WO2022065490A1 - 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 - Google Patents

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 Download PDF

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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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preferable
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coloring composition
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English (en)
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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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to CN202180064110.2A priority Critical patent/CN116323716B/zh
Priority to JP2022552105A priority patent/JPWO2022065490A1/ja
Priority to KR1020267000259A priority patent/KR20260010762A/ko
Priority to KR1020237009602A priority patent/KR102912774B1/ko
Priority to CN202511024194.3A priority patent/CN120928648A/zh
Publication of WO2022065490A1 publication Critical patent/WO2022065490A1/ja
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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
    • G03F7/09—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 [2D] 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 [2D] radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional [2D] 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
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
    • 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
    • H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
    • 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
    • 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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WO2024171841A1 (ja) * 2023-02-16 2024-08-22 富士フイルム株式会社 着色組成物、膜、光学フィルタ、固体撮像素子、画像表示装置および化合物

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019002005A (ja) * 2017-06-14 2019-01-10 山陽色素株式会社 顔料分散体及びそれを含む着色組成物
JP2019133167A (ja) * 2013-09-25 2019-08-08 三菱ケミカル株式会社 感光性着色組成物、着色スペーサー及び画像表示装置
WO2020059382A1 (ja) * 2018-09-21 2020-03-26 富士フイルム株式会社 遮光膜、遮光膜の製造方法、光学素子、固体撮像素子、ヘッドライトユニット
WO2020066420A1 (ja) * 2018-09-25 2020-04-02 富士フイルム株式会社 遮光性組成物、硬化膜、遮光膜、固体撮像素子
WO2021149595A1 (ja) * 2020-01-20 2021-07-29 富士フイルム株式会社 着色樹脂組成物、膜、カラーフィルタ、固体撮像素子、及び、画像表示装置

Family Cites Families (4)

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JP2016148767A (ja) 2015-02-12 2016-08-18 日立化成株式会社 感光性樹脂組成物、フィルム状接着剤、接着シート、接着剤パターン、接着剤層付半導体ウェハ、及び半導体装置
JP6698820B2 (ja) 2016-03-31 2020-05-27 富士フイルム株式会社 組成物、硬化膜、カラーフィルタ、遮光膜、固体撮像素子および画像表示装置
KR20190062374A (ko) 2016-10-14 2019-06-05 미쯔비시 케미컬 주식회사 감광성 착색 조성물, 경화물, 착색 스페이서, 화상 표시 장치
CN118151488A (zh) 2016-12-02 2024-06-07 三菱化学株式会社 着色感光性树脂组合物、颜料分散液、间隔壁、有机场致发光元件、图像显示装置及照明

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019133167A (ja) * 2013-09-25 2019-08-08 三菱ケミカル株式会社 感光性着色組成物、着色スペーサー及び画像表示装置
JP2019002005A (ja) * 2017-06-14 2019-01-10 山陽色素株式会社 顔料分散体及びそれを含む着色組成物
WO2020059382A1 (ja) * 2018-09-21 2020-03-26 富士フイルム株式会社 遮光膜、遮光膜の製造方法、光学素子、固体撮像素子、ヘッドライトユニット
WO2020066420A1 (ja) * 2018-09-25 2020-04-02 富士フイルム株式会社 遮光性組成物、硬化膜、遮光膜、固体撮像素子
WO2021149595A1 (ja) * 2020-01-20 2021-07-29 富士フイルム株式会社 着色樹脂組成物、膜、カラーフィルタ、固体撮像素子、及び、画像表示装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024171841A1 (ja) * 2023-02-16 2024-08-22 富士フイルム株式会社 着色組成物、膜、光学フィルタ、固体撮像素子、画像表示装置および化合物

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