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
  • C08F214/26—Tetrafluoroethene
  • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
• • 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
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • 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
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
  • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
• • 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
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
  • C08K5/57—Organo-tin 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
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
• • 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
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages

Definitions

• the present invention relates to a fluorine-containing copolymer, a fluorine-containing copolymer composition, and a crosslinked rubber article.
• Cross-linked rubber articles obtained by cross-linking a fluorine-containing copolymer are excellent in heat resistance, chemical resistance, oil resistance, weather resistance, etc., and are therefore used in various environments.
• Patent Document 1 describes a unit based on tetrafluoroethylene, a unit based on perfluoro (alkyl vinyl ether), and a nitrile group (cyano group). ) Is disclosed as a fluorine-containing copolymer having a unit based on the monomer.
• the crosslinked rubber article is manufactured, for example, by supplying a fluorine-containing copolymer to a mold and heat-molding it.
• a fluorine-containing copolymer to a mold and heat-molding it.
• the present invention has been made in view of the above problems, and it is an object of the present invention to provide a fluorine-containing copolymer capable of producing a crosslinked rubber article having excellent releasability, a fluorine-containing copolymer composition, and a crosslinked rubber article using them. And.
• a unit having a unit based on tetrafluoroethylene, a unit based on perfluoro (alkyl vinyl ether), a fluorine atom, and two or more polymerizable unsaturated bonds We have found that a crosslinked rubber article having excellent releasability can be obtained by using a fluorine-containing copolymer having a body-based unit and a monomer-based unit having a nitrile group and a fluorine atom. It led to the invention.
• CF 2 CF- OR f1 (1)
• R f1 represents a perfluoroalkyl group having 1 to 10 carbon atoms.
• a perfluorohydrocarbon group having a valence of 1 to 10 carbon atoms or a group having an ethereal oxygen atom at the terminal of the perfluorohydrocarbon group or between carbon-carbon bonds is shown.
• the plurality of R 21 , the plurality of R 22 and the plurality of R 23 may be the same as or different from each other.
• the monomer represented by the formula (2) is a monomer represented by the following formula (3) or a monomer represented by the following formula (4). Fluorine-containing copolymer according to the above.
• R 31 represents a divalent perfluorohydrocarbon group having 1 to 10 carbon atoms or a group having an ethereal oxygen atom at the terminal of the perfluorohydrocarbon group or between carbon-carbon bonds.
• (CH 2 CH) 2 R 41 (4)
• R 41 represents a divalent perfluorohydrocarbon group having 1 to 10 carbon atoms or a group having an ethereal oxygen atom at the terminal of the perfluorohydrocarbon group or between carbon-carbon bonds.
• the content of the unit based on tetrafluoroethylene is 59 to 80 mol%, and the content of the unit based on perfluoro (alkyl vinyl ether) is 19 to 19 to all the units of the fluorine-containing copolymer.
• the content of the unit based on a monomer having 40 mol% and a fluorine atom and two or more polymerizable unsaturated bonds is 0.01 to 1.0 mol%, and the nitrile group and the fluorine atom
• the fluorine-containing copolymer according to any one of [1] to [7], wherein the content of the unit based on the monomer having is 0.05 to 5 mol%.
• a fluorine-containing copolymer capable of producing a crosslinked rubber article having excellent releasability, a fluorine-containing copolymer composition, and a crosslinked rubber article using them.
• the meanings of the terms in the present invention are as follows.
• the numerical range represented by using “-” means a range including the numerical values before and after "-” as the lower limit value and the upper limit value.
• the “unit” is a general term for an atomic group derived from one molecule of the monomer, which is directly formed by polymerizing a monomer, and an atomic group obtained by chemically converting a part of the atomic group. is there.
• the "unit based on a monomer” is also simply referred to as a “unit” below.
• “Rubber” means rubber exhibiting properties as defined by JIS K 6200 (2008) and is distinguished from “resin”.
• the fluorine-containing copolymer of the present invention has a unit based on tetrafluoroethylene (hereinafter, also referred to as “TFE”), a unit based on perfluoro (alkyl vinyl ether) (hereinafter, also referred to as “PAVE”), and fluorine.
• TFE tetrafluoroethylene
• PAVE perfluoro (alkyl vinyl ether)
• DVE polymerizable unsaturated bond
• R CN monomer having a nitrile group and a fluorine atom
• the crosslinked rubber article obtained by using the fluorine-containing copolymer of the present invention is excellent in mold releasability from the mold. The details of this reason have not been clarified, but it is presumed to be due to the following reasons.
• Fluorine-containing copolymer of the present invention has a DVE unit and R CN units. As a result, the crosslinked rubber article becomes rigid, and when the crosslinked rubber article is detached from the mold, it is considered that the crosslinked rubber becomes difficult to follow the mold and is easily detached.
• fluorine-containing copolymer of the present invention as compared with the fluorine-containing copolymer comprising a DVE unit or R CN unit alone is estimated that crosslinkable groups are uniformly distributed throughout the polymer Fluorine. Therefore, it is considered that the releasability is improved by improving the hardness in the micro part of the crosslinked rubber article so that no difference can be found from the physical property values such as general rubber hardness.
• the PAVE unit is a unit based on perfluoro (alkyl vinyl ether).
• PAVE is preferably a monomer represented by the following formula (1) from the viewpoint of excellent polymerization reactivity and rubber physical characteristics.
• CF 2 CF- OR f1 (1)
• R f1 represents a perfluoroalkyl group having 1 to 10 carbon atoms.
• the number of carbon atoms of R f1 is preferably 1 to 8, more preferably 1 to 6, further preferably 1 to 5, and particularly preferably 1 to 3 from the viewpoint of more excellent polymerization reactivity.
• the perfluoroalkyl group may be linear or branched.
• PAVE perfluoro (methyl vinyl ether) (hereinafter, also referred to as “PMVE”), perfluoro (ethyl vinyl ether) (hereinafter, also referred to as “PEVE”), and perfluoro (propyl vinyl ether) (hereinafter, also referred to as “PVE”).
• PMVE perfluoro (methyl vinyl ether)
• PEVE perfluoro (ethyl vinyl ether)
• PVE perfluoro (propyl vinyl ether)
• PPVE perfluoro (propyl vinyl ether)
• the DVE unit is a unit based on a monomer having a fluorine atom and two or more polymerizable unsaturated bonds.
• the number of polymerizable unsaturated bonds in DVE is preferably 2 to 6 which is more excellent in polymerization reactivity, more preferably 2 or 3, and particularly preferably 2.
• DVE is preferably a monomer represented by the following formula (2) from the viewpoint of better releasability of the crosslinked rubber article.
• (CR 21 R 22 CR 23 ) a2 R 24 (2)
• R 21 , R 22 and R 23 independently represent a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group
• a2 represents an integer of 2 to 6
• R 24 represents a2.
• a perfluorohydrocarbon group having a valence of 1 to 10 carbon atoms or a group having an ethereal oxygen atom at the terminal of the perfluorohydrocarbon group or between carbon-carbon bonds is shown.
• the plurality of R 21 , the plurality of R 22 and the plurality of R 23 may be the same or different from each other, and it is particularly preferable that they are the same as each other. 2 or 3 is preferable for a2, and 2 is particularly preferable.
• R 21 , R 22 , and R 23 are fluorine atoms or hydrogen atoms, and all of R 21 , R 22 , and R 23 are fluorine atoms or all of them. Is more preferably a hydrogen atom, and all of R 21 , R 22 , and R 23 are particularly preferably fluorine atoms from the viewpoint that the releasability of the crosslinked rubber article is more excellent.
• R 24 may be linear, branched or cyclic, preferably linear or branched, and particularly preferably linear.
• the carbon number of R 24 is preferably 2 to 8, more preferably 3 to 7, further preferably 3 to 6, and particularly preferably 3 to 5.
• R 24 may or may not have an ethereal oxygen atom, but it preferably has an ethereal oxygen atom from the viewpoint of being more excellent in cross-linking reactivity and rubber physical characteristics.
• the number of etheric oxygen atoms in R 24 is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2.
• Etheric oxygen atom in R 24 is preferably present at the terminal of R 24.
• R 31 represents a divalent perfluorohydrocarbon group having 1 to 10 carbon atoms or a group having an ethereal oxygen atom at the terminal of the perfluorohydrocarbon group or between carbon-carbon bonds.
• CH 2 CH
• R 41 represents a divalent perfluorohydrocarbon group having 1 to 10 carbon atoms or a group having an ethereal oxygen atom at the terminal of the perfluorohydrocarbon group or between carbon-carbon bonds.
• the RCN unit is a unit based on a monomer having a nitrile group and a fluorine atom. Since the fluorine-containing copolymer has R CN units, the heat resistance of the crosslinked rubber article is excellent. From the viewpoint of polymerization reactivity, R CN preferably has a polymerizable unsaturated bond, and particularly preferably has one polymerizable unsaturated bond. Specific examples of the polymerizable unsaturated bond are as described above.
• R CN is preferably a monomer represented by the following formula (5) from the viewpoint of being more excellent in releasability and heat resistance of the crosslinked rubber article.
• CR 51 R 52 CR 53- R 54- CN (5)
• R 51 , R 52 and R 53 each independently represent a hydrogen atom, a fluorine atom or a methyl group
• R 54 is a divalent perfluorohydrocarbon group having 1 to 10 carbon atoms or the same. Indicates a group having an ethereal oxygen atom at the end of a perfluorohydrocarbon group or between carbon-carbon bonds.
• R 51 , R 52 , and R 53 are fluorine atoms or hydrogen atoms, and all of R 51 , R 52 , and R 53 are fluorine atoms or all of them. Is more preferably a hydrogen atom, and all of R 51 , R 52 , and R 53 are particularly preferably fluorine atoms from the viewpoint that the crosslinked rubber article is more excellent in mold releasability and heat resistance.
• R 54 may be linear, branched or cyclic, and is preferably linear or branched.
• the carbon number of R 54 is preferably 2 to 8, more preferably 3 to 7, further preferably 3 to 6, and particularly preferably 3 to 5.
• R 54 may or may not have an ethereal oxygen atom, but it preferably has an ethereal oxygen atom from the viewpoint of having more excellent rubber physical characteristics.
• the number of etheric oxygen atoms in R 54 is preferably 1 to 3, and particularly preferably 1 or 2.
• Fluorocopolymer may contain a unit based on a monomer other than the DVE and R CN.
• TFE, PAVE a unit based on a monomer other than the DVE and R CN, may be collectively referred to as "other monomer”.
• other monomers include a unit based on the monomer represented by the following formula (6) (hereinafter, also referred to as “formula (6) unit”) and vinylidene fluoride (hereinafter, “VdF”).
• HFP hexafluoropropylene
• CFE chlorotrifluoroethylene
• ethylene units ethylene units, and, TFE, PAVE, DVE, R CN
• Equation (6) is as follows.
• CF 2 CF- OR f2 (6)
• R f2 represents a perfluoroalkyl group containing 1 to 5 etheric oxygen atoms having 1 to 8 carbon atoms.
• the carbon number of R f2 is preferably 1 to 6, and particularly preferably 1 to 5.
• monomer represented by the formula (6) examples include perfluoro (3,6-dioxa-1-heptene), perfluoro (3,6-dioxa-1-octene), and perfluoro (5-). Methyl-3,6-dioxa-1-nonene).
• the content of the TFE unit is preferably 59 to 80 mol%, more preferably 63 to 75 mol%, and 66 to 66 to all the units of the fluorine-containing copolymer from the viewpoint of more excellent heat resistance of the crosslinked rubber article. 72 mol% is particularly preferred.
• the content of PAVE units is preferably 19 to 40 mol%, more preferably 24 to 36 mol%, and more preferably 27 to 33, based on all the units of the fluorine-containing copolymer, from the viewpoint of more excellent elasticity of the crosslinked rubber article. Mol% is particularly preferred.
• the content of the DVE unit is preferably 0.01 to 1.0 mol%, preferably 0.03 to 0.%, based on all the units of the fluorine-containing copolymer, from the viewpoint of better releasability of the crosslinked rubber article. 6 mol% is more preferable, and 0.05 to 0.4 mol% is particularly preferable.
• the content of R CN units is preferably 0.05 to 5 mol%, preferably 0.1 to 5 mol%, based on all the units of the fluorine-containing copolymer, from the viewpoint of better releasability and heat resistance of the crosslinked rubber article. 3 mol% is more preferable, and 0.2 to 1.5 mol% is particularly preferable.
• the content of the other monomer units is 0 with respect to all the units of the fluorine-containing copolymer from the viewpoint of heat resistance of the crosslinked rubber article. It is preferably 0.01 to 20 mol%, more preferably 0.5 to 10 mol%, and particularly preferably 1 to 5 mol%. From the viewpoint of better releasability and heat resistance of the crosslinked rubber article, the content of TFE units is preferably 59 to 80 mol% with respect to all the units of the fluorine-containing copolymer, and the content of PAVE units is contained. The amount is 19 to 40 mol%, the content of DVE units is 0.01 to 1.0 mol%, and the content of RC N units is 0.05 to 5 mol%.
• the molar ratio of the content of DVE unit is preferably 0.002 to 20, more preferably from 0.03 to 2, 0.1 to 1 and more It is preferable, and 0.35 to 0.59 is particularly preferable.
• the molar ratio is within the above range, the releasability and heat resistance of the crosslinked rubber article can be compatible at a high level.
• the DVE unit with respect to all the units in the fluorine-containing copolymer is calculated based on the amount of DVE used in the production of the fluorine-containing copolymer (the amount of DVE used).
• the "amount of DVE used” is a value obtained by subtracting the amount of non-polymerized DVE from the amount of DVE added to the polymerization vessel (the amount of DVE charged).
• the unpolymerized DVE is considered to be contained in the filtrate after taking out the fluorine-containing copolymer by aggregating the latex after polymerization and in the filtrate remaining after washing the latex, for example, ion chromatograph. The amount can be measured by measuring the fluoride ion with a graph measuring device.
• TFE units to total units in the fluorine-containing copolymer, PAVE units and R CN units, 19 F- calculated by nuclear magnetic resonance (NMR) analysis Specifically, the 19 F- nuclear magnetic resonance (NMR) analysis, TFE units in the fluoropolymer: PAVE units: Request R CN unit (molar ratio). Then, the value obtained by subtracting from 100 mole% content of DVE units (mol%), 19 F- nuclear magnetic resonance (NMR) TFE units of the fluorine-containing polymer as determined by analysis: PAVE units: R CN units ( The molar ratio) is applied to determine the content of each unit.
• NMR nuclear magnetic resonance
• the fluorine-containing copolymer may have an iodine atom.
• the iodine atom is a unit based on an iodine atom derived from an iodine compound that functions as a chain transfer agent described later, or a monomer having an iodine atom among the above-mentioned monomers having an iodine atom such as iodotrifluoroethylene.
• the iodine atom in the above is mentioned, and it is preferable that the iodine atom is derived from an iodine compound that functions as a chain transfer agent.
• the fluorine-containing copolymer has an iodine atom, the content thereof is preferably 0.01 to 5.0% by mass, preferably 0.05 to 2.0% by mass, based on the total mass of the fluorine-containing copolymer. Is more preferable, and 0.05 to 1.0% by mass is particularly preferable.
• the iodine atom content is in the above range, the cross-linking reactivity of the fluorine-containing copolymer is improved, and the mechanical properties of the cross-linked rubber article are excellent.
• the storage elastic modulus G'of the fluorine-containing copolymer is preferably 450 kPa or more, and particularly preferably 470 kPa or more. Although the details of the reason are unknown, when the storage elastic modulus G'is 470 kPa or more, the compression set of the crosslinked rubber article at high temperature can be made smaller.
• the storage elastic modulus G'of the fluorine-containing copolymer is preferably 650 kPa or less, more preferably 630 kPa or less, and particularly preferably 600 kPa or less, from the viewpoint of excellent processability.
• the storage elastic modulus G' is a guideline for the average molecular weight, and when it is high, it indicates that the molecular weight is large, and when it is low, it indicates that the molecular weight is small.
• the storage elastic modulus G'of the fluorine-containing copolymer in the present invention is a value measured according to ASTM D6204, and detailed measurement conditions are as shown in Examples.
• Storage modulus G '1 and the storage modulus G' 0.1 of the fluorocopolymer in the present invention is a value measured according to ASTM D4440, detailed measurement conditions were as shown in Example is there.
• Method for producing fluorine-containing copolymer there is a method of copolymerizing the above-mentioned monomers in the presence of a radical polymerization initiator.
• a water-soluble polymerization initiator and a redox polymerization initiator are preferable.
• the water-soluble polymerization initiator include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate, and organic polymerization initiators such as disuccinic acid peroxide and azobisisobutylamidine dihydrochloride. Of these, persulfates are preferable, and ammonium persulfate is more preferable.
• the redox polymerization initiator include a polymerization initiator that is a combination of persulfates and a reducing agent.
• a polymerization initiator capable of polymerizing each monomer in a polymerization temperature range of 0 to 60 ° C. is preferable.
• the persulfate constituting the redox polymerization initiator include alkali metal salts of persulfate such as ammonium persulfate, sodium persulfate, and potassium persulfate, and ammonium persulfate is preferable.
• the reducing agent to be combined with persulfates include thiosulfate, sulfite, hydrogen sulfite, pyrosulfite, and hydroxymethanesulfinate, preferably hydroxymethanesulfinate, and sodium hydroxymethanesulfinate. Salt is particularly preferred.
• the above-mentioned monomer may be copolymerized in the presence of a chain transfer agent together with a radical polymerization initiator.
• a chain transfer agent an iodine compound is preferable, and an iodine compound represented by the formula RI 2 is particularly preferable.
• R represents an alkylene group or a perfluoroalkylene group having 3 or more carbon atoms (preferably 3 to 8 carbon atoms).
• iodine compound represented by the formula RI 2 examples include 1,3-diiodopropane, 1,4-diiodobutane, 1,6-diiodohexane, 1,8-diiodooctane, and 1,3-di. Examples thereof include iodoperfluoropropane, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 1,8-diiodoperfluorooctane.
• an iodine compound having a perfluoroalkylene group is preferable, and 1,4-diiodoperfluorobutane is particularly preferable.
• an iodine atom can be introduced into the fluorine-containing copolymer.
• the fluorine-containing copolymer composition of the present invention contains the above-mentioned fluorine-containing copolymer and at least one of a cross-linking agent and a catalyst.
• the fluorine-containing copolymer composition may contain only one of the cross-linking agent and the catalyst, or may contain both.
• the cross-linking agent include organic peroxides, polyols, amines and triazines, and organic peroxides are preferable from the viewpoint of excellent productivity, heat resistance and chemical resistance of the cross-linked rubber articles.
• organic peroxides include dialkyl peroxides, ⁇ , ⁇ '-bis (tert-butylperoxy) -p-diisopropylbenzene, ⁇ , ⁇ '-bis (tert-butylperoxy) -m-. Examples thereof include diisopropylbenzene, benzoyl peroxide, tert-butylperoxybenzene and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane.
• dialkyl peroxides include 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, and tert-butyl.
• Cumylperoxide, dicumylperoxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) -3- Hexane, tert-butylperoxymaleic acid, tert-butylperoxysopropyl carbonate can be mentioned.
• Examples of amines include compounds having two or more amino groups (hereinafter, also referred to as “polyamine compounds”).
• the polyamine compound may be a compound in which a hydrogen atom of an aliphatic hydrocarbon is substituted with an amino group, or a compound in which a hydrogen atom of an aromatic hydrocarbon is substituted with an amino group.
• a compound in which the hydrogen atom of the aromatic hydrocarbon is replaced with an amino group is preferable because of the above-mentioned advantage.
• the polyamine compound preferably contains a fluorine atom. As a result, the compatibility with the specific fluorine-containing copolymer is improved, so that a crosslinked rubber article having a smaller compression set at a high temperature can be obtained.
• polyamine compound examples include hexamethylenediamine, hexamethylenediamine carbamate, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and 2,2-bis (3-amino-4-hydroxyphenyl).
• BOAP 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
• BOAP also known as bisaminophenol AF
• Examples thereof include dianiline, m-phenylenediamine, dihydrazide adipate, and a compound represented by the formula (XII) of Patent No. 5833657.
• BOAP is preferable because it is superior to compression set.
• the content of the cross-linking agent is preferably 0.3 to 10 parts by mass, preferably 0.3 to 5 parts by mass, based on 100 parts by mass of the fluorine-containing copolymer. Parts are more preferable, and 0.5 to 3 parts by mass are particularly preferable.
• the content of the cross-linking agent is within the above range, the balance between the strength and elongation of the cross-linked rubber article is excellent.
• the catalyst include organotin compounds.
• the organotin compound is preferable because it is excellent in productivity, heat resistance, and chemical resistance of the crosslinked rubber article.
• Specific examples of the organic tin compound include tetramethyltin, tetra (n-butyl) tin, and tetraphenyltin.
• the content of the catalyst is preferably 0.3 to 10 parts by mass, preferably 0.3 to 5 parts by mass, based on 100 parts by mass of the fluorine-containing copolymer. More preferably, 0.5 to 3 parts by mass is particularly preferable.
• the content of the catalyst is within the above range, the balance between the strength and elongation of the crosslinked rubber article is excellent.
• the fluorine-containing copolymer composition may contain components other than the above as long as the effects of the present invention are not impaired.
• Other components include cross-linking aids (eg, triallyl cyanurate, triallyl isocyanurate, trimetalyl isocyanurate), acid acceptors (eg, fatty acid esters, fatty acid metal salts, and divalent metal oxides (magnesium oxide).
• fillers and reinforcements eg carbon black, barium sulfate, calcium metasilicate, calcium carbonate, titanium oxide, silicon dioxide, clay, talc
• scorch retarders eg carbon black, clay, talc
• Phenolic hydroxyl group-containing compounds such as bisphenol A, quinones such as hydroquinone, ⁇ -methylstyrene dimers such as 2,4-di (3-isopropylphenyl) -4-methyl-1-pentene
• crown ether For example, 18-crown-6
• a release agent eg, sodium stearate
• the fluorine-containing copolymer composition may contain a release agent, but the release agent may bleed out from the surface of the crosslinked rubber article obtained by using the release agent, which may cause contamination. .. Therefore, from the viewpoint of being suitably used as a member (for example, an O-ring) included in the semiconductor manufacturing apparatus, it is preferable that the fluorine-containing copolymer composition does not substantially contain a release agent.
• the fluorine-containing copolymer composition does not substantially contain a release agent means that the content of the release agent is 0.1% by mass with respect to 100 parts by mass of the fluorine-containing copolymer. It means that it is not more than a part, preferably 0.01 part by mass or less, and particularly preferably 0 part by mass.
• the total content of the other components is preferably more than 0 parts by mass and 30 parts by mass or less with respect to 100 parts by mass of the fluorine-containing copolymer. 1 to 25 parts by mass is more preferable, and 5 to 15 parts by mass is particularly preferable.
• Examples of the method for preparing the fluorine-containing copolymer composition include a method of mixing the above-mentioned components. Mixing of each component can be carried out using a rubber mixing device such as a roll, a kneader, a Banbury mixer or an extruder. Further, after obtaining a mixture in which each of the above components is mixed, the mixture may be molded. Specific examples of the method for molding the mixture include compression molding, injection molding, extrusion molding, calender molding, or a method of dissolving the mixture in a solvent and dipping or coating it on a substrate or the like.
• MH - ML As an index of the cross-linking property of the fluorine-containing copolymer composition, MH - ML (hereinafter, also referred to as “cross-linking degree”) measured by the method of Examples described later can be mentioned.
• the degree of cross-linking of the cross-linked rubber is preferably 80 dNm or less, more preferably 60 dN m or less, and particularly preferably 40 dN m or less. When the degree of cross-linking of the cross-linked rubber is within the above range, the flexibility of the cross-linked rubber is excellent.
• the degree of cross-linking of the cross-linked rubber is preferably 3 dNm or more, more preferably 5 dN m or more, and particularly preferably 10 dN m or more.
• the degree of cross-linking of the cross-linked rubber is in the above range, the cross-linked rubber is excellent in excellent compression set.
• the crosslinked rubber article of the present invention is a rubber article obtained by cross-linking the fluorine-containing copolymer in the above-mentioned fluorine-containing copolymer composition.
• a method for cross-linking the fluorine-containing copolymer in the fluorine-containing copolymer composition a method for cross-linking by heating the fluorine-containing copolymer composition is preferable.
• Specific examples of the crosslinking method by heating include heating press crosslinking, steam crosslinking, and hot air crosslinking. From these methods, a fluorine-containing copolymer or a fluorine-containing copolymer composition may be appropriately selected in consideration of the shape and use.
• the heating conditions are preferably 100 to 400 ° C. for 1 second to 24 hours.
• the crosslinked rubber obtained by heating (primary cross-linking) the fluorine-containing copolymer composition may be further heated for secondary cross-linking.
• the heating conditions for the secondary cross-linking are preferably 80 to 350 ° C. for 30 minutes to 48 hours.
• Examples of the cross-linking method other than cross-linking the fluorine-containing copolymer by heating include a method of cross-linking the fluorine-containing copolymer by irradiating the fluorine-containing copolymer composition with radiation.
• Specific examples of the radiation to be irradiated include electron beams and ultraviolet rays.
• the tensile strength (tensile breaking strength) of the crosslinked rubber article is preferably 1 to 50 MPa, particularly preferably 10 to 35 MPa from the viewpoint of excellent rubber properties.
• the 100% modulus (tensile stress at 100% elongation) of the crosslinked rubber article is preferably 0.2 to 15 MPa, particularly preferably 0.5 to 9 MPa from the viewpoint of excellent rubber properties.
• the tensile elongation (elongation rate at the time of cutting) of the crosslinked rubber article is preferably 100 to 1000%, particularly preferably 120 to 600% from the viewpoint of excellent rubber properties.
• the tensile strength, 100% modulus, and elongation at cutting 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 preferably 65 to 100, more preferably 68 to 90, and particularly preferably 70 to 85, from the viewpoint of excellent rubber properties.
• the hardness (Shore-A) of the crosslinked rubber article is a value measured using a plate-shaped molded product (thickness 1 mm) of the crosslinked rubber article using a type A durometer in accordance with JIS K6253-1: 2012. Is.
• the compression set of the crosslinked rubber article at 250 ° C. is preferably 65% or less, and 60% or less because the fluorine-containing copolymer is well crosslinked and the shape recovery of the crosslinked rubber article after pressurization is excellent. More preferably, 50% or less is further preferable, and 40% or less is particularly preferable.
• the lower limit of the compression set of the crosslinked rubber article at 250 ° C. is preferably 0%, and most preferably the crosslinked rubber article has a compression set of 0% at 250 ° C.
• the compression set of the crosslinked rubber article at 250 ° C. is a value measured according to JIS K6262 using a plate-shaped molded product (thickness 1 mm) of the crosslinked rubber article.
• the above-mentioned physical characteristics of the crosslinked rubber article are, for example, the above-mentioned production conditions of the fluorine-containing copolymer (for example, the order of addition of each monomer, the number of additions, the amount of addition), and the above-mentioned fluorine-containing copolymer composition. It can be adjusted according to the type and content of each component contained, and the manufacturing conditions (for example, cross-linking conditions) of the cross-linked rubber article.
• Crosslinked rubber articles are suitable for materials such as O-rings, sheets, gaskets, oil seals, diaphragms, V-rings and the like.
• materials such as O-rings, sheets, gaskets, oil seals, diaphragms, V-rings and the like.
• heat-resistant and chemical-resistant sealing materials heat-resistant and oil-resistant sealing materials, wire coating materials, sealing materials for semiconductor devices, corrosion-resistant rubber paints, sealing materials for urea-based greases, rubber paints, adhesive rubbers, hoses, tubes, etc.
• Calendar sheet (roll), sponge, rubber roll, oil drilling member, heat dissipation sheet, solution cross-linking body, rubber sponge, bearing seal (urea grease resistant, etc.), lining (chemical resistant), automotive insulating sheet, insulation for electronic devices Sheets, rubber bands for watches, packing for endoscopes (amine resistant), bellows hose (processed from calendar sheets), water heater packing / valves, fenders (marine civil engineering, ships), fibers / non-woven fabrics (protective clothing, etc.) ), Base sealant, rubber gloves, uniaxial eccentric screw pump stator, urea SCR system parts, anti-vibration agent, anti-vibration agent, sealant, additive to other materials, toy applications.
• Examples 1 to 6 are examples, and examples 7 and 8 are comparative examples. However, the present invention is not limited to these examples.
• the content of each component in the table described later is based on mass unless otherwise specified.
• the amount of DVE used is determined from the amount of DVE added to the reactor (the amount of DVE charged) in the above ion chromatograph. The value obtained by subtracting the amount of DVE in the liquid calculated based on the measurement result was used.
• the amount of DVE charged is used as the amount of DVE charged. There was. Based on the amount of DVE units used thus obtained, the content (mol%) of DVE units with respect to all the units of the fluorine-containing copolymer was calculated.
• the storage elastic modulus of the polymer was G'.
• the storage elastic modulus G'of the fluorine-containing copolymer serves as a measure of the fluidity during molding of the crosslinked rubber article.
• the fluorine-containing copolymer composition was subjected to cross-linking characteristics using a cross-linking property measuring machine (manufactured by Alpha Technologies, trade name "RPA2000") according to ASTM D5289 at 177 ° C. for 12 minutes under the condition of an amplitude of 3 degrees. It was measured.
• the measured M H represents the maximum torque
• M L represents the minimum value of the torque
• M H -M L is the degree of crosslinking (Unit: DNM) shows a.
• the cross-linking property is a measure of the cross-linking reactivity of the fluorine-containing copolymer, and the larger the value of MH - ML , the better the cross-linking reactivity.
• Specific gravity of fluorine-containing copolymer and crosslinked rubber article The specific gravity of the fluorine-containing copolymer and the crosslinked rubber article was measured using a hydrometer (manufactured by Shinko Denshi Co., Ltd.) according to JIS K 6220-1: 2015.
• ⁇ hardness ⁇ Hardness was measured using a type A durometer according to JIS K6253-3: 2012 using a test piece of a crosslinked rubber article.
• An automatic rubber hardness tester (Digitest Shore A, manufactured by H. Burleys Testing Machine Co., Ltd.) was used as the measuring device.
• the test was carried out using three test pieces, and the value obtained by arithmetically averaging the measured values of the three test pieces was recorded.
• Test aging test After measuring the thickness of the test piece of the crosslinked rubber article with a thickness gauge, the test piece was heated at 300 ° C. for 70 hours in an air atmosphere (heat aging). After cooling the test piece after heat aging to room temperature, the tensile strength, 100% modulus and tensile elongation after heat aging were measured using the cooled test piece under the same conditions as the above-mentioned test method. .. The test was carried out using three test pieces, and the measured values of the three test pieces were recorded as arithmetic mean values.
• a fluorinated copolymer composition is introduced into a sheet-shaped mold, the fluorinated copolymer composition is crosslinked at 180 ° C. for 20 minutes, and a crosslinked rubber article (length 100 mm ⁇ ) in a state of being attached to the mold. Width 60 mm x thickness 1 mm) was obtained.
• air is injected into the interface between the cross-linked rubber article and the mold using an air gun (product name: Cyclone Star, manufactured by Chuo Koki Co., Ltd.), and the mold is released according to the following evaluation criteria. Sexual evaluation was performed.
• Example 1 ⁇ Production of Fluorine-Containing Copolymer 1> After degassing a stainless steel pressure reactor with an internal volume of 20 L equipped with anchor blades, 7.2 L of ultrapure water and 880 g of a 30 mass% solution of C 2 F 5 OCF 2 CF 2 OCF 2 COONH 4 which is an emulsifier. , 7.3 g of 8CNVE, 17.7 g of C3DVE, and 15.9 g of a 5% by mass aqueous solution of disodium hydrogen phosphate / 12hydrate were charged, and the gas phase was replaced with nitrogen.
• the monomer was press-fitted as follows.
• press-fitting the monomer after the start of polymerization is also referred to as “post-addition”
• the monomer press-fitting after the start of polymerization is also referred to as “post-addition monomer”.
• TFE was press-fitted to increase the reactor internal pressure to 0.90 MPa [gauge]. This was repeated, and each time 119.3 g of TFE was press-fitted, 3.6 g of 8CNVE, 74 g of PMVE, and 3.6 g of 8CNVE were press-fitted in this order.
• the filtrate after agglomerating the polymerized latex to take out the fluorine-containing copolymer and the filtrate remaining after washing the latex are filtered with a disk filter, and the obtained liquid is filtered by an ion chromatograph measuring device.
• no fluoride ion of 3% by mass or more was detected with respect to the charged amount of C3DVE. Therefore, assuming that all the C3DVE used for the charging was polymerized, the content of the C3DVE unit with respect to all the units in the polymer was calculated based on the charged amount of the C3DVE.
• Fluorine-Containing Copolymer Composition 1 100 parts by mass of fluoropolymer 1, 8 parts by mass of carbon black (manufactured by Tokai Carbon Co., Ltd., Seast 9), 3 parts by mass of tetraphenyltin (manufactured by Tokyo Chemical Industry Co., Ltd.), and 18-crown-6 (manufactured by Tokyo Chemical Industry Co., Ltd.) Each component was mixed at a ratio of 0.1 parts by mass of (Fuji Film Wako Pure Chemical Industries, Ltd.) and kneaded with two rolls to obtain a fluorine-containing copolymer composition 1.
• the fluorine-containing copolymer composition 1 was crosslinked and molded at 180 ° C. for 20 minutes to obtain a crosslinked rubber sheet having a length of 100 mm, a width of 60 mm and a thickness of 1 mm (primary crosslink). Then, in a nitrogen atmosphere, the crosslinked rubber sheet was heated at 90 ° C. for 3 hours, then heated to 305 ° C. over 5 hours, and further heated for 13 hours while maintaining 305 ° C. (secondary crosslinking). The obtained crosslinked rubber sheet after the secondary crosslinking was cooled to room temperature and then punched into a No. 4 dumbbell shape defined by JIS K 6251 to obtain three test pieces of the crosslinked rubber article 1.
• Example 2 to 7 Type of monomer used, addition ratio of initial addition monomer, addition ratio of post-addition monomer, addition order of post-addition monomer, number of repetitions of addition order of post-addition monomer, polymerization initiator
• the fluorine-containing copolymers 2 to 7 in Examples 2 to 7 are the same as in Example 1 except that the amount of additional addition and the polymerization conditions and the like are changed as shown in Table 1-1 and Table 1-2. , Fluorine-containing copolymer compositions 2 to 7, and crosslinked rubber articles 2 to 7 were obtained.
• Example 8 ⁇ Production of Fluorine-Containing Copolymer 8> After degassing a stainless steel pressure reactor with an internal volume of 20 L equipped with anchor blades, 7.2 L of ultrapure water and 880 g of a 30 mass% solution of C 2 F 5 OCF 2 CF 2 OCF 2 COONH 4 which is an emulsifier. , 17.5 g of C3DVE and 15.9 g of a 5% by mass aqueous solution of disodium hydrogen phosphate / 12hydrate were charged, and the gas phase was replaced with nitrogen.
• TFE was press-fitted to increase the reactor internal pressure to 0.90 MPa [gauge]. This was repeated, and 90 g of PMVE was press-fitted each time 110 g of TFE was press-fitted. Further, 7.0 g of 1,4-diiodoperfluorobutane was press-fitted into the reactor from an ampoule tube together with 50 mL of ultrapure water when 30 g of TFE was press-fitted. When the polymerization rate had decreased, a 3% by mass aqueous solution of APS was appropriately added.
• the total amount of the 3% by mass aqueous solution of APS added after the start of polymerization was 45 mL.
• the total mass of TFE added was 990 g, 110 g of TFE was press-fitted.
• the total addition mass of the post-added TFE reached 1100 g, the addition of the post-added monomer was stopped, the temperature inside the reactor was cooled to 10 ° C., the polymerization reaction was stopped, and the fluorine-containing copolymer was stopped. A latex containing 8 was obtained.
• the polymerization time was 396 minutes.
• the content of iodine atoms in the fluorine-containing copolymer 8 calculated by a device that combines an automatic sample combustion device, a pretreatment device for ion chromatography fluff (manufactured by Mitsubishi Chemical Analytech Co., Ltd., AQF-100 type) and an ion chromatograph.
• the amount was 0.20% by mass.
• the filtrate after agglomerating the polymerized latex to take out the fluorine-containing copolymer and the filtrate remaining after washing the latex are filtered with a disk filter, and the obtained liquid is filtered by an ion chromatograph measuring device.
• Fluorine-Containing Copolymer Composition 8 100 parts by mass of fluorine-containing copolymer 8, 15 parts by mass of carbon black (Thermax N990 manufactured by cancarb), 3 parts by mass of triallyl isocyanurate (TAIC WH-60 manufactured by Mitsubishi Chemical Co., Ltd.), 2,5- Each component was prepared in a proportion of 1 part by mass of dimethyl-2,5-di (tert-butylperoxy) hexane (manufactured by Nichiyu Co., Ltd., Perhexa 25B) and 1 part by mass of calcium stearate (manufactured by Kanto Chemical Co., Inc.). The mixture was kneaded with two rolls to obtain a fluorine-containing copolymer composition 8.
• the fluorine-containing copolymer composition 8 is heat-pressed (primary crosslinked) at 150 ° C. for 20 minutes and then secondarily crosslinked in an oven at 250 ° C. for 4 hours to obtain a crosslinked rubber sheet having a thickness of 1 mm. Obtained.
• the obtained crosslinked rubber sheet after the secondary crosslinking was cooled to room temperature and then punched into a No. 4 dumbbell shape defined by JIS K 6251 to obtain three test pieces of the crosslinked rubber article 8.
• the DVE unit, the use of the fluorine-containing copolymer having a R CN units, crosslinked rubber article having excellent releasability was confirmed to be obtained (Examples 1 to 6). Further, it was confirmed that the compression set of the crosslinked rubber article can be further reduced by using a fluorine-containing copolymer having a storage elastic modulus G'of 470 kPa or more (Examples 1 to 6). In contrast, in the case of using no fluorocopolymer DVE unit or R CN unit, it was confirmed releasability of crosslinked rubber article is insufficient (Examples 7 and 8).

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