CN117590691A - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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Publication number
CN117590691A
CN117590691A CN202311030078.3A CN202311030078A CN117590691A CN 117590691 A CN117590691 A CN 117590691A CN 202311030078 A CN202311030078 A CN 202311030078A CN 117590691 A CN117590691 A CN 117590691A
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China
Prior art keywords
group
general formula
fluorine
carbon atoms
resin composition
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CN202311030078.3A
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Inventor
服部啓太
坂井田悠太
兼子譲
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Central Glass Co Ltd
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Central Glass Co Ltd
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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
    • C08F220/22—Esters containing halogen
    • 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
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • 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
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • C08F267/06—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of esters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • H10K59/8792—Arrangements for improving contrast, e.g. preventing reflection of ambient light comprising light absorbing layers, e.g. black layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/106—Binder containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing

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

Abstract

The present invention relates to a photosensitive resin composition. The invention provides a photosensitive resin composition with good hardening and liquid repellency and a hardened product thereof. The photosensitive resin composition of the invention comprises an ethylenically unsaturated compound (A) and a photopolymerization initiatorThe resin composition comprises (A) a resin (E) having a structure represented by the following general formula (1), and (B) a resin (C) having an alkali solubility, and (D) 30 to 550 parts by mass of the resin (E) based on 100 parts by mass of the resin (D). [ chemical formula 1 ]]

Description

Photosensitive resin composition
Technical Field
The invention relates to a photosensitive resin composition, a resin film, a cured product, a partition wall, an organic electroluminescent element, a display, a method for manufacturing the cured product, a fluorine-containing resin and a polymer blend.
Background
In the production of display elements such as organic EL (Electroluminescence) displays, micro-LED (light-emitting diode) displays, and quantum dot displays, an inkjet method is known as a method for forming an organic layer having a function of emitting light or the like. There are several methods for the inkjet method, specifically, the following methods can be exemplified: a method of dropping ink from a nozzle to a concave portion of a pattern film formed on a substrate and having irregularities, and curing the same; or a method of forming a lyophilic section as a portion wetted with ink and a liquid-repellent section as a portion repelling ink by dropping ink droplets onto a pattern film formed on a substrate in advance so that the ink adheres only to the lyophilic section; etc.
In particular, in the former method of curing ink which is dropped from a nozzle into a concave portion of a pattern film, 2 methods are mainly used for producing such a pattern film having irregularities. One is a photolithography method in which a surface of a photosensitive resist film coated on a substrate is exposed to light in a pattern to form an exposed portion and an unexposed portion, and any portion is dissolved and removed by a developer; another is an imprint method using printing techniques.
The convex portions of the formed pattern film having the irregularities are called barrier ribs (barrier ribs), and the barrier ribs function as barrier ribs for preventing the ink from being mixed with each other when the ink is dropped into the concave portions of the pattern film. In order to enhance the effect of the barrier rib, it is required that the pattern film recess exposes the substrate surface having lyophilic properties to the ink and the barrier rib upper surface having liquid repellency to the ink.
As the resin for forming such barrier, a fluorine-containing resin is used as an ink repellent. By using a fluorine-containing resin, liquid repellency is improved.
Patent document 1 discloses a photosensitive resin containing an ethylenically unsaturated compound, a photopolymerization initiator, an alkali-soluble resin, and a liquid repellent agent. Further, a case is disclosed in which a cured product obtained by curing the photosensitive resin constitutes a partition wall.
[ Prior Art literature ]
[ patent literature ]
[ patent document 1] International publication No. 2021/090836
Disclosure of Invention
[ problem to be solved by the invention ]
It is known that a fluorine-containing resin having a high fluorine atom content is added as a liquid repellent to a photosensitive resin composition in order to improve liquid repellency. However, the fluorine-containing resin having a high fluorine atom content has low compatibility with a solvent or a compound not containing fluorine, and may have uneven distribution of the components. The cured resin of the photosensitive resin composition may be defective in curing or in bleeding, and there is room for improvement. The purpose of the present invention is to provide a photosensitive resin composition having excellent hardenability and liquid repellency, and a hardened product thereof.
[ means of solving the problems ]
The present inventors have conducted intensive studies and as a result, have found that maldistribution of a liquid repellent, an ethylenically unsaturated compound, an alkali-soluble resin, and the like causes partial hardening failure, and therefore the liquid repellent is difficult to hold in a hardened material, and liquid repellency is difficult to achieve. And has found that the problem can be solved by adding a resin having a specific group, thereby achieving the present invention.
Technical means for solving the problems include the following embodiments.
The first photosensitive resin composition of the present invention comprises an ethylenically unsaturated compound (a), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorine-containing resin (D), and a resin (E) having a structure represented by general formula (1), and contains 30 to 550 parts by mass of the resin (E) when the fluorine-containing resin (D) is 100 parts by mass;
[ chemical 1]
(in the general formula (1), ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and any number of hydrogen atoms of the alkyl group are substituted with fluorine atoms).
The second photosensitive resin composition of the present invention comprises an ethylenically unsaturated compound (a), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorine-containing resin (D), and a resin (E) having a structure represented by the general formula (1), wherein the resin (E) is a resin comprising a structural unit having a structure represented by the general formula (1) and a structural unit having a crosslinking site;
[ chemical 2]
(in the general formula (1), ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and any number of hydrogen atoms of the alkyl group are substituted with fluorine atoms).
The resin film of the present invention is obtained from the first photosensitive resin composition or the second photosensitive resin composition.
The cured product of the present invention is obtained by curing the resin film.
The partition wall of the present invention includes the cured product.
The organic electroluminescent element of the present invention comprises: the light-emitting device includes a light-emitting layer or a wavelength conversion layer disposed in a region partitioned by the partition wall.
The display of the present invention is provided with the partition wall.
The method for producing a cured product of the present invention comprises: a film forming step of applying the first photosensitive resin composition or the second photosensitive resin composition to a substrate and then heating the same, thereby obtaining a resin film; and an exposure step of exposing the resin film with high-energy rays.
The fluorine-containing resin of the present invention comprises a structural unit having a structure represented by the following general formula (1) and a structural unit having a crosslinking site;
[ chemical 3]
(in the general formula (1), ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and any number of hydrogen atoms of the alkyl group are substituted with fluorine atoms).
The polymer blend of the present invention is characterized by comprising the fluorine-containing resin.
[ Effect of the invention ]
A photosensitive resin composition having excellent hardenability and liquid repellency and a hardened product thereof can be provided.
Detailed Description
The present invention will be described in detail below. The present invention is not limited to the following embodiments, and can be appropriately carried out based on the general knowledge of the industry within a range not to impair the gist of the present invention.
In the present specification, "barrier wall" and "partition wall" are synonymous, and mean convex portions of a pattern film having irregularities in the inkjet method unless otherwise noted.
The first photosensitive resin composition of the photosensitive resin compositions of the present invention will be described below.
The first photosensitive resin composition of the present invention is characterized by comprising an ethylenically unsaturated compound (a), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorine-containing resin (D), and a resin (E) having a structure represented by general formula (1), wherein the resin (E) is contained in an amount of 30 to 550 parts by mass based on 100 parts by mass of the fluorine-containing resin (D).
[ chemical 4]
( In the general formula (1), ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and any number of hydrogen atoms of the alkyl group are substituted with a fluorine atom; here, any number is 1 or more )
The first photosensitive resin composition of the present invention solves the problem of uneven distribution of the components by containing the resin (E) having the structure represented by the general formula (1), and can produce a cured product or a partition wall having improved liquid repellency or curability even when a liquid repellent agent having a large fluorine atom content is used. The "liquid repellent" is the fluorine-containing resin (D) in the first photosensitive resin composition of the present invention. Hereinafter, the "resin (E) having a structure represented by the general formula (1)" may be referred to as "resin (E)".
< ethylenically unsaturated Compound (A) >)
When the first photosensitive resin composition of the present invention contains the ethylenically unsaturated compound (a), the hardening of the first photosensitive resin composition by light irradiation is promoted, and a shorter hardening time can be achieved. As the ethylenically unsaturated compound (a), a compound having 2 or more ethylenically unsaturated groups can be used. Conjugated stable double bonds such as those of benzene rings do not belong to ethylenic unsaturated groups. From the viewpoint of improving the reactivity, the ethylenically unsaturated compound (a) preferably has an ethylenically unsaturated group at its terminal. The ethylenically saturated compound (a) does not contain a fluorine atom.
Specific examples of the ethylenically unsaturated compound (a) include: multifunctional acrylates (e.g., product names A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP manufactured by New Zhou chemical industry Co., ltd.), polyethylene glycol diacrylates (e.g., product names A-200, A-400, A-600 manufactured by New Zhou chemical industry Co., ltd.), urethane acrylates (e.g., product names UA-122P, UA-4HA, UA-6LPA, UA-11003H, UA-53H, UA-4200, UA-200PA, UA-33H, UA-7100, UA-7200), pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc.
As the polyfunctional acrylate compound, preferred compounds are exemplified below.
[ chemical 5]
[ chemical 6]
In the illustration, V 1 M1 "-O-C (CH) 3 )H-CH 2 - "structural unit represented by" -n 1 "-O-CH 2 -C(CH 3 ) H- "is a structure in which structural units represented by m1+n1=2, 3, 7, and 12 are copolymerized in a block or random manner. V (V) 2 M2 "-O-C (CH) 3 )H-CH 2 - "structural unit represented by" -n 2 "-O-CH 2 -C(CH 3 ) H- "structural unit block or random copolymerization, m2+n2=7.
[ chemical 7]
[ chemical 8]
The content of the ethylenically unsaturated compound (a) is preferably 10 to 300 parts by mass, more preferably 50 to 200 parts by mass, based on 100 parts by mass of the total of the ethylenically unsaturated compound (a), the alkali-soluble resin (C), the fluorine-containing resin (D) and the resin (E), which will be described later. If the content of the ethylenically unsaturated compound (a) is less than 10 parts by mass, the crosslinking effect tends to be insufficient, and if it exceeds 300 parts by mass, the resolution or sensitivity tends to be lowered.
Photopolymerization initiator (B) >)
In the first photosensitive resin composition of the present invention, the photopolymerization initiator (B) is not particularly limited as long as it is a photopolymerization initiator for polymerizing a monomer having a polymerizable double bond by high-energy rays such as electromagnetic waves or electron beams, and a known photopolymerization initiator can be used.
The photopolymerization initiator (B) may be a radical photoinitiator or a photoacid initiator, and may be used alone, or a radical photoinitiator and a photoacid initiator may be used in combination, or 2 or more kinds of radical photoinitiators and/or 2 or more kinds of photoacid initiators may be mixed and used. In addition, living polymerization can also be performed as the case may be by using a photopolymerization initiator and an additive together. The additive may be any known additive.
Specifically, the photo radical initiator may be classified into an intramolecular cleavage type in which a bond in a molecule is cleaved by absorption of electromagnetic waves or electron beams to generate radicals, a hydrogen abstraction type in which a tertiary amine or an ether is used in combination to generate radicals, or the like, and either one may be used. Photo radical initiators other than the types mentioned above may also be used.
The photo radical initiator may be specifically exemplified by: benzophenone-based, acetophenone-based, diketone-based, acylphosphine oxide-based, quinone-based, acyloin-based, thioxanthone-based, and the like.
Specifically, examples of the benzophenone system include: benzophenone, 4-hydroxybenzophenone, 2-benzoylbenzoic acid, 4 '-bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, and the like. Among them, 2-benzoylbenzoic acid, 4' -bis (diethylamino) benzophenone are preferable.
Specifically, acetophenone systems can be exemplified by: acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2' -dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and the like. Among them, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferable.
Specifically, examples of the diketone system include: 4,4' -dimethoxybenzil, methyl benzoate, 9, 10-phenanthrenequinone, etc. Among them, methyl 4,4' -dimethoxybenzil and benzoyl formate are preferable.
Specific examples of the acylphosphine oxide system include bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide.
Specifically, the quinone system may be exemplified by: anthraquinone, 2-ethylanthraquinone, camphorquinone, 1, 4-naphthoquinone, etc. Among them, camphorquinone, 1, 4-naphthoquinone are preferable.
Specifically, the acyloin system may be exemplified by: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like. Among them, benzoin and benzoin methyl ether are preferable.
Examples of the thioxanthone system include 2, 4-diethylthioxanthone.
The photo radical initiator is preferably a benzophenone type, an acetophenone type or a diketone type, and more preferably a benzophenone type.
Among the commercially available photo radical initiators, preferred photo radical initiators may be exemplified by: product name manufactured by basf corporation: irgacure 127, irgacure 184, irgacure 369, irgacure 651, irgacure 819, irgacure 907, irgacure 2959, irgacure OXE-01, irgacure OXE-04, darocure 1173, lucirin TPO; product name manufactured by japan chemical company: DETXs, etc. Of these, irgacure 651 and Irgacure 369 are more preferable.
Specifically, the photoacid initiator is an onium salt containing at least 1 cation selected from the group consisting of aromatic sulfonic acid, aromatic iodonium, aromatic diazonium, aromatic ammonium, thianthrene, thioxanthonium, (2, 4-cyclopentadien-1-yl) (1-methylethylbenzene) iron, and at least 1 anion selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, pentafluorophenylborate.
Of these, bis [4- (diphenylsulfonium) phenyl ] sulfide bis hexafluorophosphate, bis [4- (diphenylsulfonium) phenyl ] sulfide tetrakis (pentafluorophenyl) borate, and diphenyliodonium hexafluorophosphate are particularly preferable.
Examples of the commercially available photo-acid initiator include: product name manufactured by San-Apro corporation: CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S; product name manufactured by dow chemical japan corporation: cyracure photo-hardening initiator UVI-6990, cyracure photo-hardening initiator UVI-6992, cyracure photo-hardening initiator UVI-6976; product name manufactured by ADEKA corporation: adeka Optomer SP-150, adeka Optomer SP-152, adeka Optomer SP-170, adeka Optomer SP-172, adeka Optomer SP-300; product name manufactured by soyama corporation, japan: CI-5102, CI-2855; product name manufactured by Sanxinshi chemical industry Co., ltd.: san-Aid SI-60L, san-Aid SI-80L, san-Aid SI-100L, san-Aid SI-110L, san-Aid SI-180L, san-Aid SI-110, san-Aid SI-180; product name manufactured by Lamberti company: esacure 1064, esacure 1187; ciba Specialty Chemicals product name manufactured by Kagaku Co., ltd.: irgacure 250, and the like.
The content of the photopolymerization initiator (B) in the first photosensitive resin composition of the present invention is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, based on 100 parts by mass of the total of the ethylenically unsaturated compound (a), the alkali-soluble resin (C), the fluorine-containing resin (D) and the resin (E). If the content of the photopolymerization initiator (B) is less than 0.1 part by mass, the crosslinking effect tends to be insufficient, and if it exceeds 30 parts by mass, the resolution or sensitivity tends to be lowered.
Alkali-soluble resin (C) >, and process for producing the same
When the first photosensitive resin composition of the present invention contains the alkali-soluble resin (C), the shape of the barrier rib obtained from the first photosensitive resin composition of the present invention can be made good. The alkali-soluble resin (C) may or may not contain fluorine atoms, but is preferably a resin containing no fluorine atoms. The type of the alkali-soluble resin (C) is not particularly limited as long as it is alkali-soluble, and is a resin other than the fluororesin (D) described below or the resin (E) having a structure represented by the general formula (1).
The alkali-soluble resin (C) may be an alkali-soluble phenol resin.
The alkali-soluble phenol resin can be obtained by condensing phenols and aldehydes in the presence of an acid catalyst.
As phenols, specifically, there can be exemplified: phenol, o-cresol, m-cresol, p-cresol, 2, 3-dimethylphenol, 2, 4-dimethylphenol, 2, 5-dimethylphenol, 3, 4-dimethylphenol, 3, 5-dimethylphenol, 2,3, 5-trimethylphenol, 3,4, 5-trimethylphenol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, hydroquinone, methylhydroquinone, catechol, 4-methyl-catechol, pyrogallol, phloroglucinol, thymol, isothymol, and the like. These phenols may be used alone or in combination of 2 or more.
As the aldehydes, specifically, there can be exemplified: formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propionaldehyde, phenylacetaldehyde, α -phenylpropionaldehyde, β -phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaraldehyde, terephthalaldehyde, m-phthalaldehyde, and the like.
As the acid catalyst, specifically, there can be exemplified: hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethylsulfuric acid, p-toluenesulfonic acid, and the like. These acid catalysts may be used alone or in combination of 2 or more.
In addition, as the alkali-soluble resin (C), an acid-modified epoxy acrylate system may be exemplified. As the commercially available acid-modified epoxy acrylate system, for example, there can be used: product name manufactured by japan chemical company, inc: CCR-1218H, CCR-1159H, CCR-1222H, CCR-1291H, CCR-1235, PCR-1050, TCR-1335H, UXE-3024, ZAR-1035, ZAR-2001H, ZAR-2050H, ZAR-2051H, ZFR-1185, ZCR-1569H, and the like.
The mass average molecular weight of the alkali-soluble resin (C) component is preferably 1,000 to 50,000 from the viewpoints of developability and resolution of the first photosensitive resin composition.
The content of the alkali-soluble resin (C) is preferably 10 to 70% by mass with respect to all solid components of the first photosensitive resin composition of the present invention. If the content of the alkali-soluble resin (C) exceeds 70 mass%, there is a tendency that the liquid repellency to ink possessed by the fluorine-containing resin (D) described below cannot be sufficiently obtained.
< fluorine-containing resin (D) >)
In the first photosensitive resin composition of the present invention, the fluorine-containing resin (D) contains a hydrocarbon-containing structural unit having a fluorine atom. The fluorine-containing resin (D) does not contain the structure of the following general formula (1). The fluorine-containing resin (D) contains no radical generating group. In the present specification, a radical generating group is a group that generates a radical by irradiation with light.
In the first photosensitive resin composition of the present invention, the fluorine-containing resin (D) may have a structure represented by the following general formula (2) or may have a structure represented by the following general formula (3).
[ chemical 9]
-CR 2 ＝CRb 2 (2)
(in the general formula (2), rb independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and any number of hydrogen atoms in the alkyl group is substituted with a fluorine atom, wherein any number is 1 or more, R 2 Represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms)
[ chemical 10]
(in the general formula (3), rb independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and any number of hydrogen atoms in the alkyl group is substituted with a fluorine atom, wherein any number is 1 or more; R 1 Represents a hydrogen atom, a fluorine atom or a methyl group; r is R 2 Represents a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms)
In the general formula (3), R 1 Preferably a hydrogen atom or a methyl group. In addition, as R 2 Examples of the "compound" may include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, t-butyl group, n-pentyl group, isopentyl group, 1-dimethylpropyl group, 1-methylbutyl group, 1-dimethylbutyl group, n-hexyl group and cyclopentyl groupAnd cyclohexyl, etc., preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, more preferably a hydrogen atom, methyl.
In addition, in the case of the optical fiber, rb in the general formula (2) or the general formula (3) is preferably a fluorine atom, trifluoromethyl, difluoromethyl, pentafluoroethyl, 2-trifluoroethyl, n-heptafluoropropyl 2, 3-pentafluoropropyl, 3-trifluoropropyl, hexafluoroisopropyl, heptafluoroisopropyl, n-nonafluorobutyl, iso-nonafluorobutyl, tert-nonafluorobutyl, more preferably a fluorine atom, trifluoromethyl, difluoromethyl, pentafluoroethyl, 2-trifluoroethyl n-heptafluoropropyl, 2, 3-pentafluoropropyl, 3-trifluoropropyl, hexafluoroisopropyl, fluorine atom, difluoromethyl group and trifluoromethyl group are particularly preferable.
The structural unit represented by the general formula (3) contained in the fluorine-containing resin (D) in the first photosensitive resin composition of the present invention may be exemplified by the following structures.
[ chemical 11]
[ chemical 12]
The content of the structural unit represented by the general formula (3) in the fluorine-containing resin (D) is preferably 5 mol% or more and 70 mol% or less, more preferably 10 mol% or more and 50 mol% or less, particularly preferably 10 mol% or more and 30 mol% or less, with respect to 100 mol% of all the structural units constituting the fluorine-containing resin (D).
If the content of the structural unit of the general formula (3) is more than 70 mol%, the fluorine-containing resin (D) tends to become difficult to dissolve in a solvent. On the other hand, if the content of the structural unit of the general formula (3) is less than 5 mol%, the resistance tends to be lowered when UV (Ultraviolet) ozone treatment or oxygen plasma treatment is performed on the cured product produced from the first photosensitive resin composition.
If the fluorine-containing resin (D) has a structural unit represented by the general formula (3), it is one of the preferable forms because it has resistance when subjected to UV ozone treatment or oxygen plasma treatment.
In the first photosensitive resin composition of the present invention, the fluorine-containing resin (D) may also include a structure represented by the following general formula (4).
[ chemical 13]
In the general formula (4), R 3 、R 4 Each independently represents a hydrogen atom or a methyl group.
In the general formula (4), W 1 Represents a 2-valent linking group, represents-O-, -O-C (=O) -, -C (=o) -O-, -O-C (=o) -NH-, -C (=o) -O-C (=o) -NH-or-C (=o) -NH-. Wherein, preferably-O-C (=O) -NH-; -C (=o) -O-C (=o) -NH-or-C (=o) -NH-.
At W 1 In the case of-O-C (=o) -NH-, the liquid repellency to ink after UV ozone treatment or after oxygen plasma treatment is more excellent, and thus one of the preferable modes.
In the general formula (4), A 1 Represents a 2-4 valent linking group, represents a linear hydrocarbon group having 1 to 10 carbon atoms, a branched hydrocarbon group having 3 to 10 carbon atoms or a cyclic hydrocarbon group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group may be represented by a hydroxyl group or-O-C (=O) -CH 3 And (3) substitution.
2-valent linking group A 1 In the case of a linear alkylene group having 1 to 10 carbon atoms, examples thereof include: methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene.
2-valent linking group A 1 In the case of a branched alkylene group having 3 to 10 carbon atoms, examples thereof include: isopropylidene, isobutylidene, sec-butylidene, tert-butylidene, isopentylidene, isohexylidene, and the like.
2-valent linking group A 1 In the case of a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include: disubstituted cyclopropanes, disubstituted cyclobutanesDisubstituted cyclopentane, disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, disubstituted 4-t-butylcyclohexane, and the like.
In the case where any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of the hydroxyl-substituted alkylene groups include: hydroxy ethylene, 1-hydroxy-n-propylene, 2-hydroxy-n-propylene, hydroxy-isopropylene (-CH (CH) 2 OH)CH 2 (-), 1-hydroxy-n-butylene, 2-hydroxy-n-butylene, hydroxy-Zhong Yading group (-CH (CH) 2 OH)CH 2 CH 2 (-), hydroxy-isobutyl (-CH) 2 CH(CH 2 OH)CH 2 (-), hydroxy-t-butylene (-C (CH) 2 OH)(CH 3 )CH 2 (-), etc.
Furthermore, any number of hydrogen atoms in these alkylene groups are replaced by-O-C (=O) -CH 3 In the case of substitution, as the substituted alkylene group, there may be mentioned, for example, the above-exemplified hydroxy-substituted alkylene group in which the hydroxy group is substituted with-O-C (=O) -CH 3 Substituted alkylene of (a).
Wherein the 2-valent linking group A 1 Preferably methylene, ethylene, propylene, n-butylene, isobutylene, sec-butylene, cyclohexyl, 2-hydroxy-n-propylene, hydroxy-isopropylene (-CH (CH) 2 OH)CH 2 (-), 2-hydroxy-n-butylene, hydroxy-Zhong Yading group (-CH (CH) 2 OH)CH 2 CH 2 (-), more preferably ethylene, propylene, 2-hydroxy-n-propylene, hydroxy-isopropylene (-CH (CH) 2 OH)CH 2 Particularly preferred are ethylene and 2-hydroxy-n-propylene.
As 3-valent linking group A 1 Can be exemplified by-C (CH) 2 -) 2 CH 3 Etc. as the 4-valent linking group A 1 Examples of the "C" (CH) 2 -) 4 Etc.
In the general formula (4), Y 1 Represents a 2-valent linking group, represents-O-or-NH-, more preferably-O-.
In the general formula (4), u represents an integer of 1 to 3, and u is particularly preferably 1.
In the general formula (4), n represents an integer of 1 to 3, and n is particularly preferably 1.
The substitution positions of the aromatic rings independently represent ortho, meta, para, and preferably para.
The following structure is preferable as the structural unit represented by the general formula (4). The substitution positions of the aromatic rings are exemplified by para-positions, but the substitution positions may be ortho-positions and meta-positions, respectively and independently.
[ chemical 14]
[ 15]
[ 16]
[ chemical 17]
The content of the structural unit represented by the general formula (4) in the fluorine-containing resin (D) is preferably 5 mol% or more and 70 mol% or less, more preferably 10 mol% or more and 50 mol% or less, particularly preferably 10 mol% or more and 30 mol% or less, with respect to 100 mol% of all the structural units constituting the fluorine-containing resin (D).
If the content of the structural unit of the general formula (4) is more than 70 mol%, the fluorine-containing resin (D) tends to become difficult to dissolve in a solvent. On the other hand, if the content of the structural unit of the general formula (4) is less than 5 mol%, the resistance tends to be lowered when UV ozone treatment or oxygen plasma treatment is performed.
Here, although the effect of the structural unit represented by the general formula (4) of the present invention is not clear, it is assumed that the cured product produced from the first photosensitive resin composition has resistance to UV ozone treatment or oxygen plasma treatment. However, the effects of the present invention are not limited to those described herein.
As described above, the fluorine-containing resin (D) may be a mixture (blend) of a copolymer comprising the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) and another copolymer comprising the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4). In particular, the fluorine-containing resin (D) is a resin containing W in the general formula (4) 1 Fluorine-containing resin which is a structural unit of-O-C (=O) -NH-and W in the general formula (4) 1 The mixture of fluorine-containing resins which are structural units of-C (=O) -NH-is one of the preferred forms of the present invention.
In the first photosensitive resin composition of the present invention, the fluorine-containing resin (D) may also include a structure represented by the following general formula (5).
[ chemical 18]
In the general formula (5), R 5 、R 6 Each independently represents a hydrogen atom or a methyl group.
In the general formula (5), W 2 Represents a 2-valent linking group, represents-O-, -O-C (=O) -, -C (=o) -O-, -O-C (=o) -NH-, -C (=o) -O-C (=o) -NH-or-C (=o) -NH-. Wherein, preferably-O-C (=O) -NH-; -C (=o) -O-C (=o) -NH-or-C (=o) -NH-.
At W 2 In the case of-O-C (=O) -NH-, the fluorine-containing resin (D) of the present invention is one of particularly preferred modes because it is excellent in liquid repellency to ink after UV ozone treatment or after oxygen plasma treatment.
In the general formula (5), A 2 Represents a 2-valent linking group, and represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms or 3 to 10 carbon atoms, any number of hydrogen atoms in the alkylene group being capable of being bonded to a hydroxyl group or-O-C (=O) -CH 3 And (3) substitution.
In the general formula (5)) In (A) 3 Represents a 2-4 valent linking group, represents a linear hydrocarbon group having 1 to 10 carbon atoms, a branched hydrocarbon group having 3 to 10 carbon atoms or a cyclic hydrocarbon group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group may be represented by a hydroxyl group or-O-C (=O) -CH 3 And (3) substitution.
2-valent linking group A 2 、A 3 When each independently represents a linear alkylene group having 1 to 10 carbon atoms, examples thereof include: methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene.
2-valent linking group A 2 、A 3 In the case of each independently a branched alkylene group having 3 to 10 carbon atoms, examples thereof include: isopropylidene, isobutylidene, sec-butylidene, tert-butylidene, isopentylidene, isohexylidene, and the like.
2-valent linking group A 2 、A 3 When each independently represents a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include: disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, disubstituted 4-t-butylcyclohexane, and the like.
In the case where any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of the hydroxyl-substituted alkylene groups include: 1-hydroxyethylene (-CH (OH) CH) 2 (-), 2-hydroxyethylene (-CH) 2 CH (OH) -), 1-hydroxy-n-propylene, 2-hydroxy-n-propylene, hydroxy-isopropylene (-CH (CH) 2 OH)CH 2 (-), 1-hydroxy-n-butylene, 2-hydroxy-n-butylene, hydroxy-Zhong Yading group (-CH (CH) 2 OH)CH 2 CH 2 (-), hydroxy-isobutyl (-CH) 2 CH(CH 2 OH)CH 2 (-), hydroxy-t-butylene (-C (CH) 2 OH)(CH 3 )CH 2 (-), etc.
Furthermore, any number of hydrogen atoms in these alkylene groups are replaced by-O-C (=O) -CH 3 In the case of substitution, as the substituted alkylene group, there may be mentioned, for example, the above-exemplified hydroxy-substituted alkylene group in which the hydroxy group is substituted with-O-C (=O) -CH 3 Substituted alkylene of (a).
Wherein the 2-valent linking group A 2 、A 3 Respectively and independently preferably methylene, ethylene, propylene, n-butylene, i-butylene, s-butylene, cyclohexyl, 1-hydroxyethylene (-CH (OH) CH) 2 (-), 2-hydroxyethylene (-CH) 2 CH (OH) -, 2-hydroxy-n-propylene, hydroxy-isopropylene (-CH (CH) 2 OH)CH 2 (-), 2-hydroxy-n-butylene, hydroxy-Zhong Yading group (-CH (CH) 2 OH)CH 2 CH 2 (-), more preferably ethylene, propylene, 1-hydroxyethylene (-CH (OH) CH) 2 (-), 2-hydroxyethylene (-CH) 2 CH (OH) -, 2-hydroxy-n-propylene, hydroxy-isopropylene (-CH (CH) 2 OH)CH 2 (-), particularly preferably ethylene, 1-hydroxyethylene (-CH (OH) CH) 2 (-), 2-hydroxyethylene (-CH) 2 CH(OH)-)。
As 3-valent linking group A 3 Can be exemplified by-C (CH) 2 -) 2 CH 3 Etc. as the 4-valent linking group A 3 Examples of the "C" (CH) 2 -) 4 Etc.
In the general formula (5), Y 2 、Y 3 Represents a 2-valent linking group, each independently represents-O-or-NH-, more preferably-O-.
In the general formula (5), n represents an integer of 1 to 3, and n is particularly preferably 1.
In the general formula (5), r represents 0 or 1. When r is 0, (-C (=o) -) represents a single bond.
The following structure is preferable as the structural unit represented by the general formula (5).
[ chemical 19]
[ chemical 20]
[ chemical 21]
[ chemical 22]
[ chemical 23]
The content of the structural unit represented by the general formula (5) in the fluorine-containing resin (D) is preferably 5 mol% or more and 70 mol% or less, more preferably 10 mol% or more and 50 mol% or less, particularly preferably 10 mol% or more and 30 mol% or less, with respect to 100 mol% of all the structural units constituting the fluorine-containing resin (D).
If the content of the structural unit of the general formula (5) is more than 70 mol%, the fluorine-containing resin (D) tends to become difficult to dissolve in a solvent. On the other hand, if the content of the structural unit of the general formula (5) is less than 5 mol%, the adhesion of the resin film or barrier obtained from the fluorine-containing resin (D) to the substrate tends to be lowered.
Although the effect of the structural unit represented by the general formula (5) is not clear, it is presumed that the inclusion of the structural unit represented by the general formula (5) in the fluorine-containing resin (D) improves the adhesion of the obtained resin film or barrier to the substrate. However, the effects of the present invention are not limited to those described herein.
The fluorine-containing resin (D) may be a mixture (blend) of a copolymer comprising the structural unit represented by the general formula (3) and the structural unit represented by the general formula (5) and another copolymer comprising the structural unit represented by the general formula (3) and the structural unit represented by the general formula (5). In particular, the fluorine-containing resin (D) is a resin containing W in the general formula (5) 2 Fluorine-containing resin which is a structural unit of-O-C (=O) -NH-and W in the general formula (5) 2 The mixture of fluorine-containing resins which are structural units of-C (=O) -NH-isOne of the preferred forms of the present invention.
In the first photosensitive resin composition of the present invention, the fluorine-containing resin (D) may also include a structure represented by the following general formula (6).
[ chemical 24]
In the general formula (6), R 7 Represents a hydrogen atom or a methyl group.
In the general formula (6), R 8 Represents a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, wherein any number of hydrogen atoms in the alkyl group are replaced with fluorine atoms, and the fluorine atom content in the structural unit is 30 mass% or more. Here, any number is 1 or more.
R 8 In the case of a linear alkyl group, specifically, there can be exemplified: a linear alkyl group in which any number of hydrogen atoms of a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, or linear alkyl group having 10 to 14 carbon atoms is substituted with a fluorine atom.
At R 8 In the case of a linear alkyl group, the structural unit represented by the general formula (6) is preferably a structural unit represented by the following general formula (6-1).
[ chemical 25]
In the general formula (6-1), R 9 R with the general formula (6) 7 Synonymous.
In the general formula (6-1), X is a hydrogen atom or a fluorine atom.
In the general formula (6-1), p is an integer of 1 to 4. q is an integer of 1 to 14. Particularly preferably, p is an integer of 1 to 2, q is an integer of 2 to 8, and X is a fluorine atom.
The following structure is preferable as the structural unit represented by the general formula (6).
[ chemical 26]
[ chemical 27]
[ chemical 28]
[ chemical 29]
The content of the structural unit represented by the general formula (6) is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, particularly preferably 10 mol% to 30 mol%, based on 100 mol% of all the structural units constituting the fluorine-containing resin (D).
If the content of the structural unit of the general formula (6) is more than 70 mol%, the fluorine-containing resin (D) tends to become difficult to dissolve in a solvent.
The structural unit represented by the general formula (6) is a structural unit which imparts liquid repellency to ink after UV ozone treatment or after oxygen plasma treatment. Therefore, when high liquid repellency to ink is desired, the fluorine-containing resin (D) preferably contains a structural unit represented by the general formula (6).
In the first photosensitive resin composition of the present invention, the fluorine-containing resin (D) may also include a structure represented by the following general formula (7).
[ chemical 30]
The general formula is%7) Wherein R is 10 Represents a hydrogen atom or a methyl group.
In the general formula (7), B independently represents hydroxy, carboxyl, -C (=O) -O-R 11 (R 11 Represents a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms or a cyclic alkyl group having 3 to 15 carbon atoms, wherein any number of hydrogen atoms in the alkyl group are replaced with fluorine atoms, R 11 The fluorine atom content in the catalyst is 30 mass% or more) or-O-C (=O) -R 12 (R 12 Represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms). M represents an integer of 0 to 3. Here, any number is 1 or more.
The following structure is preferable as the structural unit represented by the general formula (7).
[ 31]
[ chemical 32]
The content of the structural unit represented by the general formula (7) is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 50 mol%, particularly preferably 20 mol% to 40 mol%, based on 100 mol% of all the structural units constituting the fluorine-containing resin (D).
If the content of the structural unit of the general formula (7) is more than 70 mol%, the fluorine-containing resin (D) tends to become difficult to dissolve in a solvent.
In the general formula (7), when B is a hydroxyl group or a carboxyl group, the structural unit represented by the general formula (7) has solubility in an alkaline developer. Therefore, the fluorine-containing resin (D) preferably contains a structural unit represented by the general formula (7) in the case where B is a hydroxyl group or a carboxyl group.
In the first photosensitive resin composition of the present invention, the fluorine-containing resin (D) may also include a structure represented by the following general formula (8).
[ 33]
In the general formula (8), R 13 Represents a hydrogen atom or a methyl group.
In the general formula (8), A 4 Represents a 2-valent linking group, and represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms or 3 to 10 carbon atoms, any number of hydrogen atoms in the alkylene group being capable of being bonded to a hydroxyl group or-O-C (=O) -CH 3 And (3) substitution.
2-valent linking group A 4 In the case of a linear alkylene group having 1 to 10 carbon atoms, examples thereof include: methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene.
2-valent linking group A 4 In the case of a branched alkylene group having 3 to 10 carbon atoms, examples thereof include: isopropylidene, isobutylidene, sec-butylidene, tert-butylidene, isopentylidene, isohexylidene, and the like.
2-valent linking group A 4 In the case of a cyclic alkylene group having 3 to 10 carbon atoms, examples thereof include: disubstituted cyclopropane, disubstituted cyclobutane, disubstituted cyclopentane, disubstituted cyclohexane, disubstituted cycloheptane, disubstituted cyclooctane, disubstituted cyclodecane, disubstituted 4-t-butylcyclohexane, and the like.
In the case where any number of hydrogen atoms in these alkylene groups are substituted with hydroxyl groups, examples of the hydroxyl-substituted alkylene groups include: 1-hydroxyethylene (-CH (OH) CH) 2 (-), 2-hydroxyethylene (-CH) 2 CH (OH) -), 1-hydroxy-n-propylene, 2-hydroxy-n-propylene, hydroxy-isopropylene (-CH (CH) 2 OH)CH 2 (-), 1-hydroxy-n-butylene, 2-hydroxy-n-butylene, hydroxy-Zhong Yading group (-CH (CH) 2 OH)CH 2 CH 2 (-), hydroxy-isobutyl (-CH) 2 CH(CH 2 OH)CH 2 (-), hydroxy-t-butylene (-C (CH) 2 OH)(CH 3 )CH 2 (-), etc.
Furthermore, any number of hydrogen atoms in these alkylene groups are replaced by-O-C (=O) -CH 3 In the case of substitution, as the substituted alkylene group, there may be mentioned, for example, the above-exemplified hydroxy-substituted alkylene group in which the hydroxy group is substituted with-O-C (=O) -CH 3 Substituted alkylene of (a).
Wherein the 2-valent linking group A 4 Preferably methylene, ethylene, propylene, n-butylene, isobutylene, sec-butylene, cyclohexyl, 1-hydroxyethylene (-CH (OH) CH) 2 (-), 2-hydroxyethylene (-CH) 2 CH (OH) -, 2-hydroxy-n-propylene, hydroxy-isopropylene (-CH (CH) 2 OH)CH 2 (-), 2-hydroxy-n-butylene, hydroxy-Zhong Yading group (-CH (CH) 2 OH)CH 2 CH 2 (-), more preferably ethylene, propylene, 1-hydroxyethylene (-CH (OH) CH) 2 (-), 2-hydroxyethylene (-CH) 2 CH (OH) -, 2-hydroxy-n-propylene, hydroxy-isopropylene (-CH (CH) 2 OH)CH 2 (-), particularly preferred are ethylene, 1-hydroxyethylene (-CH (OH) CH) 2 (-), 2-hydroxyethylene (-CH) 2 CH(OH)-)。
In the general formula (8), Y 4 Represents a 2-valent linking group, represents-O-or-NH-, more preferably-O-.
In the general formula (8), r represents 0 or 1. When r is 0, (-C (=o) -) represents a single bond.
In the general formula (8), E 1 Represents a hydroxyl, carboxyl or oxirane (oxalane) group.
At E 1 When the epoxy group is an ethylene oxide (oxalane) group, examples thereof include: ethylene oxide (oxy) group, 1, 2-epoxypropyl group, 1, 3-epoxypropyl group, and the like. Among them, an ethylene oxide (ethylene oxide) group is preferable.
In the general formula (8), s represents 0 or 1. When s is 0, (-Y) 4 -A 4 (-) represents a single bond. When r is 0 and s is 0, E is bonded to the main chain which becomes a structural unit 1 Is a structure of (a).
The following structure is preferable as the structural unit represented by the general formula (8).
[ chemical 34]
In the general formula (8), in E 1 In the case of hydroxyl or carboxyl, the structural unit represented by the general formula (8) imparts solubility of the fluorine-containing resin (D) in an alkaline developer. Therefore, E is preferably contained in the fluorine-containing resin (D) of the present invention 1 In the case of hydroxyl or carboxyl, a structural unit represented by the general formula (8).
The fluorine-containing resin (D) may have a crosslinked portion. In the present invention, the "crosslinking site" means a site capable of undergoing polymerization reaction with other monomers. Examples of the crosslinking site include a photopolymerizable group, and a side chain introduced into a polymer is preferable. The fluorine-containing resin (D) having the structural unit represented by the general formulae (4) and (5) can be synthesized by, for example, polymerizing a monomer to obtain a fluorine-containing resin precursor having the structural unit represented by the general formulae (3) and (6) to (8), and then reacting the fluorine-containing resin precursor with a photopolymerizable group derivative to introduce a photopolymerizable group into a side chain of the polymer.
The photopolymerizable group introduced into the fluorine-containing resin precursor is preferably an acryl group, a methacryl group, a vinyl group, or an allyl group, and more preferably an acryl group.
In the case of introducing an acryl group as a photopolymerizable group, examples of the photopolymerizable group derivative include an acrylic derivative such as an isocyanate monomer having an acryl group and an epoxy monomer having an acryl group.
Examples of the isocyanate monomer having an acryl group include: 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 2- (2-methacryloyloxyethoxy) ethyl isocyanate, 1- (bisacrylyloxymethyl) ethyl isocyanate, and the like. Preferably ethyl 2-isocyanate.
Examples of the epoxy monomer having an acryl group include: glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether (4 HBAGE, manufactured by Mitsubishi chemical Co., ltd.), and the like.
The photopolymerizable group is introduced into the fluorine-containing resin precursor by an addition reaction of a hydroxyl group of the fluorine-containing resin precursor and a photopolymerizable group derivative.
The ratio of the photopolymerizable groups in the fluororesin (D) is preferably 10 mol% or more and 70 mol% or less, based on 100 mol% of the total amount of the structural units constituting the fluororesin (D). In the case where the fluorine-containing resin (D) is formed of only a structural unit having 1 photopolymerizable group, the content of the photopolymerizable group of the fluorine-containing resin (D) is 100 mol%. If the ratio of the photopolymerizable groups is less than 10 mol%, the strength of the resin film or the partition wall tends to be lowered. If the ratio of the photopolymerizable groups exceeds 70 mol%, it may be difficult to form a resin film by coating. More preferably 15 to 60 mol%.
In the first photosensitive resin composition of the present invention, the molecular weight of the fluorine-containing resin (D) is a mass average molecular weight measured by high-speed Gel Permeation Chromatography (GPC) using polystyrene as a standard substance, preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000, and particularly preferably 3,000 to 100,000. If the molecular weight is less than 1,000, the strength of the formed resin film or barrier tends to decrease, and if the molecular weight is more than 1,000,000, the solubility in a solvent may be insufficient, and it may be difficult to form a resin film by coating.
The dispersity (Mw/Mn) of the fluorine-containing resin (D) is preferably 1.01 to 5.00, more preferably 1.01 to 4.00, particularly preferably 1.01 to 3.00.
The fluorine-containing resin (D) may be a random copolymer, an alternating copolymer, a block copolymer or a graft copolymer. Random copolymers are preferred from the standpoint of dispersing the respective characteristics not locally but moderately.
Preferred modes of the fluorine-containing resin (D) in the first photosensitive resin composition of the present invention are as follows.
Form 1 >
Fluorine-containing resin (D) comprising structural unit represented by the following general formula (3), structural unit represented by the general formula (5), structural unit represented by the general formula (6-1) and structural unit represented by the general formula (7)
General formula (3): r is R 1 R is R 2 Is a hydrogen atom, rb are each independently a fluorine atom, difluoromethyl group or trifluoromethyl group
General formula (5): r is R 5 R is R 6 Each independently is a hydrogen atom or methyl group, W 2 is-O-C (=O) -NH-, -C (=O) -O-C (=O) -NH-or-C (=O) -NH-, A 2 、A 3 Each independently is ethylene, Y 2 Y and Y 3 is-O-, n is 1, r is 1
General formula (6-1): r is R 9 Is methyl, p is an integer of 2, q is an integer of 4 to 8, X is a fluorine atom
General formula (7): r is R 10 Is a hydrogen atom, B is an acetoxy group, a hydroxyl group or a carboxyl group, m is 1
< morphology 2 >
Fluorine-containing resin (D) comprising structural unit represented by the following general formula (5), structural unit represented by the general formula (6-1) and structural unit represented by the general formula (8)
General formula (5): r is R 5 R is R 6 Each independently is a hydrogen atom or methyl group, W 2 is-O-C (=O) -NH-, -C (=O) -O-C (=O) -NH-or-C (=O) -NH-, A 2 、A 3 Each independently is ethylene, Y 2 Y and Y 3 is-O-, n is 1, r is 1
General formula (6): r is R 7 Is methyl, R 8 Branched perfluoroalkyl group having 3 to 15 carbon atoms
General formula (6-1): r is R 9 Is methyl, p is an integer of 2, q is an integer of 4 to 8, X is a fluorine atom
General formula (8): r is R 13 Is methyl, A 4 Is ethylene, Y 4 is-O-, r is 1, s is 0 or 1, E 1 Is hydroxy or carboxyl
< morphology 3 >
Fluorine-containing resin (D) comprising structural unit represented by the following general formula (5) and structural unit represented by the general formula (6-1)
General formula (5): r is R 5 R is R 6 Each independently is a hydrogen atom or methyl group, W 2 is-O-C (=o) -NH-, -C (=o) -O-C (=o) -NH-or-C (=o))-NH-，A 2 、A 3 Each independently is ethylene, Y 2 Y and Y 3 is-O-, n is 1, r is 1
General formula (6-1): r is R 9 Is methyl, p is an integer of 2, q is an integer of 4 to 8, X is a fluorine atom
In the first photosensitive resin composition of the present invention, the fluorine atom content of the fluorine-containing resin (D) is preferably 20 to 60% by mass, more preferably 25 to 60% by mass.
When the fluorine atom content is within this range, the solvent is easily dissolved. By containing fluorine atoms in the fluorine-containing resin (D), a resin film or barrier excellent in liquid repellency can be obtained.
In the present specification, the term "fluorine atom content of the resin" means a value calculated from the molar ratio of the monomers constituting the resin, the molecular weight of the monomers constituting the resin, and the fluorine content contained in the monomers, which are measured by NMR (nuclear magnetic resonance, nuclear magnetic resonance spectroscopy).
Here, a method for measuring the fluorine atom content in the case where the fluorine-containing resin (D) is a resin obtained by polymerizing 1, 1-bistrifluoromethyl butadiene, 4-hydroxystyrene and 2- (perfluorohexyl) ethyl methacrylate will be described as an example.
(i) First, the ratio (molar ratio) of each composition was calculated by NMR measurement of the fluorine-containing resin (D).
(ii) The molecular weight (Mw) of each component monomer of the fluorine-containing resin (D) is multiplied by the molar ratio, and the total of the obtained values is added to obtain a total value. The weight ratio (wt%) of each component was calculated from the total value.
In addition, the molecular weight of 1, 1-bistrifluoromethyl butadiene was 190,4, the molecular weight of hydroxystyrene was 120, and the molecular weight of 2- (perfluorohexyl) ethyl methacrylate was 432.
(iii) Next, in the fluorine-containing composition, the fluorine atom content in the monomer was calculated.
(iv) The value of "fluorine atom content in monomer/(molecular weight of monomer (Mw). Times.weight ratio (wt%)" in each component was calculated and the obtained values were added.
(v) The "value obtained in (iv)" is calculated as a result of the calculation of the "total value obtained in (ii)", and the fluorine atom content of the fluorine-containing resin (D) is calculated as a result of the calculation of the "total value obtained in (ii)".
In the first photosensitive resin composition of the present invention, the difference in fluorine atom content between the alkali-soluble resin (C) and the fluorine-containing resin (D) is preferably 15 to 60% by mass, more preferably 20 to 55% by mass, and still more preferably 25 to 45% by mass. When the difference in fluorine atom content is within the range, maldistribution of the alkali-soluble resin (C) and the fluorine-containing resin (D) is eliminated.
In the first photosensitive resin composition of the present invention, 1 or 2 or more kinds of fluorine-containing resins (D) can be used.
The content of the fluorine-containing resin (D) is preferably 0.01 to 40% by mass, more preferably 0.01 to 10% by mass, relative to the total solid content of the first photosensitive resin composition of the present invention. When the amount is within this range, the resin film is excellent in water repellency and oil repellency and adhesion to a substrate.
< resin (E) >)
The first photosensitive resin composition of the present invention comprises a resin (E) having a structure represented by the following general formula (1). The resin (E) is a fluorine-containing resin, but is a resin different from the fluorine-containing resin (D). The resin (E) contains no radical generating groups. In the present specification, a radical generating group is a group that generates a radical by irradiation with light.
[ 35]
In the general formula (1), ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and any number of hydrogen atoms of the alkyl group are substituted with a fluorine atom. Here, any number is 1 or more.
Examples of the linear alkyl group having 1 to 6 carbon atoms include: trifluoromethyl, difluoromethyl, pentafluoroethyl, 2-trifluoroethyl, heptafluoropropyl, 3-trifluoropropyl, nonafluorobutyl and the like. Examples of the branched alkyl group having 3 to 6 carbon atoms include: sevoflurane isopropyl, hexafluoroisopropyl, nonafluoroisobutyl, nonafluoro-tert-butyl, and the like. Examples of the cyclic alkyl group having 3 to 6 carbon atoms include a pentafluorocyclopropyl group. Ra is preferably a linear alkyl group having 1 to 6 carbon atoms, and more preferably a trifluoromethyl group.
Specific examples of the structure represented by the general formula (1) include difluoromethyl alcohol group, tetrafluoro ethanol group, hexafluoro isopropyl alcohol group, and trifluoropropyl alcohol group, and hexafluoro isopropyl alcohol group is preferable.
The resin (E) preferably contains a structural unit having a structure represented by the general formula (1). The structure represented by the general formula (1) is preferably contained in a side chain of the resin (E). Examples of the "structural unit having the structure represented by the general formula (1) may include the structural unit represented by the following general formula (1-1).
[ 36]
In the general formula (1-1), ra is the same as Ra in the general formula (1).
Rc represents a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, and a fluoroalkyl group (the hydrocarbon group and the fluoroalkyl group may have a linear or branched chain and may have a cyclic structure). The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is particularly preferable. Examples of the "hydrocarbon" may include an alkyl group having 1 to 10 carbon atoms (the alkyl group may have a linear, branched or cyclic structure), a phenyl group, and a toluyl group, and a methyl group is particularly preferred. Examples of the "fluoroalkyl" may include fluoroalkyl having 1 to 6 carbon atoms, and trifluoromethyl is preferred. Among them, when Rc is hydrogen or methyl, the starting material for obtaining the polymerizable monomer having the structure represented by the general formula (1-1) is an acrylic acid derivative or a methacrylic acid derivative, which is particularly preferable because it is easy to obtain a large amount of the polymerizable monomer on a large scale.
Rd is an organic group having a valence of 2 (t=1) or a valence of 3 (t=2), and the organic group is a group selected from a linear or branched aliphatic hydrocarbon group which may contain a cyclic structure, an aromatic ring group, or a complex substituent thereof, and a part or all of hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups. The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Examples of the "aromatic ring group" may include an aromatic ring group having 2 or 3 bonding bonds to a benzene ring. By "compound substituent" is meant a group comprising 1 Rd in series or parallel relationship an aliphatic hydrocarbon unit and an aromatic ring unit. Among them, as Rd, an organic group having the following functional group can be a raw material of a polymer having excellent physical properties, and is therefore preferable (the broken line in the formula represents a bond).
[ 37]
[ 38]
t represents 1 or 2.
In the resin (E), the structure represented by the general formula (1) is preferably not directly bonded to the aromatic ring. The structure represented by the general formula (1) is preferably directly bonded to a linear, branched or cyclic alkylene group.
The resin (E) preferably has crosslinking sites. This is because when the resin (E) has crosslinking sites, uneven distribution of the components of the first photosensitive resin composition is further eliminated.
Examples of the crosslinking site include a photopolymerizable group exemplified as the crosslinking site of the fluororesin (D), and the photopolymerizable group is preferably introduced into a side chain of the polymer. The resin (E) preferably contains a structural unit represented by the following general formula (5).
[ 39]
The general formula (5) is the same as that exemplified for the fluorine-containing resin (D).
The resin (E) preferably contains a structural unit represented by the following general formula (1-1) and a structural unit represented by the following general formula (5).
[ 40]
The resin (E) preferably contains a structural unit represented by the following general formula (6) in addition to the structural unit represented by the following general formula (1-1) and the structural unit represented by the following general formula (5).
[ chemical 41]
The general formula (6) is the same as that exemplified for the fluorine-containing resin (D).
The resin (E) may further contain a structural unit represented by the general formula (3), a structural unit represented by the general formula (7), or the like, which are exemplified for the fluorine-containing resin (D).
The resin (E) preferably has a content of the structure represented by the general formula (1) of 0.1 mol% or more and less than 50 mol% based on 100 mol% of the total amount of the structural units constituting the resin (E). In the case where the resin (E) is formed only of the structural unit having 1 structure represented by the general formula (1), the content of the structure represented by the general formula (1) of the resin (E) is 100 mol%. If the content of the structure represented by the general formula (1) is less than 0.1 mol%, the effect of sufficiently dissolving the respective components in the first photosensitive resin composition of the present invention may not be sufficiently obtained. If the amount is 50 mol% or more, the liquid repellency may be lowered. If the content of the structure represented by the general formula (1) is 0.1 mol% or more and less than 50 mol%, sufficient liquid repellency and compatibility are maintained, and other physical properties such as adhesion, heat resistance, alkali solubility and the like can be further imparted. More preferably 1 mol% or more and less than 50 mol%.
The content of the structural unit (hereinafter, also referred to as other monomer) other than the structural unit having the structure represented by the general formula (1) in the resin (E) is preferably 99.9 mol% or less in the resin (E). If the structural unit derived from the other monomer exceeds 99.9 mol%, maldistribution of the respective components may not be eliminated in the first photosensitive resin composition of the present invention. More preferably 99 mol% or less. In addition, the structural unit derived from other monomer in the resin (E) is preferably 50 mol% or more.
The molar ratio of the structural units derived from each monomer in the resin (E) can be determined from the measurement value by NMR (nuclear magnetic resonance spectroscopy).
The weight average molecular weight of the resin (E) is preferably 1,000 to 50,000. If the weight average molecular weight of the resin (E) is outside the above range, the maldistribution of the respective components may not be sufficiently improved. More preferably 5,000 to 40,000, still more preferably 5,000 to 30,000.
The dispersity (ratio of weight average molecular weight Mw to number average molecular weight Mn; mw/Mn) of the resin (E) is preferably 1.01 to 5.00, more preferably 1.10 to 4.00, particularly preferably 1.30 to 3.00.
In the present invention, the weight average molecular weight and the dispersivity of the resin (E) are values obtained by high-speed gel permeation chromatography using polystyrene as a standard substance.
The fluorine atom content of the resin (E) is preferably 15 to 60 mass%. If the fluorine atom content of the resin (E) falls within the above-mentioned range, uneven distribution of the respective components can be eliminated in the first photosensitive resin composition of the present invention. More preferably 15 to 40% by mass, still more preferably 18 to 36% by mass.
The resin (E) can be obtained by polymerizing a monomer having a structure represented by the general formula (1) or the like.
Examples of the monomer having the structure represented by the general formula (1) include: 5, 5-trifluoro-4-hydroxy-4- (trifluoromethyl) pentan-2-yl methacrylate, 4- (1, 3-hexafluoro-2-hydroxy-2-propanyl) styrene (4-HFA-ST) 3, 5-bis (1, 3-hexafluoro-2-hydroxy-2-propanyl) styrene (3, 5-HFA-ST) 2, 4-bis (1, 3-hexafluoro-2-hydroxy-2-propanyl) cyclohexyl methacrylate 3, 5-bis (1, 3-hexafluoro-2-hydroxy-2-propanyl) cyclohexyl methacrylate 2,4, 6-tris (1, 3-hexafluoro-2-hydroxy-2-propanyl) cyclohexyl methacrylate 1, 3-bis (1, 3-hexafluoro-2-hydroxy-2-propanyl) isopropyl methacrylate, and the like. These monomers may be used in an amount of 1 or 2 or more. Preference is given to 5, 5-trifluoro-4-hydroxy-4- (trifluoromethyl) pentan-2-yl methacrylate, 3, 5-bis (1, 3-hexafluoro-2-hydroxy-2-propanyl) cyclohexyl methacrylate 1, 3-bis (1, 3-hexafluoro-2-hydroxy-2-propanyl) isopropyl methacrylate.
The resin (E) can be synthesized, for example, by dissolving a monomer in a solvent, adding a polymerization initiator, and optionally heating to react. In this reaction, a chain transfer agent is preferably optionally present. The monomer, the solvent, the polymerization initiator and the chain transfer agent may be added in the whole amount at the start of the reaction or may be added continuously.
The solvent used in the above-mentioned synthesis method is not particularly limited, and examples thereof include: ketones, alcohols, polyols, derivatives thereof, ethers, esters, aromatic solvents, fluorine solvents, and the like. These may be used alone or in combination of 2 or more.
The ketones include, specifically: acetone, methyl Ethyl Ketone (MEK), cyclopentanone, cyclohexanone, methyl isoamyl ketone, 2-heptyl cyclopentanone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone, and the like.
Specific examples of the alcohols include: isopropyl alcohol, butyl alcohol, isobutyl alcohol, n-amyl alcohol, isoamyl alcohol, t-amyl alcohol, 4-methyl-2-amyl alcohol, 3-methyl-3-amyl alcohol, 2, 3-dimethyl-2-amyl alcohol, n-hexyl alcohol, n-heptyl alcohol, 2-heptyl alcohol, n-octyl alcohol, n-decyl alcohol, sec-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butyl alcohol, lauryl alcohol, hexyldecyl alcohol, oleyl alcohol and the like.
Specifically, the polyhydric alcohol and its derivative may be exemplified by: ethylene glycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoacetate, propylene glycol monoacetate, propylene Glycol Monomethyl Ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene Glycol Monomethyl Ether Acetate (PGMEA), dipropylene glycol or dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether, and the like.
Specific examples of the ethers include: diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, anisole, and the like.
The esters may be specifically exemplified by: methyl lactate, ethyl Lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, gamma-butyrolactone, etc.
Examples of the aromatic solvent include xylene and toluene.
Examples of the fluorine-based solvent include: fluorochlorocarbide, hydrochlorofluorocarbide, perfluorinated compound, hexafluoroisopropanol, and the like.
The polymerization initiator may be a known organic peroxide, inorganic peroxide, azo compound or the like. Organic peroxides, inorganic peroxides may also be used as redox-type catalysts in combination with reducing agents.
Examples of the chain transfer agent include: mercaptans such as n-butylmercaptan, n-dodecylmercaptan, t-butylmercaptan, ethyl thioglycolate, 2-ethylhexyl thioglycolate, and 2-mercaptoethanol; halogenated alkyl groups such as chloroform, carbon tetrachloride and carbon tetrabromide.
When the resin (E) has a crosslinking site, the following method can be exemplified: the monomer having a structure represented by the general formula (1) is polymerized together with the monomer having a side chain in which a crosslinking site is introduced into the polymer by polymerization. Further, the following method can be exemplified: in the same manner as in the synthesis of the fluorine-containing resin (D) having a crosslinked site, a monomer is polymerized to obtain a precursor of the resin (E) having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (8), and then the precursor of the resin (E) is reacted with a photopolymerizable group derivative, whereby a photopolymerizable group is introduced into a side chain of the polymer.
The resin (E) may be 1 kind alone or 2 or more kinds of resins.
In the first photosensitive resin composition of the present invention, the content of the resin (E) is preferably 0.01 to 10 mass% with respect to all solid components of the first photosensitive resin composition. When the content of the resin (E) is within the above range, maldistribution of the respective components can be eliminated in the first photosensitive resin composition of the present invention. More preferably 0.03 to 5% by mass, still more preferably 0.03 to 1.0% by mass.
The first photosensitive resin composition of the present invention contains 30 to 550 parts by mass, preferably 40 to 520 parts by mass of the resin (E) based on 100 parts by mass of the fluorine-containing resin (D). When the content of the resin (E) is within the above range, maldistribution of the respective components can be eliminated in the first photosensitive resin composition of the present invention.
< solvent >
The first photosensitive resin composition of the present invention preferably contains a solvent. The solvent is not particularly limited as long as the fluorine-containing resin (D) is soluble, and examples thereof include the same solvents as exemplified in the synthesis of the resin (E). Methyl ethyl ketone, propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene Glycol Monomethyl Ether (PGME), cyclohexanone, ethyl lactate, butyl acetate, and gamma-butyrolactone are preferred.
The amount of the solvent in the first photosensitive resin composition of the present invention is preferably in the range of 50 parts by mass to 2,000 parts by mass when the total of the alkali-soluble resin (C) and the fluorine-containing resin (D) is 100 parts by mass. More preferably 100 parts by mass or more and 1,000 parts by mass or less. By adjusting the amount of the solvent, the film thickness of the formed resin film can be adjusted, and if it is within the above range, a film thickness of the resin film particularly suitable for obtaining the barrier can be obtained.
The first photosensitive resin composition of the present invention preferably further comprises at least 1 selected from the group consisting of a photoradical sensitizer, a chain transfer agent, an ultraviolet absorber, and a polymerization inhibitor.
Photo radical sensitizer
When the first photosensitive resin composition of the present invention contains a photoradical sensitizer, the exposure sensitivity of the first photosensitive resin composition of the present invention can be further improved. The photoradical sensitizer is preferably a compound which absorbs light or radiation and becomes an excited state. When the photo radical sensitizer is brought into an excited state, electron transfer, energy transfer, heat generation, or the like occurs upon contact with the photopolymerization initiator, and thus the photopolymerization initiator is likely to decompose to generate an acid. The photoradical sensitizer may have an absorption wavelength in a region of 350nm to 450nm, and examples thereof include: polynuclear aromatics, xanthenes, xanthones, cyanines, merocyanines, thiazines, acridines, acridones, anthraquinones, aromatic cyanines, styryl groups, basic styryl groups (base styryl groups) or coumarins.
Examples of polynuclear aromatics include: pyrene, perylene, triphenylene, anthracene, 9, 10-dibutoxyanthracene, 9, 10-diethoxyanthracene, 3, 7-dimethoxy anthracene or 9, 10-dipropoxy anthracene.
Examples of xanthenes include: fluorescein, eosin, erythrosine, rhodamine B, rose bengal.
Examples of xanthones include: xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone or isopropylthioxanthone.
Examples of the cyanines include: thiacarbocyanine and oxacarbocyanine.
Examples of merocyanines include: merocyanines, carbomerocyanines.
As the thiazines, there may be exemplified: thionine, methylene blue, toluidine blue.
As the acridines, there may be exemplified: acridine orange, chloroflavine, acridine flavine.
As acridones, there may be exemplified: acridone, 10-butyl-2-chloroacridone.
As the anthraquinones, anthraquinones can be exemplified.
As the aromatic acid cyanines, aromatic acid cyanines can be exemplified.
As the basic styryl group, 2- [2- [4- (dimethylamino) phenyl ] vinyl ] benzoxazole can be exemplified.
Examples of coumarins include: 7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin or 2,3,6, 7-tetrahydro-9-methyl-1H, 5H,11H [ l ] benzopyran [6,7,8-ij ] quinolizin-11-one.
These photoradical sensitizers may be used alone or in combination of 2 or more.
The photoradical sensitizer used in the first photosensitive resin composition of the present invention is preferably polynuclear aromatic, acridone, styryl, basic styryl, coumarin or xanthone, particularly preferably xanthone, from the viewpoint of a large effect of improving exposure sensitivity. Among xanthones, diethyl thioxanthone and isopropyl thioxanthone are preferred.
The content of the photoradical sensitizer is preferably 0.1 to 8 parts by mass, more preferably 1 to 4 parts by mass, relative to 100 parts by mass of the fluorine-containing resin (D). When the content of the photoradical sensitizer is within the above range, the exposure sensitivity of the photosensitive resin composition is improved, and in the pattern-forming film obtained by exposing the first photosensitive resin composition of the present invention, the boundary between the liquid repellent portion and the lyophilic portion becomes clear, and the contrast of the ink pattern after the ink is applied is improved, so that an elegant pattern can be obtained.
< chain transfer agent >)
The first photosensitive resin composition of the present invention preferably uses a chain transfer agent as necessary.
Examples of the chain transfer agent include the same compounds as those usable for the synthesis of the resin (E).
Ultraviolet absorber >, and
the first photosensitive resin composition of the present invention preferably contains an ultraviolet absorber as required, and examples of the ultraviolet absorber include: salicylic acid, benzophenone, triazole, and the like.
The content of the ultraviolet absorber in the first photosensitive resin composition is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass.
< polymerization inhibitor >)
The polymerization inhibitor used in the first photosensitive resin composition of the present invention is not particularly limited, and examples thereof include: ortho-cresol, meta-cresol, para-cresol, 6-tert-butyl-2, 4-xylenol, 2, 6-di-tert-butyl-para-cresol, hydroquinone, catechol, 4-tert-butyl catechol, 2, 5-di-tetramethylbutylhydroquinone, 2, 5-di-tert-butylhydroquinone, p-methoxyphenol, 1,2, 4-trihydroxybenzene, 1, 2-benzoquinone, 1, 3-benzoquinone, 1, 4-benzoquinone, quinizarine leuco, phenothiazine, 2-methoxyphenothiazine, tetraethylthiuram disulfide, 1-diphenyl-2-picrylhydrazine, or 1, 1-diphenyl-2-picrylhydrazine.
Examples of the commercially available polymerization inhibitor include: n, N '-di-2-naphthalene-p-phenylenediamine (trade name, NONFLEX F) manufactured by Seiko chemical Co., ltd.), N-diphenyl-p-phenylenediamine (trade name, NONFLEX H), 4' -bis (a, a-dimethylbenzyl) diphenylamine (trade name, NONFLEX DCD), 2 '-methylene-bis (4-methyl-6-t-butylphenol) (trade name, NONFLEX MBP), N- (1-methylheptyl) -N' -phenyl-p-phenylenediamine (trade name, OZONON 35) or N-nitrosophenyl-hydroxylamine ammonium (trade name, Q-1300) manufactured by Fuji film and light purity chemical Co., ltd., or N-nitrosophenyl-hydroxylamine aluminum salt (trade name, Q-1301).
The content ratio of the polymerization inhibitor in all solid components in the first photosensitive resin composition of the present invention is preferably 0.001 to 20% by mass, more preferably 0.005 to 10% by mass, and particularly preferably 0.01 to 5% by mass. When the content ratio is within the above range, the development residue of the photosensitive resin composition is reduced, and the pattern linearity is good.
The first photosensitive resin composition of the present invention may contain other additives as necessary. Examples of the other additives include dissolution inhibitors, plasticizers, stabilizers, colorants, thickeners, adhesion agents, antioxidants, and other various additives commonly used in photosensitive resin compositions. These other additives may also be known additives.
Next, a second photosensitive resin composition among the photosensitive resin compositions of the present invention will be described. The second photosensitive resin composition will be described only in terms of being different from the first photosensitive resin composition.
The second photosensitive resin composition of the present invention comprises an ethylenically unsaturated compound (a), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorine-containing resin (D), and a resin (E) having a structure represented by the general formula (1), wherein the resin (E) is a resin comprising a structural unit having a structure represented by the general formula (1) and a structural unit having a crosslinking site.
The second photosensitive resin composition preferably contains 30 to 550 parts by mass of the resin (E) based on 100 parts by mass of the fluorine-containing resin (D).
The specific types and amounts of the ethylenically unsaturated compound (a), the photopolymerization initiator (B), the alkali-soluble resin (C), the fluorine-containing resin (D), the resin (E), and other usable compounds contained in the second photosensitive resin composition are the same as those described for the first photosensitive resin composition.
The first photosensitive resin composition or the second photosensitive resin composition of the present invention is preferably used for forming a partition wall.
The resin film of the present invention is a resin film obtained from the first photosensitive resin composition or the second photosensitive resin composition. The resin film of the present invention can be produced by forming the first photosensitive resin composition or the second photosensitive resin composition into a film by a known method.
The cured product of the present invention is a cured product obtained by curing the resin film. The cured product of the present invention can be obtained by a method for producing a cured product comprising the steps of: a film forming step of applying the first photosensitive resin composition or the second photosensitive resin composition to a substrate and then heating the same, thereby obtaining a resin film; and an exposure step of exposing the resin film with high-energy rays. The specific operations in the film formation step and the exposure step are the same as those in the method for forming the barrier ribs described below. The method for producing the cured product is also one of the present invention.
The cured product obtained by using the first photosensitive resin composition or the second photosensitive resin composition of the present invention has good curability and liquid repellency by containing the resin (E). The cured product of the present invention is preferably used as a partition wall, particularly preferably used as a partition wall of an organic EL display, a quantum dot display, or the like.
The partition wall comprising the cured product of the present invention is also one of the present invention.
In addition, an organic electroluminescent element is also one of the present invention, and the organic electroluminescent element includes: the partition wall of the present invention, and a light-emitting layer or a wavelength conversion layer disposed in a region partitioned by the partition wall.
The wavelength conversion layer provided with the partition wall of the present invention is also one of the present invention.
Further, a display having the partition wall of the present invention is also one of the present invention.
Next, a method of forming a partition wall using the first photosensitive resin composition or the second photosensitive resin composition of the present invention will be described.
The method of forming the partition wall may include: (1) a film formation step, (2) an exposure step, and (3) a development step.
The steps are described below.
(1) Film formation step
First, the first photosensitive resin composition or the second photosensitive resin composition of the present invention is coated on a substrate, and then heated, thereby producing a fluorine-containing resin film from the first photosensitive resin composition or the second photosensitive resin composition.
The heating condition is not particularly limited, but is preferably 80 to 100℃for 60 to 200 seconds.
This can remove the solvent and the like contained in the first photosensitive resin composition or the second photosensitive resin composition.
The substrate may be a silicon wafer, metal, glass, ITO (Indium Tin Oxides, indium tin oxide) substrate, or the like.
Further, an organic or inorganic film may be provided in advance over the substrate. For example, there may be an anti-reflective film, an underlying layer of a multilayer photoresist, or a pattern may be formed thereon. In addition, the substrate may be cleaned in advance. For example, the washing may be performed using ultrapure water, acetone, alcohol (methanol, ethanol, isopropanol), or the like.
As a method of applying the first photosensitive resin composition or the second photosensitive resin composition of the present invention to a substrate, a known method such as a spin coater can be used.
(2) Exposure step
Next, a desired photomask is mounted on an exposure apparatus, and the fluorine-containing resin film is exposed to high-energy rays through the photomask.
The high energy rays are preferably at least 1 selected from the group consisting of ultraviolet rays, gamma rays, X rays and alpha rays.
The exposure to high-energy rays is preferably 1mJ/cm 2 200mJ/cm above 2 Hereinafter, more preferably 10mJ/cm 2 Above 100mJ/cm 2 The following is given.
(3) Development step
Then, the fluororesin film after the exposure step is developed with an alkaline aqueous solution to produce a fluororesin pattern film.
That is, the fluorine-containing resin pattern film is produced by dissolving either one of the exposed portion or the unexposed portion of the fluorine-containing resin film in an alkaline aqueous solution.
As the alkaline aqueous solution, an aqueous solution of tetramethylammonium hydroxide (TMAH), an aqueous solution of tetrabutylammonium hydroxide (TBAH), or the like can be used.
When the alkaline aqueous solution is an aqueous solution of tetramethyl ammonium hydroxide (TMAH), the concentration thereof is preferably 0.1 mass% or more and 5 mass% or less, more preferably 2 mass% or more and 3 mass% or less.
The developing method may be a known method, and examples thereof include: dipping, liquid coating, spraying, and the like.
The development time (time for which the developer is in contact with the fluorine-containing resin film) is preferably 10 seconds to 3 minutes, more preferably 30 seconds to 2 minutes.
After development, a step of cleaning the fluorine-containing resin pattern film with deionized water or the like may be optionally provided. The cleaning method and the cleaning time are preferably 10 seconds to 3 minutes, more preferably 30 seconds to 2 minutes.
The barrier ribs thus fabricated may be used as barrier ribs for displays.
The fluorine-containing resin of the present invention comprises a structural unit having a structure represented by the general formula (1) and a structural unit having a crosslinking site. The fluorine-containing resin of the present invention is one of the resins (E) having a structure represented by the general formula (1) contained in the first photosensitive resin composition or the second photosensitive resin composition.
The fluorine-containing resin of the present invention preferably contains the structural unit represented by the general formula (5) as a structural unit having a crosslinking site.
The fluorine-containing resin of the present invention preferably has a fluorine atom content of 15 to 60 mass%.
The fluorine-containing resin of the present invention preferably has a content of the structure represented by the general formula (1) of 0.1 mol% or more and less than 50 mol% based on 100 mol% of the total amount of the structural units constituting the resin.
The fluorine-containing resin of the present invention preferably has a weight average molecular weight of 5,000 to 40,000.
The fluorine-containing resin of the present invention is considered to function as a compatibilizing material for eliminating uneven distribution of the components in the composition by comprising a structural unit having a structure represented by the general formula (1) and a structural unit having a crosslinked portion. For example, by introducing the fluorine-containing resin of the present invention into a resin composition and using the resin composition, a molded article such as a resin film or a partition wall (barrier wall) having improved unevenness in distribution of each component can be produced. The fluorine-containing resin of the present invention is particularly suitable for use in a composition containing 2 or more resins having a difference in fluorine atom content of 15 to 60 mass%.
The fluorine-containing resin of the present invention also has a function as a surfactant, and thus can be used as a surfactant.
Polymer blends comprising the fluorine-containing resins of the invention are also one of the invention. The kind of the resin to be contained in the polymer blend together with the fluorine-containing resin of the present invention is not particularly limited, and examples thereof include 1 or a combination of 2 or more kinds of olefin resins, epoxy resins, (meth) acrylic resins, urethane resins, fluorine resins, and the like.
In the present specification, the following invention is disclosed.
[1] A photosensitive resin composition comprising an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorine-containing resin (D) and a resin (E) having a structure represented by the following general formula (1), wherein the resin (E) is contained in an amount of 30 to 550 parts by mass based on 100 parts by mass of the fluorine-containing resin (D);
[ chemical 42]
(in the general formula (1), ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and any number of hydrogen atoms of the alkyl group are substituted with fluorine atoms).
[2] The photosensitive resin composition according to [1], wherein the resin (E) has a crosslinking site.
[3] A photosensitive resin composition comprising an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorine-containing resin (D), and a resin (E) having a structure represented by the general formula (1), wherein the resin (E) is a resin comprising a structural unit having a structure represented by the general formula (1) below and a structural unit having a crosslinking site;
[ chemical 43]
(in the general formula (1), ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and any number of hydrogen atoms of the alkyl group are substituted with fluorine atoms).
[4] The photosensitive resin composition according to [3], wherein the resin (E) is contained in an amount of 30 to 550 parts by mass based on 100 parts by mass of the fluorine-containing resin (D).
[5] The photosensitive resin composition according to the item [3], which comprises a structural unit represented by the following general formula (5) as the structural unit having a crosslinking site;
[ 44]
(in the general formula (5), R 5 、R 6 Each independently represents a hydrogen atom or a methyl group, W 2 Represents a 2-valent linking group, represents-O-, -O-C (=o) -, -C (=o) -O-, -O-C (=o) -NH-, -C (=o) -O-C (=o) -NH-, or-C (=o) -NH-, a 2 Represents a 2-valent linking group, and represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms or 3 to 10 carbon atoms, any number of hydrogen atoms in the alkylene group being capable of being bonded to a hydroxyl group or-O-C (=O) -CH 3 Substitution, A 3 Represents a 2-4 valent linking group, represents a linear hydrocarbon group having 1 to 10 carbon atoms, a branched hydrocarbon group having 3 to 10 carbon atoms or a cyclic hydrocarbon group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group may be represented by a hydroxyl group or-O-C (=O) -CH 3 Substituted, Y 2 、Y 3 The 2-valent linking groups are independently-O-or-NH-, n is an integer of 1 to 3, and r is 0 or 1).
[6] The photosensitive resin composition according to item [5], wherein 30 to 550 parts by mass of the resin (E) is contained, based on 100 parts by mass of the fluorine-containing resin (D).
[7] The photosensitive resin composition according to the above [3], wherein the resin (E) is a resin comprising a structural unit represented by the following general formula (1-1) and a structural unit represented by the following general formula (5);
[ 45]
(in the general formula (1-1), ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, wherein any number of hydrogen atoms of the alkyl group is substituted with a fluorine atom, rc represents a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a fluoroalkyl group (the hydrocarbon group and the fluoroalkyl group are linear or branched and may include a cyclic structure), rd is a 2-or 3-valent organic group which is selected from the group consisting of a linear or branched aliphatic hydrocarbon group which may include a cyclic structure, an aromatic ring group, and a compound substituent thereof,and a part or all of the hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups; t represents 1 or 2; in the general formula (5), R 5 、R 6 Each independently represents a hydrogen atom or a methyl group, W 2 Represents a 2-valent linking group, represents-O-, -O-C (=o) -, -C (=o) -O-, -O-C (=o) -NH-, -C (=o) -O-C (=o) -NH-, or-C (=o) -NH-, a 2 Represents a 2-valent linking group, and represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms or 3 to 10 carbon atoms, any number of hydrogen atoms in the alkylene group being capable of being bonded to a hydroxyl group or-O-C (=O) -CH 3 Substitution, A 3 Represents a 2-4 valent linking group, represents a linear hydrocarbon group having 1 to 10 carbon atoms, a branched hydrocarbon group having 3 to 10 carbon atoms or a cyclic hydrocarbon group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group may be represented by a hydroxyl group or-O-C (=O) -CH 3 Substituted, Y 2 、Y 3 The 2-valent linking groups are independently-O-or-NH-, n is an integer of 1 to 3, and r is 0 or 1).
[8] The photosensitive resin composition according to item [7], wherein 30 to 550 parts by mass of the resin (E) is contained, based on 100 parts by mass of the fluorine-containing resin (D).
[9] The photosensitive resin composition according to the above [3], wherein the resin (E) is a resin comprising a structural unit represented by the following general formula (1-1), a structural unit represented by the following general formula (5) and a structural unit represented by the following general formula (6);
[ chemical 46]
(in the general formula (1-1), ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, wherein any number of hydrogen atoms of the alkyl group is substituted with a fluorine atom, rc represents a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a fluoroalkyl group (the hydrocarbon group and the fluoroalkyl group are linear or branched and may include a cyclic structure), rd is an organic group having 2 or 3 valences and the organic group is selected from the group consisting of a straight chain which may include a cyclic structure)A group in a chain or branched aliphatic hydrocarbon group, an aromatic ring group or a complex substituent thereof, and part or all of hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups; t represents 1 or 2; in the general formula (5), R 5 、R 6 Each independently represents a hydrogen atom or a methyl group, W 2 Represents a 2-valent linking group, represents-O-, -O-C (=o) -, -C (=o) -O-, -O-C (=o) -NH-, -C (=o) -O-C (=o) -NH-, or-C (=o) -NH-, a 2 Represents a 2-valent linking group, and represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms or 3 to 10 carbon atoms, any number of hydrogen atoms in the alkylene group being capable of being bonded to a hydroxyl group or-O-C (=O) -CH 3 Substitution, A 3 Represents a 2-4 valent linking group, represents a linear hydrocarbon group having 1 to 10 carbon atoms, a branched hydrocarbon group having 3 to 10 carbon atoms or a cyclic hydrocarbon group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group may be represented by a hydroxyl group or-O-C (=O) -CH 3 Substituted, Y 2 、Y 3 Represents a 2-valent linking group, each independently represents-O-or-NH-, n represents an integer from 1 to 3, and r represents 0 or 1; in the general formula (6), R 7 Represents a hydrogen atom or a methyl group, R 8 Represents a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, wherein any number of hydrogen atoms in the alkyl group are replaced with fluorine atoms).
[10] The photosensitive resin composition according to the item [9], wherein 30 to 550 parts by mass of the resin (E) is contained, based on 100 parts by mass of the fluorine-containing resin (D).
[11] The photosensitive resin composition according to any one of [1] to [10], wherein the fluorine atom content of the resin (E) is 15 to 60 mass%.
[12] The photosensitive resin composition according to any one of [1] to [11], wherein the content of the alkali-soluble resin (C) is 10 to 70% by mass relative to all solid components of the photosensitive resin composition.
[13] The photosensitive resin composition according to any one of [1] to [12], wherein the content of the fluorine-containing resin (D) is 0.01 to 10% by mass relative to all solid components of the photosensitive resin composition.
[14] The photosensitive resin composition according to any one of [1] to [13], wherein the content of the resin (E) is 0.01 to 10% by mass relative to all solid components of the photosensitive resin composition.
[15] The photosensitive resin composition according to any one of [1] to [14], wherein a difference in fluorine atom content between the alkali-soluble resin (C) and the fluorine-containing resin (D) is 15 to 60% by mass.
[16] The photosensitive resin composition according to any one of [1] to [15], wherein the content of the structure represented by the general formula (1) contained in the resin (E) is 0.1 mol% or more and less than 50 mol% when the total amount of the structural units constituting the resin (E) is 100 mol%.
[17] The photosensitive resin composition according to any one of [1] to [16], wherein the structure represented by the general formula (1) is hexafluoroisopropanol group.
[18] The photosensitive resin composition according to any one of [1] to [17], wherein the weight average molecular weight of the resin (E) is 5,000 to 40,000.
[19] The photosensitive resin composition according to any one of [1] to [18], which further comprises at least 1 selected from the group consisting of a photoradical sensitizer, a chain transfer agent, an ultraviolet absorber and a polymerization inhibitor.
[20] The photosensitive resin composition according to any one of [1] to [19], which is used for forming a partition wall.
[21] A resin film obtained from the photosensitive resin composition according to any one of [1] to [20 ].
[22] A cured product obtained by curing the resin film according to [21 ].
[23] A partition wall comprising the cured product according to [22 ].
[24] An organic electroluminescent element is provided with: the spacer according to [23], and a light-emitting layer or a wavelength conversion layer disposed in a region partitioned by the spacer.
[25] A display provided with the partition wall according to [23 ].
[26] A method for producing a cured product, comprising: a film forming step of applying the photosensitive resin composition according to any one of [1] to [20] onto a substrate, and then heating, thereby obtaining a resin film; and an exposure step of exposing the resin film with high-energy rays.
[27] A fluorine-containing resin comprising a structural unit having a structure represented by the following general formula (1) and a structural unit having a crosslinking site;
[ 47]
(in the general formula (1), ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and any number of hydrogen atoms of the alkyl group are substituted with fluorine atoms).
[28] The fluororesin according to item [27], which comprises a structural unit represented by the following general formula (5) as a structural unit having a crosslinking site;
[ 48]
(in the general formula (5), R 5 、R 6 Each independently represents a hydrogen atom or a methyl group, W 2 Represents a 2-valent linking group, represents-O-, -O-C (=o) -, -C (=o) -O-, -O-C (=o) -NH-, -C (=o) -O-C (=o) -NH-, or-C (=o) -NH-, a 2 Represents a 2-valent linking group, and represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms or 3 to 10 carbon atoms, any number of hydrogen atoms in the alkylene group being capable of being bonded to a hydroxyl group or-O-C (=O) -CH 3 Substitution, A 3 Represents a 2-4 valent linking group, and represents a linear hydrocarbon having 1 to 10 carbon atoms, a branched hydrocarbon having 3 to 10 carbon atoms, or a cyclic hydrocarbon having 3 to 10 carbon atomsA radical, any number of hydrogen atoms of which may be replaced by hydroxy or-O-C (=O) -CH 3 Substituted, Y 2 、Y 3 The 2-valent linking groups are independently-O-or-NH-, n is an integer of 1 to 3, and r is 0 or 1).
[29] The fluororesin according to item [27] or [28], wherein the fluorine atom content is 15 to 60 mass%.
[30] The fluororesin according to any one of [27] to [29], wherein the content of the structure represented by the general formula (1) is 0.1 mol% or more and less than 50 mol% when the total amount of the structural units constituting the resin is 100 mol%.
[31] The fluororesin according to any one of [27] to [30], which has a weight average molecular weight of 5,000 to 40,000.
[32] A polymer blend comprising the fluorine-containing resin according to any one of [27] to [31 ].
Examples (example)
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
[ determination of molar ratio of structural units of Polymer ]
The molar ratio of the structural units in the polymer is based on 1 H-NMR、 19 F-NMR or 13 The measurement value of C-NMR was determined.
[ determination of molecular weight of Polymer ]
The weight average molecular weight Mw and the molecular weight dispersity (ratio of the number average molecular weight Mn to the weight average molecular weight Mw; mw/Mn) of the polymer were measured by using high-speed gel permeation chromatography (hereinafter, sometimes referred to as GPC. Manufactured by Tosoh Co., ltd., model HLC-8320 GPC), connecting 1 ALPHA-M column and 1 ALPHA-2500 column (manufactured by Tosoh Co., ltd.) in series, and using Tetrahydrofuran (THF) as a developing solvent. The detector is a refractive index difference measurement detector.
1. Synthesis of fluorine-containing resin (D) (liquid repellent)
[ Synthesis of liquid precursor 1]
Into a 500ml Glass flask equipped with a stirrer, 2.7g (0.014 mol) of 1, 1-bis (trifluoromethyl) -1, 3-butadiene (hereinafter referred to as BTFBE; hereinafter referred to as "BTFBE") 2.3g (0.014 mol), 4-acetoxystyrene (hereinafter referred to as "Tokyo" industrial Co., ltd.; hereinafter referred to as "p-AcO-St; 2.3g (0.014 mol), 2- (perfluorohexyl) ethyl methacrylate (hereinafter referred to as" Tokyo "industrial Co., ltd.; hereinafter referred to as" MA-C6F) 18.2g (0.042 mol), hydroxyethyl methacrylate (Tokyo "industrial Co., ltd.; hereinafter referred to as" HEMA ") 3.9g (0.03 mol), methyl ethyl ketone (hereinafter referred to as" MEK ") 47.2g, and azobis (2-methylbutyronitrile) (hereinafter referred to as" AIO-St "industrial Co., ltd.; hereinafter referred to as" p-Account "); 2.2 g) (hereinafter referred to as" AIO-St; hereinafter referred to as "industrial Co., ltd.; hereinafter referred to as" MEK ")), were added, and the flask was degassed at a temperature of 0.005 g (0.005 ℃ C.) at one night) at the same time after the flask was heated. After 200g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. The precipitate was isolated by filtration and dried under reduced pressure at 45℃to give 24.0g of a liquid-repellent precursor as a white solid in 89% yield.
< NMR measurement results >
The composition ratio of each structural unit of the liquid repellent precursor 1 is expressed as the structural unit of BTFBE in terms of molar ratio: structural unit of p-AcO-St: structural unit of MA-C6F: building block of HEMA = 14:14:42:30.
[ 49]
< GPC measurement results >)
Mw＝9,200，Mw/Mn＝1.5
[ Synthesis of liquid preparation 1 ]
Into a 500ml glass flask equipped with a stirrer, 1.20 g (hydroxyl equivalent 0.03 mol) of a liquid-repellent precursor, 0.21g (hydroxyl equivalent 0.0021 mol) of triethylamine, 60g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), and 4.26g (hydroxyl equivalent 0.030 mol) of ethyl acrylate (product name: karenz AOI; product name: showa electric Co., ltd.) were charged, and reacted at 45℃for 4 hours. After the completion of the reaction, the reaction mixture was concentrated, 200g of n-heptane was added thereto, and a precipitate was precipitated. The precipitate was separated by filtration and dried under reduced pressure at 40℃to give 1.6g of a white solid as a plectrum solution in a yield of 90%.
[ 50]
＜ 13 C-NMR measurement results
In the liquid repellent 1, the amount of acrylic acid derivative introduced (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) derived from Karenz AOI were expressed as 99:1. in addition, it was confirmed that the composition ratio of each structural unit (structural unit of BTFBE, structural unit of p-AcO-St, structural unit of MA-C6F) which did not react with the crosslinking site was unchanged from that of the used liquid repellent precursor 1 (same as before the introduction of the crosslinking group). The fluorine atom content in the liquid repellent 1 was 38.6 mass% based on the structural unit.
< GPC measurement results >)
Mw＝13,100，Mw/Mn＝1.7
[ Synthesis of liquid precursor 2 ]
Into a 300ml glass flask equipped with a stirrer, 3.8g (0.02 mol) of BTFBE, 3.2g (0.02 mol) of p-AcO-St, 16.6g (0.05 mol) of 2- (perfluorobutyl) ethyl methacrylate (Tokyo chemical Co., ltd.; hereinafter referred to as MA-C4F), 5.2g (0.04 mol) of HEMA (Tokyo chemical Co., ltd.) and 60g of MEK were charged at room temperature (about 20 ℃ C.), and after deaeration with stirring, the flask was purged with nitrogen and heated to 79 ℃ C.for overnight reaction. After 250g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. The precipitate was isolated by filtration and dried under reduced pressure at 45℃to give 26.0g of a liquid-repellent precursor as a white solid in 90% yield.
< NMR measurement results >
The composition ratio of each structural unit of the liquid repellent precursor 2 is expressed as the structural unit of BTFBE in terms of molar ratio: structural unit of p-AcO-St: structural unit of MA-C4F: building block of HEMA = 15:16:38:31.
[ 51]
< GPC measurement results >)
Mw＝9,200，Mw/Mn＝1.4
[ Synthesis of liquid repellent 2 ]
Into a 100ml glass flask equipped with a stirrer, 2.26 g (hydroxyl equivalent 0.038 mol) of a liquid-repellent precursor, 0.21g (hydroxyl equivalent 0.0021 mol) of triethylamine, 20g of PGMEA and 5.4g (hydroxyl equivalent 0.038 mol) of Karenz AOI were added, and the mixture was reacted at 45℃for 4 hours. After the completion of the reaction, the reaction mixture was concentrated, 100g of n-heptane was added thereto, and a precipitate was precipitated. The precipitate was separated by filtration and dried under reduced pressure at 40℃to give 2.7 g of a white solid as a liquid repellent in a yield of 85%.
[ 52]
＜ 13 C-NMR measurement results
In the dip coating agent 2, the amount of the acrylic acid derivative introduced (reaction rate) and the amount of the remaining hydroxyl groups (unreacted rate) derived from Karenz AOI were expressed as 99:1. in addition, it was confirmed that the composition ratio of each structural unit (structural unit of BTFBE, structural unit of p-AcO-St, structural unit of MA-C4F) which did not react with the crosslinking site was unchanged from that of the used liquid repellent precursor 2 (same as before the introduction of the crosslinking group). The fluorine atom content in the liquid repellent 2 was 31.6 mass% based on the structural unit.
< GPC measurement results >)
Mw＝13,100，Mw/Mn＝1.5
[ Synthesis of liquid precursor 3 ]
A500 ml glass flask equipped with a stirrer was charged with 25.9g (0.06 mol) of MA-C6F, 5.2g (0.04 mol) of HEMA (Tokyo chemical Co., ltd.) and 62g of MEK, 0.84g (0.005 mol) of AIBN was added thereto, and the flask was degassed while stirring, and then the flask was purged with nitrogen, and the temperature was raised to 79℃for overnight reaction. After 250g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. The precipitate was isolated by filtration and dried under reduced pressure at 45℃to give 3 g of a liquid-repellent precursor as a white solid in 90% yield.
< NMR measurement results >
The composition ratio of each structural unit of the liquid repellent precursor 3 is expressed as structural units of MA-C6F in terms of molar ratio: building block of HEMA = 60:40.
[ 53]
/>
< GPC measurement results >)
Mw＝10,800，Mw/Mn＝1.6
[ Synthesis of liquid repellent 3]
Into a 500ml glass flask equipped with a stirrer, 3.28 g (hydroxyl equivalent 0.05 mol) of a liquid repellent precursor, 0.45g (hydroxyl equivalent 0.0045 mol) of triethylamine, 60g of PGMEA, 7.1g (hydroxyl equivalent 0.050 mol) of Karenz AOI was added, and the mixture was reacted at 45℃for 4 hours. After the completion of the reaction, the reaction mixture was concentrated, 200g of n-heptane was added thereto, and a precipitate was precipitated. The precipitate was isolated by filtration and dried under reduced pressure at 40℃to give 3 g of a liquid-repellent agent as a white solid in 85% yield.
[ 54]
＜ 13 C-NMR measurement results
In the liquid repellent 3, the amount of acrylic acid derivative introduced (reaction rate) and the amount of residual hydroxyl groups (unreacted rate) derived from Karenz AOI were expressed as 99:1. in addition, it was confirmed that the composition ratio of each structural unit (structural unit of MA-C6F) which did not react with the crosslinking site was unchanged from that of the used plectrum precursor 3 (the same as before the introduction of the crosslinking group). The fluorine atom content in the liquid repellent 3 was 40.6 mass% based on the structural unit.
< GPC measurement results >)
Mw＝14,300，Mw/Mn＝1.7
[ liquid preparation 4]
"RS-72A" (fluorine atom content 8% by mass) manufactured by DIC Co., ltd
[ liquid preparation 5]
"FTERGENT 601ADH2" (fluorine atom content 19% by mass) manufactured by NEOS Co
2. Synthesis of resin (E)
[ Synthesis of fluororesin precursor 1 ]
Into a 500ml Glass flask equipped with a stirrer, 2.9g (0.015 mol) of BTFBE, 2.4g (0.015 mol) of p-AcO-St, 13.0g (0.03 mol) of MA-C6F, 3.9g (0.03 mol) of HEMA, and 5, 5-trifluoro-4-hydroxy-4- (trifluoromethyl) pentan-2-yl ester (manufactured by Central Glass Co., ltd.; hereinafter referred to as MA-BTHB-OH) 3.0g (0.01 mol) and 50.0g of MEK were charged at room temperature (about 20 ℃), and after degassing with stirring, the flask was purged with nitrogen and the flask was heated to an internal temperature of 79℃for overnight reaction. After 300g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. The precipitate was separated by filtration and dried under reduced pressure at 45℃to give 22.6g of a fluororesin precursor as a white solid in 90% yield.
< NMR measurement results >
The composition ratio of each structural unit of the fluororesin precursor 1 is expressed as a structural unit of BTFBE in terms of molar ratio: structural unit of p-AcO-St: structural unit of MA-C6F: structural unit of HEMA: structural unit of MA-BTHB-OH = 15:15:30:30:10. the fluorine atom content in the fluororesin precursor 1 was 40.9 mass% based on the structural unit.
[ 55]
< GPC measurement results >)
Mw＝7,800，Mw/Mn＝1.4
[ Synthesis of fluororesin 1 ]
Into a 500ml glass flask equipped with a stirrer, 1.22 g (hydroxyl equivalent 0.03 mol) of a fluororesin precursor, 0.21g (hydroxyl equivalent 0.0021 mol) of triethylamine, 60g of PGMEA and 4.26g (hydroxyl equivalent 0.03 mol) of Karenz AOI were added, and the mixture was reacted at 45℃for 4 hours. After the completion of the reaction, the reaction mixture was concentrated, 200g of n-heptane was added thereto, and a precipitate was precipitated. The precipitate was separated by filtration and dried under reduced pressure at 40℃to give 1.3 g of a fluororesin as a white solid in 85% yield.
[ 56]
＜ 13 C-NMR measurement results
In the fluororesin 1, the introduced amount (reaction rate) of the acrylic acid derivative derived from Karenz AOI and the remaining hydroxyl group amount (unreacted rate) are expressed as 99 in terms of a molar ratio: 1. in addition, it was confirmed that the composition ratio of each structural unit (structural unit of BTFBE, structural unit of p-AcO-St, structural unit of MA-C6F, structural unit of MA-BTHB-OH) which did not react with the crosslinking site was unchanged from that of the fluororesin precursor 1 used (the same as before the introduction of the crosslinking group). The fluorine atom content in the fluororesin 1 was 35.2 mass% based on the structural unit.
< GPC measurement results >)
Mw＝10,100，Mw/Mn＝1.5
[ Synthesis of fluororesin precursor 2 ]
Into a 500ml glass flask equipped with a stirrer, 2.9g (0.015 mol) of BTFBE, 2.4g (0.015 mol) of p-AcO-St, 10.0g (0.03 mol) of MA-C4F, 3.9g (0.03 mol) of HEMA, 3.0g (0.01 mol) of MA-BTHB-OH and 44.0g of MEK were charged, and after deaeration while stirring, the flask was purged with nitrogen and the temperature was raised to 79℃for overnight reaction. After 300g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. The precipitate was isolated by filtration and dried under reduced pressure at 45℃to give 2.1 g of a fluororesin precursor as a white solid in 90% yield.
< NMR measurement results >
The composition ratio of each structural unit of the fluororesin precursor 2 is expressed as a structural unit of BTFBE in terms of molar ratio: structural unit of p-AcO-St: structural unit of MA-C4F: structural unit of HEMA: structural unit of MA-BTHB-OH = 15:15:30:30:10. the fluorine atom content in the fluororesin precursor 2 was 36.1 mass% based on the structural unit.
[ 57]
< GPC measurement results >)
Mw＝7,700，Mw/Mn＝1.4
[ Synthesis of fluororesin 2 ]
To a 500ml glass flask equipped with a stirrer, 2.20 g (hydroxyl equivalent 0.03 mol) of a fluororesin precursor, 0.21g (hydroxyl equivalent 0.0021 mol) of triethylamine and 60g of PGMEA were added 4.26g (hydroxyl equivalent 0.03 mol) of Karenz AOI, and the mixture was reacted at 45℃for 4 hours. After the completion of the reaction, the reaction mixture was concentrated, 200g of n-heptane was added thereto, and a precipitate was precipitated. The precipitate was separated by filtration and dried under reduced pressure at 40℃to give 2.3 g of a fluororesin as a white solid in 87% yield.
[ 58]
/>
＜ 13 C-NMR measurement results
In the fluororesin 2, the amount of the acrylic acid derivative introduced (reaction rate) and the amount of the remaining hydroxyl groups (unreacted rate) derived from Karenz AOI are expressed as 98:2. in addition, it was confirmed that the composition ratio of each structural unit (structural unit of BTFBE, structural unit of p-AcO-St, structural unit of MA-C4F, structural unit of MA-BTHB-OH) which did not react with the crosslinking site was unchanged from that of the fluororesin precursor 2 used (the same as before the introduction of the crosslinking group). The fluorine atom content in the fluororesin 2 was 30.5 mass% based on the structural unit.
< GPC measurement results >)
Mw＝9,100，Mw/Mn＝1.4
[ Synthesis of fluororesin precursor 3 ]
Into a 500ml glass flask equipped with a stirrer, 7.2g (0.055 mol) of HEMA, 13.3g (0.045 mol) of MA-BTHB-OH and 40.0g (MEK) of HEMA were charged, and 0.84g (0.005 mol) of AIBN was added to the flask, followed by deaeration while stirring, and then the flask was purged with nitrogen gas, and the temperature was raised to 79℃for overnight reaction. After 300g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. The precipitate was isolated by filtration and dried under reduced pressure at 45℃to give 3.1 g of a fluororesin precursor as a white solid in 90% yield.
< NMR measurement results >
The composition ratio of each structural unit of the fluororesin precursor 3 is expressed as structural unit of HEMA in terms of molar ratio: structural unit of MA-BTHB-OH = 55:45. the fluorine atom content in the fluororesin precursor 3 was 25.1 mass% based on the structural unit.
[ 59]
< GPC measurement results >)
Mw＝6,700，Mw/Mn＝1.3
[ Synthesis of fluororesin 3 ]
Into a 500ml glass flask equipped with a stirrer, 3.18 g (hydroxyl equivalent: 0.055 mol) of a fluororesin precursor, 0.30g (hydroxyl equivalent: 0.0050 mol) of triethylamine, 60g of PGMEA and 7.42g (hydroxyl equivalent: 0.055 mol) of Karenz AOI were added, and the mixture was reacted at 45℃for 4 hours. After the completion of the reaction, the reaction mixture was concentrated, 200g of n-heptane was added thereto, and a precipitate was precipitated. The precipitate was separated by filtration and dried under reduced pressure at 40℃to give 3g of a fluororesin as a white solid in a yield of 84%.
[ chemical 60]
＜ 13 C-NMR measurement results
In the fluororesin 3, the amount of the acrylic acid derivative introduced (reaction rate) and the amount of the remaining hydroxyl groups (unreacted rate) derived from Karenz AOI are expressed as 98:2. in addition, it was confirmed that the composition ratio of each structural unit (structural unit of MA-BTHB-OH) which did not react with the crosslinking site was unchanged from that of the fluororesin precursor 3 used (the same as before the introduction of the crosslinking group). The fluorine atom content in the fluororesin 3 was 18.4 mass% based on the structural unit.
< GPC measurement results >)
Mw＝8,100，Mw/Mn＝1.4
[ fluororesin 4]
The fluororesin precursor 1 is used as the fluororesin 4. The fluorine atom content in the fluororesin 4 (fluororesin precursor 1) was 40.9 mass% based on the structural unit.
[ fluororesin 5]
The fluororesin precursor 2 is used as the fluororesin 5. The fluorine atom content in the fluororesin 5 (fluororesin precursor 2) was 36.1 mass% based on the structural unit.
[ Synthesis of fluororesin precursor 6 ]
Into a 500ml glass flask equipped with a stirrer, 1.0g (0.005 mol) of BTFBE, 8.0g (0.015 mol) of p-AcO-St, 4.3g (0.01 mol) of MA-C6F, 3.9g (0.03 mol) of HEMA, 1.5g (0.005 mol) of MA-BTHB-OH and 50.0g of MEK were charged, and after deaeration while stirring, the flask was purged with nitrogen and the temperature was raised to 79℃for overnight reaction. After 300g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. The precipitate was separated by filtration and dried under reduced pressure at 45℃to give 16.06g of a fluororesin precursor as a white solid in 90% yield.
< NMR measurement results >
The composition ratio of each structural unit of the fluororesin precursor 6 is expressed as a structural unit of BTFBE in terms of molar ratio: structural unit of p-AcO-St: structural unit of MA-C6F: structural unit of HEMA: structural unit of MA-BTHB-OH = 5:50:10:30:5. the fluorine atom content in the fluororesin precursor 6 was 19.3 mass% based on the structural unit.
[ chemical 61]
< GPC measurement results >)
Mw＝8,900，Mw/Mn＝1.5
[ Synthesis of fluororesin 6 ]
Into a 500ml glass flask equipped with a stirrer, 6.11 g (hydroxyl equivalent 0.015 mol) of a fluororesin precursor, 0.11g (hydroxyl equivalent 0.001 mol) of triethylamine, 60g of PGMEA and 2.13g (hydroxyl equivalent 0.015 mol) of Karenz AOI were added, and the mixture was reacted at 45℃for 4 hours. After the completion of the reaction, the reaction mixture was concentrated, 200g of n-heptane was added thereto, and a precipitate was precipitated. The precipitate was separated by filtration and dried under reduced pressure at 40℃to give 6.2 g of a fluororesin as a white solid in 90% yield.
[ 62]
/>
＜ 13 C-NMR measurement results
In the fluororesin 6, the amount of the acrylic acid derivative introduced (reaction rate) and the amount of the remaining hydroxyl groups (unreacted rate) derived from Karenz AOI are expressed as 99:1. in addition, it was confirmed that the composition ratio of each structural unit (structural unit of BTFBE, structural unit of p-AcO-St, structural unit of MA-C6F, structural unit of MA-BTHB-OH) which did not react with the crosslinking site was unchanged from that of the fluororesin precursor 6 used (the same as before the introduction of the crosslinking group). The fluorine atom content in the fluororesin 6 was 14.4 mass% based on the structural unit.
< GPC measurement results >)
Mw＝10,500，Mw/Mn＝1.5
[ Synthesis of fluororesin precursor 7 ]
Into a 500ml glass flask equipped with a stirrer, 2.0g (0.010 mol) of BTFBE, 0.5g (0.003 mol) of p-AcO-St, 34.5g (0.079 mol) of MA-C6F, 0.39g (0.003 mol) of HEMA, 1.5g (0.005 mol) of MA-BTHB-OH and 100.0g of MEK were charged, and after deaeration while stirring, the flask was purged with nitrogen and the temperature was raised to 79℃for overnight reaction. After 500g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. The precipitate was isolated by filtration and dried under reduced pressure at 45℃to give 7.2 g of a fluororesin precursor as a white solid in 90% yield.
< NMR measurement results >
The composition ratio of each structural unit of the fluororesin precursor 7 is expressed as a structural unit of BTFBE in terms of molar ratio: structural unit of p-AcO-St: structural unit of MA-C6F: structural unit of HEMA: structural unit of MA-BTHB-OH = 10:3:79:3:5. the fluorine atom content in the fluororesin precursor 7 was 56.1 mass% based on the structural unit.
[ 63]
< GPC measurement results >)
Mw＝8,800，Mw/Mn＝1.5
[ Synthesis of fluororesin 7 ]
Into a 500ml glass flask equipped with a stirrer, 7.30 g (hydroxyl equivalent 0.003 mol) of a fluororesin precursor, 0.21g (hydroxyl equivalent 0.00021 mol) of triethylamine, 100g of PGMEA and 0.42g (hydroxyl equivalent 0.03 mol) of Karenz AOI were added, and the mixture was reacted at 45℃for 4 hours. After the completion of the reaction, the reaction mixture was concentrated, 500g of n-heptane was added thereto, and a precipitate was precipitated. The precipitate was separated by filtration and dried under reduced pressure at 40℃to give 7.5 g of a fluororesin as a white solid in 95% yield.
[ 64]
＜ 13 C-NMR measurement results
In the fluororesin 7, the introduced amount (reaction rate) of the acrylic acid derivative derived from Karenz AOI and the remaining hydroxyl group amount (unreacted rate) are expressed as 99 in terms of a molar ratio: 1. in addition, it was confirmed that the composition ratio of each structural unit (structural unit of BTFBE, structural unit of p-AcO-St, structural unit of MA-C6F, structural unit of MA-BTHB-OH) which did not react with the crosslinking site was unchanged from that of the fluororesin precursor 7 used (the same as before the introduction of the crosslinking group). The fluorine atom content in the fluororesin 7 was 55.2 mass% based on the structural unit.
< GPC measurement results >)
Mw＝9,100，Mw/Mn＝1.5
[ Synthesis of fluororesin precursor 8 ]
Into a 500ml glass flask equipped with a stirrer, 2.9g (0.015 mol) of BTFBE, 2.4g (0.015 mol) of p-AcO-St, 13.0g (0.03 mol) of MA-C6F, 3.9g (0.03 mol) of HEMA, 3.0g (0.01 mol) of MA-BTHB-OH and 100.0g of MEK were charged, and after deaeration while stirring, the flask was purged with nitrogen and the temperature was raised to 81℃for overnight reaction. After 400g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. The precipitate was separated by filtration and dried under reduced pressure at 45℃to give 8.1 g of a fluororesin precursor as a white solid in 80% yield.
< NMR measurement results >
The composition ratio of each structural unit of the fluororesin precursor 8 is expressed as a structural unit of BTFBE in terms of molar ratio: structural unit of p-AcO-St: structural unit of MA-C6F: structural unit of HEMA: structural unit of MA-BTHB-OH = 15:15:30:30:10. the fluorine atom content in the fluororesin precursor 8 was 40.9 mass% based on the structural unit.
[ 65]
< GPC measurement results >)
Mw＝4,100，Mw/Mn＝1.3
[ Synthesis of fluororesin 8 ]
Into a 500ml glass flask equipped with a stirrer, 8.11 g (hydroxyl equivalent 0.03 mol) of a fluororesin precursor, 0.11g (hydroxyl equivalent 0.0021 mol) of triethylamine and 30g of PGMEA were charged with 2.13g (hydroxyl equivalent 0.03 mol) of Karenz AOI, and the mixture was reacted at 45℃for 4 hours. After the completion of the reaction, the reaction mixture was concentrated, 200g of n-heptane was added thereto, and a precipitate was precipitated. The precipitate was separated by filtration and dried under reduced pressure at 40℃to give 8.2 g of a fluororesin as a white solid in 85% yield.
[ chemical 66]
/>
＜ 13 C-NMR measurement results
In the fluororesin 8, the introduced amount (reaction rate) of the acrylic acid derivative derived from Karenz AOI and the remaining hydroxyl group amount (unreacted rate) are expressed as 99 in terms of a molar ratio: 1. in addition, it was confirmed that the composition ratio of each structural unit (structural unit of BTFBE, structural unit of p-AcO-St, structural unit of MA-C6F, structural unit of MA-BTHB-OH) which did not react with the crosslinking site was unchanged from that of the fluororesin precursor 8 used (the same as before the introduction of the crosslinking group). The fluorine atom content in the fluororesin 8 was 35.2 mass% based on the structural unit.
< GPC measurement results >)
Mw＝4,500，Mw/Mn＝1.4
[ Synthesis of fluororesin precursor 9 ]
Into a 500ml glass flask equipped with a stirrer, 2.9g (0.015 mol) of BTFBE, 2.4g (0.015 mol) of p-AcO-St, 13.0g (0.03 mol) of MA-C6F, 3.9g (0.03 mol) of HEMA, 3.0g (0.01 mol) of MA-BTHB-OH and 40.0g of MEK were charged, and after deaeration while stirring, the flask was purged with nitrogen and the temperature was raised to 70℃for overnight reaction. After 300g of n-heptane was added dropwise to the reaction system, a white precipitate was obtained. The precipitate was separated by filtration and dried under reduced pressure at 45℃to give 22.1g of a fluororesin precursor 9 as a white solid in 90% yield.
< NMR measurement results >
The composition ratio of each structural unit of the fluororesin precursor 9 is expressed as a structural unit of BTFBE in terms of molar ratio: structural unit of p-AcO-St: structural unit of MA-C6F: structural unit of HEMA: structural unit of MA-BTHB-OH = 15:15:30:30:10. the fluorine atom content in the fluororesin precursor 9 was 40.9 mass% based on the structural unit.
[ 67]
< GPC measurement results >)
Mw＝38,200，Mw/Mn＝1.8
[ Synthesis of fluororesin 9 ]
To a 500ml glass flask equipped with a stirrer, 9.22 g (hydroxyl equivalent 0.03 mol) of a fluororesin precursor, 0.21g (hydroxyl equivalent 0.0021 mol) of triethylamine, 60g of PGMEA and 4.26g (hydroxyl equivalent 0.03 mol) of Karenz AOI were added, and the mixture was reacted at 45℃for 4 hours. After the completion of the reaction, the reaction mixture was concentrated, 200g of n-heptane was added thereto, and a precipitate was precipitated. The precipitate was separated by filtration and dried under reduced pressure at 40℃to give 9.1 g of a fluororesin as a white solid in 80% yield.
[ chemical 68]
＜ 13 C-NMR measurement results
In the fluororesin 9, the introduced amount (reaction rate) of the acrylic acid derivative derived from Karenz AOI and the remaining hydroxyl group amount (unreacted rate) are expressed as 99 in terms of a molar ratio: 1. in addition, it was confirmed that the composition ratio of each structural unit (structural unit of BTFBE, structural unit of p-AcO-St, structural unit of MA-C6F, structural unit of MA-BTHB-OH) which did not react with the crosslinking site was unchanged from that of the fluororesin precursor 9 used (the same as before the introduction of the crosslinking group). The fluorine atom content in the fluororesin 9 was 35.2 mass% based on the structural unit.
< GPC measurement results >)
Mw＝45,300，Mw/Mn＝1.9
3. Preparation of photosensitive resin composition
The following shows the components used in the preparation of the photosensitive resin compositions of examples and comparative examples.
< ethylenically unsaturated Compound (A) >)
Ethylenically unsaturated compound: "DPHA" (dipentaerythritol hexaacrylate) manufactured by Japanese chemical Co., ltd
Photopolymerization initiator (B) >)
Photopolymerization initiator 1: irgacure OXE-01 manufactured by Basf Co "
Photopolymerization initiator 2: "DETXs" (2, 4-diethylthioxanthone) manufactured by Japanese chemical Co., ltd
Photopolymerization initiator 3: irgacure OXE-04 manufactured by Basf Co "
Alkali-soluble resin (C) >, and process for producing the same
Alkali-soluble resin: "ZAR-2050H" (Special BIS-A type epoxy acrylate, containing no fluorine atom) manufactured by Japanese chemical Co., td
< additive >)
And (3) a sealing agent: "KAYAMER PM-21" manufactured by Japanese chemical Co., ltd "
< chain transfer agent >)
Chain transfer agent: "Karenz MT-PE1" manufactured by Showa electric company "
[ preparation of photosensitive resin base composition liquid ]
A photosensitive resin base composition was prepared by mixing 2.0 parts by mass of Karenz MT-PE1 as a chain transfer agent, 27.0 parts by mass of DPHA as an ethylenically unsaturated compound (A), 18.0 parts by mass of ZAR-2050H as an alkali-soluble resin (C), 1.0 parts by mass of PM-21 as a bonding agent, and 50 parts by mass of PGMEA as a solvent, and filtering the obtained solution with a 0.2 μm membrane filter.
[ preparation of photosensitive resin composition ]
The photosensitive resin compositions of examples 1 to 26 and comparative examples 1 to 16 were prepared by adding the photosensitive resin base composition liquid and the above-mentioned components so that the ratio of the photosensitive resin base composition liquid to the other materials became the values shown in tables 1 to 4, and stirring and dissolving the components. Using the obtained photosensitive resin composition, evaluation was performed by the following method.
4. Fluorine component amount of surface
Coating films were produced using the photosensitive resin compositions of examples 1 to 26 and comparative examples 1 to 16, and the fluorine component amounts on the surfaces of the coating films were calculated, and evaluated and compared. The results are shown in tables 1 and 2.
[ formation of coating film ]
After cleaning a 10cm square alkali-free substrate with ultrapure water followed by acetone, the substrate was subjected to UV ozone treatment for 5 minutes using a UV ozone treatment apparatus. Next, using the photosensitive resin compositions of examples 1 to 26 and comparative examples 1 to 16, the obtained UV ozone-treated substrates were coated with a spin coater at a rotation speed of 1,000rpm, and heated on a hot plate at 100℃for 150 seconds to prepare coated films having a film thickness of 1. Mu.m.
[ evaluation and comparison of fluorine component amount ]
For the coating film, the F1s spectrum of the surface was measured by X-ray photoelectron spectroscopy (abbreviated as XPS), and the intensities were compared. XPS measurements were performed using JPS-9000MC manufactured by Japanese electronics Co. To confirm the unevenness of the coating film, the measurement was performed at 10 with the position changed, and the average, maximum, minimum, and difference between the maximum and minimum values are shown. The larger the value of the spectrum measured under the described conditions, the more covalent bonds containing fluorine are contained on the film surface. From this, it can be said that a large film contains more fluorine atoms on the film surface than a film whose measured value of the spectrum is smaller.
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Peaks derived from fluorine were observed on the surfaces of the coating films of examples 1 to 26 and comparative examples 1 to 16, and the intensities were 1600 to 3300cps. It was confirmed that the difference between the maximum value and the minimum value of the peak derived from fluorine observed on the surface of the coating film in examples 1 to 26 containing the fluorine resins 1 to 9 was 400, which is the maximum, and the difference between the maximum value and the minimum value was smaller than those in comparative examples 1 to 10 and 14 to 16.
From this, it was found that the fluorine component amount on the surface of the coating film was more uniform by containing the fluorine resins 1 to 9.
The peak intensities of fluorine-derived peaks observed on the surfaces of the coating films of comparative examples 11 to 13 containing no fluorine-containing resin (D) were smaller than those of examples 1 to 26, comparative examples 1 to 10, and comparative examples 14 to 16 containing the fluorine-containing resin (D). It was found that the fluorine component amount of the coating film surface was affected by the fluorine-containing resin (D).
The difference between the maximum value and the minimum value of the peak derived from fluorine observed on the surface of the coating film in examples 1 to 20 and 23 to 26 using the fluororesin 1 to 3 and 6 to 9 having the crosslinked site was smaller than in examples 21 and 22 using the fluororesin 4 or 5 having no crosslinked site.
5. Evaluation of barrier
[ Barrier formation ]
After cleaning a 10cm square ITO substrate with ultrapure water followed by acetone, the substrate was subjected to UV ozone treatment for 5 minutes using the UV ozone treatment apparatus. Next, using the resin compositions for study examples 1 to 26 and comparative examples 1 to 16, the obtained substrates after UV ozone treatment were coated with a spin coater at a rotation speed of 1,000rpm, and heated on a heating plate at 80 ℃ for 150 seconds, to form a fluororesin film having a film thickness of 1 μm and a comparative fluororesin film. The obtained resin film was irradiated with i-rays (365 nm wavelength) through a photomask having a line-to-space of 5 μm using a photomask alignment exposure machine (product of SUSS MicroTec corporation) to expose the resin film.
The cured film after exposure was subjected to evaluation of developer solubility and barrier property (sensitivity and resolution) and measurement of contact angle.
[ solubility of developer ]
The cured film after exposure on the ITO substrate was immersed in an alkaline developer at room temperature for 80 seconds, and the solubility in the alkaline developer was evaluated. An aqueous solution of 2.38 mass% tetramethylammonium hydroxide (hereinafter, sometimes referred to as TMAH) was used as the alkaline developer. The solubility of the barrier rib was evaluated by measuring the film thickness of the immersed barrier rib by a contact film thickness meter. The case where the barrier wall is completely dissolved is referred to as "soluble", and the case where the resist film remains undissolved is referred to as "insoluble".
Barrier property (sensitivity, resolution)
The optimal exposure Eop (mJ/cm) at the time of forming barrier rib which is the pattern of the lines and gaps is obtained 2 ) As an index of sensitivity.
Further, the obtained barrier pattern was observed with a laser microscope (VX-1100) (3000 times) to evaluate the resolution. The line edge roughness was not confirmed as "excellent", and the slightly confirmed line edge roughness was confirmed as "good", and the line edge roughness was remarkably confirmed as "unacceptable".
[ contact Angle ]
After the substrate having the cured film obtained by the above-described steps was heated at 230℃for 60 minutes, the contact angle of the surface of the cured film with respect to water and Propylene Glycol Monomethyl Ether Acetate (PGMEA) was measured at 20 points on the coating film using a contact angle meter (GMs-601 manufactured by Co., ltd.).
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The developing solution solubilities, barrier properties and contact angles of the barriers (cured films) prepared from the photosensitive resin compositions of examples 1 to 26 and comparative examples 1 to 16 were compared to each other, and the resultant was a junctionAs a result, regarding the solubility of the developer, in all examples and comparative examples, the unexposed portions were soluble and the exposed portions were insoluble, so that the photosensitive resin composition of the present invention was excellent in curability. In the barrier properties, the photosensitivity was 150 to 200mJ/cm in the examples and comparative examples 2 The resolution is "good" or "excellent". As for the resolution of the barrier ribs, it was found that examples 1 to 26 were equivalent or more excellent than comparative examples 1 to 16. Regarding liquid repellency, in examples 1 to 26 including the fluorine resins 1 to 9, the difference between the maximum value and the minimum value of the contact angle was small.
The contact angle of example 23 using the fluororesin 6 having a lower fluorine atom content was slightly smaller than that of other examples.
In example 24 using the fluororesin 7 having a slightly higher fluorine atom content, the line edge roughness ("good") was slightly confirmed, and the difference between the maximum value and the minimum value of the contact angle was slightly larger than in other examples.
The contact angle of example 25 using the fluororesin 8 having a slightly smaller molecular weight was slightly smaller than that of the other examples.
Example 26 using the fluororesin 9 having a slightly larger molecular weight slightly confirmed line edge roughness.
The contact angles of comparative examples 11 to 13 containing no fluorine-containing resin (D) were smaller than those of examples 1 to 26, comparative examples 1 to 10, and comparative examples 14 to 16 containing fluorine-containing resin (D).
The difference between the maximum value and the minimum value of the contact angle of comparative examples 14 and 15 in which the content of the resin (E) is large and comparative example 16 in which the content of the resin (E) is small is large as compared with the examples.

Claims (42)

1. A photosensitive resin composition comprising an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorine-containing resin (D) and a resin (E) having a structure represented by the following general formula (1)
When the fluorine-containing resin (D) is 100 parts by mass, 30 to 550 parts by mass of the resin (E) is contained;
[ chemical 1]
(in the general formula (1), ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and any number of hydrogen atoms of the alkyl group are substituted with fluorine atoms).
2. The photosensitive resin composition according to claim 1, wherein the resin (E) has a crosslinking site.
3. The photosensitive resin composition according to claim 1, wherein the fluorine atom content of the resin (E) is 15 to 60 mass%.
4. The photosensitive resin composition according to claim 1, wherein the content of the alkali-soluble resin (C) is 10 to 70 mass% with respect to all solid components of the photosensitive resin composition.
5. The photosensitive resin composition according to claim 1, wherein the content of the fluorine-containing resin (D) is 0.01 to 10 mass% with respect to all solid components of the photosensitive resin composition.
6. The photosensitive resin composition according to claim 1, wherein the content of the resin (E) is 0.01 to 10 mass% with respect to all solid components of the photosensitive resin composition.
7. The photosensitive resin composition according to claim 1, wherein the difference in fluorine atom content between the alkali-soluble resin (C) and the fluorine-containing resin (D) is 15 to 60 mass%.
8. The photosensitive resin composition according to claim 1, wherein the content of the structure represented by the general formula (1) contained in the resin (E) is 0.1 mol% or more and less than 50 mol% when the total amount of the structural units constituting the resin (E) is 100 mol%.
9. The photosensitive resin composition according to claim 1, wherein the structure represented by the general formula (1) is hexafluoroisopropanol group.
10. The photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the resin (E) is 5,000 to 40,000.
11. The photosensitive resin composition according to claim 1, further comprising at least 1 selected from the group consisting of a photoradical sensitizer, a chain transfer agent, an ultraviolet absorber, and a polymerization inhibitor.
12. The photosensitive resin composition according to claim 1, which is used for forming a partition wall.
13. A photosensitive resin composition comprising an ethylenically unsaturated compound (A), a photopolymerization initiator (B), an alkali-soluble resin (C), a fluorine-containing resin (D) and a resin (E) having a structure represented by the general formula (1), and
the resin (E) is a resin comprising a structural unit having a structure represented by the following general formula (1) and a structural unit having a crosslinking site;
[ chemical 2]
(in the general formula (1), ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and any number of hydrogen atoms of the alkyl group are substituted with fluorine atoms).
14. The photosensitive resin composition according to claim 13, wherein the resin (E) is contained in an amount of 30 to 550 parts by mass based on 100 parts by mass of the fluorine-containing resin (D).
15. The photosensitive resin composition according to claim 13, comprising a structural unit represented by the following general formula (5) as the structural unit having a crosslinking site;
[ chemical 3]
(in the general formula (5), R 5 、R 6 Each independently represents a hydrogen atom or a methyl group, W 2 Represents a 2-valent linking group, represents-O-, -O-C (=o) -, -C (=o) -O-, -O-C (=o) -NH-, -C (=o) -O-C (=o) -NH-, or-C (=o) -NH-, a 2 Represents a 2-valent linking group, and represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms or 3 to 10 carbon atoms, any number of hydrogen atoms in the alkylene group being capable of being bonded to a hydroxyl group or-O-C (=O) -CH 3 Substitution, A 3 Represents a 2-4 valent linking group, represents a linear hydrocarbon group having 1 to 10 carbon atoms, a branched hydrocarbon group having 3 to 10 carbon atoms or a cyclic hydrocarbon group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group may be represented by a hydroxyl group or-O-C (=O) -CH 3 Substituted, Y 2 、Y 3 The 2-valent linking groups are independently-O-or-NH-, n is an integer of 1 to 3, and r is 0 or 1).
16. The photosensitive resin composition according to claim 15, wherein the resin (E) is contained in an amount of 30 to 550 parts by mass based on 100 parts by mass of the fluorine-containing resin (D).
17. The photosensitive resin composition according to claim 13, wherein the resin (E) is a resin comprising a structural unit represented by the following general formula (1-1) and a structural unit represented by the following general formula (5);
[ chemical 4]
(in the general formula (1-1), ra is the same as Ra in the general formula (1), rc represents a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a fluoroalkyl group which are linear or branched and may include a cyclic structure, rd is a 2-valent or 3-valent organic group which is a group selected from a linear or branched aliphatic hydrocarbon group which may include a cyclic structure, an aromatic ring group or a complex substituent thereof, and part or all of the hydrogen atoms may be substituted with a fluorine atom or a hydroxyl group, t represents 1 or 2, and in the general formula (5), R 5 、R 6 Each independently represents a hydrogen atom or a methyl group, W 2 Represents a 2-valent linking group, represents-O-, -O-C (=o) -, -C (=o) -O-, -O-C (=o) -NH-, -C (=o) -O-C (=o) -NH-, or-C (=o) -NH-, a 2 Represents a 2-valent linking group, and represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms or 3 to 10 carbon atoms, any number of hydrogen atoms in the alkylene group being capable of being bonded to a hydroxyl group or-O-C (=O) -CH 3 Substitution, A 3 Represents a 2-4 valent linking group, represents a linear hydrocarbon group having 1 to 10 carbon atoms, a branched hydrocarbon group having 3 to 10 carbon atoms or a cyclic hydrocarbon group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group may be represented by a hydroxyl group or-O-C (=O) -CH 3 Substituted, Y 2 、Y 3 The 2-valent linking groups are independently-O-or-NH-, n is an integer of 1 to 3, and r is 0 or 1).
18. The photosensitive resin composition according to claim 17, wherein the resin (E) is contained in an amount of 30 to 550 parts by mass based on 100 parts by mass of the fluorine-containing resin (D).
19. The photosensitive resin composition according to claim 13, wherein the resin (E) is a resin comprising a structural unit represented by the following general formula (1-1), a structural unit represented by the following general formula (5), and a structural unit represented by the following general formula (6);
[ chemical 5]
(in the general formula (1-1), ra is the same as Ra in the general formula (1), rc represents a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a fluoroalkyl group which are linear or branched and may contain a cyclic structure, rd is an organic group having a valence of 2 or 3 and which is a group selected from a linear or branched aliphatic hydrocarbon group which may contain a cyclic structure, an aromatic ring group or a complex substituent thereof, and a part or all of the hydrogen atoms may be substituted with a fluorine atom or a hydroxyl group, t represents 1 or 2, and in the general formula (5), R 5 、R 6 Each independently represents a hydrogen atom or a methyl group, W 2 Represents a 2-valent linking group, represents-O-, -O-C (=o) -, -C (=o) -O-, -O-C (=o) -NH-, -C (=o) -O-C (=o) -NH-, or-C (=o) -NH-, a 2 Represents a 2-valent linking group, and represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms or 3 to 10 carbon atoms, any number of hydrogen atoms in the alkylene group being capable of being bonded to a hydroxyl group or-O-C (=O) -CH 3 Substitution, A 3 Represents a 2-4 valent linking group, represents a linear hydrocarbon group having 1 to 10 carbon atoms, a branched hydrocarbon group having 3 to 10 carbon atoms or a cyclic hydrocarbon group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group may be represented by a hydroxyl group or-O-C (=O) -CH 3 Substituted, Y 2 、Y 3 Represents a 2-valent linking group, each independently represents-O-or-NH-, n represents an integer from 1 to 3, and r represents 0 or 1; in the general formula (6), R 7 Represents a hydrogen atom or a methyl group, R 8 Represents a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic alkyl group having 3 to 15 carbon atoms, wherein any number of hydrogen atoms in the alkyl group are replaced with fluorine atoms).
20. The photosensitive resin composition according to claim 19, wherein the resin (E) is contained in an amount of 30 to 550 parts by mass based on 100 parts by mass of the fluorine-containing resin (D).
21. The photosensitive resin composition according to claim 13, wherein the fluorine atom content of the resin (E) is 15 to 60 mass%.
22. The photosensitive resin composition according to claim 13, wherein the content of the alkali-soluble resin (C) is 10 to 70 mass% with respect to all solid components of the photosensitive resin composition.
23. The photosensitive resin composition according to claim 13, wherein the content of the fluorine-containing resin (D) is 0.01 to 10 mass% with respect to all solid components of the photosensitive resin composition.
24. The photosensitive resin composition according to claim 13, wherein the content of the resin (E) is 0.01 to 10 mass% with respect to all solid components of the photosensitive resin composition.
25. The photosensitive resin composition according to claim 13, wherein a difference in fluorine atom content between the alkali-soluble resin (C) and the fluorine-containing resin (D) is 15 to 60 mass%.
26. The photosensitive resin composition according to claim 13, wherein the content of the structure represented by the general formula (1) contained in the resin (E) is 0.1 mol% or more and less than 50 mol% when the total amount of the structural units constituting the resin (E) is 100 mol%.
27. The photosensitive resin composition according to claim 13, wherein the structure represented by the general formula (1) is hexafluoroisopropanol group.
28. The photosensitive resin composition according to claim 13, wherein the weight average molecular weight of the resin (E) is 5,000 to 40,000.
29. The photosensitive resin composition according to claim 13, further comprising at least 1 selected from the group consisting of a photoradical sensitizer, a chain transfer agent, an ultraviolet absorber, and a polymerization inhibitor.
30. The photosensitive resin composition according to claim 13, which is used for forming a partition wall.
31. A resin film obtained from the photosensitive resin composition according to claim 1 or 13.
32. A cured product obtained by curing the resin film according to claim 31.
33. A partition wall comprising the hardened substance according to claim 32.
34. An organic electroluminescent element is provided with: the partition wall according to claim 33, and a light-emitting layer or a wavelength conversion layer disposed in a region partitioned by the partition wall.
35. A display provided with the partition wall according to claim 33.
36. A method for producing a cured product, comprising:
a film forming step of applying the photosensitive resin composition according to claim 1 or 13 on a substrate, and then heating, thereby obtaining a resin film; and
And an exposure step of exposing the resin film with high-energy rays.
37. A fluorine-containing resin comprising a structural unit having a structure represented by the following general formula (1) and a structural unit having a crosslinking site;
[ chemical 6]
(in the general formula (1), ra independently represents a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, or a fluorine atom, and any number of hydrogen atoms of the alkyl group are substituted with fluorine atoms).
38. The fluorine-containing resin according to claim 37, comprising a structural unit represented by the following general formula (5) as a structural unit having a crosslinking site;
[ chemical 7]
(in the general formula (5), R 5 、R 6 Each independently represents a hydrogen atom or a methyl group, W 2 Represents a 2-valent linking group, represents-O-, -O-C (=o) -, -C (=o) -O-, -O-C (=o) -NH-, -C (=o) -O-C (=o) -NH-, or-C (=o) -NH-, a 2 Represents a 2-valent linking group, and represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, 3 to 10 carbon atoms or 3 to 10 carbon atoms, any number of hydrogen atoms in the alkylene group being capable of being bonded to a hydroxyl group or-O-C (=O) -CH 3 Substitution, A 3 Represents a 2-4 valent linking group, represents a linear hydrocarbon group having 1 to 10 carbon atoms, a branched hydrocarbon group having 3 to 10 carbon atoms or a cyclic hydrocarbon group having 3 to 10 carbon atoms, and any number of hydrogen atoms in the hydrocarbon group may be represented by a hydroxyl group or-O-C (=O) -CH 3 Substituted, Y 2 、Y 3 The 2-valent linking groups are independently-O-or-NH-, n is an integer of 1 to 3, and r is 0 or 1).
39. A fluorine-containing resin according to claim 37, wherein the fluorine atom content is 15 to 60% by mass.
40. The fluorine-containing resin according to claim 37, wherein the content of the structure represented by the general formula (1) is 0.1 mol% or more and less than 50 mol% when the total amount of structural units constituting the resin is 100 mol%.
41. A fluorine-containing resin according to claim 37, wherein the weight-average molecular weight is 5,000 or more and 40,000 or less.
42. A polymer blend comprising the fluororesin of any one of claims 37 to 41.
CN202311030078.3A 2022-08-17 2023-08-16 Photosensitive resin composition Pending CN117590691A (en)

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KR20220080728A (en) 2019-11-06 2022-06-14 미쯔비시 케미컬 주식회사 Photosensitive resin composition, cured product, partition wall, organic electroluminescent element, color filter, and image display device

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