[go: up one dir, main page]

CN117916664A - Photosensitive composition, cured product, and organic EL display device - Google Patents

Photosensitive composition, cured product, and organic EL display device Download PDF

Info

Publication number
CN117916664A
CN117916664A CN202280058174.6A CN202280058174A CN117916664A CN 117916664 A CN117916664 A CN 117916664A CN 202280058174 A CN202280058174 A CN 202280058174A CN 117916664 A CN117916664 A CN 117916664A
Authority
CN
China
Prior art keywords
component
carbon atoms
photosensitive composition
group
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202280058174.6A
Other languages
Chinese (zh)
Inventor
相原凉介
山本洋平
宫内拓也
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Publication of CN117916664A publication Critical patent/CN117916664A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • 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
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/124—Insulating layers formed between TFT elements and OLED elements

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Theoretical Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)

Abstract

The purpose of the present invention is to provide a photosensitive composition which has high light-shielding properties and sensitivity, is reduced in residues at the edge of a pattern, can form a pattern having excellent linearity in conformity with the mask size, and has few non-light-emitting pixels when the cured product is used in an organic EL display device. In order to achieve the above object, the photosensitive composition of the present invention is a photosensitive composition containing all of the following components (a) to (d), wherein the double bond equivalent of the solid content in the photosensitive composition is 1000 to 3500g/mol. Component (a): a black pigment; component (b): an alkali-soluble resin; component (c): a radical polymerizable compound; and (d) component (c): a photopolymerization initiator.

Description

Photosensitive composition, cured product, and organic EL display device
Technical Field
The invention relates to a photosensitive composition, a cured product and an organic EL display device.
Background
In recent years, many products using an organic electroluminescence (hereinafter referred to as "EL") display device have been developed in thin display devices such as smartphones, tablet PCs, and televisions.
In general, an organic EL display device has a transparent electrode such as indium tin oxide (hereinafter referred to as "ITO") on the light extraction side of a light emitting element, and a metal electrode such as an alloy of magnesium and silver on the non-light extraction side of the light emitting element. In order to divide the pixels of the light-emitting element, an insulating layer such as a pixel dividing layer is formed between the transparent electrode and the metal electrode.
In recent years, the following attempts have been made: by imparting light shielding properties to the pixel dividing layer, external light reflection such as sunlight is reduced, and visibility and contrast of the organic EL display device are improved. As a specific example thereof, a negative-type black photosensitive resin composition using a black pigment is disclosed (for example, see patent documents 1 and 2).
Prior art literature
Patent literature
Patent document 1: international publication No. 2018/061525
Patent document 2: international publication No. 2018/101314
Disclosure of Invention
Problems to be solved by the invention
However, when patterning the photosensitive compositions described in patent documents 1 and 2 with an alkaline developer having a high concentration, the exposed portion needs to be excessively photo-cured in order to improve the resistance of the exposed portion to the alkaline developer. As a result, the following problems exist: generating residues at the edge portions of the pattern; or the straightness of the pattern deteriorates. In addition, especially in the processing of a hole pattern of 10 μm or less, which is required for a high-definition display application, the absolute value of the difference between the formation width of the hole pattern and the mask design width (hereinafter, sometimes referred to as mask bias) becomes excessively large, and it is difficult to form a desired pattern.
In addition, in the negative photosensitive composition of patent document 2, since the alkali-soluble resin does not have an amine value, the particle size of the black pigment cannot be reduced, and when used in an organic EL display device using a cured product thereof, there is a problem that the electrode wiring is short-circuited from the coarse pigment and a specific pixel is not lighted.
Means for solving the problems
In order to solve the above problems, the present invention has the following configuration. That is to say,
(1) A photosensitive composition containing all of the following components (a) to (d), wherein the double bond equivalent of the solid component in the photosensitive composition is 1000 to 3500g/mol.
(A) The components are as follows: black pigment
(B) The components are as follows: alkali-soluble resin
(C) The components are as follows: radical polymerizable compound
(D) The components are as follows: photopolymerization initiator
(2) The photosensitive composition according to the above (1), wherein the component (c) comprises the following component (c-1).
(C-1) component: radical polymerizable compound having 2 ethylenically unsaturated bonds in the molecule and having double bond equivalent weight of 200 to 600g/mol
(3) The photosensitive composition according to the above (2), wherein the content of the component (c-1) is 60 to 100% by weight based on the component (c).
(4) The photosensitive composition according to any one of (1) to (3), wherein the component (b) contains the following component (b-1).
(B-1) component: alkali-soluble resin with amine value of 2.0-10.0 mgKOH/g
(5) The photosensitive composition according to the above (4), wherein the component (b-1) comprises a structural unit represented by the formula (1) and/or a structural unit represented by the formula (2), and a structural unit represented by the formula (3).
[ Chemical formula 1]
[ Chemical formula 2]
[ Chemical formula 3]
(In the formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents any one selected from an alkylene group having 1 to 4 carbon atoms, a 2-valent alkyleneoxy alkylene group having 2 to 4 carbon atoms, a 2-valent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a 2-valent aromatic hydrocarbon group having 6 to 10 carbon atoms, and R 3 and R 4 each independently represents any one selected from an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms.
In the formula (2), R 5 represents a hydrogen atom or a methyl group, R 6 represents any one selected from an alkylene group having 1 to 4 carbon atoms, a 2-valent alkyleneoxy alkylene group having 2 to 4 carbon atoms, a 2-valent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a 2-valent aromatic hydrocarbon group having 6 to 10 carbon atoms, and R 7、R8 and R 9 are each independently selected from any one selected from an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and X represents any one selected from a bromine atom, a chlorine atom, an iodine atom, a hydrogen sulfate, and a hydroxide.
In the formula (3), R 10 and R 11 each independently represent a hydrogen atom or a methyl group, and R 12 represents any one selected from an alkylene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms. )
(6) The photosensitive composition according to any one of (1) to (5), wherein the component (b) contains the following component (b-2).
(B-2) component: resin having no structural unit represented by formula (1) and structural unit represented by formula (2) and having a hydroxyl value of 60mgKOH/g or more
(7) The photosensitive composition according to the above (6), which contains the component (b-1) and the component (b-2), wherein the weight ratio W b-1/Wb-2 of the component (b-1) to the component (b-2) is 0.2 to 1.5.
(8) The photosensitive composition according to any one of (1) to (7), wherein the component (d) contains an oxime ester photopolymerization initiator having a fluorine atom in the molecule.
(9) The photosensitive composition according to any one of (1) to (8), wherein the component (a) contains at least 1 compound selected from the group consisting of a compound represented by the formula (4), a compound represented by the formula (5), and isomers thereof.
[ Chemical formula 4]
( In the formula (4) and the formula (5), R 13 and R 18 each independently represent a hydrogen atom, CH 3、CF3, or a fluorine atom. R 14、R15、R16、R17、R19、R20、R21 and R 22 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, a cycloalkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms 、COOH、COOR23、COO-、CONH2、CONHR23、CONR23R24、CN、OH、OR23、OCOR23、OCONH2、OCONHR23、OCONR23R24.R23, and R 24 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, a cycloalkenyl group having 1 to 12 carbon atoms, or an alkynyl group having 1 to 12 carbon atoms. )
(10) The photosensitive composition according to any one of (1) to (9), wherein a 50% cumulative diameter in a particle size distribution on a volume basis of a particle component in the photosensitive composition measured by a dynamic light scattering method is 20 to 60nm.
(11) The photosensitive composition according to any one of (1) to (10), further comprising the following component (e).
(E) The components are as follows: silica particles
(12) The photosensitive composition according to the above (11), wherein the average primary particle diameter of the component (e) is 10 to 30nm.
(13) The photosensitive composition according to the above (11) or (12), which contains the component (b-1), wherein the weight ratio W e/Wb-1 of the component (e) to the component (b-1) is 0.5 to 2.0.
(14) The photosensitive composition according to any one of (11) to (13), which contains the component (b-2), wherein the weight ratio W e/Wb-2 of the component (e) to the component (b-2) is 0.15 to 1.0.
(15) A cured product obtained by curing the photosensitive composition according to any one of (1) to (14) above.
(16) An organic EL display device comprising the cured product of (15) above.
ADVANTAGEOUS EFFECTS OF INVENTION
The photosensitive composition of the present invention has high light-shielding properties and sensitivity, and is capable of forming a pattern having excellent linearity in conformity with the mask size with little residue at the edge of the pattern, and a cured product thereof is provided with few non-light-emitting pixels when used in an organic EL display device.
Drawings
Fig. 1 is a schematic view of a process for manufacturing an organic EL display device according to an embodiment.
Detailed Description
The photosensitive composition of the present invention is a photosensitive composition containing all of the following components (a) to (d), and the double bond equivalent of the solid content in the photosensitive composition is 1000 to 3500g/mol.
(A) The components are as follows: black pigment
(B) The components are as follows: alkali-soluble resin
(C) The components are as follows: radical polymerizable compound
(D) The components are as follows: a photopolymerization initiator.
The photosensitive composition of the present invention contains (a) component: black pigment.
(A) The components are as follows: the BLACK color in the BLACK pigment is a number including "BLACK" in a color index universal number (Color Index Generic Number) (hereinafter, referred to as "c.i. number"). The case of the mixture or the case where no c.i. number is given means that the mixture is black when a cured product is produced. Black when cured is: in the transmission spectrum of a cured product of the composition containing the component (a), when the transmittance per 1.0 μm film thickness at a wavelength of 550nm is converted to a range of 0.1 to 1.5 μm so that the transmittance at a wavelength of 550nm becomes 10% based on the lambert-beer formula, the transmittance at a wavelength of 450 to 650nm in the converted transmission spectrum is 25% or less.
As the component (a), a black organic pigment and a black inorganic pigment can be used. Examples of the black organic pigment include perylene black, nigrosine, and benzofuranone pigments (described in japanese patent application publication No. 2012-515233). Examples of the black inorganic pigment include carbon black, titanium nitride, titanium oxynitride, titanium carbide, zirconium nitride, zirconium oxynitride, and black iron oxide.
By combining these black pigments, a photosensitive composition having desired optical characteristics can be obtained. From the viewpoints of light-blocking property per unit weight and insulation property, the component (a) preferably contains a benzofuranone pigment.
In the photosensitive composition of the present invention, the component (a) preferably contains at least 1 compound selected from the group consisting of a compound represented by the formula (4), a compound represented by the formula (5), and isomers thereof.
[ Chemical formula 5]
In the formula (4) and the formula (5), R 13 and R 18 each independently represent a hydrogen atom, CH 3、CF3, or a fluorine atom. R 14、R15、R16、R17、R19、R20、R21 and R 22 each independently represent a hydrogen atom, a halogen atom, 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, an alkynyl group 、COOH、COOR23、COO-、CONH2、CONHR23、CONR23R24、CN、OH、OR23、OCOR23、OCONH2、OCONHR23、OCONR23R24.R23 having 2 to 12 carbon atoms, and R 24 each independently represent 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 an alkynyl group having 2 to 12 carbon atoms. The compound represented by the formula (4), the compound represented by the formula (5), and isomers thereof are all benzofuranone pigments.
The content of the component (a) in the photosensitive composition is preferably 5% by weight or more, more preferably 10% by weight or more, based on 100% by weight of the solid content of the photosensitive composition, from the viewpoint of light-shielding property per unit film thickness. On the other hand, from the viewpoint of improvement of sensitivity at the time of exposure and fine line workability, the content of the component (a) is preferably 50% by weight or less, more preferably 40% by weight or less, in 100% by weight of the photosensitive composition.
In the present invention, the solid component refers to a component other than the organic solvent in the photosensitive composition.
The photosensitive composition of the present invention contains (b) component: alkali-soluble resins.
Examples of the component (b) include epoxy resin, acrylic resin, phenolic resin, silicone polymer resin, polyimide resin, and the like. Among them, the component (b) preferably contains an acrylic resin in view of the excellent storage stability and photosensitivity of the photosensitive composition.
As the acrylic resin, an acrylic resin having a carboxyl group is preferable. The acrylic resin having a carboxyl group is preferably a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and vinyl acetic acid. These may be used alone or in combination with a copolymerizable ethylenically unsaturated compound.
As the copolymerizable ethylenically unsaturated compound, for example, examples thereof include unsaturated carboxylic acid alkyl esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, benzyl acrylate, benzyl methacrylate, etc., aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, alpha-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as amino ethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate, etc., vinyl acetate, vinyl propionate, etc., vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, alpha-chloroacrylonitrile, etc., aliphatic conjugated dienes such as 1, 3-butadiene, isoprene, etc., and poly (vinyl methacrylate), poly (methyl acrylate), poly (acryl), etc. From the viewpoint of solubility in an alkaline developer, it is preferable that the component (b) contains an acrylic resin having an acid value of 70 to 150 (mgKOH/g), and the acrylic resin is a 2-to 4-membered copolymer having a structure obtained by copolymerizing an unsaturated carboxylic acid or an ethylenically unsaturated compound selected from the group consisting of methacrylic acid, acrylic acid, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, and styrene. The heat resistance and the solvent solubility can be further improved by appropriately selecting an ethylenically unsaturated compound to prepare a 2-to 4-membered copolymer. In addition, when the acid value is within this range, the dissolution rate in the high-concentration alkaline developer can be easily controlled within an appropriate range.
(B) The weight average molecular weight (Mw) of the component (A) is preferably 2 to 10 thousand, more preferably 1 to 5 thousand. When the amount of the component (b) is within this range, the dissolution rate of the component (b) in the alkaline developer can be easily adjusted to an appropriate range, and the low taper angle can be easily formed by controlling the reflow property during heat curing. The weight average molecular weight (Mw) was obtained by measuring the weight average molecular weight (Mw) in terms of polystyrene using a GPC analyzer. Specifically, the weight average molecular weight of the component (b) is measured under the following conditions.
Measurement device: waters2695 (Waters Co., ltd.)
Column temperature: 50 DEG C
Flow rate: 0.4mL/min
A detector: 2489UV/Vis Detector (measurement wavelength 260 nm)
Developing solvent: NMP (containing 0.21 wt% lithium chloride, 0.48 wt% phosphoric acid)
Protective column: TOSOH TSK guard column (manufactured by Tosoh corporation)
Column: TOSOH TSK-GEL a-2500,
TOSOH TSK-GEL a-4000 series (all manufactured by Tosoh Co., ltd.)
Number of measurements: 2 times (average value is taken as the weight average molecular weight of the component (b)).
The component (b) preferably contains an acrylic resin having an ethylenically unsaturated group in a side chain. When the acrylic resin is contained, sensitivity at the time of exposure and development is easily improved. As ethylenically unsaturated groups, acrylic groups or methacrylic groups are preferred. Such an acrylic resin can be obtained by, for example, subjecting an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to an addition reaction with a carboxyl group of an acrylic (co) polymer having a carboxyl group.
In the photosensitive composition of the present invention, the component (b) preferably contains the following component (b-1).
(B-1) component: alkali-soluble resin with amine value of 2.0-10.0 mgKOH/g
When the amine value of the component (b-1) is 2.0mgKOH/g or more, the dissolution inhibiting effect in an alkaline developer having a high concentration is easily exhibited, and the processability of a fine pattern is easily improved. By setting the amine value of the component (b-1) to 10.0mgKOH/g or less, the affinity with the developer is improved, and even in the case of a high-concentration developer to which no surfactant is added, the unexposed portion is easily and uniformly dissolved, and as a result, a cured product excellent in pattern linearity is easily obtained.
In the photosensitive composition of the present invention, the component (b-1) preferably comprises: a structural unit represented by the formula (1) and/or a structural unit represented by the formula (2); and a structural unit represented by formula (3).
[ Chemical formula 6]
[ Chemical formula 7]
[ Chemical formula 8]
In the formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents any one selected from an alkylene group having 1 to 4 carbon atoms, a 2-valent alkyleneoxy alkylene group having 2 to 4 carbon atoms, a 2-valent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a 2-valent aromatic hydrocarbon group having 6 to 10 carbon atoms, and R 3 and R 4 each independently represent any one selected from an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms.
The structural unit represented by formula (1) is a (meth) acrylic acid unit having a tertiary amino group. Examples of the (meth) acrylic acid unit include, but are not particularly limited to, (meth) acrylic acid units obtained by polymerizing 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl acrylate, 2-dipropylaminoethyl acrylate, 2-diphenylaminoethyl acrylate, 2-dibenzylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-dipropylaminoethyl methacrylate, 2-diphenylaminoethyl methacrylate, 2-benzylaminoethyl methacrylate, and the like. These (meth) acrylic acid units may be contained alone or in an amount of 2 or more.
The structural unit represented by the formula (1) can be introduced, for example, by copolymerizing an unsaturated monomer having a tertiary amino group.
In the formula (2), R 5 represents a hydrogen atom or a methyl group, R 6 represents any one selected from an alkylene group having 1 to 4 carbon atoms, a 2-valent alkyleneoxy alkylene group having 2 to 4 carbon atoms, a 2-valent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a 2-valent aromatic hydrocarbon group having 6 to 10 carbon atoms, and R 7、R8 and R 9 each independently represents any one selected from an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and X represents any one of a bromine atom, a chlorine atom, an iodine atom, a hydrogen sulfate, and a hydroxide.
The structural unit represented by formula (2) is a (meth) acrylic acid unit having a quaternary ammonium salt. Examples of the (meth) acrylic acid unit include, but are not particularly limited to, (meth) acrylic acid units obtained by polymerizing dimethylaminoethyl methyl chloride acrylate, dimethylaminoethyl benzyl chloride acrylate, dimethylaminoethyl methyl chloride methacrylate, dimethylaminoethyl benzyl chloride methacrylate, and the like. These (meth) acrylic acid units may be contained alone or in an amount of 2 or more.
The structural unit represented by the formula (2) can be introduced, for example, by copolymerizing an unsaturated monomer having a quaternary ammonium salt.
In the structural units represented by the formula (1) and the structural units represented by the formula (2), the molar ratio of the structural units represented by the formula (2) is preferably 50 mol% or less, and more preferably 20 mol% or less, relative to the total of the formulas (1) and (2), from the viewpoint of reducing wiring damage of the organic EL display device and reducing non-lighting pixels. The structural unit represented by the formula (1) is preferably a tertiary amine, more preferably 2-dimethylaminoethyl methacrylate.
In the formula (3), R 10 and R 11 each independently represent a hydrogen atom or a methyl group, and R 12 represents any one selected from an alkylene group having 1 to 4 carbon atoms, a 2-valent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a 2-valent aromatic hydrocarbon group having 6 to 10 carbon atoms. By having the structural unit represented by formula (3), the exposure sensitivity of the photosensitive composition can be easily improved.
The method of introducing the structural unit represented by the formula (3) is not particularly limited, and a known method can be used. For example, a method of adding a polymerizable unsaturated monomer having a glycidyl group to a (meth) acrylic copolymer copolymerized with an unsaturated monomer having a carboxyl group may be mentioned. In this case, examples of the unsaturated monomer containing a carboxyl group to be copolymerized include acrylic acid, methacrylic acid, and the like. Examples of the glycidyl group-containing unsaturated monomer include glycidyl acrylate and glycidyl methacrylate.
In the photosensitive composition of the present invention, the component (b) preferably contains the following component (b-2).
(B-2) component: resin having hydroxyl value of 60mgKOH/g or more and having no structural unit represented by formula (1) and no structural unit represented by formula (2)
The hydroxyl value of the component (b-2) is 60mgKOH/g or more, more preferably 80mgKOH/g or more. When the hydroxyl value is within this range, affinity with the developer can be easily improved, linearity of the pattern can be easily improved, and residues at the edge portion can be easily suppressed. The upper limit of the hydroxyl value is not particularly limited, but is usually about 450 mgKOH/g. The hydroxyl number is determined as follows. First, the component (b-2) was dried for 10 hours or more using a vacuum drier at 80℃to prepare a dried sample. Next, 2g of the dried sample was dissolved in 5ml of a 250g/L pyridine solution of acetic anhydride. Further, 1mL of water was added to decompose acetic anhydride, and then titration was performed using an ethanol solution of potassium hydroxide at a concentration of 0.5mol/L, whereby the hydroxyl value was calculated. In the case where a certain resin may be any of the component (b-1) and the component (b-2), the certain resin is the component (b-1).
The component (b-2) has a hydroxyl group. The hydroxyl group of the component (b-2) is preferably a phenolic hydroxyl group. By providing the component (b-2) with a phenolic hydroxyl group, excessive radical reaction due to exposure can be suppressed, and mask bias can be reduced.
Examples of the resin having a hydroxyl group as the component (b-2) include a hydroxyl group-containing epoxy acrylate resin, a hydroxyl group-containing acrylic resin, a phenolic resin, a hydroxyl group-containing silicone polymer resin, a hydroxyl group-containing polyimide resin, and the like. Among them, a phenol resin or a hydroxyl group-containing acrylic resin is preferable from the viewpoints of storage stability and patterning of the photosensitive composition.
The phenolic resin is a resin having a phenolic hydroxyl group, which is obtained by reacting a phenol compound with an aldehyde compound or a ketone compound, and has an aromatic structure derived from the phenol compound. In the case where the aldehyde compound and/or ketone compound have an aromatic structure, they have an aromatic structure derived from them. Therefore, by incorporating the phenolic resin in the composition, the heat resistance of the resulting cured product can be improved. Therefore, the cured product is suitable for applications requiring heat resistance.
Examples of the phenol compound include phenol, o-cresol, m-cresol, p-cresol, 2, 5-xylenol, 3, 5-xylenol, 2-ethylphenol, 3-ethylphenol, 4-n-propylphenol, 4-n-butylphenol, 4-t-butylphenol, 1-naphthol, 2-naphthol, 4' -dihydroxybiphenyl, 2-bis (4-hydroxyphenyl) propane, catechol, resorcinol, 1, 4-hydroquinone, pyrogallol, 1,2, 4-pyrogallol, and pyrogallol.
Examples of the aldehyde compound include formaldehyde, paraformaldehyde, acetaldehyde, paraldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, and the like.
Examples of the ketone compound include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone.
The phenolic resin is preferably a Novolac resin obtained by reacting a phenol compound with an aldehyde compound and/or a ketone compound in the presence of an acid catalyst. The reaction of the phenol compound with the aldehyde compound and/or ketone compound may be carried out in a solvent or without a solvent.
The phenolic resin may be Resol resin obtained by the same reaction except that a base catalyst is used instead of an acid catalyst.
Examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid, their anhydrides, and ion exchange resins. Examples of the base catalyst include triethylamine, tri-N-propylamine, tri-N-butylamine, tri-N-pentylamine, tri-N-hexylamine, tri-N-heptylamine, tri-N-octylamine, diethylamine, triethanolamine, diethanolamine, N-dimethyl-4-aminopyridine, sodium hydroxide, potassium hydroxide, and ion exchange resins.
The hydroxyl group-containing acrylic resin can be obtained, for example, by using a copolymerizable hydroxyl group-containing or phenolic hydroxyl group-containing ethylenically unsaturated compound by the same method as the aforementioned acrylic resin.
Examples of the copolymerizable hydroxyl group-containing ethylenically unsaturated compound include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, and the like.
Examples of the copolymerizable phenolic hydroxyl group-containing ethylenically unsaturated compound include 4-hydroxyphenyl methacrylate (hereinafter referred to as PQMA), methyl (4-hydroxyphenyl) methacrylate, ethyl (4-hydroxyphenyl) methacrylate, propyl (4-hydroxyphenyl) methacrylate, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2, 4-dihydroxystyrene, 2, 6-dihydroxystyrene, 2,4, 6-trihydroxystyrene, 2,3,4, 5-tetrahydroxystyrene, pentahydroxystyrene, 2-hydroxy- α -methylstyrene, 3-hydroxy- α -methylstyrene, 4-hydroxy- α -methylstyrene, 1- (2-hydroxyphenyl) propylene, 1- (3-hydroxyphenyl) propylene, 1- (4-hydroxyphenyl) propylene, and the like.
The photosensitive composition of the present invention preferably contains the component (b-1) and the component (b-2), and the weight ratio W b-1/Wb-2 of the component (b-1) to the component (b-2) is 0.2 to 1.5, more preferably 0.3 to 1.2. By setting W b-1/Wb-2 to 0.2 or more, the workability of the fine pattern can be further improved. Further, by setting W b-1/Wb-2 to 1.5 or less, compatibility with the developer is further improved, and pattern linearity can be further improved.
The content of the component (b) in the photosensitive composition of the present invention is preferably 60% by weight or less, more preferably 50% by weight or less, based on 100% by weight of the solid content of the photosensitive composition, from the viewpoint of improving sensitivity at the time of exposure. In addition, from the viewpoint of improving the flexibility of the cured film and reducing cracks, the content of the component (b) is preferably 10% by weight or more, and more preferably 20% by weight or more, based on 100% by weight of the solid content of the photosensitive composition.
The content of the component (b-1) in the photosensitive composition of the present invention is preferably 2% by weight or more, and more preferably 5% by weight or more, based on 100% by weight of the solid content of the photosensitive composition, from the viewpoint of storage stability of the photosensitive composition. In addition, from the viewpoint of reducing the residue at the pattern opening, the content of the component (b-1) is preferably 40% by weight or less, and more preferably 30% by weight or less, based on 100% by weight of the solid content of the photosensitive composition.
The content of the component (b-2) in the photosensitive composition of the present invention is preferably 10% by weight or more, and more preferably 20% by weight or more, based on 100% by weight of the solid content of the photosensitive composition, from the viewpoint of improving compatibility with a developer and improving linearity of a pattern. In addition, from the viewpoint of improving sensitivity at the time of exposure, the content of the (b-2) component is preferably 50% by weight or less, and more preferably 40% by weight or less, based on 100% by weight of the solid content of the photosensitive composition.
The photosensitive composition of the present invention contains a component (c): a radical polymerizable compound. The radical polymerizable compound is a component having a radical polymerizable group in a molecule, the radical polymerizable group is a group capable of adding a methyl radical at room temperature, and when a methyl radical is added, the radical polymerizable group is a group generating another radical. As a method for generating a methyl radical at room temperature, a method of irradiating a photopolymerization initiator having an acetoxime ester structure with active chemical rays (radiation) is exemplified. As a method for detecting another radical generated when a methyl radical is added, electron spin resonance analysis is given. Further, as a method for confirming that another radical is generated when a methyl radical is added, there is given: a method in which a composition obtained by dissolving a compound having a radical polymerizable group and a photopolymerization initiator having an acetoxime ester structure in a solvent is irradiated with active chemical rays, and the presence or absence of an appearance change such as gelation or filming is confirmed by an increase in viscosity before and after the active chemical rays are irradiated. Examples of the active chemical rays include visible light, ultraviolet light, electron beam, and X-ray. It is preferable that another radical generated when a methyl radical is added to a radical polymerizable group can be further added to another radical polymerizable group. In addition, when the radical is further added to another radical polymerizable group, it is similarly preferable to further generate another radical. The other radical generated when the methyl radical is added to the radical polymerizable group is preferably a carbon radical, an oxygen radical, a nitrogen radical, or a sulfur radical, and more preferably a carbon radical. The radical polymerizable group of the component (c) is preferably an ethylenically unsaturated bond, more preferably an acrylic group or a methacrylic group, from the viewpoint of improving sensitivity at the time of exposure. (c) The component (a) may have 2 or more radical polymerizable groups.
(C) The component (c) preferably contains a compound having 2 or more radical polymerizable groups. Examples of the component (c) include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate urethane, modified bisphenol A epoxy (meth) acrylate, adipic acid 1, 6-hexanediol (meth) acrylate, phthalic anhydride propylene oxide (meth) acrylate, diethylene glycol trimellitate (meth) acrylate, rosin-modified epoxy di (meth) acrylate, alkyd-modified (meth) acrylate, fluorene diacrylate-based oligomer, tripropylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2-bis [4- (3-acryloyloxy-2-hydroxypropoxy) phenyl ] propane, bis [4- (3-acryloyloxy) propyloxy ] phenyl ] propane, bis [ 4-oxypropyloxy ] 2-propyloxy ] phenyl ] sulfone 4,4' -bis [4- (3-acryloyloxy-2-hydroxypropoxy) phenyl ] cyclohexane, 9-bis [4- (3-acryloyloxy-2-hydroxypropoxy) phenyl ] fluorene, 9-bis [ 3-methyl-4- (3-acryloyloxy-2-hydroxypropoxy) phenyl ] fluorene, 9-bis [ 3-chloro-4- (3-acryloyloxy-2-hydroxypropoxy) phenyl ] fluorene, diphenoxyethanol fluorene diacrylate, diphenoxyethanol fluorene dimethacrylate, xylenol fluorene diacrylate, xylenol fluorene dimethacrylate, and the like. The photosensitive composition may contain two or more of them.
In the photosensitive composition of the present invention, the component (c) preferably contains the following component (c-1) from the viewpoint of suppressing deterioration of mask bias and residue at the pattern edge due to excessive photocuring at the exposed portion and the pattern edge.
(C-1) component: a radically polymerizable compound having 2 ethylenically unsaturated bonds in the molecule and having a double bond equivalent of 200 to 600 g/mol.
In order to prevent excessive curing of the exposed portion and the edge portion of the exposed pattern and generation of residues at the edge of the pattern, the double bond equivalent of the component (c-1) is preferably 200g/mol or more. In addition, from the viewpoint of improving the fine line workability and the exposure sensitivity, it is preferably 600g/mol or less, more preferably 400g/mol or less.
The double bond equivalent weight of the radical polymerizable compound referred to herein means the weight of the radical polymerizable compound corresponding to 1mol of the ethylenically unsaturated double bond group. The double bond equivalent is in g/mol. The number of ethylenically unsaturated double bond groups in the radical polymerizable compound can be determined from the value of double bond equivalent. The double bond equivalent can be calculated from the iodine value.
The iodine value herein refers to a value obtained by converting the amount of halogen reacted with 100g of a sample into the weight of iodine. The iodine number is given in units of gI/100g. After 100g of the sample was reacted with iodine monochloride, unreacted iodine was captured with an aqueous potassium iodide solution, and the unreacted iodine was titrated with an aqueous sodium thiosulfate solution, thereby obtaining the product.
When the photosensitive composition of the present invention contains the component (c-1), the content of the component (c-1) is preferably 60 to 100% by weight based on the component (c). When the content of the component (c-1) is 60 wt% or more, excessive curing of the exposed portion and the pattern edge portion can be easily suppressed, and the occurrence of edge residues can be easily suppressed.
In the photosensitive composition of the present invention, the total content of the component (b) and the component (c) is preferably 10% by weight or more, more preferably 15% by weight or more, in terms of improving sensitivity at the time of exposure, in 100% by weight. On the other hand, from the viewpoint of reflow properties in the heating and firing step, the content of the component (c) is preferably 80% by weight or less, and more preferably 60% by weight or less, in 100% by weight of the total content of the component (b) and the component (c).
In the photosensitive composition of the present invention, the double bond equivalent of the solid content in the photosensitive composition is 1000 to 3500g/mol. By setting the double bond equivalent to 1000g/mol or more, excessive photocuring at the time of exposure can be suppressed, the linearity of the pattern can be improved, and residues at the edge portion of the pattern can be suppressed. Further, by setting the double bond equivalent to 1000g/mol or more, the hardness and chemical resistance of the cured film can be improved. On the other hand, when the double bond equivalent is 3500g/mol or less, high sensitivity can be maintained even in a film having high light-shielding properties. Further, the cured film having a double bond equivalent of 3500g/mol or less is improved in flexibility and can be suitably used for a bent organic EL display device.
As used herein, the double bond equivalent weight of a solid component refers to the weight of the solid component per 1 mole of ethylenically unsaturated double bond groups. The unit of double bond equivalent of the solid component is g/mol. The number of ethylenically unsaturated double bond groups in the solid component can be determined from the value of double bond equivalent. The double bond equivalent can be calculated from the iodine value.
The photosensitive composition of the present invention contains (d) component: a photopolymerization initiator.
(D) The component (c) is a compound that generates a radical by bond cleavage and/or reaction by exposure. Examples of the component (d) include carbazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and α -aminoalkylbenzophenone-based photopolymerization initiators. The component (d) may contain two or more of them. Among them, the component (d) preferably contains an oxime ester-based photopolymerization initiator, in view of high sensitivity to mixed rays containing i-lines (365 nm), h-lines (405 nm), and g-lines (436 nm) in an exposure step described later.
Examples of the oxime ester photopolymerization initiator include 1-phenyl-1, 2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (o-benzoyl) oxime, bis (. Alpha. -isonitropropiophenone oxime) isophthaloyl, 1, 2-octadione-1- [4- (phenylthio) phenyl ] -2- (o-benzoyl oxime) ], IRGACURE (registered trademark), OXE01, IRGACURE OXE02 (trade name, manufactured by BASF corporation), N-1818, N-1919, NCI-831 (trade name, manufactured by ADEKA).
In the photosensitive composition of the present invention, the component (d) more preferably contains an oxime ester photopolymerization initiator having a fluorine atom in the molecule.
By having fluorine atoms in the molecule, the hydrophobicity of the coating film can be improved, and the dissolution rate in the high-concentration alkaline developer can be reduced.
Examples of the oxime ester photopolymerization initiator having a fluorine atom in the molecule include photopolymerization initiators represented by formula (6).
[ Chemical formula 9]
R 23 represents a fluoroalkyl group. As an example of the R 23, examples thereof include 2, 3-tetrafluoropropyl, 2-trifluoroethyl 2,3, 4, 5-octafluoropentyl, and the like. Wherein component (d) preferably comprises IRGACURE OXE03, wherein R 23 is represented by 2, 3-tetrafluoropropyl.
The content of the component (d) in the photosensitive composition is preferably 1 part by weight or more, more preferably 5 parts by weight or more, based on 100 parts by weight of the total amount of the component (b) and the component (c), from the viewpoint of improving the sensitivity to exposure. On the other hand, from the viewpoint of fine wire workability, the content of the component (d) is preferably 60 parts by weight or less, more preferably 40 parts by weight or less, relative to 100 parts by weight of the total amount of the component (b) and the component (c).
The photosensitive composition of the present invention may contain an organic solvent.
Examples of the organic solvent include ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, alcohols, and the like.
Examples of the ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and tetrahydrofuran.
Examples of the acetate esters include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), propylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, and the like.
Examples of the esters include methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, ethyl acetate, n-propyl acetate, and n-butyl acetate.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Examples of the aromatic hydrocarbon include toluene and xylene.
Examples of the amides include N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide.
Examples of the alcohols include butanol, isobutanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, diacetone alcohol, and the like.
The photosensitive composition of the present invention may contain 2 or more of these organic solvents. In addition, the boiling point of the organic solvent at 1 atmosphere is preferably 170 ℃ or less, more preferably 150 ℃ or less, from the viewpoint that the solvent is easily volatilized even when low-temperature firing is performed after patterning.
The photosensitive composition of the present invention may contain a surfactant as needed, from the viewpoint of improving wettability with a substrate or improving film thickness uniformity of a coating film. As the surfactant, commercially available compounds can be used, and specifically, examples of the silicone-based surfactant include SH series, SD series, ST series from Toray Dow Corning Silicone, BYK series from BYK-Chemie-Japan, KP series from shin-Etsu silicone, disfoam series from Japanese oil and fat, TSF series from Toshiba silicone, and the like. The fluorine-based surfactant may be a "Megafac (registered trademark)" series from the large japan ink industry company, a FLUORAD series from the Sumitomo 3M company, a "SURFLON (registered trademark)" series from the asahi guard (registered trademark) "series from the asahi nitro company, an EF series from the new autumn chemical company, or a PolyFox series from the Omnova Solution company. Examples of the surfactant containing an acrylic and/or methacrylic polymer include Polyflow series from co-division chemical company, and "dispollon (registered trademark)" series from nanji chemical company. The surfactant that may be contained in the photosensitive composition of the present invention is not limited to the above examples.
The photosensitive composition of the present invention may contain a polymeric dispersant. The polymer dispersant is a dispersant comprising: an affinity group having a chemical bonding or adsorption effect to the surface of the black pigment, and a polymer chain or group having solphilicity. Since the polymer dispersant does not have an ethylenically unsaturated group, the target photosensitive performance may be deteriorated when the polymer dispersant is added in a large amount, and the appropriate amount to be added is preferably set in consideration of the dispersion stability and the photosensitive performance. The polymer dispersant improves wettability of the black pigment to a dispersion medium in a wet medium dispersion treatment described later, promotes deagglomeration of the black pigment, stabilizes particle size and viscosity by steric hindrance and/or electrostatic repulsion effect, and exerts an effect of suppressing occurrence of color separation at the time of storage or application of the photosensitive composition.
Examples of the polymer dispersant include polyester-based polymer dispersants, acrylic-based polymer dispersants, polyurethane-based polymer dispersants, polyallylamine-based polymer dispersants, and carbodiimide-based dispersants. The polymer dispersant preferably has an amino group from the viewpoint of improving the long-term storage stability of the black pigment dispersion.
Examples of the method for producing the photosensitive composition of the present invention include: a method of directly dispersing the component (a) in the component (b), the component (c), the component (d) and the organic solvent by using a dispersing machine; and a method in which a black dispersion is prepared by dispersing the component (a) in the component (b) and an organic solvent using a dispersing machine, and then the black dispersion is mixed with the component (c) and the component (d).
Examples of the dispersing machine include a bead mill, a ball mill, a sand mill, a three-roll mill, and a high-speed impact mill. Among these, the bead mill is preferable from the viewpoints of dispersion efficiency and microdispersion. Examples of the bead mill include a double cone mill (co-ball mill), a basket mill, a pin mill, and a dano mill. Examples of the beads of the bead mill include titania beads, zirconia beads, zircon beads, and the like. The bead diameter of the bead mill is preferably 0.03 to 1.0mm. (a) When the average primary particle diameter of the component and the particle diameter of the secondary particles formed by aggregation of the primary particles are small, fine dispersion beads of 0.03 to 0.10mm are preferable. In this case, a bead mill having a separator using a centrifugal separation system is preferable, which can separate fine beads from a dispersion liquid.
On the other hand, when the component (a) containing coarse particles of submicron (submicron) order is dispersed, the beads having a bead diameter of 0.10mm or more are preferable because a sufficient pulverizing force can be obtained. The bead diameter can be calculated as follows: the equivalent circle diameter was measured for 100 randomly selected beads observed by a microscope, and the number average value was calculated.
In the photosensitive composition of the present invention, the 50% cumulative diameter in the volume-based particle size distribution of the particle components in the photosensitive composition measured by the dynamic light scattering method is preferably 20 to 60nm. Hereinafter, the above 50% cumulative diameter may be referred to as the median diameter D50. By setting the median diameter D50 to 60nm or less, the viscosity stability of the pigment dispersion is easily improved, and the resulting cured product is easily obtained with high pattern linearity, and the occurrence of non-lighting of pixels due to wiring short-circuits in an organic EL display device having the cured product is easily avoided. Further, the light-shielding property per unit weight can be easily improved by setting the median particle diameter D50 to 20nm or more, more preferably 40nm or more. The median particle diameter D50 was calculated as the cumulative volume average diameter based on the fine particle diameter side (0%) using a dynamic light scattering particle diameter measuring apparatus "nanoPartica SZ-100 (manufactured by horiba ltd.).
The photosensitive composition of the present invention may further contain the following component (e).
(E) The components are as follows: silica particles.
The silica particles referred to herein mean particles having a pure component of SiO 2 of 90 wt% or more, particles made of silica (anhydrous silicic acid), particles made of silica hydrate (hydrous silicic acid, white carbon), or particles made of silica glass in a weight other than water. Particles formed from orthosilicic acid, metasilicic acid and/or metadisilicic acid are also included. The structure of the particles is not particularly limited, and may have internal voids.
Examples of the aggregation forms controlled in the production process include fumed silica, chain silica, associated silica, and chlorella silica. These silica are regarded as secondary particles or tertiary particles composed of a plurality of primary particles.
In the photosensitive composition of the present invention, the average primary particle diameter of the component (e) is more preferably 10 to 30nm. By making the average primary particle diameter of 10nm to 30nm, the interaction between silica particles becomes strongest, and the reflow during curing is suppressed, whereby the pattern linearity and mask bias can be improved.
(E) The average primary particle diameter of the components was the BET diameter, and was calculated by the following method.
BET diameter=6/ρs
Ρ: silica density (2.65 g/cm 3)
S: BET specific surface area
The silica sol or the dispersion containing the silica particles may be dried by heating at 200℃for 1 hour, and the obtained dried sample may be subjected to vacuum degassing at 100℃by using a fully automatic gas adsorption apparatus "BELSORP (registered trademark)" 36 of silica Japanese BEL, inc., and then the adsorption isotherm of N 2 gas at the liquid nitrogen temperature (77K) may be measured, and the isotherm may be analyzed by the BET method to determine the specific surface area S.
The photosensitive composition of the present invention preferably contains the component (b-1), and the weight ratio W e/Wb-1 of the component (e) to the component (b-1) is 0.5 to 2.0. When the weight ratio W e/Wb-1 is 0.5 or more, reflow property during curing can be suppressed, and pattern linearity and mask bias can be easily improved. On the other hand, by setting the weight ratio W e/Wb-1 to 2.0 or less, the occurrence of pattern peeling can be easily suppressed.
The photosensitive composition of the present invention preferably contains the component (b-2), and the weight ratio W e/Wb-2 of the component (e) to the component (b-2) is 0.15 to 1.0. When the weight ratio W e/Wb-2 is 0.15 or more, reflow property during curing can be suppressed, and pattern linearity and mask bias can be easily improved. On the other hand, when the weight ratio W e/Wb-2 is 1.0 or less, moderate reflow property is exhibited during curing, and deterioration of the pattern linearity can be easily suppressed.
The cured product of the present invention is obtained by curing the photosensitive composition of the present invention.
The method of producing the cured product may include, for example: a step of coating a photosensitive composition; a step of drying the coating film; exposing the coating film; developing the exposed coating film; and (3) performing heating and curing.
Details of each step are set forth below. In the present invention, among the films formed on the substrate, the film between the time when the photosensitive composition is applied to the substrate and the time when the photosensitive composition is cured by heating is referred to as a coating film, and the film after the heat curing is referred to as a cured product.
First, a process of applying the photosensitive composition will be described. In this step, the photosensitive composition of the present invention is applied to a substrate by spin coating, slit coating, dip coating, spray coating, printing, or the like, to obtain a coating film. Among these, the slit coating method is preferably used. The coating speed in the slit coating method is generally in the range of 10 mm/sec to 400 mm/sec. The film thickness of the coating film varies depending on the solid content concentration, viscosity, etc. of the photosensitive composition, and is usually applied so that the film thickness after drying becomes 0.1 to 10 μm, preferably 1.0 to 5.0 μm.
Examples of the substrate include glass, quartz, silicon, ceramics, plastics, and substrates on which electrodes such as ITO, cu, ag are partially formed.
The substrate coated with the photosensitive composition may be pretreated with the adhesion improver before coating. For example, there is a method of treating the surface of a substrate with a solution obtained by dissolving 0.5 to 20% by weight of an adhesion improver in a solvent such as isopropyl alcohol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, or the like. Examples of the method for treating the surface of the substrate include spin coating, slot die coating, bar coating, dip coating, spray coating, and vapor treatment.
Next, a step of drying the coating film will be described. In this step, after the photosensitive composition is applied, the coating film is dried. Drying in this step means reduced pressure drying or heat drying. Both the reduced pressure drying and the heat drying may be performed, or only one of them may be performed.
The heat drying will be described. This process is also referred to as prebaking. Drying typically uses a heated plate, oven, infrared, etc. The heating temperature varies depending on the kind and purpose of the coating film, and is preferably in the range of 50 to 180 ℃ for 1 minute to several hours.
Next, a step of exposing the coating film will be described. In this step, in order to form a pattern from the obtained coating film, it is preferable to irradiate a chemical ray onto the coating film through a mask having a desired pattern and to photo-cure the exposed portion. Examples of chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays, and in the present invention, it is preferable to use an i-line (365 nm), an h-line (405 nm), and a g-line (436 nm) of a mercury lamp.
Next, a process of developing the exposed coating film will be described. In this step, after exposure, the unexposed portions are removed using a developer, thereby forming a desired pattern. The developer is preferably an aqueous solution of a compound exhibiting basicity such as tetramethylammonium hydroxide (hereinafter, TMAH), diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, or the like. In addition, according to circumstances, N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, gamma-butyrolactone, dimethylacrylamide and other polar solvents, methanol, ethanol, isopropanol and other alcohols, ethyl lactate, propylene glycol monomethyl ether acetate and other esters, cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone and other ketones and the like can be added to these alkaline aqueous solutions singly or in combination of several kinds.
In the case of a general photosensitive composition containing a black pigment, it is difficult to perform photocuring of the bottom portion, and for example, in the case of development using an alkaline developer having a high concentration such as 2.38 wt% TMAH, processing of a fine pattern is difficult. The reduction of double bond equivalent in the composition can cause pattern residue, but the linearity of the pattern edge portion is deteriorated, or the overcoated layer on the film surface is peeled off by development, which causes residue to be generated at the pattern edge portion. In the photosensitive composition of the present invention, the double bond equivalent of the solid content in the photosensitive composition is set to be in the range of 1000g/mol to 3500g/mol, whereby excessive curing due to light can be suppressed while maintaining a constant sensitivity, and the linearity of the pattern can be improved and the residue at the edge portion can be reduced.
Next, the pattern formed by the development is preferably rinsed with distilled water. Here, the rinsing treatment may be performed by adding alcohols such as ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate to distilled water.
Next, a step of heat curing will be described. In this step, the reaction of the radical polymerizable group can be further promoted when the photo-curing alone is insufficient by the heat curing, and therefore the heat resistance can be improved.
The heating temperature is preferably 150 to 300 ℃. The heating time is preferably 0.25 to 5 hours. The heating temperature may be changed continuously or stepwise.
The organic EL display device of the present invention includes the cured product of the present invention. The organic EL display device has at least a substrate, a first electrode, a second electrode, a light-emitting pixel, a planarization layer, and a pixel dividing layer. An active matrix organic EL display device having a plurality of pixels formed in a matrix is preferable. An active matrix organic EL display device includes light-emitting pixels on a substrate such as glass, and a planarizing layer provided so as to cover the light-emitting pixels and a lower portion of a portion other than the light-emitting pixels. Further, the planarization layer has a first electrode provided so as to cover at least a lower portion of the light-emitting pixel and a second electrode provided so as to cover at least an upper portion of the light-emitting pixel. In addition, in the active matrix organic EL display device, the cured product of the present invention can be suitably used for a pixel division layer having insulation properties for dividing between light emitting pixels.
The photosensitive composition of the present invention can be used for a black matrix and a black column spacer used for a solid-state imaging element, a black partition wall of a Micro-LED or a Mini-LED display device, or a color filter for a liquid crystal display device, because it can form a pattern that is highly precise and does not generate residue in an opening.
Examples
The present invention will be described in detail with reference to examples and comparative examples, but the mode of the present invention is not limited to these. The abbreviations used for the compounds used are shown below.
Methyl Methacrylate (MMA)
Methacrylic acid (MAA)
Styrene (St)
2-Dimethylaminoethyl Methacrylate (MLDA)
Methacrylic acid-2-dimethylaminoethyl ester hydrochloride (MLDA-Cl)
2-Ethylhexyl methacrylate (2 EHMA)
Methacrylic acid-2-Hydroxyethyl Ester (HEMA)
Glycidyl Methacrylate (GMA)
Azobisisobutyronitrile (AIBN)
N-dodecyl mercaptan (MDM)
4-Hydroxyphenyl methacrylate (PQMA).
< Evaluation method >
[ Double bond equivalent ]
An automatic potential difference titration apparatus (AT-510; manufactured by Kyoto electronic industries Co., ltd.) was used, and an iodine monochloride solution (mixed solution of iodine trichloride=7.9 g, iodine=8.9 g, acetic acid=1,000 mL) was used as an iodine supply source, a 100g/L aqueous potassium iodide solution was used as a capturing aqueous solution of unreacted iodine, and a 0.1mol/L aqueous sodium thiosulfate solution was used as a titration reagent, based on JIS K0070:1992, "method for testing unsaponifiable matter" as "6 th iodine value" of acid value, saponification value, ester value, iodine value, hydroxyl value, and chemical, and iodine value of resin was measured by the Webster method. Based on the value of the iodine value (in g I/100 g) measured, the double bond equivalent (in g/mol) was calculated.
[ Calculation of median particle diameter D50 ]
Measuring a sample: the photosensitive compositions obtained in the examples and comparative examples were mixed 3 times with the same amount of PGMEA so that the photosensitive composition/pgmea=1/99 (weight ratio), and stirred on a shaker for 10 minutes.
Measurement device: dynamic light scattering method particle size distribution measuring apparatus "nanoPartica SZ-100 (horiba manufacturing Co., ltd.)"
Light source: wavelength 532nm/10mW (semiconductor excitation solid laser)
Measuring the liquid temperature of the sample: 25+ -1 deg.C (atmospheric pressure)
The calculation method comprises the following steps: the cumulative 50% diameter based on the light scattering intensity was obtained, the average value of the measurement was calculated 3 times, and the first rounded value after the decimal point was used as the median diameter D50.
Sensitivity
The photosensitive compositions obtained in each example and comparative example were applied to an ITO substrate using a rotator (MS-A150) manufactured by MIKASA (Inc.) so as to have a predetermined film thickness, and then heated and dried on a heating plate at 100℃for 2 minutes. The film was exposed to light with a low exposure of 500mJ/cm 2 as a maximum exposure amount per 10mJ/cm 2 using a Union Optical mask aligner (PEM-6M) and a negative mask 1 (a negative mask having a pattern with a minimum value of 1 μm and a maximum value of 50 μm and a scale of 1 μm) manufactured by HOYA (incorporated herein by reference), and developed with an alkaline developer of 2.38 wt% TMAH aqueous solution for 60 seconds, to obtain a patterned substrate. Then, the obtained patterned substrate was baked at 230 ℃ for 60 minutes in a hot air oven to obtain a cured product. When the film thickness after pre-baking is (T PB) μm and the film thickness after development is (T DEV) μm, the minimum exposure amount at which the residual film developing ratio ((T DEV)/(TPB). Times.100) is 70% or more is set as sensitivity.
Evaluation
A: less than 50mJ/cm 2
B:50mJ/cm 2 or more and less than 100mJ/cm 2
C:100mJ/cm 2 or more and less than 200mJ/cm 2
D:200mJ/cm 2 or more.
[ Minimum Pattern ]
The patterned substrates obtained in each of examples and comparative examples were observed with an optical microscope, and the minimum line and gap pattern in which no defect or peeling occurred in the pattern portion was set as the minimum pattern.
Evaluation
A: minimum pattern 1-4 μm
B: minimum pattern 5-9 mu m
C: minimum pattern 10-14 mu m
D: minimum pattern 15-19 mu m
E: the minimum pattern is more than 20 mu m.
[ Pattern linearity ]
The patterned substrates obtained in each of examples and comparative examples were observed with an optical microscope, and the opening sizes (10 points) in the line-and-space pattern were measured at intervals of 10 μm with a mask opening width of 50 μm, and the difference W (μm) between the maximum width and the minimum width was calculated by the following method.
The smaller the difference between the maximum width and the minimum width, the higher the pattern linearity, and the more excellent the visibility of the organic EL display device.
Evaluation
S: the difference W between the maximum width and the minimum width is less than 0.3 μm
A: the difference W between the maximum width and the minimum width is more than 0.3 μm and less than 0.5 μm
B: the difference W between the maximum width and the minimum width is more than 0.5 μm and less than 1.0 μm
C: the difference W between the maximum width and the minimum width is 1.0 μm or more and less than 2.0 μm
D: the difference W between the maximum width and the minimum width is more than 2.0 μm
[ Residue ]
The patterned substrates obtained in each example and comparative example were observed with an optical microscope, and the number of development residues having a long diameter of 0.1 μm or more and less than 3.0 μm in each opening was counted. The average number of development residues observed per 1 part of the 50 μm opening was evaluated based on the following criterion.
Evaluation
A: development residues were not observed at all
B: less than 5 residues were observed
C: more than 5 and less than 10 development residues were observed
D: more than 10 and less than 20 development residues were observed
E: more than 20 development residues were observed.
[ Mask bias ]
In the cured products of the photosensitive compositions obtained in each of examples and comparative examples, the smaller the absolute value of the difference between the mask design value and the opening width of the cured product, the smaller the mask bias, the better the mask bias, when the opening width of the line and the opening width of the gap pattern of 50 μm at the minimum exposure amount at which the pattern can be formed were measured with an optical microscope.
Evaluation
S: mask bias less than 0.6 μm
A: the mask bias is more than 0.6 μm and less than 1.0 μm
B: the mask bias is 1.0 μm or more and less than 2.0 μm
C: the mask bias is 2.0 μm or more and less than 3.0 μm
D: the mask bias is 3.0 μm or more.
[ Display characteristics of organic EL display device ]
Fig. 1 is a schematic diagram showing a procedure for manufacturing an organic EL display device using the photosensitive compositions obtained in each of examples and comparative examples. First, an ITO transparent conductive film 10nm was formed on the entire surface of an alkali-free glass substrate 1 of 38mm×46mm by sputtering, and etched to form a first electrode (transparent electrode) 2. In addition, simultaneously, an auxiliary electrode 3 for taking out the second electrode is also formed. The obtained substrate was subjected to ultrasonic cleaning with Semico Clean (trade name, manufactured by Furuchi chemical Co., ltd.) for 10 minutes, and then to cleaning with ultrapure water. Next, the photosensitive compositions obtained in each of examples and comparative examples were applied to the entire surface of the substrate by spin coating, and baked on a heating plate at 100 ℃ for 2 minutes. After exposing the film to light with a high-pressure mercury lamp as a light source and a minimum exposure amount of each photosensitive composition via a photomask, the film was developed with a 2.38 wt% aqueous TMAH solution to dissolve unnecessary portions, and rinsed with pure water. The resulting resin pattern was heat treated in a hot air oven at 230 ℃ for 60 minutes. In this way, openings having a width of 70 μm and a length of 260 μm are arranged at a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction, and the insulating layer 4 (which has a shape in which the first electrode is exposed from each opening) is formed so as to be limited to the substrate effective region. In this way, an insulating layer having an insulating layer aperture ratio of 25% was formed in the effective region of the quadrangular substrate having a side length of 16 mm. The thickness of the insulating layer is about 1.5 μm.
Next, after nitrogen plasma treatment as pretreatment, the organic EL layer 5 including the light-emitting layer was formed by a vacuum vapor deposition method. The vacuum degree at the time of vapor deposition was 1×10 -3 Pa or less, and the substrate was rotated with respect to the vapor deposition source during the vapor deposition. First, a compound (HT-1) of 10nm was deposited as a hole injection layer, and a compound (HT-2) of 50nm was deposited as a hole transport layer. Next, a compound (GH-1) as a host material and a compound (GD-1) as a dopant material were deposited on the light-emitting layer at a thickness of 40nm so that the doping concentration became 10%. Next, a compound (ET-1) and a compound (LiQ) as electron transport materials were mixed in a ratio of 1:1 is laminated to a thickness of 40 nm. The structure of the compound used in the organic EL layer is shown below.
[ Chemical formula 10]
Next, after vapor deposition of a compound (LiQ) at 2nm, mg and Ag were mixed at 10: the volume ratio of 1 was evaporated to 10nm to prepare a second electrode (non-transparent electrode) 6. Finally, the cover glass plate was bonded with an epoxy resin adhesive under a low humidity nitrogen atmosphere, and sealed, whereby 4 quadrangular top emission type organic EL display devices having a side length of 5mm were fabricated on 1 substrate. The film thickness referred to herein is a display value of a quartz oscillation type film thickness monitor.
For each example, a total of 20 organic EL display devices were fabricated by the method described above, and display tests were performed.
Evaluation
A: all pixels are lit up
B: the number of the non-lighting devices is 1 to 4
C: the number of non-lighting devices is 5 or more.
< Production example >
Synthesis example 1 alkali-soluble resin P-1
160.0G of PGMEA was charged into a pressure-resistant vessel equipped with a stirrer, a thermometer, a reflux condenser and a dropping pump, the reaction vessel was filled with nitrogen gas, the temperature was raised to 90℃and a mixture of 8.97g of St, 9.97g of MMA, 0.55g of MLDA, 6.06g of MAA, 12.75g of 2EHMA, 2.0g of AIBN as a polymerization initiator and 3.0g of MDM was dropped over 3 hours with the dropping pump to conduct copolymerization. Then, the reaction vessel was replaced with air, and 2.24g of GMA was added dropwise with a dropwise pump over 1 hour to carry out an addition reaction, and the vessel was stirred for 2 hours. As a result, an alkali-soluble resin (P-1) solution having a solid content concentration of 20% by weight and having a characteristic value of an amine value of 5mgKOH/g, an acid value of 76mgKOH/g, a double bond equivalent of 2540g/mol and a weight average molecular weight of 7000 was obtained.
Synthesis example 2 alkali-soluble resin P-2
By the same method as in Synthesis example 1, 9.03g of St, 10.01g of MMA, 0.09g of MLDA, 6.08g of MAA, and 12.79g of 2EHMA were added as comonomers and the amount of GMA added was 2.24g, whereby a solution of an alkali-soluble resin (P-2) having a solid content concentration of 20% by weight and having a characteristic value of an amine value of 1mgKOH/g, an acid value of 76mgKOH/g, a double bond equivalent of 2532g/mol, and a weight average molecular weight of 7000 was obtained.
Synthesis example 3 alkali-soluble resin P-3
By the same method as in Synthesis example 1, 8.92g of St, 10.00g of MMA, 0.23g of MLDA, 6.07g of MAA, 12.77g of 2EHMA and 2.24g of GMA were added as comonomers, whereby a solution of an alkali-soluble resin (P-3) having a solid content concentration of 20 wt% and having an amine value of 2mgKOH/g, an acid value of 77mgKOH/g, a double bond equivalent of 2534g/mol and a characteristic value of weight average molecular weight 7200 was obtained.
Synthesis example 4 alkali-soluble resin P-4
By the same method as in Synthesis example 1, 8.31g of St, 9.94g of MMA, 1.01g of MLDA, 6.04g of MAA, and 12.71g of 2EHMA were added as comonomers and the amount of GMA added was 2.23g, whereby a solution of an alkali-soluble resin (P-4) having a solid content concentration of 20% by weight and having a characteristic value of an amine value of 10mgKOH/g, an acid value of 76mgKOH/g, a double bond equivalent of 2548g/mol, and a weight average molecular weight of 7000 was obtained.
Synthesis example 5 alkali-soluble resin P-5
By the same method as in Synthesis example 1, 7.49g of St, 9.87g of MMA, 2.05g of MLDA, 6.00g of MAA, and 12.62g of 2EHMA were added as comonomers and 2.21g of GMA was added to obtain a solid content concentration of 20 wt% alkali-soluble resin (P-5) solution having an amine value of 20mgKOH/g, an acid value of 76mgKOH/g, a double bond equivalent of 2566g/mol, and a weight average molecular weight of 7300.
Synthesis example 6 alkali-soluble resin P-6
By the same method as in Synthesis example 1, 7.10g of St, 9.84g of MMA, 2.54g of MLDA, 5.98g of MAA, and 12.57g of 2EHMA were added as the added comonomer and the amount of 2.21g of GMA was added, whereby a solution of an alkali-soluble resin (P-6) having a solid content concentration of 20% by weight and having an amine value of 25mgKOH/g, an acid value of 76mgKOH/g, a double bond equivalent of 2575g/mol, and a characteristic value of weight average molecular weight 7100 was obtained.
Synthesis example 7 alkali-soluble resin P-7
By the same method as in Synthesis example 1, 6.99g of St, 9.64g of MMA, 3.28g of MLDA-Cl, 5.85g of MAA, 12.31g of 2EHMA and 2.16g of GMA were added as comonomers, thereby obtaining a solid content concentration of 20 wt% alkali-soluble resin (P-7) solution having an amine value of 24mgKOH/g, an acid value of 75mgKOH/g, a double bond equivalent of 2629g/mol and a characteristic value of weight average molecular weight of 7200.
Synthesis example 8 alkali-soluble resin P-8
By the same method as in Synthesis example 1, 7.10g of St, 9.74g of MMA, 1.21g of MLDA, 1.63g of MLDA-Cl, 5.92g of MAA, and 12.45g of 2EHMA were added as comonomers and the amount of GMA added was 2.16g, whereby an alkali-soluble resin (P-8) solution having a solid content concentration of 20 wt% and having a characteristic value of amine value of 24mgKOH/g, acid value of 75mgKOH/g, double bond equivalent of 2600g/mol and weight average molecular weight of 7500 was obtained.
Synthesis example 9 alkali-soluble resin P-9
By the same method as in Synthesis example 1, 9.15g of St, 10.02g of MMA, 6.06g of MAA, and 12.81g of 2EHMA of the added comonomer were mixed, and the amount of added GMA was 2.20g, whereby a solution of an alkali-soluble resin (P-9) having a solid content concentration of 20% by weight and having no amine value, an acid value of 77mgKOH/g, a double bond equivalent of 2581g/mol, and a characteristic value of weight average molecular weight of 6900 was obtained.
Synthesis example 10 resin H-1 containing phenolic hydroxyl groups
A phenolic hydroxyl group-containing resin H-1 having a hydroxyl value of 384mgKOH/g was synthesized by the method described in example 1 of Japanese patent application laid-open No. 2015-74717, and 20g of H-1 was added to 80g of PGMEA to dissolve the resin component, thereby obtaining a solution of H-1 in a solid content of 20% by weight. The weight average molecular weight of the resulting reactant was 8800.
Synthesis example 11 resin H-2 containing phenolic hydroxyl groups
Separately, 25.34g PQMA and 4.28g MMA and 10.38g St were completely dissolved in 100.0g PGMEA, and 3.66g V-601 (manufactured by Fuji photo-pure Co., ltd.) as a polymerization initiator was completely dissolved in 15.0g PGMEA. In a 300mL three-necked flask, the obtained 2 kinds of solutions were simultaneously dropwise added to 45.0g of PGMEA heated to 85℃over 2 hours under a nitrogen atmosphere, and reacted at 85℃for 3 hours after completion of the dropwise addition, thereby obtaining a 20% by weight solution of the solid content of hydroxyl group-containing resin H-2 having a hydroxyl group value of 101 mgKOH/g. The weight average molecular weight of the resulting reactant was 8800.
Synthesis example 12 resin H-3 containing hydroxyl groups
A solution of a hydroxyl group-containing resin H-3 having a hydroxyl group value of 94mgKOH/g and an acid value of 70mgKOH/g in a solid content of 20% by weight was obtained by using 8.70g of HEMA, 8.93g of MAA, 6.70g of MMA and 15.67g of St as the comonomer charged in the same manner as in Synthesis example 11. The weight average molecular weight of the resulting reactant was 8500.
Synthesis example 13 resin H-4 containing hydroxyl groups
A solution of a hydroxyl group-containing resin H-4 having a hydroxyl group value of 66mgKOH/g and an acid value of 71mgKOH/g in a solid content of 20% by weight was obtained by using 6.18g of HEMA, 9.07g of MAA, 8.84g of MMA and 15.91g of St as the comonomer charged in the same manner as in Synthesis example 11. The weight average molecular weight of the resulting reactant was 8600.
Synthesis example 14 resin H-5 containing hydroxyl groups
A solution of a hydroxyl group-containing resin H-5 having a hydroxyl group value of 53mgKOH/g and an acid value of 72mgKOH/g in a solid content of 20% by weight was obtained by using 4.90g of HEMA, 9.13g of MAA, 9.93g of MMA and 16.03g of St as the comonomer charged in the same manner as in Synthesis example 11. The weight average molecular weight of the resulting reactant was 8700.
Production example 1 production of Black pigment Dispersion (DB-1)
375G of Irgaphor Black S0100CF (manufactured by BASF corporation) as a Black pigment (a-1), 937.5g of a 20 wt% PGMEA solution of an alkali-soluble resin (P-1), 187.5g of a dispersant having an amine value of 20mgKOH/g and 1500g of PGMEA as a polymer dispersant described in Synthesis example 2 of Japanese patent application laid-open No. 2020-070352 were charged into a pot, and stirred with a homogenizer for 20 minutes to obtain a pre-dispersion. The obtained pre-dispersion was supplied to a Hiroshima Metal & Machinery disperser Ultra Apex Mill equipped with a centrifugal separator filled with 70% by volume of 0.10mm phi zirconia beads, and dispersed at a rotational speed of 10m/s for 3 hours to obtain a black pigment dispersion (DB-1) having a solid content concentration of 25% by weight and a black pigment/resin (weight) =80/20.
Production examples 2 to 5 production of black pigment Dispersion (DB-2) to (DB-5)
In the same manner as in production example 1, the dispersion time was set to 6 hours (DB-2), the dispersion time was set to 4 hours (DB-3), the dispersion time was set to 2 hours (DB-4), and the dispersion time was set to 1 hour (DB-5).
Production examples 6 to 7 production of Black pigment Dispersion (DB-6) to (DB-7)
By the same method as in production example 1, the added black pigment was made (a-2) titanium nitride (NISSHIN ENGINEERING), thereby obtaining (DB-6), and the added pigment was made (a-3) carbon black (TPK 1227, cabot) with a sulfonic acid group-modified surface, thereby obtaining (DB-7).
Production example 8 production of Black pigment Dispersion (DB-8)
Using the same method as in production example 1, the amount of the alkali-soluble resin (P-1) to be charged was 468.8g, and the amount of the phenolic hydroxyl group-containing resin H-1 was 468.8g, whereby (DB-8) was obtained.
Production examples 9 to 16 production of Black pigment Dispersion (DB-9) to (DB-16)
In the same manner as in production example 1, the alkali-soluble resins (P-2) to (P-9) were charged, whereby (DB-9) to (DB-16) were obtained.
Example 1
To 120.00g of a black pigment dispersion (DB-1), 37.50g of a 20 wt% PGMEA solution of an alkali-soluble resin (P-1), 112.50g of a hydroxyl group-containing resin (H-1), 3.68g of Irgacure OXE-03 (manufactured by BASF corporation) as a photopolymerization initiator, 11.25g of HX-220 (manufactured by Japanese chemical Co., ltd.) as a radical polymerizable compound, and 0.08g of a silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie corporation) and 215.00g of PGMEA were added to give a photosensitive composition (PB-1) having a solid content concentration of 15 wt% and a black pigment/resin (weight ratio) =20/80. The cured product of the photosensitive composition obtained by the above method, and an organic EL display device provided with the cured product.
Example 2
By the same method as in example 1, 5.63g of HX-220 and 5.63g of dipentaerythritol hexaacrylate (manufactured by Japanese chemical Co., ltd.) (hereinafter sometimes referred to as DPHA) were charged as radical polymerizable compounds, to thereby obtain a photosensitive composition (PB-2) and a cured product thereof, and an organic EL display device having the cured product.
Example 3
By the same method as in example 1, the photosensitive composition (PB-3), a cured product thereof, and an organic EL display device provided with the cured product were obtained by setting the amount of the alkali-soluble resin (P-1) charged to 37.50g, the amount of the hydroxyl group-containing resin (H-1) to 131.25g, and the radical-polymerizable compound HX-220 to 37.50 g.
Example 4
By the same method as in example 1, BPE-900 (manufactured by Xinzhou Chemicals Co., ltd.) was used as the type of radical polymerizable compound to be charged, and thus a photosensitive composition (PB-4), a cured product thereof, and an organic EL display device having the cured product were obtained.
Example 5
By the same method as in example 1, the photosensitive composition (PB-5) and its cured product and an organic EL display device having the cured product were obtained by not charging the alkali-soluble resin (P-1), making the amount of the charged resin (H-1) containing hydroxyl groups 150.00g, and making the charged radical polymerizable compound type BPE-900.
Examples 6 to 11
The photosensitive compositions (PB-6) to (PB-11) and their cured products were obtained by the same method as in example 1, with the charged black pigment dispersions (DB-2) to (DB-7), respectively.
Example 12
By the same method as in example 1, the charged photopolymerization initiator was set to ADEKA ARKLS (registered trademark) NCI-831, and (PB-12) and a cured product thereof and an organic EL display device having the cured product were obtained.
Example 13
By the same procedure as in example 1, the black pigment dispersion was made to be 120.0g of (DB-8), 168.75g of a hydroxyl group-containing resin (H-1), 37.50g of HX-220, 3.68g of NCI-831, and 0.08g of BYK333, thereby obtaining (PB-13), a cured product thereof, and an organic EL display device having the cured product.
Example 14
As a black pigment dispersion, (DB-1) was used in the same manner as in example 13 to obtain (PB-14) and a cured product thereof, and an organic EL display device comprising the cured product.
Example 15
By the same method as in example 1, the black pigment dispersion was made to be 120.0g of (DB-1), 18.75g of the alkali-soluble resin (P-1), 150.00g of the hydroxyl group-containing resin (H-1), 37.50g of HX-220, 3.68g of NCI-831, and 0.08g of BYK333, whereby (PB-15), a cured product thereof, and an organic EL display device having the cured product were obtained.
Example 16
By the same method as in example 1, the black pigment dispersion was made to be 120.0g of (DB-1), 56.25g of the alkali-soluble resin (P-1), 112.50g of the hydroxyl group-containing resin (H-1), 37.50g of HX-220, 3.68g of NCI-831, and 0.08g of BYK333, whereby (PB-16) and a cured product thereof and an organic EL display device having the cured product were obtained.
Example 17
By the same method as in example 1, the black pigment dispersion was made to be 120.0g of (DB-1), 75.00g of the alkali-soluble resin (P-1), 93.75g of the hydroxyl group-containing resin (H-1), 37.50g of HX-220, 3.68g of NCI-831, and 0.08g of BYK333, whereby (PB-17), a cured product thereof, and an organic EL display device having the cured product were obtained.
Example 18
By the same procedure as in example 1, the black pigment dispersion was made to be 120.0g of (DB-1), 86.25g of the alkali-soluble resin (P-1), 82.50g of the hydroxyl-containing resin (H-1), 37.50g of HX-220, 3.68g of NCI-831, and 0.08g of BYK333, whereby (PB-18), a cured product thereof, and an organic EL display device having the cured product were obtained.
Example 19
By the same method as in example 1, the black pigment dispersion was made to be 120.0g of (DB-1), 93.75g of (P-1), 75.00g of (H-1), 37.50g of HX-220, 3.68g of NCI-831, and 0.08g of BYK333, thereby obtaining (PB-19), a cured product thereof, and an organic EL display device having the cured product.
Examples 20 to 23
By the same method as in example 19, the hydroxyl group-containing resins (H-2) to (H-5) were charged, and (PB-20) to (PB-23) and cured products thereof, and an organic EL display device comprising these cured products were obtained.
Examples 24 to 31
By the same method as in example 19, the pigment dispersion liquid to be charged was (DB-9) to (DB-16), the alkali-soluble resin was (P-2) to (P-9), and the hydroxyl group-containing resin was (H-5), whereby (PB-24) to (PB-31) and a cured product thereof, and an organic EL display device having the cured product were obtained, respectively.
Example 32
By the same method as in example 31, 30.00g of HX-220 and 7.50g of DPHA were used as the radical polymerizable compound, to obtain (PB-32), a cured product thereof, and an organic EL display device having the cured product.
Example 33
By the same method as in example 31, the fed radical polymerizable compound was made to be HX-220 of 22.50g and DPHA of 15.00g, whereby (PB-33) and a cured product thereof and an organic EL display device having the cured product were obtained.
Example 34
By the same method as in example 31, the fed radical polymerizable compound was changed to 18.75g of HX-220 and 18.75g of DPHA, whereby (PB-34) and a cured product thereof and an organic EL display device having the cured product were obtained.
Example 35
By the same method as in example 31, 37.50g of A-9300 (manufactured by Xinzhou chemical Co., ltd.) was used as the radical polymerizable compound to be charged, thereby obtaining (PB-35) and a cured product thereof, and an organic EL display device having the cured product.
Example 36
By the same method as in example 31, 18.75g of A-BPE-10 (manufactured by Xinzhou chemical Co., ltd.) and 18.75g of DPHA were used as the radical polymerizable compound to be charged, whereby (PB-36) and a cured product thereof and an organic EL display device comprising the cured product were obtained.
Example 37
By the same method as in example 31, 18.75g of BPE-900 and 18.75g of DPHA were used as the radical polymerizable compound, to obtain (PB-37) and a cured product thereof, and an organic EL display device comprising the cured product.
Example 38
By the same method as in example 31, 18.75g of BPE-1300N (manufactured by Xinzhou Chemicals Co., ltd.) and 18.75g of DPHA were used as the radical polymerizable compound to be charged, whereby (PB-38) and a cured product thereof and an organic EL display device comprising the cured product were obtained.
Example 39
A photosensitive composition (PB-39) and a cured product thereof, and an organic EL display device equipped with the cured product were obtained by adding 18.75g of a 20 wt% PGMEA solution of (P-1), 93.75g of a hydroxyl group-containing resin (H-1), 3.68g of Irgacure OXE-03, 11.25g of HX-220, 0.08g of "BYK" (registered trademark) 333, 37.5g of "snow tex" (registered trademark) ST-XS (manufactured by Nissan chemical Co., ltd.) as silica particles, and 214.99g of PGMEA to 120.00g of (DB-1) in the same manner as in example 1.
Example 40
By the same method as in example 39, 25.00g of "Organo silica sol" (registered trademark) MIBK-ST (manufactured by Nissan chemical Co., ltd.) and 49g of PGMA 227 were added as silica particles to obtain a photosensitive composition (PB-40), a cured product thereof, and an organic EL display device having the cured product.
Example 41
The photosensitive composition (PB-41) and its cured product were obtained by the same method as in example 40, and the type of silica particles added was "Organo silica sol" (registered trademark) CHO-ST-M (manufactured by Nissan chemical Co., ltd.), to thereby obtain an organic EL display device having the cured product.
Example 42
The photosensitive composition (PB-42) and its cured product were obtained by the same method as in example 40, and an organic EL display device comprising the cured product was obtained by setting the type of silica particles added to "Organo silica sol" (registered trademark) MIBK-ST-L (manufactured by Nissan chemical Co., ltd.).
Example 43
By the same method as in example 40, 33.75g of (P-1), 105.00g of (H-1), 7.50g of MIBK-ST and 218.74g of PGMEA were charged to obtain (PB-43), a cured product thereof and an organic EL display device having the cured product.
Example 44
By the same method as in example 40, 30.00g of (P-1), 101.25g of (H-1), 12.50g of MIBK-ST and 221.24g of PGMEA were charged to obtain (PB-44) and a cured product thereof, and an organic EL display device having the cured product.
Example 45
By the same method as in example 40, 75.00g of (H-1), 7.500g of HX-220, 50.00g of MIBK-ST and 224.99g of PGMEA were charged to obtain (PB-45) and a cured product thereof, and an organic EL display device comprising the cured product.
Example 46
By the same method as in example 40, 56.25g of (H-1), 7.500g of HX-220, 62.50g of MIBK-ST and 231.24g of PGMEA were charged to obtain (PB-46), a cured product thereof and an organic EL display device having the cured product.
Comparative example 1
By the same method as in example 31, 37.50g of DPHA was used as a radical polymerizable compound, and (PB-47) and a cured product thereof and an organic EL display device having the cured product were obtained.
Comparative example 2
By the same method as in example 31, the charged radical polymerizable compound was set to 37.50g of BPE-1300N, whereby (PB-48) and a cured product thereof and an organic EL display device having the cured product were obtained.
The composition of the black pigment dispersion is shown in table 1. The compositions of examples and comparative examples are shown in tables 2 and 4, and the evaluation results thereof are shown in tables 3 and 5.
TABLE 1
As a result of the photosensitive composition described in the examples, the pattern linearity was excellent, the residue at the edge was small, the mask bias was small, and the occurrence frequency of non-lit pixels in an organic EL display device using the cured product was low, while having both high light shielding properties and sensitivity.
On the other hand, as a result of the photosensitive composition of comparative example 1, the photosensitive composition of comparative example 1 had a small equivalent amount of double bonds in the solid content, and the photocuring of the exposed portion was excessively performed, so that the linearity of the pattern edge portion was deteriorated, and the layer excessively cured on the film surface was peeled off by development, and residues were generated at the pattern edge portion. Further, as a result of the photosensitive composition described in comparative example 2, since the double bond equivalent in the solid content is large and the crosslinking density in the exposed portion is insufficient, the thin line processability is poor and pattern peeling is likely to occur.
Description of the reference numerals
1: Alkali-free glass substrate
2: First electrode (transparent electrode)
3: Auxiliary electrode
4: Insulating layer
5: Organic EL layer
6: Second electrode (non-transparent electrode)

Claims (16)

1. A photosensitive composition comprising all of the following components (a) to (d), wherein the double bond equivalent of the solid component in the photosensitive composition is 1000 to 3500g/mol,
(A) The components are as follows: a black pigment;
(b) The components are as follows: an alkali-soluble resin;
(c) The components are as follows: a radical polymerizable compound;
(d) The components are as follows: a photopolymerization initiator.
2. The photosensitive composition according to claim 1, wherein the component (c) comprises the following component (c-1),
(C-1) component: a radically polymerizable compound having 2 ethylenically unsaturated bonds in the molecule and having a double bond equivalent of 200 to 600 g/mol.
3. The photosensitive composition according to claim 2, wherein the content of the component (c-1) is 60 to 100% by weight based on the component (c).
4. The photosensitive composition according to claim 1, wherein the component (b) contains the following component (b-1),
(B-1) component: an alkali-soluble resin having an amine value of 2.0 to 10.0 mgKOH/g.
5. The photosensitive composition according to claim 4, wherein the component (b-1) comprises a structural unit represented by the formula (1) and/or a structural unit represented by the formula (2) and a structural unit represented by the formula (3),
[ Chemical formula 1]
[ Chemical formula 2]
[ Chemical formula 3]
In the formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents any one selected from an alkylene group having 1 to 4 carbon atoms, a 2-valent alkyleneoxy alkylene group having 2 to 4 carbon atoms, a 2-valent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a 2-valent aromatic hydrocarbon group having 6 to 10 carbon atoms, and R 3 and R 4 each independently represent any one selected from an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms;
In the formula (2), R 5 represents a hydrogen atom or a methyl group, R 6 represents any one selected from an alkylene group having 1 to 4 carbon atoms, a 2-valent alkyleneoxy alkylene group having 2 to 4 carbon atoms, a 2-valent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a 2-valent aromatic hydrocarbon group having 6 to 10 carbon atoms, and R 7、R8 and R 9 are each independently selected from any one selected from an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and X represents any one selected from a bromine atom, a chlorine atom, an iodine atom, a hydrogen sulfate, and a hydroxide;
In the formula (3), R 10 and R 11 each independently represent a hydrogen atom or a methyl group, and R 12 represents any one selected from an alkylene group having 1 to 4 carbon atoms, a 2-valent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a 2-valent aromatic hydrocarbon group having 6 to 10 carbon atoms.
6. The photosensitive composition according to any one of claims 1 to 5, wherein the component (b) contains the following component (b-2),
(B-2) component: a resin having a hydroxyl value of 60mgKOH/g or more and not having a structural unit represented by the formula (1) and a structural unit represented by the formula (2).
7. The photosensitive composition according to claim 6, wherein the weight ratio W b-1/Wb-2 of the (b-1) component to the (b-2) component is 0.2 to 1.5.
8. The photosensitive composition according to any one of claims 1 to 5, wherein the component (d) contains an oxime ester photopolymerization initiator having a fluorine atom in a molecule.
9. The photosensitive composition according to any one of claims 1 to 5, wherein the component (a) contains at least 1 compound selected from the group consisting of a compound represented by the formula (4), a compound represented by the formula (5), and isomers thereof,
[ Chemical formula 4]
In the formula (4) and the formula (5), R 13 and R 18 each independently represent a hydrogen atom, CH 3、CF3, or a fluorine atom; r 14、R15、R16、R17、R19、R20、R21 and R 22 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, a cycloalkenyl group having 1 to 12 carbon atoms, an alkynyl group 、COOH、COOR23、COO-、CONH2、CONHR23、CONR23R24、CN、OH、OR23、OCOR23、OCONH2、OCONHR23、OCONR23R24;R23 having 1 to 12 carbon atoms, and R 24 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, a cycloalkenyl group having 1 to 12 carbon atoms, or an alkynyl group having 1 to 12 carbon atoms.
10. The photosensitive composition according to any one of claims 1 to 5, wherein a 50% cumulative diameter in a volume-based particle size distribution of the particle components in the photosensitive composition measured by a dynamic light scattering method is 20 to 60nm.
11. The photosensitive composition according to any one of claims 1 to 5, further comprising the following component (e),
(E) The components are as follows: silica particles.
12. The photosensitive composition according to claim 11, wherein the average primary particle diameter of the component (e) is 10 to 30nm.
13. The photosensitive composition according to claim 11, wherein the weight ratio W e/Wb-1 of the (e) component to the (b-1) component is 0.5 to 2.0.
14. The photosensitive composition according to claim 11, which comprises the following component (b-2), wherein the weight ratio W e/Wb-2 of the component (e) to the component (b-2) is 0.15 to 1.0,
(B-2) component: a resin having a hydroxyl value of 60mgKOH/g or more and not having a structural unit represented by the formula (1) and a structural unit represented by the formula (2).
15. A cured product obtained by curing the photosensitive composition according to any one of claims 1 to 5.
16. An organic EL display device comprising the cured product according to claim 15.
CN202280058174.6A 2021-09-29 2022-09-21 Photosensitive composition, cured product, and organic EL display device Pending CN117916664A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2021158864 2021-09-29
JP2021-158864 2021-09-29
PCT/JP2022/035171 WO2023054118A1 (en) 2021-09-29 2022-09-21 Photosensitive composition, cured object, and organic-el display device

Publications (1)

Publication Number Publication Date
CN117916664A true CN117916664A (en) 2024-04-19

Family

ID=85780663

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202280058174.6A Pending CN117916664A (en) 2021-09-29 2022-09-21 Photosensitive composition, cured product, and organic EL display device

Country Status (4)

Country Link
JP (1) JPWO2023054118A1 (en)
KR (1) KR20240063852A (en)
CN (1) CN117916664A (en)
WO (1) WO2023054118A1 (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4597830B2 (en) * 2005-09-27 2010-12-15 東京応化工業株式会社 Photosensitive resin composition for forming functional pattern and method for forming functional pattern
KR102210576B1 (en) * 2013-09-25 2021-02-01 미쯔비시 케미컬 주식회사 Photosensitive coloring composition, black matrix, coloring spacer, image display device, and pigment dispersion
JP2015151530A (en) * 2014-02-19 2015-08-24 富士フイルム株式会社 Composite and production method of the same, colored composition, cured film, color filter, production method of color filter, solid state imaging element, and image display device, as well as laminate
KR102492113B1 (en) 2016-09-30 2023-01-25 도레이 카부시키가이샤 Negative photosensitive resin composition, cured film, element and display device provided with cured film, and manufacturing method thereof
KR20240172762A (en) 2016-12-02 2024-12-10 미쯔비시 케미컬 주식회사 Colored photosensitive resin composition, pigment dispersion, partition, organic electroluminescent element, image display device, and illumination
JPWO2018173570A1 (en) * 2017-03-24 2020-05-14 富士フイルム株式会社 Photosensitive coloring composition, cured film, color filter, solid-state imaging device and image display device
JP7508231B2 (en) * 2020-01-30 2024-07-01 株式会社Ｄｎｐファインケミカル Photosensitive colored resin composition, cured product, color filter, display device
JP7423646B2 (en) * 2019-09-26 2024-01-29 富士フイルム株式会社 Curable compositions, cured films, color filters, solid-state imaging devices, and image display devices

Also Published As

Publication number Publication date
KR20240063852A (en) 2024-05-10
JPWO2023054118A1 (en) 2023-04-06
WO2023054118A1 (en) 2023-04-06

Similar Documents

Publication Publication Date Title
US10338468B2 (en) Photosensitive resin composition, photosensitive resin laminate, resin pattern production method, cured film, and display device
KR101787651B1 (en) Akali-developable photosensitive resin composition, and barrier for display element formed by using the same, and display element
WO2019065902A1 (en) Photosensitive resin composition, cured film, element having cured film, organic el display, and method for manufacturing organic el display
KR101746606B1 (en) Positive-type photosensitive resin composition, method for manufacturing cured film, cured film, organic el display device, and liquid crystal display device
TW201841983A (en) Photosensitive resin composition, cured film, element equipped with cured film, organic el display device equipped with cured film, cured film production method, and organic el display device production method
CN103765314B (en) Negative light-sensitive resin combination, partition wall and optical element
KR20160065917A (en) Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device
KR102329943B1 (en) Negative photosensitive resin composition and photo-cured pattern prepared from the same
CN104271642B (en) Partial hydrolysis condensate, refuse ink agent, negative light-sensitive resin combination, cured film, partition wall and optical element
JP2011027842A (en) Positive photosensitive resin composition, cured film, interlayer dielectric, organic el display device and liquid crystal display device
WO2013161942A1 (en) Production method for permanent film for optical material, cured film produced thereby, and organic el display device and liquid-crystal display device using same
CN103890128A (en) Method for manufacturing ink-repellent agent, negative-type photosensitive resin composition, partition wall, and optical device
CN112889002A (en) Photosensitive resin composition, cured film, and display device using the cured film
KR20170113390A (en) Photosensitive resin composition for light-shielding film, display substrate having the light-shielding film obtained by curing the same, and manufacturing method of display substrate
JP5180765B2 (en) Alkali-developable photosensitive resin composition, display element partition and display element formed using the same
JP2011064869A (en) Photosensitive resin composition, method for forming cured film, cured film, organic el display device and liquid crystal display device
JP5108300B2 (en) Photosensitive resin composition and color filter using the same
TW201137517A (en) Radiation-sensitive composition, insulation film formation method, insulation film and solid photographic component
CN106959576A (en) Photosensitive composite and its application
KR102300328B1 (en) A black colored photosensitive resin composition and display device produced using the same
JP5334755B2 (en) Photosensitive resin composition, cured film, method for forming cured film, organic EL display device, and liquid crystal display device
CN117916664A (en) Photosensitive composition, cured product, and organic EL display device
JP3893587B2 (en) Photopolymerizable unsaturated resin, process for producing the same, and alkali-soluble radiation-sensitive resin composition using the same
JP2022038599A (en) Negative photosensitive resin composition, cured film and organic EL display device
JP2024077069A (en) Photosensitive composition, cured product, and organic el display device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination