JP2020007455A - Composition containing fluorine-containing polymer - Google Patents

Abstract

To provide a composition containing a fluorine-containing polymer, capable of giving a molding which exhibits relatively good low-temperature characteristics and adhesiveness to an acrylic rubber molding and exhibits excellent amine resistance.SOLUTION: The composition contains the fluorine-containing polymer, an uncrosslinked acrylic 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 consisting only of a fluorine-containing monomer represented by the following formula: vinylidene fluoride unit / fluorine-containing unit An amorphous fluoroelastomer characterized by having a molar ratio of monomer units of 78/22 to 22/78 and a glass transition temperature of 25 ° C. or lower has been proposed.

JP, 2012-512264, A

  In the present disclosure, a composition containing a fluorine-containing polymer, which exhibits relatively good tear strength, low-temperature properties and adhesion to an acrylic rubber molded article, and is capable of obtaining a molded article exhibiting excellent amine resistance The purpose is to provide.

  Another object of the present disclosure is to provide a composite exhibiting relatively good tear strength, low-temperature properties, and adhesion, and exhibiting excellent amine resistance.

According to the present disclosure, the fluoropolymer contains a fluoropolymer, an uncrosslinked acrylic 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 is provided that contains monomer (1) units.

Preferably, the uncrosslinked acrylic rubber is capable of peroxide crosslinking.
In the general formula (1), X ¹ is preferably H, and X ² is preferably F.
Preferably, the fluorinated monomer (1) is 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.
The mass ratio of the fluoropolymer to the uncrosslinked acrylic rubber (fluoropolymer / uncrosslinked acrylic rubber) is preferably from 99/1 to 40/60.

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

  According to the present disclosure, a fluoropolymer molded article (A1) obtained by crosslinking the above composition and an acrylic rubber molded article obtained by crosslinking an acrylic rubber composition containing an uncrosslinked acrylic rubber are also provided. (B), wherein the fluoropolymer molded body (A1) and the acrylic rubber molded body (B) are bonded to each other (hereinafter, may be referred to as “composite (1)”). Is provided.

  According to the present disclosure, a fluorine-containing polymer molded article (A1) used by bonding to an acrylic rubber molded article (B) obtained by crosslinking an acrylic rubber composition containing an uncrosslinked acrylic rubber is also formed. There is provided use of a composition as described above.

According to the present disclosure, also, a fluoropolymer molded article (A2) obtained by crosslinking a fluoropolymer composition containing a fluoropolymer and an organic peroxide, and an acrylic rubber containing an uncrosslinked acrylic rubber An acrylic rubber molded article (B) obtained by crosslinking the composition, wherein the fluoropolymer molded article (A2) and the acrylic rubber molded article (B) are adhered to each other, 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 complex containing the monomer (1) unit (hereinafter sometimes referred to as “complex (2)”) is provided.

  According to the present disclosure, a fluorine-containing polymer containing relatively good tear strength, low-temperature properties and adhesion to an acrylic rubber molded article, and capable of obtaining a molded article having excellent amine resistance can be obtained. A composition can be provided.

  According to the present disclosure, it is also possible to provide a composite exhibiting relatively good tear strength, low-temperature properties and adhesiveness, and exhibiting excellent amine resistance.

  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 acrylic rubber, and an organic peroxide. By using the composition of the present disclosure, a molded article exhibiting relatively good tear strength, low-temperature properties, and adhesion to an acrylic rubber molded article, and exhibiting excellent amine resistance can be obtained. Further, the obtained molded body has the same physical properties as in the conventional moldings.

<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 fluoropolymer 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 fluoropolymer is preferably a fluoroelastomer, and is preferably an amorphous polymer. The fluoroelastomer is an uncrosslinked fluoroelastomer.

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

  The above glass transition temperature was obtained by using a differential scanning calorimeter (X-DSC823e, manufactured by Hitachi Techno Science), 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 with 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 exhibits relatively good tear strength, low-temperature properties, and adhesion to an acrylic rubber molded article. In addition, a molded article having excellent amine resistance can be obtained.

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

In the above general formula (1), tear strength, low temperature characteristics, since the more excellent moldings by adhesion and amine resistance of acrylic rubber molding is obtained, X ¹ is H, X ² is F is preferred.

As the fluorinated monomer (1), CH ₂ ＣＦCFCF 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 them, CH ₂ CFCF ₃ (2,3,3,3-tetrafluoropropene) is preferable. One or more monomers may be used as the fluorinated monomer (1).

  The fluorine-containing polymer may further contain another monomer unit other than the vinylidene fluoride unit and the fluorine-containing monomer (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) )) Represented by 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,
General 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
(Wherein, 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 providing 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 from 87/13 to 20/80, and the lower limit of the molar ratio of vinylidene fluoride units is more preferably 22. / 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 all monomer units.

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

  The fluorine-containing polymer preferably has at least one of an iodine atom and a bromine atom, since a molded article having more excellent tear strength, low-temperature properties, adhesion to an acrylic rubber molded article, and amine resistance can be obtained. And more preferably 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 the bromine terminal serves as a cross-linking point (cross-linking site), so that a cross-linked fluorine-containing polymer having a high cross-linking density can be obtained, and peroxide cross-linking can be more easily performed. become.

  As the above-mentioned fluoropolymer, a molded article having more excellent tear strength, low-temperature properties, adhesion to an acrylic rubber molded article, and amine resistance can be obtained. Therefore, a vinylidene fluoride unit and a fluoromonomer (1 A) a copolymer containing only a unit and having a molar ratio of vinylidene fluoride unit / fluoromonomer (1) unit of 87/13 to 22/78, vinylidene fluoride unit, and fluorine-containing monomer Containing only a monomer (1) unit, and other monomer units copolymerizable with vinylidene fluoride and a fluorine-containing monomer (1), vinylidene fluoride unit / fluorine-containing monomer (1) unit Is a copolymer (II) in which the other monomer unit is 1 to 50% by mole of the total monomer unit, a vinylidene fluoride unit, and a fluorine-containing copolymer. It contains a monomer (1) unit, and other monomer units copolymerizable with vinylidene fluoride and a fluorine-containing monomer (1), and comprises vinylidene fluoride unit / fluorine-containing monomer (1) The molar ratio of the units is 85/15 to 20/80, the other monomer units are 0 to 50 mol% of the total monomer units, and have at least one of an iodine atom and a bromine atom; And at least one selected from the group consisting of a copolymer (III) having a total content of bromine atoms of 0.001 to 10% by mass.

  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 / fluorine-containing monomer (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) contains 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 fluorine-containing monomer (1), or a substantially vinylidene fluoride unit and a fluorine-containing 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 contain 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 absorption solution thus obtained, the solution is burned in oxygen in a combustion flask made of quartz, left for 30 minutes, and then measured using a Shimadzu 20A ion chromatograph. The calibration curve may be a KI standard solution, one containing 0.5 ppm of iodine ions or one containing 1.0 ppm.

  The bonding position of the iodine atom and the bromine atom in the copolymer (III) may be 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 more easily performed. become.

  The copolymer (III) can be produced by a production method using iodine or a bromine-containing monomer as a monomer that provides 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), and one or more of the monomers may be used. 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 CFOCF 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 increase the crosslinking density in the crosslinking using an organic peroxide and to reduce the compression set. Is particularly preferable since 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 tear strength, low-temperature properties, adhesion to an acrylic rubber molded article, and amine resistance can be obtained, A peroxide-crosslinkable fluoropolymer having an iodine atom or a bromine atom is more preferable, and the copolymer (III) is more preferable.

  As the above-mentioned fluoropolymer, from the viewpoint of excellent sealing properties, the number average molecular weight (Mn) is preferably from 7000 to 500,000, the weight average molecular weight (Mw) is preferably from 10,000 to 1,000,000, and Mw / Mn is preferably 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 5 or more, more preferably 10 or more, because it can be easily mixed with the uncrosslinked acrylic rubber and the organic peroxide. It is more preferably 30 or more. It is preferably at most 200, more preferably at most 160, even more preferably at most 120. 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 in view of polymerization reactivity, crosslinking reactivity, availability, and the like. 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 two kinds of copolymers (I) and one kind of copolymer (II), 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 acrylic rubber>
The compositions of the present disclosure contain an uncrosslinked acrylic rubber. Since the composition of the present disclosure contains, in addition to the fluoropolymer, an uncrosslinked acrylic rubber, it exhibits relatively good tear strength, low-temperature properties and adhesion to an acrylic rubber molded article, A molded article exhibiting excellent amine resistance can be obtained. In addition, compared to a composition containing a fluoropolymer but not containing an uncrosslinked acrylic rubber, a molded article exhibiting excellent low-temperature properties can be obtained from the composition of the present disclosure.

  As the uncrosslinked acrylic rubber, among others, the same crosslinking system as that of the fluorine-containing polymer can be applied, and a molded article having more excellent tear strength, low-temperature properties, adhesiveness with an acrylic rubber molded article, and amine resistance can be obtained. Therefore, an acrylic rubber which can be crosslinked with peroxide is preferable.

The uncrosslinked acrylic rubber is a polymer comprising polymerized units based on a (meth) acrylate. In the present disclosure, the (meth) acrylate includes an acrylate monomer and a methacrylate. The uncrosslinked acrylic rubber may be a homopolymer composed of a polymer unit based on one kind of (meth) acrylic ester, or a copolymer composed of polymer units based on two or more kinds of (meth) acrylic ester. Or a copolymer composed of one or more polymerized units based on (meth) acrylates and polymerized units based on monomers copolymerizable with the (meth) acrylates It may be.
The uncrosslinked acrylic rubber can adjust the normal physical properties, low-temperature properties, oil resistance, and the like of the molded product by selecting the type of the (meth) acrylate and the amount of the polymerized units.

As the (meth) acrylate, an acrylate is preferred.
The acrylate is preferably an alkyl acrylate having an alkyl group having 1 to 12 carbons or an alkoxyalkyl acrylate having an alkoxyalkyl group having 1 to 12 carbons.
Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, n-propyl acrylate, isobutyl acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylpentyl acrylate, and n-octyl. Examples include acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, and n-octadecyl acrylate.
Examples of the alkoxyalkyl acrylate include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- (n-propoxy) ethyl acrylate, 2- (n-butoxy) ethyl acrylate, 3-methoxypropyl acrylate, and 3-ethoxypropyl. Acrylate, 2- (n-propoxy) propyl acrylate, 2- (n-butoxy) propyl acrylate and the like.

By adjusting the amount of the polymerization unit based on these acrylic acid esters, the resulting composition, the fluoropolymer molded article obtained from the composition, the low-temperature properties and oil resistance of the composite obtained from the fluoropolymer molded article, Can be adjusted.
For example, when the copolymerization ratio of n-butyl acrylate is increased, low-temperature characteristics can be improved. Further, when the copolymerization ratio of ethyl acrylate is increased, oil resistance can be improved.

The uncrosslinked acrylic rubber is also preferably a copolymer composed of a polymerized unit based on an acrylate ester and a polymerized unit based on a monomer copolymerizable with the acrylate ester.

  Examples of the monomer copolymerizable with the acrylate include at least one monomer selected from the group consisting of methacrylate, vinyl acetate, a monomer containing a crosslinking site (excluding vinyl acetate), and ethylene. The body is preferred, and ethylene is more preferred.

  Examples of the methacrylate include alkyl methacrylate and alkoxyalkyl methacrylate. The methacrylate is preferably, for example, an alkyl methacrylate having an alkyl group having 2 to 14 carbon atoms, or an alkyl methacrylate having an alkoxyalkyl group having 2 to 14 carbon atoms.

Vinyl acetate is used to maintain mechanical properties such as elongation in the composition by crosslinking between molecules of the uncrosslinked acrylic rubber when the composition containing the uncrosslinked acrylic rubber is thermally aged. By adjusting the amount of vinyl acetate, the intermolecular crosslinking of the resulting composition can be adjusted.
The main chain of the acrylic rubber may be cut by the influence of heat, ultraviolet rays, or the like, and mechanical properties such as tensile strength and elongation at break may be reduced. Therefore, if vinyl acetate having a carboxyl group that easily causes a crosslinking reaction is copolymerized in the main chain of the uncrosslinked acrylic rubber, when the main chain of the crosslinked acrylic rubber is cut, it is based on vinyl acetate. The carboxyl group in the polymerized unit serves as a cross-linking site, so that the cut molecules can be cross-linked again.

  The polymerization unit based on vinyl acetate is preferably 15% by mass or less based on all the polymerization units constituting the uncrosslinked acrylic rubber. When the content of the polymerized unit based on vinyl acetate is in this range, it is possible to suppress a decrease in mechanical properties of the composition after crosslinking while maintaining the heat aging resistance.

  The crosslinked site-containing monomer is used to copolymerize the uncrosslinked acrylic rubber as necessary, and is used for promoting intermolecular crosslinking to adjust the hardness and elongation characteristics of the obtained composition.

  As the crosslinking site-containing monomer, a monomer having at least one selected from the group consisting of an active chlorine group, an epoxy group, a carboxyl group, and a hydroxyl group (excluding the hydroxyl group contained in the carboxyl group) is preferable.

  Examples of the crosslinking site-containing monomer include, but are not particularly limited to, monomers having an active chlorine group such as 2-chloroethyl vinyl ether, 2-chloroethyl acrylate, vinylbenzyl chloride, vinyl chloroacetate, and allyl chloroacetate. Monomers containing a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, 2-pentenoic acid, maleic acid, fumaric acid, itaconic acid, monoalkyl maleate, monoalkyl fumarate and cinnamic acid; glycidyl Monomers containing an epoxy group such as acrylate, glycidyl methacrylate, allyl glycidyl ether, and methallyl glycidyl ether are exemplified.

  The hydroxyl group is preferably a phenolic hydroxyl group. Examples of the cross-linking site-containing monomer having a phenolic hydroxyl group include α-methyl-o-hydroxystyrene, o-cavicol, p, m-hydroxyvinyl benzoate, vinyl salicylate, eugenol, and isogenol. Eugenol, p-isopropenylphenol, o, m, p-allylphenol, 2,2- (o, m, p-hydroxyphenyl-4-vinylacetyl) propane and the like can be mentioned.

  Examples of the crosslinking site-containing monomer having an active chlorine group include o, m, p-hydroxystyrene, 2-chloroethyl vinyl ether, vinyl monochloroacetate, chloromethylstyrene, allyl chloride and the like.

  The polymerized unit based on the crosslinked site-containing monomer is preferably 10% by mass or less, more preferably 5% by mass or less, based on all the polymerized units constituting the uncrosslinked acrylic rubber. When the polymerized unit based on the cross-linking site-containing monomer is used in this range, cross-linking can be performed efficiently, the rubber elasticity is not lost, and the strength of the obtained molded article is excellent. When the amount of the polymerized unit based on the crosslinking site-containing monomer exceeds 10% by mass, the obtained composition may be cured and lose rubber elasticity.

  The uncrosslinked acrylic rubber has a polymerization unit based on an acrylate ester in an amount of 40 to 95% by mass based on all the polymerization units, and is a group including an active chlorine group and a hydroxyl group (however, a hydroxyl group included in a carboxyl group is excluded). It is preferable that the polymerization unit based on the monomer having at least one group selected from the above is 1 to 20% by mass. More preferably, the polymerization unit based on the acrylate is 50 to 90% by mass, and at least one group selected from the group consisting of an active chlorine group and a hydroxyl group (excluding the hydroxyl group contained in the carboxyl group). Is from 2 to 10% by mass based on a monomer having the formula:

  The uncrosslinked acrylic rubber may be copolymerized with other monomers copolymerizable with these monomers as long as the object of the present disclosure is not impaired. Examples of other copolymerizable monomers include, but are not limited to, alkyl vinyl ketones such as methyl vinyl ketone; vinyl ethers or allyl ethers such as vinyl ethyl ether and allyl methyl ether; styrene, α-methyl styrene Aromatic compounds such as styrene, chlorostyrene, vinyltoluene and vinylnaphthalene; Vinylnitrile such as acrylonitrile and methacrylonitrile; Ethylene such as acrylamide, propylene, butadiene, isoprene, pentadiene, vinyl chloride, vinylidene chloride, ethylene and vinyl propionate Unsaturated compounds.

  As the uncrosslinked acrylic rubber, ethylene acrylate rubber (AEM) is preferable. Ethylene acrylate rubber is a copolymer containing a polymerized unit based on a (meth) acrylate and a polymerized unit based on ethylene, and even a copolymer containing a polymerized unit based on a crosslinking site-containing monomer. Good. The Mooney viscosity at 100 ° C. (ML1 + 10 (100 ° C.)) of the ethylene acrylate rubber is preferably 10 to 50, and more preferably 12 to 35. The content of the polymerization unit based on the (meth) acrylate in the ethylene acrylate rubber is preferably 45 to 70% by mass, and more preferably 55 to 65% by mass. As the (meth) acrylate, at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate is preferable, and methyl (meth) acrylate is more preferable. It is also preferable that the ethylene acrylate rubber contains a polymerized unit based on a monomer containing a crosslinking site. The cross-linking site-containing monomer is not particularly limited, and includes a cross-linking site-containing monomer that can be contained in the above-mentioned uncross-linked acrylic rubber. In addition, the content of the polymerized unit based on the crosslinking site-containing monomer in the ethylene acrylate rubber may be 0.001 to 10% by mass, and may be 0.01 to 5% by mass.

  The uncrosslinked acrylic rubber can be obtained by copolymerizing the above monomers by a known method such as emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization.

  In the composition of the present disclosure, the mass ratio of the fluoropolymer to the uncrosslinked acrylic rubber (fluoropolymer / uncrosslinked acrylic rubber) is determined by the following formulas: Since a more excellent molded article can be obtained due to the amine property, the ratio is preferably from 99/1 to 40/60, and the low-temperature properties can be obtained without significantly impairing the amine resistance and the adhesion to acrylic rubber of the obtained molded article. Since it is remarkably improved, it is more preferably 96/4 or less, and since the low-temperature property is remarkably improved and the adhesiveness of the obtained molded article is remarkably improved, it is further preferably 92/8 or less. The amine resistance of the obtained molded article is remarkably improved without significantly impairing the low-temperature properties of the obtained molded article and the adhesion to acrylic rubber, and the tear strength is also improved. Since the, more preferably 70/30 or more. Surprisingly, even when the content of the fluoropolymer in the composition of the present disclosure is relatively high, the obtained molded article exhibits good adhesion to the acrylic 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 these, 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 above-mentioned organic peroxide with the fluorine-containing polymer and the uncrosslinked acrylic rubber, an organic peroxide impregnated with an inert inorganic powder or the like may be used.

  The above organic peroxides may be used in combination of two or more kinds.

  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 from 0 to 5 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 density becomes too high and the flexibility as a rubber is increased. In addition to the tendency to be economically unfavorable.

  The composition of the present disclosure preferably contains a crosslinking aid together with the organic peroxide. Examples of the crosslinking aid include triallyl cyanurate, triallyl isocyanurate, triallyl isocyanurate (TAIC), triacrylformal, triallyl trimellitate, N, N'-m-phenylenebismaleimide, dipropa 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, the uncrosslinked acrylic rubber, and the organic peroxide, 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 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, based on 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, and if the amount of the crosslinking aid is too large, the elongation of the molded article tends to decrease remarkably.

<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 them, selected from the group consisting of SAF-HS, SAF, N234, ISAF, ISAF-LS, ISAF-HS, N339, HAF-LS, HAS-HS, HAF, N351, LI-HAF, FEF, SRF and MT At least one of these is preferred.

The composition of the present disclosure can provide a molded article having further excellent low-temperature properties, adhesion to an acrylic rubber molded article, and amine resistance, and can provide a molded article having remarkably excellent tear strength. Therefore, it is preferable to contain carbon black having a nitrogen adsorption specific surface area (N ₂ SA) of 7 to 180 m ² / g and a dibutyl phthalate (DBP) or a paraffin oil absorption of 40 to 180 ml / 100 g.

From the viewpoint of improving the tear strength, the nitrogen adsorption specific surface area (N ₂ SA) of the carbon black is more preferably 70 m ² / g or more, further preferably 80 m ² / g or more, and particularly preferably. 90 m ² / g or more.
From the viewpoint of emphasizing amine resistance, the nitrogen adsorption specific surface area (N ₂ SA) of the carbon black is preferably less than 70 m ² / g, more preferably 30 m ² / g or less, further preferably 20 m ² / g or less. ² / g or less.

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

The dibutyl phthalate (DBP) or paraffin oil absorption amount of the carbon black is more preferably 50 ml / 100 g or more, further preferably 60 ml / 100 g or more, and particularly preferably 70 ml, from the viewpoint of improving tear strength. / 100 g or more.
The dibutyl phthalate (DBP) or paraffin oil absorption of the carbon black may be less than 50 ml / 100 g from the viewpoint of emphasizing amine resistance.
In addition, 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, the tear strength, low-temperature properties, since a molded article having more excellent adhesion and amine resistance to the acrylic rubber molded article is obtained, based on 100 parts by mass of the fluoropolymer, It is preferably from 5 to 100 parts by mass, more preferably from 8 to 50 parts by mass, even more preferably from 10 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, a wax, an antioxidant, 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 fluoropolymer, uncrosslinked acrylic 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 “fluorinated polymer molded article (A1)”) 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, or molding and crosslinking may be performed simultaneously.

  Examples of the molding method include, but are not limited to, 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. As the cross-linking method, a steam cross-linking method, an ordinary 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. The specific crosslinking conditions, which are not limited, may be appropriately determined usually within a temperature range of 140 to 250 ° C. and a crosslinking time of 1 minute to 24 hours depending on the type of the crosslinking agent to be used. Crosslinking may be performed in the order of primary crosslinking and secondary crosslinking. The primary crosslinking conditions include, for example, a temperature range of 150 to 180 ° C. and a crosslinking time of 2 to 60 minutes.

<Composite (1)>
The composite (1) of the present disclosure includes a fluoropolymer molded article (A1) and an acrylic rubber molded article (B). The composite (1) of the present disclosure exhibits relatively good low-temperature properties and adhesiveness because the fluoropolymer molded article (A1) is obtained by crosslinking the above composition. Shows excellent amine resistance.

  The acrylic rubber molded article (B) is obtained by crosslinking an acrylic rubber composition containing an uncrosslinked acrylic rubber.

  Examples of the uncrosslinked acrylic rubber include those similar to the uncrosslinked acrylic rubber contained in the composition of the present disclosure, and those similar to the suitable uncrosslinked acrylic rubber contained in the composition of the present disclosure are preferable. It is. Further, the uncrosslinked acrylic rubber is preferably one that can be peroxide crosslinked.

  In the composite (1) of the present disclosure, the fluoropolymer molded article (A1) and the acrylic rubber molded article (B) are adhered. The fluoropolymer molded article (A1) and the acrylic 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 (1) of the present disclosure, both can be directly bonded without providing an adhesive layer at the boundary between the fluoropolymer molded product (A1) and the acrylic rubber molded product (B). Further, the acrylic rubber composition can contain a polymer other than the uncrosslinked acrylic rubber. However, even if the acrylic rubber composition does not contain a fluorine-containing polymer, the acrylic rubber composition and the fluorine-containing polymer molded article (A1) can be used. And the acrylic rubber molded body (B).

  The acrylic rubber composition may further contain a crosslinking agent. As the cross-linking agent, compounds generally used as a cross-linking agent for acrylic rubber can be used. For example, organic ammonium-based cross-linking agents, zinc dithiocarbamate-based cross-linking agents, quaternary ammonium salt-based cross-linking agents, and metals At least one selected from the group consisting of a soap / sulfur-based cross-linking agent, a triazine-based cross-linking agent, a diamine-based cross-linking agent, a peroxide-based cross-linking agent, and a co-cross-linking agent / peroxide-based cross-linking agent is preferable. However, the present invention is not limited to this. When the uncrosslinked acrylic rubber contains a polymerized unit based on a monomer containing a crosslinking site, an appropriate crosslinking agent may be selected according to the monomer containing the crosslinking site.

  As the crosslinking agent, among these, an organic peroxide is preferable, since it can more firmly bond the fluoropolymer molded article (A1) and the acrylic rubber molded article (B). 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. is there.

  The content of the organic peroxide in the acrylic rubber composition is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 7 parts by mass, based on 100 parts by mass of the uncrosslinked acrylic rubber. is there.

  It is preferable that the acrylic rubber composition further contains a crosslinking aid. When the acrylic rubber molded article (B) is obtained by crosslinking an acrylic rubber composition further containing a crosslinking aid, the fluoropolymer molded article (A1) and the acrylic rubber molded article (B) It is possible to adhere more firmly.

  Examples of the crosslinking aid include those similar to the crosslinking aid contained in the composition of the present disclosure, and those similar to the suitable crosslinking aid contained in the composition of the present disclosure are preferable.

  The content of the crosslinking aid in the acrylic rubber composition is such that the fluoropolymer molded article (A1) and the acrylic rubber molded article (B) can be more firmly bonded 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 acrylic rubber composition may further contain carbon black. Examples of the carbon black include the same carbon blacks that can be included in the composition of the present disclosure, and the same preferable carbon blacks that can be included in the composition of the present disclosure are preferable.

  The acrylic rubber composition 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 acrylic rubber composition, 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 acrylic rubber composition may contain a processing aid such as a release agent and a plasticizer, a pigment such as an organic pigment and an inorganic pigment, a tackifier, a wax, an antioxidant, and the like.

  Thus, from the composition of the present disclosure, it is possible to obtain a fluoropolymer molded article that can be bonded to the acrylic rubber molded article (B) obtained by crosslinking the acrylic rubber composition containing the uncrosslinked acrylic rubber. it can. That is, the present disclosure relates to forming a fluoropolymer molded article (A1) used by bonding to an acrylic rubber molded article (B) obtained by crosslinking an acrylic rubber composition containing an uncrosslinked acrylic rubber. The use of a composition as described above.

  The composite (1) of the present disclosure may be a laminate including a layer formed from the fluoropolymer molded article (A1) and a layer formed from the acrylic rubber molded article (B). Also in such a laminate, both layers are firmly adhered.

  The composite (1) of the present disclosure is obtained by molding the composition of the present disclosure to obtain an uncrosslinked fluoropolymer molded article, and by molding the acrylic rubber composition to form an uncrosslinked acrylic rubber molded article. A process of obtaining a molded article, and by crosslinking an uncrosslinked fluoropolymer molded article and an uncrosslinked acrylic rubber molded article while contacting the two, the fluoropolymer molded article (A1) and the acrylic rubber molded article ( A step of obtaining a composite (1) to which B) is bonded can be suitably produced.

  In producing the composite (1) of the present disclosure, the composition of the present disclosure and the acrylic rubber composition may be molded by a compression molding method using a mold, an injection molding method, an injection molding method, or an extrusion molding method. And the like, but are not limited to these. As the cross-linking method, a steam cross-linking method, an ordinary 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. The specific crosslinking conditions, which are not limited, may be appropriately determined usually within a temperature range of 140 to 250 ° C. and a crosslinking time of 1 minute to 24 hours depending on the type of the crosslinking agent to be used.

  In addition, as a production method when the composite (1) of the present disclosure is a laminate, the composition of the present disclosure and the acrylic rubber composition are multilayer-extruded using an extruder to obtain a fluoropolymer. A step of obtaining an uncrosslinked laminate in which the molded article and the acrylic rubber molded article are bonded to each other, and crosslinking the uncrosslinked laminate to form a layer formed from the fluoropolymer molded article (A1) with the acrylic rubber molded article. Obtaining a laminate in which the layer formed from the body (B) is adhered.

<Composite (2)>
The composite (2) of the present disclosure is obtained by cross-linking a fluoropolymer composition containing a fluoropolymer and an organic peroxide (hereinafter sometimes referred to as “fluoropolymer composition (a2)”). And an acrylic rubber molded article (B) obtained by crosslinking an acrylic rubber composition containing an uncrosslinked acrylic rubber. The composites (2) of the present disclosure exhibit relatively good tear strength, low temperature properties and adhesion, as well as excellent amine resistance.

  In the composite (2) of the present disclosure, the fluoropolymer molded article (A2) and the acrylic rubber molded article (B) are adhered. The fluoropolymer molded article (A2) and the acrylic 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 (2) of the present disclosure, both can be directly bonded without providing an adhesive layer at the boundary between the fluoropolymer molded product (A2) and the acrylic rubber molded product (B). Further, the acrylic rubber composition can contain a polymer other than the uncrosslinked acrylic rubber. However, even if the acrylic rubber composition does not contain a fluoropolymer, the acrylic polymer composition has the same properties as the fluoropolymer molded article (A2). And the acrylic rubber molded body (B).

  The fluoropolymer molded article (A2) is obtained by crosslinking a fluoropolymer composition (a2) containing a fluoropolymer and an organic peroxide. The fluorine-containing polymer and the organic peroxide contained in the fluorine-containing polymer composition (a2) may be the same as the fluorine-containing polymer and the organic peroxide contained in the composition of the present disclosure. Preferred are the same fluorine-containing polymers and organic peroxides contained in the product.

  The fluoropolymer composition (a2) differs from the composition of the present disclosure in that it does not contain an uncrosslinked acrylic rubber as an essential component. The fluoropolymer composition (a2) may contain another polymer such as an uncrosslinked acrylic rubber. Examples of the uncrosslinked acrylic rubber include those similar to those contained in the composition of the present disclosure. As the content of the uncrosslinked acrylic rubber, without significantly impairing the low-temperature properties of the obtained molded article and the adhesiveness with the acrylic rubber, the amine resistance is significantly improved, and since the tear strength is also improved, Preferably it is 3% by mass or less, more preferably less than 1.0% by mass, further preferably 0.9% by mass or less, particularly preferably 0.5% by mass or less, most preferably 0.1% by mass or less. 1% by mass or less. In the composite (2) of the present disclosure, it is also preferable that the fluoropolymer composition (a2) does not contain an uncrosslinked acrylic rubber.

  The fluoropolymer composition (a2) may contain a crosslinking aid. Examples of the crosslinking aid include the same crosslinking aids that may be included in the composition of the present disclosure. 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, based on 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, and if the amount of the crosslinking aid is too large, the elongation of the molded article tends to decrease remarkably.

  The fluoropolymer composition (a2) may contain carbon black. Examples of the carbon black include those similar to the carbon black that can be contained in the composition of the present disclosure. The content of the carbon black is such that a molded article having more excellent low-temperature properties, adhesion to an acrylic rubber molded article and amine resistance can be obtained, and a molded article having remarkably excellent tear strength can be obtained. From the viewpoint, it is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, still more preferably 10 to 40 parts by mass, and particularly preferably 15 to 100 parts by mass with respect to 100 parts by mass of the fluoropolymer. ４０40 parts by mass.

  The fluoropolymer composition (a2) may include a filler. Examples of the filler include those similar to the filler that can be contained in the composition of the present disclosure.

  The fluoropolymer composition (a2) may contain a processing aid such as a release agent and a plasticizer, a pigment such as an organic pigment and an inorganic pigment, a tackifier, a wax, an antioxidant, and the like.

  For the production of the fluoropolymer composition (a2), a general rubber kneading apparatus can be used. 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.

  When producing the fluoropolymer composition (a2), the order in which the fluoropolymer, the organic peroxide, and other compounding agents are charged into the kneading apparatus is not particularly limited.

  The fluoropolymer molded article (A2) is obtained by crosslinking the fluoropolymer composition (a2). Further, the fluoropolymer molded article (A2) can also be obtained by molding and crosslinking the fluoropolymer composition (a2). The fluoropolymer composition (a2) 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, or molding and crosslinking may be performed simultaneously. As a molding method, a molding method similar to the molding method of the molded article of the present disclosure can be used.

  The acrylic rubber molded article (B) included in the composite (2) of the present disclosure may be the same as the acrylic rubber molded article (B) included in the composite (1) of the present disclosure. The same thing as the suitable acrylic rubber molding (B) with which the composite (1) is provided is preferable.

  The composite (2) of the present disclosure may be a laminate including a layer formed from the fluoropolymer molded article (A2) and a layer formed from the acrylic rubber molded article (B). Also in such a laminate, both layers are firmly adhered.

  The composite (2) of the present disclosure can be obtained by molding a fluoropolymer composition (a2) to obtain an uncrosslinked fluoropolymer molded article, and by molding the acrylic rubber composition to form an uncrosslinked polymer. A step of obtaining an acrylic rubber molded article, and, by bringing the uncrosslinked fluoropolymer molded article and the uncrosslinked acrylic rubber molded article into contact with each other, crosslinking the fluoropolymer molded article (A2) and the acrylic rubber A step of obtaining a composite (2) to which the molded article (B) is adhered;

  As a method of molding the fluoropolymer composition (a2) and the acrylic rubber composition when producing the composite (2) of the present disclosure, the same molding method as the method of producing the composite (1) of the present disclosure is used. Can be used.

  Further, as a production method when the composite (2) of the present disclosure is a laminate, a fluoropolymer composition (a2) and the acrylic rubber composition are multilayer-extruded using an extruder, A step of obtaining an uncrosslinked laminate in which the fluorinated polymer molded article and the acrylic rubber molded article are bonded to each other; and a step of crosslinking the uncrosslinked laminate to form a layer formed from the fluorinated polymer molded article (A2). A step of obtaining a laminate in which a layer formed from the acrylic rubber molded body (B) is adhered.

The fluorine-containing polymer molded body 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 the fields used include semiconductor-related fields, automotive fields, aircraft fields, space and rocket fields, marine fields, chemical fields such as chemical plants, chemical fields such as pharmaceuticals, photographic fields such as developing machines, printing machines and the like. Printing field, coating field such as coating equipment, analytical instruments, analytical instruments such as instruments, physical and chemical 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 gas delivery plate seals, wafer support seals, barrel seals, and packings are included. 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 plugs, 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, The present invention can be used for a battery substrate manufacturing device, a semiconductor transport device, and the like. Examples of such an apparatus include a gas control apparatus such as a CVD apparatus and a semiconductor gas control apparatus, a dry etching apparatus, a wet etching apparatus, a plasma etching apparatus, a reactive ion etching apparatus, a reactive ion beam etching apparatus, and a sputter etching. 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 formation 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, reflow An apparatus used in the process is exemplified.

  Specific usage forms 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 for storing devices such as semiconductor manufacturing equipment and wafers; Diaphragms for transferring chemicals used in semiconductor manufacturing processes. No.

In the automotive field, the engine body, main motion system, valve system, lubrication / cooling system, fuel system, intake / exhaust system, drive system transmission system, chassis steering system, brake system, basic electrical components, It can be used for electrical components such as system electrical components and equipment electrical components. Note that the automobile field includes a motorcycle.
In the 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 requiring 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 patterns 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-ring used for the tube body, fuel tube connector, injector, etc .; expiratory manifold, fuel filter, pressure regulating valve, canister, fuel tank cap, fuel pump, fuel tank, fuel tank sender unit, fuel Used for injection system, fuel high pressure pump, fuel line connector system, pump timing control valve, suction control valve, solenoid sub-assembly, fuel cut valve, 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 for 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 injector; an injector seal ring; a carburetor needle valve core valve; A piston; a valve seat of a combined air control device (CAC); a fuel tank main body; a sealing part for a solenoid valve.

  Specific uses of the brake system include a master back, a hydraulic brake hose, an air brake, a diaphragm used for an air brake brake chamber, and the like; 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) for master cylinders, brake cups; hydraulic brakes Master cylinders and vacuum boosters, boots for hydraulic brake wheel cylinders, and O-rings and grommets for anti-lock 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 use form in the control system electrical component, 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 examples of usage in the intake / exhaust system include packing used for an intake manifold, an exhaust manifold, and the like, and throttle body packing for a throttle; EGR (exhaust gas recirculation), pressure control (BPT), wastegate, turbowest. Gates, actuators, diaphragms used for variable turbine geometry (VTG) turbo actuators, 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, use as seals used in steam recovery canisters, catalytic converters, exhaust gas sensors, oxygen sensors, etc., as well as seals for solenoids and armatures in steam recovery and steam canisters; intake manifold gaskets, etc. Can be.
Further, in a part related to a diesel engine, it can be used as an O-ring seal for a direct 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 sealing 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 sealing 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, and camshaft oil seals.
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 / cooling system of an automobile engine, the engine oil cooler hose, oil return hose, and seal gasket of the engine oil cooler, the water hose around the radiator, the radiator seal, the radiator gasket, the radiator O-ring, and the vacuum pump In addition to a vacuum pump oil hose, it can be used for a radiator hose, a radiator tank, a diaphragm for oil pressure, 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, seal for sulfur oxide sensor, seal for temperature sensor, temperature sensor bush, seal for diesel particle filter sensor, 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 chip, 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, O-ring for car air conditioner, 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 site welt, bumper rubber, door latch, dash insulator, high tension cord, Flat belts, poly V belts, timing belts, toothed belts, V-ribbed belts, tires, wiper blades, diaphragms and plungers for LPG car regulators, diaphragms and valves for CNG car regulators, rubber parts for DME, diaphragms and boots for auto tensioners , Diaphragm and valve for idle speed control, actuator for automatic 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, and bladders used for vulcanization of tires.

In the above-mentioned aircraft field, space / rocket field, and marine 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, gaskets for hydraulic equipment, 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 anti-vibration pad, etc. Can be used.
In the marine field, for example, propeller shaft stern seals for screws, intake and exhaust valve stem seals for diesel engines, valve seals for butterfly valves, valve seats and shaft seals for butterfly valves, shaft seals for butterfly valves, stern tube seals , 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 and chemical fields include chemical equipment, chemical pumps and flow meters, chemical piping, heat exchangers, pesticide sprayers, pesticide transfer pumps, gas piping, fuel cells, Seals used in analytical equipment and physicochemical equipment (eg, column fittings for analytical equipment and instruments), shrink fittings in flue gas desulfurization equipment, nitric acid plants, power plant turbines, etc., 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 used for H-meter tube joints and glass cooler packing for sulfuric acid manufacturing equipment; Diaphragm pumps, diaphragms used for analytical instruments and physicochemical instruments; Gaskets used for analytical instruments and instruments; Analytical instruments and instruments Ferrules; Valve seats; U-cups; Linings used in chemical equipment, gas tanks, wind tunnels, etc .; Corrosion-resistant linings in anodizing tanks; Plating masking jig coatings; Analytical and scientific instruments Valve parts; expansion joints of flue gas desulfurization plants; acid-resistant hoses for concentrated sulfuric acid, chlorine gas transfer hoses, oil-resistant hoses, rainwater drain hoses for benzene and toluene storage tanks; chemical-resistant tubes used for analytical instruments and physical and chemical instruments 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 a copying machine, a belt of a copying machine, and OA equipment such as a copying machine, a printer, and a facsimile. Rolls (eg, 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 and 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 uses 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, heat exchange. Gaskets for equipment, diaphragms and packings for food processing equipment, rubber materials for food processing equipment (for example, 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 filler 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; dry cleaning equipment; Seals used for windows, etc .; cyclotron seals and (vacuum) valve seals, proton accelerator seals, automatic packaging machine seals, pump diaphragms 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 , 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 an additive for improving the properties, a fuel container for small generators and lawn mowers, a precoated metal obtained by subjecting a metal plate to a primer treatment, and the like. In addition, it can be impregnated into a woven fabric and baked to be used as a sheet and a belt.

  As a specific mode of use in the iron and steel field, there is an iron plate processing roll of iron plate processing equipment.

  Specific uses in the electrical field include insulating oil caps for bullet trains, venting seals for liquid-ring transformers, seals for transformers, jackets for oil well cables, seals for ovens such as electric furnaces, and window frames for microwave ovens. Seals, sealing materials used when bonding wedges of CRTs and necks, sealing materials for halogen lamps, fixing agents for electric components, sealing materials for terminal treatment of sheathed heaters, and insulation and moisture-proof treatment for lead terminals of electric equipment Sealing materials and the like. Also used for covering materials such as oil- and heat-resistant electric wires, high heat-resistant electric wires, chemical-resistant electric wires, high-insulation electric wires, high-voltage transmission lines, cables, electric wires used in geothermal power generators, electric wires used around automobile engines, etc. 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 tape used for joints and end portions of cables, materials used for heat-shrinkable tubes, and the like), and electric and It can also be used for electronic equipment materials (for example, lead wire materials 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, 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 radiating material, an electromagnetic wave shielding material, a gasket for a hard disk drive (magnetic recording device) of a computer, and the like. In addition, 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) binders, capacitor electrode active material binders, sealing agents, sealing agents, optical fiber quartz coating materials, optical fiber coating materials, electronic components, and circuit boards And coating / adhesive seals, fixing agents for electronic components, modifiers for sealants such as epoxy, coating agents for printed circuit boards, modifiers for prepreg resin for 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 transport 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 petroleum and gas, it is used as various sealing materials used when mining petroleum and natural gas, boots of electric connectors used in oil wells, and the like.
Specific uses in the energy resource exploration 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 for rotating blast prevention equipment (pipe wiper), seal material used for MWD (real-time drilling information detection system), gas-liquid connector, and logging used for logging equipment (logging equipment) Tool seals (for example, O-rings, seals, packings, gas-liquid connectors, boots, etc.), inflatable packers and completion packers 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 volume control seals, safety valves Seals, seals for hydraulic fracturing equipment, seals and packings for linear packers and hangers, seals and packings for wellheads, seals and packings for chalk and valves, seal materials for LWD (logging during drilling) And diaphragms used for oil exploration and drilling (eg, diaphragms for supplying lubricating oil such as oil drilling pits), gate valves, electronic boots, and seal elements for perforated guns.

  In addition, joint seals for kitchens, bathrooms, washrooms, 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 usage include a door seal, a gate valve, a pendulum valve, a solenoid tip, 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. under high temperature environment; Conveyor belts used for steelworks such as blast furnaces; Precision Conveyor belts for 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; transmission belts for transfer robots; toothed belts such as those for food machines 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 a typical example of a toothed belt for an automobile.

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 anti-vibration rubbers for automobiles include anti-vibration rubbers for engine mounts, motor mounts, member mounts, strut mounts, bushes, dampers, muffler hangers, center bearings, and the like.

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 pipes and piping equipment.They prevent vibration and noise generated from the piping system, 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 mitigation and prevention of 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 pipes, preferably used as a complex shape molded body such as for automobiles it can.
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 empty machine boots. It can be preferably used as a complex shaped article such as a boot for a pressure machine, a boot for a centralized lubricator, a boot for transferring liquid, a boot for fire fighting, a boot for transferring various liquefied gases, and various industrial boots.

  The fluoropolymer molded article of the present disclosure and the composite of the present disclosure can be used as a diaphragm for a filter press, a diaphragm for a blower, a diaphragm for a water supply, a diaphragm for a liquid storage tank, a diaphragm for a pressure switch, a diaphragm for an accumulator, and an air spring such as 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 in an environment wet with water such as rain, snow, ice and sweat. Agent is obtained.

  In addition, the fluoropolymer molded article of the present disclosure and the composite of the present disclosure are used to produce, for example, a decorative plywood, a printed board, an electrical insulating board, a rigid polyvinyl chloride laminated board or the like made of a melamine resin, a phenol resin, an epoxy resin, or 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 weapons-related sealing gaskets, protective clothing against contact with invasive chemicals. Can also.

  Lubricating oils containing engine additives (especially amine additives used as antioxidants and detergents and 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 or a lining material.

  A coating material for heat-resistant and oil-resistant electric wires used for lead wires of sensors that contact transmission oil and / or engine oil of internal combustion engines for automobiles and detect the oil temperature and / or oil pressure, and for automatic transmissions and engines 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. 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, Uses include synthetic fiber coating, bolt members or joints having a thin packing coating layer.

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

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 and baking woven sheets and belts;
The composition of the present disclosure can be used as a sealing material, a lining, or a sealant having a complicated shape by ordinary use by increasing the viscosity and the concentration of the composition. 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 of a woven fabric or a paper sheet, a printing belt, a chemical resistant tube, a chemical 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 nonwoven 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.
The coating formed from the composition of the present disclosure can be used in fields where heat resistance, solvent resistance, lubricity, and non-adhesiveness are required.Specific applications include copying machines, printers, and facsimiles. Rolls (for example, fuser 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 various materials, sealing materials and linings for pipes, metals, ceramics, glass, stone, concrete, plastic, rubber, wood, paper, fibers and the like. 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. Coatings for fuel tank pressure sensor diaphragms, coatings for oil and fuel filter seals, coatings for fuel tank sender seals and sender head fitting seals, coatings for copier fuser rolls, and polymer coating compositions. 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 friction 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 multi-layer 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.

  While the embodiments have been described, it will be understood that various changes in form and detail are possible without departing from the spirit and scope of the claims.

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

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

<Crosslinking characteristics (minimum torque (ML), maximum torque (MH), induction time (T10), proper crosslinking time (T50), and optimal crosslinking time (T90))>
For the fluorine-containing polymer composition, a crosslinking curve at 160 ° C. for 30 minutes was obtained at the time of primary crosslinking using a vulcanization tester (MDR H2030 manufactured by M & K Corporation), and the minimum torque (ML), the maximum torque (MH), and the torque were determined. , The induction time (T10), the appropriate crosslinking time (T50) and the optimum crosslinking time (T90) were determined.

<100% modulus, tensile strength and elongation at break>
Using the crosslinked sheet obtained in the experimental example, using a tensile tester (Tensilon RTG-1310 manufactured by A & D Corporation), under the conditions of 500 mm / min according to JIS K6251-1: 2015. 100% modulus at 23 ° C., tensile strength and elongation at break were measured with Dumbbell No. 5.

<Tear strength (trouser shape)>
Using the crosslinked sheet obtained in the experimental example, measurement was performed at a test speed of 100 mm / min in accordance with JIS K6252-1: 2015 (test piece: trouser type).

<Hardness>
Hardness (Peak value, value after 1 sec, and after 3 sec) using three types of the crosslinked sheets obtained in the experimental examples and using a type A durometer according to JIS K6253-3: 2012. Was measured.

<Density>
It was determined according to JIS K6268 using the crosslinked sheet obtained in the experimental example.

<Low temperature characteristics (TR10)>
It measured according to JISK6261: 2006 using the crosslinked sheet obtained by the experimental example.

<Diethanolamine resistance>
An immersion test was performed at 120 ° C. for 72 hours using the crosslinked sheet and diethanolamine obtained in the experimental examples. The volume and mass of the test piece before and after the immersion test were measured, and the volume swelling ratio (ΔV) was obtained. The volume swelling rate (ΔV) is the rate of change of the volume after the test piece is immersed under predetermined conditions (representing the degree of swelling). The original volume of the test piece is Vo, and the volume after the test is V. Then, ΔV = (V−Vo) / Vo × 100.

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): 99, glass transition temperature : -13 ° C, iodine content: 0.18% by mass)
Fluorine-containing elastomer (2):
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 is −6 ° C., iodine Content: 0.23% by mass)

Acrylic rubber (1):
Product name "Vamac DP", manufactured by DuPont

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):
Diatomaceous earth impregnated with triallyl isocyanurate at 60% by mass (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)

Processing aid (1):
stearic acid

Experimental Examples 1 to 11
Each component was blended according to the formulation in Table 1, and kneaded on an open roll to prepare a sheet-like fluoropolymer composition having a thickness of 2.5 mm. Table 1 shows the crosslinking properties of the obtained fluoropolymer composition.
The obtained fluoropolymer composition was placed in a mold having a thickness of 2.0 mm and press-crosslinked at 160 ° C. for the time shown in Table 1 to prepare a crosslinked sheet (2.0 mm thick). Table 1 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 sheet-like acrylic rubber compositions A and B having a thickness of 2.5 mm.

Acrylic rubber composition A:
Acrylic rubber (1) 100 parts by mass FEF carbon 30 parts by mass Crosslinking aid (1) 3.3 parts by mass Organic peroxide (1) 5 parts by mass Processing aid (1) 0.5 parts by mass

Acrylic rubber composition B:
Acrylic rubber (1) 100 parts by mass ISAF carbon 30 parts by mass Crosslinking aid (1) 3.3 parts by mass Organic peroxide (1) 5 parts by mass Processing aid (1) 0.5 parts by mass

  Next, the sheet-like fluorine-containing polymer composition obtained above and the sheet-like acrylic rubber composition A or B obtained above are overlapped with each other, and further used for gripping at the time of a peel test. An FEP film (thickness: 150 μm) was sandwiched between one end and about 1 to 1.5 cm of the interface to make a non-adhesive portion. The obtained composite (laminated body) was inserted into a mold having a thickness of 4 mm, and press-crosslinked at 160 ° C. for 30 minutes to obtain a sheet-shaped 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. Using a tensile tester (Tensilon RTG-1310 manufactured by A & D Co., Ltd.) for this test piece, citing a peel test between rubber and cloth according to JIS K6256-1, at 50 ° C./min at 23 ° C. The test was performed at the tensile speed, and the average of the five maximum points in the elongation-tensile strength graph was determined as the adhesive strength (N / cm). The state of peeling was observed and evaluated according to the following criteria. Table 1 shows the results.
X1: When the tensile tester showed the adhesive strength shown in Table 1, the layer formed from the fluoropolymer composition was broken.
X2: When the tensile tester showed the adhesive strength shown in Table 1, the layer formed from the acrylic rubber composition was broken.
Y: Each layer peeled off at the interface without material destruction of each layer, and the surface of each layer after peeling was rough.
Z: Each layer peeled off at the interface without material destruction of each layer, and the surface of each layer after peeling was smooth.

  As the results of Experimental Example 1 show, a composite comprising a fluoropolymer molded article obtained by crosslinking a fluoropolymer composition containing a specific fluoropolymer and an organic peroxide, and an acrylic rubber molded article The body was very good in amine resistance and also excellent in tear strength, adhesion and low temperature properties.

As shown in the results of Experimental Examples 2 to 4, the composition containing the specific fluorine-containing polymer, uncrosslinked acrylic rubber and organic peroxide has excellent amine resistance and relatively good tear strength. Was obtained, and a composite having practically acceptable adhesiveness was obtained. Further, as shown by the results of Experimental Examples 2 to 4 and the result of Experimental Example 1, when the composition contained an uncrosslinked acrylic rubber, the low-temperature characteristics of the obtained molded article were improved.
Further, as shown in the results of Experimental Examples 3 and 4 and the result of Experimental Example 2, when the ratio between the fluoropolymer and the uncrosslinked acrylic rubber was appropriately adjusted, the adhesiveness of the obtained composite was significantly improved. .

  As shown in the results of Experimental Examples 10 to 11, even when the type of carbon black contained in the composition was changed, the composition was excellent in amine resistance, and excellent in tear strength, adhesiveness, and low-temperature properties. A molded article was obtained. Furthermore, as the result of Experimental Example 11 shows, when carbon black having a specific nitrogen adsorption specific surface area and a specific amount of dibutyl phthalate (DBP) absorption was used, the obtained molded article showed extremely large tear strength.

  On the other hand, as the results of Experimental Examples 6 to 9 show, a molded article obtained by crosslinking a conventional fluoropolymer composition containing no specific fluoropolymer and containing a conventional fluoropolymer has an amine resistance In addition, tear strength, low-temperature properties, and adhesion to an acrylic rubber molded product were not balanced.

Claims (10)

Contains fluorine-containing polymer, uncrosslinked acrylic 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 acrylic 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 a mass ratio of the fluoropolymer to the uncrosslinked acrylic rubber (fluoropolymer / uncrosslinked acrylic rubber) is from 99/1 to 40/60.   A fluoropolymer molded article obtained by crosslinking the composition according to claim 1. An acrylic rubber obtained by cross-linking a fluoropolymer molded article (A1) obtained by cross-linking the composition according to any one of claims 1 to 6, and an acrylic rubber composition containing an uncross-linked acrylic rubber. And a molded body (B),
A composite in which a fluoropolymer molded article (A1) and an acrylic rubber molded article (B) are adhered.   Claims 1 to form a fluoropolymer molded article (A1) used by bonding to an acrylic rubber molded article (B) obtained by crosslinking an acrylic rubber composition containing an uncrosslinked acrylic rubber. Use of the composition according to any one of claims 6 to 10. Obtained by cross-linking a fluoropolymer molded article (A2) obtained by cross-linking a fluoropolymer composition containing a fluoropolymer and an organic peroxide, and an acrylic rubber composition containing an uncrosslinked acrylic rubber. Acrylic rubber molded body (B)
The fluoropolymer molded article (A2) and the acrylic rubber molded article (B) are adhered,
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 complex containing a fluorine-containing monomer (1) unit represented by the formula: