TW201229072A - Crosslinkable fluororubber composition and crosslinked rubber article - Google Patents

Abstract

The purpose of the present invention is to provide: a crosslinkable fluororubber composition which enables the production of a crosslinked rubber article having both excellent chemical resistance and excellent heat resistance; and a crosslinked rubber article produced using the crosslinkable fluororubber composition. A crosslinkable fluororubber composition which comprises a fluororubber and a fluoropolymer (P) that has a repeating unit derived from a fluorodiene (b) having unsaturated side chain residual performance and also has multiple polymerizable double bonds; and a crosslinked rubber article produced by crosslinking the crosslinkable fluororubber composition.

Description

201229072 VI. Description of the Invention: c Technical Field of Invention 3 Field of the Invention The present invention relates to a crosslinkable fluororubber composition and a crosslinked rubber article. [Background of the Invention 3] In the method of crosslinking a fluororubber to obtain a crosslinked rubber article, it is known that: (1) an organic peroxide is used, and a radical is generated and crosslinked by heating. Method; (2) a method of irradiating a fluororubber to irradiate a radical to form and crosslink a radical; and (3) a method of crosslinking by using a cross-linking agent such as a polyol cross-linking and a cross-linking of a polyamine. In the methods (1) and (2), in order to constrain the crosslinking property of the fluororubber and the improvement of the properties of the obtained crosslinked rubber article, a crosslinkable fluororubber composition having a polyfunctional compound blended therein is used. Crosslinking aid. For example, a cross-linking fluororubber composition in which triallyl isocyanurate (TAIC) has been blended is known as a cross-linking aid (see Non-Patent Document 1 and Patent Document 1). By using TAIC as a crosslinking aid, the crosslinking speed of the fluororubber can be increased. Moreover, the crosslinked rubber article produced by the methods (1) and (2) is used in comparison with the crosslinked rubber article produced by the method (3), using the crosslinkable fluororubber composition. Good resistance (especially amine resistance). However, in the crosslinkable fluororubber composition described above, it is difficult to obtain a crosslinked rubber article having remarkably excellent heat resistance. CITATION LIST Patent Literature No. 201229072 Patent Document Patent Literature 1: Japanese Patent Publication No. Hei 7_1797 No. 5 Non-Patent Literature Non-Patent Document 1: Lichuan, Good Resin Handbook 616 to 622, and 577 to 578 (Japanese Journal of Industry, 1990) SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION An object of the present invention is to provide a crosslinkable fluororubber composition capable of imparting a crosslinked rubber article having both good chemical resistance and heat resistance, and to crosslink the crosslinked fluororubber A crosslinked rubber article made of a fluororubber composition. MEANS FOR SOLVING THE PROBLEMS The present invention has the following constitutions in order to solve the above problems. [1] A crosslinkable fluororubber composition comprising a fluororubber and a fluoropolymer (P) having a plurality of polymerizable double bonds, the fluoropolymer (P) having a source derived from an unsaturated side A fluoropolymer of a repeating unit of a chain residual fluorodiene (b). [2] The cross-linkable fluororubber composition according to [1], wherein the fluoropolymer (P) has a repeating unit derived from fluoromonoolefin (a) and a residue derived from an unsaturated side chain a fluoropolymer of a repeating unit of fluorodiene (b). [3] The cross-linking fluororubber composition as described in [2], wherein the fluoromonoolefin (a) is selected from the group consisting of tetrafluoroethylene, chloroethylene, and CF2=CFO-Rfl (wherein Rfl is one or more selected from the group consisting of a fluoroalkyl group having 1 to 6 carbon atoms or a fluoroalkyl group having 2 or more carbon atoms having one or more inert oxygen atoms between carbon atoms and carbon atoms. The cross-linking fluororubber composition according to any one of [1] to [3], wherein the fluorodiene (b) is selected from the following fluorodiene (M) to (b3) One or more of the groups formed. (b1) CF2=CFO-Qfl-OCF=CF2; (b2) CH2=CFCF20-Qf2-0CF2CF=CH2; (b3) CH2=CFCF20-Qf3-0CF=CF2; (wherein, Qfl&Qf2 are independently carbon The fluoroalkyl group having 3 to 8 or the fluoroalkyl group having 3 to 8 carbon atoms having one or more etheric oxygen atoms between carbon atoms and carbon atoms.

Qf3 is a fluorine alkyl group having 1 to 6 carbon atoms or a fluorine alkyl group having 2 or more carbon atoms having one or more etheric oxygen atoms between carbon atoms and carbon atoms. [5] The crosslinkable fluororubber composition according to any one of [1] to [4], wherein the fluoropolymer (P) has a weight average molecular weight of 3,000 to 50,000. [6] The crosslinkable fluororubber composition according to any one of [1] to [5], wherein the content of the polymerizable double bond in the above-mentioned II polymer (P) is 0.2 to 2 mmol/g. [7] The cross-linking fluororubber composition according to any one of the above-mentioned fluororubbers, wherein the fluoropolymer (P) is contained in an amount of from 1 to 50 parts by mass based on 100 parts by mass of the fluororubber. [8] The crosslinkable fluororubber composition according to any one of [1] to [7] wherein the fluororubber is selected from the group consisting of tetrafluoroethylene/propylene copolymer, vinylidene fluoride/tetrafluoroethylene One or more of the group consisting of a hexafluoropropylene copolymer and a tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer. [9] The crosslinkable fluororubber composition according to any one of [1] to [8] further comprising an organic peroxide. 201229072 [10] A cross-linked rubber article which is obtained by crosslinking a cross-linking fluororubber composition as described in [1] or [2]. [11] The crosslinked rubber article according to [10], which is a sealing material. EFFECTS OF THE INVENTION The crosslinked fluororubber composition of the present invention can produce a crosslinked rubber article having both good chemical resistance and heat resistance. Further, since the crosslinked rubber article of the present invention is produced by crosslinking the crosslinkable fluororubber composition of the present invention, it has both good chemical resistance and heat resistance.

[Embodiment] J is a form for carrying out the invention < Crosslinkable fluororubber composition >

The crosslinkable fluororubber composition of the present invention contains a fluororubber and a composition having a plurality of polymerizable double bonds and a fluoropolymer (p) described later as essential components. [Fluoropolymer (PXI fluoropolymer (Ρ) in the cross-linking fluororubber composition of the present invention acts as a crosslinking assistant. That is, the fluoropolymer (Ρ) is by light or heat The induced radical is combined with the fluororubber to impart a crosslinked rubber article belonging to the three-dimensional crosslinked product. The fluoropolymer (Ρ) is a repeating unit having a fluorodiene (b) derived from residual side chain residues. a fluoropolymer having a plurality of polymerizable double bonds (carbon-carbon double bonds) in a molecule. The fluoropolymer (P) has a repeating unit derived from a fluoromonoolefin and a residue derived from an unsaturated side chain. The fluoropolymer of the repeating unit of the fluorodiene (b) is preferably 6 201229072 (fluoromonoolefin (a)) lL monoolefin (a) is a fluorine-containing compound having a single polymerizable double bond in the molecule. The monoolefin (a) includes, for example, tetrafluoroethylene (TFE), trifluoroethylene, gas trifluoroethylene (CTFE), and vinyl fluoride such as vinylidene fluoride, and hexafluoropropylene, and CFfCFO-R; (In the formula, Rfi is a fluoroalkyl group of carbon number 6 or a fluoroalkyl group having 2 or more carbon atoms having 1 or more etheric oxygen atoms between carbon atoms and carbon atoms) (hereinafter referred to as "fluoromonoolefin (al)"), etc. In the present invention, the fluoroalkyl group means a group in which one or more hydrogen atoms in the alkyl group are substituted by a fluorine atom. - a fluoroalkyl group having one or more etheric oxygen atoms between carbon atoms, wherein one or more hydrogen atoms having one or more etheric oxygen atoms between carbon atoms and carbon atoms are replaced by fluorine atoms Further, the perfluoroalkyl group means a group in which all hydrogen atoms of the alkyl group are replaced by fluorine atoms. The fluoromonoolefin (a) is preferably selected from the group consisting of TFE, CTFE, and fluoromonoolefin (ai). One or more of the group is formed. If TFE is used as the fluoromonoolefin (a), the fluidity of the fluoropolymer (p) can be improved, and a crosslinked rubber article having particularly excellent heat resistance can be obtained. Use of CTFE as fluorine monosulfide (a) 'When using fluorinated vinylene copolymerized fluororubber as fluororubber, 'because of its good compatibility, it can improve the crosslinking efficiency. If fluoromonoolefin (al) is used as the fluorine single The alkene (a) can make the viscosity of the fluoropolymer (p) low and facilitate the manufacture of a crosslinkable fluororubber composition. It is preferably 1 to 5, and preferably 1 to 3. As long as the carbon number is within the range, it can be used as a fluororubber without reducing the fluidity of the fluoropolymer (P) and the heat of 201229072. The auxiliary agent acts. The fluorine extending base of Rn may be linear or branched. From the viewpoint of the heat resistance of the crosslinked rubber article, the Rfl of the fluoromonoolefin (al) is an alkyl group. It is preferred that all of the hydrogen atoms are replaced by fluorine atoms. That is, as the fluorine monoolefin (al), CF2=CFO-Rfi (wherein RF1 is a carbon number of a perfluoroalkyl group, or a carbon atom- A perfluorovinyl ether (hereinafter referred to as "fluoromonoolefin") which is a perfluoroalkyl group having 2 or more carbon atoms of one or more etheric oxygen atoms between carbon atoms is preferable. From the viewpoint of further improving the fluidity of the fluoropolymer (p), it is preferred that the combination of TFE and fluoromonene (al) is used in combination with the case of using them alone. From the viewpoint of the fluidity of the fluoropolymer (P) and the heat resistance of the crosslinked rubber article, the fluoromonoolefin (a) is preferably a perfluoromonomer, the TFE is preferably a fluoromonoolefin, and the TFE is alone. It is preferred to use or use TFE in combination with fluoromonoolefin (a 11). The fluorine*monoolefin (a) may be used alone or in combination of two or more. (Fluorodiene (b)) The fluorodiene (b) is a fluorine-containing compound having an unsaturated side chain residual property of two polymerizable double bonds in the molecule. That is, the fluorodiene (b) is a compound in which at least a part of the two polymerizable double bonds do not contribute to the polymerization reaction and the double bond remains after the polymerization in the polymerization for producing the fluoropolymer (P). Specifically, two of the polymerizable double bonds of either of the fluorodiene (b) form a main chain after polymerization. At least a part of the other polymerizable double bond does not contribute to the polymerization reaction and remains as an unsaturated side chain in the fluoropolymer (P). By using the fluorodiene (b), the unsaturated side chain remains in the fluoropolymer (P), and by using the crosslinking reaction of the unsaturated side chain, the crosslinked rubber 8 201229072 can be obtained. The olefin (b) 'is, for example, an all-carbon atom composed of a pure atom of a carbon atom, or a fluorine-based auditory composition, and a fluorine-substituted one of the above-mentioned slit diene; for example, 氟 _ μ攸(10) Ten points of view, ^, from the cross-linked rubber articles heat-resistant ^ fluorofluoro-ene is better, from the fluoropolymer (ρ) fluidity, ^ cross-linked rubber articles resistance and heat resistance From the point of view of sex, it is better to use perfluorodiazole consisting of slaves, children, fluorine atoms and oxygen atoms. In the mouse-dilute (b), the number of atoms connecting the two polymerizable double bonds (total of carbon atoms) is preferably 5 to 1 Å, and preferably 5 to 8. The number of atoms in the right chain is above the lower limit value, and in the production of the I polymer (the polymerization process can inhibit the polymerization of two polymerizable double bonds in the molecule to cause intramolecular cyclization) and the polymerizable double bond It is easy to remain in the fluoropolymer (P) as an unsaturated side chain. Further, if the number of atoms of the linking chain is less than the upper limit, the polymerizable double bond remaining in the side chain of the fluoropolymer (P) is present. The storage towel of the crosslinked fluororubber composition of the present invention is less likely to cause a crosslinking reaction, so that it is difficult to form a high molecular weight or gelation of the fluoropolymer (p), thereby being light (four) when kneaded with the fluororubber. (4) The fluidity of the polymer (p) is significantly decreased. Further, the fluorodiene (9) having a number of atoms in the chain below the upper limit can be easily synthesized and purified in high purity. From the prevention of the flow of the fluoropolymer (P) From the point of view of excessive decline in sex, it is preferable that the gas (2) is a compound having no ring structure. As the gas dilute (nine), it is preferred to use the following fluorodicarbon (b1) to (b3). (bl) CF2=CF〇 -Qf,-〇CF=CF2 ; 201229072 (b2) CH2=CFCF2〇-Qf2-〇CF2CF=CH2 ; (b3) CH2=CFCF20-Qf3-0 CF=CF2. In the formula, Qfl and Qf2 are independently a fluoroalkyl group having 3 to 8 carbon atoms, or a carbon number of 3 to 8 having one or more etheric oxygen atoms between carbon atoms and carbon atoms. Fluorine alkyl.

Qf 3 is a fluorine alkyl group having 1 to 6 carbon atoms or a fluorine alkyl group having 2 to 6 carbon atoms having one or more etheric oxygen atoms between carbon atoms and carbon atoms. In the present invention, the fluoroalkyl group means a group in which one or more hydrogen atoms in the alkylene group are substituted by a fluorine atom. In addition, the fluorine-extended alkyl group having one or more etheric oxygen atoms between carbon atoms and carbon atoms means one or more alkylene groups having one or more etheric oxygen atoms between carbon atoms and carbon atoms. A group in which a hydrogen atom is replaced by a fluorine atom. Further, the perfluoroalkylene group means a group in which all hydrogen atoms of the alkylene group are replaced by fluorine atoms. The Qfl, and the fluorine alkyl group in the fluorodiene (b1) to (b3) may have a branched structure.

The fluorine atom of Qfl is preferably 3 to 6 carbon atoms.

The number of carbon atoms of the fluorine alkyl group of Qn is preferably from 3 to 6. The carbon atom number of the fluorine alkyl group of Q1 " 3 is preferably 2 to 5. As the fluorodiene (bl), the following fluorodiene (bll) and (bl2) are preferred. (bll) CF2=CFO-Qf, 1-OCF=CF2; (bl2) CF2=CFOCH2-Qf12-CH2OCF=CF2. However, in the formula, it is a perfluoroalkylene group having 3 to 8 carbon atoms or a perfluoroalkylene group having 3 to 8 carbon atoms having one or more etheric oxygen atoms between carbon atoms and carbon atoms. QFI2 is a perfluoroalkylene group having 2 to 6 carbon atoms or a perfluoroalkylene group having 2 to 6 carbon atoms which has one or more etheric oxygen atoms between carbon atoms and carbon atoms. Specific examples of the fluorodiene (b11) include the following compounds. CF2=CFO(CF2)4OCF=CF2; CF2=CFO(CF2)5OCF=CF2; CF2=CFO(CF2)6OCF=CF2; and CF2=CFO(CF2)4OCF(CF3)CF2OCF=CF2. Specific examples of the fluorodiene (M2) include the following compounds. CF2=CFOCH2(CF2)2CH2OCF=CF2; and CF2=CFOCH2(CF2)4CH2OCF=CF2. As the fluorodiene (b2), the following fluorodiene (b21) is preferred. (b21) CH2=CFCF20-QF21-0CF2CF=CH2. However, in the formula, QF21 is a perfluoroalkylene group having 3 to 8 carbon atoms or a perfluoroalkylene group having 3 to 8 carbon atoms having one or more etheric oxygen atoms between carbon atoms and carbon atoms. Specific examples of the fluorodiene (b21) include the following compounds. Ch2=cfcf2o(cf2)2ocf2cf=ch2; ch2=cfcf2o(cf2)3ocf2cf=ch2; ch2=cfcf2o(cf2)4ocf2cf=ch2; and ch2=cfcf2o(cf2)2ocf(cf3)cf2ocf2cf=ch2 and so on. As the fluorodiene (b3), the following fluorodiene (b31) is preferred. (b31) CH2=CFCF20-QF31-0CF=CF2. In the formula, QF31 is a perfluoroalkylene group having 1 to 6 carbon atoms or a perfluoroalkylene group having 2 to 6 carbon atoms having one or more etheric oxygen atoms between carbon atoms and carbon atoms. Specific examples of the fluorodiene (b31) include the following compounds. CH2=CFCF2OCF(CF3)CF2OCF=CF2; and 11 201229072 CH2=CFCF2OCF(CF3)CF2OCF(CF3)CF2OCF=CF2. When synthesized from a fluoropolymer (P), the polymerizable double bond has a viewpoint of tending to remain moderately polymerizable in the side chain, and a crosslinked rubber article having a relatively good heat resistance can be obtained from the viewpoint of fluorodiene. (b) fluorodiene (bl) is preferred, and fluorodiene (bll) is more preferred. The fluorodiene (b) may be used alone or in combination of two or more. The fluoropolymer (P) has a repeating unit mainly composed of fluorodiene (b), and at least a part of the repeating unit derived from the fluorodiene (b), an unsaturated side chain having a polymerizable double bond remains. . For example, when cf2=cf-o-(cf2)4-o-cf=cf2 is used as the fluorodiene (b), the obtained fluoropolymer (P) has at least a residue represented by the following formula having a polymerization. Repeating unit of the unsaturated side chain of a double bond. [Chemical 1] F2 / C, c〆

I 〉C(=2)4

The weight average molecular weight (hereinafter referred to as "Mw") of the fluoropolymer (P) of V f2C is preferably 3,000 to 50,000, more preferably 10,000 to 30,000. When the Mw of the fluoropolymer (?) is at least the lower limit value, the heat resistance of the crosslinked fluororubber article obtained by curing the crosslinkable fluororubber composition is improved. In addition, when the Mw of the fluoropolymer (P) is at most the upper limit, when the crosslinkable fluororubber composition is produced, it is easier to mix and disperse into the fluororubber. Thereby, it is easy to form into a desired shape, and it is easy to suppress the deviation of the characteristics of the crosslinked rubber article due to flow unevenness. 12 201229072 By setting the fluoropolymer to a high Mw within the aforementioned range, Crosslinked rubber articles having higher heat stability can be easily produced. The 'Mw of the present invention and the number average molecular weight (hereinafter referred to as "Μη") refer to the use of Asahi Glass Co., Ltd. ASAHIKLIN AK-225SEC grade 1 (dioxane and hexafluoroisopropanol mixed solvent (two gas five) Fluoropropane/hexafluoroisopropanol = 99/1 (volume ratio))) was calculated as a solvent by gel permeation chromatography (GPC) in terms of molecular weight in terms of hydrazine (polymethyl methacrylate). The content of the polymerizable double bond remaining in the side chain in the fluoropolymer (yttrium) is preferably 0.2 to 2 mmol/g, more preferably 5 to 1.5 mm 〇i/g. The content of the above polymerizable double bond can be calculated by measurement by FI9-NMR. When the content of the polymerizable double bond is at least the lower limit value, the crosslinkable fluororubber composition can be easily crosslinked easily when it is cured, and it is easy to obtain a parent-linked rubber article having good heat resistance. In addition, when the content of the polymerizable double bond is at most the upper limit value, it is easy to suppress a decrease in heat resistance due to decomposition of unreacted polymerizable double bonds remaining in the crosslinked rubber article after curing, and it is easy to prevent fluorine The gelation caused by the crosslinking reaction in the production of the polymer (P) or the decrease in fluidity due to the high molecular weight. (Synthesis of fluoropolymer (P)) The fluoropolymer (P) can be obtained by polymerizing fluorodiene (b) alone or by copolymerizing fluoromonoolefin with fluorodiene (b), either alone or in combination. At the time of polymerization, a part of the polymerizable double bond of the fluorodiene (b) does not contribute to the reaction and remains as a side chain. The polymerization method in which the fluorodiene (b) is polymerized alone or the fluoromonoolefin (a) and the fluorodiene (b) are copolymerized is not particularly limited, and suspension polymerization, solution polymerization, and emulsification polymerization of 13 201229072 may be employed. A known polymerization method such as polymerization. Among them, solution polymerization is particularly preferable from the viewpoint of being polymerizable in a solvent-diluted state and suppressing the crosslinking reaction between molecules due to the polymerizable double bond remaining in the side chain. The solution polymerization is a polymerization method in which a gas-diene (b) is separately added to a polymerization initiator in a polymerization solvent, or a polymerization method in which a fluoromonoolefin (a) and a fluorodiene (b) are polymerized is added. As the polymerization solvent for solution polymerization, a fluorine-containing solvent in which the produced fluoropolymer (P) is soluble is preferable. Examples of the fluorine-containing solvent include: difluoropentafluoride (HCFC-225), CF3CH2CF2H (HFC-245fa), CF3CF2CH2CF2H (HFC-365mfc), perfluorohexane, perfluorooctane, all-i, (2-T^ © ^Il(=-T®).CF3CF2CF2CF2CF2CF2H ^ CF3CH2OCF2CF2H, CF3CH2OCH2CF3, and CF3CF2OCF2CF2OCF2CF3, etc. In the synthesis of fluoropolymer (P), the following methods are preferred, namely: no _ people make fluorine 晞 (b) Or the fluoromonoolefin (a) reacts with the total amount of fluorodiene (b) and uses all of the amount of the towel to be pre-injected into the reaction vessel to start the polymerization reaction. Then, during the polymerization reaction Adding the remaining fluoromonoolefin (a) and fluorodiene (b) one by one to carry out polymerization. Thereby, the molecular weight distribution and composition distribution of the obtained polymer (p) can be narrowed, and the fluoropolymer is easily reduced. (P) The content of the low molecular weight component of the molecular weight of less than 1 , can also increase the yield of the fluoropolymer. The polymerizable property per molecule of the low molecular weight component is compared with the component having a molecular weight of 1 GGG or more. The content of the double bond is reduced. When the polymerizable double bond is used for the hardening reaction, it is generally accompanied by volume shrinkage. Therefore, by reducing the inclusion of the low molecular weight of 14 201229072 ^, it is easier to uniformly carry out the hardening reaction to obtain a crosslinked rubber article having good thermal stability and dimensional stability. In the fluoropolymer (P) The content of the second low molecular weight component is preferably less than 10% by mass, less than preferably. 5% by weight, in the copolymerization of the fluoromonoolefin (a) and the fluorodiene (b), in addition to the low molecular weight component described above. 'In particular, the eight-denier-derived repeating unit derived from IL-diene (8) may have a component that does not form a cross-linking aid on the parent-child Babe. However, #曰易地低低刖The method of adding fluoromonoester (4) and said diene (8) one by one can lightly produce the compound. Needless to say, in the separate polymerization of fluorodiene (b), (b) 100 mol% is used. , minus thinner (4) and fluorodiuret (b) (iv) The molar ratio of 'done mono (a) to fluorodioxin (b) is preferably 1:99~95:5. As the fluoromonoolefin (4), the vinyl fluoride and the fluorodiene (nine): the molar ratio is preferably (9) to 80:20, and the ratio of the feeding ratio of the fluoroethylene to the above is preferably Below the limit, the molecular weight of the fluoropolymer (ρ) will become too high to easily suppress the decrease in (4). In addition, the resulting bond can be improved: the elongation of the article: as the fluoropolymer (Ρ) The polymerization initiator can be used at a half-life temperature of 20 to 12 (the organic peroxide of TC, from the viewpoint of preventing a decrease in the reaction rate due to the extraction reaction of hydrogen atoms in the polymerization initiator). Preferably, a fluorine-containing peroxide such as a fluorine-containing dithiol peroxide is preferred. The concentration of the polymerization initiator in the reaction solution is preferably from 1 to 5 mass%, more preferably from 0.5 to 2 mass%. Further, although the polymerization temperature varies depending on the half-life temperature of the polymerization initiator for 1 hour and the polymerization rate of the single 15 201229072 body, it is 2 (M2 (rc is preferred, *~ thief is preferred. fluoropolymer (P) In order to adjust the molecular weight, it is preferred to use a bond transfer agent. As a chain transfer agent, for example, ccl4, CH3C1, s〇2ci2, cHFci: and the like, the milk compound 'fluorine base 峨, gas 敎 base·^, etc. And hydrocarbon-based solvents such as methanol, ethanol, isopropanol, hexane, diethyl ether, etc. Among them, = chain transfer efficiency is high and can be produced in high yield (4) from the viewpoint of polymer (p) &quot; The amount of 2Cl2 and I-(CF2)nI (n is 4 or 6) is better than the chain transfer constant, but in the use of β 2 2 temple relative to the fluorine disulfide (b) alone The use of gas dilute (9) in the polymerization ^ or relative to the monotonic (a, "two-turn" of the silk scarf in the gas monoolefin (4) pure _), in terms of molar ratio in 〇·谢~(U Preferably, 〇.〇5^ is better. If the molar ratio is above the lower limit, it is easier to prevent the molecular weight of the polymer (P) from becoming too high. Moreover, if the molar ratio is below the upper limit, Easy The molecular weight of the fluoropolymer (P) is too low. (Refining the fluoropolymer (P)) The fluoropolymer (P) obtained is preferably removed by purifying a low molecular weight component having a molecular weight of less than 1 Å after polymerization. By purifying, the low molecular weight component in the I polymer (P) can be reduced, and therefore, the obtained fluoropolymer can be made to be narrower than the molecular weight distribution expressed by MPC/Mn measured by GPC. It is easy to obtain a crosslinked rubber article having good thermal stability and dimensional stability. However, the 'fluoropolymer (P) may not be purified after polymerization. As a low molecular weight component having a molecular weight of less than 1, 〇〇〇 Removal method, Example 16 201229072 If there is a method of heating a fluoropolymer (p) under reduced pressure, a method of removing a low molecular weight component is in a supercritical state, and a method of extracting a low molecular weight component from a fluoropolymer (p) (7) (4) The solution of the polymer (ρ) is put into a poor solvent, 'the fluoropolymer (ρ) having a molecular weight above 〇, and the method of removing the un-sinked low molecular weight age; and (4) using a gel permeation chromatography to remove low Branch of molecular weight component From the viewpoint of the simplicity of the operation method and the easiness of expanding the scale, it is preferable to use the method (4) and the method (the method after the subsequent method (stone) is preferable. The decompression condition in the method (α) is 丨~丨〇〇hPa is the best for Jiajia' 1~10hPa. If the pressure is above the lower limit, it can be easily decompressed. If the pressure is below the upper limit, the removal efficiency of the component is less than '1~20hPa even if the device size The heating temperature in the low molecular method (α) can be improved by 1 〇〇 15 15 〇 < t, preferably 12 〇 15 15 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 2 points and improve removal efficiency. If the temperature is in the upper limit, (4) the local gelation reaction is generated during the suppression of heating. The method (6) is a method in which the fluoropolymer (P) is separated from the extraction solvent after the contact of the extraction solvent in the supercritical state, thereby removing the low molecular weight component contained in the fluoropolymer (P). The extraction solution _ dissolves the low molecular weight component to form the low molecular weight t from the fluoropolymer (p). The extraction _ is not particularly limited as long as it is inclined above the critical temperature of the used explosive agent and is below the temperature range of 13 Torr, and the pressure τ above the critical pressure of the solvent is extracted, and the low molecular weight component is extracted. 17 201229072 The extraction solvent may, for example, be a fluorocarbon having a carbon number of 1 to 3 such as carbon dioxide, trifluorodecane (CF3H; R23) or perfluoroethane (C#6; R116). Among them, carbon dioxide, trifluoromethane, and perfluoroethane are preferred from the viewpoints of ease of a supercritical state and good extraction efficiency, and carbon dioxide is preferred. The extraction solvent may be used alone or in combination of two or more. The temperature of the extraction solvent in the process (10,000) is preferably above the critical temperature of the extraction solvent used and below 13 Torr. (3. Further, the pressure of the extraction solvent is above the critical pressure of the extraction solvent. That is, in the method (/5), the extraction solvent and the fluorine polymerization of the supercritical fluid set below 13 〇&lt;) The method of contacting the substance (p) is preferably carried out. The temperature of the extraction bath is appropriately set according to the extraction solvent to be used, and the lower limit of the temperature of the extraction solvent is preferably higher than the critical temperature by rc. The upper limit of the temperature is 1 〇〇 t: preferably, 8 (rc is better. The pressure of the extraction solvent is appropriately set in accordance with the extraction solvent used as long as it is within the above range. The lower limit of the pressure of the extraction solvent is 10,000 Pa higher than the critical pressure. It is better to use a higher critical pressure than high pressure. In the method (point), the extraction efficiency of the low molecular weight component is improved by increasing the density of the extraction solvent. This is because the density of the extraction solvent is higher. The solubility corresponding to the extraction solvent of the low molecular component can be improved. The density of the extraction solvent during extraction _ that is, the density of the extraction solvent in the supercritical state is above 〇_2g/cm3 and below 丨3g/cm3. Further, in the method (call), a halogenated hydrocarbon solvent or a hydrocarbon solvent (hereinafter referred to as "additive (4) -)") may be used in combination as an auxiliary solvent in the extraction solvent. From the viewpoint of solubility The additive is preferably a halogenated hydrocarbon solvent. || The chemical solvent is, for example, 18 201229072 CF3CF2CHC12, CFC12CF2C, ecu, CF3CHFCHFCF2CF3, and cf3ch2ocf2cf2h, etc. The flue solvent is, for example, methanol, ethanol, propanol or isopropanol. And the dimethyl ether and the like. The additives may be used singly or in combination of two or more. The method (10,000) is carried out by using an extraction solvent in a supercritical state, so that the low molecular weight body can be efficiently reduced. The molecular weight distribution of the obtained fluoropolymer (p) is narrowly dispersed. The method (7) is carried out by introducing a poor solvent into the fluoropolymer (P) and separating the supernatant to remove the fluoropolymer (P). A method of using a low molecular weight component. The poor solvent used in the method (T) is, for example, methanol, hexane, diethyl ether or the like. It is easy to obtain a crosslinked rubber material having good heat resistance and chemical resistance. From the viewpoint of the product, the content of the terpene polymer (P) in the crosslinkable squirrel rubber composition of the present invention is preferably 1 part by mass, more preferably 2 to 45 parts by mass, per 100 parts by mass of the fluororubber. More preferably, it is 3 to 40 parts by mass, and if the content of the fluoropolymer (p) is at least the lower limit value, cross-linking can be easily sufficiently formed to easily produce a crosslinked rubber article having good heat resistance. When the content of p) is at most the upper limit value, even if an unstable terminal group (carboxyl group or the like) derived from the fluoropolymer (p) is present in the crosslinked rubber article, the thermal stability due to the base can be easily suppressed. [Fluororubber] Fluororubber can be crosslinked by the following methods: (1) using organic peroxides to generate and crosslink free radicals by heating; or (2) irradiating radiation 201229072 to free radicals The method of generating and cross-linking. Hereinafter, the cross-linking of the method (1) is referred to as organic peroxide cross-linking, and the cross-linking of the method (2) is referred to as radio cross-linking. The fluorine content of the fluororubber is 4 〇. It is preferable that it is more than 5 % by mass, and more preferably 55% by mass or more. When the fluorine content is at least the lower limit value, it is easy to obtain a parent-linked rubber article having excellent heat resistance, chemical resistance, electrical insulation properties, and steam resistance. The fluorine content of the fluororubber is a ratio of the total mass of the perfluoro atoms to the total mass of the fluororubber. Examples of the fluororubber include a vinylidene fluoride/hexafluoropropylene copolymer, a vinylidene fluoride/TFE/hexafluoropropylene copolymer, a fluorinated ethylene/CTFE copolymer, and a TFE/propylene copolymer. TFE/propylene/fluorinated vinylene copolymer, hexafluoropropylene/ethylene copolymer, TFE/perfluoroalkyl vinyl ether copolymer, and fluorinated ethylene/TFE/perfluoroalkyl vinyl ether A copolymer or the like. These may be used alone or in combination of two or more. From the viewpoint of having good chemical resistance, the fluororubber is selected from the group consisting of TFE/propylene copolymer, fluorinated vinylene/TFE/hexafluoropropylene copolymer, and TFE/Wang-fluoroethylene base. It is preferred that one or more of the groups consisting of the copolymers are copolymerized. From the viewpoint of having good heat resistance, the fluororubber is preferably a perfluoroelastomer obtained by polymerizing a perfluoromonomer in which all of the hydrogen atoms of the monomer are replaced by fluorine atoms. As a perfluoroelastomer, having a repeating unit derived from TFE, and derived from CF2=CF-0-RF2 (wherein, where rF2 is a carbon number uo of a perfluoroalkyl group, or a carbon atom-carbon The carbon number of one or more etheric oxygen atoms in the atom between the atoms. The following is called "perfluoromonomer (χ)".) The repeating unit of the bomb 20 201229072 (hereinafter referred to as "elasticity" Body (χ)") is better. In the elastomer (X), the number of repeating units derived from the perfluoromonomer (X) may be one or two or more. The perfluoroalkyl group of iRF2 in the perfluoromonomer (X) preferably has 1 to 8 carbon atoms. The perfluoroalkyl group of RF2 may be linear or branched. As perfluoromonomer (X), cf2=cf-o-cf3 &gt;cf2=cf-o-cf2cf3, cf2=cf-o-cf2cf2cf3, cf2=cf-o-cf2cf(cf3)ocf2cf2cf3, and CF2= CF-0-CF2CF2-0-CF2CF3 is preferred, and CF2=CF-0-CF3 is preferred. From the viewpoint of having good rubber physical properties, the copolymerization ratio in the elastomer (X) is a repeating unit derived from TFE / a repeating unit mainly composed of a perfluoromonomer (X) = 30/70 to 80/20 (Morbi) is better. Further, the fluororubber is not limited to a perfluoroelastomer, and when a perfluoromonomer is polymerized, an elastomer obtained by using a chain transfer agent or a comonomer containing a small amount of hydrogen atoms can also be used. Examples of the chain transfer agent containing a hydrogen atom include chain or cyclic saturated hydrocarbons such as methane, ethane, propane, butane, pentane, hexane, and cyclohexane; and alcohols such as decyl alcohol, ethanol, and propanol. And thiols such as tertiary dodecyl mercaptan, n-dodecyl mercaptan, and n-octadecyl mercaptan. These chain transfer agents may be used singly or in combination of two or more. The comonomer containing a hydrogen atom may, for example, be cf2=cf-o-ch2cf3, cf2=cf-o-ch2cf2cf2cf3, cf2=cf-o-ch2(cf2cf2)2h, CF2=CF-0-CF2CF2CH2-I, CF2 =CF-0-CF2CF2CH2-Br, cf2=cf-o-cf2cf2(cf3)-o-cf2cf2ch2-i, and cf2=CF-0-CF2CF2(CF3)-0-CF2CF2CH2-Br. These comonomers may be used alone or in combination of two or more types. When at least one of the chain transfer agent and the comonomer is used, the content of the hydrogen atom in the elastomer is preferably 0.5% by mass or less from the viewpoint of heat resistance and chemical resistance characteristics of the crosslinked rubber article. The mass% or less is preferably ,.1 mass% or less. Further, in the case of the rubber, it is preferable to use a perfluoroelastomer (hereinafter also referred to as a "sexual body (7)" having at least _ atom (four) atoms in the case of cross-linking of the organic peroxide to have The perfluoroelastomer of the atom is preferably a perfluoroelastic system having at least one of a ruthenium atom and a desert atom, and the ruthenium of the ruthenium atom of the all-I-elastomer (4) is replaced by a ruthenium atom. The total gas elastic system refers to an elastomer in which one or more atoms of the money elastomer are replaced by moth atoms. The elastomer (Y) is disclosed in, for example, Japanese Laid-Open Patent Publication No. (2), Japanese Patent Publication No. 53-4115, and Japanese Laid-Open Patent Publication No. 59-2〇31〇. Self-loaded elastomer. Specifically, for example, one or more perfluoromonomers selected from the group consisting of TFE and perfluoromonomer (X) may be added, and at least one of an iodine atom and a bromine atom may be copolymerized. An elastomer obtained by a monomer (hereinafter referred to as "monomer (y)"); and in the case of I-RF3-I (wherein, V3 is a carbon number of a perfluoroalkyl group, or a carbon atom) An elastomer obtained by copolymerizing the above monomers in the presence of a compound represented by a perfluoroalkylene group having 1 to 8 carbon atoms and having at least one etheric oxygen atom between carbon atoms. The monomer (y) can be, for example, (^2=&lt;^-汾, (:112=(:1^?2€?2-81·, CF2=CF-〇-CF2CF2-I 'CF2=CF- 0-CF2CF2-Br CF2=CF-0-CF2CF2CH2-I, CF2=CF-0-CF2CF2CH2-Br, 22 201229072 CF2=CF-〇-CF2CF2(CF3)-〇-CF2CF2CH2-I, and CF2= CF-0 -CF2CF2(CF3)-0-CF2CF2CH2-Br, etc. Specific examples of I-RF3-I include diiododifluoromethane, 1,2-diiodoperfluoroethane, and 1,3-diiodide. Perfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodoperfluoropentane, 1,6-diiodoperfluorohexane, 1J-diiodoperfluoroheptane, and 1,8 -diiodoperfluorooctane, etc. Among them, 1,4-diiodoperfluorobutane, and iota,6-diiodoperfluorohexane are preferred, and 1,4-diiodoperfluorobutane is preferred. The iodine atom and the bromine atom in the elastomer (Y) are preferably bonded to the end of the polymer. From the viewpoint of easily producing a crosslinked rubber article having good rubber properties and compressive permanent strain, the elastomer (Y) The total content of the iodine atom and the bromine atom is preferably 0.1 to 1.5% by mass, more preferably 0.2 to 1.0% by mass, and most preferably 0.25 to 1. 〇% by mass. For example, the product name "AFLAS PFE-1100" (TFE/perfluoroalkyl vinyl ether copolymer manufactured by Gunsko Co., Ltd.), the trade name "AFLAS 100S" (made by Asahi Glass Co., Ltd., tfe/propylene copolymer), and The product name "AFLAS 200P" (asahi, ε xiaozi company, TFE / propylene / fluorinated vinylene copolymer) can be used for organic peroxide cross-linking gas rubber. [Organic peroxide] by organic peroxidation When the cross-linking fluororubber composition of the present invention is cured by cross-linking, it is preferred that the cross-linkable fluororubber composition of the present invention contains an organic peroxide. The cross-linking fluororubber composition is cross-linked by radiation. In the case of hardening, it is not necessary to specifically contain an organic peroxide. 23 201229072 The organic peroxide is preferably a radical generator which can be easily heated by heating, and preferably has a half-life of 1 minute at a temperature of 130 to 220 ° C. Specifically, 'such as: 1,1-di (three-stage hexyl peroxidation) _3,5,5-trimethylcyclohexanyl, 2,5-dimercaptohexanol-2,5-dihydroperoxide , di-tertiary butyl peroxide, tertiary butyl cumyl peroxide, diisopropyl phenyl Oxide, α, α bis (tertiary butyl peroxy)-p-diisopropylbenzene, 2,5-dimercapto-2 5_(divalent butyl peroxy)-hexyl, 2,5-di Methyl-2,5-di(tributyl peroxide)-hexyne-3, a claudyl peroxide, tert-butyl benzoate, 2,5-dimethyl-2,5 - bis(phenylhydrazine peroxy)hexane, tertiary butyl peroxymaleic acid, and secondary hexylperoxyisopropyl monocarbonate. Among them, α,α'-bis(tri-butyl peroxide)-p-diisopropylbenzene is particularly preferred. The organic compound can be used alone. From the top, when the cross-linking fluororubber composition of the present invention contains organic peroxidation, the content of the organic peroxide is 1 part by mass relative to the fluororubber, and the mass is 〇ι. The portion is preferably '0.2 to 4 parts by mass, and more preferably Q 5 to 3f parts. If there is a peroxide content limit m, the crosslinking efficiency is increased. When the content of the peroxide is at most the upper limit value, it is easy to suppress the amount of the ineffective decomposition product which does not contribute to the radical. [Other Ingredients] ------Human-Jin Ying's point of view, it seems that the gel composition contains a (four) acceptor as a good acid acceptor, for example, magnesium oxide, oxidized, and about (10) m. Water slide and oxidation are preferred. The acid acceptor may be used singly or in combination with each other. 24 201229072 When the crosslinkable rubber composition of the present invention contains an acid acceptor, the content of the acid acceptor is 0.1 to 20 parts by mass based on 100 parts by mass of the fluororubber. Preferably, it is preferably 0.2 to 10 parts by mass. If the content of the acid acceptor is at least the lower limit value, the effect of the acid acceptor is easily obtained. When the content of the acid acceptor is at most the upper limit value, it is easy to suppress the rubber physical properties which may damage the crosslinked rubber article. The crosslinkable fluororubber composition of the present invention preferably contains a filler from the viewpoint of improving the strength of the obtained crosslinked rubber article. The filler is preferably carbon black. The carbon black is not particularly limited as long as it is used as a rubber blending user. Specific examples include furnace black, acetylene black, hot carbon black, black, and graphite. Among them, furnace black is preferred. The black level is preferably HAF-LS, HAF, HAF-HS, FEF, GPF, APF, SRF-LM, SRF-HM, and MT, and MT is particularly preferred. When the crosslinkable fluororubber composition of the present invention contains a filler, the content of the filler is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the fluororubber. When the content of the filler is at least the lower limit value, the effect of the filler can be easily obtained. When the content of the filler is at most the upper limit, it is easy to suppress the deterioration of the tensile properties of the crosslinked rubber article. Further, as long as the balance between the strength and the stretch of the crosslinked rubber article prepared by the inclusion of the filler in the range of the cutting agent is maintained, a good relationship can be maintained. Further, the crosslinkable fluororubber composition of the present invention may contain additives such as a reinforcing material, a processing aid, a lubricant, a lubricant, a flame retardant, an antistatic agent, a colorant, and an ultraviolet absorber. The reinforcing material may, for example, be a fluororesin such as polytetrafluoroethylene or ethylene/TFE 25 201229072 polymer, glass fiber, carbon fiber or white carbon. When the cross-linking rubber composition of the present invention contains a reinforcing material, the content of the reinforcing material is preferably 5 to 2 parts by mass, more preferably 10 to 100 parts by mass, per 100 parts by mass of the fluororubber. As the processing aid, for example, a metal salt of a higher fatty acid can be mentioned. Among them, stearate and laurate are preferred. When the crosslinkable fluororubber composition of the present invention contains a processing aid, the content of the processing aid is preferably 2 parts by mass, preferably 0.2 parts by mass to 2 parts by mass based on 4 parts by mass of the rubber. It is better if the processing aid is above the lower limit value. The tensile strength of the crosslinked rubber article will decrease significantly and it is easy to suppress the increase of the tensile or tensile strength after heat aging. When it is less than the upper limit, it is easy to suppress the occurrence of blooming on the surface of the crosslinked rubber article, or to increase the hardness of the crosslinked rubber article, or to lower the chemical resistance and the steam resistance. [Crosslinking fluororubber composition (Manufacturing method of the present invention) The method for producing the parent-linked fluororubber composition of the present invention is not particularly limited, and a conventionally known method can be employed. Among them, a double roll machine, a closed type/3⁄4 smelting machine, and a "smashing machine" are used. It is preferable to knead a fluororubber, an I polymer (P), an organic peroxide, a carbon black, an acid acceptor, and other additives as needed in a kneading machine. Further, a method of kneading and dissolving the above components in a state of being dissolved and dispersed in a solvent may be employed. In the order of mixing the above-mentioned respective components, it is preferred that the components which are difficult to react or decompose are sufficiently kneaded with the fluororubber by heat generation, and then the easily reactable component or the easily decomposable component is blended and kneaded. 26 201229072 For example, in the case of using an organic peroxide, it is preferred to blend and knead the organic peroxide. At this time, at the time of kneading, it is preferred that the kneader is water-cooled to maintain the temperature range of (10) to 丨 from the viewpoint of not allowing the crosslinking reaction to proceed. a The above-described crosslinked fluororubber group of the present invention has a good resistance to gas rubber... Since it is crosslinked by a radical by organic = parent or radiation crosslinking, the fluororubber can be prevented In the case of a decrease in the properties, a good resistance is obtained: a crosslinked rubber article, and a sufficient crosslinking can be formed by using a fluoropolymer (p) as a crosslinking assistant, so that a good crosslinking can be achieved. Heat resistance. Therefore, as long as the crosslinkable gas rubber composition of the present invention is used, a crosslinked rubber article having both good chemical properties and heat resistance can be obtained. &lt;Crosslinked rubber article&gt; The crosslinked rubber article of the present invention is an article formed by crosslinking the crosslinked rubber composition of the present invention described above. The crosslinked rubber article of the present invention can be used as an ankle ring, a seal #, a gasket, an oil seal, and a bearing seal in a wide range of fields such as automobile transportation machinery, general machinery, electric motor, chemical equipment industry, and semiconductor. It is suitable for use in various components such as sealing materials, apertures, cushioning materials, shock-proof materials, wire covering materials, industrial belts, tubes, coils, and sheets. Among them, from the viewpoint of excellent resistance at high temperatures, 'in addition to the excellent properties such as strength, hardness, modulus, and heat aging resistance, it is better to use sealing materials and oil exploration. The sealing material is preferred. [Manufacturing method of crosslinked rubber article] 27 201229072 The crosslinked rubber article of the present invention can be formed by curing the crosslinked fluororubber composition of the present invention by crosslinking with an organic peroxide or by radiation crosslinking. Got it. The formation of the crosslinkable fluororubber composition of the present invention can be known by any of the conventional organic peroxide crosslinking and radiation crosslinking, such as extrusion molding, injection molding, transfer molding, and press molding. Forming method. In the specific example of the method of crosslinking the rubber article by crosslinking with an organic peroxide, for example, there is a method of using a mold having a cavity having a shape complementary to the shape of one or several parts of the crosslinked rubber article. After filling the cavity with a crosslinkable fluororubber composition containing an organic peroxide, the mold is heated to be hardened at a heating temperature of 130 to 220. (: It is better, 140~200°C is better, 150~200 C is better. Also, it is also suitable to use electric, hot air, or steam as the heat source, etc., which will be heated and crosslinked under the aforementioned conditions. The crosslinked rubber article (primary crosslinked product) is further heated to carry out cross-linking (hereinafter referred to as "secondary cross-linking"). By performing one cross-linking, the organic peroxide contained in the cross-linked rubber article can be obtained. The residue is decomposed and volatilized to reduce its amount. - The heating temperature of the second parent is preferably 150~28〇r, 180. (: ~260°c is better, 200~250°C is better.) The heating time is preferably 1 to 48 hours, preferably 2 to 24 hours. 'Specific examples of a method for producing a crosslinked rubber article by radiation crosslinking, 'for example, the following method' is: The cross-linking i rubber composition of the present invention is dissolved and dispersed in a suitable solution as a floating solution, and is formed by applying a coating such as 28 201229072 and drying it, and then irradiating the radiation to be hardened. Either an electron beam or an arbitrary radiation such as an r line.

The irradiation amount of the free radiation is preferably 1 to 300 kGy, and preferably 1 〇 2 〇〇 kG. EXAMPLES Hereinafter, the present invention will be described in detail by way of examples. However, the invention should not be construed as limited. [GPC analysis] Μη and Mw of the fluoropolymer (P) obtained in the present Example were measured by GPC under the following conditions in accordance with the method described in JP-A-2001-208736. Mobile phase: Asahi Glass Co., Ltd., ASAHIKLINAK-225SEC grade U mixed solvent of pentafluoropropane and hexafluoroisopropanol (difluoropentafluoropropane / hexafluoroisopropanol = 99/1 (volume ratio)). Analytical column: A PLgel MIXED-E column (manufactured by Polymer Laboratories Co., Ltd.) was connected in series. Standard sample for molecular weight measurement: PMMA (polymethyl methacrylate). Mobile phase flow rate: 1.0 mL / min. Column temperature: 37 ° C. Detector: Evaporative light scattering detector. [Use Raw Material] The components used in the examples were as follows. (1) Fluororubber 29 201229072 Fluororubber (Yl): an elastomer (peroxide crosslinked type) of TFE/perfluoroalkyl vinyl ether copolymer, trade name "AFLAS PFE-1100" (made by Asahi Glass Co., Ltd.) Fluorine content: 72% by mass). (2) Cross-linking aid fluoropolymer (P1): After degassing the high-pressure dad of stainless steel with a volume of 1 L (liter), the fluoromonoolefin (a) TFE 17g is pressed into the high pressure dad. PFadiene (b) perfluorobutene divinyl ether (hereinafter referred to as "C4DVE") 76g, S02C12 3.0g, AK225cb (made by Asahi Glass Co., Ltd.) 725g, and (C3F7COO)2 6.8 containing a polymerization initiator 227 g of the AK225cb solution of g was heated while stirring to 40 ° C while stirring. Then, TFE and C4DVE were sequentially added at a pressure of 0.2 MPa so that the additional feed amount of TFE was 29 g and the additional feed amount of C4DVE was 44 g, and the polymerization reaction was carried out for 4 hours. Thereafter, the mixture was cooled to room temperature, and the unreacted TFE was drained, and the contents were taken out and placed in a glass beaker having an inner volume of 2 L. Subsequently, 500 g of methanol was added thereto, and the produced fluoropolymer was precipitated, and the supernatant liquid was removed to remove the low molecular weight component, and then dissolved in AK225cb to obtain a fluoropolymer solution 1. Next, the fluoropolymer solution 1 was washed with water to separate the lower layer, and then filtered using a membrane filter made of PTFE (polytetrafluoroethylene) having a pore diameter of lem to obtain a substantially transparent fluoropolymer solution 2. Then, the solvent was distilled off from the fluoropolymer solution 2 using an evaporator, and then vacuum-dried at 100 ° C for 2 hours to obtain 52 g of a colorless transparent high-viscosity liquid fluoropolymer (P1). The average molecular weight of the fluoropolymer (P1) obtained by GPC measurement was 30 201229072. Mw was 22,800 and Μη was 7,300. Further, by measuring the composition of the fluoropolymer (P1) and the content of the polymerizable double bond by 19F-NMR, it was found that the molar ratio derived from the repeating unit derived from TFE and the repeating unit derived from C4DVE was 69/31, and polymerization was carried out. The content of the double bond was 1.18 mmol/g. Fluoropolymer (P2): V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) containing C4DVE 497g, I(CF2)6I 2_5g, and a polymerization initiator in a glass flask containing 500 ml of an internal volume and a stirrer and a cooler. 0.7 g, the solution nitrogen was bubbled for 1 minute, stirred and simultaneously heated to 70 ° C in a water bath with a water bath. The internal temperature was maintained at 70 ° C and the polymerization was allowed to proceed for 25 hours. Thereafter, after cooling to room temperature, the contents were dissolved in C6F13H, and taken out to a glass beaker having an inner volume of 2 L. Next, stirring was carried out and 374 g of methanol was introduced to precipitate the resulting polymer, and the supernatant was removed to remove low molecular weight components. Take 5 〇.真空 Drying under vacuum for 12 hours gave 124 g of a colorless, transparent, highly viscous liquid fluoropolymer (P2). The average molecular weight of the fluoropolymer (P2) obtained by GPC measurement revealed Mw of 25,700 and Μη of 6,800. Further, the content of the polymerizable double bond of the fluoropolymer (?2) was measured by 19F-NMR to find that the content of the polymerizable double bond was 2.68 mmol/g. TAIC: Triallyl isocyanurate. (3) Organic peroxide PERBUTYL P: 〇:, 〇: '-bis (tertiary butyl peroxy) _ p-diisopropylbenzene (trade name "Perkadox 14", manufactured by Oyster Sauce Co., Ltd.). 31 201229072 (4) Acid acceptor KYOWAMAG #150 : Magnesium oxide (manufactured by Kyowa Chemical Industry Co., Ltd.). (5) Filler MT carbon: carbon black (grade: MT carbon, manufactured by CANCARB). (6) Processing aid NONSOUL SN-1 : Sodium sulphate (made by Nippon Oil Co., Ltd.). [Example 1] A fluorine-containing rubber (Y1), a mass fraction of PERHEXA 25B (manufactured by Sakamoto Oil Co., Ltd.), 1 part by mass, a fluoropolymer (Ρ1), 33·8 parts by mass, and a ruthenium carbon 10, were prepared by a biaxial roll. The mass fraction and 3 parts by mass of KYOWAMAG #150 were kneaded to obtain a crosslinkable fluororubber composition (i). The crosslinked fluororubber composition (1) thus obtained was formed into a sheet shape (primary cross-linking) having a length of 100 mm x a width of 100 mm and a thickness of 2 mm at a hot pressure of 170 ° C for 20 minutes. The obtained sheet was further placed in a Geer Oven at 250 ° C for 2 hours, and a second cross-linking was carried out to obtain a sheet. After the sample was punched from the prepared sheet with the No. 3 dumbbell, the hardness (HS), tensile strength (TB), tensile (EB), and 100% tensile stress (M100) were measured for normal physical property evaluation, and then measured. The hardness (HS), tensile strength (tb), and elongation (EB) after heat treatment at 250 ° C for 70 hours in a Gil oven were evaluated and evaluated for heat aging. [Example 2] A sheet was produced in the same manner as in Example 1 except that 5 parts by mass of TAIC was used instead of fluoropolymer (ρι) 33 8 parts by mass as a crosslinking aid' and KY〇WAMAG #150 was not used. characteristic. 32 201229072 [Example 3] A sheet was produced in the same manner as in Example 1 except that 5 parts by mass of TAIC was used instead of 33.8 parts by mass of the fluoropolymer (Pl) as a crosslinking assistant, and the properties were measured. [Example 4] A sheet was produced in the same manner as in Example 1 except that 21.3 parts by mass of the fluoropolymer (P2) was used instead of the fluoropolymer (?1) of 33.8 parts by mass as a crosslinking assistant, and the properties were measured. [Example 5] A sheet was produced in the same manner as in Example 1 except that 14.2 parts by mass of a fluoropolymer (?2) was used instead of the fluoropolymer (?1) 333.8 parts by mass as a crosslinking assistant, and the properties were measured. Examples [1], [4], and [5] are examples, and examples [2] and [3] are comparative examples. [Measurement method] (1) Hardness (HS) The hardness (HS) was measured by a rubber hardness tester hardness test at 23 ° C in accordance with JIS Κ 6253-1997. In terms of the hardness of the sheet, it is suitably 60 to 95°. (2) Tensile strength (TB) The tensile strength (TB) was measured at 23 ° C according to JIS K6251-2004. The tensile strength (TB) of the sheet is preferably 10 MPa or more. (3) Stretching (EB) The stretching (EB) was measured at 23 ° C according to JIS K6251-2004. The sheet stretching (EB) is preferably 130% or more. (4) 100% tensile stress (modulus) 33 201229072 100% tensile stress (Μιοο) was measured at 23 ° C according to JIS K6251-2004. For the 100% tensile stress (M100) of the sheet, it is appropriate to use 3 to 17 MPa. (5) Air heating aging test (hardness change rate) After heat treatment at 250 °C for 70 hours in a Gil oven, the stone hardness was determined by a rubber hardness tester A hardness test at 23 ° C according to Jis K6253-1997. HS), and compared with the hardness of (1), calculate the rate of change. (6) Air heating aging test (tension rate change rate) After heat treatment at 250 ° C for 70 hours in a Gil oven, the tensile strength (TB) is measured at 23 ° C according to K6251-2〇04, and (2) The tensile strength is compared and the rate of change is calculated. (7) Air heating aging test (tensile change rate) After heat treatment in a Gil oven for 250 hours at 2501, the tensile (EB) was measured at 23 ° C according to JIS K6251-2004, and the stretching was performed with (3) Compare, to calculate the rate of change. Table 1 shows the composition (parts by mass) of each material used for sheet production in Examples [1] to [5], and the evaluation results of the above characteristics. 34 201229072 Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Fluororubber fluororubber (Y1) 100 100 100 100 100 Crosslinking aid fluoropolymer (P1) 33.8 - - - - Fluoropolymer (P2) - - - 21.3 14.2 TAIC - 5 5 - - Organic peroxide PERBUTYL P 1 1 1 1 1 Acid acceptor KYOWAMAG#150 3 - 3 3 3 Filler MT carbon 10 10 10 10 10 Processing aid NONSOUL SN-1 1 1 1 1 1 Hardness (HS) [°] 86 72 74 82 77 Tensile strength (TB) [MPa] 24.9 24.9 23.9 25.2 24.0 Tensile (EB) [%] 140 200 187 159 180 __ 100% tensile stress [MPa] 12.6 7.5 8.5 15.4 10.1 Air heating aging test (70 hours at 250 ° C) Hardness change rate [%] -1 0 0 -2 -2 Tensile strength change rate [%] +4 -13 -20 -3 -5 Tensile change rate [%] +19 +47 +6 +12 +27 As shown in Table 1, 'The fluoropolymers (P1 and P2) used as cross-linking aids, the sheets of Examples 4 and 5, and the cross-linking aid In the case of the TAIC, the sheets of Example 2 and Example 3 were used to suppress the change in the tensile strength of the reduced air heat aging test, and the heat resistance was better. INDUSTRIAL APPLICABILITY By using the crosslinkable fluororubber composition of the present invention, a crosslinked rubber article having both good chemical resistance (especially amine resistance) and heat resistance can be obtained, which can be used for an anthracene ring. Sealing materials such as sheets, gaskets, oil seals, bearing seals, etc., especially for the sealing materials used in petroleum exploration. The entire contents of the specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. Hei. No. Hei. 35 201229072 I: Simple description of the diagram 3 (none) [Description of main component symbols] (none) 36

Claims (1)

201229072 VII. Patent application scope: L—a cross-linking fluororubber composition containing fluororubber and the following fluorine-containing compound (P) having a majority of polymerizable properties, fluoropolymer (P): having a source Repetitive unit of fluorodiene (b) from the residual side chain of unsaturated. The cross-linking fluororubber composition of claim 1, wherein the fluoropolymer (P) has a repeating unit derived from fluoromonoolefin (a) and derived from an unsaturated side chain Repetitive unit of residual fluorodiene (b). 3) The cross-linkable fluororubber composition according to claim 2, wherein the fluoromonoolefin (a) is selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, and CF2=CFO-Rn (wherein Rf丨 is at least one selected from the group consisting of a fluoroalkyl group of carbon number 6 or a fluoroalkyl group having 2 or more carbon atoms having one or more etheric oxygen atoms between carbon atoms and carbon atoms. 4. The crosslinkable I rubber composition of any one of claims 1 to 3 wherein the fluorodiene (b) is selected from the group consisting of fluorodiene (b1) to (b3) One or more of the group consisting of: (bl) CF2=CF〇-Qfl.〇cF=CF2; (b2) CHfCFCFA-QtOCFzCFsC%; (b3) CH2=CFCF2〇-Qf3-OCF=CF2 ; Wherein (^ and 卩17 are each independently a fluoroalkyl group having 3 to 8 carbon atoms; or a fluoroalkyl group having 3 to 8 carbon atoms having one or more etheric oxygen atoms between carbon atoms and carbon atoms; Qf3 It is a fluorine alkyl group having 1 to 6 carbon atoms, or a carbon number of 2 to 6 having one or more etheric sulfonium atoms between carbon atoms and carbon atoms. 37 201229072 5. The cross-linking fluororubber composition according to any one of items 1 to 4, wherein the fluoropolymer (P) has a weight average molecular weight of 3,000 to 50,000. 6. The method of any one of claims 1 to 5 A crosslinkable fluororubber composition in which the content of the polymerizable double bond in the fluoropolymer (P) is 0.2 to 2 mmol/g. 7. Crosslinkability as claimed in any one of claims 1 to 6. Fluororubber composition, relative to The cross-linking fluororubber composition of any one of the above-mentioned fluoropolymers, wherein the fluororubber is contained in an amount of from 1 to 50 parts by weight of the fluoropolymer (P). Selected from the group consisting of a tetrafluoroethylene/propylene copolymer, a vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymer, and a tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer A cross-linking fluororubber composition according to any one of claims 1 to 8, which further contains an organic peroxide. 10. A cross-linked rubber article, the system Cross-linking is the result of applying the cross-linking fluororubber composition of the first or second patent scope. 11. If the cross-linked rubber article of claim 10 is a sealing material, it is a sealing material. : (1) The representative representative of the case is: ( ) (No) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: ) 2