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WO2025187462A1 - Composition de copolymère fluoré ainsi que procédé de fabrication de celle-ci, et article de caoutchouc réticulé ainsi que procédé de fabrication de celui-ci - Google Patents

Composition de copolymère fluoré ainsi que procédé de fabrication de celle-ci, et article de caoutchouc réticulé ainsi que procédé de fabrication de celui-ci

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Publication number
WO2025187462A1
WO2025187462A1 PCT/JP2025/006205 JP2025006205W WO2025187462A1 WO 2025187462 A1 WO2025187462 A1 WO 2025187462A1 JP 2025006205 W JP2025006205 W JP 2025006205W WO 2025187462 A1 WO2025187462 A1 WO 2025187462A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluorine
containing copolymer
silicon carbide
copolymer composition
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/006205
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English (en)
Japanese (ja)
Other versions
WO2025187462A8 (fr
Inventor
翼 田村
剛 河合
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
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Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of WO2025187462A1 publication Critical patent/WO2025187462A1/fr
Publication of WO2025187462A8 publication Critical patent/WO2025187462A8/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene

Definitions

  • the present invention relates to a fluorocopolymer composition and a method for producing the same, as well as a crosslinked rubber article and a method for producing the same.
  • the present invention relates to a fluorocopolymer composition that can produce a crosslinked rubber article with improved resistance to plasma treatment and a method for producing the same, as well as a crosslinked rubber article obtained from the fluorocopolymer composition and a method for producing the same.
  • sealing materials are used to seal various connecting parts and movable parts.
  • a crosslinked rubber (so-called fluororubber) article obtained by crosslinking a fluorine-containing copolymer composition is sometimes used from the viewpoint of excellent heat resistance, chemical resistance, oil resistance, weather resistance, etc.
  • the above-mentioned sealing material is exposed to plasma of various gases in the manufacturing process, it is required to have resistance to plasma treatment.
  • Patent Document 1 discloses that a molded article obtained by crosslinking a crosslinkable fluorine-containing elastomer composition containing a crosslinkable fluorine-containing elastomer and silicon carbide particles having a bulk density of 0.15 g/ cm3 or less has resistance to O2 plasma treatment and O2 / CF4 plasma treatment.
  • Patent Document 2 discloses that a fluororubber molded article made from a crosslinkable elastomer composition containing a crosslinkable elastomer (e.g., a copolymer of tetrafluoroethylene and perfluoro(alkyl vinyl ether)) and a non-oxide ceramic filler (e.g., silicon carbide ) whose surface is oxidized has plasma resistance to O2 and NF3 .
  • a crosslinkable elastomer e.g., a copolymer of tetrafluoroethylene and perfluoro(alkyl vinyl ether)
  • a non-oxide ceramic filler e.g., silicon carbide
  • Patent Document 3 discloses that a molded article made of a crosslinkable elastomer composition containing 100 parts by weight of a crosslinkable elastomer (e.g., a copolymer of tetrafluoroethylene and perfluoro(alkyl vinyl ether)) and 1 to 50 parts by weight of a filler made of a non-oxide ceramic (e.g., carbide, nitride) has resistance to NF3 plasma treatment and O3 treatment.
  • a crosslinkable elastomer e.g., a copolymer of tetrafluoroethylene and perfluoro(alkyl vinyl ether)
  • a filler made of a non-oxide ceramic e.g., carbide, nitride
  • the present invention has been made in light of these circumstances, and aims to provide a fluorocopolymer composition that can yield crosslinked rubber articles with improved resistance to plasma treatment, a method for producing the same, and a crosslinked rubber article obtained from the fluorocopolymer composition, and a method for producing the same.
  • the present invention is based on the discovery that crosslinked rubber articles obtained from a fluorocopolymer composition comprising a fluorocopolymer and silicon carbide, wherein the silicon carbide has a specific ⁇ -type crystal lattice, have improved resistance to plasma treatment, particularly plasma treatment with O2 and N2 / NF3 -based gases. Although the detailed mechanism by which resistance to plasma treatment is improved is unknown, it is presumed that the wide band gap and crystal anisotropy of silicon carbide with an ⁇ -type crystal lattice contribute to this.
  • the present invention is as follows.
  • a composite material comprising a fluorine-containing copolymer and silicon carbide, the silicon carbide comprises silicon carbide of an ⁇ -type crystal lattice;
  • a fluorine-containing copolymer composition wherein the content of the ⁇ -type crystal lattice is 50% or more, based on 100% of all crystal lattices in the silicon carbide.
  • the content of units based on tetrafluoroethylene (TFE) is 50 to 90 mol% based on all units based on monomers constituting the fluorine-containing copolymer
  • the fluorine-containing copolymer is a unit based on a monomer having two or more polymerizable unsaturated bonds, a unit based on a monomer having at least one atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom, and a unit based on a monomer having a nitrile group,
  • [13] A method for producing the crosslinked rubber article according to [11] above, The fluorine-containing copolymer composition, First heating at 100 to 400°C for 1 second to 24 hours, After the primary heating, the product is subjected to secondary heating at 80 to 400°C for 30 minutes to 48 hours.
  • the present invention provides a fluorocopolymer composition that can be used to obtain crosslinked rubber articles with improved resistance to plasma treatment, a method for producing the same, and a crosslinked rubber article obtained from the fluorocopolymer composition and a method for producing the same.
  • the description "preferably 10 to 90, more preferably 30 to 60” can be combined with the “preferable lower limit (10)” and the “more preferable upper limit (60)” to form “10 to 60.”
  • the upper or lower limit of the numerical range may be replaced with a value shown in the examples.
  • Room temperature means 20-25°C.
  • unit refers collectively to an atomic group derived from one molecule of the monomer that is formed directly by polymerizing the monomer, and an atomic group obtained by chemically converting a part of the atomic group.
  • a unit based on a monomer may be simply referred to as “unit.”
  • “Rubber” means rubber exhibiting properties defined by JIS K 6200:2008, and is distinguished from “resin.”
  • Melting point means the temperature corresponding to the maximum value of the melting peak as measured by differential scanning calorimetry (DSC).
  • ⁇ -SiC silicon carbide with an ⁇ crystal lattice
  • ⁇ -SiC silicon carbide with a ⁇ crystal lattice
  • the content (% by mass) of iodine atoms in the fluorinated copolymer was calculated using an apparatus combining an automatic sample combustion apparatus, a pretreatment device for ion chromatography (manufactured by Mitsubishi Chemical Analytech Co., Ltd., Model AQF-100), and an ion chromatograph, as described in the Examples section.
  • the fluorine-containing copolymer composition according to an embodiment of the present invention (hereinafter may be simply referred to as "the fluorine-containing copolymer composition of the present embodiment") is not particularly limited as long as it contains a fluorine-containing copolymer and silicon carbide, and may or may not contain a crosslinking agent, a crosslinking aid, other components, and the like, as necessary.
  • the fluorine-containing copolymer is not particularly limited, and examples thereof include those having no melting point and those having a melting point, with those having no melting point being preferred. Furthermore, the fluorine-containing copolymer is preferably one which has a melting peak ( ⁇ H) magnitude of 4.5 J/g or less when a differential scanning calorimeter is used with the fluorine-containing copolymer as a sample.
  • a specific method for measuring the melting peak ( ⁇ H) is to weigh out 5 mg of a sample into an aluminum pan and heat it from 20°C to 360°C at a heating rate of 10°C/min in an air atmosphere using a Hitachi DSC600.
  • fluorine-containing copolymer examples include (a) a copolymer having tetrafluoroethylene (hereinafter sometimes simply referred to as "TFE") units and perfluoro(alkyl vinyl ether) (hereinafter sometimes simply referred to as "PAVE”) units, (b) a copolymer having vinylidene fluoride (hereinafter sometimes simply referred to as "VdF”) units, etc. These may be used alone or in combination of two or more. Among these, (a) a copolymer having TFE units and PAVE units is preferred from the viewpoint of heat resistance and chemical resistance.
  • TFE tetrafluoroethylene
  • PAVE perfluoro(alkyl vinyl ether)
  • VdF vinylidene fluoride
  • the content of the fluorine-containing copolymer relative to the total mass of the fluorine-containing copolymer composition is not particularly limited, but from the viewpoint of heat resistance and chemical resistance, it is preferably 60.00 to 99.70 mass%, more preferably 65.00 to 99.30 mass%, and particularly preferably 70.00 to 99.00 mass%.
  • the fluorine-containing copolymer preferably includes a copolymer containing a unit based on at least one monomer selected from the group consisting of: a unit based on a monomer having two or more polymerizable unsaturated bonds; a unit based on a monomer having at least one atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom; and a unit based on a monomer having a nitrile group.
  • the unit based on a monomer having at least one atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom is not particularly limited as long as it can cause the fluorine-containing copolymer to contain a unit having at least one of the above atoms, and examples thereof include a unit obtained by copolymerizing a monomer having at least one of the above atoms, and a unit obtained by introducing at least one of the above atoms into a unit at the main chain terminal using a chain transfer agent described later. These may be used alone or in combination of two or more.
  • TFE is a monomer represented by CF 2 ⁇ CF 2 .
  • the proportion of TFE units in all units constituting the fluorine-containing copolymer is not particularly limited, but from the viewpoint of heat resistance and chemical resistance, it is preferably from 50 to 90 mol %, more preferably from 55 to 80 mol %, particularly preferably from 60 to 75 mol %.
  • R f1 is a perfluoroalkyl group having 1 to 10 carbon atoms.
  • the number of carbon atoms in R f1 is not particularly limited as long as it is 1 to 10, but is preferably 1 to 8, more preferably 1 to 6, and particularly preferably 1 to 5.
  • PAVE perfluoro(methyl vinyl ether)
  • CF2 CFOCF3 : perfluoro(methyl vinyl ether)
  • PPVE perfluoro( propyl vinyl ether)
  • CF2 CFOCF2CF2CF2CF2CF3 .
  • the proportion of PAVE units in all units constituting the fluorinated copolymer is not particularly limited, but from the viewpoint of heat resistance and chemical resistance, it is preferably 10 to 50 mol %, more preferably 20 to 40 mol %, particularly preferably 25 to 35 mol %.
  • the suitable proportion is the same whether the PAVE is PMVE, PEVE or PPVE, or a mixture of two or more of these is used.
  • the total content of TFE units and PAVE units in all units constituting the fluorinated copolymer is not particularly limited, but from the viewpoint of heat resistance and chemical resistance, it is preferably from 79 to 100 mol %, more preferably from 89 to 100 mol %, particularly preferably from 95 to 100 mol %.
  • copolymers having TFE units and PAVE units include: (i) copolymers having TFE units, PAVE units, and at least one atom selected from the group consisting of chlorine atoms, bromine atoms, and iodine atoms at the ends and/or in the chain; (ii) copolymers having TFE units, PAVE units, C3DVE units, C4DVE units, C4-DV units, or C6-DV units described below, and at least one of chlorine atoms, bromine atoms, and iodine atoms at the ends and/or in the chain; (iii) copolymers having TFE units, PAVE units, and 8CNVE units or MV5CN units described below; and (iv) copolymers having TFE units, PAVE units, C3DVE units, C4DVE units, C4-DV units, or C6-DV units described below, and 8CNVE units or MV5CN units described below.
  • VdF is a monomer represented by CF 2 ⁇ CH 2 .
  • Specific examples of the copolymer having VdF units include, for example, (i) a copolymer having VdF units and units based on hexafluoropropylene (hereinafter, sometimes simply referred to as "HFP units"), (ii) a copolymer having VdF units, HFP units, and TFE units, and (iii) a copolymer having VdF units, PMVE units, and HFP units.
  • HFP units hexafluoropropylene
  • VdF units there are no particular restrictions on the proportion of VdF units in all units constituting the fluorinated copolymer, but from the perspective of suppressing sticking, it is preferably 40 to 90 mol%, more preferably 45 to 85 mol%, and particularly preferably 50 to 80 mol%.
  • the fluorine-containing copolymer may have units other than TFE units, PAVE units, and VdF units, and specific examples thereof include units based on a monomer having two or more polymerizable unsaturated bonds, units based on a monomer having a nitrile group, units based on a monomer represented by the following general formula (5) (hereinafter sometimes simply referred to as "formula (5) units"), HFP units, units based on chlorotrifluoroethylene, etc. These may be used alone or in combination of two or more. Among these, from the viewpoint of heat resistance, units based on a monomer having two or more polymerizable unsaturated bonds and units based on a monomer having a nitrile group are preferred.
  • the fluorine-containing copolymer further has units based on a monomer having two or more polymerizable unsaturated bonds.
  • the unit based on a monomer having two or more polymerizable unsaturated bonds is not particularly limited, but from the viewpoint of achieving better effects of the present invention, it is preferable that it has a fluorine atom, and it is preferably a unit based on a fluorine-containing monomer having two or more polymerizable unsaturated bonds.
  • the polymerizable double bonds at the ends of the units based on the fluorine-containing monomer having two or more polymerizable unsaturated bonds react during polymerization to give a copolymer having a branched chain.
  • the polymerizable unsaturated bond include a carbon-carbon double bond (C ⁇ C) and a triple bond (C ⁇ C), etc. These may be used alone or in combination of two or more. Among these, double bonds are preferred from the viewpoint of heat resistance.
  • the number of polymerizable unsaturated bonds is not particularly limited, but is preferably 2 to 6, more preferably 2 or 3, and particularly preferably 2, from the viewpoint of heat resistance.
  • a compound represented by the following general formula (2) is preferred, since the fluorine-containing copolymer has excellent rubber properties when made into a crosslinked rubber article:
  • R 31 , R 32 and R 33 each independently represent a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
  • R 34 represents a trivalent perfluorohydrocarbon group having 1 to 10 carbon atoms, or a group having an etheric oxygen atom at the end of the perfluorohydrocarbon group or between carbon-carbon bonds.
  • a3 represents an integer of 2 to 6, preferably 2 or 3, and more preferably 2.
  • multiple R 31 s , multiple R 32 s , and multiple R 33 s may be the same or different from one another, and are preferably the same from one another.
  • R 31 , R 32 and R 33 are preferably fluorine atoms or hydrogen atoms in order to improve the polymerization reactivity of the fluorine-containing monomer having two or more polymerizable unsaturated bonds, more preferably all fluorine atoms or all hydrogen atoms, and particularly preferably all fluorine atoms in order to improve the heat resistance and chemical resistance of the crosslinked rubber article.
  • R 34 may be linear, branched, or cyclic, preferably linear or branched, and more preferably linear.
  • R 34 preferably has 2 to 10 carbon atoms, more preferably 3 to 8, even more preferably 3 to 6, and particularly preferably 3 to 5.
  • R 34 may or may not have an etheric oxygen atom, but preferably has an etheric oxygen atom in view of better crosslinking reactivity and rubber physical properties.
  • the number of etheric oxygen atoms in R 34 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2.
  • the etheric oxygen atom in R 34 is preferably present at the terminal of R 34 .
  • Suitable monomers represented by formula (2) include monomers represented by general formula (2-1) and monomers represented by general formula (2-2).
  • R 41 represents a divalent perfluorohydrocarbon group having 2 to 10 carbon atoms, or a group having an etheric oxygen atom at the end or between the carbon-carbon bonds of the perfluorohydrocarbon group.
  • R 41 represents a divalent perfluorohydrocarbon group having 2 to 10 carbon atoms, or a group having an etheric oxygen atom at the end or between the carbon-carbon bonds of the perfluorohydrocarbon group.
  • Specific examples of the monomer represented by general formula (2-1) include the following. The description after the formula is the abbreviation of the compound. One type may be used alone, or two or more types may be used.
  • R 51 represents a divalent perfluorohydrocarbon group having 2 to 10 carbon atoms, or a group having an etheric oxygen atom at the end or between the carbon-carbon bonds of the perfluorohydrocarbon group.
  • R 51 represents a divalent perfluorohydrocarbon group having 2 to 10 carbon atoms, or a group having an etheric oxygen atom at the end or between the carbon-carbon bonds of the perfluorohydrocarbon group.
  • Specific examples of the monomer represented by general formula (2-2) include the following. The description after the formula is the abbreviation of the compound. One type may be used alone, or two or more types may be used.
  • CH 2 CH(CF 2 ) 6
  • CH CH 2 :C6-DV
  • the monomer represented by formula (2-2) is preferably C6-DV.
  • the proportion of units based on a fluorine-containing monomer having two or more polymerizable unsaturated bonds among all units constituting the fluorine-containing copolymer is not particularly limited, but from the viewpoint of heat resistance, it is preferably from 0.01 to 1.00 mol %, more preferably from 0.05 to 0.50 mol %, particularly preferably from 0.10 to 0.30 mol %.
  • the proportion of units based on a fluorine-containing monomer having two or more polymerizable unsaturated bonds is equal to or greater than the lower limit of the above range, the crosslinking reactivity is excellent, and the crosslinked rubber article after crosslinking has better tensile strength and compression set at high temperatures.
  • the proportion is equal to or less than the upper limit of the above range, cracking can be further reduced while maintaining the excellent physical properties of the crosslinked rubber article after crosslinking.
  • the fluorine-containing copolymer further has units based on a monomer having a nitrile group (hereinafter, sometimes simply referred to as "R CN ").
  • R 3 CN preferably contains a fluorine atom, and more preferably is a unit based on a monomer represented by general formula (4), in order to obtain better effects of the present invention.
  • R 11 R 12 CR 13 -R 14 -CN...
  • R 11 , R 12 and R 13 each independently represent a hydrogen atom, a fluorine atom or a methyl group
  • R 14 represents a divalent perfluorohydrocarbon group having 1 to 10 carbon atoms or a group having an etheric oxygen atom at the end or between the carbon-carbon bonds of the perfluorohydrocarbon group.
  • R 11 , R 12 and R 13 are preferably fluorine atoms or hydrogen atoms in terms of excellent polymerization reactivity of R CN , more preferably all fluorine atoms or all hydrogen atoms, and particularly preferably all fluorine atoms in terms of excellent mold releasability and heat resistance of the crosslinked rubber article.
  • R 14 may be linear, branched, or cyclic, but is preferably linear or branched.
  • the number of carbon atoms in R 14 is not particularly limited, but from the viewpoints of reactivity and availability, it is preferably 2 to 8, more preferably 3 to 7, even more preferably 3 to 6, and particularly preferably 3 to 5.
  • R 14 may or may not have an etheric oxygen atom, but preferably has an etheric oxygen atom in view of better rubber properties.
  • the number of etheric oxygen atoms in R 14 is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2, from the viewpoints of reactivity and availability.
  • Specific examples of the monomer represented by general formula (4) include the following. The description after the formula is the abbreviation of the compound. These may be used alone or in combination of two or more.
  • the proportion of units based on monomers having a nitrile group among all units constituting the fluorinated copolymer is preferably 0.01 to 2.00 mol%, more preferably 0.05 to 1.00 mol%, and particularly preferably 0.10 to 0.60 mol%.
  • R f4 is a perfluoroalkyl group containing an etheric oxygen atom and having 1 to 8 carbon atoms.
  • the number of carbon atoms in R f4 is preferably 1 to 7, more preferably 1 to 6, in terms of excellent low-temperature properties.
  • Specific examples of the monomer represented by general formula (5) include the following. The description after the formula is the abbreviation of the compound. One type may be used alone, or two or more types may be used.
  • C9PEVE, C7PEVE and EEAVE are preferred because they provide better low-temperature properties when the fluorocopolymer is made into a crosslinked rubber article.
  • the proportion of units of formula (5) in all units constituting the fluorine-containing copolymer is not particularly limited, but from the viewpoint of excellent low-temperature properties, it is preferably 1 to 57 mol%, more preferably 2 to 30 mol%, and particularly preferably 2 to 20 mol%.
  • the fluorine-containing copolymer may have units based on other monomers than those mentioned above.
  • examples of other monomers include other fluorine-containing monomers and non-fluorine-containing monomers.
  • Specific examples of other fluorine-containing monomers include vinyl fluoride; pentafluoropropylene; perfluorocyclobutene; (perfluoroalkyl)ethylenes such as CH 2 ⁇ CHCF 3 , CH 2 ⁇ CHCF 2 CF 3 , CH 2 ⁇ CHCF 2 CF 2 CF 3 , CH 2 ⁇ CHCF 2 CF 2 CF 3 , CH 2 ⁇ CHCF 2 CF 2 CF 3 , CH 2 ⁇ CHCF 2 CF 2 CF 3 ; and the like.
  • non-fluorine-containing monomers include ⁇ -olefins such as isobutylene and pentene; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and butyl vinyl ether; and vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate and vinyl caprylate.
  • ⁇ -olefins such as isobutylene and pentene
  • vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and butyl vinyl ether
  • vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate and vinyl caprylate.
  • the fluorine-containing copolymer contains units based on other monomers than those mentioned above
  • the content of units based on other monomers than those mentioned above in all units constituting the fluorine-containing copolymer is not particularly limited, but in terms of excellent heat resistance and chemical resistance, it is preferably 0.001 to 2.00 mol %, more preferably 0.01 to 1.00 mol %, and particularly preferably 0.01 to 0.50 mol %.
  • a monomer having at least one atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom may be used.
  • a monomer having at least one atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom is copolymerized, at least one of a chlorine atom, a bromine atom, and an iodine atom can be introduced into the side chain of the fluorine-containing copolymer.
  • Suitable examples of the monomer having at least one of a chlorine atom, a bromine atom, and an iodine atom include Compound A represented by General Formula (6) and Compound B represented by General Formula (7).
  • CR 21 R 22 CR 23 R 24 ...General formula (6)
  • compound A and compound B each have one or more chlorine atoms, bromine atoms, and iodine atoms.
  • R 21 , R 22 and R 23 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • R24 is an alkyl group, an alkyl group having an etheric oxygen, a fluoroalkyl group, or a fluoroalkyl group having an etheric oxygen.
  • R24 may have at least one of a chlorine atom, a bromine atom, and an iodine atom.
  • R24 may be linear or branched.
  • R25 is a group having one or more polymerizable unsaturated bonds. The polymerizable unsaturated bond may be bonded to an alkyl group, an alkyl group having etheric oxygen, a fluoroalkyl group, or a fluoroalkyl group having etheric oxygen.
  • R25 may have at least one of a chlorine atom, a bromine atom, and an iodine atom.
  • R25 may be linear or branched.
  • Specific examples of the monomer having a bromine atom include bromotrifluoroethylene, 4-bromo-3,3,4,4-tetrafluorobutene-1, vinyl bromide, 1-bromo-2,2-difluoroethylene, perfluoroallyl bromide, 4-bromo-1,1,2-trifluorobutene-1, 4-bromo-1,1,3,3,4,4-hexafluorobutene, 4-bromo-3-chloro-1,1,3,4,4-pentafluorobutene, 6-bromo-5,5,6,6-tetrafluorohexene, 4-bromoperfluorobutene-1, 3,3-difluoroallyl bromide, 2-bromo-perfluoroethyl perfluorovinyl ether,
  • the monomer having an iodine atom include iodoethylene, 4-iodo-3,3,4,4-tetrafluoro-1-butene, 2-iodo-1,1,2,2-tetrafluoro-1-vinyloxyethane, 2-iodoethyl vinyl ether, allyl iodide, 1,1,2,3,3,3-hexafluoro-2-iodo-1-(perfluorovinyloxy)propane, 3,3,4,5,5,5-hexafluoro-4-iodopentene, iodotrifluoroethylene, 2-iodoperfluoro(ethyl vinyl ether), CF 2 ⁇ CFOCF(CF 3 )CF 2 OCF 2 CF 2 CH 2 I, CF 2 ⁇ CFOCF 2 CF 2 CH 2 I, CH 2 ⁇ CHCF 2 CF 2 I, and the like.
  • the monomer having an iodine atom and a bromine atom include 3-bromo-4-iodoperfluorobutene-1, 2-bromo-4-iodoperfluorobutene-1, etc. These may be used alone or in combination of two or more.
  • the fluorine-containing copolymer preferably has at least one atom selected from the group consisting of chlorine, bromine and iodine atoms, and particularly preferably has at least one of a chlorine, bromine and iodine atom at the terminal of the fluorine-containing copolymer (polymer chain).
  • terminal means both the terminal of the main chain and the terminal of the branched chain of the fluorine-containing copolymer.
  • Examples of the chlorine atom, bromine atom, and iodine atom include those derived from a compound having at least one of a chlorine atom, a bromine atom, and an iodine atom that functions as a chain transfer agent described below, and those derived from the above-mentioned monomer having at least one of a chlorine atom, a bromine atom, and an iodine atom, and preferably those derived from a compound having at least one of a chlorine atom, a bromine atom, and an iodine atom that functions as a chain transfer agent described below.
  • the fluorine-containing copolymer has at least one of a chlorine atom, a bromine atom and an iodine atom
  • the content of at least one of a chlorine atom, a bromine atom and an iodine atom relative to the total mass of the fluorine-containing copolymer is not particularly limited, but is preferably 0.01 to 5.00% by mass, more preferably 0.03 to 2.00% by mass, particularly preferably 0.05 to 1.00% by mass, in terms of better crosslinking reactivity of the fluorine-containing copolymer and better mechanical properties of the crosslinked rubber article.
  • the mass ratio of the content of at least one of chlorine atoms, bromine atoms, and iodine atoms to the content of crosslinking agent in the fluorine-containing copolymer composition is not particularly limited, but is preferably 0.01 to 0.50, more preferably 0.02 to 0.30, and particularly preferably 0.03 to 0.20. If the ratio is above the lower limit of the above range, the crosslinking reaction will proceed more easily, and if the ratio is below the upper limit of the above range, the hardness will be better.
  • the mass ratio of the content of at least one of chlorine atoms, bromine atoms, and iodine atoms to the content of cross-linking aid in the fluorine-containing copolymer composition is not particularly limited, but is preferably 0.01 to 0.50, more preferably 0.02 to 0.30, and particularly preferably 0.03 to 0.20. If the ratio is above the lower limit of the above range, the cross-linking reaction will proceed more easily, and if the ratio is below the upper limit of the above range, the hardness will be better.
  • An example of the method for producing the fluorine-containing copolymer is a method in which the above-mentioned monomers are copolymerized in the presence of a chain transfer agent and a radical polymerization initiator.
  • a chain transfer agent for example, paragraphs 0019 to 0034 of WO 2010/082633, paragraphs 0027 to 0048 of WO 2018/225586, paragraphs 0030 to 0033 of WO 2020/184427, and paragraphs 0035 to 0038 of WO 2021/210502.
  • the chain transfer agent is preferably a compound having at least one of a chlorine atom, a bromine atom, and an iodine atom.
  • a chlorine atom, a bromine atom, and an iodine atom can be introduced into the fluorine-containing copolymer by making a chain transfer agent having at least one of a chlorine atom, a bromine atom, and an iodine atom present in the polymerization system.
  • a chain transfer agent When the monomer components are polymerized in the presence of a chain transfer agent, at least one of a chlorine atom, a bromine atom, and an iodine atom can be introduced into a unit at the terminal of the main chain of the fluorine-containing copolymer.
  • the chain transfer agent having at least one of a chlorine atom, a bromine atom, and an iodine atom include compound C represented by general formula (8), compound D represented by general formula (9), compound E represented by general formula (10), and compound F represented by general formula (12).
  • R f4 to R f7 in the general formulae (8) to (10) and (12) are each independently an alkylene group having 1 to 16 carbon atoms, a fluoroalkylene group, or a skeleton having an aromatic ring, and are preferably an alkylene group or perfluoroalkylene group having 3 or more carbon atoms (preferably 3 to 8).
  • the alkylene or fluoroalkylene groups of R f4 to R f7 may be linear or branched, and are preferably perfluoroalkylene groups.
  • Examples of the compound C represented by the general formula (8) include 1,2-diiodoperfluoroethane, 1,3-diiodoperfluoropropane, 1,4-diiodoperfluorobutane (C4DI), 1,5-diiodoperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,5-diiodo-2,4-dichloroperfluoropentane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodopropane (1,3-
  • Examples of compound D represented by general formula (9) include 1-iodo-4-bromoperfluorobutane, 1-iodo-6-bromoperfluorohexane, 1-iodo-8-bromoperfluoroctane, 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluorobutene-1, 2-bromo-4-iodoperfluorobutene-1, monoiodomonobromo-substituted benzene, and diiodomonobromo-substituted benzene. These may be used alone or in combination of two or more.
  • Examples of the compound E represented by general formula (10) include CF 2 Br 2 , BrCF 2 CF 2 Br, CF 3 CFBrCF 2 Br, CFClBr 2 , BrCF 2 CFClBr, CFBrClCFClBr, BrCF 2 CF 2 CF 2 Br, BrCF 2 CFBrOCF 3 , and (2-bromoethyl)-substituted benzene. These may be used alone or in combination of two or more.
  • the silicon carbide contained in the fluorinated copolymer composition of this embodiment is not particularly limited as long as it is silicon carbide containing silicon carbide of an ⁇ -type crystal lattice, and may or may not contain silicon carbide of a ⁇ -type crystal lattice, amorphous silicon carbide, etc. Furthermore, the silicon carbide may or may not contain impurities within a range that does not impair the effects of the present invention. As the silicon carbide, known silicon carbide can be used. The silicon carbides may be used singly or in combination of two or more.
  • the content of silicon carbide in the ⁇ -type crystal lattice relative to 100% of the total crystal lattice in silicon carbide is not particularly limited as long as it is 50% or more, but from the viewpoint of improving plasma resistance and ease of availability, it is preferably 55 to 99%, more preferably 65 to 98%, even more preferably 75 to 96%, and particularly preferably 85 to 94%.
  • the content of silicon carbide in the ⁇ -type crystal lattice relative to 100% of the total crystal lattice of all silicon carbides used can be calculated by taking a weighted average of the silicon carbide content of the ⁇ -type crystal lattice of each silicon carbide based on the blending amounts of the two or more types of silicon carbide.
  • the content of silicon carbide of the ⁇ -type crystal lattice can be calculated by Rietveld analysis of the X-ray diffraction data of silicon carbide obtained by X-ray diffraction measurement.
  • the particle shape of silicon carbide is not particularly limited, and examples thereof include amorphous particles, spheres, whiskers, fibers, plates, aggregates thereof, etc. These may be used alone or in combination of two or more. Among these, spherical shapes are preferred from the viewpoint of isotropy of physical properties.
  • the particle diameter d50 of silicon carbide is not particularly limited, but from the viewpoint of improving plasma resistance, it is preferably 60 ⁇ m or less, more preferably 0.01 to 10 ⁇ m, even more preferably 0.1 to 5 ⁇ m, and particularly preferably 0.2 to 0.5 ⁇ m.
  • the "particle diameter d50" here is measured by the method described in the Examples section below.
  • the content of silicon carbide per 100 parts by mass of the fluorocopolymer is preferably 1 to 100 parts by mass, more preferably 10 to 80 parts by mass, and particularly preferably 20 to 70 parts by mass.
  • the specific surface area of silicon carbide is not particularly limited, but from the viewpoint of ensuring voids and suppressing granule collapse, it is preferably 1.18 to 15.00 m 2 /g, more preferably 1.21 to 14.00 m 2 /g, and particularly preferably 1.24 to 13.00 m 2 /g.
  • the "specific surface area” herein is a value measured using a specific surface area measuring device (model: Macsorb, manufactured by Mountech Co., Ltd.) in accordance with JIS Z 8830: 2013. If the specific surface area of the silicon carbide is known when it is obtained, the known specific surface area can be used.
  • pore size of silicon carbide there are no particular restrictions on the pore size of silicon carbide, but from the viewpoint of ensuring voids and suppressing granule collapse, it is preferably 0.10 to 5.00 ⁇ m.
  • the "pore diameter” here is a value measured using a pore diameter measuring device (model: POREMASTER-60, manufactured by Quantachrome Corp.). If the pore diameter is known when the silicon carbide is obtained, the known pore diameter can be used.
  • the cumulative pore volume of silicon carbide with pore diameters of 0.10 to 5.00 ⁇ m is preferably 0.35 to 1.00 cm 3 /g, more preferably 0.40 to 0.85 cm 3 /g, and particularly preferably 0.45 to 0.80 cm 3 /g.
  • the "cumulative pore volume” herein is a value measured using a pore size measuring device (Model: POREMASTER-60, manufactured by Quantachrome). If the cumulative pore volume is known when the silicon carbide is obtained, the known cumulative pore volume can be used.
  • the loose bulk density of silicon carbide is not particularly limited, but from the viewpoint of ensuring voids and suppressing granule collapse, it is preferably 0.30 to 0.70 g/cm 3 , more preferably 0.30 to 0.65 g/cm 3 , and particularly preferably 0.30 to 0.60 g/cm 3 .
  • the "loose bulk density” herein is a value measured using a bulk density measuring device (manufactured by Tsutsui Scientific Instruments Co., Ltd.) in accordance with JIS K 5101: 2004. If the loose bulk density of the silicon carbide is known at the time of procurement, the known loose bulk density can be used.
  • silicon carbide can be synthesized by a sublimation recrystallization method (modified Lely method); a vapor phase growth method such as chemical vapor deposition; a liquid phase growth method; an Acheson method; or the like, followed by pulverization, classification, or the like to obtain silicon carbide.
  • the synthesis method may be used alone or in combination of two or more. Among the synthesis methods, the Acheson method is preferred from the viewpoint of productivity.
  • the Acheson process is a method in which silicon dioxide and carbon-based materials are sintered in a reducing atmosphere.
  • the sintering temperature There are no particular restrictions on the sintering temperature, but from the perspective of increasing the proportion of ⁇ -SiC in the silicon carbide, it is preferably 2000°C or higher.
  • ⁇ -type crystal lattice silicon carbide examples include 15R-SiC, 6H-SiC, 4H-SiC, 21R-SiC, and 2H-SiC, which are expressed in Ramsdell notation. These may be used alone or in combination of two or more. Among these, 6H-SiC and 4H-SiC are preferred from the viewpoint of chemical stability, with 6H-SiC being more preferred.
  • the content of silicon carbide with a ⁇ -type crystal lattice relative to 100% of all crystal lattices in silicon carbide is not particularly limited as long as it is less than 50%, but from the viewpoint of improving plasma resistance, it is preferably 0 to 40%, more preferably 0 to 20%, and particularly preferably 0 to 10%.
  • the content of silicon carbide of the ⁇ -type crystal lattice can be calculated in the same manner as the content of silicon carbide of the ⁇ -type crystal lattice.
  • silicon carbide with a ⁇ -type crystal lattice is 3C-SiC, which is expressed in Ramsdell notation.
  • the content of impurities relative to the total mass of silicon carbide (100 mass%) is not particularly limited as long as it is within a range that does not impair the effects of the present invention. From the viewpoint of excellent resistance to plasma treatment, however, the content is preferably 30.0 ppm by mass or less, more preferably 10.0 ppm by mass or less, and particularly preferably 5.0 ppm by mass or less.
  • impurities contained in silicon carbide include boron, aluminum, phosphorus, iron, copper, sodium, titanium, chromium, etc. These may be contained alone or in combination of two or more.
  • the content of boron is a value measured by ICP-AES using the alkali fusion method described in "Technical Letter: Geological Standards by Alkali Fusion/Inductively Coupled Plasma Atomic Emission Spectrometry," by Shigeru Terashima, Takashi Okai, and Masahiro Taniguchi, Japan Society for Analytical Chemistry, BUNSEKI KAGAKU Vol. 47 (1998) No. 7, pp. 451-454.
  • the content of aluminum, phosphorus, iron, copper, titanium, and chromium is a value measured by ICP-AES in accordance with JIS R 1616:2007.
  • the content of sodium is a value measured by the following method. To 50 mg of a sample to be measured, 2 mL of hydrofluoric acid was added, followed by 20 mL of concentrated hydrochloric acid. The resulting slurry was sealed with a lid and heated to 1100°C in an oven to melt the sample. The resulting solution was diluted with ultrapure water to prepare 50 mL of a measurement sample. The resulting measurement sample was measured under the following conditions.
  • Measuring equipment CCD multi-ICP optical emission spectrometer (manufactured by SPECTRO Analytical Instruments) Interference removal gas mode: Ar Measurement method: Radial photometry Measurement method (calibration curve method): A standard solution containing a known concentration of the measured element, its 2-fold diluted solution and 10-fold diluted solution, and a control solution were prepared, and a calibration curve was created by introducing the control solution, 10-fold diluted solution, 2-fold diluted solution, and standard solution (mother liquor) into the ICP-AES in that order.
  • the fluorine-containing copolymer composition of the present embodiment may or may not contain a crosslinking agent.
  • the crosslinking agent is used to crosslink the fluorine-containing copolymer, and examples thereof include organic peroxides, amines, polyols, triazines, etc. These may be used alone or in combination of two or more. Among these, organic peroxides and amines are preferred in view of the superior crosslinking reactivity of the fluorocopolymer, productivity of the crosslinked rubber article, heat resistance of the crosslinked rubber article, and chemical resistance of the crosslinked rubber article.
  • organic peroxides include alkyl peroxides, benzoyl peroxide, tert-butylperoxybenzene, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,3-bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butylperoxymaleic acid, tert-butylperoxyisopropyl carbonate, tert-butylcumyl peroxide, dicumyl peroxide, ⁇ , ⁇ '-bis(tert-butylperoxy)-p-diisopropylbenzene, ⁇ , ⁇ '-bis(tert-butylperoxy)-m-diisopropylbenzene, 2,5-dimethylhexane-2,5-dihydroxyperoxide, tert-but
  • alkyl peroxides ⁇ , ⁇ '-bis(tert-butylperoxy)-p-diisopropylbenzene, and ⁇ , ⁇ '-bis(tert-butylperoxy)-m-diisopropylbenzene are preferred from the viewpoint of crosslinkability.
  • alkyl peroxides include 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, and 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane. These may be used alone or in combination of two or more. Of these, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is preferred.
  • the fluorine-containing copolymer composition contains an organic peroxide and further contains a crosslinking aid described below, the crosslinking efficiency becomes higher.
  • amine Specific examples of amines include hexamethylenediamine, hexamethylenediamine carbamate, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter sometimes simply referred to as "BOAP"; also known as bisaminophenol AF), 2,2-bis(3,4-diaminophenyl)propane, 2,2-bis(3,4-diaminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-(N-phenylamino)phenyl)hexafluoropropane, 4,4'-methylenedianiline, m-phenylenediamine, adipic acid dihydrazide, and the compound represented by formula (XII) of Japanese Patent No. 5,833,
  • the content of the crosslinking agent relative to the total mass of the fluorocopolymer composition is not particularly limited, but is preferably 0.30 to 10.00 mass%, more preferably 0.30 to 5.00 mass%, and particularly preferably 0.31 to 1.00 mass%. If the amount of crosslinking agent is within this range, the crosslinked rubber article will have an excellent balance between strength and elongation.
  • the fluorine-containing copolymer composition of the present embodiment may or may not contain a crosslinking aid (co-crosslinking agent).
  • the crosslinking aid is suitably used to improve the crosslinking efficiency when the fluorine-containing copolymer is crosslinked with an organic peroxide. After the crosslinking reaction is completed, the crosslinking aid bonds with the fluorine-containing copolymer and becomes part of the crosslinked structure.
  • the crosslinking aid is preferably a compound having two or more reactive functional groups in the same molecule.
  • the reactive functional group include an unsaturated bond, a halogen atom, an acid anhydride residue, a carboxy group, an amino group, a cyano group, and a hydroxyl group.
  • the multiple reactive functional groups present in the same molecule of the crosslinking aid may be the same or different.
  • the unsaturated bond may, for example, be a carbon-carbon double bond-containing group.
  • Specific examples of the carbon-carbon double bond-containing group include alkenyl groups such as a vinyl group, an allyl group, and a methallyl group; unsaturated acyl groups such as an acryloyl group and a methacryloyl group; and a maleimide group.
  • the carbon-carbon double bond-containing group is preferably an alkenyl group having 2 to 4 carbon atoms, and more preferably an allyl group.
  • crosslinking aid examples include compounds represented by the following general formula (11), triallyl cyanurate, triallyl isocyanurate, trimethallyl isocyanurate, 1,3,5-triacryloylhexahydro-1,3,5-triazine, triallyl trimellitate, m-phenylenediamine bismaleimide, p-quinonedioxime, p,p'-dibenzoylquinonedioxime, dipropargyl terephthalate, diallyl phthalate, N,N',N'',N'''-tetraallyl terephthalamide, and vinyl group-containing siloxane oligomers (polymethylvinylsiloxane, polymethylphenylvinylsiloxane, etc.).
  • general formula (11) triallyl cyanurate, triallyl isocyanurate, trimethallyl isocyanurate, 1,3,5-triacryloylhexahydr
  • the compound represented by the following general formula (11), triallyl cyanurate, triallyl isocyanurate, and trimethallyl isocyanurate are preferred, the compound represented by the following general formula (11) and triallyl isocyanurate are more preferred, and triallyl isocyanurate is particularly preferred.
  • R 61 , R 62 , and R 63 are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms
  • R 64 is a divalent fluorohydrocarbon group having 1 to 18 carbon atoms, or a group having an etheric oxygen atom at the end of the fluorohydrocarbon group or between carbon-carbon bonds.
  • Multiple R 61 s , multiple R 62 s , and multiple R 63 s may be the same or different.
  • R 61 , R 62 and R 63 are alkyl groups or fluoroalkyl groups, they may be linear or branched, but are preferably linear.
  • R 61 , R 62 and R 63 are alkyl groups or fluoroalkyl groups, the number of carbon atoms therein is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2. It is preferable that R 61 , R 62 and R 63 are all hydrogen atoms, as this will result in better crosslinking reactivity.
  • the fluorohydrocarbon group for R 64 is preferably a perfluorohydrocarbon group, since the crosslinked rubber article will have better heat resistance.
  • R 64 may be linear, branched, or cyclic, preferably linear or branched, and more preferably linear.
  • the number of carbon atoms in R 64 is not particularly limited, but is preferably 1 to 18, more preferably 2 to 8, and particularly preferably 3 to 7.
  • R 64 has an etheric oxygen atom the number of etheric oxygen atoms in R 64 is not particularly limited, but is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2.
  • R 64 has an etheric oxygen atom, it is preferable that the etheric oxygen atom is present at the terminal of R 64 .
  • the compound represented by general formula (11) is not particularly limited, but from the viewpoint of heat resistance and chemical resistance, C3DVE, C4DVE, CH 2 ⁇ CH(CF 2 ) 2 CH ⁇ CH 2 , C4-DV, and C6-DV are preferred, with C6-DV being more preferred.
  • the content of the crosslinking aid per 100.00 parts by mass of the fluorine-containing copolymer is not particularly limited, but is preferably from 0.10 to 10.00 parts by mass, more preferably from 0.20 to 5.00 parts by mass, and particularly preferably from 0.40 to 2.50 parts by mass.
  • the amount of the crosslinking aid is within the above range, the crosslinked rubber article has an excellent balance between strength and elongation.
  • the mass ratio of the content of the crosslinking agent to the content of the crosslinking aid is not particularly limited, but is preferably from 0.2 to 7.0, more preferably from 0.4 to 5.0, particularly preferably from 0.5 to 2.0, in terms of preventing unreacted crosslinking aid from remaining and allowing the crosslinking reaction to proceed well.
  • the total content of the crosslinking agent and crosslinking aid per 100.00 parts by mass of the fluorine-containing copolymer is not particularly limited, but is preferably 0.10 to 5.00 parts by mass, more preferably 0.50 to 4.00 parts by mass, and particularly preferably 0.80 to 3.00 parts by mass.
  • the total content of the crosslinking agent and crosslinking aid is not less than the lower limit, the hardness of the crosslinked rubber article tends to be excellent.
  • the total content of the crosslinking agent and crosslinking aid is not more than the upper limit, the crosslinking reactivity is excellent.
  • the content of the crosslinking aid relative to the total mass of the fluorocopolymer composition is not particularly limited, but from the viewpoint of heat resistance and chemical resistance, it is preferably 0.30 to 10.00 mass%, more preferably 0.30 to 5.00 mass%, and particularly preferably 0.31 to 1.00 mass%.
  • the fluorine-containing copolymer composition may contain other components in addition to those described above, provided that the effects of the present invention are not impaired.
  • processing aids e.g., acid acceptors such as fatty acid esters (glycerin monooleate, etc.), fatty acid metal salts (sodium stearate, calcium stearate, etc.), and oxides of divalent metals (magnesium oxide, calcium oxide, zinc oxide, lead oxide, etc.), synthetic waxes (polyethylene wax, etc.), fillers and reinforcing agents (e.g., carbon black, barium sulfate, calcium metasilicate, calcium carbonate, titanium oxide, silicon dioxide, aromatic polyesters, polyamideimides, thermoplastic polyimides, clay, talc, and the fluorine-containing copolymers described below other than the above-mentioned fluorine-containing copolymers having no melting point (hereinafter also referred to as "specific fluorine-containing
  • the specific fluorine-containing copolymer preferably has a melting point.
  • the melting point is a value measured by weighing 5 mg of a sample into an aluminum pan and heating it from 20°C to 360°C at a heating rate of 10°C/min in an air atmosphere using a differential scanning calorimeter (model: DSC600, manufactured by Hitachi High-Tech Science Corporation).
  • the melt flow rate (hereinafter referred to as "MFR") of the specific fluorine-containing copolymer at a temperature 20°C or more higher than the melting point of the specific fluorine-containing copolymer (usually 372°C is adopted) is not particularly limited, but is preferably from 0.1 to 1000g/10 minutes, more preferably from 0.5 to 100g/10 minutes, still more preferably from 1 to 30g/10 minutes, and particularly preferably from 5 to 20g/10 minutes.
  • the specific fluorine-containing copolymer preferably has a TFE unit.
  • the proportion of TFE units in all units constituting the specific fluorinated copolymer is not particularly limited, but from the viewpoint of heat resistance and chemical resistance, it is preferably from more than 90 to 100 mol%, more preferably from 95 to 99 mol%, particularly preferably from 96 to 98 mol%.
  • An example of the specific fluorine-containing copolymer is "Fluorine-containing copolymer (X1-1)" in the Examples section of WO 2016/017801.
  • the content of components other than the fluorine-containing copolymer in the fluorine-containing copolymer composition per 100.00 parts by mass of the fluorine-containing copolymer is not particularly limited, but is preferably 0.50 to 50.00 parts by mass, more preferably 1.00 to 40.00 parts by mass, and particularly preferably 2.00 to 30.00 parts by mass. If the content is at least the lower limit of the above range, the hardness of the crosslinked rubber article will be superior, and if it is at most the upper limit of the above range, the transparency of the crosslinked rubber article will be superior.
  • the content of other components relative to the total mass of the fluorocopolymer composition is not particularly limited, but from the viewpoint of heat resistance and chemical resistance, it is preferably 0.50 to 33.33 mass%, more preferably 0.99 to 28.57 mass%, and particularly preferably 1.96 to 23.08 mass%.
  • the method for producing the fluorine-containing copolymer composition of the present invention is a method of kneading the fluorine-containing copolymer and the silicon carbide.
  • the above-mentioned kneading can be achieved by kneading the fluorine-containing copolymer, silicon carbide containing silicon carbide of an ⁇ -type crystal lattice, and, if necessary, other components, by a kneading method using a known rubber kneading apparatus such as a two-roll mill, a kneader, a Banbury mixer or an extruder.
  • the components may be kneaded together to obtain a mixture, which may then be molded. That is, the fluorine-containing copolymer composition may be a molded product.
  • Specific examples of methods for molding the mixture include compression molding, injection molding, extrusion molding, calendar molding, or a method in which the mixture is dissolved in a solvent and then dipped or coated to form a molded product.
  • Crosslinked rubber article of the present invention is obtained by crosslinking the fluorocopolymer in the fluorocopolymer composition of the present invention.
  • the method for producing a crosslinked rubber article of the present invention is a method for producing the crosslinked rubber of the present invention, which comprises primarily heating the fluorocopolymer composition at 100 to 400°C for 1 second to 24 hours and, after the primary heating, secondary heating at 80 to 400°C for 30 minutes to 48 hours.
  • the crosslinked rubber article is obtained by crosslinking the fluorocopolymer in the fluorocopolymer composition.
  • Examples of a method for crosslinking the fluorine-containing copolymer in the fluorine-containing copolymer composition include a method for crosslinking the fluorine-containing copolymer composition by heating, and a method for crosslinking by irradiating with ionizing radiation.
  • Specific examples of the crosslinking method by heating include heat press crosslinking, steam crosslinking and hot air crosslinking, from which an appropriate method may be selected taking into consideration the shape and application of the fluorocopolymer composition.
  • molding methods include injection molding, extrusion molding, coextrusion molding, blow molding, compression molding, inflation molding, transfer molding, and calendar molding.
  • extrusion molding method include a method in which a fluorine-containing copolymer or a fluorine-containing copolymer composition is extruded and molded into the shape of a hose or an electric wire.
  • crosslinking by heating is preferred.
  • a specific example of a method for producing a crosslinked rubber article by thermal crosslinking is hot press molding, which uses a heated mold, fills a cavity of the mold having a desired shape with a fluorocopolymer composition, and heats the composition to crosslink the composition simultaneously with molding (hot press crosslinking), thereby obtaining a crosslinked rubber article.
  • the heating temperature is not particularly limited, but is preferably 100 to 400° C., more preferably 130 to 220° C., even more preferably 140 to 200° C., and particularly preferably 150 to 180° C.
  • the heating time is not particularly limited, but is preferably 1 second to 24 hours, more preferably 1 minute to 1 hour, and particularly preferably 5 minutes to 40 minutes.
  • the hot press molding method it is also preferable to further heat the crosslinked rubber article obtained by hot press crosslinking (sometimes referred to as primary crosslinking or primary heating) in an oven or the like using electricity, hot air, steam or the like as a heat source, as necessary, to advance the crosslinking (sometimes referred to as secondary crosslinking or secondary heating).
  • the temperature during secondary crosslinking is not particularly limited, but is preferably 80 to 400°C, more preferably 80 to 350°C, even more preferably 150 to 280°C, even more preferably 180 to 260°C, and particularly preferably 200 to 250°C.
  • the secondary crosslinking time is not particularly limited, but is preferably 30 minutes to 48 hours, more preferably 1 hour to 48 hours, and particularly preferably 4 hours to 24 hours.
  • the rubber physical properties (mechanical properties, compression set, and other properties) of the crosslinked rubber article are improved.
  • peroxide residues contained in the crosslinked rubber article are decomposed, volatilized, and reduced.
  • the hot press molding method is preferably applied to molding of sealing materials, etc.
  • Examples of the ionizing radiation in the method of irradiating with ionizing radiation include electron beams, ultraviolet rays, gamma rays, etc.
  • a preferred method is to first mold the fluorine-containing copolymer or the fluorine-containing copolymer composition into a desired shape and then irradiate it with ionizing radiation to crosslink it.
  • the dose of ionizing radiation is appropriately set, preferably 1 to 300 kGy, more preferably 10 to 200 kGy.
  • the tensile strength of the crosslinked rubber article is not particularly limited, but is preferably 1 to 50 MPa, more preferably 10 to 40 MPa, and particularly preferably 15 to 40 MPa, in order to provide the crosslinked rubber article with better rubber properties.
  • the tensile elongation of the crosslinked rubber article is not particularly limited, but in terms of excellent rubber properties, it is preferably 100 to 1000%, more preferably 150 to 600%, even more preferably 150 to 500%, and particularly preferably 150 to 400%.
  • the tensile strength and tensile elongation of the crosslinked rubber article are values measured by a method conforming to JIS K 6251:2010 (corresponding international standard ISO 37:2005).
  • the hardness (Shore-A) of the crosslinked rubber article is not particularly limited, but is preferably 55 to 100, more preferably 55 to 90, even more preferably 60 to 85, and particularly preferably 65 to 80, in terms of excellent rubber properties.
  • the hardness (Shore-A) of the crosslinked rubber article is a value measured using a type A durometer in accordance with JIS K6253-1:2012 using a plate-shaped molded product (thickness 1 mm) of the crosslinked rubber article.
  • the compression set CS of the crosslinked rubber article at 200°C for 70 hours is not particularly limited, but is preferably 70% or less, more preferably 50% or less, and particularly preferably 40% or less, in view of the fact that the fluorocopolymer is well crosslinked and the crosslinked rubber article has better shape recovery after pressure application.
  • the compression set of the crosslinked rubber article at 200° C. for 70 hours is measured by the method described in the Examples section below.
  • the crosslinked rubber article is suitable as a material for O-rings, sheets, gaskets, oil seals, diaphragms, V-rings, and the like.
  • the crosslinked rubber articles can also be used in semiconductor manufacturing equipment parts, heat-resistant and chemical-resistant sealing materials, heat-resistant and oil-resistant sealing materials, wire coating materials, sealing materials for liquid crystal display panel manufacturing equipment, sealing materials for light-emitting diode manufacturing equipment, corrosion-resistant rubber paints, sealing materials for urea-resistant grease, rubber paints, adhesive rubbers, hoses, tubes, calendered sheets (rolls), sponges, rubber rolls, oil drilling components, heat-dissipating sheets, solution-crosslinked products, rubber sponges, bearing seals (urea-resistant grease and the like), linings (chemical-resistant), insulating sheets for automobiles, insulating sheets for electronic devices, rubber bands for watches, endoscope packings (amine-resistant), bellows hoses (processed from calendered sheets), water heater packings/va
  • Examples of semiconductor manufacturing equipment parts using crosslinked rubber articles include sealing materials (O-rings, square rings, gaskets, packings, oil seals, bearing seals, lip seals, etc.), tubes, hoses, various rubber rolls, diaphragms, linings, etc.
  • sealing materials O-rings, square rings, gaskets, packings, oil seals, bearing seals, lip seals, etc.
  • tubes hoses, various rubber rolls, diaphragms, linings, etc.
  • Examples of semiconductor manufacturing equipment include etching equipment (dry etching equipment, plasma etching equipment, reactive ion etching equipment, reactive ion beam etching equipment, sputter etching equipment, ion beam etching equipment, wet etching equipment, ashing equipment, etc.), cleaning equipment (dry etching cleaning equipment, UV/ O3 cleaning equipment, ion beam cleaning equipment, laser beam cleaning equipment, plasma cleaning equipment, gas etching cleaning equipment, extraction cleaning equipment, Soxhlet extraction cleaning equipment, high temperature and high pressure extraction cleaning equipment, microwave extraction cleaning equipment, supercritical extraction cleaning equipment, etc.), exposure equipment (stepper, coater developer, etc.), polishing equipment (CMP equipment, etc.), film formation equipment (CVD equipment, sputtering equipment, etc.), diffusion/ion implantation equipment (oxidation diffusion equipment, ion implantation equipment, etc.), etc.
  • etching equipment dry etching equipment, plasma etching equipment, reactive ion etching equipment, reactive ion beam etching equipment,
  • Examples 1 to 3, 9, 11, 13, 15 to 16, and 19 are working examples, and Examples 4 to 8, 10, 12, 14, 17 to 18, and 20 are comparative examples.
  • the content (mol %) of each unit in Fluorocopolymer 1 and Fluorocopolymer 2 was calculated by nuclear magnetic resonance (NMR) analysis.
  • the content of iodine atoms in the copolymer was calculated using an apparatus combining an automatic sample combustion apparatus, a pretreatment device for ion chromatography (manufactured by Mitsubishi Chemical Analytech Co., Ltd., Model AQF-100) and an ion chromatograph.
  • SiC1 90% ⁇ -SiC (6H-SiC), specific surface area 4.0 m 2 /g, "Shinano Random GP#10000", manufactured by Shin-Etsu Electric Refining Co., Ltd.
  • SiC2 88% ⁇ -SiC (6H-SiC), loose bulk density 0.48 g/cm 3 , "GC-#40000”, manufactured by Fujimi Incorporated Co., Ltd.
  • SiC3 93% ⁇ -SiC (6H-SiC), "GC-#4000”, manufactured by Fujimi Incorporated Co., Ltd.
  • SiC4 97% ⁇ -SiC (3C-SiC), specific surface area 20 m 2 /g, " ⁇ SiC3000A” Superior Graphite SiC5: 97% ⁇ -SiC (3C-SiC), “NM-SiC”, Nanomakers Inc.
  • SiC6 90% ⁇ -SiC (3C-SiC)/10% amorphous, specific surface area 35 m 2 /g, loose bulk density 0.05 g/cm 3 , "NP-SIC-8", EM Japan Co., Ltd.
  • SiC7 90% ⁇ -SiC (3C-SiC)/10% amorphous, specific surface area 60 m 2 /g, loose bulk density 0.05 g/cm 3 , "NP-SiC-9", EM Japan Co., Ltd.
  • SiC9 50% ⁇ -SiC (6H-SiC) / 40% ⁇ -SiC (3C-SiC) / 10% amorphous, "NP-SiC-7", manufactured by EM Japan Co., Ltd.
  • SIC10 99% ⁇ -SiC (3C-SiC) specific surface area 15 m 2 /g, " ⁇ SiC220” Superior, manufactured by Graphite Co., Ltd.
  • Fluorine-containing copolymers 1 and 2 were produced as follows. ⁇ Fluorine-containing copolymer 1> After degassing a stainless steel pressure reactor with an internal volume of 2100 mL, 804 g of ultrapure water, 80.1 g of a 30 mass% solution of C 2 F 5 OCF 2 CF 2 OCF 2 COONH 4 , 0.72 g of C3DVE, 1.8 g of a 5 mass% aqueous solution of disodium hydrogen phosphate dodecahydrate, and 0.87 g of C4DI were charged, and the gas phase was replaced with nitrogen.
  • Nitric acid was dissolved in ultrapure water to prepare a 3 mass% aqueous solution of nitric acid.
  • the latex was added to the nitric acid aqueous solution in a TFE/PMVE copolymer (PFA) container to coagulate the fluorocopolymer.
  • the amount of the nitric acid aqueous solution was 150 mass parts per 100 mass parts of the fluorocopolymer in the latex.
  • the aggregated fluorocopolymer was recovered by filtration, poured into ultrapure water in a PFA container, and washed by stirring at 200 rpm for 30 minutes.
  • the amount of ultrapure water was 100 parts by mass per 100 parts by mass of the copolymer. Washing was repeated 10 times.
  • the washed fluorocopolymer was recovered by filtration and dried at 50°C under reduced pressure of 10 kPa to obtain a white fluorocopolymer 1.
  • Fluorocopolymer 2 was obtained by the same production method as for "Copolymer (A-1)" in the examples of WO 2021/210502.
  • Examples 1 to 14 The components and amounts (parts by mass) shown in Table 1 were mixed and kneaded with a two-roll mill at room temperature for 10 minutes to obtain a mixed fluorine-containing copolymer composition.
  • the obtained fluorine-containing copolymer composition was hot-pressed at 150°C for 20 minutes using a hydraulic press (model: SA-301 50T type, manufactured by Tester Sangyo Co., Ltd., ram diameter: 180 mm) to obtain an O-ring (P-26 (standard specified in JIS B2401:2012)) (primary crosslinking).
  • the O-rings were then heated in an oven at 250°C for 4 hours in an air atmosphere (secondary crosslinking), and then cooled to room temperature to obtain O-rings that were crosslinked rubber articles of Examples 1 to 14.
  • the following physical properties of the resulting crosslinked rubber article were measured. The measurement results are shown in Table 1.
  • Examples 15 to 20 The components and amounts (parts by mass) shown in Table 2 were mixed and kneaded with a two-roll mill at room temperature for 10 minutes to obtain a mixed fluorine-containing copolymer composition.
  • the obtained fluorine-containing copolymer composition was hot-pressed at 180°C for 20 minutes using a hydraulic press (model: SA-301 50T type, manufactured by Tester Sangyo Co., Ltd., ram diameter: 180 mm) to obtain an O-ring (P-26 (standard specified in JIS B2401:2012)) (primary crosslinking).
  • the O-ring was then heated in an oven under a nitrogen atmosphere under the following conditions (secondary crosslinking): After heating at 90°C for 2 hours, the temperature was increased to 200°C over 2 hours and maintained at 200°C for 4 hours, then the temperature was increased to 305°C over 2 hours and further heated at 305°C for 13 hours.
  • second crosslinking By the above method, O-rings, which are crosslinked rubber articles of Examples 15 to 20, were obtained. The following physical properties of the resulting crosslinked rubber article were measured. The measurement results are shown in Table 2.
  • Compression set rate (%) (original thickness of test piece (wire diameter) - thickness 30 minutes after removing the test piece from the compression device (thickness after compression treatment) ⁇ (original thickness of test piece - thickness of spacer) ⁇ 100
  • [Particle diameter d50] A laser diffraction/scattering particle size distribution analyzer (model: LA-300, manufactured by Horiba, Ltd.) was used to determine the particle size (particle size d50) at which the cumulative particle volume from the small particle size side in the volume-based cumulative particle size distribution was 50% of the total particle volume. The results are shown in Tables 1 and 2. However, when the median diameter (particle diameter d50) of the silicon carbide was known at the time of procurement, the known median diameter (particle diameter d50) was used.
  • the crosslinked rubber articles obtained by crosslinking the fluorine-containing copolymer composition of the present invention showed smaller mass loss after plasma treatment with O2 and NF3- based gases, i.e., higher plasma resistance, than the crosslinked rubber articles obtained by crosslinking a fluorine-containing copolymer composition not of the present invention (Examples 4 to 8, 10, 12, and 14).
  • the crosslinked rubber articles obtained by crosslinking the fluorocopolymer composition of the present invention showed a smaller amount of mass loss after plasma treatment with O2 and NF3- based gas, i.e., higher plasma resistance, than the crosslinked rubber articles obtained by crosslinking a fluorocopolymer composition not of the present invention (Examples 17 to 18 and Example 20).

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

L'invention concerne une composition de copolymère fluoré qui contient un copolymère fluoré et un carbure de silicium. Ledit carbure de silicium contient un carbure de silicium d'un réseau cristallin de type α. La teneur en réseau cristallin de type α est supérieure ou égale à 50% pour 100% de l'ensemble des réseaux cristallins contenu dans ledit carbure de silicium.
PCT/JP2025/006205 2024-03-05 2025-02-25 Composition de copolymère fluoré ainsi que procédé de fabrication de celle-ci, et article de caoutchouc réticulé ainsi que procédé de fabrication de celui-ci Pending WO2025187462A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6262841A (ja) * 1985-09-13 1987-03-19 Mitsuboshi Belting Ltd 感圧導電性ゴムシ−ト
JP2006240957A (ja) * 2005-03-07 2006-09-14 Showa Denko Kk 導電性炭化ケイ素セラミックス及びその製造方法
JP2009030064A (ja) * 2001-12-17 2009-02-12 Daikin Ind Ltd 架橋性エラストマー組成物および該組成物からなる成形品
JP2017537052A (ja) * 2014-09-25 2017-12-14 メリオール イノベイションズ インクＭｅｌｉｏｒ Ｉｎｎｏｖａｔｉｏｎｓ， Ｉｎｃ． ポリシロカルブに基づいた炭化ケイ素材料、用途および装置
WO2021210435A1 (fr) * 2020-04-15 2021-10-21 株式会社バルカー Matériau d'étanchéité
WO2023189547A1 (fr) * 2022-03-31 2023-10-05 ダイキン工業株式会社 Composition, produit réticulé et matériau d'étanchéité

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6262841A (ja) * 1985-09-13 1987-03-19 Mitsuboshi Belting Ltd 感圧導電性ゴムシ−ト
JP2009030064A (ja) * 2001-12-17 2009-02-12 Daikin Ind Ltd 架橋性エラストマー組成物および該組成物からなる成形品
JP2006240957A (ja) * 2005-03-07 2006-09-14 Showa Denko Kk 導電性炭化ケイ素セラミックス及びその製造方法
JP2017537052A (ja) * 2014-09-25 2017-12-14 メリオール イノベイションズ インクＭｅｌｉｏｒ Ｉｎｎｏｖａｔｉｏｎｓ， Ｉｎｃ． ポリシロカルブに基づいた炭化ケイ素材料、用途および装置
WO2021210435A1 (fr) * 2020-04-15 2021-10-21 株式会社バルカー Matériau d'étanchéité
WO2023189547A1 (fr) * 2022-03-31 2023-10-05 ダイキン工業株式会社 Composition, produit réticulé et matériau d'étanchéité

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