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WO2019077986A1 - Élastomère contenant du fluor, composition réticulable, et article moulé en caoutchouc réticulé - Google Patents

Élastomère contenant du fluor, composition réticulable, et article moulé en caoutchouc réticulé Download PDF

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Publication number
WO2019077986A1
WO2019077986A1 PCT/JP2018/036701 JP2018036701W WO2019077986A1 WO 2019077986 A1 WO2019077986 A1 WO 2019077986A1 JP 2018036701 W JP2018036701 W JP 2018036701W WO 2019077986 A1 WO2019077986 A1 WO 2019077986A1
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Prior art keywords
fluorine
seals
containing elastomer
group
crosslinking
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English (en)
Japanese (ja)
Inventor
喬大 古谷
純平 寺田
滋 能登
祐輔 神谷
竹村　光平
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Daikin Industries Ltd
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Daikin Industries Ltd
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    • 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
    • C08F214/22—Vinylidene fluoride
    • 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
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride

Definitions

  • the present invention relates to a novel fluorine-containing elastomer, a crosslinkable composition using the same, and a crosslinked rubber molded article.
  • Fluorine-containing elastomers containing VdF as an essential component monomer such as vinylidene fluoride (VdF) / hexafluoropropylene (HFP) copolymer or VdF / HFP / tetrafluoroethylene (TFE) copolymer are outstanding Parts that require severe operating conditions such as high temperature and exposure to various chemicals due to their properties such as heat resistance, chemical resistance and oil resistance, for example, various parts in the fields of automobile industry, aircraft industry, semiconductor industry etc. It is used as a material of
  • Patent Documents 1 and 2 give polymers by copolymerizing VdF and 2,3,3,3-tetrafluoropropene. Is described.
  • Patent Documents 1 and 2 do not describe amorphous fluorine-containing elastomers.
  • An amorphous fluorine-containing elastomer has been proposed which is characterized in that it is 1 to 50 mol% of the monomeric unit and the glass transition temperature is 25 ° C. or less.
  • a crosslinkable composition has been proposed which is characterized in that it comprises 1 to 50% by mole of the monomeric unit and has an amorphous fluorine-containing elastomer having a glass transition temperature of 25 ° C. or less and a crosslinking agent.
  • An object of the present invention is to provide an amorphous fluorine-containing elastomer having excellent amine resistance and cold resistance.
  • the present inventors have found that cold resistance can be improved while maintaining amine resistance by using a small amount of tetrafluoroethylene together with vinylidene fluoride and a fluorine-containing monomer represented by CH 2 CCFR f.
  • the present invention has been completed.
  • a copolymer comprising a fluorine-containing monomer (1) unit represented by the formula: and a tetrafluoroethylene unit,
  • the molar ratio of vinylidene fluoride unit / fluorinated monomer (1) unit / tetrafluoroethylene unit is (85 to 75) / (23 to 13) / (0.1 to 6), Glass transition temperature is -5 ° C or less, It is an amorphous fluorine-containing elastomer characterized by
  • the fluorine-containing monomer (1) is preferably 2,3,3,3-tetrafluoropropene.
  • the above-mentioned fluorine-containing elastomer further has at least one of an iodine atom and a bromine atom, and the total content thereof is preferably 0.001 to 10% by weight.
  • the monomer (2) unit is preferably 0.001 to 0.06 mol% of the total polymer units.
  • the present invention is also a crosslinkable composition comprising the above-mentioned fluorine-containing elastomer and a crosslinking agent.
  • the present invention is also a crosslinked rubber molded article obtained by crosslinking the above-mentioned crosslinkable composition.
  • the fluorine-containing elastomer of the present invention has good rubber elasticity and is also excellent in amine resistance and cold resistance.
  • amorphous means that the magnitude of the melting peak ( ⁇ H) appearing in DSC measurement (temperature rise temperature: 20 ° C./min) is 2.0 J / g or less.
  • the fluorine-containing elastomer of the present invention can have a glass transition temperature of ⁇ 5 ° C. or less, can also be ⁇ 10 ° C. or less, and can also be ⁇ 13 ° C. or less, It is also possible to make it 15 degrees C or less. Since the fluorine-containing elastomer of the present invention exhibits such an extremely low glass transition temperature, the cold resistance is also excellent.
  • the glass transition temperature is obtained by raising the temperature of 10 mg of the sample at 20 ° C./min using a differential scanning calorimeter (X-DSC 823e manufactured by Hitachi Techno-Science Co., Ltd.) to obtain a DSC curve, before and after the second-order transition of the DSC curve It can be determined as a temperature indicating the intersection of the extension of the baseline of and the tangent at the inflection point of the DSC curve.
  • X-DSC 823e manufactured by Hitachi Techno-Science Co., Ltd.
  • the molar ratio is preferably (83 to 75) / (22 to 13) / (1 to 6).
  • the content of each monomer unit is a value measured by NMR method.
  • the fluorine-containing elastomer of the present invention as the fluorine-containing monomer (1) represented by the formula (1), a monomer in which R f is a linear fluoroalkyl group is preferable, and R f is a linear one.
  • the monomer which is a perfluoro alkyl group is more preferable.
  • the carbon number of R f is preferably 1 to 6.
  • the fluorine-containing elastomer of the present invention preferably further has at least one of an iodine atom and a bromine atom, and more preferably an iodine atom.
  • the fluorine-containing elastomer of the present invention further has at least one of an iodine atom and a bromine atom, and the total content thereof is preferably 0.001 to 10% by weight.
  • the total content of iodine atom and bromine atom is more preferably 0.01 to 5% by weight, still more preferably 0.1 to 5% by weight, and 0.1 to 3% by weight Is even more preferred.
  • the iodine content was determined by mixing 12 mg of sample (fluorinated elastomer) with 5 mg of Na 2 SO 3 and mixing 20 ml of pure water with Na 2 CO 3 and K 2 CO 3 at a ratio of 1 to 1 (weight ratio)
  • the absorption liquid in which 30 mg is dissolved is burned in oxygen in a quartz combustion flask, and after standing for 30 minutes, it can be measured using Shimadzu 20A ion chromatograph.
  • the calibration curve may be KI standard solution, one containing 0.5 ppm of iodine ion, or one containing 1.0 ppm.
  • the bonding position of the iodine atom and the bromine atom may be at the end of the main chain of the fluorine-containing elastomer or at the end of the side chain, or both of them.
  • the iodine end or bromine end becomes a crosslinking point (crosslinking site), and a crosslinked fluorine-containing elastomer having a high crosslinking density can be obtained, and peroxide crosslinking can be more easily performed. become.
  • the fluorine-containing elastomer of the present invention is produced by using an iodine or bromine-containing monomer as a monomer giving a crosslinking site, using a bromine compound or an iodine compound as a polymerization initiator or a chain transfer agent, or the like. Can.
  • the fluorine-containing elastomer of the present invention contains a monomer (2) unit, a crosslinked rubber molded article having excellent heat resistance can be obtained.
  • the compression set measured at 200 ° C. for 70 hours is 20% or less A crosslinked rubber molded article can be obtained.
  • CF 2 CFOCF 2 CF 2 CH 2 I , and the like.
  • the monomer (2) unit is preferably 0.001 to 0.06 mol%, more preferably 0.001 to 0.05 mol%, of the total polymer units. preferable.
  • the fluorine-containing elastomer of the present invention can be produced by a general radical polymerization method.
  • the polymerization form may be any form of bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization, but is preferably emulsion polymerization because industrial implementation is easy.
  • a polymerization initiator a chain transfer agent, a surfactant, and a solvent can be used, and each of those conventionally known can be used.
  • an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used as a polymerization initiator.
  • the oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, for example, dialkylperoxy carbonates such as diisopropyl peroxy dicarbonate, di sec-butyl peroxy dicarbonate, etc., t-butyl peroxy Peroxy esters such as isobutyrate, t-butylperoxypivalate, and dialkyl peroxides such as di-t-butyl peroxide; di ( ⁇ -hydro-dodecafluoroheptanoyl) peroxide; ( ⁇ -hydro-tetradecafluoroheptanoyl) peroxide, di ( ⁇ -hydro-hexadecafluorononanoyl) peroxide, di (perfluorobutyryl) peroxide, di (perflupareryl) peroxide, di (perfluoro) Hexanoyl) Oxides, di (perfluoroheptanoyl) peroxide, di (perfluoro
  • the water-soluble radical polymerization initiator may be a known water-soluble peroxide, for example, persulfate, perborate, perchlorate, perphosphate, ammonium salt such as percarbonate, potassium salt, sodium salt And t-butyl permaleate, t-butyl hydroperoxide and the like.
  • a reducing agent such as sulfites and sulfites may also be included, and the amount used may be 0.1 to 20 times the amount of peroxide.
  • the addition amount of the radical polymerization initiator is not particularly limited, but an amount (for example, several ppm to water concentration) or more to such an extent that the polymerization rate does not significantly decrease is collectively or sequentially or continuously in the initial stage of polymerization. May be added.
  • the upper limit is a range in which the heat of polymerization reaction can be removed from the device surface.
  • nonionic surfactants nonionic surfactants, anionic surfactants, cationic surfactants and the like can be used, and linear or branched fluorine-containing anions having 4 to 20 carbon atoms such as ammonium perfluorooctanoate Surfactants are preferred.
  • the addition amount (relative to polymerization water) is preferably 10 to 5000 ppm. More preferably, it is 50 to 5000 ppm.
  • reactive emulsifiers can be used as surfactants.
  • the addition amount is preferably 10 to 5000 ppm. More preferably, it is 50 to 5000 ppm.
  • the solvent is preferably a solvent having no chain transferability.
  • dichloropentafluoropropane R-225
  • water or a mixture of water and a water-soluble organic solvent is mentioned.
  • a bromine compound or an iodine compound as a chain transfer agent.
  • a polymerization method carried out using a bromine compound or an iodine compound for example, a method of carrying out an emulsion polymerization in an aqueous medium under pressure in the presence of a bromine compound or an iodine compound substantially in the absence of oxygen can be mentioned. (Iodine transfer polymerization method).
  • R 2 I x Br y (Wherein, x and y each represent an integer of 0 to 2 and satisfy 1 ⁇ x + y ⁇ 2, and R 2 represents a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or chlorofluorocarbon) And a compound represented by the group consisting of a hydrocarbon group or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom.
  • the bromine compound or iodine compound is, for example, 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1 3,5-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodo perfluoro hexadecane, diiodomethane, 1,2-diiodoethane, 1,3-diiodo -n- propane, CF 2 Br 2, BrCF 2 CF 2 Br, CF 3 CFBrCF 2 Br, CFClBr 2, BrCF 2 C
  • 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are used in view of polymerization reactivity, crosslinking reactivity, availability and the like. Is preferred.
  • examples of the chain transfer agent include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate and dimethyl succinate, isopentane, methane and ethane. Propane, isopropanol, acetone, various mercaptans, carbon tetrachloride, cyclohexane and the like can also be used.
  • the polymerization temperature, the polymerization pressure and the polymerization time vary depending on the type of solvent and polymerization initiator, but are -15 to 150 ° C, atmospheric pressure to 6.5 MPa, 1 to 24 hours. You may In particular, when using an oil-soluble radical polymerization initiator containing a fluorine atom as a polymerization initiator in solution polymerization, the polymerization temperature is preferably ⁇ 15 to 50 ° C., and more preferably 10 to 35 ° C.
  • the polymerization temperature is preferably 30 to 95.degree.
  • the polymerization temperature is preferably 0 to 100 ° C., and more preferably 10 to 95 ° C.
  • the fluorine-containing elastomer of the present invention may be in any form such as aqueous dispersion, powder and the like.
  • the powder of the fluorine-containing elastomer can be obtained by coagulating the dispersion after polymerization, washing with water, dehydrating and drying.
  • the coagulation can be carried out by adding an inorganic salt such as aluminum sulfate or inorganic acid, applying mechanical shear force, or freezing the dispersion.
  • suspension polymerization it can be obtained by recovering from the dispersion after polymerization and drying.
  • solution polymerization it can be obtained by directly drying a solution containing a fluorine-containing elastomer, or can be obtained by purifying a poor solvent dropwise.
  • a surfactant may be further added to the dispersion after polymerization in the above coagulation in order to improve the coagulation property.
  • a commonly used surfactant can be used.
  • a nonionic surfactant, an anionic surfactant, a cationic surfactant and the like can be used, and a C4 to C20 linear Alternatively, branched anionic surfactants are preferred.
  • a fluorine-containing surfactant or a non-fluorinated surfactant may be used.
  • fluorine-containing surfactant examples include linear or branched fluorine-containing anionic surfactants having 4 to 20 carbon atoms.
  • CH 2 CFCF 2 OCF ( CF 3) CF 2 OCF (CF 3) COONH 4, ammonium perfluorooctanoate, F (CF 2) 7 COO - M +, F (CF 2) 8 COO - M +, CF 3 CF 2 CF 2 OCF (CF 3) CF 2 OCF (CF 3) COO - M +, CF 3 CF 2 OCF (CF 3) CF 2 OCF (CF 3) COO - M +, CF 3 OCF (CF 3 ) CF 2 OCF (CF 3 ) COO - M + , H (CF 2 CF 2 ) 2 CH 2 OCF (CF 3 ) COO - M + , H (CF 2 ) 6 COO - M + , H (CF 3 ) 2) 7 COO - M +, H (CF 2) 8 COO - M
  • Examples of monovalent cations include lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion and ammonium ion, but sodium ion and ammonium ion are preferable from the economical point of view.
  • R 2 is an alkyl group or an alkenyl group, and R 3 and R 4 may be the same or different and each is a hydrogen atom, or an alkyl group or an alkenyl group
  • R 5 Is an alkylene group or an alkylene group having an unsaturated bond, or a direct bond
  • R 2 to R 5 may contain an oxygen atom, and the total carbon number of R 2 to R 4 is 2 to 25.
  • L - is -SO 3 -, -OSO 3 -, -PO 3 -, -OPO 3 - or -COO - a group represented by
  • M + is a monovalent surfactants represented by the cation is a
  • Agents are preferred.
  • the total carbon number of R 2 to R 4 is 2 to 25, preferably 5 to 20, and more preferably 10 to 20.
  • the total carbon number of R 2 to R 4 is more than 25, it is difficult to be dissolved in water, and the concentration in the aqueous phase tends not to be increased.
  • the alkyl group or alkenyl group may be linear or branched and, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group And hexyl group, heptyl group, octyl group, nonyl group, decyl group, 2-ethylhexyl group, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptanyl group, octenyl group, etc. It may contain an oxygen atom such as an oxygen atom constituting an oxygen atom or a carbonyl group. Also, the hydrogen atom of these groups may be a fluorine-containing alkyl group substituted by a fluorine atom, or a fluorine-containing alkenyl group.
  • alkylene group or the alkylene group having an unsaturated bond for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, nonylene group, decylene group, propenylene group, butenylene Groups, pentenylene group, heptenylene group, octenylene group and the like may be mentioned, and they may contain an oxygen atom such as an ether bondable oxygen atom or an oxygen atom constituting a carbonyl group.
  • L - is, -SO 3 -, -OSO 3 - , -PO 3 -, -OPO 3 - or -COO - in is a group represented, -SO 3 -, -OSO 3 - , -COO - is It is more preferable that the surfactant remains in the polymer obtained by coagulating the dispersion, since the effect on vulcanization is small.
  • Examples of monovalent cations include lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion and ammonium ion, but sodium ion and ammonium ion are preferable from the economical point of view.
  • R 4 is preferably a hydrogen atom in terms of the level of emulsifying power.
  • R 6 to R 11 and R 15 each represent an alkyl group or an alkenyl group
  • R 12 to R 14 each represent an alkyl group having 1 to 10 carbon atoms which may contain an oxygen atom.
  • n and m are integers of 1 or more, and M + is a monovalent cation.
  • alkyl group examples include those mentioned above.
  • the amount of surfactant added to the dispersion after polymerization is preferably 100 to 30000 ppm, more preferably 200 to 28,000 ppm, with respect to the total amount of the dispersion of fluorine-containing elastomer obtained by polymerization.
  • these surfactants may be used in combination.
  • the fluorine-containing elastomer of the present invention preferably has a number average molecular weight (Mn) of 7,000 to 500,000 and a weight average molecular weight (Mw) of 10,000 to 1,000,000 because it is also suitable for cold seal applications.
  • Mw / Mn is preferably 1.3 to 4.0, more preferably 1.4 to 3.9, and still more preferably 1.4 to 3.8.
  • the said number average molecular weight (Mn), weight average molecular weight (Mw), and Mw / Mn are values measured by GPC method.
  • the present invention is also a crosslinkable composition having excellent crosslinkability characterized by containing the above-mentioned fluorine-containing elastomer and a crosslinking agent.
  • the compounding amount of the crosslinking agent is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the fluorine-containing elastomer. If the amount of the crosslinking agent is less than 0.01 parts by mass, the degree of crosslinking will be insufficient, and the performance of the fluorine-containing molded article tends to be impaired. If it exceeds 10 parts by mass, the crosslinking density becomes too high. In addition to becoming longer, it also tends to be economically undesirable.
  • the crosslinking agent is not particularly limited as long as it is a crosslinking agent generally used in polyamine crosslinking, polyol crosslinking and peroxide crosslinking, but at least one selected from the group consisting of polyamine compounds, polyhydroxy compounds and organic peroxides. It is preferably a species.
  • polyamine compound examples include hexamethylene diamine carbamate, N, N'-dicinnamylidene-1,6-hexamethylene diamine, 4,4'-bis (aminocyclohexyl) methane carbamate and the like.
  • N, N'-dicin amylidene-1,6-hexamethylene diamine is preferable.
  • a polyhydroxy aromatic compound is suitably used from the point which is excellent in heat resistance.
  • the polyhydroxy aromatic compound is not particularly limited.
  • 2,2-bis (4-hydroxyphenyl) propane hereinafter referred to as bisphenol A
  • 2,2-bis (4-hydroxyphenyl) perfluoropropane (Hereinafter referred to as bisphenol AF)
  • resorcinol 1,3-dihydroxybenzene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, 4,4 ' -Dihydroxystilbene, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2-bis (4-hydroxyphenyl) butane (hereinafter referred to as bisphenol B), 4,4-bis (4-hydroxyphenyl) valeric acid, 2 , 2-bis (4-hydroxyphenyl) Tetrafluorodichloropropane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphen
  • the crosslinkable composition of the present invention preferably contains a crosslinking accelerator.
  • the crosslinking accelerator promotes the formation of an intramolecular double bond in the dehydrofluorination reaction of the fluorine-containing elastomer main chain and the addition of the polyhydroxy compound to the formed double bond.
  • crosslinking accelerator examples include onium compounds, and among onium compounds, ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, It is preferably at least one selected from the group consisting of functional amine compounds, and more preferably at least one selected from the group consisting of quaternary ammonium salts and quaternary phosphonium salts.
  • the quaternary ammonium salt is not particularly limited.
  • the quaternary phosphonium salt is not particularly limited.
  • BTPPC benzyltriphenylphosphonium chloride
  • BTPPC benzyltriphenylphosphonium chloride
  • crosslinking accelerator a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, and a chlorine free crosslinking accelerator disclosed in JP-A-11-147891 can also be used.
  • the compounding amount of the crosslinking accelerator is preferably 0.01 to 8 parts by mass, more preferably 0.02 to 5 parts by mass with respect to 100 parts by mass of the fluorine-containing elastomer.
  • amount of the crosslinking accelerator is less than 0.01 parts by mass, the crosslinking of the fluorine-containing elastomer does not proceed sufficiently, and the heat resistance and oil resistance of the resulting molded article tend to decrease, and when it exceeds 8 parts by mass The moldability of the crosslinkable composition tends to decrease.
  • any organic peroxide which can easily generate a peroxy radical in the presence of heat or a redox system may be used, for example, 1,1-bis (t-butylperoxy) -3, 5,5-Trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, ⁇ , ⁇ -bis (t- Butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne -3, benzoyl peroxide, t-butylperoxybenzene, t-butylperoxymaleic acid, t-butylperoxyisopropy
  • 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 are preferable.
  • the crosslinkable composition of the present invention preferably contains a crosslinking coagent.
  • crosslinking assistants include triallyl cyanurate, triallyl isocyanurate (TAIC), triacrylic formal, triallyl trimellitate, N, N'-m-phenylenebismaleimide, dipropargyl terephthalate, diallyl phthalate, Tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris (2,3,3-trifluoro-2-propenyl) -1,3,5-triazine-2 (4,6-trione), tris (diallylamine) -S-triazine, triallyl phosphite, N, N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallylphosphoramide, N, N, N, N
  • the compounding amount of the crosslinking assistant is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the fluorine-containing elastomer. If the amount of the coagent is less than 0.01 parts by mass, the crosslinking time tends to be too long for practical use, and if it is more than 10 parts by mass, the crosslinking time becomes too fast and the compression set of the molded article becomes permanent. The distortion also tends to decrease.
  • Crosslinking may be appropriately determined depending on the type of crosslinking agent used, etc. Usually, baking is carried out at a temperature of 150 to 300 ° C. for 1 minute to 24 hours. In addition, crosslinking can be performed under normal pressure, increased pressure, reduced pressure, and also in air.
  • the crosslinking method is not particularly limited, and a conventional method in which a crosslinking reaction is initiated by steam crosslinking, pressure molding, heating, or the like may be employed, and radiation crosslinking at normal temperature and pressure may be employed.
  • a post-treatment step called secondary crosslinking may be applied.
  • Polyamine crosslinking using a polyamine compound as a crosslinking agent can be carried out in a conventional manner.
  • the fluorine-containing elastomer of the present invention and a crosslinking agent, if necessary, a crosslinking accelerator, and, if necessary, other additives which can be suitably mixed are roll-kneaded and then pressurized in a mold to perform primary crosslinking and then secondary crosslinking.
  • the conditions for primary crosslinking are adopted at a temperature of 100 to 200 ° C., for 5 to 120 minutes, and under pressure of 2 to 10 MPa
  • the conditions for secondary crosslinking are at a temperature of 150 to 300 ° C. for 30 minutes to 30 minutes. It is adopted from the range of time.
  • Polyol crosslinking using polyhydroxy compounds as crosslinking agents can be carried out in a conventional manner.
  • the fluorine-containing elastomer of the present invention and a crosslinking agent, if necessary, a crosslinking accelerator, and, if necessary, other additives which can be suitably mixed are roll-kneaded and then pressurized in a mold to perform primary crosslinking and then secondary crosslinking.
  • a crosslinking agent if necessary, a crosslinking accelerator, and, if necessary, other additives which can be suitably mixed
  • an internal mixer, a Banbury mixer and the like can be preferably used.
  • primary crosslinking can be carried out at 2 to 10 MPa and 100 to 200 ° C. for 5 to 60 minutes
  • secondary crosslinking can be carried out at 150 to 300 ° C. for 30 minutes to 30 hours.
  • Peroxide crosslinking using organic peroxides as crosslinking agents, can be carried out in a conventional manner.
  • the fluorine-containing elastomer of the present invention and a crosslinking agent, if necessary, a crosslinking accelerator, and, if necessary, other additives which can be suitably mixed are roll-kneaded and then pressurized in a mold to perform primary crosslinking and then secondary crosslinking.
  • primary crosslinking can be carried out at 2 to 10 MPa and 100 to 200 ° C. for 5 to 60 minutes
  • secondary crosslinking can be carried out at 150 to 300 ° C. for 30 minutes to 30 hours.
  • the crosslinkable composition of the present invention more preferably contains an organic peroxide as a crosslinking agent.
  • the above-mentioned fluorine-containing elastomer has at least one of an iodine atom and a bromine atom, containing an organic peroxide makes it possible to perform peroxide crosslinking more easily.
  • organic peroxide examples include those described above, among which 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t- Preferably, it is at least one compound of butylperoxy) -hexyne-3.
  • the fluorine-containing composition preferably contains a crosslinking aid, and the above-mentioned crosslinking aid includes those mentioned above. Among them, triallyl isocyanurate (TAIC) is preferable because of its excellent crosslinking properties and physical properties of molded articles. Is preferred.
  • the crosslinkable composition of the present invention contains a filler.
  • Fillers include metal oxides such as calcium oxide, titanium oxide and aluminum oxide; metal hydroxides such as magnesium hydroxide, aluminum hydroxide and calcium hydroxide; magnesium carbonate, aluminum carbonate, calcium carbonate and barium carbonate Carbonates; Silicates such as magnesium silicate, calcium silicate, sodium silicate and aluminum silicate; Sulfates such as aluminum sulfate, calcium sulfate and barium sulfate; Synthetic hydrotalcite, molybdenum disulfide, iron sulfide, sulfide Metal sulfides such as copper; diatomaceous earth, asbestos, lithopone (zinc sulfide / barium sulfide), graphite, carbon black, carbon fluoride, calcium fluoride, coke, fine quartz powder, zinc flower, talc, mica powder, wax Last night, carbon fiber, aramid fiber Various whiskers, glass fiber, organic reinforcing agents, organic fillers,
  • the crosslinkable composition of the present invention contains a plasticizer.
  • the plasticizer include dioctyl phthalic acid and pentaerythritol.
  • the crosslinkable composition of the present invention preferably comprises a processing aid.
  • a processing aid higher fatty acids such as stearic acid, oleic acid, palmitic acid and lauric acid; higher fatty acids such as sodium stearate and zinc stearate Salts; higher fatty acid amides such as stearic acid amide and oleic acid amide; higher fatty acid esters such as ethyl oleate; higher aliphatic amines such as stearylamine and oleylamine; petroleum waxes such as carnauba wax and ceresin wax; ethylene glycol and glycerin , Polyethylene glycols such as diethylene glycol; aliphatic hydrocarbons such as petrolatum and paraffin; silicone oils, silicone polymers, low molecular weight polyethylene, phthalic esters, phosphoric esters, rosin, (halogenated) dialkyl amides , Surfactants, sulfone compounds, fluorine-based aid
  • the crosslinkable composition of the present invention comprises an acid acceptor, a mold release agent, a pigment, a flame retardant, a lubricant, a light stabilizer, a weathering stabilizer, an antistatic agent, an ultraviolet absorber, an antioxidant, a foaming agent, a fragrance, an oil And softeners may be included as long as the effects of the present invention are not affected.
  • the crosslinkable composition of the present invention may contain a solvent.
  • a solvent When the fluorine-containing elastomer is dissolved in a solvent, it can be used as a paint.
  • the solvent include ketone solvents and ester solvents.
  • the crosslinkable composition of the present invention may contain other polymers different from the fluorine-containing elastomer of the present invention.
  • Other polymers include nitrile rubber, acrylic rubber, epichlorohydrin rubber, fluorosilicone rubber, silicone rubber, fluorine-containing thermoplastic elastomer, polyvinylidene fluoride and the like.
  • the crosslinkable composition of the present invention is preferably obtained by kneading at least the fluorine-containing elastomer of the present invention, a crosslinking agent, and optionally, the above-mentioned crosslinking accelerator and the like.
  • the present invention is also a crosslinked rubber molded article obtained by crosslinking the above-mentioned crosslinkable composition.
  • the crosslinked rubber molded article of the present invention can be produced by molding the above-mentioned crosslinkable composition and crosslinking the resulting molded article, or can be produced by simultaneously carrying out molding and crosslinking. . Moreover, it can also be obtained as a coating film by apply
  • the molding method is not particularly limited, and examples thereof include compression molding, extrusion molding, transfer molding, injection molding and the like.
  • the crosslinked rubber molded article of the present invention has excellent heat resistance, oil resistance, amine resistance, chemical resistance and cold resistance, and slides in contact with other materials or seals other materials and substances. It is generally used in parts intended for sealing, sealing, anti-vibration and soundproofing, and can be used as various parts in various fields such as automobile industry, aircraft industry and semiconductor industry.
  • the fields to be used include, for example, semiconductor related fields, automobile fields, aircraft fields, space / rocket fields, ship fields, chemical fields such as chemical plants, medicine fields such as pharmaceuticals, photography fields such as developing machines, printing machines etc.
  • Printing field such as painting equipment, analytical instrument, analytical / physical chemical machine field such as instrument, food equipment field including food plant equipment and household goods, beverage food production field, pharmaceutical production field, medical parts field, chemistry Chemical transportation equipment field, Nuclear power plant equipment field, Steel field such as iron plate processing equipment, General industrial field, Electricity field, Fuel cell field, Electronic parts field, Optical parts field, Space equipment field, Petrochemical plant field And energy resources such as oil and gas, etc., mining equipment parts, oil refining, oil transportation parts and the like.
  • the use forms of the crosslinked rubber molded article of the present invention include, for example, rings, packings, gaskets, diaphragms, oil seals, bearing seals, lip seals, plunger seals, door seals, door seals, lip and face seals, gas delivery plate seals, wafer supports
  • Various sealing materials such as seals and barrel seals and packings can be mentioned.
  • the sealing material can be used in applications where heat resistance, solvent resistance, chemical resistance and non-adhesiveness are required.
  • the cross-sectional shape of the ring, the packing, and the seal may be various shapes.
  • the shape may be a square, an O-shape, a hem-rule or the like, a D-shape, It may have an irregular shape such as L, T, V, X, or Y.
  • semiconductor manufacturing apparatus liquid crystal panel manufacturing apparatus, plasma panel manufacturing apparatus, plasma display panel manufacturing apparatus, plasma addressed liquid crystal panel manufacturing apparatus, organic EL panel manufacturing apparatus, field emission display panel manufacturing apparatus, solar It can be used for a battery substrate manufacturing apparatus, a semiconductor transfer apparatus, and the like.
  • an apparatus for example, CVD apparatus, gas control apparatus such as gas control apparatus for semiconductor, dry etching apparatus, wet etching apparatus, plasma etching apparatus, reactive ion etching apparatus, reactive ion beam etching apparatus, sputter etching Apparatus, ion beam etching apparatus, oxidation diffusion apparatus, oxidation apparatus, sputtering apparatus, ashing apparatus, plasma ashing apparatus, cleaning apparatus, ion implantation apparatus, plasma CVD apparatus, exhaust apparatus, exposure apparatus, polishing apparatus, film forming apparatus, dry etching cleaning apparatus, UV / O 3 cleaning device ion beam cleaning device laser beam cleaning device plasma cleaning device gas etching cleaning device extraction cleaning equipment Soxhlet extractive cleaning machine, high temperature and high pressure extractive cleaning machine, microwave extraction cleaning device, supercritical extraction Washing equipment , Cleaning equipment using hydrofluoric acid, hydrochloric acid, sulfuric acid, ozone water, etc., stepper, coater / developer, CMP apparatus, excimer laser exposure machine
  • Specific usage modes in the semiconductor related field include, for example, various sealing materials such as gate valves, quartz windows, chambers, chamber lit, gates, bell jars, couplings, pump O-rings and gaskets; resist developer and peeling Various sealing materials such as O-rings for liquids, hoses and tubes; Resist developer tank, stripping liquid tank, wafer cleaning liquid tank, lining and coating of wet etching tank; Pump diaphragm; Wafer transfer roll; Wafer cleaning liquid Sealing materials for clean equipment such as clean equipment and sealants for clean equipment; Sealing materials for storage for storing devices such as semiconductor manufacturing equipment and wafers; Diaphragms for chemical solution transfer used in the process of manufacturing semiconductors It can be mentioned.
  • various sealing materials such as gate valves, quartz windows, chambers, chamber lit, gates, bell jars, couplings, pump O-rings and gaskets
  • resist developer and peeling Various sealing materials such as O-rings for liquids, hoses and tubes; Resist developer tank, stripping liquid
  • the engine body In the above automobile field, the engine body, main motion system, valve system, lubrication / cooling system, fuel system, intake / exhaust system, drive system transmission system, chassis steering system, brake system, basic electric parts, control It can be used for electrical components such as system electrical components and equipment electrical components.
  • the above-mentioned field of automobiles also includes motorcycles.
  • the molded product of the present invention can be used for various sealing materials that are required to have heat resistance, oil resistance, fuel oil resistance, antifreeze liquid resistance for engine cooling, and steam resistance.
  • a sealing material for example, a seal such as a gasket, a shaft seal, a valve stem seal or the like, a self seal packing, a piston ring, a split ring type packing, a mechanical seal, an oil seal etc.
  • a seal such as a gasket, a shaft seal, a valve stem seal or the like, a self seal packing, a piston ring, a split ring type packing, a mechanical seal, an oil seal etc.
  • bellows, diaphragms, hoses and tubes, electric wires, shock absorbing materials, anti-vibration materials, and various sealing materials used for the belt AT device can be mentioned.
  • Seal canister purge solenoid valve seal, onboard refueling vapor recovery (ORVR) valve seal, oil seal for fuel pump, fuel sender seal, fuel tank rollover valve seal, filler seal, Injector seal, filler cap seal, filler cap valve seal; fuel hose, fuel supply hose, fuel return hose, vapor (evaporo) hose, vent (breather) hose, filler hose, filler neck hose, hose in fuel tank (in Tank hoses), carburetor control hoses, fuel inlet hoses, fuel breather hoses and other hoses; Gas filters used for fuel filters, fuel line connector systems, etc.
  • ORVR refueling vapor recovery
  • Flange gaskets used in castings, carburetors, etc . Line materials such as steam recovery lines, fuel feed lines, vapor / ORVR lines, etc. Canisters, ORVRs, fuel pumps, fuel tank pressure sensors, gasoline pumps, carburetor sensors, combined air control Equipment (CAC), pulsation dampers, diaphragms for canisters, autococks, etc., pressure regulator diaphragms of fuel injection devices; valves for fuel pumps, carburetor needle valves, roll over check valves, check valves, etc .; Breather), tube used in fuel tank; tank packing such as fuel tank, packing of acceleration pump piston of carburetor, fuel sender anti-vibration parts for fuel tank O-rings and diaphragms to control fuel pressure; accelerator pump cups; in-tank fuel pump mounts; injector cushion rings of fuel injectors; injector seal rings; carburetor needle valve core valves; carburetor acceleration pumps Piston; valve seat of complex air control device (CAC); fuel tank
  • a diaphragm used for a master back As a concrete usage form in the above-mentioned brake system, a diaphragm used for a master back, a hydraulic brake hose air brake, a brake chamber of an air brake, etc .; a hose used for a brake hose, a brake oil hose, a vacuum brake hose etc .; Various sealing materials such as O-rings, packings, brake piston seals, etc .; Atmospheric valves and vacuum valves for master back; check valves for brake valves; piston cups (rubber cups) for master cylinder; brake cups; hydraulic brakes Master cylinders, vacuum boosters, boots for hydraulic brake wheel cylinders, O-rings for antilock brake systems (ABS) and grommets.
  • ABS antilock brake systems
  • the basic electrical component examples include an insulator or sheath of a wire (harness), a tube of a harness external component, a grommet for a connector, and the like.
  • Specific examples of usage in control system electrical components include coating materials for various sensor wires.
  • Specific usages of the above-mentioned electrical components include O-rings, packings, cooler hoses, high pressure air conditioner hoses, air conditioner hoses, gaskets for electronic throttle units, plug boots for direct ignition, diaphragms for distributors, etc. Can be mentioned. It can also be used to bond electrical components.
  • seals used for steam recovery canisters, catalytic converters, exhaust gas sensors, oxygen sensors, etc., seals of steam recovery and steam canister solenoid armatures; used as intake manifold gaskets etc. Can.
  • it can be used as an O-ring seal for a direct injection injector, a rotary pump seal, a control diaphragm, a fuel hose, an EGR, a priming pump, and a diaphragm of a boost compensator.
  • transmission-related bearing seals examples include transmission-related bearing seals, oil seals, O-rings, packings, torque converter hoses and the like.
  • Mission oil seals AT transmission oil hoses, ATF hoses, O-rings, packings, etc. may also be mentioned.
  • the transmissions include AT (automatic transmission), MT (manual transmission), CVT (continuously variable transmission), DCT (dual clutch transmission) and the like.
  • oil seals for manual or automatic transmissions gaskets, O-rings, packings, oil seals for continuously variable transmissions (belt type or toroidal type), gaskets, O-rings, packings, ATF linear solenoids Packings, oil hoses for manual transmissions, ATF hoses for automatic transmissions, and CVTF hoses for continuously variable transmissions (belt type or toroidal type).
  • a power steering oil hose, a high pressure power steering hose, etc. are mentioned.
  • cylinder head gasket As a form used in an engine body of an automobile engine, for example, cylinder head gasket, cylinder head cover gasket, oil pan packing, gasket such as general gasket, O-ring, packing, seal such as timing belt cover gasket, control hose etc.
  • Hoses anti-vibration rubber for engine mounts, control valve diaphragms, camshaft oil seals, etc.
  • shaft seals such as crankshaft seals and camshaft seals.
  • valve system of an automobile engine it can be used as a valve stem oil seal of an engine valve, a valve seat of a butterfly valve or the like.
  • radiator hoses In automobile engine lubrication and cooling systems, engine oil cooler hoses, oil return hoses, seal gaskets, water hoses around radiators, radiator seals, radiator gaskets, radiator O-rings, vacuum pumps, etc. In addition to vacuum pump oil hoses, it can be used for radiator hoses, radiator tanks, diaphragms for oil pressure, fan coupling seals, etc.
  • aircraft field space / rocket field, and ship field, it can be used particularly for a fuel system and a lubricating oil system.
  • aircraft field for example, various seal parts for aircraft, various parts for aircraft for engine oil applications, jet engine valve stem seals, gaskets, O-rings, rotating shaft seals, gaskets for hydraulic equipment, firewall seals It can be used as fuel supply hoses, gaskets, O-rings, aircraft cables, oil seals, shaft seals, etc.
  • lip seals for spacecraft, jet engines, missiles etc. diaphragms, O-rings, oil O-rings for gas turbine engines, vibration isolation pads for missile ground control etc. It can be used.
  • Specific modes of use in the above-mentioned chemical products field and chemical field include chemical devices, chemical pumps and flow meters, chemical pipes, heat exchangers, agrochemical sprayers, agrochemical transfer pumps, gas pipes, fuel cells, Seals used in analytical equipment and physicochemical equipment (for example, columns and fittings of analytical equipment and instruments, etc.), shrink joints of exhaust gas desulfurization equipment, nitric acid plants, power plant turbines, etc., seals used in medical sterilization processes, Seals for plating solutions, Coro seals for paper belts, joint seals for wind tunnels, chemical devices such as reactors and stirrers, O-rings used in analytical instruments and instruments, chemical pumps, pump housings, valves, tachometers, etc.
  • the field of printing such as printing machines, and the field of painting such as coating equipment
  • it can be used as rolls, belts, seals and valve parts of dry copiers.
  • specific usage forms in the above-mentioned photography field, printing field and painting field surface layer of transfer roll of copying machine, cleaning blade of copying machine, belt of copying machine; for OA equipment such as copying machine, printer, facsimile etc.
  • Rolls for example, fixing rolls, pressure rolls, pressure rolls, etc.
  • belts rolls of PPC copying machines, roll blades, belts
  • rolls of film developing machines rolls of X-ray film developing machines
  • printing rolls of printing machines Scrapers, tubes, valve parts, belts
  • printer ink tubes rolls, belts
  • coating painting equipment paint rolls, scrapers, tubes, valve parts
  • developing rolls gravure rolls, guide rolls, magnetic tape production coating line Guide Roll, Gravure Roll for Magnetic Tape Production Coating Line, Coating Row And the like.
  • packings, gaskets, tubes, diaphragms, hoses, joint sleeves, and the like used in products such as liquors and soft drinks, filling devices, food sterilization devices, brewing devices, brewing devices, water heaters, various automatic food vending machines, etc. may be mentioned.
  • nuclear power plant equipment field it can be used as a check valve or a pressure reducing valve around a nuclear reactor, a seal of a uranium hexafluoride enrichment apparatus, or the like.
  • sealing materials for hydraulic machines such as machine tools, construction machines, hydraulic machines, etc .
  • seals for hydraulic and lubricating machines and bearing seals sealing materials used for mandrels etc
  • dry cleaning equipment Seals used for windows, etc . Cyclotron seals and (vacuum) valve seals, seals of proton accelerators, seals of automatic packaging machines, diaphragms of pumps for sulfur dioxide and chlorine gas analyzers (pollution measuring instruments) in air, snakes Pump linings, rolls and belts for printing machines, conveyor belts (conveyor belts), squeeze rolls for pickling such as iron plates, cables for robots, solvent squeeze rolls such as aluminum rolling lines, coupler O-rings, acid-resistant cushioning materials , Dust seal and lip rubber of sliding part of cutting machine, garbage incinerator Basket, friction materials, metal or a surface modifier for rubbers, and the like dressing.
  • gaskets and sealing materials for equipment used in papermaking processes sealing agents for clean room filter units, sealing agents for construction, protective coatings such as concrete and cement, glass cloth impregnated materials, polyolefin processing aids, polyethylene molding It can also be used as a property improving additive, a fuel container such as a small generator or a lawn mower, a precoated metal obtained by subjecting a metal plate to a primer treatment, and the like. In addition, it can be impregnated into a woven fabric and baked to be used as a sheet and a belt.
  • Specific use forms in the above-mentioned electric field include insulating oil caps for Shinkansen, venting seals for liquid-filled transformers, transformer seals, oil well cable jackets, oven oven seals such as electric furnaces, microwave oven window frames Seals, sealing materials used when bonding CRT wedges and necks, sealing materials for halogen lamps, fixing agents for electrical parts, sealing materials for end treatment of sheathed heaters, insulation of lead wires for electrical equipment, and insulation treatment Sealing materials and the like.
  • covering materials such as oil resistant / heat resistant electric wire, high heat resistant electric wire, chemical resistant electric wire, high insulating electric wire, high voltage transmission line, cable, electric wire used for geothermal power generation equipment, electric wire used around automobile engine You can also.
  • electrical insulating materials eg, materials used for insulating spacers of various electric devices, insulating tapes used for cable joints or ends, heat-shrinkable tubes, etc.
  • electricity used in high temperature atmosphere It can also be used for electronic device materials (for example, lead wire materials for motors, wire materials around high-temperature furnaces).
  • electronic device materials for example, lead wire materials for motors, wire materials around high-temperature furnaces.
  • sealing layer and protective film (back sheet) of a solar cell back sheet
  • the electronic component field it can be used as a heat sink material, an electromagnetic wave shield material, a gasket for a hard disk drive (magnetic recording device) of a computer, or the like.
  • buffer rubber (crash stopper) of hard disk drive binder of electrode active material of nickel hydrogen secondary battery, binder of active material of lithium ion battery, polymer electrolyte of lithium secondary battery, binder of positive electrode of alkaline storage battery, Binders for EL devices (electroluminescent devices), binders for electrode active materials of capacitors, sealants, sealing agents, quartz covering materials for optical fibers, films and sheets such as optical fiber covering materials, CMOS electronic circuits, transistors, integration Circuits, organic transistors, light emitting elements, actuators, memories, sensors, coils, capacitors, electronic components such as resistors, potting and coating of circuit boards and adhesive seals, fixing agents for electronic components, modifiers for sealants such as epoxy, Coating agent for printed circuit board, d Dexts of printed
  • energy resource search and mining equipment parts such as oil and gas
  • it is used as various sealing materials used in mining of oil, natural gas and the like, boots of electrical connectors used in oil wells and the like.
  • a drill bit seal As a specific usage form in the above-mentioned energy resource search and mining equipment parts field, it is used for a drill bit seal, a pressure control diaphragm, a seal of a horizontal drilling motor (stator), a stator bearing (shaft) seal, and a blowout prevention device (BOP) Seal material, seal material used for rotational blowout prevention device (pipe wiper), seal material used for MWD (real time drilling information detection system), air / liquid connector, logging used for logging equipment (logging equipment) Tool seals (for example, O-rings, seals, packings, gas-liquid connectors, boots, etc.), expansion type packers and completion packers, packers seals used therefor, seals, packings, and perforations used in cementing devices Used in Seals, seals and packings
  • a door seal a gate valve, a pendulum valve, a tip of a solenoid, a piston seal or a diaphragm coupled to a metal, and a metal rubber component coupled to a metal such as a metal gasket.
  • a metal gasket a metal rubber component coupled to a metal such as a metal gasket.
  • it can be used for rubber parts in bicycles, brake shoes, brake pads and the like.
  • a belt is mentioned as one of the forms of the crosslinked rubber molded article of this invention.
  • the following are illustrated as the said belt.
  • Power transmission belts including flat belts, V-belts, V-ribbed belts, toothed belts, etc.
  • transport belts conveyor belts
  • various high-temperature parts such as agricultural machinery, machine tools, engines of industrial machines, etc.
  • Conveyor belts for transporting loose materials and granular materials such as coal, crushed stone, earth and sand, ores, wood chips under high temperature environment; Conveyor belts used in steelworks such as blast furnaces; Precision Conveyor belts for applications exposed to high-temperature environments in equipment assembly plants, food plants, etc .; Agricultural machines, general equipment (eg, OA equipment, printing machines, industrial dryers, etc.), V-belts for automobiles, etc. V-ribbed belts; Transmission belts for transfer robots; Toothed belts such as food machines and transmission belts for machine tools; Used for automobiles, OA equipment, medical equipment, printing machines, etc. Such as a toothed belt to be like. In particular, a timing belt is typical as a toothed belt for a motor vehicle.
  • the belt may have a single layer structure or a multilayer structure.
  • the belt may be composed of a layer obtained by crosslinking the crosslinkable composition of the present invention and a layer composed of other materials.
  • layers made of other materials include layers made of other rubbers, layers made of thermoplastic resin, various fiber reinforced layers, canvas, metal foil layers and the like.
  • the crosslinked rubber molded article of the present invention can also be used as an industrial antivibration pad, antivibration mat, railway slab mat, pads, antivibration rubber for automobiles, and the like.
  • anti-vibration rubbers for automobiles anti-vibration rubbers for engine mounts, motor mounts, member mounts, strut mounts, bushes, dampers, muffler hangers, center bearings, etc. may be mentioned.
  • the joint member is a joint used for piping and piping equipment, prevents vibration and noise generated from piping system, absorption of expansion and displacement due to temperature change, pressure change, absorption of dimensional fluctuation, earthquake, ground settlement
  • Flexible joints and expansion joints are preferably used as complex shape moldings for shipbuilding piping, for mechanical piping such as pumps and compressors, for chemical plant piping, for electrical piping, for civil engineering / water piping, for automobiles, etc. it can.
  • Boots include, for example, constant velocity joint boots, dust covers, rack and pinion steering boots, pin boots, boots for automobiles such as piston boots, boots for agricultural machines, boots for industrial vehicles, boots for construction machines, boots for hydraulic machines, empty It can be preferably used as a complex-shaped molded product such as various industrial boots such as boots for pressure machines, boots for intensive lubricating machines, boots for liquid transfer, boots for fire fighting, and boots for transferring liquefied gas.
  • the crosslinked rubber molded article of the present invention can also be used for filter press diaphragms, blower diaphragms, water supply diaphragms, liquid storage tank diaphragms, pressure switch diaphragms, accumulator diaphragms, air spring diaphragms such as suspensions, etc. .
  • an anti-slip agent By adding the crosslinked rubber molded article of the present invention to a rubber or a resin, an anti-slip agent can be obtained to obtain a molded article or a coating film which is not slippery in an environment wet with water such as rain, snow, ice and sweat.
  • the crosslinked rubber molded article of the present invention is, for example, a cushion for hot press molding when producing a decorative plywood made of melamine resin, phenol resin, epoxy resin or the like, a printed board, an electric insulating board, a rigid polyvinyl chloride laminate, etc. It can also be used as a material.
  • the crosslinked rubber molded article of the present invention can also contribute to the impermeability of various supports such as weapon-related sealing gaskets and protective clothing against contact with invasive chemical agents.
  • lubricating oils engine oils, mission oils, gear oils, etc.
  • amine additives especially antioxidants, amine additives used as detergents and dispersants
  • O corner
  • V-ring, X-ring, packing, gasket, diaphragm, oil seal, bearing seal, lip seal Can be used for plunger seals, door seals, lip and face seals, gas delivery plate seals, wafer support seals, barrel seals and other various sealing materials, etc.
  • valve bodies of tubes, hoses, various rubber rolls, coatings, belts, valves It can also be used as Moreover, it can also be used as Moreover, it can also be used as a laminating material and a lining material.
  • a vulcanized film may be formed and used for the crosslinked rubber molded article of the present invention.
  • non-adhesive oil-resistant rolls for copiers, weather strips for anti-icing, rubber stoppers for infusion, vial rubber stoppers, mold release agents, non-adhesive light transfer belts, anti-adhesive coatings for pre-gaskets of automobile engine mounts, Applications include coating of synthetic fibers, bolted members or joints with thin packing layers.
  • the use of the cross-linked rubber molded article of the present invention for automobile-related parts also includes the use of parts of motorcycles of the same structure.
  • fuels in the above-mentioned automobile-related matters there are diesel fuel, gasoline, fuel for diesel engine (including biodiesel fuel) and the like.
  • the crosslinked rubber molded article of the present invention can also be used as a rolling bearing seal member.
  • the deep groove ball bearings are used, for example, in electric motors, home electric appliances, office automation equipment, and the like.
  • the above-mentioned angular contact ball bearings include single-row angular contact ball bearings, combined angular contact ball bearings, double-row angular contact ball bearings, etc.
  • the single-row angular contact ball bearings are motors, household electrical appliances, OA equipment, etc. In addition, it is used for hydraulic pumps, vertical pumps, etc. to which an axial load is applied.
  • the combination angular contact ball bearing is used as a main spindle, a grinding spindle, etc. of a machine tool that requires improvement in shaft rotational accuracy and rigidity improvement.
  • Double-row angular contact ball bearings are used, for example, in electromagnetic clutches for automobile air conditioners.
  • the above-mentioned four-point contact ball bearing is used for a reduction gear or the like in which axial load from both directions is applied and the space of the bearing width can not be enlarged.
  • the above-described self-aligning ball bearing is used for a portion where alignment between the shaft and the housing is difficult, a transmission shaft in which the shaft is flexible, and the like.
  • the above thrust ball bearings include single type thrust ball bearings and double thrust ball bearings, which can be applied to conventionally known applications in which these ball bearings are used.
  • the above-described thrust angular contact ball bearing is used in combination with a double-row cylindrical roller bearing as an axial load receiver for a main shaft of a machine tool.
  • roller bearing As said roller bearing, a radial roller bearing, a thrust roller bearing, etc. are mentioned.
  • Examples of the radial roller bearings include cylindrical roller bearings, needle roller bearings, tapered roller bearings, and self-aligning roller bearings.
  • the cylindrical roller bearing is used for a general machine, a machine tool, an electric motor, a reduction gear, a railway axle, an aircraft and the like.
  • Needle roller bearings are used in general machines, automobiles, motors and the like.
  • Tapered roller bearings are used in machine tools, automobile and railway axles, rolling machines, reduction gears, and the like.
  • Spherical roller bearings are used in general machines, rolling mills, paper machines, axles and the like.
  • the thrust roller bearings include thrust cylindrical roller bearings, thrust needle roller bearings, thrust tapered roller bearings, thrust self-aligning roller bearings and the like.
  • Thrust cylindrical roller bearings are used in machine tools, general machines and the like.
  • Thrust needle roller bearings are used in automobiles, pumps, general machines and the like.
  • Thrust tapered roller bearings are used in general machines, rolling mills and the like.
  • Thrust spherical roller bearings are used in cranes, extruders, general machines and the like.
  • crosslinkable composition of this invention can also be used as various components in various industrial fields other than bridge
  • the crosslinkable composition of the present invention is a surface modifier such as metal, rubber, plastic, glass, etc .; a sealing material such as a metal gasket, oil seal, etc. which is required to have heat resistance, chemical resistance, oil resistance and non-adhesiveness Coating material: Non-adhesive coating material such as rolls for OA equipment, belts for OA equipment, or bleed barriers. It can be used for impregnation on woven sheets and belts, coating by baking, etc.
  • the crosslinkable composition of the present invention can be used as a sealing material, lining, sealant of complicated shape by high viscosity and high concentration by usual usage, and thin film of several microns by low viscosity It can be used to form a film, and can be used to apply precoat metals, O-rings, diaphragms, and reed valves by making the medium viscosity. Furthermore, it can be used for coating of transport rolls or belts for woven fabrics and paper sheets, belts for printing, chemical resistant tubes, stoppers, fuel hoses and the like.
  • the article substrate coated with the crosslinkable composition of the present invention includes metals such as iron, stainless steel, copper, aluminum and brass; glass products such as glass plates and woven and non-woven fabrics of glass fibers; Molded articles and coatings of general-purpose and heat-resistant resins such as methylene, polyimide, polyamideimide, polysulfone, polyether sulfone, polyether ether ketone; general-purpose rubbers such as SBR, butyl rubber, NBR, EPDM, and silicone rubbers, fluororubbers Molded articles and coatings of heat-resistant rubber such as; woven and non-woven fabrics of natural fibers and synthetic fibers; etc. can be used.
  • metals such as iron, stainless steel, copper, aluminum and brass
  • glass products such as glass plates and woven and non-woven fabrics of glass fibers
  • Molded articles and coatings of general-purpose and heat-resistant resins such as methylene, polyimide, polyamideimide, polysulfone, polyether sulfone
  • the coating formed from the crosslinkable composition of the present invention can be used in the fields where heat resistance, solvent resistance, lubricity and non-stickiness are required, and specific applications include copiers, printers and facsimiles.
  • Rolls for office automation equipment eg fuser roll, crimp roll
  • conveyor belts sheets and belts
  • O-rings diaphragms, chemical resistant tubes, fuel hoses, valve seals, gaskets for chemical plants, engine gaskets, etc. It can be mentioned.
  • the crosslinkable composition of the present invention can also be dissolved in a solvent and used as a paint, an adhesive. In addition, it can be used as a coating as an emulsified dispersion (latex).
  • the composition is a surface treatment agent for a structure comprising various devices, sealing materials such as piping, linings, metals, ceramics, glass, stone, concrete, plastics, rubber, wood, paper, inorganic materials such as paper, fibers, and organic substrates Used as etc.
  • the composition can be applied to a substrate or the like by dispenser coating or screen printing coating.
  • the crosslinkable compositions of the present invention may be used as paint compositions for casting films or for immersing substrates such as fabrics, plastics, metals or elastomers.
  • the crosslinkable composition of the present invention is in the form of a latex, coated fabric, protective gloves, impregnated fiber, O-ring coating, coating for fuel system quick connect O-ring, coating for fuel system sealing, fuel tank rollover Coating for valve diaphragm, coating for fuel tank pressure sensor diaphragm, coating for oil filter and fuel filter seal, coating for fuel tank sender seal and sender head fitting seal, coating for copier fuser roll, and polymer coating composition May be used for They are useful for the coating of silicone rubbers, nitrile rubbers, and other elastomers.
  • compositions are also useful for the coating of parts made from such elastomers, for the purpose of enhancing both the permeation resistance and the chemical resistance of the substrate elastomer as well as its thermal stability.
  • Other applications include heat exchangers, expansion joints, butts, tanks, fans, flue ducts and other conduits, and coatings for storage structures, such as concrete storage structures.
  • the composition may be applied to the exposed cross section of the multilayer part structure, for example in a method of manufacturing a hose structure and a diaphragm. Sealing members at joints and joints are often made of hard materials, and the crosslinkable compositions of the present invention have enhanced dimensions with an improved frictional interface, reduced traces of leakage along the sealing surface. Provide a tight fit.
  • the latex enhances seal durability in various automotive system applications. They can also be used in the manufacture of power steering systems, fuel systems, air conditioning systems, and any connections where hoses and tubes are connected to other parts.
  • a further utility of the above composition is in the repair of manufacturing defects (and damage due to use) in multilayer rubber structures such as three-layer fuel hoses.
  • the composition is also useful for the application of thin steel plates that can be formed or embossed before or after the paint is applied. For example, multiple layers of coated steel can be assembled to make a gasket between two rigid metal members. The sealing effect is obtained by applying the crosslinkable composition of the invention between the layers. This process reduces the bolting force and strain of assembled parts while engine head gaskets and exhaust manifold gaskets for the purpose of providing good fuel savings and low emissions due to low cracking, deflection and hole strain Can be used to make
  • the crosslinkable composition of the present invention may further comprise: a coating agent; an integrated base gasket formed by dispenser molding on a base material containing an inorganic material such as metal or ceramic; packings; a base containing an inorganic material such as metal or ceramic It can be used also as a multilayer product etc. which are coated by material.
  • the crosslinkable composition of the present invention is also suitable as a wiring material of a light and bendable electronic device, and can be used for known electronic components.
  • Electronic components such as CMOS electronic circuits, transistors, integrated circuits, organic transistors, light emitting elements, actuators, memories, sensors, coils, capacitors, resistors, and the like can be given.
  • flexible electronic devices such as solar cells, various displays, sensors, actuators, electronic artificial skin, sheet type scanners, Braille displays, wireless power transmission sheets and the like.
  • Glass transition temperature (Tg) Glass transition temperature (Tg)
  • a DSC curve is obtained by raising the temperature of 10 mg of the sample at 20 ° C./min, and an extension line of the baseline before and after the second-order transition of the DSC curve The temperature which shows the intersection of the tangent at the inflexion point of a DSC curve, and DSC curve was made into glass transition temperature.
  • Example 1 In a 3 L stainless steel autoclave, 1500 ml of pure water, 0.3008 g of 50% aqueous solution of CH 2 CFCFCF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) COONH 4 , 6.0021 g of 50% aqueous solution of C 5 F 11 COONH 4 Then, purge with nitrogen, use VdF as a slight pressure, adjust temperature to 80 ° C while stirring at 600 rpm, press in VdF to 0.200 MPa, press in TFE to 0.248 MPa, and further add VdF, TFE and 1234yf The mixed liquid monomer having a molar ratio of 77.3 / 4. 9 / 17.8 was injected to 1.47 MPa.
  • the solids content of the dispersion was 25.94 wt% (polymer amount 534.6 g).
  • the dispersion was coagulated by adding aluminum sulfate, and dried to obtain 530.2 g of a polymer.
  • the obtained polymer contained 1234yf, VdF and TFE in a molar ratio of 17.2 / 78.1 / 4.7.
  • the Tg of the resulting polymer was determined to be -18.9 ° C. by DSC. Also, the heat of fusion was not observed in the second run.
  • the number average molecular weight (Mn) was 164000
  • the weight average molecular weight (Mw) was 397000
  • Mw / Mn was 2.43.
  • the iodine content was 0.16% by weight.
  • Example 2 In a 3 L stainless steel autoclave, 1500 ml of pure water, 0.3008 g of 50% aqueous solution of CH 2 CFCFCF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) COONH 4 , 6.0021 g of 50% aqueous solution of C 5 F 11 COONH 4 Then, purge with nitrogen, use VdF as a slight pressure, adjust temperature to 80 ° C while stirring at 600 rpm, press in VdF to 0.200 MPa, press in TFE to 0.248 MPa, and further add VdF, TFE and 1234yf The mixed liquid monomer having a molar ratio of 77.3 / 4. 9 / 17.8 was injected to 1.47 MPa.
  • the resulting polymer has a ratio of 17.1 / 77.5 / 5.4 in molar ratio of 1234yf, VdF and TFE, and 0 for perfluoro-6,6-dihydro-6-iodo-3-oxa-1-hexene It contained .02 mol%.
  • the Tg of the resulting polymer was determined to be -19.1 ° C. by DSC. Also, the heat of fusion was not observed in the second run.
  • the number average molecular weight (Mn) was 133,000, the weight average molecular weight (Mw) was 337000, and Mw / Mn was 2.53.
  • the iodine content was 0.35% by weight.
  • Comparative Example 1 In a 3 L stainless steel autoclave, 1500 ml of pure water, 0.3027 g of a 50% aqueous solution of CH 2 CFCFCF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) COONH 4 , 6.00051 g of a 50% aqueous solution of C 5 F 11 COONH 4 Then, the mixture is purged with nitrogen, mixed with a monomer mixture of VdF, TFE, and 1234yf in a molar ratio of 76.3 / 11.2 / 12.5, slightly pressurized, and the temperature is adjusted to 80 ° C. while stirring at 600 rpm for mixing.
  • the liquid monomer was pressurized to 0.22 MPa, TFE was pressurized to 0.30 MPa, and VdF was further pressed to 1.47 MPa.
  • 0.0606 g of ammonium persulfate dissolved in 2 ml of pure water was pressurized with nitrogen.
  • the pressure dropped to 1.44 MPa the continuous monomer was pressurized to 1.50 MPa. This was repeated, and after about 10 minutes, 13 g of the continuous monomer was charged, and 1.8268 g of 1,4-diiodoperfluorobutane and 2 g of water for pressing were injected with nitrogen.
  • the dispersion was coagulated by adding aluminum sulfate, and dried to obtain 528.0 g of a polymer.
  • the obtained polymer contained 1234yf, VdF and TFE in a molar ratio of 11.9 / 77.3 / 11.8.
  • the Tg of the resulting polymer was determined to be -21.4 ° C by DSC.
  • the number average molecular weight (Mn) was 175,000
  • the weight average molecular weight (Mw) was 422000
  • Mw / Mn was 2.41
  • the iodine content was 0.14% by weight.
  • Comparative example 2 In a 3 L stainless steel autoclave, 1500 ml of pure water, 0.3003 g of a 50% aqueous solution of CH 2 CFCFCF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) COONH 4 , 6.0012 g of a 50% aqueous solution of C 5 F 11 COONH 4 The temperature is adjusted to 80 ° C. while stirring at 600 rpm, and VdF is forced to 1.21 MPa while the molar ratio of VdF to 1234yf is 77.4 / 22.6. The mixed solution monomer of the above was pressed to 1.47 MPa.
  • the gas in the autoclave was released and cooled to recover 2089 g of the dispersion.
  • Ammonium persulfate was added as needed along the way.
  • the solid content of the dispersion was 25.76 wt% (polymer amount: 538.0 g).
  • the dispersion was coagulated by adding aluminum sulfate, and dried to obtain 520.5 g of a polymer.
  • the obtained polymer contains 1234yf and VdF in a molar ratio of 22.9 / 77.1, and contains 0.01 mol% of perfluoro-6,6-dihydro-6-iodo-3-oxa-1-hexene It was.
  • the Tg of the resulting polymer was determined to be ⁇ 13.5 ° C. by DSC. Also, the heat of fusion was not observed in the second run.
  • the number average molecular weight (Mn) was 142000
  • the weight average molecular weight (Mw) was 353000
  • Mw / Mn was 2.49.
  • Comparative example 3 In a 3 L stainless steel autoclave, 1500 ml of pure water, 0.3005 g of a 50% aqueous solution of CH 2 CFCFCF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) COONH 4 , 6.0003 g of a 50% aqueous solution of C 5 F 11 COONH 4 The temperature is adjusted to 80 ° C. while stirring at 600 rpm, and VdF is forced to 1.21 MPa while the molar ratio of VdF to 1234yf is 77.4 / 22.6. The mixed solution monomer of the above was pressed to 1.47 MPa.
  • the Tg of the resulting polymer was determined to be ⁇ 13.5 ° C. by DSC. Also, the heat of fusion was not observed in the second run.
  • the number average molecular weight (Mn) was 153,000
  • the weight average molecular weight (Mw) was 392000
  • Mw / Mn was 2.56.
  • Comparative example 4 In a 100 ml stainless steel (SUS) autoclave, 40 ml of dichloropentafluoropropane (R-225) is charged, cooled to dry ice temperature, and di- (2,2,3,3,4,4,5,5,6,6, A solution of 1.31 g of a perfluorohexane solution containing 8 wt% of 6,7,7-dodecafluoroheptanoyl peroxide is quickly charged, cooled to dry ice temperature, and purged with nitrogen, then 0.2 g of 1234yf and 1 of TFE are added. 0 g of 13.0 g of VdF was charged and shaken at 25 ° C. for 2.0 hours using a shaker.
  • SUS stainless steel
  • the obtained colorless and transparent solution was dried to obtain 1.5 g of a colorless and transparent polymer.
  • the obtained polymer contained 1234yf, VdF and TFE in a molar ratio of 27/68/5.
  • the Tg of the resulting polymer was determined to be ⁇ 12.3 ° C. by DSC. Moreover, the melting peak was not confirmed. Mn was 29000, Mw was 47000, and Mw / Mn was 1.6.
  • the polymers obtained in Examples 1 and 2 exhibit good cold resistance even when copolymerized with TFE having a homopolymer Tg higher than 1234yf, and have a Tg equivalent to that of a binary fluororubber (fluororubber A). It shows.
  • crosslinkable compositions 1 to 6 having the compositions shown in Table 2 were produced.
  • the crosslinkable composition was prepared by mixing each raw rubber and the additive in the required amount using an 8-inch oven roll in the usual manner.
  • Vulcanization characteristics are determined by RUBBER PROCESS ANALYZER RPA 2000 (manufactured by Alpha Technologies Acquisition Corporation) according to JIS K 6300-2, minimum torque (ML), maximum torque (MH), induction time (T10) and optimum vulcanization time (T90). Was measured. The results are shown in Table 3.
  • the fluorine-containing elastomer of the present invention, the crosslinkable composition of the present invention containing the fluorine-containing elastomer and a crosslinking agent, and a crosslinked rubber molded article obtained by crosslinking the composition are used in the automobile industry, aircraft industry, semiconductor industry Etc. can be suitably used as various parts in various industrial fields such as.

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Abstract

L'invention a pour objet de fournir un élastomère contenant du fluor non cristallin qui présente une excellente résistance aux amines et au froid. Plus précisément, l'invention concerne un élastomère contenant du fluor non cristallin qui est caractéristique en ce qu'il consiste en un copolymère contenant une unité fluorure de vinylidène, une unité de monomère contenant du fluor (1) représentée par la formule générale (1) ＣＨ２＝ＣＦＲｆ（１） (Dans la formule, Ｒｆ représente un groupe fluoroalkyle à chaîne droite ou ramifié de 1 à 12 atomes de carbone.), et une unité tétrafluoroéthylène, le rapport molaire unité fluorure de vinylidène / unité de monomère contenant du fluor (1) / unité tétrafluoroéthylène satisfaisant （８５～７５）／（２３～１３）／（０,１～６）, et en ce que sa température de transition vitreuse est inférieure ou égale à -5°C.
PCT/JP2018/036701 2017-10-19 2018-10-01 Élastomère contenant du fluor, composition réticulable, et article moulé en caoutchouc réticulé Ceased WO2019077986A1 (fr)

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CN116034131A (zh) * 2020-09-18 2023-04-28 大金工业株式会社 氟橡胶交联用组合物和成型品
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CN116034131B (zh) * 2020-09-18 2023-10-10 大金工业株式会社 氟橡胶交联用组合物和成型品

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