Heat-resistant crosslinked fluorocarbon rubber formed body and method for producing the same, silane master batch, master batch mixture and formed body thereof, and heat-resistant product

Abstract

A method for producing a heat-resistant crosslinked fluorocarbon rubber formed body, comprising: (a) a step of melt-kneading 0.003 to 0.5 part by mass of an organic peroxide, 0.5 to 400 parts by mass of an inorganic filler, and more than 2.0 parts by mass and 15.0 parts by mass or less of a silane coupling agent, with respect to 100 parts by mass of a base rubber containing a fluorocarbon rubber, at a temperature equal to or higher than a decomposition temperature of the organic peroxide, to prepare a silane master batch; a heat-resistant crosslinked fluorocarbon rubber formed body obtained by the method, a silane master batch, a mixture and a formed body thereof, and a heat-resistant product.

Claims

1. A method for producing a heat-resistant crosslinked fluorocarbon rubber formed body, comprising: (a) melt-kneading a mixture comprising a base rubber and 0.003 to 0.5 part by mass of an organic peroxide, 0.5 to 400 parts by mass of an inorganic filler, and more than 2.0 parts by mass and 15.0 parts by mass or less of a silane coupling agent, with respect to 100 parts by mass of of the base rubber, at a temperature equal to or higher than a decomposition temperature of the organic peroxide, to prepare a silane master batch, wherein the base rubber contains a fluorocarbon rubber and a resin selected from the group consisting of an ethylene-vinyl acetate copolymer, an ethylene-(meth)acrylate copolymer, an ethylene-(meth)acrylic acid copolymer, an acrylic rubber, and combinations thereof; (b) mixing the silane master batch obtained in the step (a) with a silanol condensation catalyst, and then forming the resultant mixture; and (c) bringing the formed body obtained in the step (b) into contact with moisture, to cause silane crosslinking.

2. The method for producing the heat-resistant crosslinked fluorocarbon rubber formed body described in the claim 1, wherein the fluorocarbon rubber is tetrafluoroethylene-propylene copolymer rubber.

3. The method for producing the heat-resistant crosslinked fluorocarbon rubber formed body described in claim 1, wherein a content of the organic peroxide is 0.005 to 0.5 part by mass.

4. The method for producing the heat-resistant crosslinked fluorocarbon rubber formed body described in claim 1, wherein a content of the silane coupling agent is 3 to 12.0 parts by mass.

5. The method for producing the heat-resistant crosslinked fluorocarbon rubber formed body described in claim 1, wherein a content of the silane coupling agent is 4 to 12.0 parts by mass.

6. The method for producing the heat-resistant crosslinked fluorocarbon rubber formed body described in claim 1, wherein the silane coupling agent is vinyltrimethoxysilane or vinyltriethoxysilane.

7. The method for producing the heat-resistant crosslinked fluorocarbon rubber formed body described in claim 1, wherein the inorganic filler is silica, calcium carbonate, zinc oxide or calcined clay, or any combination of these.

8. The method for producing the heat-resistant crosslinked fluorocarbon rubber formed body described in claim 1, wherein melt-kneading in the step (a) is performed by using an enclosed mixer.

9. The method for producing the heat-resistant crosslinked fluorocarbon rubber formed body described in claim 1, wherein a fluorocarbon resin is contained in the base rubber.

10. The method for producing the heat-resistant crosslinked fluorocarbon rubber formed body described in claim 9, wherein a melting point of the fluorocarbon resin is 250° C. or lower.

11. The method for producing the heat-resistant crosslinked fluorocarbon rubber formed body described in claim 9, wherein a melting point of the fluorocarbon resin is 200° C. or lower.

12. The method for producing the heat-resistant crosslinked fluorocarbon rubber formed body described in claim 9, wherein the fluorocarbon resin contains an ethylene-tetrafluoroethylene-hexafluoropropylene copolymer resin, an ethylene-tetrafluoroethylene copolymer resin or a polyvinylidene fluoride resin, or any combination of these.

13. The method for producing the heat-resistant crosslinked fluorocarbon rubber formed body described in claim 9, wherein a percentage content of the fluorocarbon resin is 3 to 45% by mass in 100% by mass of the base rubber.

14. The method for producing the heat-resistant crosslinked fluorocarbon rubber formed body described in claim 1, wherein part of the base rubber is melt-mixed in the step (a), a remainder of the base rubber is mixed in the step (b), and a fluorocarbon resin is contained in the remainder of the base rubber.

15. A heat-resistant crosslinked fluorocarbon rubber formed body, produced according to the method for producing the heat-resistant crosslinked fluorocarbon rubber formed body described in claim 1.

16. The heat-resistant crosslinked fluorocarbon rubber formed body described in claim 15, formed by crosslinking the base rubber with the inorganic filler through a silanol bond.

17. A heat-resistant product, comprising the heat-resistant crosslinked fluorocarbon rubber formed body described in claim 15.

18. The heat-resistant product described in claim 17, wherein the heat-resistant crosslinked fluorocarbon rubber formed body is a coating of an electric wire or an optical fiber cable.

19. A master batch mixture, comprising a silane master batch and a silanol condensation catalyst, wherein the silane master batch is prepared by mixing 0.003 to 0.5 part by mass of an organic peroxide, 0.5 to 400 part by mass of an inorganic filler, more than 2.0 parts by mass and 15.0 parts by mass or less of a silane coupling agent, with respect to 100 parts by mass of a base rubber containing a fluorocarbon rubber, and a silanol condensation catalyst, wherein the silane master batch is obtained by melt-kneading all or part of the base rubber, the organic peroxide, the inorganic filler and the silane coupling agent, at a temperature equal to or higher than a decomposition temperature of the organic peroxide.

20. A formed body, formed by introducing a master batch mixture obtained by dry-blending a silane master batch and a silanol condensation catalyst, into a forming machine, wherein the silane master batch is prepared by mixing 0.003 to 0.5 part by mass of an organic peroxide, 0.5 to 400 part by mass of an inorganic filler, more than 2.0 parts by mass and 15.0 parts by mass or less of a silane coupling agent, with respect to 100 parts by mass of a base rubber containing a fluorocarbon rubber, and a silanol condensation catalyst, wherein the silane master batch is obtained by melt-kneading all or part of the base rubber, the organic peroxide, the inorganic filler and the silane coupling agent, at a temperature equal to or higher than a decomposition temperature of the organic peroxide.

Description

EXAMPLES

(1) The present invention will be described in more detail based on examples given below, but the invention is not meant to be limited by these.

(2) In Tables 1 to 4, the numerical values for the content of the respective Examples and Comparative Examples are in terms of part by mass, unless otherwise specified.

(3) Examples and Comparative Examples were carried out by using the following components, and setting respective specifications to conditions shown in Tables 1 to 4, and the results of evaluation as mentioned later are collectively shown in Tables 1 to 4.

(4) Details of each compound listed in Tables 1 to 4 are described below.

(5) A fluorine content of fluorocarbon rubber is expressed in terms of a value according to the above-described “potassium carbonate pyrohydrolysis method”.

(6) <Base Rubber>

(7) (Fluorocarbon Rubber)

(8) “AFLAS 150P” (trade name, manufactured by AGC Asahi Glass Co., Ltd., tetrafluoroethylene-propylene copolymer rubber, fluorine content: 57% by mass)

(9) “AFLAS 150E” (trade name, manufactured by AGC Asahi Glass Co., Ltd., tetrafluoroethylene-propylene copolymer rubber, fluorine content: 57% by mass)

(10) “DAI-EL G801” (trade name, manufactured by Daikin Industries, Ltd., vinylidene fluoride-hexafluoropropylene copolymer rubber, fluorine content: 66% by mass)

(11) “Viton GBL200” (trade name, manufactured by DuPont Elastomers Co., Ltd., fluorine content: 66%)

(12) “Viton GBL900” (trade name, manufactured by DuPont Elastomers Co., Ltd., fluorine content: 66%)

(13) “Viton A500” (trade name, manufactured by DuPont Elastomers Co., Ltd., vinylidene fluoride-hexafluoropropylene copolymer rubber, fluorine content: 66% by mass)

(14) (Other Components)

(15) “VF120T” (trade name, manufactured by Ube Industries, Ltd., resin of ethylene-vinyl acetate copolymer, VA content: 20% by mass)

(16) “Evaflex EV360” (trade name, manufactured by Du Pont-Mitsui Polychemicals Co., Ltd., resin of ethylene-vinyl acetate copolymer, VA content: 25% by mass)

(17) “NUC 6510” (trade name, manufactured by Nippon Unicar Co., Ltd., ethylene-ethyl acrylate resin, EA content: 23% by mass, density: 0.93 g/cm.sup.3)

(18) “Evaflex EV180” (trade name, manufactured by Du Pont-Mitsui Polychemicals Co., Ltd., resin of ethylene-vinyl acetate copolymer, VA content: 33% by mass)

(19) “Vamac DP” (trade name, manufactured by Mitsui-Du Pont Chemicals Co., acrylic rubber)

(20) “RP-4020” (trade name, manufactured by Daikin Industries, Ltd., resin of ethylene-tetrafluoroethylene-hexafluoropropylene (ethylene-FEP) copolymer, melting point: 160° C.)

(21) “LH-8000” (trade name, manufactured by Asahi Glass Co., Ltd., resin of ethylene-tetrafluoroethylene (ETFE) copolymer, melting point: 180° C.)

(22) “EP521” (trade name, manufactured by Daikin Industries, Ltd., resin of ethylene-tetrafluoroethylene (ETFE) copolymer, melting point: 260° C.)

(23) “EP610” (trade name, manufactured by Daikin Industries, Ltd., resin of ethylene-tetrafluoroethylene (ETFE) copolymer, melting point: 180° C.)

(24) “KAYNER740” (trade name, manufactured by Arkema S.A., polyvinylidene fluoride (PVDF) resin, melting point: 170° C.)

(25) <Organic Peroxide>

(26) “PERHEXA 25B” (trade name, manufactured by NOF CORPORATION., 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, decomposition temperature 149° C.)

(27) <Inorganic Filler>

(28) “Zinc Oxide No. 1” (trade name, manufactured by Mitsui Mining & Smelting Co., Ltd., zinc oxide)

(29) “SOFTON 1200” (trade name, manufactured by BIHOKU FUNKA KOGYO CO., LTD., calcium carbonate)

(30) “Aerosil 200” (trade name, manufactured by Nippon Aerosil Co., Ltd., hydrophilic fumed silica, amorphous silica)

(31) “CRYSTALITE 5X” (trade name, manufactured by Tatsumori Ltd., crystalline silica)

(32) “Satitone SP-33” (trade name, manufactured by Engelhard Corporation, calcined clay)

(33) “MV Talc” (trade name, manufactured by Nihon Mistron Co., Ltd., talc)

(34) <Silane Coupling Agent>

(35) “KBM-1003” (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane)

(36) “KBE-1003” (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., vinyltriethoxysilane)

(37) <Silanol Condensation Catalyst>

(38) “ADKSTAB OT-1” (trade name, manufactured by ADEKA CORPORATION, dioctyltin dilaurate)

(39) <Antioxidizing Agent>

(40) “IRGANOX 1010” (trade name, manufactured by BASF, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate])

Examples 1 to 27 and Comparative Examples 1 to 6

(41) In Examples 1 to 18 and 20 to 27 and Comparative Examples 1 to 6, part of base rubber was used as carrier rubber of a catalyst MB.

(42) First, an inorganic filler and a silane coupling agent, in mass ratios listed in Tables 1 to 4, were placed in a 10L Henschel mixer manufactured by Toyo Seiki Seisaku-sho, Ltd. and the resultant mixture was mixed at room temperature (25° C.) for 1 hour to obtain a powder mixture. Next, the power mixture thus obtained, and each component listed in the base rubber column and the organic peroxide in Tables 1 to 4, in mass ratios listed in Tables 1 to 4, were placed in a 2 L Banbury mixer manufactured by Nippon Roll MFG. Co., Ltd., and the resultant mixture was kneaded at a temperature equal to or higher than a decomposition temperature of the organic peroxide, specifically, at 190° C., for 10 minutes, and then discharged at a material discharge temperature of 200° C., to obtain a silane MB. The silane MB obtained contains a silane crosslinkable rubber in which the silane coupling agent is graft-reacted onto the base rubber.

(43) Meanwhile, in Examples 1 to 27 and Comparative Examples 1 to 6, a catalyst MB was arranged as described below.

(44) In Examples 1 to 12, 22 and 24 to 27 and Comparative Examples 1 to 6, carrier rubber, a silanol condensation catalyst and an antioxidant were melt-mixed by a Banbury mixer at 180 to 190° C., in mass ratios listed in Tables 1 to 4, and the resultant mixture was discharged at a material discharge temperature of 180 to 190° C., to obtain the catalyst MB. This catalyst MB is a mixture of the carrier rubber and the silanol condensation catalyst.

(45) In Example 19, a silanol condensation catalyst and an antioxidant were arranged.

(46) In Examples 13, 14 and 23, a catalyst MB was obtained as described below. Crumb-shaped fluorocarbon rubber was pulverized into a flake shape. Subsequently, the fluorocarbon rubber obtained, a fluorocarbon resin, an antioxidant and a silanol condensation catalyst were dry-blended, the resultant mixture was introduced into a twin screw extruder, and melt-mixed at a head temperature of 230 to 270° C., and then extruded into a strand form. The strand obtained was cut to obtain a pellet-form catalyst MB.

(47) In Examples 15 to 18, 20 and 21, a pellet-form catalyst MB was obtained in the same manner as in Example 13 except that no fluorocarbon rubber was used.

(48) Subsequently, a silane MB and a catalyst MB, and further a fluorocarbon resin in Examples 19 and 27 were placed in an enclosed ribbon blender, and the resultant mixture was dry-blended at room temperature (25° C.) for 5 minutes, to obtain a dry-blended product (master batch mixture). At this time, a mixing ratio of the silane MB and the catalyst MB, and further the fluorocarbon resin in Examples 19 and 27 was expressed in terms of a mass ratio listed in Tables 1 to 4.

(49) Subsequently, the obtained dry-blended product was introduced into an extruder equipped with a screw having a screw diameter of 30 mm with L/D=24 (ratio of screw effective length L to diameter D) (compression zone screw temperature: 170° C., head temperature: 200° C.; except that compression zone screw temperature: 190° C., head temperature: 220° C. for Example 19). While the dry-blended product was melt-mixed in this extruder, the melted mixture was coated on an outside of a 1/0.8 TA conductor at a thickness of 1 mm, to obtain a coated conductor having an outer diameter of 2.8 mm. This coated conductor was left to stand for one week under an atmosphere of a temperature of 40° C. and a relative humidity of 95%.

(50) Thus, an electric wire having a coating layer formed of the heat-resistant crosslinked fluorocarbon rubber formed body on an outer periphery of the above-described conductor was produced. The heat-resistant crosslinked fluorocarbon rubber formed body as the coating layer has the above-mentioned silane crosslinked fluorocarbon rubber.

(51) In Comparative Example 1, a large number of aggregated substances were generated and extrusion forming was unable to be performed.

(52) A heat-resistant crosslinkable fluorocarbon rubber composition was prepared by melt-mixing the above-described dry-blended product in the extruder before extrusion forming. This heat-resistant crosslinkable fluorocarbon rubber composition is a melt mixture of the silane MB and the catalyst MB, and contains the above-mentioned silane crosslinkable rubber.

(53) The following tests were conducted on each electric wire produced, and the results are shown in Tables 1 to 4.

(54) <Heat Deformation Test>

(55) A heat deformation test was conducted on each electric wire produced at a measuring temperature of 150° C. and a load of 5 N based on UL1581. In this test, with regard to heat deformation, a case where a deformation ratio was 50% or less was deemed as pass.

(56) <Hot Set Test>

(57) A hot set test was conducted by using a tubular piece prepared by extracting a conductor from each electric wire produced. In the hot set test, marker lines having a length of 50 mm were attached on the tubular piece, and then the tubular piece to which a weight of 117 g was attached was left to stand in a constant temperature chamber at a temperature of 200° C. for 15 minutes, and elongation was determined by measuring a length after being left to stand. In addition, a case where the elongation is 100% or less was deemed as pass in this test, and was expressed as “A”. A case where the elongation was over 100% was expressed as “C”.

(58) <Winding Heating Test>

(59) Each electric wire (sample) produced was wound by 6 turns with a self-diameter, and the resultant material was left to stand in a constant temperature chamber at 236° C. for 4 hours. After being left to stand, the sample was removed, and loosened into a linear shape.

(60) A case where the sample was thoroughly loosened is deemed as “A”, a case where the sample was loosened in a state of the coating layer attached (keeping the electric wire form), although a surface of the coating layer was melted, is deemed as “B”, and a case where the coating layer was significantly melted and broken and the conductor is exposed is deemed as “C”.

(61) In this test, the “B” evaluation or better is a pass level.

(62) <Adhesion of Electric Wire After Electric Wire Production>

(63) The coated conductor obtained as described above was wound around a bobbin by 200 m (four stack) after being produced, and then left to stand at 30° C. for 48 hours and brought into contact with water, and adhesion between the electric wires obtained was confirmed.

(64) A case where no electric wires were adhered with each other at all when the electric wires were pulled out from the bobbins is deemed as “A”, a case where the electric wires were adhered with each other a little is deemed as “B”, and a case where the electric wires were adhered with each other to cause a scratch is deemed as “C”.

(65) The “B” evaluation or better is a pass level.

(66) <Extrusion Outer Appearance Test>

(67) As an extrusion outer appearance test, outer appearance of a coated conductor was observed and evaluated in producing the coated conductor.

(68) A product which was able to be formed into an electric wire form without the aggregated substance on the outer appearance of the coated conductor was expressed as “A”, a product which was able to be formed into an electric wire form, although generation of the aggregated substance was able to be confirmed even at a degree of having no problem on the outer appearance, was expressed as “B”, and a product which was unable to be formed into an electric wire form by significant generation of poor outer appearance was expressed as “C”. The extrusion outer appearance test is a reference test, and “B” evaluation or better is deemed as a pass level in this test.

(69) Further, among the electric wires produced, the following tests were conducted on the electric wires in Examples 1, 2, 12 to 23, and 27, and the results are shown in Tables 1 to 4.

(70) <Tensile Test>

(71) Tensile strength (MPa) and tensile elongation (%) were measured by using a tubular piece prepared by extracting a conductor from each electric wire, under conditions of a gauge length of 20 mm and a tensile speed of 200 mm/min, based on JIS C 3005.

(72) The tensile strength is preferably 8 MPa or more, and more preferably 8.5 MPa or more.

(73) The tensile elongation is preferably 100% or more, and more preferably 150% or more.

(74) <Heat Aging Test>

(75) The tubular piece used in the above-mentioned tensile test was kept at a heating temperature of 236° C. for 168 hours. Tensile strength (MPa) after being kept and tensile elongation (%) after being kept were measured by using the tubular piece after being kept, under conditions of a gauge length of 20 mm and a tensile speed of 200 mm/min, based on JIS C 3005.

(76) A retention rate (%) of tensile strength was calculated by dividing the tensile strength after being kept by the tensile strength before being kept (tensile strength obtained by the above-mentioned tensile test). A retention rate (%) of tensile elongation was calculated in a similar manner.

(77) It is preferable that the retention rate of tensile strength is 70% or more and the retention rate of tensile elongation is 60% or more, and it is more preferable that the retention rate of tensile strength is 70% or more and the retention rate of tensile elongation is 70% or more.

(78) TABLE-US-00001 TABLE 1 This invention 1 2 3 4 5 Silane MB Base rubber Fluorocarbon rubber AFLAS 150P 90 70 75 50 70 Fluorocarbon rubber AFLAS 150E Fluorocarbon rubber DAI-EL G801 Fluorocarbon rubber Viton GBL200 Fluorocarbon rubber Viton GBL900 Fluorocarbon rubber Viton A500 EVA VF120T EVA Evaflex EV360 20 EEA NUC6510 15 EVA Evaflex EV180 40 Acrylic rubber Vamac DP 20 Et-FEP copolymer RP4020 (mp 160° C.) Organic PERHEXA 25B 0.2 0.1 0.1 0.05 0.1 peroxide Inorganic Zinc oxide Zinc Oxide No. 1 10 10 10 10 filler Calcium carbonate SOFTON 1200 50 100 30 30 Silica Aerosil 200 1 4 1 Silica CRYSTALITE 5X Calcined clay Satitone SP-33 Talc MVTalc Silane Vinyltrimethoxysilane KBM-1003 5 12 2.5 12 8 coupling Vinyltriethoxysilane KBE-1003 agent Catalyst MB Carrier Fluorocarbon rubber AFLAS 150P 10 10 10 10 10 rubber Fluorocarbon rubber DAI-EL G801 Fluorocarbon rubber Viton GBL200 Fluorocarbon rubber Viton A500 Et-FEP copolymer RP4020 (mp 160° C.) ETFE resin LH-8000 (mp 180° C.) ETFE resin EP610 (mp 180° C.) PVDF resin KAYNER740 (mp 170° C.) Silanol Dioctyltin dilaurate ADKSTAB OT-1 0.05 0.05 0.05 0.05 0.05 condensation catalyst Antioxidizing IRGANOX 1010 0.1 0.1 0.1 0.1 0.1 agent Mixed at ETFE resin EP521 (mp 260° C.) extrusion Et-FEP copolymer RP4020 (160° C.) Evaluation Heat deformation test (%) 32 28 45 18 32 Hot set test A A A A A Winding heating test A A B A A Adhesion of electric wire after electric wire production B B B B B Extrusion outer appearance A A A A A Tensile strength (MPa) 4.1 5.2 Tensile elongation (%) 380 240 Heat aging test Tensile strength retention rate (%) 118 125 (236° C. × 168 hr) Tensile elongation retention rate (%) 88 80 This invention 6 7 8 9 Silane MB Base rubber Fluorocarbon rubber AFLAS 150P Fluorocarbon rubber AFLAS 150E 90 Fluorocarbon rubber DAI-EL G801 70 Fluorocarbon rubber Viton GBL200 70 Fluorocarbon rubber Viton GBL900 90 Fluorocarbon rubber Viton A500 EVA VF120T EVA Evaflex EV360 20 20 EEA NUC6510 EVA Evaflex EV180 Acrylic rubber Vamac DP Et-FEP copolymer RP4020 (mp 160° C.) Organic PERHEXA 25B 0.4 0.1 0.1 0.25 peroxide Inorganic Zinc oxide Zinc Oxide No. 1 50 40 filler Calcium carbonate SOFTON 1200 50 50 Silica Aerosil 200 1 Silica CRYSTALITE 5X Calcined clay Satitone SP-33 30 Talc MVTalc 50 Silane Vinyltrimethoxysilane KBM-1003 5 5 5 coupling Vinyltriethoxysilane KBE-1003 15 agent Catalyst MB Carrier Fluorocarbon rubber AFLAS 150P 10 rubber Fluorocarbon rubber DAI-EL G801 10 10 Fluorocarbon rubber Viton GBL200 10 Fluorocarbon rubber Viton A500 Et-FEP copolymer RP4020 (mp 160° C.) ETFE resin LH-8000 (mp 180° C.) ETFE resin EP610 (mp 180° C.) PVDF resin KAYNER740 (mp 170° C.) Silanol Dioctyltin dilaurate ADKSTAB OT-1 0.05 0.05 0.05 0.05 condensation catalyst Antioxidizing IRGANOX 1010 0.1 0.1 0.1 0.1 agent Mixed at ETFE resin EP521 (mp 260° C.) extrusion Et-FEP copolymer RP4020 (160° C.) Evaluation Heat deformation test (%) 25 35 36 33 Hot set test A A A A Winding heating test A A A A Adhesion of electric wire after electric wire production B B B B Extrusion outer appearance B A B A Tensile strength (MPa) Tensile elongation (%) Heat aging test Tensile strength retention rate (%) (236° C. × 168 hr) Tensile elongation retention rate (%) Note: “Et-FEP copolymer” stands for Ethylene-FEP copolymer.

(79) TABLE-US-00002 TABLE 2 This invention 10 11 12 24 25 26 Silane MB Base rubber Fluorocarbon rubber AFLAS 150P 70 Fluorocarbon rubber AFLAS 150E 50 60 Fluorocarbon rubber DAI-EL G801 Fluorocarbon rubber Viton GBL200 Fluorocarbon rubber Viton GBL900 Fluorocarbon rubber Viton A500 90 50 70 EVA VF120T 20 EVA Evaflex EV360 20 EEA NUC6510 40 EVA Evaflex EV180 40 40 Acrylic rubber Vamac DP Et-FEP copolymer RP4020 (mp 160° C.) Organic PERHEXA 25B 0.2 0.05 0.1 0.15 0.15 0.2 peroxide Inorganic Zinc oxide Zinc Oxide No. 1 10 150 10 10 10 150 filler Calcium carbonate SOFTON 1200 50 150 50 50 150 Silica Aerosil 200 Silica CRYSTALITE 5X 60 Calcined clay Satitone SP-33 Talc MVTalc Silane Vinyltrimethoxysilane KBM-1003 5 7 12 5 5 7 coupling Vinyltriethoxysilane KBE-1003 agent Catalyst MB Carrier Fluorocarbon rubber AFLAS 150P 10 10 10 rubber Fluorocarbon rubber DAI-EL G801 Fluorocarbon rubber Viton GBL200 Fluorocarbon rubber Viton A500 10 10 10 Et-FEP copolymer RP4020 (mp 160° C.) ETFE resin LH-8000 (mp 180° C.) ETFE resin EP610 (mp 180° C.) PVDF resin KAYNER740 (mp 170° C.) Silanol Dioctyltin dilaurate ADKSTAB OT-1 0.05 0.05 0.05 0.05 0.05 0.05 condensation catalyst Antioxidizing IRGANOX 1010 0.1 0.1 0.1 0.1 0.1 0.1 agent Mixed at ETFE resin EP521 (mp 260° C.) extrusion Et-FEP copolymer RP4020 (160° C.) Evaluation Heat deformation test (%) 32 22 28 28 26 29 Hot set test A A A A A A Winding heating test A A A A A A Adhesion of electric wire after electric wire production B B B B B B Extrusion outer appearance B A A A A A Tensile strength (MPa) 6.2 Tensile elongation (%) 250 Heat aging test Tensile strength retention rate (%) 122 (236° C. × 168 hr) Tensile elongation retention rate (%) 82 Comparative example 1 2 3 Silane MB Base rubber Fluorocarbon rubber AFLAS 150P 90 Fluorocarbon rubber AFLAS 150E 90 90 Fluorocarbon rubber DAI-EL G801 Fluorocarbon rubber Viton GBL200 Fluorocarbon rubber Viton GBL900 Fluorocarbon rubber Viton A500 EVA VF120T EVA Evaflex EV360 EEA NUC6510 EVA Evaflex EV180 Acrylic rubber Vamac DP Et-FEP copolymer RP4020 (mp 160° C.) Organic PERHEXA 25B 0.6 0.001 0.05 peroxide Inorganic Zinc oxide Zinc Oxide No. 1 10 10 0.2 filler Calcium carbonate SOFTON 1200 50 60 Silica Aerosil 200 Silica CRYSTALITE 5X Calcined clay Satitone SP-33 Talc MVTalc Silane Vinyltrimethoxysilane KBM-1003 5 5 5 coupling Vinyltriethoxysilane KBE-1003 agent Catalyst MB Carrier Fluorocarbon rubber AFLAS 150P 10 10 10 rubber Fluorocarbon rubber DAI-EL G801 Fluorocarbon rubber Viton GBL200 Fluorocarbon rubber Viton A500 Et-FEP copolymer RP4020 (mp 160° C.) ETFE resin LH-8000 (mp 180° C.) ETFE resin EP610 (mp 180° C.) PVDF resin KAYNER740 (mp 170° C.) Silanol Dioctyltin dilaurate ADKSTAB OT-1 0.05 0.05 0.05 condensation catalyst Antioxidizing IRGANOX 1010 0.1 0.1 0.1 agent Mixed at ETFE resin EP521 (mp 260° C.) extrusion Et-FEP copolymer RP4020 (160° C.) Evaluation Heat deformation test (%) Could 84 78 Hot set test not C C Winding heating test formed C C Adhesion of electric wire after electric wire production C C Extrusion outer appearance C A C Tensile strength (MPa) Tensile elongation (%) Heat aging test Tensile strength retention rate (%) (236° C. × 168 hr) Tensile elongation retention rate (%) Note: “Et-FEP copolymer” stands for Ethylene-FEP copolymer.

(80) TABLE-US-00003 TABLE 3 Comparative example 4 5 6 Silane MB Base rubber Fluorocarbon rubber AFLAS 150P 90 Fluorocarbon rubber AFLAS 150E 50 Fluorocarbon rubber DAI-EL G801 Fluorocarbon rubber Viton GBL200 90 Fluorocarbon rubber Viton GBL900 Fluorocarbon rubber Viton A500 EVA VF120T EVA Evaflex EV360 EEA NUC6510 EVA Evaflex EV180 40 Acrylic rubber Vamac DP Et-FEP copolymer RP4020 (mp 160° C.) Organic PERHEXA 25B 0.05 0.05 0.05 peroxide Inorganic filler Zinc oxide Zinc Oxide No. 1 4 4 4 Calcium carbonate SOFTON 1200 300 100 100 Silica Aerosil 200 Silica CRYSTALITE 5X Calcined clay Satitone SP-33 150 Talc MVTalc Silane Vinyltrimethoxysilane KBM-1003 7 16 1 coupling Vinyltriethoxysilane KBE-1003 4 agent Catalyst MB Carrier rubber Fluorocarbon rubber AFLAS 150P 10 10 10 Fluorocarbon rubber DAI-EL G801 Fluorocarbon rubber Viton GBL200 Fluorocarbon rubber Viton A500 Et-FEP copolymer RP4020 (mp 160° C.) ETFE resin LH-8000 (mp 180° C.) ETFE resin EP610 (mp 180° C.) PVDF resin KAYNER740 (mp 170° C.) Silanol Dioctyltin dilaurate ADKSTAB OT-1 0.05 0.05 0.05 condensation catalyst Antioxidizing IRGANOX 1010 0.1 0.1 0.1 agent Mixed at ETFE resin EP521 (mp 260° C.) extrusion Et-FEP copolymer RP4020 (160° C.) Evaluation Heat deformation test (%) 62 40 83 Hot set test C C C Winding heating test C B C Adhesion of electric wire after electric wire production B B C Extrusion outer appearance C C A Tensile strength (MPa) Tensile elongation (%) Heat aging test Tensile strength retention rate (%) (236° C. × 168 hr) Tensile elongation retention rate (%) This invention 13 14 15 16 17 18 Silane MB Base rubber Fluorocarbon rubber AFLAS 150P 70 60 50 40 60 Fluorocarbon rubber AFLAS 150E Fluorocarbon rubber DAI-EL G801 Fluorocarbon rubber Viton GBL200 60 Fluorocarbon rubber Viton GBL900 Fluorocarbon rubber Viton A500 EVA VF120T 20 20 20 20 EVA Evaflex EV360 EEA NUC6510 20 20 EVA Evaflex EV180 Acrylic rubber Vamac DP Et-FEP copolymer RP4020 (mp 160° C.) Organic PERHEXA 25B 0.1 0.1 0.1 0.1 0.1 0.1 peroxide Inorganic filler Zinc oxide Zinc Oxide No. 1 10 10 10 10 10 10 Calcium carbonate SOFTON 1200 Silica Aerosil 200 Silica CRYSTALITE 5X 60 60 60 60 60 60 Calcined clay Satitone SP-33 Talc MVTalc Silane Vinyltrimethoxysilane KBM-1003 12 12 12 12 12 12 coupling Vinyltriethoxysilane KBE-1003 agent Catalyst MB Carrier rubber Fluorocarbon rubber AFLAS 150P 5 5 Fluorocarbon rubber DAI-EL G801 Fluorocarbon rubber Viton GBL200 Fluorocarbon rubber Viton A500 Et-FEP copolymer RP4020 (mp 160° C.) 5 15 20 30 40 ETFE resin LH-8000 (mp 180° C.) 20 ETFE resin EP610 (mp 180° C.) PVDF resin KAYNER740 (mp 170° C.) Silanol Dioctyltin dilaurate ADKSTAB OT-1 0.05 0.05 0.05 0.05 0.05 0.05 condensation catalyst Antioxidizing IRGANOX 1010 0.1 0.1 0.1 0.1 0.1 0.1 agent Mixed at ETFE resin EP521 (mp 260° C.) extrusion Et-FEP copolymer RP4020 (160° C.) Evaluation Heat deformation test (%) 22 16 14 14 12 20 Hot set test A A A A A A Winding heating test A A A A A A Adhesion of electric wire after electric wire production A A A A A A Extrusion outer appearance A A A A B A Tensile strength (MPa) 8.5 9.2 10.4 12.4 13.9 11.2 Tensile elongation (%) 230 230 210 200 180 180 Heat aging test Tensile strength retention rate (%) 123 125 126 128 125 125 (236° C. × 168 hr) Tensile elongation retention rate (%) 81 78 80 78 75 73 Note: “Et-FEP copolymer” stands for Ethylene-FEP copolymer.

(81) TABLE-US-00004 TABLE 4 This invention 19 20 21 22 23 27 Silane MB Base rubber Fluorocarbon rubber AFLAS 150P 60 60 60 60 50 60 Fluorocarbon rubber AFLAS 150E Fluorocarbon rubber DAI-EL G801 Fluorocarbon rubber Viton GBL200 Fluorocarbon rubber Viton GBL900 Fluorocarbon rubber Viton A500 EVA VF120T 20 20 20 20 20 EVA Evaflex EV360 EEA NUC6510 20 EVA Evaflex EV180 Acrylic rubber Vamac DP Et-FEP copolymer RP4020 (mp 160° C.) 10 10 Organic PERHEXA 25B 0.1 0.1 0.1 0.1 0.1 0.1 peroxide Inorganic Zinc oxide Zinc Oxide No. 1 10 10 10 10 10 10 filler Calcium carbonate SOFTON 1200 Silica Aerosil 200 Silica CRYSTALITE 5X 60 60 60 60 60 60 Calcined clay Satitone SP-33 Talc MVTalc Silane Vinyltrimethoxysilane KBM-1003 12 12 12 12 12 12 coupling Vinyltriethoxysilane KBE-1003 agent Catalyst MB Carrier Fluorocarbon rubber AFLAS 150P 10 10 10 rubber Fluorocarbon rubber DAI-EL G801 Fluorocarbon rubber Viton GBL200 Fluorocarbon rubber Viton A500 Et-FEP copolymer RP4020 (mp 160° C.) ETFE resin LH-8000 (mp 180° C.) ETFE resin EP610 (mp 180° C.) 20 10 PVDF resin KAYNER740 (mp 170° C.) 20 Silanol Dioctyltin dilaurate ADKSTAB OT-1 0.05 0.05 0.05 0.05 0.05 0.05 condensation catalyst Antioxidizing IRGANOX 1010 0.1 0.1 0.1 0.1 0.1 0.1 agent Mixed at ETFE resin EP521 (mp 260° C.) 20 extrusion Et-FEP copolymer RP4020 (160° C.) 10 Evaluation Heat deformation test (%) 22 21 25 24 23 21 Hot set test A A A A A A Winding heating test A A A A A A Adhesion of electric wire after electric wire production A A A A A A Extrusion outer appearance B A A B B A Tensile strength (MPa) 8 12.2 8.6 8 8.4 8.4 Tensile elongation (%) 110 180 160 130 140 240 Heat aging test Tensile strength retention rate (%) 130 124 130 128 132 121 (236° C. × 168 hr) Tensile elongation retention rate (%) 72 78 68 68 66 83 Note: “Et-FEP copolymer” stands for Ethylene-FEP copolymer.

(82) As is apparent from the results shown in Tables 1 to 4, all in Examples 1 to 27 passed the heat deformation test, the hot set test and the winding heating test. Thus, according the present invention, the electric wire having the crosslinked fluorocarbon rubber formed body which was excellent in heat resistance and was not melted even at a high temperature as the coating was able to be produced. Furthermore, it is found that the crosslinked fluorocarbon rubber formed body contains the crosslinked body of the fluorocarbon rubber, and therefore is excellent also in oil resistance. Further, the electric wires in Examples 1 to 27 passed also the outer appearance test, and the electric wire having the crosslinked fluorocarbon rubber formed body having excellent outer appearance as the coating was able to be produced. In particular, if the resin of the ethylene-vinyl acetate copolymer is simultaneously used, it is found that by far higher heat resistance can be provided. In addition, all in Examples 1, 2, 12 to 23 and 27 exhibited excellent results in the heat aging test, and had long-term heat resistance.

(83) Further, Examples 13 to 23 and 27 all containing the fluorocarbon resins were excellent in tensile strength and excellent in mechanical characteristics.

(84) In contrast, in Comparative Example 1 in which the content of the organic peroxide was excessively large, even extrusion forming was unable to be performed. Comparative Example 2 in which the content of the organic peroxide was excessively small, failed to pass the heat deformation test, the hot set test, and the winding heating test. Even when the content of the inorganic filler was excessively small (Comparative Example 3) or when the content of the inorganic filler was excessively large (Comparative Example 4), these examples failed to pass the heat deformation test, the hot set test, and the winding heating test. Comparative Example 5 in which the content of the silane coupling agent was excessively large, failed to pass the hot set test, and Comparative Example 6 in which the content of the silane coupling agent was excessively small, failed to pass the heat deformation test and the winding heating test.

(85) Having described our invention as related to the present embodiments, it is our intention that the invention not be limited by any of the details of the description, unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the accompanying claims.