WO2022172921A1 - Résine thermodurcissable contenant du fluor, son procédé de production et composition de résine thermodurcissable contenant du fluor - Google Patents

Résine thermodurcissable contenant du fluor, son procédé de production et composition de résine thermodurcissable contenant du fluor Download PDF

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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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fluorine
thermosetting resin
containing thermosetting
group
monomer
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PCT/JP2022/004936
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English (en)
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/fr

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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.

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Abstract

L'invention concerne une résine thermodurcissable contenant du fluor ayant une excellente solubilité dans les solvants et une excellente propriété thermodurcissable. L'invention concerne notamment une résine thermodurcissable contenant du fluor ayant une liaison C-F entre un atome de fluor et un atome de carbone formant la chaîne principale, cette résine thermodurcissable contenant du fluor ayant au moins un élément choisi dans le groupe constitué par des groupes dicyclopentényle représentés par la formule (I-1) et un groupe dicyclopentényle représenté par la formule (I-2). [Formule Chimique 1]
PCT/JP2022/004936 2021-02-09 2022-02-08 Résine thermodurcissable contenant du fluor, son procédé de production et composition de résine thermodurcissable contenant du fluor WO2022172921A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62138579A (ja) * 1985-12-13 1987-06-22 Nippon Mektron Ltd 撥水撥油剤
EP0243605A2 (fr) * 1986-02-27 1987-11-04 Dainippon Ink And Chemicals, Inc. Composition de résine contenant du fluor et ayant un faible indice de réfraction
JPH01271406A (ja) * 1988-03-23 1989-10-30 Hoechst Celanese Corp 自動酸化性フルオロカーボンポリマーおよび組成物
JPH0264143A (ja) * 1988-08-31 1990-03-05 Japan Synthetic Rubber Co Ltd ゴム組成物
JP2004115792A (ja) * 2002-09-06 2004-04-15 Kanto Denka Kogyo Co Ltd 含フッ素共重合体類及びこれらの製造方法
CN108047374A (zh) * 2018-01-23 2018-05-18 河北工业大学 压敏胶粘剂用聚四氟乙烯/聚丙烯酸酯类核壳乳液的制备方法
JP2018537561A (ja) * 2015-11-18 2018-12-20 アルタナ アーゲー 電子デバイスにおける誘電体層用の架橋性ポリマー材料

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62138579A (ja) * 1985-12-13 1987-06-22 Nippon Mektron Ltd 撥水撥油剤
EP0243605A2 (fr) * 1986-02-27 1987-11-04 Dainippon Ink And Chemicals, Inc. Composition de résine contenant du fluor et ayant un faible indice de réfraction
JPH01271406A (ja) * 1988-03-23 1989-10-30 Hoechst Celanese Corp 自動酸化性フルオロカーボンポリマーおよび組成物
JPH0264143A (ja) * 1988-08-31 1990-03-05 Japan Synthetic Rubber Co Ltd ゴム組成物
JP2004115792A (ja) * 2002-09-06 2004-04-15 Kanto Denka Kogyo Co Ltd 含フッ素共重合体類及びこれらの製造方法
JP2018537561A (ja) * 2015-11-18 2018-12-20 アルタナ アーゲー 電子デバイスにおける誘電体層用の架橋性ポリマー材料
CN108047374A (zh) * 2018-01-23 2018-05-18 河北工业大学 压敏胶粘剂用聚四氟乙烯/聚丙烯酸酯类核壳乳液的制备方法

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