CN116893571A - Photosensitive composition - Google Patents

Photosensitive composition Download PDF

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Publication number
CN116893571A
CN116893571A CN202310303053.XA CN202310303053A CN116893571A CN 116893571 A CN116893571 A CN 116893571A CN 202310303053 A CN202310303053 A CN 202310303053A CN 116893571 A CN116893571 A CN 116893571A
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China
Prior art keywords
group
meth
formula
substituent
photosensitive composition
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CN202310303053.XA
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Chinese (zh)
Inventor
古谷和之
引田二郎
居岛洋一郎
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Tokyo Ohka Kogyo Co Ltd
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Tokyo Ohka Kogyo Co Ltd
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Publication of CN116893571A publication Critical patent/CN116893571A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • 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
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/12—N-Vinylcarbazole
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/075—Silicon-containing 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
    • G03F7/20—Exposure; Apparatus therefor

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention provides a photosensitive composition which provides a transparent cured product with high refractive index and excellent solvent resistance, a cured product of the photosensitive composition, and a method for forming a cured film by using the photosensitive composition. In a photosensitive composition containing an alkali-soluble resin (a), a photopolymerizable compound (B) and a photopolymerization initiator (C), a (meth) acrylic resin (a-1) containing a crosslinkable (meth) acrylate unit (a 1) having an ethylenically unsaturated double bond and an aromatic unit (a 2) which is a unit derived from N-vinylcarbazole which may have a substituent on an aromatic ring or from 9-vinylfluorene which may have a substituent on an aromatic ring is used as the alkali-soluble resin (a).

Description

Photosensitive composition
Technical Field
The present invention relates to a photosensitive composition, a cured product of the photosensitive composition, and a method for forming a cured film using the photosensitive composition.
Background
Conventionally, photosensitive compositions containing a photopolymerizable compound having an unsaturated double bond and a photopolymerization initiator and providing a transparent cured product have been used as coating materials for hard coatings and the like, light-transmitting materials constituting display panels such as liquid crystal display panels and organic EL display panels, and materials for forming protective films, insulating films, and the like in touch panels.
As such a photosensitive composition, for example, a photosensitive composition for forming a protective film, an insulating film, or the like in a touch panel, which contains a photopolymerizable monomer, a transparent resin that is a mixture of resins having a specific structure, a photopolymerization initiator, and a solvent, has been proposed (see patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2013-064973
Disclosure of Invention
Technical problem to be solved by the invention
However, a transparent cured product applied to a display panel often requires a high refractive index. In addition, in a process for manufacturing a display panel or the like, a transparent cured product formed using a photosensitive composition is often brought into contact with an organic solvent when other layers are stacked or in a process such as cleaning.
In view of the above, a photosensitive composition providing a transparent cured product having a high refractive index and excellent solvent resistance has been demanded.
The present invention has been made in view of the above-described problems, and an object thereof is to provide a photosensitive composition which provides a transparent cured product having a high refractive index and excellent solvent resistance, a cured product of the photosensitive composition, and a method for forming a cured film using the photosensitive composition.
Solution to the above technical problems
The present inventors have found that the above technical problems can be solved by using the following photosensitive composition, and have completed the present invention: a photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable compound (B) and a photopolymerization initiator (C), wherein a (meth) acrylic resin (a-1) comprising a crosslinkable (meth) acrylate unit (a 1) and an aromatic unit (a 2) is used as the alkali-soluble resin (A), the crosslinkable (meth) acrylate unit (a 1) having an ethylenically unsaturated double bond, and the aromatic unit (a 2) being a unit derived from N-vinylcarbazole which may have a substituent on an aromatic ring or from 9-vinylfluorene which may have a substituent on an aromatic ring. More specifically, the present invention provides the following scheme.
The 1 st aspect of the present invention is a photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable compound (B) and a photopolymerization initiator (C),
the alkali-soluble resin (A) comprises a (meth) acrylic resin comprising a crosslinkable (meth) acrylate unit (a 1) and an aromatic unit (a 2),
the crosslinkable (meth) acrylate unit (a 1) has an ethylenically unsaturated double bond,
The aromatic unit (a 2) is a unit derived from N-vinylcarbazole which may have a substituent on an aromatic ring or from 9-vinylfluorene which may have a substituent on an aromatic ring.
In the invention according to claim 2, the photosensitive composition according to claim 1 is a cured product.
A 3 rd aspect of the present invention is a method for forming a cured film, comprising: coating the photosensitive composition of the 1 st aspect on a substrate to form a coating film;
the coated film is exposed to light.
A 4 th aspect of the present invention is a method for forming a patterned cured film, comprising: coating the photosensitive composition of the 1 st aspect on a substrate to form a coating film;
exposing the coating film positionally selectively;
the exposed coating film is developed.
Effects of the invention
According to the present invention, a photosensitive composition providing a transparent cured product having a high refractive index and excellent solvent resistance, a cured product of the photosensitive composition, and a method for forming a cured film using the photosensitive composition can be provided.
Detailed Description
Photosensitive composition
The photosensitive composition comprises an alkali-soluble resin (A), a photopolymerizable compound (B) and a photopolymerization initiator (C).
The alkali-soluble resin (A) comprises a (meth) acrylic resin (a-1), and the (meth) acrylic resin (a-1) comprises a crosslinkable (meth) acrylate unit (a 1) and an aromatic unit (a 2).
The crosslinkable (meth) acrylate unit (a 1) has an ethylenically unsaturated double bond.
The aromatic unit (a 2) is a unit derived from N-vinylcarbazole which may have a substituent on an aromatic ring or from 9-vinylfluorene which may have a substituent on an aromatic ring.
In the description and claims of the present application, "(meth) acrylate" means both acrylate and methacrylate. In the description and claims of the present application, "(meth) acrylic" means both acrylic acid and methacrylic acid. In the description and claims of the present application, "(meth) acryl" means both acryl and methacryl.
The photosensitive composition having the above-described structure is cured well by exposure to light, and provides a transparent cured product having a high refractive index and excellent solvent resistance.
Hereinafter, the essential or optional components contained in the photosensitive composition will be described.
< alkali-soluble resin (A) >)
The photosensitive composition contains an alkali-soluble resin (A). The alkali-soluble resin (A) comprises a (meth) acrylic resin (a-1), and the (meth) acrylic resin (a-1) comprises a crosslinkable (meth) acrylate unit (a 1) and an aromatic unit (a 2).
The crosslinkable (meth) acrylate unit (a 1) has an ethylenically unsaturated double bond.
The aromatic unit (a 2) is a unit derived from N-vinylcarbazole which may have a substituent on an aromatic ring or from 9-vinylfluorene which may have a substituent on an aromatic ring.
The alkali-soluble resin (a) may contain an alkali-soluble resin other than the (meth) acrylic resin (a-1) within a range that does not impair the desired effect.
The ratio of the mass of the (meth) acrylic resin (a-1) to the mass of the alkali-soluble resin (a) is preferably 70 mass% or more, more preferably 80 mass% or more, still more preferably 90 mass% or more, and particularly preferably 100 mass% in view of the transparency and refractive index of the cured product formed using the photosensitive composition.
Hereinafter, the alkali-soluble resin (A) will be described with respect to the (meth) acrylic resin (a-1) and alkali-soluble resins other than the (meth) acrylic resin (a-1).
[ meth) acrylic resin (a-1) ]
The (meth) acrylic resin (a-1) contains a crosslinkable (meth) acrylate unit (a 1) and an aromatic unit (a 2).
The crosslinkable (meth) acrylate unit (a 1) has an ethylenically unsaturated double bond.
The aromatic unit (a 2) is a unit derived from N-vinylcarbazole which may have a substituent on an aromatic ring or from 9-vinylfluorene which may have a substituent on an aromatic ring.
The (meth) acrylic resin (a-1) may contain other structural units than the crosslinkable (meth) acrylate unit (a 1) and the aromatic unit (a 2).
Hereinafter, the essential or optional structural units that can be contained in the (meth) acrylic resin (a-1) will be described.
(crosslinkable (meth) acrylate unit (a 1))
The crosslinkable (meth) acrylate unit (a 1) has an ethylenically unsaturated double bond. The crosslinkable (meth) acrylate unit (a 1) is not particularly limited as long as it is a structural unit which can be derived from (meth) acrylic acid or (meth) acrylate and has an ethylenically unsaturated double bond.
For example, in a (meth) acrylic resin containing a structural unit having an epoxy group, the structural unit having an epoxy group is reacted with an unsaturated carboxylic acid such as (meth) acrylic acid, whereby a crosslinkable (meth) acrylate unit can be produced in the (meth) acrylic resin.
In this case, the hydroxyl group is formed by the reaction of the epoxy group with the unsaturated carboxylic acid. For the purpose of imparting alkali solubility to the (meth) acrylic resin (a-1), a polybasic acid anhydride such as dicarboxylic acid anhydride may be reacted with a hydroxyl group formed by the reaction after the unsaturated carboxylic acid is reacted with a structural unit having an epoxy group.
Specifically, when acrylic acid is reacted with a structural unit derived from glycidyl methacrylate, a structural unit having a (meth) acryloyl group and a hydroxyl group represented by the following reaction formula is formed. By reacting a polybasic acid anhydride such as tetrahydrophthalic anhydride with the above-mentioned structural unit having a hydroxyl group, a structural unit having a carboxyl group and an unsaturated double bond, which imparts alkali solubility to the resin, is produced.
[ chemical formula 1 ]
Examples of the compound providing the structural unit having an epoxy group to the (meth) acrylic resin include (meth) acrylic alkylene oxide esters such as glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, and 6, 7-epoxyheptyl (meth) acrylate.
In addition, as the compound that provides the structural unit having an epoxy group to the (meth) acrylic resin, an alicyclic epoxy group-containing (meth) acrylate is also preferable. The alicyclic group constituting the alicyclic epoxy group may be a single ring or multiple rings. Examples of the alicyclic group as a single ring include cyclopentyl and cyclohexyl. Examples of the polycyclic alicyclic group include norbornyl, isobornyl, tricyclononyl, tricyclodecyl and tetracyclododecyl.
Specific examples of the alicyclic epoxy group-containing (meth) acrylate include compounds represented by the following formulas (a-1-1 a) to (a-1-1 o). Among these, compounds represented by the following formulas (a-1-1 a) to (a-1-1 e) are preferable, and compounds represented by the following formulas (a-1-1 a) to (a-1-1 c) are more preferable.
[ chemical formula 2 ]
[ chemical 3 ]
[ chemical formula 4 ]
In the above formula, R a20 Represents a hydrogen atom or a methyl group. R is R a21 Represents a 2-valent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms. R is R a22 A 2-valent hydrocarbon group having 1 to 10 carbon atoms. t represents an integer of 0 to 10 inclusive. As R a21 The alkylene group is preferably a linear or branched alkylene group. Examples of the "alkylene" may include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene and hexamethylene. As R a22 Examples of the "methylene", "ethylene", "propylene", "tetramethylene", "ethylethylene", "pentamethylene", "hexamethylene", "phenylene", "cyclohexylene", "CH" and the like may be mentioned 2 -Ph-CH 2 - (Ph represents phenylene).
Specific examples of the polybasic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, and 4-ethyltetrahydrophthalic anhydride.
In addition, in the (meth) acrylic resin having a structural unit derived from (meth) acrylic acid, the unsaturated group-containing epoxy compound can be reacted with the structural unit derived from (meth) acrylic acid to produce the crosslinkable (meth) acrylate unit (a 1).
The unsaturated group-containing epoxy compound is preferably the above-mentioned alkylene oxide (meth) acrylate or alicyclic epoxy group-containing (meth) acrylate.
When an unsaturated group-containing epoxy compound is reacted with a structural unit derived from (meth) acrylic acid, a hydroxyl group is also formed by the reaction of an epoxy group with a carboxyl group. For the purpose of imparting alkali solubility to the (meth) acrylic resin (a-1), an unsaturated group-containing epoxy compound may be reacted with a structural unit derived from (meth) acrylic acid, and then a polybasic acid anhydride such as dicarboxylic acid anhydride may be reacted with a hydroxyl group formed by the reaction.
In the case where the (meth) acrylic resin has a structural unit derived from a (meth) acrylate having a hydroxyl group, the hydroxyl group in the structural unit may be acylated with an unsaturated carboxylic acid halide such as (meth) acryloyl chloride or etherified with a halogenated alkene such as allyl chloride to produce the crosslinkable (meth) acrylate unit (a 1).
Examples of the (meth) acrylate having a hydroxyl group include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, and hydroxyaryl (meth) acrylates such as 4-hydroxyphenyl (meth) acrylate, 3-hydroxyphenyl (meth) acrylate and 2-hydroxyphenyl (meth) acrylate.
The following structural units are preferable specific examples of the crosslinkable (meth) acrylate unit (a 1).
[ chemical 5 ]
[ 6 ] A method for producing a polypeptide
The ratio of the crosslinkable (meth) acrylate unit (a 1) to the entire structural units of the (meth) acrylic resin (a-1) is not particularly limited as long as the desired effect is not impaired.
The ratio of the crosslinkable (meth) acrylate unit (a 1) to the total structural units of the (meth) acrylic resin (a-1) is preferably 5 mol% or more and 30 mol% or less, more preferably 5 mol% or more and 20 mol% or less.
(aromatic unit (a 2))
The aromatic unit (a 2) is a unit derived from N-vinylcarbazole which may have a substituent on an aromatic ring or from 9-vinylfluorene which may have a substituent on an aromatic ring.
The aromatic unit (a 2) contributes to high solvent resistance and high refractive index of a cured product formed using the photosensitive composition.
The aromatic unit (a 2) may have a substituent on the carbazolyl group or the fluorenyl group.
The type of substituent that the aromatic unit (a 2) may have on the carbazolyl group or the fluorenyl group is not particularly limited as long as the desired effect is not impaired.
Specific examples of the substituent include an alkyl group, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a cyano group, an isocyano group, a cyanooxy group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxyl group, a carboxylate group, an acyl group, an acyloxy group, a sulfinyl group, a sulfo group, a phosphino group, a phosphono group, a phosphate group, a hydroxyimino group, an alkyl ether group, an alkyl thioether group, an aryl ether group, an aryl thioether group, and an amino group (-NH) 2 -NHR, -NRR': r and R' each independently represent a hydrocarbon group), and the like. The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. The hydrocarbon group contained in the substituent may be any of linear, branched, and cyclic.
When the aromatic unit (a 2) has 2 or more substituents on the carbazolyl or fluorenyl group, 2 or more substituents may be bonded to form a ring. The ring formed by bonding 2 substituents may be an aliphatic hydrocarbon ring, an aliphatic heterocyclic ring, or an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
The ratio of the aromatic unit (a 2) to the entire structural units of the (meth) acrylic resin (a-1) is not particularly limited as long as the desired effect is not impaired.
The ratio of the aromatic unit (a 2) to the entire structural units of the (meth) acrylic resin (a-1) is preferably 60 mol% or more, more preferably 60 mol% or more and 95 mol% or less, and still more preferably 70 mol% or more and 90 mol% or less.
(unsaturated carboxylic acid unit (a 3))
The (meth) acrylic resin (a-1) is an alkali-soluble resin. Therefore, the (meth) acrylic resin (a-1) preferably contains an unsaturated carboxylic acid unit (a 3) derived from an unsaturated carboxylic acid.
In the case where the crosslinkable (meth) acrylate unit (a 1) or the aromatic unit (a 2) has an alkali-soluble group such as a carboxyl group or a phenolic hydroxyl group, the (meth) acrylic resin (a-1) does not necessarily have an unsaturated carboxylic acid unit (a 3).
Examples of the unsaturated carboxylic acids include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; anhydrides of these dicarboxylic acids, and the like. Among them, (meth) acrylic acid is preferable.
The ratio of the unsaturated carboxylic acid unit (a 3) to the entire structural units of the (meth) acrylic resin (a-1) is not particularly limited as long as the desired effect is not impaired.
The ratio of the unsaturated carboxylic acid unit (a 3) to the total structural units of the (meth) acrylic resin (a-1) is preferably 5 mol% or more and 20 mol% or less, more preferably 5 mol% or more and 15 mol% or less.
(other units (a 4))
The (meth) acrylic resin (a-1) may contain other units (a 4) in addition to the crosslinkable (meth) acrylate unit (a 1), the aromatic unit (a 2) and the unsaturated carboxylic acid unit (a 3) as long as the desired effect is not impaired.
Examples of the other unit (a 4) may include a structural unit derived from a (meth) acrylate represented by the following formula (a-1-1).
[ chemical 7 ]
In the above formula (a-1-1), R a9 Is a hydrogen atom or a methyl group, R a10 Is a 1-valent organic group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a heteroatom. The organic group may be any of linear, branched, and cyclic. Wherein R is as R a10 The 1-valent organic group of (2) has an ethylenically unsaturated double bond.
As R a10 The substituent other than the hydrocarbon group in the organic group of (C) is not particularly limited as long as the effect of the present invention is not impaired, and examples thereof include a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a cyano group, an isocyano group, a cyanooxy group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxyl group, a carboxylate group, an acyl group, an acyloxy group, a sulfinyl group, a sulfo group, a phosphino group, a phosphono group, a phosphate group, a hydroxyimino group, an alkyl ether group, an alkyl thioether group, an aryl ether group, an aryl thioether group, an amino group (-NH) 2 -NHR, -NRR': r and R' each independently represent a hydrocarbon group), and the like. The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. The hydrocarbon group contained in the substituent may be a linear hydrocarbon groupAny of branched and cyclic.
In addition, as R a10 The organic group of (2) may have a reactive functional group such as an epoxy group or an oxetanyl group.
As R a10 Preferably an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, which may be substituted with a halogen atom, a hydroxyl group, an alkyl group or a heterocyclic group. In addition, in the case where these groups contain an alkylene moiety, the alkylene moiety may also be interrupted by an ether bond, a thioether bond, or an ester bond.
When the alkyl group is linear or branched, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10. Examples of the preferable alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, isodecyl and the like.
When the alkyl group is an alicyclic group or a group containing an alicyclic group, preferable alicyclic groups contained in the alkyl group include monocyclic alicyclic groups such as cyclopentyl and cyclohexyl, and polycyclic alicyclic groups such as adamantyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl and tetracyclododecyl.
The compound represented by the formula (a-1-1) contains a chain-like group having an epoxy group as R a10 Specific examples of the compound represented by the formula (a-1-1) include (meth) acrylic acid alkylene oxide esters such as glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, and 6, 7-epoxyheptyl (meth) acrylate.
The compound represented by the formula (a-1-1) may be a (meth) acrylate containing an alicyclic epoxy group. The alicyclic group constituting the alicyclic epoxy group may be a single ring or multiple rings. Examples of the alicyclic group as a single ring include cyclopentyl and cyclohexyl. Examples of the polycyclic alicyclic group include norbornyl, isobornyl, tricyclononyl, tricyclodecyl and tetracyclododecyl.
Specific examples of the case where the compound represented by the formula (a-1-1) is an alicyclic epoxy group-containing (meth) acrylate include compounds represented by the above-mentioned formulas (a-1-1 a) to (a-1-1 o). Among these, in order to make the developability within an appropriate range, the compounds represented by the above-mentioned formulae (a-1-1 a) to (a-1-1 e) are preferable, and the compounds represented by the above-mentioned formulae (a-1-1 a) to (a-1-1 c) are more preferable.
The other unit (a 4) may be a structural unit derived from a monomer such as (meth) acrylamide, an allyl compound, a vinyl ether, a vinyl ester, or a styrene. These monomers can be used singly or in combination of 2 or more.
Examples of the (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N-dialkyl (meth) acrylamide, N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, and N-hydroxyethyl-N-methyl (meth) acrylamide.
Examples of the "allyl compound" may include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol, and the like.
Examples of the vinyl ether include alkyl vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2, 2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, and the like; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2, 4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthryl ether.
Examples of the vinyl ester include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl-. Beta. -phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.
As the styrenes, styrene may be mentioned; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.; and halogenated styrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene.
The weight average molecular weight of the (meth) acrylic resin (a-1) is preferably 2000 to 50000, more preferably 3000 to 30000. When the content is within the above range, the film forming ability of the photosensitive composition and the developability after exposure tend to be easily balanced.
[ resin having a Kaduo structure (a-2) ]
The photosensitive composition may contain the resin (a-2) having a carbopol structure described below as the alkali-soluble resin (a) as long as the desired effect is not impaired.
Hereinafter, the resin (a-2) having a card-multiple structure is also referred to as "card-multiple resin (a-2)".
As the caddy resin (a-2), a resin having a caddy structure and a predetermined alkali solubility in its structure can be used. The carbomer structure is a structure in which the 2 nd and 3 rd ring structures are bonded to 1 ring carbon atom constituting the 1 st ring structure. The 2 nd and 3 rd ring structures may be the same or different.
Typical examples of the carbopol structure include a structure in which 2 aromatic rings (for example, benzene rings) are bonded to the carbon atom at the 9-position of the fluorene ring.
The card resin (a-2) is not particularly limited, and conventionally known resins can be used. Among them, a resin represented by the following formula (a-1) is preferable. The following formula (a-1) shows a carbopol resin (a-2) having a (meth) acryloyl group, and therefore also belongs to the photopolymerizable resin (A1-1).
[ chemical formula 8 ]
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In the formula (a-1), X a The group represented by the following formula (a-2). t1 represents an integer of 0 to 20 inclusive.
[ chemical formula 9 ]
In the above formula (a-2), R a1 Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R a2 Each independently represents a hydrogen atom or a methyl group, R a3 Each independently represents a linear or branched alkylene group, t2 represents 0 or 1, W a The group represented by the following formula (a-3).
[ chemical formula 10 ]
In the formula (a-2), asR a3 Alkylene having 1 to 20 carbon atoms is preferred, alkylene having 1 to 10 carbon atoms is more preferred, alkylene having 1 to 6 carbon atoms is particularly preferred, and ethane-1, 2-diyl, propane-1, 2-diyl and propane-1, 3-diyl are most preferred.
The ring A in the formula (a-3) represents an aliphatic ring which may be condensed with an aromatic ring or may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.
Examples of the aliphatic ring include monocycloparaffins, bicycloparaffins, tricycloparaffins and tetracycloparaffins.
Specifically, monocycloparaffins such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane are exemplified.
The aromatic ring which may be condensed with the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Specifically, benzene rings and naphthalene rings are preferable.
As preferable examples of the 2-valent group represented by the formula (a-3), the following groups can be given.
[ chemical formula 11 ]
A 2-valent group X in the formula (a-1) a By providing residues Z a The tetracarboxylic dianhydride represented by the following formula (a-2 a) is reacted with a diol compound to be introduced into the cado resin (a-2).
[ chemical formula 12 ]
In formula (a-2 a), R a1 、R a2 、R a3 And t2 are as described for formula (a-2). Ring A in formula (a-2 a) is as described for formula (a-3).
The diol compound represented by the formula (a-2 a) can be produced, for example, by the following method.
First, the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (a-2 b) is replaced with-R according to a conventional method as required a3 After the group represented by-OH, glycidylation is performed using epichlorohydrin or the like to obtain an epoxy compound represented by the following formula (a-2 c).
Next, the diol compound represented by the formula (a-2 a) is obtained by reacting the epoxy compound represented by the formula (a-2 c) with acrylic acid or methacrylic acid.
In the formula (a-2 b) and the formula (a-2 c), R a1 、R a3 And t2 are as described for formula (a-2). Ring A in the formulae (a-2 b) and (a-2 c) is as described for the formula (a-3).
The method for producing the diol compound represented by the formula (a-2 a) is not limited to the above method.
[ chemical formula 13 ]
As preferable examples of the diol compound represented by the formula (a-2 b), the following diol compounds are given.
[ chemical formula 14 ]
In the above formula (a-1), R a0 Is a hydrogen atom or in the form of-CO-Y a -COOH represents a group. Here, Y a Represents the residue after removal of the anhydride group (-CO-O-CO-) from the dicarboxylic anhydride. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl bridging tetrahydrophthalic anhydride, chlorendic anhydride, methyl tetrahydrophthalic anhydride, glutaric anhydride, and the like.
In the above formula (a-1), Z a Represents the residue after removal of 2 anhydride groups from a tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include tetracarboxylic dianhydride represented by the following formula (a-4), pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like. Among them, pyromellitic dianhydride or biphenyl tetracarboxylic dianhydride is preferable, and pyromellitic dianhydride is preferable in view of a wider development process margin.
In the above formula (a-1), t1 represents an integer of 0 to 20 inclusive.
[ 15 ] A method of producing a polypeptide
(in the formula (a-4), R a4 、R a5 R is R a6 Each independently represents 1 selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and t3 represents an integer of 0 to 12. )
Optionally R in formula (a-4) a4 The alkyl group of (a) is an alkyl group having 1 to 10 carbon atoms. By setting the number of carbon atoms in the alkyl group to this range, the heat resistance of the obtained carboxylic acid ester can be further improved. At R a4 In the case of the alkyl group, the number of carbon atoms is preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4, and particularly preferably 1 to 3, from the viewpoint of easy obtaining of a card resin excellent in heat resistance.
At R a4 In the case of an alkyl group, the alkyl group may be linear or branched.
R in the formula (a-4) is a group of R in the form of easily obtainable card multi-resin excellent in heat resistance a4 More preferably, each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R in formula (a-4) a4 Further preferred is a hydrogen atom, methyl group, ethyl group, n-propyl group or isopropyl group, and particularly preferred is a hydrogen atom or methyl group.
Multiple R's in formula (a-4) due to the ease of preparation of high purity tetracarboxylic dianhydrides a4 Preferably the same groups.
T3 in the formula (a-4) represents an integer of 0 to 12 inclusive. By setting t3 to 12 or less, purification of tetracarboxylic dianhydride can be facilitated.
The upper limit of t3 is preferably 5, more preferably 3, from the viewpoint of easy purification of tetracarboxylic dianhydride.
The lower limit of t3 is preferably 1, more preferably 2, from the viewpoint of chemical stability of the tetracarboxylic dianhydride.
T3 in the formula (a-4) is particularly preferably 2 or 3.
Optionally R in formula (a-4) a5 R is R a6 Alkyl having 1 to 10 carbon atoms and optionally R a4 The same as the alkyl group having 1 to 10 carbon atoms.
R is from the viewpoint of easier purification of tetracarboxylic dianhydride a5 R is R a6 The hydrogen atom or the alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 4 carbon atoms, particularly preferably 1 to 3 carbon atoms) is preferable, and the hydrogen atom or the methyl group is particularly preferable.
Examples of the tetracarboxylic dianhydride represented by the formula (a-4) include: norbornane-2-spiro-alpha-cyclopentanone-alpha ' -spiro-2 "-norbornane-5, 5",6 "-tetracarboxylic dianhydride (the alias" norbornane-2-spiro-2 ' -cyclopentanone-5 ' -spiro-2 "-norbornane-5, 5",6, 6' -tetracarboxylic dianhydride), methyl norbornane-2-spiro-alpha-cyclopentanone-alpha ' -spiro-2 ' - (methyl norbornane) -5, 5', 6, 6' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclohexanone-alpha ' -spiro-2 ' -norbornane-5, 5', 6, 6' -tetracarboxylic dianhydride (alias "norbornane-2-spiro-2 ' -cyclohexanone-6 ' -spiro-2 ' -norbornane-5, 5', 6, 6' -tetracarboxylic dianhydride), methyl norbornane-2-spiro-alpha-cyclohexanone-alpha ' -spiro-2 ' - (methyl norbornane) -5, 5', 6, 6' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cycloacetone-alpha ' -spiro-2 ' -norbornane-5, 5', 6' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclobutanone-alpha ' -spiro-2 "-norbornane-5, 5",6, 6' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cycloheptanone-alpha ' -spiro-2 ' -norbornane-5, 5', 6, 6' -tetracarboxylic dianhydride norbornane-2-spiro-alpha-cycloheptanone-alpha ' -spiro-2 "-norbornane-5, 5",6, 6' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclodecyl-alpha ' -spiro-2 ' -norbornane-5, 5', 6, 6' -tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cycloundecone-alpha ' -spiro-2 ' -norbornane-5, 5', 6,6 "-Tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclododecanone-alpha ' -spiro-2" -norbornane-5, 5", 6" -Tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclotridenone-alpha ' -spiro-2 "-norbornane-5, 5",6 "-Tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2 "-norbornane-5, 5",6 "-tetracarboxylic dianhydride, norbornane-2-spiro-alpha-cyclopentanone-alpha' -spiro-2" -norbornane-5, 5",6,6" -tetracarboxylic dianhydride, norbornane-2-spiro- α - (methylcyclopentanone) - α '-spiro-2 "-norbornane-5, 5",6 "-tetracarboxylic dianhydride, norbornane-2-spiro- α - (methylcyclohexanone) - α' -spiro-2" -norbornane-5, 5", 6" -tetracarboxylic dianhydride, and the like.
The weight average molecular weight of the caddy resin (a-2) is preferably 1000 or more and 40000 or less, more preferably 1500 or more and 30000 or less, and still more preferably 2000 or more and 10000 or less. By setting the range as described above, good developability can be obtained, and heat resistance and mechanical strength sufficient for the cured product can be obtained.
[ novolak resin (a-3) ]
The alkali-soluble resin (a) may contain the novolak resin (a-3) within a range not impairing the desired effect.
As the novolak resin (a-3), various novolak resins conventionally blended in photosensitive compositions can be used. The novolak resin (a-3) is preferably a resin obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenols") with an aldehyde in the presence of an acid catalyst.
(phenols)
Examples of phenols used in the production of the novolak resin (a-3) include: phenol; cresols such as o-cresol, m-cresol, and p-cresol; xylenols such as 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, and 3, 5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; alkylphenols such as 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol and p-tert-butylphenol; trialkylphenols such as 2,3, 5-trimethylphenol and 3,4, 5-trimethylphenol; polyvalent phenols such as resorcinol, catechol, hydroquinone monomethyl ether, pyrogallol, and phloroglucinol; alkyl polyvalent phenols (wherein each alkyl group has 1 to 4 carbon atoms) such as alkyl resorcinol, alkyl catechol and alkyl hydroquinone; alpha-naphthol; beta-naphthol; a hydroxybiphenyl; bisphenol a, and the like. These phenols may be used alone or in combination of 2 or more.
Among these phenols, m-cresol and p-cresol are preferable, and m-cresol and p-cresol are more preferable in combination. In this case, by adjusting the blending ratio of the two, various properties such as heat resistance of a cured product formed using the photosensitive composition can be adjusted.
The mixing ratio of m-cresol and p-cresol is not particularly limited, and the molar ratio of m-cresol/p-cresol is preferably 3/7 to 8/2. By using m-cresol and p-cresol in a ratio in this range, a photosensitive composition which can form a cured product excellent in heat resistance can be easily obtained.
Furthermore, a novolak resin produced by using m-cresol and 2,3, 5-trimethylphenol in combination is also preferable. When such a novolak resin is used, a photosensitive composition which can form a cured product which is less likely to excessively flow by heating during post baking is particularly easily obtained.
The mixing ratio of m-cresol and 2,3, 5-trimethylphenol is not particularly limited, and the molar ratio of m-cresol to 2,3, 5-trimethylphenol is preferably 70/30 to 95/5.
(aldehydes)
Examples of the aldehydes used for producing the novolak resin (a-3) include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde and acetaldehyde. These aldehydes may be used alone or in combination of 2 or more.
(acid catalyst)
Examples of the acid catalyst used in the production of the novolak resin (a-3) include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfuric acid and p-toluenesulfonic acid; metal salts such as zinc acetate, and the like. These acid catalysts may be used alone or in combination of 2 or more.
(molecular weight)
From the viewpoint of resistance to flow by heating of a cured product formed using the photosensitive composition, the weight average molecular weight (Mw; hereinafter also simply referred to as "weight average molecular weight") of the novolak resin (a-3) in terms of polystyrene is preferably 2000 as a lower limit value, more preferably 5000, particularly preferably 10000, further preferably 15000, most preferably 20000, preferably 50000, more preferably 45000, further preferably 40000, most preferably 35000.
As the novolak resin (a-3), at least 2 kinds of resins having different weight average molecular weights in terms of polystyrene can be used in combination. By using a combination of resins having different weight average molecular weights, the developability of the photosensitive composition can be balanced with the heat resistance of a cured product formed using the photosensitive composition.
[ modified epoxy resin (a-4) ]
The alkali-soluble resin (A) may contain an adduct obtained by adding the polybasic acid anhydride (a-4 c) to a reaction product of the epoxy compound (a-4 a) and the unsaturated group-containing carboxylic acid (a-4 b) within a range that does not impair the desired effect. Such an adduct is also referred to as "modified epoxy resin (a-4)".
In the description and claims of the present application, a compound which is not the resin (a-2) having a kami structure and which is a compound satisfying the above definition is used as the modified epoxy resin (a-4).
The epoxy compound (a-4 a), the unsaturated group-containing carboxylic acid (a-4 b) and the polybasic acid anhydride (a-4 c) will be described below.
< epoxy Compound (a-4 a) >)
The epoxy compound (a-4 a) is not particularly limited as long as it is a compound having an epoxy group, and may be an aromatic epoxy compound having an aromatic group, or may be an aliphatic epoxy compound containing no aromatic group, and is preferably an aromatic epoxy compound having an aromatic group.
The epoxy compound (a-4 a) may be a monofunctional epoxy compound, or may be a polyfunctional epoxy compound having 2 or more functions, and is preferably a polyfunctional epoxy compound.
Specific examples of the epoxy compound (a-4 a) include 2-functional epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AD-type epoxy resins, naphthalene-type epoxy resins, and biphenyl-type epoxy resins; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; glycidyl amine type epoxy resins such as tetraglycidyl aminodiphenylmethane, triglycidyl para-aminophenol, tetraglycidyl meta-xylylenediamine and tetraglycidyl bisaminomethyl cyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; 3-functional epoxy resins such as phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenyl methane triglycidyl ether, glycerol triglycidyl ether, 2- [4- (2, 3-glycidoxy) phenyl ] -2- [4- [1, 1-bis [4- (2, 3-glycidoxy) phenyl ] ethyl ] phenyl ] propane and 1, 3-bis [4- [1- [4- (2, 3-glycidoxy) phenyl ] -1-methylethyl ] phenyl ] ethyl ] phenoxy ] -2-propanol; 4-functional epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether and tetraepoxypropoxy biphenyl.
Further, as the epoxy compound (a-4 a), an epoxy compound having a biphenyl skeleton is preferable.
The epoxy compound having a biphenyl skeleton preferably has at least 1 or more biphenyl skeleton represented by the following formula (a-4 a-1) in the main chain.
The epoxy compound having a biphenyl skeleton is preferably a multifunctional epoxy compound having 2 or more epoxy groups.
By using an epoxy compound having a biphenyl skeleton, a photosensitive composition having excellent balance between sensitivity and developability and capable of forming a cured product having excellent adhesion to a substrate can be easily obtained.
[ 16 ] the preparation method
(in the formula (a-4 a-1), R a7 Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent, and j is an integer of 1 to 4. )
As at R a7 Specific examples of the alkyl group in the case of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl and n-dodecyl.
At R a7 In the case of a halogen atom, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
At R a7 In the case of a phenyl group which may have a substituent, the number of substituents on the phenyl group is not particularly limited. The number of substituents on the phenyl group is 0 to 5, preferably 0 or 1.
Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aliphatic acyl group having 2 to 4 carbon atoms, a halogen atom, a cyano group, and a nitro group.
The epoxy compound (a-4 a) having a biphenyl skeleton represented by the above formula (a-4 a-1) is not particularly limited, and examples thereof include epoxy compounds represented by the following formula (a-4 a-2).
[ chemical formula 17 ]
(in the formula (a-4 a-2), R a7 And j is the same as formula (a-4 a-1), k is the average number of repeating structural units in parentheses and is 0 to 10. )
Among the epoxy compounds represented by the formula (a-4 a-2), a compound represented by the following formula (a-4 a-3) is preferable because a photosensitive composition excellent in balance between sensitivity and developability is particularly easy to obtain.
[ chemical formula 18 ]
(in the formula (a-4 a-3), k is the same as in the formula (a-4 a-2))
(unsaturated group-containing carboxylic acid (a-4 b))
In the preparation of the modified epoxy compound (a-4), the epoxy compound (a-4 a) is reacted with the unsaturated group-containing carboxylic acid (a-4 b).
As the unsaturated group-containing carboxylic acid (a-4 b), monocarboxylic acids having a reactive unsaturated double bond such as an acrylic group or a methacrylic group in the molecule are preferable. Examples of the unsaturated group-containing carboxylic acid include acrylic acid, methacrylic acid, β -styrylacrylic acid, β -furfurylacrylic acid, α -cyanocinnamic acid, and cinnamic acid. Further, the unsaturated group-containing carboxylic acids (a-4 b) may be used singly or in combination of 2 or more.
The epoxy compound (a-4 a) and the unsaturated group-containing carboxylic acid (a-4 b) can be reacted by a known method. The preferred reaction method is, for example, the following method: in the presence of a tertiary amine such as triethylamine or benzylethylamine, a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride or benzyltriethylammonium chloride, pyridine or triphenylphosphine as a catalyst, an epoxy compound (a-3 a) is reacted with an unsaturated group-containing carboxylic acid (a-4 b) in an organic solvent at a reaction temperature of 50 to 150 ℃ for several hours to several tens of hours.
The ratio of the amount of both used in the reaction of the epoxy compound (a-4 a) with the unsaturated group-containing carboxylic acid (a-4 b) is generally preferably 1 as the ratio of the epoxy equivalent of the epoxy compound (a-4 a) to the carboxylic acid equivalent of the unsaturated group-containing carboxylic acid (a-4 b): 0.5 to 1: 2. more preferably 1:0.8 to 1:1.25, particularly preferably 1:0.9 to 1:1.1.
if the ratio of the amount of the epoxy compound (a-4 a) to the amount of the unsaturated group-containing carboxylic acid (a-4 b) used is 1 in terms of the above equivalent ratio: 0.5 to 1:2 is preferable because it tends to improve the crosslinking efficiency.
(polybasic acid anhydride (a-4 c))
The polybasic acid anhydride (a-4 c) is a carboxylic acid anhydride having 2 or more carboxyl groups.
The polybasic acid anhydride (a-4 c) is not particularly limited, and examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, 3-methyl hexahydrophthalic anhydride, 4-methyl hexahydrophthalic anhydride, 3-ethyl hexahydrophthalic anhydride, 4-ethyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyl tetrahydrophthalic anhydride, 4-methyl tetrahydrophthalic anhydride, 3-ethyl tetrahydrophthalic anhydride, 4-ethyl tetrahydrophthalic anhydride, and compounds represented by the following formula (a-4 c-1) and compounds represented by the following formula (a-4 c-2). In addition, the polybasic acid anhydrides (a-4 c) may be used singly or in combination of 2 or more.
[ chemical formula 19 ]
(in the formula (a-4 c-2), R a8 An alkylene group which may have a substituent(s) and has 1 to 10 carbon atoms. )
The polybasic acid anhydride (a-4 c) is preferably a compound having 2 or more benzene rings because it is easy to obtain a photosensitive composition having an excellent balance between sensitivity and developability. The polybasic acid anhydride (a-4 c) more preferably contains at least one compound represented by the above formula (a-4 c-1) and a compound represented by the above formula (a-4 c-2).
The method of reacting the polybasic acid anhydride (a-4 c) after reacting the epoxy compound (a-4 a) with the unsaturated group-containing carboxylic acid (a-4 b) can be appropriately selected from known methods.
The ratio of the molar number of OH groups in the component after the reaction of the epoxy compound (a-4 a) with the unsaturated group-containing carboxylic acid (a-4 b) to the equivalent ratio of the acid anhydride groups of the polybasic acid anhydride (a-4 c) is usually 1:1 to 1:0.1, preferably 1:0.8 to 1:0.2. when the content is within the above range, a photosensitive composition having good developability can be easily obtained.
The acid value of the modified epoxy resin (a-4) is preferably 10 to 150mgKOH/g, more preferably 70 to 110mgKOH/g, in terms of resin solid content. By setting the acid value of the resin to 10mgKOH/g or more, sufficient solubility in the developer can be obtained, and by setting the acid value to 150mgKOH/g or less, sufficient curability can be obtained, and the surface properties of the cured product can be improved.
The weight average molecular weight of the modified epoxy resin (a-4) is preferably 1000 to 40000, more preferably 2000 to 30000. When the weight average molecular weight is 1000 or more, a cured product excellent in heat resistance and strength can be easily formed. Further, when the weight average molecular weight is 40000 or less, a photosensitive composition exhibiting sufficient solubility in a developer can be easily obtained.
The content of the alkali-soluble resin (a) in the photosensitive composition is preferably 30 mass% to 90 mass%, more preferably 40 mass% to 80 mass%, based on the mass of the metal oxide particles (D) and the mass of the solvent (S) removed from the mass of the photosensitive composition.
[ photopolymerizable Compound (B) ]
The photosensitive composition contains a photopolymerizable compound (B). As the photopolymerizable compound (B), a compound conventionally blended in a photosensitive composition can be used without particular limitation.
Examples of the monofunctional photopolymerizable compound include: (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethacrylamide, (meth) acrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, t-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2-trifluoroethyl ester, 2, 3-tetrafluoropropyl (meth) acrylate, and a semi (meth) acrylate of a phthalic acid derivative. These monofunctional photopolymerizable compounds may be used alone or in combination of 2 or more.
Examples of the polyfunctional photopolymerizable compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, and diglycidyl phthalate di (meth) acrylate, and multifunctional monomers such as glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., toluene diisocyanate), reactants of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, condensates of polyhydric alcohol and N-methylol (meth) acrylamide, or triacrylamide formals. These polyfunctional photopolymerizable compounds may be used singly or in combination of 2 or more.
Among these photopolymerizable compounds (B), from the viewpoint of the tendency to increase the strength of the cured product, a polyfunctional compound having 3 or more functions is preferable, a polyfunctional compound having 4 or more functions is more preferable, and a polyfunctional compound having 5 or more functions is further preferable.
From the viewpoint of improving curability, the photosensitive composition may contain a compound represented by the following formula (B-2 a) or the following formula (B-2B) as the photopolymerizable compound (B).
[ chemical formula 20 ]
(MA-(O-R b1 ) nb1 -X-CH 2 ) 2 -CH-X-(R b1 -O) nb1 -MA…(B-2b)
(in the formula (B-2 a) and the formula (B-2B), MA is (methyl) acryloyl independently, X is oxygen atom, -NH-or-N (CH) 3 )-，R b1 Respectively are provided withIndependently is ethane-1, 2-diyl, propane-1, 2-diyl or propane-1, 3-diyl, R b2 Is hydroxy, alkyl having 1 to 4 carbon atoms or-X- (R) b1 -O) nb1 Groups represented by MA (X is the same as above), and nb1 and nb2 are each independently 0 or 1. )
In the formula (B-2 a), R is b2 Examples of the "alkyl" having 1 to 4 carbon atoms may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. Among these alkyl groups, methyl and ethyl are preferred.
Preferable examples of the compound represented by the formula (B-2 a) and the compound represented by the formula (B-2B) include pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate and the following compounds 1) to 32). In the compounds 1) to 32) below, MA is a (meth) acryloyl group.
1)(MA-NH-CH 2 ) 4 -C
2)(MA-N(CH 3 )-CH 2 ) 4 -C
3)(MA-O-CH 2 CH 2 CH 2 -O-CH 2 ) 4 -C
4)(MA-O-CH 2 CH 2 -O-CH 2 ) 4 -C
5)(MA-O-CH 2 CH 2 CH 2 -NH-CH 2 ) 4 -C
6)(MA-O-CH 2 CH 2 -NH-CH 2 ) 4 -C
7)(MA-O-CH 2 CH 2 CH 2 -N(CH 3 )-CH 2 ) 4 -C
8)(MA-O-CH 2 CH 2 -N(CH 3 )-CH 2 ) 4 -C
9)(MA-NH-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -NH-MA) 3
10)(MA-N(CH 3 )-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -N(CH 3 )-MA) 3
11)(MA-O-CH 2 CH 2 CH 2 -O-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -O-CH 2 CH 2 CH 2 -O-MA)3
12)(MA-O-CH 2 CH 2 -O-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -O-CH 2 CH 2 -O-MA)3
13)(MA-O-CH 2 CH 2 CH 2 -NH-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -NH-CH 2 CH 2 CH 2 -O-MA) 3
14)(MA-O-CH 2 CH 2 -NH-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -NH-CH 2 CH 2 -O-MA)3
15)(MA-O-CH 2 CH 2 CH 2 -N(CH 3 )-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -N(CH 3 )-CH 2 CH 2 CH 2 -O-MA) 3
16)(MA-O-CH 2 CH 2 -N(CH 3 )-CH 2 ) 3 -C-CH 2 -O-CH 2 -C-(CH 2 -N(CH 3 )-CH 2 CH 2 -O-MA) 3
17)(MA-NH-CH 2 ) 2 -CH-NH-MA
18)(MA-N(CH 3 )-CH 2 ) 2 -CH-N(CH 3 )-MA
19)(MA-O-CH 2 CH 2 CH 2 -O-CH 2 ) 2 -CH-O-CH 2 CH 2 CH 2 -O-MA
20)(MA-O-CH 2 CH 2 -O-CH 2 ) 2 -CH-C-O-CH 2 CH 2 -O-MA
21)(MA-O-CH 2 CH 2 CH 2 -NH-CH 2 ) 2 -CH-NH-CH 2 CH 2 CH 2 -O-MA
22)(MA-O-CH 2 CH 2 -NH-CH 2 ) 2 -CH 2 -NH-CH 2 CH 2 -O-MA
23)(MA-O-CH 2 CH 2 CH 2 -N(CH 3 )-CH 2 ) 2 -CH 2 -N(CH 3 )-CH 2 CH 2 CH 2 -O-MA
24)(MA-O-CH 2 CH 2 -N(CH 3 )-CH 2 ) 2 -CH 2 -N(CH 3 )-CH 2 CH 2 -O-MA
25)(MA-NH-CH 2 ) 3 -C-CH 2 CH 3
26)(MA-N(CH 3 )-CH 2 ) 3 -C-CH 2 CH 3
27)(MA-O-CH 2 CH 2 CH 2 -O-CH 2 ) 3 -C-CH 2 CH 3
28)(MA-O-CH 2 CH 2 -O-CH 2 ) 3 -C-CH 2 CH 3
29)(MA-O-CH 2 CH 2 CH 2 -NH-CH 2 ) 3 -C-CH 2 CH 3
30)(MA-O-CH 2 CH 2 -NH-CH 2 ) 3 -C-CH 2 CH 3
31)(MA-O-CH 2 CH 2 CH 2 -N(CH 3 )-CH 2 ) 3 -C-CH 2 CH 3
32)(MA-O-CH 2 CH 2 -N(CH 3 )-CH 2 ) 3 -C-CH 2 CH 3
The ratio of the total of the mass of the compound represented by the formula (B-2 a) and the mass of the compound represented by the formula (B-2B) to the mass of the photopolymerizable compound (B) is preferably 50 mass% or less, more preferably 5 mass% or more and 50 mass% or less, still more preferably 10 mass% or more and 45 mass% or less, and still more preferably 10 mass% or more and 40 mass% or less, from the viewpoint of improving the curability of the photosensitive composition.
The photosensitive composition may contain a compound represented by the following formula (B-2 c) as the photopolymerizable compound (B) in view of easy formation of a cured product having a high refractive index.
[ chemical formula 21 ]
In the formula (B-2 c), R 1 R is R 2 Each independently is a hydrogen atom or a methyl group. R is R 3 R is R 4 Each independently represents an alkyl group having 1 to 5 carbon atoms. p and q are each independently 0 or 1.
R 1 R is R 2 Each independently is a hydrogen atom or a methyl group. R is R 1 R is R 2 May be different from each other or the same. From the viewpoint of easy synthesis or obtaining of the compound represented by the formula (B-2 c), R is preferable 1 R is R 2 The same applies.
R 3 R is R 4 Each independently represents an alkyl group having 1 to 5 carbon atoms. R is R 3 R is R 4 May be different from each other or the same. From the viewpoint of easy synthesis or obtaining of the compound represented by the formula (B-2 c), R is preferable 3 R is R 4 The same applies.
As R 3 R is R 4 The alkyl group having 1 to 5 carbon atoms may be linear or branched. As R 3 R is R 4 Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl and tert-pentyl.
As preferable specific examples of the compound represented by the formula (B-2 c), the following compounds are given.
[ chemical formula 22 ]
When the photosensitive composition contains the compound represented by the formula (B-2 c) as the photopolymerizable compound (B), the ratio of the mass of the compound represented by the formula (B-2 c) to the mass of the photopolymerizable compound (B) is preferably 70 mass% or less, more preferably 10 mass% or more and 70 mass% or less, and still more preferably 20 mass% or more and 70 mass% or less.
The photosensitive composition may contain, as the photopolymerizable compound (B), a sulfur-containing (meth) acrylate represented by the following formula (B-2 d) in order to improve curability of the photosensitive composition.
Ar b1 -R b21 -S-R b22 -O-CO-CR b23 ＝CH 2 …(B-2d)
(in the formula (B-2 d), ar b1 Is phenyl which may be substituted by halogen atoms, R b21 Is a single bond or an alkylene group having 1 to 6 carbon atoms, R b22 Is alkylene having 1 to 6 carbon atoms, R b23 Is a hydrogen atom or a methyl group. )
Ar b1 Is phenyl which may be substituted by halogen atoms. In the case where the phenyl group is substituted with a halogen atom, the number of halogen atoms bonded to the phenyl group is not particularly limited. The number of halogen atoms bonded to the phenyl group is preferably 1 or 2, more preferably 1. In the case where 2 or more halogen atoms are bonded to the phenyl group, the plurality of halogen atoms bonded to the phenyl group may be constituted by only the same kind of halogen atoms or may be constituted by 2 or more halogen atoms. Examples of the halogen atom capable of bonding to the phenyl group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and fluorine atom, chlorine atom and bromine atom are preferable.
As Ar b1 Unsubstituted phenyl is preferred.
R b21 Is a single bond or an alkylene group having 1 to 6 carbon atoms. Examples of the "alkylene" having 1 to 6 carbon atoms may include methylene, ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl and hexane-1, 6-diyl.
As R b21 Preferably a single bondMethylene, more preferably a single bond.
R b22 Is an alkylene group having 1 to 6 carbon atoms. Examples of the "alkylene" having 1 to 6 carbon atoms may include methylene, ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl and hexane-1, 6-diyl.
As R b22 Methylene, ethane-1, 2-diyl and propane-1, 3-diyl are preferred, and ethane-1, 2-diyl and propane-1, 3-diyl are more preferred.
In particular, ar in the formula (B-2 d) is preferable from the viewpoints of easiness in obtaining sulfur-containing (meth) acrylate and improvement of curability of the photosensitive composition b1 Is phenyl, R b21 Is a single bond.
As preferable specific examples of the sulfur-containing (meth) acrylate represented by the formula (B-2 d), 2-phenylthioethyl (meth) acrylate, 3-phenylthiopropyl (meth) acrylate, 2-benzylthioethyl (meth) acrylate, 3-benzylthiopropyl (meth) acrylate, 2- (2-chlorophenyl) ethyl (meth) acrylate, 2- (3-chlorophenyl) ethyl (meth) acrylate, 2- (4-chlorophenyl) ethyl (meth) acrylate, 3- (2-chlorophenyl) propyl (meth) acrylate, 3- (3-chlorophenyl) propyl (meth) acrylate, 3- (4-chlorophenyl) propyl (meth) acrylate, 2- (2-fluorophenyl) ethyl (meth) acrylate, 2- (3-fluorophenyl) ethyl (meth) acrylate, 2- (4-fluorophenyl) ethyl (meth) acrylate, 3- (2-fluorophenyl) propyl (meth) acrylate, 3- (3-fluorophenyl) propyl (meth) acrylate, 3- (4-fluorophenyl) propyl (meth) acrylate, 2- (2-bromophenyl) ethyl (meth) acrylate, 2- (3-bromophenyl) ethyl (meth) acrylate, 2- (4-bromophenyl) ethyl (meth) acrylate, 3- (2-bromophenyl) propyl (meth) acrylate, 3- (3-bromophenyl) propyl (meth) acrylate, and 3- (4-bromophenyl) propyl (meth) acrylate.
When the photosensitive composition contains the sulfur-containing (meth) acrylate represented by the formula (B-2 d) as the photopolymerizable compound (B), the ratio of the mass of the sulfur-containing (meth) acrylate represented by the formula (B-2 d) to the mass of the photopolymerizable compound (B) is preferably 40 mass% or more and 50 mass% or less.
The photosensitive composition may contain a compound represented by the following formula (B-2 e) as the photopolymerizable compound (B) in view of easy obtaining of a cured product having a high refractive index.
[ chemical formula 23 ]
(in the formula (B-2 e), R B1 、R B2 R is R B3 Each independently is an organic group as R B1 As R B2 As R B3 At least 2 of the organic groups of (a) have a radical polymerizable group-containing group. )
As a preferred example of the compound represented by the formula (B-2 e), a compound represented by the following formula (B-2 e-a) can be mentioned.
[ chemical 24 ]
In the formula (B-2 e-a), R B01 Is quinolinyl which may have a substituent, isoquinolinyl which may have a substituent, or 2-substituted benzothiazolyl which may have a substituent.
2-substituted benzothiazolyl has the amino group in the 2-position with the amino group in the-S-R B0 A group represented by the formula (I). R is R B0 Is a hydrogen atom, a radical-polymerizable group-containing group.
R B02 R is R B03 Are aromatic ring-containing groups having groups containing radically polymerizable groups.
-NH-group bonded to triazine ring with R B02 R is R B03 The aromatic ring of (C) is bonded.
The quinolinyl group which may have a substituent, the isoquinolinyl group which may have a substituent, and the 2-substituted benzothiazolyl group which may have a substituent all have a larger polarizability and a smaller volume as a functional group. Thus, the first and second substrates are bonded together,can be considered as R B01 Is a quinolinyl group which may have a substituent, an isoquinolinyl group which may have a substituent, or a 2-substituted benzothiazolyl group which may have a substituent contributes to a high refractive index of a cured product of the photosensitive composition.
As R B01 The quinolinyl group of (a) may be any of quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl and quinolin-8-yl. Among these groups, quinolin-3-yl and quinolin-4-yl are preferable from the viewpoint of easy availability of the starting compound of the compound represented by the formula (B2 e-a) or easy synthesis of the compound represented by the formula (B2 e-a).
As R B01 The isoquinolinyl group of (a) may be any of isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl and isoquinolin-8-yl.
As R B01 The substituents which the quinolinyl and isoquinolinyl groups may have are not particularly limited as long as the desired effect is not impaired. Examples of the substituent include a halogen atom, a hydroxyl group, a mercapto group, a cyano group, a nitro group and a 1-valent organic group.
Examples of the "halogen" atom as a substituent may include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the "1-valent organic group" may include an alkyl group, an alkoxy group, an alkoxyalkyl group, an aliphatic acyl group, an aliphatic acyloxy group, an alkoxycarbonyl group, an alkylthio group, and an aliphatic acyl group.
The radical polymerizable group-containing group described later is also preferably a 1-valent organic group.
The number of carbon atoms of the 1-valent organic group as a substituent is not particularly limited as long as the desired effect is not impaired. The number of carbon atoms of the 1-valent organic group as a substituent is, for example, preferably 1 to 20, more preferably 1 to 12, still more preferably 1 to 8. The lower limit of the number of carbon atoms in the alkoxyalkyl group, the aliphatic acyl group, the aliphatic acyloxy group, the alkoxycarbonyl group, the alkoxyalkylthio group, and the aliphatic acylthio group is 2.
Preferred examples of the alkyl group as a substituent include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.
Preferred examples of the alkoxy group as a substituent include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, n-hexoxy, n-heptoxy and n-octoxy.
Preferred specific examples of the alkoxyalkyl group as a substituent include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, n-butoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-n-butoxyethyl group, 3-methoxy-n-propoxy group, 3-ethoxy-n-propoxy group, 3-n-butoxy-n-propoxy group, 4-methoxy-n-butoxy group, 4-ethoxy-n-butoxy group, 4-n-propoxy-n-butoxy group and 4-n-butoxy group.
Preferred examples of the aliphatic acyl group as a substituent include acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl and octanoyl.
Preferable examples of the aliphatic acyloxy group as a substituent include an acetoxy group, a propionyloxy group, a butyryloxy group, a pentanoyloxy group, a hexanoyloxy group, a heptanoyloxy group and a octanoyloxy group.
Preferred examples of the alkoxycarbonyl group as a substituent include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl and n-octyloxycarbonyl.
Preferred examples of the alkylthio group as a substituent include a methylthio group, an ethylthio group, a n-propylthio group, an isopropylthio group, a n-butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a n-pentylthio group, a n-hexylthio group, a n-heptylthio group and a n-octylthio group.
Preferred examples of the aliphatic acyl sulfide group as a substituent include acetyl sulfide group, propionyl sulfide group, butyryl sulfide group, valeryl sulfide group, hexanoyl sulfide group, heptanoyl sulfide group and Xin Xianliu group.
In the case where the quinolinyl group and the isoquinolinyl group have substituents, the number of substituents is not particularly limited as long as the desired effect is not impaired. In the case where the quinolinyl group and the isoquinolinyl group have a substituent, the number of substituents is preferably 1 to 4, more preferably 1 or 2, and particularly preferably 1.
In the case where the quinolinyl group and the isoquinolinyl group have a plurality of substituents, the plurality of substituents may be different from each other.
As R B01 2-substituted benzothiazolyl of (2) having a substituent of-S-R at the 2-position B0 A group represented by the formula (I). As R B01 The 2-substituted benzothiazolyl group of (2) may have a substituent represented by-S-R in a position other than 2 B0 Substituents other than the groups represented. R is R B0 Is a hydrogen atom, a radical-polymerizable group-containing group. The radical-polymerizable group-containing group will be described later.
As preferable examples of the 2-substituted benzothiazolyl group, the following groups can be mentioned.
[ chemical 25 ]
As R B01 The substituents which may be possessed by the 2-substituted benzothiazolyl group are the same as those which may be possessed by the quinolinyl group and the isoquinolinyl group.
In the case where the 2-substituted benzothiazolyl group has a substituent, the number of substituents is not particularly limited as long as the desired effect is not impaired. In the case where the 2-substituted benzothiazolyl group has a substituent, the number of substituents is preferably 1 or 2, more preferably 1.
In the case where the 2-substituted benzothiazolyl group has plural substituents, the plural substituents may be different from each other.
R B02 R is R B03 Are aromatic ring-containing groups having groups containing radically polymerizable groups.
In addition, an-NH-group bonded to the triazine ringGroup and R B02 R is R B03 The aromatic ring of (C) is bonded.
As R B02 R is R B03 The bonding position of the radical-polymerizable group-containing group in the aromatic ring-containing group is not particularly limited.
As R B02 The number of radical-polymerizable group-containing groups in the aromatic ring-containing groups, and R as B03 The number of radical-polymerizable group-containing groups in the aromatic ring-containing groups is not particularly limited. As R B02 The number of radical-polymerizable group-containing groups in the aromatic ring-containing groups, and R as B03 The number of radical-polymerizable group-containing groups in the aromatic ring-containing group is preferably an integer of 1 to 3, more preferably 1 or 2, particularly preferably 1.
As R B02 R is R B03 The aromatic ring-containing group of (2) may contain only 1 monocyclic aromatic ring or 1 condensed aromatic ring, or may contain 2 or more monocyclic aromatic rings and/or condensed aromatic rings. At R as B02 R is R B03 When the aromatic ring-containing group of (a) contains 2 or more monocyclic aromatic rings and/or condensed aromatic rings, the types of the linking groups that link the monocyclic aromatic rings to each other, link the condensed aromatic rings to each other, or link the monocyclic aromatic rings and the condensed aromatic rings are not particularly limited. The linking group may be a 2-valent linking group, or may be a 3-valent or more-valent linking group, and is preferably a 2-valent linking group.
As a linking group of valence 2, examples of the "aliphatic hydrocarbon group" may include a 2-valent aliphatic hydrocarbon group, a 2-valent halogenated aliphatic hydrocarbon group, -CONH-; -NH-, -n=n-, -ch=n-, -COO-, -O-, -CO-, -SO 2 -, -S-, and combinations of more than 2 of these.
Furthermore, as the 2-valent linking group, it is also preferable to use-CR b001 R b002 -a group represented.
R b001 R is R b002 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms. R is R b001 And R is R b002 Can be mutually bondedAnd are combined to form a ring. As a base-CR b001 R b002 Specific examples of the group represented by (E) -include methylene, ethane-1, 1-diyl, propane-2, 2-diyl, butane-2, 2-diyl, 1, 3-hexafluoropropane-2, 2-diyl, cyclopentylene, cyclohexylene and cycloheptylene.
As R B02 R is R B03 The aromatic ring-containing group of (2) has a radical-polymerizable group-containing group. The radical-polymerizable group-containing group is as described above.
As a preferable example of the radical-polymerizable group-containing group, a group which is not a vinyloxy group-containing group represented by the following formula (B-I) or the following formula (B-II) can be mentioned.
-(A 01 ) nb -R 01 …(B-I)
-(A 01 ) nb -R 02 -A 02 -R 01 …(B-II)
In the formula (B-I) and the formula (B-II), R 01 Is an alkenyl group having 2 to 10 carbon atoms. R is R 02 Is an alkylene group having 1 to 10 carbon atoms.
A 01 is-O-, -S-, -CO-O-, and-CO-S-, -O-CO-, -S-CO-, -CO-NH-, -NH-CO-, or-NH-.
A 02 is-O-, -S-, -CO-O-, and-CO-S-, -O-CO-, -S-CO-, -CO-NH-, -NH-CO-, or-NH-.
nb is 0 or 1.
As a preferred specific example of the radical-polymerizable group-containing group, there may be mentioned
-O-R 03 、
-S-R 03 、
-O-CH 2 CH 2 -O-R 03 、
-O-CH 2 CH 2 CH 2 -O-R 03 、
-O-CH 2 CH 2 CH 2 CH 2 -O-R 03 、
-CO-O-CH 2 CH 2 -O-R 03 、
-CO-O-CH 2 CH 2 CH 2 -O-R 03 、
-CO-O-CH 2 CH 2 CH 2 CH 2 -O-R 03 、
-O-CH 2 CH 2 -NH-R 03 、
-O-CH 2 CH 2 CH 2 -NH-R 03 、
-O-CH 2 CH 2 CH 2 CH 2 -NH-R 03 、
-CO-O-CH 2 CH 2 -NH-R 03 、
-CO-O-CH 2 CH 2 CH 2 -NH-R 03 、
-CO-O-CH 2 CH 2 CH 2 CH 2 -R 03 、
-NH-R 03 、
-NH-CH 2 CH 2 -O-R 03 、
-NH-CH 2 CH 2 CH 2 -O-R 03 、
-NH-CH 2 CH 2 CH 2 CH 2 -O-R 03 、
-CO-NH-CH 2 CH 2 -O-R 03 、
-CO-NH-CH 2 CH 2 CH 2 -O-R 03 、
-CO-NH-CH 2 CH 2 CH 2 CH 2 -O-R 03 、
-NH-CH 2 CH 2 -NH-R 03 、
-NH-CH 2 CH 2 CH 2 -NH-R 03 、
-NH-CH 2 CH 2 CH 2 CH 2 -NH-R 03 、
-CO-NH-CH 2 CH 2 -NH-R 03 、
-CO-NH-CH 2 CH 2 CH 2 -NH-R 03 And
-CO-NH-CH 2 CH 2 CH 2 CH 2 -NH-R 03 A group represented by the formula (I). R in these groups 03 Is allyl or (meth) acryl.
At R as B02 R is R B03 In the case where the aromatic ring-containing group has 1 radical-polymerizable group-containing group, R is defined as B02 R is R B03 Preferable examples of (a) include groups of the following formula. In the following formula, PG is a radical-polymerizable group-containing group.
[ chemical 26 ]
As a preferable specific example of the compound represented by the formula (B-2 e), a compound of the following formula can be given. In the following formula, X B Is a group selected from the group consisting of (meth) acryloyloxy, (meth) acryloylthio and 3- (meth) acryloyloxy-2-hydroxy-n-propoxycarbonyl.
[ chemical formula 27 ]
[ chemical 28 ]
[ chemical 29 ]
The method for producing the compound represented by the formula (B-2 e-a) is not particularly limited. Typically, the catalyst can be prepared by reacting cyanuric halide such as cyanuric chloride with R B01 -NH 2 、R B02 -NH 2 R is R B03 -NH 2 The aromatic amine represented is produced by reaction. These various amines can be reacted simultaneously with the halogenated cyanuratesIt is also possible to react with the halogenated cyanuric acid in succession, preferably in succession.
In addition, R in formula (B-2 e-a) B02 R is R B03 It can also be generated by: an aromatic amine having a functional group such as a hydroxyl group, a mercapto group, a carboxyl group, or an amino group is reacted with a halogenated cyanuric acid, and then these functional groups are reacted with a compound which provides a radical polymerizable group-containing group. Examples of the compound having a radical polymerizable group include compounds having a radical polymerizable group such as (meth) acrylic acid, (meth) acrylic acid halides and halogenated olefins.
As the reaction of the functional group such as a hydroxyl group, a mercapto group, a carboxyl group, or an amino group with the compound having a polymerizable group, a known reaction for forming an ether bond, a carboxylic ester bond, a carboxylic amide bond, or a thioether bond can be used.
The reaction to form the radical-polymerizable group-containing group may be a multistage reaction. For example, a radical polymerizable group-containing group represented by the following formula can be introduced into an aromatic ring by reacting an aromatic amine having a phenolic hydroxyl group with a halogenated cyanuric acid, then reacting the phenolic hydroxyl group with epichlorohydrin to glycidate, and then reacting acrylic acid with a glycidyl group.
-O-CH 2 -CHOH-CH 2 -O-CO-CH＝CH 2
The above reaction is an example, and the radical-polymerizable group-containing group can be formed by combining various reactions.
The compound represented by the formula (B-2 e-a) is usually synthesized in an organic solvent. The organic solvent is not particularly limited as long as it is an inert solvent that does not react with halogenated cyanuric acid, aromatic amine, radical polymerizable group, and the like. As the solvent, an organic solvent or the like exemplified as a specific example of the solvent (S) described later can be used.
In the production of the compound represented by the formula (B-2 e-a), halogenated cyanuric acid is reacted with R B01 -NH 2 、R B02 -NH 2 R is R B03 -NH 2 Indicated temperature of reaction of aromatic amine such as aromatic amineThere is no particular limitation. Typically, the reaction temperature is preferably from 0℃to 150 ℃.
As another preferable example of the compound represented by the formula (B-2 e), a compound represented by the following formula (B-2 e-B) can be mentioned.
[ chemical formula 30 ]
In the formula (B-2 e-B), R B11 、R B12 R is R B13 Respectively containing aromatic ring groups.
R B12 R is R B13 At least 1 of them is a group represented by the following formula (B-2 e-B1).
[ chemical 31 ]
the-NH-groups bound to the triazine ring being bound to R B11 、R B12 R is R B13 The aromatic ring of (C) is bonded.
In the formula (B-2 e-B1), R b11 R is R b12 Each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.
Each of nB1 and nB2 is independently an integer of 0 to 4.
R b13 R is R b14 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a phenyl group.
R b13 And R is R b14 Can be bonded to each other to form a ring.
R B14 Is a radical-polymerizable group-containing group.
At R B12 R is R B13 R in the case of the groups represented by the formula (B-2 e-B1) B12 R is R B13 All having free radically polymerizable group-containing groups.
As described aboveIn the formula (B-2 e-B), R B11 、R B12 R is R B13 Respectively containing aromatic ring groups. In the formula (B-2 e-B), the-NH-groups bonded to the triazine ring are each bonded to R B11 、R B12 R is R B13 The aromatic ring of (C) is bonded.
When the aromatic ring-containing group is a group other than the group represented by the formula (B-2 e-B1), the aromatic ring-containing group is not particularly limited as long as the above-specified condition is satisfied.
The aromatic ring-containing group other than the group represented by the formula (B-2 e-B1) may contain only 1 monocyclic aromatic ring or 1 condensed aromatic ring, or may contain 2 or more monocyclic aromatic rings and/or condensed aromatic rings. When the aromatic ring-containing group contains 2 or more monocyclic aromatic rings and/or condensed aromatic rings, the types of the linking groups that link the monocyclic aromatic rings to each other, link the condensed aromatic rings to each other, or link the monocyclic aromatic rings and the condensed aromatic rings are not particularly limited. The linking group may be a 2-valent linking group, or may be a 3-valent or more-valent linking group, and is preferably a 2-valent linking group.
As a linking group of valence 2, examples of the "aliphatic hydrocarbon group" may include a 2-valent aliphatic hydrocarbon group, a 2-valent halogenated aliphatic hydrocarbon group, -CONH-; -NH-, -n=n-, -ch=n-, -COO-, -O-, -CO-, -SO 2 -, -S-, and combinations of more than 2 of these.
Preferable examples of the aromatic ring-containing group include a quinolinyl group which may have a substituent, an isoquinolinyl group which may have a substituent, and a 2-substituted benzothiazolyl group which may have a substituent. These groups are related to R in formula (B-2 e-a) B01 The illustrated quinolinyl group which may have a substituent, isoquinolinyl group which may have a substituent, and 2-substituted benzothiazolyl group which may have a substituent are the same.
Examples of other preferable aromatic ring-containing groups include a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a biphenyl group which may have a substituent, a phenylsulfanyl group which may have a substituent, a phenoxyphenyl group which may have a substituent, a phenylsulfonylphenyl group which may have a substituent, a benzothiazolyl group which may have a substituent, a benzoxazolyl group which may have a substituent, and a terphenyl group which may have a substituent.
In the case where these groups have substituents, the substituents are the same as those which quinolyl groups and isoquinolyl groups may have. In the case where these groups have a plurality of substituents, the plurality of substituents may be different from each other.
As preferable specific examples of the phenyl group which may have a substituent(s), phenyl group, 4-cyanophenyl group, 3-cyanophenyl group, 2, 3-dicyanophenyl group, 2, 4-dicyanophenyl group, 2, 5-dicyanophenyl group, 2, 6-dicyanophenyl group, 3, 4-dicyanophenyl group, 3, 5-dicyanophenyl group, 4-nitrophenyl group, 3-nitrophenyl group, 2-nitrophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 3-bromophenyl group, 2-bromophenyl group, 4-iodophenyl group, 3-iodophenyl group, 2-iodophenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-methylphenyl group, 3-methylphenyl group and 2-methylphenyl group may be mentioned.
Preferred examples of the optionally substituted naphthyl group include naphthalen-1-yl and naphthalen-2-yl.
Preferable examples of the biphenyl group which may have a substituent(s) include 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4- (4-nitrophenyl) phenyl group, 3- (4-nitrophenyl) phenyl group, 2- (4-nitrophenyl) phenyl group, 4- (4-cyanophenyl) phenyl group, 3- (4-cyanophenyl) phenyl group and 2- (4-cyanophenyl) phenyl group.
Preferable specific examples of the phenylthiophenyl group which may have a substituent include 4-phenylthiophenyl group, 3-phenylthiophenyl group and 2-phenylthiophenyl group.
Preferable specific examples of the phenoxyphenyl group which may have a substituent include a 4-phenoxyphenyl group, a 3-phenoxyphenyl group and a 2-phenoxyphenyl group.
Preferable specific examples of the phenylsulfonylphenyl group which may have a substituent include 4-phenylsulfonylphenyl group, 3-phenylsulfonylphenyl group and 2-phenylsulfonylphenyl group.
Preferred specific examples of the benzothiazolyl group which may have a substituent include benzothiazol-2-yl, benzothiazol-4-yl, benzothiazol-5-yl, benzothiazol-6-yl and benzothiazol-7-yl.
Preferred specific examples of the benzoxazolyl group which may have a substituent include benzoxazol-2-yl, benzoxazol-4-yl, benzoxazol-5-yl, benzoxazol-6-yl and benzoxazol-7-yl.
Preferable examples of the terphenyl group which may have a substituent(s) include 4- (4-phenylphenyl) phenyl, 3- (4-phenylphenyl) phenyl, 2- (4-phenylphenyl) phenyl, 4- (3-phenylphenyl) phenyl, 3- (3-phenylphenyl) phenyl, 2- (3-phenylphenyl) phenyl, 4- (2-phenylphenyl) phenyl, 3- (2-phenylphenyl) phenyl and 2- (2-phenylphenyl) phenyl.
As described above, the aromatic ring-containing group other than the group represented by the formula (B-2 e-B1) may have a radical-polymerizable group-containing group as a substituent.
The bonding position of the radical-polymerizable group-containing group in the aromatic ring-containing group is not particularly limited.
The number of radical-polymerizable group-containing groups in the aromatic ring-containing group is not particularly limited. The number of radical-polymerizable group-containing groups in the aromatic ring-containing group is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.
In the case where the aromatic ring-containing group has 1 radical-polymerizable group, a group of the following formula is exemplified as a preferable example of such a group. In the following formula, PG is a radical-polymerizable group-containing group.
[ chemical formula 32 ]
In the formula (B-2 e-B), R B12 R is R B13 At least 1 of them is a group represented by the following formula (B-2 e-B1).
[ chemical formula 33 ]
In the formula (B-2 e-B1), R b11 R is R b12 Each independently represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.
Each of nB1 and nB2 is independently an integer of 0 to 4.
R b13 R is R b14 Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a phenyl group.
R b13 And R is R b14 Can be bonded to each other to form a ring.
R B14 Is a radical-polymerizable group-containing group.
At R B12 R is R B13 R in the case of the groups represented by the formula (B-2 e-B1) B12 R is R B13 All having free radically polymerizable group-containing groups.
As R b11 R is R b12 Examples of the "alkyl" having 1 to 4 carbon atoms may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
As R b11 R is R b12 Examples of the "alkoxy" having 1 to 4 carbon atoms may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy.
As R b11 R is R b12 Examples of the "halogen" may include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As R b13 R is R b14 Specific examples of the alkyl group having 1 to 4 carbon atoms and R b11 R is R b12 Specific examples of the alkyl group having 1 to 4 carbon atoms are the same.
As R b13 R is R b14 Specific examples of the haloalkyl group having 1 to 4 carbon atoms include chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 3-trifluoroethyl, pentafluoroethyl and heptafluoropropyl.
As a preferred example of the group represented by the formula (B-2 e-B1), a group represented by the following formula can be given.
[ chemical 34 ]
The radical having a radical-polymerizable group represented by the formula (B-2 e-B1) as R B14 . The radical-polymerizable group-containing group is as described above.
Preferred specific examples of the radical-polymerizable group-containing group are the same as those described for the compound represented by the formula (B-2 e-a).
As a preferable specific example of the compound represented by the formula (B-2 e-B), a compound of the following formula can be given. In the following formula, X B Is a group selected from the group consisting of (meth) acryloyloxy, (meth) acryloylthio and 3- (meth) acryloyloxy-2-hydroxy-n-propoxycarbonyl.
Y B Is a group selected from the group consisting of quinolin-3-yl, phenyl, 4-cyanophenyl, 3-cyanophenyl, 2-cyanophenyl, 3, 4-dicyanophenyl, 4-nitrophenyl, 4-methoxyphenyl, 4-phenylsulfanylphenyl, 4-phenylsulfonylphenyl, 4-iodophenyl, benzothiazol-2-yl, 2-mercaptobenzothiazol-5-yl, 4-phenylphenyl, 4- (4-nitrophenyl) phenyl, 4- (4-cyanophenyl) phenyl, naphthalen-1-yl and 4- (4-phenylphenyl) phenyl.
[ 35 ]
The method for producing the compound represented by the formula (B-2 e-B) is not particularly limited. Typically, the catalyst can be prepared by reacting cyanuric halide such as cyanuric chloride with R B11 -NH 2 、R B12 -NH 2 R is R B13 -NH 2 The aromatic amine represented is produced by reaction. These multipleThe seed amines may be reacted simultaneously with the halocyanuric acid or sequentially with the halocyanuric acid, preferably sequentially with the halocyanuric acid.
In addition, in the case where an aromatic ring-containing group bonded to a triazine ring via-NH-has a radical-containing polymerizable group, a radical-containing polymerizable group can also be formed by reacting an aromatic amine having a functional group such as a hydroxyl group, a mercapto group, a carboxyl group, or an amino group with a halogenated cyanuric acid, and then reacting a compound that provides a radical-containing polymerizable group with these functional groups. Examples of the compound providing a radical-polymerizable group include compounds having a polymerizable group such as (meth) acrylic acid, (meth) acrylic acid halide, halogenated olefin, epichlorohydrin, and glycidyl (meth) acrylate.
As the reaction of the functional group such as a hydroxyl group, a mercapto group, a carboxyl group, or an amino group with the compound having a polymerizable group, a known reaction for forming an ether bond, a carboxylic ester bond, a carboxylic amide bond, or a thioether bond can be used.
The reaction to form the radical-polymerizable group-containing group may be a multistage reaction. For example, a radical polymerizable group-containing group represented by the following formula can be introduced into an aromatic ring by reacting an aromatic amine having a phenolic hydroxyl group with a halogenated cyanuric acid, then reacting the phenolic hydroxyl group with epichlorohydrin to glycidate, and then reacting acrylic acid with a glycidyl group.
-O-CH 2 -CHOH-CH 2 -O-CO-CH＝CH 2
The above reaction is an example, and the radical-polymerizable group-containing group can be formed by combining various reactions.
The compound represented by the formula (B-2 e-B) is usually synthesized in an organic solvent. The organic solvent is not particularly limited as long as it is an inert solvent that does not react with halogenated cyanuric acid, aromatic amine, radical polymerizable group, and the like. As the solvent, an organic solvent or the like exemplified as a specific example of the solvent (S) can be used.
In the production of the compound represented by the formula (B-2 e-B), halogenated cyanuric acid is reacted with R B11 -NH 2 、R B12 -NH 2 R is R B13 -NH 2 The temperature at which the aromatic amine such as aromatic amine is reacted is not particularly limited. Typically, the reaction temperature is preferably from 0℃to 150 ℃.
The content of the photopolymerizable compound (B) in the photosensitive composition is preferably 10 mass% to 70 mass%, more preferably 20 mass% to 60 mass%, based on the mass of the metal oxide particles (D) and the mass of the solvent (S) removed from the mass of the photosensitive composition.
< photopolymerization initiator (C) >)
In order to cure the photopolymerizable compound (B), the photosensitive composition preferably contains a photopolymerization initiator (C). The photopolymerization initiator (C) may be a radical photopolymerization initiator in view of being capable of positionally selectively curing the photosensitive composition and avoiding the fear of deterioration, volatilization, sublimation, and the like of the components of the photosensitive composition due to heat.
The photopolymerization initiator (C) is not particularly limited, and various conventionally known polymerization initiators can be used.
Specifically, the photopolymerization initiator (C) may be exemplified by 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-dimethoxy-1, 2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl ] ethanone oxime, (9-Ethyl-6-nitro-9H-carbazol-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl ] methanone O-acetoxime, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl ] -1-octanone, 2,4, 6-trimethylbenzoyldiphenyl phosphine oxide, 4-benzoyl-4' -methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoate, 4-dimethylamino-2-isopentylbenzoic acid, benzyl-. Beta. -methoxyethyl acetal, benzyl dimethylketal, 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl O-benzoylbenzoate, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 1-chlorothioketone, 2-propylthioxanthone, 2-ethylthioxanthone, 2-isopropylanthraquinone, 2-methylthioanthraquinone, 2-ethylthioxanthone, 2-phenylthioxanthone, 2-ethylthioxanthone, 2-oxoethyl-2-xanthone, 2-chlorothioketone and 2-ethylthioxanthone, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4, 5-bis (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p ' -bis-dimethylaminobenzophenone, 4' -bis-diethylaminobenzophenone, 4' -dichlorobenzophenone, 3-dimethyl-4-methoxybenzophenone, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2-diethoxyacetophenone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-hydroxy-2-methylbenzophenone, dichloroacetophenone, trichloroacetophenone, p-t-butylacetophenone, p-dimethylaminoacetophenone, p-t-butyltrichloroacetophenone, p-t-butyldichloroacetophenone, alpha, alpha-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, dibenzocycloheptanone, pentyl-4-dimethylaminobenzoate, 9-benzacridine, 1, 7-bis- (9-acridinyl) heptane, 1, 5-bis- (9-acridinyl) pentane, 1, 3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4, 6-tris (trichloromethyl) -s-triazine, 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (3, 4-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2, 4-bis-methoxyphenyl-s-triazine, 2- (4-methoxyphenyl) bromo-4-s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2, 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, and the like. These photopolymerization initiators (C) can be used alone or in combination of 2 or more.
Among the photopolymerization initiators (C), oxime ester compounds are preferable from the viewpoint of sensitivity of the photosensitive composition.
As the oxime ester compound, a compound having a partial structure represented by the following formula (c 1) is preferable.
[ chemical formula 36 ]
(in the formula (c 1),
n1 is either 0 or 1 and,
R c2 is an organic group having a valence of 1,
R c3 an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent,
* Is a chemical bond. )
The compound having a local structure represented by the formula (c 1) preferably has a carbazole skeleton, a fluorene skeleton, a diphenyl ether skeleton, and a phenylene sulfide skeleton.
The compound having a partial structure represented by formula (c 1) is preferably a compound having 1 or 2 partial structures represented by formula (c 1).
The compound having a local structure represented by the formula (c 1) may be a compound represented by the following formula (c 2).
[ FORMS 37 ]
(in the formula (c 2), R c1 Is a group represented by the following formula (c 3), (c 4) or (c 5),
n1 is either 0 or 1 and,
R c2 is an organic group having a valence of 1,
R c3 an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. )
[ chemical 38 ]
(in the formula (c 3), R c4 R is R c5 Each independently is a 1-valent organic group,
n2 is an integer of 0 to 3,
in the case where n2 is 2 or 3, a plurality of R c5 The R's may be the same or different c5 May bond to each other to form a ring.
* Is a chemical bond. )
[ chemical formula 39 ]
(in the formula (c 4), R c6 R is R c7 Each independently represents a substituent-containing chain alkyl group, substituent-containing chain alkoxy group, substituent-containing cyclic organic group or hydrogen atom,
R c6 and R is R c7 Can be bonded to each other to form a ring,
R c7 can bond with benzene rings in fluorene skeletons to form a ring,
R c8 is nitro or 1-valent organic group,
n3 is an integer of 0 to 4,
* Is a chemical bond. )
[ 40 ]
(in the formula (c 5), R c9 Is a 1-valent organic group, a halogen atom, a nitro group or a cyano group,
a is S or O, and the total content of the catalyst is S,
n4 is an integer of 0 to 4,
* Is a chemical bond. )
In the formula (c 3), R c4 Is a 1-valent organic group. R is R c4 Can be selected from various organic groups within a range that does not hinder the object of the present invention. The organic group is preferably a group containing carbon atoms, more preferably a group composed of 1 or more carbon atoms and 1 or more atoms selected from the group consisting of H, O, S, se, N, B, P, si and halogen atoms. The number of carbon atoms of the carbon atom-containing group is not particularly limited, but is preferably 1 to 50, more preferably 1 to 20.
As R c4 Examples of the preferable group(s) include an alkyl group which may have a substituent having 1 to 20 carbon atoms, a cycloalkyl group which may have a substituent having 3 to 20 carbon atoms, a saturated aliphatic acyl group which may have a substituent having 2 to 20 carbon atoms, an alkoxycarbonyl group which may have a substituent having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group which may have a substituent having 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group which may have a substituent having 11 to 20 carbon atoms, a heterocyclic group which may have a substituent, and a heterocyclic carbonyl group which may have a substituent.
At R c4 Among them, an alkyl group having 1 to 20 carbon atoms is preferable. The alkyl group may be linear or branched. The compound represented by the formula (c 3) has good solubility in the photosensitive compositionR c4 The number of carbon atoms of the alkyl group is preferably 2 or more, more preferably 5 or more, and particularly preferably 7 or more. In addition, R is a compound represented by the formula (c 3) in the photosensitive composition, which has good compatibility with other components c4 The number of carbon atoms of the alkyl group is preferably 15 or less, more preferably 10 or less.
At R c4 In the case of having a substituent, preferable examples of the substituent include a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, an aliphatic acyloxy group having 2 to 20 carbon atoms, a phenoxy group, a benzoyl group, a benzoyloxy group, and a group represented by-PO (OR) 2 A group represented by (R is an alkyl group having 1 to 6 carbon atoms), a halogen atom, a cyano group, a heterocyclic group, or the like.
At R c4 In the case of a heterocyclic group, the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. At R c4 In the case of a heterocyclic group, the heterocyclic group is a five-membered or six-membered monocyclic ring containing 1 or more N, S, O, or is a heterocyclic group obtained by condensing the monocyclic rings and a benzene ring. When the heterocyclic group is a condensed ring, the number of rings is 3 or less. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran.
At R c4 In the case of a heterocyclic group, examples of the substituent that the heterocyclic group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, and the like.
R as described above c4 Preferable specific examples of (a) include methyl, ethyl, n-propyl,Isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, pentan-3-yl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl and 2-ethylhexyl.
In addition, from the viewpoint of good solubility of the compound represented by formula (c 3) in the photosensitive composition, n-octyl and 2-ethylhexyl are preferable, and 2-ethylhexyl is more preferable.
In the formula (c 3), R c5 Is a 1-valent organic group, a halogen atom or a nitro group. As R c5 The 1-valent organic group of (2) can be selected from various organic groups within a range that does not hinder the object of the present invention. The organic group is preferably a group containing carbon atoms, more preferably a group composed of 1 or more carbon atoms and 1 or more atoms selected from the group consisting of H, O, S, se, N, B, P, si and halogen atoms. The number of carbon atoms of the carbon atom-containing group is not particularly limited, but is preferably 1 to 50, more preferably 1 to 20.
As R c5 Examples of the preferable 1-valent organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyl oxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoxyoxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an aminocarbonyl group which may have a substituent, an amino group substituted with 1, 2 organic groups, morpholin-1-yl, piperazin-1-yl, halogen, nitro, cyano, and compounds containing HX 2 C-or H 2 Substituents of the group represented by XC-wherein X is each independently a halogen atom, and the like.
At R c5 In the case of an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 6. In addition, in the case of the optical fiber,at R c5 In the case of an alkyl group, the alkyl group may be straight-chain or branched. As R c5 Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl and isodecyl. In addition, at R c5 In the case of alkyl groups, the alkyl groups may contain ether linkages (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propoxyethoxyethyl group, and methoxypropyl group.
At R c5 In the case of an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 6. In addition, at R c5 In the case of an alkoxy group, the alkoxy group may be straight-chain or branched. As R c5 Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, sec-pentoxy, tert-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, isooctoxy, zhong Xinyang, tert-octoxy, n-nonoxy, isononyl, n-decyloxy and isodecyloxy. In addition, at R c5 In the case of alkoxy groups, the alkoxy groups may contain ether linkages (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propoxyethoxyethoxy, and methoxypropoxy groups.
At R c5 In the case of cycloalkyl or cycloalkoxy, the number of carbon atoms of the cycloalkyl or cycloalkoxy is preferably 3 to 10, more preferably 3 to 6. As R c5 Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As R c5 Specific examples of the cycloalkoxy group includeExamples of the "cyclopropyloxy" include cyclopropyloxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy and cyclooctyloxy.
At R c5 In the case of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. As R c5 Specific examples of the saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropanoyl, n-pentanoyl, 2-dimethylpropionyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl and n-hexadecanoyl. As R c5 Specific examples of the saturated aliphatic acyloxy group include an acetyloxy group, a propionyloxy group, a n-butyryloxy group, a 2-methylpropanoyloxy group, a n-pentanoyloxy group, a 2, 2-dimethylpropionyloxy group, a n-caproyloxy group, a n-heptanoyloxy group, a n-octanoyloxy group, a n-nonanoyloxy group, a n-decanoyloxy group, a n-undecanoyloxy group, a n-dodecanoyloxy group, a n-tridecanoyloxy group, a n-tetradecanoyloxy group, a n-pentadecanoyloxy group, and a n-hexadecanoyloxy group.
At R c5 In the case of an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 20, more preferably 2 to 7. As R c5 Specific examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, zhong Xinyang-ylcarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl and isodecyloxycarbonyl.
At R c5 In the case of phenylalkyl, the number of carbon atoms of the phenylalkyl is preferably 7 to 20, more preferably 7 to 10The following is given. In addition, at R c5 In the case of the naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably 11 to 20, more preferably 11 to 14. As R c5 Specific examples of the phenylalkyl group include benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl. As R c5 Specific examples of the naphthylalkyl group include an α -naphthylmethyl group, a β -naphthylmethyl group, a 2- (α -naphthyl) ethyl group and a 2- (β -naphthyl) ethyl group. At R c5 In the case of phenylalkyl or naphthylalkyl, R c5 Further, a substituent may be present on the phenyl group or the naphthyl group.
At R c5 In the case of a heterocyclic group, the heterocyclic group is the same as R in formula (c 3) c4 The same applies to the heterocyclic group, and the heterocyclic group may further have a substituent.
At R c5 In the case of a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group and R c5 The same applies to the heterocyclic group.
At R c5 In the case of an amino group substituted with 1 or 2 organic groups, preferable examples of the organic groups include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group which may have 11 to 20 carbon atoms which may have a substituent, a heterocyclic group, and the like. Specific examples of these preferred organic groups and R c5 The same applies. Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-pentanoylamino, n-hexanoylamino, n-heptanylamino, n-octanoylaminoN-decanoylamino, benzoylamino, alpha-naphthoylamino, beta-naphthoylamino and the like.
As R c5 Examples of the "substituent" in the case where the phenyl group, naphthyl group and heterocyclic group contained in the composition further have a substituent may include HX 2 C-or H 2 Substituents of the group represented by XC (e.g. containing a substituent represented by HX 2 C-or H 2 Haloalkoxy groups of groups represented by XC-containing a radical represented by HX 2 C-or H 2 A haloalkyl group of a group represented by XC), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, benzoyl, halogen, nitro, cyano and the like. At R c5 In the case where the phenyl group, the naphthyl group and the heterocyclic group contained in the above are further substituted, the number of the substituents is not limited within a range that does not hinder the object of the present invention, and is preferably 1 to 4. At R c5 In the case where the phenyl group, the naphthyl group and the heterocyclic group contained in (a) have a plurality of substituents, the plurality of substituents may be the same or different.
As at R c5 Examples of the "substituent" in the case where the benzoyl group contained in (a) further includes an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, 2-thenoyl (thiophen-2-ylcarbonyl), furan-3-ylcarbonyl and phenyl.
Examples of the "halogen" atom represented by X may include a fluorine atom, a chlorine atom and a bromine atom, and a fluorine atom is preferred.
As a contained HX 2 C-or H 2 Examples of the "substituent" of the "XC" may include the "HX" and the "X" may be the same or different 2 C-or H 2 Haloalkoxy groups having a group represented by XC-having a structure comprising a group represented by HX 2 C-or H 2 A haloalkoxy group of the group represented by XC-, comprising a group represented by HX 2 C-or H 2 Haloalkyl having a group denoted XC-with a terminal group comprising a group denoted HX 2 C-or H 2 The group containing a haloalkyl group of the group represented by XC-, etc., more preferably HX 2 C-or H 2 Haloalkoxy groups or having groups represented by XC-or having groups containing a radical represented by HX 2 C-or H 2 And XC-represents a haloalkoxy group of the group.
As a solution containing HX 2 C-or H 2 Examples of the "haloalkyl" group as the "XC" group may include those containing HX 2 C-or H 2 Haloalkyl-substituted aromatic groups of the group represented by XC-such as phenyl, naphthyl and the like, which are contained with HX 2 C-or H 2 Haloalkyl-substituted cycloalkyl (e.g., cyclopentyl, cyclohexyl, etc.) of the group represented by XC-, and the like, are preferably contained with HX 2 C-or H 2 Haloalkyl-substituted aromatic groups of the group represented by XC-.
As a solution containing HX 2 C-or H 2 Examples of the "haloalkoxy" related to the "XC" related to the "group may include those related to the" HX 2 C-or H 2 Haloalkoxy-substituted aromatic groups (e.g., phenyl, naphthyl, etc.) of the group represented by XC-and HX-contained therein 2 C-or H 2 Haloalkoxy-substituted alkyl groups of the group represented by XC-such as methyl, ethyl, n-propyl, isopropyl and the like, which are contained with HX 2 C-or H 2 Haloalkoxy-substituted cycloalkyl (e.g., cyclopentyl, cyclohexyl, etc.) of the group represented by XC-, and the like, preferably contained with HX 2 C-or H 2 Haloalkoxy-substituted aromatic groups of the group represented by XC-.
In addition, as R c5 Also preferred are cycloalkylalkyl groups, phenoxyalkyl groups which may have a substituent on the aromatic ring, and phenylthioalkyl groups which may have a substituent on the aromatic ring. Phenoxyalkyl and phenylthioalkyl may have a substituent and R c5 The phenyl groups contained may have the same substituents.
In the 1-valent organic groups, R is as c5 Preferably, an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, a phenylthioalkyl group which may have a substituent on an aromatic ring. As alkyl groupsThe alkyl group having 1 to 20 carbon atoms is preferable, the alkyl group having 1 to 8 carbon atoms is more preferable, the alkyl group having 1 to 4 carbon atoms is particularly preferable, and the methyl group is most preferable. Among phenyl groups which may have a substituent, methylphenyl is preferable, and 2-methylphenyl is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 to 8, more preferably 1 to 4, particularly preferably 2. Among phenylthioalkyl groups which may have a substituent on the aromatic ring, 2- (4-chlorophenylthio) ethyl is preferred.
In the group represented by the formula (c 3), there are plural R' s c5 A plurality of R c5 When the rings are bonded to each other to form a ring, examples of the formed ring include a hydrocarbon ring and a heterocyclic ring. Examples of the "hetero atom" contained in the heterocyclic ring may include N, O, S. As a plurality of R c5 The ring formed by bonding each other is particularly preferably an aromatic ring. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The aromatic ring is preferably an aromatic hydrocarbon ring. In formula (c 3), a plurality of R c5 Specific examples of the case where benzene rings are bonded to each other are as follows.
[ chemical formula 41 ]
In the group represented by the formula (c 4), R c8 Is nitro or 1-valent organic group. R is R c8 Bonded to the condensed ring in formula (c 4) and to the ring in- (CO) n1 -a six-membered aromatic ring different from the aromatic ring to which the represented group is bonded. In the formula (c 4), R c8 The bonding position of (c) is not particularly limited. The group represented by the formula (c 4) has 1 or more R c8 In the case of (c), a compound represented by the formula (c 4)The synthesis of the product is easier, and preferably 1 or more R c8 Is bonded to the 7-position of the fluorene skeleton. That is, the group represented by the formula (c 4) has 1 or more R c8 In the case of (c), the group represented by the formula (c 4) is preferably represented by the following formula (c 6). At R c8 In the case of a plurality of R c8 May be the same or different.
[ chemical 42 ]
(in the formula (c 6), R c6 、R c7 、R c8 N3 are respectively the same as R in formula (c 4) c6 、R c7 、R c8 N3 are the same. )
At R c8 In the case of a 1-valent organic group, R c8 The range that does not hinder the object of the present invention is not particularly limited. The organic group is preferably a group containing carbon atoms, more preferably a group composed of 1 or more carbon atoms and 1 or more atoms selected from the group consisting of H, O, S, se, N, B, P, si and halogen atoms. The number of carbon atoms of the carbon atom-containing group is not particularly limited, but is preferably 1 to 50, more preferably 1 to 20.
As R c8 Preferable examples of the organic group having 1 valence include R in the formula (c 3) c5 The same groups as those of the 1-valent organic groups are preferable.
In the formula (c 4), R c6 R is R c7 Each is a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R is R c6 R is R c7 May bond to each other to form a ring. Among these groups, R is the radical c6 R is R c7 A chain alkyl group which may have a substituent is preferable. At R c6 R is R c7 In the case of a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched alkyl group.
At R c6 R is R c7 In the case of a chain alkyl group having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 6. As R c6 R is R c7 Specific examples of the chain alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl and isodecyl. In addition, at R c6 R is R c7 In the case of alkyl groups, the alkyl groups may contain ether linkages (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propoxyethoxyethyl group, and methoxypropyl group.
At R c6 R is R c7 In the case of a substituted chain alkyl group, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The substituted chain alkyl group is preferably linear.
The substituent that the alkyl group may have is not particularly limited insofar as it does not hinder the object of the present invention. Preferable examples of the substituent include an alkoxy group, a cyano group, a halogen atom, a haloalkyl group, a cyclic organic group, and an alkoxycarbonyl group. Examples of the "halogen" may include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these atoms, preferred are fluorine atom, chlorine atom and bromine atom. Examples of the "cyclic organic group" may include cycloalkyl, aromatic hydrocarbon, and heterocyclic groups. As a specific example of cycloalkyl, R c8 The same preferable examples are given for cycloalkyl groups. Specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthryl, and phenanthryl. As a specific example of the heterocyclic group, R c8 The same preferable examples are the case of the heterocyclic group. At R c8 In the case of an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may beThe chain may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 to 10, more preferably 1 to 6.
In the case where the chain alkyl group has a substituent, the number of substituents is not particularly limited. The number of preferred substituents varies depending on the number of carbon atoms of the chain alkyl group. The number of substituents is typically 1 to 20, preferably 1 to 10, more preferably 1 to 6.
At R c6 R is R c7 In the case of a chain alkoxy group having no substituent, the number of carbon atoms of the chain alkoxy group is preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 6. As R c6 R is R c7 Specific examples of the chain alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, sec-pentoxy, tert-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, isooctoxy, zhong Xinyang, tert-octoxy, n-nonoxy, isononyl, n-decoxy, isodecoxy and the like. In addition, at R c6 R is R c7 In the case of alkoxy groups, the alkoxy groups may contain ether linkages (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propoxyethoxyethoxy, and methoxypropoxy groups.
At R c6 R is R c7 In the case of a chain alkoxy group having a substituent, the alkoxy group may have a substituent and R c6 R is R c7 The same applies to chain alkyl groups.
At R c6 R is R c7 In the case of a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. At R c6 R is R c7 In the case of a cyclic organic group, the cyclic organic group may have a substituentAnd R is R c6 R is R c7 The same applies to chain alkyl groups.
At R c6 R is R c7 In the case of an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a phenyl group, a group in which a plurality of benzene rings are bonded through carbon-carbon bonds, or a group in which a plurality of benzene rings are condensed. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Preferred specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthryl, and phenanthryl.
At R c6 R is R c7 In the case of the aliphatic cyclic hydrocarbon group, the aliphatic cyclic hydrocarbon group may be a single ring or multiple rings. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 10. Examples of the monocyclic cyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl, and adamantyl.
At R c6 R is R c7 In the case of a heterocyclic group, R in the formula (c 3) is exemplified as c5 Is the same as the heterocyclic group.
R c6 R is R c7 May bond to each other to form a ring. From R c6 R is R c7 The group formed by the ring is preferably cycloalkylene. At R c6 R is R c7 When the cycloalkyl group is bonded to form a cycloalkylene group, the ring constituting the cycloalkyl group is preferably a five-membered to six-membered ring, more preferably a five-membered ring.
At R c7 In the case of forming a ring with the benzene ring of the fluorene skeleton, the ring may be an aromatic ring or an aliphatic ring.
At R c6 R is R c7 When the group formed by bonding is a cycloalkylene group, the cycloalkylene group may be condensed with 1 or more other rings. As examples of the ring which can be condensed with the cycloalkylene group, there may be mentionedExamples of the "ring" include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a pyrazine ring, and a pyrimidine ring.
R as described above c6 R is R c7 Examples of the preferred groups include those represented by the formula-A 1 -A 2 A group represented by the formula (I). In the formula, A is exemplified by 1 Is a linear alkylene group, A 2 Is an alkoxy group, a cyano group, a halogen atom, a haloalkyl group, a cyclic organic group, or an alkoxycarbonyl group.
A 1 The number of carbon atoms of the linear alkylene group is preferably 1 to 10, more preferably 1 to 6. At A 2 In the case of an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 6. At A 2 In the case of a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a fluorine atom, a chlorine atom, and a bromine atom are more preferable. At A 2 In the case of a haloalkyl group, the halogen atom contained in the haloalkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom. The haloalkyl group may be linear or branched, and is preferably linear. At A 2 In the case of a cyclic organic group, examples of cyclic organic groups and R c6 R is R c7 The cyclic organic groups which are provided as substituents are the same. At A 2 In the case of alkoxycarbonyl, examples of alkoxycarbonyl and R c6 R is R c7 The alkoxycarbonyl groups which are the substituents are the same.
As R c6 R is R c7 Examples of the preferable specific examples of (a) include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl and n-octyl; 2-methoxyethyl, 3-methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy-n-octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl and 8-ethoxy-n-octyl; cyanoalkyl groups such as 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; phenylalkyl groups such as 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl; cycloalkylalkyl groups such as 2-cyclohexylethyl, 3-cyclohexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; alkoxycarbonylalkyl groups such as 2-methoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4-ethoxycarbonyl-n-butyl, 5-ethoxycarbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl, and 8-ethoxycarbonyl-n-octyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-octyl, 2-bromoethyl, 3-bromo-n-propyl 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl 8-bromo-n-octyl haloalkyl such as 3, 3-trifluoropropyl and 3,4, 5-heptafluoro-n-pentyl.
As R c6 R is R c7 Preferred groups in the above are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl 2-bromoethyl group 3, 3-trifluoropropyl and 3,4, 5-heptafluoro-n-pentyl.
In the formula (c 5), a is particularly preferably S, from the viewpoint of easy availability of a photopolymerization initiator excellent in sensitivity.
In the formula (c 5), R c9 Is 1 priceA radical, a halogen atom, a nitro group or a cyano group.
R in formula (c 5) c9 In the case of the 1-valent organic group, the organic group can be selected from various organic groups within a range that does not hinder the object of the present invention. The organic group is preferably a group containing carbon atoms, more preferably a group composed of 1 or more carbon atoms and 1 or more atoms selected from the group consisting of H, O, S, se, N, B, P, si and halogen atoms. The number of carbon atoms of the carbon atom-containing group is not particularly limited, but is preferably 1 to 50, more preferably 1 to 20.
As R in the formula (c 5) c9 As preferable examples of the organic group, R in the formula (c 3) can be mentioned c5 The same as the 1-valent organic group.
At R c9 Preferably a benzoyl group; a naphthoyl group; benzoyl substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, and phenyl; a nitro group; benzofuranylcarbonyl which may have a substituent, more preferably benzoyl; a naphthoyl group; 2-methylphenyl carbonyl; 4- (piperazin-1-yl) phenylcarbonyl; 4- (phenyl) phenylcarbonyl.
In formula (c 5), n4 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. In the case where n4 is 1, R c9 The position of the bond is preferably relative to R c9 The chemical bond of the bonded phenyl group bonded with the oxygen atom or the sulfur atom is para.
In the formulae (c 1) and (c 2), R is c2 The 1-valent organic group of (2) is not particularly limited insofar as it does not interfere with the object of the present invention. The organic group is preferably a group containing carbon atoms, more preferably a group composed of 1 or more carbon atoms and 1 or more atoms selected from the group consisting of H, O, S, se, N, B, P, si and halogen atoms. The number of carbon atoms of the carbon atom-containing group is not particularly limited, but is preferably 1 to 50, more preferably 1 to 20.
As R c2 Preferable examples of the 1-valent organic group of (2) may be mentionedAnd R in formula (c 3) c5 The same as the 1-valent organic group. Specific examples of these groups and R in the formula (c 3) c5 The radicals specified are identical.
In addition, as R c2 Also preferred are cycloalkylalkyl groups, phenoxyalkyl groups which may have a substituent on the aromatic ring, and phenylthioalkyl groups which may have a substituent on the aromatic ring. Phenoxyalkyl and phenylthioalkyl may have a substituent with R in formula (c 3) c5 The substituents in the case where the phenyl group, the naphthyl group and the heterocyclic group further have a substituent are the same.
In the organic radical, R is as c2 Preferably, the above-mentioned components are contained as HX 2 C-or H 2 Substituents for the group represented by XC-, alkyl, cycloalkyl, phenyl which may have substituents, or cycloalkylalkyl, phenylthioalkyl which may have substituents on the aromatic ring. An alkyl group, a phenyl group which may have a substituent(s), a carbon atom number of a cycloalkyl group contained in a cycloalkylalkyl group, a carbon atom number of an alkylene group contained in a cycloalkylalkyl group, a carbon atom number of an alkylene group contained in a phenylthioalkyl group which may have a substituent(s) on an aromatic ring, or a phenylthioalkyl group which may have a substituent(s) on an aromatic ring, and R of the formula (c 3) c5 The same applies.
In addition, as R c2 Also preferably in form of-A 3 -CO-O-A 4 A group represented by the formula (I). A is that 3 Is a 2-valent organic group, preferably a 2-valent hydrocarbon group, preferably an alkylene group. A is that 4 Is a 1-valent organic group, preferably a 1-valent hydrocarbon group.
At A 3 In the case of an alkylene group, the alkylene group may be linear or branched, and is preferably linear. At A 3 In the case of an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, particularly preferably 1 to 4.
As A 4 Examples of the (c) may include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. As A 4 Preferable specific examples of (a) may include methyl, ethyl, n-propyl, and iso-propylPropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, alpha-naphthylmethyl, beta-naphthylmethyl, and the like.
As a mixture of-A 3 -CO-O-A 4 Preferred specific examples of the group represented are 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, 2-n-butoxycarbonylethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonyl ethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propoxycarbonyl-n-propyl, 3-n-butoxycarbonyl-n-propyl, 3-n-pentyloxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl and 3-phenoxycarbonyl-n-propyl.
In addition, as R c2 Also preferred are groups represented by the following formula (c 7) or (c 8).
[ chemical formula 43 ]
(in the formulae (c 7) and (c 8), R c10 R is R c11 Each independently is a 1-valent organic group,
n5 is an integer of 0 to 4,
at R c10 R is R c11 In the case where R is present at an adjacent position on the benzene ring c10 And R is R c11 Can be bonded to each other to form a ring,
R c12 is an organic group having a valence of 1,
n6 is an integer of 1 to 8,
n7 is an integer of 1 to 5,
n8 is an integer of 0 to (n7+3). )
In formula (c 7) as R c10 R is R c11 And R in formula (c 4) c8 The same applies. As R c10 Preferably with HX 2 C-or H 2 Haloalkoxy groups of groups represented by XC-containing a radical represented by HX 2 C-or H 2 A haloalkyl group, an alkyl group or a phenyl group of a group represented by XC-. At R c10 And R is R c11 When the ring is formed by bonding, the ring may be an aromatic ring or an aliphatic ring. As represented by formula (c 7) and R c10 And R is R c11 Preferred examples of the group forming the ring include naphthalen-1-yl and 1,2,3, 4-tetrahydronaphthalen-5-yl.
In the above formula (c 7), n5 is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
In the above formula (c 8), R c12 Is an organic group. Examples of the "organic" may include R in the formula (c 4) c8 The organic groups illustrated are identical. Among the organic groups, alkyl groups are preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3. As R c12 Methyl, ethyl, propyl, isopropyl, butyl, etc. may be preferably exemplified, and among these groups, methyl is more preferred.
In the above formula (c 8), n7 is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2. In the above formula (c 8), n8 is an integer of 0 to (n7+3), preferably 0 to 3, more preferably 0 to 2, and particularly preferably 0.
In the above formula (c 8), n6 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.
In the formula (c 2), R c3 An aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As R c3 The substituent which may be present in the case of an aliphatic hydrocarbon group is preferably exemplified by phenyl, naphthyl, and the like.
In the formula (c 1) and the formula (c 2), R is c3 Preferred examples of the hydrogen atom include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-cyclopentylethyl, 2-cyclobutylethyl and cyclohexyl
Methyl, phenyl, benzyl, methylphenyl, naphthyl, and the like,of these, methyl or benzene is more preferable 5 A base.
As R is a group represented by the formula (c 2) and having the formula (c 3) c1 Preferable specific examples of the compound (iv) include the following compounds.
[ 44 ]
[ chemical 45 ]
[ chemical 46 ]
[ chemical formula 47 ]
As R is a group represented by the formula (c 2) and having the formula (c 4) c1 Preferable specific examples of the compound (iv) include the following compounds.
[ chemical formula 48 ]
[ chemical formula 49 ]
[ 50 ] of the formula
[ chemical formula 51 ]
[ chemical formula 52 ]
As R is a group represented by the formula (c 2) and having the formula (c 5) c1 Preferable specific examples of the compound (iv) include the following compounds.
[ FORMATION 53 ]
The photopolymerization initiator (C) is preferably a phosphine oxide compound because of good deep curability of the photosensitive composition. The phosphine oxide compound is preferably a phosphine oxide compound comprising a partial structure represented by the following formula (c 9).
[ FORMS 54 ]
In the formula (c 9), R c21 R is R c22 Each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aliphatic acyl group having 2 to 20 carbon atoms, or an aromatic acyl group having 7 to 20 carbon atoms. Wherein R is c21 R is R c22 Both are not aliphatic acyl or aromatic acyl.
As R c21 R is R c22 The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 8, and still more preferably 1 to 4. As R c21 R is R c22 The alkyl group of (2) may be linear or branched.
Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2, 4-trimethylpentyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.
As R c21 R is R c22 The number of carbon atoms of the cycloalkyl group is preferably 5 to 12. Specific examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl.
As R c21 R is R c22 The number of carbon atoms of the aryl group is preferably 6 to 12. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. Specific examples of the aryl group include phenyl and naphthyl.
As R c21 R is R c22 The aliphatic acyl group has 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 6 carbon atoms. The aliphatic acyl group may be linear or branched.
Specific examples of the aliphatic acyl group include acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl and eicosanoyl.
As R c21 R is R c22 The number of carbon atoms of the aromatic acyl group is 7 to 20. The aromatic acyl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. Specific examples of the aromatic acyl group include benzoyl, o-tolyl, m-tolyl, p-tolyl, 2, 6-dimethylbenzoyl, 2, 6-dimethoxybenzoyl and 2,4, 6-trimethylBenzoyl, α -naphthoyl and β -naphthoyl.
Preferable specific examples of the phosphine oxide compound including the structural moiety represented by the formula (c 9) include 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, and bis (2, 6-dimethoxybenzoyl) -2, 4-trimethyl-pentylphosphine oxide.
From the viewpoint of deep curability of the photosensitive composition, the phosphine oxide compound comprising a structural moiety represented by the formula (c 9) is also preferably used together with an initiator of α -hydroxyalkanophenone such as 2-hydroxy-2-methylpropenone.
In the case of using an initiator of α -hydroxyalkanophenone type, such as phosphine oxide compound containing a structural moiety represented by the formula (c 9) and 2-hydroxy-2-methylpropaneketone, the ratio of the mass of the phosphine oxide compound containing a structural moiety represented by the formula (c 9) to the total mass of both is preferably 20 mass% or more and 80 mass% or less, more preferably 30 mass% or more and 70 mass% or less, and still more preferably 40 mass% or more and 60 mass% or less.
The content of the photopolymerization initiator (C) in the photosensitive composition is not particularly limited. The content of the photopolymerization initiator (C) may be appropriately determined depending on the kind of the photopolymerizable group and the kind of the photopolymerization initiator (C).
When the mass of the photosensitive composition from which the mass of the solvent (S) to be described later is removed is taken as 100 parts by mass, the content of the photopolymerization initiator (C) in the photosensitive composition is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.1 parts by mass or more and 15 parts by mass or less, and still more preferably 1 part by mass or more and 10 parts by mass or less.
< Metal oxide particle (D) >)
The photosensitive composition may contain metal oxide particles (D).
When the photosensitive composition contains the metal oxide particles (D), a cured product having a high refractive index is easily formed.
The kind of metal oxide constituting the metal oxide particles (D) is not particularly limited as long as the desired effect is not impaired. The metal oxide particles (D) may be preferably at least 1 selected from the group consisting of zirconia particles, titania particles, barium titanate particles, cerium oxide particles and niobium pentoxide particles.
The photosensitive composition may contain 1 kind of these metal oxide particles (D) alone or 2 or more kinds thereof in combination.
The average particle diameter of the metal oxide particles (D) is preferably 500nm or less, more preferably 2nm or more and 100nm or less, from the viewpoints of transparency of the cured product and stability of dispersion of the inorganic fine particles (B) in the photosensitive composition.
The surface of the metal oxide particles (D) is preferably modified with groups containing ethylenically unsaturated double bonds.
When the surface of the metal oxide particles (D) is modified with a group containing an ethylenically unsaturated double bond, the alkali-soluble resin (a) and the photopolymerizable compound (B) are polymerized together with the metal oxide particles (D) at the time of forming a cured product, and the metal oxide particles (D) are immobilized in a matrix composed of the reactants of the alkali-soluble resin (a) and the photopolymerizable compound (B). Thus, it is preferable in view of the difficulty in causing aggregation of the metal oxide particles (D).
For example, a capping agent containing an ethylenically unsaturated double bond is applied to the surface of the metal oxide particle (D), whereby the metal oxide particle (D) having its surface modified with a group containing an ethylenically unsaturated double bond via a chemical bond such as a covalent bond is obtained.
The method of bonding the capping agent containing an ethylenically unsaturated double bond to the surface of the metal oxide particle (D) via a chemical bond such as a covalent bond is not particularly limited. Hydroxyl groups are generally present on the surface of the metal oxide particles (D). The hydroxyl group is reacted with a reactive group of the capping agent, whereby the capping agent is covalently bonded to the surface of the metal oxide particle (D).
Preferable examples of the reactive group of the blocking agent include a trialkoxysilyl group such as a trimethoxysilyl group and a triethoxysilyl group; dimethoxy silyl group two (II)Dialkoxysilyl groups such as ethoxysilyl groups; mono-alkoxysilyl groups such as mono-methoxysilyl groups and mono-ethoxysilyl groups; trihalosilyl groups such as trichlorosilyl groups; dihalosilyl groups such as dichlorosilyl groups; monohalosilyl groups such as a monochlorosilyl group; a carboxyl group; halocarbonyl groups such as chlorocarbonyl groups; a hydroxyl group; phosphono (-P (=o) (OH) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Phosphate group (-O-P (=O) (OH) 2 )。
The trialkoxysilyl group, dialkoxysilyl group, monoalkoxysilyl group, trihalosilyl group, dihalosilyl group, and monohalosilyl group form siloxane bonds with the surface of the metal oxide particle (D).
The carboxyl group and the halocarbonyl group form bonds represented by (metal oxide-O-CO-) with the surface of the metal oxide particle (D).
The hydroxyl groups form bonds represented by (metal oxide-O-) with the surface of the metal oxide particles (D).
The phosphonyl group and the phosphate group form bonds represented by (metal oxide-O-P (=o) <) with the surface of the metal oxide particle (D).
Examples of the "group bonded to the reactive group" in the blocking agent include a hydrogen atom and various organic groups. The organic group may contain a heteroatom such as O, N, S, P, B, si and a halogen atom.
Examples of the group bonded to the reactive group include an alkyl group which may be linear or branched and may be interrupted by an oxygen atom (-O-), an alkenyl group which may be linear or branched and may be interrupted by an oxygen atom (-O-), an alkynyl group which may be linear or branched and may be interrupted by an oxygen atom (-O-), a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group.
These groups may be substituted with a substituent such as a halogen atom, an epoxy group-containing group such as a glycidyl group, a hydroxyl group, a mercapto group, an amino group, a (meth) acryloyl group, and an isocyanate group. The number of substituents is not particularly limited.
The group bonded to the reactive group is preferably a group having- (SiR) d1 R d2 -O-) r -(SiR d3 R d4 -O-) s -R d5 A group represented by the formula (I). R is R d1 、R d2 、R d3 R is R d4 The organic groups may be the same or different. Preferable examples of the organic group include an alkyl group such as a methyl group and an ethyl group; alkenyl groups such as vinyl and allyl; aromatic hydrocarbon groups such as phenyl, naphthyl, and tolyl; epoxy-containing groups such as 3-glycidoxypropyl; (meth) acryloyloxy, and the like.
In the above formula, R is d5 Examples thereof include-Si (CH) 3 ) 3 、-Si(CH 3 ) 2 H、-Si(CH 3 ) 2 (CH＝CH 2 ) -Si (CH) 3 ) 2 (CH 2 CH 2 CH 2 CH 3 ) And end groups.
R and s in the above formula are each independently an integer of 0 to 60. R and s in the above formula are not both 0.
Preferable specific examples of the blocking agent include alkoxysilanes having an unsaturated group such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 1-hexenyltrimethoxysilane, 1-hexenyltriethoxysilane, 1-octenyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane; unsaturated group-containing alcohols such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, allyl alcohol, ethylene glycol monoallyl ether, propylene glycol monoallyl ether, and 3-allyloxypropanol; (meth) acrylic acid; (meth) acrylic acid halides such as (meth) acrylic acid chloride, and the like.
The amount of the capping agent to be used in bonding the capping agent to the surface of the metal oxide particles (D) via a chemical bond such as a covalent bond is not particularly limited. It is preferable to use an amount of the capping agent sufficient to react with almost all of the hydroxyl groups on the surface of the metal oxide particles (D).
The content of the metal oxide particles (D) in the photosensitive composition is not particularly limited within a range that does not hinder the object of the present invention. The content of the metal oxide particles (D) in the photosensitive composition is preferably 5 mass% to 95 mass%, more preferably 35 mass% to 93 mass%, and even more preferably 40 mass% to 90 mass%, based on the mass of the photosensitive composition after the removal of the solvent (S).
When the content of the metal oxide particles (D) in the photosensitive composition is within the above range, the photosensitive composition in which the inorganic fine particles (B) are stably dispersed can be easily obtained, and a cured product having a desired effect due to the use of the metal oxide particles (D) can be easily formed.
In particular, the content of the metal oxide particles (D) in the photosensitive composition is preferably 50 mass% or more, more preferably 50 mass% or more and 98 mass% or less, and still more preferably 50 mass% or more and 95 mass% or less, relative to the mass of the photosensitive composition after removal of the solvent (S), in view of the ease of forming a cured product having a high refractive index.
In addition, when the surface of the metal oxide particle (D) is modified with a group containing an ethylenically unsaturated double bond, the mass of the capping agent having a group containing an ethylenically unsaturated double bond present on the surface of the metal oxide particle (D) is included in the mass of the metal oxide particle (D).
< solvent (S) >
The photosensitive composition may contain a solvent (S) for the purpose of adjusting coatability, for example. The type of the solvent (S) is not particularly limited, and is typically an organic solvent.
Examples of the organic solvent that can be blended in the photosensitive composition include (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and the like; (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
The content of the solvent (S) in the photosensitive composition is not particularly limited within a range that does not hinder the object of the present invention. For example, the content of the solvent (S) in the photosensitive composition may be 95 mass% or less, 80 mass% or less, 50 mass% or less, 30 mass% or less, or 20 mass% or less, based on the mass of the photosensitive composition.
When the photosensitive composition contains the solvent (S), the content of the solvent (S) in the photosensitive composition may be 1 mass% or more, or may be 5 mass% or more, or may be 10 mass% or more, or may be 20 mass% or more, or may be 30 mass% or more.
When the cured product of the photosensitive composition is a cured film, the cured film is often used for forming a high refractive index film in a display panel such as an organic EL panel.
In this case, in order not to damage various members constituting the display panel, it is desirable that volatilization of the solvent (S) at the time of forming the high refractive index film or generation of outgas from the solvent (S) remaining in the high refractive index film is small.
The problems of volatilization and outgassing of the solvent (S) can be eliminated by reducing the content of the solvent (S) in the photosensitive composition. However, in general, when the content of the solvent is reduced in a photosensitive composition or the like, the coatability of the composition is significantly impaired, and in particular, it is difficult to apply the composition to a coating method such as an inkjet method.
However, the photosensitive composition containing the thioether compound (A2-1) and the (meth) acrylate compound (A2-2) in combination can realize low viscosity to such an extent that it can be applied to the inkjet method even when the photosensitive composition contains no solvent (S) or only a small amount of solvent (S).
The viscosity of the photosensitive composition is preferably 40cP or less, more preferably 30cP or less, further preferably 28cP or less, and particularly preferably 25cP or less, as measured at 25 ℃ using an E-type viscometer.
The viscosity of the photosensitive composition can be adjusted by adjusting the contents of the base material component (a) and the solvent (S), for example.
The content of the solvent (S) in the photosensitive composition is preferably 5 mass% or less, from the viewpoints of volatilization and outgas of the solvent (S) described above. Further, the content of the solvent (S) in the photosensitive composition is preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, further preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.
In consideration of the problems of volatilization and outgassing of the solvent (S), the photosensitive composition most preferably contains substantially no solvent (S). The fact that the photosensitive composition contains substantially no solvent (S) means that the solvent (S) is not intentionally added to the photosensitive composition except that a very small amount of solvent (S) is inevitably carried into the photosensitive composition with the raw materials and the like.
When the photosensitive composition does not substantially contain the solvent (S), the content of the solvent (S) in the photosensitive composition is, for example, 0.2 mass% or less, preferably 0.15 mass% or less, more preferably 0.1 mass% or less, and even more preferably 0.05 mass% or less.
[ other Components ]
The photosensitive composition may contain various additives which have been conventionally blended in the photosensitive composition, in addition to the components described above, within a range which does not hinder the object of the present invention. Preferable additives to be blended in the photosensitive composition include a dispersant, an adhesion promoter such as a silane coupling agent, an antioxidant, an anticoagulant, a defoaming agent, a surfactant, and the like. The surfactant is not particularly limited, and known components such as a fluorine-based surfactant and a silicon-based surfactant can be used.
< method for producing photosensitive composition >
After mixing the above-described components in predetermined amounts, the mixture was stirred uniformly, thereby obtaining a photosensitive composition.
Method for producing cured product
The photosensitive composition described above can be molded into a desired shape, and then exposed to light to produce a cured product.
The method for forming the photosensitive composition is not particularly limited, and may be appropriately selected according to the shape of the cured product. Examples of the molding method include coating and injection molding into a mold.
Hereinafter, a method for producing a cured film will be described as a typical example of a method for producing a cured product.
Typically, the photosensitive composition is applied to a substrate to form a coating film,
The cured film is produced by exposing the coated film to light.
First, a photosensitive composition is coated on a desired substrate to form a coating film, and then at least a part of the solvent (S) is removed from the coating film as needed to form the coating film.
The method of applying the photosensitive composition to the substrate is not particularly limited. For example, a curable composition can be coated on a substrate to a desired film thickness using a contact transfer type coating apparatus such as a roll coater, a reverse coater, a bar coater, or a slot coater, a spin coater (spin coater), or a curtain coater, or a non-contact type coating apparatus, to form a coating film.
As a method for forming the coating film, a printing method such as a screen printing method or an inkjet printing method can be applied.
Preferably, after the photosensitive composition is applied to the substrate, the coating film is baked as necessary, and at least a part of the solvent (S) is removed from the coating film. The baking temperature is appropriately determined in consideration of the boiling point of the solvent (S) and the like. The baking may be performed at a low temperature under reduced pressure.
The baking method is not particularly limited, and examples thereof include a method of drying at a temperature of 80 ℃ to 150 ℃, preferably 85 ℃ to 120 ℃ for 60 seconds to 500 seconds using a heating plate.
The film thickness of the coating film formed as described above is not particularly limited. The film thickness of the coating film can be appropriately determined according to the use of the cured film. The film thickness of the coating film can be suitably adjusted, and typically, it is preferable to suitably adjust the film thickness to form a cured film having a film thickness of 0.1 μm or more and 10 μm or less, more preferably 0.2 μm or more and 5 μm or less.
After forming the coating film by the above method, the coating film is exposed to light, whereby a cured film can be obtained.
The conditions for exposing the coating film are not particularly limited as long as curing advances well. The exposure is performed by, for example, irradiation with active energy rays such as ultraviolet rays and excimer laser light. The amount of the energy ray to be irradiated is not particularly limited, and may be, for example, 30mJ/cm 2 Above 5000mJ/cm 2 The following is given. After exposure, the same heating as after coating can be usedIn this method, the exposed coating film is baked.
Further, after the coating film is exposed to light in a position-selective manner, the exposed coating film is developed, whereby a cured film patterned into any shape such as a line shape and a dot shape can be formed. The position-selective exposure is typically performed by exposing the coating film through a mask of a shape corresponding to the pattern shape.
Examples of the developer include organic developers such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.
In the development treatment, it is preferable that the developer is sufficiently removed by a method such as drying by heating after development.
By the method described above, a transparent cured product having a high refractive index and excellent solvent resistance can be formed.
Examples
The present invention is further specifically described by the following examples, but the scope of the present invention is not limited by the following examples.
[ example 1, example 2, and comparative examples 1 to 6 ]
In the examples, as the alkali-soluble Resin (A) ((A) component), resin-A1 described below was used. In the comparative example, as alkali-soluble resins (A ') ((A') components) similar to the alkali-soluble resins (A), the following resins Resin-A2 to Resin-A4 were used.
In the following structures, the numerical values below right brackets are the contents (% by mass) of the respective structural units in the resin.
[ chemical formula 55 ]
In examples and comparative examples, dipentaerythritol hexaacrylate was used as the photopolymerizable compound (B) ((B) component).
In examples and comparative examples, a compound having the following structure was used as the photopolymerization initiator (C) ((C) component).
[ chemical formula 56 ]
In examples and comparative examples, as the metal oxide particles (D) ((D) component), a zirconia particle dispersion liquid containing 40 mass% of zirconia particles and 10 mass% of a dispersant was used. The average particle diameter of the zirconia particles was 10nm.
In examples and comparative examples, dipentaerythritol tetrakis [3- (4-hydroxy-3, 5-di-tetra-butylphenyl) propionate ] was used as an antioxidant.
In examples and comparative examples, 3-acryloxypropyl trimethoxysilane was used as a silane coupling agent.
In examples and comparative examples, BYK-310 (polyester modified silicone surfactant, manufactured by Pick chemical Co., ltd.) was used as the surfactant.
The types and amounts of the alkali-soluble resin (a) or the alkali-soluble resin (a') shown in table 1, the photopolymerizable compound (B) shown in table 1, the photopolymerization initiator (C) shown in table 1, the metal oxide particles (D) shown in table 1, 0.1 part by mass of the antioxidant, 0.9 part by mass of the silane coupling agent, and 0.1 part by mass of the surfactant were uniformly dissolved and dispersed in Propylene Glycol Monomethyl Ether Acetate (PGMEA) so that the solid content concentration became 25% by mass, to obtain photosensitive compositions of examples and comparative examples.
In example 1, comparative example 3 and comparative example 5, the metal oxide particles (D) were not used.
Using the photosensitive compositions of each of the examples and comparative examples obtained, the refractive index and light transmittance of the cured film were measured and the solvent resistance was evaluated in the following manner. These measurement results and evaluation results are shown in table 1.
< refractive index measurement method >
On a 6 inch diameter silicon wafer using a spin coaterCoating the photosensitive composition. Subsequently, the coated photosensitive composition was heated at 100℃for 120 seconds to obtain a coating film. Then, an ultraviolet irradiation apparatus (HMW-532D, manufactured by ORC Co.) was used to expose 100mJ/cm 2 The coated film is subjected to full-face exposure and cured. The exposed coating film was heated at 100℃for 20 minutes to obtain a cured film having a film thickness of 3. Mu.m. For this film, a refractive index at a light wavelength of 550nm was evaluated using a spectroscopic ellipsometer (trade name: manufactured by M-2000,J.A.Woollam Japan Co.).
< method for measuring light transmittance >
The transmittance of light having a wavelength of 400nm of the film obtained by film formation in refractive index measurement was measured using a multichannel spectroscope (MCPD-3000) manufactured by Otsuka electronics.
< evaluation of solvent resistance >
The cured film produced in the same manner as the refractive index measurement was immersed in Propylene Glycol Monomethyl Ether Acetate (PGMEA) or N-methyl-2-pyrrolidone (NMP) at 85 ℃ for 20 minutes. The solvent resistance was evaluated based on the ratio of the film thickness after dipping to the film thickness before dipping according to the following criteria.
And (3) the following materials: the ratio of the film thickness after immersion to the film thickness before immersion is 99% or more.
O: the ratio of the film thickness after immersion to the film thickness before immersion is 97% or more and less than 99%.
X: the ratio of the film thickness after immersion to the film thickness before immersion was less than 97%.
TABLE 1
As is clear from table 1, when the photosensitive composition of the example is used, a cured product having a high refractive index and excellent solvent resistance can be formed, and the photosensitive composition of the example contains an alkali-soluble resin (a), a photopolymerizable compound (B), and a photopolymerization initiator (C), and the alkali-soluble resin (a) contains a (meth) acrylic resin (a-1) containing a crosslinkable (meth) acrylate unit (a 1) having an ethylenically unsaturated double bond and an aromatic unit (a 2) derived from N-vinylcarbazole.
On the other hand, when the photosensitive composition of the comparative example is used, a cured product having both a high refractive index and excellent solvent resistance cannot be formed, and the photosensitive composition of the comparative example uses an alkali-soluble resin (a') comprising a crosslinkable (meth) acrylate unit (a 1) having an ethylenically unsaturated double bond, an aromatic unit derived from an N-vinylcarbazole which may have a substituent on an aromatic ring, and an aromatic monomer other than 9-vinylfluorene which may have a substituent on an aromatic ring.

Claims (7)

1. A photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable compound (B) and a photopolymerization initiator (C),
the alkali-soluble resin (A) comprises a (meth) acrylic resin (a-1), the (meth) acrylic resin (a-1) comprises a crosslinkable (meth) acrylate unit (a 1) and an aromatic unit (a 2),
the crosslinkable (meth) acrylate unit (a 1) has an ethylenically unsaturated double bond,
the aromatic unit (a 2) is a unit derived from N-vinylcarbazole which may have a substituent on an aromatic ring or from 9-vinylfluorene which may have a substituent on an aromatic ring.
2. The photosensitive composition according to claim 1, wherein a ratio of the aromatic unit (a 2) to the total structural units of the (meth) acrylic resin (a-1) is 60 mol% or more.
3. The photosensitive composition according to claim 1, wherein a ratio of the crosslinkable (meth) acrylate unit (a 1) to the total structural units of the (meth) acrylic resin (a-1) is 5 mol% or more and 30 mol% or less.
4. A photosensitive composition according to any one of claims 1 to 3, comprising metal oxide particles (D).
5. A cured product of the photosensitive composition according to any one of claims 1 to 4.
6. A method for forming a cured film, comprising:
coating the photosensitive composition according to any one of claims 1 to 4 on a substrate to form a coating film;
exposing the coating film.
7. A method of forming a patterned cured film, comprising:
coating the photosensitive composition according to any one of claims 1 to 4 on a substrate to form a coating film;
exposing the coating film positionally selectively;
and developing the exposed coating film.
CN202310303053.XA 2022-03-29 2023-03-27 Photosensitive composition Pending CN116893571A (en)

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