Classifications

• • 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
  • C08F20/00—Homopolymers and 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/62—Halogen-containing esters
  • C07C69/65—Halogen-containing esters of unsaturated acids
  • C07C69/653—Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid 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
  • C08F16/00—Homopolymers and 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F16/02—Homopolymers and 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
• • 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
  • C08F20/00—Homopolymers and 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/12—Esters of monohydric alcohols or phenols
• • 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
  • C08F20/00—Homopolymers and 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
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/22—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
• • 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
  • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L29/00—Compositions of homopolymers or 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
  • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
  • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
• • 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 invention relates to resin compositions, resin films, substrates, polymers and polymerizable monomers. More specifically, a polymerizable monomer having a specific structure, a polymer having a structural unit derived from the polymerizable monomer, a resin composition containing the polymer, a resin film formed using the resin composition, the The present invention relates to a substrate provided with a pattern formed from a resin composition.
• fluorine-containing polymers Due to the electronic specificity of fluorine atoms, fluorine-containing polymers often exhibit different physical properties (eg, water repellency, low refractive index, etc.) from ordinary organic polymers. Therefore, applications of fluorine-containing polymers to various functional materials/resin compositions have been investigated.
• Patent Document 1 describes that a fluorine-containing polymer containing a repeating unit represented by a specific general formula gives a highly sensitive and high-resolution pattern.
• Patent Document 2 describes that a fluoropolymer containing a repeating unit represented by a specific general formula is effective for forming a fine resist pattern with little roughness.
• Fluorine-containing polymers generally tend to have high water repellency and relatively low solubility in alkaline aqueous solutions.
• attempts are known to introduce, for example, a hexafluoroisopropanol group (--C(CF 3 ) 2 --OH) into the polymer.
• a hexafluoroisopropanol group (--C(CF 3 ) 2 --OH) into the polymer.
• --C(CF 3 ) 2 --OH hexafluoroisopropanol group
• the present invention was made in view of such circumstances.
• One of the objects of the present invention is to provide a resin composition containing a fluorine-containing polymer capable of forming a resin film having good solubility in an alkaline aqueous solution.
• the present invention is the following resin composition.
• R 1 is a group containing at least one polymerizable group
• R 2 and R 3 are each independently a hydrogen atom or a linear or branched aliphatic hydrocarbon group
• R 4 is a hydrogen atom or a linear or branched aliphatic hydrocarbon group, wherein some or all of the hydrogen atoms of the aliphatic hydrocarbon group are substituted with an acid group or a hydroxy group
• R 5 is a divalent to tetravalent straight-chain or branched aliphatic hydrocarbon group, wherein some or all of the hydrogen atoms in the aliphatic hydrocarbon group are substituted with fluorine atoms or hydroxy groups
• R 6 and R 7 each independently represent a fluorine-containing alkyl group
• n represents an integer of 1 to 5, and when n is 2 or more, multiple R 2 may be the
• the present invention A resin film formed from the above resin composition.
• the present invention is the following polymer.
• R 1 is a group containing at least one polymerizable group
• R 2 and R 3 are each independently a hydrogen atom or a linear or branched aliphatic hydrocarbon group
• R 4 is a hydrogen atom or a linear or branched aliphatic hydrocarbon group, wherein some or all of the hydrogen atoms of the aliphatic hydrocarbon group are substituted with an acid group or a hydroxy group
• R 5 is a divalent to tetravalent straight-chain or branched aliphatic hydrocarbon group, wherein some or all of the hydrogen atoms in the aliphatic hydrocarbon group are substituted with fluorine atoms or hydroxy groups
• R 6 and R 7 each independently represent a fluorine-containing alkyl group
• n represents an integer of 1 to 5, and when n is 2 or more, multiple R 2 may be the same or different, and multiple R 2 may be the same or different, and multiple
• the present invention is the following polymerizable monomer.
• R 1 is a group containing at least one polymerizable group
• R 2 and R 3 are each independently a hydrogen atom or a linear or branched aliphatic hydrocarbon group
• R 4 is a hydrogen atom or a linear or branched aliphatic hydrocarbon group, wherein some or all of the hydrogen atoms of the aliphatic hydrocarbon group are substituted with an acid group or a hydroxy group
• R 5 is a divalent to tetravalent straight-chain or branched aliphatic hydrocarbon group, wherein some or all of the hydrogen atoms in the aliphatic hydrocarbon group are substituted with fluorine atoms or hydroxy groups
• R 6 and R 7 each independently represent a fluorine-containing alkyl group
• n represents an integer of 1 to 5, and when n is 2 or more, multiple R 2 may be the same or different, and multiple R 3 may be the same or different.
• a resin composition containing a fluorine-containing polymer capable of forming a resin film having good solubility in an alkaline aqueous solution.
• X to Y in the description of numerical ranges means X or more and Y or less, unless otherwise specified.
• “1 to 5% by mass” means “1% by mass or more and 5% by mass or less”.
• alkyl group includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
• (meth)acryl used herein represents a concept that includes both acryl and methacryl. The same applies to similar notations such as “(meth)acrylate”.
• organic group as used herein means an atomic group obtained by removing one or more hydrogen atoms from an organic compound, unless otherwise specified.
• a "monovalent organic group” represents an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.
• the polymerizable monomer will be explained first, then the polymer having a structural unit derived from the polymerizable monomer will be explained, and then the resin composition containing the polymer will be explained.
• polymerizable monomer (hereinafter also simply referred to as "polymerizable monomer”, “monomer”, etc.) is represented by general formula (I) below.
• R 1 is a group containing at least one polymerizable group
• R 2 and R 3 are each independently a hydrogen atom or a linear or branched aliphatic hydrocarbon group
• R 4 is a hydrogen atom or a linear or branched aliphatic hydrocarbon group, wherein some or all of the hydrogen atoms of the aliphatic hydrocarbon group are substituted with an acid group or a hydroxy group
• R 5 is a divalent to tetravalent straight-chain or branched aliphatic hydrocarbon group, wherein some or all of the hydrogen atoms in the aliphatic hydrocarbon group are substituted with fluorine atoms or hydroxy groups
• R 6 and R 7 each independently represent a fluorine-containing alkyl group
• n represents an integer of 1 to 5, and when n is 2 or more, multiple R 2 may be the same or different, and multiple R 3 may be the same or different.
• m represents an integer of 1 to 3, and when m is 2 or 3,
• R 1 is preferably a group containing at least one of a (meth)acryloyl group, a vinyl group and an epoxy group.
• R 1 contains a methacryloyl group, some or all of the hydrogen atoms of the ⁇ -position methyl group of the methacryloyl group may be substituted with fluorine atoms.
• a group containing a (meth)acryloyl group preferably the (meth)acryloyl group itself can be mentioned.
• the group containing a vinyl group include a vinyl group itself, an allyl group, and a group containing a styrene skeleton (eg, CH 2 ⁇ CH—C 6 H 4 —).
• the group containing an epoxy group examples include epoxy group itself, glycidyl group, glycidyloxy group, and the like.
• the portion of R 1 that can be the main chain and/or side chain of the polymer may not contain an alicyclic structure.
• a specific example thereof is a cyclic olefin structure such as a norbornene structure.
• Linear or branched aliphatic hydrocarbon groups for R 2 and R 3 include linear or branched alkyl groups.
• Linear or branched alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, Examples include hexyl group, heptyl group, octyl group, nonyl group, and decyl group.
• the number of carbon atoms in the linear or branched aliphatic hydrocarbon group for R 2 and R 3 is, for example, 1-10, preferably 1-6, more preferably 1-4.
• R 2 and R 3 are preferably hydrogen atoms.
• Examples of the linear or branched aliphatic hydrocarbon group for R 4 include the same linear or branched aliphatic hydrocarbon groups for R 2 and R 3 .
• R 4 is a linear or branched aliphatic hydrocarbon group, some or all of the hydrogen atoms of this aliphatic hydrocarbon group may be substituted with acid groups or hydroxy groups.
• acid groups include a carboxy group, a phenolic hydroxy group, a phosphoric acid group, and a hexafluoroisopropanol group (--C(CF 3 ) 2 --OH).
• R4 is preferably a hydrogen atom.
• R 5 may be a divalent to tetravalent linear or branched aliphatic hydrocarbon group. Some or all of the hydrogen atoms in this linear or branched aliphatic hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. When R 5 is a divalent straight-chain or branched aliphatic hydrocarbon group, R 5 is preferably a straight-chain or branched alkylene group.
• methylene group (—CH 2 —), 1,2-ethylene group, 1,6-hexylene group, 1,4-butylene group, 1,6-(2,4,4-trimethylhexylene) group, 1,4-(4-methylpentylene) group, 1,5-(5-methylhexylene) group, 1,6-(6-methylheptylene) group, 1,5-(2,2,5- trimethylhexylene) group, 1,7-(3,7-dimethyloctylene) group, and the like.
• R 5 is a trivalent or tetravalent straight-chain or branched aliphatic hydrocarbon group
• R 5 is, for example, the above-mentioned divalent straight-chain or branched aliphatic hydrocarbon group plus one hydrogen atom. It can be a group with one or two removed.
• the number of carbon atoms in R 5 is, for example, 1-12, preferably 1-10, more preferably 1-6, still more preferably 1-4.
• a particularly preferred R 5 is a methylene group (--CH 2 --).
• the fluorine-containing alkyl group for R 6 and R 7 is preferably a linear or branched fluoroalkyl group having 1 to 10 carbon atoms, more preferably a linear or branched fluoroalkyl group having 1 to 6 carbon atoms. , and particularly preferably a linear or branched fluoroalkyl group having 1 to 3 carbon atoms.
• R 6 and R 7 are preferably perfluoroalkyl groups.
• a polymer containing a structural unit derived from a monomer represented by general formula (I) can have a particularly low refractive index.
• R 6 and R 7 are particularly preferably a perfluoromethyl group, a perfluoroethyl group or a perfluorobutyl group, particularly preferably a perfluoromethyl group (trifluoromethyl group).
• n may be an integer of 1 to 5, preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.
• n may be an integer of 1 to 3, preferably 1 to 2, more preferably 1.
• the polymerizable monomer represented by the general formula (I) includes, for example, a compound A represented by the following general formula (A), and a compound B having a group that reacts with a polymerizable group and an epoxy group to form a bond. , can be produced by reacting. This reaction is preferably carried out in the presence of a base such as an amine compound.
• a preferred example of compound B is (meth)acrylic acid.
• the carboxy group of (meth)acrylic acid reacts with the epoxy group of compound A.
• R 1 is a (meth)acryloyl group
• Other examples of compound B include vinylmagnesium chloride, allylmagnesium chloride, organolithium compounds, amine compounds, glycidol, and the like.
• the epoxy group of compound A is allowed to react with the --OH group of compound A, which is another molecule.
• R4 is converted to a linear or branched aliphatic hydrocarbon group. or convert R4 to a group substituted by an acid group or a hydroxy group.
• compound A can be obtained, for example, by reacting the carbon-carbon double bond of the compound represented by general formula (A') below with an epoxidation reagent.
• epoxidizing reagents include peroxides such as meta-chloroperbenzoic acid.
• the polymer of the present embodiment (hereinafter also simply referred to as "polymer”) has a structural unit derived from the polymerizable monomer represented by general formula (I) above.
• the polymer of this embodiment has a structural unit formed by polymerizing the polymerizable group in R 1 of the polymerizable monomer represented by general formula (I). Since general formula (I) has been described in the section ⁇ Polymerizable Monomer> above, further description will be omitted.
• the polymer may be (i) a homopolymer composed only of structural units derived from the polymerizable monomer represented by the general formula (I), or (ii) a polymer represented by the general formula (I) It may be a copolymer having a structural unit derived from a functional monomer and one or more other structural units (copolymerized units). From the viewpoint of adjustment/improvement of various properties, the polymer is preferably (ii) a copolymer.
• the monomer constituting the copolymerization unit is not particularly limited as long as it can be copolymerized with the polymerizable monomer represented by general formula (I). Also, when the polymer is a copolymer, the polymer may contain only one copolymerized unit or may contain two or more copolymerized units.
• copolymer units examples include olefins, fluorine-containing olefins, (meth)acrylic acid esters, fluorine-containing (meth)acrylic acid esters, norbornene compounds, fluorine-containing norbornene compounds, styrene compounds, fluorine-containing styrene compounds, vinyl ethers, and It may be a copolymer unit derived from one or more monomers selected from the group consisting of fluorine vinyl ethers. These are preferably used together when R 1 contains a polymerizable carbon-carbon double bond as the polymerizable monomer represented by formula (I).
• Preferred copolymerization units include structural units derived from fluorine-containing monomers such as fluorine-containing (meth)acrylic acid esters.
• fluorine-containing monomers such as fluorine-containing (meth)acrylic acid esters.
• the copolymer unit is a structural unit derived from a fluorine monomer, the fluorine content of the polymer as a whole can be easily increased. This contributes to adjusting the refractive index and water repellency of the polymer.
• R' is a hydrogen atom, a methyl group or a trifluoromethyl group
• Rf is a fluorine-containing organic group.
• the fluorine-containing organic group for R f include linear or branched fluorine-containing alkyl groups, fluorine-containing alicyclic groups, fluorine-containing aryl groups, and fluorine-containing aralkyl groups.
• all hydrogen atoms may be substituted with fluorine atoms (perfluoro groups may be used), or only a part of the hydrogen atoms may be substituted with fluorine atoms.
• the number of carbon atoms in the fluorine-containing organic group is, for example, 1-20, preferably 1-10, more preferably 1-6.
• the monomer constituting the copolymerization unit may be a monofunctional epoxy compound having only one epoxy group, Any epoxy compound can be used, including multifunctional epoxy compounds having two or more epoxy groups.
• monofunctional epoxy compounds include 4-tert-butylphenyl glycidyl ether, m,p-cresyl glycidyl ether, phenyl glycidyl ether, and cresyl glycidyl ether.
• Polyfunctional epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane.
• Polyglycidyl ethers such as polyglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenated bisphenol A type diglycidyl ether etc.
• the monomer constituting the copolymerization unit may be an alicyclic epoxy compound, a polymer having an epoxy structure, a novolac Compounds such as epoxy resins and siloxane monomers having an epoxy structure can also be used.
• alicyclic epoxy compounds include monofunctional epoxy 1,2-epoxy-4-vinylcyclohexane (trade name: Celoxide 2000, manufactured by Daicel), and polyfunctional epoxy 3′,4′-epoxy. Cyclohexylmethyl-3,4-epoxycyclohexane carboxylate (trade name: Celoxide 2021P, manufactured by Daicel) and the like.
• Polymers having an epoxy structure include polymers obtained by polymerizing or copolymerizing (meth)acrylate monomers having an epoxy structure.
• (meth)acrylate-based monomers having an epoxy structure include monofunctional epoxy glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether (abbreviation: 4HBAGE: manufactured by Mitsubishi Chemical Corporation), and 3,4-epoxycyclohexyl.
• Methyl methacrylate (trade name: Cychromer M100, manufactured by Daicel) and the like.
• siloxane-based monomers having an epoxy structure examples include monofunctional epoxy 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (trade name: KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxy Propyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned.
• the novolak-based epoxy resin include jER 152 (manufactured by Mitsubishi Chemical Corporation), EPICLON N730-A (manufactured by DIC Corporation), YDPN-638 (manufactured by Nippon Steel Chemical & Materials Corporation), and the like.
• the ratio of structural units derived from the polymerizable monomer represented by general formula (I) in the polymer is, for example, 30-90 mol%, preferably 40-70 mol%.
• the ratio of the structural units derived from the polymerizable monomer represented by the general formula (I) for example, the effect of the structural units derived from the polymerizable monomer represented by the general formula (I) (alkali While obtaining sufficient solubility in an aqueous solution, other performances can be easily improved.
• the ratio of structural units in the polymer can be known through measurement data such as 1 H-NMR, 19 F-NMR and 13 C-NMR.
• a particularly preferred polymer is a polymer (copolymer) containing a structural unit represented by general formula (II) below and a structural unit represented by general formula (III) below.
• R 8 is a hydrogen atom or a methyl group
• R9 is a hydrogen atom or a methyl group
• R 10 and R 11 are each independently a hydrogen atom or a fluorine-containing alkyl group.
• R 10 and R 11 are fluorine-containing alkyl groups. Examples of the fluorine-containing alkyl group include groups similar to the fluorine - containing alkyl groups for R6 and R7 .
• fluorine-containing alkyl groups are not limited to perfluoroalkyl groups, and perfluoroalkyl groups in which one of the terminal fluorine atoms is substituted with a hydrogen atom may be used.
• perfluoroalkyl groups in which one of the terminal fluorine atoms is replaced with a hydrogen atom include -CF 2 H, -CF 2 CF 2 H, -CF 2 CF 2 CF 2 H, -CF 2 CF 2 CF 2 H, -CF 2 CF 2 CF 2 CF 2 H, -CF 2 CF 2 CF 2 CF 2 H, -CF 2 CF 2 CF 2 CF 2 CF 2 H and the like.
• the fluorine content in the structural unit represented by general formula (III) in the polymer is preferably 40 to 75 mass %, more preferably 45 to 70 mass %. This may make it easier to achieve both solubility in an alkaline aqueous solution and water repellency.
• the composition ratio of the structural unit represented by general formula (III) in the polymer is 100 mol% in total of the structural unit represented by general formula (II) and the structural unit represented by general formula (III). , preferably 30 to 70 mol %, preferably 40 to 60 mol %. This may make it easier to achieve both solubility in an alkaline aqueous solution and water repellency.
• the fluorine content of the polymer is preferably 30-75% by mass, more preferably 40-60% by mass.
• An appropriate fluorine content may make it possible to further optimize the refractive index, or make it easier to achieve both solubility in an alkaline aqueous solution and water repellency.
• the weight average molecular weight of the polymer is, for example, 3000-30000, preferably 5000-20000, more preferably 6000-15000.
• the dispersity of the polymer is, for example, 1.2-2.5, preferably 1.4-1.8.
• the weight average molecular weight and dispersity can be determined by gel permeation chromatography.
• the polymer of the present embodiment is obtained by polymerizing only the polymerizable monomer represented by general formula (I), or by copolymerizing the polymerizable monomer represented by general formula (I) and other monomers. It can be manufactured (synthesized).
• R 1 contains a polymerizable carbon-carbon double bond
• the monomer is treated with a radical polymerization initiator in the presence of a suitable polymerization solvent. is preferably used for polymerization.
• any solvent that sufficiently dissolves the monomer and the radical polymerization initiator can be used without particular limitation.
• ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate.
• esters such as 3-methoxybutyl acetate
• alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether
• aromatic hydrocarbons such as toluene, xylene, ethylbenzene; chloroform; dimethyl sulfoxide; and the like.
• the polymerization solvent is not limited to these.
• the polymerization solvent may contain only one organic solvent, or may contain two or more organic solvents.
• radical polymerization initiators examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2′-azobis[2-(5-methyl- 2-imidazolin-2-yl)propane]dihydrochloride, 2,2′-azobis(2-methylpropionamidine) disulfate, 2,2′-azobis(N,N′-dimethyleneisobutyramidine), 2, Azo initiators such as 2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate (VA-057 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) can be mentioned.
• persulfates such as potassium persulfate and ammonium persulfate, di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylperoxydicarbonate, t -butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutyl Peroxy-2-ethylhexanoate, di(4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butyl peroxyisobutyrate, 1,1-di(t-hexylperoxy)cyclohexane, t-butyl Peroxide initiators such as hydroperoxides and hydrogen per
• the monomer when R 1 contains an epoxy group, the monomer can be polymerized using a cationic polymerization initiator in the presence of a suitable polymerization solvent.
• a cationic polymerization initiator include at least one cation selected from aromatic sulfonium, aromatic iodonium, aromatic diazonium and pyridinium, and BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , CF 3 SO 3 - , (CF 3 SO 2 ) 2 N - and at least one anion selected from B(C 6 F 5 ) 4 - and a thermal cationic polymerization initiator such as an onium salt or an aluminum complex; can be mentioned.
• unreacted monomers and impurities can be appropriately removed or reduced by techniques known in the technical field of polymer synthesis, such as precipitation using a poor solvent, decantation, and the like. preferable.
• the resin composition of the present embodiment (hereinafter sometimes simply referred to as “resin composition”) contains a polymer having a structural unit derived from the polymerizable monomer represented by general formula (I) above. Since the polymerizable monomer represented by the general formula (I) and the polymer having the structural unit derived from the monomer have been described above, further description will be omitted.
• a resin film formed using the resin composition of the present embodiment has good solubility in an alkaline aqueous solution.
• the structural unit derived from the polymerizable monomer represented by general formula (I) in the polymer has a functional group represented by -OR 4 in addition to the functional group represented by -CR 6 R 7 OH. This is presumed to be due to having It is speculated that the presence of these two functional groups particularly improves the affinity of the polymer for alkaline aqueous solutions.
• the resin film formed using the resin composition of the present embodiment has good adhesion to the substrate.
• the structural unit derived from the polymerizable monomer represented by general formula (I) in the polymer is a functional group represented by -OR 4 in addition to the functional group represented by -CR 6 R 7 OH. It is speculated that it is due to having In particular, it is speculated that the functional group represented by —OR 4 interacts with the substrate to develop good adhesion to the substrate.
• the resin film formed using the resin composition of the present embodiment has favorable optical properties due to the inclusion of fluorine atoms, and therefore has applicability to optical members.
• the resin composition of this embodiment typically contains an organic solvent.
• the resin composition of this embodiment typically has at least a polymer dissolved or dispersed in an organic solvent.
• the resin film can be easily obtained by a process of coating the resin composition on the substrate and drying it.
• organic solvent can be used as the organic solvent as long as it can dissolve or disperse the polymer.
• organic solvents such as esters, ethers, ketones, hydrocarbons, amides, alcohols, and glycols can be used.
• Organic solvents that can be preferably used include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, ⁇ -butyrolactone, diacetone alcohol, diglyme, methyl isobutyl ketone, 3-methoxybutyl acetate, 2-heptanone, Examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and the like.
• glycols, glycol ethers, glycol ether esters, etc. can also be mentioned as usable solvents.
• Specific examples thereof include Celtol (registered trademark) manufactured by Daicel Corporation and Hysolve (registered trademark) manufactured by Toho Chemical Industry Co., Ltd.
• the amount used is not particularly limited, but the total solid content (components other than the organic solvent) in the resin composition is usually 5 to 60% by mass, preferably 10 to 50% by mass. Used. Appropriate adjustment of the total solid concentration tends to improve the ease of forming a thin film, the uniformity of the film thickness, and the like.
• the resin composition of the present embodiment can have aspects (i) to (iii) below.
• a photoacid generator in the resin composition, the resin composition becomes photosensitive, and patterning by a photolithography process may be possible.
• the resin composition contains a cross-linking agent, the resin composition can be cured (by an external stimulus such as light or heat).
• the resin composition contains a polymer and a photoacid generator.
• the resin composition contains a polymer and a cross-linking agent.
• the resin composition contains a polymer, a photoacid generator, and a cross-linking agent.
• photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethanes, N-sulfonyloxyimides, oxime-O-sulfonates, and the like. When a photoacid generator is used, it may be used alone, or two or more of them may be used in combination.
• photoacid generators include trade names: Irgacure PAG121, Irgacure PAG103, Irgacure CGI1380, Irgacure CGI725 (manufactured by BASF, USA), trade names: PAI-101, PAI-106, NAI-105, NAI- 106, TAZ-110, TAZ-204 (manufactured by Midori Chemical Co., Ltd.), trade names: CPI-200K, CPI-210S, CPI-101A, CPI-110A, CPI-100P, CPI-110P, CPI-100TF, CPI-110TF, HS-1, HS-1A, HS-1P, HS-1N, HS-1TF, HS-1NF, HS-1MS, HS-1CS, LW-S1, LW-S1NF (manufactured by San-Apro Co., Ltd. ), trade names: TFE-triazine, TME-triazine or MP-tri
• a photoacid generator When a photoacid generator is used, its amount is, for example, 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the polymer. By using an appropriate amount of the photoacid generator, it is possible to achieve both sufficient sensitivity and resolution and storage stability of the composition.
• cross-linking agent a compound having a cross-linkable group capable of cross-linking with the —OH site and/or —OR 4 site in the polymer can be used.
• Cross-linking agents typically contain two or more cross-linkable groups per molecule. A crosslinked structure connecting the polymers is formed, and the resin film is cured.
• the number of crosslinkable groups contained in one molecule of the crosslinker is usually 2 to 8, preferably 2 to 6, more preferably 2 to 4.
• cross-linking agent examples include the following compounds (a) to (d).
• a cross-linking agent only one type may be used, or a plurality of types may be used in combination.
• crosslinkers with alkoxymethyl and/or methylol groups e.g. benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone , hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl) ) diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, hexamethoxymethylmelamine; commercial products Cymel 300, 301, 303 , 370, 325, 327, 701, 26
• (d) compounds having a bismaleimide group for example, 4,4'-diphenylmethanebismaleimide, phenylmethanemaleimide, m-phenylenebismaleimide, bisphenol A diphenylether bismaleimide, 3,3'-dimethyl-5,5'-diethyl -4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene and the like.
• a bismaleimide group for example, 4,4'-diphenylmethanebismaleimide, phenylmethanemaleimide, m-phenylenebismaleimi
• the resin composition contains a cross-linking agent
• its content is usually 1-100 parts by mass, preferably 5-50 parts by mass, per 100 parts by mass of the polymer.
• the content is 1 part by mass or more, a cured film having sufficient mechanical strength can be obtained, and when the content is 100 parts by mass or less, the storage stability of the resin composition can be enhanced.
• the resin composition preferably contains a photoacid generator and/or a thermal acid generator from the viewpoint of the reaction efficiency of the crosslinker.
• the photoacid generator are as described above. Any known thermal acid generator can be used without particular limitation.
• the resin composition of this embodiment is preferably used to form a protective film for a photosensitive resin film in a photolithography process.
• the photosensitive resin film (resist film) and the immersion liquid (usually pure water) are treated with a water-repellent material to prevent direct contact with the immersion liquid (usually pure water). May be covered with a protective film.
• this water-repellent protective film is often referred to as a "topcoat”.
• the resin film formed using the resin composition of the present embodiment has good solubility in an alkaline aqueous solution, it can be easily removed with an alkaline developer.
• the resin film formed using the resin composition of the present embodiment is moderately water-repellent, it is possible to suppress penetration of the immersion liquid into the photosensitive resin film.
• the resin composition includes use as a material that can be patterned by a photolithography process (photosensitive resin composition, photoresist, etc.), and application to optical members (antireflection film, planarizing film, etc.). is also mentioned.
• a resin film can be formed by using the resin composition of the present embodiment.
• the resin film can be formed by spin coating using a spinner, spray coating using a spray coater, immersion, printing, roll coating, inkjet method, or the like. After coating, pre-baking is usually performed at 80 to 140° C., preferably 90 to 120° C., to sufficiently volatilize the organic solvent.
• the base material for forming the resin film is not particularly limited. Examples include glass, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, and GaN wafers. In order to improve adhesion, the substrate surface may be treated with an adhesion aid such as a silane coupling agent.
• the resin composition is photosensitive (such as when it contains a photoacid generator)
• the resin film is appropriately irradiated with light (exposed) and then developed to obtain a patterned substrate. can be done.
• the exposure and development are described below.
• Actinic rays used for exposure include, for example, X-rays, electron beams, ultraviolet rays, and visible rays. In terms of wavelength, actinic rays of 200 to 500 nm are preferred. From the viewpoint of pattern resolution and handleability, the light source is preferably g-line, h-line or i-line of a mercury lamp, and particularly preferably i-line. Also, two or more rays may be mixed and used. A contact aligner, mirror projection or stepper is preferred as the exposure device. A photomask having a desired pattern is usually used for the exposure.
• the resin film may be heated again (heating after exposure: Post Exposure Bake).
• the temperature is, for example, 80-150°C, preferably 90-120°C.
• the time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds.
• a patterned resin film can be obtained by developing the exposed resin film. That is, development is carried out using a suitable developer, for example, by dipping, puddle, rotary spraying, or the like. By development, the exposed portion (in the case of a positive type) or the unexposed portion (in the case of a negative type) is eluted and removed from the resin film, and a substrate having a pattern can be obtained.
• alkaline aqueous solutions more specifically, (i) inorganic alkaline aqueous solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, (ii) organic amine aqueous solutions such as ethylamine, diethylamine, triethylamine, and triethanolamine, ( iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide; Organic solvents such as cyclopentanone, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate can also be used.
• inorganic alkaline aqueous solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia
• organic amine aqueous solutions such as ethylamine, diethylamine, triethylamine, and triethanolamine
• quaternary ammonium salts such as
• a water-soluble organic solvent such as methanol or ethanol, or a surfactant may be added to the developer.
• an aqueous tetramethylammonium hydroxide solution is preferred.
• the concentration of tetramethylammonium hydroxide in this aqueous solution is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass.
• rinse liquids include distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, and the like. These can be used alone or in combination of two or more.
• a cured film can be obtained, for example, by heating the resin film.
• heating causes the portion corresponding to R4 and/or the —OH portion in the polymer to react with the crosslinker to form a bond.
• Heating can be performed using a hot plate, an oven, or the like.
• the heating temperature is, for example, 50 to 200°C, preferably 80 to 150°C.
• the heating time is, for example, 30 to 600 seconds, preferably 60 to 300 seconds.
• R 1 is a group containing at least one polymerizable group
• R 2 and R 3 are each independently a hydrogen atom or a linear or branched aliphatic hydrocarbon group
• R4 is a crosslinkable group
• R 5 is a divalent to tetravalent straight-chain or branched aliphatic hydrocarbon group, wherein some or all of the hydrogen atoms in the aliphatic hydrocarbon group are substituted with fluorine atoms or hydroxy groups
• R 6 and R 7 each independently represent a fluorine-containing alkyl group
• n represents an integer of 1 to 5, and when n is 2 or more, multiple R 2 may be the same or different, and multiple R 3 may be the same or different.
• m represents an integer of 1 to 3, and when m is 2 or 3, multiple R 6 may be the same or different, and multiple R 7 may be the same or different.
• R 4 is not particularly limited as long as it can react with the crosslinkable group of the crosslinker to form a bond.
• R 4 can be a hydrogen atom, a linear or branched aliphatic hydrocarbon group substituted by an acid group or a hydroxy group, and the like.
• straight-chain or branched aliphatic hydrocarbon group substituted by an acid group or a hydroxy group see the description in general formula (I).
• Methacrylic acid (17.22 g, 200 mmol) and acetonitrile (35 ml) were mixed in a 300 mL three-necked eggplant flask, cooled with ice, and triethylamine (10.1 g, 100 mmol) was slowly added dropwise. After that, the mixture was heated to 60° C., and BTHB-epo (22.41 g, 100 mmol) (manufactured by Central Glass Co., Ltd.) was added over 1 hour. After that, the mixture was stirred at 80° C. for 2 hours.
• reaction solution was cooled to room temperature, it was washed once with 5% by mass sodium hydrogen carbonate, washed with 0.1% hydrochloric acid, and washed once with distilled water, and concentrated by an evaporator to obtain a concentrated solution. After adding 120 g of heptane to the concentrate to precipitate crystals, the crystals were filtered and dried. MA-IPA-HFA (21.7 g, 70% yield) was thus obtained.
• BTHB 166.46 g, 800 mmol
• dichloromethane 800 mL
• mCPBA mCPBA (195.26 g, 792 mmol) was added in small portions. Then, after stirring overnight at 35° C., the mixture was washed once with 10% by mass sodium thiosulfate water and once with 5% by mass sodium bicarbonate water, and concentrated by an evaporator to obtain a concentrate. The concentrate was distilled under reduced pressure (2 kPa, 67-70° C. collected) to obtain BTHB-epo (146.9 g, yield 82%). (“mCPBA” is an abbreviation for meta-chloroperbenzoic acid.)
• A-IPA-HFA (19.2 g, yield 65%) was obtained in the same procedure as the synthesis of MA-IPA-HFA, except that acrylic acid was used instead of methacrylic acid.
• ⁇ CF3A-IPA-HFA (14.5 g, yield 40%) was obtained in the same procedure as the synthesis of MA-IPA-HFA, except that ⁇ -trifluoromethylacrylic acid was used instead of methacrylic acid. .
• ALPHA-M column and ALPHA-2500 column were connected in series one by one, and the measurement was performed using tetrahydrofuran (THF) as a developing solvent.
• THF tetrahydrofuran
• a refractive index difference measurement detector was used as the detector.
• Mw and Mn are values obtained using polystyrene as a standard.
• fluorine-containing resin 1 was performed in the same manner as in the synthesis of fluorine-containing resin 1, except that 1H,1H,5H-octafluoropentyl methacrylate (a product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as OFP-M) was used instead of HFIP-M.
• OFP-M 1H,1H,5H-octafluoropentyl methacrylate
• a fluorine-containing resin 4 containing the above structural unit was obtained with a yield of 84% in the same procedure as the synthesis of the fluorine-containing resin 3, except that OFP-M was used instead of HFIP-M.
• a fluorine-containing resin 6 containing the above structural unit was obtained with a yield of 81% in the same procedure as the synthesis of the fluorine-containing resin 5, except that OFP-M was used instead of HFIP-M.
• composition ratio of each structural unit of the fluorine-containing resin 6 was expressed in mol%, and the structural unit derived from ⁇ CF3A-IPA-HFA: structural unit derived from OFP-M was 49:51. .
• HFIP-A hexafluoroisopropyl acrylate
• HFIP-M hexafluoroisopropyl acrylate
• a fluorine-containing resin 8 containing the above structural unit was obtained with a yield of 82% in the same procedure as the synthesis of the fluorine-containing resin 1, except that HFIP-A was used instead of HFIP-M.
• a comparative fluororesin 2 containing the following structural units was obtained with a yield of 80% in the same procedure as the synthesis of the comparative fluororesin 1, except that OFP-M was used instead of HFIP-M.
• a comparative fluororesin 4 containing the above structural unit was obtained with a yield of 78% in the same procedure as the synthesis of the comparative fluororesin 3, except that OFP-M was used instead of HFIP-M.
• a comparative fluororesin 6 containing the following structural units was obtained with a yield of 75% in the same procedure as the synthesis of the comparative fluororesin 5, except that OFP-M was used instead of HFIP-M.
• a comparative fluororesin 7 containing the following structural units was obtained with a yield of 82% in the same procedure as the synthesis of the comparative fluororesin 3, except that HFIP-A was used instead of HFIP-M.
• photosensitive resin composition 1 20 parts by mass of the produced fluorine-containing resin 1, 2 parts by mass of hexamethoxymethylmelamine (a product of Tokyo Chemical Industry Co., Ltd., hereinafter referred to as HMMM) as an acid cross-linking agent, and Irgacure PAG121 (a product of BASF) as a photoacid generator ) was blended with 77 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) as a solvent to obtain a solution. The resulting solution was filtered through a 0.2 ⁇ m membrane filter. Thus, a photosensitive resin composition 1 was prepared.
• HMMM hexamethoxymethylmelamine
• Irgacure PAG121 a product of BASF
• a photosensitive resin composition 2 was prepared in the same manner as the photosensitive resin composition 1, except that the fluorine-containing resin 2 was used instead of the fluorine-containing resin 1.
• a photosensitive resin composition 3 was prepared in the same manner as the photosensitive resin composition 1, except that the fluorine-containing resin 3 was used instead of the fluorine-containing resin 1.
• a photosensitive resin composition 4 was prepared in the same manner as the photosensitive resin composition 1, except that the fluorine-containing resin 4 was used instead of the fluorine-containing resin 1.
• a photosensitive resin composition 5 was prepared in the same manner as the photosensitive resin composition 1, except that the fluorine-containing resin 5 was used instead of the fluorine-containing resin 1.
• a photosensitive resin composition 6 was prepared in the same manner as the photosensitive resin composition 1, except that the fluorine-containing resin 6 was used instead of the fluorine-containing resin 1.
• a photosensitive resin composition 7 was prepared in the same manner as the preparation of the photosensitive resin composition 1, except that the fluorine-containing resin 7 was used instead of the fluorine-containing resin 1.
• a photosensitive resin composition 8 was prepared in the same procedure as the preparation of the photosensitive resin composition 1, except that the fluorine-containing resin 8 was used instead of the fluorine-containing resin 1.
• Comparative Photosensitive Resin Composition 1 (Comparison 1)
• a comparative photosensitive resin composition 1 was prepared in the same manner as the photosensitive resin composition 1, except that the comparative fluororesin 1 was used instead of the fluororesin 1.
• Comparative Photosensitive Resin Composition 2 (Comparison 2)
• a comparative photosensitive resin composition 2 was prepared in the same manner as the photosensitive resin composition 1, except that the comparative fluororesin 2 was used instead of the fluororesin 1.
• Comparative photosensitive resin composition 3 was prepared in the same manner as for photosensitive resin composition 1, except that comparative fluorine-containing resin 3 was used instead of fluorine-containing resin 1.
• Comparative photosensitive resin composition 4 was prepared in the same manner as for photosensitive resin composition 1, except that comparative fluorine-containing resin 4 was used instead of fluorine-containing resin 1.
• Comparative Photosensitive Resin Composition 5 (Comparative 5)
• a comparative photosensitive resin composition 5 was prepared in the same manner as the preparation of the photosensitive resin composition 1, except that the comparative fluororesin 5 was used instead of the fluororesin 1.
• Comparative Photosensitive Resin Composition 6 (Comparative 6)
• a comparative photosensitive resin composition 6 was prepared in the same manner as the preparation of the photosensitive resin composition 1, except that the comparative fluororesin 6 was used instead of the fluororesin 1.
• Comparative Photosensitive resin composition 7 was prepared in the same manner as for photosensitive resin composition 1, except that comparative fluorine-containing resin 7 was used instead of fluorine-containing resin 1.
• the obtained post-exposure resin film was evaluated for developer solubility and patterning (sensitivity, resolution) as follows.
• TMAH tetramethylammonium hydroxide aqueous solution
• the optimum exposure dose Eop (mJ/cm 2 ) for forming a line-and-space pattern was determined and used as an index of sensitivity.
• the obtained pattern was observed with a microscope to evaluate the resolution. When the line edge roughness could not be confirmed, it was evaluated as "excellent”, when it was slightly confirmed, it was evaluated as "good”, and when it was noticeable, it was evaluated as "improper". By the way, those for which no pattern was obtained were indicated by -.
• a patterned glass substrate was prepared as described in [Pattern Formation] above.
• a patterned silicon wafer was prepared by performing the same operation as in the above [formation of pattern] except that a silicon wafer was used instead of the glass substrate as the substrate.
• a cross-cut test JIS K 5600 5-6) was performed. The results of the cross-cut test were classified as 0 as pass (o), and the others as disqualified (x).
• the unexposed portions of the resin films (pattern-exposed films) formed using the photosensitive resin compositions 1 to 8 dissolved well in the alkaline developer.
• the photosensitive resin compositions 1 to 8 it was possible to obtain substrates with good patterns.
• the refractive indices of the resin films formed using the photosensitive resin compositions 1 to 8 are approximately the same as the refractive indices of the resin films formed using the comparative photosensitive resin compositions 1 to 7, and the optical members can be used. Applicability was shown.
• the adhesion of the resin films formed using the photosensitive resin compositions 1 to 8 to the substrate was good.
• the measurement method is performed using the droplet method.
• a droplet of 0.5 ⁇ L of pure water is dropped onto a resin film placed horizontally. values were measured.
• the contact angle was calculated by the ⁇ /2 method. Table 2 shows the results.
• a resin film having a thickness of 10 ⁇ m was formed on a glass substrate using the film-forming solution described above to prepare a substrate for measuring the dissolution rate of the developer. It was measured. Specifically, the developer dissolution rate measurement substrate was immersed in an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass as a developer. By changing the immersion time to 10 s, 20 s, 30 s, . . . , the relationship between immersion time and residual film thickness was obtained. From this relationship, the dissolution rate (DR) of the resin film was obtained. Incidentally, the remaining film thickness was measured using a laser microscope (Keyence VX-1100).
• the evaluation substrate obtained as described above (other than the one used for contact angle evaluation and developer solubility evaluation) was cut in half, and half of them was subjected to a temperature condition of 23 ⁇ 2 ° C. , immersed in pure water for 30 minutes and then taken out. At the time of immersion, about 1 cm of water was made to exist on the substrate. Swelling and dissolution of the films were evaluated by comparing soaked and unimmersed substrates.
• a specific evaluation method is as follows. The substrate with and without the immersion was observed and evaluated with a laser microscope. As a laser microscope, VX-1100 manufactured by Keyence Corporation was used. Evaluation criteria are as follows. O (Good): Neither swelling nor dissolution of the film occurred. That is, the membrane had excellent water repellency. x (bad): Swelling and dissolution of the film occurred. That is, the water repellency of the film was inferior.

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