light transmittance at the exposure wavelength with a thin film, and the material in that case is, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.). , MoSi, Si, W, Al.
　露光量としては、特に限定されないが、通常、１ｍＪ／ｃｍ２以上、好ましくは５ｍＪ／ｃｍ２以上、より好ましくは１０ｍＪ／ｃｍ２以上であり、通常３００ｍＪ／ｃｍ２以下、好ましくは２００ｍＪ／ｃｍ２以下、より好ましくは１５０ｍＪ／ｃｍ２以下である。
　近接露光方式の場合には、露光対象とマスクパターンとの距離としては、特に限定されないが、通常１０μｍ以上、好ましくは５０μｍ以上、より好ましくは７５μｍ以上であり、通常５００μｍ以下、好ましくは４００μｍ以下、より好ましくは３００μｍ以下である。 The exposure amount is not particularly limited, but is usually 1 mJ / cm 2 or more, preferably 5 mJ / cm 2 or more, more preferably 10 mJ / cm 2 or more, and usually 300 mJ / cm 2 or less, preferably 200 mJ / cm 2 . Below, it is more preferably 150 mJ / cm 2 or less.
In the case of the proximity exposure method, the distance between the exposure target and the mask pattern is not particularly limited, but is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less. It is more preferably 300 μm or less.
［４］現像方法
　上記の露光を行った後、アルカリ性化合物の水溶液、又は有機溶剤を用いる現像によって、基板上に画像パターンを形成することができる。アルカリ性化合物の水溶液は、さらに、例えば、界面活性剤、有機溶剤、緩衝剤、錯化剤、染料又は顔料が含まれていてもよい。 [4] Development method After the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution of the alkaline compound may further contain, for example, a surfactant, an organic solvent, a buffer, 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等の無機アルカリ性化合物、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）、コリン等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。 Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and 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, Organic alkaline compounds such as mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline. Can be mentioned. These alkaline compounds may be a mixture of two or more kinds.
　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等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等のアニオン性界面活性剤；アルキルベタイン類、アミノ酸類等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 alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; alkylbenzene sulfonic acids. Anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; and amphoteric surfactants such as alkyl betaines 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が挙げられる。これらの有機溶剤は、２種以上を併用してもよい。また、有機溶剤は、単独で使用してもよく、水やアルカリ性化合物の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, and diacetone alcohol. Two or more of these organic solvents may be used in combination. Further, the organic solvent may be used alone or in combination with water or an aqueous solution of an alkaline compound.
　現像処理の条件は特に制限はなく、通常、現像温度は１０～５０℃、好ましくは１５～４５℃、より好ましくは２０～４０℃である。現像方法は、例えば、浸漬現像法、スプレー現像法、ブラシ現像法、超音波現像法によることができる。 The conditions of the development treatment are not particularly limited, and the development temperature is usually 10 to 50 ° C, preferably 15 to 45 ° C, and more preferably 20 to 40 ° C. The developing method can be, for example, a dipping developing method, a spray developing method, a brush developing method, or an ultrasonic developing method.
［５］追露光及び熱硬化処理
　現像の後の基板には、必要により上記の露光方法と同様な方法により追露光を行ってもよい。現像後、又は追露光後、熱硬化処理（焼成ともいう）を行ってもよい。熱硬化処理条件は、温度が好ましくは１００℃～２８０℃、より好ましくは１５０℃～２５０℃であり、時間が５分間～６０分間である。 [5] Re-exposure and thermosetting treatment If necessary, the substrate after development may be re-exposed by the same method as the above-mentioned exposure method. After development or additional exposure, a thermosetting treatment (also referred to as firing) may be performed. The thermosetting treatment conditions are such that the temperature is preferably 100 ° C. to 280 ° C., more preferably 150 ° C. to 250 ° C., and the time is 5 minutes to 60 minutes.
　本発明の感光性着色組成物を隔壁として使用する場合の大きさや形状等は、これを適用する有機電界発光素子の仕様等によって適宜調整されるが、本発明の感光性着色組成物より形成される隔壁の高さは通常０．５～１０μｍ程度である。
　また、本発明の隔壁としての１μｍ当たりの光学濃度（ＯＤ）は、遮光性の観点から、０．７以上が好ましく、１．２以上がより好ましく、１．５以上がさらに好ましく、１．８以上が特に好ましい。また４．０以下であることが好ましく、３．０以下であることがより好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、０．７～４．０が好ましく、１．２～４．０がより好ましく、１．５～３．０がさらに好ましく、１．８～３．０が特に好ましい。ここで光学濃度（ＯＤ）は後述する方法にて測定した値である。 The size, shape, and the like when the photosensitive coloring composition of the present invention is used as a partition wall are appropriately adjusted according to the specifications of the organic electroluminescent element to which the photosensitive coloring composition is applied, but are formed from the photosensitive coloring composition of the present invention. The height of the partition wall is usually about 0.5 to 10 μm.
Further, the optical density (OD) per 1 μm as the partition wall of the present invention is preferably 0.7 or more, more preferably 1.2 or more, still more preferably 1.5 or more, and 1.8 or more, from the viewpoint of light-shielding property. The above is particularly preferable. Further, it is preferably 4.0 or less, and more preferably 3.0 or less. The above upper and lower limits can be combined arbitrarily. For example, 0.7 to 4.0 is preferable, 1.2 to 4.0 is more preferable, 1.5 to 3.0 is further preferable, and 1.8 to 3.0 is particularly preferable. Here, the optical density (OD) is a value measured by a method described later.
［有機電界発光素子］
　本発明の有機電界発光素子は、本発明の硬化物、例えば隔壁を備える。
　例えば、上述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、上述した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。 [Organic electroluminescent device]
The organic electroluminescent device of the present invention comprises a cured product of the present invention, for example, a partition wall.
For example, various organic electroluminescent devices are manufactured using a substrate having a partition wall pattern manufactured by the above method. The method for forming the organic electroluminescent device is not particularly limited, but preferably, after forming the pattern of the partition wall on the substrate by the above-mentioned method, the functional material is sublimated in a vacuum state and the region surrounded by the partition wall on the substrate. An organic electroluminescent device is manufactured by forming an organic layer such as a pixel by a wet process such as a vapor deposition method of adhering to the inside to form a film, a casting method, a spin coating method, or an inkjet printing method.
　有機電界発光素子のタイプとしては、ボトムエミッション型やトップエミッション型が挙げられる。
　ボトムエミッション型では、例えば、透明電極を積層したガラス基板上に隔壁を形成し、隔壁で囲まれた開口部に正孔輸送層、発光層、電子輸送層、金属電極層を積層して作成される。一方でトップエミッション型では、例えば、反射層として金属電極層を積層したガラス基板上に隔壁を形成し、隔壁で囲まれた開口部に電子輸送層、発光層、正孔輸送層、透明電極層を積層して作成される。
　なお、発光層としては、日本国特開２００９－１４６６９１号公報や日本国特許第５７３４６８１号公報に記載されているような有機電界発光層が挙げられる。また、日本国特許第５６５３３８７号公報や日本国特許第５６５３１０１号公報に記載されているような量子ドットを用いてもよい。 Examples of the type of the organic electroluminescent element include a bottom emission type and a top emission type.
In the bottom emission type, for example, a partition wall is formed on a glass substrate on which transparent electrodes are laminated, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the partition wall. To. On the other hand, in the top emission type, for example, a partition wall is formed on a glass substrate on which a metal electrode layer is laminated as a reflection layer, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are formed in an opening surrounded by the partition wall. Is created by stacking.
Examples of the light emitting layer include an organic electroluminescent layer as described in Japanese Patent Application Laid-Open No. 2009-146691 and Japanese Patent No. 5734681. Further, quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.
　層構成はこれに限定されず、例えば、正孔輸送層、電子輸送層の各層は発光効率の観点から二層以上からなる積層構成でもよい。各層の厚みは特に限定されないが、発光効率や輝度の観点から、通常１～５００ｎｍである。 The layer structure is not limited to this, and for example, each layer of the hole transport layer and the electron transport layer may have a laminated structure consisting of two or more layers from the viewpoint of luminous efficiency. The thickness of each layer is not particularly limited, but is usually 1 to 500 nm from the viewpoint of luminous efficiency and brightness.
　有機電界発光素子は、開口部ごとにＲＧＢ各色を分けて形成してもよく、１つの開口部に二色以上を積層してもよい。有機電界発光素子は信頼性向上の観点から、封止層を備えていてもよい。封止層は空気中の水分が有機電界発光素子に吸着し、発光効率を低下することを防ぐ機能を有する。有機電界発光素子は、光取り出し効率向上の観点から、空気との界面に低反射膜を備えていてもよい。低反射膜を空気と素子との界面に配置することで屈折率のギャップを小さくし、界面での反射を抑制することが期待できる。このような低反射膜には、例えば、モスアイ構造、超多層膜の技術が適用されうる。 The organic electroluminescent element may be formed by separating each RGB color for each opening, or two or more colors may be laminated in one opening. The organic electroluminescent device may be provided with a sealing layer from the viewpoint of improving reliability. The sealing layer has a function of preventing moisture in the air from adsorbing to the organic electroluminescent element and lowering the luminous efficiency. The organic electroluminescent device may be provided with a low reflection film at the interface with air from the viewpoint of improving the light extraction efficiency. By arranging the low-reflection film at the interface between the air and the element, it can be expected that the gap in the refractive index is reduced and the reflection at the interface is suppressed. For such a low-reflection film, for example, a technique of a moth-eye structure or a super-multilayer film can be applied.
　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有機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 the light of the light emitting layer of one pixel from leaking to another pixel, and further, when the electrode or the like is made of metal, it is outside. Since it is necessary to prevent deterioration of image quality due to light reflection, it is preferable to impart light-shielding property to the partition wall constituting the organic electroluminescent element.
Further, in the organic electroluminescent device, since it is necessary to provide electrodes on the upper surface and the lower surface of the partition wall, it is preferable that the partition wall has high resistance and low dielectric constant from the viewpoint of insulating property. Therefore, when a colorant is used to impart light-shielding properties to the partition wall, it is preferable to use the organic pigment having high resistance and low dielectric constant.
［画像表示装置］
　本発明の画像表示装置としては、本発明の硬化物を含む隔壁や本発明の有機電界発光素子を有する有機ＥＬ表示装置を挙げることができる。
　有機ＥＬ表示装置は、上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。 [Image display device]
Examples of the image display device of the present invention include an organic EL display device having a partition wall containing the cured product of the present invention and the organic electroluminescent element of the present invention.
The organic EL display device is not particularly limited in terms of the model and structure of the image display device as long as it includes the above-mentioned organic electroluminescent element. For example, the organic EL display device can be assembled according to a conventional method using an active drive type organic electroluminescent element. can. For example, it can be formed by the method described in "Organic EL Display" (Ohmsha, published on August 20, 2004, by Shizushi Tokito, Chihaya Adachi, Hideyuki Murata). For example, an organic electroluminescent element that emits white light and a color filter may be combined to display an image, or an organic electroluminescent element having a different emission color such as RGB may be combined to display an image.
［照明］
　本発明の硬化物を含む有機電界発光素子は、照明に用いられうる。照明の型式や構造について特に制限はなく、本発明の硬化物を含む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。
　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。 [illumination]
The organic electroluminescent device containing the cured product of the present invention can be used for lighting. There are no particular restrictions on the type and structure of the lighting, and it can be assembled according to a conventional method using the organic electroluminescent device containing the cured product of the present invention. The organic electroluminescent device may be a simple matrix drive system or an active matrix drive system.
In order for the illumination to emit white light, an organic electroluminescent device that emits white light may be used. Further, organic electroluminescent elements having different emission colors may be combined so that the colors are mixed to be white, or the color mixing ratio may be adjusted to provide a toning function.
　以下、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感光性着色組成物の構成成分、並びにそれらの評価方法は次の通りである。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.
The constituents of the photosensitive coloring composition used in the following Examples and Comparative Examples, and their evaluation methods are as follows.
＜アルカリ可溶性樹脂－Ｉ＞
　日本化薬社製「ＸＤ１０００」（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、エポキシ当量２５２）３００質量部、アクリル酸８７質量部、ｐ－メトキシフェノール０．２質量部、トリフェニルホスフィン５質量部、及びプロピレングリコールモノメチルエーテルアセテート２５５質量部を反応容器に仕込み、１００℃で酸価が３．０ｍｇＫＯＨ／ｇになるまで攪拌した。次いでさらにテトラヒドロ無水フタル酸１４５質量部を添加し、１２０℃で４時間反応させた。こうして得られたアルカリ可溶性樹脂－ＩのＧＰＣにより測定した重量平均分子量Ｍｗは２６００、酸価は１０６ｍｇＫＯＨ／ｇであった。 <Alkali-soluble resin-I>
300 parts by mass of "XD1000" (polyglycidyl ether of dicyclopentadiene-phenol polymer, epoxy equivalent 252) manufactured by Nippon Kayaku Co., Ltd., 87 parts by mass of acrylic acid, 0.2 parts by mass of p-methoxyphenol, 5 parts by mass of triphenylphosphine. A portion and 255 parts by mass of propylene glycol monomethyl ether acetate were charged in a reaction vessel, and the mixture was stirred at 100 ° C. until the acid value reached 3.0 mgKOH / g. Then, 145 parts by mass of tetrahydrophthalic anhydride was further added, and the mixture was reacted at 120 ° C. for 4 hours. The weight average molecular weight Mw of the alkali-soluble resin-I thus obtained measured by GPC was 2600, and the acid value was 106 mgKOH / g.
＜アルカリ可溶性樹脂－ＩＩ＞ <Alkali-soluble resin-II>
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
　上記構造のエポキシ化合物（エポキシ当量２４８）５０．０質量部、アクリル酸１４．２質量部、メトキシブチルアセテート５２．６質量部、トリフェニルホスフィン１．２９質量部、及びパラメトキシフェノール０．０４４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に、メトキシブチルアセテート４２．９質量部、トリメチロールプロパン（ＴＭＰ）１．９８質量部、ビフェニルテトラカルボン酸２無水物（ＢＰＤＡ）２４．９質量部、テトラヒドロフタル酸無水物（ＴＨＰＡ）５．３９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、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１００ｍｇＫＯＨ／ｇ、重量平均分子量（Ｍｗ）１２０００のアルカリ可溶性樹脂（ＩＩ）を得た。 50.0 parts by mass of an epoxy compound (epoxy equivalent 248) having the above structure, 14.2 parts by mass of acrylic acid, 52.6 parts by mass of methoxybutyl acetate, 1.29 parts by mass of triphenylphosphine, and 0.044 parts by mass of paramethoxyphenol. The parts were placed in a flask equipped with a thermometer, a stirrer and a cooling tube, and reacted at 90 ° C. at 90 ° C. until the acid value became 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
In the above epoxy acrylate solution, 42.9 parts by mass of methoxybutyl acetate, 1.98 parts by mass of trimethylolpropane (TMP), 24.9 parts by mass of biphenyltetracarboxylic acid anhydride (BPDA), and tetrahydrophthalic acid anhydride (THPA). ) 5.39 parts by mass was placed in 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 became transparent, it was diluted with methoxybutyl acetate to have a solid content of 50% by mass to obtain an alkali-soluble resin (II) having an acid value of 100 mgKOH / g and a weight average molecular weight (Mw) of 12000. ..
＜アルカリ可溶性樹脂－ＩＩＩ＞
　日本化薬社製「ＺＣＲ－８０３５Ｈ」（重量平均分子量Ｍｗ＝７０００、酸価＝８２ｍｇＫＯＨ／ｇ）。下記式（Ｃ―１）で表される部分構造を有する。 <Alkali-soluble resin-III>
"ZCR-8035H" manufactured by Nippon Kayaku Co., Ltd. (weight average molecular weight Mw = 7000, acid value = 82 mgKOH / g). It has a partial structure represented by the following formula (C-1).
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
＜顔料－Ｉ＞
　ＢＡＳＦ社製、Ｉｒｇａｐｈｏｒ（登録商標）　Ｂｌａｃｋ　Ｓ　０１００　ＣＦ（下記式（２）で表される化学構造を有する） <Pigment-I>
Made by BASF, Irgaphor (registered trademark) Black S 0100 CF (having a chemical structure represented by the following formula (2))
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
＜顔料－ＩＩ＞
　Ｃ．Ｉ．　ピグメントオレンジ６４
＜顔料－ＩＩＩ＞
　Ｃ．Ｉ．　ピグメントバイオレット２９
＜顔料－ＩＶ＞
　Ｃ．Ｉ．ピグメントブルー６０ <Pigment-II>
C. I. Pigment Orange 64
<Pigment-III>
C. I. Pigment Violet 29
<Pigment-IV>
C. I. Pigment Blue 60
＜分散剤－Ｉ＞
　親溶媒基を有する繰り返し単位を含むＡブロックと、顔料吸着基を有する繰り返し単位を含むＢブロックからなるメタクリル系Ａ－Ｂジブロック共重合体。下記式（ａ）～（ｆ）の繰り返し単位を有する。アミン価は１２０ｍｇＫＯＨ／ｇである。重量平均分子量は９０００である。分散剤中には塩素原子を実質的に含有していない。 <Dispersant-I>
A methacrylic AB diblock copolymer comprising an A block containing a repeating unit having a parent solvent group and a B block containing a repeating unit having a pigment adsorbing group. It has a repeating unit of the following formulas (a) to (f). The amine value is 120 mgKOH / g. The weight average molecular weight is 9000. The dispersant contains substantially no chlorine atom.
　全繰り返し単位中における、下記式（ａ）～（ｆ）の繰り返し単位の含有割合はそれぞれ（ａ）３３．３モル％、（ｂ）１３．３モル％、（ｃ）６．７モル％、（ｄ）６．７モル％、（ｅ）６．７モル％、（ｆ）３３．３モル％である。 The content ratios of the repeating units of the following formulas (a) to (f) in all the repeating units are (a) 33.3 mol%, (b) 13.3 mol%, and (c) 6.7 mol%, respectively. (D) is 6.7 mol%, (e) is 6.7 mol%, and (f) is 33.3 mol%.
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
＜分散剤－ＩＩ＞
　親溶媒基を有する繰り返し単位を含むＡブロックと、顔料吸着基を有する繰り返し単位を含むＢブロックからなるメタクリル系Ａ－Ｂジブロック共重合体。下記式（ｈ）～（ｎ）の繰り返し単位を有する。アミン価は７０ｍｇＫＯＨ／ｇである。アミノ基を４級化する前の重量平均分子量は、９０００である。分散剤中の塩素原子の含有量は２．１質量％である。 <Dispersant-II>
A methacrylic AB diblock copolymer comprising an A block containing a repeating unit having a parent solvent group and a B block containing a repeating unit having a pigment adsorbing group. It has a repeating unit of the following formulas (h) to (n). The amine value is 70 mgKOH / g. The weight average molecular weight before quaternizing the amino group is 9000. The content of chlorine atoms in the dispersant is 2.1% by mass.
　全繰り返し単位中における、下記式（ｈ）～（ｎ）の繰り返し単位の含有割合はそれぞれ（ｈ）３３．３モル％、（ｉ）１３．３モル％、（ｊ）６．７モル％、（ｋ）６．７モル％、（ｌ）６．７モル％、（ｍ）２４．０モル％、（ｎ）９．３モル％である。 The content ratios of the repeating units of the following formulas (h) to (n) in all the repeating units are (h) 33.3 mol%, (i) 13.3 mol%, (j) 6.7 mol%, respectively. (K) is 6.7 mol%, (l) is 6.7 mol%, (m) is 24.0 mol%, and (n) is 9.3 mol%.
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
＜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 <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＞
　以下の化学構造を有するオキシムエステル系光重合開始剤 <Photopolymerization Initiator-I>
Oxime ester-based photopolymerization initiator having the following chemical structure
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
＜エチレン性不飽和化合物＞
　ＤＰＨＡ－４０Ｈ：日本化薬社製　ウレタンアクリレート
＜界面活性剤＞
　ＤＩＣ社製　メガファック　Ｆ－５５９ <Ethylene unsaturated compound>
DPHA-40H: Urethane acrylate manufactured by Nippon Kayaku Co., Ltd. <surfactant>
DIC Megafuck F-559
＜粘度の評価＞
　調製した顔料分散液の粘度は、東機産業社製　ＲＥ－８５Ｌ型粘度計（測定条件：２３℃、２０ｒｐｍ）により測定した。 <Evaluation of viscosity>
The viscosity of the prepared pigment dispersion was measured with a RE-85L type viscometer manufactured by Toki Sangyo Co., Ltd. (measurement conditions: 23 ° C., 20 rpm).
＜塩素原子含有量の測定＞
　燃焼イオンクロマトグラフ法（Ｃｏｍｂｕｓｔｉｏｎ　ｉｏｎ　ｃｈｒｏｍａｔｏｇｒａｐｈｙ）にて測定を行った。三菱ケミカルアナリテック社（現　日東精工アナリテック社）の燃焼吸収イオンクロマトグラフ（ＣＩＣ）装置ＡＱＦ２１００Ｈにて、検量線法で、感光性着色組成物中の塩素原子含有量を定量した。 <Measurement of chlorine atom content>
The measurement was carried out by a combustion ion chromatograph method (Combustion ion chromatography). The chlorine atom content in the photosensitive coloring composition was quantified by the calibration curve method using the combustion absorption ion chromatograph (CIC) device AQF2100H of Mitsubishi Chemical Analytech Co., Ltd. (currently Nittoseiko Analytech Co., Ltd.).
＜単位膜厚当たりの光学濃度（単位ＯＤ値）の測定＞
　単位膜厚当たりの光学濃度は以下の手順にて測定した。
　まず、調製した感光性着色組成物を、焼成後の膜厚が１．５μｍとなるようにスピンコーターにてガラス基板に塗布し、１分間減圧乾燥した後に、ホットプレートにて１００℃で１２０秒間乾燥した。得られた塗布膜に対し、露光マスクを用いず、露光を行った。照射光源としては波長３６５ｎｍでの強度が４０ｍＷ／ｃｍ２である高圧水銀灯を用い、露光量は５０ｍＪ／ｃｍ２とした。続いてオーブン２３０℃で３０分間加熱硬化する事で、レジスト塗工基板１を得た。
　得られたレジスト塗工基板１の光学濃度（ＯＤ値）をＸ－Ｒｉｔｅ社製３６１Ｔ（Ｖ）透過濃度計（照明光源の色温度：約２８５０Ｋ（ＣＩＥ標準光源Ａ相当）、受光部の分光感度特性：ＩＳＯ　５－３規格でのＩＳＯ　ｖｉｓｕａｌ　ｄｅｎｓｉｔｙ）を用いて測定し、膜厚を菱化システム社製非接触表面・層断面形状計測システム　ＶｅｒｔＳｃａｎ（Ｒ）２．０により測定し、光学濃度（ＯＤ値）及び膜厚から、単位膜厚（１μｍ）当たりの光学濃度（単位ＯＤ値）を算出した。なお、ＯＤ値は遮光能力を示す数値であり、数値が大きいほど高遮光性であることを示す。 <Measurement of optical density (unit OD value) per unit film thickness>
The optical density per unit film thickness was measured by the following procedure.
First, the prepared photosensitive coloring composition is applied to a glass substrate with a spin coater so that the film thickness after firing is 1.5 μm, dried under reduced pressure for 1 minute, and then dried on a hot plate at 100 ° C. for 120 seconds. It was dry. The obtained coating film was exposed without using an exposure mask. As the irradiation light source, a high-pressure mercury lamp having an intensity of 40 mW / cm 2 at a wavelength of 365 nm was used, and the exposure amount was 50 mJ / cm 2 . Subsequently, the resist-coated substrate 1 was obtained by heating and curing at 230 ° C. for 30 minutes.
The optical density (OD value) of the obtained resist coated substrate 1 is measured by a 361T (V) transmission densitometer manufactured by X-Rite (color temperature of an illumination light source: about 2850K (equivalent to CIE standard light source A), spectral sensitivity of a light receiving portion). Characteristics: Measured using ISO visual density in ISO 5-3 standard), and the film thickness was measured by VertScan (R) 2.0, a non-contact surface / layer cross-sectional shape measurement system manufactured by Ryoka System Co., Ltd., and the optical density ( The optical density (unit OD value) per unit film thickness (1 μm) was calculated from the OD value) and the film thickness. The OD value is a numerical value indicating the light-shielding ability, and the larger the value is, the higher the light-shielding property is.
＜電極表面荒れ評価＞
　ガラス基板上の全面に膜厚６０ｎｍの銀の薄膜が蒸着された電極基板の上に、各感光性着色組成物を、焼成後の膜厚が１．５μｍとなるようにスピンコーターで塗布し、１分間減圧乾燥した後に、ホットプレートにて１００℃で１２０秒間乾燥した。次に、得られた塗膜基板に一辺が５０μｍの正方形の開口パターンが形成可能なフォトマスクを用いて、高圧水銀灯にて３３０ｎｍ以下の波長をカットして、露光ギャップ５μｍにて５０ｍＪ／ｃｍ２の紫外線露光を行った。この時の波長３６５ｎｍにおける光強度は４０ｍＷ／ｃｍ２であった。続いて、２．３８質量％のＴＭＡＨ（水酸化テトラメチルアンモニウム）水溶液を現像液として、２５℃において現像液水圧０．０５ＭＰａのシャワー現像を６０秒間施した後、純水で現像液を流して現像を停止し、水洗スプレーにて６０秒間洗浄した。
　これらの操作により開口部分を現像除去し、隔壁がパターニングされた電極基板を得た。当該パターンの形成された基板をオーブン中、２３０℃で３０分間加熱（焼成）してパターンを硬化させた。
　得られた５０μｍ開口パターンが形成された電極基板を光学顕微鏡にて２００倍で観察し、開口パターン内に電極表面の形状変化（表面荒れ）の有無を確認した。Ａ，Ｂ、Ｃの順に表面荒れが良好であり、Ａが最も良好であることを表す。
　Ａ：加熱硬化後に、電極表面の表面荒れが発生していない。
　Ｂ：加熱硬化後に、電極表面の若干表面荒れが発生しているが、実用上問題がなく、許容できる。
　Ｃ：加熱硬化後に、電極表面に凹凸が見え、表面荒れが発生しており、実用上問題があり、許容しがたい。 <Evaluation of electrode surface roughness>
Each photosensitive coloring composition was applied to an electrode substrate on which a silver thin film having a thickness of 60 nm was vapor-deposited on the entire surface of the glass substrate with a spin coater so that the thickness after firing was 1.5 μm. After drying under reduced pressure for 1 minute, it was dried on a hot plate at 100 ° C. for 120 seconds. Next, using a photomask capable of forming a square aperture pattern with a side of 50 μm on the obtained coating film substrate, a wavelength of 330 nm or less was cut with a high-pressure mercury lamp, and an exposure gap of 5 μm was 50 mJ / cm 2 . UV exposure was performed. At this time, the light intensity at a wavelength of 365 nm was 40 mW / cm 2 . Subsequently, using a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution as a developing solution, shower development at 25 ° C. and a developer water pressure of 0.05 MPa was performed for 60 seconds, and then the developing solution was poured with pure water. Development was stopped and washed with a washing spray for 60 seconds.
By these operations, the opening portion was developed and removed to obtain an electrode substrate having a patterned partition wall. The substrate on which the pattern was formed was heated (baked) at 230 ° C. for 30 minutes in an oven to cure the pattern.
The obtained electrode substrate on which the 50 μm aperture pattern was formed was observed with an optical microscope at a magnification of 200, and the presence or absence of a shape change (surface roughness) of the electrode surface in the aperture pattern was confirmed. The surface roughness is good in the order of A, B, and C, indicating that A is the best.
A: After heat curing, the surface of the electrode surface is not roughened.
B: After heat curing, the surface of the electrode is slightly roughened, but there is no problem in practical use and it is acceptable.
C: After heat curing, unevenness is visible on the electrode surface and surface roughness is generated, which is practically problematic and unacceptable.
＜発光特性評価＞
　ガラス上にインジウム・スズ酸化物（ＩＴＯ）透明導電膜を７０ｎｍの厚さに堆積したものを通常のフォトリソグラフィー技術と塩酸エッチングを用いて陽極を形成した基板の上に、各感光性着色組成物を、焼成後の膜厚が１．５μｍとなるようにスピンコーターで塗布し、１分間減圧乾燥した後に、ホットプレートにて１００℃で１２０秒間乾燥した。次に、得られた塗膜基板に、露光マスク（長方形状の被覆部（縦４０μｍ×横８０μｍ）を、縦６０μｍ、横１００μｍのピッチで複数有するもの）を用い、３３０ｎｍ以下の波長をカットした高圧水銀灯にて、露光ギャップ５μｍにて５０ｍＪ／ｃｍ２の紫外線露光を行った。この時の波長３６５ｎｍにおける光強度は４０ｍＷ／ｃｍ２であった。続いて、２．３８質量％のＴＭＡＨ（水酸化テトラメチルアンモニウム）水溶液を現像液として、２５℃において現像液水圧０．０５ＭＰａのシャワー現像を６０～１２０秒間施した後、純水で現像液を流して現像を停止し、水洗スプレーにて６０秒間洗浄した。シャワー現像時間は塗膜の未露光部が溶解除去される時間の１．２倍以上とした。
　これらの操作により開口部分を現像除去し、隔壁がパターニングされた電極基板を得た。当該パターンの形成された基板をオーブン中、２３０℃で３０分間加熱（焼成）してパターンを硬化させた。 <Evaluation of light emission characteristics>
Each photosensitive coloring composition is obtained by depositing an indium tin oxide (ITO) transparent conductive film to a thickness of 70 nm on glass and forming an anode on a substrate using ordinary photolithography technology and hydrochloric acid etching. Was applied with a spin coater so that the film thickness after firing was 1.5 μm, dried under reduced pressure for 1 minute, and then dried at 100 ° C. for 120 seconds on a hot plate. Next, a wavelength of 330 nm or less was cut by using an exposure mask (a rectangular covering portion (length 40 μm × width 80 μm) having a plurality of pieces at a pitch of 60 μm in length and 100 μm in width) on the obtained coating film substrate. Ultraviolet exposure of 50 mJ / cm 2 was performed with a high-pressure mercury lamp with an exposure gap of 5 μm. At this time, the light intensity at a wavelength of 365 nm was 40 mW / cm 2 . Subsequently, using a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution as a developing solution, shower development at 25 ° C. and a developer water pressure of 0.05 MPa was performed for 60 to 120 seconds, and then the developing solution was prepared with pure water. The development was stopped by flushing, and the mixture was washed with a washing spray for 60 seconds. The shower development time was set to 1.2 times or more the time for dissolving and removing the unexposed portion of the coating film.
By these operations, the opening portion was developed and removed to obtain an electrode substrate having a patterned partition wall. The substrate on which the pattern was formed was heated (baked) at 230 ° C. for 30 minutes in an oven to cure the pattern.
＜有機電界発光素子の作製＞
　作製した隔壁がパターニングされた電極基板上全面に、正孔注入層として酸化モリブデンを膜厚１０ｎｍ、正孔輸送層としてＮ－（［１，１’－ビフェニル］－４－イル）－９，９－ジメチル－Ｎ－［４－（９－フェニル－９Ｈ－カルバゾール－３－イル）フェニル］－９Ｈ－フルオレン－２－アミンを膜厚６０ｎｍ、発光層としてトリス（８－ヒドロキシキノリナート）アルミニウムを膜厚６０ｎｍ、電子注入層として８－ヒドロキシキノリノラト－リチウムを膜厚１ｎｍ、陰極としてアルミニウムを膜厚８０ｎｍとなるように真空蒸着法によって順に積層して有機電界発光素子を作製した。
　次に、中央に凹部を有する封止ガラスの該凹部に乾燥剤を貼り付けて、凹部の周囲の枠部分にＵＶ硬化樹脂を塗布した。封止ガラスの凹部が前記電極基板上の有機電界発光素子をすべて覆うように配置し、封止ガラスを前記電極基板に貼り付け、ＵＶ硬化樹脂にＵＶを照射し硬化させ、中空構造の封止をすることで有機電界発光素子評価用デバイスを作製した。 <Manufacturing of organic electroluminescent device>
On the entire surface of the electrode substrate on which the prepared partition wall was patterned, molybdenum oxide was applied as a hole injection layer with a thickness of 10 nm, and N- ([1,1'-biphenyl] -4-yl) -9,9 as a hole transport layer. -Dimethyl-N- [4- (9-phenyl-9H-carbazole-3-yl) phenyl] -9H-fluoren-2-amine with a film thickness of 60 nm, and tris (8-hydroxyquinolinate) aluminum as a light emitting layer. An organic electroluminescent element was prepared by sequentially laminating 8-hydroxyquinolinolato-lithium as an electron injection layer having a film thickness of 60 nm and aluminum as a cathode having a film thickness of 80 nm by a vacuum vapor deposition method.
Next, a desiccant was attached to the recess of the sealing glass having a recess in the center, and the UV curable resin was applied to the frame portion around the recess. The concave portion of the sealing glass is arranged so as to cover all the organic electroluminescent elements on the electrode substrate, the sealing glass is attached to the electrode substrate, the UV curable resin is irradiated with UV and cured, and the hollow structure is sealed. A device for evaluating an organic electroluminescent element was manufactured.
＜有機電界発光素子の発光特性評価＞
　作製した素子に電流密度１０ｍＡ／ｃｍ２の直流電流を通電した際の電圧値（駆動電圧）を測定した。
　セル作成時に、電流密度で１０ｍＡ／ｃｍ２通電した際の電圧値（駆動電圧）
　　Ａ：電圧　６．５Ｖ以下
　　Ｂ：電圧　６．５Ｖより高い
　次いで、作成した素子を６０℃環境下において電流密度５０ｍＡ／ｃｍ２の直流電流を定電流駆動させた際に、初期輝度から９０％の値となるまでの時間（ｈ）を駆動寿命として測定した。
　初期の輝度に対して、９０％の輝度となるまでの時間（寿命）
　　Ａ：２５時間より長い
　　Ｂ：２５時間以下 <Evaluation of light emission characteristics of organic electroluminescent device>
The voltage value (driving voltage) when a DC current having a current density of 10 mA / cm 2 was applied to the manufactured element was measured.
Voltage value (drive voltage) when energized at a current density of 10 mA / cm 2 at the time of cell creation
A: Voltage 6.5V or less B: Voltage higher than 6.5V Next, when the created element is driven by a DC current with a current density of 50mA / cm 2 under a 60 ° C environment, the initial brightness is 90%. The time (h) until the value was reached was measured as the drive life.
Time (life) to reach 90% of the initial brightness
A: longer than 25 hours B: 25 hours or less
＜顔料分散液１～３の調製＞
　表１に記載の顔料、分散剤、アルカリ可溶性樹脂、及び溶剤を、表１に記載の質量比となるように混合した。この混合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１～３を調製した。
　なお、表１中の溶剤の量は、分散剤及びアルカリ可溶性樹脂由来の溶剤の量も含まれる。また、前述の方法にて測定した顔料分散液の粘度の評価結果を表１に示す。 <Preparation of pigment dispersions 1 to 3>
The pigments, dispersants, alkali-soluble resins, and solvents shown in Table 1 were mixed so as to have the mass ratios shown in Table 1. This mixed solution was dispersed with a paint shaker in the range of 25 to 45 ° C. for 3 hours. As the beads, 0.5 mmφ zirconia beads were used, and a mass 2.5 times that 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 3.
The amount of the solvent in Table 1 also includes the amount of the solvent derived from the dispersant and the alkali-soluble resin. Table 1 shows the evaluation results of the viscosity of the pigment dispersion liquid measured by the above method.
Figure JPOXMLDOC01-appb-T000062
Figure JPOXMLDOC01-appb-T000062
［実施例１、２、比較例１］
　全固形分量中に占める各成分の固形分の含有割合が表２に記載の値になるように各成分を加え、さらにＰＧＭＥＡ／ＭＢ／ＭＢＡ＝７２／２０／８、全固形分量の含有割合が１７質量％となるように溶剤を加え、攪拌、溶解させて、実施例１、２及び比較例１の感光性着色組成物を調製した。また、前述の方法にて測定した塩素原子含有量や、単位ＯＤ値、電極の表面荒れの評価結果を表２及び表３に示す。 [Examples 1 and 2, Comparative Example 1]
Add each component so that the solid content ratio of each component in the total solid content is as shown in Table 2, and further add PGMEA / MB / MBA = 72/20/8, and the content ratio of the total solid content is A solvent was added so as to be 17% by mass, and the mixture was stirred and dissolved to prepare the photosensitive coloring compositions of Examples 1 and 2 and Comparative Example 1. Tables 2 and 3 show the chlorine atom content measured by the above method, the unit OD value, and the evaluation results of the surface roughness of the electrode.
Figure JPOXMLDOC01-appb-T000063
Figure JPOXMLDOC01-appb-T000063
　比較例１の感光性着色組成物を用いた基板は銀（電極）表面に凹凸が形成され、荒れていることが確認された。これは分散剤－ＩＩ中に含まれる塩素原子量が多いため、感光性着色組成物中にも多く含有し、焼成時に塩素を含有するガスが発生し、銀（電極）表面と反応し、表面に凹凸を形成した、と考えられる。
　一方、実施例１の感光性着色組成物を用いた基板では、銀（電極）表面の凹凸が形成されている様子は観察されなかった。これは分散剤－Ｉ中には塩素原子量がなく、その結果、感光性着色組成物中の含有量も少なかったため、銀（電極）に表面荒れを生じることなく正常な電極基板が得られた、と考えられる。
　有機電界発光素子の発光特性において、実施例１は比較例１に比べて寿命が長くなっている。これは塩素量が少ないことにより、発光素子の経時劣化が抑制されたため、と考えられる。 It was confirmed that the substrate using the photosensitive coloring composition of Comparative Example 1 had irregularities on the silver (electrode) surface and was rough. Since the amount of chlorine atom contained in the dispersant-II is large, it is also contained in a large amount in the photosensitive coloring composition, and chlorine-containing gas is generated at the time of firing and reacts with the silver (electrode) surface to be on the surface. It is probable that unevenness was formed.
On the other hand, in the substrate using the photosensitive coloring composition of Example 1, it was not observed that the surface of silver (electrode) was uneven. This is because there was no chlorine atomic weight in the dispersant-I, and as a result, the content in the photosensitive coloring composition was also small, so that a normal electrode substrate was obtained without causing surface roughness on the silver (electrode). it is conceivable that.
In the light emitting characteristics of the organic electroluminescent device, Example 1 has a longer life than Comparative Example 1. It is considered that this is because the amount of chlorine is small and the deterioration of the light emitting element with time is suppressed.
Figure JPOXMLDOC01-appb-T000064
Figure JPOXMLDOC01-appb-T000064
　実施例２の感光性着色組成物を用いた基板でも、銀（電極）表面の凹凸は実質上問題のないレベルであった。実施例２よりも実施例１の方が、銀（電極）表面荒れが良好だったのは、顔料－Ｉが芳香環からなる剛直な骨格のため、微量の塩素原子さえも膜外に放出されなかったため、と考えられる。 Even in the substrate using the photosensitive coloring composition of Example 2, the unevenness of the silver (electrode) surface was at a level where there was virtually no problem. The reason why the silver (electrode) surface roughness was better in Example 1 than in Example 2 is that even a small amount of chlorine atoms are released to the outside of the film because the pigment-I has a rigid skeleton consisting of an aromatic ring. It is probable that it was not.
　有機電界発光素子の発光特性において、実施例２は初期駆動電圧が低くなり、良好であった。また実施例１よりも良好であった。 In the light emitting characteristics of the organic electroluminescent device, the initial drive voltage of Example 2 was low, which was good. It was also better than Example 1.

Claims (11)

  1. 　（ａ）着色剤、（ｂ）アルカリ可溶性樹脂、（ｃ）光重合開始剤、（ｄ）エチレン性不飽和化合物、（ｅ）溶剤、及び（ｆ）分散剤を含有する感光性着色組成物であって、
    　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より選ばれる少なくとも１種を含有し、
    　前記（ｆ）分散剤が、少なくとも下記一般式（１）、（２）及び（３）で表される繰り返し単位を含有し、４級アンモニウム基を含む繰り返し単位を有しないアクリル共重合体（ｆ１）を含有し、
    　かつ、感光性着色組成物中の塩素原子の含有量が、感光性着色組成物の全固形分量に対して０．０５質量％以下であることを特徴とする感光性着色組成物。
    Figure JPOXMLDOC01-appb-C000001
     　（式（Ｉ）中、Ｒ１及びＲ６は互いに独立して水素原子、ＣＨ３、ＣＦ３、フッ素原子又は塩素原子である；
    　Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ７、Ｒ８、Ｒ９及びＲ１０は他の全てから互いに独立して水素原子、ハロゲン原子、Ｒ１１、ＣＯＯＨ、ＣＯＯＲ１１、ＣＯＯ－、ＣＯＮＨ２、ＣＯＮＨＲ１１、ＣＯＮＲ１１Ｒ１２、ＣＮ、ＯＨ、ＯＲ１１、ＣＯＣＲ１１、ＯＯＣＮＨ２、ＯＯＣＮＨＲ１１、ＯＯＣＮＲ１１Ｒ１２、ＮＯ２、ＮＨ２、ＮＨＲ１１、ＮＲ１１Ｒ１２、ＮＨＣＯＲ１２、ＮＲ１１ＣＯＲ１２、Ｎ＝ＣＨ２、Ｎ＝ＣＨＲ１１、Ｎ＝ＣＲ１１Ｒ１２、ＳＨ、ＳＲ１１、ＳＯＲ１１、ＳＯ２Ｒ１１、ＳＯ３Ｒ１１、ＳＯ３Ｈ、ＳＯ３ －、ＳＯ２ＮＨ２、ＳＯ２ＮＨＲ１１又はＳＯ２ＮＲ１１Ｒ１２である；
    　Ｒ２とＲ３、Ｒ３とＲ４、Ｒ４とＲ５、Ｒ７とＲ８、Ｒ８とＲ９、及びＲ９とＲ１０からなる群から選ばれる少なくとも１つの組み合わせは、互いに直接結合し、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することもできる；
    　Ｒ１１及びＲ１２は互いに独立して、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のアルキニル基である。）
    Figure JPOXMLDOC01-appb-C000002
     　（式（１）中、Ｒ３１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る。
    　Ｒ３２は水素原子又はメチル基である。
    　＊は結合手を表す。）
    Figure JPOXMLDOC01-appb-C000003
     　（式（２）中、Ｒ３３はメチレン基、エチレン基又はプロピレン基であり、Ｒ３４は置換基を有していてもよいアルキル基であり、Ｒ３５は水素原子又はメチル基である。
    　ｎは１～２０の整数である。
    　＊は結合手を表す。）
    Figure JPOXMLDOC01-appb-C000004
     　（式（３）中、Ｒ３６及びＲ３７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、Ｒ３６及びＲ３７が互いに結合して環状構造を形成してもよい。
    　Ｒ３８は水素原子又はメチル基である。
    　Ｚは２価の連結基である。
    　＊は結合手を表す。）     A photosensitive coloring composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. There,
    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. Contains,
    The acrylic copolymer (f1) in which the dispersant (f) contains at least the repeating units represented by the following general formulas (1), (2) and (3) and does not have the repeating unit containing the quaternary ammonium group. ) Containing,
    Moreover, the photosensitive coloring composition is characterized in that the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less with respect to the total solid content of the photosensitive coloring composition.
    Figure JPOXMLDOC01-appb-C000001
     (In formula (I), R 1 and R 6 are independent hydrogen atoms, CH 3 , CF 3 , fluorine atoms or chlorine atoms;
    R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 and R 10 are independent of each other from hydrogen atom, halogen atom, R 11 , COOH, COOR 11 , COO- , CONH. 2 , CONHR 11 , CONR 11 R 12 , CN, OH, OR 11 , COCR 11 , OOCNH 2 , OOCNHR 11 , OOCNR 11 R 12 , NO 2 , NH 2 , NHR 11 , NR 11 R 12 , NHCOR 12 , NR 11 COR 12 , N = CH 2 , N = CHR 11 , N = CR 11 R 12 , SH, SR 11 , SOR 11 , SO 2 R 11 , SO 3 R 11 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR 11 or SO 2 NR 11 R 12 ;
    At least one combination selected from the group consisting of R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 7 and R 8 , R 8 and R 9 , and R 9 and R 10 is direct to each other. They can also be bonded or bonded to each other by oxygen, sulfur, NH or NR 11 bridges;
    R 11 and R 12 are independent of each other, 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 carbon. It is an alkynyl group of the number 2-12. )
    Figure JPOXMLDOC01-appb-C000002
     (In the formula (1), R 31 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 32 is a hydrogen atom or a methyl group.
    * Represents a bond. )
    Figure JPOXMLDOC01-appb-C000003
     (In the formula (2), R 33 is a methylene group, an ethylene group or a propylene group, R 34 is an alkyl group which may have a substituent, and R 35 is a hydrogen atom or a methyl group.
    n is an integer from 1 to 20.
    * Represents a bond. )
    Figure JPOXMLDOC01-appb-C000004
     (In the formula (3), R 36 and R 37 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. It is an aralkyl group which may be present, and R 36 and R 37 may be bonded to each other to form a cyclic structure.
    R 38 is a hydrogen atom or a methyl group.
    Z is a divalent linking group.
    * Represents a bond. )
  2. 　前記（ａ）着色剤が、有機着色顔料を含む、請求項１に記載の感光性着色組成物。 The photosensitive coloring composition according to claim 1, wherein the (a) colorant contains an organic coloring pigment.
  3. 　（ａ）着色剤、（ｂ）アルカリ可溶性樹脂、（ｃ）光重合開始剤、（ｄ）エチレン性不飽和化合物、（ｅ）溶剤、及び（ｆ）分散剤を含有する感光性着色組成物であって、
    　硬化した塗膜の膜厚１μｍあたりの光学濃度が０．５以上であり、
    　前記（ｆ）分散剤が、少なくとも下記一般式（１）、（２）及び（３）で表される繰り返し単位を含有し、４級アンモニウム基を含む繰り返し単位を有しないアクリル共重合体（ｆ１）を含有し、
    　かつ、感光性着色組成物中の塩素原子の含有量が、感光性着色組成物の全固形分量に対して０．０５質量％以下であることを特徴とする感光性着色組成物。
    Figure JPOXMLDOC01-appb-C000005
     　（式（１）中、Ｒ３１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る。
    　Ｒ３２は水素原子又はメチル基である。
    　＊は結合手を表す。）
    Figure JPOXMLDOC01-appb-C000006
     　（式（２）中、Ｒ３３はメチレン基、エチレン基又はプロピレン基であり、Ｒ３４は置換基を有していてもよいアルキル基であり、Ｒ３５は水素原子又はメチル基である。
    　ｎは１～２０の整数である。
    　＊は結合手を表す。）
    Figure JPOXMLDOC01-appb-C000007
     　（式（３）中、Ｒ３６及びＲ３７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、Ｒ３６及びＲ３７が互いに結合して環状構造を形成してもよい。
    　Ｒ３８は水素原子又はメチル基である。
    　Ｚは２価の連結基である。
    　＊は結合手を表す。）     A photosensitive coloring composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. There,
    The optical density per 1 μm film thickness of the cured coating film is 0.5 or more.
    The acrylic copolymer (f1) in which the dispersant (f) contains at least the repeating units represented by the following general formulas (1), (2) and (3) and does not have the repeating unit containing the quaternary ammonium group. ) Containing,
    Moreover, the photosensitive coloring composition is characterized in that the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less with respect to the total solid content of the photosensitive coloring composition.
    Figure JPOXMLDOC01-appb-C000005
     (In the formula (1), R 31 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 32 is a hydrogen atom or a methyl group.
    * Represents a bond. )
    Figure JPOXMLDOC01-appb-C000006
     (In the formula (2), R 33 is a methylene group, an ethylene group or a propylene group, R 34 is an alkyl group which may have a substituent, and R 35 is a hydrogen atom or a methyl group.
    n is an integer from 1 to 20.
    * Represents a bond. )
    Figure JPOXMLDOC01-appb-C000007
     (In the formula (3), R 36 and R 37 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. It is an aralkyl group which may be present, and R 36 and R 37 may be bonded to each other to form a cyclic structure.
    R 38 is a hydrogen atom or a methyl group.
    Z is a divalent linking group.
    * Represents a bond. )
  4. 　前記（ａ）着色剤が、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種を含む、請求項３に記載の感光性着色組成物。 The photosensitive coloring according to claim 3, wherein the (a) colorant comprises 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. Composition.
  5. 　前記アクリル共重合体（ｆ１）がブロック共重合体である、請求項１～４のいずれか１項に記載の感光性着色組成物。 The photosensitive coloring composition according to any one of claims 1 to 4, wherein the acrylic copolymer (f1) is a block copolymer.
  6. 　前記アクリル共重合体（ｆ１）のアミン価が、９０ｍｇＫＯＨ／ｇ以上である、請求項１～５のいずれか１項に記載の感光性着色組成物。 The photosensitive coloring composition according to any one of claims 1 to 5, wherein the acrylic copolymer (f1) has an amine value of 90 mgKOH / g or more.
  7. 　前記（ａ）着色剤が、感光性着色組成物の全固形分量に対して１０質量％以上含む、請求項１～６のいずれか１項に記載の感光性着色組成物。 The photosensitive coloring composition according to any one of claims 1 to 6, wherein the (a) colorant contains 10% by mass or more with respect to the total solid content of the photosensitive coloring composition.
  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項に記載の感光性着色組成物。 The photosensitive coloring composition according to any one of claims 1 to 7, which is used for forming a partition wall of an organic electroluminescent device.
  9. 　請求項１～８のいずれか１項に記載の感光性着色組成物を硬化させた硬化物。 A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 8.
  10. 　請求項９に記載の硬化物を含む有機電界発光素子。 An organic electroluminescent device containing the cured product according to claim 9.
  11. 　請求項１０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 including the organic electroluminescent element according to claim 10.
PCT/JP2021/035403 2020-09-28 2021-09-27 Photosensitive coloring composition, cured product, organic electroluminescent element, and image display device WO2022065490A1 (en)

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JP2019133167A (en) * 2013-09-25 2019-08-08 三菱ケミカル株式会社 Photosensitive coloring composition, coloring spacer, and image display device
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JP2019002005A (en) * 2017-06-14 2019-01-10 山陽色素株式会社 Pigment dispersion and coloring composition containing the same
WO2020059382A1 (en) * 2018-09-21 2020-03-26 富士フイルム株式会社 Light-shielding film, method for manufacturing light-shielding film, optical element, solid-state imaging element, and headlight unit
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