WO2015178309A1 - Fluorine rubber composition and fluorine rubber molded article - Google Patents

Fluorine rubber composition and fluorine rubber molded article Download PDF

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Publication number
WO2015178309A1
WO2015178309A1 PCT/JP2015/064031 JP2015064031W WO2015178309A1 WO 2015178309 A1 WO2015178309 A1 WO 2015178309A1 JP 2015064031 W JP2015064031 W JP 2015064031W WO 2015178309 A1 WO2015178309 A1 WO 2015178309A1
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fluororubber
seals
rubber
oil
crosslinking
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PCT/JP2015/064031
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French (fr)
Japanese (ja)
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一良 川崎
北市　雅紀
Yutaka UETA (植田 豊)
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ダイキン工業株式会社
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Publication of WO2015178309A1 publication Critical patent/WO2015178309A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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

Definitions

  • the present invention relates to a fluororubber composition containing fluororubber, lamp black and a crosslinking agent, and a fluororubber molded product obtained therefrom.
  • Fluoro rubber is used in various applications because of its excellent properties such as heat resistance, oil resistance, and chemical resistance. Depending on the application, high mechanical properties are required, so carbon black is added to fluororubber to improve mechanical strength.
  • Patent Document 1 describes a fluororubber composition comprising fluororubber and carbon black, and the carbon adsorption has a nitrogen adsorption specific surface area (N 2 SA) of 25 m 2 / g or more and 180 m 2 / g.
  • N 2 SA nitrogen adsorption specific surface area
  • DBP dibutyl phthalate
  • Patent Document 2 discloses a copolymer comprising 35 to 60 mol% of ethylene structural units, 25 to 50 mol% of hexafluoropropylene structural units, and 0 to 15 mol% of structural units derived from monomers copolymerizable therewith.
  • An elastomer vulcanizate useful as an oil sealant having excellent properties is described, and examples of fillers include carbon black and lamp black.
  • Patent Document 3 discloses an ethylene-hexafluoropropylene elastomer composition
  • an ethylene-hexafluoropropylene elastomer composition comprising an ethylene-hexafluoropropylene elastomer, a peroxide vulcanizing agent, and a vulcanization aid capable of generating a substituted or unsubstituted benzoyloxy radical.
  • the filler include carbon black and lamp black.
  • Patent Document 4 describes an elastomer composition containing a rubber polymer, a silane-modified inorganic additive having a pH> 7, and an acid acceptor.
  • Carbon black is described as an additional filler, which is prepared by the lamp black method, furnace black method or gas black method, and preferably BET (DIN 66 131 within the range of 20 to 200 m 2 / g. ) It has a specific surface area and is described as SAF, ISAF, HAF, FEF, GPF carbon black or the like.
  • the present invention provides a fluororubber molded article having hardness equivalent to that of a conventional product and exhibiting excellent tear strength, compression set, and tensile stress at cutting at high temperature.
  • An object of the present invention is to provide a fluororubber composition that can be used.
  • the present invention is a fluororubber composition
  • a fluororubber composition comprising fluororubber, lamp black, and a crosslinking agent.
  • the fluororubber composition of the present invention preferably contains 5 to 70 parts by mass of lamp black with respect to 100 parts by mass of the fluororubber.
  • Fluoro rubbers are vinylidene fluoride fluoro rubber, tetrafluoroethylene / propylene fluoro rubber, tetrafluoroethylene / propylene / vinylidene fluoride fluoro rubber, ethylene / hexafluoropropylene fluoro rubber, ethylene / hexafluoropropylene / vinylidene fluoride. It is preferably at least one selected from the group consisting of a ride type fluororubber and an ethylene / hexafluoropropylene / tetrafluoroethylene type fluororubber.
  • the present invention is also a fluororubber molded product obtained from the above fluororubber composition.
  • the fluororubber composition of the present invention has the above-described configuration, it has the same hardness as a conventional product by molding and crosslinking, and has excellent tear strength, compression set and high temperature. A fluororubber molded article exhibiting a tensile stress during cutting can be obtained.
  • the fluororubber molded product of the present invention has a hardness equivalent to that of a conventional product and exhibits excellent tear strength, compression set, and tensile stress at cutting at high temperatures.
  • the fluororubber composition of the present invention contains fluororubber, lamp black, and a crosslinking agent.
  • Lamp black is what is called oil smoke, which has been produced as a colorant for ink, ink, paper, etc. for a long time.
  • a method for producing lamp black a channel method, a dish cooking method, a platter cooking method, and the like are known. Specifically, an aromatic oil such as naphthalene oil is placed in a shallow open dish and sealed indoors. There is a method in which air is supplied and burned, and lamp black is settled and recovered from the generated smoke.
  • the characteristics of the lamp black are that it varies depending on the amount of air supplied at the time of manufacture, but has a fine thermal class particle size, a developed aggregation structure, and a highly acidic surface.
  • the lamp black preferably has a nitrogen adsorption specific surface area (N 2 SA) of 1 m 2 / g or more and 80 m 2 / g or less.
  • the lamp black preferably has a dibutyl phthalate (DBP) oil absorption of 40 ml / 100 g or more and 180 ml / 100 g or less.
  • the lamp black is obtained by dividing the dibutyl phthalate (DBP) oil absorption (ml / 100 g) by the nitrogen adsorption specific surface area (N 2 SA) (m 2 / g) (hereinafter sometimes referred to as A value). Is preferably 3.0 or more and 8.0 or less.
  • the lamp black characterized by the nitrogen adsorption specific surface area (N 2 SA) and dibutyl phthalate (DBP) oil absorption is generally used as a black pigment, and the use as a rubber reinforcing agent is ethylene / propylene. / There are blending examples with diene rubber, but there is no blending example with fluororubber.
  • the nitrogen adsorption specific surface area (N 2 SA) is preferably not less than 1 m 2 / g, more preferably at least 10 m 2 / g, more 15 m 2 / g is particularly preferred.
  • the upper limit is preferably 80 m 2 / g or less from the viewpoint of easy availability, and if the nitrogen adsorption specific surface area (N 2 SA) is too large, the compression set characteristic of the obtained fluororubber molded product may be deteriorated.
  • N 2 SA nitrogen adsorption specific surface area
  • the dibutyl phthalate (DBP) oil absorption is preferably 40 ml / 100 g or more, more preferably 60 ml / 100 g or more, still more preferably 80 ml / 100 g or more, and even more preferably 100 ml / 100 g or more.
  • the upper limit is preferably 180 ml / 100 g, more preferably 140 ml / 100 g, and still more preferably 120 ml / 100 g.
  • the dibutyl phthalate (DBP) oil absorption can be measured by the method described in JIS K6217-4: 2008.
  • the lamp black has the above-mentioned dibutyl phthalate (DBP) oil absorption (ml / 100 g) from the point that a fluororubber molded article having excellent tear strength, compression set, and tensile stress at cutting at high temperature can be obtained.
  • the value (A value) obtained by dividing the above by the nitrogen adsorption specific surface area (N 2 SA) (m 2 / g) is preferably 3.0 to 8.0, and more preferably 3.5 to 7.0. More preferably, it is 3.5 to 5.0.
  • lamp black having the specific nitrogen adsorption specific surface area (N 2 SA) and dibutyl phthalate (DBP) oil absorption described above
  • the lamp black preferably has an average primary particle size of 10 to 300 nm, more preferably 80 nm or more, more preferably 150 nm or less, and still more preferably 110 nm or less.
  • the average primary particle size was determined by obtaining an enlarged aggregate image according to the procedure described in “ASTM D3849-Carbon Black Standard Test Method-Morphological Characterization by Electron Microscopy”. It can be calculated by measuring the diameter of 000 particles and determining the average value.
  • the fluororubber composition of the present invention preferably contains 5 to 70 parts by mass of lamp black with respect to 100 parts by mass of the fluororubber.
  • the content of lamp black is more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, more preferably 60 parts by mass or less, and further preferably 55 parts by mass or less. . If the amount of lamp black is too small, there is a possibility that a fluororubber molded product having excellent tear strength, compression set and tensile stress at cutting at high temperature cannot be obtained. If the amount of lamp black is too large, the content is commensurate with the content. May not be obtained, or the flexibility expected of fluororubber may be impaired.
  • the fluoro rubber may be a partially fluorinated rubber or a perfluoro rubber.
  • Partially fluorinated rubbers include vinylidene fluoride (VdF) fluorine rubber, tetrafluoroethylene (TFE) / propylene (Pr) fluorine rubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) fluorine rubber.
  • the vinylidene fluoride-based fluororubber is preferably a copolymer comprising 25 to 85 mol% of vinylidene fluoride and 75 to 15 mol% of at least one other monomer copolymerizable with vinylidene fluoride. . More preferably, it is a copolymer comprising 45 to 80 mol% of vinylidene fluoride and 55 to 20 mol% of at least one other monomer copolymerizable with vinylidene fluoride.
  • TFE tetrafluoroethylene
  • HFP hexafluor
  • Monomers monomers ethylene, propylene, and a non-fluorinated monomer such as an alkyl vinyl ether. These can be used alone or in any combination. Among these, it is preferable to use at least one selected from the group consisting of TFE, HFP, fluoroalkyl vinyl ether and CTFE.
  • the fluororubber may be a copolymer containing a monomer that provides a crosslinking site.
  • a monomer that gives a crosslinking site Formula (4):
  • CY 1 2 CY 2 R f 2 X 3 (4)
  • Y 1 and Y 2 are a fluorine atom, a hydrogen atom or —CH 3 ;
  • R f 2 may have one or more ether-bonded oxygen atoms, and may have an aromatic ring.
  • X 3 is an iodine atom or a bromine atom
  • Linear or branched fluorine-containing alkylene group that is, a linear or branched fluorine-containing alkylene group in which some or all of the hydrogen atoms are substituted with fluorine atoms, and part or all of the hydrogen atoms are fluorine a linear or branched fluorine-containing oxyalkylene group substituted with atoms or a fluorine-containing polyoxyalkylene group partially or entirely a linear or branched substituted with fluorine atoms of the hydrogen atom,;
  • R 1 is Hydrogen atom or methyl group
  • CY 4 2 CY 4 (CF 2 ) n -X 3 (6)
  • Y 4 is the same or different and is a hydrogen atom or a fluorine atom, and n is an integer of 1 to 8.
  • CF 2 CFCF 2 R f 4 -X 3 (7) (Where
  • CF 2 CFCF 2 (OCF (CF 3 ) CF 2 ) m (OCH 2 CF 2 CF 2 ) n OCH 2 CF 2 —X 3 (8)
  • m is an integer of 0 to 5, and n is an integer of 0 to 5)
  • CF 2 CFCF 2 (OCH 2 CF 2 CF 2 ) m (OCF (CF 3 ) CF 2 ) n OCF (CF 3 ) -X 3 (9)
  • m is an integer of 0 to 5, and n is an integer of 0 to 5) CF 2 ⁇ CF (OCF 2 CF (CF 3 )) m O (CF 2 ) n —X 3 (10)
  • CF 2 CF (OCF 2 CF (CF 3 )) m -X 3 (11) (Where m is an integer is an integer from 0 to 8)
  • Preferred examples include iodine-containing fluorinated vinyl ethers represented by:
  • ICH 2 CF 2 CF 2 OCF ⁇ CF 2 is preferable among these. More specifically, preferred examples of the iodine-containing monomer or bromine-containing monomer represented by the formula (6) include ICF 2 CF 2 CF ⁇ CH 2 and I (CF 2 CF 2 ) 2 CF ⁇ CH 2 . More specifically, the iodine-containing monomer or bromine-containing monomer represented by the formula (10) is preferably I (CF 2 CF 2 ) 2 OCF ⁇ CF 2 . More specifically, preferred examples of the iodine-containing monomer or bromine-containing monomer represented by the formula (23) include CH 2 ⁇ CHCF 2 CF 2 I and I (CF 2 CF 2 ) 2 CH ⁇ CH 2 .
  • R 2 R 3 C ⁇ CR 4 —Z—CR 5 CR 6 R 7 (Wherein R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different, and all are H or an alkyl group having 1 to 5 carbon atoms; Z is linear (linear ) Or a branched, optionally containing oxygen atom, preferably an at least partially fluorinated alkylene or cycloalkylene group having 1 to 18 carbon atoms, or (per) fluoropolyoxyalkylene group) Bisolefin compounds are also preferred as monomers that provide a crosslinking site.
  • Z is preferably a (per) fluoroalkylene group having 4 to 12 carbon atoms, and R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are preferably hydrogen atoms.
  • Z is a (per) fluoropolyoxyalkylene group, - (Q) p -CF 2 O- (CF 2 CF 2 O) m - (CF 2 O) n -CF 2 - (Q) p - (In the formula, Q is an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having 2 to 10 carbon atoms, p is 0 or 1, and m and n have an m / n ratio of 0.2 to 5.
  • the (per) fluoropolyoxyalkylene group is preferably an integer such that the molecular weight of the (per) fluoropolyoxyalkylene group is in the range of 500 to 10,000, preferably 1000 to 4000.
  • Preferred bisolefins are CH 2 ⁇ CH— (CF 2 ) 4 —CH ⁇ CH 2 , CH 2 ⁇ CH— (CF 2 ) 6 —CH ⁇ CH 2 , Formula: CH 2 ⁇ CH—Z 1 —CH ⁇ CH 2 (Wherein Z 1 is —CH 2 OCH 2 —CF 2 O— (CF 2 CF 2 O) m — (CF 2 O) n —CF 2 —CH 2 OCH 2 — (m / n is 0.5)) ) Etc.
  • VdF / HFP rubber VdF / HFP / TFE rubber
  • VdF / CTFE rubber VdF / CTFE / TFE rubber
  • VdF / general formula (1) Fluoromonomer rubber, VdF / fluoromonomer / TFE rubber represented by the general formula (1), VdF / perfluoro (methyl vinyl ether) (PMVE) rubber, VdF / PMVE / TFE rubber, VdF / PMVE / Examples include TFE / HFP rubber.
  • the tetrafluoroethylene / propylene-based fluororubber is preferably a copolymer composed of 45 to 70 mol% of tetrafluoroethylene, 55 to 30 mol% of propylene, and 0 to 5 mol% of a fluoromonomer providing a crosslinking site. .
  • the fluoro rubber may be perfluoro rubber.
  • TFE / General formula (5): CF 2 CFO (CF 2 CF (Y) O) m (CF 2 ) n F (Wherein Y represents a fluorine atom or a trifluoromethyl group, m is an integer of 1 to 4, and n is an integer of 1 to 4) and TFE / general Formula (3), (4 Or (5) at least one member selected from the group consisting of monomer copolymer providing a fluoromonomer / crosslinking moiety represented by is preferable.
  • the composition is preferably 45 to 90/10 to 55 (mol%), more preferably 55 to 80/20 to 45, and still more preferably 55 to 70/30 to 45.
  • a monomer copolymer that provides a TFE / PMVE / cross-linking site it is preferably 45 to 89.9 / 10 to 54.9 / 0.01 to 4 (mol%), and more preferably 55 to 77. It is 9/20 to 49.9 / 0.1 to 3.5, and more preferably 55 to 69.8 / 30 to 44.8 / 0.2 to 3.
  • the fluoromonomer copolymer represented by the general formula (3), (4) or (5) having 4 to 12 TFE / carbon it is preferably 50 to 90/10 to 50 (mol%). More preferably, it is 60 to 88/12 to 40, and still more preferably 65 to 85/15 to 35.
  • the composition is out of the range, the properties as a rubber elastic body are lost, and the properties tend to be similar to those of a resin.
  • perfluoro rubber examples include TFE / fluoromonomer represented by the general formula (5) / fluoromonomer copolymer that gives a crosslinking site, TFE / perfluorovinyl ether copolymer represented by the general formula (5), and TFE. / At least one selected from the group consisting of a fluoromonomer copolymer represented by the general formula (3) and a TFE / fluoromonomer represented by the general formula (3) / a monomer copolymer that gives a crosslinking site It is preferable that
  • perfluoro rubber examples include perfluoro rubbers described in International Publication No. 97/24381, Japanese Patent Publication No. 61-57324, Japanese Patent Publication No. 4-81608, Japanese Patent Publication No. 5-13961, and the like. Can do.
  • the fluororubber preferably has a glass transition temperature of ⁇ 70 ° C. or higher, more preferably ⁇ 60 ° C. or higher, and still more preferably ⁇ 50 ° C. or higher from the viewpoint of excellent compression set at high temperatures. . Further, from the viewpoint of good cold resistance, it is preferably 5 ° C. or lower, more preferably 0 ° C. or lower, and further preferably ⁇ 3 ° C. or lower.
  • the glass transition temperature is obtained by using a differential scanning calorimeter (Mettler Toledo, DSC822e) to obtain a DSC curve by raising the temperature of 10 mg of the sample at 10 ° C./min. It can be determined as the temperature indicating the midpoint of the two intersections of the extension of the line and the tangent at the inflection point of the DSC curve.
  • the fluororubber preferably has a Mooney viscosity ML (1 + 20) at 170 ° C. of 30 or more, more preferably 40 or more, and still more preferably 50 or more, from the viewpoint of good heat resistance. Further, in terms of good workability, it is preferably 150 or less, more preferably 120 or less, and even more preferably 110 or less.
  • the fluororubber preferably has a Mooney viscosity ML (1 + 20) at 140 ° C. of 30 or more, more preferably 40 or more, and still more preferably 50 or more from the viewpoint of good heat resistance. Moreover, it is preferable that it is 180 or less at a point with favorable workability, It is more preferable that it is 150 or less, It is still more preferable that it is 110 or less.
  • the fluororubber preferably has a Mooney viscosity ML (1 + 10) at 100 ° C. of 10 or more, more preferably 20 or more, and still more preferably 30 or more from the viewpoint of good heat resistance. Further, in terms of good workability, it is preferably 120 or less, more preferably 100 or less, and still more preferably 80 or less.
  • crosslinking agent and crosslinking method The amount of the above crosslinking agent is preferably 0.3 to 10 parts by mass, more preferably 0.4 to 5 parts by mass, and still more preferably 0 to 100 parts by mass of the fluororubber. 4 to 3 parts by mass. If the cross-linking agent is less than 0.3 parts by mass, the degree of cross-linking will be insufficient, and the performance of the fluororubber molded product will tend to be impaired. In addition to being long, it tends to be economically undesirable.
  • the crosslinking agent is not particularly limited as long as it is a crosslinking agent usually 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. Preferably it is a seed.
  • polyamine compound examples include hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexamethylenediamine, and 4,4′-bis (aminocyclohexyl) methanecarbamate.
  • N, N′-dicinnamylidene-1,6-hexamethylenediamine is preferable.
  • a polyhydroxy aromatic compound is used suitably 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)
  • resorcin 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-Bis (4-hydroxyphenyl) Tetrafluorodichloropropane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphen
  • the fluororubber composition of the present invention preferably contains a crosslinking accelerator.
  • a crosslinking accelerator accelerates
  • crosslinking accelerator examples include onium compounds.
  • onium compounds ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, and 1 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.
  • tetrabutylphosphonium chloride benzyltriphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyltributylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl. -2-Methoxypropylphosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride, and the like.
  • BTPPC benzyltriphenylphosphonium chloride
  • BTPPC benzyltriphenylphosphonium chloride
  • crosslinking accelerator a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, or a chlorine-free crosslinking accelerator disclosed in JP-A-11-147891 can be used.
  • the blending amount of the crosslinking accelerator is preferably 0.1 to 5 parts by mass, more preferably 0.15 to 3 parts by mass with respect to 100 parts by mass of the fluororubber. If the cross-linking accelerator is less than 0.1 parts by mass, the cross-linking of the fluororubber does not proceed sufficiently, and the heat resistance and oil resistance of the resulting fluororubber molded product tend to decrease, exceeding 5 parts by mass. And there exists a tendency for the moldability of a fluororubber composition to fall.
  • the organic peroxide may be an organic peroxide that can easily generate radicals in the presence of heat or a redox system.
  • 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 are preferable.
  • the fluororubber composition of the present invention preferably contains a crosslinking aid.
  • crosslinking aids include triallyl cyanurate, trimethallyl isocyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N, N′-m-phenylenebismaleimide, dipropargyl.
  • the blending amount of the crosslinking aid is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass with respect to 100 parts by mass of the fluororubber.
  • amount of the crosslinking aid is less than 0.1 parts by mass, the compression set of the fluororubber molded product tends to decrease, and when it exceeds 10 parts by mass, the elongation of the fluororubber molded product tends to decrease remarkably.
  • the fluororubber composition of the present invention preferably contains an acid acceptor.
  • the acid acceptor include metal oxides such as magnesium oxide, calcium oxide, bismuth oxide, and zinc oxide, metal hydroxides such as calcium hydroxide, synthetic hydrotalcites, and sodium metasilicate.
  • the compounding amount of the acid acceptor is preferably 0.5 to 30 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the fluororubber.
  • amount of the acid acceptor is less than 0.5 parts by mass, the crosslinking time tends to be too long to be practically used, and when it exceeds 30 parts by mass, the compression set of the fluororubber molded product also tends to decrease.
  • the fluororubber composition of this invention may contain an acid acceptor in the range which does not affect the effect of this invention.
  • Crosslinking may be appropriately determined depending on the type of the crosslinking agent used, but is usually fired at a temperature of 140 to 300 ° C. for 1 minute to 24 hours. Moreover, it can bridge
  • the cross-linking method is not particularly limited, and a steam cross-linking method, a pressure forming method, a normal method in which a cross-linking reaction is started by heating can be adopted, and a radiation cross-linking method at normal temperature and normal pressure may be used.
  • a post-treatment step called secondary crosslinking may be performed.
  • Polyamine crosslinking using a polyamine compound as a crosslinking agent can be carried out in the same manner as before.
  • a method in which the fluororubber and the cross-linking agent in the present invention, if necessary, a cross-linking accelerator, and other additives that can be mixed as appropriate are roll-kneaded and then put into a mold and pressurized to perform primary cross-linking and then secondary cross-linking Is mentioned.
  • primary crosslinking conditions are employed at a temperature of 130 to 200 ° C., a time of 1 to 120 minutes, and a pressure of about 2 to 15 MPa.
  • Secondary crosslinking conditions are a temperature of 150 to 300 ° C. and a time of 30 minutes to 30 hours. Adopted from a range of degrees.
  • Polyol crosslinking using a polyhydroxy compound as a crosslinking agent can be carried out in the same manner as before.
  • a method in which the fluororubber and the cross-linking agent in the present invention, if necessary, a cross-linking accelerator, and other additives that can be mixed as appropriate are roll-kneaded and then put into a mold and pressurized to perform primary cross-linking and then secondary cross-linking Is mentioned.
  • an internal mixer, a Banbury mixer or the like can be preferably used.
  • primary crosslinking can be performed at 2 to 15 MPa at 130 to 200 ° C. for 1 to 60 minutes
  • secondary crosslinking can be performed at 150 to 300 ° C. for 30 minutes to 30 hours.
  • Peroxide crosslinking using an organic peroxide as a crosslinking agent can be carried out in the same manner as before.
  • a method in which the fluororubber and the cross-linking agent in the present invention, if necessary, a cross-linking accelerator, and other additives that can be mixed as appropriate are roll-kneaded and then put into a mold and pressurized to perform primary cross-linking and then secondary cross-linking Is mentioned.
  • primary crosslinking can be performed at 2 to 15 MPa at 130 to 200 ° C. for 1 to 60 minutes
  • secondary crosslinking can be performed at 150 to 300 ° C. for 30 minutes to 30 hours.
  • the fluororubber composition of the present invention preferably contains a filler.
  • Fillers include metal oxides such as titanium oxide and aluminum oxide; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; carbonates such as magnesium carbonate, aluminum carbonate, calcium carbonate and barium carbonate; magnesium silicate, Silicates such as calcium silicate and aluminum silicate; sulfates such as aluminum sulfate, calcium sulfate and barium sulfate; metal sulfides such as molybdenum disulfide, iron sulfide and copper sulfide; diatomaceous earth, asbestos and lithopone (sulfurized) Zinc / barium sulfide), graphite, carbon black (excluding lamp black), carbon fluoride, calcium fluoride, coke, quartz fine powder, zinc white, talc, mica powder, wollastonite, carbon fiber, aramid fiber, various Whisker, glass fiber, organic reinforcing agent, organic filler Polyte
  • the fluororubber composition of the present invention preferably contains a plasticizer.
  • the plasticizer include dioctyl phthalic acid and pentaerythritol.
  • the fluororubber composition of the present invention preferably contains a processing aid.
  • processing aids higher fatty acids such as stearic acid, oleic acid, palmitic acid and lauric acid; higher fatty acid salts such as sodium stearate and zinc stearate; higher fatty acid amides such as stearic acid amide and oleic acid amide; oleic acid Higher fatty acid esters such as ethyl; fatty acid diesters such as di-n-octyl sebacate, di-n-butyl sebacate and bis-2-ethylhexyl sebacate; higher aliphatic amines such as stearylamine and oleylamine; stearyl alcohol and the like Higher aliphatic alcohols; petroleum waxes such as carnauba wax and ceresin wax; polyglycols such as ethylene glycol, glycerin and diethylene glycol; aliphatic hydrocarbons such as petroleum jelly and par
  • the fluororubber composition of the present invention comprises a release agent, pigment, flame retardant, lubricant, light stabilizer, weathering stabilizer, antistatic agent, ultraviolet absorber, antioxidant, foaming agent, perfume, oil, and softening agent. Etc. may be included within a range that does not affect the effects of the present invention.
  • the fluororubber composition of the present invention may contain another polymer different from the fluororubber in the present invention.
  • the other polymer include nitrile rubber, acrylic rubber, epichlorohydrin rubber, fluorosilicone rubber, silicone rubber, and fluorine-containing thermoplastic elastomer.
  • the fluororubber composition of the present invention is obtained by kneading at least fluororubber, lamp black, a crosslinking agent, and the above-mentioned crosslinking accelerator, if desired. Is preferred.
  • an open roll a Banbury mixer, a pressure kneader, an extruder or the like can be used, but an extruder such as a pressure kneader or a twin screw extruder can be used in that a high shear force can be applied. preferable.
  • the fluororubber composition of this invention can be manufactured by the method etc. which are described in international publication 2012/026007, international publication 2012/026534, and international publication 2012/026552.
  • a predetermined amount of fluororubber, lamp black, a filler as required, and an acid acceptor as required are put into a closed kneader, and the average shear rate of the rotor is 50 to 1000 (1 / second), preferably 100 to A method of kneading under the condition that the maximum temperature Tm of the kneading temperature is 80 to 220 ° C. (preferably 120 to 200 ° C.) by adjusting to 1000 (1 / sec), more preferably 200 to 1000 (1 / sec) ( That is, it is preferable that the maximum temperature Tm of the kneaded material during kneading is 80 ° C.
  • the closed kneader examples include a pressure kneader, a Banbury mixer, a uniaxial kneader, and a biaxial kneader.
  • a predetermined amount of fluororubber, lamp black, a filler as required, and an acid acceptor as required are put into a roll kneader, and the average shear rate of the rotor is 50 (1 / second) or more, and the maximum kneading temperature Tm Kneading under the conditions of 80 to 220 ° C (preferably 120 to 200 ° C).
  • composition obtained by the above methods (1) and (2) does not contain a crosslinking agent (and / or a crosslinking aid) or a crosslinking accelerator. Moreover, you may perform kneading
  • the second and subsequent kneading conditions may be the same as the methods (1) and (2) except that the maximum temperature Tm of the kneading temperature is 140 ° C. or lower.
  • One of the methods for preparing the fluororubber composition of the present invention is obtained, for example, by the above methods (1) and (2) or by repeating the above methods (1) and (2) a plurality of times.
  • a cross-linking agent (and / or a cross-linking aid) and a cross-linking accelerator are further added to the composition and kneaded.
  • the crosslinking agent (and / or crosslinking aid) and the crosslinking accelerator may be blended and kneaded at the same time. First, the crosslinking accelerator is blended and kneaded, and then the crosslinking agent (and / or crosslinking aid) is blended and kneaded. Also good.
  • the kneading conditions for the cross-linking agent (and / or the cross-linking aid) and the cross-linking accelerator may be the same conditions as the methods (1) and (2) except that the maximum temperature Tm of the kneading temperature is 130 ° C. or less.
  • Another method for preparing the fluororubber composition of the present invention is, for example, using a roll kneader in an appropriate sequence of fluororubber, lamp black, optionally filler, crosslinking agent (and / or crosslinking aid) and optionally crosslinking accelerator. And a kneading method under the condition that the average shear rate of the rotor is 50 (1 / second) or more and the maximum kneading temperature Tm is 130 ° C. or less.
  • a uniform dispersion obtained by previously mixing fluororubber, a cross-linking agent, and a cross-linking accelerator may be used.
  • fluororubber, polyol-based crosslinking agent and crosslinking accelerator are first kneaded, then lamp black and filler are blended and kneaded, and the maximum temperature Tm of the kneading temperature is set to 80 to 220 ° C.
  • an acid acceptor is blended and kneaded so that the maximum temperature Tm of the kneading temperature is 130 ° C. or less.
  • the present invention is also a fluororubber molded product obtained by crosslinking the fluororubber composition of the present invention.
  • the fluororubber molded article of the present invention can be produced by molding the fluororubber composition of the present invention and crosslinking the resulting molded article, or by simultaneously performing molding and crosslinking. it can. Moreover, it can also be obtained as a coating film by coating and crosslinking the crosslinkable composition.
  • the molding method is not particularly limited, and examples thereof include compression molding, extrusion molding, transfer molding, and injection molding.
  • the fluororubber molded article of the present invention may have an unprecedented characteristic that the tensile stress at cutting at 200 ° C. exceeds 9 MPa.
  • the fluororubber molded products of the present invention have excellent heat resistance, oil resistance, amine resistance, chemical resistance and cold resistance, and can slide in contact with other materials. It is generally used for parts for sealing and sealing other materials and substances, and for the purpose of vibration proofing and sound proofing, and can be used as various parts in various fields such as the automobile industry, aircraft industry, and semiconductor industry. Fields used include, for example, semiconductor-related fields, automotive fields, aircraft fields, space / rocket fields, ship fields, chemical fields such as chemical plants, pharmaceutical fields such as pharmaceuticals, photographic fields such as developing machines, printing machines, etc.
  • Printing field such as coating equipment, analysis equipment, analysis / physical machinery field such as instruments, food equipment field including food plant equipment and household goods, beverage food production equipment field, pharmaceutical production equipment field, medical parts field, chemical Chemical transportation equipment field, nuclear plant equipment field, steel field such as iron plate processing equipment, general industrial field, electrical field, fuel cell field, electronic parts field, optical equipment parts field, space equipment parts field, petrochemical plant equipment field Oil, gas and other energy resource exploration equipment parts field, oil refining field, oil transportation equipment parts field.
  • Examples of usage forms of the fluororubber molded product of the present invention include, for example, a ring, packing, gasket, diaphragm, oil seal, bearing seal, lip seal, plunger seal, door seal, lip and face seal, gas delivery plate seal, and wafer support.
  • Examples include various sealing materials such as seals and barrel seals, and packing.
  • As a sealing material it can be used for applications requiring heat resistance, solvent resistance, chemical resistance, and non-adhesiveness.
  • the cross-sectional shapes of the ring, packing, and seal may be various shapes.
  • the ring, the packing, and the seal may have a square shape, an O shape, a ferrule shape, a D shape, Different shapes such as L, T, V, X, Y may be used.
  • semiconductor manufacturing apparatus liquid crystal panel manufacturing apparatus, plasma panel manufacturing apparatus, plasma display panel manufacturing apparatus, plasma address 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.
  • examples of such an apparatus include a gas control apparatus such as a CVD apparatus and a semiconductor gas control apparatus, a dry etching apparatus, a wet etching apparatus, a plasma etching apparatus, a reactive ion etching apparatus, a reactive ion beam etching apparatus, and a sputter etching.
  • Apparatus ion beam etching apparatus, oxidation diffusion 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 device, Soxhlet extraction cleaning device, high temperature high pressure extraction cleaning device, microwave extraction cleaning device, supercritical extraction Cleaning equipment Equipment, cleaning equipment using hydrofluoric acid, hydrochloric acid, sulfuric acid, ozone water, stepper, coater / developer, CMP equipment, excimer laser exposure machine, chemical piping, gas piping, NF 3 plasma treatment, O 2 plasma treatment, fluorine plasma treatment Equipment for plasma processing such as heat treatment film forming equipment, wafer transfer equipment, wafer cleaning equipment, silicon wafer cleaning equipment, silicon wafer processing equipment, equipment used in LP-CVD processes, equipment used in lamp
  • Specific usage forms in the field of semiconductors include, for example, various sealing materials such as gate valves, quartz windows, chambers, chamber lits, gates, bell jars, couplings, pump O-rings and gaskets; resist developers and stripping Various sealing materials such as O-rings for liquid, hoses and tubes; resist developer tank, stripper tank, wafer cleaning liquid tank, wet etching tank lining and coating; pump diaphragm; wafer transfer roll; wafer cleaning liquid Hose tube; Clean equipment sealant for clean equipment such as clean rooms; Sealing material for storage equipment for storing semiconductor manufacturing equipment and wafers; Diaphragm for transferring chemicals used in semiconductor manufacturing processes Can be mentioned.
  • various sealing materials such as gate valves, quartz windows, chambers, chamber lits, gates, bell jars, couplings, pump O-rings and gaskets
  • resist developers and stripping Various sealing materials such as O-rings for liquid, hoses and tubes; resist developer tank, stripper tank, wafer cleaning liquid tank, wet etching
  • the engine body In the automotive 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 electrical components, control It can be used for electrical components such as system electrical components and equipment electrical components.
  • the automobile field includes a motorcycle.
  • the fluororubber molded product of the present invention is used for various sealing materials that require heat resistance, oil resistance, fuel oil resistance, engine cooling antifreeze resistance, and steam resistance.
  • sealing materials include seals such as gaskets, shaft seals, valve stem seals, and non-contact or contact types such as self-seal packing, piston rings, split ring packings, mechanical seals, and oil seals.
  • seals such as gaskets, shaft seals, valve stem seals, and non-contact or contact types such as self-seal packing, piston rings, split ring packings, mechanical seals, and oil seals.
  • Specific usage forms in the above fuel system include fuel injectors, cold start injectors, fuel line quick connectors, sender flange quick connectors, fuel pumps, fuel tank quick connectors, gasoline mixing pumps, gasoline pumps, fuel O-ring used for tube body, fuel tube connector, injector, etc .; exhalation system manifold, fuel filter, pressure regulating valve, canister, fuel tank cap, fuel pump, fuel tank, fuel tank sender unit, fuel Used in injection devices, high-pressure fuel pumps, fuel line connector systems, pump timing control valves, suction control valves, solenoid subassemblies, fuel cut valves, etc.
  • Seals Canister, purge, solenoid, valve seal, on-board, recirculating, 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 (evaporation) 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 in fuel filters, fuel line connector systems, etc.
  • ORVR vapor, recovery
  • Flange gaskets used for carburetors, etc . Line materials such as steam recovery lines, fuel feed lines, vapor / ORVR lines; canisters, ORVR, fuel pumps, fuel tank pressure sensors, gasoline pumps, carburetor sensors, combined air control devices (CAC), pulsation dampers, canisters, diaphragms used for autococks, etc., fuel injector pressure regulator diaphragms; fuel pump valves, carburetor needle valves, rollover check valves, check valves; vents (breathers) ), Tubes used in fuel tanks; tank packings for fuel tanks, accelerating pump piston packings for carburetors; fuel sender anti-vibration parts for fuel tanks; O-ring and diaphragm for controlling fuel pressure; accelerator pump cup; in-tank fuel pump mount; fuel injector injector cushion ring; injector seal ring; carburetor needle valve core valve; carburetor acceleration pump piston A valve seat of a composite air control device (CAC); a fuel tank body; a
  • Specific usage forms in the brake system include: a diaphragm used for a master back, a hydraulic brake hose air brake, a brake chamber of an air brake; a hose used for a brake hose, a brake oil hose, a vacuum brake hose, etc .; an oil seal Various sealing materials such as O-rings, packings, brake piston seals, atmospheric valves and vacuum valves for master backs, check valves for brake valves, piston cups (rubber cups) for master cylinders, brake cups, hydraulic brakes Master cylinders and vacuum boosters, hydraulic brake wheel cylinder boots, anti-lock brake system (ABS) O-rings and grommets.
  • sealing materials such as O-rings, packings, brake piston seals, atmospheric valves and vacuum valves for master backs, check valves for brake valves, piston cups (rubber cups) for master cylinders, brake cups, hydraulic brakes Master cylinders and vacuum boosters, hydraulic brake wheel cylinder boots, anti-lock brake system (ABS) O-rings
  • Specific usage forms of the basic electrical component include an insulator and sheath of an electric wire (harness), a tube of a harness exterior component, a grommet for a connector, and the like.
  • Specific examples of usage in the control system electrical component include coating materials for various sensor wires.
  • Specific usage forms for the above-mentioned electrical components include car air conditioner O-rings, packing, cooler hoses, high pressure air conditioner hoses, air conditioner hoses, gaskets for electronic throttle units, plug plugs for direct ignition, distributor diaphragms, etc. Is mentioned. It can also be used for bonding electrical components.
  • Specific usage forms in the intake / exhaust system include packing used for intake manifolds, exhaust manifolds, etc., throttle body packing of throttles; EGR (exhaust gas recirculation), pressure control (BPT), wastegate, turbo waist Diaphragms used for gates, actuators, variable turbine geometry (VTG) turbo actuators, exhaust purification valves, etc .; EGR (exhaust recirculation) control hoses, emission control hoses, turbocharger turbo oil hoses (supply), turbo Oil hose (return), turbo air hose, intercooler hose, turbocharger hose, hose connected to compressor of turbo engine equipped with intercooler, exhaust Hose such as air hose, air intake hose, turbo hose, DPF (diesel particulate filter) sensor hose; air duct or turbo air duct; intake manifold gasket; EGR seal material, AB valve afterburn prevention valve seat, (turbocharger etc. And a seal member used for groove parts such as a rocker cover and an air
  • seals used for steam recovery canisters, catalytic converters, exhaust gas sensors, oxygen sensors, etc., steam recovery and steam canister solenoid armature seals; intake manifold gaskets, etc. Can do.
  • it can be used as O-ring seals for direct injection injectors, rotary pump seals, control diaphragms, fuel hoses, EGR, priming pumps, boost compensator diaphragms, and the like. It can also be used for O-rings, sealing materials, hoses, tubes, diaphragms used in urea SCR systems, urea water tank bodies of urea SCR systems, and sealing materials for urea water tanks.
  • Transmissions include AT (automatic transmission), MT (manual transmission), CVT (continuously variable transmission), DCT (dual clutch transmission), and the like.
  • oil seals, gaskets, O-rings and packings for manual or automatic transmissions oil seals, gaskets, O-rings and packings for continuously variable transmissions (belt type or toroidal type), ATF linear solenoids Packing, oil hose for manual transmission, ATF hose for automatic transmission, CVTF hose for continuous transmission (belt type or toroidal type), and the like.
  • Specific usage forms in the steering system include a power steering oil hose and a high pressure power steering hose.
  • cylinder head gaskets For example, cylinder head gaskets, cylinder head cover gaskets, oil pan packings, gaskets such as general gaskets, seals such as O-rings, packings, timing belt cover gaskets, control hoses, etc.
  • gaskets such as general gaskets
  • seals such as O-rings, packings, timing belt cover gaskets, control hoses, etc.
  • hoses In a main motion system of an automobile engine, it can be used for a shaft seal such as a crankshaft seal and a camshaft seal.
  • a valve system of an automobile engine it can be used for a valve stem oil seal of an engine valve, a valve seat of a butterfly valve, and the like.
  • engine oil cooler hoses In automotive 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.
  • a vacuum pump oil hose In addition to a vacuum pump oil hose, etc., it can be used for a radiator hose, a radiator tank, an oil pressure diaphragm, a fan coupling seal, and the like.
  • specific examples of use in the automotive field include engine head gaskets, oil pan gaskets, manifold packings, oxygen sensor seals, oxygen sensor bushings, nitrogen oxide (NOx) sensor seals, and nitrogen oxide (NOx).
  • Sensor bushing sulfur oxide sensor seal, temperature sensor seal, temperature sensor bush, diesel particle filter sensor seal, diesel particle filter sensor bush, injector O-ring, injector packing, fuel pump O-ring and diaphragm, gearbox Seal, power piston seal, cylinder liner seal, valve stem seal, static valve stem seal, dynamic valve stem seal, automatic modification Machine front pump seal, rear axle pinion seal, universal joint gasket, speedometer pinion seal, foot brake piston cup, torque transmission device O-ring and oil seal, exhaust gas recombustion device seal and bearing seal, Combustion device hose, carburetor sensor diaphragm, anti-vibration rubber (engine mount, exhaust, muffler hanger, suspension bush, center bearing, strut bumper rubber, etc.), anti-vibration rubber for suspension (strut mount, bush,
  • the fuel system and the lubricating oil system can be used.
  • various types of sealing parts for aircraft various types of aircraft parts for aircraft engine oil, jet engine valve stem seals, gaskets and O-rings, rotating shaft seals, hydraulic equipment gaskets, firewall seals, etc. It can be used as a fuel supply hose, gasket, O-ring, aircraft cable, oil seal, shaft seal, and the like.
  • lip seals for diaphragms, jet engines, missiles, diaphragms, O-rings, O-rings for gas turbine engine oils, anti-vibration stand pads for missile ground control, etc. Can be used.
  • the photographic field such as the developing machine, the printing field such as a printing machine, and the coating field such as a coating facility, it can be used as a roll, a belt, a seal, a valve part, etc. of a dry copying machine.
  • Specific usage forms in the photographic field, printing field, and painting field include a surface layer of a transfer roll of a copying machine, a cleaning blade of a copying machine, a belt of a copying machine; for OA equipment such as a copying machine, a printer, and a facsimile machine.
  • Rolls for example, fixing rolls, pressure rolls, pressure rolls, etc.
  • belts rolls for PPC copiers, roll blades, belts; rolls for film developing machines and X-ray film developing machines; printing rolls for printing machines , Scrapers, tubes, valve parts, belts; printer ink tubes, rolls, belts; coating, painting equipment coating rolls, scrapers, tubes, valve parts; development rolls, gravure rolls, guide rolls, magnetic tape production coating lines Guide rolls, gravure rolls for magnetic tape production coating lines, coating lows And the like.
  • packing, a gasket, a tube, a diaphragm, a hose, a joint sleeve etc. which are used for products, such as alcoholic beverages and soft drinks, a filling apparatus, a food sterilization apparatus, a brewing apparatus, a water heater, various automatic food vending machines, etc. are mentioned.
  • the nuclear plant equipment field it can be used as a check valve, a pressure reducing valve, a seal of a uranium hexafluoride concentrator, etc. around the reactor.
  • Specific usage forms in the general industrial field include: sealing materials for hydraulic equipment such as machine tools, construction machines, hydraulic machines; seals and bearing seals for hydraulic and lubrication machines; sealing materials used for mandrels, etc .; dry cleaning equipment Seals used for windows, etc .; cyclotron seals, (vacuum) valve seals, proton accelerator seals, automatic packaging machine seals, pump diaphragms and snakes for sulfur dioxide and chlorine gas analyzers (pollution measuring instruments) in the air Pump lining, printing press rolls and belts, transport belts (conveyor belts), pickling squeezing rolls such as iron plates, robot cables, solvent squeezing rolls such as aluminum rolling lines, coupler O-rings, acid-resistant cushioning materials , Dust seals and lip rubber on sliding parts of cutting machines, garbage incinerators Basket, friction materials, metal or a surface modifier for rubbers, and the like dressing.
  • gaskets and sealants for equipment used in the papermaking process sealants for clean room filter units, sealants for construction, protective coatings for 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 pre-coated 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 examples of usage in the steel field include iron plate processing rolls for iron plate processing equipment.
  • Specific usage forms in the electrical field include: Shinkansen insulating oil caps, liquid-sealed transformer benching seals, transformer seals, oil well cable jackets, electric furnace oven oven seals, microwave oven window frames, etc. Used for sealing, sealing materials used when bonding CRT wedges and necks, halogen lamp sealing materials, electrical component fixing agents, sheathing heater end treatment sealing materials, electrical equipment lead wire terminals Sealing materials that can be used. Also used for coating materials such as oil and heat resistant wires, high heat resistant wires, chemical resistant wires, high insulating wires, high voltage transmission lines, cables, wires used in geothermal power generation equipment, wires used around automobile engines, etc. You can also. It can also be used for oil seals and shaft seals for vehicle cables.
  • electrical insulating materials for example, insulating spacers for various electrical equipment, insulating tapes used for cable joints and terminals, materials used for heat-shrinkable tubes, etc.
  • electronic equipment 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 can be used also for the sealing layer and protective film (back sheet) of a solar cell.
  • buffer rubber (crash stopper) for hard disk drives binder for electrode active materials for nickel hydride secondary batteries, binder for active materials for lithium ion batteries, polymer electrolyte for lithium secondary batteries, binder for positive electrodes for alkaline storage batteries, EL element (electroluminescent element) binder, capacitor electrode active material binder, sealant, sealing agent, optical fiber quartz coating, optical fiber coating film and sheets, electronic parts, circuit board potting And coating and adhesive seals, electronic component fixing agents, epoxy and other sealant modifiers, printed circuit board coating agents, epoxy and other printed wiring board prepreg resin modifiers, light bulbs and other anti-scattering materials, computer gaskets , Large computer cooling hose, secondary battery, Packing such as gaskets and O- ring for a lithium secondary battery, a sealing layer covering one or both surfaces of the
  • Sealing material sealing material used for rotation blowout prevention device (pipe wiper), sealing material used for MWD (real-time excavation information detection system), gas-liquid connector, logging used for logging equipment (logging equipment) Tool seals (for example, O-rings, seals, packings, gas-liquid connectors, boots, etc.), inflatable packers and completion packers, packer seals used in them, seals and packings used in cementing devices, perforators (perforators) ) Seals, seals used for mud pumps, packing, motor lining, underground detector covers, U cups, composition seating cups, rotating seals, laminated elastomeric bearings, flow control seals, sand control seals, safety valves Seals, hydraulic fracturing equipment (fracturing equipment) seals, linear packer and linear hanger seals and packing, wellhead seals and packing, choke and valve seals and packing, LWD (logging during logging), Diaphragms used in oil exploration and oil drilling applications (for example, diaphragms for supplying lubricating
  • joint seals for kitchens, bathrooms, toilets, etc . outdoor tent pulling cloth; seals for printing materials; rubber heat hoses for gas heat pumps, refractory rubber hoses; agricultural films, linings, weatherproof covers; It can also be used for tanks such as laminated steel plates used in the above.
  • a belt is mentioned as one of the forms of the fluororubber molded product of this invention. The following are illustrated as said belt.
  • Power transmission belts including flat belts, V-belts, V-ribbed belts, toothed belts, etc.
  • conveyor belts conveyor belts
  • the belt may have a single layer structure or a multilayer structure.
  • the belt may be composed of a layer obtained by crosslinking the fluororubber composition of the present invention and a layer made of another material.
  • the layer made of another material include a layer made of other rubber, a layer made of a thermoplastic resin, various fiber reinforcing layers, a canvas, and a metal foil layer.
  • the fluororubber molded article of the present invention can also be used for industrial vibration-proof pads, vibration-proof mats, railway slab mats, pads, automobile vibration-proof rubbers, and the like.
  • Anti-vibration rubbers for automobiles include anti-vibration rubbers for engine mount, motor mount, member mount, strut mount, bush, damper, muffler hanger, and center bearing.
  • joint members such as flexible joints and expansion joints, boots, grommets, and the like. If it is a ship field, a marine pump etc. will be mentioned, for example.
  • a joint member is a joint used for piping and piping equipment. It prevents vibration and noise generated from the piping system, absorbs expansion and contraction due to temperature changes and pressure changes, absorbs dimensional fluctuations, earthquakes, and subsidence. It is used for applications such as mitigating and preventing the effects of Flexible joints and expansion joints are preferably used as complex shaped molded bodies for shipbuilding piping, mechanical piping such as pumps and compressors, chemical plant piping, electrical piping, civil engineering / water supply piping, automobiles, etc. it can.
  • Boots include, for example, constant velocity joint boots, dust covers, rack and pinion steering boots, pin boots, piston boots and other automobile boots, agricultural machinery boots, industrial vehicle boots, building machinery boots, hydraulic machinery boots, empty It can be preferably used as a compact shaped article such as various industrial boots such as pressure machine boots, centralized lubricator boots, liquid transfer boots, fire fighting boots and various liquefied gas transfer boots.
  • the fluorororubber molded article of the present invention can be used for filter press diaphragms, blower diaphragms, water supply diaphragms, liquid storage tank diaphragms, pressure switch diaphragms, accumulator diaphragms, diaphragms for air springs such as suspensions, and the like. .
  • the fluororubber molded product of the present invention is a cushion for hot press molding when manufacturing decorative plywood, printed circuit boards, electrical insulating boards, rigid polyvinyl chloride laminates, etc. made of melamine resin, phenol resin, epoxy resin, etc. It can also be used as a material.
  • the fluororubber 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 oil, mission oil, gear oil, etc.
  • amine additives especially amine additives used as antioxidants and detergent dispersants
  • a vulcanized film may be formed on the fluororubber molded product of the present invention.
  • non-adhesive oil-resistant rolls for copiers, weather strips for weathering and anti-icing, infusion rubber stoppers, vial rubber stoppers, mold release agents, non-adhesive light transport belts, anti-adhesion coatings on automobile engine mount play gaskets, Applications include synthetic fiber coating, bolt members or joints having a thin packing coating layer, and the like.
  • fluororubber molded article of the present invention for automobile-related parts includes parts for motorcycles having the same structure.
  • the fuel for the automobile include light oil, gasoline, diesel engine fuel (including biodiesel fuel), and the like.
  • the fluororubber composition of the present invention can be used as various parts in various industrial fields, besides being crosslinked and used as a fluororubber molded article. Then, next, the use of the fluororubber composition of this invention is demonstrated.
  • the fluororubber composition of the present invention comprises a surface modifying material such as metal, rubber, plastic, and glass; a sealing material that requires heat resistance, chemical resistance, oil resistance, and non-adhesiveness, such as a metal gasket and an oil seal; Coating materials: Non-adhesive coating materials such as rolls for OA equipment, belts for OA equipment, or bleed barriers; Can be used for impregnation of woven fabric sheets and belts and application by baking.
  • the fluorororubber composition of the present invention can be used as a sealing material, lining or sealant with a complicated shape by a normal usage by increasing the viscosity and concentration, and by reducing the viscosity to a thin film of several microns. It can be used to form a film, and can be used to apply pre-coated metal, O-rings, diaphragms, and reed valves by setting the viscosity to medium. Further, it can also be used for coating woven fabrics and paper sheet transport rolls or belts, printing belts, chemical resistant tubes, chemical stoppers, fuel hoses, and the like.
  • Article substrates to be coated with the fluororubber composition of the present invention include metals such as iron, stainless steel, copper, aluminum and brass; glass products such as glass plates, glass fiber woven fabrics and nonwoven fabrics; polypropylene, polyoxy Molded and coated products of general-purpose and heat-resistant resins such as methylene, polyimide, polyamideimide, polysulfone, polyethersulfone, polyetheretherketone; general-purpose rubber such as SBR, butyl rubber, NBR, EPDM, and silicone rubber, fluorine rubber Heat-resistant rubber moldings and coatings such as; natural and synthetic fiber woven and non-woven fabrics; and the like can be used.
  • metals such as iron, stainless steel, copper, aluminum and brass
  • glass products such as glass plates, glass fiber woven fabrics and nonwoven fabrics
  • polypropylene, polyoxy Molded and coated products of general-purpose and heat-resistant resins such as methylene, polyimide, polyamideimide, polysulfone, polyethersulfone,
  • the coating formed from the fluororubber composition of the present invention can be used in fields where heat resistance, solvent resistance, lubricity, and non-adhesiveness are required. Specific applications include copying machines, printers, and facsimiles. Rolls for OA equipment such as fixing rolls, pressure rolls and conveyor belts; sheets and belts; O-rings, diaphragms, chemical resistant tubes, fuel hoses, valve seals, chemical plant gaskets, engine gaskets, etc. Can be mentioned.
  • the fluororubber composition of the present invention can also be dissolved in a solvent and used as a paint or an adhesive. Moreover, it can be used as a coating material as an emulsified dispersion (latex).
  • the above composition is a surface treatment agent for structures composed of various materials, sealing materials for pipes and the like, linings, metals, ceramics, glass, stones, concrete, plastics, rubber, wood, paper, fibers, and other inorganic and organic substrates. Used as etc.
  • the said composition can be apply
  • the fluororubber composition of the present invention may be used as a coating composition for casting films or dipping substrates such as fabrics, plastics, metals, or elastomers.
  • the fluorororubber composition of the present invention in the form of latex, is coated fabric, protective gloves, impregnated fiber, O-ring coating, fuel system quick coupling O-ring coating, fuel system seal coating, fuel tank rollover Manufacture valve diaphragm coating, fuel tank pressure sensor diaphragm coating, oil filter and fuel filter seal coating, fuel tank sender seal and sender head fitting seal coating, copier fuser roll coating, and polymer coating composition May be used for They are useful for coating silicone rubber, nitrile rubber, and other elastomers.
  • the base elastomer For the purpose of increasing both the permeation resistance and chemical resistance of the base elastomer as well as its thermal stability, they are also useful for coating parts made from such elastomers.
  • Other applications include coatings for heat exchangers, expansion joints, bats, tanks, fans, flue ducts and other conduits, and 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 hose structure and a method of manufacturing a diaphragm. Sealing members at joints and joints are often made of a hard material, and the fluororubber composition of the present invention has an improved frictional interface, increased dimensions with reduced trace leakage along the sealing surface. Provide an interference fit.
  • the latex enhances seal durability in various automotive system applications.
  • compositions can also be used in the manufacture of power steering systems, fuel systems, air conditioning systems, and any joint where hoses and tubes are connected to other parts.
  • a further utility of the composition is in repairing 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 sheets that can be formed or embossed before or after the paint is applied. For example, multiple layers of coated steel can be assembled to create a gasket between two rigid metal members. The sealing effect can be obtained by applying the fluororubber composition of the present invention between the layers. This process reduces the bolt force and strain of the assembled parts, while engine head gaskets and exhaust manifold gaskets for the purpose of providing better fuel savings and low emissions due to low cracks, deflections and hole strains Can be used to manufacture.
  • the fluororubber composition of the present invention includes a base material-integrated gasket and packing formed by dispenser molding on a base material containing an inorganic material such as a coating agent; metal, ceramic, etc .; a base containing an inorganic material such as metal, ceramic, etc. It can also be used as a multilayer product formed by coating a material.
  • ⁇ Tear strength> Using the cross-linked sheet having a thickness of 2 mm obtained in Examples and Comparative Examples, using a tensile tester (Tensilon, manufactured by Orientec Corp.), according to JIS K6252 (2007), conditions of 500 mm / min. Below, the tear strength at 23 ° C. was measured with an angled shape without incision.
  • the Mooney viscosity is 50 (ML 1 + 10 , 100 ° C.).
  • the Mooney viscosity is 60 (ML 1 + 10 , 100 ° C.).
  • the Mooney viscosity is 75 (ML 1 + 10 , 100 ° C.).
  • Crosslinking aid 1 Tyke (trade name) (triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd.)
  • Crosslinking aid 2 Thaik M60 (trade name) (powder containing 60% by mass of triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd.)
  • Organic peroxide 1 Perhexa 25B (trade name) (2,5-dimethyl-2,5-di (t-butylperoxy) hexane manufactured by NOF Corporation)
  • Organic peroxide 2 Perhexa 25B-40 (trade name) (powder containing 40% by mass of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane manufactured by NOF Corporation) .
  • Organic peroxide 3 Perhexine 25B-40 (trade name) (40% by mass of 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 manufactured by NOF Corporation) powder.) Calcium hydro
  • Examples 1 to 5 and Comparative Examples 1 to 9 The respective components were blended according to the formulations shown in Tables 1 and 2, and kneaded on an open roll to prepare a rubber composition.
  • Tables 1 and 2 show the crosslinking characteristics of the obtained rubber composition.
  • the prepared rubber composition was subjected to primary cross-linking (press cross-linking) and secondary cross-linking (oven cross-linking) according to the formulations shown in Table 1 and Table 2, and a test sample of a cross-linked sheet having a thickness of 2 mm and JIS K6262 (2006) The small test piece as described in 1 was produced.
  • Tables 1 and 2 show the results of normal physical property evaluation (hardness, tensile stress during cutting, elongation during cutting, and tear strength) of the obtained crosslinked sheet.
  • Table 1 shows the results of compression set at a compression rate of 25% and 200 ° C. ⁇ 72 hours using the obtained small test pieces.
  • Example 6 and Comparative Examples 10 to 13 Using a kneading machine (MixLabo 0.5L manufactured by Moriyama Co., Ltd., rotor diameter: 6.6 cm, tip clearance: 0.05 cm), the kneading conditions were as follows: front rotor rotation speed: 60 rpm, back rotor rotation speed: 50 rpm.
  • the fluororubber 3, carbon 1, 2, 4, and stearic acid were kneaded according to the formulation of 3, respectively, to prepare a fluororubber pre-compound.
  • the maximum temperature of the discharged kneaded product was 160 to 170 ° C.
  • the prepared rubber composition was subjected to primary cross-linking (press cross-linking) and secondary cross-linking (oven cross-linking) according to the formulation in Table 3, and a test sample of a cross-linked sheet having a thickness of 2 mm and JIS K6262 (2006) A small test piece was prepared. Results of evaluation of normal physical properties of the obtained crosslinked sheet (hardness, tensile stress at break, elongation at break and tear strength), and compression rate of 25% using the obtained small test piece at 200 ° C. ⁇ 72 hours The results of compression set are shown in Table 3.

Abstract

The purpose of the present invention is to provide a fluorine rubber composition that makes it possible to obtain a fluorine rubber molded article that has the same hardness as conventional articles and that exhibits excellent tear strength, compression set, and tensile stress during cutting under high temperatures. The present invention is a fluorine rubber composition that is characterized by comprising a fluorine rubber, lampblack, and a crosslinking agent.

Description

フッ素ゴム組成物及びフッ素ゴム成形品Fluoro rubber composition and fluoro rubber molding
本発明は、フッ素ゴム、ランプブラック及び架橋剤を含むフッ素ゴム組成物並びにそれから得られるフッ素ゴム成形品に関する。 The present invention relates to a fluororubber composition containing fluororubber, lamp black and a crosslinking agent, and a fluororubber molded product obtained therefrom.
フッ素ゴムは、耐熱性、耐油性、耐薬品性などの諸特性に優れていることから様々な用途に使用される。用途によっては高い機械的特性が要求されることから、フッ素ゴムにカーボンブラックを添加して、機械的強度を向上させている。 Fluoro rubber is used in various applications because of its excellent properties such as heat resistance, oil resistance, and chemical resistance. Depending on the application, high mechanical properties are required, so carbon black is added to fluororubber to improve mechanical strength.
例えば、特許文献１には、フッ素ゴム及びカーボンブラックを含んでなるフッ素ゴム組成物が記載されており、カーボンブラックとして、窒素吸着比表面積（Ｎ２ＳＡ）が２５ｍ２／ｇ以上１８０ｍ２／ｇ以下、ジブチルフタレート（ＤＢＰ）吸収量が６０ｍｌ／１８０ｇ以上１８０ｍｌ／１００ｇ以下であるものを使用することが記載されている。 For example, Patent Document 1 describes a fluororubber composition comprising fluororubber and carbon black, and the carbon adsorption has a nitrogen adsorption specific surface area (N 2 SA) of 25 m 2 / g or more and 180 m 2 / g. Hereinafter, it is described that a dibutyl phthalate (DBP) absorption amount of 60 ml / 180 g or more and 180 ml / 100 g or less is used.
特許文献２には、エチレン構造単位３５～６０モル％、ヘキサフルオロプロピレン構造単位２５～５０モル％およびこれらと共重合可能なモノマーから誘導される構造単位０～１５モル％からなる共重合体であって、フッ素含有量が６０重量％以上で、数平均分子量が３０００～５０００００のエチレン－ヘキサフルオロプロピレン系共重合体、その共重合体を用いた加硫可能な組成物、および耐熱性や耐油性に優れたオイルシール材として有用なエラストマー加硫物が記載されており、充填材としてカーボンブラック、ランプブラック等が例示されている。 Patent Document 2 discloses a copolymer comprising 35 to 60 mol% of ethylene structural units, 25 to 50 mol% of hexafluoropropylene structural units, and 0 to 15 mol% of structural units derived from monomers copolymerizable therewith. An ethylene-hexafluoropropylene copolymer having a fluorine content of 60% by weight or more and a number average molecular weight of 3000 to 500,000, a vulcanizable composition using the copolymer, and heat and oil resistance An elastomer vulcanizate useful as an oil sealant having excellent properties is described, and examples of fillers include carbon black and lamp black.
特許文献３には、エチレン－ヘキサフルオロプロピレン系エラストマー、パーオキサイド加硫剤、および置換または非置換のベンゾイルオキシラジカルを発生し得る加硫助剤とからなるエチレン－ヘキサフルオロプロピレン系エラストマー組成物が記載されており、充填材としてカーボンブラック、ランプブラック等が例示されている。 Patent Document 3 discloses an ethylene-hexafluoropropylene elastomer composition comprising an ethylene-hexafluoropropylene elastomer, a peroxide vulcanizing agent, and a vulcanization aid capable of generating a substituted or unsubstituted benzoyloxy radical. Examples of the filler include carbon black and lamp black.
特許文献４には、ゴムポリマー、ｐＨ＞７を有するシラン修飾無機質添加物、および酸受容体を含むエラストマー組成物が記載されている。追加的フィラーとしてカーボンブラックが記載されており、カーボンブラックは、ランプブラック法、ファーネスブラック法またはガスブラック法により調製され、また好ましくは、２０～２００ｍ２／ｇの範囲内のＢＥＴ（ＤＩＮ　６６　１３１）比表面積を有し、たとえばＳＡＦ、ＩＳＡＦ、ＨＡＦ、ＦＥＦまたはＧＰＦカーボンブラック等であることが記載されている。 Patent Document 4 describes an elastomer composition containing a rubber polymer, a silane-modified inorganic additive having a pH> 7, and an acid acceptor. Carbon black is described as an additional filler, which is prepared by the lamp black method, furnace black method or gas black method, and preferably BET (DIN 66 131 within the range of 20 to 200 m 2 / g. ) It has a specific surface area and is described as SAF, ISAF, HAF, FEF, GPF carbon black or the like.
特許文献５には、（Ａ）分子中に少なくとも２個のアルケニル基を有し、かつ主鎖中に２価のパーフルオロアルキレン又は２価のパーフルオロポリエーテル構造を有する液状パーフルオロ化合物に、（Ｂ）分子中に少なくとも２個のヒドロシリル基を含む付加反応可能な化合物を（Ｂ）成分のヒドロシリル基／（Ａ）成分のアルケニル基（モル比）＝０．１～０．９９となる量で付加反応触媒の存在下でプレキュアしてなるプレキュアベース、（Ｃ）補強性フィラー：（Ａ）成分１００重量部に対して１～１００重量部、（Ｄ）分子中にイソプロピルモノカーボネイト基を含有するパーオキサイド架橋剤：（Ａ）成分１００重量部に対して０．１～１０重量部を含有してなることを特徴とするフッ素ゴム組成物が記載されている。上記フッ素ゴム組成物には耐熱性向上剤を添加してもよいことが記載されており、耐熱性向上剤の例として挙げられるカーボンブラックとして、ランプブラック、各種ファーネスブラック及びアセチレンブラックが記載されている。 In Patent Document 5, (A) a liquid perfluoro compound having at least two alkenyl groups in the molecule and having a divalent perfluoroalkylene or divalent perfluoropolyether structure in the main chain, (B) A compound containing at least two hydrosilyl groups in the molecule and capable of undergoing addition reaction is an amount such that (B) component hydrosilyl group / (A) alkenyl group (molar ratio) = 0.1 to 0.99 (C) Reinforcing filler: (A) 1 to 100 parts by weight per 100 parts by weight of component (D) Isopropyl monocarbonate group in the molecule Peroxide crosslinking agent contained: A fluororubber composition characterized by containing 0.1 to 10 parts by weight per 100 parts by weight of component (A) is described. It is described that a heat resistance improver may be added to the fluororubber composition, and lamp black, various furnace blacks, and acetylene black are described as carbon blacks exemplified as heat resistance improvers. Yes.
しかしながら、更に高い機械的特性を実現できるフッ素ゴム組成物が求められている。 However, there is a need for a fluororubber composition that can achieve higher mechanical properties.
国際公開第２０１２／０２６００７号International Publication No. 2012/026007 特開２００２－１７９７３７号公報JP 2002-179737 A 国際公開第２００２／１０２８９２号International Publication No. 2002/102892 特表２０１２－５０２１７４号公報Special table 2012-502174 gazette 特開２００４－１０８０８号公報Japanese Patent Laid-Open No. 2004-10808
本発明は、このような現状に鑑み、従来品と同等の硬さを有し、かつ、優れた引裂き強さ、圧縮永久ひずみ及び高温時の切断時引張応力を示すフッ素ゴム成形品を得ることができるフッ素ゴム組成物を提供することを目的とする。 In view of such a current situation, the present invention provides a fluororubber molded article having hardness equivalent to that of a conventional product and exhibiting excellent tear strength, compression set, and tensile stress at cutting at high temperature. An object of the present invention is to provide a fluororubber composition that can be used.
本発明者らは、特定の窒素吸着比表面積（Ｎ２ＳＡ）及びジブチルフタレート（ＤＢＰ）吸油量を有するランプブラックを使用すると、優れた引裂き強さ、圧縮永久ひずみ及び高温時の切断時引張応力を実現できることを見出し、本発明を完成するに至った。 When using lamp blacks having a specific nitrogen adsorption specific surface area (N 2 SA) and dibutyl phthalate (DBP) oil absorption, we have excellent tear strength, compression set and tensile stress at break at high temperature. The present invention has been completed.
すなわち、本発明は、フッ素ゴム、ランプブラック、及び、架橋剤を含むことを特徴とするフッ素ゴム組成物である。 That is, the present invention is a fluororubber composition comprising fluororubber, lamp black, and a crosslinking agent.
本発明のフッ素ゴム組成物は、フッ素ゴム１００質量部に対して５～７０質量部のランプブラックを含むことが好ましい。 The fluororubber composition of the present invention preferably contains 5 to 70 parts by mass of lamp black with respect to 100 parts by mass of the fluororubber.
フッ素ゴムは、ビニリデンフルオライド系フッ素ゴム、テトラフルオロエチレン／プロピレン系フッ素ゴム、テトラフルオロエチレン／プロピレン／ビニリデンフルオライド系フッ素ゴム、エチレン／ヘキサフルオロプロピレン系フッ素ゴム、エチレン／ヘキサフルオロプロピレン／ビニリデンフルオライド系フッ素ゴム、及び、エチレン／ヘキサフルオロプロピレン／テトラフルオロエチレン系フッ素ゴムからなる群より選択される少なくとも１種であることが好ましい。 Fluoro rubbers are vinylidene fluoride fluoro rubber, tetrafluoroethylene / propylene fluoro rubber, tetrafluoroethylene / propylene / vinylidene fluoride fluoro rubber, ethylene / hexafluoropropylene fluoro rubber, ethylene / hexafluoropropylene / vinylidene fluoride. It is preferably at least one selected from the group consisting of a ride type fluororubber and an ethylene / hexafluoropropylene / tetrafluoroethylene type fluororubber.
本発明はまた、上述のフッ素ゴム組成物から得られるフッ素ゴム成形品でもある。 The present invention is also a fluororubber molded product obtained from the above fluororubber composition.
本発明のフッ素ゴム組成物は、上記の構成を有することから、成形及び架橋することによって、従来品と同等の硬さを有し、かつ、優れた引裂き強さ、圧縮永久ひずみ及び高温時の切断時引張応力を示すフッ素ゴム成形品を得ることができる。
本発明のフッ素ゴム成形品は、従来品と同等の硬さを有し、かつ、優れた引裂き強さ、圧縮永久ひずみ及び高温時の切断時引張応力を示す。 Since the fluororubber composition of the present invention has the above-described configuration, it has the same hardness as a conventional product by molding and crosslinking, and has excellent tear strength, compression set and high temperature. A fluororubber molded article exhibiting a tensile stress during cutting can be obtained.
The fluororubber molded product of the present invention has a hardness equivalent to that of a conventional product and exhibits excellent tear strength, compression set, and tensile stress at cutting at high temperatures.
以下、本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described.
本発明のフッ素ゴム組成物は、フッ素ゴム、ランプブラック、及び、架橋剤を含む。 The fluororubber composition of the present invention contains fluororubber, lamp black, and a crosslinking agent.
１．ランプブラック
上記ランプブラックは、古くから墨、墨汁、紙などの着色剤として製造されてきた油煙と称されているものである。ランプブラックの製造方法は、チャンネル法、皿炊き法、大皿炊き法等が知られており、具体的には、ナフタリン油などの芳香族油を浅い開放された皿に入れて密閉された室内で空気を供給して燃焼させ、生じた煙からランプブラックを沈降分離して回収する方法等がある。 1. Lamp black The lamp black is what is called oil smoke, which has been produced as a colorant for ink, ink, paper, etc. for a long time. As a method for producing lamp black, a channel method, a dish cooking method, a platter cooking method, and the like are known. Specifically, an aromatic oil such as naphthalene oil is placed in a shallow open dish and sealed indoors. There is a method in which air is supplied and burned, and lamp black is settled and recovered from the generated smoke.
上記ランプブラックの特徴は、製造時の空気の供給量でも変化するが、ファインサーマルクラスの粒子径を持ち、発達した凝集構造を備え、酸性度の高い表面を有することである。 The characteristics of the lamp black are that it varies depending on the amount of air supplied at the time of manufacture, but has a fine thermal class particle size, a developed aggregation structure, and a highly acidic surface.
上記ランプブラックは、窒素吸着比表面積（Ｎ２ＳＡ）が１ｍ２／ｇ以上８０ｍ２／ｇ以下であることが好ましい。上記ランプブラックは、ジブチルフタレート（ＤＢＰ）吸油量が４０ｍｌ／１００ｇ以上１８０ｍｌ／１００ｇ以下であることが好ましい。また上記ランプブラックは、上記ジブチルフタレート（ＤＢＰ）吸油量（ｍｌ／１００ｇ）を上記窒素吸着比表面積（Ｎ２ＳＡ）（ｍ２／ｇ）で除した値（以下、Ａ値ということがある）が３．０以上８．０以下であることが好ましい。上記窒素吸着比表面積（Ｎ２ＳＡ）及びジブチルフタレート（ＤＢＰ）吸油量で特徴付けられるランプブラックは、黒色顔料として使用されるのが一般的であり、ゴムの補強剤としての使用はエチレン／プロピレン／ジエン系ゴムでの配合例はあるが、フッ素ゴムへの配合例はない。 The lamp black preferably has a nitrogen adsorption specific surface area (N 2 SA) of 1 m 2 / g or more and 80 m 2 / g or less. The lamp black preferably has a dibutyl phthalate (DBP) oil absorption of 40 ml / 100 g or more and 180 ml / 100 g or less. The lamp black is obtained by dividing the dibutyl phthalate (DBP) oil absorption (ml / 100 g) by the nitrogen adsorption specific surface area (N 2 SA) (m 2 / g) (hereinafter sometimes referred to as A value). Is preferably 3.0 or more and 8.0 or less. The lamp black characterized by the nitrogen adsorption specific surface area (N 2 SA) and dibutyl phthalate (DBP) oil absorption is generally used as a black pigment, and the use as a rubber reinforcing agent is ethylene / propylene. / There are blending examples with diene rubber, but there is no blending example with fluororubber.
上記窒素吸着比表面積（Ｎ２ＳＡ）が小さすぎると、得られるフッ素ゴム成形品の引張強度及び引張伸びが小さくなるおそれがある。上記窒素吸着比表面積（Ｎ２ＳＡ）は、１ｍ２／ｇ以上が好ましく、１０ｍ２／ｇ以上がより好ましく、１５ｍ２／ｇ以上が特に好ましい。上限は、一般的に入手しやすい観点から８０ｍ２／ｇ以下が好ましく、また上記窒素吸着比表面積（Ｎ２ＳＡ）が大きすぎると得られるフッ素ゴム成形品の圧縮永久ひずみ特性が悪くなるおそれがあることから、６０ｍ２／ｇ以下が好ましく、４０ｍ２／ｇ以下がより好ましく、３５ｍ２／ｇ以下が特に好ましい。上記窒素吸着比表面積（Ｎ２ＳＡ）は、ＪＩＳ　Ｋ６２１７－２：２００１に記載の方法で測定できる。 When the nitrogen adsorption specific surface area (N 2 SA) is too small, there is a possibility that the tensile strength and tensile elongation of the fluororubber molded article obtained becomes small. The nitrogen adsorption specific surface area (N 2 SA) is preferably not less than 1 m 2 / g, more preferably at least 10 m 2 / g, more 15 m 2 / g is particularly preferred. The upper limit is preferably 80 m 2 / g or less from the viewpoint of easy availability, and if the nitrogen adsorption specific surface area (N 2 SA) is too large, the compression set characteristic of the obtained fluororubber molded product may be deteriorated. since there is preferably not more than 60 m 2 / g, more preferably not more than 40m 2 / g, 35m 2 / g or less is particularly preferred. The nitrogen adsorption specific surface area (N 2 SA) can be measured by the method described in JIS K6217-2: 2001.
上記ジブチルフタレート（ＤＢＰ）吸油量が上記の範囲にあると、優れた引張強度及び引張伸びを有するフッ素ゴム成形品を得ることができる。上記ジブチルフタレート（ＤＢＰ）吸油量は、４０ｍｌ／１００ｇ以上が好ましく、６０ｍｌ／１００ｇ以上がより好ましく、８０ｍｌ／１００ｇ以上が更に好ましく、１００ｍｌ／１００ｇ以上が更により好ましい。上限は一般的に入手しやすい観点から、１８０ｍｌ／１００ｇが好ましく、１４０ｍｌ／１００ｇがより好ましく、１２０ｍｌ／１００ｇが更に好ましい。上記ジブチルフタレート（ＤＢＰ）吸油量は、ＪＩＳ　Ｋ６２１７－４：２００８に記載の方法により測定できる。
また上記ランプブラックは、優れた引裂き強さ、圧縮永久ひずみ及び高温時の切断時引張応力を有するフッ素ゴム成形品を得ることができる点から、上記ジブチルフタレート（ＤＢＰ）吸油量（ｍｌ／１００ｇ）を上記窒素吸着比表面積（Ｎ２ＳＡ）（ｍ２／ｇ）で除した値（Ａ値）が３．０～８．０であることが好ましく、３．５～７．０であることがより好ましく、３．５～５．０であることが更に好ましい。 When the dibutyl phthalate (DBP) oil absorption is in the above range, a fluororubber molded article having excellent tensile strength and tensile elongation can be obtained. The dibutyl phthalate (DBP) oil absorption is preferably 40 ml / 100 g or more, more preferably 60 ml / 100 g or more, still more preferably 80 ml / 100 g or more, and even more preferably 100 ml / 100 g or more. From the viewpoint of easy availability, the upper limit is preferably 180 ml / 100 g, more preferably 140 ml / 100 g, and still more preferably 120 ml / 100 g. The dibutyl phthalate (DBP) oil absorption can be measured by the method described in JIS K6217-4: 2008.
In addition, the lamp black has the above-mentioned dibutyl phthalate (DBP) oil absorption (ml / 100 g) from the point that a fluororubber molded article having excellent tear strength, compression set, and tensile stress at cutting at high temperature can be obtained. The value (A value) obtained by dividing the above by the nitrogen adsorption specific surface area (N 2 SA) (m 2 / g) is preferably 3.0 to 8.0, and more preferably 3.5 to 7.0. More preferably, it is 3.5 to 5.0.
上述した特定の窒素吸着比表面積（Ｎ２ＳＡ）及びジブチルフタレート（ＤＢＰ）吸油量を有するランプブラックとしては、オリオンエンジニアドカーボンズ社製のＬａｍｐ１０１（Ｂ）等を挙げることができる。 Examples of the lamp black having the specific nitrogen adsorption specific surface area (N 2 SA) and dibutyl phthalate (DBP) oil absorption described above include Lamp 101 (B) manufactured by Orion Engineered Carbons.
上記ランプブラックは、平均一次粒子径が１０～３００ｎｍであることが好ましく、８０ｎｍ以上であることがより好ましく、１５０ｎｍ以下であることがより好ましく、１１０ｎｍ以下であることが更に好ましい。平均一次粒子径は、「ＡＳＴＭ　Ｄ３８４９－カーボンブラックの標準試験法－電子顕微鏡法による形態的特徴付け」に記載の手順によりアグリゲート拡大画像を取得し、撮影アグリゲート画像から単位構成粒子として３，０００個の粒子径を測定し、平均値を求めることにより算出できる。 The lamp black preferably has an average primary particle size of 10 to 300 nm, more preferably 80 nm or more, more preferably 150 nm or less, and still more preferably 110 nm or less. The average primary particle size was determined by obtaining an enlarged aggregate image according to the procedure described in “ASTM D3849-Carbon Black Standard Test Method-Morphological Characterization by Electron Microscopy”. It can be calculated by measuring the diameter of 000 particles and determining the average value.
本発明のフッ素ゴム組成物は、フッ素ゴム１００質量部に対して５～７０質量部のランプブラックを含むことが好ましい。ランプブラックの含有量は、１０質量部以上であることがより好ましく、１５質量部以上であることが更に好ましく、６０質量部以下であることがより好ましく、５５質量部以下であることが更に好ましい。ランプブラックが少なすぎると、優れた引裂き強さ、圧縮永久ひずみ及び高温時の切断時引張応力を有するフッ素ゴム成形品を得ることができないおそれがあり、ランプブラックが多すぎると、含有量に見合った効果が得られなかったり、フッ素ゴムに期待される柔軟性が損なわれたりするおそれがある。 The fluororubber composition of the present invention preferably contains 5 to 70 parts by mass of lamp black with respect to 100 parts by mass of the fluororubber. The content of lamp black is more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, more preferably 60 parts by mass or less, and further preferably 55 parts by mass or less. . If the amount of lamp black is too small, there is a possibility that a fluororubber molded product having excellent tear strength, compression set and tensile stress at cutting at high temperature cannot be obtained. If the amount of lamp black is too large, the content is commensurate with the content. May not be obtained, or the flexibility expected of fluororubber may be impaired.
２．フッ素ゴム
上記フッ素ゴムは、部分フッ素化ゴムであってもよいし、パーフルオロゴムであってもよい。 2. Fluoro rubber The fluoro rubber may be a partially fluorinated rubber or a perfluoro rubber.
部分フッ素化ゴムとしては、ビニリデンフルオライド（ＶｄＦ）系フッ素ゴム、テトラフルオロエチレン（ＴＦＥ）／プロピレン（Ｐｒ）系フッ素ゴム、テトラフルオロエチレン（ＴＦＥ）／プロピレン／ビニリデンフルオライド（ＶｄＦ）系フッ素ゴム、エチレン／ヘキサフルオロプロピレン（ＨＦＰ）系フッ素ゴム、エチレン／ヘキサフルオロプロピレン（ＨＦＰ）／ビニリデンフルオライド（ＶｄＦ）系フッ素ゴム、エチレン／ヘキサフルオロプロピレン（ＨＦＰ）／テトラフルオロエチレン（ＴＦＥ）系フッ素ゴム等が挙げられる。なかでも、ビニリデンフルオライド系フッ素ゴム及びテトラフルオロエチレン／プロピレン系フッ素ゴムからなる群より選択される少なくとも１種であることが好ましい。 Partially fluorinated rubbers include vinylidene fluoride (VdF) fluorine rubber, tetrafluoroethylene (TFE) / propylene (Pr) fluorine rubber, tetrafluoroethylene (TFE) / propylene / vinylidene fluoride (VdF) fluorine rubber. , Ethylene / hexafluoropropylene (HFP) fluorine rubber, ethylene / hexafluoropropylene (HFP) / vinylidene fluoride (VdF) fluorine rubber, ethylene / hexafluoropropylene (HFP) / tetrafluoroethylene (TFE) fluorine rubber Etc. Especially, it is preferable that it is at least 1 sort (s) selected from the group which consists of vinylidene fluoride type | system | group fluorine rubber and tetrafluoroethylene / propylene type fluorine rubber.
上記ビニリデンフルオライド系フッ素ゴムは、ビニリデンフルオライド２５～８５モル％と、ビニリデンフルオライドと共重合可能な少なくとも１種の他のモノマー７５～１５モル％とからなる共重合体であることが好ましい。より好ましくは、ビニリデンフルオライド４５～８０モル％と、ビニリデンフルオライドと共重合可能な少なくとも１種の他のモノマー５５～２０モル％とからなる共重合体である。 The vinylidene fluoride-based fluororubber is preferably a copolymer comprising 25 to 85 mol% of vinylidene fluoride and 75 to 15 mol% of at least one other monomer copolymerizable with vinylidene fluoride. . More preferably, it is a copolymer comprising 45 to 80 mol% of vinylidene fluoride and 55 to 20 mol% of at least one other monomer copolymerizable with vinylidene fluoride.
上記ビニリデンフルオライドと共重合可能な少なくとも１種の他のモノマーとしては、テトラフルオロエチレン（ＴＦＥ）、へキサフルオロプロピレン（ＨＦＰ）、フルオロアルキルビニルエーテル、クロロトリフルオロエチレン（ＣＴＦＥ）、トリフルオロエチレン、トリフルオロプロピレン、ペンタフルオロプロピレン、トリフルオロブテン、テトラフルオロイソブテン、ヘキサフルオロイソブテン、フッ化ビニル、一般式（１）：ＣＨ２＝ＣＦＲｆ１１（式中、Ｒｆ１１は炭素数１～１２の直鎖又は分岐したフルオロアルキル基）で表されるフルオロモノマー、一般式（２）：ＣＨ２＝ＣＨ－（ＣＦ２）ｎ－Ｘ２（式中、Ｘ２はＨ又はＦであり、ｎは３～１０の整数である。）で表されるフルオロモノマー、架橋部位を与えるモノマー等のモノマー；エチレン、プロピレン、アルキルビニルエーテル等の非フッ素化モノマーが挙げられる。これらをそれぞれ単独で、又は、任意に組み合わせて用いることができる。これらのなかでも、ＴＦＥ、ＨＦＰ、フルオロアルキルビニルエーテル及びＣＴＦＥからなる群より選択される少なくとも１種を用いることが好ましい。フルオロアルキルビニルエーテルとしては、一般式（３）：ＣＦ２＝ＣＦ－ＯＲｆ３１（式中、Ｒｆ３１は、炭素数１～１０のパーフルオロアルキル基を表す。）で表されるフルオロモノマーが好ましい。 Examples of at least one other monomer copolymerizable with the vinylidene fluoride include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), fluoroalkyl vinyl ether, chlorotrifluoroethylene (CTFE), trifluoroethylene, Trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, hexafluoroisobutene, vinyl fluoride, general formula (1): CH 2 = CFRf 11 (wherein Rf 11 is a straight chain having 1 to 12 carbon atoms) Or a branched fluoroalkyl group), a general formula (2): CH 2 ═CH— (CF 2 ) n —X 2 (wherein X 2 is H or F, and n is 3 to Is an integer of 10.) and gives a crosslinking site. Monomers monomers, ethylene, propylene, and a non-fluorinated monomer such as an alkyl vinyl ether. These can be used alone or in any combination. Among these, it is preferable to use at least one selected from the group consisting of TFE, HFP, fluoroalkyl vinyl ether and CTFE. The fluoroalkyl vinyl ether is preferably a fluoromonomer represented by the general formula (3): CF 2 = CF—ORf 31 (wherein Rf 31 represents a perfluoroalkyl group having 1 to 10 carbon atoms).
上記フッ素ゴムは架橋部位を与えるモノマーを含む共重合体であってよい。
架橋部位を与えるモノマーとしては、
式（４）：
ＣＹ１ ２＝ＣＹ２Ｒｆ ２Ｘ３　　　　　　　　　　　　　　　　　　　　（４）
（式中、Ｙ１、Ｙ２はフッ素原子、水素原子または－ＣＨ３；Ｒｆ ２は１個以上のエーテル結合性酸素原子を有していてもよく、芳香環を有していてもよい、水素原子の一部または全部がフッ素原子で置換された直鎖状または分岐状の含フッ素アルキレン基；Ｘ３はヨウ素原子または臭素原子）
で示される化合物が挙げられる。具体的には、たとえば、式（５）：
ＣＹ１ ２＝ＣＹ２Ｒｆ ３ＣＨＲ１－Ｘ３　　　　　　　　　　　　　　　（５）
（式中、Ｙ１、Ｙ２、Ｘ３は前記同様であり、Ｒｆ ３は１個以上のエーテル結合性酸素原子を有していてもよく水素原子の一部または全部がフッ素原子で置換された直鎖状または分岐状の含フッ素アルキレン基、すなわち水素原子の一部または全部がフッ素原子で置換された直鎖状または分岐状の含フッ素アルキレン基、水素原子の一部または全部がフッ素原子で置換された直鎖状または分岐状の含フッ素オキシアルキレン基、または水素原子の一部または全部がフッ素原子で置換された直鎖状または分岐状の含フッ素ポリオキシアルキレン基；Ｒ１は水素原子またはメチル基）
で示されるヨウ素含有モノマー、臭素含有モノマー、一般式（６）～（２３）：
ＣＹ４ ２＝ＣＹ４（ＣＦ２）ｎ－Ｘ３　　　　　　　　　　　　　　　　（６）
（式中、Ｙ４は、同一又は異なり、水素原子またはフッ素原子、ｎは１～８の整数）
ＣＦ２＝ＣＦＣＦ２Ｒｆ ４－Ｘ３　　　　　　　　　　　　　　　　　　（７）
（式中、 The fluororubber may be a copolymer containing a monomer that provides a crosslinking site.
As a monomer that gives a crosslinking site,
Formula (4):
CY 1 2 = CY 2 R f 2 X 3 (4)
(Wherein Y 1 and Y 2 are a fluorine atom, a hydrogen atom or —CH 3 ; R f 2 may have one or more ether-bonded oxygen atoms, and may have an aromatic ring. , A linear or branched fluorine-containing alkylene group in which part or all of the hydrogen atoms are substituted with fluorine atoms; X 3 is an iodine atom or a bromine atom)
The compound shown by these is mentioned. Specifically, for example, Formula (5):
CY 1 2 = CY 2 R f 3 CHR 1 -X 3 (5)
(In the formula, Y 1 , Y 2 and X 3 are the same as described above, and R f 3 may have one or more ether-bonded oxygen atoms, and a part or all of the hydrogen atoms are substituted with fluorine atoms. Linear or branched fluorine-containing alkylene group, that is, a linear or branched fluorine-containing alkylene group in which some or all of the hydrogen atoms are substituted with fluorine atoms, and part or all of the hydrogen atoms are fluorine a linear or branched fluorine-containing oxyalkylene group substituted with atoms or a fluorine-containing polyoxyalkylene group partially or entirely a linear or branched substituted with fluorine atoms of the hydrogen atom,; R 1 is Hydrogen atom or methyl group)
Iodine-containing monomers, bromine-containing monomers represented by general formulas (6) to (23):
CY 4 2 = CY 4 (CF 2 ) n -X 3 (6)
Wherein Y 4 is the same or different and is a hydrogen atom or a fluorine atom, and n is an integer of 1 to 8.
CF 2 = CFCF 2 R f 4 -X 3 (7)
(Where
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
であり、ｎは０～５の整数）
ＣＦ２＝ＣＦＣＦ２（ＯＣＦ（ＣＦ３）ＣＦ２）ｍ
　　　　　　　　　（ＯＣＨ２ＣＦ２ＣＦ２）ｎＯＣＨ２ＣＦ２－Ｘ３　　（８）
（式中、ｍは０～５の整数、ｎは０～５の整数）
ＣＦ２＝ＣＦＣＦ２（ＯＣＨ２ＣＦ２ＣＦ２）ｍ
　　　　　　　（ＯＣＦ（ＣＦ３）ＣＦ２）ｎＯＣＦ（ＣＦ３）－Ｘ３　（９）
（式中、ｍは０～５の整数、ｎは０～５の整数）
ＣＦ２＝ＣＦ（ＯＣＦ２ＣＦ（ＣＦ３））ｍＯ（ＣＦ２）ｎ－Ｘ３　　　（１０）
（式中、ｍは０～５の整数、ｎは１～８の整数）
ＣＦ２＝ＣＦ（ＯＣＦ２ＣＦ（ＣＦ３））ｍ－Ｘ３　　　　　　　　　（１１）
（式中、ｍは１～５の整数）
ＣＦ２＝ＣＦＯＣＦ２（ＣＦ（ＣＦ３）ＯＣＦ２）ｎＣＦ（－Ｘ３）ＣＦ３
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　（１２）
（式中、ｎは１～４の整数）
ＣＦ２＝ＣＦＯ（ＣＦ２）ｎＯＣＦ（ＣＦ３）－Ｘ３　　　　　　　　　（１３）
（式中、ｎは２～５の整数）
ＣＦ２＝ＣＦＯ（ＣＦ２）ｎ－（Ｃ６Ｈ４）－Ｘ３　　　　　　　　　　（１４）
（式中、ｎは１～６の整数）
ＣＦ２＝ＣＦ（ＯＣＦ２ＣＦ（ＣＦ３））ｎＯＣＦ２ＣＦ（ＣＦ３）－Ｘ３
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　（１５）
（式中、ｎは１～２の整数）
ＣＨ２＝ＣＦＣＦ２Ｏ（ＣＦ（ＣＦ３）ＣＦ２Ｏ）ｎＣＦ（ＣＦ３）－Ｘ３
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　（１６）
（式中、ｎは０～５の整数）、
ＣＦ２＝ＣＦＯ（ＣＦ２ＣＦ（ＣＦ３）Ｏ）ｍ（ＣＦ２）ｎ－Ｘ３　　　（１７）
（式中、ｍは０～５の整数、ｎは１～３の整数）
ＣＨ２＝ＣＦＣＦ２ＯＣＦ（ＣＦ３）ＯＣＦ（ＣＦ３）－Ｘ３　　　　（１８）
ＣＨ２＝ＣＦＣＦ２ＯＣＨ２ＣＦ２－Ｘ３　　　　　　　　　　　　　（１９）
ＣＦ２＝ＣＦＯ（ＣＦ２ＣＦ（ＣＦ３）Ｏ）ｍＣＦ２ＣＦ（ＣＦ３）－Ｘ３
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　（２０）
（式中、ｍは０以上の整数）
ＣＦ２＝ＣＦＯＣＦ（ＣＦ３）ＣＦ２Ｏ（ＣＦ２）ｎ－Ｘ３　　　　　（２１）
（式中、ｎは１以上の整数）
ＣＦ２＝ＣＦＯＣＦ２ＯＣＦ２ＣＦ（ＣＦ３）ＯＣＦ２－Ｘ３　　　　（２２）
ＣＨ２＝ＣＨ－（ＣＦ２）ｎＸ３　　　　　　　　　　　　　　　　　（２３）
（式中、ｎは２～８の整数）
（一般式（６）～（２３）中、Ｘ３は前記と同様）
で表されるヨウ素含有モノマーまたは臭素含有モノマーなどが挙げられ、これらをそれぞれ単独で、または任意に組合わせて用いることができる。
式（５）で示されるヨウ素含有モノマーまたは臭素含有モノマーとしては、一般式（２４）： Where n is an integer from 0 to 5)
CF 2 = CFCF 2 (OCF (CF 3 ) CF 2 ) m
(OCH 2 CF 2 CF 2 ) n OCH 2 CF 2 —X 3 (8)
(In the formula, m is an integer of 0 to 5, and n is an integer of 0 to 5)
CF 2 = CFCF 2 (OCH 2 CF 2 CF 2 ) m
(OCF (CF 3 ) CF 2 ) n OCF (CF 3 ) -X 3 (9)
(In the formula, m is an integer of 0 to 5, and n is an integer of 0 to 5)
CF 2 ═CF (OCF 2 CF (CF 3 )) m O (CF 2 ) n —X 3 (10)
(Where m is an integer from 0 to 5, and n is an integer from 1 to 8)
CF 2 = CF (OCF 2 CF (CF 3 )) m -X 3 (11)
(Where m is an integer from 1 to 5)
CF 2 = CFOCF 2 (CF (CF 3 ) OCF 2 ) n CF (—X 3 ) CF 3
(12)
(Where n is an integer from 1 to 4)
CF 2 = CFO (CF 2 ) n OCF (CF 3 ) -X 3 (13)
(Where n is an integer from 2 to 5)
CF 2 ═CFO (CF 2 ) n — (C 6 H 4 ) —X 3 (14)
(Where n is an integer from 1 to 6)
CF 2 ═CF (OCF 2 CF (CF 3 )) n OCF 2 CF (CF 3 ) —X 3
(15)
(Where n is an integer from 1 to 2)
CH 2 = CFCF 2 O (CF (CF 3) CF 2 O) n CF (CF 3) -X 3
(16)
(Where n is an integer from 0 to 5),
CF 2 ═CFO (CF 2 CF (CF 3 ) O) m (CF 2 ) n —X 3 (17)
(Where m is an integer from 0 to 5, and n is an integer from 1 to 3)
CH 2 = CFCF 2 OCF (CF 3 ) OCF (CF 3 ) -X 3 (18)
CH 2 = CFCF 2 OCH 2 CF 2 -X 3 (19)
CF 2 = CFO (CF 2 CF (CF 3) O) m CF 2 CF (CF 3) -X 3
(20)
(Where m is an integer of 0 or more)
CF 2 = CFOCF (CF 3 ) CF 2 O (CF 2 ) n —X 3 (21)
(Where n is an integer of 1 or more)
CF 2 = CFOCF 2 OCF 2 CF (CF 3 ) OCF 2 —X 3 (22)
CH 2 = CH- (CF 2 ) n X 3 (23)
(Where n is an integer from 2 to 8)
(In the general formulas (6) to (23), X 3 is the same as above)
These include iodine-containing monomers or bromine-containing monomers represented by the above, and these can be used alone or in any combination.
As the iodine-containing monomer or bromine-containing monomer represented by the formula (5), the general formula (24):
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
（式中、ｍは１～５の整数であり、ｎは０～３の整数）
で表されるヨウ素含有フッ素化ビニルエーテルが好ましく挙げられ、より具体的には、 (In the formula, m is an integer of 1 to 5, and n is an integer of 0 to 3)
Preferred examples include iodine-containing fluorinated vinyl ethers represented by:
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
などが挙げられるが、これらの中でも、ＩＣＨ２ＣＦ２ＣＦ２ＯＣＦ＝ＣＦ２が好ましい。　
式（６）で示されるヨウ素含有モノマーまたは臭素含有モノマーとしてより具体的には、ＩＣＦ２ＣＦ２ＣＦ＝ＣＨ２、Ｉ（ＣＦ２ＣＦ２）２ＣＦ＝ＣＨ２が好ましく挙げられる。　
式（１０）で示されるヨウ素含有モノマーまたは臭素含有モノマーとしてより具体的には、Ｉ（ＣＦ２ＣＦ２）２ＯＣＦ＝ＣＦ２が好ましく挙げられる。　
式（２３）で示されるヨウ素含有モノマーまたは臭素含有モノマーとしてより具体的には、ＣＨ２＝ＣＨＣＦ２ＣＦ２Ｉ、Ｉ（ＣＦ２ＣＦ２）２ＣＨ＝ＣＨ２が好ましく挙げられる。　
また、式：Ｒ２Ｒ３Ｃ＝ＣＲ４－Ｚ－ＣＲ５＝ＣＲ６Ｒ７　　
（式中、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７は同じかまたは異なり、いずれもＨ、または炭素数１～５のアルキル基；Ｚは、線状（直鎖状）もしくは分岐状の、酸素原子を含んでいてもよい、好ましくは少なくとも部分的にフッ素化された炭素数１～１８のアルキレンもしくはシクロアルキレン基、または（パー）フルオロポリオキシアルキレン基）で示されるビスオレフィン化合物も架橋部位を与えるモノマーとして好ましい。　
Ｚは好ましくは炭素数４～１２の（パー）フルオロアルキレン基であり、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７は好ましくは水素原子である。　
Ｚが（パー）フルオロポリオキシアルキレン基である場合、
－（Ｑ）ｐ－ＣＦ２Ｏ－（ＣＦ２ＣＦ２Ｏ）ｍ－（ＣＦ２Ｏ）ｎ－ＣＦ２－（Ｑ）ｐ－
（式中、Ｑは炭素数１～１０のアルキレン基または炭素数２～１０のオキシアルキレン基であり、ｐは０または１であり、ｍ及びｎはｍ／ｎ比が０．２～５となり且つ該（パー）フルオロポリオキシアルキレン基の分子量が５００～１００００、好ましくは１０００～４０００の範囲となるような整数である。）で表される（パー）フルオロポリオキシアルキレン基であることが好ましい。この式において、Ｑは好ましくは、－ＣＨ２ＯＣＨ２－及び－ＣＨ２Ｏ（ＣＨ２ＣＨ２Ｏ）ｓＣＨ２－（ｓ＝１～３）の中から選ばれる。　
好ましいビスオレフィンは、
ＣＨ２＝ＣＨ－（ＣＦ２）４－ＣＨ＝ＣＨ２、
ＣＨ２＝ＣＨ－（ＣＦ２）６－ＣＨ＝ＣＨ２、
式：ＣＨ２＝ＣＨ－Ｚ１－ＣＨ＝ＣＨ２　　　　
（式中、Ｚ１は－ＣＨ２ＯＣＨ２－ＣＦ２Ｏ－（ＣＦ２ＣＦ２Ｏ）ｍ－（ＣＦ２Ｏ）ｎ－ＣＦ２－ＣＨ２ＯＣＨ２－（ｍ／ｎは０．５））
などが挙げられる。　
なかでも、ＣＨ２＝ＣＨ－（ＣＦ２）６－ＣＨ＝ＣＨ２で示される３，３，４，４，５，５，６，６，７，７，８，８－ドデカフルオロ－１，９－デカジエンが好ましい。 Among them, ICH 2 CF 2 CF 2 OCF═CF 2 is preferable among these.
More specifically, preferred examples of the iodine-containing monomer or bromine-containing monomer represented by the formula (6) include ICF 2 CF 2 CF═CH 2 and I (CF 2 CF 2 ) 2 CF═CH 2 .
More specifically, the iodine-containing monomer or bromine-containing monomer represented by the formula (10) is preferably I (CF 2 CF 2 ) 2 OCF═CF 2 .
More specifically, preferred examples of the iodine-containing monomer or bromine-containing monomer represented by the formula (23) include CH 2 ═CHCF 2 CF 2 I and I (CF 2 CF 2 ) 2 CH═CH 2 .
Further, the formula: R 2 R 3 C═CR 4 —Z—CR 5 = CR 6 R 7
(Wherein R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are the same or different, and all are H or an alkyl group having 1 to 5 carbon atoms; Z is linear (linear ) Or a branched, optionally containing oxygen atom, preferably an at least partially fluorinated alkylene or cycloalkylene group having 1 to 18 carbon atoms, or (per) fluoropolyoxyalkylene group) Bisolefin compounds are also preferred as monomers that provide a crosslinking site.
Z is preferably a (per) fluoroalkylene group having 4 to 12 carbon atoms, and R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are preferably hydrogen atoms.
When Z is a (per) fluoropolyoxyalkylene group,
- (Q) p -CF 2 O- (CF 2 CF 2 O) m - (CF 2 O) n -CF 2 - (Q) p -
(In the formula, Q is an alkylene group having 1 to 10 carbon atoms or an oxyalkylene group having 2 to 10 carbon atoms, p is 0 or 1, and m and n have an m / n ratio of 0.2 to 5. The (per) fluoropolyoxyalkylene group is preferably an integer such that the molecular weight of the (per) fluoropolyoxyalkylene group is in the range of 500 to 10,000, preferably 1000 to 4000. . In this formula, Q is preferably selected from —CH 2 OCH 2 — and —CH 2 O (CH 2 CH 2 O) s CH 2 — (s = 1 to 3).
Preferred bisolefins are
CH 2 ═CH— (CF 2 ) 4 —CH═CH 2 ,
CH 2 ═CH— (CF 2 ) 6 —CH═CH 2 ,
Formula: CH 2 ═CH—Z 1 —CH═CH 2
(Wherein Z 1 is —CH 2 OCH 2 —CF 2 O— (CF 2 CF 2 O) m — (CF 2 O) n —CF 2 —CH 2 OCH 2 — (m / n is 0.5)) )
Etc.
Among them, CH 2 = CH- (CF 2 ) 6 represented by -CH = CH 2 3,3,4,4,5,5,6,6,7,7,8,8- dodecafluoro -1, 9-decadiene is preferred.
ビニリデンフルオライド系フッ素ゴムの具体例としては、ＶｄＦ／ＨＦＰ系ゴム、ＶｄＦ／ＨＦＰ／ＴＦＥ系ゴム、ＶｄＦ／ＣＴＦＥ系ゴム、ＶｄＦ／ＣＴＦＥ／ＴＦＥ系ゴム、ＶｄＦ／一般式（１）で表されるフルオロモノマー系ゴム、ＶｄＦ／一般式（１）で表されるフルオロモノマー／ＴＦＥ系ゴム、ＶｄＦ／パーフルオロ（メチルビニルエーテル）（ＰＭＶＥ）系ゴム、ＶｄＦ／ＰＭＶＥ／ＴＦＥ系ゴム、ＶｄＦ／ＰＭＶＥ／ＴＦＥ／ＨＦＰ系ゴム等が挙げられる。ＶｄＦ／一般式（１）で表されるフルオロモノマー系ゴムとしては、ＶｄＦ／ＣＨ２＝ＣＦＣＦ３系ゴムが好ましく、ＶｄＦ／一般式（１）で表されるフルオロモノマー／ＴＦＥ系ゴムとしては、ＶｄＦ／ＴＦＥ／ＣＨ２＝ＣＦＣＦ３系ゴムが好ましい。 Specific examples of vinylidene fluoride-based fluororubber are represented by VdF / HFP rubber, VdF / HFP / TFE rubber, VdF / CTFE rubber, VdF / CTFE / TFE rubber, VdF / general formula (1). Fluoromonomer rubber, VdF / fluoromonomer / TFE rubber represented by the general formula (1), VdF / perfluoro (methyl vinyl ether) (PMVE) rubber, VdF / PMVE / TFE rubber, VdF / PMVE / Examples include TFE / HFP rubber. VdF / CH 2 = CFCF 3 rubber is preferred as the fluoromonomer rubber represented by VdF / general formula (1), and as the fluoromonomer / TFE rubber represented by VdF / general formula (1), VdF / TFE / CH 2 ═CFCF 3 rubber is preferable.
上記ＶｄＦ／ＣＨ２＝ＣＦＣＦ３系ゴムは、ＶｄＦ４０～９９．５モル％、及び、ＣＨ２＝ＣＦＣＦ３０．５～６０モル％からなる共重合体であることが好ましく、ＶｄＦ５０～８５モル％、及び、ＣＨ２＝ＣＦＣＦ３２０～５０モル％からなる共重合体であることがより好ましい。 The VdF / CH 2 = CFCF 3 rubber is preferably a copolymer composed of VdF 40 to 99.5 mol% and CH 2 = CFCF 3 0.5 to 60 mol%, and VdF 50 to 85 mol%. And a copolymer of 20 to 50 mol% of CH 2 ═CFCF 3 is more preferable.
上記テトラフルオロエチレン／プロピレン系フッ素ゴムは、テトラフルオロエチレン４５～７０モル％、プロピレン５５～３０モル％、及び、架橋部位を与えるフルオロモノマー０～５モル％からなる共重合体であることが好ましい。 The tetrafluoroethylene / propylene-based fluororubber is preferably a copolymer composed of 45 to 70 mol% of tetrafluoroethylene, 55 to 30 mol% of propylene, and 0 to 5 mol% of a fluoromonomer providing a crosslinking site. .
上記フッ素ゴムは、パーフルオロゴムであってもよい。上記パーフルオロゴムとしては、ＴＦＥを含むパーフルオロゴム、例えばＴＦＥ／一般式（３）で表されるフルオロモノマー共重合体、ＴＦＥ／一般式（４）：ＣＦ２＝ＣＦＯＣＦ２ＯＲｆ４１（式中、Ｒｆ４１は炭素数１～６の直鎖又は分岐状パーフルオロアルキル基、炭素数５～６の環式パーフルオロアルキル基、１～３個の酸素原子を含む炭素数２～６の直鎖又は分岐状パーフルオロオキシアルキル基である。）で表されるフルオロモノマー共重合体、ＴＦＥ／一般式（５）：ＣＦ２＝ＣＦＯ（ＣＦ２ＣＦ（Ｙ）Ｏ）ｍ（ＣＦ２）ｎＦ（式中、Ｙはフッ素原子又はトリフルオロメチル基を表す。ｍは１～４の整数である。ｎは１～４の整数である。）で表されるフルオロモノマー共重合体及びＴＦＥ／一般式（３）、（４）又は（５）で表されるフルオロモノマー／架橋部位を与えるモノマー共重合体からなる群より選択される少なくとも１種が好ましい。
その組成は、ＴＦＥ／ＰＭＶＥ共重合体の場合、好ましくは、４５～９０／１０～５５（モル％）であり、より好ましくは、５５～８０／２０～４５であり、更に好ましくは、５５～７０／３０～４５である。
ＴＦＥ／ＰＭＶＥ／架橋部位を与えるモノマー共重合体の場合、好ましくは、４５～８９．９／１０～５４．９／０．０１～４（モル％）であり、より好ましくは、５５～７７．９／２０～４９．９／０．１～３．５であり、更に好ましくは、５５～６９．８／３０～４４．８／０．２～３である。
ＴＦＥ／炭素数が４～１２の一般式（３）、（４）又は（５）で表されるフルオロモノマー共重合体の場合、好ましくは、５０～９０／１０～５０（モル％）であり、より好ましくは、６０～８８／１２～４０であり、更に好ましくは、６５～８５／１５～３５である。
ＴＦＥ／炭素数が４～１２の一般式（３）、（４）又は（５）で表されるフルオロモノマー／架橋部位を与えるモノマー共重合体の場合、好ましくは、５０～８９．９／　１０～４９．９／０．０１～４（モル％）であり、より好ましくは、６０～８７．９／１２～３９．９／０．１～３．５であり、更に好ましくは、６５～８４．８／１５～３４．８／０．２～３である。
これらの組成の範囲を外れると、ゴム弾性体としての性質が失われ、樹脂に近い性質となる傾向がある。 The fluoro rubber may be perfluoro rubber. Examples of the perfluoro rubber include TFE-containing perfluoro rubber, for example, TFE / fluoromonomer copolymer represented by the general formula (3), TFE / general formula (4): CF 2 = CFOCF 2 ORf 41 (wherein Rf 41 is a straight or branched perfluoroalkyl group having 1 to 6 carbon atoms, a cyclic perfluoroalkyl group having 5 to 6 carbon atoms, or a straight chain having 2 to 6 carbon atoms containing 1 to 3 oxygen atoms. Or a branched perfluorooxyalkyl group.), TFE / General formula (5): CF 2 = CFO (CF 2 CF (Y) O) m (CF 2 ) n F (Wherein Y represents a fluorine atom or a trifluoromethyl group, m is an integer of 1 to 4, and n is an integer of 1 to 4) and TFE / general Formula (3), (4 Or (5) at least one member selected from the group consisting of monomer copolymer providing a fluoromonomer / crosslinking moiety represented by is preferable.
In the case of a TFE / PMVE copolymer, the composition is preferably 45 to 90/10 to 55 (mol%), more preferably 55 to 80/20 to 45, and still more preferably 55 to 70/30 to 45.
In the case of a monomer copolymer that provides a TFE / PMVE / cross-linking site, it is preferably 45 to 89.9 / 10 to 54.9 / 0.01 to 4 (mol%), and more preferably 55 to 77. It is 9/20 to 49.9 / 0.1 to 3.5, and more preferably 55 to 69.8 / 30 to 44.8 / 0.2 to 3.
In the case of the fluoromonomer copolymer represented by the general formula (3), (4) or (5) having 4 to 12 TFE / carbon, it is preferably 50 to 90/10 to 50 (mol%). More preferably, it is 60 to 88/12 to 40, and still more preferably 65 to 85/15 to 35.
In the case of TFE / monomer copolymer which gives a fluoromonomer / crosslinking site represented by the general formula (3), (4) or (5) having 4 to 12 carbon atoms, preferably 50 to 89.9 / 10 To 49.9 / 0.01 to 4 (mol%), more preferably 60 to 87.9 / 12 to 39.9 / 0.1 to 3.5, and still more preferably 65 to 84. 8/15 to 34.8 / 0.2 to 3.
When the composition is out of the range, the properties as a rubber elastic body are lost, and the properties tend to be similar to those of a resin.
上記パーフルオロゴムとしては、ＴＦＥ／一般式（５）で表されるフルオロモノマー／架橋部位を与えるフルオロモノマー共重合体、ＴＦＥ／一般式（５）で表されるパーフルオロビニルエーテル共重合体、ＴＦＥ／一般式（３）で表されるフルオロモノマー共重合体、及び、ＴＦＥ／一般式（３）で表されるフルオロモノマー／架橋部位を与えるモノマー共重合体からなる群より選択される少なくとも１種であることが好ましい。 Examples of the perfluoro rubber include TFE / fluoromonomer represented by the general formula (5) / fluoromonomer copolymer that gives a crosslinking site, TFE / perfluorovinyl ether copolymer represented by the general formula (5), and TFE. / At least one selected from the group consisting of a fluoromonomer copolymer represented by the general formula (3) and a TFE / fluoromonomer represented by the general formula (3) / a monomer copolymer that gives a crosslinking site It is preferable that
上記パーフルオロゴムとしては、国際公開第９７／２４３８１号、特公昭６１－５７３２４号公報、特公平４－８１６０８号公報、特公平５－１３９６１号公報等に記載されているパーフルオロゴムも挙げることができる。 Examples of the perfluoro rubber include perfluoro rubbers described in International Publication No. 97/24381, Japanese Patent Publication No. 61-57324, Japanese Patent Publication No. 4-81608, Japanese Patent Publication No. 5-13961, and the like. Can do.
上記フッ素ゴムは、高温における圧縮永久ひずみに優れる点から、ガラス転移温度が－７０℃以上であることが好ましく、－６０℃以上であることがより好ましく、－５０℃以上であることが更に好ましい。また、耐寒性が良好であるという点から、５℃以下であることが好ましく、０℃以下であることがより好ましく、－３℃以下であることが更に好ましい。 The fluororubber preferably has a glass transition temperature of −70 ° C. or higher, more preferably −60 ° C. or higher, and still more preferably −50 ° C. or higher from the viewpoint of excellent compression set at high temperatures. . Further, from the viewpoint of good cold resistance, it is preferably 5 ° C. or lower, more preferably 0 ° C. or lower, and further preferably −3 ° C. or lower.
上記ガラス転移温度は、示差走査熱量計（メトラー・トレド社製、ＤＳＣ８２２ｅ）を用い、試料１０ｍｇを１０℃／ｍｉｎで昇温することによりＤＳＣ曲線を得て、ＤＳＣ曲線の二次転移前後のベースラインの延長線と、ＤＳＣ曲線の変曲点における接線との２つの交点の中点を示す温度として求めることができる。 The glass transition temperature is obtained by using a differential scanning calorimeter (Mettler Toledo, DSC822e) to obtain a DSC curve by raising the temperature of 10 mg of the sample at 10 ° C./min. It can be determined as the temperature indicating the midpoint of the two intersections of the extension of the line and the tangent at the inflection point of the DSC curve.
上記フッ素ゴムは、耐熱性が良好な点で、１７０℃におけるムーニー粘度ＭＬ（１＋２０）が３０以上であることが好ましく、４０以上であることがより好ましく、５０以上であることが更に好ましい。また、加工性が良好な点で、１５０以下であることが好ましく、１２０以下であることがより好ましく、１１０以下であることが更に好ましい。 The fluororubber preferably has a Mooney viscosity ML (1 + 20) at 170 ° C. of 30 or more, more preferably 40 or more, and still more preferably 50 or more, from the viewpoint of good heat resistance. Further, in terms of good workability, it is preferably 150 or less, more preferably 120 or less, and even more preferably 110 or less.
上記フッ素ゴムは、耐熱性が良好な点で、１４０℃におけるムーニー粘度ＭＬ（１＋２０）が３０以上であることが好ましく、４０以上であることがより好ましく、５０以上であることが更に好ましい。また、加工性が良好な点で、１８０以下であることが好ましく、１５０以下であることがより好ましく、１１０以下であることが更に好ましい。 The fluororubber preferably has a Mooney viscosity ML (1 + 20) at 140 ° C. of 30 or more, more preferably 40 or more, and still more preferably 50 or more from the viewpoint of good heat resistance. Moreover, it is preferable that it is 180 or less at a point with favorable workability, It is more preferable that it is 150 or less, It is still more preferable that it is 110 or less.
上記フッ素ゴムは、耐熱性が良好な点で、１００℃におけるムーニー粘度ＭＬ（１＋１０）が１０以上であることが好ましく、２０以上であることがより好ましく、３０以上であることが更に好ましい。また、加工性が良好な点で、１２０以下であることが好ましく、１００以下であることがより好ましく、８０以下であることが更に好ましい。 The fluororubber preferably has a Mooney viscosity ML (1 + 10) at 100 ° C. of 10 or more, more preferably 20 or more, and still more preferably 30 or more from the viewpoint of good heat resistance. Further, in terms of good workability, it is preferably 120 or less, more preferably 100 or less, and still more preferably 80 or less.
３．架橋剤及び架橋方法
上記架橋剤の配合量はフッ素ゴム１００質量部に対して０．３～１０質量部であることが好ましく、より好ましくは０．４～５質量部であり、更に好ましくは０．４～３質量部である。架橋剤が、０．３質量部より少ないと、架橋度が不足するため、フッ素ゴム成形品の性能が損なわれる傾向があり、１０質量部をこえると、架橋密度が高くなりすぎるため架橋時間が長くなることに加え、経済的にも好ましくない傾向がある。 3. Crosslinking agent and crosslinking method The amount of the above crosslinking agent is preferably 0.3 to 10 parts by mass, more preferably 0.4 to 5 parts by mass, and still more preferably 0 to 100 parts by mass of the fluororubber. 4 to 3 parts by mass. If the cross-linking agent is less than 0.3 parts by mass, the degree of cross-linking will be insufficient, and the performance of the fluororubber molded product will tend to be impaired. In addition to being long, it tends to be economically undesirable.
上記架橋剤としては、ポリアミン架橋、ポリオール架橋及びパーオキサイド架橋で通常使用される架橋剤であれば特に限定されないが、ポリアミン化合物、ポリヒドロキシ化合物及び有機過酸化物からなる群より選択される少なくとも１種であることが好ましい。 The crosslinking agent is not particularly limited as long as it is a crosslinking agent usually 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. Preferably it is a seed.
上記ポリアミン化合物としては、たとえば、ヘキサメチレンジアミンカーバメート、Ｎ，Ｎ’－ジシンナミリデン－１，６－ヘキサメチレンジアミン、４，４’－ビス（アミノシクロヘキシル）メタンカルバメートなどが挙げられる。これらの中でも、Ｎ，Ｎ’－ジシンナミリデン－１，６－ヘキサメチレンジアミンが好ましい。 Examples of the polyamine compound include hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexamethylenediamine, and 4,4′-bis (aminocyclohexyl) methanecarbamate. Among these, N, N′-dicinnamylidene-1,6-hexamethylenediamine is preferable.
上記ポリヒドロキシ化合物としては、耐熱性に優れる点からポリヒドロキシ芳香族化合物が好適に用いられる。 As said polyhydroxy compound, a polyhydroxy aromatic compound is used suitably from the point which is excellent in heat resistance.
上記ポリヒドロキシ芳香族化合物としては、特に限定されず、たとえば、２，２－ビス（４－ヒドロキシフェニル）プロパン（以下、ビスフェノールＡという）、２，２－ビス（４－ヒドロキシフェニル）パーフルオロプロパン（以下、ビスフェノールＡＦという）、レゾルシン、１，３－ジヒドロキシベンゼン、１，７－ジヒドロキシナフタレン、２，７－ジヒドロキシナフタレン、１，６－ジヒドロキシナフタレン、４，４’―ジヒドロキシジフェニル、４，４’－ジヒドロキシスチルベン、２，６－ジヒドロキシアントラセン、ヒドロキノン、カテコール、２，２－ビス（４－ヒドロキシフェニル）ブタン（以下、ビスフェノールＢという）、４，４－ビス（４－ヒドロキシフェニル）吉草酸、２，２－ビス（４－ヒドロキシフェニル）テトラフルオロジクロロプロパン、４，４’－ジヒドロキシジフェニルスルホン、４，４’－ジヒドロキシジフェニルケトン、トリ（４－ヒドロキシフェニル）メタン、３，３’，５，５’－テトラクロロビスフェノールＡ、３，３’，５，５’－テトラブロモビスフェノールＡなどが挙げられる。これらのポリヒドロキシ芳香族化合物は、アルカリ金属塩、アルカリ土類金属塩などであってもよいが、酸を用いて共重合体を凝析した場合は、上記金属塩は用いないことが好ましい。 The polyhydroxy aromatic compound is not particularly limited. For example, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 2,2-bis (4-hydroxyphenyl) perfluoropropane (Hereinafter referred to as bisphenol AF), resorcin, 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-Bis (4-hydroxyphenyl) Tetrafluorodichloropropane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl ketone, tri (4-hydroxyphenyl) methane, 3,3 ′, 5,5′-tetrachlorobisphenol A, 3,3 Examples include ', 5,5'-tetrabromobisphenol A. These polyhydroxy aromatic compounds may be an alkali metal salt, an alkaline earth metal salt or the like, but when the copolymer is coagulated using an acid, it is preferable not to use the metal salt.
架橋剤がポリヒドロキシ化合物である場合、本発明のフッ素ゴム組成物は架橋促進剤を含むことが好ましい。架橋促進剤は、フッ素ゴム主鎖の脱フッ酸反応における分子内二重結合の生成と、生成した二重結合へのポリヒドロキシ化合物の付加を促進する。 When the crosslinking agent is a polyhydroxy compound, the fluororubber composition of the present invention preferably contains a crosslinking accelerator. A crosslinking accelerator accelerates | stimulates the production | generation of the intramolecular double bond in the dehydrofluorination reaction of a fluororubber principal chain, and the addition of the polyhydroxy compound to the produced | generated double bond.
架橋促進剤としては、オニウム化合物が挙げられ、オニウム化合物のなかでも、第４級アンモニウム塩等のアンモニウム化合物、第４級ホスホニウム塩等のホスホニウム化合物、オキソニウム化合物、スルホニウム化合物、環状アミン、及び、１官能性アミン化合物からなる群より選択される少なくとも１種であることが好ましく、第４級アンモニウム塩及び第４級ホスホニウム塩からなる群より選択される少なくとも１種であることがより好ましい。 Examples of the crosslinking accelerator include onium compounds. Among onium compounds, ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, and 1 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.
第４級アンモニウム塩としては特に限定されず、たとえば、８－メチル－１，８－ジアザビシクロ［５．４．０］－７－ウンデセニウムクロライド、８－メチル－１，８－ジアザビシクロ［５．４．０］－７－ウンデセニウムアイオダイド、８－メチル－１，８－ジアザビシクロ［５．４．０］－７－ウンデセニウムハイドロキサイド、８－メチル－１，８－ジアザビシクロ［５．４．０］－７－ウンデセニウムメチルスルフェート、８－エチル－１，８―ジアザビシクロ［５．４．０］－７－ウンデセニウムブロミド、８－プロピル－１，８－ジアザビシクロ［５．４．０］－７－ウンデセニウムブロミド、８－ドデシル－１，８－ジアザビシクロ［５．４．０］－７－ウンデセニウムクロライド、８－ドデシル－１，８－ジアザビシクロ［５，４，０］－７－ウンデセニウムハイドロキサイド、８－エイコシル－１，８－ジアザビシクロ［５．４．０］－７－ウンデセニウムクロライド、８－テトラコシル－１，８－ジアザビシクロ［５．４．０］－７－ウンデセニウムクロライド、８－ベンジル－１，８－ジアザビシクロ［５．４．０］－７－ウンデセニウムクロライド（以下、ＤＢＵ－Ｂとする）、８－ベンジル－１，８－ジアザビシクロ［５．４．０］－７－ウンデセニウムハイドロキサイド、８－フェネチル－１，８－ジアザビシクロ［５．４．０］－７―ウンデセニウムクロライド、８－（３－フェニルプロピル）－１，８－ジアザビシクロ［５．４．０］－７－ウンデセニウムクロライドなどが挙げられる。これらの中でも、架橋性及びフッ素ゴム成形品の物性が優れる点から、ＤＢＵ－Ｂが好ましい。 The quaternary ammonium salt is not particularly limited. For example, 8-methyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8-methyl-1,8-diazabicyclo [5. 4.0] -7-undecenium iodide, 8-methyl-1,8-diazabicyclo [5.4.0] -7-undecenium hydroxide, 8-methyl-1,8-diazabicyclo [5] 4.0] -7-undecenium methyl sulfate, 8-ethyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide, 8-propyl-1,8-diazabicyclo [5 4.0] -7-undecenium bromide, 8-dodecyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8-dodecyl-1,8-diazabicyclo 5,4,0] -7-undecenium hydroxide, 8-eicosyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8-tetracosyl-1,8-diazabicyclo [ 5.4.0] -7-undecenium chloride, 8-benzyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride (hereinafter referred to as DBU-B), 8-benzyl -1,8-diazabicyclo [5.4.0] -7-undecenium hydroxide, 8-phenethyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8- ( And 3-phenylpropyl) -1,8-diazabicyclo [5.4.0] -7-undecenium chloride. Among these, DBU-B is preferable from the viewpoint of excellent crosslinkability and physical properties of the fluororubber molded product.
また、第４級ホスホニウム塩としては特に限定されず、たとえば、テトラブチルホスホニウムクロライド、ベンジルトリフェニルホスホニウムクロライド（以下、ＢＴＰＰＣとする）、ベンジルトリメチルホスホニウムクロライド、ベンジルトリブチルホスホニウムクロライド、トリブチルアリルホスホニウムクロライド、トリブチル－２－メトキシプロピルホスホニウムクロライド、ベンジルフェニル（ジメチルアミノ）ホスホニウムクロライドなどを挙げることができ、これらの中でも、架橋性及びフッ素ゴム成形品の物性が優れる点から、ベンジルトリフェニルホスホニウムクロライド（ＢＴＰＰＣ）が好ましい。 The quaternary phosphonium salt is not particularly limited. For example, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyltributylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl. -2-Methoxypropylphosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride, and the like. Among these, benzyltriphenylphosphonium chloride (BTPPC) is preferred because of its excellent crosslinkability and physical properties of the fluororubber molded product. preferable.
また、架橋促進剤として、第４級アンモニウム塩、第４級ホスホニウム塩とビスフェノールＡＦの固溶体、特開平１１－１４７８９１号公報に開示されている塩素フリー架橋促進剤を用いることもできる。 Further, as a crosslinking accelerator, a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, or a chlorine-free crosslinking accelerator disclosed in JP-A-11-147891 can be used.
架橋促進剤の配合量は、フッ素ゴム１００質量部に対して、０．１～５質量部であることが好ましく、より好ましくは０．１５～３質量部である。架橋促進剤が、０．１質量部未満であると、フッ素ゴムの架橋が充分に進行せず、得られるフッ素ゴム成形品の耐熱性および耐油性が低下する傾向があり、５質量部をこえると、フッ素ゴム組成物の成形加工性が低下する傾向がある。 The blending amount of the crosslinking accelerator is preferably 0.1 to 5 parts by mass, more preferably 0.15 to 3 parts by mass with respect to 100 parts by mass of the fluororubber. If the cross-linking accelerator is less than 0.1 parts by mass, the cross-linking of the fluororubber does not proceed sufficiently, and the heat resistance and oil resistance of the resulting fluororubber molded product tend to decrease, exceeding 5 parts by mass. And there exists a tendency for the moldability of a fluororubber composition to fall.
有機過酸化物としては、熱や酸化還元系の存在下で容易にラジカルを発生し得る有機過酸化物であればよく、たとえば１，１－ビス（ｔ－ブチルパーオキシ）－３，５，５－トリメチルシクロヘキサン、２，５－ジメチルヘキサン－２，５－ジヒドロパーオキサイド、ジ－ｔ－ブチルパーオキサイド、ｔ－ブチルクミルパーオキサイド、ジクミルパーオキサイド、α，α－ビス（ｔ－ブチルパーオキシ）－ｐ－ジイソプロピルベンゼン、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）－ヘキシン－３、ベンゾイルパーオキサイド、ｔ－ブチルパーオキシベンゼン、ｔ－ブチルパーオキシマレイン酸、ｔ－ブチルパーオキシイソプロピルカーボネート、ｔ－ブチルパーオキシベンゾエイトなどを挙げることができる。これらの中でも、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）－ヘキシン－３が好ましい。 The organic peroxide may be an organic peroxide that can easily generate radicals in the presence of heat or a redox system. 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, α, α-bis (t-butylperoxide Oxy) -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-butylperoxyisopropyl carbonate, t-butylperoxide -Oxybenzoate can be mentioned. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 are preferable.
架橋剤が有機過酸化物である場合、本発明のフッ素ゴム組成物は架橋助剤を含むことが好ましい。架橋助剤としては、例えば、トリアリルシアヌレート、トリメタリルイソシアヌレート、トリアリルイソシアヌレート（ＴＡＩＣ）、トリアクリルホルマール、トリアリルトリメリテート、Ｎ，Ｎ’－ｍ－フェニレンビスマレイミド、ジプロパギルテレフタレート、ジアリルフタレート、テトラアリルテレフタレートアミド、トリアリルホスフェート、ビスマレイミド、フッ素化トリアリルイソシアヌレート（１，３，５－トリス（２，３，３－トリフルオロ－２－プロペニル）－１，３，５－トリアジン－２，４，６－トリオン）、トリス（ジアリルアミン）－Ｓ－トリアジン、亜リン酸トリアリル、Ｎ，Ｎ－ジアリルアクリルアミド、１，６－ジビニルドデカフルオロヘキサン、ヘキサアリルホスホルアミド、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラアリルフタルアミド、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラアリルマロンアミド、トリビニルイソシアヌレート、２，４，６－トリビニルメチルトリシロキサン、トリ（５－ノルボルネン－２－メチレン）シアヌレート、トリアリルホスファイトなどが挙げられる。これらの中でも、架橋性及びフッ素ゴム成形品の物性が優れる点から、トリアリルイソシアヌレート（ＴＡＩＣ）が好ましい。 When the crosslinking agent is an organic peroxide, the fluororubber composition of the present invention preferably contains a crosslinking aid. Examples of crosslinking aids include triallyl cyanurate, trimethallyl isocyanurate, triallyl isocyanurate (TAIC), triacryl 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'-teto Allylphthalamide, N, N, N ′, N′-tetraallylmalonamide, trivinylisocyanurate, 2,4,6-trivinylmethyltrisiloxane, tri (5-norbornene-2-methylene) cyanurate, triallyl Examples include phosphite. Among these, triallyl isocyanurate (TAIC) is preferable from the viewpoint of excellent crosslinkability and physical properties of the fluororubber molded article.
架橋助剤の配合量は、フッ素ゴム１００質量部に対して０．１～１０質量部であることが好ましく、より好ましくは０．３～７質量部である。架橋助剤が、０．１質量部より少ないと、フッ素ゴム成形品の圧縮永久ひずみが低下する傾向があり、１０質量部をこえると、フッ素ゴム成形品の伸びが著しく低下する傾向がある。 The blending amount of the crosslinking aid is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass with respect to 100 parts by mass of the fluororubber. When the amount of the crosslinking aid is less than 0.1 parts by mass, the compression set of the fluororubber molded product tends to decrease, and when it exceeds 10 parts by mass, the elongation of the fluororubber molded product tends to decrease remarkably.
架橋剤がポリアミン化合物またはポリヒドロキシ化合物である場合には、本発明のフッ素ゴム組成物は受酸剤を含むことが好ましい。受酸剤として、例えば酸化マグネシウム、酸化カルシウム、酸化ビスマス、酸化亜鉛等の金属酸化物、水酸化カルシウム等の金属水酸化物、合成ハイドロタルサイト類、メタケイ酸ナトリウム等が挙げられる。 When the crosslinking agent is a polyamine compound or a polyhydroxy compound, the fluororubber composition of the present invention preferably contains an acid acceptor. Examples of the acid acceptor include metal oxides such as magnesium oxide, calcium oxide, bismuth oxide, and zinc oxide, metal hydroxides such as calcium hydroxide, synthetic hydrotalcites, and sodium metasilicate.
受酸剤の配合量は、フッ素ゴム１００質量部に対して０．５～３０質量部であることが好ましく、より好ましくは１～１５質量部である。受酸剤が、０．５質量部より少ないと、架橋時間が実用に耐えないほど長くなる傾向があり、３０質量部をこえると、フッ素ゴム成形品の圧縮永久ひずみも低下する傾向がある。 The compounding amount of the acid acceptor is preferably 0.5 to 30 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the fluororubber. When the amount of the acid acceptor is less than 0.5 parts by mass, the crosslinking time tends to be too long to be practically used, and when it exceeds 30 parts by mass, the compression set of the fluororubber molded product also tends to decrease.
また架橋剤が有機過酸化物である場合には、本発明のフッ素ゴム組成物は、本発明の効果に影響を及ぼさない範囲で受酸剤を含んでもよい。 Moreover, when a crosslinking agent is an organic peroxide, the fluororubber composition of this invention may contain an acid acceptor in the range which does not affect the effect of this invention.
架橋は、使用する架橋剤などの種類により適宜決めればよいが、通常、１４０～３００℃の温度で、１分～２４時間焼成する。また、常圧、加圧、減圧下においても、また、空気中においても、架橋することができる。 Crosslinking may be appropriately determined depending on the type of the crosslinking agent used, but is usually fired at a temperature of 140 to 300 ° C. for 1 minute to 24 hours. Moreover, it can bridge | crosslink under normal pressure, pressurization, pressure reduction, and also in the air.
架橋方法としては、特に限定されず、スチーム架橋、加圧成形法、加熱により架橋反応が開始される通常の方法が採用でき、常温常圧での放射線架橋法であってもよい。 The cross-linking method is not particularly limited, and a steam cross-linking method, a pressure forming method, a normal method in which a cross-linking reaction is started by heating can be adopted, and a radiation cross-linking method at normal temperature and normal pressure may be used.
最初の架橋処理（一次架橋という）を施した後に二次架橋と称される後処理工程を施してもよい。 After the first crosslinking treatment (referred to as primary crosslinking), a post-treatment step called secondary crosslinking may be performed.
架橋剤としてポリアミン化合物を使用するポリアミン架橋は、従来と同様に行うことができる。たとえば、本発明におけるフッ素ゴムと架橋剤、要すれば架橋促進剤、さらには適宜混合可能な他の添加剤とをロール練り後金型に入れ加圧して一次架橋し、ついで二次架橋する方法が挙げられる。一般に一次架橋の条件は、温度１３０～２００℃で、時間１～１２０分間、圧力２～１５ＭＰａ程度の範囲から採用され、二次架橋の条件は温度１５０～３００℃で、時間３０分間～３０時間程度の範囲から採用される。 Polyamine crosslinking using a polyamine compound as a crosslinking agent can be carried out in the same manner as before. For example, a method in which the fluororubber and the cross-linking agent in the present invention, if necessary, a cross-linking accelerator, and other additives that can be mixed as appropriate are roll-kneaded and then put into a mold and pressurized to perform primary cross-linking and then secondary cross-linking Is mentioned. In general, primary crosslinking conditions are employed at a temperature of 130 to 200 ° C., a time of 1 to 120 minutes, and a pressure of about 2 to 15 MPa. Secondary crosslinking conditions are a temperature of 150 to 300 ° C. and a time of 30 minutes to 30 hours. Adopted from a range of degrees.
架橋剤としてポリヒドロキシ化合物を使用するポリオール架橋は、従来と同様に行うことができる。たとえば、本発明におけるフッ素ゴムと架橋剤、要すれば架橋促進剤、さらには適宜混合可能な他の添加剤とをロール練り後金型に入れ加圧して一次架橋し、ついで二次架橋する方法が挙げられる。混練はインターナルミキサー、バンバリーミキサーなどが好ましく使用できる。一般に一次架橋は、２～１５ＭＰａ、１３０～２００℃で１～６０分間行うことができ、二次架橋は１５０～３００℃で３０分間～３０時間行うことができる。 Polyol crosslinking using a polyhydroxy compound as a crosslinking agent can be carried out in the same manner as before. For example, a method in which the fluororubber and the cross-linking agent in the present invention, if necessary, a cross-linking accelerator, and other additives that can be mixed as appropriate are roll-kneaded and then put into a mold and pressurized to perform primary cross-linking and then secondary cross-linking Is mentioned. For the kneading, an internal mixer, a Banbury mixer or the like can be preferably used. In general, primary crosslinking can be performed at 2 to 15 MPa at 130 to 200 ° C. for 1 to 60 minutes, and secondary crosslinking can be performed at 150 to 300 ° C. for 30 minutes to 30 hours.
架橋剤として有機過酸化物を使用するパーオキサイド架橋は、従来と同様に行うことができる。たとえば、本発明におけるフッ素ゴムと架橋剤、要すれば架橋促進剤、さらには適宜混合可能な他の添加剤とをロール練り後金型に入れ加圧して一次架橋し、ついで二次架橋する方法が挙げられる。一般に一次架橋は、２～１５ＭＰａ、１３０～２００℃で１～６０分間行うことができ、二次架橋は１５０～３００℃で３０分間～３０時間行うことができる。 Peroxide crosslinking using an organic peroxide as a crosslinking agent can be carried out in the same manner as before. For example, a method in which the fluororubber and the cross-linking agent in the present invention, if necessary, a cross-linking accelerator, and other additives that can be mixed as appropriate are roll-kneaded and then put into a mold and pressurized to perform primary cross-linking and then secondary cross-linking Is mentioned. In general, primary crosslinking can be performed at 2 to 15 MPa at 130 to 200 ° C. for 1 to 60 minutes, and secondary crosslinking can be performed at 150 to 300 ° C. for 30 minutes to 30 hours.
４．その他の成分
本発明のフッ素ゴム組成物は充填剤を含むことも好ましい。充填剤としては、酸化チタン、酸化アルミニウムなどの金属酸化物；水酸化マグネシウム、水酸化アルミニウムなどの金属水酸化物；炭酸マグネシウム、炭酸アルミニウム、炭酸カルシウム、炭酸バリウムなどの炭酸塩；ケイ酸マグネシウム、ケイ酸カルシウム、ケイ酸アルミニウムなどのケイ酸塩；硫酸アルミニウム、硫酸カルシウム、硫酸バリウムなどの硫酸塩；二硫化モリブデン、硫化鉄、硫化銅などの金属硫化物；ケイ藻土、アスベスト、リトポン（硫化亜鉛／硫化バリウム）、グラファイト、カーボンブラック（ランプブラックを除く）、フッ化カーボン、フッ化カルシウム、コークス、石英微粉末、亜鉛華、タルク、雲母粉末、ワラストナイト、炭素繊維、アラミド繊維、各種ウィスカー、ガラス繊維、有機補強剤、有機充填剤、ポリテトラフルオロエチレン、含フッ素熱可塑性樹脂、マイカ、シリカ、セライト、クレー等が挙げられる。 4). Other Components The fluororubber composition of the present invention preferably contains a filler. Fillers include metal oxides such as titanium oxide and aluminum oxide; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; carbonates such as magnesium carbonate, aluminum carbonate, calcium carbonate and barium carbonate; magnesium silicate, Silicates such as calcium silicate and aluminum silicate; sulfates such as aluminum sulfate, calcium sulfate and barium sulfate; metal sulfides such as molybdenum disulfide, iron sulfide and copper sulfide; diatomaceous earth, asbestos and lithopone (sulfurized) Zinc / barium sulfide), graphite, carbon black (excluding lamp black), carbon fluoride, calcium fluoride, coke, quartz fine powder, zinc white, talc, mica powder, wollastonite, carbon fiber, aramid fiber, various Whisker, glass fiber, organic reinforcing agent, organic filler Polytetrafluoroethylene, fluorine-containing thermoplastic resin, mica, silica, Celite, clay and the like.
本発明のフッ素ゴム組成物は可塑剤を含むことも好ましい。可塑剤としては、ジオクチルフタル酸、ペンタエリスリトール等が挙げられる。 The fluororubber composition of the present invention preferably contains a plasticizer. Examples of the plasticizer include dioctyl phthalic acid and pentaerythritol.
本発明のフッ素ゴム組成物は加工助剤を含むことも好ましい。加工助剤としては、ステアリン酸、オレイン酸、パルミチン酸、ラウリン酸などの高級脂肪酸；ステアリン酸ナトリウム、ステアリン酸亜鉛などの高級脂肪酸塩；ステアリン酸アミド、オレイン酸アミドなどの高級脂肪酸アミド；オレイン酸エチルなどの高級脂肪酸エステル；セバシン酸ジ－ｎ－オクチル、セバシン酸ジ－ｎ－ブチル、セバシン酸ビス－２－エチルヘキシルなどの脂肪酸ジエステル；ステアリルアミン、オレイルアミンなどの高級脂肪族アミン；ステアリルアルコールなどの高級脂肪族アルコール；カルナバワックス、セレシンワックスなどの石油系ワックス；エチレングリコール、グリセリン、ジエチレングリコールなどのポリグリコール；ワセリン、パラフィンなどの脂肪族炭化水素；シリコーン系オイル、シリコーン系ポリマー、低分子量ポリエチレン、フタル酸エステル類、リン酸エステル類、ロジン、（ハロゲン化）ジアルキルアミン、界面活性剤、スルホン化合物、フッ素系助剤等が挙げられる。 The fluororubber composition of the present invention preferably contains a processing aid. As processing aids, higher fatty acids such as stearic acid, oleic acid, palmitic acid and lauric acid; higher fatty acid salts such as sodium stearate and zinc stearate; higher fatty acid amides such as stearic acid amide and oleic acid amide; oleic acid Higher fatty acid esters such as ethyl; fatty acid diesters such as di-n-octyl sebacate, di-n-butyl sebacate and bis-2-ethylhexyl sebacate; higher aliphatic amines such as stearylamine and oleylamine; stearyl alcohol and the like Higher aliphatic alcohols; petroleum waxes such as carnauba wax and ceresin wax; polyglycols such as ethylene glycol, glycerin and diethylene glycol; aliphatic hydrocarbons such as petroleum jelly and paraffin; silicone oils and silicones Polymers, low molecular weight polyethylene, phthalic acid esters, phosphoric acid esters, rosin, (halogenated) dialkylamines, surfactants, sulfone compounds, fluorine-based aids, and the like.
本発明のフッ素ゴム組成物は、離型剤、顔料、難燃剤、滑剤、光安定剤、耐候安定剤、帯電防止剤、紫外線吸収剤、酸化防止剤、発泡剤、香料、オイル、柔軟化剤などを、本発明の効果に影響を及ぼさない範囲で含んでもよい。 The fluororubber composition of the present invention comprises a release agent, pigment, flame retardant, lubricant, light stabilizer, weathering stabilizer, antistatic agent, ultraviolet absorber, antioxidant, foaming agent, perfume, oil, and softening agent. Etc. may be included within a range that does not affect the effects of the present invention.
本発明のフッ素ゴム組成物は、本発明におけるフッ素ゴムとは異なる他のポリマーを含んでもよい。他のポリマーとしては、ニトリルゴム、アクリルゴム、エピクロルヒドリンゴム、フルオロシリコーンゴム、シリコーンゴム、含フッ素熱可塑性エラストマー等が挙げられる。 The fluororubber composition of the present invention may contain another polymer different from the fluororubber in the present invention. Examples of the other polymer include nitrile rubber, acrylic rubber, epichlorohydrin rubber, fluorosilicone rubber, silicone rubber, and fluorine-containing thermoplastic elastomer.
５．フッ素ゴム組成物の製造方法
本発明のフッ素ゴム組成物は、少なくともフッ素ゴム、ランプブラック、及び、架橋剤、並びに、所望により上述した架橋促進剤等を、混練して得られたものであることが好ましい。 5. Production method of fluororubber composition The fluororubber composition of the present invention is obtained by kneading at least fluororubber, lamp black, a crosslinking agent, and the above-mentioned crosslinking accelerator, if desired. Is preferred.
上記混練には、オープンロール、バンバリーミキサー、加圧ニーダー、押出機等を使用できるが、高剪断力を加えることができる点で、加圧ニーダー又は二軸押出機等の押出機を用いることが好ましい。 For the kneading, an open roll, a Banbury mixer, a pressure kneader, an extruder or the like can be used, but an extruder such as a pressure kneader or a twin screw extruder can be used in that a high shear force can be applied. preferable.
また、本発明のフッ素ゴム組成物は、国際公開第２０１２／０２６００７号、国際公開第２０１２／０２６５３４号、及び国際公開第２０１２／０２６５５２号に記載されている方法等によって製造することができる。 Moreover, the fluororubber composition of this invention can be manufactured by the method etc. which are described in international publication 2012/026007, international publication 2012/026534, and international publication 2012/026552.
より具体的には、つぎの各方法が挙げられるが、これらの方法に限定されるものではない。 More specifically, the following methods may be mentioned, but the present invention is not limited to these methods.
（１）密閉式混練機にフッ素ゴム、ランプブラック、所望により充填剤、および所望により受酸剤を所定量投入し、ローターの平均剪断速度を５０～１０００（１／秒）、好ましくは１００～１０００（１／秒）、更に好ましくは２００～１０００（１／秒）に調整して、混練温度の最高温度Ｔｍが８０～２２０℃（好ましくは１２０～２００℃）となる条件で混練する方法（つまり、混練時の混練物の最高温度Ｔｍを８０℃～２２０℃とし、その温度で排出する条件にて混練することが好ましい。以下同様）。なお、密閉式混練機としては、加圧ニーダーやバンバリーミキサー、一軸混練機、二軸混練機などが挙げられる。 (1) A predetermined amount of fluororubber, lamp black, a filler as required, and an acid acceptor as required are put into a closed kneader, and the average shear rate of the rotor is 50 to 1000 (1 / second), preferably 100 to A method of kneading under the condition that the maximum temperature Tm of the kneading temperature is 80 to 220 ° C. (preferably 120 to 200 ° C.) by adjusting to 1000 (1 / sec), more preferably 200 to 1000 (1 / sec) ( That is, it is preferable that the maximum temperature Tm of the kneaded material during kneading is 80 ° C. to 220 ° C., and kneading is performed under the condition of discharging at that temperature (the same applies hereinafter). Examples of the closed kneader include a pressure kneader, a Banbury mixer, a uniaxial kneader, and a biaxial kneader.
（２）ロール練り機にフッ素ゴム、ランプブラック、所望により充填剤、および所望により受酸剤を所定量投入し、ローターの平均剪断速度を５０（１／秒）以上、混練温度の最高温度Ｔｍが８０～２２０℃（好ましくは１２０～２００℃）となる条件で混練する方法。 (2) A predetermined amount of fluororubber, lamp black, a filler as required, and an acid acceptor as required are put into a roll kneader, and the average shear rate of the rotor is 50 (1 / second) or more, and the maximum kneading temperature Tm Kneading under the conditions of 80 to 220 ° C (preferably 120 to 200 ° C).
上記（１）、（２）の方法で得られる組成物は架橋剤（および／または架橋助剤）や架橋促進剤などを含んでいない。また、上記（１）、（２）の方法の混練を複数回行ってもよい。複数回行う場合、２回目以降の混練条件は、混練温度の最高温度Ｔｍを１４０℃以下とする以外は上記（１）、（２）の方法と同じ条件でよい。 The composition obtained by the above methods (1) and (2) does not contain a crosslinking agent (and / or a crosslinking aid) or a crosslinking accelerator. Moreover, you may perform kneading | mixing of the method of said (1) and (2) in multiple times. When performing a plurality of times, the second and subsequent kneading conditions may be the same as the methods (1) and (2) except that the maximum temperature Tm of the kneading temperature is 140 ° C. or lower.
本発明のフッ素ゴム組成物の調製法の１つは、たとえば、上記（１）、（２）の方法で得られた、あるいは上記（１）、（２）の方法を複数回繰り返して得られた組成物に、更に架橋剤（および／または架橋助剤）および架橋促進剤を配合し混練する方法である。 One of the methods for preparing the fluororubber composition of the present invention is obtained, for example, by the above methods (1) and (2) or by repeating the above methods (1) and (2) a plurality of times. In this method, a cross-linking agent (and / or a cross-linking aid) and a cross-linking accelerator are further added to the composition and kneaded.
架橋剤（および／または架橋助剤）と架橋促進剤は同時に配合し混練してもよいし、まず架橋促進剤を配合混練し、ついで架橋剤（および／または架橋助剤）を配合混練してもよい。架橋剤（および／または架橋助剤）と架橋促進剤の混練条件は、混練温度の最高温度Ｔｍが１３０℃以下であるほかは、上記（１）、（２）の方法と同じ条件でよい。 The crosslinking agent (and / or crosslinking aid) and the crosslinking accelerator may be blended and kneaded at the same time. First, the crosslinking accelerator is blended and kneaded, and then the crosslinking agent (and / or crosslinking aid) is blended and kneaded. Also good. The kneading conditions for the cross-linking agent (and / or the cross-linking aid) and the cross-linking accelerator may be the same conditions as the methods (1) and (2) except that the maximum temperature Tm of the kneading temperature is 130 ° C. or less.
本発明のフッ素ゴム組成物の別の調製法は、たとえばロール練り機にフッ素ゴム、ランプブラック、所望により充填剤、架橋剤（および／または架橋助剤）および所望により架橋促進剤を適切な順序で所定量投入し、ローターの平均剪断速度を５０（１／秒）以上、混練温度の最高温度Ｔｍが１３０℃以下の条件で混練する方法が挙げられる。 Another method for preparing the fluororubber composition of the present invention is, for example, using a roll kneader in an appropriate sequence of fluororubber, lamp black, optionally filler, crosslinking agent (and / or crosslinking aid) and optionally crosslinking accelerator. And a kneading method under the condition that the average shear rate of the rotor is 50 (1 / second) or more and the maximum kneading temperature Tm is 130 ° C. or less.
また、ポリオール架橋系の場合は、予めフッ素ゴムと架橋剤と架橋促進剤を混合し、均一分散体にしたものを使用してもよい。たとえば、フッ素ゴムとポリオール系架橋剤と架橋促進剤をまず混練し、ついでランプブラックおよび充填剤を配合して混練し、混練温度の最高温度Ｔｍを８０～２２０℃とする。そして、最後に受酸剤を配合して混練し、混練温度の最高温度Ｔｍを１３０℃以下とする方法が挙げられる。なお混練するにあたっては、平均剪断速度を５０（１／秒）以上で混練する方法を採用するのがより好ましい。 In the case of a polyol cross-linking system, a uniform dispersion obtained by previously mixing fluororubber, a cross-linking agent, and a cross-linking accelerator may be used. For example, fluororubber, polyol-based crosslinking agent and crosslinking accelerator are first kneaded, then lamp black and filler are blended and kneaded, and the maximum temperature Tm of the kneading temperature is set to 80 to 220 ° C. Finally, there is a method in which an acid acceptor is blended and kneaded so that the maximum temperature Tm of the kneading temperature is 130 ° C. or less. In the kneading, it is more preferable to employ a method of kneading at an average shear rate of 50 (1 / second) or more.
平均剪断速度（１／秒）は、つぎの式により算出される。
平均剪断速度（１／秒）＝（π×Ｄ×Ｒ）／（６０（秒）×ｃ）
（式中、
Ｄ：ローター径またはロール径（ｃｍ）
Ｒ：回転速度（ｒｐｍ）
ｃ：チップクリアランス（ｃｍ。ローターとケーシングとの間隙の距離、またはロール同士の間隙の距離）） The average shear rate (1 / second) is calculated by the following formula.
Average shear rate (1 / second) = (π × D × R) / (60 (second) × c)
(Where
D: Rotor diameter or roll diameter (cm)
R: Rotational speed (rpm)
c: Chip clearance (cm. Distance between rotor and casing, or distance between rolls)
６．フッ素ゴム成形品の製造方法及び特徴
本発明は、本発明のフッ素ゴム組成物を架橋して得られるフッ素ゴム成形品でもある。 6). Production method and characteristics of fluororubber molded product The present invention is also a fluororubber molded product obtained by crosslinking the fluororubber composition of the present invention.
本発明のフッ素ゴム成形品は、本発明のフッ素ゴム組成物を成形し、得られた成形品を架橋することにより製造することもできるし、成形と架橋とを同時に行うことによって製造することもできる。また、架橋性組成物を塗装し、架橋することによって、塗膜として得ることもできる。 The fluororubber molded article of the present invention can be produced by molding the fluororubber composition of the present invention and crosslinking the resulting molded article, or by simultaneously performing molding and crosslinking. it can. Moreover, it can also be obtained as a coating film by coating and crosslinking the crosslinkable composition.
成形方法は、特に限定されず、例えば、圧縮成形、押出し成形、トランスファー成形、射出成形等が挙げられる。 The molding method is not particularly limited, and examples thereof include compression molding, extrusion molding, transfer molding, and injection molding.
本発明のフッ素ゴム成形品は、２００℃における切断時引張応力が９ＭＰａを超えるという従来にない特性を有するものであってよい。 The fluororubber molded article of the present invention may have an unprecedented characteristic that the tensile stress at cutting at 200 ° C. exceeds 9 MPa.
７．フッ素ゴム成形品の用途
本発明のフッ素ゴム成形品は、優れた耐熱性、耐油性、耐アミン性、耐薬品性及び耐寒性を有しており、他材と接触して摺動したり、他材、物質を封止、密封したり、防振、防音を目的とする部位一般に用いられ、自動車産業、航空機産業、半導体産業等の各分野において各種部品として使用することができる。
用いられる分野としては例えば、半導体関連分野、自動車分野、航空機分野、宇宙・ロケット分野、船舶分野、化学プラント等の化学品分野、医薬品等の薬品分野、現像機等の写真分野、印刷機械等の印刷分野、塗装設備等の塗装分野、分析機器、計器等の分析・理化学機械分野、食品プラント機器及び家庭用品を含む食品機器分野、飲料食品製造装置分野、医薬品製造装置分野、医療部品分野、化学薬品輸送用機器分野、原子力プラント機器分野、鉄板加工設備等の鉄鋼分野、一般工業分野、電気分野、燃料電池分野、電子部品分野、光学機器部品分野、宇宙用機器部品分野、石油化学プラント機器分野、石油、ガス等のエネルギー資源探索採掘機器部品分野、石油精製分野、石油輸送機器部品分野などが挙げられる。 7). Applications of fluororubber molded products The fluororubber molded products of the present invention have excellent heat resistance, oil resistance, amine resistance, chemical resistance and cold resistance, and can slide in contact with other materials. It is generally used for parts for sealing and sealing other materials and substances, and for the purpose of vibration proofing and sound proofing, and can be used as various parts in various fields such as the automobile industry, aircraft industry, and semiconductor industry.
Fields used include, for example, semiconductor-related fields, automotive fields, aircraft fields, space / rocket fields, ship fields, chemical fields such as chemical plants, pharmaceutical fields such as pharmaceuticals, photographic fields such as developing machines, printing machines, etc. Printing field, painting field such as coating equipment, analysis equipment, analysis / physical machinery field such as instruments, food equipment field including food plant equipment and household goods, beverage food production equipment field, pharmaceutical production equipment field, medical parts field, chemical Chemical transportation equipment field, nuclear plant equipment field, steel field such as iron plate processing equipment, general industrial field, electrical field, fuel cell field, electronic parts field, optical equipment parts field, space equipment parts field, petrochemical plant equipment field Oil, gas and other energy resource exploration equipment parts field, oil refining field, oil transportation equipment parts field.
本発明のフッ素ゴム成形品の使用形態としては、例えば、リング、パッキン、ガスケット、ダイアフラム、オイルシール、ベアリングシール、リップシール、プランジャーシール、ドアシール、リップ及びフェースシール、ガスデリバリープレートシール、ウエハサポートシール、バレルシール等の各種シール材やパッキンなどが挙げられる。シール材としては、耐熱性、耐溶剤性、耐薬品性、非粘着性が要求される用途に用いることができる。
また、チューブ、ホース、ロール、各種ゴムロール、フレキシブルジョイント、ゴム板、コーティング、ベルト、ダンパー、バルブ、バルブシート、バルブの弁体、耐薬品用コーティング材料、ラミネート用材料、ライニング用材料などとしても使用できる。
なお、上記リング、パッキン、シールの断面形状は、種々の形状のものであってよく、具体的には、例えば、四角、Ｏ字、へルールなどの形状であってもよいし、Ｄ字、Ｌ字、Ｔ字、Ｖ字、Ｘ字、Ｙ字などの異形状であってもよい。 Examples of usage forms of the fluororubber molded product of the present invention include, for example, a ring, packing, gasket, diaphragm, oil seal, bearing seal, lip seal, plunger seal, door seal, lip and face seal, gas delivery plate seal, and wafer support. Examples include various sealing materials such as seals and barrel seals, and packing. As a sealing material, it can be used for applications requiring heat resistance, solvent resistance, chemical resistance, and non-adhesiveness.
Also used as tubes, hoses, rolls, various rubber rolls, flexible joints, rubber plates, coatings, belts, dampers, valves, valve seats, valve discs, chemical-resistant coating materials, laminating materials, lining materials, etc. it can.
The cross-sectional shapes of the ring, packing, and seal may be various shapes. Specifically, for example, the ring, the packing, and the seal may have a square shape, an O shape, a ferrule shape, a D shape, Different shapes such as L, T, V, X, Y may be used.
上記半導体関連分野においては、例えば、半導体製造装置、液晶パネル製造装置、プラズマパネル製造装置、プラズマディスプレイパネル製造装置、プラズマアドレス液晶パネル製造装置、有機ＥＬパネル製造装置、フィールドエミッションディスプレイパネル製造装置、太陽電池基板製造装置、半導体搬送装置等に用いることができる。そのような装置としては、例えば、ＣＶＤ装置、半導体用ガス制御装置等のガス制御装置、ドライエッチング装置、ウェットエッチング装置、プラズマエッチング装置、反応性イオンエッチング装置、反応性イオンビームエッチング装置、スパッタエッチング装置、イオンビームエッチング装置、酸化拡散装置、スパッタリング装置、アッシング装置、プラズマアッシング装置、洗浄装置、イオン注入装置、プラズマＣＶＤ装置、排気装置、露光装置、研磨装置、成膜装置、乾式エッチング洗浄装置、ＵＶ／Ｏ３洗浄装置、イオンビーム洗浄装置、レーザービーム洗浄装置、プラズマ洗浄装置、ガスエッチング洗浄装置、抽出洗浄装置、ソックスレー抽出洗浄装置、高温高圧抽出洗浄装置、マイクロウェーブ抽出洗浄装置、超臨界抽出洗浄装置、フッ酸、塩酸、硫酸、オゾン水等を用いる洗浄装置、ステッパー、コータ・デベロッパー、ＣＭＰ装置、エキシマレーザー露光機、薬液配管、ガス配管、ＮＦ３プラズマ処理、Ｏ２プラズマ処理、フッ素プラズマ処理等のプラズマ処理が行われる装置、熱処理成膜装置、ウエハ搬送機器、ウエハ洗浄装置、シリコンウエハ洗浄装置、シリコンウエハ処理装置、ＬＰ－ＣＶＤ工程に用いられる装置、ランプアニーリング工程に用いられる装置、リフロー工程に用いられる装置などが挙げられる。 In the semiconductor related field, for example, semiconductor manufacturing apparatus, liquid crystal panel manufacturing apparatus, plasma panel manufacturing apparatus, plasma display panel manufacturing apparatus, plasma address 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. Examples of such an apparatus include a gas control apparatus such as a CVD apparatus and a semiconductor gas control apparatus, a dry etching apparatus, a wet etching apparatus, a plasma etching apparatus, a reactive ion etching apparatus, a reactive ion beam etching apparatus, and a sputter etching. Apparatus, ion beam etching apparatus, oxidation diffusion 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 device, Soxhlet extraction cleaning device, high temperature high pressure extraction cleaning device, microwave extraction cleaning device, supercritical extraction Cleaning equipment Equipment, cleaning equipment using hydrofluoric acid, hydrochloric acid, sulfuric acid, ozone water, stepper, coater / developer, CMP equipment, excimer laser exposure machine, chemical piping, gas piping, NF 3 plasma treatment, O 2 plasma treatment, fluorine plasma treatment Equipment for plasma processing such as heat treatment film forming equipment, wafer transfer equipment, wafer cleaning equipment, silicon wafer cleaning equipment, silicon wafer processing equipment, equipment used in LP-CVD processes, equipment used in lamp annealing processes, reflow Examples include an apparatus used in the process.
半導体関連分野における具体的な使用形態としては、例えば、ゲートバルブ、クォーツウィンドウ、チャンバー、チャンバーリット、ゲート、ベルジャー、カップリング、ポンプのＯ－リングやガスケット等の各種シール材；レジスト現像液や剥離液用のＯ－リング等の各種シール材、ホースやチューブ；レジスト現像液槽、剥離液槽、ウエハ洗浄液槽、ウェットエッチング槽のライニングやコーティング；ポンプのダイアフラム；ウエハ搬送用のロール；ウエハ洗浄液用のホースチューブ；クリーンルーム等のクリーン設備用シーラントといったクリーン設備用シール材；半導体製造装置やウエハ等のデバイスを保管する保管庫用のシーリング材；半導体を製造する工程で用いられる薬液移送用ダイアフラムなどが挙げられる。 Specific usage forms in the field of semiconductors include, for example, various sealing materials such as gate valves, quartz windows, chambers, chamber lits, gates, bell jars, couplings, pump O-rings and gaskets; resist developers and stripping Various sealing materials such as O-rings for liquid, hoses and tubes; resist developer tank, stripper tank, wafer cleaning liquid tank, wet etching tank lining and coating; pump diaphragm; wafer transfer roll; wafer cleaning liquid Hose tube; Clean equipment sealant for clean equipment such as clean rooms; Sealing material for storage equipment for storing semiconductor manufacturing equipment and wafers; Diaphragm for transferring chemicals used in semiconductor manufacturing processes Can be mentioned.
上記自動車分野においては、エンジン本体、主運動系、動弁系、潤滑・冷却系、燃料系、吸気・排気系、駆動系のトランスミッション系、シャーシのステアリング系、ブレーキ系や、基本電装部品、制御系電装部品、装備電装部品等の電装部品などに用いることができる。なお、上記自動車分野には、自動二輪車も含まれる。
上述のようなエンジン本体やその周辺装置では、耐熱性、耐油性、燃料油耐性、エンジン冷却用不凍液耐性、耐スチーム性が要求される各種シール材に本発明のフッ素ゴム成形品を用いることができ、そのようなシール材としては、例えば、ガスケット、シャフトシール、バルブステムシール等のシールや、セルフシールパッキン、ピストンリング、割リング形パッキン、メカニカルシール、オイルシール等の非接触型又は接触型のパッキン類、ベローズ、ダイアフラム、ホース、チューブの他、電線、緩衝材、防振材、ベルトＡＴ装置に用いられる各種シール材などが挙げられる。 In the automotive 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 electrical components, control It can be used for electrical components such as system electrical components and equipment electrical components. Note that the automobile field includes a motorcycle.
In the engine body and its peripheral devices as described above, the fluororubber molded product of the present invention is used for various sealing materials that require heat resistance, oil resistance, fuel oil resistance, engine cooling antifreeze resistance, and steam resistance. Examples of such sealing materials include seals such as gaskets, shaft seals, valve stem seals, and non-contact or contact types such as self-seal packing, piston rings, split ring packings, mechanical seals, and oil seals. In addition to the above packings, bellows, diaphragms, hoses, tubes, electric wires, cushioning materials, anti-vibration materials, various sealing materials used for belt AT devices, and the like.
上記燃料系における具体的な使用形態としては、燃料インジェクター、コールドスタートインジェクター、燃料ラインのクイックコネクター、センダー・フランジ・クイックコネクター、燃料ポンプ、燃料タンク・クイック・コネクター、ガソリン混合ポンプ、ガソリンポンプ、燃料チューブのチューブ本体、燃料チューブのコネクター、インジェクター等に用いられるＯ－リング；呼気系マニホールド、燃料フィルター、圧力調整弁、キャニスター、燃料タンクのキャップ、燃料ポンプ、燃料タンク、燃料タンクのセンダーユニット、燃料噴射装置、燃料高圧ポンプ、燃料ラインコネクターシステム、ポンプタイミングコントロールバルブ、サクションコントロールバルブ、ソレノイドサブアッシー、フューエルカットバルブ等に用いられるシール；キャニスタ・パージ・ソレノイド・バルブシール、オンボード・リフューエリング・ベイパー・リカバリー（ＯＲＶＲ）バルブシール、燃料ポンプ用のオイルシール、フューエルセンダーシール、燃料タンクロールオーバー・バルブシール、フィラーシール、インジェクターシール、フィラーキャップシール、フィラーキャップバルブのシール；燃料ホース、燃料供給ホース、燃料リターンホース、ベーパー（エバポ）ホース、ベント（ブリーザー）ホース、フィラーホース、フィラーネックホース、燃料タンク内のホース（インタンクホース）、キャブレターのコントロールホース、フューエルインレットホース、フューエルブリーザホース等のホース；燃料フィルター、燃料ラインコネクターシステム等に用いられるガスケットや、キャブレター等に用いられるフランジガスケット；蒸気回収ライン、フューエルフィードライン、ベーパー・ＯＲＶＲライン等のライン材；キャニスター、ＯＲＶＲ、燃料ポンプ、燃料タンク圧力センサー、ガソリンポンプ、キャブレターのセンサー、複合空気制御装置（ＣＡＣ）、パルセーションダンパー、キャニスター用、オートコック等に用いられるダイアフラムや、燃料噴射装置のプレッシャーレギュレーターダイアフラム；燃料ポンプ用のバルブ、キャブレーターニードルバルブ、ロールオーバーチェックバルブ、チェックバルブ類；ベント（ブリーザー）、燃料タンク内に用いられるチューブ；燃料タンク等のタンクパッキン、キャブレターの加速ポンプピストンのパッキン；燃料タンク用のフューエルセンダー防振部品；燃料圧力を制御するためのＯ－リングや、ダイアフラム；アクセレレータ・ポンプ・カップ；インタンクフューエルポンプマウント；燃料噴射装置のインジェクタークッションリング；インジェクターシールリング；キャブレターのニードルバルブ芯弁；キャブレターの加速ポンプピストン；複合空気制御装置（ＣＡＣ）のバルブシート；フューエルタンク本体；ソレノイドバルブ用シール部品などが挙げられる。 Specific usage forms in the above fuel system include fuel injectors, cold start injectors, fuel line quick connectors, sender flange quick connectors, fuel pumps, fuel tank quick connectors, gasoline mixing pumps, gasoline pumps, fuel O-ring used for tube body, fuel tube connector, injector, etc .; exhalation system manifold, fuel filter, pressure regulating valve, canister, fuel tank cap, fuel pump, fuel tank, fuel tank sender unit, fuel Used in injection devices, high-pressure fuel pumps, fuel line connector systems, pump timing control valves, suction control valves, solenoid subassemblies, fuel cut valves, etc. Seals: Canister, purge, solenoid, valve seal, on-board, recirculating, 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 (evaporation) 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 in fuel filters, fuel line connector systems, etc. Flange gaskets used for carburetors, etc .; Line materials such as steam recovery lines, fuel feed lines, vapor / ORVR lines; canisters, ORVR, fuel pumps, fuel tank pressure sensors, gasoline pumps, carburetor sensors, combined air control devices (CAC), pulsation dampers, canisters, diaphragms used for autococks, etc., fuel injector pressure regulator diaphragms; fuel pump valves, carburetor needle valves, rollover check valves, check valves; vents (breathers) ), Tubes used in fuel tanks; tank packings for fuel tanks, accelerating pump piston packings for carburetors; fuel sender anti-vibration parts for fuel tanks; O-ring and diaphragm for controlling fuel pressure; accelerator pump cup; in-tank fuel pump mount; fuel injector injector cushion ring; injector seal ring; carburetor needle valve core valve; carburetor acceleration pump piston A valve seat of a composite air control device (CAC); a fuel tank body; a sealing part for a solenoid valve;
上記ブレーキ系における具体的な使用形態としては、マスターバック、油圧ブレーキホースエアーブレーキ、エアーブレーキのブレーキチャンバー等に用いられるダイアフラム；ブレーキホース、ブレーキオイルホース、バキュームブレーキホース等に用いられるホース；オイルシール、Ｏ－リング、パッキン、ブレーキピストンシール等の各種シール材；マスターバック用の大気弁や真空弁、ブレーキバルブ用のチェック弁；マスターシリンダー用のピストンカップ（ゴムカップ）や、ブレーキカップ；油圧ブレーキのマスターシリンダーやバキュームブースター、油圧ブレーキのホイールシリンダー用のブーツ、アンチロック・ブレーキ・システム（ＡＢＳ）用のＯ－リングやグロメットなどが挙げられる。 Specific usage forms in the brake system include: a diaphragm used for a master back, a hydraulic brake hose air brake, a brake chamber of an air brake; a hose used for a brake hose, a brake oil hose, a vacuum brake hose, etc .; an oil seal Various sealing materials such as O-rings, packings, brake piston seals, atmospheric valves and vacuum valves for master backs, check valves for brake valves, piston cups (rubber cups) for master cylinders, brake cups, hydraulic brakes Master cylinders and vacuum boosters, hydraulic brake wheel cylinder boots, anti-lock brake system (ABS) O-rings and grommets.
上記基本電装部品における具体的な使用形態としては、電線（ハーネス）の絶縁体やシース、ハーネス外装部品のチューブ、コネクター用のグロメットなどが挙げられる。
上記制御系電装部品における具体的な使用形態としては、各種センサー線の被覆材料などが挙げられる。
上記装備電装部品における具体的な使用形態としては、カーエアコンのＯ－リング、パッキンや、クーラーホース、高圧エアコンホース、エアコンホース、電子スロットルユニット用ガスケット、ダイレクトイグニッション用プラグブーツ、ディストリビューター用ダイアフラムなどが挙げられる。また、電装部品の接着にも用いることができる。 Specific usage forms of the basic electrical component include an insulator and sheath of an electric wire (harness), a tube of a harness exterior component, a grommet for a connector, and the like.
Specific examples of usage in the control system electrical component include coating materials for various sensor wires.
Specific usage forms for the above-mentioned electrical components include car air conditioner O-rings, packing, cooler hoses, high pressure air conditioner hoses, air conditioner hoses, gaskets for electronic throttle units, plug plugs for direct ignition, distributor diaphragms, etc. Is mentioned. It can also be used for bonding electrical components.
上記吸気・排気系における具体的な使用形態としては、吸気マニホールド、排気マニホールド等に用いられるパッキンや、スロットルのスロットルボディパッキン；ＥＧＲ（排気再循環）、押圧コントロール（ＢＰＴ）、ウエストゲート、ターボウエストゲート、アクチュエーター、バリアブル・タービン・ジオメトリー（ＶＴＧ）ターボのアクチュエーター、排気浄化バルブ等に用いられるダイアフラム；ＥＧＲ（排気再循環）のコントロールホース、エミッションコントロールホース、ターボチャージャーのターボオイルホース（供給）、ターボオイルホース（リターン）、ターボエアホース、インタークーラーホース、ターボチャージャーホース、インタークーラーを備えたターボエンジンのコンプレッサーと接続されるホース、排気ガスホース、エアインテークホース、ターボホース、ＤＰＦ（ディーゼル微粒子捕集フィルター）センサーホース等のホース；エアダクトやターボエアダクト；インテークマニホールドガスケット；ＥＧＲのシール材、ＡＢバルブのアフターバーン防止バルブシート、（ターボチャージャーなどの）タービンシャフトシールや、自動車のエンジンにおいて使用されるロッカーカバーや空気吸い込みマニホールドなどの溝部品に用いられるシール部材などが挙げられる。 Specific usage forms in the intake / exhaust system include packing used for intake manifolds, exhaust manifolds, etc., throttle body packing of throttles; EGR (exhaust gas recirculation), pressure control (BPT), wastegate, turbo waist Diaphragms used for gates, actuators, variable turbine geometry (VTG) turbo actuators, exhaust purification valves, etc .; EGR (exhaust recirculation) control hoses, emission control hoses, turbocharger turbo oil hoses (supply), turbo Oil hose (return), turbo air hose, intercooler hose, turbocharger hose, hose connected to compressor of turbo engine equipped with intercooler, exhaust Hose such as air hose, air intake hose, turbo hose, DPF (diesel particulate filter) sensor hose; air duct or turbo air duct; intake manifold gasket; EGR seal material, AB valve afterburn prevention valve seat, (turbocharger etc. And a seal member used for groove parts such as a rocker cover and an air suction manifold used in an automobile engine.
その他、排出ガス制御部品において、蒸気回収キャニスター、触媒式転化装置、排出ガスセンサー、酸素センサー等に用いられるシールや、蒸気回収および蒸気キャニスターのソレノイド・アーマチュアのシール；吸気系マニホールドガスケットなどとして用いることができる。
また、ディーゼルエンジンに関する部品において、直噴インジェクター用のＯ－リングシール、回転ポンプシール、制御ダイアフラム、燃料ホース、ＥＧＲ，プライミングポンプ，ブーストコンペンセーターのダイアフラムなどとして用いることができる。また、尿素ＳＣＲシステムに用いられるＯ－リング、シール材、ホース、チューブ、ダイアフラムや、尿素ＳＣＲシステムの尿素水タンク本体、および尿素水タンクのシール材などにも用いることができる。 In addition, in exhaust gas control parts, seals used for steam recovery canisters, catalytic converters, exhaust gas sensors, oxygen sensors, etc., steam recovery and steam canister solenoid armature seals; intake manifold gaskets, etc. Can do.
Further, in parts related to diesel engines, it can be used as O-ring seals for direct injection injectors, rotary pump seals, control diaphragms, fuel hoses, EGR, priming pumps, boost compensator diaphragms, and the like. It can also be used for O-rings, sealing materials, hoses, tubes, diaphragms used in urea SCR systems, urea water tank bodies of urea SCR systems, and sealing materials for urea water tanks.
上記トランスミッション系における具体的な使用形態としては、トランスミッション関連のベアリングシール、オイルシール、Ｏ－リング、パッキン、トルコンホースなどが挙げられる。
ミッションオイルシールや、ＡＴのミッションオイルホース、ＡＴＦホース、Ｏ－リング、パッキン類なども挙げられる。
なお、トランスミッションには、ＡＴ（オートマチック・トランスミッション）、ＭＴ（マニュアル・トランスミッション）、ＣＶＴ（連続可変トランスミッション）、ＤＣＴ（デュアル・クラッチ・トランスミッション）などがある。
また、手動または自動変速機用のオイルシール、ガスケット、Ｏ－リング、パッキンや、無段変速機（ベルト式またはトロイダル式）用のオイルシール、ガスケット、Ｏ－リング、パッキンの他、ＡＴＦリニアソレノイド用パッキング、手動変速機用オイルホース、自動変速機用ＡＴＦホース、無断変速機（ベルト式またはトロイダル式）用ＣＶＴＦホースなども挙げられる。
上記ステアリング系における具体的な使用形態としては、パワーステアリングオイルホースや高圧パワーステアリングホースなどが挙げられる。 Specific usage forms in the transmission system include transmission-related bearing seals, oil seals, O-rings, packings, torque converter hoses, and the like.
Also included are mission oil seals, AT mission oil hoses, ATF hoses, O-rings, packings, and the like.
Transmissions include AT (automatic transmission), MT (manual transmission), CVT (continuously variable transmission), DCT (dual clutch transmission), and the like.
In addition to oil seals, gaskets, O-rings and packings for manual or automatic transmissions, oil seals, gaskets, O-rings and packings for continuously variable transmissions (belt type or toroidal type), ATF linear solenoids Packing, oil hose for manual transmission, ATF hose for automatic transmission, CVTF hose for continuous transmission (belt type or toroidal type), and the like.
Specific usage forms in the steering system include a power steering oil hose and a high pressure power steering hose.
自動車エンジンのエンジン本体において用いられる形態としては、例えば、シリンダーヘッドガスケット、シリンダーヘッドカバーガスケット、オイルパンパッキン、一般ガスケットなどのガスケット、Ｏ－リング、パッキン、タイミングベルトカバーガスケットなどのシール、コントロールホースなどのホース、エンジンマウントの防振ゴム、コントロールバルブダイアフラム、カムシャフトオイルシールなどが挙げられる。
自動車エンジンの主運動系においては、クランクシャフトシール、カムシャフトシールなどのシャフトシールなどに用いることができる。
自動車エンジンの動弁系においては、エンジンバルブのバルブステムオイルシール、バタフライバルブのバルブシートなどに用いることができる。
自動車エンジンの潤滑・冷却系においては、エンジンオイルクーラーのエンジンオイルクーラーホース、オイルリターンホース、シールガスケットや、ラジエータ周辺のウォーターホース、ラジエータのシール、ラジエータのガスケット、ラジエータのＯ－リング、バキュームポンプのバキュームポンプオイルホースなどの他、ラジエーターホース、ラジエータータンク、オイルプレッシャー用ダイアフラム、ファンカップリングシールなどに用いることができる。 For example, cylinder head gaskets, cylinder head cover gaskets, oil pan packings, gaskets such as general gaskets, seals such as O-rings, packings, timing belt cover gaskets, control hoses, etc. These include hoses, anti-vibration rubber for engine mounts, control valve diaphragms, and camshaft oil seals.
In a main motion system of an automobile engine, it can be used for a shaft seal such as a crankshaft seal and a camshaft seal.
In a valve system of an automobile engine, it can be used for a valve stem oil seal of an engine valve, a valve seat of a butterfly valve, and the like.
In automotive 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 a vacuum pump oil hose, etc., it can be used for a radiator hose, a radiator tank, an oil pressure diaphragm, a fan coupling seal, and the like.
このように、自動車分野における使用の具体例の一例としては、エンジンヘッドガスケット、オイルパンガスケット、マニホールドパッキン、酸素センサー用シール、酸素センサーブッシュ、酸化窒素（ＮＯｘ）センサー用シール、酸化窒素（ＮＯｘ）センサーブッシュ、酸化硫黄センサー用シール、温度センサー用シール、温度センサーブッシュ、ディーゼルパーティクルフィルターセンサー用シール、ディーゼルパーティクルフィルターセンサーブッシュ、インジェクターＯ－リング、インジェクターパッキン、燃料ポンプのＯ－リングやダイアフラム、ギアボックスシール、パワーピストンパッキン、シリンダーライナーのシール、バルブステムのシール、スタティックバルブステムシール、ダイナミックバルブステムシール、自動変速機のフロントポンプシール、リアーアクスルピニオンシール、ユニバーサルジョイントのガスケット、スピードメーターのピニオンシール、フートブレーキのピストンカップ、トルク伝達装置のＯ－リングやオイルシール、排ガス再燃焼装置のシールやベアリングシール、再燃焼装置用ホース、キャブレターのセンサー用ダイアフラム、防振ゴム（エンジンマウント、排気部、マフラーハンガー、サスペンションブッシュ、センターベアリング、ストラットバンパーラバー等）、サスペンション用防振ゴム（ストラットマウント、ブッシュ等）、駆動系防振ゴム（ダンパー等）、燃料ホース、ＥＧＲのチューブやホース、ツインキャブチューブ、キャブレターのニードルバルブの芯弁、キャブレターのフランジガスケット、オイルホース、オイルクーラーホース、ＡＴＦホース、シリンダーヘッドガスケット、水ポンプシール、ギアボックスシール、ニードルバルブチップ、オートバイ用リードバルブのリード、自動車エンジンのオイルシール、ガソリンホースガンのシール、カーエアコン用シール、エンジンのインタークーラー用ゴムホース、送油経路コネクター装置（ｆｕｅｌ　ｌｉｎｅ　ｃｏｎｎｅｃｔｏｒ　ｓｙｓｔｅｍｓ）のシール、ＣＡＣバルブ、ニードルチップ、エンジン回り電線、フィラーホース、カーエアコンＯ－リング、インテークガスケット、燃料タンク材料、ディストリビューター用ダイアフラム、ウォーターホース、クラッチホース、ＰＳホース、ＡＴホース、マスターバックホース、ヒーターホース、エアコンホース、ベンチレーションホース、オイルフィラーキャップ、ＰＳラックシール、ラック＆ピニオンブーツ、ＣＶＪブーツ、ボールジョイントダストカバー、ストラットダストカバー、ウェザーストリップ、グラスラン、センターユニットパッキン、ボディーサイトウェルト、バンパーラバー、ドアラッチ、ダッシュインシュレーター、ハイテンションコード、平ベルト、ポリＶベルト、タイミングベルト、歯付きベルト、Ｖリブドベルト、タイヤ、ワイパーブレード、ＬＰＧ車レギュレータ用ダイアフラムやプランジャー、ＣＮＧ車レギュレータ用ダイアフラムやバルブ、ＤＭＥ対応ゴム部品、オートテンショナのダイアフラムやブーツ、アイドルスピードコントロールのダイアフラムやバルブ、オートスピードコントロールのアクチュエーター，負圧ポンプのダイアフラムやチェックバルブやプランジャー、Ｏ．Ｐ．Ｓ．のダイアフラムやＯ－リング、ガソリン圧抜きバルブ、エンジンシリンダースリーブのＯ－リングやガスケット、ウェットシリンダースリーブのＯ－リングやガスケット、ディファレンシャルギヤのシールやガスケット（ギヤ油のシールやガスケット）、パワーステアリング装置のシールやガスケット（ＰＳＦのシールやガスケット）、ショックアブソーバのシールやガスケット（ＳＡＦのシールやガスケット）、等速ジョイントのシールやガスケット、ホイール軸受のシールやガスケット、メタルガスケットのコーティング剤、キャリパーシール、ブーツ類、ホイールベアリングシール、タイヤの加硫成形に使用されるブラダーなどが挙げられる。 Thus, specific examples of use in the automotive field include engine head gaskets, oil pan gaskets, manifold packings, oxygen sensor seals, oxygen sensor bushings, nitrogen oxide (NOx) sensor seals, and nitrogen oxide (NOx). Sensor bushing, sulfur oxide sensor seal, temperature sensor seal, temperature sensor bush, diesel particle filter sensor seal, diesel particle filter sensor bush, injector O-ring, injector packing, fuel pump O-ring and diaphragm, gearbox Seal, power piston seal, cylinder liner seal, valve stem seal, static valve stem seal, dynamic valve stem seal, automatic modification Machine front pump seal, rear axle pinion seal, universal joint gasket, speedometer pinion seal, foot brake piston cup, torque transmission device O-ring and oil seal, exhaust gas recombustion device seal and bearing seal, Combustion device hose, carburetor sensor diaphragm, anti-vibration rubber (engine mount, exhaust, muffler hanger, suspension bush, center bearing, strut bumper rubber, etc.), anti-vibration rubber for suspension (strut mount, bush, etc.), drive Anti-vibration rubber (damper, etc.), fuel hose, EGR tube and hose, twin cab tube, carburetor needle valve core valve, carburetor flange gasket, oil hose, Ill cooler hose, ATF hose, cylinder head gasket, water pump seal, gear box seal, needle valve tip, motorcycle reed valve lead, automobile engine oil seal, gasoline hose gun seal, car air conditioner seal, engine intercooler Rubber hose, seal for fuel line connector systems (fuel line connector systems), CAC valve, needle tip, engine wire, filler hose, car air conditioner O-ring, intake gasket, fuel tank material, distributor diaphragm, water hose , Clutch hose, PS hose, AT hose, master back hose, heater hose, air conditioner hose, ventilation hose, oy Filler cap, PS rack seal, rack & pinion boot, CVJ boot, ball joint dust cover, strut dust cover, weather strip, glass run, center unit packing, body sight welt, bumper rubber, door latch, dash insulator, high tension cord, Flat belts, poly V belts, timing belts, toothed belts, V-ribbed belts, tires, wiper blades, diaphragms and plungers for LPG car regulators, diaphragms and valves for CNG car regulators, DME compatible rubber parts, diaphragms and boots for auto tensioners , Idle speed control diaphragms and valves, Auto speed control actuators, Negative pressure pump diaphragms and valves Kkubarubu and plunger, O. P. S. Diaphragms and O-rings, gasoline pressure relief valves, engine cylinder sleeve O-rings and gaskets, wet cylinder sleeve O-rings and gaskets, differential gear seals and gaskets (gear oil seals and gaskets), power steering devices Seals and gaskets (PSF seals and gaskets), shock absorber seals and gaskets (SAF seals and gaskets), constant velocity joint seals and gaskets, wheel bearing seals and gaskets, metal gasket coating agents, caliper seals, Examples include boots, wheel bearing seals, and bladders used for vulcanization molding of tires.
上記航空機分野、宇宙・ロケット分野、船舶分野においては、特に燃料系統や潤滑油系統に用いることができる。
上記航空機分野においては、例えば、航空機用各種シール部品、航空機用エンジンオイル用途の航空機用各種部品、ジェットエンジンバルブステムシールやガスケットやＯ－リング、ローテーティングシャフトシール、油圧機器のガスケット、防火壁シール、燃料供給用ホースやガスケットやＯ－リング、航空機用ケーブルやオイルシールやシャフトシールなどとして用いることが可能である。 In the aircraft field, space / rocket field, and ship field, the fuel system and the lubricating oil system can be used.
In the above-mentioned aircraft field, for example, various types of sealing parts for aircraft, various types of aircraft parts for aircraft engine oil, jet engine valve stem seals, gaskets and O-rings, rotating shaft seals, hydraulic equipment gaskets, firewall seals, etc. It can be used as a fuel supply hose, gasket, O-ring, aircraft cable, oil seal, shaft seal, and the like.
上記宇宙・ロケット分野においては、例えば、宇宙船、ジェットエンジン、ミサイル等のリップシール、ダイアフラム、Ｏ－リングや、耐ガスタービンエンジン用オイルのＯ－リング、ミサイル地上制御用防振台パッドなどとして用いることができる。
また、船舶分野においては、例えば、スクリューのプロペラシャフト船尾シール、ディーゼルエンジンの吸排気用バルブステムシール、バタフライバルブのバルブシール、バタフライバルブのバルブシートや軸シール、バタフライ弁の軸シール、船尾管シール、燃料ホース、ガスケット、エンジン用のＯ－リング、船舶用ケーブル、船舶用オイルシール、船舶用シャフトシールなどとして使用することができる。 In the space and rocket field, for example, lip seals for diaphragms, jet engines, missiles, diaphragms, O-rings, O-rings for gas turbine engine oils, anti-vibration stand pads for missile ground control, etc. Can be used.
In the marine field, for example, screw propeller shaft stern seals, diesel engine intake and exhaust valve stem seals, butterfly valve valve seals, butterfly valve valve seats and shaft seals, butterfly valve shaft seals, stern tube seals , Fuel hoses, gaskets, engine O-rings, marine cables, marine oil seals, marine shaft seals, and the like.
上記化学プラント等の化学品分野、医薬品等の薬品分野においては、高度の耐薬品性が要求されるような工程、例えば、医薬品、農薬、塗料、樹脂等の化学品を製造する工程に用いることができる。
上記化学品分野及び薬品分野における具体的な使用形態としては、化学装置、化学薬品用ポンプや流量計、化学薬品用配管、熱交換器、農薬散布機、農薬移送ポンプ、ガス配管、燃料電池、分析機器や理化学機器（例えば、分析機器や計器類のカラム・フィッティングなど）、排煙脱硫装置の収縮継ぎ手、硝酸プラント、発電所タービン等に用いられるシールや、医療用滅菌プロセスに用いられるシール、メッキ液用シール、製紙用ベルトのコロシール、風洞のジョイントシール；反応機、攪拌機等の化学装置、分析機器や計器類、ケミカルポンプ、ポンプハウジング、バルブ、回転計等に用いられるＯ－リングや、メカニカルシール用Ｏ－リング、コンプレッサーシーリング用のＯ－リング；高温真空乾燥機、ガスクロマトグラフィーやｐＨメーターのチューブ結合部等に用いられるパッキンや、硫酸製造装置のガラス冷却器パッキン；ダイアフラムポンプ、分析機器や理化学機器等に用いられるダイアフラム；分析機器、計器類に用いられるガスケット；分析機器や計器類に用いられるはめ輪（フェルール）；バルブシート；Ｕカップ；化学装置、ガソリンタンク、風洞等に用いられるライニングや、アルマイト加工槽の耐食ライニング；メッキ用マスキング冶具のコーティング；分析機器や理化学機器の弁部品；排煙脱硫プラントのエキスパンジョンジョイント；濃硫酸等に対する耐酸ホース、塩素ガス移送ホース、耐油ホース、ベンゼンやトルエン貯槽の雨水ドレンホース；分析機器や理化学機器等に用いられる耐薬品性チューブや医療用チューブ；繊維染色用の耐トリクレン用ロールや染色用ロール；医薬品の薬栓；医療用のゴム栓；薬液ボトル、薬液タンク、バッグ、薬品容器；耐強酸、耐溶剤の手袋や長靴等の保護具などが挙げられる。 In the chemical field such as the above chemical plant and in the pharmaceutical field such as pharmaceuticals, it should be used in processes that require a high degree of chemical resistance, for example, processes for manufacturing chemicals such as pharmaceuticals, agricultural chemicals, paints, and resins. Can do.
Specific usage forms in the chemical field and chemical field include chemical equipment, chemical pumps and flow meters, chemical pipes, heat exchangers, agricultural chemical sprayers, agricultural chemical transfer pumps, gas piping, fuel cells, Analytical instruments and physics and chemistry instruments (for example, analytical instruments and instrument column fittings), exhaust gas desulfurization fittings, seals used in nitric acid plants, power plant turbines, etc., seals used in medical sterilization processes, Seals for plating solutions, roller seals for papermaking belts, joint seals for wind tunnels; chemical devices such as reactors and stirrers, analytical instruments and instruments, chemical pumps, pump housings, valves, tachometers, etc. O-ring for mechanical seal, O-ring for compressor sealing; high-temperature vacuum dryer, gas chromatography and p Packing used for tube connection parts of meters, glass cooler packing of sulfuric acid production equipment; Diaphragms used for diaphragm pumps, analytical instruments and physics and chemistry instruments; Gaskets used for analytical instruments and instruments; Analytical instruments and instruments Ferrules used in the field; valve seats; U cups; linings used in chemical equipment, gasoline tanks, wind tunnels, etc., corrosion resistant linings in anodized processing tanks; coating of masking jigs for plating; valves for analytical instruments and physics and chemistry instruments Parts; Expansion joints of flue gas desulfurization plants; Acid-resistant hoses for concentrated sulfuric acid, chlorine gas transfer hoses, oil-resistant hoses, rainwater drain hoses for benzene and toluene storage tanks; chemical-resistant tubes used for analytical instruments and physics and chemistry instruments Medical tube; anti-trick for textile dyeing Down roll and dyeing roll; pharmaceutical Kusurisen; rubber stopper for medical, chemical bottle, chemical tank, bags, drug containers; Resistant acid, and the like protection gloves and boots, etc. solvent.
上記現像機等の写真分野、印刷機械等の印刷分野、塗装設備等の塗装分野においては、乾式複写機のロール、ベルト、シール、弁部品等として用いることができる。
上記写真分野、印刷分野及び塗装分野における具体的な使用形態としては、複写機の転写ロールの表面層、複写機のクリーニングブレード、複写機のベルト；複写機、プリンター、ファクシミリ等のＯＡ機器用のロール（例えば、定着ロール、圧着ロール、加圧ロールなどが挙げられる。）、ベルト；ＰＰＣ複写機のロール、ロールブレード、ベルト；フィルム現像機、Ｘ線フィルム現像機のロール；印刷機械の印刷ロール、スクレーパー、チューブ、弁部品、ベルト；プリンターのインキチューブ、ロール、ベルト；塗布、塗装設備の塗装ロール、スクレーパー、チューブ、弁部品；現像ロール、グラビアロール、ガイドロール、磁気テープ製造塗工ラインのガイドロール、磁気テープ製造塗工ラインのグラビアロール、コーティングロールなどが挙げられる。 In the photographic field such as the developing machine, the printing field such as a printing machine, and the coating field such as a coating facility, it can be used as a roll, a belt, a seal, a valve part, etc. of a dry copying machine.
Specific usage forms in the photographic field, printing field, and painting field include a surface layer of a transfer roll of a copying machine, a cleaning blade of a copying machine, a belt of a copying machine; for OA equipment such as a copying machine, a printer, and a facsimile machine. Rolls (for example, fixing rolls, pressure rolls, pressure rolls, etc.), belts; rolls for PPC copiers, roll blades, belts; rolls for film developing machines and X-ray film developing machines; printing rolls for printing machines , Scrapers, tubes, valve parts, belts; printer ink tubes, rolls, belts; coating, painting equipment coating rolls, scrapers, tubes, valve parts; development rolls, gravure rolls, guide rolls, magnetic tape production coating lines Guide rolls, gravure rolls for magnetic tape production coating lines, coating lows And the like.
上記食品プラント機器及び家庭用品を含む食品機器分野においては、食品製造工程や、食品移送器用または食品貯蔵器用に用いることができる。
上記食品機器分野における具体的な使用形態としては、プレート式熱交換器のシール、自動販売機の電磁弁シール、ジャーポットのパッキン、サニタリーパイプパッキン、圧力鍋のパッキン、湯沸器シール、熱交換器用ガスケット、食品加工処理装置用のダイアフラムやパッキン、食品加工処理機用ゴム材料（例えば、熱交換器ガスケット、ダイアフラム、Ｏ－リング等の各種シール、配管、ホース、サニタリーパッキン、バルブパッキン、充填時にビンなどの口と充填剤との間のジョイントとして使用される充填用パッキン）などが挙げられる。また、酒類、清涼飲料水等の製品、充填装置、食品殺菌装置、醸造装置、湯沸し器、各種自動食品販売機等に用いられるパッキン、ガスケット、チューブ、ダイアフラム、ホース、ジョイントスリーブなども挙げられる。 In the field of food equipment including the above-mentioned food plant equipment and household goods, it can be used for food production processes, food transporters or food reservoirs.
Specific uses in the food equipment field include plate heat exchanger seals, vending machine solenoid valve seals, jar pot packing, sanitary pipe packing, pressure cooker packing, water heater seals, heat exchange. Gaskets for equipment, diaphragms and packing for food processing equipment, rubber materials for food processing equipment (for example, heat exchanger gaskets, diaphragms, O-rings and other seals, piping, hoses, sanitary packing, valve packing, when filling And packing for use as a joint between a mouth such as a bottle and a filler. Moreover, packing, a gasket, a tube, a diaphragm, a hose, a joint sleeve etc. which are used for products, such as alcoholic beverages and soft drinks, a filling apparatus, a food sterilization apparatus, a brewing apparatus, a water heater, various automatic food vending machines, etc. are mentioned.
上記原子力プラント機器分野においては、原子炉周辺の逆止弁や減圧弁、六フッ化ウランの濃縮装置のシールなどに用いることができる。 In the nuclear plant equipment field, it can be used as a check valve, a pressure reducing valve, a seal of a uranium hexafluoride concentrator, etc. around the reactor.
上記一般工業分野における具体的な使用形態としては、工作機械、建設機械、油圧機械等の油圧機器用シール材；油圧、潤滑機械のシールやベアリングシール；マンドレル等に用いられるシール材；ドライクリーニング機器の窓等に用いられるシール；サイクロトロンのシールや（真空）バルブシール、プロトン加速器のシール、自動包装機のシール、空気中の亜硫酸ガスや塩素ガス分析装置（公害測定器）用ポンプのダイアフラム、スネークポンプライニング、印刷機のロールやベルト、搬送用のベルト（コンベアベルト）、鉄板等の酸洗い用絞りロール、ロボットのケーブル、アルミ圧延ライン等の溶剤絞りロール、カプラーのＯ－リング、耐酸クッション材、切削加工機械の摺動部分のダストシールやリップゴム、生ごみ焼却処理機のガスケット、摩擦材、金属またはゴムの表面改質剤、被覆材などが挙げられる。また、製紙プロセスで用いられる装置のガスケットやシール材、クリーンルーム用フィルターユニットのシーリング剤、建築用シーリング剤、コンクリートやセメント等の保護コーティング剤、ガラスクロス含浸材料、ポリオレフィンの加工助剤、ポリエチレンの成形性改良添加剤、小型発電機や芝刈機等の燃料容器、金属板にプライマー処理を施すことによって得られるプレコートメタルなどとしても使用することができる。その他、織布に含浸させて焼付けてシート及びベルトとして使用することもできる。 Specific usage forms in the general industrial field include: sealing materials for hydraulic equipment such as machine tools, construction machines, hydraulic machines; seals and bearing seals for hydraulic and lubrication machines; sealing materials used for mandrels, etc .; dry cleaning equipment Seals used for windows, etc .; cyclotron seals, (vacuum) valve seals, proton accelerator seals, automatic packaging machine seals, pump diaphragms and snakes for sulfur dioxide and chlorine gas analyzers (pollution measuring instruments) in the air Pump lining, printing press rolls and belts, transport belts (conveyor belts), pickling squeezing rolls such as iron plates, robot cables, solvent squeezing rolls such as aluminum rolling lines, coupler O-rings, acid-resistant cushioning materials , Dust seals and lip rubber on sliding parts of cutting machines, garbage incinerators Basket, friction materials, metal or a surface modifier for rubbers, and the like dressing. Also, gaskets and sealants for equipment used in the papermaking process, sealants for clean room filter units, sealants for construction, protective coatings for 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 pre-coated 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.
上記鉄鋼分野における具体的な使用形態としては、鉄板加工設備の鉄板加工ロールなどが挙げられる。 Specific examples of usage in the steel field include iron plate processing rolls for iron plate processing equipment.
上記電気分野における具体的な使用形態としては、新幹線の絶縁油キャップ、液封型トランスのベンチングシール、変圧器のシール、油井ケーブルのジャケット、電気炉等のオーブンのシール、電子レンジの窓枠シール、ＣＲＴのウェッジとネックとを接着させる際に用いられるシール材、ハロゲンランプのシール材、電気部品の固定剤、シーズヒーターの末端処理用シール材、電気機器リード線端子の絶縁防湿処理に用いられるシール材などが挙げられる。また、耐油・耐熱電線、高耐熱性電線、耐薬品性電線、高絶縁性電線、高圧送電線、ケーブル、地熱発電装置に用いられる電線、自動車エンジン周辺に用いられる電線等の被覆材に用いることもできる。車両用ケーブルのオイルシールやシャフトシールに用いることもできる。更には、電気絶縁材料（例えば、各種電気機器の絶縁用スペーサ、ケーブルのジョイントや末端部などに用いる絶縁テープ、熱収縮性のチューブなどに使用される材料）や、高温雰囲気で用いられる電気および電子機器材料（例えば、モータ用口出線材料、高熱炉まわりの電線材料）にも使用可能である。また、太陽電池の封止層や保護フィルム（バックシート）にも使用できる。 Specific usage forms in the electrical field include: Shinkansen insulating oil caps, liquid-sealed transformer benching seals, transformer seals, oil well cable jackets, electric furnace oven oven seals, microwave oven window frames, etc. Used for sealing, sealing materials used when bonding CRT wedges and necks, halogen lamp sealing materials, electrical component fixing agents, sheathing heater end treatment sealing materials, electrical equipment lead wire terminals Sealing materials that can be used. Also used for coating materials such as oil and heat resistant wires, high heat resistant wires, chemical resistant wires, high insulating wires, high voltage transmission lines, cables, wires used in geothermal power generation equipment, wires used around automobile engines, etc. You can also. It can also be used for oil seals and shaft seals for vehicle cables. Furthermore, electrical insulating materials (for example, insulating spacers for various electrical equipment, insulating tapes used for cable joints and terminals, materials used for heat-shrinkable tubes, etc.) It can also be used for electronic equipment materials (for example, lead wire materials for motors, wire materials around high-temperature furnaces). Moreover, it can be used also for the sealing layer and protective film (back sheet) of a solar cell.
上記燃料電池分野においては、固体高分子形燃料電池、リン酸塩型燃料電池等における、電極間、電極－セパレーター間のシール材や、水素、酸素、生成水等の配管のシールやパッキン、セパレーターなどとして用いることができる。 In the above-mentioned fuel cell field, sealing materials between electrodes, electrode-separators, piping seals, packings, separators for hydrogen, oxygen, produced water, etc. in polymer electrolyte fuel cells, phosphate fuel cells, etc. It can be used as such.
上記電子部品分野においては、放熱材原料、電磁波シールド材原料、コンピュータのハードディスクドライブ（磁気記録装置）用のガスケット等に用いることができる。また、ハードディスクドライブの緩衝ゴム（クラッシュストッパー）、ニッケル水素二次電池の電極活物質のバインダー、リチウムイオン電池の活物質のバインダー、リチウム二次電池のポリマー電解質、アルカリ蓄電池の正極の結着剤、ＥＬ素子（エレクトロルミネセンス素子）のバインダー、コンデンサーの電極活物質のバインダー、封止剤、シーリング剤、光ファイバーの石英の被覆材、光ファイバー被覆材等のフィルムやシート類、電子部品、回路基板のポッティングやコーティングや接着シール、電子部品の固定剤、エポキシ等の封止剤の変性剤、プリント基板のコーティング剤、エポキシ等のプリント配線板プリプレグ樹脂の変性材、電球等の飛散防止材、コンピュータ用ガスケット、大型コンピュータ冷却ホース、二次電池、特にリチウム二次電池用のガスケットやＯ－リング等のパッキン、有機ＥＬ構造体の外表面の片面または両面を覆う封止層、コネクター、ダンパーなどとしても用いられる。 In the electronic component field, it can be used as a heat radiating material, an electromagnetic shielding material, a gasket for a computer hard disk drive (magnetic recording device), and the like. In addition, buffer rubber (crash stopper) for hard disk drives, binder for electrode active materials for nickel hydride secondary batteries, binder for active materials for lithium ion batteries, polymer electrolyte for lithium secondary batteries, binder for positive electrodes for alkaline storage batteries, EL element (electroluminescent element) binder, capacitor electrode active material binder, sealant, sealing agent, optical fiber quartz coating, optical fiber coating film and sheets, electronic parts, circuit board potting And coating and adhesive seals, electronic component fixing agents, epoxy and other sealant modifiers, printed circuit board coating agents, epoxy and other printed wiring board prepreg resin modifiers, light bulbs and other anti-scattering materials, computer gaskets , Large computer cooling hose, secondary battery, Packing such as gaskets and O- ring for a lithium secondary battery, a sealing layer covering one or both surfaces of the outer surface of the organic EL structure, the connector is also used as such a damper.
上記化学薬品輸送用機器分野においては、トラック、トレーラー、タンクローリー、船舶等の安全弁や積出しバルブなどに用いることができる。 In the chemical transport equipment field, it can be used as a safety valve or a shipping valve for trucks, trailers, tank trucks, ships, etc.
上記石油、ガス等のエネルギー資源探索採掘機器部品分野においては、石油、天然ガス等の採掘の際に用いられる各種シール材、油井に使われる電気コネクターのブーツなどとして用いられる。
上記エネルギー資源探索採掘機器部品分野における具体的な使用形態としては、ドリルビットシール、圧力調整ダイアフラム、水平掘削モーター（ステーター）のシール、ステーターベアリング（シャフト）シール、暴噴防止装置（ＢＯＰ）に用いられるシール材、回転暴噴防止装置（パイプワイパー）に用いられるシール材、ＭＷＤ（リアルタイム掘削情報探知システム）に用いられるシール材や気液コネクター、検層装置（ロギングエクイップメント）に用いられる検層ツールシール（例えば、Ｏ－リング、シール、パッキン、気液コネクター、ブーツなど）、膨張型パッカーやコンプリーションパッカー及びそれらに用いるパッカーシール、セメンチング装置に用いられるシールやパッキン、パーフォレーター（穿孔装置）に用いられるシール、マッドポンプに用いられるシールやパッキンやモーターライニング、地中聴検器カバー、Ｕカップ、コンポジションシーティングカップ、回転シール、ラミネートエラストメリックベアリング、流量制御のシール、砂量制御のシール、安全弁のシール、水圧破砕装置（フラクチャリングエクイップメント）のシール、リニアーパッカーやリニアーハンガーのシールやパッキン、ウェルヘッドのシールやパッキン、チョークやバルブのシールやパッキン、ＬＷＤ（掘削中検層）用シール材、石油探索・石油掘削用途で用いられるダイアフラム（例えば、石油掘削ピットなどの潤滑油供給用ダイアフラム）、ゲートバルブ、電子ブーツ、穿孔ガンのシールエレメントなどが挙げられる。 In the field of parts for exploring and mining energy resources such as oil and gas, they are used as various sealing materials used in the mining of oil and natural gas, boots for electrical connectors used in oil wells, and the like.
Specific uses in the energy resource search and mining equipment parts field include drill bit seals, pressure adjustment diaphragms, horizontal drilling motor (stator) seals, stator bearing (shaft) seals, and blowout prevention devices (BOP). Sealing material, sealing material used for rotation blowout prevention device (pipe wiper), sealing material used for MWD (real-time excavation information detection system), gas-liquid connector, logging used for logging equipment (logging equipment) Tool seals (for example, O-rings, seals, packings, gas-liquid connectors, boots, etc.), inflatable packers and completion packers, packer seals used in them, seals and packings used in cementing devices, perforators (perforators) ) Seals, seals used for mud pumps, packing, motor lining, underground detector covers, U cups, composition seating cups, rotating seals, laminated elastomeric bearings, flow control seals, sand control seals, safety valves Seals, hydraulic fracturing equipment (fracturing equipment) seals, linear packer and linear hanger seals and packing, wellhead seals and packing, choke and valve seals and packing, LWD (logging during logging), Diaphragms used in oil exploration and oil drilling applications (for example, diaphragms for supplying lubricating oil such as oil drilling pits), gate valves, electronic boots, drill gun seal elements, and the like.
その他、厨房、浴室、洗面所等の目地シール；屋外テントの引き布；印材用のシール；ガスヒートポンプ用ゴムホース、耐フロン性ゴムホース；農業用のフィルム、ライニング、耐候性カバー；建築や家電分野等で使用されるラミネート鋼板等のタンク類などにも用いることができる。 In addition, joint seals for kitchens, bathrooms, toilets, etc .; outdoor tent pulling cloth; seals for printing materials; rubber heat hoses for gas heat pumps, refractory rubber hoses; agricultural films, linings, weatherproof covers; It can also be used for tanks such as laminated steel plates used in the above.
更には、アルミ等の金属と結合させた物品として使用することも可能である。そのような使用形態としては、例えば、ドアシール、ゲートバルブ、振り子バルブ、ソレノイド先端の他、金属と結合されたピストンシールやダイアフラム、金属ガスケット等の金属と結合された金属ゴム部品などが挙げられる。
また、自転車におけるゴム部品、ブレーキシュー、ブレーキパッドなどにも用いることができる。 Furthermore, it can be used as an article combined with a metal such as aluminum. Examples of such usage include door seals, gate valves, pendulum valves, and solenoid tips, as well as metal rubber parts combined with metals such as piston seals, diaphragms, and metal gaskets combined with metals.
It can also be used for rubber parts, brake shoes, brake pads, etc. in bicycles.
また、本発明のフッ素ゴム成形品の形態の１つとしてベルトが挙げられる。
上記ベルトとしては、次のものが例示される。動力伝達ベルト（平ベルト、Ｖベルト、Ｖリブドベルト、歯付きベルトなどを含む）、搬送用ベルト（コンベアベルト）として、農業用機械、工作機械、工業用機械等のエンジン周りなど各種高温となる部位に使用される平ベルト；石炭、砕石、土砂、鉱石、木材チップなどのバラ物や粒状物を高温環境下で搬送するためのコンベアベルト；高炉等の製鉄所などで使用されるコンベアベルト；精密機器組立工場、食品工場等において、高温環境下に曝される用途におけるコンベアベルト；農業用機械、一般機器（例えば、ＯＡ機器、印刷機械、業務用乾燥機等）、自動車用などのＶベルトやＶリブドベルト；搬送ロボットの伝動ベルト；食品機械、工作機械の伝動ベルトなどの歯付きベルト；自動車用、ＯＡ機器、医療用、印刷機械などで使用される歯付きベルトなどが挙げられる。
特に、自動車用歯付きベルトとしては、タイミングベルトが代表的である。 Moreover, a belt is mentioned as one of the forms of the fluororubber molded product of this invention.
The following are illustrated as said belt. Power transmission belts (including flat belts, V-belts, V-ribbed belts, toothed belts, etc.) and conveyor belts (conveyor belts), such as parts around the engine of agricultural machinery, machine tools, industrial machinery, etc. Flat belts used in slabs; conveyor belts for transporting loose and granular materials such as coal, crushed stone, earth and sand, ore, and wood chips in a high-temperature environment; conveyor belts used in steelworks such as blast furnaces; precision Conveyor belts in applications exposed to high temperatures in equipment assembly factories, food factories, etc .; agricultural machinery, general equipment (eg, OA equipment, printing machines, commercial dryers, etc.), V belts for automobiles, etc. V-ribbed belts; Transmission belts for conveyor robots; Toothed belts for food machines and machine tools; Used in automobiles, OA equipment, medical devices, printing machines, etc. Such as a toothed belt to be like.
In particular, a timing belt is typical as a toothed belt for automobiles.
上記ベルトは、単層構造であってもよいし、多層構造であってもよい。
多層構造である場合、上記ベルトは、本発明のフッ素ゴム組成物を架橋して得られる層及び他の材料からなる層からなるものであってもよい。
多層構造のベルトにおいて、他の材料からなる層としては、他のゴムからなる層や熱可塑性樹脂からなる層、各種繊維補強層、帆布、金属箔層などが挙げられる。 The belt may have a single layer structure or a multilayer structure.
In the case of a multilayer structure, the belt may be composed of a layer obtained by crosslinking the fluororubber composition of the present invention and a layer made of another material.
In the multilayer belt, examples of the layer made of another material include a layer made of other rubber, a layer made of a thermoplastic resin, various fiber reinforcing layers, a canvas, and a metal foil layer.
本発明のフッ素ゴム成形品はまた、産業用防振パッド、防振マット、鉄道用スラブマット、パッド類、自動車用防振ゴムなどに使用できる。自動車用防振ゴムとしては、エンジンマウント用、モーターマウント用、メンバマウント用、ストラットマウント用、ブッシュ用、ダンパー用、マフラーハンガー用、センターベアリング用などの防振ゴムが挙げられる。 The fluororubber molded article of the present invention can also be used for industrial vibration-proof pads, vibration-proof mats, railway slab mats, pads, automobile vibration-proof rubbers, and the like. Anti-vibration rubbers for automobiles include anti-vibration rubbers for engine mount, motor mount, member mount, strut mount, bush, damper, muffler hanger, and center bearing.
また、他の使用形態として、フレキシブルジョイント、エキスパンションジョイント等のジョイント部材、ブーツ、グロメットなどが挙げられる。船舶分野であれば、例えばマリンポンプ等が挙げられる。
ジョイント部材とは、配管および配管設備に用いられる継ぎ手のことであり、配管系統から発生する振動、騒音の防止、温度変化、圧力変化による伸縮や変位の吸収、寸法変動の吸収や地震、地盤沈下による影響の緩和、防止などの用途に用いられる。
フレキシブルジョイント、エキスパンションジョイントは、例えば、造船配管用、ポンプやコンプレッサーなどの機械配管用、化学プラント配管用、電気配管用、土木・水道配管用、自動車用などの複雑形状成形体として好ましく用いることができる。
ブーツは、例えば、等速ジョイントブーツ、ダストカバー、ラックアンドピニオンステアリングブーツ、ピンブーツ、ピストンブーツなどの自動車用ブーツ、農業機械用ブーツ、産業車両用ブーツ、建築機械用ブーツ、油圧機械用ブーツ、空圧機械用ブーツ、集中潤滑機用ブーツ、液体移送用ブーツ、消防用ブーツ、各種液化ガス移送用ブーツなどの各種産業用ブーツなどの複雑形状成形体として好ましく用いることができる。 Other usage forms include joint members such as flexible joints and expansion joints, boots, grommets, and the like. If it is a ship field, a marine pump etc. will be mentioned, for example.
A joint member is a joint used for piping and piping equipment. It prevents vibration and noise generated from the piping system, absorbs expansion and contraction due to temperature changes and pressure changes, absorbs dimensional fluctuations, earthquakes, and subsidence. It is used for applications such as mitigating and preventing the effects of
Flexible joints and expansion joints are preferably used as complex shaped molded bodies for shipbuilding piping, mechanical piping such as pumps and compressors, chemical plant piping, electrical piping, civil engineering / water supply piping, automobiles, etc. it can.
Boots include, for example, constant velocity joint boots, dust covers, rack and pinion steering boots, pin boots, piston boots and other automobile boots, agricultural machinery boots, industrial vehicle boots, building machinery boots, hydraulic machinery boots, empty It can be preferably used as a compact shaped article such as various industrial boots such as pressure machine boots, centralized lubricator boots, liquid transfer boots, fire fighting boots and various liquefied gas transfer boots.
本発明のフッ素ゴム成形品は、フィルタープレス用ダイアフラム、ブロワー用ダイアフラム、給水用ダイアフラム、液体貯蔵タンク用ダイアフラム、圧力スイッチ用ダイアフラム、アキュムレーター用ダイアフラム、サスペンション等の空気ばね用ダイアフラムなどにも使用できる。 The fluororubber molded article of the present invention can be used for filter press diaphragms, blower diaphragms, water supply diaphragms, liquid storage tank diaphragms, pressure switch diaphragms, accumulator diaphragms, diaphragms for air springs such as suspensions, and the like. .
本発明のフッ素ゴム成形品をゴムや樹脂に添加することにより、雨、雪、氷や汗等の水に濡れる環境下において滑りにくいフッ素ゴム成形品やコーティング被膜を得る滑り防止剤が得られる。 By adding the fluororubber molded product of the present invention to rubber or resin, it is possible to obtain an anti-slip agent for obtaining a fluororubber molded product or a coating film which is not slippery in an environment wet with water such as rain, snow, ice or sweat.
また、本発明のフッ素ゴム成形品は、例えば、メラミン樹脂、フェノール樹脂、エポキシ樹脂等による化粧合板、プリント基板、電気絶縁板、硬質ポリ塩化ビニル積層板等を製造する際の熱プレス成形用クッション材としても用いることができる。 In addition, the fluororubber molded product of the present invention is a cushion for hot press molding when manufacturing decorative plywood, printed circuit boards, electrical insulating boards, rigid polyvinyl chloride laminates, etc. made of melamine resin, phenol resin, epoxy resin, etc. It can also be used as a material.
本発明のフッ素ゴム成形品は、その他、兵器関連の封止ガスケット、侵襲性化学剤との接触に対する保護衣服のような各種支持体の不浸透性化に寄与することもできる。 The fluororubber 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.
また、自動車、船舶などの輸送機関などに使われるアミン系添加剤（特に酸化防止剤、清浄分散剤として用いられるアミン系添加剤）が含まれる潤滑油（エンジンオイル、ミッションオイル、ギヤーオイルなど）や燃料油、グリース（特にウレア系グリース）をシール、封止するために使われるＯ（角）－リング、Ｖ－リング、Ｘ－リング、パッキン、ガスケット、ダイアフラム、オイルシール、ベアリングシール、リップシール、プランジャーシール、ドアシール、リップおよびフェースシール、ガスデリバリープレートシール、ウエハサポートシール、バレルシールその他の各種シール材等に用いることができ、チューブ、ホース、各種ゴムロール、コーティング、ベルト、バルブの弁体などとしても使用できる。また、ラミネート用材料、ライニング用材料としても使用できる。 Lubricating oils (engine oil, mission oil, gear oil, etc.) containing amine additives (especially amine additives used as antioxidants and detergent dispersants) used in automobiles, ships and other transportation systems O-ring, V-ring, X-ring, packing, gasket, diaphragm, oil seal, bearing seal, lip seal used for sealing and sealing oil, fuel oil and grease (especially urea grease) 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., tube, hose, various rubber rolls, coatings, belts, valve discs It can also be used as such. It can also be used as a laminating material and a lining material.
自動車等の内燃機関のトランスミッション油及び／又はエンジン油に接触しその油温及び／又は油圧を検出するセンサーのリード電線などに使用される耐熱耐油性電線の被覆材料や、オートマチック・トランスミッションやエンジンのオイルパン内等の高温油雰囲気中においても使用することが可能である。 Coating materials for heat and oil resistant wires used for lead wires of sensors that detect the oil temperature and / or oil pressure when contacting with the oil and / or engine oil of an internal combustion engine such as an automobile, as well as for automatic transmissions and engines It can also be used in a high temperature oil atmosphere such as in an oil pan.
その他、本発明のフッ素ゴム成形品に加硫被膜を形成させて使用する場合がある。具体的には、複写機用非粘着耐油ロール、耐候結氷防止用ウェザーストリップ、輸液用ゴム栓、バイアルゴム栓、離型剤、非粘着軽搬送ベルト、自動車エンジンマウントのプレーガスケットの粘着防止被膜、合成繊維の被覆加工、パッキング被覆薄層をもつボルト部材または継ぎ手等の用途が挙げられる。 In addition, a vulcanized film may be formed on the fluororubber molded product of the present invention. Specifically, non-adhesive oil-resistant rolls for copiers, weather strips for weathering and anti-icing, infusion rubber stoppers, vial rubber stoppers, mold release agents, non-adhesive light transport belts, anti-adhesion coatings on automobile engine mount play gaskets, Applications include synthetic fiber coating, bolt members or joints having a thin packing coating layer, and the like.
なお、本発明のフッ素ゴム成形品の自動車関連部品用途については、同様の構造の自動二輪車の部品用途も含まれる。
また、上記自動車関連における燃料としては、軽油、ガソリン、ディーゼルエンジン用燃料（バイオディーゼルフューエルを含む）などが挙げられる。 Note that the use of the fluororubber molded article of the present invention for automobile-related parts includes parts for motorcycles having the same structure.
Examples of the fuel for the automobile include light oil, gasoline, diesel engine fuel (including biodiesel fuel), and the like.
また、本発明のフッ素ゴム組成物は、架橋してフッ素ゴム成形品として使用する以外にも、種々の工業分野において各種部品として使用することもできる。そこで次に、本発明のフッ素ゴム組成物の用途について説明する。
本発明のフッ素ゴム組成物は、金属、ゴム、プラスチック、ガラスなどの表面改質材；メタルガスケット、オイルシールなど、耐熱性、耐薬品性、耐油性、非粘着性が要求されるシール材および被覆材；ＯＡ機器用ロール、ＯＡ機器用ベルトなどの非粘着被覆材、またはブリードバリヤー；織布製シートおよびベルトへの含浸、焼付による塗布などに用いることができる。
本発明のフッ素ゴム組成物は、高粘度、高濃度にすることによって、通常の用法により複雑な形状のシール材、ライニング、シーラントとして用いることができ、低粘度にすることによって、数ミクロンの薄膜フィルムの形成に用いることができ、また中粘度にすることによりプレコートメタル、Ｏ－リング、ダイアフラム、リードバルブの塗布に用いることができる。
さらに、織布や紙葉の搬送ロールまたはベルト、印刷用ベルト、耐薬品性チューブ、薬栓、ヒューエルホースなどの塗布にも用いることができる。 Moreover, the fluororubber composition of the present invention can be used as various parts in various industrial fields, besides being crosslinked and used as a fluororubber molded article. Then, next, the use of the fluororubber composition of this invention is demonstrated.
The fluororubber composition of the present invention comprises a surface modifying material such as metal, rubber, plastic, and glass; a sealing material that requires heat resistance, chemical resistance, oil resistance, and non-adhesiveness, such as a metal gasket and an oil seal; Coating materials: Non-adhesive coating materials such as rolls for OA equipment, belts for OA equipment, or bleed barriers; Can be used for impregnation of woven fabric sheets and belts and application by baking.
The fluororubber composition of the present invention can be used as a sealing material, lining or sealant with a complicated shape by a normal usage by increasing the viscosity and concentration, and by reducing the viscosity to a thin film of several microns. It can be used to form a film, and can be used to apply pre-coated metal, O-rings, diaphragms, and reed valves by setting the viscosity to medium.
Further, it can also be used for coating woven fabrics and paper sheet transport rolls or belts, printing belts, chemical resistant tubes, chemical stoppers, fuel hoses, and the like.
本発明のフッ素ゴム組成物により被覆する物品基材としては、鉄、ステンレス鋼、銅、アルミニウム、真鍮などの金属類；ガラス板、ガラス繊維の織布及び不織布などのガラス製品；ポリプロピレン、ポリオキシメチレン、ポリイミド、ポリアミドイミド、ポリスルホン、ポリエーテルサルホン、ポリエーテルエーテルケトンなどの汎用および耐熱性樹脂の成形品および被覆物；ＳＢＲ、ブチルゴム、ＮＢＲ、ＥＰＤＭなどの汎用ゴム、およびシリコーンゴム、フッ素ゴムなどの耐熱性ゴムの成形品および被覆物；天然繊維および合成繊維の織布および不織布；などを使用することができる。
本発明のフッ素ゴム組成物から形成される被覆物は、耐熱性、耐溶剤性、潤滑性、非粘着性が要求される分野で使用でき、具体的な用途としては、複写機、プリンター、ファクシミリなどのＯＡ機器用のロール（例えば、定着ロール、圧着ロール）および搬送ベルト；シートおよびベルト；Ｏ－リング、ダイアフラム、耐薬品性チューブ、燃料ホース、バルブシール、化学プラント用ガスケット、エンジンガスケットなどが挙げられる。 Article substrates to be coated with the fluororubber composition of the present invention include metals such as iron, stainless steel, copper, aluminum and brass; glass products such as glass plates, glass fiber woven fabrics and nonwoven fabrics; polypropylene, polyoxy Molded and coated products of general-purpose and heat-resistant resins such as methylene, polyimide, polyamideimide, polysulfone, polyethersulfone, polyetheretherketone; general-purpose rubber such as SBR, butyl rubber, NBR, EPDM, and silicone rubber, fluorine rubber Heat-resistant rubber moldings and coatings such as; natural and synthetic fiber woven and non-woven fabrics; and the like can be used.
The coating formed from the fluororubber composition of the present invention can be used in fields where heat resistance, solvent resistance, lubricity, and non-adhesiveness are required. Specific applications include copying machines, printers, and facsimiles. Rolls for OA equipment such as fixing rolls, pressure rolls and conveyor belts; sheets and belts; O-rings, diaphragms, chemical resistant tubes, fuel hoses, valve seals, chemical plant gaskets, engine gaskets, etc. Can be mentioned.
本発明のフッ素ゴム組成物はまた、溶剤に溶解し、塗料、接着剤として使用できる。また、乳化分散液（ラテックス）として、塗料としても使用できる。
上記組成物は、各種装置、配管等のシール材やライニング、金属、セラミックス、ガラス、石、コンクリート、プラスチック、ゴム、木材、紙、繊維等の無機及び有機基材からなる構造物の表面処理剤等として使用される。
上記組成物は、ディスペンサー方式塗装やスクリーン印刷塗装により基材等に塗布することができる。 The fluororubber composition of the present invention can also be dissolved in a solvent and used as a paint or an adhesive. Moreover, it can be used as a coating material as an emulsified dispersion (latex).
The above composition is a surface treatment agent for structures composed of various materials, sealing materials for pipes and the like, linings, metals, ceramics, glass, stones, concrete, plastics, rubber, wood, paper, fibers, and other inorganic and organic substrates. Used as etc.
The said composition can be apply | coated to a base material etc. by dispenser system coating or screen printing coating.
本発明のフッ素ゴム組成物は、フィルムを流延するため、またはファブリック、プラスチック、金属、またはエラストマーのような基材を浸漬するための塗料組成物として使用されてもよい。
特に、本発明のフッ素ゴム組成物は、ラテックスの形態として、被覆ファブリック、保護手袋、含浸繊維、Ｏ－リング被覆、燃料系クイック連結Ｏ－リング用被覆、燃料系シール用被覆、燃料タンクロールオーバーバルブダイヤフラム用被覆、燃料タンク圧力センサーダイヤフラム用被覆、オイルフィルターおよび燃料フィルターシール用被覆、燃料タンクセンダーシールおよびセンダーヘッドフィッテングシール用被覆、複写機定着機構ロール用被覆、並びにポリマー塗料組成物を製造するために使用されてもよい。
それらはシリコーンラバー、ニトリルラバー、および他のエラストマーの被覆に有用である。その熱安定性と同様に基材エラストマーの耐透過性および耐薬品性の両方を高める目的のために、それらはそのようなエラストマーから製造される部品の被覆にも有用である。他の用途は、熱交換器、エキスパンジョンジョイント、バット、タンク、ファン、煙道ダクトおよび他の管路、並びに収納構造体、例えばコンクリート収納構造体用の被覆を含む。上記組成物は、多層部品構造の露出した断面に、例えばホース構造およびダイアフラムの製造方法において塗布されてもよい。接続部および結合部におけるシーリング部材は、硬質材料からしばしば成り、そして本発明のフッ素ゴム組成物は、改良された摩擦性界面、シーリング面に沿って低減された微量の漏れを伴う高められた寸法締りばめを提供する。そのラテックスは、種々の自動車システム用途におけるシール耐久性を高める。
それらは、パワーステアリング系統、燃料系統、エアーコンディショニング系統、並びに、ホースおよびチューブが別の部品に接続されるいかなる結合部の製造においても使用されることもできる。上記組成物のさらなる有用性は、３層燃料ホースのような多層ラバー構造における、製造欠陥（および使用に起因する損傷）の補修においてである。上記組成物は、塗料が塗布される前または後に、形成され、またはエンボス加工され得る薄鋼板の塗布にも有用である。例えば、被覆された鋼の多数の層は組み立てられて、２つの剛性金属部材の間にガスケットを作ることもできる。シーリング効果は、その層の間に本発明のフッ素ゴム組成物を塗布することにより得られる。このプロセスは、組み立てられた部品のボルト力およびひずみを低下させ、一方、低い亀裂、たわみ、および穴ひずみにより良好な燃料節約および低放出を提供する目的のために、エンジンヘッドガスケットおよび排気マニホールドガスケットを製造するために使用され得る。 The fluororubber composition of the present invention may be used as a coating composition for casting films or dipping substrates such as fabrics, plastics, metals, or elastomers.
In particular, the fluororubber composition of the present invention, in the form of latex, is coated fabric, protective gloves, impregnated fiber, O-ring coating, fuel system quick coupling O-ring coating, fuel system seal coating, fuel tank rollover Manufacture valve diaphragm coating, fuel tank pressure sensor diaphragm coating, oil filter and fuel filter seal coating, fuel tank sender seal and sender head fitting seal coating, copier fuser roll coating, and polymer coating composition May be used for
They are useful for coating silicone rubber, nitrile rubber, and other elastomers. For the purpose of increasing both the permeation resistance and chemical resistance of the base elastomer as well as its thermal stability, they are also useful for coating parts made from such elastomers. Other applications include coatings for heat exchangers, expansion joints, bats, tanks, fans, flue ducts and other conduits, and 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 hose structure and a method of manufacturing a diaphragm. Sealing members at joints and joints are often made of a hard material, and the fluororubber composition of the present invention has an improved frictional interface, increased dimensions with reduced trace leakage along the sealing surface. Provide an interference 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 joint where hoses and tubes are connected to other parts. A further utility of the composition is in repairing 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 sheets that can be formed or embossed before or after the paint is applied. For example, multiple layers of coated steel can be assembled to create a gasket between two rigid metal members. The sealing effect can be obtained by applying the fluororubber composition of the present invention between the layers. This process reduces the bolt force and strain of the assembled parts, while engine head gaskets and exhaust manifold gaskets for the purpose of providing better fuel savings and low emissions due to low cracks, deflections and hole strains Can be used to manufacture.
本発明のフッ素ゴム組成物は、その他、コーティング剤；金属、セラミック等の無機材料を含む基材にディスペンサー成形してなる基材一体型ガスケット、パッキン類；金属、セラミック等の無機材料を含む基材にコーティングしてなる複層品などとしても使用することができる。 The fluororubber composition of the present invention includes a base material-integrated gasket and packing formed by dispenser molding on a base material containing an inorganic material such as a coating agent; metal, ceramic, etc .; a base containing an inorganic material such as metal, ceramic, etc. It can also be used as a multilayer product formed by coating a material.
つぎに本発明を実施例を挙げて説明するが、本発明はかかる実施例のみに限定されるものではない。 Next, the present invention will be described with reference to examples. However, the present invention is not limited to such examples.
実施例の各数値は以下の方法により測定した。 Each numerical value of the examples was measured by the following method.
＜架橋特性＞
フッ素ゴム組成物について、プレス架橋時にＪＳＲ型キュラストメーターＩＩ型を用いて表１～３に記載の温度における架橋曲線を求め、トルクの変化より、最適架橋時間（Ｔ９０）を求めた。 <Crosslinking characteristics>
With respect to the fluororubber composition, a crosslinking curve at temperatures shown in Tables 1 to 3 was obtained using a JSR type curlastometer type II during press crosslinking, and an optimum crosslinking time (T90) was determined from a change in torque.
＜切断時引張応力及び切断時伸び＞
実施例及び比較例で得られた厚さ２ｍｍの架橋シートを用いて、引張試験機（テンシロン、オリエンテック社製）を使用して、ＪＩＳ　Ｋ６２５１（１９９３年）に準じて、５００ｍｍ／分の条件下、ダンベル５号にて、２３℃における切断時引張応力及び切断時伸びを測定した。また（株）島津製作所製ＡＧ－Ｉを使用して、ＪＩＳ　Ｋ６２５１（１９９３年）に準じて、５００ｍｍ／分の条件下、ダンベル６号にて、２００℃における切断時引張応力及び切断時伸びを測定した。 <Tensile stress at cutting and elongation at cutting>
Using the cross-linked sheet having a thickness of 2 mm obtained in Examples and Comparative Examples, using a tensile tester (Tensilon, manufactured by Orientec Co., Ltd.), according to JIS K6251 (1993), conditions of 500 mm / min. Below, with dumbbell No. 5, the tensile stress at break and the elongation at break at 23 ° C. were measured. Also, using AG-I manufactured by Shimadzu Corporation, in accordance with JIS K6251 (1993), the tensile stress at break and elongation at break at 200 ° C. were measured with dumbbell No. 6 under the condition of 500 mm / min. It was measured.
＜硬さ＞
実施例及び比較例で得られた厚さ２ｍｍの架橋シートを用いて、タイプＡデュロメーター（商品名：ＡＳＫＥＲ、高分子計器社製）を使用して、ＪＩＳ　Ｋ６２５３（１９９７年）に準拠してピーク値を測定した。 <Hardness>
Using a cross-linked sheet having a thickness of 2 mm obtained in Examples and Comparative Examples, using a type A durometer (trade name: ASKER, manufactured by Kobunshi Keiki Co., Ltd.), the peak is obtained in accordance with JIS K6253 (1997). The value was measured.
＜引裂き強さ＞
実施例及び比較例で得られた厚さ２ｍｍの架橋シートを用いて、引張試験機（テンシロン、オリエンテック社製）を使用して、ＪＩＳ　Ｋ６２５２（２００７年）に準じて、５００ｍｍ／分の条件下、切込みなしアングル形にて、２３℃における引裂き強さを測定した。 <Tear strength>
Using the cross-linked sheet having a thickness of 2 mm obtained in Examples and Comparative Examples, using a tensile tester (Tensilon, manufactured by Orientec Corp.), according to JIS K6252 (2007), conditions of 500 mm / min. Below, the tear strength at 23 ° C. was measured with an angled shape without incision.
＜圧縮永久ひずみ＞
実施例及び比較例で得られたＪＩＳ　Ｋ６２６２（２００６年）に記載の小型試験片を用い、ＪＩＳ　Ｋ６２６２（２００６年）に準じて、圧縮率２５％、２００℃×所定時間における圧縮永久ひずみを測定した。 <Compression set>
Using the small test pieces described in JIS K6262 (2006) obtained in Examples and Comparative Examples, the compression set at a compression rate of 25% and 200 ° C. × predetermined time was measured according to JIS K6262 (2006). did.
表１～３中の成分は、それぞれ次に示すものである。
フッ素ゴム１：ヨウ素移動重合法で製造されたパーオキサイド架橋可能な３元フッ素ゴム（ＶｄＦ／ＨＦＰ／ＴＦＥ＝５０／３０／２０（モル％））。ムーニー粘度は、５０（ＭＬ１＋１０、１００℃）。
フッ素ゴム２：２元フッ素ゴム（ＶｄＦ／ＨＦＰ＝７８／２２（モル％））に、２元フッ素ゴム１００質量部に対し１．５質量部のビスフェノールＡＦ、及び０．３部のＤＢＵ－Ｂを混練したポリオール架橋可能なプレコンパウンド。ムーニー粘度は、６０（ＭＬ１＋１０、１００℃）。
フッ素ゴム３：ヨウ素移動重合法で製造されたパーオキサイド架橋可能な２元フッ素ゴム（ＶｄＦ／ＨＦＰ＝７８／２２（モル％））。ムーニー粘度は、６９（ＭＬ１＋１０、１００℃）。
フッ素ゴム４：架橋部位を与えるヨウ素含有モノマー単位としてＩＣＨ２ＣＦ２ＣＦ２ＯＣＦ＝ＣＦ２を含む、ヨウ素移動重合法で製造されたパーオキサイド架橋可能な３元フッ素ゴム（ＶｄＦ／ＨＦＰ／ＴＦＥ／（ＩＣＨ２ＣＦ２ＣＦ２ＯＣＦ＝ＣＦ２）＝４９．７／２９．８／２０．０／０．５（モル％））。ムーニー粘度は、７５（ＭＬ１＋１０、１００℃）。
カーボン１：Ｌａｍｐ　１０１（Ｂ）（商品名）（Ｎ２ＳＡ＝２９ｍ２／ｇ、ＤＢＰ吸油量＝１１７ｍｌ／１００ｇ、平均一次粒子径＝９５ｎｍ、Ａ値＝４．０、オリオンエンジニアドカーボンズ社製のランプブラック）
カーボン２：サーマックス　ＭＴ（商品名）（Ｎ２ＳＡ＝１０ｍ２／ｇ、ＤＢＰ吸油量＝４４ｍｌ／１００ｇ、平均一次粒子径＝２８０ｎｍ、Ａ値＝４．４、Ｃａｎｃａｒｂ社製のＮ９９０カーボン）
カーボン３：シーストＳ（商品名）（Ｎ２ＳＡ＝２７ｍ２／ｇ、ＤＢＰ吸油量＝６８ｍｌ／１００ｇ、平均一次粒子径＝６６ｎｍ、Ａ値＝２．５、東海カーボン（株）製のＮ７７０　ＳＲＦカーボン）
カーボン４：シースト６（商品名）（Ｎ２ＳＡ＝１１９ｍ２／ｇ、ＤＢＰ吸油量＝１１４ｍｌ／１００ｇ、平均一次粒子径＝２２ｎｍ、Ａ値＝１．０、東海カーボン（株）製のＮ２２０　ＩＳＡＦカーボン）
架橋助剤１：タイク（商品名）（日本化成（株）製　トリアリルイソシアヌレート）
架橋助剤２：タイク　Ｍ６０（商品名）（日本化成（株）製　トリアリルイソシアヌレートを６０質量％含有している粉体。）
有機過酸化物１：パーヘキサ２５Ｂ（商品名）（日油（株）製　２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン）
有機過酸化物２：パーヘキサ２５Ｂ－４０（商品名）（日油（株）製　２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサンを４０質量％含有している粉体。）
有機過酸化物３：パーヘキシン２５Ｂ－４０（商品名）（日油（株）製　２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキシン－３を４０質量％含有している粉体。）
水酸化カルシウム：カルディック２０００（商品名）（近江化学工業（株）製）
酸化マグネシウム：キョーワマグ１５０（商品名）（協和化学工業（株）製）
ステアリン酸：関東化学（株）製 The components in Tables 1 to 3 are as follows.
Fluororubber 1: A peroxide-crosslinkable ternary fluororubber (VdF / HFP / TFE = 50/30/20 (mol%)) produced by an iodine transfer polymerization method. The Mooney viscosity is 50 (ML 1 + 10 , 100 ° C.).
Fluoro rubber 2: Binary fluoro rubber (VdF / HFP = 78/22 (mol%)), 1.5 parts by mass of bisphenol AF and 0.3 part of DBU-B with respect to 100 parts by mass of the binary fluoro rubber A pre-compound capable of cross-linking polyol. The Mooney viscosity is 60 (ML 1 + 10 , 100 ° C.).
Fluoro rubber 3: Peroxide-crosslinkable binary fluoro rubber produced by an iodine transfer polymerization method (VdF / HFP = 78/22 (mol%)). The Mooney viscosity is 69 (ML 1 + 10 , 100 ° C.).
Fluorine Rubber 4: As iodine-containing monomer units that provide a crosslinking site containing ICH 2 CF 2 CF 2 OCF = CF 2, peroxide crosslinkable ternary fluororubber prepared by iodine transfer polymerization method (VdF / HFP / TFE / (ICH 2 CF 2 CF 2 OCF═CF 2 ) = 49.7 / 29.8 / 20.0 / 0.5 (mol%)). The Mooney viscosity is 75 (ML 1 + 10 , 100 ° C.).
Carbon 1: Lamp 101 (B) (trade name) (N 2 SA = 29 m 2 / g, DBP oil absorption = 117 ml / 100 g, average primary particle size = 95 nm, A value = 4.0, Orion Engineered Carbons) Made of lamp black)
Carbon 2: Thermax MT (trade name) (N 2 SA = 10 m 2 / g, DBP oil absorption = 44 ml / 100 g, average primary particle size = 280 nm, A value = 4.4, N990 carbon manufactured by Cancarb)
Carbon 3: Seast S (trade name) (N 2 SA = 27 m 2 / g, DBP oil absorption = 68 ml / 100 g, average primary particle size = 66 nm, A value = 2.5, N770 SRF manufactured by Tokai Carbon Co., Ltd. carbon)
Carbon 4: Seast 6 (trade name) (N 2 SA = 119 m 2 / g, DBP oil absorption = 114 ml / 100 g, average primary particle size = 22 nm, A value = 1.0, N220 ISAF manufactured by Tokai Carbon Co., Ltd. carbon)
Crosslinking aid 1: Tyke (trade name) (triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd.)
Crosslinking aid 2: Thaik M60 (trade name) (powder containing 60% by mass of triallyl isocyanurate manufactured by Nippon Kasei Co., Ltd.)
Organic peroxide 1: Perhexa 25B (trade name) (2,5-dimethyl-2,5-di (t-butylperoxy) hexane manufactured by NOF Corporation)
Organic peroxide 2: Perhexa 25B-40 (trade name) (powder containing 40% by mass of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane manufactured by NOF Corporation) .)
Organic peroxide 3: Perhexine 25B-40 (trade name) (40% by mass of 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 manufactured by NOF Corporation) powder.)
Calcium hydroxide: Caldic 2000 (trade name) (Omi Chemical Industry Co., Ltd.)
Magnesium oxide: Kyowa Mag 150 (trade name) (manufactured by Kyowa Chemical Industry Co., Ltd.)
Stearic acid: manufactured by Kanto Chemical Co., Inc.
実施例１～５及び比較例１～９
表１及び２の処方に従ってそれぞれの成分を配合し、オープンロール上で混練りしてゴム組成物を調製した。得られたゴム組成物の架橋特性を表１及び２に示す。 Examples 1 to 5 and Comparative Examples 1 to 9
The respective components were blended according to the formulations shown in Tables 1 and 2, and kneaded on an open roll to prepare a rubber composition. Tables 1 and 2 show the crosslinking characteristics of the obtained rubber composition.
次に調製したゴム組成物を表１及び表２の処方に従って、一次架橋（プレス架橋）及び二次架橋（オーブン架橋）を施し、厚さ２ｍｍの架橋シートの被験サンプル及びＪＩＳ　Ｋ６２６２（２００６年）に記載の小型試験片を作製した。得られた架橋シートの常態物性評価（硬さ、切断時引張応力、切断時伸び及び引裂き強さ）の結果を表１及び表２に示す。実施例１、２及び比較例１～６については、得られた小型試験片を用いた圧縮率２５％、２００℃×７２時間における圧縮永久ひずみの結果を表１に示す。実施例３～５及び比較例７～９については、得られた架橋シートの２００℃での物性評価（切断時引張応力）及び得られた小型試験片を用いた圧縮率２５％、２００℃×２２時間または７２時間における圧縮永久ひずみの結果を表２に示す。 Next, the prepared rubber composition was subjected to primary cross-linking (press cross-linking) and secondary cross-linking (oven cross-linking) according to the formulations shown in Table 1 and Table 2, and a test sample of a cross-linked sheet having a thickness of 2 mm and JIS K6262 (2006) The small test piece as described in 1 was produced. Tables 1 and 2 show the results of normal physical property evaluation (hardness, tensile stress during cutting, elongation during cutting, and tear strength) of the obtained crosslinked sheet. For Examples 1 and 2 and Comparative Examples 1 to 6, Table 1 shows the results of compression set at a compression rate of 25% and 200 ° C. × 72 hours using the obtained small test pieces. For Examples 3 to 5 and Comparative Examples 7 to 9, physical properties of the obtained crosslinked sheets were evaluated at 200 ° C. (tensile stress at the time of cutting), and the compression rate was 25% using the obtained small test pieces, 200 ° C. × Table 2 shows the results of compression set at 22 hours or 72 hours.
実施例６及び比較例１０～１３
混練機（（株）モリヤマ製のＭｉｘＬａｂｏ０．５Ｌ、ローター直径：６．６ｃｍ、チップクリアランス：０．０５ｃｍ）を用いて、フロントローター回転数：６０ｒｐｍ、バックローター回転数：５０ｒｐｍの混練条件で、表３の処方に従ってそれぞれフッ素ゴム３、カーボン１、２、４、およびステアリン酸を混練し、フッ素ゴムプレコンパウンドを調製した。なお、排出された混練物の最高温度は１６０～１７０℃であった。 Example 6 and Comparative Examples 10 to 13
Using a kneading machine (MixLabo 0.5L manufactured by Moriyama Co., Ltd., rotor diameter: 6.6 cm, tip clearance: 0.05 cm), the kneading conditions were as follows: front rotor rotation speed: 60 rpm, back rotor rotation speed: 50 rpm. The fluororubber 3, carbon 1, 2, 4, and stearic acid were kneaded according to the formulation of 3, respectively, to prepare a fluororubber pre-compound. The maximum temperature of the discharged kneaded product was 160 to 170 ° C.
得られたフッ素ゴムプレコンパウンドに、８インチオープンロール（関西ロール（株）製）を用いて、フロントロール回転数２１ｒｐｍ、バックロール回転数１９ｒｐｍ、ロール間隙０．１ｃｍの混練条件で、表３の処方に従って架橋助剤２および有機過酸化物２を１５分間かけて混練し、ゴム組成物を調製した。なお、排出された混練物の最高温度は５０～６０℃であった。得られたゴム組成物の架橋特性を表３に示す。 Using the obtained fluororubber pre-compound, an 8-inch open roll (manufactured by Kansai Roll Co., Ltd.), a kneading condition of a front roll rotation speed of 21 rpm, a back roll rotation speed of 19 rpm, and a roll gap of 0.1 cm is shown in Table 3. According to the formulation, the crosslinking aid 2 and the organic peroxide 2 were kneaded for 15 minutes to prepare a rubber composition. The maximum temperature of the discharged kneaded material was 50 to 60 ° C. Table 3 shows the crosslinking characteristics of the rubber composition obtained.
次に調製したゴム組成物を表３の処方に従って、一次架橋（プレス架橋）及び二次架橋（オーブン架橋）を施し、厚さ２ｍｍの架橋シートの被験サンプル及びＪＩＳ　Ｋ６２６２（２００６年）に記載の小型試験片を作製した。得られた架橋シートの常態物性評価の結果（硬さ、切断時引張応力、切断時伸び及び引裂き強さ）、および得られた小型試験片を用いた圧縮率２５％、２００℃×７２時間における圧縮永久ひずみの結果を表３に示す。 Next, the prepared rubber composition was subjected to primary cross-linking (press cross-linking) and secondary cross-linking (oven cross-linking) according to the formulation in Table 3, and a test sample of a cross-linked sheet having a thickness of 2 mm and JIS K6262 (2006) A small test piece was prepared. Results of evaluation of normal physical properties of the obtained crosslinked sheet (hardness, tensile stress at break, elongation at break and tear strength), and compression rate of 25% using the obtained small test piece at 200 ° C. × 72 hours The results of compression set are shown in Table 3.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006

Claims (4)

  1. フッ素ゴム、ランプブラック、及び、架橋剤を含むことを特徴とするフッ素ゴム組成物。 A fluororubber composition comprising fluororubber, lamp black, and a crosslinking agent.
  2. フッ素ゴム１００質量部に対して５～７０質量部のランプブラックを含む請求項１記載のフッ素ゴム組成物。 The fluororubber composition according to claim 1, comprising 5 to 70 parts by mass of lamp black with respect to 100 parts by mass of the fluororubber.
  3. フッ素ゴムは、ビニリデンフルオライド系フッ素ゴム、テトラフルオロエチレン／プロピレン系フッ素ゴム、テトラフルオロエチレン／プロピレン／ビニリデンフルオライド系フッ素ゴム、エチレン／ヘキサフルオロプロピレン系フッ素ゴム、エチレン／ヘキサフルオロプロピレン／ビニリデンフルオライド系フッ素ゴム、及び、エチレン／ヘキサフルオロプロピレン／テトラフルオロエチレン系フッ素ゴムからなる群より選択される少なくとも１種である請求項１又は２記載のフッ素ゴム組成物。 Fluoro rubbers are vinylidene fluoride fluoro rubber, tetrafluoroethylene / propylene fluoro rubber, tetrafluoroethylene / propylene / vinylidene fluoride fluoro rubber, ethylene / hexafluoropropylene fluoro rubber, ethylene / hexafluoropropylene / vinylidene fluoride. The fluororubber composition according to claim 1 or 2, which is at least one selected from the group consisting of a ride-type fluororubber and an ethylene / hexafluoropropylene / tetrafluoroethylene-based fluororubber.
  4. 請求項１、２又は３記載のフッ素ゴム組成物から得られるフッ素ゴム成形品。 A fluororubber molded product obtained from the fluororubber composition according to claim 1, 2 or 3.
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