CN116323716A - Photosensitive coloring composition, cured product, organic electroluminescent element, and image display device - Google Patents

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

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Publication number
CN116323716A
CN116323716A CN202180064110.2A CN202180064110A CN116323716A CN 116323716 A CN116323716 A CN 116323716A CN 202180064110 A CN202180064110 A CN 202180064110A CN 116323716 A CN116323716 A CN 116323716A
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mass
coloring composition
photosensitive coloring
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泽井良尚
力武信夫
三岛康太郎
宫下贺子
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Mitsubishi Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
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    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
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    • C09B57/02—Coumarine dyes
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    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
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    • C09B67/006—Preparation of organic pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
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Abstract

A photosensitive coloring composition which rarely causes surface roughness of an electrode after heat treatment is provided. The photosensitive coloring composition is characterized by comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant, wherein the (a) colorant comprises a compound represented by a specific general formula (I), a geometric isomer of the compound, a salt of the compound, or a salt of the geometric isomer of the compound, and the (f) dispersant comprises an acrylic copolymer (f 1), the acrylic copolymer (f 1) comprises a repeating unit represented by specific general formulae (1), (2), and (3) and does not have a repeating unit comprising a quaternary ammonium group, and the content of chlorine atoms in the photosensitive coloring composition is 0.05 mass% or less relative to the total solid component amount of the photosensitive coloring composition.

Description

Photosensitive coloring composition, cured product, organic electroluminescent element, and image display device
Technical Field
The invention relates to a photosensitive coloring composition, a cured product, an organic electroluminescent element and an image display device.
The present application claims priority from japanese patent application nos. 2020-162460 and 2021, 2 and 18, which are filed in japan, based on 28, 9, 2020, and 2021, 024490, the contents of which are incorporated herein by reference.
Background
A Liquid Crystal Display (LCD) uses the property that the arrangement of liquid crystal molecules is switched according to the on/off voltage of liquid crystal. The members constituting the case of the LCD are often formed by a method using a photosensitive composition, typically photolithography. The photosensitive composition is easy to form a fine structure, and is easy to process for a substrate for large-screen use, and for these reasons, its application range is expanding further.
Image display devices including organic electroluminescent elements (also referred to as organic electroluminescence and organic el) are attracting attention as next-generation Flat Panel Displays (FPDs) because of their excellent visual visibility and responsiveness, low power consumption, thin and lightweight, and flexibility in display main bodies.
The organic electroluminescent element has the following structure: an organic layer including a light-emitting layer or various functional layers is sandwiched between a pair of electrodes at least one of which has light transmittance. The image display device performs image display by driving a panel in which an organic electroluminescent element is disposed at each pixel.
Conventionally, such an organic electroluminescent element is manufactured by forming partition walls (banks) on a substrate, and then laminating a light-emitting layer or various functional layers in a region surrounded by the partition walls.
When a light-emitting layer is formed in a region surrounded by a partition wall, the following vapor deposition method is mainly used: the material is sublimated in a vacuum state and attached to the substrate, thereby forming a film.
In addition, in recent years, a method of forming a film by a wet process such as a casting method, a spin coating method, or an inkjet printing method has been attracting attention. In particular, the inkjet printing method is suitable as a method for forming an organic layer in a large panel because it is capable of reducing film thickness unevenness when a large area is formed, and achieving high definition of a display, reduction in material consumption, and improvement in yield by separate coating at the time of coating.
As a method for easily forming the partition wall, a method of forming the partition wall by photolithography using a photosensitive composition is known. In addition, as a method for imparting light-shielding property to the partition wall and suppressing light leakage between pixels, a method of adding a colorant to a photosensitive composition is known.
Patent document 1 describes a colored photosensitive resin composition that suppresses the generation of an evolved gas by using a specific organic black pigment and an alkali-soluble resin.
Prior art literature
Patent literature
Patent document 1 International publication No. 2018/101314
Disclosure of Invention
Problems to be solved by the invention
In the organic electroluminescent element, there are panel forms of a top emission type and a bottom emission type. In the case of top emission, a reflective electrode such as silver is used as an electrode and a cured product such as a partition wall is formed thereon, and during the heat treatment, the components in the photosensitive composition act, and corrosion, migration, and the like of the metal electrode may occur. When irregularities (hereinafter also referred to as surface roughness) are generated on the electrode surface, the light-emitting layer cannot be uniformly formed in the surface, and display defects due to short circuits or the like may occur when the organic electroluminescent element is manufactured.
The present inventors have studied and found that the colored photosensitive resin composition described in patent document 1 causes roughness of the surface of an electrode, which is practically problematic.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive coloring composition which rarely causes surface roughness in an electrode after heat treatment, and to provide an organic light-emitting element and an image display device which are free from display defects and have high reliability.
Solution for solving the problem
As a result of intensive studies, the present inventors have found that the above problems can be solved by using a specific dispersant and a specific colorant, and have completed the present invention.
Namely, the gist of the present invention is as follows.
[1] A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant,
the colorant of the above (a) contains at least 1 selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the above compound, a salt of the above compound and a salt of the geometric isomer of the above compound,
the dispersant (f) contains an acrylic copolymer (f 1), the acrylic copolymer (f 1) contains at least a repeating unit represented by the following general formulae (1), (2) and (3) and does not contain a repeating unit containing a quaternary ammonium group,
the content of chlorine atoms in the photosensitive coloring composition is 0.05 mass% or less relative to the total solid component content of the photosensitive coloring composition.
Figure BDA0004133603210000031
(in the formula (I), R 1 And R is 6 Independently of one another, are hydrogenAtomic, CH 3 、CF 3 A fluorine atom or a chlorine atom,
R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 and R is 10 Independently of the others, are hydrogen atoms, halogen atoms, R 11 、COOH、COOR 11 、COO - 、CONH 2 、CONHR 11 、CONR 11 R 12 、CN、OH、OR 11 、COCR 11 、OOCNH 2 、OOCNHR 11 、OOCNR 11 R 12 、NO 2 、NH 2 、NHR 11 、NR 11 R 12 、NHCOR 12 、NR 11 COR 12 、N＝CH 2 、N＝CHR 11 、N＝CR 11 R 12 、SH、SR 11 、SOR 11 、SO 2 R 11 、SO 3 R 11 、SO 3 H、SO 3 - 、SO 2 NH 2 、SO 2 NHR 11 Or SO 2 NR 11 R 12 ，
Selected from R 2 And R is R 3 、R 3 And R is R 4 、R 4 And R is R 5 、R 7 And R is R 8 、R 8 And R is R 9 And R is 9 And R is R 10 At least 1 of the combinations of the group consisting are also optionally directly bonded to each other or through an oxygen atom, a sulfur atom, NH or NR 11 The bridges are bonded to each other and,
R 11 and R is 12 Independently of each other, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms. )
Figure BDA0004133603210000041
(in the formula (1), R 31 Is an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group,
R 32 is a hydrogen atom or a methyl group,
and represents a connecting bond. )
Figure BDA0004133603210000042
(in the formula (2), R 33 Is methylene, ethylene or propylene, R 34 Is optionally substituted alkyl, R 35 Is a hydrogen atom or a methyl group,
n is an integer of 1 to 20,
and represents a connecting bond. )
Figure BDA0004133603210000051
(in the formula (3), R 36 And R is 37 Each independently is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, R 36 And R is R 37 Optionally bonded to each other to form a cyclic structure,
R 38 is a hydrogen atom or a methyl group,
z is a 2-valent linking group,
and represents a connecting bond. )
[2] The photosensitive coloring composition according to [1], wherein the colorant (a) contains an organic coloring pigment.
[3] A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant,
The optical density of the coating film obtained by curing the photosensitive coloring composition is more than 0.5 per 1 mu m film thickness,
the dispersant (f) contains an acrylic copolymer (f 1), the acrylic copolymer (f 1) contains at least a repeating unit represented by the following general formulae (1), (2) and (3) and does not contain a repeating unit containing a quaternary ammonium group,
the content of chlorine atoms in the photosensitive coloring composition is 0.05 mass% or less relative to the total solid component content of the photosensitive coloring composition.
Figure BDA0004133603210000052
(in the formula (1), R 31 Is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group.
R 32 Is a hydrogen atom or a methyl group.
And represents a connecting bond. )
Figure BDA0004133603210000061
(in the formula (2), R 33 Is methylene, ethylene or propylene, R 34 Is optionally substituted alkyl, R 35 Is a hydrogen atom or a methyl group.
n is an integer of 1 to 20.
And represents a connecting bond. )
Figure BDA0004133603210000062
(in the formula (3), R 36 And R is 37 Each independently is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, R 36 And R is R 37 Optionally bonded to each other to form a cyclic structure.
R 38 Is a hydrogen atom or a methyl group.
Z is a 2-valent linking group.
And represents a connecting bond. )
[4] The photosensitive coloring composition according to [3], wherein the colorant (a) contains at least 1 selected from the group consisting of red pigments and orange pigments and contains at least 1 selected from the group consisting of blue pigments and violet pigments.
[5] The photosensitive coloring composition according to any one of [1] to [4], wherein the acrylic copolymer (f 1) is a block copolymer.
[6] The photosensitive coloring composition according to any one of [1] to [5], wherein the amine value of the acrylic copolymer (f 1) is 90mgKOH/g or more.
[7] The photosensitive coloring composition according to any one of [1] to [6], wherein the colorant (a) is contained in an amount of 10% by mass or more relative to the total solid content of the photosensitive coloring composition.
[8] The photosensitive coloring composition according to any one of [1] to [7], which is used for forming a partition wall of an organic electroluminescent element.
[9] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [8 ].
[10] An organic electroluminescent element comprising the cured product according to [9 ].
[11] An image display device comprising the organic electroluminescent element described in [10 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a photosensitive coloring composition in which surface roughness of an electrode is less likely to occur after heat treatment can be provided.
Detailed Description
The embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments and can be variously modified and implemented within the scope of the gist thereof.
In the present invention, "(meth) acrylic" means "acrylic and/or methacrylic", "(meth) acrylate", "(meth) acryl" as well.
The term "(co) polymer" is meant to include both homopolymers and copolymers, and the term "acid (anhydride)" and "acid (anhydrous) … acid" are meant to include both acids and their anhydrides.
In the present invention, the "acrylic resin" refers to a (co) polymer containing (meth) acrylic acid or a (co) polymer containing (meth) acrylic acid ester having a carboxyl group.
In the present invention, "monomer" is a term for a so-called high molecular substance (polymer) and includes a dimer, a trimer, and an oligomer in addition to a monomer (monomer) in a narrow sense.
In the present invention, the "total solid component amount" refers to the total component amount excluding the solvent contained in the photosensitive coloring composition or the pigment dispersion. The components other than the solvent may be liquid at ordinary temperature, and the components are not included in the solvent but in the total solid component amount.
In the present invention, the term "weight average molecular weight" means a weight average molecular weight (Mw) in terms of polystyrene obtained by GPC (gel permeation chromatography).
In the present invention, unless otherwise specified, the term "amine value" means an amine value in terms of an effective solid content, and is a value expressed by mass of KOH corresponding to the amount of alkali per 1g of the solid content of the dispersant. In addition, the measurement method will be described later. The "acid value" means an acid value in terms of an effective solid content, calculated by neutralization titration unless otherwise specified.
With respect to pigments, "c.i." refers to the dye Index (Color Index).
In the present specification, the percentages and parts expressed by "mass" are the same as the percentages and parts expressed by "weight".
[ photosensitive coloring composition ]
The photosensitive coloring composition of the present invention comprises:
(a) Coloring agent
(b) Alkali-soluble resin
(c) Photopolymerization initiator
(d) Olefinically unsaturated compounds
(e) Solvent(s)
(f) The dispersant is used as an essential component.
As the first embodiment, at least 1 selected from the group consisting of the compound represented by the general formula (I), a geometric isomer of the compound represented by the general formula (I), a salt of the compound represented by the general formula (I), and a salt of a geometric isomer of the compound represented by the general formula (I) is contained as the (a) colorant.
As a second aspect, the optical density of the coating film obtained by curing the photosensitive coloring composition of the present invention is 0.5 or more per 1 μm film thickness.
Further, if necessary, an adhesion improver such as a silane coupling agent, a surfactant, a pigment derivative, a photoacid generator, a crosslinking agent, a mercapto compound, a polymerization inhibitor, and other compounding ingredients are contained, and each compounding ingredient is usually used in a state of being dissolved or dispersed in a solvent.
(a) colorant
The photosensitive coloring composition of the present invention contains (a) a colorant. By containing the colorant (a), a suitable light absorptivity can be obtained, and particularly, a suitable light-shielding property can be obtained when the colorant is used for forming a light-shielding member such as a partition wall.
In the first embodiment, at least 1 selected from the group consisting of the compound represented by the general formula (I), a geometric isomer of the compound represented by the general formula (I), a salt of the compound represented by the general formula (I), and a salt of a geometric isomer of the compound represented by the general formula (I) is contained as the (a) colorant.
The compound represented by the general formula (I) (hereinafter also referred to as "compound (I)") is an organic black pigment. It is presumed that by having a rigid skeleton containing an aromatic ring, chlorine-containing gas generated during heat treatment is less likely to penetrate into the coating film. Further, since the ultraviolet transmittance is high, the photosensitive composition after application is easily photocured, and is useful in these respects.
Figure BDA0004133603210000091
In the formula (I), R 11 And R is 16 Each independently represents a hydrogen atom, CH 3 、CF 3 A fluorine atom or a chlorine atom;
R 12 、R 13 、R 14 、R 15 、R 17 、R 18 、R 19 and R is 20 Each independently represents a hydrogen atom, a halogen atom, R 21 、COOH、COOR 21 、COO - 、CONH 2 、CONHR 21 、CONR 21 R 22 、CN、OH、OR 21 、COCR 21 、OOCNH 2 、OOCNHR 21 、OOCNR 21 R 22 、NO 2 、NH 2 、NHR 21 、NR 21 R 22 、NHCOR 22 、NR 21 COR 22 、N＝CH 2 、N＝CHR 21 、N＝CR 21 R 22 、SH、SR 21 、SOR 21 、SO 2 R 21 、SO 3 R 21 、SO 3 H、SO 3 - 、SO 2 NH 2 、SO 2 NHR 21 Or SO 2 NR 21 R 22 ；
Selected from R 12 And R is R 13 、R 13 And R is R 14 、R 14 And R is R 15 、R 17 And R is R 18 、R 18 And R is R 19 And R is 19 And R is R 20 At least 1 combination of the group consisting of optionally directly bonded to each other or through an oxygen atom, a sulfur atom, NH or NR 21 The bridges are bonded to each other;
R 21 and R is 22 Each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms.
The geometric isomers of the compounds (I) and (I) have the following core structures (wherein substituents in the structural formula have been omitted), the trans-trans isomers being probably most stable.
Figure BDA0004133603210000101
When the compound (I) is anionic, it is preferably a salt in which the charge is compensated by any known suitable cation, for example, a metal, organic, inorganic or metal-organic cation, specifically, a quaternary ammonium or organic metal complex such as alkali metal, alkaline earth metal, transition metal, tertiary ammonium such as primary ammonium, secondary ammonium, trialkylammonium or tetraalkylammonium. In addition, when the geometric isomer of the compound (I) is anionic, the same salt is preferable.
The following substituents are preferred in the substituents of the general formula (I) and their definitions, from the viewpoint of having a tendency to improve the shielding rate. This is because the following substituents are not considered to be absorbed and do not affect the hue of the pigment.
R 12 、R 14 、R 15 、R 17 、R 19 And R is 20 Each independently is preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.
R 13 And R is 18 Each independently is preferably a hydrogen atom, NO 2 、OCH 3 、OC 2 H 5 Bromine atom, chlorine atom, CH 3 、C 2 H 5 、N(CH 3 ) 2 、N(CH 3 )(C 2 H 5 )、N(C 2 H 5 ) 2 Alpha-naphthyl, beta-naphthyl, SO 3 H or SO 3 - Further preferably a hydrogen atom or SO 3 H is particularly preferably a hydrogen atom.
R 11 And R is 16 Each independently is preferably a hydrogen atom, CH 3 Or CF (CF) 3 More preferably a hydrogen atom.
Preferably selected from R 11 And R is R 16 、R 12 And R is R 17 、R 13 And R is R 18 、R 14 And R is R 19 And R is 15 And R is R 20 At least 1 of the combinations in the group consisting are identical, more preferably R 11 And R is R 16 Identical, R 12 And R is R 17 Identical, R 13 And R is R 18 Identical, R 14 And R is R 19 Identical, and R 15 And R is R 20 The same applies.
The alkyl group having 1 to 12 carbon atoms is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, 2-pentyl, 3-pentyl, 2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1, 3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl or dodecyl.
Cycloalkyl having 3 to 12 carbon atoms is, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, biotyl (thujyl), norbornyl, bornyl, norcarayl (norcarayl), carayl (caryl), menthyl, norpinyl (Norpinyl), pinyl (pinyl), adamantan-1-yl or adamantan-2-yl.
Alkenyl having 2 to 12 carbon atoms is, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1, 3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1, 4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl or dodecenyl.
Cycloalkenyl having 3 to 12 carbon atoms is, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2, 4-cyclohexadien-1-yl, 1-p-menthen-8-yl, 4 (10) -bioten-10-yl, 2-norbornen-1-yl, 2, 5-norbornen-1-yl, 7-dimethyl-2, 4-norcaradien-3-yl or camphene.
Alkynyl having 2 to 12 carbon atoms is, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1, 4-pentadiyn-3-yl, 1, 3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1, 3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl or 1-dodecyn-12-yl.
The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The compound represented by the above general formula (I) is preferably a compound containing at least 1 selected from the group consisting of a compound represented by the following general formula (II) (hereinafter also referred to as "compound (II)") and a geometric isomer of the compound (II).
Figure BDA0004133603210000121
Examples of such a compound include Irgaphor (registered trademark) Black S0100 CF (manufactured by BASF corporation).
The organic black pigment is preferably used after being dispersed by a method described later. Further, if there is a sulfonic acid derivative of the compound (I) or a sulfonic acid derivative of a geometric isomer of the compound (I), particularly a sulfonic acid derivative of the compound (II) or a sulfonic acid derivative of a geometric isomer of the compound (II) at the time of dispersion, dispersibility and preservability may be improved.
In the first embodiment of the present invention, the colorant (a) may contain other colorants in addition to the compound of the general formula (I). As the other colorant, a pigment is preferable, and the pigment may be an organic pigment or an inorganic pigment. From the viewpoints of high resistance and low dielectric constant, organic pigments are more preferable, and in particular, organic coloring pigments described later are more preferable.
Among the organic coloring pigments, the compound (I) and the blue pigment are preferably used from the viewpoint of making the transmittance in the high wavelength region of the visible light region more uniform. Pigment blue B60, 15: 6. 16, pigment blue B60 is more preferred.
On the other hand, from the viewpoint of making the transmittance in the entire visible light region more uniform, it is preferable to use at least 1 selected from the group consisting of red pigments and orange pigments and at least 1 selected from the group consisting of blue pigments and violet pigments in addition to the compound (I).
In the second aspect, the optical density (hereinafter, sometimes referred to as "OD per unit film thickness") of the coating film obtained by curing the photosensitive coloring composition of the present invention per 1 μm film thickness is 0.5 or more. By containing the colorant (a) and setting the OD per unit film thickness to the above lower limit or more, the light-shielding properties of the resulting cured product, particularly the barrier ribs, are improved.
The OD per unit film thickness can be calculated by measuring the optical density and film thickness of a coating film obtained by curing the photosensitive coloring composition and dividing the optical density by the film thickness. The conditions for producing the coating film are not particularly limited, and for example, the conditions described in examples below can be employed.
In order to set the OD per unit film thickness to the above lower limit value or more, for example, the type of the colorant (a) and the content ratio in the total solid component amount may be appropriately adjusted.
In the second aspect of the present invention, the type of the colorant (a) that can be used in the photosensitive coloring composition is not particularly limited, and pigments or dyes may be used. Among these, pigments are preferably used from the viewpoint of durability.
(a) The number of pigments contained in the colorant may be 1 or 2 or more. In particular, 2 or more types are preferable from the viewpoint of achieving both uniform light shielding in the visible region and OD per unit film thickness.
The type of pigment that can be used as the colorant (a) is not particularly limited, and examples thereof include organic coloring pigments and black pigments. The organic coloring pigment herein means an organic pigment exhibiting a color other than black, and examples thereof include a red pigment, an orange pigment, a blue pigment, a violet pigment, a green pigment, and a yellow pigment.
Among pigments, organic coloring pigments are preferably used from the viewpoints of high resistance and low dielectric constant. In addition, from the viewpoint of light-shielding properties, the compound (I) or another black pigment is preferably used.
The organic coloring pigment may be used alone or in combination of 1 or more than 2. In particular, from the viewpoint of having an OD per unit film thickness of 0.5 or more, it is more preferable to use a combination of organic coloring pigments having different colors, and it is still more preferable to use a combination of organic coloring pigments exhibiting colors close to black.
The chemical structure of these organic coloring pigments is not particularly limited, and examples thereof include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, perylene-based, and the like. Specific examples of usable pigments are shown below by pigment index numbers. The "c.i." in "c.i. pigment red 2" and the like listed below means the dye Index (Color Index).
Examples of the red pigment include c.i. pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48: 1. 48: 2. 48: 3. 48: 4. 49, 49: 1. 49: 2. 50: 1. 52: 1. 52: 2. 53, 53: 1. 53: 2. 53: 3. 57, 57: 1. 57: 2. 58: 4. 60, 63: 1. 63: 2. 64, 64: 1. 68, 69, 81: 1. 81: 2. 81: 3. 81: 4. 83, 88, 90: 1. 101, 101: 1. 104, 108: 1. 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. From the viewpoints of light-shielding property and dispersibility, c.i. pigment red 48: 1. 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, c.i. pigment red 177, 209, 224, 254 may be further preferably enumerated. From the viewpoints of dispersibility and light-shielding properties, c.i. pigment red 177, 254, 272 are preferable, and when the photosensitive coloring composition is cured by ultraviolet rays, the red pigment is preferably a low ultraviolet absorption, and from this viewpoint, c.i. pigment red 254, 272 are more preferable.
Examples of orange (orange) pigments include c.i. pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. From the viewpoints of dispersibility and light-shielding properties, c.i. pigment orange 13, 43, 64, and 72 are preferable, and when the photosensitive coloring composition is cured by ultraviolet rays, an orange pigment having low ultraviolet absorptivity is preferable, and from this viewpoint, c.i. pigment orange 64 and 72 are more preferable.
Examples of the blue pigment include c.i. pigment blue 1 and 1: 2. 9, 14, 15: 1. 15: 2. 15: 3. 15: 4. 15:6. 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56: 1. 60, 61: 1. 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. From the viewpoint of light-shielding properties, c.i. pigment blue 15, 15: 1. 15: 2. 15: 3. 15: 4. 15:6. 60, c.i. pigment blue 15:6. from the viewpoints of dispersibility and light-shielding properties, c.i. pigment blue 15:6. 16, 60, when the photosensitive coloring composition is cured by ultraviolet rays, the blue pigment is preferably one having low ultraviolet absorptivity, and from this point of view, c.i. pigment blue 60 is more preferred.
Examples of violet pigments include c.i. pigment violet 1, 1: 1. 2, 2: 2. 3, 3: 1. 3: 3. 5, 5: 1. 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. From the viewpoint of light-shielding properties, c.i. pigment violet 19, 23, 29 are preferable, and c.i. pigment violet 23 is more preferable. From the viewpoints of dispersibility and light-shielding properties, c.i. pigment violet 23 and c.i. pigment violet 29 are preferable, and from the viewpoint of low ultraviolet absorptivity, c.i. pigment violet 29 is more preferable when the photosensitive coloring composition is cured with ultraviolet rays.
Examples of the green pigment include c.i. pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59. C.i. pigment green 7, 36 can be preferably cited.
Examples of the yellow pigment include c.i. pigment yellow 1, 1: 1. 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35: 1. 36, 36: 1. 37, 37: 1. 40, 41, 42, 43, 48, 53, 55, 61, 62: 1. 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127: 1. 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191). 1. 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208. C.i. pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 may be preferably cited, and c.i. pigment yellow 83, 138, 139, 150, 180 may be more preferably cited.
From the viewpoints of light-shielding properties of the cured product and control of the shape and height difference, at least 1 selected from the group consisting of red pigment, orange pigment, blue pigment and violet pigment is preferable.
From the viewpoint of light-shielding properties of the cured product and control of the shape and height difference, it is preferable to contain at least 1 or more of the following pigments.
Red pigment: c.i. pigment red 177, 254, 272
Orange pigment: c.i. pigment orange 43, 64, 72
Blue pigment: c.i. pigment blue 15: 6. 60 (60)
Violet pigment: c.i. pigment violet 23, 29
The combination of the organic coloring pigments when 2 or more organic coloring pigments are used in combination is not particularly limited, and from the viewpoint of light-shielding properties, it is preferable to use at least 1 selected from the group consisting of red pigments and orange pigments and at least 1 selected from the group consisting of blue pigments and violet pigments in combination.
The combination of colors is not particularly limited, and examples thereof include a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment and an orange pigment and a violet pigment from the viewpoint of light-shielding properties.
Organic coloring pigments, organic black pigments other than the organic black pigment represented by the general formula (I), and inorganic black pigments can be used.
Examples of the organic black pigment other than the organic black pigment represented by the general formula (I) include aniline black and perylene black.
Examples of the inorganic black pigment include inorganic black pigments described in International publication No. 2018/101314.
When these colorants are used, the amount of chlorine atoms contained in the colorants may be adjusted so as to avoid excessively increasing the amount of chlorine.
These pigments are preferably used in such a manner that the average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less. The average particle diameter is referred to herein as the number of pigment particles.
In the photosensitive coloring composition of the present invention, the average particle diameter of the pigment is a value obtained from the particle diameter of the pigment measured by Dynamic Light Scattering (DLS). Particle diameter measurement is performed on a photosensitive coloring composition after sufficient dilution (usually, the pigment concentration is adjusted to about 0.005 to 0.2 mass% by dilution, however, if the recommended concentration is present in the measurement equipment, the measurement is performed at 25 ℃.
In the photosensitive coloring composition according to the second aspect of the present invention, 1 kind of colorant such as an organic coloring pigment or a black pigment may be used alone or 2 or more kinds may be used in combination.
In addition to the above-mentioned organic coloring pigments and black pigments, dyes may also be used. Examples of dyes that can be used as the colorant include dyes described in International publication No. 2018/101314.
Alkali-soluble resin
The alkali-soluble resin (b) used in the present invention is not particularly limited as long as it contains a carboxyl group or a hydroxyl group, and examples thereof include epoxy (meth) acrylate resins, acrylic resins, carboxyl group-containing epoxy resins, carboxyl group-containing urethane resins, novolak resins, and polyvinyl phenol resins. Among them, from the viewpoint of excellent platemaking properties, it is preferable to use:
(b1) Epoxy (meth) acrylate resin
(b2) Acrylic copolymer resin.
These may be used singly or in combination of 1 or more than 2.
(b 1) epoxy (meth) acrylate-based resin
(b1) The epoxy (meth) acrylate resin is: a resin obtained by reacting an epoxy compound (epoxy resin) with an α, β -unsaturated monocarboxylic acid and/or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group in an ester moiety, and further reacting the resultant hydroxyl group with a compound having 2 or more substituents capable of reacting with a hydroxyl group, such as a polybasic acid and/or an acid anhydride thereof.
The resin obtained by reacting a polybasic acid and/or an acid anhydride thereof with a hydroxyl group before reacting the polybasic acid and/or an acid anhydride thereof with the hydroxyl group, and then reacting the polybasic acid and/or an acid anhydride thereof with a compound having 2 or more substituents capable of reacting with the hydroxyl group is also included in the (b 1) epoxy (meth) acrylate resin.
The resin obtained by further reacting the carboxyl group of the resin obtained by the above reaction with a compound having a functional group capable of reacting is also included in the (b 1) epoxy (meth) acrylate resin.
As described above, the epoxy (meth) acrylate resin has substantially no epoxy group in chemical structure and is not limited to "(meth) acrylate", but is named as usual since an epoxy compound (epoxy resin) is used as a raw material and "(meth) acrylate" is used as a representative example.
As the (b 1) epoxy (meth) acrylate resin used in the present invention, the following epoxy (meth) acrylate resin (b 1-1) and/or epoxy (meth) acrylate resin (b 1-2) (hereinafter, sometimes referred to as "carboxyl group-containing epoxy (meth) acrylate resin") are particularly preferably used from the viewpoints of developability and reliability.
In addition, as the (b 1) epoxy (meth) acrylate resin, one having an aromatic ring in the main chain can be more preferably used from the viewpoint of the evolved gas.
< epoxy (meth) acrylate-based resin (b 1-1) >)
An alkali-soluble resin obtained by adding an α, β -unsaturated monocarboxylic acid or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and optionally reacting an isocyanate group-containing compound, and then further reacting a polybasic acid and/or an acid anhydride thereof.
< epoxy (meth) acrylate-based resin (b 1-2) >)
An alkali-soluble resin obtained by adding an α, β -unsaturated monocarboxylic acid or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and optionally reacting an isocyanate group-containing compound, and then further reacting a polyhydric alcohol with a polybasic acid and/or an acid anhydride thereof.
The epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin may be appropriately selected from known epoxy resins. The epoxy resin may be a compound obtained by reacting a phenol compound with an epihalohydrin. The phenol compound is preferably a compound having a phenolic hydroxyl group of 2 or more members, and may be a monomer or a polymer.
As the type of the epoxy resin to be used as the raw material, for example, cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, triphenol methane type epoxy resin, biphenyl novolak type epoxy resin, naphthol novolak type epoxy resin, epoxy resin which is a reaction product of dicyclopentadiene and phenol or cresol addition polymerization product with epihalohydrin, adamantyl-containing epoxy resin, fluorene type epoxy resin, and the one having an aromatic ring in the main chain can be preferably used.
As the epoxy resin, for example, 828 of bisphenol A type epoxy resin (for example, "jER (registered trademark, the same applies hereinafter), jER-1001", "jER-1002", "jER-1004", etc. manufactured by Mitsubishi chemical corporation), epoxy resin obtained by reaction of an alcoholic hydroxyl group of bisphenol A type epoxy resin with epichlorohydrin (for example, "NER-1302" (epoxy equivalent 323, softening point 76 ℃) manufactured by Mitsubishi chemical corporation), bisphenol F type resin (for example, "jER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Mitsubishi chemical corporation), epoxy resin obtained by reaction of an alcoholic hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin (for example, "NER-7406" (epoxy equivalent 350, softening point 66 ℃) manufactured by Mitsubishi chemical corporation), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi chemical corporation "), phenol novolac type epoxy resin (for example," EPPN-201 "manufactured by Mitsubishi chemical corporation", "EP-152", "Dochemical corporation", "manufactured by DOW-154", manufactured by Mitsubishi chemical corporation "," EOC "),438" manufactured by Semic chemical corporation, etc. epoxy resin (for example, manufactured by Semic chemical corporation "), the same applies hereinafter) -102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (e.g., TEPIC (registered trademark) manufactured by Nissan chemical Co., ltd.), and, triphenolmethane-type epoxy resins (for example, "EPPN (registered trademark, the same applies hereinafter) -501", "EPPN-502", "EPPN-503", manufactured by Japanese chemical Co., ltd.), alicyclic epoxy resins (Celloxide (registered trademark, the same applies hereinafter) 2021P ", manufactured by Celloxide EHPE", manufactured by Daxiu chemical Co., ltd.), epoxy resins obtained by glycidylating a phenolic resin produced by the reaction of dicyclopentadiene with phenol (for example, "EXA-7200", manufactured by DIC Co., ltd., NC-7300", manufactured by Japanese chemical Co., ltd.), and epoxy resins represented by the following general formulae (B1) to (B4). Specifically, "XD-1000" manufactured by Japanese chemical drug Co., ltd. As an epoxy resin represented by the following general formula (B1), "NC-3000" manufactured by Japanese chemical drug Co., as an epoxy resin represented by the following general formula (B2), "E-201" manufactured by Osaka organic chemical industry Co., as an epoxy resin represented by the following general formula (B3), and "ESF-300" manufactured by Nippon iron Hokki chemical Co., as an epoxy resin represented by the following general formula (B4) can be cited.
Figure BDA0004133603210000191
In the general formula (B1), a is an average value, and represents a number of 0 to 10, R 111 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group.
The plural R's present in 1 molecule 111 The two may be the same or different.
Figure BDA0004133603210000201
In the above general formula (B2), B1 and B2 are each independently an average value, and represent a number of 0 to 10, R 121 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group orA biphenyl group. The plural R's present in 1 molecule 121 The two may be the same or different.
Figure BDA0004133603210000202
In the above general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2), wherein the molecular structure contains 1 or more adamantane structures, and c represents 2 or 3.
Figure BDA0004133603210000203
In the above general formulae (B3-1) and (B3-2), R 131 ～R 134 And R is 135 ～R 137 Each independently represents an adamantyl group optionally having a substituent, a hydrogen atom, an alkyl group optionally having a substituent having 1 to 12 carbon atoms, or a phenyl group optionally having a substituent, and represents a bond.
Figure BDA0004133603210000211
In the above general formula (B4), p and q each independently represent an integer of 0 to 4, R 141 And R is 142 Each independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, R 143 And R is 144 Each independently represents an alkylene group having 1 to 4 carbon atoms, and x and y each independently represent an integer of 0 or more.
Among these, the epoxy resins represented by any one of the general formulae (B1) to (B4) are preferably used.
Examples of the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group include: monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-or p-vinylbenzoic acid, alpha-haloalkyl, alkoxy, halogen, nitro, cyano substituents and the like, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, and the like 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutyl hydrogen phthalic acid, 2- (meth) acryloyloxybutyl maleic acid, monomers as products obtained by adding lactones such as epsilon-caprolactone, beta-propiolactone, gamma-butyrolactone, delta-valerolactone to (meth) acrylic acid, or addition of succinic acid (anhydride) to hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and (meth) acrylic acid dimers, and the like.
Among these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.
As a method for adding an α, β -unsaturated monocarboxylic acid or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, an α, β -unsaturated monocarboxylic acid or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group may be reacted with an epoxy resin in the presence of an esterification catalyst at a temperature of 50 to 150 ℃. As the esterification catalyst used herein, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride, and the like can be used.
The epoxy resin, the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group and the esterification catalyst may be used by selecting 1 component for each component, or 2 or more components may be used in combination.
The amount of the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group to be used is preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents, relative to 1 equivalent of the epoxy group of the epoxy resin. When the amount of the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group is not less than the above lower limit, the insufficient amount of the unsaturated group to be introduced can be suppressed, and the subsequent reaction with the polybasic acid and/or the acid anhydride thereof tends to be easily and sufficiently performed. On the other hand, when the upper limit value is less than or equal to the above, it is possible to suppress the residue of the unreacted product of the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group, and it is possible to easily improve the curing property.
Examples of the polybasic acid and/or the acid anhydride thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylene tetrahydrophthalic acid, chlorobridge acid, methyltetrahydrophthalic acid, biphenyl tetracarboxylic acid, and acid anhydrides thereof.
Preference is given to maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid or anhydrides of these. Tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride or biphenyltetracarboxylic dianhydride is particularly preferred.
The addition reaction of the polybasic acid and/or the acid anhydride thereof may be carried out by a known method, and the reaction may be continued under the same conditions as the addition reaction of the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group to the epoxy resin to obtain the target product. The amount of the polybasic acid and/or the acid anhydride component thereof added is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150mg KOH/g, more preferably in the range of 20 to 140mg KOH/g. When the alkali developability is not less than the lower limit, the alkali developability tends to be good. When the upper limit value is less than or equal to the above, the curing performance tends to be good.
In the addition reaction of the polybasic acid and/or its acid anhydride, a polyfunctional alcohol (polyhydric alcohol) such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2, 3-glycerol may be added to introduce a multi-branched structure. In this case, the order of mixing the polybasic acid and/or anhydride thereof with the polyfunctional alcohol is not particularly limited. Any hydroxyl groups present in the mixture of the epoxy resin and the alpha, beta-unsaturated monocarboxylic acid or the alpha, beta-unsaturated monocarboxylic acid ester having a carboxyl group, and the polyfunctional alcohol are subjected to an addition reaction by heating.
By using a polyol, the molecular weight of the epoxy (meth) acrylate resin (b 1) can be increased, and a branch can be introduced into the molecule, so that the balance between the molecular weight and the viscosity tends to be obtained. In addition, the rate of introduction of the acid group into the molecule can be increased, and a balance of sensitivity, adhesion, and the like tends to be easily achieved.
Examples of the carboxyl group-containing epoxy (meth) acrylate resin include those described in korean laid-open patent No. 10-2013-0022955, in addition to the foregoing examples.
The weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth) acrylate resin in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, more preferably 3000 or more, more preferably 4000 or more, particularly preferably 5000 or more, usually 30000 or less, preferably 20000 or less, more preferably 15000 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1000 to 30000, more preferably 1500 to 20000, still more preferably 1500 to 15000, still more preferably 2000 to 15000. By setting the lower limit value or more, it is possible to suppress an excessive increase in solubility with respect to the developer. When the solubility in the developer is less than the upper limit, the solubility in the developer tends to be good.
The acid value of the carboxyl group-containing epoxy (meth) acrylate resin is not particularly limited, but is preferably 20mgKOH/g or more, more preferably 40mgKOH/g or more, still more preferably 60mgKOH/g or more, still more preferably 80mgKOH/g or more, particularly preferably 100mgKOH/g or more, and is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, still more preferably 130mgKOH/g or less, and particularly preferably 120mgKOH/g or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 20 to 200mgKOH/g, more preferably 60 to 150mgKOH/g, still more preferably 80 to 130mgKOH/g, still more preferably 100 to 130mgKOH/g. When the lower limit value is not less than the above, the developing solubility tends to be improved and the resolution tends to be improved. When the ratio is equal to or less than the upper limit, the residual film ratio of the photosensitive coloring composition tends to be good.
The chemical structure of the epoxy (meth) acrylate resin is not particularly limited, and from the viewpoints of developability and reliability, an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (b 1-I) (hereinafter, sometimes simply referred to as "(b 1-I) epoxy (meth) acrylate resin") and/or an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (b 1-II) (hereinafter, sometimes simply referred to as "(b 1-II) epoxy (meth) acrylate resin") are preferable.
Figure BDA0004133603210000241
In the formula (b 1-I), R 11 Represents a hydrogen atom or a methyl group, R 12 Represents an optionally substituted 2-valent hydrocarbon group, k represents 1 or 2, and x represents a bond.
The benzene ring in the formula (b 1-I) is optionally further substituted with an optional substituent.
Figure BDA0004133603210000242
In the formula (b 1-II), R 13 Each independently represents a hydrogen atom or a methyl group, R 14 Represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R 15 And R is 16 Each independently represents an aliphatic group having a valence of 2, which may have a substituent, m and n each independently represent an integer of 0 to 2, and x represents a bond.
(b 1-I) epoxy (meth) acrylate-based resin
First, the epoxy (meth) acrylate resin having a partial structure represented by the general formula (b 1-I) will be described in detail.
Figure BDA0004133603210000251
In the formula (b 1-I), R 11 Represents a hydrogen atom or a methyl group, R 12 Represents an optionally substituted 2-valent hydrocarbon group, k represents 1 or 2, and x represents a bond.
The benzene ring in the formula (b 1-I) is optionally further substituted with an optional substituent.
(R 12 )
In the above formula (b 1-I), R 12 Represents a 2-valent hydrocarbon group optionally having a substituent.
Examples of the 2-valent hydrocarbon group include a 2-valent aliphatic group, a 2-valent aromatic ring group, and a group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic ring groups are bonded.
Examples of the aliphatic group having a valence of 2 include linear, branched and cyclic aliphatic groups. Among these, a linear aliphatic group is preferable from the viewpoint of developing solubility. On the other hand, from the viewpoint of reducing penetration of the developer into the exposed portion, a cyclic aliphatic group is preferable. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, more preferably 10 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10. When the lower limit is not less than the above, a strong film is easily obtained, surface roughness which occurs during development is less likely to occur, and adhesion to a substrate tends to be good. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
Examples of the linear aliphatic group having a valence of 2 include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, and n-heptylene. Among these, methylene is preferable from the viewpoint of rigidity of the skeleton.
Examples of the branched aliphatic group having a valence of 2 include a structure in which the above-mentioned linear aliphatic group having a valence of 2 has a side chain of, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.
The number of rings of the cyclic aliphatic group having a valence of 2 is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 12 or less, preferably 10 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1 to 12, more preferably 1 to 10, and still more preferably 2 to 10. When the lower limit value is not less than the above, a strong film tends to be formed, and the substrate adhesion tends to be good. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
Examples of the cyclic aliphatic group having a valence of 2 include: a group formed by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, a dicyclopentadiene ring, or a dicyclopentane ring. Among these, from the viewpoint of rigidity of the skeleton, a group in which 2 hydrogen atoms are removed from the dicyclopentadiene ring, the dicyclopentane ring, or the adamantane ring is preferable.
Examples of the substituent optionally contained in the aliphatic group having a valence of 2 include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; cyano group; and (3) carboxyl. Among these, from the viewpoint of ease of synthesis, unsubstituted ones are preferable.
Examples of the 2-valent aromatic ring group include a 2-valent aromatic hydrocarbon ring group and a 2-valent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, more preferably 10 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 4 to 20, more preferably 5 to 15, and still more preferably 6 to 10. When the lower limit is not less than the above, a strong film is easily obtained, surface roughness which occurs during development is less likely to occur, and adhesion to a substrate tends to be good. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, and the like having 2 free valences,
Figure BDA0004133603210000271
Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.
The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the aromatic heterocyclic group include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, perigedine ring, quinazoline ring, quinazolinone ring, azulene ring.
Among these, from the viewpoint of patterning characteristics, a benzene ring or naphthalene ring having 2 free valences is preferable, and a benzene ring having 2 free valences is more preferable.
Examples of the substituent optionally contained in the 2-valent aromatic ring group include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, from the viewpoint of developing solubility, unsubstituted ones are preferable.
Examples of the group in which 1 or more aliphatic groups having 2 valences are linked to 1 or more aromatic ring groups having 2 valences include a group in which 1 or more aliphatic groups having 2 valences are linked to 1 or more aromatic ring groups having 2 valences.
The number of aliphatic groups having a valence of 2 is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, more preferably 3 or less. For example, it is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit is not less than the above, a strong film is easily obtained, surface roughness which occurs during development is less likely to occur, and adhesion to a substrate tends to be good. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
The number of the 2-valent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, more preferably 3 or less. For example, it is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit is not less than the above, a strong film is easily obtained, surface roughness which occurs during development is less likely to occur, and adhesion to a substrate tends to be good. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
Examples of the group in which 1 or more aliphatic groups having 2 valences and 1 or more aromatic ring groups having 2 valences are linked include: groups represented by the following formulas (b 1-I-A) to (b 1-I-F). Among these, from the viewpoints of rigidity of the skeleton and hydrophobization of the film, the group represented by the following formula (b 1-I-A) is preferable.
Figure BDA0004133603210000291
In the above formula (b 1-I), k represents 1 or 2. From the viewpoints of adhesion and patterning, k is preferably 1. From the viewpoint of NMP resistance, k is preferably 2. The (b 1-I) epoxy (meth) acrylate may contain both a partial structure having k of 1 and a partial structure having k of 2.
The benzene ring in the formula (b 1-I) is optionally further substituted with an optional substituent. Examples of the substituent acceptable on the benzene ring in the formula (b 1-I) include: hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, propoxy. When the benzene ring in the formula (b 1-I) has a substituent, the number of the substituent is not particularly limited, and may be 1 or 2 or more.
The benzene ring in the formula (b 1-I) is preferably unsubstituted from the viewpoint of patterning characteristics.
From the viewpoint of ease of synthesis, the partial structure represented by the formula (b 1-I) is preferably a partial structure represented by the following formula (b 1-I-1).
Figure BDA0004133603210000301
In the formula (b 1-I-1), R 11 、R 12 And k has the same meaning as in the above formula (b 1-I), R X Represents a hydrogen atom or a polyacid residue, and represents a bond.
The benzene ring in the formula (b 1-I-1) is optionally further substituted with an optional substituent.
The polyacid residue refers to a 1-valent group formed by removing 1 OH group from a polyacid or anhydride thereof. Examples of the polybasic acid include: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylene tetrahydrophthalic acid, chlorobridge acid, methyltetrahydrophthalic acid, biphenyl tetracarboxylic acid.
From the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable.
The benzene ring in the formula (b 1-I-1) is optionally further substituted with an optional substituent. As the substituent, those exemplified for the benzene ring in the formula (b 1-I) can be preferably used.
The partial structure represented by the above formula (b 1-I-1) contained in the (b 1-I) epoxy (meth) acrylate resin of 1 molecule may be 1 or 1 More than 2 kinds of R may be mixed with, for example X Is a hydrogen atom and R X Is a polyacid residue.
The number of the partial structures represented by the above formula (b 1-I) contained in the (b 1-I) epoxy (meth) acrylate resin of 1 molecule is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 15 or less. Preferably 1 to 20, more preferably 1 to 15, and still more preferably 3 to 15. When the lower limit is not less than the above, a strong film is easily obtained, and surface roughness which occurs during development is less likely to occur. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
The weight average molecular weight (Mw) of the (b 1-I) epoxy (meth) acrylate resin in terms of polystyrene measured by Gel Permeation Chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, more preferably 2000 or more, more preferably 3000 or more, particularly preferably 4000 or more, most preferably 5000 or more, usually 30000 or less, preferably 20000 or less, more preferably 15000 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1000 to 30000, more preferably 1500 to 2000, still more preferably 1500 to 15000, still more preferably 2000 to 1500. When the lower limit value is not less than the above, the residual film ratio of the photosensitive coloring composition tends to be good. When the solubility in the developer is less than the upper limit, the solubility in the developer tends to be good.
The acid value of the (b 1-I) epoxy (meth) acrylate resin is not particularly limited, but is preferably 20mgKOH/g or more, more preferably 40mgKOH/g or more, still more preferably 60mgKOH/g or more, still more preferably 80mgKOH/g or more, particularly preferably 100mgKOH/g or more, and is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, still more preferably 130mgKOH/g or less, particularly preferably 120mgKOH/g or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 20 to 200mgKOH/g, more preferably 60 to 150mgKOH/g, still more preferably 80 to 130mgKOH/g, still more preferably 100 to 130mgKOH/g. When the lower limit value is not less than the above, the developing solubility tends to be improved and the resolution tends to be improved. When the ratio is equal to or less than the upper limit, the residual film ratio of the photosensitive coloring composition tends to be good.
Specific examples of the (b 1-I) epoxy (meth) acrylate resin are shown below. In the example, the term "connection" means a connection.
Figure BDA0004133603210000321
Figure BDA0004133603210000331
(b 1-II) epoxy (meth) acrylate-based resin
The epoxy (meth) acrylate resin having a partial structure represented by the above general formula (b 1-II) will be described in detail.
Figure BDA0004133603210000332
In the formula (b 1-II), R 13 Each independently represents a hydrogen atom or a methyl group, R 14 Represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R 15 And R is 16 Each independently represents an aliphatic group having a valence of 2, which may have a substituent, m and n each independently represent an integer of 0 to 2, and x represents a bond.
(R 14 )
In the above general formula (b 1-II), R 14 Represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.
The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. For example, it is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit is not less than the above, a strong film is easily obtained, and surface roughness which occurs during development is less likely to occur. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
The aliphatic ring group has a carbon number of usually 4 or more, preferably 6 or more, more preferably 8 or more, and further preferably 40 or less, more preferably 30 or less, further preferably 20 or less, particularly preferably 15 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 4 to 40, more preferably 4 to 30, still more preferably 6 to 20, and particularly preferably 8 to 15. When the lower limit is not less than the above, a strong film is easily obtained, and surface roughness which occurs during development is less likely to occur. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
Examples of the aliphatic ring in the aliphatic cyclic group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoints of film residue ratio and resolution of the photosensitive coloring composition.
The number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less, more preferably 4 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 4, further preferably 2 to 4, and particularly preferably 3 to 4. When the lower limit is not less than the above, a strong film is easily obtained, and surface roughness which occurs during development is less likely to occur. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, and is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, particularly preferably 15 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 4 to 40, more preferably 6 to 40, still more preferably 8 to 30, still more preferably 10 to 20, and particularly preferably 12 to 15. When the lower limit is not less than the above, a strong film is easily obtained, and surface roughness which occurs during development is less likely to occur. When the upper limit value is less than or equal to the above, patterning characteristics tend to be improved.
Examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,
Figure BDA0004133603210000351
Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of patterning characteristics.
The 2-valent hydrocarbon group of the 2-valent hydrocarbon groups having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include: a group in which a 2-valent aliphatic group, a 2-valent aromatic ring group, 1 or more 2-valent aliphatic groups, and 1 or more 2-valent aromatic ring groups are bonded.
Examples of the aliphatic group having a valence of 2 include linear, branched and cyclic aliphatic groups. Among these, a linear aliphatic group is preferable from the viewpoint of developing solubility. On the other hand, from the viewpoint of reducing penetration of the developer into the exposed portion, a cyclic aliphatic group is preferable. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and further preferably 25 or less, more preferably 20 or less, further preferably 15 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1 to 25, more preferably 3 to 20, and still more preferably 6 to 15. When the lower limit is not less than the above, a strong film is easily obtained, surface roughness which occurs during development is less likely to occur, and adhesion to a substrate tends to be good. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
Examples of the linear aliphatic group having a valence of 2 include: methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene. Among these, methylene is preferable from the viewpoint of rigidity of the skeleton.
Examples of the branched aliphatic group having a valence of 2 include: the above-mentioned 2-valent linear aliphatic group has a structure in which a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group are side chains.
The number of rings included in the cyclic aliphatic group having a valence of 2 is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, it is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit value is not less than the above, a strong film tends to be formed, and the substrate adhesion tends to be good. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
Examples of the cyclic aliphatic group having a valence of 2 include: a group formed by removing 2 hydrogen atoms from a ring of a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring or a cyclododecane ring. Among these, from the viewpoint of rigidity of the skeleton, a group in which 2 hydrogen atoms are removed from the adamantane ring is preferable.
Examples of the substituent optionally contained in the aliphatic group having a valence of 2 include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; cyano group; and (3) carboxyl. Among these, from the viewpoint of ease of synthesis, unsubstituted ones are preferable.
Examples of the 2-valent aromatic ring group include a 2-valent aromatic hydrocarbon ring group and a 2-valent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and further preferably 30 or less, more preferably 20 or less, further preferably 15 or less. For example, it is preferably 4 to 30, more preferably 5 to 20, and still more preferably 6 to 15. When the lower limit is not less than the above, a strong film is easily obtained, surface roughness which occurs during development is less likely to occur, and adhesion to a substrate tends to be good. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, and the like having 2 free valences,
Figure BDA0004133603210000361
Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.
The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the aromatic heterocyclic group include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perigedine ring, quinazoline ring, quinazolinone ring, azulene ring. Among these, from the viewpoint of patterning characteristics, a benzene ring or naphthalene ring having 2 free valences is preferable, and a benzene ring having 2 free valences is more preferable.
Examples of the substituent optionally contained in the 2-valent aromatic ring group include: hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, propoxy. Among these, from the viewpoint of developing solubility, unsubstituted ones are preferable.
Examples of the group in which 1 or more aliphatic groups having 2 valences are bonded to 1 or more aromatic ring groups having 2 valences include a group in which 1 or more aliphatic groups having 2 valences are bonded to 1 or more aromatic ring groups having 2 valences.
The number of aliphatic groups having a valence of 2 is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, more preferably 3 or less. For example, it is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit is not less than the above, a strong film is easily obtained, surface roughness which occurs during development is less likely to occur, and adhesion to a substrate tends to be good. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
The number of the 2-valent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, more preferably 3 or less. For example, it is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit is not less than the above, a strong film is easily obtained, surface roughness which occurs during development is less likely to occur, and adhesion to a substrate tends to be good. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
Examples of the group in which 1 or more aliphatic groups having 2 valences and 1 or more aromatic ring groups having 2 valences are linked include groups represented by the above-mentioned formulae (b 1-I-A) to (b 1-I-F). Among these, the groups represented by the above formula (b 1-I-C) are preferable from the viewpoints of rigidity of the skeleton and hydrophobization of the film.
The bonding method of the cyclic hydrocarbon group as the side chain is not particularly limited, and examples thereof include: a method in which 1 hydrogen atom of an aliphatic group or an aromatic ring group is substituted with a cyclic hydrocarbon group as a side chain, or a method in which a cyclic hydrocarbon group as a side chain is formed by containing 1 carbon atom of an aliphatic group.
(R 15 、R 16 )
In the general formula (b 1-II), R 15 And R is 16 Each independently represents an aliphatic group having a valence of 2, which may have a substituent.
Examples of the aliphatic group having a valence of 2 include linear, branched and cyclic aliphatic groups. Of these, a linear aliphatic group is preferable from the viewpoint of developing solubility, and a cyclic aliphatic group is preferable from the viewpoint of reducing penetration of the developing solution into the exposed portion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, more preferably 10 or less. For example, it is preferably 1 to 20, more preferably 3 to 15, and still more preferably 6 to 10. When the lower limit is not less than the above, a strong film is easily obtained, surface roughness which occurs during development is less likely to occur, and adhesion to a substrate tends to be good. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
Examples of the linear aliphatic group having a valence of 2 include: methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene. Among these, methylene is preferable from the viewpoint of rigidity of the skeleton.
Examples of the branched aliphatic group having a valence of 2 include a structure in which the above-mentioned linear aliphatic group having a valence of 2 has a side chain of, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.
The number of rings of the cyclic aliphatic group having a valence of 2 is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 12 or less, preferably 10 or less. For example, it is preferably 1 to 12, more preferably 2 to 10. When the lower limit value is not less than the above, a strong film tends to be formed, and the substrate adhesion tends to be good. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
Examples of the cyclic aliphatic group having a valence of 2 include: a group formed by removing 2 hydrogen atoms from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, or a dicyclopentadiene ring. Among these, from the viewpoint of rigidity of the skeleton, a group formed by removing 2 hydrogen atoms from dicyclopentadiene ring or adamantane ring is preferable.
Examples of the substituent optionally contained in the aliphatic group having a valence of 2 include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; cyano group; and (3) carboxyl. Among these, from the viewpoint of ease of synthesis, unsubstituted ones are preferable.
(m、n)
In the general formula (b 1-II), m and n each independently represent an integer of 0 to 2. When the lower limit value is not less than the upper limit value, patterning suitability is improved, surface roughness which occurs during development is less likely to occur, and when the upper limit value is not more than the upper limit value, development is improved. From the viewpoint of developability, m and n are preferably 0. On the other hand, from the viewpoints of patterning suitability and surface roughness that may occur during development, m and n are preferably 1 or more.
From the viewpoint of adhesion to a substrate, the partial structure represented by the general formula (b 1-II) is preferably a partial structure represented by the following general formula (b 1-II-1).
Figure BDA0004133603210000391
In the formula (b 1-II-1), R 13 、R 15 、R 16 M and n have the same meaning as in the formula (b 1-II), R α Represents an optionally substituted cyclic hydrocarbon group having a valence of 1, p represents an integer of 1 or more, and x represents a bond. The benzene ring in the formula (b 1-II-1) is optionally further substituted with an optional substituent.
(R α )
In the general formula (b 1-II-1), R α Represents a 1-valent cyclic hydrocarbon group optionally having a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.
The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 6 or less, preferably 4 or less, more preferably 3 or less. For example, it is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit is not less than the above, a strong film is easily obtained, and surface roughness which occurs during development is less likely to occur. When the upper limit value is less than or equal to the above, patterning characteristics tend to be improved.
The aliphatic ring group has a carbon number of usually 4 or more, preferably 6 or more, more preferably 8 or more, and further preferably 40 or less, more preferably 30 or less, further preferably 20 or less, particularly preferably 15 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 4 to 40, more preferably 4 to 30, still more preferably 6 to 20, and particularly preferably 8 to 15. When the lower limit is not less than the above, a strong film is easily obtained, and surface roughness which occurs during development is less likely to occur. When the upper limit value is less than or equal to the above, patterning characteristics tend to be improved.
Examples of the aliphatic ring in the aliphatic cyclic group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of firm film characteristics.
The number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1 to 10, more preferably 1 to 5, still more preferably 2 to 5, and particularly preferably 3 to 5. When the lower limit is not less than the above, a strong film is easily obtained, and surface roughness which occurs during development is less likely to occur. When the upper limit value is less than or equal to the above, patterning characteristics tend to be improved.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and is preferably 30 or less, more preferably 20 or less, more preferably 15 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 4 to 30, more preferably 5 to 20, and still more preferably 6 to 15. When the lower limit is not less than the upper limit, a strong film is easily obtained, and surface roughness which occurs during development is less likely to occur, and when the upper limit is not more than the upper limit, patterning characteristics tend to be good.
Examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of developing solubility.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl and isopentyl groups; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; cyano group; and (3) carboxyl. Among these, unsubstituted ones are preferable from the viewpoint of ease of synthesis.
p represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. For example, it is preferably 1 to 3, more preferably 2 to 3. When the lower limit value is not less than the above, the film curing degree and the film residue ratio tend to be good. When the upper limit value is less than or equal to the above, development tends to be good.
Among these, R is from the viewpoint of the degree of curing of a firm film α Preferably a 1-valent aliphatic cyclic group, more preferably an adamantyl group.
The benzene ring in the formula (b 1-II-1) is optionally further substituted with an optional substituent. Examples of the substituent acceptable on the benzene ring in the formula (b 1-II-1) include: hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, propoxy. When the benzene ring in the formula (b 1-II-1) has a substituent, the number of the substituent is not particularly limited, and may be 1 or 2 or more.
From the viewpoint of patterning characteristics, the benzene ring in the formula (b 1-II-1) is preferably unsubstituted.
Specific examples of the partial structure represented by the following formula (b 1-II-1) are given below.
Figure BDA0004133603210000411
Figure BDA0004133603210000421
From the viewpoints of rigidity of the skeleton and membrane hydrophobization, the partial structure represented by the general formula (b 1-II) is preferably a partial structure represented by the following general formula (b 1-II-2).
Figure BDA0004133603210000422
In the formula (b 1-II-2), R 13 、R 15 、R 16 M and n have the same meaning as in the formula (b 1-II), R β Represents a cyclic hydrocarbon group of 2 valences optionally having a substituent, and represents a bond.
The benzene ring in the formula (b 1-II-2) is optionally further substituted with an optional substituent.
(R β )
In the formula (b 1-II-2), R β Represents a cyclic hydrocarbon group of 2 valences optionally having a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.
The number of rings in the aliphatic cyclic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less. For example, it is preferably 1 to 10, more preferably 2 to 5. When the lower limit is not less than the above, a strong film is easily obtained, and surface roughness which occurs during development is less likely to occur. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
The aliphatic ring group has a carbon number of usually 4 or more, preferably 6 or more, more preferably 8 or more, and further preferably 40 or less, more preferably 35 or less, and further preferably 30 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 4 to 40, more preferably 6 to 35, and still more preferably 8 to 30. When the lower limit value is not less than the above, the film roughness during development tends to be suppressed. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration of sensitivity and film reduction during development tend to be easily suppressed.
Examples of the aliphatic ring in the aliphatic cyclic group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring. Among these, the adamantane ring is preferable from the viewpoints of film reduction and resolution at the time of development.
On the other hand, the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1 to 10, more preferably 1 to 5, still more preferably 2 to 5, and particularly preferably 3 to 5. When the lower limit is not less than the above, a strong film is easily obtained, and surface roughness which occurs during development is less likely to occur. When the upper limit value is less than or equal to the above, deterioration in sensitivity, film reduction, and resolution improvement tend to be easily suppressed.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, and is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, particularly preferably 15 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, particularly preferably 10 to 15. When the lower limit is not less than the above, a strong film is easily obtained, and surface roughness which occurs during development is less likely to occur. When the upper limit value is less than or equal to the above, resolution is improved, and deterioration in sensitivity and reduction in film tend to be suppressed.
Examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of developability.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl and isopentyl groups; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; cyano group; and (3) carboxyl. Among these, from the viewpoint of ease of synthesis, unsubstituted ones are preferable.
Among these, R is from the viewpoint of suppression of film reduction and resolution β Preferably a 2-valent aliphatic ring radical, more preferably a 2-valent adamantane ring radical.
On the other hand, from the viewpoint of patterning characteristics, R β An aromatic ring group having a valence of 2 is preferable, and a fluorene ring group having a valence of 2 is more preferable.
The benzene ring in the formula (b 1-II-2) is optionally further substituted with an optional substituent. Examples of the substituent acceptable on the benzene ring in the formula (b 1-II-2) include: hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, propoxy. When the benzene ring in the formula (b 1-II-2) has a substituent, the number of the substituent is not particularly limited, and may be 1 or 2 or more.
In addition, 2 benzene rings may be linked via substituents. As a substituent in this case, can be exemplified by-O-, -S-; -NH-, -CH 2 -an equivalent 2-valent group.
From the viewpoint of patterning characteristics, the benzene ring in the formula (b 1-II-2) is preferably unsubstituted. In addition, the benzene ring in the formula (b 1-II-2) is preferably substituted with a methyl group from the viewpoint of less tendency to cause film reduction or the like.
Specific examples of the partial structure represented by the above formula (b 1-II-2) are given below. In the examples, the term "connection" means a connection.
Figure BDA0004133603210000451
From the viewpoints of film residue and patterning characteristics, the partial structure represented by the formula (b 1-II) is preferably a partial structure represented by the following formula (b 1-II-3).
Figure BDA0004133603210000461
In the formula (b 1-II-3), R 13 、R 14 、R 15 、R 16 M and n have the same meaning as in the formula (b 1-II), R Z Represents a hydrogen atom or a polyacid residue.
The polyacid residue refers to a 1-valent group formed by removing 1 OH group from a polyacid. It is also possible to remove 1 OH group and to remove R from the other molecule represented by the formula (b 1-II-3) Z Commonly, i.e. by means of R Z A plurality of formulae (b 1-II-3) are linked.
Examples of the polybasic acid include: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylene tetrahydrophthalic acid, chlorobridge acid, methyltetrahydrophthalic acid, biphenyl tetracarboxylic acid.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable from the viewpoint of patterning characteristics, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable.
The partial structure represented by the formula (b 1-II-3) contained in the (b 1-II) epoxy (meth) acrylate resin of 1 molecule may be 1 or 2 or more, and may be mixed with R Z Is a hydrogen atom and R Z Is a polyacid residue.
The number of the partial structures represented by the formula (b 1-II) contained in the (b 1-II) epoxy (meth) acrylate resin of 1 molecule is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. For example, it is preferably 1 to 20, more preferably 1 to 15, and still more preferably 3 to 10. When the lower limit is not less than the above, a strong film is easily obtained, and surface roughness which occurs during development is less likely to occur. When the upper limit value is less than or equal to the above, the resolution is improved, and the tendency of deterioration in sensitivity and reduction in film is easily suppressed.
The weight average molecular weight (Mw) of the (b 1-II) epoxy (meth) acrylate resin in terms of polystyrene measured by Gel Permeation Chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, more preferably 2000 or more, more preferably 3000 or more, particularly preferably 4000 or more, most preferably 5000 or more, generally 10000 or less, preferably 8000 or less, more preferably 7000 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1000 to 10000, more preferably 1500 to 10000, still more preferably 1500 to 8000, still more preferably 2000 to 8000, particularly preferably 2000 to 7000. When the lower limit value is not less than the above, the residual film ratio of the photosensitive coloring composition tends to be good. When the solubility in the developer is less than the upper limit, the solubility in the developer tends to be good.
The acid value of the (b 1-II) epoxy (meth) acrylate resin is not particularly limited, but is preferably 20mgKOH/g or more, more preferably 40mgKOH/g or more, still more preferably 60mgKOH/g or more, still more preferably 80mgKOH/g or more, particularly preferably 100mgKOH/g or more, and is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, still more preferably 130mgKOH/g or less, particularly preferably 120mgKOH/g or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 20 to 200mgKOH/g, more preferably 60 to 150mgKOH/g, still more preferably 80 to 130mgKOH/g, still more preferably 100 to 130mgKOH/g. When the lower limit value is not less than the above, the developing solubility tends to be improved and the resolution tends to be improved. When the ratio is equal to or less than the upper limit, the residual film ratio of the photosensitive coloring composition tends to be good.
The carboxyl group-containing epoxy (meth) acrylate resin may be used alone in an amount of 1 kind, or may be used in an amount of 2 or more kinds.
Part of the carboxyl group-containing epoxy (meth) acrylate resin may be replaced with another binder resin. That is, the carboxyl group-containing epoxy (meth) acrylate resin may be used in combination with other binder resins. In this case, the ratio of the carboxyl group-containing epoxy (meth) acrylate resin in the alkali-soluble resin (b) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, particularly preferably 80% by mass or more, and usually 100% by mass or less.
As the alkali-soluble resin (b), from the viewpoint of compatibility with pigments, dispersants, and the like, (b 2) an acrylic copolymer resin is preferably used, and the acrylic copolymer resin described in japanese patent application laid-open No. 2014-137466 can be preferably used.
Examples of the acrylic copolymer resin include: copolymers of ethylenically unsaturated monomers having 1 or more carboxyl groups (hereinafter referred to as "unsaturated monomers (b 2-1)") with other ethylenically unsaturated monomers capable of copolymerization (hereinafter referred to as "unsaturated monomers (b 2-2)").
Examples of the unsaturated monomer (b 2-1) include: unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α -chloroacrylic acid, cinnamic acid, etc.; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, citraconic anhydride, mesaconic acid, and the like, or anhydrides thereof; mono- [ (meth) acryloyloxyalkyl ] esters of polybasic acids having 2 or more atoms such as mono- [ 2- (meth) acryloyloxyethyl ] succinate and mono- [ 2- (meth) acryloyloxyethyl ] phthalate; mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω -carboxyl polycaprolactone mono (meth) acrylate; p-vinylbenzoic acid.
These unsaturated monomers (b 2-1) may be used alone or in combination of 2 or more.
Examples of the unsaturated monomer (b 2-2) include: n-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
aromatic vinyl compounds such as styrene, α -methylstyrene, p-hydroxystyrene, p-hydroxy- α -methylstyrene, p-vinylbenzyl glycidyl ether and acenaphthene;
methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (having a degree of polymerization of 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (having a degree of polymerization of 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (having a degree of polymerization of 2 to 10) mono (meth) acrylate, polypropylene glycol (having a degree of polymerization of 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ] acrylate 2,6 ](meth) acrylic esters such as decan-8-yl ester, dicyclopentadienyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of p-cumylphenol, glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3- [ (meth) acryloyloxymethyl ] oxetane, 3- [ (meth) acryloyloxymethyl ] -3-ethyloxetane;
Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 2,6 ]Vinyl ethers such as decan-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, and 3- (vinyloxymethyl) -3-ethyloxetane;
a macromer having a mono (meth) acryloyl group at the terminal of a polymer molecular chain such as polystyrene, poly (meth) acrylic acid methyl ester, poly (meth) acrylic acid n-butyl ester, and polysiloxane.
These unsaturated monomers (b 2-2) may be used alone or in combination of 2 or more.
In the copolymer of the unsaturated monomer (b 2-1) and the unsaturated monomer (b 2-2), the copolymerization ratio of the unsaturated monomer (b 2-1) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. When the unsaturated monomer (b 2-1) is copolymerized in such a range, a photosensitive coloring composition excellent in alkali developability and storage stability tends to be obtained.
Examples of the copolymer of the unsaturated monomer (b 2-1) and the unsaturated monomer (b 2-2) include copolymers disclosed in JP-A-7-140654, JP-A-8-259876, JP-A-10-31308, JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118 and JP-A-2004-101728.
The copolymer of the unsaturated monomer (b 2-1) and the unsaturated monomer (b 2-2) can be produced by a known method, and for example, the structure, mw and Mw/Mn can be controlled by the methods disclosed in Japanese patent laid-open publication No. 2003-222717, japanese patent laid-open publication No. 2006-259680 and International publication No. 2007/029871.
Further, resins described in International publication Nos. 2016/194619 and 2017/154439 may be used.
(c) photopolymerization initiator
(c) The photopolymerization initiator is a component having a function of directly absorbing light to cause a decomposition reaction or a hydrogen abstraction reaction and generating a polymerization active radical. Additives such as a polymerization accelerator (chain transfer agent) and a sensitizing dye may be added and used as needed.
Examples of the photopolymerization initiator include: japanese patent application laid-open No. 59-152396, japanese patent application laid-open No. 61-151197 discloses a metallocene compound including a titanocene compound; hexaarylbisimidazole derivatives described in Japanese patent application laid-open No. 2000-56118; halomethylated oxadiazole derivatives and halomethyl s-triazine derivatives described in JP-A-10-39503; alpha-aminoalkylbenzophenone derivatives; an oxime ester compound described in Japanese patent application laid-open No. 2000-80068, japanese patent application laid-open No. 2006-367550, and the like.
Examples of the metallocene compound include: bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) diphenyl titanium, bis (cyclopentadienyl) bis (2, 3,4,5, 6-pentafluorophenyl) titanium, bis (cyclopentadienyl) bis (2, 3,5, 6-tetrafluorophenyl) titanium, bis (cyclopentadienyl) bis (2, 4, 6-trifluorophenyl) titanium, bis (cyclopentadienyl) bis (2, 6-difluorophenyl) titanium, bis (cyclopentadienyl) bis (2, 4-difluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2, 3,4,5, 6-pentafluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2, 6-difluorophenyl) titanium, bis (cyclopentadienyl) - [ 2, 6-difluoro-3- (pyrrol-1-yl) phenyl ] titanium.
Examples of the hexaarylbiimidazole derivatives include: 2- (2 '-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (2' -chlorophenyl) -4, 5-bis (3 '-methoxyphenyl) imidazole dimer, 2- (2' -fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (2 '-methoxyphenyl) -4, 5-diphenylimidazole dimer, (4' -methoxyphenyl) -4, 5-diphenylimidazole dimer.
Examples of the halomethylated oxadiazole derivatives include: 2-trichloromethyl-5- (2 ' -benzofuranyl) -1,3, 4-oxadiazole, 2-trichloromethyl-5- [ beta- (2 ' -benzofuranyl) vinyl ] -1,3, 4-oxadiazole, 2-trichloromethyl-5- [ beta- (2 ' - (6 "-benzofuranyl) vinyl) ] 1,3, 4-oxadiazole, 2-trichloromethyl-5-furanyl-1, 3, 4-oxadiazole.
Examples of halomethyl s-triazine derivatives include: 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-ethoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4, 6-bis (trichloromethyl) s-triazine.
Examples of the α -aminoalkylbenzophenone derivatives include: 2-methyl-1- [ 4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl 1, 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone.
As the photopolymerization initiator, particularly, an oxime ester compound is effective in terms of sensitivity and platemaking, and for example, when an alkali-soluble resin containing a phenolic hydroxyl group is used, such an oxime ester compound having excellent sensitivity is particularly useful. Since the oxime ester compound has a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals in its structure, the oxime ester compound has high sensitivity even in a small amount and is stable to thermal reaction, and a photosensitive coloring composition having high sensitivity can be obtained in a small amount.
Examples of the oxime ester compound include compounds represented by the following general formula (IV).
Figure BDA0004133603210000511
In the above formula (IV), R 21a Represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R 21b Represents any substituent comprising an aromatic ring.
R 22a Represents an alkanoyl group which may be substituted or an aroyl group which may be substituted.
n represents an integer of 0 or 1.
R 21a The carbon number of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoints of solubility in a solvent and sensitivity. For example, 1 to 20, preferably 1 to 15, more preferably 2 to 10. Examples of the alkyl group include methyl, ethyl, propyl and cyclopentylethyl.
Examples of the substituent optionally included in the alkyl group include: the aromatic ring group, hydroxyl group, carboxyl group, halogen atom, amino group, amide group, 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl group or N-acetyl-N-acetoxyamino group is preferably unsubstituted from the viewpoint of ease of synthesis.
As R 21a Examples of the aromatic ring group in (a) include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. In addition, from the viewpoint of developability, it is preferable The content is selected to be 30 or less, more preferably 20 or less, and still more preferably 12 or less. For example, it is 5 to 30, preferably 5 to 20, more preferably 5 to 12 or less.
Examples of the aromatic ring group include: among these, phenyl, naphthyl, pyridyl and furyl are preferable, and phenyl or naphthyl is more preferable from the viewpoint of developability.
Examples of the substituent optionally included in the aromatic ring group include: the hydroxyl group, carboxyl group, halogen atom, amino group, amide group, alkyl group, alkoxy group, and a group formed by linking these substituents are preferable from the viewpoint of developability, and alkyl group, alkoxy group, and a group formed by linking these are more preferable.
Among these, R is from the viewpoint of developability 21a The aromatic ring group is preferably an aromatic ring group optionally having a substituent, and more preferably an aromatic ring group having an alkoxy group bonded thereto as a substituent.
In addition, as R 21b Examples thereof include an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, and an optionally substituted diphenyl sulfide group. Among these, an optionally substituted carbazolyl group is preferable from the viewpoint of sensitivity, and an optionally substituted diphenyl sulfide group is preferable from the viewpoint of electrical reliability.
In addition, R 22a The carbon number of the alkanoyl group is not particularly limited, but is usually 2 or more, preferably 3 or more, and is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less from the viewpoints of solubility in a solvent and sensitivity. For example, it is 2 to 20, preferably 2 to 15, more preferably 3 to 10, still more preferably 3 to 5. Examples of the alkanoyl group include acetyl, propionyl and butyryl.
Examples of the substituent optionally included in the alkanoyl group include: the aromatic ring group, hydroxyl group, carboxyl group, halogen atom, amino group, amide group are preferably unsubstituted from the viewpoint of ease of synthesis.
In addition, R 22a The number of carbons of the aroyl group is not particularly limited, and is soluble in a solvent,From the viewpoint of sensitivity, it is usually 7 or more, preferably 8 or more, and it is usually 20 or less, preferably 15 or less, more preferably 10 or less. For example, 7 to 20, preferably 7 to 15, more preferably 8 to 10. Examples of the aroyl group include benzoyl and naphthoyl.
Examples of the substituent optionally included in the aroyl group include: hydroxyl group, carboxyl group, halogen atom, amino group, amide group, and alkyl group, and is preferably unsubstituted from the viewpoint of ease of synthesis.
Among these, R is from the viewpoint of sensitivity 22a Alkanoyl groups optionally having a substituent are preferred, unsubstituted alkanoyl groups are more preferred, and acetyl groups are further preferred.
From the viewpoint of reducing contamination of the liquid crystal layer by the colorant, it is also preferable to use an initiator described in Japanese patent application laid-open No. 2016-133574.
The photopolymerization initiator may be used alone or in combination of 1 or more than 2.
In order to improve the sensitivity, a sensitizing dye or a polymerization accelerator corresponding to the wavelength of the image exposure light source may be added to the photopolymerization initiator as needed. Examples of the sensitizing dye include: JP-A-4-221958, JP-A-4-219756, JP-A-3-239703, JP-A-5-289335, heterocyclic coumarin pigment, JP-A-3-239703, JP-A-5-289335, 3-coumarin (3-Ketocoumarin) compound, JP-A-6-19240, pyrromethene pigment, JP-A-47-2528, JP-A-54-155292, and JP-A-54-155292 the pigment having a dialkylaminobenzene skeleton described in Japanese patent application laid-open No. 45-37377, japanese patent application laid-open No. 48-84183, japanese patent application laid-open No. 52-112681, japanese patent application laid-open No. 58-15503, japanese patent application laid-open No. 60-88005, japanese patent application laid-open No. 59-56403, japanese patent application laid-open No. 2-69, japanese patent application laid-open No. 57-168088, japanese patent application laid-open No. 5-107761, japanese patent application laid-open No. 5-210240, and Japanese patent application laid-open No. 4-288818.
Among these sensitizing dye, amino group-containing sensitizing dye is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable. Examples of the preferred sensitizing dye include benzophenone-based compounds such as 4,4 '-dimethylaminobenzophenone, 4' -diethylaminobenzophenone, 2-aminobenzophenone, 4 '-diaminobenzophenone, 3' -diaminobenzophenone, and 3, 4-diaminobenzophenone; and compounds containing p-dialkylaminophenyl groups such as 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2, 5-bis (p-diethylaminophenyl) -1,3, 4-oxazol, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2, 5-bis (p-diethylaminophenyl) -1,3, 4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, and (p-diethylaminophenyl) pyrimidine. Of these, 4' -dialkylaminobenzophenone is particularly preferred.
The sensitizing dye may be used alone or in combination of at least 2 kinds.
As the polymerization accelerator, for example, there can be used: aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate; aliphatic amines such as N-butylamine and N-methyldiethanolamine; mercapto compounds described below. The polymerization accelerator may be used alone or in combination of 1 or more than 2.
(d) ethylenically unsaturated Compound
The photosensitive coloring composition of the present invention comprises (d) an ethylenically unsaturated compound. By including (d) an ethylenically unsaturated compound, the sensitivity is improved.
The ethylenically unsaturated compound used in the present invention is a compound having at least 1 ethylenically unsaturated group in the molecule. Specifically, examples thereof include: (meth) acrylic acid, alkyl (meth) acrylates, acrylonitrile, styrene, monoesters of carboxylic acids, polyols or monohydric alcohols having 1 ethylenically unsaturated bond.
In the present invention, it is particularly preferable to use a polyfunctional olefinic monomer having 2 or more ethylenically unsaturated groups in 1 molecule. The number of the ethylenically unsaturated groups included in the polyfunctional olefinic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and is preferably 8 or less, more preferably 7 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 2 to 8, more preferably 2 to 7, still more preferably 4 to 7, particularly preferably 5 to 7. When the lower limit value is equal to or higher than the upper limit value, the sensitivity tends to be high, and when the lower limit value is equal to or lower than the upper limit value, the solubility in a solvent tends to be improved.
Examples of the polyfunctional olefinic monomer include: esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; esters obtained by esterification of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polycarboxylic acids.
Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include: aliphatic polyhydroxy compound acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, methacrylates obtained by converting these acrylates into methacrylates, itaconates obtained by converting these acrylates into itaconates, crotonates obtained by converting them into crotonates, and maleates obtained by converting them into maleates.
Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include: aromatic polyhydroxy compound acrylates and methacrylates such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and trimellitic acid ester.
The ester obtained by the esterification reaction of the polycarboxylic acid and the unsaturated carboxylic acid with the polyhydroxy compound is not necessarily a single substance, and examples thereof include: condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid and diethylene glycol; condensation products of methacrylic acid, terephthalic acid and pentaerythritol; condensate of acrylic acid, adipic acid, butanediol and glycerol.
In addition, as the polyfunctional olefinic monomer used in the present invention, for example, urethane (meth) acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or reacting a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth) acrylate; epoxy acrylates such as addition reaction products of a polyvalent epoxy compound and a hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate are useful.
Examples of urethane (meth) acrylates include: DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Japanese chemical Co., ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Sanyo chemical Co., ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Co-common Equiz chemical Co., ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Mitsubishi chemical Co., ltd.).
Among these, from the viewpoint of curability, as the (d) ethylenically unsaturated compound, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids or urethane (meth) acrylates, urethane (meth) acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth) acrylate are preferably used, alkyl (meth) acrylates are more preferably used, and dipentaerythritol hexaacrylate is more preferably used.
These may be used alone or in combination of 1 or more than 2.
Solvent < (e)
The photosensitive coloring composition of the present invention comprises (e) a solvent. By containing the solvent (e), the colorant (a) can be dispersed or dissolved in the solvent, and further coating becomes easy.
The photosensitive coloring composition of the present invention is usually used in a state of being dissolved or dispersed in a solvent (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and other various materials as needed. Among the solvents, organic solvents are preferred from the viewpoints of dispersibility and coatability.
Among the organic solvents, from the viewpoint of coatability, an organic solvent having a boiling point of 100 to 300 ℃ is preferably selected, and an organic solvent having a boiling point of 120 to 280 ℃ is more preferable. The boiling point here means a boiling point at a pressure of 1013.25hPa, and the boiling points are the same as described below.
Examples of such an organic solvent include: glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether and other glycol monoalkyl ethers;
glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;
glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate and the like;
Glycol diacetates such as ethylene glycol diacetate, 1, 3-butanediol diacetate and 1, 6-hexanediol diacetate;
alkyl acetates such as cyclohexanol acetate;
ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethylisobutyl ether, dihexyl ether, and the like;
ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxy methyl amyl ketone;
1-or polyalcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;
alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexyl;
aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;
chain or cyclic esters such as amyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and gamma butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
halogenated hydrocarbons such as chlorobutane and chloropentane;
ether ketones such as methoxy methyl pentanone;
nitriles such as acetonitrile and benzonitrile.
As the commercially available organic solvent, for example, there can be used: mineral spirits, varsol #2, apc #18solvent, apc thinner, socal solvent nos. 1 and 2, solvesso #150, shell TS28solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("cellosolve" is a registered trademark, the same applies hereinafter), ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether (diglyme) (all trade names).
These organic solvents may be used alone or in combination of 2 or more.
When forming the partition wall by photolithography, the organic solvent is preferably selected from those having a boiling point of 100 to 240 ℃, more preferably 120 to 200 ℃, and still more preferably 120 to 170 ℃.
Among the above organic solvents, glycol alkyl ether acetates are preferred from the viewpoint of good balance of coatability, surface tension and the like, and high solubility of constituent components in the composition.
The glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferable. Propylene glycol monomethyl ether is preferred from the viewpoint of the solubility of the constituent components in the composition. The proportion of the glycol monoalkyl ether in the solvent is preferably 5 to 30% by mass, more preferably 5 to 20% by mass, because the polarity of the glycol monoalkyl ether is high, and if the amount of the glycol monoalkyl ether added is too large, pigment tends to aggregate easily, and the storage stability such as viscosity of the photosensitive coloring composition to be obtained thereafter increases.
It is also preferable to use an organic solvent having a boiling point of 150 ℃ or higher (hereinafter, sometimes referred to as "high boiling point solvent") in combination. By using a high boiling point solvent in combination, although the photosensitive coloring composition becomes difficult to dry, there is an effect of preventing the uniformly dispersed state of the pigment in the composition from being damaged in the case of rapid drying. That is, for example, the effect of preventing occurrence of a foreign matter defect due to precipitation and solidification of a colorant or the like at the tip of the slit nozzle is obtained. Among the above solvents, diethylene glycol mono-n-butyl ether acetate and diethylene glycol monoethyl ether acetate are particularly preferable from the viewpoint of high effect.
When the high boiling point solvent is used in combination, the content of the high boiling point solvent in the organic solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass. When the lower limit value is set to the above lower limit value, for example, foreign matter defects due to precipitation and solidification of coloring materials or the like at the tip of the slit nozzle can be suppressed, and when the upper limit value is set to the lower limit value, the drying rate of the composition can be suppressed, and problems such as a beat defect and a needle mark due to pre-baking in a reduced pressure drying process can be suppressed.
The high boiling point solvent having a boiling point of 150 ℃ or higher may be glycol alkyl ether acetate, or glycol alkyl ether, and in this case, the high boiling point solvent having a boiling point of 150 ℃ or higher may not be additionally contained.
Among the above various solvents, examples of the preferred high boiling point solvents include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1, 3-butanediol diacetate, 1, 6-hexanol diacetate, and triacetin.
Dispersing agent < (f)
The photosensitive coloring composition of the present invention contains (f) a dispersant. By containing the dispersant (f), the colorant (a) can be stably dispersed.
The dispersant (f) in the photosensitive coloring composition of the present invention contains an acrylic copolymer (f 1) having a repeating unit represented by the following general formulae (1) to (3) (hereinafter, sometimes referred to as "dispersant (f 1)") and does not have a repeating unit containing a quaternary ammonium group.
Figure BDA0004133603210000591
(in the formula (1), R 31 Is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group.
R 32 Is a hydrogen atom or a methyl group.
And represents a connecting bond. )
Figure BDA0004133603210000592
(in the formula (2), R 33 Is methylene, ethylene or propylene, R 34 Is optionally substituted alkyl, R 35 Is a hydrogen atom or a methyl group.
n is an integer of 1 to 20.
And represents a connecting bond. )
Figure BDA0004133603210000601
(in the formula (3), R 36 And R is 37 Each independently is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, R 36 And R is 37 Optionally bonded to each other to form a cyclic structure.
R 38 Is a hydrogen atom or a methyl group.
Z is a 2-valent linking group.
And represents a connecting bond. )
The dispersant (f 1) has a repeating unit represented by the following general formula (1) from the viewpoint of improving the compatibility with a solvent or an alkali-soluble resin and improving the dispersion stability.
Figure BDA0004133603210000602
(in the formula (1), R 31 Is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group.
R 32 Is a hydrogen atom or a methyl group.
And represents a connecting bond. )
(R 31 )
In the above formula (1), R is 31 Examples of the alkyl group in (a) include linear, branched or cyclic alkyl groups, and from the viewpoint of compatibility with a solvent or an alkali-soluble resin, linear is preferable, and from the viewpoint of affinity with a pigment, branched is preferable.
The carbon number of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, and is preferably 10 or less, more preferably 8 or less, more preferably 6 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1 to 10, more preferably 2 to 8, and still more preferably 4 to 6. When the content is not less than the above lower limit, the affinity for pigments tends to be improved. When the content is not more than the upper limit, the compatibility with solvents and alkali-soluble resins tends to be improved, and the dispersibility tends to be improved.
Examples of the alkyl group include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethylhexyl are preferred, and methyl and ethyl are more preferred from the standpoint of compatibility with solvents and alkali-soluble resins.
Examples of the substituent optionally included in the alkyl group include: alkoxy groups such as methoxy and ethoxy; halogen atoms such as fluorine atom, chlorine atom and bromine atom; aryl groups such as phenyl and naphthyl are preferably unsubstituted from the viewpoint of compatibility with solvents and alkali-soluble resins, and phenyl is preferred from the viewpoint of affinity with pigments.
As R 31 Examples of the aryl group include a 1-valent aromatic hydrocarbon ring group and a 1-valent aromatic heterocyclic group.
The carbon number of the aryl group is not particularly limited, but is usually 6 or more, and is preferably 16 or less, more preferably 12 or less, and further preferably 10 or less. When the content is not more than the upper limit, the affinity for pigments tends to be improved. Examples of the aryl group include: phenyl, naphthyl and anthracenyl are preferable from the viewpoint of dispersibility, and phenyl and naphthyl are more preferable.
Examples of the substituent optionally included in the aryl group include: alkyl groups such as methyl and ethyl; alkoxy groups such as methoxy and ethoxy; halogen atoms such as fluorine atom, chlorine atom and bromine atom; aryl groups such as phenyl and naphthyl; aralkyl groups such as benzyl and phenethyl are preferably unsubstituted from the viewpoint of dispersibility.
Among these, R is the group from the viewpoint of compatibility with solvents and alkali-soluble resins 31 Alkyl groups optionally having substituents are preferred, and methyl, butyl, ethylhexyl, or benzyl groups are more preferred.
From the standpoint of compatibility with solvents and alkali-soluble resins, the dispersant (f 1) has a repeating unit represented by the following general formula (2).
Figure BDA0004133603210000621
(in the formula (2), R 33 Is methylene, ethylene or propylene, R 34 Is optionally substituted alkyl, R 35 Is a hydrogen atom or a methyl group.
n is an integer of 1 to 20.
And represents a connecting bond. )
In the above formula (2), R 33 Ethylene is preferable from the viewpoint of compatibility with solvents and alkali-soluble resins.
In the above formula (2), R 34 In order to form an alkyl group which may have a substituent, a methyl group or an ethyl group is preferable from the viewpoint of compatibility with a solvent or an alkali-soluble resin.
In the above formula (2), n is an integer of 1 to 20, preferably 1 or more, more preferably 2 or more, and further preferably 10 or less, more preferably 5 or less. For example, it is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 to 5. When the lower limit value is not less than the above, compatibility with a solvent or an alkali-soluble resin tends to be improved. When the content is not more than the upper limit, the affinity for the pigment tends to be improved and the dispersibility tends to be improved.
The dispersant (f 1) has a repeating unit represented by the above general formula (3). From the viewpoint of surface roughness of the electrode, it is preferably used.
Figure BDA0004133603210000622
(in the formula (3), R 36 And R is 37 Each independently is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, R 36 And R is 37 Optionally bonded to each other to form a cyclic structure.
R 38 Is a hydrogen atom or a methyl group.
Z is a 2-valent linking group.
And represents a connecting bond. )
In the above formula (3), R 36 And R is 37 Each independently is a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, or an optionally substituted aralkyl group. As the optionally substituted alkyl group, the optionally substituted aryl group, R in the above formula (1) may be preferably employed 31 The radicals listed.
In the above formula (3), R 36 And R is 37 Optionally bonded to each other to form a cyclic structure. Examples of the cyclic structure include: a nitrogen-containing heterocyclic single ring having 5 to 7 membered rings or condensed rings obtained by condensing 2 of these. The nitrogen-containing heterocycle is preferably not aromatic, and more preferably is a saturated ring. Specifically, the following examples are given.
Figure BDA0004133603210000631
(these cyclic structures may optionally further have a substituent.
And represents a connecting bond. )
(Z)
In the above formula (3), Z is a 2-valent linking group.
Examples of the 2-valent linking group include: single bond, C1-C10 alkylene, C6-C12 arylene, -CONH-R 39 -group, -COOR 40 -a radical (wherein R 39 And R is 40 Each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkoxyalkyl group) having 2 to 10 carbon atoms. ) From the standpoint of dispersibility, preferred is-COOR 7 -a radical. R is R 40 In this case, from the viewpoint of the stability of the dispersion over time, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is still more preferable.
The content of the repeating unit represented by the general formula (1) (hereinafter, sometimes referred to as "repeating unit (1)") in the dispersant (f 1) is not particularly limited, but is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, still more preferably 50 mol% or more, particularly preferably 60 mol% or more, and further preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less, and particularly preferably 75 mol% or less, of the total repeating units. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 20 to 90 mol%, more preferably 30 to 90 mol%, still more preferably 40 to 80 mol%, still more preferably 50 to 80 mol%, particularly preferably 60 to 80 mol%. When the content is not less than the above lower limit, the affinity for pigments tends to be improved. When the upper limit value is less than or equal to the above, the compatibility with solvents and alkali-soluble resins tends to be improved.
The content of the repeating unit represented by the general formula (2) (hereinafter, sometimes referred to as "repeating unit (2)") in the dispersant (f 1) is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 2.5 mol% or more, particularly preferably 3 mol% or more, and is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 15 mol% or less, still more preferably 10 mol% or less, particularly preferably 8 mol% or less, of the total repeating units. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1 to 30 mol%, more preferably 1 to 20 mol%, still more preferably 1 to 15 mol%, still more preferably 1 to 10 mol%, particularly preferably 2 to 10 mol%. When the lower limit value is not less than the above, the compatibility with solvents and alkali-soluble resins tends to be improved. When the content is not more than the upper limit, the affinity for pigments tends to be improved.
The content of the repeating unit represented by the general formula (3) (hereinafter, sometimes referred to as "repeating unit (3)") in the dispersant (f 1) is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 25 mol% or more, particularly preferably 30 mol% or more, and is preferably 50 mol% or less, more preferably 45 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, of the total repeating units. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 10 to 50 mol%, more preferably 20 to 40 mol%, further preferably 25 to 35 mol%, particularly preferably 30 to 35 mol%. When the lower limit value is not less than the above, dispersibility tends to be excellent. When the upper limit value is less than or equal to the above, the dispersion tends to be excellent in stability with time.
The dispersant (f 1) may be contained in any form of random copolymerization or block copolymerization, and from the viewpoint of dispersibility, a block copolymer is preferable, and the block copolymer preferably contains: an a block comprising repeat units having a solphilic group and a B block comprising repeat units having a pigment adsorbing group.
When the dispersant (f 1) has the repeating unit (1) and the repeating unit (2), they are preferably contained in the a block, and may be contained in any of random copolymerization and block copolymerization. In addition, the a block may contain 2 or more kinds of repeating units (1) and (2), respectively, and in this case, the repeating units may be contained in the a block in any of random copolymerization and block copolymerization.
The a block may contain a repeating unit other than the repeating units (1) and (2), and as such a repeating unit, a repeating unit derived from: styrene monomers such as styrene and α -methylstyrene; (meth) acrylic acid salt-based monomers such as (meth) acryloyl chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; n-methacryloyl morpholine.
Among these, the block copolymer comprising an A block having ase:Sub>A repeating unit (1) and ase:Sub>A repeating unit (2) and ase:Sub>A B block having ase:Sub>A repeating unit (3) is more preferably an A-B block copolymer or an A-B-A block copolymer.
The amine value of the dispersant (f 1) is not particularly limited, but is preferably 50mgKOH/g or more, more preferably 80mgKOH/g or more, still more preferably 90mgKOH/g or more, particularly preferably 100mgKOH/g or more, and is preferably 200mgKOH/g or less, more preferably 160mgKOH/g or less, still more preferably 140mgKOH/g or less, particularly preferably 130mgKOH/g or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 50 to 200mgKOH/g, more preferably 80 to 160mgKOH/g, still more preferably 100 to 140mgKOH/g, particularly preferably 100 to 130mgKOH/g. When the lower limit value is not less than the above, the surface roughness of the electrode tends to be suppressed. When the upper limit value is less than or equal to the above, the dispersion tends to be improved in stability with time. The amine number is expressed as KOH mass corresponding to the amount of alkali per 1g of the solid content of the dispersant (f 1).
The acid value of the dispersant (f 1) is not particularly limited, but is preferably 10mgKOH/g or less, more preferably 5mgKOH/g or less, further preferably 1mgKOH/g, particularly preferably 0mgKOH/g, from the viewpoint of dispersibility.
The weight average molecular weight of the dispersant (f 1) is not particularly limited, but is preferably 3000 or more, more preferably 5000 or more, further preferably 7000 or more, and is preferably 100000 or less, more preferably 50000 or less, further preferably 10000 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 3000 to 100000, more preferably 5000 to 50000, and still more preferably 7000 to 10000. When the lower limit value is not less than the above, dispersibility tends to be improved. When the upper limit value is less than or equal to the above, the dispersion tends to be improved in stability with time.
The content of chlorine atoms in the dispersant (f 1) is not particularly limited, but is preferably 1.0 mass% or less, more preferably 0.5 mass% or less, still more preferably 0.2 mass% or less, and particularly preferably substantially no chlorine atoms, that is, 0.1 mass% or less. When the upper limit value is less than or equal to the above, surface roughness tends to be suppressed.
The method for producing the dispersant (f 1) is not particularly limited, and a known method can be used. Examples include: japanese patent application laid-open No. Hei 01-299014, japanese patent application laid-open No. 2017-019937, japanese patent application laid-open No. 2018-172530, japanese patent application laid-open No. 2018-203795, japanese patent application laid-open No. 2019-099801, international publication No. 2019/079659.
The dispersant (f) in the photosensitive coloring composition of the present invention may contain a dispersant other than the dispersant (f 1) (hereinafter, sometimes referred to as "other dispersant").
As the other dispersant, for example, a dispersant having the following groups as functional groups is preferable from the viewpoint of dispersion stability: a carboxyl group; or a salt group thereof; primary, secondary or tertiary amino groups; a quaternary ammonium salt group; and nitrogen-containing heterocyclic groups derived from pyridine, pyrimidine, pyrazine and the like. Among them, a dispersant having a basic functional group such as a primary amino group, a secondary amino group or a tertiary amino group is more preferable; a quaternary ammonium salt group; and nitrogen-containing heterocyclic groups derived from pyridine, pyrimidine, pyrazine and the like.
In addition, a polymeric dispersant is preferable from the viewpoint of being able to disperse with a small amount of dispersant when dispersing the pigment.
Examples of the polymer dispersant include: acrylic dispersants, urethane dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants made of amino group-containing monomers and macromers, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, and the like other than the dispersant (f 1).
Examples of such polymer dispersants include EFKA (registered trademark, manufactured by BASF corporation), DISPEBYK (registered trademark, manufactured by BYK-Chemie corporation), DISPARON (registered trademark, manufactured by Nanj chemical Co., ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol corporation, manufactured by KP (manufactured by Xinyue chemical industry Co., ltd.), POLYFLOW (manufactured by Kyowa chemical Co., ltd.), and AJISPER (manufactured by registered trademark, manufactured by Weisu corporation).
Examples of the urethane-based and acrylic-based polymer dispersants include: the DISPERBYK 160-166, 182 series (all of urethane series), DISPERBYK2000, 2001, BYK-LPN21116 (all of acrylic series) (all of which are manufactured by BYK-Chemie Co.).
The other dispersant may be used in an amount of 1 or 2 or more.
< other ingredients of photosensitive coloring composition >
In addition to the above components, the photosensitive coloring composition of the present invention may be suitably blended with an adhesion-improving agent such as a silane coupling agent, a surfactant, a pigment derivative, a photoacid generator, a crosslinking agent, a mercapto compound, a polymerization inhibitor, and other additives.
(1) Adhesion improving agent
In order to improve the adhesion to the substrate, the photosensitive coloring composition of the present invention may contain an adhesion improving agent. As the adhesion improving agent, a silane coupling agent, a phosphate group-containing compound, and the like are preferable.
As the kind of the silane coupling agent, 1 kind of various silane coupling agents such as epoxy-based, (meth) acrylic-based and amino-based can be used alone or 2 or more kinds thereof can be mixed and used.
Examples of the silane coupling agent include: (meth) acryloyloxy silanes such as 3-methacryloxypropyl methyl dimethoxy silane and 3-methacryloxypropyl trimethoxy silane; epoxysilanes such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, and 3-epoxypropoxypropyltriethoxysilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; isocyanate silanes such as 3-isocyanatopropyltriethoxysilane. Particularly preferred are epoxy silane-based silane coupling agents.
The phosphate group-containing compound is preferably a (meth) acryloyl phosphate group-containing compound represented by the following general formula (g 1), (g 2) or (g 3).
Figure BDA0004133603210000681
In the above general formulae (g 1), (g 2) and (g 3), R 51 Represents a hydrogen atom or a methyl group, l and l' are integers of 1 to 10, and m is 1, 2 or 3.
These phosphate group-containing compounds may be used alone or in combination of 1 or more than 2.
(2) Surface active agent
In order to improve the coatability, the photosensitive coloring composition of the present invention may contain a surfactant.
As the surfactant, various surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be used. Among them, nonionic surfactants are preferably used because of low possibility of adversely affecting various properties, and among them, fluorine-based and silicon-based surfactants are effective from the viewpoint of coatability.
Examples of such a surfactant include: TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by NEOS), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340 (manufactured by Xinyue silicone), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Dow Corning Toray), DS-401 (manufactured by Dain corporation), L-77 (manufactured by Izod, japan), and FC4430 (manufactured by 3M).
The surfactant may be used in 1 kind, or may be used in combination of 2 or more kinds in any combination and ratio.
(3) Pigment derivative
In order to improve dispersibility and preservability, the photosensitive coloring composition of the present invention may further contain a pigment derivative as a dispersing aid.
Examples of the pigment derivative include: azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, pyrenone, diketopyrrolopyrrole, dioxazine derivatives, among which phthalocyanine and quinophthalone derivatives are preferred.
Examples of the substituent of the pigment derivative include: the substituent bonded to the pigment skeleton directly or via alkyl, aryl, heterocyclic group or the like is preferably a sulfonic acid group. In addition, a plurality of these substituents may be substituted on one pigment skeleton.
Examples of the pigment derivative include: a sulfonic acid derivative of phthalocyanine, a sulfonic acid derivative of quinophthalone, a sulfonic acid derivative of anthraquinone, a sulfonic acid derivative of quinacridone, a sulfonic acid derivative of diketopyrrolopyrrole, a sulfonic acid derivative of dioxazine. These may be used alone or in combination of 1 or more than 2.
(4) Mercapto compounds
In order to improve the adhesion to the substrate, a mercapto compound may be added as a polymerization accelerator.
Examples of the mercapto compound include: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1, 4-dimethylmercaptobenzene, butandiol dimercaptopropionate, butandiol dimercaptoacetate, ethylene glycol dimercaptoacetate, trimethylolpropane trimercaptate, butandiol dimercaptopropionate, trimethylolpropane trimercaptate, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoacetate, trishydroxyethyl trimercaptate, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), 1, 5-tris (3-mercaptoethyl) -triazine, and the like have a heterocyclic ring of 1, 5H-functional groups. These may be used alone or in combination of 1 or more than 2.
(5) Polymerization inhibitor
The photosensitive coloring composition of the present invention may contain a polymerization inhibitor from the viewpoint of shape control of a cured product. It is considered that the inclusion of the polymerization inhibitor prevents radical polymerization of the lower layer of the coating film, and thus the taper angle (angle formed between the support and the cured product in the cross section of the cured product) can be controlled.
Examples of the polymerization inhibitor include: hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, 2, 6-di-tert-butyl-4-methylphenol (BHT). Among these, 2, 6-di-t-butyl-4-methylphenol is preferred from the viewpoint of shape control. In addition, hydroquinone monomethyl ether and methyl hydroquinone are preferable from the viewpoint of being particularly excellent in safety to the human body.
The polymerization inhibitor may be used alone or in combination of at least 2 kinds.
In the production of the alkali-soluble resin (b), a polymerization inhibitor may be contained in the resin, and the resin may be used as the polymerization inhibitor of the present invention, or a polymerization inhibitor similar to or different from the polymerization inhibitor may be added in the production of the photosensitive resin composition in addition to the polymerization inhibitor in the resin.
When the photosensitive coloring composition contains a polymerization inhibitor, the content thereof is not particularly limited, but is usually 0.0005 mass% or more, preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and is usually 0.3 mass% or less, preferably 0.2 mass% or less, more preferably 0.1 mass% or less, based on the total solid content of the photosensitive coloring composition. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 0.0005 to 0.3 mass%, more preferably 0.001 to 0.2 mass%, and still more preferably 0.01 to 0.1 mass%. When the lower limit value is not less than the above, the shape of the cured product tends to be controlled. When the upper limit value is less than or equal to the above, the desired sensitivity tends to be maintained.
< content ratio of each component in photosensitive coloring composition >
The content of the colorant (a) in the photosensitive coloring composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, still more preferably 20% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 25% by mass or less, based on the total solid content. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 15 to 30% by mass, and particularly preferably 15 to 25% by mass. When the lower limit value is not less than the above, the light shielding property tends to be ensured. When the amount is equal to or less than the upper limit, the amount of the dispersant can be reduced, and surface roughness can be suppressed.
In the first aspect, the content of the compound (I) in the photosensitive coloring composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, particularly preferably 20% by mass or more, and is usually 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, particularly preferably 25% by mass or less, relative to the total solid content of the photosensitive coloring composition. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 5 to 70% by mass, more preferably 20 to 70% by mass, still more preferably 20 to 60% by mass, particularly preferably 20 to 50% by mass. When the lower limit value is not less than the above, the loss of ultraviolet light required for curing tends to be suppressed and the light shielding property tends to be improved. When the amount is equal to or less than the upper limit, the amount of the dispersant can be reduced, and surface roughness can be suppressed.
In the first aspect, when the colorant (a) contains the compound (I) and other pigments, the total content thereof is not particularly limited, and the content of the compound (I) in the colorant (a) is preferably 10 mass% or more, more preferably 20 mass% or more, still more preferably 30 mass% or more, and further preferably 90 mass% or less, more preferably 80 mass% or less, and particularly preferably 70 mass% or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass. When the lower limit value is not less than the above, the light-shielding property tends to be improved, and a color tone close to black tends to be achieved. When the upper limit value is less than or equal to the above, residues at the time of development are reduced, and reliability at the time of element fabrication tends to be improved.
In the first aspect, when the colorant (a) contains the compound (I) and the organic coloring pigment, the total content ratio thereof is not particularly limited, and the content ratio of the compound (I) in the colorant (a) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and further preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass. When the lower limit value is not less than the above, the light-shielding property tends to be improved, and a color tone close to black tends to be achieved. When the upper limit value is less than or equal to the above, residues at the time of development are reduced, and reliability at the time of element fabrication tends to be improved.
When the photosensitive coloring composition contains an organic coloring pigment, the content thereof is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, and is usually 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, particularly preferably 25% by mass or less, based on the total solid content of the photosensitive coloring composition. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 5 to 70% by mass, more preferably 20 to 70% by mass, still more preferably 20 to 60% by mass, particularly preferably 20 to 50% by mass. When the light shielding property is set to the lower limit or more, the light shielding property tends to be improved. When the amount is equal to or less than the upper limit, the amount of the dispersant can be reduced, and surface roughness can be suppressed.
(a) When the colorant contains a red pigment and/or an orange pigment, the total content of the red pigment and the orange pigment is not particularly limited, but in (a), the colorant is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, particularly preferably 12% by mass or more, and further preferably 40% by mass or less, more preferably 30% by mass or less, particularly preferably 20% by mass or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 5 to 40% by mass, more preferably 8 to 40% by mass, still more preferably 10 to 30% by mass, particularly preferably 12 to 20% by mass. When the lower limit value is equal to or higher than the above, a color tone close to black tends to be achieved. When the upper limit value is less than or equal to the above, the sensitivity tends to be high.
(a) When the colorant contains a blue pigment and/or a violet pigment, the total content of the blue pigment and the violet pigment is not particularly limited, but in (a), the colorant is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, particularly preferably 80% by mass or more, and further preferably 95% by mass or less, more preferably 92% by mass or less, particularly preferably 90% by mass or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 30 to 95% by mass, more preferably 50 to 95% by mass, still more preferably 70 to 92% by mass, particularly preferably 80 to 90% by mass. When the lower limit value is equal to or higher than the above, a color tone close to black tends to be achieved. When the upper limit value is less than or equal to the above, sensitivity and light shielding properties tend to be good.
(a) When the colorant contains a red pigment and/or an orange pigment and a blue pigment and/or a violet pigment, the content of the red pigment and/or the orange pigment is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, particularly preferably 8% by mass or more, and further preferably 300% by mass or less, more preferably 100% by mass or less, particularly preferably 50% by mass or less, relative to the content of the blue pigment and/or the violet pigment. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1 to 300% by mass, more preferably 3 to 100% by mass, still more preferably 5 to 100% by mass, and particularly preferably 8 to 50% by mass. When the lower limit value is not less than the above, the blue light transmission tends to be suppressed, and the light-shielding property tends to be improved. When the upper limit value is less than or equal to the above, a color tone close to black tends to be achieved.
When the photosensitive coloring composition contains an organic black pigment, the content thereof is not particularly limited, but is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, particularly preferably 20% by mass or more, and further preferably 60% by mass or less, more preferably 50% by mass or less, particularly preferably 40% by mass or less, based on the total solid content of the photosensitive coloring composition. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 3 to 60% by mass, more preferably 5 to 60% by mass, still more preferably 10 to 50% by mass, particularly preferably 20 to 40% by mass. When the light shielding property is set to the lower limit or more, the light shielding property tends to be improved. When the amount is less than the upper limit, the amount of the dispersant can be reduced, and surface roughness can be suppressed.
When the photosensitive coloring composition contains carbon black as an inorganic black pigment, the content thereof is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and further preferably 30% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass or less, relative to the total solid content of the photosensitive coloring composition. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass. When the light shielding property is set to the lower limit or more, the light shielding property tends to be improved. When the upper limit value is less than or equal to the above, a cured product having high resistance and low dielectric constant tends to be formed.
(a) When the colorant contains a black pigment and an organic coloring pigment, the total content ratio thereof is not particularly limited, and the content ratio of the black pigment in the colorant (a) is preferably 10 mass% or more, more preferably 20 mass% or more, further preferably 30 mass% or more, and further preferably 90 mass% or less, more preferably 80 mass% or less, particularly preferably 70 mass% or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass. When the lower limit value is not less than the above, the light-shielding property tends to be improved, and a color tone close to black tends to be achieved. When the upper limit value is less than or equal to the above, residues at the time of development are reduced, and reliability at the time of element fabrication tends to be improved.
(b) The content ratio of the alkali-soluble resin is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, and is usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, still more preferably 55% by mass or less, relative to the total solid content of the photosensitive coloring composition of the present invention. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass, still more preferably 30 to 60% by mass, particularly preferably 30 to 55% by mass, and particularly preferably 40 to 55% by mass. By setting the lower limit value or more, the solubility of the unexposed portion in the developer is suppressed from decreasing, and development failure is suppressed. When the upper limit value is less than or equal to the above, the dissolution of the exposed portion by the developer can be suppressed, and the lowering of the sharpness and adhesion of the pattern can be suppressed while maintaining the appropriate sensitivity.
(b1) The content of the epoxy (meth) acrylate resin is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, particularly preferably 30% by mass or more, particularly preferably 40% by mass or more, usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, particularly preferably 55% by mass or less, based on the total solid content of the photosensitive coloring composition of the present invention. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass, still more preferably 30 to 60% by mass, particularly preferably 30 to 55% by mass, and particularly preferably 40 to 55% by mass. When the lower limit value is not less than the above, solubility of the unexposed portion in the developer tends to be ensured. When the upper limit value is less than or equal to the above, the dissolution of the exposed portion by the developer is suppressed, and the lowering of the sharpness and adhesion of the pattern is suppressed.
(b) The content ratio of the (b 1) epoxy (meth) acrylate resin contained in the alkali-soluble resin is not particularly limited, and is usually 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, and is usually 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, and still more preferably 40 to 80% by mass. When the lower limit value is not less than the above, solubility of the unexposed portion in the developer tends to be ensured. When the upper limit value is less than or equal to the above, the dissolution of the exposed portion by the developer is suppressed, and the lowering of the sharpness and adhesion of the pattern is suppressed.
(c) The content ratio of the photopolymerization initiator is not particularly limited, but is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, still more preferably 3% by mass or more, usually 15% by mass or less, preferably 10% by mass or less, still more preferably 8% by mass or less, still more preferably 6% by mass or less, based on the total solid content of the photosensitive coloring composition of the present invention. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 0.1 to 15% by mass, more preferably 0.5 to 15% by mass, further preferably 1 to 10% by mass, further preferably 2 to 8% by mass, and particularly preferably 3 to 6% by mass. When the lower limit value is not less than the above, the sensitivity tends to be suppressed from decreasing. By setting the upper limit value or less, the solubility of the unexposed portion in the developer can be suppressed from decreasing, and development failure can be suppressed.
When the polymerization accelerator is used together with the photopolymerization initiator (c), the content of the polymerization accelerator is not particularly limited, but is preferably 0.05% by mass or more, usually 10% by mass or less, and preferably 5% by mass or less, based on the total solid content of the photosensitive coloring composition of the present invention. The polymerization accelerator is preferably used in an amount of usually 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass, based on 100 parts by mass of the photopolymerization initiator (c). When the content ratio of the polymerization accelerator is not less than the lower limit, the sensitivity to exposure light tends to be suppressed. By setting the upper limit value or less, the solubility of the unexposed portion in the developer is suppressed from decreasing, and development failure is suppressed.
When the sensitizing dye is used together with the photopolymerization initiator (c), the content thereof is not particularly limited, but from the viewpoint of sensitivity, the content of the sensitizing dye is usually 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less, relative to the total solid content in the photosensitive coloring composition.
(d) The content of the ethylenically unsaturated compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and is usually 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, based on the total solid content of the photosensitive coloring composition of the present invention. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, and still more preferably 10 to 20% by mass. When the lower limit value is set to be equal to or larger than the above-described lower limit value, the dissolution of the exposed portion by the developer is suppressed, and the lowering of the sharpness and adhesion of the pattern is suppressed. When the upper limit value is less than or equal to the above, the improvement in the permeability of the developer to the exposed portion is suppressed, and a good image tends to be easily obtained.
The photosensitive coloring composition of the present invention can be prepared as a liquid so that the content of the total solid component is preferably 5 mass% or more, more preferably 10 mass% or more, still more preferably 15 mass% or more and preferably 50 mass% or less, more preferably 30 mass% or less, still more preferably 25 mass% or less, by using the solvent (e). The upper and lower limits mentioned above may be combined arbitrarily. For example, the liquid is prepared preferably at 5 to 50% by mass, more preferably at 10 to 30% by mass, and still more preferably at 15 to 25% by mass.
(f) The content of the dispersant is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and is usually 20% by mass or less, 15% by mass or less, more preferably 10% by mass or less, more preferably 7% by mass or less, based on the total solid content of the photosensitive coloring composition. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, still more preferably 3 to 10% by mass, particularly preferably 3 to 7% by mass. When the lower limit value is not less than the above, sufficient dispersibility tends to be easily obtained. When the upper limit value is less than or equal to the above, surface roughness of the electrode surface tends to be suppressed.
The content ratio of the dispersant (f 1) is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and is usually 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, more preferably 7% by mass or less, based on the total solid content of the photosensitive coloring composition. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, still more preferably 3 to 10% by mass, particularly preferably 3 to 7% by mass. When the lower limit value is not less than the above, sufficient dispersibility tends to be easily obtained. When the upper limit value is less than or equal to the above, surface roughness of the electrode surface tends to be suppressed.
The content of the dispersant (f 1) is not particularly limited, but is usually 20 mass% or more, preferably 40 mass% or more, more preferably 60 mass% or more, still more preferably 80 mass% or more, and is usually 100 mass% or less in the dispersant (f). When the lower limit value is not less than the above, surface roughness on the electrode surface tends to be suppressed.
(f) The content ratio of the dispersant is not particularly limited, but is usually 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, usually 50 parts by mass or less, particularly preferably 30 parts by mass or less, relative to 100 parts by mass of the colorant (a). The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 15 to 30 parts by mass. When the lower limit value is not less than the above, sufficient dispersibility tends to be easily obtained. When the upper limit value is less than or equal to the above, surface roughness of the electrode surface tends to be suppressed.
(b) The content ratio of the alkali-soluble resin to 100 parts by mass of the ethylenically unsaturated compound (d) is not particularly limited, but is usually 100 parts by mass or more, preferably 200 parts by mass or more, more preferably 250 parts by mass or more, further preferably 300 parts by mass or more, particularly preferably 350 parts by mass or more, and is usually 700 parts by mass or less, preferably 500 parts by mass or less, more preferably 450 parts by mass or less, further preferably 400 parts by mass or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 100 to 700 parts by mass, more preferably 200 to 700 parts by mass, still more preferably 250 to 500 parts by mass, still more preferably 250 to 450 parts by mass, and particularly preferably 250 to 400 parts by mass. When the lower limit value is not less than the above, the developing state tends to be a proper dissolution developing state such as no peeling. When the upper limit value is less than or equal to the above, a suitable dissolution time with respect to the developer tends to be obtained.
When the adhesion improving agent is used, the content thereof is not particularly limited, but is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4 to 2% by mass, based on the total solid content of the photosensitive coloring composition. When the lower limit value is not less than the above-mentioned lower limit value, the effect of improving the adhesion tends to be sufficiently obtained. When the upper limit value is less than or equal to the above, the sensitivity is reduced, and the residue remaining after development tends to be defective.
When the surfactant is used, the content is not particularly limited, but is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, and most preferably 0.03 to 0.3% by mass, based on the total solid content of the photosensitive coloring composition. When the lower limit value is not less than the above, the coating film tends to be smooth and uniform. When the upper limit value is less than or equal to the above, the coating film tends to be smooth and uniform, and other properties tend to be suppressed from deteriorating.
< chlorine atom content in photosensitive coloring composition >
In the photosensitive coloring composition of the present invention, the content of chlorine atoms in the photosensitive coloring composition is 0.05 mass% or less relative to the total solid component amount of the photosensitive coloring composition.
In the process of producing the partition wall, a step of curing the photosensitive coloring composition by performing a heat treatment is carried out as will be described later. In this case, the surface of the electrode may be roughened. The surface roughness can be observed by an optical microscope, and the surface roughness also becomes high. When the surface roughness is generated on the electrode surface, the light-emitting layer cannot be uniformly formed in the portion, and display failure due to short circuit or the like may occur when the organic electroluminescent element is produced. It is assumed that this is because chlorine atoms in the photosensitive coloring composition decompose, volatilize or sublimate during the heat treatment, particularly during the baking, and act on a metal electrode such as silver to cause corrosion or etching, and the like, and the surface roughness can be suppressed by setting the content of chlorine atoms to a certain value or less.
The chlorine atom in the photosensitive coloring composition is mainly contained in constituent materials such as (a) a colorant, (b) an alkali-soluble resin, and (f) a dispersant, and may be contained in other materials. In order to bring the chlorine atom content within the predetermined numerical range of the present invention, the chlorine content of one constituent material may be reduced, or the chlorine content in each material may be reduced so as to fall within the predetermined numerical range.
The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is preferably 0.05 mass% or less, more preferably 0.04 mass% or less, still more preferably 0.03 mass% or less, and still more preferably 0.01 mass% or less, based on the total solid content of the photosensitive coloring composition. When the upper limit value is less than or equal to the above, the surface roughness of the electrode tends to be suppressed.
The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is usually 0.0005 mass% or more, preferably 0.001 mass% or more, and more preferably 0.002 mass%. When the lower limit is not less than the above lower limit, it is effective to facilitate purification in manufacturing each constituent material.
The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 0.0005 to 0.05 mass%, more preferably 0.0005 to 0.04 mass%, further preferably 0.001 to 0.03 mass%, particularly preferably 0.002 to 0.01 mass%.
The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is preferably 100 μg/g or less, more preferably 80 μg/g or less, still more preferably 50 μg/g or less, still more preferably 30 μg/g or less, and particularly preferably 10 μg/g or less, relative to the total mass of the photosensitive coloring composition containing the solvent. When the upper limit value is less than or equal to the above, the surface roughness of the electrode tends to be suppressed.
The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is usually 0.5. Mu.g/g or more, preferably 1.0. Mu.g/g or more, and more preferably 2.0. Mu.g/g or more. When the lower limit is not less than the lower limit, the purification is effective for the production of each constituent material in a simple manner.
The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 0.5 to 100. Mu.g/g, more preferably 0.5 to 80. Mu.g/g, still more preferably 1.0 to 50. Mu.g/g, still more preferably 1.0 to 30. Mu.g/g, particularly preferably 2.0 to 10. Mu.g/g.
The content of the chlorine atom in the photosensitive coloring composition is not particularly limited, but is preferably 0.20 mass% or less, more preferably 0.15 mass% or less, still more preferably 0.10 mass% or less, still more preferably 0.05 mass% or less, and particularly preferably 0.03 mass% or less, based on 100 mass% of the colorant (a) in the photosensitive coloring composition. When the upper limit value is less than or equal to the above, the surface roughness of the electrode tends to be suppressed.
The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is usually 0.001 mass% or more, preferably 0.005 mass% or more, and more preferably 0.010 mass%. When the lower limit is not less than the lower limit, it is effective to facilitate purification in the production of each constituent material.
The upper and lower limits mentioned above may be combined arbitrarily. For example, the content of the colorant (a) is preferably 0.001 to 0.20 mass%, more preferably 0.001 to 0.15 mass%, still more preferably 0.005 to 0.10 mass%, still more preferably 0.005 to 0.05 mass%, and particularly preferably 0.010 to 0.03 mass% relative to 100 mass% of the photosensitive coloring composition.
The chlorine atom content in the photosensitive coloring composition can be measured by, for example, combustion ion chromatography (Combustion ion chromatography).
Physical Properties of photosensitive coloring composition
In the photosensitive coloring composition of the present invention, the Optical Density (OD) of the coating film per 1 μm film thickness is not particularly limited in the first embodiment, but is preferably 0.5 or more. In the second embodiment, the ratio is 0.5 or more. More preferably 0.7 or more, still more preferably 1.0 or more, still more preferably 1.3 or more, particularly preferably 1.5 or more, usually 4.0 or less, preferably 3.0 or less, and still more preferably 2.0 or less. The upper and lower limits mentioned above may be combined arbitrarily. In any of the first and second aspects, for example, it is preferably 0.5 to 4.0, more preferably 0.7 to 4.0, still more preferably 1.0 to 3.0, still more preferably 1.3 to 3.0, and particularly preferably 1.5 to 2.0. When the lower limit value is not less than the above, sufficient light-shielding properties tend to be obtained. When the upper limit value is less than or equal to the above, the surface roughness of the electrode tends to be good.
The Optical Density (OD) of the coating film per 1 μm film thickness can be measured using a coating film formed by curing the photosensitive coloring composition of the present invention, and can be measured using a coating film formed by heat curing at 230 ℃ for 20 minutes.
Optical density refers to: the transmission optical density of the spectral sensitivity characteristic of the light receiving section is expressed in terms of the ISO visual density in the ISO 5-3 standard. Generally, an a light source specified by CIE (international commission on illumination) is used as the light source. As a measuring instrument which can be used for the measurement of the transmitted light density, for example, SAKATA INX ENG.CO., X-Rite 361T (V) of LTD can be mentioned.
Process for producing photosensitive coloring composition
The photosensitive coloring composition of the present invention can be prepared by a conventional method.
In general, (a) the colorant is preferably dispersed in advance using a paint shaker, a sand mill, a ball mill, a roller mill, a stone mill, a jet mill, a homogenizer, or the like. By the dispersion treatment, (a) the colorant is micronized, and thus, the coating characteristics of the resist are improved.
The dispersion treatment is generally preferably performed in a system in which (a) a colorant, (e) a solvent, and (f) a dispersant are used in combination with a part or all of (b) an alkali-soluble resin (hereinafter, a mixture to be subjected to the dispersion treatment and a composition obtained by the dispersion treatment are sometimes referred to as "pigment dispersion"). In particular, if a polymeric dispersant is used as the dispersant (f), thickening of the obtained pigment dispersion and photosensitive coloring composition with time, that is, dispersion stability is excellent can be suppressed, and thus it is preferable.
Therefore, in the step of producing the photosensitive coloring composition, it is preferable to produce a pigment dispersion liquid containing at least (a) a colorant, (e) a solvent, and (f) a dispersant.
As the (a) colorant, (e) solvent, and (f) dispersant that can be used in the pigment dispersion, examples described as those that can be used in the photosensitive coloring composition can be preferably employed, respectively. The content ratio of each of the colorants in (a) the pigment dispersion may be preferably the content ratio described as the content ratio in the photosensitive coloring composition.
When a dispersion treatment is performed on a liquid containing all the components to be blended in the colored resin composition, there is a possibility that highly reactive components may be modified due to heat release generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
When the colorant (a) is dispersed by a sand mill, glass beads or zirconia beads having a particle diameter of about 0.1 to 8mm are preferably used. In terms of dispersion treatment conditions, the temperature is usually in the range of 0℃to 100℃and preferably in the range of room temperature to 80 ℃. The dispersion time may be appropriately adjusted depending on the composition of the liquid, the size of the dispersion treatment apparatus, and the like. The criteria for dispersion are: the gloss of the pigment dispersion is controlled so that the 20-degree specular gloss (JIS Z8741) of the photosensitive coloring composition is in the range of 50 to 300. When the glossiness of the photosensitive coloring composition is low, generally, the dispersion treatment is insufficient, coarse pigment (coloring material) particles remain, and there is a possibility that the developability, the adhesion, the resolution, and the like become insufficient. If the dispersion treatment is carried out until the gloss value exceeds the above range, the pigment is broken to generate a large amount of ultrafine particles, and therefore the dispersion stability tends to be impaired instead.
The dispersion particle diameter of the pigment dispersed in the pigment dispersion is usually 0.03 to 0.3. Mu.m, and can be measured by a dynamic light scattering method.
Next, the pigment dispersion liquid obtained by the dispersion treatment is mixed with the other components contained in the photosensitive coloring composition to prepare a uniform solution or dispersion liquid. In the production process of the photosensitive coloring composition, fine dust may be mixed into the liquid, and thus it is desirable to filter the obtained photosensitive coloring composition with a filter or the like.
[ cured product ]
The cured product of the present invention can be obtained by curing the photosensitive coloring composition of the present invention. The cured product obtained by curing the photosensitive coloring composition of the present invention can be preferably used as a partition wall.
[ partition wall ]
The photosensitive coloring composition of the present invention can be preferably used for forming a partition wall, particularly a partition wall for dividing an organic layer of an organic electroluminescent element. Examples of the organic layer used for the organic electroluminescent element include an organic layer used for a hole injection layer, a hole transport layer, or a hole transport layer on a hole injection layer described in japanese patent application laid-open No. 2016-165396.
Next, a partition wall using the photosensitive coloring composition of the present invention will be described in terms of its production method.
(1) Support body
The material of the support for forming the partition walls is not particularly limited as long as the support has an appropriate strength. The substrate is mainly used, and examples of the material include: a sheet made of a thermoplastic resin such as a polyester resin such as polyethylene terephthalate, a polyolefin resin such as polypropylene and polyethylene, a polycarbonate, polymethyl methacrylate, and polysulfone; thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, and poly (meth) acrylic resins, and various glasses. Among them, glass and heat-resistant resins are preferable from the viewpoint of heat resistance. In addition, transparent electrodes such as ITO and IZO, or metal electrodes such as silver, gold, platinum, aluminum and magnesium may be formed on the surface of the substrate. In addition to the above-described substrate, it may be formed on a TFT array.
In order to improve the surface physical properties such as adhesion, the support may be subjected to a film formation treatment of various resins such as corona discharge treatment, ozone treatment, silane coupling agent, urethane resin, and the like, as required.
The thickness of the substrate is usually in the range of 0.05 to 10mm, preferably 0.1 to 7 mm. In addition, when film formation treatment of various resins is performed, the film thickness is usually in the range of 0.01 to 10. Mu.m, preferably 0.05 to 5. Mu.m.
(2) Partition wall
The photosensitive coloring composition of the present invention is used in the same applications as those of the known photosensitive coloring compositions for color filters, and the following description will be given of the case of using the photosensitive coloring composition of the present invention as a partition wall according to a specific example of a partition wall forming method.
In general, a photosensitive coloring composition is supplied in a film or pattern form by a method such as coating on a substrate on which partition walls are to be provided, and the solvent is dried. Next, patterning is performed by a method such as photolithography in which exposure and development are performed. Thereafter, additional exposure and heat curing treatment are performed as needed, whereby barrier ribs are formed on the substrate.
(3) Formation of partition walls
[1] Method for supplying substrate
The photosensitive coloring composition of the present invention is usually supplied onto a substrate in a state of being dissolved or dispersed in a solvent. The method of supplying the molten metal may be performed by a conventionally known method such as spin coating, wire bar (Wire bar) method, flow coating, die coating, roll coating, or spray coating. The supply may be performed in a pattern by, for example, an inkjet method or a printing method. Among them, the use of the die coating method is preferable from the standpoint of greatly reducing the amount of the coating liquid to be used, and suppressing the generation of foreign matters without any influence of mist or the like adhering to the coating liquid in the spin coating method.
The coating amount varies depending on the application, and for example, in the case of the partition wall, the coating is performed so that the dry film thickness is usually 0.5 μm to 10 μm, preferably 1 μm to 9 μm, and particularly preferably 1 μm to 7 μm. It is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire substrate. By reducing the variation, the light-emitting layer can be uniformly formed, and display defects during light emission can be suppressed.
When the photosensitive coloring composition of the present invention is used to form spacers having different heights at one time by photolithography, the heights of the spacers to be finally formed may be different.
As the substrate, a known substrate such as a glass substrate or an array substrate may be used. The substrate surface is preferably planar.
[2] Drying method
Drying after the photosensitive coloring composition is supplied onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. The reduced pressure drying method may be combined in which drying is performed in a reduced pressure chamber without increasing the temperature.
The drying conditions may be appropriately selected depending on the kind of the solvent component, the performance of the dryer used, and the like. The drying time is selected depending on the kind of the solvent component, the performance of the dryer used, and the like, and is usually selected in the range of 40 to 130℃for 15 seconds to 5 minutes, preferably 50 to 110℃for 30 seconds to 3 minutes.
[3] Exposure method
The exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive coloring composition and irradiating the coating film with ultraviolet light or visible light through the mask pattern. In the case of performing exposure using an exposure mask, a method of bringing the exposure mask close to a coating film of the photosensitive coloring composition may be employed; an exposure mask is disposed at a position distant from the coating film of the photosensitive coloring composition, and exposure light is projected through the exposure mask. A scanning exposure method using a laser beam without using a mask pattern may be used. If necessary, exposure may be performed in a deoxidized atmosphere or after an oxygen barrier layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent the sensitivity of the photopolymerizable layer from decreasing due to oxygen.
In a preferred embodiment of the present invention, when the spacers having different heights are formed simultaneously by photolithography, for example, an exposure mask having a light shielding portion (light transmittance 0%) and a plurality of openings (intermediate transmission openings) having an average light transmittance smaller than that of the opening having the highest average light transmittance (full transmission openings) is used. In this method, the difference in residual film rate is generated by the difference in average light transmittance between the intermediate transmission opening and the full transmission opening, that is, the difference in exposure amount.
A method of forming a medium transmission opening by a matrix-like light shielding pattern having light shielding units of a minute polygon is known. In addition, a method of manufacturing a film of chromium-based, molybdenum-based, tungsten-based, or silicon-based material by controlling light transmittance by using the film as an absorber is known.
The light source used for the exposure is not particularly limited. Examples of the light source include: light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, and the like; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium-cadmium laser, blue-violet semiconductor laser, and near infrared semiconductor laser. When light of a specific wavelength is irradiated and used, a filter may be used.
The filter may be of a type capable of controlling the transmittance of the exposure wavelength with a thin film, for example, and the material in this case may be: cr compound (oxide, nitride, oxynitride, fluoride, etc. of Cr), moSi, si, W, al.
The exposure amount is not particularly limited, but is usually 1mJ/cm 2 Above, preferably 5mJ/cm 2 Above, more preferably 10mJ/cm 2 Above, typically 300mJ/cm 2 Below, preferably 200mJ/cm 2 Hereinafter, more preferably 150mJ/cm 2 The following is given.
The distance between the exposure target and the mask pattern is not particularly limited in the vicinity of the exposure method, but is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and is usually 500 μm or less, preferably 400 μm or less, more preferably 300 μm or less.
[4] Development method
After the exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution of the basic compound may further contain, for example, a surfactant, an organic solvent, a buffer, a complexing agent, a dye, or a pigment.
As the basic compound, there may be mentioned: inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide; organic basic compounds such as mono-, di-or triethanolamine, mono-, di-or trimethylamine, mono-, di-or triethylamine, mono-or diisopropylamine, n-butylamine, mono-, di-or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline and the like. These basic compounds may be a mixture of 2 or more.
Examples of the surfactant include: nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters; anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinates, and the like; amphoteric surfactants such as alkyl betaines and amino acids.
Examples of the organic solvent include: isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol. These organic solvents may be used in combination of 2 or more. The organic solvent may be used alone or in combination with water or an aqueous solution of an alkaline compound.
The conditions of the development treatment are not particularly limited, and the development temperature is usually 10 to 50 ℃, preferably 15 to 45 ℃, more preferably 20 to 40 ℃. Examples of the developing method include immersion developing method, spray developing method, brush developing method, and ultrasonic developing method.
[5] Additional exposure and thermal curing treatment
The substrate after development may be subjected to additional exposure according to the same method as the above-described exposure method, if necessary. After development or after additional exposure, a heat curing treatment (also referred to as baking) may be performed. The heat curing conditions are preferably 100 to 280 ℃, more preferably 150 to 250 ℃ for 5 to 60 minutes.
The size, shape, etc. of the partition wall when the photosensitive coloring composition of the present invention is used can be appropriately adjusted according to the specifications of the organic electroluminescent element using the same, and the height of the partition wall formed from the photosensitive coloring composition of the present invention is usually about 0.5 to 10 μm.
In view of light-shielding properties, the Optical Density (OD) of the barrier ribs of the present invention is preferably 0.7 or more, more preferably 1.2 or more, still more preferably 1.5 or more, and particularly preferably 1.8 or more per 1 μm. The content is preferably 4.0 or less, more preferably 3.0 or less. The upper and lower limits mentioned above may be combined arbitrarily. For example, it is preferably 0.7 to 4.0, more preferably 1.2 to 4.0, further preferably 1.5 to 3.0, and particularly preferably 1.8 to 3.0. Here, the Optical Density (OD) is a value measured by a method described later.
[ organic electroluminescent element ]
The organic electroluminescent element of the present invention includes the cured product of the present invention, for example, a partition wall.
For example, various organic electroluminescent elements may be manufactured using a substrate having a partition wall pattern manufactured using the above-described method. The method of forming the organic electroluminescent element is not particularly limited, and it is preferable to form an organic layer such as a pixel by a wet process such as a vapor deposition method, a casting method, a spin coating method, or an ink jet printing method after forming a pattern of the partition wall on the substrate by the above-described method, and the vapor deposition method is a method of sublimating a functional material in a vacuum state and attaching the sublimated functional material to a region surrounded by the partition wall on the substrate to form a film.
As the type of the organic electroluminescent element, a bottom emission type and a top emission type are exemplified.
The bottom emission type is produced, for example, by forming a partition wall on a glass substrate on which a transparent electrode is laminated, and laminating a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer on an opening surrounded by the partition wall. On the other hand, the top emission type is produced by forming a partition wall on a glass substrate on which a metal electrode layer is laminated as a reflective layer, and laminating an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer in an opening surrounded by the partition wall.
The light-emitting layer may be an organic electroluminescent layer described in japanese patent application laid-open No. 2009-146691 and japanese patent No. 5734681. Further, quantum dots described in japanese patent No. 5653387 and japanese patent No. 5653101 may be used.
The layer structure is not limited to this, and may be a stacked structure of two or more hole transport layers and two or more electron transport layers, for example, from the viewpoint of light emission efficiency. The thickness of each layer is not particularly limited, but is usually 1 to 500nm from the viewpoints of luminous efficiency and luminance.
The organic electroluminescent element may be formed by dividing each of RGB colors for each opening, or may be formed by stacking two or more colors in 1 opening. The organic electroluminescent element may be provided with a sealing layer from the viewpoint of improving reliability. The sealing layer has a function of preventing moisture in the air from adsorbing to the organic electroluminescent element, thereby reducing luminous efficiency. The organic electroluminescent element may have a low reflection film at an interface with air from the viewpoint of improving light extraction efficiency. By disposing a low reflection film at the interface between air and the element, it is possible to reduce the difference in refractive index and suppress reflection at the interface. For such a low reflection film, a technique such as a moth-eye structure or a super multilayer film can be applied.
When the organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent light of a light emitting layer of some pixels from leaking to other pixels, and when the electrode or the like is made of metal, it is necessary to prevent degradation of image quality associated with reflection of external light, and therefore, it is preferable to impart light shielding properties to a partition wall constituting the organic electroluminescent element.
In addition, in the organic electroluminescent element, since electrodes need to be provided on the upper and lower surfaces of the partition wall, the partition wall is preferably high in resistance and low in dielectric constant from the viewpoint of insulation. Therefore, in order to impart light-shielding properties to the partition wall, when a colorant is used, the above-mentioned organic pigment having high resistance and low dielectric constant is preferably used.
[ image display device ]
The image display device of the present invention includes an organic EL display device having a partition wall containing the cured product of the present invention and the organic electroluminescent element of the present invention.
The organic EL display device may include the organic electroluminescent element described above, and the type and structure of the image display device are not particularly limited, and for example, an active-driving organic electroluminescent element may be used and assembled according to a conventional method. For example, the organic EL display (issued by OHM corporation in 8 months and 20 days of the year of year, time Ren Jingshi, dakubo vector, village Tian Yingxing) can be formed by the method described in the literature. For example, an organic electroluminescent element that emits white light may be combined with a color filter to display an image, or an organic electroluminescent element that emits light of different colors such as RGB may be combined to display an image.
Lighting
The organic electroluminescent element comprising the cured product of the present invention can be used for illumination. The type and structure of illumination are not particularly limited, and an organic electroluminescent element containing the cured product of the present invention can be used and assembled according to a conventional method. The organic electroluminescent element may be driven by a simple matrix or an active matrix.
In order to emit white light from illumination, an organic electroluminescent element that emits white light may be used. The organic electroluminescent elements having different emission colors may be combined to mix the colors into white, or the color mixing ratio may be adjusted to provide a color mixing function.
Examples
The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to the following examples unless the gist of the present invention is exceeded.
The constituent components of the photosensitive coloring compositions used in the following examples and comparative examples and the evaluation methods thereof are as follows.
< alkali-soluble resin-I >
300 parts by mass of "XD1000" (polyglycidyl ether of dicyclopentadiene-phenol polymer, epoxy equivalent 252), 87 parts by mass of acrylic acid, 0.2 part by mass of p-methoxyphenol, 5 parts by mass of triphenylphosphine, and 255 parts by mass of propylene glycol monomethyl ether acetate, manufactured by Japanese chemical Co., ltd.) were added to a reaction vessel, and stirred at 100℃until the acid value reached 3.0 mgKOH/g. Then, 145 parts by mass of tetrahydrophthalic anhydride was further added thereto, and the mixture was reacted at 120℃for 4 hours. The alkali-soluble resin I thus obtained had a weight average molecular weight Mw of 2600 and an acid value of 106mgKOH/g as measured by GPC.
< alkali-soluble resin-II >
Figure BDA0004133603210000891
50.0 parts by mass of the epoxy compound (epoxy equivalent 248) having the above-described structure, 14.2 parts by mass of acrylic acid, 52.6 parts by mass of methoxybutyl acetate, 1.29 parts by mass of triphenylphosphine and 0.044 parts by mass of p-methoxyphenol were charged into a flask equipped with a thermometer, a stirrer and a condenser, and reacted at 90℃until the acid value became 5mgKOH/g or less while stirring. The reaction took 12 hours to obtain an epoxyacrylate solution.
The epoxy acrylate solution was reacted by adding 42.9 parts by mass of methoxybutyl acetate, 1.98 parts by mass of Trimethylolpropane (TMP), 24.9 parts by mass of biphenyltetracarboxylic dianhydride (BPDA) and 5.39 parts by mass of tetrahydrophthalic anhydride (THPA) to a flask equipped with a thermometer, a stirrer and a condenser tube, and slowly heating to 105℃while stirring.
When the resin solution became transparent, it was diluted with methoxybutyl acetate to adjust the solid content to 50 mass%, thereby obtaining an alkali-soluble resin (II) having an acid value of 100mgKOH/g and a weight-average molecular weight (Mw) of 12000.
< alkali-soluble resin-III >
"ZCR-8035H" (weight average molecular weight Mw=7000, acid value=82 mgKOH/g) manufactured by Japanese chemical Co. Has a partial structure represented by the following formula (C-1).
Figure BDA0004133603210000901
pigment-I
Irgaphor (registered trademark) Black S0100 CF (having a chemical structure represented by the following formula (2)) manufactured by BASF corporation.
Figure BDA0004133603210000902
pigment-II
C.i. pigment orange 64
< pigment-III >
C.i. pigment violet 29
pigment-IV >
C.i. pigment blue 60
< dispersant-I >)
A methacrylic A-B diblock copolymer comprising an A block comprising repeating units having a solvophilic group and a B block comprising repeating units having a pigment adsorbing group. The repeating units of the following formulas (a) to (f). The amine number was 120mgKOH/g. The weight average molecular weight was 9000. The dispersant contains substantially no chlorine atoms.
The content of the repeating units represented by the following formulas (a) to (f) in the total repeating units was (a) 33.3 mol%, (b) 13.3 mol%, (c) 6.7 mol%, (d) 6.7 mol%, (e) 6.7 mol%, and (f) 33.3 mol%, respectively.
A block
Figure BDA0004133603210000911
B block
Figure BDA0004133603210000912
< dispersant-II >
A methacrylic A-B diblock copolymer comprising an A block comprising repeating units having a solvophilic group and a B block comprising repeating units having a pigment adsorbing group. The repeating units of the following formulas (h) to (n). The amine number was 70mgKOH/g. The weight average molecular weight of the amino group before quaternization was 9000. The content of chlorine atoms in the dispersant was 2.1 mass%.
The content of the repeating units represented by the following formulas (h) to (n) in the total repeating units was (h) 33.3 mol%, (i) 13.3 mol%, (j) 6.7 mol%, (k) 6.7 mol%, (1) 6.7 mol%, (m) 24.0 mol%, and (n) 9.3 mol%, respectively.
A block
Figure BDA0004133603210000921
B block
Figure BDA0004133603210000922
< solvent-I >, a process for preparing the same
PGMEA: propylene glycol monomethyl ether acetate
< solvent-II >
MB: 3-methoxy-1-butanol
< solvent-III >
MBA: acetic acid 3-methoxybutyl ester
< photopolymerization initiator-I >)
An oxime ester photopolymerization initiator having the following chemical structure.
Figure BDA0004133603210000931
< olefinically unsaturated Compounds >
DPHA-40H: urethane acrylate manufactured by Japanese chemical Co
< surfactant >)
MEGAFAC F-559 manufactured by DIC Co
< evaluation of viscosity >
The viscosity of the pigment dispersion was measured by an RE-85L viscometer (measurement conditions: 23 ℃ C., 20 rpm) manufactured by Toku industries, ltd.
< determination of chlorine atom content >)
The measurement was performed by combustion ion chromatography (Combustion ion chromatography). The chlorine atom content in the photosensitive coloring composition was quantified by a standard curve method using a combustion absorption ion chromatography (CIC) device AQF2100H from MITSUBISHI CHEMICAL ANALYTECH (now Nittoseiko analytical co., ltd.).
< measurement of optical Density per film thickness (Unit OD value >)
The optical density per unit film thickness was measured as follows.
First, the prepared photosensitive coloring composition was applied to a glass substrate by a spin coater so that the film thickness after baking was 1.5. Mu.m, dried under reduced pressure for 1 minute, and then dried at 100℃for 120 seconds by a hot plate. The obtained coating film was exposed without using an exposure mask. As the irradiation light source, an intensity of 40mW/cm at 365nm was used 2 Is set to 50mJ/cm 2 . Then, heat-cured in an oven at 230℃for 30 minutes, thereby obtaining an anti-aging propertyThe etchant coats the substrate 1.
The optical density (OD value) of the obtained resist-coated substrate 1 was measured by a 361T (V) transmission densitometer (color temperature of an illumination light source: about 2850K (corresponding to CIE standard light source A), spectral sensitivity characteristic of a light receiving portion: ISO visual density under ISO 5-3 standard) manufactured by X-Rite corporation, and the film thickness was measured by a non-contact surface/layer cross-sectional shape measuring system VertScan (R) 2.0 manufactured by Ryoka Systems Inc., and the optical density (unit OD value) per unit film thickness (1 μm) was calculated from the optical density (OD value) and the film thickness. The OD value is a value indicating light-shielding ability, and a larger value indicates a higher light-shielding property.
< evaluation of roughness of electrode surface >
The entire surface of the glass substrate was vapor-deposited with a silver thin film having a thickness of 60nm, and each photosensitive coloring composition was applied to the electrode substrate by a spin coater so that the film thickness after baking was 1.5. Mu.m, dried under reduced pressure for 1 minute, and then dried at 100℃for 120 seconds by a hot plate. Then, using a photomask capable of forming a square opening pattern having a side length of 50 μm on the obtained coated substrate, 50mJ/cm was performed by cutting off a wavelength of 330nm or less with a high-pressure mercury lamp so that an exposure gap was 5 μm 2 Ultraviolet exposure of (a). At this time, the light intensity at 365nm was 40mW/cm 2 . Then, after spray development was performed at 25℃for 60 seconds with a 2.38 mass% aqueous TMAH (tetramethylammonium hydroxide) solution as a developer and a water pressure of the developer of 0.05MPa, the developer was rinsed off with pure water to stop development, and the developer was washed with a water-washing spray for 60 seconds.
The opening portions are developed and removed by these operations, resulting in an electrode substrate in which the partition walls are patterned. The patterned substrate was heated (baked) in an oven at 230 ℃ for 30 minutes to cure the pattern.
The electrode substrate having the 50 μm opening pattern formed therein was observed with an optical microscope at 200 times, and the presence or absence of a change in the shape (surface roughness) of the electrode surface in the opening pattern was confirmed. The surface roughness was in the order A, B, C, with A indicating the best.
A: after heat curing, no surface roughness occurred on the electrode surface.
B: after curing by heating, the electrode surface produced a number of surface roughness, but there were no practical problems and it was acceptable.
C: after heat curing, the surface of the electrode is visible as concave-convex, which causes surface roughness, which is practically problematic and unacceptable.
< evaluation of luminescence Property >)
On a substrate on which an anode was formed by depositing an Indium Tin Oxide (ITO) transparent conductive film on glass at a thickness of 70nm and etching with a conventional photolithography technique and hydrochloric acid, each photosensitive coloring composition was coated with a spin coater so that the film thickness after firing was 1.5 μm, dried under reduced pressure for 1 minute, and then dried with a hot plate at 100℃for 120 seconds. Then, the obtained coated substrate was subjected to 50mJ/cm with an exposure gap of 5. Mu.m using an exposure mask (a mask having a plurality of rectangular covering portions (40 μm in the longitudinal direction. Times. 80 μm in the transverse direction) at a pitch of 60 μm in the longitudinal direction and 100 μm in the transverse direction) with a high-pressure mercury lamp which cuts a wavelength of 330nm or less 2 Ultraviolet exposure of (a). At this time, the light intensity at 365nm was 40mW/cm 2 . Then, after spray development with a water pressure of 0.05MPa for a developing solution of 60 to 120 seconds at 25 ℃ was performed using a 2.38 mass% aqueous solution of TMAH (tetramethylammonium hydroxide) as the developing solution, the developing solution was rinsed with pure water to stop the development, and the solution was washed with water by spraying for 60 seconds. The development time of the shower is 1.2 times or more the time for dissolving and removing the unexposed portion of the coating film.
The opening portions are developed and removed by these operations, resulting in an electrode substrate in which the partition walls are patterned. The patterned substrate was heated (baked) in an oven at 230 ℃ for 30 minutes to cure the pattern.
< fabrication of organic electroluminescent element >
An organic electroluminescent element was fabricated by sequentially stacking molybdenum oxide having a film thickness of 10nm as a hole injection layer, N- ([ 1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-N- [4- (9-phenyl-9H-carbazol-3-yl) phenyl ] -9H-fluoren-2-amine having a film thickness of 60nm as a hole transport layer, tris (8-hydroxyquinoline) aluminum having a film thickness of 60nm as a light emitting layer, 8-hydroxyquinoline lithium having a film thickness of 1nm as an electron injection layer, and aluminum having a film thickness of 80nm as a cathode on the entire surface of the electrode substrate on which the fabricated spacers were patterned by a vacuum evaporation method.
Then, a desiccant is attached to the concave portion of the sealing glass having the concave portion in the center, and a UV curable resin is applied to the frame portion around the concave portion. The organic electroluminescent element evaluation device was manufactured by disposing the concave portion of the sealing glass so as to completely cover the organic electroluminescent element on the electrode substrate, bonding the sealing glass to the electrode substrate, and curing the sealing glass by UV irradiation with UV-curable resin to seal the hollow structure.
< evaluation of light emission characteristics of organic electroluminescent element >
The current density of the manufactured element was measured to be 10mA/cm 2 Voltage value (driving voltage) at the time of direct current of (a) a (b).
At the time of cartridge fabrication, the current density was 10mA/cm 2 Voltage value (driving voltage) at power-on:
a: the voltage is below 6.5V and,
b: the voltage is higher than 6.5V.
Next, the current density of 50mA/cm at 60℃was measured 2 The driving life of the manufactured element was defined as the time (h) from the initial luminance to a value of 90% of the initial luminance when the manufactured element was driven with a constant current.
Time (lifetime) until the initial luminance reaches 90% luminance:
a: for a period of time longer than 25 hours,
b: and less than 25 hours.
Preparation of pigment Dispersion 1-3
The pigment, the dispersant, the alkali-soluble resin and the solvent described in table 1 were mixed in the mass ratio described in table 1. The mixture was subjected to dispersion treatment with a paint shaker at 25 to 45℃for 3 hours. As beads, use was made of
Figure BDA0004133603210000961
Is added to the dispersion in an amount of 2.5 times the mass of the beads. After the completion of the dispersion, the beads were separated from the dispersion by a filter, whereby pigment dispersions 1 to 3 were prepared.
The amounts of solvents in table 1 also include the amounts of solvents from the dispersant and the alkali-soluble resin. The results of evaluating the viscosity of the pigment dispersion liquid measured by the above method are shown in table 1.
TABLE 1
Figure BDA0004133603210000971
Examples 1 and 2 and comparative example 1
The photosensitive coloring compositions of examples 1 and 2 and comparative example 1 were prepared by adding the components so that the content ratio of the solid components of the components to the total solid component was the values shown in table 2, and further adding the solvent so that the content ratio of PGMEA/MB/mba=72/20/8 and the total solid component was 17 mass%, and stirring the mixture to dissolve the components. The results of evaluating the chlorine atom content, the unit OD value, and the surface roughness of the electrode, which were measured by the above-described method, are shown in tables 2 and 3.
TABLE 2
Figure BDA0004133603210000981
The substrate using the photosensitive coloring composition of comparative example 1 was confirmed to have a roughened silver (electrode) surface. This is considered to be because the dispersant-II contains a large amount of chlorine atoms, and therefore the photosensitive coloring composition also contains a large amount of chlorine atoms, and chlorine-containing gas is generated during firing, and reacts with the silver (electrode) surface to form irregularities on the surface.
On the other hand, in the substrate using the photosensitive coloring composition of example 1, no formation of irregularities on the silver (electrode) surface was observed. This is considered to be because the dispersant-I has no chlorine atom and, as a result, the content of the photosensitive coloring composition is small, and thus, the silver (electrode) does not have surface roughness, and a normal electrode substrate is obtained.
Regarding the light emission characteristics of the organic electroluminescent element, example 1 has an extended lifetime compared to comparative example 1. This is considered to be because the degradation of the light-emitting element with time is suppressed by reducing the chlorine amount.
TABLE 3
Figure BDA0004133603210000991
For the substrate using the photosensitive coloring composition of example 2, the surface roughness of silver (electrode) was also at a level substantially free of problems. It is considered that the reason why example 1 is superior to example 2 in terms of the surface roughness of silver (electrode) is that pigment-I is a rigid skeleton containing an aromatic ring, and therefore even a small amount of chlorine atoms are not released outside the film.
Regarding the light emission characteristics of the organic electroluminescent element, the initial driving voltage of example 2 was reduced to be good. In addition, the composition was better than example 1.

Claims (11)

1. A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant,
the colorant of (a) contains at least 1 selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound and a salt of the geometric isomer of the compound,
the dispersant (f) contains an acrylic copolymer (f 1), the acrylic copolymer (f 1) contains at least a repeating unit represented by the following general formulae (1), (2) and (3) and does not have a repeating unit containing a quaternary ammonium group,
The content of chlorine atoms in the photosensitive coloring composition is 0.05 mass% or less relative to the total solid component content of the photosensitive coloring composition,
Figure FDA0004133603180000011
in the formula (I), R 1 And R is 6 Independently of one another, is a hydrogen atom, CH 3 、CF 3 A fluorine atom or a chlorine atom,
R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 and R is 10 Independently of the others, are hydrogen atoms, halogen atoms, R 11 、COOH、COOR 11 、COO - 、CONH 2 、CONHR 11 、CONR 11 R 12 、CN、OH、OR 11 、COCR 11 、OOCNH 2 、OOCNHR 11 、OOCNR 11 R 12 、NO 2 、NH 2 、NHR 11 、NR 11 R 12 、NHCOR 12 、NR 11 COR 12 、N＝CH 2 、N＝CHR 11 、N＝CR 11 R 12 、SH、SR 11 、SOR 11 、SO 2 R 11 、SO 3 R 11 、SO 3 H、SO 3 - 、SO 2 NH 2 、SO 2 NHR 11 Or SO 2 NR 11 R 12 ，
Selected from R 2 And R is R 3 、R 3 And R is R 4 、R 4 And R is R 5 、R 7 And R is R 8 、R 8 And R is R 9 And R is 9 And R is R 10 At least 1 of the combinations of the group consisting are also optionally directly bonded to each other or through an oxygen atom, a sulfur atom, NH or NR 11 The bridges are bonded to each other and,
R 11 and R is 12 Independently of one another, alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, cycloalkenyl groups having 3 to 12 carbon atoms or alkynyl groups having 2 to 12 carbon atoms,
Figure FDA0004133603180000021
in the formula (1), R 31 Is an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group,
R 32 is a hydrogen atom or a methyl group,
the term "connection" means a connection bond,
Figure FDA0004133603180000022
in the formula (2), R 33 Is methylene, ethylene or propylene, R 34 Is optionally substituted alkyl, R 35 Is a hydrogen atom or a methyl group,
n is an integer of 1 to 20,
the term "connection" means a connection bond,
Figure FDA0004133603180000023
in the formula (3), R 36 And R is 37 Each independently is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, R 36 And R is R 37 Optionally bonded to each other to form a cyclic structure,
R 38 is a hydrogen atom or a methyl group,
z is a 2-valent linking group,
and represents a connecting bond.
2. The photosensitive coloring composition according to claim 1, wherein the (a) colorant comprises an organic coloring pigment.
3. A photosensitive coloring composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant,
the optical density of the coating film obtained by curing the photosensitive coloring composition is more than 0.5 per 1 mu m film thickness,
the dispersant (f) contains an acrylic copolymer (f 1), the acrylic copolymer (f 1) contains at least a repeating unit represented by the following general formulae (1), (2) and (3) and does not have a repeating unit containing a quaternary ammonium group,
the content of chlorine atoms in the photosensitive coloring composition is 0.05 mass% or less relative to the total solid component content of the photosensitive coloring composition,
Figure FDA0004133603180000031
in the formula (1), R 31 Is an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group,
R 32 is a hydrogen atom or a methyl group,
the term "connection" means a connection bond,
Figure FDA0004133603180000032
in the formula (2), R 33 Is methylene, ethylene or propylene, R 34 Is optionally substituted alkyl, R 35 Is a hydrogen atom or a methyl group,
n is an integer of 1 to 20,
the term "connection" means a connection bond,
Figure FDA0004133603180000041
in the formula (3), R 36 And R is 37 Each independently is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, R 36 And R is R 37 Optionally bonded to each other to form a cyclic structure,
R 38 is a hydrogen atom or a methyl group,
z is a 2-valent linking group,
and represents a connecting bond.
4. The photosensitive coloring composition according to claim 3, wherein the (a) colorant comprises at least 1 selected from the group consisting of red pigments and orange pigments and comprises at least 1 selected from the group consisting of blue pigments and violet pigments.
5. The photosensitive coloring composition according to any one of claims 1 to 4, wherein the acrylic copolymer (f 1) is a block copolymer.
6. The photosensitive coloring composition according to any one of claims 1 to 5, wherein said acrylic copolymer (f 1) has an amine value of 90mgKOH/g or more.
7. The photosensitive coloring composition according to any one of claims 1 to 6, wherein the (a) colorant is contained in an amount of 10% by mass or more relative to the total solid content of the photosensitive coloring composition.
8. The photosensitive coloring composition according to any one of claims 1 to 7, which is used for forming a partition wall of an organic electroluminescent element.
9. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 8.
10. An organic electroluminescent element comprising the cured product according to claim 9.
11. An image display device comprising the organic electroluminescent element according to claim 10.
CN202180064110.2A 2020-09-28 2021-09-27 Photosensitive coloring composition, cured product, organic electroluminescent element, and image display device Pending CN116323716A (en)

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