WO2022092155A1 - 含フッ素樹脂、撥液剤、感光性樹脂組成物、硬化物およびディスプレイ - Google Patents

含フッ素樹脂、撥液剤、感光性樹脂組成物、硬化物およびディスプレイ Download PDF

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Publication number
WO2022092155A1
WO2022092155A1 PCT/JP2021/039671 JP2021039671W WO2022092155A1 WO 2022092155 A1 WO2022092155 A1 WO 2022092155A1 JP 2021039671 W JP2021039671 W JP 2021039671W WO 2022092155 A1 WO2022092155 A1 WO 2022092155A1
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Prior art keywords
fluororesin
group
carbon atoms
formula
photosensitive resin
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PCT/JP2021/039671
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English (en)
French (fr)
Japanese (ja)
Inventor
啓太 服部
悠太 坂井田
勇希 古屋
譲 兼子
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セントラル硝子株式会社
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Priority to CN202180074320.XA priority Critical patent/CN116438218A/zh
Priority to JP2022559202A priority patent/JPWO2022092155A1/ja
Priority to KR1020237017117A priority patent/KR20230096006A/ko
Publication of WO2022092155A1 publication Critical patent/WO2022092155A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(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
    • 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
    • C08F220/42—Nitriles
    • 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
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present disclosure relates to fluororesins, liquid repellents, photosensitive resin compositions, cured products and displays.
  • an inkjet method is known as a method for forming an organic layer having a function such as light emission.
  • the inkjet method specifically, a method of solidifying the ink dropped from the nozzle into the concave portion of the pattern film having irregularities formed on the substrate, or a method of solidifying the ink dropped from the nozzle, or the parent liquid part and the ink which are the parts that get wet with the ink.
  • the liquid-repellent portion which is a portion for repelling ink, include a method in which ink droplets are dropped onto a pattern film formed on a substrate in advance and the ink is adhered only to the parent liquid portion.
  • two main methods can be adopted for producing the pattern film having such unevenness.
  • One is a photolithography method in which an exposed portion and an unexposed portion are formed by exposing the surface of a photosensitive resist film coated on a substrate in a pattern, and either portion is dissolved and removed with a developing solution.
  • the other is an inprint method that uses printing technology.
  • UV ozone treatment or oxygen plasma treatment After forming a patterned film having irregularities, it is common to perform UV ozone treatment or oxygen plasma treatment on the entire surface of the substrate. By this UV ozone treatment or oxygen plasma treatment, in particular, the residual organic matter in the recesses of the pattern film can be removed, and by reducing the uneven wetting of the dropped ink, it is possible to prevent the display element from malfunctioning.
  • the convex portion of the formed uneven pattern film is called a bank (partition wall), and the bank acts as a barrier to prevent the inks from mixing with each other when the ink is dropped into the concave portion of the pattern film.
  • the bank acts as a barrier to prevent the inks from mixing with each other when the ink is dropped into the concave portion of the pattern film.
  • the surface of the substrate is exposed in the concave portion of the pattern film, the surface of the substrate is required to be liquid-friendly to ink, and the upper surface of the bank is required to be liquid-repellent to ink. ..
  • a fluororesin is used as a resin for forming such a bank. Liquid repellency is improved by using a fluororesin.
  • Patent Document 1 contains, as a resist composition containing a fluororesin, a monomer unit formed from a monomer represented by the formula 1 and having a fluoroatomic content of 7 to 35% by mass.
  • a resist composition containing a fluororesin (A) and a photosensitive component that reacts with light having a wavelength of 100 to 600 nm, and the ratio of the fluororesin (A) to the total solid content of the resist composition is 0.1 to 0.1.
  • the photosensitive component is 30% by mass, and the photosensitive component reacts with a photoacid generator (B), an alkali-soluble resin (C) having a carboxyl group and / or a phenolic hydroxyl group, and a carboxyl group or a phenolic hydroxyl group by the action of an acid.
  • a resist composition comprising an acid cross-linking agent (D), which is a compound having two or more possible groups, is disclosed.
  • CH 2 C (R 1 ) COOXR f ...
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group
  • X represents an organic group containing no divalent fluorine atom having 1 to 6 carbon atoms
  • R f represents a divalent fluorine atom having 4 to 6 carbon atoms. Shows a perfluoroalkyl group.
  • Patent Document 2 as an ink-repellent agent containing a polymerization unit containing a fluorine atom, an alkyl group having 20 or less carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom (however, the alkyl group contains etheric oxygen. It consists of a polymer having a polymerization unit (b1) having a polymerization unit (b1) and a polymerization unit (b2) having an ethylenic double bond, having a fluorine content of 5 to 25% by mass and a number average molecular weight of 500.
  • An ink repellent agent characterized by being less than 10,000 is disclosed.
  • Patent Document 3 as a resist composition containing a fluororesin, it has a monomer unit formed from a monomer represented by the formula 1, has an ethylenic double bond, and has a fluoroatomic content.
  • a fluororesin (A) containing 7 to 35% by mass and a photosensitive component that reacts with light having a wavelength of 100 to 600 nm, wherein the fluororesin with respect to the total solid content of the resist composition ( The ratio of A) is 0.1 to 30% by mass, and the photosensitive component is an alkali-soluble resin having a photoradical initiator (E), an acidic group in one molecule, and two or more ethylenic double bonds.
  • a resist composition comprising (F) and is disclosed.
  • R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group
  • X represents an organic group containing no divalent fluorine atom having 1 to 6 carbon atoms
  • R f represents a divalent fluorine atom having 4 to 6 carbon atoms. Shows a perfluoroalkyl group.
  • Patent Document 4 describes, as a negative photosensitive resin composition containing an ink-repellent agent having a fluorine atom, a photocurable alkali-soluble resin or an alkali-soluble monomer (A) and a photoradical polymerization initiator (B). ), A photoacid generator (C), an acid curing agent (D), and a negative ink-repellent resin composition containing an ink-repellent agent (E) having a fluorine atom, wherein the ink-repellent agent ( A negative photosensitive resin composition characterized in that the content of the fluorine atom in E) is 1 to 40% by mass and the ink repellent (E) has an ethylenic double bond is disclosed. There is.
  • Patent Document 5 contains at least a fluororesin having a crosslinked moiety, a solvent, and a photopolymerization initiator as a photosensitive resin composition having good liquid repellency, and the fluororesin is a fluoropolymer.
  • a photosensitive resin composition comprising a repeating unit comprising a hydrocarbon having a above is disclosed.
  • An object of the present disclosure is to provide a fluororesin capable of producing a bank (partition wall) whose liquid repellency does not easily decrease even if UV ozone treatment or oxygen plasma treatment is performed.
  • the present inventors have conducted diligent studies in view of the above problems. As a result, we have found that the above problems can be solved by using a monomer having a triple bond in the side chain, and have reached the present disclosure.
  • the fluororesin-containing resin of the present disclosure is characterized by containing a repeating unit (U) containing a monomer (A) having a triple bond in the side chain as a monomer unit.
  • the fluororesin of the present disclosure preferably has a fluorine atom content of 5% by mass or more.
  • the fluororesin of the present disclosure preferably contains a fluorine atom in the side chain of at least a part of the above-mentioned monomer (A).
  • the triple bond is a carbon-nitrogen triple bond of a nitrile group.
  • At least a part of the above-mentioned monomer (A) preferably has a structure represented by the following formula (1) or formula (1').
  • CH 2 C (R 1 ) C ⁇ CR 2 ...
  • CH 2 C (R 1 ) XC ⁇ CR 2 ... (1')
  • R 1 represents a hydrogen atom, a fluorine atom or a methyl group.
  • X represents a divalent linking group, which is a linear chain having 1 to 10 carbon atoms and a carbon number of carbon atoms.
  • Represents a branched alkylene group of 3 to 10 or a cyclic alkylene group having 3 to 10 carbon atoms, in which any number of hydrogen atoms in the alkylene group are substituted with a hydroxyl group or —O—C ( O) —CH3 .
  • R2 may represent 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, and any number of hydrogen atoms in the alkyl group. May be substituted with a fluorine atom.
  • the structure represented by the above formula (1) or (1') is preferably the structure represented by the following formula (2) or formula (2').
  • CH 2 C (R 1 ) C ⁇ CR f ... (2)
  • CH 2 C (R 1 ) XC ⁇ CR f ... (2')
  • R 1 represents a hydrogen atom, a fluorine atom or a methyl group.
  • X represents a divalent linking group, which is a linear chain having 1 to 10 carbon atoms and a carbon number of carbon atoms.
  • R f may represent a linear perfluoroalkyl group having 1 to 6 carbon atoms, a branched group having 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group having 3 to 6 carbon atoms.
  • the repeating unit (U) is simply a monomer (A) and a monomer (B) having a structure represented by the following formula (3) or formula (3'). It is preferable to include it as a weight unit.
  • CH 2 C (R 1 ) COOR 2 ... (3)
  • CH 2 C (R 1 ) COOXR 2 ... (3')
  • R 1 represents a hydrogen atom, a fluorine atom or a methyl group.
  • X represents a divalent linking group, which is a linear chain having 1 to 10 carbon atoms and a carbon number of carbon atoms.
  • Represents a branched alkylene group of 3 to 10 or a cyclic alkylene group having 3 to 10 carbon atoms, in which any number of hydrogen atoms in the alkylene group are substituted with a hydroxyl group or —O—C ( O) —CH3 .
  • R2 may represent 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, and any number of hydrogen atoms in the alkyl group. May be substituted with a fluorine atom.
  • the structure represented by the above formula (3) or the formula (3') is preferably the structure represented by the following formula (4) or the formula (4').
  • CH 2 C (R 1 ) COOR f ... (4)
  • CH 2 C (R 1 ) COOXR f ... (4')
  • R 1 represents a hydrogen atom, a fluorine atom or a methyl group.
  • X represents a divalent linking group, which is a linear chain having 1 to 10 carbon atoms and a carbon number of carbon atoms.
  • R f may represent a linear perfluoroalkyl group having 1 to 6 carbon atoms, a branched group having 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group having 3 to 6 carbon atoms.
  • the liquid repellent of the present disclosure is characterized by containing the above-mentioned fluororesin containing the present disclosure.
  • the photosensitive resin composition of the present disclosure is characterized by containing at least the fluororesin-containing resin of the present disclosure, a solvent, and a photopolymerization initiator.
  • the photosensitive resin composition of the present disclosure preferably further contains a cross-linking agent and an alkali-soluble resin.
  • the photosensitive resin composition of the present disclosure is preferably used for forming a partition wall.
  • the cured product of the present disclosure is characterized in that the photosensitive resin composition of the present disclosure is cured.
  • the display of this disclosure is The partition wall made of the cured product of the present disclosure and It is characterized by including a light emitting element including a light emitting layer arranged in a region partitioned by the partition wall.
  • the display of the present disclosure is preferably an organic EL display or a quantum dot display.
  • bank and “partition wall” are synonyms, and unless otherwise noted, they mean a convex portion of a pattern film having irregularities in an inkjet method.
  • the fluororesin-containing resin of the present disclosure is characterized by containing a repeating unit (U) containing a monomer (A) having a triple bond in the side chain as a monomer unit.
  • a bank (partition wall) having sufficiently high liquid repellency can be produced. Further, the prepared bank (partition wall) does not easily deteriorate in liquid repellency even if it is subjected to UV ozone treatment or oxygen plasma treatment.
  • the reason why a bank (partition wall) having sufficiently high liquid repellency can be produced is expected to be as follows. First, when the fluorine-containing alkyl group is surface segregated, the liquid repellency is improved. As will be described later, when a bank (partition wall) is produced using the fluororesin of the present disclosure, after forming a pattern film, UV ozone treatment or oxygen plasma treatment is performed, and then heat treatment is performed.
  • the ⁇ electrons of the triple bond and the -CH, -OH, and -NH bonds interact with each other.
  • the functional group of is immobilized.
  • a fluorine-containing alkyl group having a weak interaction with ⁇ electrons of a triple bond tends to segregate on the surface. Subsequent heating is thought to promote rearrangement and improve liquid repellency.
  • the term "monomer (A) having a triple bond in the side chain” means a single having a triple bond at a position that becomes the side chain of the polymer when the monomer (A) forms a polymer. It means a polymer.
  • the "repeating unit (U)” means a monomer unit constituting the main chain of the fluororesin and a plurality of monomer units existing in the main chain. ..
  • the repeating unit (U) may continuously form the main chain of the fluororesin, and the fluororesin so that another monomer unit exists between the repeating units (U). May constitute the main chain of. Further, a monomer unit other than the repeating unit (U) may be present at the end of the main chain of the fluororesin.
  • the fluororesin of the present disclosure preferably has a fluorine atom content of 5% by mass or more.
  • the content of fluorine atoms is preferably 50% by mass or less. When the content of fluorine atoms is 5% by mass or more, a bank having higher liquid repellency can be produced.
  • the "content of fluorine atom of fluororesin” is the molar ratio of the monomers constituting the fluororesin measured by NMR (nuclear magnetic resonance spectroscopy), and the monomers constituting the fluororesin. It means a value calculated from the molecular weight of the above and the content of fluorine contained in the monomer.
  • a method for measuring the fluorine content when the fluororesin is a resin obtained by polymerizing 1,1-bistrifluoromethylbutadiene, 4-hydroxystyrene and 2- (perfluorohexyl) ethyl methacrylate will be described. do.
  • the ratio of each composition is calculated by NMR measurement of the fluororesin (molar ratio).
  • (Ii) Multiply the molecular weight (Mw) of the monomer of each composition of the fluororesin by the molar ratio, and add the obtained values to obtain the total value.
  • the weight ratio (wt%) of each composition is calculated from the total value.
  • the molecular weight of 1,1-bistrifluoromethylbutadiene is 190, the molecular weight of 1,1-bistrifluoromethylbutadiene is 120, and the molecular weight of 2- (perfluorohexyl) ethyl methacrylate is 432.
  • the monomer (A) has a structure represented by the following formula (1) or formula (1').
  • CH 2 C (R 1 ) C ⁇ CR 2 ...
  • CH 2 C (R 1 ) XC ⁇ CR 2 ... (1')
  • R 1 represents a hydrogen atom, a fluorine atom or a methyl group.
  • X represents a divalent linking group, which is a linear chain having 1 to 10 carbon atoms and a carbon number of carbon atoms.
  • Represents a branched alkylene group of 3 to 10 or a cyclic alkylene group having 3 to 10 carbon atoms, in which any number of hydrogen atoms in the alkylene group are substituted with a hydroxyl group or —O—C ( O) —CH3 .
  • R2 may represent 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, and any number of hydrogen atoms in the alkyl group. May be substituted with a fluorine atom.
  • the structure represented by the above formula (1) or (1') is preferably the structure represented by the following formula (2) or formula (2').
  • CH 2 C (R 1 ) C ⁇ CR f ... (2)
  • CH 2 C (R 1 ) XC ⁇ CR f ... (2')
  • R 1 represents a hydrogen atom, a fluorine atom or a methyl group.
  • X represents a divalent linking group, which is a linear chain having 1 to 10 carbon atoms and a carbon number of carbon atoms.
  • R f may represent a linear perfluoroalkyl group having 1 to 6 carbon atoms, a branched group having 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group having 3 to 6 carbon atoms.
  • the repeating unit (U) is the above-mentioned monomer (A) and the monomer (B) having a structure represented by the following formula (3) or formula (3'). It is preferably contained as a monomer unit.
  • R 1 represents a hydrogen atom, a fluorine atom or a methyl group.
  • R2 may represent 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, and any number of hydrogen atoms in the alkyl group. May be substituted with a fluorine atom.
  • the monomer represented by the formulas (3) and (3') preferably has a structure represented by the following formulas (4) and (4').
  • R 1 represents a hydrogen atom, a fluorine atom or a methyl group.
  • R f may represent a linear perfluoroalkyl group having 1 to 6 carbon atoms, a branched group having 3 to 6 carbon atoms, or a cyclic perfluoroalkyl group having 3 to 6 carbon atoms.
  • the repeating unit (U) of the fluororesin of the present disclosure is the formula (1), the formula (1'), the formula (2), the formula (2'), the formula (3), the formula (3'), the formula (4). ) And two or more of the structures represented by the formula (4') of different types, R 1 , R 2 , R f and X may be the same or different in each structure. May be.
  • the side chain of at least a part of the monomer (A) contains a fluorine atom.
  • the fluorine atom may be arranged at a position that becomes a side chain in the structure represented by the above formula (1), formula (1'), formula (2) or formula (2'), and in other structures. It may be arranged at a position that becomes a side chain.
  • the fluorine atom may be arranged at a position that becomes a side chain in the structure represented by the above formula (1), formula (1'), formula (2) or formula (2'), and in other structures. It may be arranged at a position that becomes a side chain.
  • the molecular weight of the fluororesin of the present disclosure is a mass average molecular weight measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, and is preferably 1,000 or more and 1,000,000 or less, more preferably. Is 2,000 or more and 500,000 or less, and particularly preferably 3,000 or more and 100,000 or less. If the molecular weight is less than 1,000, the strength of the fluororesin film or the bank for organic EL to be formed tends to decrease, and if the molecular weight is more than 1,000,000, the solubility in a solvent is insufficient and the fluorine-containing by coating tends to decrease. It may be difficult to form a resin film.
  • GPC gel permeation chromatography
  • the degree of dispersion (Mw / Mn) is preferably 1.01 to 5.00, more preferably 1.01 to 4.00, and particularly preferably 1.01 to 3.00.
  • the fluororesin-containing resin of the present disclosure can be used for a liquid repellent agent or a photosensitive resin composition.
  • the photosensitive resin composition of the present disclosure is characterized by containing at least the fluororesin-containing resin of the present disclosure, a solvent, and a photopolymerization initiator.
  • the photosensitive resin composition of the present disclosure can be used to form a bank (partition wall). Since the fluororesin-containing resin of the present disclosure is contained, a bank (partition wall) having sufficiently high liquid repellency can be produced. Further, the prepared bank (partition wall) does not easily deteriorate in liquid repellency even if it is subjected to UV ozone treatment or oxygen plasma treatment.
  • the solvent contained in the photosensitive resin composition of the present disclosure is not particularly limited as long as the fluororesin is soluble, but ketones, alcohols, polyhydric alcohols and derivatives thereof, ethers, esters, aromatics. Examples thereof include a system solvent and a fluororesin. These may be used alone or in combination of two or more.
  • ketones include acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl isoamyl ketone, 2-heptanone cyclopentanone, methyl isobutyl ketone, methyl isopentyl ketone, and 2-heptanone.
  • alcohols include isopropanol, butanol, isobutanol, n-pentanol, isopentanol, tert-pentanol, 4-methyl-2-pentanol, 3-methyl-3-pentanol, 2, 3-Dimethyl-2-pentanol, n-hexanol, n-heptanol, 2-heptanol, n-octanol, n-decanol, s-amyl alcohol, t-amyl alcohol, isoamyl alcohol, 2-ethyl-1-butanol, Examples include lauryl alcohol, hexyl decanol, and oleyl alcohol.
  • polyhydric alcohols and their derivatives include ethylene glycol, ethylene glycol monoacetate, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, and propylene glycol monomethyl ether (PGME).
  • PGME propylene glycol monomethyl ether
  • ethers include diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, anisole and the like.
  • esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ⁇ -butyrolactone and the like.
  • aromatic solvent include xylene and toluene.
  • fluorine-based solvent examples include chlorofluorocarbons, alternative chlorofluorocarbons, perfluoro compounds, hexafluoroisopropyl alcohol and the like.
  • turpentine-based petroleum naphtha solvent a paraffin-based solvent, or the like, which is a high boiling point weak solvent, can be used for the purpose of improving the coatability.
  • the solvents are methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, propylene glycol, propylene glycol monoacetate, and propylene glycol monomethyl.
  • PGME Propylene Glycol Monomethyl Ether Acetate
  • PMEA Propylene Glycol Monomethyl Ether Acetate
  • Dipropylene Glycol Dipropylene Glycol Monoacetate Monomethyl Ether, Dipropylene Glycol Monoacetate Monoethyl Ether, Dipropylene Glycol Monoacetate Monopropyl Ether, Dipropylene Glycol Monoacetate Mono Butyl ether, dipropylene glycol monoacetate monophenyl ether, 1,4-dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ⁇ -butyrolactone and hexafluoroisopropyl alcohol It is preferably at least one selected from the group consisting of.
  • PGMEA propylene glycol monomethyl ether acetate
  • PGME propylene glycol monomethyl ether
  • cyclohexanone ethyl lactate, butyl acetate and ⁇ -butyrolactone
  • the amount of the solvent in the photosensitive resin composition of the present disclosure is 100 parts by mass of the concentration of the fluororesin (however, when the photosensitive resin composition contains an alkali-soluble resin described later, the concentration of the resin combined) is 100 parts by mass. On the other hand, it is preferably in the range of 50 parts by mass or more and 2,000 parts by mass or less. More preferably, it is 100 parts by mass or more and 1,000 parts by mass or less.
  • the photopolymerization initiator contained in the photosensitive resin composition of the present disclosure is particularly limited as long as it polymerizes a monomer having a polymerizable double bond by a high energy ray such as an electromagnetic wave or an electron beam.
  • a known photopolymerization initiator can be used.
  • a photo-radical initiator or a photoacid initiator can be used, and these may be used alone, or a photo-radical initiator and a photoacid initiator may be used in combination, or two types thereof.
  • the above photoradical initiator or photoacid initiator may be mixed and used. Further, by using an additive together with the photopolymerization initiator, it is possible to carry out living polymerization in some cases, and a known additive can be used.
  • photoradical initiator specifically, an intramolecular cleavage type in which a bond in the molecule is cleaved by absorption of an electromagnetic wave or an electron beam to generate a radical, or a hydrogen donor such as a tertiary amine or ether is used in combination. It can be classified into a hydrogen extraction type that generates radicals, and any of them may be used. Photoradical initiators other than those listed above can also be used.
  • photoradical initiator examples include benzophenone-based, acetophenone-based, diketone-based, acylphosphine oxide-based, quinone-based, and acyloin-based.
  • benzophenone system examples include benzophenone, 4-hydroxybenzophenone, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis (diethylamino) benzophenone. And so on. Of these, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, and 4,4'-bis (diethylamino) benzophenone are preferable.
  • acetophenone system examples include acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, and p-methoxyacetophenone, 2 -Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanol, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one and the like can be mentioned. Of these, p-dimethylaminoacetophenone and p-methoxyacetophenone are preferable.
  • diketone system examples include 4,4'-dimethoxybenzyl, methyl benzoylate, and 9,10-phenanthrenequinone. Of these, 4,4'-dimethoxybenzyl and methyl benzoyl formate are preferable.
  • acylphosphine oxide system examples include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
  • quinone system examples include anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone. Of these, camphorquinone and 1,4-naphthoquinone are preferable.
  • acyloin system examples include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Of these, benzoin and benzoin methyl ether are preferable.
  • a benzophenone type As the photoradical initiator, a benzophenone type, an acetophenone type, or a diketone type is preferable, and a benzophenone type is more preferable.
  • the preferred ones are those manufactured by BAS Co., Ltd.
  • Product names: Irgacure 127, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Lugacure 907, Irgacure 2959, Irgacure OXE-01, Darocure. 1173, radical TPO and the like can be mentioned.
  • Irgacure 651 and Irgacure 369 are more preferable.
  • photoacid initiator examples include aromatic sulfonic acid, aromatic iodonium, aromatic diazonium, aromatic ammonium, thianthrenium, thioxanthonium, (2,4-cyclopentadiene-1-yl) (1-yl).
  • Methylethylbenzene) Onium consisting of a pair of at least one cation selected from the group consisting of iron and at least one anion selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, pentafluorophenylborate. It is salt.
  • bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate bis [4- (diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, and diphenyliodonium hexafluorophosphate are particularly preferable.
  • Examples of commercially available photoacid initiators include product names manufactured by Sun Apro Co., Ltd .: CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S, and product names manufactured by Dow Chemical Japan Co., Ltd .: Cyracure Photocuring Initiator UVI-6990, Cyracure Photocuring Initiator UVI-6992, Cyracure Photocuring Initiator UVI-6996, Product Names manufactured by ADEKA Corporation: ADEKA PTOMER SP-150, ADEKA PTOMER SP-152, ADEKA Optomer SP-170, ADEKA CORPORATION SP-172, ADEKA CORPORATION SP-300, Product names manufactured by Nippon Soda Co., Ltd .: CI-5102, CI-2855, Product names manufactured by Sanshin Chemical Industry Co., Ltd .: Sun Aid SI -60L, Sun Aid SI-80L, Sun Aid SI-100L, Sun Aid SI-110L, Sun Aid SI
  • the content of the photopolymerization initiator in the photosensitive resin composition of the present disclosure is a fluororesin (however, when the photosensitive resin composition contains an alkali-soluble resin described later, the total concentration of the resin) 100. It is preferably 0.1 part by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less with respect to the mass part. If the content of the photopolymerization initiator is less than 0.1 part by mass, the cross-linking effect tends not to be sufficiently obtained, and if it exceeds 30 parts by mass, the resolution and sensitivity tend to decrease.
  • the photosensitive resin composition of the present disclosure contains a cross-linking agent, an alkali-soluble resin, a naphthoquinonediazide group-containing compound, a basic compound, and other additives. It may be included.
  • the cross-linking agent contained in the photosensitive resin composition of the present disclosure reacts with the repeating unit (U) of the fluororesin to allow the resin to form a cross-linked structure and improve the mechanical strength of the film to be formed. be able to.
  • a known cross-linking agent can be used. Specifically, an amino group-containing compound such as melamine, acetoguanamine, benzoguanamine, urea, ethyleneurea, propyleneurea, or glycoluril is reacted with formaldehyde or formaldehyde and a lower alcohol. Examples thereof include compounds in which the hydrogen atom of the amino group is replaced with a hydroxymethyl group or a lower alkoxymethyl group, a polyfunctional epoxy compound, a polyfunctional oxetane compound, a polyfunctional isocyanate compound, a polyfunctional acrylate compound and the like.
  • the one using melamine was used as a melamine-based cross-linking agent
  • the one using urea was used as a urea-based cross-linking agent
  • the one using alkylene urea such as ethylene urea and propylene urea was used as an alkylene urea-based cross-linking agent and glycol uryl.
  • the one is called a glycoluria-based cross-linking agent.
  • These cross-linking agents may be used alone or in combination of two or more.
  • the cross-linking agent is preferably at least one selected from these cross-linking agents, and a glycoluril-based cross-linking agent and a polyfunctional acrylate compound are particularly preferable.
  • melamine-based cross-linking agent examples include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like, and hexamethoxymethyl melamine is preferable.
  • urea-based cross-linking agent examples include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, with bismethoxymethylurea being preferred.
  • alkylene urea-based cross-linking agent examples include mono and / or dihydroxymethylated ethylene urea, mono and / or dimethoxymethylated ethylene urea, mono and / or diethoxymethylated ethylene urea, mono and / or dipropoxymethylated ethylene.
  • Ethylene urea-based cross-linking agents such as urea, mono and / or dibutoxymethylated ethyleneurea; mono and / or dihydroxymethylated propylene urea, mono and / or dimethoxymethylated propylene urea, mono and / or diethoxymethylated propylene urea.
  • Glycol uryl-based cross-linking agents include, for example, mono, di, tri and / or tetrahydroxymethylated glycol uryl, mono, di, tri and / or tetramethoxymethylated glycol uri, mono, di, tri and / or tetraethoxymethyl.
  • Glycol uryl, mono, di, tri and / or tetrapropoxymethylated glycol uryl, mono, di, tri and / or tetrabutoxymethylated glycol uryl and the like can be mentioned.
  • polyfunctional acrylate compound examples include polyfunctional acrylates (for example, product names manufactured by Shin-Nakamura Chemical Industry Co., Ltd .: A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD- TMP), polyethylene glycol diacrylate (for example, product name manufactured by Shin Nakamura Chemical Industry Co., Ltd .: A-200, A-400, A-600), urethane acrylate (for example, product name manufactured by Shin Nakamura Chemical Industry Co., Ltd .: UA-122P, UA-4HA, UA-6HA, UA-6LPA, UA-11003H, UA-53H, UA-4200, UA-200PA, UA-33H, UA-7100, UA-7200), pentaerythritol tetraacrylate, etc. Can be mentioned.
  • polyfunctional acrylates for example, product names manufactured by Shin-Nakamura Chemical Industry Co., Ltd .: A-TM
  • Preferred polyfunctional acrylate compounds are exemplified below.
  • the content of the cross-linking agent in the photosensitive resin composition of the present disclosure is 100 parts by mass of a fluororesin (however, when the photosensitive resin composition contains an alkali-soluble resin described later, the total concentration of the resin) is 100 parts by mass. It is preferably 10 parts by mass or more and 300 parts by mass or less, and more preferably 50 parts by mass or more and 200 parts by mass or less. If the content of the cross-linking agent is less than 10 parts by mass, the cross-linking effect tends not to be sufficiently obtained, and if it exceeds 300 parts by mass, the resolution and sensitivity tend to decrease.
  • the shape of the bank obtained from the photosensitive resin composition of the present disclosure can be improved.
  • alkali-soluble resin examples include an alkali-soluble novolak resin.
  • the alkali-soluble novolak resin can be obtained by condensing phenols and aldehydes in the presence of an acidic catalyst.
  • phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, and 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, Fluoroglucinol, Timor, Isotimol and the like can be exemplified. These phenols may be used alone or in combination of two or more.
  • aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, ⁇ -phenylpropylaldehyde, ⁇ -phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, and p-.
  • Examples thereof include hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, nitrobenzaldehyde, furfural, glyoxal, glutaaldehyde, terephthalaldehyde, isophthalaldehyde and the like.
  • Specific examples of the acid catalyst include hydrochloric acid, nitrate, sulfuric acid, phosphoric acid, phosphite, formic acid, oxalic acid, acetic acid, methanesulfonic acid, diethylsulfate, p-toluenesulfonic acid and the like. These acid catalysts may be used alone or in combination of two or more.
  • an acid-modified epoxy acrylate system can be mentioned.
  • an acid-modified epoxy acrylate system for example, product names manufactured by Nippon Kayaku Co., Ltd .: CCR-1218H, CCR-1159H, CCR-1222H, CCR-1291H, CCR-1235, PCR-1050, TCR-1335H, UXE -3024, ZAR-1035, ZAR-2001H, ZFR-1185, ZCR-1569H and the like can be used.
  • the mass average molecular weight of the alkali-soluble resin component is preferably 1,000 to 50,000 from the viewpoint of developability and resolvability of the photosensitive resin composition.
  • the content of the alkali-soluble resin in the photosensitive resin composition of the present disclosure is preferably 500 parts by mass or more and 10,000 parts by mass or less with respect to 100 parts by mass of the fluororesin, and more preferably 1,000 parts by mass. More than 7,000 parts by mass or less.
  • the fluororesin of the present disclosure tends to have insufficient liquid repellency to the ink after UV ozone treatment or oxygen plasma treatment.
  • the shape of the bank obtained from the photosensitive resin composition of the present disclosure can be improved.
  • the naphthoquinone diazide group-containing compound is not particularly limited, and a compound usually used as a photosensitive component of an i-line resist composition can be used.
  • naphthoquinone diazide group-containing compound examples include naphthoquinone-1,2-diazide-4-sulfonic acid ester compound, naphthoquinone-1,2-diazide-5-sulfonic acid ester compound, and naphthoquinone-1,2-diazide-.
  • Examples thereof include a 6-sulfonic acid ester compound, a naphthoquinone-1,2-diazide sulfonic acid ester compound, an orthobenzoquinone diazido sulfonic acid ester compound, and an orthoanthraquinone diazido sulfonic acid ester compound.
  • naphthoquinone-1,2-diazide-4-sulfonic acid ester compound naphthoquinone-1,2-diazide-5-sulfonic acid ester compound, and naphthoquinone-1,2-diazide-6-sulfone are excellent in solubility.
  • Acid ester compounds are preferred. These compounds may be used alone or in combination of two or more.
  • the content of the naphthoquinone diazide group-containing compound in the photosensitive resin composition of the present disclosure is a fluororesin (however, when the photosensitive resin composition contains the above-mentioned alkali-soluble resin, the total concentration of the resin). It is preferably 10 parts by mass to 60 parts by mass, and more preferably 20 parts by mass to 50 parts by mass with respect to 100 parts by mass. If it exceeds 60 parts by weight, it tends to be difficult to obtain the sensitivity as a photosensitive resin composition.
  • the acid generated by the photoacid generator acts to slow down the diffusion rate when the acid is diffused into the film of the photosensitive resin composition of the present disclosure. be.
  • the acid diffusion distance can be adjusted and the shape of the bank can be improved.
  • the bank is less likely to be deformed even if the leaving time from bank formation to exposure is long, and a bank with a desired accuracy can be stably formed.
  • Examples of the basic compound include aliphatic amines, aromatic amines, heterocyclic amines, and aliphatic polycyclic amines. Among them, aliphatic amines are preferable, and specific examples thereof include secondary or tertiary aliphatic amines and alkyl alcohol amines. These basic compounds may be used alone or in combination of two or more.
  • aliphatic amines examples include alkyl amines or alkyl alcohol amines in which at least one hydrogen atom of ammonia (NH 3 ) is replaced with an alkyl group or a hydroxyalkyl group having 12 or less carbon atoms.
  • Specific examples thereof include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, and tri-n-octylamine.
  • dialkylamines, trialkylamines and alkylalcoholamines are preferable, and alkylalcoholamines are more preferable.
  • alkyl alcohol amines triethanolamine and triisopropanolamine are particularly preferable.
  • aromatic amines and heterocyclic amines include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4 -Methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N , N-dimethyltoluidine and other aniline derivatives, 1,5-diazabicyclo [4.3.0] nona-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-en, 1,4 -Diazabicyclo [2.2.2] Octane, pyridine, bipyridine, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline and other heterocyclic amines, bis (1,
  • the content of the basic compound is 100% by mass of a fluororesin (however, when the above-mentioned alkali-soluble resin is contained in the photosensitive resin composition, the concentration of the resin is combined). It is preferably 0.001 part to 2 parts by mass, and more preferably 0.01 part by mass to 1 part by mass with respect to the part. If the blending amount of the basic compound is less than 0.001 part by mass, it becomes difficult to sufficiently obtain the effect as an additive, and if it exceeds 2 parts by mass, the resolution and sensitivity tend to decrease.
  • the photosensitive resin composition of the present disclosure may contain other additives, if necessary.
  • Other additives include various additives such as dissolution inhibitors, plasticizers, stabilizers, colorants, surfactants, thickeners, leveling agents, defoamers, compatibilizers, adhesives, and antioxidants. be able to. These other additives may be known.
  • the surfactant may be either a fluorine-based or a silicon-based surfactant (a fluorine-based surfactant and a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom), or two types. It is preferable to contain the above.
  • the method for forming the partition wall may include (1) a film forming step, (2) an exposure step, and (3) a developing step. Each process will be described below.
  • the photosensitive resin composition of the present disclosure is applied to a substrate and then heated to form the photosensitive resin composition into a fluororesin film.
  • the heating conditions are not particularly limited, but are preferably 80 to 100 ° C. and 60 to 200 seconds. Thereby, the solvent and the like contained in the photosensitive resin composition can be removed.
  • a silicon wafer, metal, glass, an ITO substrate, or the like can be used.
  • an organic or inorganic film may be provided on the substrate in advance.
  • there may be an antireflection film, an underlayer of a multilayer resist, or a pattern may be formed on the underlayer.
  • the substrate may be cleaned in advance. For example, it can be washed with ultrapure water, acetone, alcohol (methanol, ethanol, isopropyl alcohol) or the like.
  • a known method such as spin coating can be used as a method for applying the photosensitive resin composition of the present disclosure to the substrate.
  • the high energy ray is preferably at least one selected from the group consisting of ultraviolet rays, gamma rays, X-rays, and ⁇ rays.
  • the exposure amount of the high energy ray is preferably 1 mJ / cm 2 or more and 200 mJ / cm 2 or less, and more preferably 10 mJ / cm 2 or more and 100 mJ / cm 2 or less.
  • the fluororesin film after the exposure step is developed with an alkaline aqueous solution to obtain a fluororesin pattern film. That is, either the fluororesin-containing film exposed portion or the film unexposed portion is dissolved in an alkaline aqueous solution to obtain a fluororesin-containing resin pattern film.
  • TMAH tetramethylammonium hydroxide
  • TBAH tetrabutylammonium hydroxide
  • the concentration thereof is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 2% by mass or more and 3% by mass or less. ..
  • a known method can be used, and examples thereof include a dip method, a paddle method, and a spray method.
  • the developing time (time in which the developing solution comes into contact with the fluororesin film) is preferably 10 seconds or more and 3 minutes or less, and more preferably 30 seconds or more and 2 minutes or less.
  • the washing method and washing time are preferably 10 seconds or more and 3 minutes or less, and more preferably 30 seconds or more and 2 minutes or less.
  • the partition wall manufactured in this way can be used as a bank for a display.
  • the display of the present disclosure is characterized by including a light emitting element including a partition wall made of the photosensitive resin composition of the present disclosure and a light emitting layer arranged in a region partitioned by the partition wall.
  • a light emitting element including a partition wall made of the photosensitive resin composition of the present disclosure and a light emitting layer arranged in a region partitioned by the partition wall.
  • Examples of the display include an organic EL display and a quantum dot display.
  • TFMPO 5,5,5-trifluoro-2-methyl-3-pentine-. 2-ol
  • the obtained reaction solution was extracted with 360 g of methyl-t-butyl ether at room temperature (about 20 ° C.). Then, it was washed twice with 330 g of purified water. 1,3,5-trihydroxybenzene was added to the obtained organic layer so as to correspond to 1% by mass of 4-hydroxystyrene. Then, 4-hydroxystyrene was concentrated to 72% by mass, poured into n-octane, which is a poor solvent cooled to 0 ° C., and then the solution was immersed in an ice bath and stirred for 1 hour to 4-hydroxylene. Styrene crystals were precipitated. The crystals were filtered off and washed with n-octane. Then, the crystals were dried under reduced pressure at 25 ° C. to obtain white crystals of 4-hydroxystyrene (hereinafter referred to as p-HO-St) (yield 66%).
  • p-HO-St 4-hydroxystyren
  • GPC The weight average molecular weight Mw and the molecular weight dispersion (ratio of number average molecular weight Mn and weight average molecular weight Mw; Mw / Mn) of the polymer are referred to as high-speed gel permeation chromatography (hereinafter, may be referred to as GPC, manufactured by Toso Co., Ltd.).
  • GPC high-speed gel permeation chromatography
  • HLC-8320GPC an ALPHA-M column and an ALPHA-2500 column (both manufactured by Toso Co., Ltd.) were connected in series one by one, and measurement was performed using tetrahydrofuran (THF) as a developing solvent.
  • THF tetrahydrofuran
  • HEMA methyl ethyl ketone
  • AIBN 2,2'-azobis (2-methylbutylonitrile)
  • composition ratio of the repeating unit of the fluororesin precursor 7 is expressed in mol%
  • the monomer unit derived from AN the monomer unit derived from MA-C4F: the monomer unit derived from HEMA: MAA.
  • the monomer unit derived from 33:24:26:17.
  • the fluororesin precursor 8 containing the following repeating units was obtained in the same procedure as the synthesis of the fluororesin precursor 7 except that MN was used instead of AN and MA-C6F was used instead of MA-C4F. Obtained at a rate of 81%.
  • a fluororesin precursor 10 containing the following repeating units was obtained in a yield of 82% by the same procedure as the synthesis of the fluororesin precursor 7 except that MN was used instead of AN and AA was used instead of MAA. rice field.
  • composition ratio of each repeating unit of the comparative fluororesin precursor 1 is expressed in mol ratio
  • monomer unit derived from MA-C6F the monomer unit derived from HFIP-M: the single amount derived from MAA.
  • the body unit was 26:20:54.
  • composition ratio of each repeating unit of the comparative fluororesin precursor 2 is expressed in mol ratio
  • monomer unit derived from HEMA the monomer unit derived from MA-C6F: the single amount derived from HFIP-M.
  • composition ratio of each repeating unit of the comparative fluororesin precursor 3 is expressed in mol ratio, and is derived from the monomer unit derived from HEVE: the monomer unit derived from MA-C6F: p-HO-St.
  • the monomer unit was 35:31:34.
  • the comparative fluororesin 1 was obtained in a yield of 89% by the same procedure as the synthesis of the fluororesin 1 except that the comparative fluororesin precursor 1 was used instead of the fluororesin precursor 1.
  • the comparative fluororesin 2 was obtained in a yield of 90% by the same procedure as the synthesis of the fluororesin 1 except that the comparative fluororesin precursor 2 was used instead of the fluororesin precursor 1.
  • the comparative fluororesin 3 was obtained in a yield of 90% by the same procedure as the synthesis of the fluororesin 1 except that the comparative fluororesin precursor 3 was used instead of the fluororesin precursor 1.
  • photosensitive resin composition 1 0.5 parts by mass of the manufactured fluorine-containing resin 1, 0.5 parts by mass of Irgacure 369 (product of BASF Co., Ltd.) as a photopolymerization initiator, and pentaerythritol tetraacrylate (product of Tokyo Kasei Kogyo Co., Ltd.) as a cross-linking agent. 50 parts by mass, 50 parts by mass of ZAR2051H (Nippon Kayaku Co., Ltd.
  • the photosensitive resin composition 2 was prepared in the same procedure as the preparation of the photosensitive resin composition 1 except that the fluororesin 2 was used instead of the fluororesin 1.
  • the photosensitive resin composition 3 was prepared in the same procedure as the preparation of the photosensitive resin composition 1 except that the fluororesin 3 was used instead of the fluororesin 1.
  • the photosensitive resin composition 4 was prepared in the same procedure as the preparation of the photosensitive resin composition 1 except that the fluororesin 4 was used instead of the fluororesin 1.
  • the photosensitive resin composition 5 was prepared in the same procedure as the preparation of the photosensitive resin composition 1 except that the fluororesin 5 was used instead of the fluororesin 1.
  • the photosensitive resin composition 6 was prepared in the same procedure as the preparation of the photosensitive resin composition 1 except that the fluororesin 6 was used instead of the fluororesin 1.
  • the photosensitive resin composition 7 was prepared in the same procedure as the preparation of the photosensitive resin composition 1 except that the fluororesin 7 was used instead of the fluororesin 1.
  • the photosensitive resin composition 8 was prepared in the same procedure as the preparation of the photosensitive resin composition 1 except that the fluororesin 8 was used instead of the fluororesin 1.
  • the photosensitive resin composition 9 was prepared in the same procedure as the preparation of the photosensitive resin composition 1 except that the fluororesin 9 was used instead of the fluororesin 1.
  • the photosensitive resin composition 10 was prepared in the same procedure as the preparation of the photosensitive resin composition 1 except that the fluororesin 10 was used instead of the fluororesin 1.
  • Comparative Photosensitive Resin Composition 1 The comparative photosensitive resin composition 1 was prepared in the same procedure as the preparation of the photosensitive resin composition 1 except that the comparative fluororesin 1 was used instead of the fluororesin 1.
  • Comparative Photosensitive Resin Composition 2 The comparative photosensitive resin composition 2 was prepared in the same procedure as the preparation of the photosensitive resin composition 1 except that the comparative fluororesin 2 was used instead of the fluororesin 1.
  • Comparative Photosensitive Resin Composition 3 The comparative photosensitive resin composition 3 was prepared in the same procedure as the preparation of the photosensitive resin composition 1 except that the comparative fluororesin 3 was used instead of the fluororesin 1.
  • the obtained resin film was irradiated with i-line (wavelength 365 nm) through a mask having a line and space of 5 ⁇ m, and exposed.
  • i-line wavelength 365 nm
  • the developer solubility, bank performance evaluation (sensitivity, resolution), and contact angle of the obtained exposed resin film were measured.
  • TMAH tetramethylammonium hydroxide aqueous solution
  • the substrate having the bank obtained by the above step was heated at 230 ° C. for 60 minutes, and then the entire surface of the substrate was subjected to UV ozone treatment or oxygen plasma treatment for 10 minutes. Then, heating was performed at 230 ° C. for 60 seconds. Before and after UV ozone treatment or oxygen plasma treatment, and after the heating step after that, the contact angle of each bank surface with anisole, PGMEA, and water was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model number: DMs-601). It was measured. The results are shown in Table 2.
  • the UV ozone treatment device used was the same as described above.
  • a plasma dry cleaner PDC210 manufactured by Yamato Kagaku Co., Ltd. was used to perform oxygen plasma processing under the conditions of an oxygen gas flow rate of 30 cc / min and an output of 300 W.
  • both the bank and the comparative bank of the present disclosure are negative resists in which only the unexposed portion dissolves in the evaluation of developer solubility, and show the same sensitivity in the evaluation of bank performance, and the mask has the same sensitivity.
  • the line and space of 5 ⁇ m was transferred with good resolution, and the resolution was “excellent” with no line edge roughness. That is, in these evaluations, it was found that the fluororesin-containing resin compared with the fluororesin-containing resin of the present disclosure has little influence on the bank.
  • the contact angle of the exposed portion (corresponding to the upper surface of the bank) with respect to anisole, PGMEA and water was reduced by UV ozone treatment or oxygen plasma treatment, but the subsequent heating was performed. It increased with the process and showed good liquid repellency.
  • the contact angle was lowered by the UV ozone treatment or the oxygen plasma treatment, and the contact angle remained low by the subsequent heating step with almost no change.

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PCT/JP2021/039671 2020-10-28 2021-10-27 含フッ素樹脂、撥液剤、感光性樹脂組成物、硬化物およびディスプレイ WO2022092155A1 (ja)

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