JP2020002198A - Composition containing fluorine-containing polymer - Google Patents

Abstract

To provide a composition containing a fluorine-containing polymer, capable of giving a molding excellent in amine resistance and low-temperature characteristics and also excellent in adhesiveness to a silicone rubber molding.SOLUTION: The present invention provides the composition containing a fluorine-containing polymer, an uncrosslinked silicone rubber, and an organic peroxide. The fluorine-containing polymer has a glass transition temperature of 25°C or lower and contains a vinylidene fluoride unit and a fluorine-containing monomer (1) unit represented by general formula (1): CHX=CXRf (where one of Xand Xis H and the other is F; and Rf is a C1-12 linear or branched fluoroalkyl group).SELECTED DRAWING: None

Description

  The present disclosure relates to a composition containing a fluoropolymer.

Patent Document 1 discloses vinylidene fluoride [VdF] and the following general formula (1) as an amorphous fluorine-containing elastomer having a low glass transition temperature, excellent amine resistance, and an amorphous property.
CH ₂ = CFRf (1)
(Wherein, Rf is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), which is a copolymer comprising only a fluorine-containing monomer represented by the following formula: vinylidene fluoride unit / fluorine-containing unit An amorphous fluoroelastomer characterized in that the molar ratio of monomer units is 78/22 to 22/78 and the glass transition temperature is 25 ° C. or lower.

JP, 2012-512264, A

  An object of the present disclosure is to provide a composition containing a fluorine-containing polymer, which is capable of obtaining a molded article having excellent amine resistance and low-temperature properties and excellent adhesion to a silicone rubber molded article.

According to the present disclosure, the fluoropolymer contains a fluoropolymer, an uncrosslinked silicone rubber, and an organic peroxide. The fluoropolymer has a glass transition temperature of 25 ° C. or less, a vinylidene fluoride unit, and the following general formula (1) ):
CHX ¹ = CX ² Rf (1)
(In the formula, ^one of X ¹ and X ² is H, the other is F, and Rf is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms.) A composition containing the monomer (1) unit is provided.

Preferably, the uncrosslinked silicone rubber is capable of peroxide crosslinking.
In the general formula (1), X ¹ is preferably H and X ² is preferably F.
The fluorinated monomer (1) is preferably 2,3,3,3-tetrafluoropropene.
The fluorine-containing polymer preferably has a Mooney viscosity at 100 ° C. (ML1 + 10 (100 ° C.)) of 2 to 200.
In the composition of the present disclosure, it is preferable that the mass ratio of the fluoropolymer to the uncrosslinked silicone rubber (fluoropolymer / uncrosslinked silicone rubber) is 5/95 to 99/1.
The composition of the present disclosure further contains carbon black, the nitrogen adsorption specific surface area of the carbon black is 70 to 180 m ² / g or less, and the carbon black has an absorption amount of dibutyl phthalate (DBP) or paraffin oil, It is preferably 40 to 180 ml / 100 g or less, and the content of the carbon black is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the fluoropolymer.

  Further, according to the present disclosure, there is provided a fluoropolymer molded article obtained by crosslinking the above composition.

  According to the present disclosure, a fluorine-containing polymer molded article (A) obtained by crosslinking the above composition and a silicone rubber composition containing a peroxide-crosslinkable uncrosslinked silicone rubber are crosslinked. And a silicone rubber molded article (B) obtained by the above method, wherein the fluoropolymer molded article (A) and the silicone rubber molded article (B) are bonded to each other.

  In the composite of the present disclosure, the silicone rubber composition further contains a crosslinking aid, and the content of the crosslinking aid is 0.1 to 10 parts by mass with respect to 100 parts by mass of the uncrosslinked silicone rubber. Preferably, there is.

  Further, according to the present disclosure, a fluorine-containing polymer molded article used by bonding to a silicone rubber molded article (B) obtained by crosslinking a silicone rubber composition containing a peroxide-crosslinkable uncrosslinked silicone rubber is used. Use of the above composition for forming body (A) is provided.

  According to the present disclosure, it is possible to provide a composition containing a fluorine-containing polymer, which is capable of obtaining a molded article having excellent amine resistance and low-temperature properties and excellent adhesion to a silicone rubber molded article.

  Hereinafter, specific embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

  The composition of the present disclosure contains a fluoropolymer, an uncrosslinked silicone rubber, and an organic peroxide. By using the composition of the present disclosure, a molded article excellent in amine resistance and low-temperature properties and excellent in adhesion to a silicone rubber molded article can be obtained. Further, the obtained molded article has comparable tensile strength and elongation at break as compared with conventional molded articles.

<Fluorine-containing polymer>
The fluorine-containing polymer contained in the composition of the present disclosure has a glass transition temperature of 25 ° C. or lower and contains a vinylidene fluoride unit and a fluorine-containing monomer (1) unit.

  The glass transition temperature of the fluorine-containing polymer is 25 ° C. or lower, preferably 0 ° C. or lower, more preferably −5 ° C. or lower, and still more preferably −10 ° C. or lower. Further, the temperature can be set to -20 ° C or lower. When the glass transition temperature of the fluoropolymer is within the above range, a molded article having excellent low-temperature properties can be obtained. The fluorine-containing polymer is preferably a fluorine-containing elastomer, and is preferably an amorphous polymer.

  In the present disclosure, “amorphous” means that the size of a melting peak (ΔH) that appears in DSC measurement (heating temperature: 10 ° C./min) is 2.0 J / g or less.

  Using a differential scanning calorimeter (X-DSC823e, manufactured by Hitachi Techno Science), the above glass transition temperature was obtained by cooling a 10 mg sample to −75 ° C. and increasing the temperature at 20 ° C./min to obtain a DSC curve. , The temperature at the intersection of the extension of the baseline before and after the second order transition of the DSC curve and the tangent at the inflection point of the DSC curve is determined as the glass transition temperature.

The unit of the fluorine-containing monomer (1) is represented by the following general formula (1):
CHX ¹ = CX ² Rf (1)
(In the formula, ^one of X ¹ and X ² is H, the other is F, and Rf is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms.)
Is a unit based on the fluorine-containing monomer (1) represented by Since the composition of the present disclosure contains the above-mentioned fluorine-containing polymer containing the fluorine-containing monomer (1) unit, it is excellent in amine resistance and low-temperature properties, and excellent in adhesion to a silicone rubber molded article. You can get the body.

  As Rf in the general formula (1), a linear fluoroalkyl group is preferable, and a linear perfluoroalkyl group is more preferable, since a molded article having more excellent amine resistance and low-temperature properties can be obtained. Further, the carbon number of Rf is preferably 1 to 6.

In the general formula (1), it is preferable that X ¹ is H and X ² is F, since a molded article having more excellent amine resistance and low-temperature properties can be obtained.

As the fluorinated monomer (1), CH ₂ CFCF ₃ , CH ₂ ＣＦCFCF ₂ CF ₃ , CH ₂ ＣＦCFCF ₂ CF ₂ CF ₃ , CH ₂ ＣＦCFCF ₂ CF ₂ CF ₂ CF ₃ , CHF ＝ CHCF ₃ (1,3,3,3-tetrafluoropropene) and the like, among which CH ₂ CFCF ₃ (2,3,3,3-tetrafluoropropene) is preferable. One or more monomers may be used as the fluorinated monomer (1).

  The fluoropolymer may further contain other monomer units other than the vinylidene fluoride unit and the fluoromonomer (1) unit. The other monomer is not particularly limited as long as it is a monomer copolymerizable with vinylidene fluoride and the fluorine-containing monomer (1), and one or more monomers may be used. Good.

  Examples of the other monomers include tetrafluoroethylene [TFE], hexafluoropropylene [HFP], perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), chlorotrifluoroethylene, and trifluoroethylene. At least one selected from the group consisting of fluoroethylene, hexafluoroisobutene, vinyl fluoride, ethylene, propylene, alkyl vinyl ether, and a monomer providing a crosslinking site is preferable, and TFE, hexafluoropropylene, perfluoro (methyl Vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), chlorotrifluoroethylene, trifluoroethylene, hexafluoroisobutene, vinyl fluoride, Styrene, alkyl vinyl ether, and, more preferably at least one selected from the group consisting of monomer giving a crosslinking site, TFE is more preferred. It is also a preferable embodiment to use only TFE as the other monomer.

Examples of the monomer that provides the crosslinking site include, for example,
Formula _{^{(2): CX 3 2 =}} CX 3 -Rf 1 CHR 1 X 4
(Wherein X ³ is the same or different and H, F or —CH ₃ , Rf ¹ is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro (poly) oxyalkylene group) , R ¹ is H or —CH ₃ , X ⁴ is I or Br.), Iodine or bromine-containing monomer represented by the formula:
Formula _{^{(3): CX 5 2 =}} CX 5 -Rf 2 X 6
(Wherein X ⁵ is the same or different and H, F or —CH ₃ , Rf ² is a fluoroalkylene group, a perfluoroalkylene group, a fluoro (poly) oxyalkylene group or a perfluoro (poly) oxyalkylene group) , X ⁶ is I or Br.) (Preferably a general formula: CH ₂ ＣＨCH (CF ₂ ) _n I (n is an integer of 2 to 8) )) Iodine-containing monomer),
Formula _{(4): CF 2 = CFO} (CF 2 CF (CF 3) O) m (CF 2) n -X 7
(Wherein m is an integer of 0 to 5, n is an integer of 1 to 3, and X ⁷ is a cyano group, a carboxyl group, an alkoxycarbonyl group, I or Br).
Formula _{(5): CH 2 = CFCF} 2 O (CF (CF 3) CF 2 O) m (CF (CF 3)) n -X 8
(In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ⁸ is a cyano group, a carboxyl group, an alkoxycarbonyl group, I, Br or —CH ₂ OH.) Monomer,
Formula ^{(6): CR 2 R 3} = CR 4 -Z-CR 5 = CR 6 R 7
(Wherein, R ^{2 to} R ⁷ are the same or different and are H or an alkyl group having 1 to 5 carbon atoms. Z is a linear or branched carbon atom which may have an oxygen atom. An alkylene group having 1 to 18 carbon atoms, a cycloalkylene group having 3 to 18 carbon atoms, an alkylene or oxyalkylene group having 1 to 10 carbon atoms which is at least partially fluorinated, or
_{- (Q) p -CF 2 O-} (CF 2 CF 2 O) m (CF 2 O) n -CF 2 - (Q) p -
(Wherein Q is an alkylene or oxyalkylene group; p is 0 or 1; m / n is 0.2 to 5); and (per) fluoro having a molecular weight of 500 to 10,000. It is a polyoxyalkylene group. And the like.

Examples of the monomer represented by the general formula (6), for _{example, CH 2 = CH- (CF 2} ) 2 -CH = CH 2, CH 2 = CH- (CF 2) 4 -CH = CH 2, CH _{2 = CH- (CF 2) 6} -CH = CH 2, the general ^{_{formula: CH 2 = CH-Z 1}} -CH = CH 2
(In the formula, Z ¹ is a fluoropolyoxyalkylene group represented by —CH ₂ OCH ₂ —CF ₂ O— (CF ₂ CF ₂ O) _m1 (CF ₂ O) _n1 —CF ₂ —CH ₂ OCH ₂ — And m1 / n1 is 0.5 and the molecular weight is 2000.).

Among the monomers that provide the crosslinking site, CF ₂ ＣＦCFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CN, CF ₂ ＣＦCFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOH, CF ₂ ＣＦCFOCF _{2 CF 2 CH 2 I, CF} 2 = CFOCF 2 CF (CF 3) OCF 2 CF 2 CH 2 I, CH 2 = CFCF 2 OCF (CF 3) CF 2 OCF (CF 3) CN, CH 2 = CFCF 2 OCF At least one selected from the group consisting of (CF ₃ ) CF ₂ OCF (CF ₃ ) COOH and CH ₂ ＣＦCFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ OH is preferable.

As the monomer that provides the crosslinking site, CF ₂ ＣＦCFOCF ₂ CF ₂ CH ₂ I can improve the crosslinking density and improve the compression set in crosslinking using an organic peroxide. Therefore, it is particularly preferable.

  The molar ratio of vinylidene fluoride units / fluoromonomer (1) units in the fluoropolymer is preferably 87/13 to 20/80, and the lower limit of the molar ratio of vinylidene fluoride units is more preferably 22/13. / 78 or more, more preferably 50/50 or more, particularly preferably 60/40 or more, and the upper limit of the molar ratio of vinylidene fluoride units is more preferably 78/22 or less. Further, the content of the other monomer units is preferably 0 to 50 mol%, more preferably 1 to 40 mol% of the total monomer units.

  The fluorine-containing polymer is preferably a copolymer consisting of only a vinylidene fluoride unit, a fluorine-containing monomer (1) unit and another monomer unit.

  Since the above-mentioned fluorine-containing polymer is more excellent in amine resistance and low-temperature properties and can obtain a molded article further excellent in adhesion to a silicone rubber molded article, it has at least one of an iodine atom and a bromine atom. More preferably, it has an iodine atom. The total content of iodine atoms and bromine atoms in the fluoropolymer is preferably 0.001 to 10% by mass, and the upper limit of the total content of iodine atoms and bromine atoms is more preferably 5.0% by mass. % Or less, more preferably 1.0% by mass or less, particularly preferably 0.7% by mass or less, most preferably 0.5% by mass or less, and the content of iodine atom and bromine atom The lower limit of the total is more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, particularly preferably 0.08% by mass or more, and most preferably 0.1% by mass or more. It is. The bonding position of the iodine atom and the bromine atom in the fluoropolymer may be at the end of the main chain or the end of the side chain of the fluoropolymer, or may be both. In such a fluorine-containing polymer, the iodine terminal or bromine terminal serves as a crosslinking point (crosslinking site), so that a crosslinked fluorine-containing polymer having a high crosslinking density can be obtained, and peroxide crosslinking can be more easily performed. become.

  As the above-mentioned fluoropolymer, it is possible to obtain a molded article having more excellent amine resistance and low-temperature properties. Therefore, the fluoropolymer contains only a vinylidene fluoride unit and a fluorine-containing monomer (1) unit, and contains a vinylidene fluoride unit / A copolymer (I) having a molar ratio of the fluorine-containing monomer (1) unit of 87/13 to 22/78, a vinylidene fluoride unit, a fluorine-containing monomer (1) unit, and vinylidene fluoride; It contains only other monomer units copolymerizable with the fluorine-containing monomer (1), and the molar ratio of vinylidene fluoride unit / fluorine-containing monomer (1) unit is 85/15 to 20/80. A copolymer (II) in which other monomer units are 1 to 50 mol% of all monomer units, a vinylidene fluoride unit, a fluorine-containing monomer (1) unit, and vinyl It contains dendrifluoride and another monomer unit copolymerizable with the fluorine-containing monomer (1), and the molar ratio of vinylidene fluoride unit / fluorine-containing monomer (1) unit is 85/15 to 20. / 80, the other monomer unit is 0 to 50 mol% of the total monomer unit, has at least one of an iodine atom and a bromine atom, and has a total content of the iodine atom and the bromine atom of 0. At least one selected from the group consisting of 0.0001 to 10% by mass of the copolymer (III).

  The copolymer (I) contains only vinylidene fluoride units and fluorine-containing monomer (1) units, and the molar ratio of vinylidene fluoride units / fluorine-containing monomer (1) units is 87/13 to 22. / 78. The molar ratio of vinylidene fluoride units / fluoromonomer (1) units of the copolymer (I) is preferably 82/18, since a molded article having more excellent amine resistance and low-temperature properties can be obtained. ６０60/40.

  The copolymer (II) contains only a vinylidene fluoride unit, a fluorine-containing monomer (1) unit, and other monomer units copolymerizable with vinylidene fluoride and the fluorine-containing monomer (1). And the molar ratio of vinylidene fluoride units / fluoromonomer (1) units is 85/15 to 20/80, and the other monomer units are 1 to 50 mol% of all monomer units. is there.

  The molar ratio of vinylidene fluoride units / fluoromonomer (1) units in the copolymer (II) is preferably 85/15, since a molded article having more excellent amine resistance and low-temperature properties can be obtained. ５０50/50, more preferably 85 / 15-60 / 40.

  The content of the other monomer units of the copolymer (II) is 1 to 40 mol% of the total monomer units, since a molded article having more excellent amine resistance and low-temperature properties can be obtained. Is preferred. As the other monomer contained in the copolymer (II), those described above are preferable.

  The copolymer (III) comprises a vinylidene fluoride unit, a fluorine-containing monomer (1) unit, and vinylidene fluoride and another monomer unit copolymerizable with the fluorine-containing monomer (1). And the molar ratio of vinylidene fluoride units / fluoromonomer (1) units is 85/15 to 20/80, and the other monomer units are 0 to 50 mol% of all monomer units. And has at least one of an iodine atom and a bromine atom, and the total content of the iodine atom and the bromine atom is 0.001 to 10% by mass.

  As the copolymer (III), a copolymer containing substantially only a vinylidene fluoride unit and a fluorinated monomer (1), or a substantially vinylidene fluoride unit and a fluorinated monomer (1) A) and a copolymer containing only vinylidene fluoride and another monomer unit copolymerizable with the fluorine-containing monomer (1). In this case, the copolymer (III) may be one produced using a reactive emulsifier as long as the effects of the present disclosure are not impaired. Further, it may include an I-terminal or the like derived from the chain transfer agent.

  The copolymer (III) contains substantially only a vinylidene fluoride unit and a fluorine-containing monomer (1) unit, and has a molar ratio of vinylidene fluoride unit / fluorine-containing monomer (1) unit of 80. / 20 to 20/80 is more preferable.

  The copolymer (III) may also contain substantially vinylidene fluoride units, fluorine-containing monomer (1) units, and other units copolymerizable with vinylidene fluoride and the fluorine-containing monomer (1). Monomer unit only, the molar ratio of vinylidene fluoride unit / fluorinated monomer (1) unit is 85/15 to 50/50, and the other monomer unit is 1/5 of all monomer units. It is more preferable that the content is 50 mol% or less.

  In the present disclosure, the content of each monomer unit is a value measured by an NMR method.

  The copolymer (III) has at least one of an iodine atom and a bromine atom, and the total content of the iodine atom and the bromine atom is 0.001 to 10% by mass. The upper limit of the total content of iodine atoms and bromine atoms is more preferably 5.0% by mass or less, further preferably 1.0% by mass or less, and particularly preferably 0.7% by mass or less, Most preferably 0.5% by mass or less, the lower limit of the total content of iodine atoms and bromine atoms is more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, It is particularly preferably at least 0.08% by mass, and most preferably at least 0.1% by mass.

The iodine content was obtained by mixing 5 mg of Na ₂ SO ₃ with 12 mg of a sample (fluoropolymer) and dissolving 30 mg of a mixture of Na ₂ CO ₃ and K ₂ CO ₃ in a ratio of 1: 1 (mass ratio) in 20 ml of pure water. Using the absorbing solution thus obtained, it is burned in oxygen in a combustion flask made of quartz, left for 30 minutes, and then measured using a Shimadzu 20A ion chromatograph. As the calibration curve, a KI standard solution, one containing 0.5 ppm of iodine ion or one containing 1.0 ppm can be used.

  The bonding position of the iodine atom and the bromine atom in the copolymer (III) may be at the terminal of the main chain or the terminal of the side chain of the copolymer (III), or may be both. In such a copolymer, an iodine terminal or a bromine terminal serves as a crosslinking point (crosslinking site), so that a crosslinked fluorine-containing polymer having a high crosslinking density can be obtained, and peroxide crosslinking can be performed more easily. become.

  The copolymer (III) can be produced by a production method using iodine or a bromine-containing monomer as a monomer providing a crosslinking site, a production method using a bromine compound or an iodine compound as a polymerization initiator or a chain transfer agent, or the like. Can be manufactured.

  In the copolymer (III), the other monomer is not particularly limited as long as it is a monomer copolymerizable with vinylidene fluoride and the fluorinated monomer (1). Monomers may be used.

  The content of the other monomer units in the copolymer (III) is preferably 0 to 50 mol% of all monomer units, and more preferably 1 to 50 mol% of all monomer units. .

  In the copolymer (III), examples of the monomer that provides a crosslinking site include the monomers represented by the general formulas (2) to (6) described above.

In the copolymer (III), as a monomer providing a crosslinking site, CF ₂ ＣＦCFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CN, CF ₂ ＣＦCFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOH, _{CF 2 = CFOCF 2 CF (CF} 3) OCF 2 CF 2 CH 2 I, CF 2 = CFOCF 2 CF 2 CH 2 I, CH 2 = CFCF 2 OCF (CF 3) CF 2 OCF (CF 3) CN, CH 2 _{= CFCF 2 OCF (CF 3)} CF 2 OCF (CF 3) COOH, CH 2 = CFCF 2 OCF (CF 3) CF 2 OCF (CF 3) CH 2 OH, CH 2 = CHCF 2 CF 2 I, and, CH _At least one selected from the group consisting of ₂ ＣＨCH (CF ₂ ) ₂ CH ＝ CH ₂ is preferable.

In the copolymer (III), as a monomer that gives a crosslinking site, CF ₂ ＣＦCFOCF ₂ CF ₂ CH ₂ I is used to improve the crosslinking density in the crosslinking using an organic peroxide and to reduce the compression set. Is particularly preferable because it can improve the

  In the copolymer (III), the amount of the monomer providing the crosslinking site is preferably 0.01 to 10 mol%, more preferably 0.01 to 2 mol% of the total monomer units.

  As the fluorine-containing polymer, a peroxide-crosslinkable fluorine-containing polymer is preferable because a molded article having more excellent amine resistance and low-temperature properties and further excellent adhesion to a silicone rubber molded article can be obtained. A peroxide-crosslinkable fluorine-containing polymer having an iodine atom or a bromine atom is more preferable, and a copolymer (III) is more preferable.

  From the viewpoint of excellent sealing properties, the fluoropolymer preferably has a number average molecular weight (Mn) of 7000 to 500,000, a weight average molecular weight (Mw) of 10,000 to 1,000,000, and Mw / Mn of It is preferably from 1.3 to 4.0. The number average molecular weight (Mn), weight average molecular weight (Mw), and Mw / Mn are values measured by a GPC method.

  The Mooney viscosity at 100 ° C. (ML1 + 10 (100 ° C.)) of the fluorine-containing polymer is preferably 2 or more, more preferably 5 or more, because it can be easily mixed with the uncrosslinked silicone rubber and the organic peroxide. It is more preferably at least 10 and particularly preferably at least 30. Further, it is preferably 200 or less, more preferably 150 or less, further preferably 100 or less, and particularly preferably 80 or less. The Mooney viscosity is a value measured according to ASTM-D1646-15 and JIS K6300-1: 2013.

  The fluorine-containing polymer can be produced by a general radical polymerization method. The polymerization form may be any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, but is preferably emulsion polymerization because it is industrially easy to carry out.

  In the above polymerization, a polymerization initiator, a chain transfer agent, a surfactant, and a solvent can be used, and conventionally known ones can be used.

  Examples of the chain transfer agent include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, dimethyl succinate, isopentane, methane, ethane, propane, 2-propanol, acetone, various Mercaptan, carbon tetrachloride, cyclohexane and the like.

A bromine compound or an iodine compound may be used as a chain transfer agent. Examples of the polymerization method performed using a bromine compound or an iodine compound include a method of performing emulsion polymerization in an aqueous medium while applying pressure in the presence of a bromine compound or an iodine compound in a substantially oxygen-free state. (Iodine transfer polymerization method). Representative examples of the bromine compound or iodine compound used include, for example,
General formula: R ⁸ I _x Br _y
(Wherein x and y are each an integer of 0 to 2 and satisfy 1 ≦ x + y ≦ 2, and R ⁸ is a saturated or unsaturated fluorohydrocarbon group having 1 to 16 carbon atoms or chlorofluorocarbon. A hydrocarbon group or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom). By using a bromine compound or an iodine compound, an iodine atom or a bromine atom is introduced into the fluoropolymer, and functions as a crosslinking point.

Examples of the iodine compound include 1,3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, and 1,5-diiodoperfluoropropane. Diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane , diiodomethane, 1,2-diiodoethane, 1,3-diiodo -n- _{propane, CF 2 Br 2, BrCF 2} CF 2 Br, CF 3 CFBrCF 2 Br, CFClBr 2, BrCF 2 CFClBr, CFBrClCFClBr, BrCF 2 CF 2 CF _{2 Br,} BrCF ₂ CFBrO F _3, 1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo -4-iodoperfluorobutene-1, 2-bromo-4-iodoperfluorobutene-1, monoiodomonobromo-substituted benzene, diiodomonobromo-substituted benzene, and (2-iodoethyl) and (2-bromoethyl And the like. These compounds may be used alone or in combination with each other.

  Among these, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 2-iodoperfluoropropane are used from the viewpoints of polymerization reactivity, crosslinking reactivity, and availability. Is preferred.

  In the polymerization for producing the copolymer (III) among the above-mentioned fluoropolymers, it is preferable to use a bromine compound or an iodine compound as a chain transfer agent.

  As the fluoropolymer, one type may be used, or two or more types may be used. In particular, a form in which two types of copolymers having different molecular structures are used in combination may be used.

  Examples of the form in which two kinds of copolymers having different molecular structures are used in combination include a form using two kinds of copolymers (I) having different molecular structures, a form using two kinds of copolymers (II) having different molecular structures, A form using two kinds of copolymers (III) having different molecular structures, a form using both kinds of copolymer (I) and one kind of copolymer (II), and one kind of copolymer (I) An embodiment in which one type of copolymer (III) is used in combination, an embodiment in which one type of copolymer (II) is used in combination with one type of copolymer (III), and the like.

<Uncrosslinked silicone rubber>
The compositions of the present disclosure contain an uncrosslinked silicone rubber. The uncrosslinked silicone rubber contains a polyorganosiloxane having a siloxane bond composed of silicon and oxygen, and the polyorganosiloxane constitutes a main skeleton of the silicone rubber.

  Examples of the polyorganosiloxane constituting the uncrosslinked silicone rubber include peroxide-crosslinkable polyorganosiloxane, and polyorganosiloxane cured by an addition reaction using a platinum compound as a catalyst. As the uncrosslinked silicone rubber, among others, the same crosslinking system as that of the fluorine-containing polymer can be applied, and a molded article having more excellent amine resistance and low-temperature properties and further excellent adhesiveness with a silicone rubber molded article can be obtained. For this reason, a peroxide-crosslinkable silicone rubber is preferred.

  As the polyorganosiloxane constituting the uncrosslinked silicone rubber, a polyorganosiloxane having a plurality of polymerizable unsaturated bonds in one molecule is preferable because it is cured by a crosslinking reaction. In the polyorganosiloxane, it is preferable that the group having a polymerizable unsaturated bond is bonded to a silicon atom in the polyorganosiloxane. The group other than the group having a polymerizable unsaturated bond bonded to the silicon atom may be any of an organic group and a hydrogen atom. As such a polyorganosiloxane, known ones can be appropriately used. The number of the polymerizable unsaturated bonds in the polyorganosiloxane may be two or more, and may be two or three or more.

  The polyorganosiloxane preferably has, as the polymerizable unsaturated bond, an unsaturated bond between carbon atoms, preferably has a double bond, and more preferably has an alkenyl group.

  Examples of the alkenyl group include an ethenyl group (vinyl group), a 2-propenyl group (allyl group), and a 1-propenyl group. The plurality of alkenyl groups in the polyorganosiloxane may be the same, all may be different, or only some may be different. The alkenyl group is preferably bonded to a silicon atom constituting the main skeleton of the polyorganosiloxane.

  Examples of the organic group other than the alkenyl group constituting the polyorganosiloxane include an alkyl group and an aryl group which may have a substituent. The alkyl group may be linear, branched, or cyclic, but preferably has 1 to 10 carbon atoms.

  Examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-alkyl group. Pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl Group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group , 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, nonyl, decyl, etc. Ones 10 may be mentioned as preferred alkyl groups.

  The cyclic alkyl group may be monocyclic or polycyclic, and is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, norbornyl. Examples thereof include a group, an isobornyl group, a 1-adamantyl group, a 2-adamantyl group and a tricyclodecyl group having 3 to 10 carbon atoms.

  The aryl group may be monocyclic or polycyclic, and is preferably a phenyl group, an o-tolyl group (2-methylphenyl group), an m-tolyl group (3-methylphenyl group), or a p-tolyl group. Examples thereof include those having 6 to 15 carbon atoms, such as a group (4-methylphenyl group), a 1-naphthyl group, and a 2-naphthyl group.

  The alkyl group and the aryl group may have a substituent. Here, “the alkyl group (aryl group) has a substituent” means that at least one hydrogen atom constituting the alkyl group (aryl group) is substituted with a group other than a hydrogen atom, or It means that one or more carbon atoms constituting (aryl group) are substituted with a group other than carbon atoms. Then, both the hydrogen atom and the carbon atom may be substituted with a substituent. The above-mentioned alkyl group and aryl group having a substituent preferably have a carbon number within the above range including the substituent.

  Examples of the substituent that substitutes a hydrogen atom of the alkyl group and the aryl group include an alkyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, an alkoxy group, an alkylcarbonyl group, an alkenyl group, an alkenyloxy group, an aryl group, and an alkylaryl group. , An arylalkyl group, an aryloxy group, an arylalkyloxy group, an alkylaryloxy group, a hydroxyl group (-OH), a cyano group (-CN) and a halogen atom.

Examples of the alkyl group that substitutes for a hydrogen atom include the same alkyl groups as those described above for the organic group.
Examples of the alkyloxycarbonyl group that substitutes for a hydrogen atom include a monovalent group in which the alkyl group in the above organic group is bonded to the oxycarbonyl group.
Examples of the alkylcarbonyloxy group that replaces a hydrogen atom include a monovalent group in which the alkyl group in the above organic group is bonded to a carbonyloxy group.
Examples of the alkoxy group for substituting a hydrogen atom include a monovalent group in which an alkyl group in the above organic group is bonded to an oxygen atom.
Examples of the alkylcarbonyl group that substitutes for a hydrogen atom include a monovalent group in which the alkyl group in the organic group is bonded to a carbonyl group.

The alkenyl group for substituting a hydrogen atom is an alkyl group in the above organic group, wherein one single bond (C—C) between carbon atoms is replaced by a double bond (C ＝ C), and Those which do not correspond to the above-mentioned alkenyl group having an unsaturated bond can be exemplified. The position of the double bond between carbon atoms in the alkenyl group that replaces a hydrogen atom is not particularly limited.
Examples of the alkenyloxy group for substituting a hydrogen atom include a monovalent group in which the alkenyl group as a substituent is bonded to an oxygen atom.

As the aryl group for substituting a hydrogen atom, the same as the aryl group in the above organic group can be exemplified.
Examples of the alkylaryl group that replaces a hydrogen atom include a group in which one hydrogen atom bonded to a carbon atom that constitutes the aromatic ring of the aryl group in the organic group is substituted with an alkyl group in the organic group. it can.
Examples of the arylalkyl group that substitutes a hydrogen atom include a group in which one hydrogen atom of the alkyl group in the organic group is substituted with an aryl group in the organic group.
Examples of the aryloxy group that substitutes for a hydrogen atom include a monovalent group in which the aryl group in the above organic group is bonded to an oxygen atom.
Examples of the arylalkyloxy group that replaces a hydrogen atom include a monovalent group in which an alkyl group in the organic group obtained by removing one hydrogen atom from the alkyl group is combined with an aryl group and an oxygen atom in the organic group.
Examples of the alkylaryloxy group for substituting a hydrogen atom include an arylene group in the above organic group, in which an arylene group obtained by removing one hydrogen atom bonded to a carbon atom constituting an aromatic ring is an alkyl group in the above organic group. And a monovalent group in which an oxygen atom is bonded.

  Examples of the halogen atom that replaces a hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  The number of substituents for substituting hydrogen atoms is not particularly limited, and may be one or more, and all hydrogen atoms may be substituted with substituents. Further, the position of the hydrogen atom substituted with the substituent is not particularly limited.

The carbon atoms of the alkyl group and the aryl group may be substituted with the following substituents. Examples of the substituent include a carbonyl group (—C (＝ O) —), an ester bond (—C (＝ O) —O—), an amide bond (—NH—C (＝ O) —), and a hetero atom. it can.
Examples of the hetero atom that substitutes for a carbon atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a boron atom.
The number of substituents for substituting carbon atoms is not particularly limited, and may be one or more. Further, the position of the carbon atom substituted by the substituent is not particularly limited.

  As the polyorganosiloxane, a commercially available product may be used, or a product synthesized according to a known method may be used. The polyorganosiloxanes may be used alone or in combination of two or more. When two or more kinds are used in combination, the combination and ratio may be appropriately selected according to the purpose.

  Examples of commercially available products (trade names) of the polyorganosiloxane and commercially available products (trade names) containing the polyorganosiloxane are as follows.

Asahi Kasei Wacker Silicone Co., Ltd. ELASTOSIL EL 1000 series, ELASTOSIL EL 4000 series, ELASTOSIL EL 3000 series, ELASTOSIL EL 7000 series, ELASTOSIL R401 series, etc.

Toray Dow Corning SH800 series, SH50 series, SH70 series, SH700 series, SE4000 series, SE1000 series, SH500 series, SE6000 series, SH80 series, SRX400 series, DY32-400 series, DY32-500 series, DY32-1000 Series, DY32-7000 series, DY32-4000 series, etc.

Shin-Etsu Chemical's rubber compound KE-600 series, KE-900 series, KE-9000 series, KE-700 series, KE-800 series, KE-5590-U, KE-500 series, etc. KE-655-U, KE-675-U, KE-931-U, KE-941-U, KE-951-U, KE-961-U, KE-971-U, KE-981-U, KE-961TU, KE- 971TU, KE-871CU, KE-9410-U, KE-9510-U, KE-9610-U, KE-9710-U, KE-742-U, KE-752-U, KE-762 U, KE-772-U, KE-782-U, KE-850-U, KE-870-U, KE-880-U, KE-890-U, KE-9590-U, KE- 590-U, KE-552-U, KE-552DU, KE-582-U, KE-552BU, KE-555-U, KE-575-U, KE-541-U, KE-551-U, KE-561-U, KE-571-U, KE-581-U, KE-520-U, KE-530B-2-U, KE-540B-2-U, KE-1551-U, KE-1571 U, KE-153-U, KE-174-U, KE-3601SB-U, KE-3711-U, KE-3801MU, KE-5612G-U, KE-5620BLU, KE-5620W-U, KE- 5634-U, KE-7511-U, KE-7611-U, KE-7711-U, KE-765-U, KE-785-U, KE-7008-U, KE-7005-U, KE-503 U, KE 5042-U, KE-505-U, KE-6801-U, KE-136Y-U, X-30-4084-U, X-30-3888-U, X-30-4079-U, etc.

  As the uncrosslinked silicone rubber, a millable type silicone rubber is preferable to a liquid type silicone rubber.

  In the composition of the present disclosure, the mass ratio of the fluoropolymer to the uncrosslinked silicone rubber (fluoropolymer / uncrosslinked silicone rubber) is more excellent in amine resistance and low-temperature properties, and the adhesion to the silicone rubber molded article is improved. Since it is possible to obtain a molded article having even better properties, the ratio is preferably 5/95 to 99/1, more preferably 20/80 to 99/1, and 50/50 to 97/3. More preferably, there is. Surprisingly, even when the content of the fluorine-containing polymer in the composition of the present disclosure is relatively high, the obtained molded article shows good adhesion to the silicone rubber.

<Organic peroxide>
The compositions of the present disclosure contain an organic peroxide. The organic peroxide may be any organic peroxide that can easily generate radicals in the presence of heat or an oxidation-reduction 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-butyl Peroxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne- 3, benzoyl peroxide, t-butyl peroxybenzene, t-butyl peroxymaleic acid, t-butyl peroxyisopropyl carbonate, t-butyl Luperoxybenzoate and the like can be mentioned. Among them, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α-bis (t-butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2, 5-Di (t-butylperoxy) -hexyne-3 is preferred. When kneading the organic peroxide with the fluorine-containing polymer and the uncrosslinked silicone rubber, the organic peroxide is impregnated with an inert inorganic powder or the like, or the organic peroxide is mixed with the organic peroxide. A crosslinker for silicone rubber kneaded with polyorganosiloxane or the like may be used. The above-mentioned organic peroxides may be used in combination of two or more kinds.

  Examples of commercially available products (trade names) of the crosslinking agent for silicone rubber are as follows.

Shin-Etsu Chemical Co., Ltd. C-1A, C3, C4, C-8A, C-8B, C-8, C-11A, C-14, C-15, C-23N, C-25A / B, etc. C series etc.

TC series manufactured by Dow Corning Toray Co., Ltd.

DS series such as DS-3 and DS-8 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.

  The content of the organic peroxide is preferably from 0.3 to 10 parts by mass, more preferably from 0.4 to 5 parts by mass, and still more preferably 0 to 10 parts by mass, based on 100 parts by mass of the fluoropolymer. 0.4 to 3 parts by mass. If the amount of the organic peroxide is too small, the degree of crosslinking is insufficient, and the performance of the molded article tends to be impaired.If the amount of the organic peroxide is too large, the crosslinking time becomes long because the crosslinking density becomes too high. In addition, it tends to be economically unfavorable.

  The composition of the present disclosure preferably contains a crosslinking aid together with the organic peroxide. Examples of the crosslinking assistant include triallyl cyanurate, triallyl isocyanurate, triallyl isocyanurate (TAIC), triacrylformal, triallyl trimellitate, N, N'-m-phenylenebismaleimide, dipropamate Gil 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' Tetraallylphthalamide, N, N, N ', N'-tetraallylmalonamide, trivinyl isocyanurate, 2,4,6-trivinylmethyltrisiloxane, tri (5-norbornene-2-methylene) cyanurate, tri Allyl phosphite and the like can be mentioned. Among these, triallyl isocyanurate (TAIC) is preferred from the viewpoint of excellent crosslinkability and physical properties of the molded article. When kneading the crosslinking aid with the fluorine-containing polymer and the uncrosslinked silicone rubber, one obtained by impregnating the crosslinking aid with an inert inorganic powder or the like may be used.

  The content of the crosslinking aid is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and still more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the fluoropolymer. It is 5 to 5 parts by mass. If the amount of the crosslinking aid is too small, the compression set of the molded article tends to decrease. If the amount of the crosslinking aid is too large, the elongation of the molded article tends to decrease significantly.

  The compositions of the present disclosure may contain an acid acceptor. Examples of the acid acceptor include metal oxides such as magnesium oxide, calcium oxide and bismuth oxide, metal hydroxides such as calcium hydroxide, synthetic hydrotalcites, and sodium metasilicate.

  The content of the acid acceptor is preferably 0.5 to 30 parts by mass, more preferably 1 to 15 parts by mass, based on 100 parts by mass of the fluoropolymer. If the amount of the acid acceptor is too small, the crosslinking time tends to be too long for practical use, and if the amount of the acid acceptor is too large, the compression set of the molded article tends to decrease.

<Carbon black>
The compositions of the present disclosure can contain carbon black. Examples of the carbon black include furnace black, acetylene black, thermal black, channel black, and graphite. Specifically, for example, SAF-HS (N ₂ SA: 142 m ² / g, DBP: 130 ml / 100 g), SAF (N ₂ SA: 142 m ² / g, DBP: 115 ml / 100 g), N234 (N ₂ SA: 126 m ² / g, DBP: 125 ml / 100 g), ISAF (N ₂ SA: 119 m ² / g, DBP: 114 ml / 100 g), ISAF-LS (N ₂ SA: 106 m ² / g, DBP: 75 ml / 100 g), ISAF-HS (N ₂ SA: 99 m ² / g, DBP: 129 ml / 100 g), N339 (N ₂ SA: 93 m) ² / g, DBP: 119 ml / 100 g), HAF-LS (N ₂ SA: 84 m ² / g, DBP: 75 ml / 100 g), HAS-HS (N ₂ SA: 82 m ² / g, DBP: 126 ml / 100 g), HAF (N ₂ SA: 79 m ² / g, DBP: ^{_{101ml / 100g), N351 (N}} 2 SA: 74m 2 / g, DBP: 127ml / 100g), LI-HAF (N 2 SA: 74m 2 / g, DBP: 101ml / 100g), MAF-HS (N 2 SA : 56 m ² / g, DBP: 158 ml / 100 g), MAF (N ₂ SA: 49 m ² / g, DBP: 133 ml / 100 g), FEF-HS (N ₂ SA: 42 m ² / g, DBP: 160 ml / 100 g) , FEF (N ₂ SA: 42 m ² / g, DBP: 115 ml / 100 g), SRF-HS (N ₂ SA: 32 m ² / g, DBP: ^{_{140ml / 100g), SRF-HS}} (N 2 SA: 29m 2 / g, DBP: 152ml / 100g), GPF (N 2 SA: 27m 2 / g, DBP: 87ml / 100g), SRF (N 2 SA: 27m ² / g, DBP: 68 ml / 100 g), SRF-LS (N ₂ SA: 23 m ² / g, DBP: 51 ml / 100 g), FT (N ₂ SA: 19 m ² / g, DBP: 42 ml / 100 g), MT (N ₂ SA: 8 m ² / g, DBP: 43 ml / 100 g). These carbon blacks may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of SAF-HS, SAF, N234, ISAF, ISAF-LS, ISAF-HS, N339, HAF-LS, HAS-HS, HAF, N351 and LI-HAF. preferable.

The composition of the present disclosure can provide a molded article having more excellent amine resistance and low-temperature properties, and a molded article having more excellent adhesion to a silicone rubber molded article, and having excellent tear strength. Since it can be obtained, it contains carbon black having a nitrogen adsorption specific surface area (N ₂ SA) of 70 to 180 m ² / g and a dibutyl phthalate (DBP) or paraffin oil absorption of 40 to 180 ml / 100 g. Is preferred. When the composition of the present disclosure contains such a carbon black, a molded article obtained from the composition of the present disclosure contains such a carbon black, and only one of the fluoropolymer or the silicone rubber. It shows a significantly higher tear strength than molded articles obtained from the composition.

The nitrogen adsorption specific surface area (N ₂ SA) of the carbon black is more preferably 80 m ² / g or more, and still more preferably 90 m ² / g, since a molded article having more excellent tear strength can be obtained. That is all.

The nitrogen adsorption specific surface area (N ₂ SA) can be measured by the method described in JIS K6217-2: 2001.

  The absorption amount of dibutyl phthalate (DBP) or paraffin oil of the carbon black is more preferably 50 ml / 100 g or more, and still more preferably 60 ml / 100 g or more, since a molded article having more excellent tear strength can be obtained. And particularly preferably 70 ml / 100 g or more. Further, the upper limit of the absorption amount of dibutyl phthalate (DBP) or paraffin oil of the carbon black is preferably 175 ml / 100 g or less, more preferably 170 ml / 100 g or less, from the viewpoint of easy availability.

  The dibutyl phthalate (DBP) or paraffin oil absorption can be measured by the method described in JIS K6217-4: 2008.

  The content of the carbon black is more excellent in amine resistance and low-temperature properties, and it is possible to obtain a molded article which is more excellent in adhesion to a silicone rubber molded article, and has a further excellent tear strength. Since a body can be obtained, the amount is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and still more preferably 10 to 40 parts by mass, based on 100 parts by mass of the fluoropolymer. And particularly preferably 15 to 40 parts by mass.

  The composition of the present disclosure may further contain a filler.

  Examples of the filler include metal oxides such as titanium oxide, aluminum oxide and zinc oxide; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; carbonates such as magnesium carbonate, aluminum carbonate, calcium carbonate and barium carbonate; Silicates such as magnesium silicate, 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 (Zinc sulfide / barium sulfide), graphite, carbon fluoride, calcium fluoride, coke, fine quartz powder, talc, mica powder, wollastonite, carbon fiber, aramid fiber, various whiskers, glass fiber, organic reinforcing agent, organic Filler, polytetrafluoroethylene, fluorine-containing Plastic resin, mica, silica, Celite, clay and the like.

  The composition of the present disclosure includes, as the filler, silica, titanium oxide, zinc oxide, barium sulfate, calcium carbonate, magnesium silicate, quartz fine powder, talc, mica powder, wollastonite, mica, celite, clay, or And diatomaceous earth. The silica may be either dry silica or wet silica, and examples thereof include fumed silica, fused silica, precipitated silica, and colloidal silica.

  The composition of the present disclosure may include a processing aid such as a release agent and a plasticizer, a pigment such as an organic pigment and an inorganic pigment, a tackifier, and the like.

  A general rubber kneading apparatus can be used for producing the composition of the present disclosure. For example, a rubber kneading apparatus such as a roll, a kneader, a Banbury mixer, an internal mixer, and a twin screw extruder can be exemplified, but the invention is not limited thereto.

  In producing the composition of the present disclosure, the order in which the fluorine-containing polymer, uncrosslinked silicone rubber, organic peroxide, and other compounding agents are charged into the kneading device is not particularly limited.

<Molded body>
The fluoropolymer molded article of the present disclosure (hereinafter sometimes referred to as “fluoropolymer molded article (A)”) is obtained by crosslinking the above composition. Further, the fluoropolymer molded article of the present disclosure can also be obtained by molding and crosslinking the above composition. The above composition can be formed by a conventionally known method. Molding and crosslinking methods and conditions may be within the range of known methods and conditions for molding and crosslinking to be employed. The order of molding and crosslinking is not limited, and crosslinking may be performed after molding, molding may be performed after crosslinking, or molding and crosslinking may be performed simultaneously.

  Examples of the molding method include a compression molding method using a mold or the like, an injection molding method, an injection molding method, an extrusion molding method, and the like, but are not limited thereto. As the cross-linking method, a steam cross-linking method, a normal method in which a cross-linking reaction is started by heating, a radiation cross-linking method, and the like can be employed. Among them, a steam cross-linking method and a cross-linking reaction by heating are preferable. Specific non-limiting cross-linking conditions may be appropriately determined in general within a temperature range of 140 to 250 ° C. and a cross-linking time of 1 minute to 24 hours depending on the type of a cross-linking agent to be used.

<Composite>
The composite of the present disclosure includes a fluoropolymer molded article (A) and a silicone rubber molded article (B).

  The silicone rubber molded product (B) is obtained by crosslinking a silicone rubber composition containing an uncrosslinked peroxide-crosslinkable silicone rubber.

  Examples of the peroxide-crosslinkable uncrosslinked silicone rubber include those similar to the uncrosslinked silicone rubber contained in the composition of the present disclosure. Suitable uncrosslinked silicone rubbers contained in the composition of the present disclosure The same as described above is preferable.

  In the composite of the present disclosure, the fluoropolymer molded article (A) and the silicone rubber molded article (B) are adhered. The fluoropolymer molded article (A) and the silicone rubber molded article (B) may be directly adhered or may be adhered via another layer such as an adhesive layer. Preferably, they are adhered. In the composite of the present disclosure, the fluoropolymer molded article (A) and the silicone rubber molded article (B) can be directly bonded to each other without providing an adhesive layer at the boundary. The reason why the two molded articles can be directly bonded to each other in the composite of the present disclosure is that the composition forming the fluoropolymer molded article (A) contains an organic peroxide, and the silicone rubber molded article (B This is presumed to be due to the fact that the composition forming the above contains an uncrosslinked silicone rubber capable of peroxide crosslinking.

  The silicone rubber composition may further contain an organic peroxide. Examples of the organic peroxide include those similar to the organic peroxides contained in the composition of the present disclosure, and those similar to the suitable organic peroxides contained in the composition of the present disclosure are preferable. It is.

  The content of the organic peroxide in the silicone rubber composition is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 3 parts by mass, based on 100 parts by mass of the uncrosslinked silicone rubber. is there.

  It is preferable that the silicone rubber composition further contains a crosslinking aid. When the silicone rubber molded article (B) is obtained by crosslinking a silicone rubber composition further containing a crosslinking aid, the fluoropolymer molded article (A) and the silicone rubber molded article (B) It can be more firmly bonded.

  Examples of the crosslinking assistant include triallyl cyanurate, triallyl isocyanurate, triallyl isocyanurate (TAIC), triacrylformal, triallyl trimellitate, N, N'-m-phenylenebismaleimide, dipropamate Gil 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' Tetraallylphthalamide, N, N, N ', N'-tetraallylmalonamide, trivinyl isocyanurate, 2,4,6-trivinylmethyltrisiloxane, tri (5-norbornene-2-methylene) cyanurate, tri Allyl phosphite and the like can be mentioned. Among these, triallyl isocyanurate (TAIC) is preferred from the viewpoint of excellent crosslinkability and physical properties of the molded article. When kneading the crosslinking aid and the uncrosslinked silicone rubber, a material obtained by impregnating the crosslinking aid with an inert inorganic powder or the like may be used.

  The content of the crosslinking aid in the silicone rubber composition is such that the fluoropolymer molded article (A) and the silicone rubber molded article (B) can be more firmly adhered to each other. Parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.5 to 6 parts by mass, and still more preferably 1 to 4 parts by mass.

  The silicone rubber composition may contain a polymer other than the uncrosslinked silicone rubber. Even if the silicone rubber composition does not contain a fluoropolymer, the fluoropolymer molded article (A) and the silicone The rubber molded body (B) is firmly adhered. In addition, the silicone rubber composition may contain a processing aid such as a filler, a release agent, a plasticizer, a pigment such as an organic pigment or an inorganic pigment, a tackifier, and the like.

  Thus, from the composition of the present disclosure, a fluorine-containing polymer that can be adhered to a silicone rubber molded product (B) obtained by crosslinking a silicone rubber composition containing a peroxide-crosslinkable uncrosslinked silicone rubber A molded article can be obtained. That is, in the present disclosure, a fluorine-containing polymer molded article used by being bonded to a silicone rubber molded article (B) obtained by crosslinking a silicone rubber composition containing a peroxide-crosslinkable uncrosslinked silicone rubber ( Includes the use of the composition described above to form A).

  The composite of the present disclosure may be a laminate including a layer formed from the fluoropolymer molded article (A) and a layer formed from the silicone rubber molded article (B). Also in such a laminate, both layers are firmly adhered.

  The composite of the present disclosure is a step of obtaining an uncrosslinked fluoropolymer molded article by molding the composition of the present disclosure, and obtaining an uncrosslinked silicone rubber molded article by molding the silicone rubber composition. The steps and, while contacting the uncrosslinked fluoropolymer molded article and the uncrosslinked silicone rubber molded article with each other, crosslinking the fluoropolymer molded article (A) with the silicone rubber molded article (B). Can be suitably produced by a production method including a step of obtaining a composite to which is adhered.

  In producing the composite of the present disclosure, examples of the method of molding the composition of the present disclosure and the silicone rubber composition include a compression molding method using a mold, an injection molding method, an injection molding method, and an extrusion molding method. It is possible, but not limited to these. As the cross-linking method, a steam cross-linking method, a normal method in which a cross-linking reaction is started by heating, a radiation cross-linking method, and the like can be employed. Among them, a steam cross-linking method and a cross-linking reaction by heating are preferable. Specific non-limiting cross-linking conditions may be appropriately determined in general within a temperature range of 140 to 250 ° C. and a cross-linking time of 1 minute to 24 hours depending on the type of a cross-linking agent to be used.

  In addition, as a production method when the composite of the present disclosure is a laminate, the composition of the present disclosure and the silicone rubber composition are multilayer-extruded using an extruder, thereby forming a fluoropolymer molded article. A step of obtaining an uncrosslinked laminate to which the silicone rubber molded article adheres, and crosslinking the uncrosslinked laminate to form a layer formed from the fluoropolymer molded article (A) with the silicone rubber molded article (B) A) obtaining a laminated body in which the layer formed in step (a) is adhered.

The fluoropolymer molded article of the present disclosure and the composite of the present disclosure are used in general for parts that are slid in contact with other materials, seal or seal other materials or substances, or provide vibration and sound insulation. It can be used as various components in various fields such as the automobile industry, the aircraft industry, and the semiconductor industry.
Examples of fields used include semiconductor-related fields, automotive fields, aircraft fields, space and rocket fields, marine fields, chemical fields such as chemical plants, pharmaceutical fields and other chemical fields, developing machines and other photographic fields, printing machines and the like. Printing field, coating field such as coating equipment, analytical instruments, analytical instruments such as instruments, physics and chemistry machines field, food equipment field including food plant equipment and household goods, beverage food manufacturing equipment field, pharmaceutical manufacturing equipment field, medical parts field, chemistry Chemical transport equipment field, nuclear power plant equipment field, iron and steel field such as iron plate processing equipment, general industrial field, electric field, fuel cell field, electronic parts field, optical equipment parts field, space equipment parts field, petrochemical plant equipment field , Oil, gas and other energy resources exploration and mining equipment parts field, oil refining field, oil transportation equipment parts field, and the like.

Use forms of the fluoropolymer molded article of the present disclosure and the composite of the present disclosure include, for example, a ring, a packing, a gasket, a diaphragm, an oil seal, a bearing seal, a lip seal, a plunger seal, a door seal, a lip and a face seal, Various sealing materials such as a gas delivery plate seal, a wafer support seal, and a barrel seal, and a packing are exemplified. As a sealing material, it can be used for applications requiring heat resistance, solvent resistance, chemical resistance, and non-adhesion.
Also used as tubes, hoses, rolls, various rubber rolls, flexible joints, rubber plates, coatings, belts, dampers, valves, valve seats, valve bodies, chemical resistant coating materials, laminating materials, lining materials, etc. it can.
The cross-sectional shape of the ring, the packing, and the seal may be various shapes, and specifically, for example, may be a square, an O shape, a shape such as a ferrule, a D shape, L-shaped, T-shaped, V-shaped, X-shaped, Y-shaped or other different shapes may be used.

In the semiconductor-related field, for example, a semiconductor manufacturing apparatus, a liquid crystal panel manufacturing apparatus, a plasma panel manufacturing apparatus, a plasma display panel manufacturing apparatus, a plasma addressed liquid crystal panel manufacturing apparatus, an organic EL panel manufacturing apparatus, a field emission display panel manufacturing apparatus, It can be used for a battery substrate manufacturing device, a semiconductor transfer device, and the like. Examples of such an apparatus include a gas control apparatus such as a CVD apparatus and a gas control apparatus for a semiconductor, 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. Equipment, ion beam etching equipment, oxidation diffusion equipment, sputtering equipment, ashing equipment, plasma ashing equipment, cleaning equipment, ion implantation equipment, plasma CVD equipment, exhaust equipment, exposure equipment, polishing equipment, film forming equipment, dry etching cleaning equipment, UV / O ₃ cleaning device ion beam cleaning device laser beam cleaning device plasma cleaning device gas etching cleaning device extraction cleaning equipment Soxhlet extractive cleaning machine, high temperature and high pressure extractive cleaning machine, microwave extraction cleaning device, supercritical extraction Washing equipment Location, hydrofluoric acid, hydrochloric acid, sulfuric acid, washing apparatus using ozone water or the like, stepper, coater-developer, CMP apparatus, excimer laser exposure machine, agent pipe, gas pipe, NF ₃ plasma treatment, O ₂ plasma treatment, fluorine plasma treatment Such as plasma processing equipment, heat treatment film forming equipment, wafer transfer equipment, wafer cleaning equipment, silicon wafer cleaning equipment, silicon wafer processing equipment, equipment used in the LP-CVD process, equipment used in the lamp annealing process, and reflow An apparatus used for the process is exemplified.

  Specific uses in the semiconductor-related field include, for example, various sealing materials such as gate valves, quartz windows, chambers, chamber lits, gates, bell jars, couplings, O-rings of pumps, gaskets, etc .; Various sealing materials such as O-rings for liquids, hoses and tubes; linings and coatings for resist developer tanks, stripper tanks, wafer cleaning tanks, and wet etching tanks; diaphragms for pumps; rolls for transporting wafers; Hose tubes; sealing materials for clean equipment such as sealants for clean equipment such as clean rooms; sealing materials for storage devices that store semiconductor manufacturing equipment and devices such as wafers; diaphragms for transferring chemicals used in the semiconductor manufacturing process. No.

In the automobile field, the engine body, main motion system, valve system, lubrication / cooling system, fuel system, intake / exhaust system, drive system transmission system, chassis steering system, brake system, basic electrical components, It can be used for electrical components such as system electrical components and equipment electrical components. The automobile field includes a motorcycle.
In the above-mentioned engine body and its peripheral devices, the fluorine-containing polymer molded article of the present disclosure and the present disclosure are used for various sealing materials that are required to have heat resistance, oil resistance, fuel oil resistance, antifreeze resistance for engine cooling, and steam resistance. The sealing materials include, for example, seals such as gaskets, shaft seals, valve stem seals, self-sealing packings, piston rings, split ring type packings, mechanical seals, oil seals and the like. Non-contact or contact type packings, bellows, diaphragms, hoses, tubes, electric wires, cushioning materials, vibration proof materials, various sealing materials used for belt AT devices, and the like.

  Specific usage modes for the above fuel system include fuel injector, cold start injector, fuel line quick connector, sender flange quick connector, fuel pump, fuel tank quick connector, gasoline mixing pump, gasoline pump, fuel O-rings used for tube tubes, fuel tube connectors, injectors, etc .; expiratory manifolds, fuel filters, pressure regulating valves, canisters, fuel tank caps, fuel pumps, fuel tanks, fuel tank sender units, fuel Used for injection devices, high-pressure fuel pumps, fuel line connector systems, pump timing control valves, suction control valves, solenoid sub-assemblies, fuel cut valves, etc. Seals; canister purge solenoid valve seals, onboard refueling vapor recovery (ORVR) valve seals, oil seals for fuel pumps, fuel sender seals, fuel tank rollover valve seals, filler seals, 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, etc .; gas filters used in fuel filters, fuel line connector systems, etc. Flange gaskets used for gas turbines, carburetors, etc .; Line materials such as steam recovery lines, fuel feed lines, vapor / ORVR lines; canisters, ORVRs, fuel pumps, fuel tank pressure sensors, gasoline pumps, carburetor sensors, combined air control Diaphragm used for device (CAC), pulsation damper, canister, auto cock, etc., pressure regulator diaphragm of fuel injection device; valve for fuel pump, carburetor needle valve, rollover check valve, check valve; vent ( Breather), tube used in fuel tank; tank packing for fuel tank, etc., packing for acceleration pump piston of carburetor; fuel sender anti-vibration parts for fuel tank An O-ring or a diaphragm for controlling fuel pressure; an accelerator pump cup; an in-tank fuel pump mount; an injector cushion ring of a fuel injection device; an injector seal ring; a carburetor needle valve core valve; Piston; valve seat of combined air control device (CAC); fuel tank main body; sealing part for solenoid valve.

  Specific uses of the brake system include a diaphragm used for a master back, a hydraulic brake hose, an air brake, a brake chamber of an air brake, a hose used for a brake hose, a brake oil hose, a vacuum brake hose, and the like; an oil seal. , O-rings, packing, brake piston seals, etc .; air and vacuum valves for master back, check valves for brake valves; piston cups (rubber cups) and brake cups for master cylinders; hydraulic brakes Master cylinders and vacuum boosters, boots for hydraulic brake wheel cylinders, and O-rings and grommets for antilock brake systems (ABS).

Specific usage forms of the basic electrical components include an insulator or sheath of a wire (harness), a tube of a harness exterior component, a grommet for a connector, and the like.
As a specific usage form in the control system electrical components, there are coating materials for various sensor wires and the like.
Specific usage forms of the above-mentioned electrical components include O-rings and packings for car air conditioners, cooler hoses, high-pressure air conditioner hoses, air conditioner hoses, gaskets for electronic throttle units, plug boots for direct ignition, diaphragms for distributors, etc. Is mentioned. It can also be used for bonding electrical components.

  Specific usage patterns in the intake / exhaust system include packing used for an intake manifold, an exhaust manifold, a throttle body packing of a throttle; EGR (exhaust gas recirculation), a pressure control (BPT), a wastegate, and a turbowest. Gates, actuators, actuators for variable turbine geometry (VTG) turbos, diaphragms used for exhaust purification valves, etc .; EGR (exhaust gas 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 Hoses, such as hoses, air intake hoses, turbo hoses, DPF (Diesel Particulate Filter) sensor hoses; air ducts and turbo air ducts; intake manifold gaskets; EGR seal materials; afterburn prevention valve seats for AB valves; A) turbine shaft seals, and seal members used for groove parts such as rocker covers and air intake manifolds used in automobile engines.

In addition, in exhaust gas control parts, seals used for steam recovery canisters, catalytic converters, exhaust gas sensors, oxygen sensors, etc., solenoids and armature seals for steam recovery and steam canisters, and intake manifold gaskets Can be.
Further, in a part relating to a diesel engine, it can be used as an O-ring seal for a direct injection injector, a rotary pump seal, a control diaphragm, a fuel hose, an EGR, a priming pump, a diaphragm of a boost compensator, and the like. Further, it can be used for an O-ring, a seal material, a hose, a tube, a diaphragm used in the urea SCR system, a urea water tank main body of the urea SCR system, and a seal material for the urea water tank.

Specific usage forms in the transmission system include transmission-related bearing seals, oil seals, O-rings, packing, torque converter hoses, and the like.
Mission oil seals, AT mission oil hoses, ATF hoses, O-rings, packings and the like are also included.
The transmission includes an automatic transmission (AT), a manual transmission (MT), a continuously variable transmission (CVT), and a dual clutch transmission (DCT).
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), and ATF linear solenoids Packing, an oil hose for a manual transmission, an ATF hose for an automatic transmission, a CVTF hose for a continuously variable transmission (belt type or toroidal type), and the like.
Specific modes of use in the steering system include a power steering oil hose and a high-pressure power steering hose.

Examples of the form used in the engine body of an automobile engine include a gasket such as a cylinder head gasket, a cylinder head cover gasket, an oil pan packing, a general gasket, an O-ring, a packing, a seal such as a timing belt cover gasket, and a control hose. Examples include hoses, anti-vibration rubber for engine mounts, control valve diaphragms, camshaft oil seals, and the like.
In the main motion system of an automobile engine, it can be used for shaft seals such as crankshaft seals and camshaft seals.
In a valve train 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 the lubrication and cooling systems of automobile engines, engine oil cooler hoses, oil return hoses, seal gaskets for engine oil coolers, water hoses around radiators, radiator seals, radiator gaskets, radiator O-rings, and vacuum pumps In addition to a vacuum pump oil hose, it can be used for a radiator hose, a radiator tank, an oil pressure diaphragm, a fan coupling seal, and the like.

  Thus, specific examples of use in the automotive field include engine head gaskets, oil pan gaskets, manifold packings, seals for oxygen sensors, oxygen sensor bushes, seals for nitrogen oxide (NOx) sensors, and nitrogen oxide (NOx). Sensor bush, 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 packing, cylinder liner seal, valve stem seal, static valve stem seal, dynamic valve stem seal, automatic Speed pump 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 reburning device seal and bearing seal, Hose for reburning device, diaphragm for carburetor sensor, 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 system anti-vibration rubber (damper, etc.), fuel hose, EGR tube and hose, twin cab tube, carburetor needle valve core valve, carburetor flange gasket, oil hose Oil cooler hose, ATF hose, cylinder head gasket, water pump seal, gear box seal, needle valve tip, lead for motorcycle reed valve, oil seal for automobile engine, seal for gasoline hose gun, seal for car air conditioner, engine intercooler Rubber hose, seal for fuel line connector systems, CAC valve, needle tip, electric wire around engine, filler hose, car air conditioner O-ring, intake gasket, fuel tank material, diaphragm for distributor, water hose , Clutch hose, PS hose, AT hose, master back hose, heater hose, air conditioner hose, ventilation hose, oil Filler cap, PS rack seal, rack & pinion boots, CVJ boots, 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 belt, poly V belt, timing belt, toothed belt, V-ribbed belt, tire, wiper blade, diaphragm and plunger for LPG car regulator, diaphragm and valve for CNG car regulator, rubber parts for DME, diaphragm and boot for auto tensioner , Diaphragm and valve for idle speed control, actuator for auto speed control, diaphragm and valve for negative pressure pump Kkubarubu and plunger, O. P. S. O-rings and gaskets for engine cylinder sleeves, O-rings and gaskets for wet cylinder sleeves, differential gear seals and gaskets (gear oil seals and gaskets), power steering devices Seal and gasket (PSF seal and gasket), shock absorber seal and gasket (SAF seal and gasket), constant velocity joint seal and gasket, wheel bearing seal and gasket, metal gasket coating agent, caliper seal, Examples include boots, wheel bearing seals, bladders used for vulcanization of tires, and the like.

In the aircraft field, the space / rocket field, and the ship field, it can be used particularly for fuel systems and lubricating oil systems.
In the aircraft field, for example, various seal parts for aircraft, various parts for aircraft for aircraft engine oil, jet engine valve stem seals and gaskets and O-rings, rotating shaft seals, hydraulic equipment gaskets, fire wall seals It can be used as a fuel supply hose, gasket, O-ring, aircraft cable, oil seal, shaft seal, and the like.

In the space and rocket field, for example, spacecraft, jet engines, missiles and other lip seals, diaphragms, O-rings, gas turbine engine oil O-rings, missile ground control vibration isolator pad and the like Can be used.
In the marine field, for example, a propeller shaft stern seal for a screw, a valve stem seal for intake and exhaust of a diesel engine, a valve seal for a butterfly valve, a valve seat and a shaft seal for a butterfly valve, a shaft seal for a butterfly valve, a stern tube seal , Fuel hoses, gaskets, O-rings for engines, marine cables, marine oil seals, marine shaft seals and the like.

In the field of chemicals such as the above-mentioned chemical plants, and the field of medicine such as pharmaceuticals, use in processes where high chemical resistance is required, for example, processes for manufacturing chemicals such as pharmaceuticals, agricultural chemicals, paints, resins, etc. Can be.
Specific forms of use in the chemical field and the chemical field include chemical equipment, chemical pumps and flow meters, chemical pipes, heat exchangers, pesticide sprayers, pesticide transfer pumps, gas pipes, fuel cells, Seals used in analytical and physicochemical equipment (eg, column fittings for analytical instruments and instruments), shrink fittings in flue gas desulfurization equipment, nitric acid plants, power plant turbines, and seals used in medical sterilization processes; Sealing for plating solution, roller seal for papermaking belt, joint seal for wind tunnel; O-ring used for 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, Gasket packing for H-meter tube joints and glass cooler packing for sulfuric acid production equipment; Diaphragm pumps, Diaphragms used for analytical instruments and physical and chemical instruments; Gaskets used for analytical instruments and instruments; Analytical instruments and instruments U-cup; Lining used for chemical equipment, gasoline tanks, wind tunnels, etc .; Corrosion-resistant lining for alumite processing tanks; Coating of masking jigs for plating; Analytical and scientific instruments Valve parts; expansion joints in 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 in analytical equipment and physical and chemical equipment And medical tubing; Ren 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.

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 rolls, belts, seals, valve parts and the like of a dry copying machine.
Specific use forms in the photographic field, the printing field, and the coating field include a surface layer of a transfer roll of a copying machine, a cleaning blade of the copying machine, a belt of the copying machine, and OA equipment such as a copying machine, a printer, and a facsimile. Rolls (for example, fixing rolls, pressure rolls, pressure rolls, etc.), belts; rolls of PPC copying machines, roll blades, belts; rolls of film developing machines, X-ray film developing machines; printing rolls of printing machines , Scrapers, tubes, valve parts, belts; printer ink tubes, rolls, belts; coating, coating equipment coating rolls, scrapers, tubes, valve parts; developing rolls, gravure rolls, guide rolls, magnetic tape manufacturing coating lines Guide rolls, gravure rolls and coating rolls for magnetic tape production coating lines Le and the like.

In the field of food equipment including the above-mentioned food plant equipment and household goods, it can be used for a food manufacturing process, a food transfer device or a food storage device.
Specific usage forms in the food equipment field include plate-type heat exchanger seals, vending machine solenoid valve seals, jar pot packing, sanitary pipe packing, pressure cooker packing, water heater seals, and heat exchange. Gaskets for containers, diaphragms and packings for food processing equipment, rubber materials for food processing machines (eg, heat exchanger gaskets, diaphragms, various seals such as O-rings, piping, hoses, sanitary packing, valve packing, filling Packing for use as a joint between a mouth such as a bottle and a filler). In addition, packings, gaskets, tubes, diaphragms, hoses, joint sleeves, and the like used for products such as alcoholic beverages and soft drinks, filling devices, food sterilizing devices, brewing devices, water heaters, various automatic food vending machines, and the like are also included.

  In the field of the above-mentioned nuclear power plant equipment, it can be used for a check valve and a pressure reducing valve around a reactor, a seal of a uranium hexafluoride enrichment device, and the like.

  Specific uses in the general industrial field include sealing materials for hydraulic equipment such as machine tools, construction machines, and hydraulic machines; seals and bearing seals for hydraulic and lubricating machines; sealing materials used for mandrels; and dry cleaning equipment. Seals used for windows, etc .; seals for cyclotrons and (vacuum) valves, seals for proton accelerators, seals for automatic packaging machines, diaphragms for pumps for sulfur dioxide and chlorine gas analyzers (pollution measuring instruments) in air, snakes Pump linings, rolls and belts for printing presses, conveyor belts (conveyor belts), squeezing rolls for pickling iron plates, etc., robot cables, solvent squeezing rolls for aluminum rolling lines, coupler O-rings, acid-resistant cushioning materials Of dust seals and lip rubber for sliding parts of cutting machines, garbage incinerators Basket, friction materials, metal or a surface modifier for rubbers, and the like dressing. In addition, gaskets and sealing materials for equipment used in the papermaking process, sealing agents for filter units for clean rooms, sealing agents for construction, protective coating agents for concrete and cement, glass cloth impregnating materials, processing aids for polyolefins, molding of polyethylene It can also be used as a performance improving additive, a fuel container for a small generator or lawn mower, or a precoated metal obtained by subjecting a metal plate to a primer treatment. In addition, it can be impregnated into a woven fabric and baked to be used as a sheet and a belt.

  As a specific use form in the above-mentioned steel field, there is an iron sheet processing roll of an iron sheet processing facility.

  Specific usage forms in the electric field include insulating oil caps for Shinkansen, venting seals for liquid ring type transformers, seals for transformers, jackets for oil well cables, oven seals for electric furnaces, etc., and window frames for microwave ovens. Seals, seal materials used when bonding wedges and necks of CRTs, seal materials for halogen lamps, fixing agents for electrical components, seal materials for terminal treatment of sheathed heaters, and insulation and moisture-proof treatment for electrical equipment lead wire terminals Sealing material. Also used for covering materials such as oil-resistant and heat-resistant wires, high heat-resistant wires, chemical-resistant wires, high-insulation wires, high-voltage transmission wires, cables, wires used in geothermal power generators, wires used around automobile engines, etc. You can also. It can also be used for oil seals and shaft seals of vehicle cables. Furthermore, electric insulating materials (for example, insulating spacers for various electric devices, insulating tapes used for cable joints and end portions, materials used for heat-shrinkable tubes, etc.), and electric and It can also be used for electronic equipment materials (for example, lead wires for motors, electric wire materials around high-temperature furnaces). Further, it can be used as a sealing layer or a protective film (back sheet) of a solar cell.

  In the fuel cell field, polymer electrolyte fuel cells, phosphate type fuel cells, etc., between the electrodes, between the electrodes and the separator between the separator, hydrogen, oxygen, seals and packing of piping such as water generated, separators, etc. It can be used as such.

  In the field of the above electronic components, it can be used as a heat radiation material, an electromagnetic wave shielding material, a gasket for a hard disk drive (magnetic recording device) of a computer, and the like. Also, buffer rubber (crash stopper) for hard disk drives, binder for electrode active material of nickel-metal hydride secondary battery, binder for active material of lithium ion battery, polymer electrolyte for lithium secondary battery, binder for positive electrode of alkaline storage battery, Potting of films and sheets such as EL element (electroluminescence element) binder, capacitor electrode active material binder, sealant, sealing agent, optical fiber quartz coating material, optical fiber coating material, electronic parts, circuit board And coating and adhesive seals, fixing agents for electronic components, modifiers for sealants such as epoxy, coating agents for printed circuit boards, modifiers for prepreg resin on printed wiring boards such as epoxy, materials for preventing scattering of light bulbs, gaskets for computers , 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.

  In the field of the above-mentioned chemical transportation equipment, it can be used for safety valves and unloading valves of trucks, trailers, tank trucks, ships and the like.

In the field of mining equipment for exploring energy resources such as oil and gas, it is used as various sealing materials used when mining oil and natural gas, boots of electric 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, seals for horizontal drilling motors (stators), stator bearings (shafts) seals, and blowout prevention devices (BOPs). Seal material used in rotating blast prevention equipment (pipe wiper), seal material used in MWD (real-time drilling information detection system), gas-liquid connector, and logging used in logging equipment (logging equipment) Tool seals (for example, O-rings, seals, packings, gas-liquid connectors, boots, etc.), inflatable packers and completion packers and packer seals used therefor, seals and packings used for cementing devices, perforators (perforators) Used for Seals, seals and packings used in mud pumps, motor linings, underground stethoscope covers, U-cups, composition seating cups, rotating seals, laminated elastomeric bearings, flow control seals, sand control seals, safety valves Seals, seals for hydraulic fracturing equipment (fracturing equipment), seals and packings for linear packers and linear hangers, seals and packings for well heads, seals and packings for chalk and valves, seal materials for LWD (logging during drilling) And diaphragms used in oil exploration and drilling applications (for example, diaphragms for supplying lubricating oil such as oil drilling pits), gate valves, electronic boots, and sealing elements for perforated guns.

  In addition, joint seals for kitchens, bathrooms, lavatories, etc .; outdoor tent pulling cloths; seals for stamping materials; rubber hoses for gas heat pumps, chlorofluorocarbon rubber hoses; agricultural films, linings, weatherproof covers; It can also be used for tanks such as laminated steel plates used in the above.

Further, it can be used as an article bonded to a metal such as aluminum. Examples of such a use form include a door seal, a gate valve, a pendulum valve, a tip of a solenoid, a metal seal such as a piston seal, a diaphragm, and a metal gasket.
It can also be used for rubber parts, brake shoes, brake pads, etc. in bicycles.

A belt is one of the forms of the fluoropolymer molded article of the present disclosure and the composite of the present disclosure.
Examples of the belt include the following. Power transmission belts (including flat belts, V-belts, V-ribbed belts, toothed belts, etc.) and transport belts (conveyor belts), such as those around engines such as agricultural machines, machine tools, and industrial machines, where various temperatures are high. Conveyor belts for transporting loose and granular materials such as coal, crushed stone, earth and sand, ore, wood chips, etc. in high temperature environments; Conveyor belts used for steelworks such as blast furnaces; Precision Conveyor belts in applications exposed to high temperatures in equipment assembly factories, food factories, etc .; V-belts for agricultural machinery, general equipment (eg, OA equipment, printing machines, commercial dryers, etc.), automobiles, etc. V-ribbed belts; power transmission belts for transfer robots; toothed belts such as power transmission belts for food and machine tools; used in automobiles, office automation equipment, medical equipment, printing machines, etc. Such as a toothed belt to be like.
In particular, a timing belt is typical as a toothed belt for automobiles.

The belt may have a single-layer structure or a multilayer structure.
When the belt has a multilayer structure, the belt may include a layer obtained by crosslinking the composition of the present disclosure and a layer made of another material.
In the belt having a multilayer structure, examples of the layer made of another material include a layer made of another rubber, a layer made of a thermoplastic resin, various fiber reinforcing layers, a canvas, and a metal foil layer.

  The fluoropolymer molded article of the present disclosure and the composite of the present disclosure can also be used for industrial anti-vibration pads, anti-vibration mats, railway slab mats, pads, anti-vibration rubber for automobiles, and the like. Examples of the anti-vibration rubber for automobiles include anti-vibration rubber for engine mount, motor mount, member mount, strut mount, bush, damper, muffler hanger, and center bearing.

Further, as other usage forms, a joint member such as a flexible joint and an expansion joint, a boot, a grommet, and the like can be given. In the marine field, for example, marine pumps and the like are mentioned.
Joint members are joints used for piping and piping equipment.They prevent vibration and noise generated from piping systems, absorb temperature changes, absorb expansion and contraction due to pressure changes, absorb dimensional changes, earthquakes, and land subsidence. It is used for applications such as mitigating and preventing the effects of
Flexible joints, expansion joints, for example, for shipbuilding piping, for mechanical piping such as pumps and compressors, for chemical plant piping, for electrical piping, for civil engineering and water piping, preferably used as a complex shape molded body for automobiles and the like it can.
The boots include, for example, constant velocity joint boots, dust covers, rack and pinion steering boots, pin boots, automotive boots such as piston boots, agricultural machine boots, industrial vehicle boots, construction machine boots, hydraulic machine boots, and sky. It can be preferably used as a molded article having a complicated shape such as a boot for a pressure machine, a boot for a centralized lubricator, a boot for transferring a liquid, a boot for fire fighting, a boot for transferring various liquefied gases, and various industrial boots.

  The fluorine-containing polymer molded article of the present disclosure and the composite of the present disclosure can be used as an air spring for a filter press diaphragm, a blower diaphragm, a water supply diaphragm, a liquid storage tank diaphragm, a pressure switch diaphragm, an accumulator diaphragm, and a suspension. It can also be used for diaphragms and the like.

  By adding the fluoropolymer molded article of the present disclosure and the composite of the present disclosure to rubber or resin, anti-slip to obtain a molded article or a coating film that is hard to slip under water, such as rain, snow, ice, or sweat. Agent is obtained.

  Further, the fluoropolymer molded article of the present disclosure and the composite of the present disclosure are used to produce, for example, decorative plywood made of melamine resin, phenol resin, epoxy resin, and the like, printed boards, electric insulating boards, rigid polyvinyl chloride laminated boards, and the like. It can also be used as a cushion material for hot press molding at that time.

  The fluoropolymer moldings of the present disclosure and the composites of the present disclosure may also contribute to the impermeability of various supports such as weapon-related sealing gaskets, protective clothing against contact with invasive chemicals. You can also.

  Lubricating oils containing engine additives (particularly amine additives used as antioxidants and detergents / dispersants) used in transportation such as automobiles and ships (engine oil, transmission oil, gear oil, etc.) (Square) -ring, V-ring, X-ring, packing, gasket, diaphragm, oil seal, bearing seal, lip seal used to seal and seal oil, fuel oil, and grease (especially urea grease) , Plunger seals, door seals, lip and face seals, gas delivery plate seals, wafer support seals, barrel seals and other various sealing materials, etc., tubes, hoses, various rubber rolls, coatings, belts, valve valves It can also be used as such. Further, it can be used as a laminating material and a lining material.

  A coating material for heat-resistant and oil-resistant electric wires used as a lead wire for sensors that detect the oil temperature and / or oil pressure by contacting the transmission oil and / or engine oil of internal combustion engines of automobiles, etc .; It can be used in a high-temperature oil atmosphere such as in an oil pan.

  In addition, the fluoropolymer molded article of the present disclosure and the composite of the present disclosure may be used after forming a vulcanized film thereon. Specifically, non-adhesive oil-resistant rolls for copiers, weather strips for weathering and icing prevention, rubber stoppers for infusions, vial rubber stoppers, mold release agents, non-adhesive light transport belts, anti-adhesion coatings for automobile engine mount play gaskets, Applications include synthetic fiber coating, bolt members or joints with thin packing coatings.

The application of the fluoropolymer molded article of the present disclosure and the composite of the present disclosure to automobile-related parts includes motorcycle parts having a similar structure.
Further, examples of the fuel related to the automobile include light oil, gasoline, and fuel for diesel engines (including biodiesel fuel).

Further, the composition of the present disclosure can be used as various parts in various industrial fields, in addition to being used as a molded product after being crosslinked. Therefore, next, the use of the composition of the present disclosure will be described.
The composition of the present disclosure is a surface modifying material such as metal, rubber, plastic, and glass; a sealing material and a coating material requiring heat resistance, chemical resistance, oil resistance, and non-adhesion, such as a metal gasket and an oil seal. Non-adhesive coating materials such as rolls for OA equipment and belts for OA equipment, or bleed barriers; can be used for impregnating or baking woven sheets and belts.
The composition of the present disclosure can be used as a sealing material, a lining, or a sealant of a complicated shape by ordinary usage by increasing the viscosity and the concentration, and by decreasing the viscosity, a thin film of several microns can be formed. It can be used for forming, and it can be used for application of pre-coated metal, O-ring, diaphragm and reed valve by making it medium viscosity.
Furthermore, it can also be used for applying a transfer roll or belt for woven fabric or paper, a printing belt, a chemical resistant tube, a medicine stopper, a fuel hose, and the like.

Article substrates coated with the composition of the present disclosure include metals such as iron, stainless steel, copper, aluminum and brass; glass products such as glass plates and glass fiber woven and non-woven fabrics; polypropylene, polyoxymethylene, Molded products and coatings of general-purpose and heat-resistant resins such as polyimide, polyamide-imide, polysulfone, polyethersulfone, and polyetheretherketone; general-purpose rubbers such as SBR, butyl rubber, NBR, EPDM, and silicone rubbers and fluorine rubbers Molded articles and coatings of heat-resistant rubber; woven and non-woven fabrics of natural and synthetic fibers; and the like can be used.
A coating formed from the composition of the present disclosure can be used in fields where heat resistance, solvent resistance, lubricity, and non-adhesion are required, and specific applications include copying machines, printers, and facsimile machines. Rolls (for example, fixing rolls, pressure rolls) and transport belts for OA equipment; sheets and belts; O-rings, diaphragms, chemical resistant tubes, fuel hoses, valve seals, gaskets for chemical plants, engine gaskets, and the like. .

The composition of the present disclosure can also be dissolved in a solvent and used as a paint or an adhesive. It can also be used as a coating material as an emulsified dispersion (latex).
The above composition is a surface treatment agent for structures composed of inorganic and organic base materials such as sealing materials and linings for various devices and pipes, metals, ceramics, glass, stone, concrete, plastic, rubber, wood, paper, and fibers. Used as etc.
The composition can be applied to a substrate or the like by dispenser coating or screen printing.

The compositions of the present disclosure may be used as coating compositions for casting films or dipping substrates such as fabrics, plastics, metals, or elastomers.
In particular, the compositions of the present disclosure may be provided in latex form as coated fabrics, protective gloves, impregnated fibers, O-ring coatings, coatings for fuel-based quick connect O-rings, coatings for fuel-based seals, fuel tank rollover valve diaphragms. Coating, coating for fuel tank pressure sensor diaphragm, coating for oil filter and fuel filter seal, coating for fuel tank sender seal and sender head fitting seal, coating for copier fixing mechanism roll, and polymer coating composition May be used.
They are useful for coating silicone rubber, nitrile rubber, and other elastomers. For the purpose of increasing both the permeation resistance and the 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 heat exchangers, expansion joints, butts, tanks, fans, flue ducts and other conduits, and coatings for storage structures, such as concrete storage structures. The composition may be applied to the exposed cross-section of the multilayer component structure, for example, in a method of making a hose structure and diaphragm. Sealing members at connections and joints often consist of hard materials, and the compositions of the present disclosure provide improved frictional interfaces, increased dimensional interference with reduced traces of leakage along the sealing surface. Provide 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 joints where hoses and tubes are connected to separate 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 compositions are also useful for coating steel sheets that can be formed or embossed before or after the paint is applied. For example, multiple layers of coated steel could be assembled to create a gasket between two rigid metal members. The sealing effect is obtained by applying the composition of the present disclosure between the layers. This process reduces the bolting force and strain of the assembled parts, while providing the engine head gasket and exhaust manifold gasket for the purpose of providing better fuel savings and lower emissions due to lower cracks, flexure, and hole strain. Can be used to produce

  The composition of the present disclosure may further include a coating agent; a substrate-integrated gasket and a packing formed by dispensing a substrate containing an inorganic material such as a metal or a ceramic; and a substrate containing an inorganic material such as a metal or a ceramic. It can also be used as a coated multi-layer product.

  Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

  Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to these examples.

  Each numerical value in the examples was measured by the following method.

<Crosslinking properties (optimal crosslinking time (T90))>
For the fluorinated polymer composition, a crosslinking curve at 160 ° C. for 30 minutes was determined at the time of primary crosslinking using a vulcanization tester (MDR H2030 manufactured by M & K Corporation), and the optimal crosslinking time (T90) was determined from the change in torque. .

<Tensile strength and elongation at break>
Using the crosslinked sheet having a thickness of 2 mm obtained in Examples and Comparative Examples, using a tensile tester (Tensilon RTG-1310 manufactured by A & D Corporation) according to JIS K6251-1: 2015. The tensile strength at 23 ° C. and the elongation at break were measured with a dumbbell No. 5 under the conditions of 500 mm / min.

<Tear strength (trouser shape)>
Using the crosslinked sheets having a thickness of 2 mm obtained in Examples and Comparative Examples, the measurement was carried out in accordance with JIS K6252-1: 2015 (test piece: trouser type).

<Hardness>
Using the three crosslinked sheets having a thickness of 2 mm obtained in Examples and Comparative Examples, using a type A durometer in accordance with JIS K6253-3: 2012, the hardness (Peak value and 3 sec).

<Density>
It was determined according to JIS K6268 using the crosslinked sheets having a thickness of 2 mm obtained in Examples and Comparative Examples.

<Low temperature characteristics (TR10)>
It measured according to JISK6261: 2006 using the crosslinked sheet of thickness 2mm obtained by the Example and the comparative example.

<Diethanolamine resistance>
An immersion test was performed at 120 ° C. for 72 hours using diethanolamine. The volume and the mass of the test piece before and after the immersion test were measured, and the volume swelling rate (ΔV) and the mass change rate (ΔW) were obtained. The volume swelling rate (ΔV) is the rate of change of the volume after the sample piece is immersed under predetermined conditions (representing the degree of swelling). The original volume of the sample piece is Vo, and the volume after the test is V. Then, it is represented by ΔV = (V−Vo) / Vo × 100. The mass change rate (ΔW) is represented by ΔW = (W−Wo) / Wo × 100, where Wo is the original mass of the sample piece and W is the mass after the test.

Fluorine-containing elastomer (1):
Peroxide-crosslinkable polymer prepared by iodine transfer polymerization (VdF / 2,3,3,3-tetrafluoropropene = 77/23 (molar ratio), Mooney viscosity at 100 ° C. (ML1 + 10): 45, glass transition temperature : -13 ° C, iodine content: 0.21% by mass)
Fluorine-containing elastomer (2):
Product name "Afras 150P", fluorinated elastomer (3) manufactured by Asahi Glass Co., Ltd.
Peroxide-crosslinkable polymer prepared by iodine transfer polymerization (VdF / HFP / TFE = 50/30/20 (molar ratio), Mooney viscosity at 100 ° C. (ML1 + 10): 50, glass transition temperature −6 ° C., iodine Content: 0.23% by mass)
Fluorine-containing elastomer (4):
Peroxide-crosslinkable polymer prepared by iodine transfer polymerization (VdF / HFP = 78/22 (molar ratio), Mooney viscosity at 100 ° C. (ML1 + 10): 40, glass transition temperature: −20 ° C., iodine content: 0 .21 mass%)
Fluorine-containing elastomer (5):
Peroxide crosslinkable polymer prepared by iodine transfer polymerization (VdF / 2,3,3,3-tetrafluoropropene = 77/23 (molar ratio), Mooney viscosity at 100 ° C. (ML1 + 10): 99, glass transition temperature : -13 ° C, iodine content: 0.18% by mass)

Wet silica:
Product name "Carplex 1120" (manufactured by DSL Japan Co., Ltd.)

MT carbon (N ₂ SA: 8 m ² / g, DBP: 43 ml / 100 g)
FEF carbon (N ₂ SA: 42 m ² / g, DBP: 115 ml / 100 g)
ISAF carbon (N ₂ SA: 119 m ² / g, DBP: 114 ml / 100 g)

Crosslinking aid (1):
Triallyl isocyanurate impregnated in silica at 60% by mass (trade name "TAIC WH-60", manufactured by Mitsubishi Chemical Corporation)
Crosslinking aid (2):
Trial isocyanurate impregnated with 60% by mass of diatomaceous earth (trade name "TAIC M-60", manufactured by Mitsubishi Chemical Corporation)

Organic peroxide (1):
An inorganic powder impregnated with 2,5-dimethyl-2,5-di (t-butylperoxy) hexane at 40% by mass (trade name "Perhexa 25B-40", manufactured by NOF CORPORATION)
Organic peroxide (2):
α, α-bis (t-butylperoxy) -p-diisopropylbenzene impregnated with 40% by mass of inorganic powder (trade name “Perbutyl P-40”, manufactured by NOF Corporation)

Silicone rubber (1):
Peroxide-crosslinkable silicone rubber (trade name "KE-551-U", manufactured by Shin-Etsu Chemical Co., Ltd.)
Silicone rubber (2):
Peroxide-crosslinkable silicone rubber (trade name “ELASTOSIL R401 / 60S”, manufactured by Asahi Kasei Wacker Silicone Co., Ltd.)
Crosslinking agent for silicone rubber:
A mixture of about 25% by weight of an organic peroxide and about 75% by weight of a silicone rubber (trade name "C-8", manufactured by Shin-Etsu Chemical Co., Ltd.)

Examples 1 to 9, Comparative Examples 1 to 10
Each component was blended according to the formulation in Table 1 and kneaded on an open roll to prepare a fluoropolymer composition. Table 1 shows the crosslinking properties (T90) of the obtained fluoropolymer composition. After press-crosslinking the obtained fluoropolymer composition at 160 ° C for 20 minutes, it was oven-crosslinked at 180 ° C for 4 hours to prepare a crosslinked sheet (2 mm thick). Table 1 shows the evaluation results of the obtained crosslinked sheets.
In Comparative Example 10, the crosslinked product was fixed to the mold and could not be released, and a crosslinked sheet for measuring physical properties in a normal state could not be obtained.

Examples 10 to 11, Comparative Examples 11 to 14
Each component was blended according to the formulation in Table 2 and kneaded on an open roll to prepare a sheet-like fluoropolymer composition having a thickness of about 2 mm. Table 2 shows the crosslinking properties (T90) of the obtained fluoropolymer composition. After press-crosslinking the obtained fluoropolymer composition at 160 ° C for 10 minutes, it was oven-crosslinked at 180 ° C for 4 hours to prepare a crosslinked sheet (2 mm thick). Table 2 shows the evaluation results of the obtained crosslinked sheets.

  Further, the respective components were blended according to the following formulation and kneaded on an open roll to prepare a sheet-like silicone rubber composition A having a thickness of about 3 mm.

Silicone rubber composition A:
Silicone rubber (1) 100 parts by mass MT carbon 20 parts by mass Crosslinking agent for silicone rubber (C-8) 1.25 parts by mass Crosslinking aid (2) (TAIC M-60) 3.3 parts by mass

  Next, the sheet-like fluorine-containing polymer composition having a thickness of about 2 mm obtained above and the silicone rubber composition A having a sheet thickness of about 3 mm obtained above are overlapped with each other. An FEP film (thickness: 150 μm) was sandwiched between one end and about 1 to 1.5 cm of the interface in order to make a non-adhesive part for gripping during the peeling test. The resulting composite (laminate) was inserted into a mold having a thickness of 4 mm, press-crosslinked at 160 ° C for 10 minutes, and then oven-crosslinked at 180 ° C for 4 hours to obtain a sheet-like composite.

<Adhesion evaluation>
The FEP film was peeled off from the obtained composite, and cut into a strip having a width of 25 mm and a length of 100 mm to prepare a test piece. This test piece was subjected to a T-type peel test at 23 ° C. at a tensile speed of 50 mm / min using a tensile tester (Tensilon RTG-1310 manufactured by A & D Corporation) to observe a fracture mode. Evaluation was made according to the following criteria. Table 2 shows the results.
：: Either the sheet of the fluoropolymer composition or the layer formed from the sheet of the silicone rubber composition destroyed the material, and it was impossible to peel off at the interface.
Δ: Each layer could be peeled off at the interface, but the surface of each layer after peeling was rough.
X: Each layer could be peeled off at the interface, and the surface of each layer after peeling was smooth.

Claims (11)

Contains fluorine-containing polymer, uncrosslinked silicone rubber and organic peroxide,
The fluorine-containing polymer has a glass transition temperature of 25 ° C. or lower, a vinylidene fluoride unit and the following general formula (1):
CHX ¹ = CX ² Rf (1)
(In the formula, ^one of X ¹ and X ² is H, the other is F, and Rf is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms.)
A composition containing a fluorine-containing monomer (1) unit represented by the formula:   The composition of claim 1, wherein the uncrosslinked silicone rubber is peroxide crosslinkable. 3. The composition according to claim ¹ , wherein in the general formula (1), X ¹ is H and X ² is F. 4.   The composition according to any one of claims 1 to 3, wherein the fluorinated monomer (1) is 2,3,3,3-tetrafluoropropene.   The composition according to claim 1, wherein the fluoropolymer has a Mooney viscosity at 100 ° C. (ML1 + 10 (100 ° C.)) of 2 to 200. 6.   The composition according to any one of claims 1 to 5, wherein the mass ratio of the fluoropolymer to the uncrosslinked silicone rubber (fluoropolymer / uncrosslinked silicone rubber) is 5/95 to 99/1. Further contains carbon black,
The nitrogen adsorption specific surface area of the carbon black is 70 to 180 m ² / g or less, the dibutyl phthalate (DBP) or paraffin oil absorption of the carbon black is 40 to 180 ml / 100 g or less,
The composition according to any one of claims 1 to 6, wherein the content of the carbon black is 5 to 100 parts by mass based on 100 parts by mass of the fluoropolymer.   A fluoropolymer molded article obtained by crosslinking the composition according to claim 1. Crosslinking the fluorine-containing polymer molded article (A) obtained by crosslinking the composition according to any one of claims 1 to 7 and a silicone rubber composition containing a peroxide-crosslinkable uncrosslinked silicone rubber. And a silicone rubber molded product (B) obtained by
A composite in which a fluoropolymer molded article (A) and a silicone rubber molded article (B) are adhered.   The silicone rubber composition according to claim 9, further comprising a crosslinking aid, wherein the content of the crosslinking aid is 0.1 to 10 parts by mass with respect to 100 parts by mass of the uncrosslinked silicone rubber. Complex.   To form a fluoropolymer molded article (A) to be used by bonding to a silicone rubber molded article (B) obtained by crosslinking a silicone rubber composition containing a peroxide-crosslinkable uncrosslinked silicone rubber. Use of the composition according to any of claims 1 to 7.