WO2022172921A1 - Fluorine-containing thermosetting resin, method for producing same, and fluorine-containing thermosetting resin composition - Google Patents

Fluorine-containing thermosetting resin, method for producing same, and fluorine-containing thermosetting resin composition Download PDF

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Publication number
WO2022172921A1
WO2022172921A1 PCT/JP2022/004936 JP2022004936W WO2022172921A1 WO 2022172921 A1 WO2022172921 A1 WO 2022172921A1 JP 2022004936 W JP2022004936 W JP 2022004936W WO 2022172921 A1 WO2022172921 A1 WO 2022172921A1
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Prior art keywords
fluorine
thermosetting resin
containing thermosetting
group
monomer
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PCT/JP2022/004936
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French (fr)
Japanese (ja)
Inventor
卓司 石川
琢磨 川部
良成 福原
良弥 穂垣
克彦 井本
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ダイキン工業株式会社
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Priority to JP2022580635A priority Critical patent/JPWO2022172921A1/ja
Publication of WO2022172921A1 publication Critical patent/WO2022172921A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • 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
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • 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
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 ether 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
    • 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
    • C08F220/40—Esters of unsaturated alcohols, e.g. allyl (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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present disclosure relates to a fluorine-containing thermosetting resin, a method for producing the same, and a fluorine-containing thermosetting resin composition.
  • Patent Document 1 discloses an invention relating to a composition containing a predetermined fluorine-containing thermosetting resin, a siloxane compound, and a hydrosilylation reaction catalyst.
  • fluorine-containing thermosetting resins is nothing more than those obtained by introducing cross-linking groups into OH group-containing fluorine resins by polymer reaction.
  • Patent Literature 2 discloses an invention relating to a given laminate, and describes introducing a cross-linking group using a fluorine-containing thermosetting resin. However, it is only described that a cross-linking group is introduced into an OH group-containing fluororesin by a polymer reaction.
  • Patent Document 3 discloses an invention relating to a specific curable resin composition comprising a fluoropolymer and a hydrosilylation cross-linking agent, and describes examples of dicyclopentadiene and fluoroolefin. However, it cannot be said that the polymerization efficiency is good. Further, although a curing system using a cross-linking agent is disclosed, a curing reaction by heat alone is not disclosed.
  • the present disclosure provides a fluorine-containing thermosetting resin having excellent solvent solubility and thermosetting properties.
  • the present disclosure is a fluorine-containing thermosetting resin having a C—F bond between carbon atoms and fluorine atoms forming the main chain
  • the present invention relates to a fluorine-containing thermosetting resin having at least one selected from the group consisting of a dicyclopentenyl group represented by the following formula (I-1) and a dicyclopentenyl group represented by the following formula (I-2).
  • the fluorine-containing thermosetting resin is preferably a copolymer of a fluorine-containing monomer and a fluorine-free monomer.
  • the fluorine-containing monomer preferably contains at least one selected from the group consisting of a fluorine-containing vinyl monomer, a fluorine-containing acrylic monomer, a fluorine-containing styrene monomer, a hydrogen-containing fluoroolefin, and a fluorine-containing norbornene.
  • the fluorine-containing monomer preferably contains at least one selected from the group consisting of fluorine-containing ethylene, fluorine-containing propylene, and fluorine-containing vinyl ether.
  • the fluorine-containing monomer preferably contains at least one selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, vinyl fluoride, hexafluoropropylene, and perfluoro(alkyl vinyl ether). .
  • the fluorine-containing monomer preferably contains at least one compound represented by the following formula.
  • the fluorine-free monomer preferably contains at least one compound represented by the following formula.
  • the fluorine content in the fluorine-containing thermosetting resin is preferably 1% by mass or more and 15% by mass or less with respect to the total mass of the fluorine-containing thermosetting resin.
  • the fluorine-containing thermosetting resin preferably has a glass transition temperature of 80° C. or higher.
  • the fluorine-containing thermosetting resin preferably has a number average molecular weight of 1,000 to 30,000.
  • the present disclosure relates to a fluorine-containing thermosetting resin composition containing the fluorine-containing thermosetting resin and a solvent.
  • the present disclosure relates to a film containing the fluorine-containing thermosetting resin.
  • the present disclosure relates to a laminate including a substrate and a resin layer provided on the substrate, wherein the resin layer contains the fluorine-containing thermosetting resin.
  • the present disclosure relates to a metal-clad laminate comprising a metal foil and a resin layer provided on the metal foil, wherein the resin layer contains the fluorine-containing thermosetting resin.
  • the present disclosure relates to a printed board comprising a pattern circuit formed by etching the metal foil of the metal-clad laminate.
  • thermosetting resin having excellent solvent solubility and thermosetting properties.
  • cross-linking groups are generally introduced by synthesizing a polymer containing OH groups and introducing acrylic groups through a polymer reaction.
  • acrylic monomers having isocyanate are reacted with OH groups to introduce them.
  • the method is simple and widely used.
  • there is a method of simply copolymerizing a diene monomer at the time of polymerization but there are problems such as gelation during polymerization and the introduction amount of cross-linking groups being limited.
  • the present inventors have found that excellent solvent solubility and thermosetting properties can be imparted by using the fluorine-containing thermosetting resin of the present disclosure having a group, and have completed the process.
  • the fluorine-containing thermosetting resin of the present disclosure has a C—F bond between a carbon atom and a fluorine atom forming the main chain, and a dicyclopentenyl group represented by the following formula (I-1) and It has at least one selected from the group consisting of dicyclopentenyl groups represented by formula (I-2). Since the fluorine-containing thermosetting resin of the present disclosure has the structure described above, it is excellent in solvent solubility and thermosetting properties. In addition, it is excellent in low dielectric constant and low dielectric loss tangent, and has low linear expansion. Furthermore, by introducing formulas (I-1) and (I-2) into the polymer, the dicyclopentenyl skeleton enables thermal cross-linking. The thermal cross-linking can also be self-cross-linking without using a cross-linking agent.
  • the fluorine-containing thermosetting resin of the present disclosure contains fluorine atoms and has C—F bonds between the carbon atoms forming the main chain and the fluorine atoms.
  • the fluorine atoms in the fluorine-containing thermosetting resin can be introduced into the resin, for example, by introducing polymerized units based on a fluorine-containing monomer (hereinafter also referred to as "fluorine-containing monomer units").
  • the fluorine-containing monomer may be either a cyclic monomer or an acyclic monomer. Cyclic monomers and non-cyclic monomers preferably have a C—F bond between the carbon atoms forming the main chain of the fluorine-containing thermosetting resin and the fluorine atoms.
  • fluorine-containing monomer examples include fluorine-containing vinyl monomers, fluorine-containing acrylic monomers, fluorine-containing styrene monomers, hydrogen-containing fluoroolefins, and fluorine-containing norbornene.
  • the fluorine-containing monomer preferably contains at least one selected from the group consisting of a fluorine-containing vinyl monomer, a fluorine-containing acrylic monomer, a fluorine-containing styrene monomer, a hydrogen-containing fluoroolefin, and a fluorine-containing norbornene. Vinyl monomers and fluorine-containing acrylic monomers are more preferred.
  • the fluorine-containing vinyl monomer is at least one selected from the group consisting of tetrafluoroethylene [TFE], chlorotrifluoroethylene [CTFE], hexafluoropropylene [HFP] and perfluoro(alkyl vinyl ether). is preferred, and at least one selected from the group consisting of TFE, CTFE, HFP and perfluoro(alkyl vinyl ether) is more preferred.
  • TFE tetrafluoroethylene
  • CTFE chlorotrifluoroethylene
  • HFP hexafluoropropylene
  • perfluoro(alkyl vinyl ether) perfluoro(alkyl vinyl ether
  • TFE perfluoro(alkyl vinyl ether)
  • PVE perfluoro(methyl vinyl ether)
  • PEVE perfluoro(ethyl vinyl ether)
  • PPVE perfluoro(propyl vinyl ether)
  • butyl vinyl ether perfluoro(butyl vinyl ether)
  • fluorine-containing vinyl monomers it is preferable to include at least one selected from the group consisting of fluorine-containing ethylene, fluorine-containing propylene, and fluorine-containing vinyl ether, and tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and Perfluoro(alkyl vinyl ether) is more preferred.
  • fluorine-containing vinyl monomers represented by the following formula are suitable.
  • R 71 to R 74 are each independently a monovalent group, and at least one of R 71 to R 73 is a fluorine atom or a CF 3 group.
  • the monovalent groups of R 71 to R 74 include, for example, hydrogen atoms, halogen atoms (fluorine atom, chlorine atom, etc.), monovalent hydrocarbon groups and the like.
  • the above monovalent hydrocarbon group may have a heteroatom such as a nitrogen atom or an oxygen atom.
  • the above monovalent hydrocarbon group may be linear, branched or cyclic.
  • the number of carbon atoms in the monovalent hydrocarbon group is preferably 1-8, more preferably 1-5, still more preferably 1-3.
  • Examples of the monovalent hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups having the number of carbon atoms described above.
  • the monovalent group is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a fluorinated alkyl group having the above carbon number, or a fluorinated alkoxy group having the above carbon number.
  • fluorine-containing acrylic monomer examples include compounds represented by the following formula, since they can introduce a C—F bond into the main chain of the polymer and increase the glass transition temperature of the polymer.
  • R41 represents an alkyl group optionally substituted with one or more fluorine atoms.
  • R42 represents an alkyl group optionally substituted with one or more fluorine atoms.
  • Examples of the alkyl group of the “alkyl group optionally substituted with one or more fluorine atoms” represented by R 41 and R 42 include methyl group, ethyl group, propyl group and butyl group. Among them, a methyl group, an ethyl group and a t-butyl group are preferable, and a methyl group is more preferable.
  • fluorine-containing acrylic monomers represented by the following formula are suitable.
  • fluorine-containing acrylic monomer represented by the above formula examples include methyl-2-fluoroacrylate and ethyl-2-fluoroacrylate.
  • fluorine-containing acrylic monomer examples include monomers represented by the following formulas (monomers having a dicyclopentenyl group represented by formulas (I-1) and (I-2) above).
  • monomers having a dicyclopentenyl group represented by formulas (I-1) and (I-2) above for example, by using these monomers, the dicyclopentenyl groups represented by the above formulas (I-1) and (I-2) can be introduced into the fluorine-containing thermosetting resin.
  • the fluorine-containing norbornene may have a polymerizable group, and may have one norbornene skeleton or a plurality of norbornene skeletons.
  • a fluorine-containing norbornene is produced by a Diels-Alder addition reaction between an unsaturated compound and a diene compound.
  • Examples of the unsaturated compound include fluorine-containing olefin, fluorine-containing allyl alcohol, fluorine-containing homoallyl alcohol, ⁇ -fluoroacrylic acid, ⁇ -trifluoromethyl acrylic acid, fluorine-containing acrylic acid ester or fluorine-containing methacrylic acid ester, 2- (benzoyloxy)pentafluoropropane, 2-(methoxyethoxymethyloxy)pentafluoropropene, 2-(tetrahydroxypyranyloxy)pentafluoropropene, 2-(benzoyloxy)trifluoroethylene, 2-(methoxymethyloxy) Examples include trifluoroethylene. Examples of the diene compound include cyclopentadiene and cyclohexadiene.
  • fluorine-containing norbornene examples include compounds represented by the following formulas.
  • the fluorine-containing monomer preferably contains at least one selected from the group consisting of fluorine-containing ethylene, fluorine-containing propylene, and fluorine-containing vinyl ether, vinylidene fluoride, tetrafluoroethylene, More preferably, it contains at least one selected from the group consisting of chlorotrifluoroethylene, vinyl fluoride, hexafluoropropylene, and perfluoro(alkyl vinyl ether).
  • the fluorine-containing monomer preferably contains at least one of a compound represented by the following formula, tetrafluoroethylene, and hexafluoropropylene.
  • the fluorine-containing monomer preferably contains at least one compound represented by the following formula.
  • the fluorine-containing monomer contains at least one compound represented by the following formula.
  • the fluorine-containing thermosetting resin of the present disclosure may be a copolymer of a fluorine-containing monomer and a fluorine-free monomer described below.
  • the fluorine-containing monomer unit is excellent in low dielectric constant and low dielectric loss tangent, so that the total polymerization constituting the fluorine-containing thermosetting resin
  • the unit is preferably 5 mol% or more, more preferably 10 mol% or more, more preferably 15 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less, and 60 mol%. More preferred are:
  • the fluorine-containing thermosetting resin of the present disclosure may contain polymerized units based on non-fluorine-containing monomers other than the fluorine-containing monomer units (hereinafter referred to as "non-fluorine-containing monomer units").
  • fluorine-free monomer examples include a fluorine-free monomer reactive with the fluorine-containing monomer.
  • fluorine-free monomer include hydrocarbon-based monomers.
  • the fluorine-free monomer unit (polymerized unit based on the fluorine-free monomer) is excellent in low dielectric constant and low dielectric loss tangent, so it is 20 mol% or more based on the total polymerized units constituting the fluorine-containing thermosetting resin. is preferably 30 mol % or more, more preferably 40 mol % or more, and preferably 90 mol % or less, more preferably 80 mol % or less.
  • the non-fluorine-containing monomer is not particularly limited, but a monomer having a dicyclopentenyl group can be preferably used because of its excellent low dielectric constant and low dielectric loss tangent.
  • the fluorine-containing thermosetting resin has at least one selected from the group consisting of a dicyclopentenyl group represented by the following formula (I-1) and a dicyclopentenyl group represented by the following formula (I-2). and can be prepared, for example, by using monomers having a dicyclopentenyl group represented by the following formulas (I-1) and (I-2).
  • Examples of the monomer having a dicyclopentenyl group represented by the above formulas (I-1) and (I-2) include the following compounds. (Wherein, R 51 is a hydrogen atom or a methyl group.)
  • Dicyclopentenyl acrylate, dicyclopentenyl methacrylate and the like are exemplified as the monomer having a dicyclopentenyl group represented by formulas (I-1) and (I-2).
  • Examples of the dicyclopentenyl group-containing monomer represented by formulas (I-1) and (I-2) include the following compounds. (Wherein, R 61 is a hydrogen atom or a methyl group.)
  • Examples of the dicyclopentenyl group-containing monomer represented by formula (I-2) include dicyclopentadiene vinyl ether.
  • Polymerization based on a monomer unit having a dicyclopentenyl group represented by the above formulas (I-1) and (I-2) is preferably 20 mol% or more, more preferably 30 mol% or more, based on the total polymer units constituting the fluorine-containing thermosetting resin, because it is excellent in low dielectric constant and low dielectric loss tangent. 40 mol% or more is more preferable, 90 mol% or less is preferable, 80 mol% or less is more preferable, and 76 mol% or less is even more preferable.
  • the amount of the monomer units is the total amount of the monomer units represented by formulas (I-1) and (I-2).
  • non-fluorine-containing monomers examples include non-fluorine-containing monomers other than the dicyclopentenyl group-containing monomers represented by the above formulas (I-1) and (I-2). for example, alkenes such as ethylene, propylene, butylene, and isobutylene; Alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether; Vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl valerate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl versatate, vinyl laurate, vinyl myristate, palmitic acid Vinyl, vinyl stearate, vinyl benzoate, vinyl para-t-butylbenzoate, vinyl cyclohexanecarboxylate, vinyl monochloroacetate, vinyl adipate, vinyl acrylate
  • the vinyl ester units are preferably 20 mol% or more, more preferably 30 mol% or more, relative to the total polymerization units constituting the fluorine-containing thermosetting resin. 40 mol% or more is more preferable, 90 mol% or less is preferable, 80 mol% or less is more preferable, and 76 mol% or less is even more preferable.
  • a monomer having an alicyclic structure is preferably selected because it can impart solvent solubility to the fluorine-containing thermosetting resin.
  • the monomer having an alicyclic structure one or more selected from the group consisting of isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentanyl acrylate and dicyclopentanyl methacrylate ( Meth)acrylates are preferred.
  • the fluorine-containing thermosetting resin In terms of increasing the glass transition temperature of the fluorine-containing thermosetting resin, it is preferable to use a monomer having a homopolymer glass transition temperature of 80° C. or higher, 100° C. or higher, preferably 120° C. or higher, as the fluorine-free monomer. More preferably, (meth)acrylic acid esters and N-substituted maleimides having the above alicyclic structure are preferably selected.
  • N-substituted maleimides include N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-(4-acetylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(4- Dimethylamino-3,5-dinitrophenyl)maleimide and N-[4-(2-benzoxazolyl)phenyl]maleimide are preferred.
  • the non-fluorine-containing monomer may also be a functional group-containing hydrocarbon-based monomer.
  • the functional group-containing hydrocarbon-based monomers include OH group-containing monomers.
  • the functional group-containing hydrocarbon-based monomers include fluorine-free monomers having an OH group (hydroxyl group) such as hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, and hydroxycyclohexyl vinyl ether.
  • fluorine-free monomers having a carboxyl group such as itaconic acid, succinic acid, succinic anhydride, fumaric acid, fumaric anhydride, crotonic acid, maleic acid, maleic anhydride
  • fluorine-free monomers having a glycidyl group such as glycidyl vinyl ether and glycidyl allyl ether
  • non-fluorine-containing monomers having amino groups such as aminoalkyl vinyl ethers and aminoalkyl allyl ethers
  • Non-fluorine-containing monomers having an amide group such as (meth)acrylamide and methylolacrylamide are included.
  • the fluorine-free monomer preferably contains at least one compound having a dicyclopentenyl group represented by the following formula.
  • the fluorine-containing thermosetting resin of the present disclosure is excellent in low dielectric constant and low dielectric loss tangent, the molar ratio of fluorine-containing monomer units/fluorine-free monomer units is (1 to 90)/(10 to 99). (1 to 70)/(30 to 99) is more preferred, and (3 to 50)/(50 to 97) is even more preferred.
  • the total content of the fluorine-containing monomer units and fluorine-free monomer units is preferably 70 mol% or more, more preferably 80 mol% or more, and 90 mol % or more is more preferable, 95 mol % or more is even more preferable, and 97 mol % or more is particularly preferable. It may be 100 mol % with respect to all polymerized units.
  • the fluorine content of the fluorine-containing thermosetting resin of the present disclosure is excellent in low dielectric constant and low dielectric loss tangent, it is preferably 1% by mass or more, more preferably It is 3% by mass or more, more preferably 5% by mass or more, and preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less.
  • the fluorine content of the fluorine-containing thermosetting resin can be determined by elemental analysis using an automatic sample combustion apparatus.
  • the fluorine-containing thermosetting resin of the present disclosure preferably has a number average molecular weight of 1,000 to 30,000. When the number average molecular weight of the fluorine-containing thermosetting resin is within this range, solvent solubility and thermosetting properties are improved.
  • the number average molecular weight of the fluorine-containing thermosetting resin is more preferably 1,000 to 20,000, still more preferably 1,000 to 15,000.
  • the number average molecular weight of the fluorine-containing thermosetting resin can be measured by gel permeation chromatography (GPC).
  • the glass transition temperature of the fluorine-containing thermosetting resin of the present disclosure is preferably 80° C. or higher, more preferably 90° C. or higher, and even more preferably 100° C. or higher in terms of excellent electrical properties, particularly in terms of low dielectric loss tangent. , 110° C. or higher are particularly preferred.
  • the above glass transition temperature is a value determined by the midpoint method from heat absorption in the second run using a DSC measuring device under the following conditions according to ASTM E1356-98. Measurement conditions Heating rate; 20°C/min Sample amount; 10 mg Heat cycle; -50°C to 150°C, temperature rise, cooling, temperature rise
  • the fluorine-containing thermosetting resin of the present disclosure preferably has at least one selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2).
  • R 11 is each independently a hydrogen atom or a monovalent hydrocarbon group which may have a substituent
  • m 1 is an integer of 1 to 5.
  • R 21 is each It is independently a hydrogen atom or a monovalent hydrocarbon group which may have a substituent
  • m2 is an integer of 1 to 4.
  • the optionally substituted monovalent hydrocarbon group for R 11 and R 21 may have a heteroatom such as a nitrogen atom or an oxygen atom.
  • the above monovalent hydrocarbon group may be linear, branched or cyclic.
  • the number of carbon atoms in the monovalent hydrocarbon group is preferably 1-8, more preferably 1-5, still more preferably 1-3.
  • Examples of the monovalent hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups having the number of carbon atoms described above.
  • R 11 and R 21 are preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom.
  • n 1 in formula (1) is an integer of 1-5
  • m 2 in formula (2) is an integer of 1-4.
  • the fluorine-containing thermosetting resin preferably has at least one selected from the group consisting of a group represented by the following formula (1-1) and a group represented by the following formula (2-1).
  • a group represented by the following formula (1-1) a group represented by the following formula (2-1).
  • R 11 , m 1 , R 21 and m 2 are the same as defined above.
  • R 12 and R 22 are divalent hydrocarbon groups which may have a substituent.
  • the divalent hydrocarbon group which may have a substituent for R 12 and R 22 may have a heteroatom such as a nitrogen atom or an oxygen atom.
  • the divalent hydrocarbon group may be linear, branched, or cyclic.
  • the number of carbon atoms in the divalent hydrocarbon group is preferably 1-8, more preferably 1-5, still more preferably 1-3.
  • Examples of the divalent hydrocarbon group include alkylene groups and alkenylene groups having the above carbon number, which may have a nitrogen atom and/or an oxygen atom.
  • R 11 and R 12 are preferably a methylene group, ethylene group, ethylidene group, propylidene group, or isopropylidene group which may have a nitrogen atom and/or an oxygen atom, and have a nitrogen atom and/or an oxygen atom. is more preferred.
  • the composition of the fluorine-containing thermosetting resin is appropriately adjusted as described above, and the fluorine-containing monomer and the non-fluorine-containing monomer are mixed in the presence of a chain transfer agent.
  • a monomer having a dicyclopentenyl group represented by the formulas (I-1) and (I-2) is used as the fluorine-containing acrylic monomer; , by using monomers having a dicyclopentenyl group represented by the above formulas (I-1) and (I-2) as fluorine-free monomers (method for producing fluorine-containing thermosetting resin).
  • the fluorine-containing thermosetting resin further includes at least one selected from the group consisting of the group represented by the above formula (1) and the group represented by the above formula (2) at the end of the polymer.
  • at least one selected from the group consisting of the group represented by the above formula (1) and the group represented by the above formula (2) can be introduced at the end of the polymer as the chain transfer agent.
  • the groups represented by the above formulas (1) and (2) can be introduced at the ends of the polymer (manufacturing method 1).
  • At least one selected from the group consisting of the group represented by the above formula (1) and the group represented by the above formula (2) can be introduced at the end of the polymer after polymerization.
  • the groups represented by the above formulas (1) and (2) can be introduced at the ends of the polymer (manufacturing method 2).
  • the fluorine-containing thermosetting resin of the present disclosure can be produced by a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or a bulk polymerization method in polymerization. Among them, those obtained by the solution polymerization method are preferable.
  • the fluorine-containing thermosetting resin of the present disclosure is polymerized by polymerizing the fluorine-containing monomer and the fluorine-free monomer by a solution polymerization method using an organic solvent, a polymerization initiator, a chain transfer agent, and the like. It is preferably produced by reacting a styrenic compound.
  • the polymerization temperature is usually 0 to 150°C, preferably 5 to 120°C.
  • the polymerization pressure is usually 0.1-10 MPaG (1-100 kgf/cm 2 G).
  • organic solvent examples include esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, and tert-butyl acetate; ketones such as acetone, methyl ethyl ketone and cyclohexanone; hexane, cyclohexane, octane, nonane, decane, and undecane.
  • dodecane mineral spirits
  • aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, solvent naphtha
  • cyclic ethers such as tetrahydrofuran, tetrahydropyran and dioxane; dimethylsulfoxide and the like, or mixtures thereof.
  • polymerization initiator examples include persulfates such as ammonium persulfate and potassium persulfate (reducing agents such as sodium hydrogensulfite, sodium pyrosulfite, cobalt naphthenate, and dimethylaniline can also be used in combination, if necessary); oxidizing agent; (e.g. ammonium peroxide, potassium peroxide, etc.), a reducing agent (e.g. sodium sulfite, etc.) and a transition metal salt (e.g. iron sulfate, etc.); diacyl peroxides such as acetyl peroxide, benzoyl peroxide, etc.
  • dialkoxycarbonyl peroxides such as isopropoxycarbonyl peroxide and tert-butoxycarbonyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide; Hydroperoxides such as oxides; Dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide; Alkyl peroxyesters such as tert-butyl peroxyacetate and tert-butyl peroxypivalate;2 ,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(2-methylvaleronitrile), 2,2′-azobis(2- cyclopropylpropionitrile), dimethyl 2,2′-azobisisobutyrate, 2,2
  • thiol compounds can be used as the chain transfer agent.
  • the thiol compound may be any thiol compound known to act as a chain transfer agent, preferably t-dodecylmercaptan, n-dodecylmercaptan, t-octylmercaptan, n-octylmercaptan, trimethylolpropane.
  • t-dodecylmercaptan, n-dodecylmercaptan, t-octylmercaptan, n-octylmercaptan and the like are particularly preferably used from the viewpoint of ease of polymerization control and toughness of the resulting copolymer.
  • alcohols can be used, preferably alcohols having 1 to 10 carbon atoms, more preferably monohydric alcohols having 1 to 10 carbon atoms.
  • methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, 2-methylpropanol, cyclohexanol, methylcyclohexanol, cyclopentanol, methylcyclopentanol and dimethylcyclopentanol can be used.
  • methanol, isopropanol, t-butanol, cyclohexanol, methylcyclohexanol, cyclopentanol, methylcyclopentanol and the like are preferable, and methanol and isopropanol are particularly preferable.
  • a compound capable of introducing at least one selected from the group consisting of the group represented by the above formula (1) and the group represented by the above formula (2) can be used.
  • Diphenyl-4-methyl-pentene is preferred.
  • gelation can be prevented and, in one step, the above formulas (1) to ( 2) can introduce a crosslinkable group.
  • At least one selected from the group consisting of the group represented by the above formula (1) and the group represented by the above formula (2) can be introduced at the end of the polymer.
  • a known method capable of such a reaction can be used.
  • a solution obtained by dissolving the obtained polymer in a solvent is mixed with the styrene-based compound, and the reaction can proceed by appropriately selecting the temperature and time for the reaction to proceed.
  • the reaction temperature is generally 0 to 150°C, preferably 5 to 120°C.
  • the reaction time is usually 0.1 to 100 hours, preferably 1 to 30 hours.
  • halogenated alkylstyrene can be preferably used as the styrene-based compound.
  • halogenated alkylstyrenes include chloromethylstyrene, bromomethylstyrene, iodomethylstyrene, chloroethylstyrene, bromoethylstyrene, iodoethylstyrene, chloropentylstyrene, bromopentylstyrene, iodopentylstyrene, chlorohexylstyrene, Bromohexylstyrene, iodohexylstyrene, chloropropylstyrene, bromopropylstyrene, iodopropylstyrene, chlorobutylstyrene, bromobutylstyrene, brom
  • the fluorine-containing thermosetting resin composition of the present disclosure contains the fluorine-containing thermosetting resin and a solvent.
  • the fluorine-containing thermosetting resin composition of the present disclosure is excellent in solvent solubility and thermosetting properties because the fluorine-containing thermosetting resin has the above configuration. Also, by using it in a resin layer, the resin layer can be made to have a low dielectric constant and a low dielectric loss tangent.
  • the fluorine-containing thermosetting resin is the same as the fluorine-containing thermosetting resin of the present disclosure. Therefore, all suitable embodiments of the fluorine-containing thermosetting resin described in the fluorine-containing thermosetting resin of the present disclosure can be employed.
  • the fluorine-containing thermosetting resin composition of the present disclosure contains a solvent.
  • the above solvent is preferably an organic solvent, and the organic solvent is not particularly limited.
  • Esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, and propylene glycol methyl ether acetate; Ketones such as ketones and cyclohexanone; Cyclic ethers such as tetrahydrofuran and dioxane; Amides such as N,N-dimethylformamide and N,N-dimethylacetamide; Aromatic hydrocarbons such as toluene and xylene; Propylene glycol methyl ether alcohols such as hexane; hydrocarbons such as hexane and heptane; and mixed solvents thereof.
  • the fluorine-containing thermosetting resin composition of the present disclosure may further contain the aforementioned monomers and other monomer components such as styrene and methyl (meth)acrylate.
  • the monomer component may be a monomer component containing multiple vinyl groups such as divinylbenzene or pentaerythritol tri(meth)acrylate.
  • the above-mentioned polymerization initiator and photopolymerization initiator may be included.
  • Photoinitiators include, for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl ]-Acetophenones such as 2-morpholinopropan-1-one; Anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; 2,4-diethylthioxanthone, 2- Thio
  • the fluorine-containing thermosetting resin composition of the present disclosure may not contain a cross-linking agent (curing agent), or may contain neither a cross-linking agent (curing agent) nor a curing accelerator. Since the fluorine-containing thermosetting resin contains a dicyclopentenyl group, it can be self-crosslinked without using a crosslinking agent or a curing accelerator. Therefore, it is possible to improve electrical properties without adding extra components.
  • the fluorine-containing thermosetting resin is preferably 10% by mass or more, more preferably 25% by mass or more, and 40% by mass or more relative to the solid content of 100% by mass. More preferably, it may be 100% by mass or less, or may be 80% by mass or less.
  • the fluorine-containing thermosetting resin composition of the present disclosure may contain flame retardants, inorganic fillers, silane coupling agents, release agents, pigments, emulsifiers and the like.
  • the fluorine-containing thermosetting resin composition of the present disclosure may contain various additives according to required properties.
  • Additives include pigment dispersants, antifoaming agents, leveling agents, UV absorbers, light stabilizers, thickeners, adhesion improvers, matting agents and the like.
  • the method of preparing the fluorine-containing thermosetting resin composition of the present disclosure is not particularly limited. Examples thereof include a method of mixing a solution or dispersion of a fluorine-containing thermosetting resin with other components.
  • the fluorine-containing thermosetting resin composition of the present disclosure can be suitably used as a resin layer of a laminate comprising a substrate and a resin layer provided on the substrate, and is particularly suitable as a resin layer of a metal-clad laminate. Available. It can also be used for resins for powder coatings, resins for optical applications, and resist materials.
  • the fluorine-containing thermosetting resin composition of the present disclosure is a metal-clad laminate comprising a metal foil and a resin layer provided on the metal foil, wherein the resin layer is the fluorine-containing thermosetting resin of the present disclosure. It can be suitably used for a metal-clad laminate formed from a resin composition. A resin layer can be formed by curing the fluorine-containing thermosetting resin composition of the present disclosure.
  • the metal-clad laminate includes a metal foil and a resin layer.
  • the resin layer has excellent insulating properties and plays a role as a base material of the metal-clad laminate.
  • metal foils examples include metal foils made of copper, aluminum, iron, nickel, chromium, molybdenum, tungsten, zinc, or alloys thereof, preferably copper foil.
  • chemical or mechanical surface treatment may be applied with siding, nickel plating, copper-zinc alloy plating, aluminum alcoholate, aluminum chelate, silane coupling agent, or the like.
  • the metal-clad laminate comprises the metal foil and the resin layer
  • the metal-clad laminate may further include other layers, and each of the metal foil and the resin layer may be one kind, or two or more kinds. may be
  • the metal-clad laminate may further include a second resin layer provided on the resin layer (hereinafter referred to as "first resin layer"). That is, the metal-clad laminate may be formed by laminating a metal foil, a first resin layer, and a second resin layer in this order.
  • the first resin layer not only serves as a base material, but may also serve as an adhesive layer that bonds the metal foil and the second resin layer.
  • the first resin layer may be provided on the surface of the metal foil different from the surface on which the first resin layer is provided (the opposite side). That is, the metal-clad laminate may be one in which the first resin layer, the metal foil, and the first resin layer are laminated in this order, or the first resin layer, the metal foil, and the first resin layer. , and the second resin layer.
  • Resins used in conventional printed circuit boards can be used for the second resin layer, but the second resin layer is at least one selected from the group consisting of polyethylene terephthalate and polyimide. It is preferably made of resin, and more preferably made of polyimide from the viewpoint of heat resistance.
  • a film having a thickness of 1 to 150 ⁇ m can be used as the first resin layer.
  • the thickness of the first resin layer after drying can be 1 to 100 ⁇ m.
  • a resin film having a thickness of 1 to 150 ⁇ m can be used as the second resin layer.
  • the metal-clad laminate can be obtained by a manufacturing method including a step of obtaining a metal-clad laminate by bonding a metal foil and a film made of the fluorine-containing thermosetting resin composition.
  • a bonding method a method of stacking the metal foil and the film containing the fluorine-containing thermosetting resin composition and then thermocompression bonding them at 50 to 300° C. using a hot press is suitable.
  • the above production method may further include the step of molding the fluorine-containing thermosetting resin composition to obtain a film made of the fluorine-containing thermosetting resin. Examples of the molding method include, but are not limited to, methods such as melt extrusion molding, solvent casting, and spraying.
  • the fluorine-containing thermosetting resin composition may contain an organic solvent, a curing agent, etc., and may contain a curing accelerator, a pigment dispersant, an antifoaming agent, a leveling agent, a UV absorber, a light stabilizer, Thickeners, adhesion improvers, matting agents and the like may also be included.
  • the metal-clad laminate can also be obtained by a manufacturing method including the step of applying the fluorine-containing thermosetting resin composition to a metal foil to form a first resin layer.
  • a resin film to be the second resin layer is further adhered on the first resin layer, and the metal foil and the first and second It may include a step of obtaining a metal-clad laminate including a resin layer.
  • the resin film include a film made of a resin suitable for forming the second resin layer.
  • a method for adhering the resin film a method of thermocompression bonding at 50 to 300° C. using a hot press is suitable.
  • methods for applying the composition for forming the first resin layer to the metal foil include brush coating, dip coating, spray coating, comma coating, knife coating, die coating, lip coating, and roll coating. , curtain coating, and the like. After applying the composition, it can be cured by drying in a hot air drying oven or the like at 25 to 200° C. for 1 minute to 1 week.
  • the metal-clad laminate includes a step of applying the fluorine-containing thermosetting resin composition to a resin film that will be the second resin layer to form a first resin layer, and a first resin layer obtained by the forming step. a step of bonding a metal foil to a first resin layer of a laminate comprising a resin layer and a second resin layer to obtain a metal-clad laminate comprising the metal foil and the first and second resin layers; It can also be manufactured by a manufacturing method including: Examples of the resin film include a film made of a resin suitable for forming the second resin layer.
  • Methods for applying the composition for forming the first resin layer to the resin film include brush coating, dip coating, spray coating, comma coating, knife coating, die coating, lip coating, roll coater coating, curtain coating, and the like. method. After applying the composition, it can be cured by drying in a hot air drying oven or the like at 25 to 200° C. for 1 minute to 1 week.
  • the method of bonding the metal foil to the first resin layer of the laminate composed of the first resin layer and the second resin layer includes: A preferred method is to laminate the laminate and the metal foil so that the first resin layer and the metal foil of the laminate are adhered, and then thermocompress them with a hot press at 50 to 300 ° C. .
  • the metal-clad laminate can be applied to a printed circuit board provided with a pattern circuit formed by etching the metal foil of the metal-clad laminate.
  • the printed board may be a flexible board or a rigid board, but is preferably a rigid board.
  • the printed circuit board may include a coverlay film on the metal-clad laminate, and the coverlay film may be adhered to the metal-clad laminate via the resin layer.
  • the etching method is not limited, and conventionally known methods can be employed.
  • the pattern circuit is not limited, and a printed circuit board having any pattern circuit may be used.
  • the printed circuit board has a resin layer with a low dielectric constant and a low dielectric loss tangent, it is used in applications with high frequency bands such as 4G (37.5 Mbps) and 5G (several G to 20 Gbps). It can also be used for substrates.
  • Thermosetting evaluation (gel fraction) 10 g of the solution prepared in the solvent solubility evaluation was placed in an aluminum cup, dried at room temperature for 1 hour, and then dried by heating at 150° C. for 3 hours to obtain a thermoset. The cured material was taken and wrapped in a pre-weighed 400 mesh metal wire mesh. 25 ml of acetone and the cured product wrapped in a wire mesh were placed in a 50 ml sample tube, and the cured product was immersed in acetone for 12 hours. After that, the wire mesh was taken out, dried, and the mass after drying was measured, and the mass of the dried and cured product after immersion in acetone was calculated. The gel fraction was calculated as (mass of dried cured product after immersion in acetone/mass of cured product before immersion in acetone ⁇ 100).
  • thermosetting temperature is the peak top temperature of the exothermic peak observed during measurement with a DSC measurement device, or a differential thermal/thermogravimetry device [TG-DTA] (trade name: TG/DTA7200 , Hitachi High-Tech Science Co., Ltd.), 10 mg of the sample was heated from room temperature at a heating rate of 10 ° C./min, and the temperature of the peak top of the exothermic peak seen in the temperature range where the weight loss was less than 1% was heat cured. temperature.
  • TG-DTA differential thermal/thermogravimetry device
  • Synthesis example 1 800 g of acetone in a stainless steel autoclave with a capacity of 3000 ml, vinyl ether 1 (DCPD-VE) represented by the following formula: 130 g of tetrafluoroethylene (TFE) was introduced, and the vacuum nitrogen replacement operation was performed. The temperature was raised to 65.0° C. while stirring, and 8 g of a peroxide polymerization initiator was charged to initiate polymerization. When the internal pressure of the reactor decreased from 0.9 MPaG to 0.5 MPaG, the reaction was terminated to obtain a uniform solution containing the copolymer. After concentrating the obtained solution, the concentrated liquid was poured into a large amount of methanol to precipitate the copolymer. The resulting copolymer was washed with methanol, filtered and dried to obtain a copolymer.
  • DCPD-VE vinyl ether 1
  • TFE tetrafluoroethylene
  • the resulting copolymer had a composition of 55 mol % tetrafluoroethylene and 45 mol % vinyl ether 1.
  • Molecular weight analysis revealed a number average molecular weight (Mn) of 13,000 and a weight average molecular weight (Mw) of 26,000.
  • the glass transition temperature (Tg) was 92°C.
  • Elemental analysis showed a fluorine content of 31.5% by mass. As a result of DSC measurement, an exothermic peak was observed around 140°C.
  • Synthesis example 2 800 g of acetone and 45 g of vinyl crotonate were charged into a stainless steel autoclave having a capacity of 3000 ml, and the autoclave was subjected to vacuum nitrogen replacement, and 130 g of tetrafluoroethylene (TFE) was charged. The temperature was raised to 65.0° C. while stirring, and 2 g of a peroxide polymerization initiator was charged to initiate polymerization. The reaction was stopped when the internal pressure of the reactor decreased from 0.9 MPaG to 0.8 MPaG. The reaction solution was a heterogeneous solution, and the copolymer solid was insoluble in the solvent and precipitated at the bottom of the autoclave.
  • TFE tetrafluoroethylene
  • Synthesis example 3 A stainless steel autoclave with a capacity of 3000 ml was charged with 800 g of acetone and vinyl ether 2 represented by the following formula: 130 g of tetrafluoroethylene (TFE) was introduced, and the vacuum nitrogen replacement operation was performed. The temperature was raised to 65.0° C. while stirring, and 8 g of a peroxide polymerization initiator was charged to initiate polymerization. When the internal pressure of the reactor decreased from 0.9 MPaG to 0.5 MPaG, the reaction was terminated to obtain a heterogeneous solution containing the copolymer. After concentrating the obtained solution, the concentrated liquid was poured into a large amount of methanol to precipitate the copolymer. The resulting copolymer was washed with methanol, filtered and dried to obtain a copolymer.
  • TFE tetrafluoroethylene
  • the resulting copolymer had a composition of 55 mol % tetrafluoroethylene and 45 mol % vinyl ether 2.
  • Molecular weight analysis revealed a number average molecular weight (Mn) of 8,000 and a weight average molecular weight (Mw) of 15,000.
  • the glass transition temperature (Tg) was 62°C. Elemental analysis showed a fluorine content of 30.4% by mass.
  • Synthesis example 4 800 g of acetone and 400 g of vinyl 4-t-butylbenzoate were charged into a stainless steel autoclave having a capacity of 3000 ml, two operations of vacuum nitrogen replacement were performed, and 130 g of tetrafluoroethylene (TFE) was charged. The temperature was raised to 65.0° C. while stirring, and 2 g of a peroxide polymerization initiator was charged to initiate polymerization. When the internal pressure of the reactor decreased from 0.9 MPaG to 0.5 MPaG, the reaction was terminated to obtain a uniform solution containing the copolymer. After concentrating the obtained solution, the concentrated liquid was poured into a large amount of methanol to precipitate the copolymer. The resulting copolymer was washed with methanol, filtered and dried to obtain a copolymer.
  • TFE tetrafluoroethylene
  • the resulting copolymer had a composition of 26 mol % tetrafluoroethylene and 74 mol % vinyl 4-t-butylbenzoate.
  • Molecular weight analysis revealed a number average molecular weight (Mn) of 30,000 and a weight average molecular weight (Mw) of 74,000.
  • the glass transition temperature (Tg) was 120°C. Elemental analysis showed a fluorine content of 12.6% by mass.
  • Synthesis example 5 60 g of methyl isobutyl ketone, 19.5 g of dicyclopentenyl acrylate, 12.4 g of methyl-2-fluoroacrylate, and 1.3 g of 2,4-diphenyl-4-methyl-1-pentene were introduced into a 300 ml four-necked flask. The internal temperature was adjusted to 90° C., 0.6 g of t-butylperoxy-2-ethylhexanoate was added, and the reaction was allowed to proceed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer.
  • the obtained copolymer was washed with hexane, filtered and dried to obtain 8 g of copolymer. Elemental analysis and NMR analysis revealed that the obtained copolymer had a composition of 47 mol % of the structure derived from dicyclopentenyl acrylate and 53 mol % of the structure derived from methyl-2-fluoroacrylate. Further, the terminal groups of the structure derived from 2,4-diphenyl-4-methyl-1-pentene are a structure derived from dicyclopentanyl acrylate, a structure derived from methyl-2-fluoroacrylate and 2,4-diphenyl-4- It was 3.0 mol % with respect to the total terminal groups of the structure derived from methyl-1-pentene. Of these, 16 mol % were found to have the group represented by the above formula (1-1).
  • Synthesis example 6 60 g of methyl isobutyl ketone, 21.5 g of dicyclopentenyl acrylate, 16.5 g of 1,2,2-trifluoroethenylbenzene, and 0.8 g of 2,4-diphenyl-4-methyl-1-pentene were placed in a 300 ml four-necked flask. put in. The internal temperature was adjusted to 90° C., 0.8 g of t-butylperoxy-2-ethylhexanoate was added, and the reaction was allowed to proceed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer.
  • the obtained copolymer was washed with hexane, filtered and dried to obtain a copolymer. Elemental analysis and NMR analysis revealed that the obtained copolymer had a composition of 76 mol % of the structure derived from dicyclopentenyl acrylate and 24 mol % of the structure derived from 1,2,2-trifluoroethenylbenzene. Molecular weight analysis revealed a number average molecular weight (Mn) of 6,500 and a weight average molecular weight (Mw) of 14,000. The glass transition temperature (Tg) was 105°C. Elemental analysis showed a fluorine content of 6.2% by mass. As a result of DSC measurement, an exothermic peak was observed around 140°C.
  • Synthesis example 7 In a 300 ml four-neck flask, 200 g of methyl isobutyl ketone, vinyl ether 1 (DCPD-VE) represented by the following formula: 32 g of 1,2,2-trifluoroethenylbenzene, 30 g of N-cyclohexylmaleimide, and 66 g of N-cyclohexylmaleimide were added, and nitrogen substitution was performed. The internal temperature was adjusted to 70° C., 8 g of t-butyl peroxypivalate was added, and the mixture was reacted for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The resulting copolymer was washed with methanol, filtered and dried to obtain a copolymer.
  • DCPD-VE vinyl ether 1
  • the obtained copolymer had a composition of 5 mol % of 1,2,2-trifluoroethenylbenzene, 32 mol % of vinyl ether 1 and 63 mol % of N-cyclohexylmaleimide.
  • Molecular weight analysis revealed a number average molecular weight (Mn) of 4,100 and a weight average molecular weight (Mw) of 11,000.
  • the glass transition temperature (Tg) was 250°C. Elemental analysis showed a fluorine content of 1.7% by mass. As a result of TGDTA measurement, an exothermic peak was observed around 220°C.
  • the copolymers obtained in Synthesis Examples 1, 5, 6, and 7 have at least It was found to have one. From Table 1, the copolymers obtained in Synthesis Examples 1, 5, 6 and 7 were excellent in thermosetting properties (gel fraction) and had good solvent solubility.

Abstract

Provided is a fluorine-containing thermosetting resin having excellent solvent solubility and thermosetting property. A fluorine-containing thermosetting resin having a C-F bond between a fluorine atom and a carbon atom forming the main chain, wherein the fluorine-containing thermosetting resin has at least one selected from the group consisting of dicyclopentenyl groups represented by formula (I-1) and dicyclopentenyl group represented by formula (I-2). [Chemical formula 1]

Description

含フッ素熱硬化性樹脂、その製造方法、及び含フッ素熱硬化性樹脂組成物Fluorine-Containing Thermosetting Resin, Method for Producing Same, and Fluorine-Containing Thermosetting Resin Composition
本開示は、含フッ素熱硬化性樹脂、その製造方法、及び含フッ素熱硬化性樹脂組成物に関する。 The present disclosure relates to a fluorine-containing thermosetting resin, a method for producing the same, and a fluorine-containing thermosetting resin composition.
近年、電気機器や、電子機器、通信機器は、目覚ましく発展している。現在、これらの機器では、より高周帯域の周波数が使用される傾向にある。通常、これらの機器には、様々なプリント基板が使用されている。したがって、プリント基板にも、高周帯域の周波数に対応する優れた電気的特性や、ハンダ作業に耐え得るだけの優れた耐熱性等が求められている。 In recent years, electrical equipment, electronic equipment, and communication equipment have developed remarkably. These devices now tend to use higher frequencies. Various printed circuit boards are usually used in these devices. Therefore, the printed circuit board is also required to have excellent electrical characteristics corresponding to frequencies in the high frequency band and excellent heat resistance to withstand soldering work.
例えば、特許文献１は、所定の含フッ素熱硬化性樹脂、シロキサン化合物、ヒドロシリル化反応用触媒を含む組成物に係る発明を開示している。しかしながら、含フッ素熱硬化性樹脂として具体的に開示されているのは、ＯＨ基含有フッ素樹脂にポリマー反応で架橋基を導入したものなどにすぎない。 For example, Patent Document 1 discloses an invention relating to a composition containing a predetermined fluorine-containing thermosetting resin, a siloxane compound, and a hydrosilylation reaction catalyst. However, what is specifically disclosed as fluorine-containing thermosetting resins is nothing more than those obtained by introducing cross-linking groups into OH group-containing fluorine resins by polymer reaction.
特許文献２は、所定の積層体に係る発明を開示し、含フッ素熱硬化性樹脂を用いて架橋基を導入することが記載されている。しかしながら、ＯＨ基含有フッ素樹脂にポリマー反応で、架橋基を導入することなどが記載されているにすぎない。 Patent Literature 2 discloses an invention relating to a given laminate, and describes introducing a cross-linking group using a fluorine-containing thermosetting resin. However, it is only described that a cross-linking group is introduced into an OH group-containing fluororesin by a polymer reaction.
特許文献３は、含フッ素重合体とヒドロシリル化架橋剤とからなる所定の硬化性樹脂組成物に係る発明を開示し、ジシクロペンタジエンとフッ素オレフィンの例示が記載されている。しかしながら、重合効率は良いとは言えない。また、架橋剤を併用した硬化系が開示されているが、熱だけでの硬化反応は開示されていない。 Patent Document 3 discloses an invention relating to a specific curable resin composition comprising a fluoropolymer and a hydrosilylation cross-linking agent, and describes examples of dicyclopentadiene and fluoroolefin. However, it cannot be said that the polymerization efficiency is good. Further, although a curing system using a cross-linking agent is disclosed, a curing reaction by heat alone is not disclosed.
国際公開第２００８／０４４７６５号WO2008/044765 特開２０１４－２６６１９号公報JP 2014-26619 A 国際公開第２０１１／１１５０４２号WO2011/115042
本開示は、溶剤溶解性、熱硬化性に優れる含フッ素熱硬化性樹脂を提供する。 The present disclosure provides a fluorine-containing thermosetting resin having excellent solvent solubility and thermosetting properties.
本開示は、主鎖を形成する炭素原子とフッ素原子との間のＣ－Ｆ結合を有する含フッ素熱硬化性樹脂であって、
下記式（Ｉ－１）で示されるジシクロペンテニル基及び下記式（Ｉ－２）で示されるジシクロペンテニル基からなる群より選択される少なくとも１種を有する含フッ素熱硬化性樹脂に関する。
Figure JPOXMLDOC01-appb-C000004
 The present disclosure is a fluorine-containing thermosetting resin having a C—F bond between carbon atoms and fluorine atoms forming the main chain,
The present invention relates to a fluorine-containing thermosetting resin having at least one selected from the group consisting of a dicyclopentenyl group represented by the following formula (I-1) and a dicyclopentenyl group represented by the following formula (I-2).
Figure JPOXMLDOC01-appb-C000004
上記含フッ素熱硬化性樹脂が含フッ素モノマーとフッ素非含有モノマーとの共重合体であることが好ましい。 The fluorine-containing thermosetting resin is preferably a copolymer of a fluorine-containing monomer and a fluorine-free monomer.
上記含フッ素モノマーは、含フッ素ビニルモノマー、含フッ素アクリルモノマー、含フッ素スチレンモノマー、水素含有フルオロオレフィン、及び含フッ素ノルボルネンからなる群より選択される少なくとも１種を含むことが好ましい。 The fluorine-containing monomer preferably contains at least one selected from the group consisting of a fluorine-containing vinyl monomer, a fluorine-containing acrylic monomer, a fluorine-containing styrene monomer, a hydrogen-containing fluoroolefin, and a fluorine-containing norbornene.
上記含フッ素モノマーは、含フッ素エチレン、含フッ素プロピレン、及び含フッ素ビニルエーテルからなる群より選択される少なくとも１種を含むことが好ましい。 The fluorine-containing monomer preferably contains at least one selected from the group consisting of fluorine-containing ethylene, fluorine-containing propylene, and fluorine-containing vinyl ether.
上記含フッ素モノマーは、フッ化ビニリデン、テトラフルオロエチレン、クロロトリフルオロエチレン、フッ化ビニル、へキサフルオロプロピレン、及びパーフルオロ（アルキルビニルエーテル）からなる群より選択される少なくとも１種を含むことが好ましい。 The fluorine-containing monomer preferably contains at least one selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, vinyl fluoride, hexafluoropropylene, and perfluoro(alkyl vinyl ether). .
上記含フッ素モノマーは、下記式で示される化合物の少なくとも１種を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000005
 The fluorine-containing monomer preferably contains at least one compound represented by the following formula.
Figure JPOXMLDOC01-appb-C000005
上記フッ素非含有モノマーは、下記式で示される化合物の少なくとも１種を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000006
 The fluorine-free monomer preferably contains at least one compound represented by the following formula.
Figure JPOXMLDOC01-appb-C000006
上記含フッ素熱硬化性樹脂に含まれるフッ素含有量は、上記含フッ素熱硬化性樹脂の全質量に対して、１質量％以上１５質量％以下であることが好ましい。 The fluorine content in the fluorine-containing thermosetting resin is preferably 1% by mass or more and 15% by mass or less with respect to the total mass of the fluorine-containing thermosetting resin.
上記含フッ素熱硬化性樹脂は、ガラス転移温度が８０℃以上であることが好ましい。 The fluorine-containing thermosetting resin preferably has a glass transition temperature of 80° C. or higher.
上記含フッ素熱硬化性樹脂は、数平均分子量が１０００～３００００であることが好ましい。 The fluorine-containing thermosetting resin preferably has a number average molecular weight of 1,000 to 30,000.
本開示は、上記含フッ素熱硬化性樹脂と、溶剤とを含む含フッ素熱硬化性樹脂組成物に関する。 The present disclosure relates to a fluorine-containing thermosetting resin composition containing the fluorine-containing thermosetting resin and a solvent.
本開示は、上記含フッ素熱硬化性樹脂を含むフィルムに関する。 The present disclosure relates to a film containing the fluorine-containing thermosetting resin.
本開示は、基材と、上記基材上に設けられた樹脂層とを備える積層体であって、上記樹脂層が、上記含フッ素熱硬化性樹脂を含む積層体に関する。 The present disclosure relates to a laminate including a substrate and a resin layer provided on the substrate, wherein the resin layer contains the fluorine-containing thermosetting resin.
本開示は、金属箔と、上記金属箔上に設けられた樹脂層とを備える金属張積層板であって、上記樹脂層が、上記含フッ素熱硬化性樹脂を含む金属張積層板に関する。 The present disclosure relates to a metal-clad laminate comprising a metal foil and a resin layer provided on the metal foil, wherein the resin layer contains the fluorine-containing thermosetting resin.
本開示は、上記金属張積層板の金属箔をエッチングして形成されたパターン回路を備えることを特徴とするプリント基板に関する。 The present disclosure relates to a printed board comprising a pattern circuit formed by etching the metal foil of the metal-clad laminate.
本開示によれば、溶剤溶解性、熱硬化性に優れる含フッ素熱硬化性樹脂を提供することができる。 According to the present disclosure, it is possible to provide a fluorine-containing thermosetting resin having excellent solvent solubility and thermosetting properties.
特許文献１、２などに記載のとおり、一般に、フッ素樹脂を熱硬化樹脂とするためには架橋基を導入する必要がある。そして、これまでの架橋基の導入は、ＯＨ基を含有するポリマーを合成し、ポリマー反応でアクリル基を導入する方法が一般的であり、特にイソシアネートを有するアクリルモノマーをＯＨ基に反応させて導入する方法が簡便であり、よく利用されている。他の手法として、簡便にジエンモノマーを重合時に共重合する方法もあるが、重合中にゲル化したり、架橋基の導入量が制限されるという問題がある。 As described in Patent Documents 1 and 2, it is generally necessary to introduce a cross-linking group in order to convert a fluororesin into a thermosetting resin. Conventionally, cross-linking groups are generally introduced by synthesizing a polymer containing OH groups and introducing acrylic groups through a polymer reaction. In particular, acrylic monomers having isocyanate are reacted with OH groups to introduce them. The method is simple and widely used. As another technique, there is a method of simply copolymerizing a diene monomer at the time of polymerization, but there are problems such as gelation during polymerization and the introduction amount of cross-linking groups being limited.
本開示者の鋭意検討により、主鎖を形成する炭素原子とフッ素原子との間のＣ－Ｆ結合を有し、かつ上記式（Ｉ－１）、（Ｉ－２）で示されるジシクロペンテニル基を有する本開示の含フッ素熱硬化性樹脂を用いることで、優れた溶剤溶解性及び熱硬化性を付与できることを見出し、完成に至った。 As a result of intensive studies by the present disclosure, dicyclopentenyl having a C—F bond between a carbon atom and a fluorine atom forming the main chain and represented by the above formulas (I-1) and (I-2) The present inventors have found that excellent solvent solubility and thermosetting properties can be imparted by using the fluorine-containing thermosetting resin of the present disclosure having a group, and have completed the process.
本開示の含フッ素熱硬化性樹脂は、主鎖を形成する炭素原子とフッ素原子との間のＣ－Ｆ結合を有し、かつ下記式（Ｉ－１）で示されるジシクロペンテニル基及び下記式（Ｉ－２）で示されるジシクロペンテニル基からなる群より選択される少なくとも１種を有する。
Figure JPOXMLDOC01-appb-C000007
 本開示の含フッ素熱硬化性樹脂は、上記構造を有するので、溶剤溶解性、熱硬化性に優れる。また、低誘電率及び低誘電正接に優れ、線膨張も低い。更に、ポリマーに式（Ｉ－１）、（Ｉ－２）を導入することで、該ジシクロペンテニル骨格により熱架橋が可能となる。上記熱架橋は、架橋剤を使用しない自己架橋とすることもできる。 The fluorine-containing thermosetting resin of the present disclosure has a C—F bond between a carbon atom and a fluorine atom forming the main chain, and a dicyclopentenyl group represented by the following formula (I-1) and It has at least one selected from the group consisting of dicyclopentenyl groups represented by formula (I-2).
Figure JPOXMLDOC01-appb-C000007
 Since the fluorine-containing thermosetting resin of the present disclosure has the structure described above, it is excellent in solvent solubility and thermosetting properties. In addition, it is excellent in low dielectric constant and low dielectric loss tangent, and has low linear expansion. Furthermore, by introducing formulas (I-1) and (I-2) into the polymer, the dicyclopentenyl skeleton enables thermal cross-linking. The thermal cross-linking can also be self-cross-linking without using a cross-linking agent.
本開示の含フッ素熱硬化性樹脂は、フッ素原子を含み、主鎖を形成する炭素原子とフッ素原子との間のＣ－Ｆ結合を有している。
上記含フッ素熱硬化性樹脂中のフッ素原子は、例えば、含フッ素モノマーに基づく重合単位（以下「含フッ素モノマー単位」とも記載する）の導入により、樹脂中に導入できる。上記含フッ素モノマーは、環状モノマー、非環状モノマーのいずれでもよい。環状モノマー、非環状モノマーは、含フッ素熱硬化性樹脂の主鎖を形成する炭素原子とフッ素原子との間のＣ－Ｆ結合を有するものが好ましい。 The fluorine-containing thermosetting resin of the present disclosure contains fluorine atoms and has C—F bonds between the carbon atoms forming the main chain and the fluorine atoms.
The fluorine atoms in the fluorine-containing thermosetting resin can be introduced into the resin, for example, by introducing polymerized units based on a fluorine-containing monomer (hereinafter also referred to as "fluorine-containing monomer units"). The fluorine-containing monomer may be either a cyclic monomer or an acyclic monomer. Cyclic monomers and non-cyclic monomers preferably have a C—F bond between the carbon atoms forming the main chain of the fluorine-containing thermosetting resin and the fluorine atoms.
上記含フッ素モノマーとしては、含フッ素ビニルモノマー、含フッ素アクリルモノマー、含フッ素スチレンモノマー、水素含有フルオロオレフィン、含フッ素ノルボルネンなどが挙げられる。上記含フッ素モノマーは、含フッ素ビニルモノマー、含フッ素アクリルモノマー、含フッ素スチレンモノマー、水素含有フルオロオレフィン、及び含フッ素ノルボルネンからなる群より選択される少なくとも１種を含むことが好ましく、中でも、含フッ素ビニルモノマー、含フッ素アクリルモノマーがより好ましい。 Examples of the fluorine-containing monomer include fluorine-containing vinyl monomers, fluorine-containing acrylic monomers, fluorine-containing styrene monomers, hydrogen-containing fluoroolefins, and fluorine-containing norbornene. The fluorine-containing monomer preferably contains at least one selected from the group consisting of a fluorine-containing vinyl monomer, a fluorine-containing acrylic monomer, a fluorine-containing styrene monomer, a hydrogen-containing fluoroolefin, and a fluorine-containing norbornene. Vinyl monomers and fluorine-containing acrylic monomers are more preferred.
上記含フッ素ビニルモノマーとしては、テトラフルオロエチレン〔ＴＦＥ〕、クロロトリフルオロエチレン〔ＣＴＦＥ〕、へキサフルオロプロピレン〔ＨＦＰ〕及びパーフルオロ（アルキルビニルエーテル）からなる群より選択される少なくとも１種であることが好ましく、ＴＦＥ、ＣＴＦＥ、ＨＦＰ及びパーフルオロ（アルキルビニルエーテル）からなる群より選択される少なくとも１種であることがより好ましい。低誘電率及び低誘電正接であり、分散性、耐湿性、耐熱性、難燃性、接着性、及び耐薬品性等に優れている点、また、低誘電率及び低誘電正接であり、耐候性及び防湿性にも優れている点で、ＴＦＥ、ＣＴＦＥ及びＨＦＰからなる群より選択される少なくとも１種であることがより好ましく、塩素を含まない点でＴＦＥ及びＨＦＰからなる群より選択される少なくとも１種であることが更に好ましく、共重合性に優れている点で、ＴＦＥが特に好ましい。
上記パーフルオロ（アルキルビニルエーテル）としては、パーフルオロ（メチルビニルエーテル）〔ＰＭＶＥ〕、パーフルオロ（エチルビニルエーテル）〔ＰＥＶＥ〕、パーフルオロ（プロピルビニルエーテル）〔ＰＰＶＥ〕、パーフルオロ（ブチルビニルエーテル）等が挙げられるがこれらに限定されるものではない。 The fluorine-containing vinyl monomer is at least one selected from the group consisting of tetrafluoroethylene [TFE], chlorotrifluoroethylene [CTFE], hexafluoropropylene [HFP] and perfluoro(alkyl vinyl ether). is preferred, and at least one selected from the group consisting of TFE, CTFE, HFP and perfluoro(alkyl vinyl ether) is more preferred. Low dielectric constant and low dielectric loss tangent, excellent dispersibility, moisture resistance, heat resistance, flame retardancy, adhesion, and chemical resistance. It is more preferably at least one selected from the group consisting of TFE, CTFE and HFP in terms of excellent resistance and moisture resistance, and is selected from the group consisting of TFE and HFP in terms of not containing chlorine. At least one type is more preferable, and TFE is particularly preferable in terms of excellent copolymerizability.
Examples of the perfluoro(alkyl vinyl ether) include perfluoro(methyl vinyl ether) [PMVE], perfluoro(ethyl vinyl ether) [PEVE], perfluoro(propyl vinyl ether) [PPVE], perfluoro(butyl vinyl ether), and the like. are not limited to these.
上記含フッ素ビニルモノマーの中でも、含フッ素エチレン、含フッ素プロピレン、及び含フッ素ビニルエーテルからなる群より選択される少なくとも１種を含むことが好ましく、テトラフルオロエチレン、クロロトリフルオロエチレン、へキサフルオロプロピレン及びパーフルオロ（アルキルビニルエーテル）がより好ましい。 Among the fluorine-containing vinyl monomers, it is preferable to include at least one selected from the group consisting of fluorine-containing ethylene, fluorine-containing propylene, and fluorine-containing vinyl ether, and tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and Perfluoro(alkyl vinyl ether) is more preferred.
特に、下記式で示される含フッ素ビニルモノマーが好適である。
Figure JPOXMLDOC01-appb-C000008
 （式中、Ｒ７１～Ｒ７４は、互いに独立して、１価の基であり、Ｒ７１～Ｒ７３の少なくとも１つがフッ素原子又はＣＦ３基である。） In particular, fluorine-containing vinyl monomers represented by the following formula are suitable.
Figure JPOXMLDOC01-appb-C000008
 (In the formula, R 71 to R 74 are each independently a monovalent group, and at least one of R 71 to R 73 is a fluorine atom or a CF 3 group.)
Ｒ７１～Ｒ７４の１価の基としては、例えば、水素原子、ハロゲン原子（フッ素原子、塩素原子等）、１価の炭化水素基などが挙げられる。
上記１価の炭化水素基は、窒素原子、酸素原子などのヘテロ原子を有するものでもよい。上記１価の炭化水素基は、直鎖状、分岐状、環状のいずれでもよい。上記１価の炭化水素基の炭素数は、好ましくは１～８、より好ましくは１～５、更に好ましくは１～３である。上記１価の炭化水素基としては、上記炭素数のアルキル基、アルケニル基、アルキニル基等が挙げられる。
上記１価の基としては、水素原子、フッ素原子、塩素原子、上記炭素数のフッ素化アルキル基、上記炭素数のフッ素化アルコキシ基が好ましい。 The monovalent groups of R 71 to R 74 include, for example, hydrogen atoms, halogen atoms (fluorine atom, chlorine atom, etc.), monovalent hydrocarbon groups and the like.
The above monovalent hydrocarbon group may have a heteroatom such as a nitrogen atom or an oxygen atom. The above monovalent hydrocarbon group may be linear, branched or cyclic. The number of carbon atoms in the monovalent hydrocarbon group is preferably 1-8, more preferably 1-5, still more preferably 1-3. Examples of the monovalent hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups having the number of carbon atoms described above.
The monovalent group is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a fluorinated alkyl group having the above carbon number, or a fluorinated alkoxy group having the above carbon number.
上記含フッ素アクリルモノマーとしては、ポリマー主鎖にＣ－Ｆ結合を導入でき、ポリマーのガラス転移温度を高くできる点で、例えば、下記式で表される化合物などが挙げられる。
Figure JPOXMLDOC01-appb-C000009
 （式中、Ｒ４１は、１個以上のフッ素原子で置換されてもよいアルキル基を表す。） Examples of the fluorine-containing acrylic monomer include compounds represented by the following formula, since they can introduce a C—F bond into the main chain of the polymer and increase the glass transition temperature of the polymer.
Figure JPOXMLDOC01-appb-C000009
 ( In the formula, R41 represents an alkyl group optionally substituted with one or more fluorine atoms.)
Figure JPOXMLDOC01-appb-C000010
 （式中、Ｒ４２は、１個以上のフッ素原子で置換されてもよいアルキル基を表す。）
Figure JPOXMLDOC01-appb-C000010
 (In the formula, R42 represents an alkyl group optionally substituted with one or more fluorine atoms.)
Ｒ４１、Ｒ４２で表される「１個以上のフッ素原子で置換されてもよいアルキル基」のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基などが挙げられる。中でも、メチル基、エチル基、ｔ－ブチル基が好ましく、メチル基がより好ましい。 Examples of the alkyl group of the “alkyl group optionally substituted with one or more fluorine atoms” represented by R 41 and R 42 include methyl group, ethyl group, propyl group and butyl group. Among them, a methyl group, an ethyl group and a t-butyl group are preferable, and a methyl group is more preferable.
特に、下記式で示される含フッ素アクリルモノマーが好適である。
Figure JPOXMLDOC01-appb-C000011
 In particular, fluorine-containing acrylic monomers represented by the following formula are suitable.
Figure JPOXMLDOC01-appb-C000011
上記式で表される含フッ素アクリルモノマーの具体例としては、メチル－２－フルオロアクリレート、エチル－２－フルオロアクリレートなどが例示される。 Specific examples of the fluorine-containing acrylic monomer represented by the above formula include methyl-2-fluoroacrylate and ethyl-2-fluoroacrylate.
上記含フッ素アクリルモノマーとしては、下記式で表されるモノマー（上記式（Ｉ－１）、（Ｉ－２）で示されるジシクロペンテニル基を有するモノマー）も挙げられる。例えば、これらのモノマーを用いることで、上記式（Ｉ－１）、（Ｉ－２）で示されるジシクロペンテニル基を含フッ素熱硬化性樹脂内に導入できる。
Figure JPOXMLDOC01-appb-C000012
 Examples of the fluorine-containing acrylic monomer include monomers represented by the following formulas (monomers having a dicyclopentenyl group represented by formulas (I-1) and (I-2) above). For example, by using these monomers, the dicyclopentenyl groups represented by the above formulas (I-1) and (I-2) can be introduced into the fluorine-containing thermosetting resin.
Figure JPOXMLDOC01-appb-C000012
上記含フッ素スチレンモノマーとしては、ポリマー主鎖にＣ－Ｆ結合を導入でき、ポリマーのガラス転移温度を高くできる点で、ＣＦ２＝ＣＦ－Ｃ６Ｈ５、ＣＦ２＝ＣＦ－Ｃ６Ｈ４－ＣＨ３、及び、ＣＦ２＝ＣＦ－Ｃ６Ｈ４－ＣＦ３からなる群より選択される少なくとも１種が好ましく、中でも、下記式で示される含フッ素スチレンモノマーが好適である。
Figure JPOXMLDOC01-appb-C000013
 As the fluorine-containing styrene monomer, CF 2 =CF--C 6 H 5 and CF 2 =CF--C 6 H 4 can be used in that a CF bond can be introduced into the polymer main chain and the glass transition temperature of the polymer can be increased. At least one selected from the group consisting of —CH 3 and CF 2 =CF—C 6 H 4 —CF 3 is preferable, and fluorine-containing styrene monomers represented by the following formulas are particularly preferable.
Figure JPOXMLDOC01-appb-C000013
上記水素含有フルオロオレフィンとしては、エチレンの水素原子がフッ素原子に置き換わったものが好ましく、フッ化ビニル、トリフルオロエチレン、フッ化ビニリデン〔ＶＤＦ〕等が挙げられる。中でも、フッ化ビニルが好ましい。 As the above-mentioned hydrogen-containing fluoroolefin, those in which the hydrogen atoms of ethylene are replaced with fluorine atoms are preferable, and vinyl fluoride, trifluoroethylene, vinylidene fluoride [VDF] and the like can be mentioned. Among them, vinyl fluoride is preferred.
上記含フッ素ノルボルネンは、重合性基を有していればよく、１個のノルボルネン骨格を有するものでも、複数のノルボルネン骨格を有するものでもよい。含フッ素ノルボルネンは、不飽和化合物とジエン化合物のとのＤｉｅｌｓ－Ａｌｄｅｒ付加反応で生成する。 The fluorine-containing norbornene may have a polymerizable group, and may have one norbornene skeleton or a plurality of norbornene skeletons. A fluorine-containing norbornene is produced by a Diels-Alder addition reaction between an unsaturated compound and a diene compound.
上記不飽和化合物としては、含フッ素オレフィン、含フッ素アリルアルコール、含フッ素ホモアリルアルコール、α－フルオロアクリル酸、α－トリフルオロメチルアクリル酸、含フッ素アクリル酸エステル又は含フッ素メタクリル酸エステル、２－（ベンゾイルオキシ）ペンタフルオロプロパン、２－（メトキシエトキシメチルオキシ）ペンタフルオロプロペン、２－（テトラヒドロキシピラニルオキシ）ペンタフルオロプロペン、２－（ベンゾイルオキシ）トリフルオロエチレン、２－（メトキメチルオキシ）トリフルオロエチレンなどを例示できる。
上記ジエン化合物としては、シクロペンタジエン、シクロヘキサジエンなどを例示できる。 Examples of the unsaturated compound include fluorine-containing olefin, fluorine-containing allyl alcohol, fluorine-containing homoallyl alcohol, α-fluoroacrylic acid, α-trifluoromethyl acrylic acid, fluorine-containing acrylic acid ester or fluorine-containing methacrylic acid ester, 2- (benzoyloxy)pentafluoropropane, 2-(methoxyethoxymethyloxy)pentafluoropropene, 2-(tetrahydroxypyranyloxy)pentafluoropropene, 2-(benzoyloxy)trifluoroethylene, 2-(methoxymethyloxy) Examples include trifluoroethylene.
Examples of the diene compound include cyclopentadiene and cyclohexadiene.
上記含フッ素ノルボルネンとしては、例えば、下記式で示される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000014
 Examples of the fluorine-containing norbornene include compounds represented by the following formulas.
Figure JPOXMLDOC01-appb-C000014
上述の含フッ素モノマーの中でも、上記含フッ素モノマーは、含フッ素エチレン、含フッ素プロピレン、及び含フッ素ビニルエーテルからなる群より選択される少なくとも１種を含むことが好ましく、フッ化ビニリデン、テトラフルオロエチレン、クロロトリフルオロエチレン、フッ化ビニル、へキサフルオロプロピレン、及びパーフルオロ（アルキルビニルエーテル）からなる群より選択される少なくとも１種を含むことがより好ましい。 Among the fluorine-containing monomers described above, the fluorine-containing monomer preferably contains at least one selected from the group consisting of fluorine-containing ethylene, fluorine-containing propylene, and fluorine-containing vinyl ether, vinylidene fluoride, tetrafluoroethylene, More preferably, it contains at least one selected from the group consisting of chlorotrifluoroethylene, vinyl fluoride, hexafluoropropylene, and perfluoro(alkyl vinyl ether).
また、上記含フッ素モノマーは、下記式で示される化合物、テトラフルオロエチレン、及びヘキサフルオロプロピレンの少なくとも１種を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000015
 Moreover, the fluorine-containing monomer preferably contains at least one of a compound represented by the following formula, tetrafluoroethylene, and hexafluoropropylene.
Figure JPOXMLDOC01-appb-C000015
更に、上記含フッ素モノマーは、下記式で示される化合物の少なくとも１種を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000016
 Furthermore, the fluorine-containing monomer preferably contains at least one compound represented by the following formula.
Figure JPOXMLDOC01-appb-C000016
上記含フッ素モノマーは、下記式で示される化合物の少なくとも１種を含むことがより好ましい。
Figure JPOXMLDOC01-appb-C000017
 More preferably, the fluorine-containing monomer contains at least one compound represented by the following formula.
Figure JPOXMLDOC01-appb-C000017
本開示の含フッ素熱硬化性樹脂が含フッ素モノマーと後述のフッ素非含有モノマーとの共重合体であってもよい。上記含フッ素モノマーと後述のフッ素非含有モノマーとを共重合する場合は、上記含フッ素モノマー単位は、低誘電率及び低誘電正接に優れることから、上記含フッ素熱硬化性樹脂を構成する全重合単位に対して５モル％以上であることが好ましく、１０モル％以上がより好ましく、１５モル％以上がより好ましく、また、８０モル％以下が好ましく、７０モル％以下がより好ましく、６０モル％以下が更に好ましい。 The fluorine-containing thermosetting resin of the present disclosure may be a copolymer of a fluorine-containing monomer and a fluorine-free monomer described below. When the fluorine-containing monomer and the fluorine-free monomer described later are copolymerized, the fluorine-containing monomer unit is excellent in low dielectric constant and low dielectric loss tangent, so that the total polymerization constituting the fluorine-containing thermosetting resin The unit is preferably 5 mol% or more, more preferably 10 mol% or more, more preferably 15 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less, and 60 mol%. More preferred are:
本開示の含フッ素熱硬化性樹脂は、上記含フッ素モノマー単位以外のフッ素非含有モノマーに基づく重合単位（以下「フッ素非含有モノマー単位」と記載する）を含んでもよい。 The fluorine-containing thermosetting resin of the present disclosure may contain polymerized units based on non-fluorine-containing monomers other than the fluorine-containing monomer units (hereinafter referred to as "non-fluorine-containing monomer units").
上記フッ素非含有モノマーとしては、上記含フッ素モノマーと反応性を有するフッ素を含まないモノマーが挙げられる。上記フッ素非含有モノマーとしては、炭化水素系モノマー等が挙げられる。 Examples of the fluorine-free monomer include a fluorine-free monomer reactive with the fluorine-containing monomer. Examples of the fluorine-free monomer include hydrocarbon-based monomers.
上記フッ素非含有モノマー単位（フッ素非含有モノマーに基づく重合単位）は、低誘電率及び低誘電正接に優れることから、上記含フッ素熱硬化性樹脂を構成する全重合単位に対して２０モル％以上であることが好ましく、３０モル％以上がより好ましく、４０モル％以上が更に好ましく、また、９０モル％以下が好ましく、８０モル％以下がより好ましい。 The fluorine-free monomer unit (polymerized unit based on the fluorine-free monomer) is excellent in low dielectric constant and low dielectric loss tangent, so it is 20 mol% or more based on the total polymerized units constituting the fluorine-containing thermosetting resin. is preferably 30 mol % or more, more preferably 40 mol % or more, and preferably 90 mol % or less, more preferably 80 mol % or less.
上記フッ素非含有モノマーとしては、特に限定されないが、低誘電率及び低誘電正接に優れることから、ジシクロペンテニル基を有するモノマーを好適に使用できる。上記含フッ素熱硬化性樹脂は、下記式（Ｉ－１）で示されるジシクロペンテニル基及び下記式（Ｉ－２）で示されるジシクロペンテニル基からなる群より選択される少なくとも１種有するものであり、例えば、以下の式（Ｉ－１）、（Ｉ－２）で示されるジシクロペンテニル基を有するモノマーなどを用いることで調製できる。 The non-fluorine-containing monomer is not particularly limited, but a monomer having a dicyclopentenyl group can be preferably used because of its excellent low dielectric constant and low dielectric loss tangent. The fluorine-containing thermosetting resin has at least one selected from the group consisting of a dicyclopentenyl group represented by the following formula (I-1) and a dicyclopentenyl group represented by the following formula (I-2). and can be prepared, for example, by using monomers having a dicyclopentenyl group represented by the following formulas (I-1) and (I-2).
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
上記式（Ｉ－１）、（Ｉ－２）で示されるジシクロペンテニル基を有するモノマーとしては、以下の化合物などが挙げられる。
Figure JPOXMLDOC01-appb-C000019
 （式中、Ｒ５１は、水素原子又はメチル基である。） Examples of the monomer having a dicyclopentenyl group represented by the above formulas (I-1) and (I-2) include the following compounds.
Figure JPOXMLDOC01-appb-C000019
 (Wherein, R 51 is a hydrogen atom or a methyl group.)
中でも、下記式で示される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000020
 Among them, compounds represented by the following formulas are preferable.
Figure JPOXMLDOC01-appb-C000020
上記式（Ｉ－１）、（Ｉ－２）で示されるジシクロペンテニル基を有するモノマーとしては、ジシクロペンタニルアクリレート、ジシクロペンテニルメタクリレートなどが例示される。 Dicyclopentenyl acrylate, dicyclopentenyl methacrylate and the like are exemplified as the monomer having a dicyclopentenyl group represented by formulas (I-1) and (I-2).
上記式（Ｉ－１）、（Ｉ－２）で示されるジシクロペンテニル基を有するモノマーとしては、以下の化合物なども挙げられる。
Figure JPOXMLDOC01-appb-C000021
 （式中、Ｒ６１は、水素原子又はメチル基である。） Examples of the dicyclopentenyl group-containing monomer represented by formulas (I-1) and (I-2) include the following compounds.
Figure JPOXMLDOC01-appb-C000021
 (Wherein, R 61 is a hydrogen atom or a methyl group.)
中でも、下記式で示される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000022
 Among them, compounds represented by the following formulas are preferable.
Figure JPOXMLDOC01-appb-C000022
上記式（Ｉ－２）で示されるジシクロペンテニル基を有するモノマーとしては、ジシクロペンタジエンビニルエーテルなどが例示される。 Examples of the dicyclopentenyl group-containing monomer represented by formula (I-2) include dicyclopentadiene vinyl ether.
上記式（Ｉ－１）及び（Ｉ－２）で示されるジシクロペンテニル基を有するモノマー単位（式（Ｉ－１）、（Ｉ－２）で示されるジシクロペンテニル基を有するモノマーに基づく重合単位）は、低誘電率及び低誘電正接に優れることから、上記含フッ素熱硬化性樹脂を構成する全重合単位に対して２０モル％以上であることが好ましく、３０モル％以上がより好ましく、４０モル％以上が更に好ましく、また、９０モル％以下が好ましく、８０モル％以下がより好ましく、７６モル％以下が更に好ましい。なお、該モノマー単位の量は、式（Ｉ－１）及び（Ｉ－２）で示されるモノマー単位の総量である。 Polymerization based on a monomer unit having a dicyclopentenyl group represented by the above formulas (I-1) and (I-2) (monomers having a dicyclopentenyl group represented by formulas (I-1) and (I-2) unit) is preferably 20 mol% or more, more preferably 30 mol% or more, based on the total polymer units constituting the fluorine-containing thermosetting resin, because it is excellent in low dielectric constant and low dielectric loss tangent. 40 mol% or more is more preferable, 90 mol% or less is preferable, 80 mol% or less is more preferable, and 76 mol% or less is even more preferable. The amount of the monomer units is the total amount of the monomer units represented by formulas (I-1) and (I-2).
上記フッ素非含有モノマーとしては、上記式（Ｉ－１）及び（Ｉ－２）で示されるジシクロペンテニル基を有するモノマー以外のフッ素非含有モノマーも挙げられる。例えば、
エチレン、プロピレン、ブチレン、イソブチレン等のアルケン類；
エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、イソブチルビニルエーテル、シクロヘキシルビニルエーテル等のアルキルビニルエーテル類；
酢酸ビニル、プロピオン酸ビニル、ｎ－酪酸ビニル、イソ酪酸ビニル、吉草酸ビニル、ピバリン酸ビニル、カプロン酸ビニル、カプリル酸ビニル、カプリン酸ビニル、バーサチック酸ビニル、ラウリン酸ビニル、ミリスチン酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、パラ－ｔ－ブチル安息香酸ビニル、シクロヘキサンカルボン酸ビニル、モノクロル酢酸ビニル、アジピン酸ビニル、アクリル酸ビニル、メタクリル酸ビニル、クロトン酸ビニル、ソルビン酸ビニル、桂皮酸ビニル、ウンデシレン酸ビニル、ヒドロキシ酢酸ビニル、ヒドロキシプロピオイン酸ビニル、ヒドロキシ酪酸ビニル、ヒドロキシ吉草酸ビニル、ヒドロキシイソ酪酸ビニル、ヒドロキシシクロヘキサンカルボン酸ビニル等のビニルエステル類；
エチルアリルエーテル、プロピルアリルエーテル、ブチルアリルエーテル、イソブチルアリルエーテル、シクロヘキシルアリルエーテル等のアルキルアリルエーテル類；
エチルアリルエステル、プロピルアリルエステル、ブチルアリルエステル、イソブチルアリルエステル、シクロヘキシルアリルエステル等のアルキルアリルエステル類
等も挙げられる。
中でも、ビニルエステル類が好ましく、酢酸ビニル、パラ－ｔ－ブチル安息香酸がより好ましく、酢酸ビニルが更に好ましい。 Examples of the non-fluorine-containing monomers include non-fluorine-containing monomers other than the dicyclopentenyl group-containing monomers represented by the above formulas (I-1) and (I-2). for example,
alkenes such as ethylene, propylene, butylene, and isobutylene;
Alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether;
Vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl valerate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl versatate, vinyl laurate, vinyl myristate, palmitic acid Vinyl, vinyl stearate, vinyl benzoate, vinyl para-t-butylbenzoate, vinyl cyclohexanecarboxylate, vinyl monochloroacetate, vinyl adipate, vinyl acrylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, cinnamic acid Vinyl esters such as vinyl, vinyl undecylenate, vinyl hydroxyacetate, vinyl hydroxypropionate, vinyl hydroxybutyrate, vinyl hydroxyvalerate, vinyl hydroxyisobutyrate, and vinyl hydroxycyclohexanecarboxylate;
Alkyl allyl ethers such as ethyl allyl ether, propyl allyl ether, butyl allyl ether, isobutyl allyl ether, cyclohexyl allyl ether;
Alkyl allyl esters such as ethyl allyl ester, propyl allyl ester, butyl allyl ester, isobutyl allyl ester, cyclohexyl allyl ester and the like are also included.
Among them, vinyl esters are preferred, vinyl acetate and para-t-butylbenzoic acid are more preferred, and vinyl acetate is even more preferred.
上記ビニルエステル類単位（ビニルエステル類に基づく重合単位）は、上記含フッ素熱硬化性樹脂を構成する全重合単位に対して２０モル％以上であることが好ましく、３０モル％以上がより好ましく、４０モル％以上が更に好ましく、また、９０モル％以下が好ましく、８０モル％以下がより好ましく、７６モル％以下が更に好ましい。 The vinyl ester units (polymerized units based on vinyl esters) are preferably 20 mol% or more, more preferably 30 mol% or more, relative to the total polymerization units constituting the fluorine-containing thermosetting resin. 40 mol% or more is more preferable, 90 mol% or less is preferable, 80 mol% or less is more preferable, and 76 mol% or less is even more preferable.
上記フッ素非含有モノマーとしては、上記含フッ素熱硬化性樹脂に溶剤溶解性を付与できる点で、脂環式構造を有するモノマーが好ましく選ばれる。
脂環式構造を有するモノマーとしては、イソボルニルメタクリレート、イソボルニルアクリレート、シクロヘキシルメタクリレート、シクロヘキシルアクリレート、ジシクロペンタニルアクリレ－ト及びジシクロペンタニルメタクリレートからなる群から選ばれる一種以上の（メタ）アクリル酸エステル類が好ましい。 As the fluorine-free monomer, a monomer having an alicyclic structure is preferably selected because it can impart solvent solubility to the fluorine-containing thermosetting resin.
As the monomer having an alicyclic structure, one or more selected from the group consisting of isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentanyl acrylate and dicyclopentanyl methacrylate ( Meth)acrylates are preferred.
含フッ素熱硬化性樹脂のガラス転移温度を高くできる点で、上記フッ素非含有モノマーは、そのホモポリマーのガラス転移温度が８０℃以上、１００℃以上、好ましくは１２０℃以上のモノマーを用いることがより好ましく、上記脂環式構造を有する（メタ）アクリル酸エステル類やＮ置換マレイミド類が好ましく選ばれる。
Ｎ置換マレイミド類としては、Ｎ－シクロヘキシルマレイイミド、Ｎ－ベンジルマレイミド、Ｎ－フェニルマレイミド、Ｎ－（４－アセチルフェニル）マレイミド、Ｎ－（２，６－ジエチルフェニル）マレイミド、Ｎ－（４－ジメチルアミノ－３，５－ジニトロフェニル）マレイミド、及びＮ－［４－（２－ベンズオキサゾリル）フェニル］マレイミドが好ましい。 In terms of increasing the glass transition temperature of the fluorine-containing thermosetting resin, it is preferable to use a monomer having a homopolymer glass transition temperature of 80° C. or higher, 100° C. or higher, preferably 120° C. or higher, as the fluorine-free monomer. More preferably, (meth)acrylic acid esters and N-substituted maleimides having the above alicyclic structure are preferably selected.
N-substituted maleimides include N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-(4-acetylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(4- Dimethylamino-3,5-dinitrophenyl)maleimide and N-[4-(2-benzoxazolyl)phenyl]maleimide are preferred.
上記フッ素非含有モノマーとしては、また、官能基含有炭化水素系モノマーであってもよい。前記官能基含有炭化水素系モノマーとしては、ＯＨ基含有モノマーなどが挙げられる。上記官能基含有炭化水素系モノマーとしては、例えば、ヒドロキシエチルビニルエーテル、ヒドロキシプロピルビニルエーテル、ヒドロキシブチルビニルエーテル、ヒドロキシイソブチルビニルエーテル、ヒドロキシシクロヘキシルビニルエーテル等のヒドロキシアルキルビニルエーテル類等のＯＨ基（水酸基）を有するフッ素非含有モノマー；
イタコン酸、コハク酸、無水コハク酸、フマル酸、無水フマル酸、クロトン酸、マレイン酸、無水マレイン酸等のカルボキシル基を有するフッ素非含有モノマー；
グリシジルビニルエーテル、グリシジルアリルエーテル等のグリシジル基を有するフッ素非含有モノマー；
アミノアルキルビニルエーテル、アミノアルキルアリルエーテル等のアミノ基を有するフッ素非含有モノマー；
（メタ）アクリルアミド、メチロールアクリルアミド等のアミド基を有するフッ素非含有モノマー
等が挙げられる。 The non-fluorine-containing monomer may also be a functional group-containing hydrocarbon-based monomer. Examples of the functional group-containing hydrocarbon-based monomers include OH group-containing monomers. Examples of the functional group-containing hydrocarbon-based monomers include fluorine-free monomers having an OH group (hydroxyl group) such as hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, and hydroxycyclohexyl vinyl ether. monomer;
fluorine-free monomers having a carboxyl group such as itaconic acid, succinic acid, succinic anhydride, fumaric acid, fumaric anhydride, crotonic acid, maleic acid, maleic anhydride;
fluorine-free monomers having a glycidyl group such as glycidyl vinyl ether and glycidyl allyl ether;
non-fluorine-containing monomers having amino groups such as aminoalkyl vinyl ethers and aminoalkyl allyl ethers;
Non-fluorine-containing monomers having an amide group such as (meth)acrylamide and methylolacrylamide are included.
上述のフッ素非含有モノマーの中でも、上記フッ素非含有モノマーは、下記式で示されるジシクロペンテニル基を有する化合物の少なくとも１種を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000023
 Among the fluorine-free monomers described above, the fluorine-free monomer preferably contains at least one compound having a dicyclopentenyl group represented by the following formula.
Figure JPOXMLDOC01-appb-C000023
本開示の含フッ素熱硬化性樹脂は、低誘電率及び低誘電正接に優れることから、含フッ素モノマー単位／フッ素非含有モノマー単位のモル比が（１～９０）／（１０～９９）であることが好ましく、（１～７０）／（３０～９９）であることがより好ましく、（３～５０）／（５０～９７）であることが更に好ましい。
上記含フッ素熱硬化性樹脂において、上記含フッ素モノマー単位とフッ素非含有モノマー単位との合計含有量は、全重合単位に対して、７０モル％以上が好ましく、８０モル％以上がより好ましく、９０モル％以上が更に好ましく、９５モル％以上が更により好ましく、９７モル％以上が特に好ましい。全重合単位に対して、１００モル％であってもよい。 Since the fluorine-containing thermosetting resin of the present disclosure is excellent in low dielectric constant and low dielectric loss tangent, the molar ratio of fluorine-containing monomer units/fluorine-free monomer units is (1 to 90)/(10 to 99). (1 to 70)/(30 to 99) is more preferred, and (3 to 50)/(50 to 97) is even more preferred.
In the fluorine-containing thermosetting resin, the total content of the fluorine-containing monomer units and fluorine-free monomer units is preferably 70 mol% or more, more preferably 80 mol% or more, and 90 mol % or more is more preferable, 95 mol % or more is even more preferable, and 97 mol % or more is particularly preferable. It may be 100 mol % with respect to all polymerized units.
本開示の含フッ素熱硬化性樹脂のフッ素含有量は、低誘電率及び低誘電正接に優れることから、含フッ素熱硬化性樹脂の全質量に対して、好ましくは１質量％以上、より好ましくは３質量％以上、更に好ましくは５質量％以上であり、また、好ましくは１５質量％以下、より好ましくは１２質量％以下、更に好ましくは１０質量％以下である。
上記含フッ素熱硬化性樹脂のフッ素含有量は、自動試料燃焼装置を用いた元素分析により求めることができる。 Since the fluorine content of the fluorine-containing thermosetting resin of the present disclosure is excellent in low dielectric constant and low dielectric loss tangent, it is preferably 1% by mass or more, more preferably It is 3% by mass or more, more preferably 5% by mass or more, and preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less.
The fluorine content of the fluorine-containing thermosetting resin can be determined by elemental analysis using an automatic sample combustion apparatus.
本開示の含フッ素熱硬化性樹脂の数平均分子量は、１０００～３００００であることが好ましい。上記含フッ素熱硬化性樹脂の数平均分子量がこのような範囲であると、溶剤溶解性、熱硬化性が向上する。上記含フッ素熱硬化性樹脂の数平均分子量として、より好ましくは１０００～２００００、更に好ましくは１０００～１５０００である。
上記含フッ素熱硬化性樹脂の数平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により測定することができる。 The fluorine-containing thermosetting resin of the present disclosure preferably has a number average molecular weight of 1,000 to 30,000. When the number average molecular weight of the fluorine-containing thermosetting resin is within this range, solvent solubility and thermosetting properties are improved. The number average molecular weight of the fluorine-containing thermosetting resin is more preferably 1,000 to 20,000, still more preferably 1,000 to 15,000.
The number average molecular weight of the fluorine-containing thermosetting resin can be measured by gel permeation chromatography (GPC).
本開示の含フッ素熱硬化性樹脂のガラス転移温度は、電気特性が優れる点、特に、誘電正接を低くできる点で、８０℃以上が好ましく、９０℃以上がより好ましく、１００℃以上が更に好ましく、１１０℃以上が特に好ましい。ガラス転移温度は高い方がよいが、加工性の観点からは、３００℃以下であることが好ましい。
上記ガラス転移温度は、ＡＳＴＭ　Ｅ１３５６－９８に従い、下記条件のＤＳＣ測定装置を使用してセカンドランにおける熱吸収から中点法によって決定した値である。
測定条件
昇温速度；２０℃／ｍｉｎ
試料量；１０ｍｇ
ヒートサイクル；－５０℃～１５０℃、昇温、冷却、昇温 The glass transition temperature of the fluorine-containing thermosetting resin of the present disclosure is preferably 80° C. or higher, more preferably 90° C. or higher, and even more preferably 100° C. or higher in terms of excellent electrical properties, particularly in terms of low dielectric loss tangent. , 110° C. or higher are particularly preferred. The higher the glass transition temperature, the better, but from the viewpoint of workability, it is preferably 300° C. or less.
The above glass transition temperature is a value determined by the midpoint method from heat absorption in the second run using a DSC measuring device under the following conditions according to ASTM E1356-98.
Measurement conditions Heating rate; 20°C/min
Sample amount; 10 mg
Heat cycle; -50°C to 150°C, temperature rise, cooling, temperature rise
本開示の含フッ素熱硬化性樹脂は、下記式（１）で示される基及び下記式（２）で示される基からなる群より選択される少なくとも１種を有することが好ましい。
Figure JPOXMLDOC01-appb-C000024
 （式中、Ｒ１１は、互いに独立して、水素原子、又は置換基を有してもよい１価の炭化水素基であり、ｍ１は１～５の整数である。Ｒ２１は、互いに独立して、水素原子、又は置換基を有してもよい１価の炭化水素基であり、ｍ２は１～４の整数である。）
本開示の含フッ素熱硬化性樹脂は、上記構造を有するので、溶剤溶解性、熱硬化性に優れる。また、低誘電率及び低誘電正接に優れる。 The fluorine-containing thermosetting resin of the present disclosure preferably has at least one selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2).
Figure JPOXMLDOC01-appb-C000024
 (In the formula, R 11 is each independently a hydrogen atom or a monovalent hydrocarbon group which may have a substituent, m 1 is an integer of 1 to 5. R 21 is each It is independently a hydrogen atom or a monovalent hydrocarbon group which may have a substituent, and m2 is an integer of 1 to 4.)
Since the fluorine-containing thermosetting resin of the present disclosure has the structure described above, it is excellent in solvent solubility and thermosetting properties. In addition, it is excellent in low dielectric constant and low dielectric loss tangent.
Ｒ１１、Ｒ２１の置換基を有してもよい１価の炭化水素基は、窒素原子、酸素原子などのヘテロ原子を有するものでもよい。上記１価の炭化水素基は、直鎖状、分岐状、環状のいずれでもよい。上記１価の炭化水素基の炭素数は、好ましくは１～８、より好ましくは１～５、更に好ましくは１～３である。上記１価の炭化水素基としては、上記炭素数のアルキル基、アルケニル基、アルキニル基等が挙げられる。中でも、Ｒ１１、Ｒ２１は、水素原子、メチル基、エチル基が好ましく、水素原子がより好ましい。 The optionally substituted monovalent hydrocarbon group for R 11 and R 21 may have a heteroatom such as a nitrogen atom or an oxygen atom. The above monovalent hydrocarbon group may be linear, branched or cyclic. The number of carbon atoms in the monovalent hydrocarbon group is preferably 1-8, more preferably 1-5, still more preferably 1-3. Examples of the monovalent hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups having the number of carbon atoms described above. Among them, R 11 and R 21 are preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom.
式（１）のｍ１は１～５の整数、式（２）のｍ２は１～４の整数である。 m 1 in formula (1) is an integer of 1-5, and m 2 in formula (2) is an integer of 1-4.
上記含フッ素熱硬化性樹脂は、下記式（１－１）で示される基、及び下記式（２－１）で示される基からなる群より選択される少なくとも１種を有することが好ましい。
Figure JPOXMLDOC01-appb-C000025
 （式中、Ｒ１１、ｍ１、Ｒ２１及びｍ２は前記と同様である。Ｒ１２及びＲ２２は、置換基を有してもよい２価の炭化水素基である。） The fluorine-containing thermosetting resin preferably has at least one selected from the group consisting of a group represented by the following formula (1-1) and a group represented by the following formula (2-1).
Figure JPOXMLDOC01-appb-C000025
 (In the formula, R 11 , m 1 , R 21 and m 2 are the same as defined above. R 12 and R 22 are divalent hydrocarbon groups which may have a substituent.)
Ｒ１２及びＲ２２の置換基を有してもよい２価の炭化水素基は、窒素原子、酸素原子などのヘテロ原子を有するものでもよい。上記２価の炭化水素基は、直鎖状、分岐状、環状のいずれでもよい。上記２価の炭化水素基の炭素数は、好ましくは１～８、より好ましくは１～５、更に好ましくは１～３である。上記２価の炭化水素基としては、窒素原子及び／又は酸素原子を有してもよい上記炭素数のアルキレン基、アルケニレン基等が挙げられる。中でも、Ｒ１１及びＲ１２は、窒素原子及び／又は酸素原子を有してもよいメチレン基、エチレン基、エチリデン基、プロピリデン基、イソプロピリデン基が好ましく、窒素原子及び／又は酸素原子を有してもよいメチレン基がより好ましい。 The divalent hydrocarbon group which may have a substituent for R 12 and R 22 may have a heteroatom such as a nitrogen atom or an oxygen atom. The divalent hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms in the divalent hydrocarbon group is preferably 1-8, more preferably 1-5, still more preferably 1-3. Examples of the divalent hydrocarbon group include alkylene groups and alkenylene groups having the above carbon number, which may have a nitrogen atom and/or an oxygen atom. Among them, R 11 and R 12 are preferably a methylene group, ethylene group, ethylidene group, propylidene group, or isopropylidene group which may have a nitrogen atom and/or an oxygen atom, and have a nitrogen atom and/or an oxygen atom. is more preferred.
上記式（１）～（２）で示される基のなかでも、特に下記２式で示される基が好適である。
Figure JPOXMLDOC01-appb-C000026
 Among the groups represented by the above formulas (1) and (2), groups represented by the following two formulas are particularly suitable.
Figure JPOXMLDOC01-appb-C000026
本開示の含フッ素熱硬化性樹脂は、例えば、該含フッ素熱硬化性樹脂の組成を上記のように適宜調整し、連鎖移動剤の存在下において、上記含フッ素モノマー及び上記フッ素非含有モノマーを重合する工程を含む含フッ素熱硬化性樹脂の製造方法において、上記含フッ素アクリルモノマーとしての上記式（Ｉ－１）、（Ｉ－２）で示されるジシクロペンテニル基を有するモノマーを用いることや、上記フッ素非含有モノマーとしての上記式（Ｉ－１）、（Ｉ－２）で示されるジシクロペンテニル基を有するモノマーを用いることにより製造できる（含フッ素熱硬化性樹脂の製法）。 In the fluorine-containing thermosetting resin of the present disclosure, for example, the composition of the fluorine-containing thermosetting resin is appropriately adjusted as described above, and the fluorine-containing monomer and the non-fluorine-containing monomer are mixed in the presence of a chain transfer agent. In the method for producing a fluorine-containing thermosetting resin including the step of polymerizing, a monomer having a dicyclopentenyl group represented by the formulas (I-1) and (I-2) is used as the fluorine-containing acrylic monomer; , by using monomers having a dicyclopentenyl group represented by the above formulas (I-1) and (I-2) as fluorine-free monomers (method for producing fluorine-containing thermosetting resin).
ここで、更に、ポリマーの末端に上記式（１）で示される基及び上記式（２）で示される基からなる群より選択される少なくとも１種が導入されている上記含フッ素熱硬化性樹脂は、前記製法において、該連鎖移動剤として、ポリマーの末端に、上記式（１）で示される基及び上記式（２）で示される基からなる群より選択される少なくとも１種の導入が可能な化合物を用いることにより、上記式（１）～（２）で示される基をポリマーの末端に導入できる（製法１）。 Here, the fluorine-containing thermosetting resin further includes at least one selected from the group consisting of the group represented by the above formula (1) and the group represented by the above formula (2) at the end of the polymer. In the production method, at least one selected from the group consisting of the group represented by the above formula (1) and the group represented by the above formula (2) can be introduced at the end of the polymer as the chain transfer agent. By using such compounds, the groups represented by the above formulas (1) and (2) can be introduced at the ends of the polymer (manufacturing method 1).
また、前記製法において、重合後、ポリマーの末端に、上記式（１）で示される基及び上記式（２）で示される基からなる群より選択される少なくとも１種の導入が可能なスチレン系化合物を反応させることにより、上記式（１）～（２）で示される基をポリマーの末端に導入できる（製法２）。 Further, in the production method, at least one selected from the group consisting of the group represented by the above formula (1) and the group represented by the above formula (2) can be introduced at the end of the polymer after polymerization. By reacting the compounds, the groups represented by the above formulas (1) and (2) can be introduced at the ends of the polymer (manufacturing method 2).
本開示の含フッ素熱硬化性樹脂は、重合において、溶液重合法、乳化重合法、懸濁重合法、又は塊重合法で製造できるが、なかでも溶液重合法で得られたものが好ましい。 The fluorine-containing thermosetting resin of the present disclosure can be produced by a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or a bulk polymerization method in polymerization. Among them, those obtained by the solution polymerization method are preferable.
本開示の含フッ素熱硬化性樹脂は、重合において、上記含フッ素モノマー、上記フッ素非含有モノマーを有機溶媒、重合開始剤や連鎖移動剤などを用いる溶液重合法により重合し、必要に応じて上記スチレン系化合物を反応させることにより製造することが好ましい。重合温度は、通常０～１５０℃、好ましくは５～１２０℃である。重合圧は通常０．１～１０ＭＰａＧ（１～１００ｋｇｆ／ｃｍ２Ｇ）である。 The fluorine-containing thermosetting resin of the present disclosure is polymerized by polymerizing the fluorine-containing monomer and the fluorine-free monomer by a solution polymerization method using an organic solvent, a polymerization initiator, a chain transfer agent, and the like. It is preferably produced by reacting a styrenic compound. The polymerization temperature is usually 0 to 150°C, preferably 5 to 120°C. The polymerization pressure is usually 0.1-10 MPaG (1-100 kgf/cm 2 G).
上記有機溶媒としては、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ｎ－ブチル、酢酸ｔｅｒｔ－ブチルなどのエステル類；アセトン、メチルエチルケトン、シクロヘキサノンなどのケトン類；ヘキサン、シクロヘキサン、オクタン、ノナン、デカン、ウンデカン、ドデカン、ミネラルスピリットなどの脂肪族炭化水素類；ベンゼン、トルエン、キシレン、ナフタレン、ソルベントナフサなどの芳香族炭化水素類；メタノール、エタノール、ｔｅｒｔ－ブタノール、ｉｓｏ－プロパノール、エチレングリコールモノアルキルエーテルなどのアルコール類；テトラヒドロフラン、テトラヒドロピラン、ジオキサンなどの環状エーテル類；ジメチルスルホキシドなど、又はこれらの混合物などが挙げられる。 Examples of the organic solvent include esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, and tert-butyl acetate; ketones such as acetone, methyl ethyl ketone and cyclohexanone; hexane, cyclohexane, octane, nonane, decane, and undecane. , dodecane, mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, solvent naphtha; methanol, ethanol, tert-butanol, iso-propanol, ethylene glycol monoalkyl ether, etc. alcohols; cyclic ethers such as tetrahydrofuran, tetrahydropyran and dioxane; dimethylsulfoxide and the like, or mixtures thereof.
上記重合開始剤としては、たとえば過硫酸アンモニウム、過硫酸カリウムなどの過硫酸塩類（更に必要に応じて亜硫酸水素ナトリウム、ピロ亜硫酸ナトリウム、ナフテン酸コバルト、ジメチルアニリンなどの還元剤も併用できる）；酸化剤（たとえば過酸化アンモニウム、過酸化カリウムなど）と還元剤（たとえば亜硫酸ナトリウムなど）及び遷移金属塩（たとえば硫酸鉄など）からなるレドックス開始剤類；アセチルパーオキサイド、ベンゾイルパーオキサイドなどのジアシルパーオキサイド類；イソプロポキシカルボニルパーオキサイド、ｔｅｒｔ－ブトキシカルボニルパーオキサイドなどのジアルコキシカルボニルパーオキサイド類；メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイドなどのケトンパーオキサイド類；過酸化水素、ｔｅｒｔ－ブチルハイドロパーオキサイド、クメンハイドロパーオキサイドなどのハイドロパーオキサイド類；ジ－ｔｅｒｔ－ブチルパーオキサイド、ジクミルパーオキサイドなどのジアルキルパーオキサイド類；ｔｅｒｔ－ブチルパーオキシアセテート、ｔｅｒｔ－ブチルパーオキシピバレートなどのアルキルパーオキシエステル類；２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２－メチルバレロニトリル）、２，２’－アゾビス（２－シクロプロピルプロピオニトリル）、２，２’－アゾビスイソ酪酸ジメチル、２，２’－アゾビス［２－（ヒドロキシメチル）プロピオニトリル］、４，４’－アゾビス（４－シアノペンテン酸）などのアゾ系化合物などが使用できる。 Examples of the polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate (reducing agents such as sodium hydrogensulfite, sodium pyrosulfite, cobalt naphthenate, and dimethylaniline can also be used in combination, if necessary); oxidizing agent; (e.g. ammonium peroxide, potassium peroxide, etc.), a reducing agent (e.g. sodium sulfite, etc.) and a transition metal salt (e.g. iron sulfate, etc.); diacyl peroxides such as acetyl peroxide, benzoyl peroxide, etc. dialkoxycarbonyl peroxides such as isopropoxycarbonyl peroxide and tert-butoxycarbonyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide; Hydroperoxides such as oxides; Dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide; Alkyl peroxyesters such as tert-butyl peroxyacetate and tert-butyl peroxypivalate;2 ,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(2-methylvaleronitrile), 2,2′-azobis(2- cyclopropylpropionitrile), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis[2-(hydroxymethyl)propionitrile], 4,4′-azobis(4-cyanopentenoic acid), etc. compounds, etc. can be used.
上記連鎖移動剤としては、２，４－ジフェニル－４－メチルーペンテンなどのこのような化合物の他、たとえば、チオール化合物が使用できる。チオール化合物としては、連鎖移動剤として作用することが知られているチオール化合物であればよいが、好ましくはｔ－ドデシルメルカプタン、ｎ－ドデシルメルカプタン、ｔ－オクチルメルカプタン、ｎ－オクチルメルカプタン、トリメチロールプロパントリス－３－メルカプトプロピオネート、ペンタエリスリトールテトラキス－３－メルカプトプロピオネート、ジペンタエリスリトールヘキサ－３－メルカプトプロピオネート及び（トリス－［（３－メルカプトプロピオニロキシ）－エチル］－イソシアヌレート）等である。これらの内、重合制御の容易さ、生成した共重合体の靱性の観点から、特に好適に使用されるのは、ｔ－ドデシルメルカプタン、ｎ－ドデシルメルカプタン、ｔ－オクチルメルカプタン、ｎ－オクチルメルカプタンなどの炭素数５～３０のモノアルキルメルカプタンである。
また、たとえば、アルコール類を使用でき、好ましくは炭素数１～１０のアルコール類、より好ましくは炭素数１～１０の１価のアルコール類である。具体的には、メタノール、エタノール、プロパノール、イソプロパノール、ｎ－ブタノール、ｔ－ブタノール、２－メチルプロパノール、シクロヘキサノール、メチルシクロヘキサノール、シクロペンタノール、メチルシクロペンタノール、ジメチルシクロペンタノールが使用できる。なかでもメタノール、イソプロパノール、ｔ－ブタノール、シクロヘキサノール、メチルシクロヘキサノール、シクロペンタノール、メチルシクロペンタノールなどが好ましく、特にメタノール、イソプロパノールが好ましい。 As the chain transfer agent, in addition to such compounds such as 2,4-diphenyl-4-methyl-pentene, for example, thiol compounds can be used. The thiol compound may be any thiol compound known to act as a chain transfer agent, preferably t-dodecylmercaptan, n-dodecylmercaptan, t-octylmercaptan, n-octylmercaptan, trimethylolpropane. tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol hexa-3-mercaptopropionate and (tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate ), etc. Among these, t-dodecylmercaptan, n-dodecylmercaptan, t-octylmercaptan, n-octylmercaptan and the like are particularly preferably used from the viewpoint of ease of polymerization control and toughness of the resulting copolymer. is a monoalkyl mercaptan having 5 to 30 carbon atoms.
Also, for example, alcohols can be used, preferably alcohols having 1 to 10 carbon atoms, more preferably monohydric alcohols having 1 to 10 carbon atoms. Specifically, methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, 2-methylpropanol, cyclohexanol, methylcyclohexanol, cyclopentanol, methylcyclopentanol and dimethylcyclopentanol can be used. Among them, methanol, isopropanol, t-butanol, cyclohexanol, methylcyclohexanol, cyclopentanol, methylcyclopentanol and the like are preferable, and methanol and isopropanol are particularly preferable.
上記製法１では、上記式（１）で示される基及び上記式（２）で示される基からなる群より選択される少なくとも１種の導入が可能な化合物を使用でき、中でも、２，４－ジフェニル－４－メチルーペンテンが好ましい。例えば、上記ジシクロペンテニル基を有するモノマーなどの反応性の違うモノマーを組み合わせ、更にこのような連鎖移動剤を用いることで、ゲル化を防止して、一段階で、上記式（１）～（２）で示される架橋性基を導入できる。 In the production method 1, a compound capable of introducing at least one selected from the group consisting of the group represented by the above formula (1) and the group represented by the above formula (2) can be used. Diphenyl-4-methyl-pentene is preferred. For example, by combining monomers with different reactivity such as the monomer having the dicyclopentenyl group and further using such a chain transfer agent, gelation can be prevented and, in one step, the above formulas (1) to ( 2) can introduce a crosslinkable group.
上記製法２では、重合後、ポリマーの末端に、上記式（１）で示される基及び上記式（２）で示される基からなる群より選択される少なくとも１種の導入が可能なスチレン系化合物を反応させることになるが、該反応は、このような反応が可能な公知の方法を使用できる。例えば、得られたポリマーを溶媒に溶解して得られた溶液と、上記スチレン系化合物とを混合し、反応が進行する温度、時間を適宜選択して反応を進行させることができる。反応温度は、通常０～１５０℃、好ましくは５～１２０℃である。反応時間は、通常０．１～１００時間、好ましくは１～３０時間である。 In the production method 2, after polymerization, at least one selected from the group consisting of the group represented by the above formula (1) and the group represented by the above formula (2) can be introduced at the end of the polymer. For this reaction, a known method capable of such a reaction can be used. For example, a solution obtained by dissolving the obtained polymer in a solvent is mixed with the styrene-based compound, and the reaction can proceed by appropriately selecting the temperature and time for the reaction to proceed. The reaction temperature is generally 0 to 150°C, preferably 5 to 120°C. The reaction time is usually 0.1 to 100 hours, preferably 1 to 30 hours.
上記スチレン系化合物としては、例えば、ハロゲン化アルキルスチレンなどを好適に使用できる。ハロゲン化アルキルスチレンの具体例としては、クロロメチルスチレン、ブロモメチルスチレン、ヨードメチルスチレン、クロロエチルスチレン、ブロモエチルスチレン、ヨードエチルスチレン、クロロペンチルスチレン、ブロモペンチルスチレン、ヨードペンチルスチレン、クロロヘキシルスチレン、ブロモヘキシルスチレン、ヨードヘキシルスチレン、クロロプロピルスチレン、ブロモプロピルスチレン、ヨードプロピルスチレン、クロロブチルスチレン、ブロモブチルスチレン、ヨードブチルスチレン等が挙げられる。中でも、クロロメチルスチレン、ブロモメチルスチレンが好ましい。 As the styrene-based compound, for example, halogenated alkylstyrene can be preferably used. Specific examples of halogenated alkylstyrenes include chloromethylstyrene, bromomethylstyrene, iodomethylstyrene, chloroethylstyrene, bromoethylstyrene, iodoethylstyrene, chloropentylstyrene, bromopentylstyrene, iodopentylstyrene, chlorohexylstyrene, Bromohexylstyrene, iodohexylstyrene, chloropropylstyrene, bromopropylstyrene, iodopropylstyrene, chlorobutylstyrene, bromobutylstyrene, iodobutylstyrene and the like. Among them, chloromethylstyrene and bromomethylstyrene are preferred.
本開示の含フッ素熱硬化性樹脂組成物は、上記含フッ素熱硬化性樹脂と、溶剤とを含む。
本開示の含フッ素熱硬化性樹脂組成物は、含フッ素熱硬化性樹脂が上記構成を有することによって、溶剤溶解性、熱硬化性に優れる。また、樹脂層に用いることで該樹脂層を低誘電率及び低誘電正接にできる。 The fluorine-containing thermosetting resin composition of the present disclosure contains the fluorine-containing thermosetting resin and a solvent.
The fluorine-containing thermosetting resin composition of the present disclosure is excellent in solvent solubility and thermosetting properties because the fluorine-containing thermosetting resin has the above configuration. Also, by using it in a resin layer, the resin layer can be made to have a low dielectric constant and a low dielectric loss tangent.
本開示の含フッ素熱硬化性樹脂組成物において、上記含フッ素熱硬化性樹脂は、本開示の含フッ素熱硬化性樹脂と同じである。従って、本開示の含フッ素熱硬化性樹脂において記載した含フッ素熱硬化性樹脂の好適な態様を全て採用できる。 In the fluorine-containing thermosetting resin composition of the present disclosure, the fluorine-containing thermosetting resin is the same as the fluorine-containing thermosetting resin of the present disclosure. Therefore, all suitable embodiments of the fluorine-containing thermosetting resin described in the fluorine-containing thermosetting resin of the present disclosure can be employed.
本開示の含フッ素熱硬化性樹脂組成物は、溶剤を含む。上記溶剤としては、有機溶媒が好ましく、有機溶媒としては特に限定されないが、酢酸エチル、酢酸ブチル、酢酸イソプロピル、酢酸イソブチル、酢酸セロソルブ、プロピレングリコールメチルエーテルアセテートなどのエステル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン類；テトラヒドロフラン、ジオキサンなどの環状エーテル類；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミドなどのアミド類；トルエン、キシレンなどの芳香族炭化水素類；プロピレングリコールメチルエーテルなどのアルコール類；ヘキサン、ヘプタンなどの炭化水素類；これらの混合溶媒などがあげられる。 The fluorine-containing thermosetting resin composition of the present disclosure contains a solvent. The above solvent is preferably an organic solvent, and the organic solvent is not particularly limited. Esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, and propylene glycol methyl ether acetate; Ketones such as ketones and cyclohexanone; Cyclic ethers such as tetrahydrofuran and dioxane; Amides such as N,N-dimethylformamide and N,N-dimethylacetamide; Aromatic hydrocarbons such as toluene and xylene; Propylene glycol methyl ether alcohols such as hexane; hydrocarbons such as hexane and heptane; and mixed solvents thereof.
本開示の含フッ素熱硬化性樹脂組成物は、更に前述のモノマーやその他のモノマー成分、例えば、スチレンや（メタ）アクリル酸メチルのようなモノマー成分を含んでいてもよい。モノマー成分は、ジビニルベンゼンやペンタエリスリトールトリ（メタ）アクリレートの複数のビニル基を含むモノマー成分であってもよい。
更に、前述の重合開始剤や光重合開始剤を含んでいてもよい。光重合開始剤は、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン類；アセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、１，１－ジクロロアセトフェノン、２－ヒドロキシ－２－メチル－フェニルプロパン－１－オン、ジエトキシアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－１－〔４－（メチルチオ）フェニル〕－２－モルホリノプロパン－１－オンなどのアセトフェノン類；２－エチルアントラキノン、２－ターシャリーブチルアントラキノン、２－クロロアントラキノン、２－アミルアントラキノンなどのアントラキノン類；２，４－ジエチルチオキサントン、２－イソプロピルチオキサントン、２－クロロチオキサントンなどのチオキサントン類；アセトフエノンジメチルケタール、ベンジルジメチルケタールなどのケタール類；ベンゾフェノン、４－ベンゾイル－４'－メチルジフェニルサルファイド、４，４'－ビスメチルアミノベンゾフェノンなどのベンゾフェノン類；２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド等のホスフィンオキサイド類等が挙げられる。
これらはそれぞれ単独で用いてもよいし、２種類以上を併用してもよい。 The fluorine-containing thermosetting resin composition of the present disclosure may further contain the aforementioned monomers and other monomer components such as styrene and methyl (meth)acrylate. The monomer component may be a monomer component containing multiple vinyl groups such as divinylbenzene or pentaerythritol tri(meth)acrylate.
Furthermore, the above-mentioned polymerization initiator and photopolymerization initiator may be included. Photoinitiators include, for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl ]-Acetophenones such as 2-morpholinopropan-1-one; Anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; 2,4-diethylthioxanthone, 2- Thioxanthones such as isopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone benzophenones; and phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.
Each of these may be used alone, or two or more of them may be used in combination.
本開示の含フッ素熱硬化性樹脂組成物は、架橋剤（硬化剤）を含まないものであってもよく、架橋剤（硬化剤）及び硬化促進剤を含まないものであってもよい。上記含フッ素熱硬化性樹脂はジシクロペンテニル基を含むので、架橋剤や硬化促進剤を使用しなくても自己架橋することができる。このため、余分な成分を添加する必要がなく、電気特性を向上させることができる。 The fluorine-containing thermosetting resin composition of the present disclosure may not contain a cross-linking agent (curing agent), or may contain neither a cross-linking agent (curing agent) nor a curing accelerator. Since the fluorine-containing thermosetting resin contains a dicyclopentenyl group, it can be self-crosslinked without using a crosslinking agent or a curing accelerator. Therefore, it is possible to improve electrical properties without adding extra components.
本開示の含フッ素熱硬化性樹脂組成物は、固形分１００質量％に対して、上記含フッ素熱硬化性樹脂が１０質量％以上が好ましく、２５質量％以上がより好ましく、４０質量％以上が更に好ましく、また、１００質量％以下であってもよく、８０質量％以下であってもよい。 In the fluorine-containing thermosetting resin composition of the present disclosure, the fluorine-containing thermosetting resin is preferably 10% by mass or more, more preferably 25% by mass or more, and 40% by mass or more relative to the solid content of 100% by mass. More preferably, it may be 100% by mass or less, or may be 80% by mass or less.
本開示の含フッ素熱硬化性樹脂組成物は、難燃剤、無機質充填材、シランカップリング剤、離型剤、顔料、乳化剤等を含んでもよい。 The fluorine-containing thermosetting resin composition of the present disclosure may contain flame retardants, inorganic fillers, silane coupling agents, release agents, pigments, emulsifiers and the like.
本開示の含フッ素熱硬化性樹脂組成物は、要求特性に応じて各種の添加剤を含むものであってもよい。添加剤としては、顔料分散剤、消泡剤、レベリング剤、ＵＶ吸収剤、光安定剤、増粘剤、密着改良剤、つや消し剤などがあげられる。 The fluorine-containing thermosetting resin composition of the present disclosure may contain various additives according to required properties. Additives include pigment dispersants, antifoaming agents, leveling agents, UV absorbers, light stabilizers, thickeners, adhesion improvers, matting agents and the like.
本開示の含フッ素熱硬化性樹脂組成物を調製する方法は特に限定されない。例えば、含フッ素熱硬化性樹脂の溶液又は分散液と、他の成分とを混合する方法等が挙げられる。 The method of preparing the fluorine-containing thermosetting resin composition of the present disclosure is not particularly limited. Examples thereof include a method of mixing a solution or dispersion of a fluorine-containing thermosetting resin with other components.
本開示の含フッ素熱硬化性樹脂組成物は、基材と該基材上に設けられた樹脂層とを備える積層の樹脂層として好適に使用でき、特に金属張積層板の樹脂層として好適に使用できる。また、粉体塗料用樹脂、光学用途用樹脂、レジスト材料にも使用できる。 The fluorine-containing thermosetting resin composition of the present disclosure can be suitably used as a resin layer of a laminate comprising a substrate and a resin layer provided on the substrate, and is particularly suitable as a resin layer of a metal-clad laminate. Available. It can also be used for resins for powder coatings, resins for optical applications, and resist materials.
本開示の含フッ素熱硬化性樹脂組成物は、金属箔と、該金属箔上に設けられた樹脂層とを備える金属張積層板であって、上記樹脂層が本開示の含フッ素熱硬化性樹脂組成物から形成される金属張積層板に好適に使用できる。上記本開示の含フッ素熱硬化性樹脂組成物を硬化させることによって樹脂層を形成できる。 The fluorine-containing thermosetting resin composition of the present disclosure is a metal-clad laminate comprising a metal foil and a resin layer provided on the metal foil, wherein the resin layer is the fluorine-containing thermosetting resin of the present disclosure. It can be suitably used for a metal-clad laminate formed from a resin composition. A resin layer can be formed by curing the fluorine-containing thermosetting resin composition of the present disclosure.
上記金属張積層板は、金属箔と樹脂層とを備える。上記樹脂層は絶縁性に優れており、金属張積層板の基材としての役割を果たす。 The metal-clad laminate includes a metal foil and a resin layer. The resin layer has excellent insulating properties and plays a role as a base material of the metal-clad laminate.
金属箔としては、銅、アルミニウム、鉄、ニッケル、クロム、モリブデン、タングステン、亜鉛、又はこれらの合金からなる金属箔が例示され、好ましくは銅箔である。また、接着力の向上を目的として、サイディング、ニッケルメッキ、銅－亜鉛合金メッキ、又はアルミニウムアルコラート、アルミニウムキレート、シランカップリング剤などによって、化学的あるいは機械的な表面処理を施してもよい。 Examples of metal foils include metal foils made of copper, aluminum, iron, nickel, chromium, molybdenum, tungsten, zinc, or alloys thereof, preferably copper foil. In addition, for the purpose of improving adhesive strength, chemical or mechanical surface treatment may be applied with siding, nickel plating, copper-zinc alloy plating, aluminum alcoholate, aluminum chelate, silane coupling agent, or the like.
上記金属張積層板は、金属箔と上記樹脂層とを備える限り、更にその他の層を含んでいてもよく、金属箔及び上記樹脂層はそれぞれ、１種であってもよいし、２種以上であってもよい。 As long as the metal-clad laminate comprises the metal foil and the resin layer, the metal-clad laminate may further include other layers, and each of the metal foil and the resin layer may be one kind, or two or more kinds. may be
上記金属張積層板は、更に、上記樹脂層（以下「第一の樹脂層」と記載する）上に設けられた第二の樹脂層を備えるものであってもよい。すなわち、上記金属張積層板は、金属箔、第一の樹脂層、及び、第二の樹脂層がこの順に積層されたものであってもよい。第一の樹脂層は基材としての役割を果たす他、金属箔と第二の樹脂層とを接着する接着剤層としての役割を果たしてもよい。
また、上記金属張積層板においては、金属箔の第一の樹脂層が設けられている面とは異なる面（反対側の面）にも第一の樹脂層が設けられていてもよい。すなわち、上記金属張積層板は、第一の樹脂層、金属箔、第一の樹脂層の順に積層されたものであってもよいし、第一の樹脂層、金属箔、第一の樹脂層、第二の樹脂層の順に積層されたものであってもよい。 The metal-clad laminate may further include a second resin layer provided on the resin layer (hereinafter referred to as "first resin layer"). That is, the metal-clad laminate may be formed by laminating a metal foil, a first resin layer, and a second resin layer in this order. The first resin layer not only serves as a base material, but may also serve as an adhesive layer that bonds the metal foil and the second resin layer.
In addition, in the metal-clad laminate, the first resin layer may be provided on the surface of the metal foil different from the surface on which the first resin layer is provided (the opposite side). That is, the metal-clad laminate may be one in which the first resin layer, the metal foil, and the first resin layer are laminated in this order, or the first resin layer, the metal foil, and the first resin layer. , and the second resin layer.
上記第二の樹脂層には、従来のプリント基板に使用されている樹脂を使用することができるが、上記第二の樹脂層は、ポリエチレンテレフタレート及びポリイミドからなる群より選択される少なくとも１種の樹脂からなることが好ましく、耐熱性の観点から、ポリイミドからなることがより好ましい。 Resins used in conventional printed circuit boards can be used for the second resin layer, but the second resin layer is at least one selected from the group consisting of polyethylene terephthalate and polyimide. It is preferably made of resin, and more preferably made of polyimide from the viewpoint of heat resistance.
第一の樹脂層としては、厚みが１～１５０μｍのフィルムを用いることができる。第一の樹脂層を介して金属箔と第二の接着層とを接着する場合、第一の樹脂層は、乾燥後の厚みを１～１００μｍとすることができる。 A film having a thickness of 1 to 150 μm can be used as the first resin layer. When the metal foil and the second adhesive layer are bonded via the first resin layer, the thickness of the first resin layer after drying can be 1 to 100 μm.
上記第二の樹脂層としては、厚みが１～１５０μｍの樹脂フィルムを用いることができる。 A resin film having a thickness of 1 to 150 μm can be used as the second resin layer.
上記金属張積層板は、金属箔と、上記含フッ素熱硬化性樹脂組成物からなるフィルムと、を接着することにより金属張積層板を得る工程を含む製造方法により得ることができる。
上記接着の方法としては、金属箔と上記含フッ素熱硬化性樹脂組成物を含むフィルムとを重ねた後、５０～３００℃で加熱プレス機により熱圧着させる方法が好適である。
上記製造方法は、更に、上記含フッ素熱硬化性樹脂組成物を成形して、上記含フッ素熱硬化性樹脂からなるフィルムを得る工程を含むものであってもよい。
成形方法としては、溶融押出成形法、溶媒キャスト法、スプレー法などの方法が挙げられるが、特に限定されるものではない。上記含フッ素熱硬化性樹脂組成物は、有機溶剤、硬化剤等を含むものであってもよいし、硬化促進剤、顔料分散剤、消泡剤、レベリング剤、ＵＶ吸収剤、光安定剤、増粘剤、密着改良剤、つや消し剤等を含んでもよい。 The metal-clad laminate can be obtained by a manufacturing method including a step of obtaining a metal-clad laminate by bonding a metal foil and a film made of the fluorine-containing thermosetting resin composition.
As the bonding method, a method of stacking the metal foil and the film containing the fluorine-containing thermosetting resin composition and then thermocompression bonding them at 50 to 300° C. using a hot press is suitable.
The above production method may further include the step of molding the fluorine-containing thermosetting resin composition to obtain a film made of the fluorine-containing thermosetting resin.
Examples of the molding method include, but are not limited to, methods such as melt extrusion molding, solvent casting, and spraying. The fluorine-containing thermosetting resin composition may contain an organic solvent, a curing agent, etc., and may contain a curing accelerator, a pigment dispersant, an antifoaming agent, a leveling agent, a UV absorber, a light stabilizer, Thickeners, adhesion improvers, matting agents and the like may also be included.
上記金属張積層板は、金属箔に、上記含フッ素熱硬化性樹脂組成物を塗布して第一の樹脂層を形成する工程を含む製造方法によっても得ることができる。
上記製造方法は、上記第一の樹脂層を形成する工程の後、更に上記第一の樹脂層上に第二の樹脂層となる樹脂フィルムを接着させ、金属箔と、第一及び第二の樹脂層とを備える金属張積層板を得る工程を含むものであってもよい。樹脂フィルムとしては、第二の樹脂層を形成するのに好適な樹脂からなるフィルムが挙げられる。
上記樹脂フィルムを接着する方法としては、５０～３００℃で加熱プレス機により熱圧着させる方法が好適である。
上記製造方法において、第一の樹脂層を形成するための組成物を金属箔に塗布する方法としては、刷毛塗り、浸漬塗布、スプレー塗布、コンマコート、ナイフコート、ダイコート、リップコート、ロールコーター塗布、カーテン塗布等の方法が挙げられる。組成物を塗布した後、熱風乾燥炉等により２５～２００℃で１分～１週間乾燥し、硬化させることができる。 The metal-clad laminate can also be obtained by a manufacturing method including the step of applying the fluorine-containing thermosetting resin composition to a metal foil to form a first resin layer.
In the above manufacturing method, after the step of forming the first resin layer, a resin film to be the second resin layer is further adhered on the first resin layer, and the metal foil and the first and second It may include a step of obtaining a metal-clad laminate including a resin layer. Examples of the resin film include a film made of a resin suitable for forming the second resin layer.
As a method for adhering the resin film, a method of thermocompression bonding at 50 to 300° C. using a hot press is suitable.
In the above production method, methods for applying the composition for forming the first resin layer to the metal foil include brush coating, dip coating, spray coating, comma coating, knife coating, die coating, lip coating, and roll coating. , curtain coating, and the like. After applying the composition, it can be cured by drying in a hot air drying oven or the like at 25 to 200° C. for 1 minute to 1 week.
上記金属張積層板は、上記含フッ素熱硬化性樹脂組成物を第二の樹脂層となる樹脂フィルムに塗布し第一の樹脂層を形成する工程、及び、当該形成工程により得られる第一の樹脂層と第二の樹脂層とからなる積層体の第一の樹脂層に金属箔を接着させて、金属箔と、第一及び第二の樹脂層とを備える金属張積層板を得る工程を含む製造方法によっても製造できる。上記樹脂フィルムとしては、第二の樹脂層を形成するのに好適な樹脂からなるフィルムが挙げられる。
第一の樹脂層を形成するための組成物を樹脂フィルムに塗布する方法としては、刷毛塗り、浸漬塗布、スプレー塗布、コンマコート、ナイフコート、ダイコート、リップコート、ロールコーター塗布、カーテン塗布等の方法が挙げられる。組成物を塗布した後、熱風乾燥炉等により２５～２００℃で１分～１週間乾燥し、硬化させることができる。
上記製造方法において、第一の樹脂層と第二の樹脂層とからなる積層体の第一の樹脂層に金属箔を接着させる方法としては、第一の樹脂層と第二の樹脂層とからなる積層体と金属箔とを当該積層体の第一の樹脂層と金属箔とが接着することとなるように重ねた後、５０～３００℃で加熱プレス機により熱圧着させる方法が好適である。 The metal-clad laminate includes a step of applying the fluorine-containing thermosetting resin composition to a resin film that will be the second resin layer to form a first resin layer, and a first resin layer obtained by the forming step. a step of bonding a metal foil to a first resin layer of a laminate comprising a resin layer and a second resin layer to obtain a metal-clad laminate comprising the metal foil and the first and second resin layers; It can also be manufactured by a manufacturing method including: Examples of the resin film include a film made of a resin suitable for forming the second resin layer.
Methods for applying the composition for forming the first resin layer to the resin film include brush coating, dip coating, spray coating, comma coating, knife coating, die coating, lip coating, roll coater coating, curtain coating, and the like. method. After applying the composition, it can be cured by drying in a hot air drying oven or the like at 25 to 200° C. for 1 minute to 1 week.
In the above manufacturing method, the method of bonding the metal foil to the first resin layer of the laminate composed of the first resin layer and the second resin layer includes: A preferred method is to laminate the laminate and the metal foil so that the first resin layer and the metal foil of the laminate are adhered, and then thermocompress them with a hot press at 50 to 300 ° C. .
上記金属張積層板は、該金属張積層板の金属箔をエッチングして形成されたパターン回路を備えるプリント基板に適用できる。上記プリント基板は、フレキシブル基板であってもよいし、リジット基板であってもよいが、リジット基板であることが好ましい。
上記プリント基板は、上記金属張積層板上にカバーレイフィルムを備えるものであってもよく、上記カバーレイフィルムは上記樹脂層を介して金属張積層板と接着していてもよい。
上記エッチングの方法は限定されず従来公知の方法を採用することができる。また、パターン回路は限定されず、どのようなパターン回路のプリント基板でもよい。 The metal-clad laminate can be applied to a printed circuit board provided with a pattern circuit formed by etching the metal foil of the metal-clad laminate. The printed board may be a flexible board or a rigid board, but is preferably a rigid board.
The printed circuit board may include a coverlay film on the metal-clad laminate, and the coverlay film may be adhered to the metal-clad laminate via the resin layer.
The etching method is not limited, and conventionally known methods can be employed. Moreover, the pattern circuit is not limited, and a printed circuit board having any pattern circuit may be used.
上記プリント基板の用途は限定されるものではない。例えば、上記プリント基板は、低誘電率及び低誘電正接である樹脂層を有するため、４Ｇ（３７．５Ｍｂｐｓ）、５Ｇ（数Ｇ～２０Ｇｂｐｓ）のように使用周波数帯が高い用途で使用されるプリント基板にも使用可能である。 Applications of the printed circuit board are not limited. For example, since the printed circuit board has a resin layer with a low dielectric constant and a low dielectric loss tangent, it is used in applications with high frequency bands such as 4G (37.5 Mbps) and 5G (several G to 20 Gbps). It can also be used for substrates.
次に本開示を実施例をあげて説明するが、本開示はかかる実施例のみに限定されるものではない。
以下、実施例により本開示を更に具体的に説明する。 The present disclosure will now be described with reference to examples, but the present disclosure is not limited only to such examples.
EXAMPLES Hereinafter, the present disclosure will be described more specifically with reference to examples.
本明細書に記載された物性は以下の測定方法で測定したものである。 The physical properties described in this specification are measured by the following measuring methods.
（１）ＮＭＲ分析：
測定装置：ＮＭＲ測定装置：ＶＡＲＩＡＮ社製
１Ｈ－ＮＭＲ測定条件：４００ＭＨｚ（テトラメチルシラン＝０ｐｐｍ） (1) NMR analysis:
Measurement device: NMR measurement device: 1H-NMR measurement conditions manufactured by VARIAN: 400 MHz (tetramethylsilane = 0 ppm)
（２）元素分析（フッ素含有量（質量％）の測定）
測定装置：自動試料燃焼装置（三菱化学（株）製　ＡＱＦ－１００）　イオンクロマト（ＤＩＯＮＥＸ社製　ＩＣＳ－１５００　Ｉｏｎ　Ｃｈｒｏｍａｔｏｇｒａｐｈｙ　Ｓｙｓｔｅｍ）内蔵
試料　３ｍｇ (2) Elemental analysis (measurement of fluorine content (mass%))
Measuring device: automatic sample combustion device (Mitsubishi Chemical Co., Ltd. AQF-100) ion chromatography (DIONEX ICS-1500 Ion Chromatography System) built-in sample 3 mg
（３）分子量
測定装置：昭和電工（株）製Ｓｈｏｄｅｘ　ＧＰＣ－１０４
測定条件：溶離液としてはテトラヒドロフランを使用し、分子量の標準サンプルとしては分子量既知のポリスチレンを使用する。 (3) Molecular weight measuring device: Shodex GPC-104 manufactured by Showa Denko Co., Ltd.
Measurement conditions: Tetrahydrofuran is used as an eluent, and polystyrene with a known molecular weight is used as a molecular weight standard sample.
（４）ガラス転移温度
ＡＳＴＭ　Ｅ１３５６－９８に従い、ＭＥＴＬＥＲ　ＴＯＬＥＤＯ製のＤＳＣ測定装置を使用してセカンドランにおける熱吸収から中点法によってガラス転移温度及び結晶融点を決定した。
測定条件
昇温速度；２０℃／ｍｉｎ
試料量；１０ｍｇ
ヒートサイクル；－５０℃～１５０℃、昇温、冷却、昇温 (4) Glass transition temperature According to ASTM E1356-98, the glass transition temperature and crystalline melting point were determined by the midpoint method from the heat absorption in the second run using a DSC measurement device manufactured by METLER TOLEDO.
Measurement conditions Heating rate; 20°C/min
Sample amount; 10 mg
Heat cycle; -50°C to 150°C, temperature rise, cooling, temperature rise
（５）溶剤溶解性評価
合成例で作成した共重合体２０ｇをメチルエチルケトン２０ｇを１００ｍｌサンプル瓶に秤量し振り交ぜて、溶解性を目視によって確認した。 (5) Evaluation of Solvent Solubility 20 g of the copolymer prepared in Synthesis Example was weighed in 20 g of methyl ethyl ketone in a 100 ml sample bottle and shaken to visually confirm the solubility.
（６）熱硬化性評価（ゲル分率）
上記溶剤溶解性評価で作成した溶液をアルミカップに１０ｇ取り、室温で１時間乾燥後、１５０℃で３時間加熱乾燥し、熱硬化物を得た。この硬化物を取り、あらかじめ重さをはかった４００メッシュの金属金網で包んだ。５０ｍｌのサンプル管に２５ｍｌのアセトンと金網に包まれた硬化物を入れ、１２時間アセトン中で硬化物を浸漬した。その後、金網を取り出し、乾燥させ乾燥後の質量を測定し、アセトン浸漬後の乾燥硬化物の質量を算出した。
ゲル分率は、アセトン浸漬後の乾燥硬化物の質量／アセトン浸漬前の硬化物の質量×１００として算出した。 (6) Thermosetting evaluation (gel fraction)
10 g of the solution prepared in the solvent solubility evaluation was placed in an aluminum cup, dried at room temperature for 1 hour, and then dried by heating at 150° C. for 3 hours to obtain a thermoset. The cured material was taken and wrapped in a pre-weighed 400 mesh metal wire mesh. 25 ml of acetone and the cured product wrapped in a wire mesh were placed in a 50 ml sample tube, and the cured product was immersed in acetone for 12 hours. After that, the wire mesh was taken out, dried, and the mass after drying was measured, and the mass of the dried and cured product after immersion in acetone was calculated.
The gel fraction was calculated as (mass of dried cured product after immersion in acetone/mass of cured product before immersion in acetone×100).
（７）熱硬化温度
熱硬化温度は、ＤＳＣ測定装置での測定時に見られた発熱ピークのピークトップの温度、または、示差熱・熱重量測定装置〔ＴＧ－ＤＴＡ〕（商品名：ＴＧ／ＤＴＡ７２００、日立ハイテクサイエンス社製）を用い、試料１０ｍｇを昇温速度１０℃／分で室温から昇温し、重量減少が１％未満の温度域で見られた発熱ピークのピークトップの温度を熱硬化温度とした。 (7) Thermosetting temperature The thermosetting temperature is the peak top temperature of the exothermic peak observed during measurement with a DSC measurement device, or a differential thermal/thermogravimetry device [TG-DTA] (trade name: TG/DTA7200 , Hitachi High-Tech Science Co., Ltd.), 10 mg of the sample was heated from room temperature at a heating rate of 10 ° C./min, and the temperature of the peak top of the exothermic peak seen in the temperature range where the weight loss was less than 1% was heat cured. temperature.
合成例１
容量３０００ｍｌのステンレス製オートクレーブにアセトン８００ｇ、下記式で示されるビニルエーテル１（ＤＣＰＤ－ＶＥ）：
Figure JPOXMLDOC01-appb-C000027
 １３０ｇを投入し、減圧窒素置換の操作を行い、テトラフルオロエチレン（ＴＦＥ）１３０ｇを仕込んだ。撹拌下に６５．０℃まで昇温し、過酸化物系重合開始剤８ｇを仕込み重合を開始した。反応器内圧が０．９ＭＰａＧから０．５ＭＰａＧへ低下した時点で反応を停止し、共重合体を含む均一な溶液を得た。得られた溶液を濃縮後、大量のメタノールに濃縮液を投入し、共重合体を析出させた。得られた共重合体をメタノールで洗浄、濾別、乾燥して共重合体を得た。 Synthesis example 1
800 g of acetone in a stainless steel autoclave with a capacity of 3000 ml, vinyl ether 1 (DCPD-VE) represented by the following formula:
Figure JPOXMLDOC01-appb-C000027
 130 g of tetrafluoroethylene (TFE) was introduced, and the vacuum nitrogen replacement operation was performed. The temperature was raised to 65.0° C. while stirring, and 8 g of a peroxide polymerization initiator was charged to initiate polymerization. When the internal pressure of the reactor decreased from 0.9 MPaG to 0.5 MPaG, the reaction was terminated to obtain a uniform solution containing the copolymer. After concentrating the obtained solution, the concentrated liquid was poured into a large amount of methanol to precipitate the copolymer. The resulting copolymer was washed with methanol, filtered and dried to obtain a copolymer.
得られた共重合体は、ＮＭＲ分析より、テトラフルオロエチレンが５５モル％、ビニルエーテル１が４５モル％の組成であった。分子量分析より、数平均分子量（Ｍｎ）は、１３０００、重量平均分子量（Ｍｗ）は、２６０００であった。ガラス転移温度（Ｔｇ）は９２℃であった。元素分析の結果は、フッ素含有量３１．５質量％であった。ＤＳＣ測定の結果、１４０℃付近に発熱のピークが認められた。 According to NMR analysis, the resulting copolymer had a composition of 55 mol % tetrafluoroethylene and 45 mol % vinyl ether 1. Molecular weight analysis revealed a number average molecular weight (Mn) of 13,000 and a weight average molecular weight (Mw) of 26,000. The glass transition temperature (Tg) was 92°C. Elemental analysis showed a fluorine content of 31.5% by mass. As a result of DSC measurement, an exothermic peak was observed around 140°C.
合成例２
容量３０００ｍｌのステンレス製オートクレーブにアセトン８００ｇ、クロトン酸ビニル４５ｇを投入し、減圧窒素置換の操作を行い、テトラフルオロエチレン（ＴＦＥ）１３０ｇを仕込んだ。撹拌下に６５．０℃まで昇温し、過酸化物系重合開始剤２ｇを仕込み重合を開始した。反応器内圧が０．９ＭＰａＧから０．８ＭＰａＧへ低下した時点で反応を停止した。反応溶液は不均一な溶液で、共重合体の固形物は溶媒に不溶で、オートクレーブの底に沈殿していた。 Synthesis example 2
800 g of acetone and 45 g of vinyl crotonate were charged into a stainless steel autoclave having a capacity of 3000 ml, and the autoclave was subjected to vacuum nitrogen replacement, and 130 g of tetrafluoroethylene (TFE) was charged. The temperature was raised to 65.0° C. while stirring, and 2 g of a peroxide polymerization initiator was charged to initiate polymerization. The reaction was stopped when the internal pressure of the reactor decreased from 0.9 MPaG to 0.8 MPaG. The reaction solution was a heterogeneous solution, and the copolymer solid was insoluble in the solvent and precipitated at the bottom of the autoclave.
合成例３
容量３０００ｍｌのステンレス製オートクレーブにアセトン８００ｇ、下記式で示されるビニルエーテル２：
Figure JPOXMLDOC01-appb-C000028
 １３０ｇを投入し、減圧窒素置換の操作を行い、テトラフルオロエチレン（ＴＦＥ）１３０ｇを仕込んだ。撹拌下に６５．０℃まで昇温し、過酸化物系重合開始剤８ｇを仕込み重合を開始した。反応器内圧が０．９ＭＰａＧから０．５ＭＰａＧへ低下した時点で反応を停止し、共重合体を含む不均一な溶液を得た。得られた溶液を濃縮後、大量のメタノールに濃縮液を投入し、共重合体を析出させた。得られた共重合体をメタノールで洗浄、濾別、乾燥して共重合体を得た。 Synthesis example 3
A stainless steel autoclave with a capacity of 3000 ml was charged with 800 g of acetone and vinyl ether 2 represented by the following formula:
Figure JPOXMLDOC01-appb-C000028
 130 g of tetrafluoroethylene (TFE) was introduced, and the vacuum nitrogen replacement operation was performed. The temperature was raised to 65.0° C. while stirring, and 8 g of a peroxide polymerization initiator was charged to initiate polymerization. When the internal pressure of the reactor decreased from 0.9 MPaG to 0.5 MPaG, the reaction was terminated to obtain a heterogeneous solution containing the copolymer. After concentrating the obtained solution, the concentrated liquid was poured into a large amount of methanol to precipitate the copolymer. The resulting copolymer was washed with methanol, filtered and dried to obtain a copolymer.
得られた共重合体は、ＮＭＲ分析より、テトラフルオロエチレンが５５モル％、ビニルエーテル２が４５モル％の組成であった。分子量分析より、数平均分子量（Ｍｎ）は、８０００、重量平均分子量（Ｍｗ）は、１５０００であった。ガラス転移温度（Ｔｇ）は６２℃であった。元素分析の結果は、フッ素含有量３０．４質量％であった。 According to NMR analysis, the resulting copolymer had a composition of 55 mol % tetrafluoroethylene and 45 mol % vinyl ether 2. Molecular weight analysis revealed a number average molecular weight (Mn) of 8,000 and a weight average molecular weight (Mw) of 15,000. The glass transition temperature (Tg) was 62°C. Elemental analysis showed a fluorine content of 30.4% by mass.
合成例４
容量３０００ｍｌのステンレス製オートクレーブにアセトン８００ｇ、４－ｔ－ブチル安息香酸ビニル４００ｇを投入し、減圧窒素置換の２操作を行い、テトラフルオロエチレン（ＴＦＥ）１３０ｇを仕込んだ。撹拌下に６５．０℃まで昇温し、過酸化物系重合開始剤２ｇを仕込み重合を開始した。反応器内圧が０．９ＭＰａＧから０．５ＭＰａＧへ低下した時点で反応を停止し、共重合体を含む均一な溶液を得た。得られた溶液を濃縮後、大量のメタノールに濃縮液を投入し、共重合体を析出させた。得られた共重合体をメタノールで洗浄、濾別、乾燥して共重合体を得た。 Synthesis example 4
800 g of acetone and 400 g of vinyl 4-t-butylbenzoate were charged into a stainless steel autoclave having a capacity of 3000 ml, two operations of vacuum nitrogen replacement were performed, and 130 g of tetrafluoroethylene (TFE) was charged. The temperature was raised to 65.0° C. while stirring, and 2 g of a peroxide polymerization initiator was charged to initiate polymerization. When the internal pressure of the reactor decreased from 0.9 MPaG to 0.5 MPaG, the reaction was terminated to obtain a uniform solution containing the copolymer. After concentrating the obtained solution, the concentrated liquid was poured into a large amount of methanol to precipitate the copolymer. The resulting copolymer was washed with methanol, filtered and dried to obtain a copolymer.
得られた共重合体は、ＮＭＲ分析より、テトラフルオロエチレンが２６モル％、４－ｔ－ブチル安息香酸ビニルが７４モル％の組成であった。分子量分析より、数平均分子量（Ｍｎ）は、３００００、重量平均分子量（Ｍｗ）は、７４０００であった。ガラス転移温度（Ｔｇ）は１２０℃であった。元素分析の結果は、フッ素含有量１２．６質量％であった。 According to NMR analysis, the resulting copolymer had a composition of 26 mol % tetrafluoroethylene and 74 mol % vinyl 4-t-butylbenzoate. Molecular weight analysis revealed a number average molecular weight (Mn) of 30,000 and a weight average molecular weight (Mw) of 74,000. The glass transition temperature (Tg) was 120°C. Elemental analysis showed a fluorine content of 12.6% by mass.
合成例５
３００ｍｌ４つ口フラスコに、メチルイソブチルケトン６０ｇ、ジシクロペンテニルアクリレート１９．５ｇ、メチル－２－フルオロアクリレート１２．４ｇ、２，４－ジフェニル－４－メチル－１－ペンテン１．３ｇを投入した。内温を９０℃としてｔ－ブチルパーオキシ－２－エチルヘキサノエート０．６ｇを添加し、３時間反応させた。反応容器を冷却後、室温で反応混合液を大量のメタノールに投入し、共重合体を析出させた。得られた共重合体をヘキサンで洗浄、濾別、乾燥して共重合体を８ｇ得た。
得られた共重合体は、元素分析及びＮＭＲ分析より、ジシクロペンテニルアクリレート由来の構造が４７モル％、メチル－２－フルオロアクリレート由来の構造が５３モル％の組成であった。また、２，４－ジフェニル－４－メチル－１－ペンテン由来の構造の末端基は、ジシクロペンタニルアクリレート由来の構造とメチル－２－フルオロアクリレート由来の構造と２，４－ジフェニル－４－メチル－１－ペンテン由来の構造の末端基の総計に対して、３．０モル％であった。このうち１６モル％が上記式（１－１）で示される基を有していることが分かった。 Synthesis example 5
60 g of methyl isobutyl ketone, 19.5 g of dicyclopentenyl acrylate, 12.4 g of methyl-2-fluoroacrylate, and 1.3 g of 2,4-diphenyl-4-methyl-1-pentene were introduced into a 300 ml four-necked flask. The internal temperature was adjusted to 90° C., 0.6 g of t-butylperoxy-2-ethylhexanoate was added, and the reaction was allowed to proceed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The obtained copolymer was washed with hexane, filtered and dried to obtain 8 g of copolymer.
Elemental analysis and NMR analysis revealed that the obtained copolymer had a composition of 47 mol % of the structure derived from dicyclopentenyl acrylate and 53 mol % of the structure derived from methyl-2-fluoroacrylate. Further, the terminal groups of the structure derived from 2,4-diphenyl-4-methyl-1-pentene are a structure derived from dicyclopentanyl acrylate, a structure derived from methyl-2-fluoroacrylate and 2,4-diphenyl-4- It was 3.0 mol % with respect to the total terminal groups of the structure derived from methyl-1-pentene. Of these, 16 mol % were found to have the group represented by the above formula (1-1).
分子量分析より、数平均分子量（Ｍｎ）は、６４００、重量平均分子量（Ｍｗ）は、１１０００であった。ガラス転移温度（Ｔｇ）は９５℃であった。元素分析の結果は、フッ素含有量５．９質量％であった。
ＤＳＣ測定の結果、１４０℃付近に発熱のピークが認められた。 Molecular weight analysis revealed a number average molecular weight (Mn) of 6,400 and a weight average molecular weight (Mw) of 11,000. The glass transition temperature (Tg) was 95°C. Elemental analysis showed a fluorine content of 5.9% by mass.
As a result of DSC measurement, an exothermic peak was observed around 140°C.
合成例６
３００ｍｌ４つ口フラスコに、メチルイソブチルケトン６０ｇ、ジシクロペンテニルアクリレート２１．５ｇ、１，２，２－トリフルオロエテニルベンゼン１６．５ｇ、２，４－ジフェニル－４－メチル－１－ペンテン０．８ｇを投入した。内温を９０℃としてｔ－ブチルパーオキシ－２－エチルヘキサノエート０．８ｇを添加し、３時間反応させた。反応容器を冷却後、室温で反応混合液を大量のメタノールに投入し、共重合体を析出させた。得られた共重合体をヘキサンで洗浄、濾別、乾燥して共重合体を得た。
得られた共重合体は、元素分析及びＮＭＲ分析より、ジシクロペンテニルアクリレート由来の構造が７６モル％、１，２，２－トリフルオロエテニルベンゼン由来の構造が２４モル％の組成であった。
分子量分析より、数平均分子量（Ｍｎ）は、６５００、重量平均分子量（Ｍｗ）は、１４０００であった。ガラス転移温度（Ｔｇ）は１０５℃であった。元素分析の結果は、フッ素含有量６．２質量％であった。
ＤＳＣ測定の結果、１４０℃付近に発熱のピークが認められた。 Synthesis example 6
60 g of methyl isobutyl ketone, 21.5 g of dicyclopentenyl acrylate, 16.5 g of 1,2,2-trifluoroethenylbenzene, and 0.8 g of 2,4-diphenyl-4-methyl-1-pentene were placed in a 300 ml four-necked flask. put in. The internal temperature was adjusted to 90° C., 0.8 g of t-butylperoxy-2-ethylhexanoate was added, and the reaction was allowed to proceed for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The obtained copolymer was washed with hexane, filtered and dried to obtain a copolymer.
Elemental analysis and NMR analysis revealed that the obtained copolymer had a composition of 76 mol % of the structure derived from dicyclopentenyl acrylate and 24 mol % of the structure derived from 1,2,2-trifluoroethenylbenzene.
Molecular weight analysis revealed a number average molecular weight (Mn) of 6,500 and a weight average molecular weight (Mw) of 14,000. The glass transition temperature (Tg) was 105°C. Elemental analysis showed a fluorine content of 6.2% by mass.
As a result of DSC measurement, an exothermic peak was observed around 140°C.
合成例７
３００ｍｌ４つ口フラスコに、メチルイソブチルケトン２００ｇ、下記式で示されるビニルエーテル１（ＤＣＰＤ－ＶＥ）：
Figure JPOXMLDOC01-appb-C000029
 ３２ｇ、１，２，２－トリフルオロエテニルベンゼン３０ｇ、Ｎ－シクロヘキシルマレイイミド６６ｇを投入し、窒素置換した。内温を７０℃としてｔ－ブチルパーオキシピバレート８ｇを添加し、３時間反応させた。反応容器を冷却後、室温で反応混合液を大量のメタノールに投入し、共重合体を析出させた。得られた共重合体をメタノールで洗浄、濾別、乾燥して共重合体を得た。 Synthesis example 7
In a 300 ml four-neck flask, 200 g of methyl isobutyl ketone, vinyl ether 1 (DCPD-VE) represented by the following formula:
Figure JPOXMLDOC01-appb-C000029
 32 g of 1,2,2-trifluoroethenylbenzene, 30 g of N-cyclohexylmaleimide, and 66 g of N-cyclohexylmaleimide were added, and nitrogen substitution was performed. The internal temperature was adjusted to 70° C., 8 g of t-butyl peroxypivalate was added, and the mixture was reacted for 3 hours. After cooling the reaction vessel, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a copolymer. The resulting copolymer was washed with methanol, filtered and dried to obtain a copolymer.
得られた共重合体は、ＮＭＲ分析より、１，２，２－トリフルオロエテニルベンゼンが５モル％、ビニルエーテル１が３２モル％、Ｎ－シクロヘキシルマレイイミドが６３モル％の組成であった。分子量分析より、数平均分子量（Ｍｎ）は、４１００、重量平均分子量（Ｍｗ）は、１１０００であった。ガラス転移温度（Ｔｇ）は２５０℃であった。元素分析の結果は、フッ素含有量１．７質量％であった。ＴＧＤＴＡの測定の結果、２２０℃付近に発熱のピークが認められた。 According to NMR analysis, the obtained copolymer had a composition of 5 mol % of 1,2,2-trifluoroethenylbenzene, 32 mol % of vinyl ether 1 and 63 mol % of N-cyclohexylmaleimide. Molecular weight analysis revealed a number average molecular weight (Mn) of 4,100 and a weight average molecular weight (Mw) of 11,000. The glass transition temperature (Tg) was 250°C. Elemental analysis showed a fluorine content of 1.7% by mass. As a result of TGDTA measurement, an exothermic peak was observed around 220°C.
合成例１～７で作成したポリマー、該ポリマーを用いて作成した含フッ素熱硬化性樹脂のフィルムについて、物性を測定し、表１に結果を記した。 The physical properties of the polymers prepared in Synthesis Examples 1 to 7 and the fluorine-containing thermosetting resin films prepared using the polymers were measured, and the results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000030
ＮＭＲ分析より、合成例１、５、６、７で得られた共重合体では、上記式（Ｉ－１）及び（Ｉ－２）で示されるジシクロペンテニル基からなる群より選択される少なくとも１種を有していることが分かった。
表１から、合成例１、５、６、７で得られた共重合体は、熱硬化性（ゲル分率）に優れ、また、溶剤溶解性も良好であった。 According to NMR analysis, the copolymers obtained in Synthesis Examples 1, 5, 6, and 7 have at least It was found to have one.
From Table 1, the copolymers obtained in Synthesis Examples 1, 5, 6 and 7 were excellent in thermosetting properties (gel fraction) and had good solvent solubility.

Claims (15)

  1. 主鎖を形成する炭素原子とフッ素原子との間のＣ－Ｆ結合を有する含フッ素熱硬化性樹脂であって、
    下記式（Ｉ－１）で示されるジシクロペンテニル基及び下記式（Ｉ－２）で示されるジシクロペンテニル基からなる群より選択される少なくとも１種を有する含フッ素熱硬化性樹脂。
    Figure JPOXMLDOC01-appb-C000001
         A fluorine-containing thermosetting resin having a C—F bond between a carbon atom forming a main chain and a fluorine atom,
    A fluorine-containing thermosetting resin having at least one selected from the group consisting of a dicyclopentenyl group represented by the following formula (I-1) and a dicyclopentenyl group represented by the following formula (I-2).
    Figure JPOXMLDOC01-appb-C000001
  2. 前記含フッ素熱硬化性樹脂が含フッ素モノマーとフッ素非含有モノマーとの共重合体である請求項１記載の含フッ素熱硬化性樹脂。 2. The fluorine-containing thermosetting resin according to claim 1, wherein said fluorine-containing thermosetting resin is a copolymer of a fluorine-containing monomer and a fluorine-free monomer.
  3. 前記含フッ素モノマーは、含フッ素ビニルモノマー、含フッ素アクリルモノマー、含フッ素スチレンモノマー、水素含有フルオロオレフィン、及び含フッ素ノルボルネンからなる群より選択される少なくとも１種を含む請求項２記載の含フッ素熱硬化性樹脂。 3. The fluorine-containing heat according to claim 2, wherein the fluorine-containing monomer contains at least one selected from the group consisting of a fluorine-containing vinyl monomer, a fluorine-containing acrylic monomer, a fluorine-containing styrene monomer, a hydrogen-containing fluoroolefin, and a fluorine-containing norbornene. Hardening resin.
  4. 前記含フッ素モノマーは、含フッ素エチレン、含フッ素プロピレン、及び含フッ素ビニルエーテルからなる群より選択される少なくとも１種を含む請求項２記載の含フッ素熱硬化性樹脂。 3. The fluorine-containing thermosetting resin according to claim 2, wherein the fluorine-containing monomer contains at least one selected from the group consisting of fluorine-containing ethylene, fluorine-containing propylene, and fluorine-containing vinyl ether.
  5. 前記含フッ素モノマーは、フッ化ビニリデン、テトラフルオロエチレン、クロロトリフルオロエチレン、フッ化ビニル、へキサフルオロプロピレン、及びパーフルオロ（アルキルビニルエーテル）からなる群より選択される少なくとも１種を含む請求項２記載の含フッ素熱硬化性樹脂。 2. The fluorine-containing monomer contains at least one selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, vinyl fluoride, hexafluoropropylene, and perfluoro(alkyl vinyl ether). A fluorine-containing thermosetting resin as described.
  6. 前記含フッ素モノマーは、下記式で示される化合物の少なくとも１種を含む請求項２記載の含フッ素熱硬化性樹脂。
    Figure JPOXMLDOC01-appb-C000002
         3. The fluorine-containing thermosetting resin according to claim 2, wherein the fluorine-containing monomer contains at least one compound represented by the following formula.
    Figure JPOXMLDOC01-appb-C000002
  7. 前記フッ素非含有モノマーは、下記式で示される化合物の少なくとも１種を含む請求項２記載の含フッ素熱硬化性樹脂。
    Figure JPOXMLDOC01-appb-C000003
         3. The fluorine-containing thermosetting resin according to claim 2, wherein the fluorine-free monomer contains at least one compound represented by the following formula.
    Figure JPOXMLDOC01-appb-C000003
  8. 前記含フッ素熱硬化性樹脂に含まれるフッ素含有量は、前記含フッ素熱硬化性樹脂の全質量に対して、１質量％以上１５質量％以下である請求項１～７のいずれかに記載の含フッ素熱硬化性樹脂。 8. The fluorine-containing thermosetting resin according to any one of claims 1 to 7, wherein the content of fluorine contained in the fluorine-containing thermosetting resin is 1% by mass or more and 15% by mass or less with respect to the total mass of the fluorine-containing thermosetting resin. Fluorine-containing thermosetting resin.
  9. ガラス転移温度が８０℃以上である請求項１～８のいずれかに記載の含フッ素熱硬化性樹脂。 The fluorine-containing thermosetting resin according to any one of claims 1 to 8, which has a glass transition temperature of 80°C or higher.
  10. 数平均分子量が１０００～３００００である請求項１～９のいずれかに記載の含フッ素熱硬化性樹脂。 The fluorine-containing thermosetting resin according to any one of claims 1 to 9, which has a number average molecular weight of 1,000 to 30,000.
  11. 請求項１～１０のいずれかに記載の含フッ素熱硬化性樹脂と、溶剤とを含む含フッ素熱硬化性樹脂組成物。 A fluorine-containing thermosetting resin composition comprising the fluorine-containing thermosetting resin according to any one of claims 1 to 10 and a solvent.
  12. 請求項１～１０のいずれかに記載の含フッ素熱硬化性樹脂を含むフィルム。 A film comprising the fluorine-containing thermosetting resin according to any one of claims 1 to 10.
  13. 基材と、前記基材上に設けられた樹脂層とを備える積層体であって、前記樹脂層が、請求項１～１０のいずれかに記載の含フッ素熱硬化性樹脂を含む積層体。 A laminate comprising a substrate and a resin layer provided on the substrate, wherein the resin layer comprises the fluorine-containing thermosetting resin according to any one of claims 1 to 10.
  14. 金属箔と、前記金属箔上に設けられた樹脂層とを備える金属張積層板であって、前記樹脂層が、請求項１～１０のいずれかに記載の含フッ素熱硬化性樹脂を含む金属張積層板。 A metal-clad laminate comprising a metal foil and a resin layer provided on the metal foil, wherein the resin layer comprises the fluorine-containing thermosetting resin according to any one of claims 1 to 10. tension laminate.
  15. 請求項１４の金属張積層板の金属箔をエッチングして形成されたパターン回路を備えることを特徴とするプリント基板。 A printed circuit board comprising a pattern circuit formed by etching the metal foil of the metal-clad laminate according to claim 14 .
PCT/JP2022/004936 2021-02-09 2022-02-08 Fluorine-containing thermosetting resin, method for producing same, and fluorine-containing thermosetting resin composition WO2022172921A1 (en)

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JPS62138579A (en) * 1985-12-13 1987-06-22 Nippon Mektron Ltd Water-and oil-repellent
EP0243605A2 (en) * 1986-02-27 1987-11-04 Dainippon Ink And Chemicals, Inc. Fluorine-containing resin composition having a low refractive index
JPH01271406A (en) * 1988-03-23 1989-10-30 Hoechst Celanese Corp Autooxidative fluorocarbon polymer and composition
JPH0264143A (en) * 1988-08-31 1990-03-05 Japan Synthetic Rubber Co Ltd Rubber composition
JP2004115792A (en) * 2002-09-06 2004-04-15 Kanto Denka Kogyo Co Ltd Fluorine-containing copolymers and manufacturing method for these copolymers
CN108047374A (en) * 2018-01-23 2018-05-18 河北工业大学 The preparation method of pressure-sensitive adhesive polytetrafluoroethyl/ne /ne polypropylene esters of gallic acid core-shell emulsion
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JPS62138579A (en) * 1985-12-13 1987-06-22 Nippon Mektron Ltd Water-and oil-repellent
EP0243605A2 (en) * 1986-02-27 1987-11-04 Dainippon Ink And Chemicals, Inc. Fluorine-containing resin composition having a low refractive index
JPH01271406A (en) * 1988-03-23 1989-10-30 Hoechst Celanese Corp Autooxidative fluorocarbon polymer and composition
JPH0264143A (en) * 1988-08-31 1990-03-05 Japan Synthetic Rubber Co Ltd Rubber composition
JP2004115792A (en) * 2002-09-06 2004-04-15 Kanto Denka Kogyo Co Ltd Fluorine-containing copolymers and manufacturing method for these copolymers
JP2018537561A (en) * 2015-11-18 2018-12-20 アルタナ アーゲー Crosslinkable polymer materials for dielectric layers in electronic devices
CN108047374A (en) * 2018-01-23 2018-05-18 河北工业大学 The preparation method of pressure-sensitive adhesive polytetrafluoroethyl/ne /ne polypropylene esters of gallic acid core-shell emulsion

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