US20200332037A1 - Insulated communication wire - Google Patents

Insulated communication wire Download PDF

Info

Publication number
US20200332037A1
US20200332037A1 US16/921,727 US202016921727A US2020332037A1 US 20200332037 A1 US20200332037 A1 US 20200332037A1 US 202016921727 A US202016921727 A US 202016921727A US 2020332037 A1 US2020332037 A1 US 2020332037A1
Authority
US
United States
Prior art keywords
wire
tfe
insulated communication
communication wire
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US16/921,727
Inventor
Tadaharu Isaka
Ryouichi Fukagawa
Takeshi Shimono
Keizou Shiotsuki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Daikin America Inc
Original Assignee
Daikin Industries Ltd
Daikin America Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd, Daikin America Inc filed Critical Daikin Industries Ltd
Priority to US16/921,727 priority Critical patent/US20200332037A1/en
Assigned to DAIKIN INDUSTRIES, LTD., DAIKIN AMERICA, INC. reassignment DAIKIN INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FUKAGAWA, RYOUICHI, SHIMONO, TAKESHI, SHIOTSUKI, KEIZOU, ISAKA, TADAHARU
Publication of US20200332037A1 publication Critical patent/US20200332037A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18Monomers containing fluorine
    • C08F214/26Tetrafluoroethene
    • C08F214/262Tetrafluoroethene with fluorinated vinyl ethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18Monomers containing fluorine
    • C08F214/26Tetrafluoroethene
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18Homopolymers or copolymers of tetrafluoroethene
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • H01B3/445Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds

Definitions

  • the present invention relates to an insulated communication wire comprising a conductive metal core wire and an insulative coating, which insulated communication wire may connect a computer with a peripheral device, and which insulated communication wire may be a data transmission cable or LAN cable.
  • the insulative coating comprises a tetrafluoroethylene/hexafluoropropylene copolymer.
  • Fluororesins which have excellent characteristics such as thermal resistance, chemical resistance, solvent resistance, and insulation properties, are processed into various products such as tubes, pipes, and filaments by melt extrusion molding, for example, and the products are widely commercially available.
  • tetrafluoroethylene/hexafluoropropylene copolymers have a lower dielectric constant, a lower dielectric loss tangent, and better insulation properties than other fluororesins. Therefore, tetrafluoroethylene/hexafluoropropylene copolymers are suitably used for coating of electric wires such as cables and wires.
  • Production sites of coated electric wires currently require improvement in productivity and reduction in cost. Consequently, various considerations to increase the molding speed and to reduce defects in molding are proposed in the production sites.
  • Patent Literature 1 suggests as a fluorine-containing copolymer having a good formability even in high-speed extrusion coating of an electric wire which enables coating of an electric wire without the formation of melt fracture and the fluctuation of a wire diameter, a fluorine-containing copolymer including constitutional units derived from tetrafluoroethylene, hexafluoropropylene, and at least one perfluoroalkyl vinyl ether of the formula:
  • n is 0 to 3
  • a weight ratio of the constitutional units being (75 to 92):(8 to 20):(0 to 5)
  • the fluorine-containing copolymer having a melt flow rate at 372° C. and a load of 5000 g of 10 to 35 g/10 min and a die swell of 5% to 20%.
  • Patent Literature 2 suggests a tetrafluoroethylene/hexafluoropropylene copolymer formed from at least tetrafluoroethylene and hexafluoropropylene and, optionally, a third monomer, wherein the copolymer is not in admixture with a resin having a melting point at least 20° C.
  • the tetrafluoroethylene/hexafluoropropylene copolymer has a complex viscosity of from 2.0 ⁇ 10 3 to 10.0 ⁇ 10 3 Pa ⁇ s and a storage modulus of from 0.1 to 3.5 Pa in melt viscoelasticity measurement under conditions of ambient temperature of 310° C. and angular frequency of 0.01 rad/s.
  • Patent Literature 3 discloses an FEP pellet having a volatile content of 0.2% by weight or less and satisfying the requirement that an adhesive strength between the insulating material and the core wire is 0.8 kg or more, and an average number of cone-breaks in the insulating material is one or less per 50,000 ft of the coated core wire.
  • Patent Literature 4 discloses a fluororesin composition including polytetrafluoroethylene (PTFE) having a standard specific gravity of 2.15 to 2.30 and a tetrafluoroethylene/hexafluoropropylene copolymer (FEP), the content of the PTFE being 0.01 to 3 parts by mass per 100 parts by mass of the FEP, the alkali metal content being less than 5 ppm on the resin composition solid matter basis, the composition being obtained by a method including the step (1) of preparing a coagulated fluororesin powder by mixing an aqueous dispersion containing the FEP and an aqueous dispersion containing the PTFE together, followed by coagulation, the step (2) of melt extruding the coagulated powder, and the step (3) of subjecting the extrusion product to treatment for stabilizing unstable terminal groups of the PTFE and FEP.
  • PTFE polytetrafluoroethylene
  • FEP tetrafluoroethylene/hexafluoropropy
  • Patent Literature 1 WO 01/036504
  • Patent Literature 2 JP 2011-514407 T
  • Patent Literature 3 US 2003/0157324
  • Patent Literature 4 JP 2010-539252 T
  • the present invention aims to provide a tetrafluoroethylene/hexafluoropropylene copolymer which is less likely to form a lump, or is less likely to form a large lump even if a lump is formed, during the formation of an electric wire.
  • the present inventors have intensively studied about a tetrafluoroethylene/hexafluoropropylene copolymer which is less likely to form a lump during the formation of an electric wire, and found that a tetrafluoroethylene/hexafluoropropylene copolymer having a melt flow rate (MFR) within a specific range, a swell within a specific range, and a specific number or less of specific end groups is less likely to form a lump, or is less likely to form a large lump even if a lump is formed, during the formation of an electric wire.
  • MFR melt flow rate
  • the present invention relates to a tetrafluoroethylene/hexafluoropropylene copolymer having a melt flow rate measured at 372° C. of 35.0 to 45.0 g/10 minutes and a swell of ⁇ 8.0% to 5.0%, the sum of the numbers of —CF 2 H groups and unstable end groups being 120 or less per 1 ⁇ 10 6 carbon atoms.
  • the sum of the numbers of —CF 2 H groups and unstable end groups is preferably 50 or less, more preferably 20 or less per 1 ⁇ 10 6 carbon atoms.
  • the swell is preferably ⁇ 6.0% to 4.9%.
  • the tetrafluoroethylene/hexafluoropropylene copolymer of the present invention preferably has a heating weight loss of 0.1% by weight or less after heating at 372° C. for 30 minutes.
  • the tetrafluoroethylene/hexafluoropropylene copolymer of the present invention preferably has a melting point of 245° C. to 280° C.
  • the tetrafluoroethylene/hexafluoropropylene copolymer of the present invention preferably includes a polymerized unit derived from tetrafluoroethylene, a polymerized unit derived from hexafluoropropylene, and a polymerized unit derived from a perfluoro(alkyl vinyl ether).
  • the perfluoro(alkyl vinyl ether) is preferably a perfluoro(propyl vinyl ether).
  • the present invention also relates to an electric wire including:
  • a coating including the tetrafluoroethylene/hexafluoropropylene copolymer including the tetrafluoroethylene/hexafluoropropylene copolymer.
  • the electric wire is preferably a foamed electric wire.
  • the tetrafluoroethylene/hexafluoropropylene copolymer of the present invention has the aforementioned configuration, it is less likely to form a lump, or is less likely to form a large lump even if a lump is formed, during the formation of an electric wire.
  • the tetrafluoroethylene (TFE)/hexafluoropropylene (HFP) copolymer of the present invention has a MFR within a specific range, a swell within a specific range, and a specific number or less of specific end groups.
  • the TFE/HFP copolymer of the present invention includes a polymerized unit derived from TFE (TFE unit) and a polymerized unit derived from HFP (HFP unit).
  • the TFE/HFP copolymer of the present invention may be a bipolymer consisting only of a TFE unit and a HFP unit, or may be a terpolymer or multicomponent polymer containing a TFE unit, a HFP unit, and a polymerized unit(s) derived from a monomer(s) copolymerizable with TFE and HFP.
  • the copolymerizable monomer may be any monomer, and can appropriately be selected from ethylene, propylene, perfluoro(alkyl vinyl ethers) (PAVEs), (perfluoroalkyl)ethylenes, hydrofluoroolefins, (fluoroalkyl)ethylenes, perfluoro(alkyl allyl ethers), and the like.
  • PAVEs perfluoro(alkyl vinyl ethers)
  • (perfluoroalkyl)ethylenes hydrofluoroolefins
  • fluoroalkyl)ethylenes perfluoro(alkyl allyl ethers
  • the perfluoroalkyl group of these monomers preferably has 1 to 10 carbon atoms.
  • PAVEs include perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) (PEVE), and perfluoro(propyl vinyl ether) (PPVE).
  • the TFE/HFP copolymer of the present invention is also preferably a perfluoro copolymer because it has better electrical properties.
  • the copolymerizable monomer is preferably PAVE, more preferably PPVE, in terms of crack resistance.
  • the TFE/HFP copolymer of the present invention is preferably a TFE/HFP/PAVE copolymer that includes a TFE unit, a HFP unit, and a polymerized unit derived from PAVE (PAVE unit), more preferably a TFE/HFP/PPVE copolymer.
  • the TFE/HFP copolymer of the present invention has a mass ratio of TFE/HFP of preferably (80 to 97)/(3 to 20), more preferably (84 to 92)/(8 to 16) in terms of formability.
  • the TFE/HFP copolymer of the present invention is a TFE/HFP/PAVE copolymer
  • the TFE/HFP/PAVE copolymer has a mass ratio of TFE/HFP/PAVE of preferably (70 to 97)/(3 to 20)/(0.1 to 10), more preferably (81 to 92)/(5 to 16)/(0.3 to 5).
  • the TFE/HFP copolymer of the present invention has a melt flow rate (MFR) measured at 372° C. of 35.0 to 45.0 g/10 min.
  • the TFE/HFP copolymer of the present invention having a MFR within the above range is less likely to form a lump, or is less likely to form a large lump even if a lump is formed, during the formation of an electric wire.
  • the lower limit of the MFR is preferably 35.1/10 min, more preferably 35.5 g/10 min, still more preferably 36.0 g/10 min, and the upper limit thereof is preferably 44.5 g/10 min, more preferably 44.0 g/10 min, still more preferably 42.0 g/10 min.
  • the TFE/HFP copolymer having such a MFR may further prevent the formation of a lump during the formation of an electric wire.
  • the MFR is a value determined in conformity with ASTM D 1238 at a load of 5 kg and a temperature of 372° C. using a die having a diameter of 2.0 m and a length of 8 mm.
  • the TFE/HFP copolymer of the present invention has a swell of ⁇ 8.0% to 5.0%.
  • the TFE/HFP copolymer of the present invention having a swell within the above range is less likely to form a lump, or is less likely to form a large lump even if a lump is formed, during the formation of an electric wire.
  • the lower limit of the swell is preferably ⁇ 6.0%, more preferably ⁇ 5.0%, still more preferably ⁇ 4.0%.
  • the swell is preferably less than 5.0%, more preferably 4.9% or less, still more preferably 4.5% or less, further still more preferably 4.0% or less.
  • the TFE/HFP copolymer having such a swell may further prevent the formation of a lump during the formation of an electric wire.
  • the TFE/HFP copolymer having a swell within the above range enables selection of the temperature in molding from a wide temperature range.
  • the swell can be adjusted, for example, by controlling the screw speed (rpm) of a twin screw extruder used when a dry powder of the TFE/HFP copolymer obtained by polymerization is formed into pellets.
  • the swell is also referred to as a “die swell”, and is defined as a “percentage of swelling” in JP S48-20788 B and is also expressed as a “swelling rate” in JP H02-7963 B, for example.
  • TFE/HFP copolymer Since the TFE/HFP copolymer is insoluble and has a high molecular weight, it is impossible to directly measure its molecular weight distribution. Therefore, expansion tendency (swell) on melt extrusion, which is considered to be associated with the molecular weight distribution, is usually used as a measure of the molecular weight distribution.
  • the swell is determined in the following way.
  • melt indexer e.g. KAYNESS melt indexer (Model 4002)
  • about 2 g of a resin is placed in a 0.376-inch cylinder maintained at 372° C. ⁇ 0.5° C., and the cylinder is allowed to stand for 5 minutes to cause the temperature to reach equilibrium.
  • the resin is extruded through an orifice for die swell measurement having a diameter of 1 mm (margin of error: +0.002 mm or less) under a load of 5000 g with a piston.
  • the extruded strand is allowed to cool to room temperature, and the diameter thereof is measured.
  • the length of the strand is 30 ⁇ 5 mm, and the diameter is measured at a portion 5 ⁇ 1 mm from the tip portion extruded first of the strand.
  • the average of the diameters of three strands obtained in the same period is determined, and the die swell is calculated using the following formula:
  • the sum of the numbers of —CF 2 H groups and unstable end groups is 120 or less per 1 ⁇ 10 6 carbon atoms.
  • the TFE/HFP copolymer is less likely to form a lump, or is less likely to form a large lump even if a lump is formed, during the formation of an electric wire.
  • the sum of the numbers of —CF 2 H groups and unstable end groups is preferably 50 or less, more preferably 20 or less per 1 ⁇ 10 6 carbon atoms. With such a sum of the numbers of —CF 2 H groups and unstable end groups, the TFE/HFP copolymer can further prevent the formation of a lump during the formation of an electric wire.
  • the sum of the numbers of —CF 2 H groups and unstable end groups in the TFE/HFP copolymer may be 30 or more.
  • the number of lumps formed may be slightly larger than in the case of a copolymer in which the sum of the numbers of —CF 2 H groups and unstable end groups is less than 30, while, when such a TFE/HFP copolymer is used for a coating of an electric wire, higher adhesion strength is expected between the core wire and the coating.
  • the unstable end group refers to a —COF group, a —COOH group, a —COOCH 3 group, a —CONH 2 group, and a —CH 2 OH group, which are present at an end of the main chain.
  • the numbers of —CF 2 H groups and unstable end groups can be determined by NMR measurement or infrared absorption spectroscopy as described in WO 2008/047906 and WO 2009/044753.
  • the number of —CF 2 H groups can be determined from the integration value of the peak derived from the —CF 2 H groups obtained by 19 F-NMR measurement at a temperature of “melting point of polymer+20° C.” using a nuclear magnetic resonance apparatus AC300 (available from Bruker-Biospin Co., Ltd).
  • the number of the unstable end groups is determined as follows: a film with a thickness of 0.25 to 0.30 mm is prepared by compressing powder of the TFE/HFP copolymer of the present invention at 350° C. for 30 minutes or by cold-pressing pellets of the TFE/HFP copolymer; the resulting film is subjected to infrared absorption spectroscopy; the resulting infrared absorption spectrum is compared to the infrared absorption spectrum of a known film to identify the type of the end group; and the number of the unstable end groups is determined from the differential spectrum using the following formula:
  • the correction factor can be determined from the infrared absorption spectrum of a model compound, and the correction factors shown in Table 1 can be used.
  • TFE/HFP copolymer in which the sum of the numbers of —CF 2 H groups and unstable end groups is as described above can be obtained by fluorination.
  • Non-fluorinated copolymers may contain a —CF 2 H group or a thermally or electrically unstable end group (unstable end group) in some cases.
  • the number of these end groups can be reduced by fluorination.
  • the non-fluorinated copolymer may or may not be completely fluorinated by fluorination.
  • the sum of the numbers of —CF 2 H groups and unstable end groups can be controlled by generating —CF 2 H groups and unstable end groups through the decomposition of the TFE/HFP copolymer, or by mixing two or more TFE/HFP copolymers different in the sum of the numbers of —CF 2 H groups and unstable end groups.
  • the fluorination can be performed by bringing a non-fluorinated TFE/HFP copolymer into contact with a fluorine-containing compound.
  • the fluorine-containing compound may be any compound, and examples thereof include fluorine radical sources that generate fluorine radicals under the fluorination conditions.
  • fluorine radical sources include F 2 gas, CoF 3 , AgF 2 , UF 6 , OF 2 , N 2 F 2 , CF 3 OF, and halogen fluorides (e.g., IF 5 , ClF 3 ).
  • the fluorine radical source such as F 2 gas may have a concentration of 100%.
  • the fluorine radical source is diluted with an inert gas to preferably 5% to 50% by mass, preferably 15% to 30% by mass.
  • the inert gas include nitrogen gas, helium gas, and argon gas. In order to save the cost, nitrogen gas is preferred.
  • the fluorination can be performed under any conditions, and may be performed by bringing a molten TFE/HFP copolymer into contact with a fluorine-containing compound.
  • the fluorination is usually performed at a temperature of not higher than the melting point of the TFE/HFP copolymer, preferably 20° C. to 220° C., more preferably 100° C. to 200° C.
  • the fluorination is usually performed for 1 to 30 hours, preferably 5 to 20 hours.
  • the fluorination is preferably performed by bringing a non-fluorinated TFE/HFP copolymer into contact with a fluorine gas (F 2 gas).
  • F 2 gas fluorine gas
  • an appropriate degree of fluorination can be achieved by controlling the temperature or time of the fluorination.
  • the TFE/HFP copolymer of the present invention has a high volatile matter content, air cells tend to be generated when the copolymer is molded into a coating of an electric wire, which tends to result in instable molding.
  • the TFE/HFP copolymer has a heating weight loss of preferably 0.1% by weight or less, more preferably 0.09% by weight or less, still more preferably 0.08% by weight or less, particularly preferably 0.07% by weight, further more preferably 0.06% by weight, still further more preferably 0.05% by weight, after heating at 372° C. for 30 minutes.
  • the heating weight loss is determined by the following procedures.
  • a sample (TFE/HFP copolymer in the form of pellets) is placed on an aluminum cup which is already baked at 372° C. for 1 hour (the weight is expressed as A) and accurately weighed to 20 ⁇ 0.1 g using a precision scale (which measures in 0.1 mg increments). The entire weight is expressed by B.
  • the two samples are quickly placed on the turntable of the electric furnace heated to 372° C. This turntable turns at 6 rpm.
  • the samples are taken out from the furnace 30 minutes after the temperature in the furnace has reached 372° C. again, and quickly put into a desiccator.
  • the samples are allowed to cool for one hour or more, and then each sample is accurately weighed with the precision scale.
  • the measured weight is defined as C.
  • the heating weight loss of each sample heated at 372° C. for 30 minutes is calculated from the equation below, and the average of the heating weight losses (% by weight) of the two samples is determined.
  • Heating weight loss (% by weight) [( B ⁇ C )/( B ⁇ A )] ⁇ 100
  • the lower limit of the melting point of the TFE/HFP copolymer of the present invention is preferably 245° C., more preferably 250° C. in terms of thermal resistance.
  • the upper limit of the melting point of the TFE/HFP copolymer is preferably 280° C., more preferably 270° C., still more preferably 265° C. because such a TFE/HFP copolymer is readily processed.
  • the melting point is a temperature corresponding to the peak obtained by measurement using a differential scanning calorimeter at a temperature rise rate of 10° C./min.
  • the TFE/HFP copolymer of the present invention can be synthesized by polymerizing TFE, HFP, and, optionally, a monomer copolymerizable with TFE and HFP, such as PAVE, by a usual polymerization method, such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or gas phase polymerization.
  • a usual polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or gas phase polymerization.
  • the polymerization may be performed under usual conditions.
  • a chain transfer agent such as methanol may be used in some cases.
  • the TFE/HFP copolymer of the present invention may be produced by polymerization and isolation without using a metal-ion-containing reagent.
  • the TFE/HFP copolymer of the present invention is molded into a coating that covers a core wire with a diameter of 20.1 mil at a coat-molding speed of 1600 ft/min continuously for 2 hours so that a wire with a diameter of 33.7 mil is prepared, the number of lumps with a size of 20 mil or larger formed at the coating can be reduced to 10 or less, further to 7 or less.
  • the size (height) of each lump and the number of lumps can be measured with a lump detector KW32TRIO (available from Zumbach).
  • the TFE/HFP copolymer of the present invention is particularly suitable as a material of the coating of an electric wire.
  • the TFE/HFP copolymer of the present invention may be in the form of pellets.
  • the pellets can be prepared by kneading with a known melt kneader such as a single screw extruder or twin screw extruder.
  • the pellets are preferably prepared by kneading with a twin screw extruder.
  • the swell can be adjusted by controlling the screw speed (number of rotations) of a twin screw extruder in kneading.
  • the electric wire of the present invention includes a core wire and a coating containing the TFE/HFP copolymer of the present invention.
  • the coating is usually arranged on the periphery of the core wire.
  • the coating of the electric wire of the present invention is formed from the TFE/HFP copolymer of the present invention, the coating has only a small number of lumps, or has small lumps even if lumps are formed.
  • the material of the core wire may be a conductive metal material such as copper or aluminum.
  • the diameter of the core wire is preferably 0.02 to 3 mm, more preferably 0.04 mm or more, still more preferably 0.05 mm or more, particularly preferably 0.1 mm or more.
  • the diameter of the core wire is more preferably 2 mm or less.
  • core wire examples include those satisfying AWG-46 (40- ⁇ m-diameter solid copper wires), those satisfying AWG-26 (404- ⁇ m-diameter solid copper wires), those satisfying AWG-24 (510- ⁇ m-diameter solid copper wires), and those satisfying AWG-22 (635- ⁇ m-diameter solid copper wires).
  • AWG represents the American wire gauge.
  • the coating contains the TFE/HFP copolymer of the present invention.
  • the coating may consist only of the TFE/HFP copolymer of the present invention, or may contain a conventionally known filler and other components in addition to the TFE/HFP copolymer of the present invention, as long as the effects of the present invention are not impaired.
  • the amount of the TFE/HFP copolymer of the present invention is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, particularly preferably 95% by mass or more, more particularly preferably substantially 100% by mass relative to the coating.
  • the filler examples include graphite, carbon fiber, coke, silica, zinc oxide, magnesium oxide, tin oxide, antimony oxide, calcium carbonate, magnesium carbonate, glass, talc, mica, mica, aluminum nitride, calcium phosphate, sericite, diatomite, silicon nitride, fine silica, alumina, zirconia, quartz powder, kaolin, bentonite, and titanium oxide.
  • the filler may be in any form, and may be in the form of, for example, fibers, needles, powder, particles, or beads.
  • the coating may further contain a thermoplastic resin other than the TFE/HFP copolymer of the present invention.
  • thermoplastic resin other than the TFE/HFP copolymer of the present invention include general-purpose resins such as polyethylene resin, polypropylene resin, vinyl chloride resin, and polystyrene resin; and engineering plastics such as nylon, polycarbonate, polyether ether ketone resin, and polyphenylene sulfide resin.
  • the coating may further contain any other components such as additives.
  • additives include fillers such as glass fiber, glass powder, and asbestos fiber, reinforcing agents, stabilizers, lubricants, pigments, and other additives.
  • the coating may further contain a foam nucleating agent.
  • a foam nucleating agent is used when the coating is foamed as described below. Therefore, the coating usually contains a foam nucleating agent.
  • foam nucleating agent examples include sulfonic acid, phosphonic acid, salts thereof, boron nitride, and inorganic salts containing a polyatomic anion.
  • the amount of the foam nucleating agent in the coating may be appropriately adjusted to suit the use of a resulting electric wire, and is, for example, 0.1% to 10% by mass relative to the coating.
  • the boron nitride may be pulverized and/or classified.
  • polyatomic anion-containing inorganic salt examples include those disclosed in U.S. Pat. No. 4,764,538 A.
  • the coating may or may not be foamed.
  • the electric wire having a foamed coating is called a foamed electric wire.
  • the electric wire of the present invention is also preferably a foamed electric wire.
  • the use of the foamed coating can provide a coated electric wire with small transmission loss.
  • the coating preferably has a foam content of 10% to 80%.
  • the coating preferably has air cells with an average diameter of 5 to 100 ⁇ m.
  • the foam content of the coating means a percentage of change in specific gravity of the material before and after foaming, and is determined by measuring, by the water displacement method, the percentage of change between the characteristic specific gravity of a material constituting a foam and the apparent specific gravity of the foam.
  • the average diameter of air cells can be calculated from a microscope photograph of the cross-section of the foam.
  • the coating can be foamed by a conventionally known method.
  • the method include (1) a method in which pellets of the TFE/HFP copolymer of the present invention containing a foam nucleating agent are prepared, and then extrusion coated while gas is continually introduced to the pellets, and (2) a method in which gas is generated by decomposing a chemical foaming agent, which has been mixed with the molten TFE/HFP copolymer of the present invention, through extrusion coating to provide air cells.
  • the foam nucleating agent may be a well-known one such as boron nitride (BN).
  • BN boron nitride
  • the gas include chlorodifluoromethane, nitrogen, carbon dioxide, and a mixture of these.
  • Examples of the chemical foaming agent in the method (2) include azodicarbonamide and 4,4′-oxybis-benzenesulfonyl hydrazide.
  • the conditions in each method such as the amount of the foam nucleating agent added and the amount of the gas introduced in the method (1) and the amount of the chemical foaming agent added in the method (2), can be appropriately adjusted according to the kinds of the resin and the core wire to be used or a desired thickness of the coating.
  • the electric wire of the present invention may include a layer formed from a material other than the coating on the periphery of the coating or may include a layer formed from a material other than the coating between the core wire and the coating.
  • the layer may be any resin layer formed from a polyolefin resin such as a TFE/PAVE copolymer, a TFE/ethylene copolymer, a vinylidene fluoride polymer, or polyethylene (PE), or a resin such as polyvinyl chloride (PVC). Preferred among these are PE and PVC in view of cost effectiveness.
  • Each of the layer and the coating may have any thickness, and the thickness of the layer is preferably 1 mil to 20 mil and the thickness of the coating is preferably 1 mil to 20 mil.
  • the electric wire of the present invention when it is a foamed electric wire, it may have a double-layered (skin-foam) structure including a core wire, the coating, and a non-foamed layer disposed between the core wire and the coating, a double-layered (foam-skin) structure including a non-foamed layer that coats the outer layer of the coating, or a triple-layered (skin-foam-skin) structure including a non-foamed layer that coats the outer layer of the skin-foam structure.
  • a double-layered (skin-foam) structure including a core wire, the coating, and a non-foamed layer disposed between the core wire and the coating
  • a double-layered (foam-skin) structure including a non-foamed layer that coats the outer layer of the coating
  • a triple-layered (skin-foam-skin) structure including a non-foamed layer that coats the outer
  • the non-foamed layer of the foamed electric wire may be any resin layer formed of a polyolefin resin such as a TFE/HFP copolymer, a TFE/PAVE copolymer, a TFE/ethylene copolymer, a vinylidene fluoride polymer, or polyethylene (PE), or a resin such as PVC.
  • a polyolefin resin such as a TFE/HFP copolymer, a TFE/PAVE copolymer, a TFE/ethylene copolymer, a vinylidene fluoride polymer, or polyethylene (PE), or a resin such as PVC.
  • the electric wire of the invention is suitable as an insulated wire for communication.
  • Examples of the insulated wire for communication include cables for connecting a computer with a peripheral device such as data transmission cables (e.g. LAN cables).
  • the insulated wire is also suitable for plenum cables to be installed in a space in the ceiling cavity (plenum area) of a building.
  • the electric wire of the present invention is also suitable for high-frequency coaxial cables, flat cables, and heat-proof cables.
  • the electric wire is suitable for high-frequency coaxial cables.
  • the outer layer of a coaxial cable is not limited, and may be a conductive layer made of an outer conductor such as a metal mesh, or may be a resin layer (sheath layer) made of a TFE unit-containing fluorine-containing copolymer such as a TFE/HFP copolymer or a TFE/PAVE copolymer, PVC, PE, or any other resin.
  • the coaxial cable may be a cable that includes an outer conductive layer made of a metal on the periphery of the coated electric wire of the present invention, and the resin layer (sheath layer) on the periphery of the outer conductive layer.
  • the electric wire of the present invention can be prepared by a production method including the step of forming a coating by coating a core wire with the TFE/HFP copolymer of the present invention.
  • the core wire may be coated with the TFE/HFP copolymer of the present invention by a conventionally known coating method using an extruder.
  • the coating may be formed by applying a composition containing the TFE/HFP copolymer of the present invention, the filler described above, a thermoplastic resin other than the TFE/HFP copolymer of the present invention, other components such as additives, a foam nucleating agent, and a chemical foaming agent.
  • the composition can be prepared by mixing the TFE/HFP copolymer of the present invention, the filler described above, a thermoplastic resin other than the TFE/HFP copolymer of the present invention, other components such as additives, and a foam nucleating agent.
  • the composition can also be prepared by mixing a non-fluorinated TFE/HFP copolymer, the filler described above, a thermoplastic resin other than the TFE/HFP copolymer of the present invention, other components such as additives, a foam nucleating agent, and a chemical foaming agent, and then fluorinating the non-fluorinated TFE/HFP copolymer.
  • the mixing may be performed by a method using a Henschel mixer, a ribbon mixer, a V-blender, or a ball mill, for example.
  • the mixing may also be performed, for example, by melt-kneading.
  • the composition may be prepared by kneading the above mixture obtained by mixing.
  • the kneading can provide pellets.
  • the kneading can be performed by a method using a conventionally known melt-kneader such as a single screw extruder or a twin screw extruder.
  • the fluorination may be performed on the composition (e.g. pellets) after kneading.
  • the fluorination may be performed by bringing the pellets prepared through the kneading into contact with the fluorine-containing compound.
  • the coating speed in the formation of the coating is preferably 500 to 2500 ft/min, more preferably 1000 to 1600 ft/min.
  • the electric wire of the present invention is also preferably a foamed electric wire.
  • the electric wire of the present invention can be prepared by a conventional method except that the TFE/HFP copolymer of the present invention is used.
  • the electric wire can be produced by extrusion foaming. Preferred molding conditions can be appropriately selected according to the formulation of the composition to be used and the size of the core wire.
  • the core wire is coated with the TFE/HFP copolymer of the present invention, for example, by a method in which the TFE/HFP copolymer of the present invention is fed into a screw extruder designed for foaming operations, and a continuous gas injection method is performed using a gas soluble in the molten TFE/HFP copolymer of the present invention (molten resin).
  • the gas may be the same as that used in the method for producing a foam.
  • the resulting coating includes a melt-solidified matter of the TFE/HFP copolymer of the present invention and air cells, and the air cells are uniformly distributed in the melt-solidified matter.
  • the air cells may have any average cell size.
  • the average cell size is preferably 60 ⁇ m or smaller, more preferably 45 ⁇ m or smaller, still more preferably 35 ⁇ m or smaller, much more preferably 30 ⁇ m or smaller, particularly preferably 25 ⁇ m or smaller, more particularly preferably 23 ⁇ m or smaller.
  • the average cell size is also preferably 0.1 ⁇ m or greater, more preferably 1 ⁇ m or greater.
  • the average cell size is determined as follows: an image of the cross section of the coating is taken by a scanning electron microscope (SEM), the image is processed to determine the diameter of each air cell, and the average cell size of the air cells is calculated.
  • SEM scanning electron microscope
  • the coating preferably has a foam content of 10% or higher. It is more preferably 20% or higher, still more preferably 30% or higher, much more preferably 35% or higher.
  • the upper limit thereof may be, but not limited to, for example, 80%.
  • the upper limit of the foam content may be 60%.
  • the foam content is determined by [ ⁇ (specific gravity of TFE/HFP copolymer) ⁇ (specific gravity of foamed body) ⁇ /(specific gravity of TFE/HFP copolymer)] ⁇ 100.
  • the foam content can appropriately be adjusted to suit the use of the electric wire by, for example, controlling the amount of gas introduced into the extruder or selecting the type of gas to be dissolved.
  • the mass ratio of the polymerized units in the TFE/HFP copolymer was determined by measuring the proportions of the polymerized units using an NMR analyzer (e.g. AC300 available from Bruker Biospin Co., Ltd., high temperature probe) or an infrared spectrometer (model 1760 available from PerkinElmer, Inc.).
  • NMR analyzer e.g. AC300 available from Bruker Biospin Co., Ltd., high temperature probe
  • an infrared spectrometer model 1760 available from PerkinElmer, Inc.
  • the melting point of the TFE/HFP copolymer was a temperature corresponding to the peak obtained by measurement using a differential scanning calorimeter (RDC220 available from Seiko Instruments Inc.) at a temperature rise rate of 10° C./min.
  • the MFR of the TFE/HFP copolymer was measured in conformity with ASTM D 1238 using a KAYENESS melt indexer (Series 4000 available from YASUDA SEIKI SEISAKUSHO, LTD.) with a die having a diameter of 2.1 mm and a length of 8 mm at a temperature of 372° C. and a load of 5 kg.
  • the length of the strand was 30 ⁇ 5 mm, and the diameter was measured at a portion 5 ⁇ 1 mm from the tip portion extruded first of the strand.
  • the average of the diameters of three strands obtained in the same period was determined, and the die swell was calculated using the following formula:
  • OD the diameter of the orifice (1 mm).
  • the number of —CF 2 H groups was determined from the integration value of the peak derived from the —CF 2 H groups obtained by 19 F-NMR measurement at a temperature of “melting point of polymer+20° C.” using a nuclear magnetic resonance apparatus AC300 (available from Bruker-Biospin Co., Ltd).
  • the number of the unstable end groups was determined as follows: a film with a thickness of 0.25 to 0.30 mm was prepared by cold-pressing the resulting pellets; the film was subjected to infrared absorption spectroscopy; the resulting infrared absorption spectrum was compared to the infrared absorption spectrum of a known film to identify the type of the end group; and the number of the unstable end groups was determined from the differential spectrum using the following formula:
  • Table 1 shows the correction factors and absorption frequencies of the target end groups.
  • the correction factor was determined from the infrared absorption spectrum of a model compound so that the number of the end groups per 1 ⁇ 10 6 carbon atoms is calculated.
  • a sample (TFE/HFP copolymer in the form of pellets) was placed on an aluminum cup which was already baked at 372° C. for 1 hour (the weight was expressed as A), and accurately weighed to 20 ⁇ 0.1 g using a precision scale (which measured in 0.1 mg increments). The entire weight was expressed as B.
  • the two samples were quickly placed on the turntable of the electric furnace heated to 372° C. This turntable turned at 6 rpm.
  • the samples were taken out from the furnace 30 minutes after the temperature in the furnace had reached 372° C. again, and quickly put into a desiccator. The samples were allowed to cool for one hour or more, and then each sample was accurately weighed with the precision scale. The measured weight was defined as C.
  • the heating weight loss of each sample heated at 372° C. for 30 minutes was calculated from the equation below, and the average of the heating weight losses (% by weight) of the two samples was determined.
  • Heating weight loss (% by weight) [( B ⁇ C )/( B ⁇ A )] ⁇ 100
  • the size (height) of lumps with a size of 20 mil or larger was measured using a lump detector KW32TRIO (available from Zumbach).
  • the average of the sizes of lumps in Table 2 was the arithmetic average of the sizes of lumps formed during two-hour molding.
  • the frequency of lumps (number of formed lumps) with a size of 20 mil or larger was determined with a lump detector KW32TRIO (available from Zumbach).
  • An autoclave (1000 L) equipped with a stiffer was charged with 265 kg of deionized water, and sufficiently purged with nitrogen under vacuum. Thereafter, the air was removed to create a vacuum in the autoclave, and the autoclave was charged with 274 kg of HFP, 31 kg of TFE, and 3.0 kg of PPVE under vacuum, and heated to 32° C. Next, 1.7 kg of a 8% solution of di(w-hydroperfluorohexanoyl)peroxide (hereinafter, abbreviated to “DHP”) in perfluorohexane was put into the autoclave to initiate polymerization.
  • DHP di(w-hydroperfluorohexanoyl)peroxide
  • the internal pressure of the autoclave at the start of the polymerization was set at 1.04 MPa, and this pressure was maintained by successively adding TFE.
  • 1.7 kg of a 8% solution of DHP in perfluorohexane was added and the internal pressure was reduced by 0.01 MP.
  • 1.3 kg of a 8% solution of DHP in perfluorohexane was added and the internal pressure was reduced by 0.01 MP.
  • 1.7 kg of a 8% solution of DHP in perfluorohexane was added and the internal pressure was reduced by 0.01 MP every 2 hours.
  • 0.7 kg of PPVE was added when the total amount of TFE successively added reached 53 kg, 106 kg, and 159 kg.
  • the polymerization was terminated when the total amount of TFE successively added reached 233 kg. After the termination of the polymerization, unreacted TFE and HFP were discharged to give wet powder. The wet powder was combined with pure water, and washed by stirring. Thereafter, the wet powder was dried at 150° C. for 10 hours to give 273 kg of dry powder.
  • the resulting dry powder was pelletized using a twin screw extruder at 370° C. and a screw speed of 300 rpm, and the pellets were subjected to deaeration at 200° C. for 8 hours.
  • the resulting pellets were placed in a vacuum vibration reactor, and heated to 200° C. After vacuuming, F 2 gas diluted to 20% with N 2 gas was introduced so that the pressure was increased to atmospheric pressure. After 3 hours from the introduction of the F 2 gas, vacuuming was performed and then F 2 gas was again introduced. The introduction of F 2 gas and the vacuuming were repeated 6 times in total. Finally, the inside of the reactor was purged with N 2 gas to terminate the reaction.
  • the resulting pellets had a MFR of 37.4 g/10 min, a swell of ⁇ 0.1%, no CF 2 H groups and no unstable end groups, a heating weight loss of 0.05% by weight, and a melting point of 256.5° C.
  • the formulation of the TFE/HFP/PPVE copolymer was evaluated to give a weight ratio of TFE/HFP/PPVE of 87.5/11.5/1.0.
  • Dry powder was prepared by performing polymerization in the same manner as in Example 1 except that the amount of methanol was changed to 4.1 kg.
  • the resulting dry powder was pelletized in the same manner as in Example 1 except that the screw speed was changed to 297 rpm.
  • the pellets treated with F 2 gas had a MFR of 36.3 g/10 min.
  • the swell, the sum of the numbers of CF 2 H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • the formulation of the TFE/HFP/PPVE copolymer was evaluated to give a weight ratio of TFE/HFP/PPVE of 87.5/11.5/1.0.
  • Dry powder was prepared by performing polymerization in the same manner as in Example 1 except that the amount of methanol was changed to 3.2 kg.
  • the resulting dry powder was pelletized in the same manner as in Example 1 except that the screw speed was changed to 315 rpm.
  • the pellets treated with F 2 gas had a MFR of 35.1 g/10 min.
  • the swell, the sum of the numbers of CF 2 H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • the formulation of the TFE/HFP/PPVE copolymer was evaluated to give a weight ratio of TFE/HFP/PPVE of 87.5/11.5/1.0.
  • Dry powder was prepared by performing polymerization in the same manner as in Example 1 except that the amount of methanol was changed to 4.2 kg.
  • the resulting dry powder was pelletized in the same manner as in Example 1 except that the screw speed was changed to 320 rpm.
  • the pellets treated with F 2 gas had a MFR of 44.1 g/10 min.
  • the swell, the sum of the numbers of CF 2 H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • the formulation of the TFE/HFP/PPVE copolymer was evaluated to give a weight ratio of TFE/HFP/PPVE of 87.5/11.5/1.0.
  • Dry powder was prepared by performing polymerization in the same manner as in Example 1 except that the amount of methanol was changed to 4.9 kg.
  • the resulting dry powder was pelletized in the same manner as in Example 1 except that the screw speed was changed to 275 rpm.
  • the pellets treated with F 2 gas had a MFR of 37.0 g/10 min.
  • the swell, the sum of the numbers of CF 2 H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • the formulation of the TFE/HFP/PPVE copolymer was evaluated to give a weight ratio of TFE/HFP/PPVE of 87.5/11.5/1.0.
  • Dry powder was prepared by performing polymerization in the same manner as in Example 1 except that the amount of methanol was changed to 1.6 kg.
  • the resulting dry powder was pelletized in the same manner as in Example 1 except that the screw speed was changed to 360 rpm.
  • the resulting pellets prepared using an extruder had a MFR of 34.9 g/10 min, and the pellets treated with F 2 gas had a MFR of 35.8 g/10 min.
  • the swell, the sum of the numbers of CF 2 H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • the formulation of the TFE/HFP/PPVE copolymer was evaluated to give a weight ratio of TFE/HFP/PPVE of 87.5/11.5/1.0.
  • the dry powder prepared in Comparative Example 1 was pelletized in the same manner as in Example 1 except that the screw speed was changed to 325 rpm.
  • the pellets treated with F 2 gas had a MFR of 52.2 g/10 min.
  • the swell, the sum of the numbers of CF 2 H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • Dry powder was prepared by performing polymerization in the same manner as in Example 1 except that the amount of methanol was changed to 3.1 kg.
  • the resulting dry powder was pelletized in the same manner as in Example 1 except that the screw speed was changed to 295 rpm.
  • the resulting pellets prepared using an extruder had a MFR of 29.0 g/10 min, and the pellets treated with F 2 gas had a MFR of 30.5 g/10 min.
  • the swell, the sum of the numbers of CF 2 H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • the formulation of the TFE/HFP/PPVE copolymer was evaluated to give a weight ratio of TFE/HFP/PPVE of 87.5/11.5/1.0.
  • Example 4 The dry powder prepared in Example 4 was pelletized in the same manner as in Example 4 except that no F 2 gas treatment was performed.
  • the resulting pellets prepared using an extruder had a MFR of 42.0 g/10 min.
  • the swell, the sum of the numbers of CF 2 H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • Electric wires were produced using the pellets prepared in Examples 1 to 4 and Comparative Examples 1 to 5, and evaluated for lump size and lump frequency.
  • Comparative Example 3 an electric wire could not be continuously formed due to surging. Accordingly, a lump could not be evaluated.
  • a single-screw extruder (available from Davis-Standard) having a cylinder with a cylinder diameter of 2 inches and an L/D ratio of 30 was provided with a crosshead (available from Unitek).
  • the crosshead was equipped with a die having an inner diameter of 0.280 inches and a chip having an outer diameter of 0.160 inches.
  • An electric wire was produced so as to have a final outer diameter of 0.0337 inches using a core wire (AWG 24) with an outer diameter of 0.0201 inches under the conditions of a time of 2 hours, a speed of 1600 ft/min, and a temperature shown in Table 3. Thereafter, the lump size and the number of lumps were evaluated.
  • Zone-1 Zone-2 Zone-3 Zone-4 Zone-5 Clump Adaptor Crosshead Die Condition (° C.) 580 650 680 700 720 730 730 730 750
  • the TFE/HFP copolymer of the present invention is suitable for a material for forming a coating of an electric wire.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Organic Insulating Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Insulated Conductors (AREA)

Abstract

An insulated communication wire comprising a conductive metal core wire and an insulative coating, which insulated communication wire may connect a computer with a peripheral device, and which insulated communication wire may be a data transmission cable or LAN cable.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This is a Rule 53(b) Continuation of application Ser. No. 16/274,119 filed Feb. 12, 2019, which a Rule 53(b) Divisional Application of application Ser. No. 15/116,406 filed Aug. 3, 2016, which is a National Stage of International Application No. PCT/JP2015/052661, filed Jan. 30, 2015, which claims benefit of U.S. Provisional Application No. 61/935,949, filed Feb. 5, 2014, the disclosures of which are incorporated herein by reference in their respective entireties.
  • TECHNICAL FIELD
  • The present invention relates to an insulated communication wire comprising a conductive metal core wire and an insulative coating, which insulated communication wire may connect a computer with a peripheral device, and which insulated communication wire may be a data transmission cable or LAN cable. The insulative coating comprises a tetrafluoroethylene/hexafluoropropylene copolymer.
  • BACKGROUND ART
  • Fluororesins, which have excellent characteristics such as thermal resistance, chemical resistance, solvent resistance, and insulation properties, are processed into various products such as tubes, pipes, and filaments by melt extrusion molding, for example, and the products are widely commercially available. In particular, tetrafluoroethylene/hexafluoropropylene copolymers have a lower dielectric constant, a lower dielectric loss tangent, and better insulation properties than other fluororesins. Therefore, tetrafluoroethylene/hexafluoropropylene copolymers are suitably used for coating of electric wires such as cables and wires.
  • Production sites of coated electric wires currently require improvement in productivity and reduction in cost. Consequently, various considerations to increase the molding speed and to reduce defects in molding are proposed in the production sites.
  • For example, Patent Literature 1 suggests as a fluorine-containing copolymer having a good formability even in high-speed extrusion coating of an electric wire which enables coating of an electric wire without the formation of melt fracture and the fluctuation of a wire diameter, a fluorine-containing copolymer including constitutional units derived from tetrafluoroethylene, hexafluoropropylene, and at least one perfluoroalkyl vinyl ether of the formula:

  • CF2═CFO(CF2)nCF3
  • (wherein n is 0 to 3),
    a weight ratio of the constitutional units being (75 to 92):(8 to 20):(0 to 5), the fluorine-containing copolymer having a melt flow rate at 372° C. and a load of 5000 g of 10 to 35 g/10 min and a die swell of 5% to 20%.
  • Further, Patent Literature 2 suggests a tetrafluoroethylene/hexafluoropropylene copolymer formed from at least tetrafluoroethylene and hexafluoropropylene and, optionally, a third monomer, wherein the copolymer is not in admixture with a resin having a melting point at least 20° C. different from the melting point of the tetrafluoroethylene/hexafluoropropylene copolymer; and wherein the tetrafluoroethylene/hexafluoropropylene copolymer has a complex viscosity of from 2.0×103 to 10.0×103 Pa·s and a storage modulus of from 0.1 to 3.5 Pa in melt viscoelasticity measurement under conditions of ambient temperature of 310° C. and angular frequency of 0.01 rad/s.
  • Patent Literature 3 discloses an FEP pellet having a volatile content of 0.2% by weight or less and satisfying the requirement that an adhesive strength between the insulating material and the core wire is 0.8 kg or more, and an average number of cone-breaks in the insulating material is one or less per 50,000 ft of the coated core wire.
  • Patent Literature 4 discloses a fluororesin composition including polytetrafluoroethylene (PTFE) having a standard specific gravity of 2.15 to 2.30 and a tetrafluoroethylene/hexafluoropropylene copolymer (FEP), the content of the PTFE being 0.01 to 3 parts by mass per 100 parts by mass of the FEP, the alkali metal content being less than 5 ppm on the resin composition solid matter basis, the composition being obtained by a method including the step (1) of preparing a coagulated fluororesin powder by mixing an aqueous dispersion containing the FEP and an aqueous dispersion containing the PTFE together, followed by coagulation, the step (2) of melt extruding the coagulated powder, and the step (3) of subjecting the extrusion product to treatment for stabilizing unstable terminal groups of the PTFE and FEP.
  • CITATION LIST Patent Literature
  • Patent Literature 1: WO 01/036504
  • Patent Literature 2: JP 2011-514407 T
  • Patent Literature 3: US 2003/0157324
  • Patent Literature 4: JP 2010-539252 T
  • SUMMARY OF INVENTION Technical Problem
  • Conventional techniques, however, fail to sufficiently prevent the formation of lumps (mass of resin), particularly, large lumps. Accordingly, there is room for improvement in such conventional techniques.
  • In view of the current state of the art described above, the present invention aims to provide a tetrafluoroethylene/hexafluoropropylene copolymer which is less likely to form a lump, or is less likely to form a large lump even if a lump is formed, during the formation of an electric wire.
  • Solution to Problem
  • The present inventors have intensively studied about a tetrafluoroethylene/hexafluoropropylene copolymer which is less likely to form a lump during the formation of an electric wire, and found that a tetrafluoroethylene/hexafluoropropylene copolymer having a melt flow rate (MFR) within a specific range, a swell within a specific range, and a specific number or less of specific end groups is less likely to form a lump, or is less likely to form a large lump even if a lump is formed, during the formation of an electric wire.
  • That is, the present invention relates to a tetrafluoroethylene/hexafluoropropylene copolymer having a melt flow rate measured at 372° C. of 35.0 to 45.0 g/10 minutes and a swell of −8.0% to 5.0%, the sum of the numbers of —CF2H groups and unstable end groups being 120 or less per 1×106 carbon atoms.
  • The sum of the numbers of —CF2H groups and unstable end groups is preferably 50 or less, more preferably 20 or less per 1×106 carbon atoms.
  • The swell is preferably −6.0% to 4.9%.
  • The tetrafluoroethylene/hexafluoropropylene copolymer of the present invention preferably has a heating weight loss of 0.1% by weight or less after heating at 372° C. for 30 minutes.
  • The tetrafluoroethylene/hexafluoropropylene copolymer of the present invention preferably has a melting point of 245° C. to 280° C.
  • The tetrafluoroethylene/hexafluoropropylene copolymer of the present invention preferably includes a polymerized unit derived from tetrafluoroethylene, a polymerized unit derived from hexafluoropropylene, and a polymerized unit derived from a perfluoro(alkyl vinyl ether).
  • The perfluoro(alkyl vinyl ether) is preferably a perfluoro(propyl vinyl ether).
  • The present invention also relates to an electric wire including:
  • a core wire; and
  • a coating including the tetrafluoroethylene/hexafluoropropylene copolymer.
  • The electric wire is preferably a foamed electric wire.
  • Advantageous Effects of Invention
  • Since the tetrafluoroethylene/hexafluoropropylene copolymer of the present invention has the aforementioned configuration, it is less likely to form a lump, or is less likely to form a large lump even if a lump is formed, during the formation of an electric wire.
  • DESCRIPTION OF EMBODIMENTS
  • The tetrafluoroethylene (TFE)/hexafluoropropylene (HFP) copolymer of the present invention has a MFR within a specific range, a swell within a specific range, and a specific number or less of specific end groups.
  • The present invention will be described in detail below.
  • The TFE/HFP copolymer of the present invention includes a polymerized unit derived from TFE (TFE unit) and a polymerized unit derived from HFP (HFP unit).
  • The TFE/HFP copolymer of the present invention may be a bipolymer consisting only of a TFE unit and a HFP unit, or may be a terpolymer or multicomponent polymer containing a TFE unit, a HFP unit, and a polymerized unit(s) derived from a monomer(s) copolymerizable with TFE and HFP.
  • The copolymerizable monomer may be any monomer, and can appropriately be selected from ethylene, propylene, perfluoro(alkyl vinyl ethers) (PAVEs), (perfluoroalkyl)ethylenes, hydrofluoroolefins, (fluoroalkyl)ethylenes, perfluoro(alkyl allyl ethers), and the like.
  • The perfluoroalkyl group of these monomers preferably has 1 to 10 carbon atoms.
  • Examples of the PAVEs include perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) (PEVE), and perfluoro(propyl vinyl ether) (PPVE).
  • The TFE/HFP copolymer of the present invention is also preferably a perfluoro copolymer because it has better electrical properties.
  • The copolymerizable monomer is preferably PAVE, more preferably PPVE, in terms of crack resistance.
  • That is, the TFE/HFP copolymer of the present invention is preferably a TFE/HFP/PAVE copolymer that includes a TFE unit, a HFP unit, and a polymerized unit derived from PAVE (PAVE unit), more preferably a TFE/HFP/PPVE copolymer.
  • The TFE/HFP copolymer of the present invention has a mass ratio of TFE/HFP of preferably (80 to 97)/(3 to 20), more preferably (84 to 92)/(8 to 16) in terms of formability.
  • When the TFE/HFP copolymer of the present invention is a TFE/HFP/PAVE copolymer, the TFE/HFP/PAVE copolymer has a mass ratio of TFE/HFP/PAVE of preferably (70 to 97)/(3 to 20)/(0.1 to 10), more preferably (81 to 92)/(5 to 16)/(0.3 to 5).
  • The mass ratio of the polymerized units in the TFE/HFP copolymer can be determined by measuring the proportions of the polymerized units using an NMR analyzer (e.g. AC300 available from Bruker Biospin Co., Ltd., high temperature probe) or an infrared spectrometer (model 1760 available from PerkinElmer, Inc.).
  • The TFE/HFP copolymer of the present invention has a melt flow rate (MFR) measured at 372° C. of 35.0 to 45.0 g/10 min.
  • The TFE/HFP copolymer of the present invention having a MFR within the above range is less likely to form a lump, or is less likely to form a large lump even if a lump is formed, during the formation of an electric wire.
  • The lower limit of the MFR is preferably 35.1/10 min, more preferably 35.5 g/10 min, still more preferably 36.0 g/10 min, and the upper limit thereof is preferably 44.5 g/10 min, more preferably 44.0 g/10 min, still more preferably 42.0 g/10 min. The TFE/HFP copolymer having such a MFR may further prevent the formation of a lump during the formation of an electric wire.
  • The MFR is a value determined in conformity with ASTM D 1238 at a load of 5 kg and a temperature of 372° C. using a die having a diameter of 2.0 m and a length of 8 mm.
  • The TFE/HFP copolymer of the present invention has a swell of −8.0% to 5.0%.
  • The TFE/HFP copolymer of the present invention having a swell within the above range is less likely to form a lump, or is less likely to form a large lump even if a lump is formed, during the formation of an electric wire.
  • The lower limit of the swell is preferably −6.0%, more preferably −5.0%, still more preferably −4.0%. The swell is preferably less than 5.0%, more preferably 4.9% or less, still more preferably 4.5% or less, further still more preferably 4.0% or less. The TFE/HFP copolymer having such a swell may further prevent the formation of a lump during the formation of an electric wire.
  • The TFE/HFP copolymer having a swell within the above range enables selection of the temperature in molding from a wide temperature range.
  • The swell can be adjusted, for example, by controlling the screw speed (rpm) of a twin screw extruder used when a dry powder of the TFE/HFP copolymer obtained by polymerization is formed into pellets.
  • The swell is also referred to as a “die swell”, and is defined as a “percentage of swelling” in JP S48-20788 B and is also expressed as a “swelling rate” in JP H02-7963 B, for example.
  • Since the TFE/HFP copolymer is insoluble and has a high molecular weight, it is impossible to directly measure its molecular weight distribution. Therefore, expansion tendency (swell) on melt extrusion, which is considered to be associated with the molecular weight distribution, is usually used as a measure of the molecular weight distribution.
  • The larger the swell, the wider the molecular weight distribution. Conversely, the smaller the swell, the narrower the molecular weight distribution.
  • The swell is determined in the following way.
  • First, using a melt indexer (e.g. KAYNESS melt indexer (Model 4002)), about 2 g of a resin is placed in a 0.376-inch cylinder maintained at 372° C.±0.5° C., and the cylinder is allowed to stand for 5 minutes to cause the temperature to reach equilibrium. Thereafter, the resin is extruded through an orifice for die swell measurement having a diameter of 1 mm (margin of error: +0.002 mm or less) under a load of 5000 g with a piston. The extruded strand is allowed to cool to room temperature, and the diameter thereof is measured.
  • Here, the length of the strand is 30±5 mm, and the diameter is measured at a portion 5±1 mm from the tip portion extruded first of the strand. The average of the diameters of three strands obtained in the same period is determined, and the die swell is calculated using the following formula:

  • Die swell (%)=[(SD−OD)/OD]×100
  • SD: the diameter of strand (average of the diameters of three strands)
  • OD: the diameter of the orifice (1 mm).
  • In the TFE/HFP copolymer of the present invention, the sum of the numbers of —CF2H groups and unstable end groups is 120 or less per 1×106 carbon atoms.
  • With such a sum of the numbers of —CF2H groups and unstable end groups, the TFE/HFP copolymer is less likely to form a lump, or is less likely to form a large lump even if a lump is formed, during the formation of an electric wire.
  • The sum of the numbers of —CF2H groups and unstable end groups is preferably 50 or less, more preferably 20 or less per 1×106 carbon atoms. With such a sum of the numbers of —CF2H groups and unstable end groups, the TFE/HFP copolymer can further prevent the formation of a lump during the formation of an electric wire.
  • The sum of the numbers of —CF2H groups and unstable end groups in the TFE/HFP copolymer may be 30 or more. In this case, the number of lumps formed may be slightly larger than in the case of a copolymer in which the sum of the numbers of —CF2H groups and unstable end groups is less than 30, while, when such a TFE/HFP copolymer is used for a coating of an electric wire, higher adhesion strength is expected between the core wire and the coating.
  • The unstable end group refers to a —COF group, a —COOH group, a —COOCH3 group, a —CONH2 group, and a —CH2OH group, which are present at an end of the main chain.
  • The numbers of —CF2H groups and unstable end groups can be determined by NMR measurement or infrared absorption spectroscopy as described in WO 2008/047906 and WO 2009/044753.
  • Specifically, the number of —CF2H groups can be determined from the integration value of the peak derived from the —CF2H groups obtained by 19F-NMR measurement at a temperature of “melting point of polymer+20° C.” using a nuclear magnetic resonance apparatus AC300 (available from Bruker-Biospin Co., Ltd).
  • The number of the unstable end groups is determined as follows: a film with a thickness of 0.25 to 0.30 mm is prepared by compressing powder of the TFE/HFP copolymer of the present invention at 350° C. for 30 minutes or by cold-pressing pellets of the TFE/HFP copolymer; the resulting film is subjected to infrared absorption spectroscopy; the resulting infrared absorption spectrum is compared to the infrared absorption spectrum of a known film to identify the type of the end group; and the number of the unstable end groups is determined from the differential spectrum using the following formula:

  • Number of end groups(per 1×106 carbon atoms)=(l×K)/t
  • l: absorbance
  • K: correction factor
  • t: film thickness (mm).
  • The correction factor can be determined from the infrared absorption spectrum of a model compound, and the correction factors shown in Table 1 can be used.
  • The TFE/HFP copolymer in which the sum of the numbers of —CF2H groups and unstable end groups is as described above can be obtained by fluorination.
  • Non-fluorinated copolymers may contain a —CF2H group or a thermally or electrically unstable end group (unstable end group) in some cases.
  • The number of these end groups can be reduced by fluorination.
  • The sum of the numbers of —CF2H groups and unstable end groups can be adjusted by controlling the degree of fluorination. Therefore, the non-fluorinated copolymer may or may not be completely fluorinated by fluorination.
  • Further, the sum of the numbers of —CF2H groups and unstable end groups can be controlled by generating —CF2H groups and unstable end groups through the decomposition of the TFE/HFP copolymer, or by mixing two or more TFE/HFP copolymers different in the sum of the numbers of —CF2H groups and unstable end groups.
  • The fluorination can be performed by bringing a non-fluorinated TFE/HFP copolymer into contact with a fluorine-containing compound.
  • The fluorine-containing compound may be any compound, and examples thereof include fluorine radical sources that generate fluorine radicals under the fluorination conditions. Examples of the fluorine radical sources include F2 gas, CoF3, AgF2, UF6, OF2, N2F2, CF3OF, and halogen fluorides (e.g., IF5, ClF3).
  • The fluorine radical source such as F2 gas may have a concentration of 100%. In order to ensure the safety, the fluorine radical source is diluted with an inert gas to preferably 5% to 50% by mass, preferably 15% to 30% by mass. Examples of the inert gas include nitrogen gas, helium gas, and argon gas. In order to save the cost, nitrogen gas is preferred.
  • The fluorination can be performed under any conditions, and may be performed by bringing a molten TFE/HFP copolymer into contact with a fluorine-containing compound. The fluorination is usually performed at a temperature of not higher than the melting point of the TFE/HFP copolymer, preferably 20° C. to 220° C., more preferably 100° C. to 200° C. The fluorination is usually performed for 1 to 30 hours, preferably 5 to 20 hours.
  • The fluorination is preferably performed by bringing a non-fluorinated TFE/HFP copolymer into contact with a fluorine gas (F2 gas).
  • In particular, an appropriate degree of fluorination can be achieved by controlling the temperature or time of the fluorination.
  • If the TFE/HFP copolymer of the present invention has a high volatile matter content, air cells tend to be generated when the copolymer is molded into a coating of an electric wire, which tends to result in instable molding. Based on this point of view, the TFE/HFP copolymer has a heating weight loss of preferably 0.1% by weight or less, more preferably 0.09% by weight or less, still more preferably 0.08% by weight or less, particularly preferably 0.07% by weight, further more preferably 0.06% by weight, still further more preferably 0.05% by weight, after heating at 372° C. for 30 minutes.
  • The heating weight loss is determined by the following procedures.
  • Using an electric furnace equipped with a turntable, a sample (TFE/HFP copolymer in the form of pellets) is placed on an aluminum cup which is already baked at 372° C. for 1 hour (the weight is expressed as A) and accurately weighed to 20±0.1 g using a precision scale (which measures in 0.1 mg increments). The entire weight is expressed by B.
  • Two samples accurately weighed on aluminum cups are prepared for one measurement.
  • The two samples are quickly placed on the turntable of the electric furnace heated to 372° C. This turntable turns at 6 rpm.
  • The samples are taken out from the furnace 30 minutes after the temperature in the furnace has reached 372° C. again, and quickly put into a desiccator. The samples are allowed to cool for one hour or more, and then each sample is accurately weighed with the precision scale. The measured weight is defined as C.
  • The heating weight loss of each sample heated at 372° C. for 30 minutes is calculated from the equation below, and the average of the heating weight losses (% by weight) of the two samples is determined.

  • Heating weight loss (% by weight)=[(B−C)/(B−A)]×100
  • The lower limit of the melting point of the TFE/HFP copolymer of the present invention is preferably 245° C., more preferably 250° C. in terms of thermal resistance. Also, the upper limit of the melting point of the TFE/HFP copolymer is preferably 280° C., more preferably 270° C., still more preferably 265° C. because such a TFE/HFP copolymer is readily processed.
  • The melting point is a temperature corresponding to the peak obtained by measurement using a differential scanning calorimeter at a temperature rise rate of 10° C./min.
  • The TFE/HFP copolymer of the present invention can be synthesized by polymerizing TFE, HFP, and, optionally, a monomer copolymerizable with TFE and HFP, such as PAVE, by a usual polymerization method, such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or gas phase polymerization. The polymerization may be performed under usual conditions.
  • In the polymerization, a chain transfer agent such as methanol may be used in some cases.
  • The TFE/HFP copolymer of the present invention may be produced by polymerization and isolation without using a metal-ion-containing reagent.
  • When the TFE/HFP copolymer of the present invention is molded into a coating that covers a core wire with a diameter of 20.1 mil at a coat-molding speed of 1600 ft/min continuously for 2 hours so that a wire with a diameter of 33.7 mil is prepared, the number of lumps with a size of 20 mil or larger formed at the coating can be reduced to 10 or less, further to 7 or less.
  • The size (height) of each lump and the number of lumps can be measured with a lump detector KW32TRIO (available from Zumbach).
  • As described above, since being capable of forming a coating with a small number of lumps, the TFE/HFP copolymer of the present invention is particularly suitable as a material of the coating of an electric wire.
  • The TFE/HFP copolymer of the present invention may be in the form of pellets. The pellets can be prepared by kneading with a known melt kneader such as a single screw extruder or twin screw extruder.
  • The pellets are preferably prepared by kneading with a twin screw extruder. The swell can be adjusted by controlling the screw speed (number of rotations) of a twin screw extruder in kneading.
  • The electric wire of the present invention includes a core wire and a coating containing the TFE/HFP copolymer of the present invention. The coating is usually arranged on the periphery of the core wire.
  • Since the coating of the electric wire of the present invention is formed from the TFE/HFP copolymer of the present invention, the coating has only a small number of lumps, or has small lumps even if lumps are formed.
  • The material of the core wire may be a conductive metal material such as copper or aluminum. The diameter of the core wire is preferably 0.02 to 3 mm, more preferably 0.04 mm or more, still more preferably 0.05 mm or more, particularly preferably 0.1 mm or more. The diameter of the core wire is more preferably 2 mm or less.
  • Specific examples of the core wire include those satisfying AWG-46 (40-μm-diameter solid copper wires), those satisfying AWG-26 (404-μm-diameter solid copper wires), those satisfying AWG-24 (510-μm-diameter solid copper wires), and those satisfying AWG-22 (635-μm-diameter solid copper wires). Here, AWG represents the American wire gauge.
  • The coating contains the TFE/HFP copolymer of the present invention. The coating may consist only of the TFE/HFP copolymer of the present invention, or may contain a conventionally known filler and other components in addition to the TFE/HFP copolymer of the present invention, as long as the effects of the present invention are not impaired.
  • The amount of the TFE/HFP copolymer of the present invention is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, particularly preferably 95% by mass or more, more particularly preferably substantially 100% by mass relative to the coating.
  • Examples of the filler include graphite, carbon fiber, coke, silica, zinc oxide, magnesium oxide, tin oxide, antimony oxide, calcium carbonate, magnesium carbonate, glass, talc, mica, mica, aluminum nitride, calcium phosphate, sericite, diatomite, silicon nitride, fine silica, alumina, zirconia, quartz powder, kaolin, bentonite, and titanium oxide. The filler may be in any form, and may be in the form of, for example, fibers, needles, powder, particles, or beads.
  • The coating may further contain a thermoplastic resin other than the TFE/HFP copolymer of the present invention. Examples of the thermoplastic resin other than the TFE/HFP copolymer of the present invention include general-purpose resins such as polyethylene resin, polypropylene resin, vinyl chloride resin, and polystyrene resin; and engineering plastics such as nylon, polycarbonate, polyether ether ketone resin, and polyphenylene sulfide resin.
  • The coating may further contain any other components such as additives. Examples of such components include fillers such as glass fiber, glass powder, and asbestos fiber, reinforcing agents, stabilizers, lubricants, pigments, and other additives.
  • The coating may further contain a foam nucleating agent. A foam nucleating agent is used when the coating is foamed as described below. Therefore, the coating usually contains a foam nucleating agent.
  • Examples of the foam nucleating agent include sulfonic acid, phosphonic acid, salts thereof, boron nitride, and inorganic salts containing a polyatomic anion.
  • The amount of the foam nucleating agent in the coating may be appropriately adjusted to suit the use of a resulting electric wire, and is, for example, 0.1% to 10% by mass relative to the coating.
  • The boron nitride may be pulverized and/or classified.
  • Examples of the polyatomic anion-containing inorganic salt include those disclosed in U.S. Pat. No. 4,764,538 A.
  • The coating may or may not be foamed.
  • The electric wire having a foamed coating is called a foamed electric wire. The electric wire of the present invention is also preferably a foamed electric wire.
  • The use of the foamed coating can provide a coated electric wire with small transmission loss.
  • The coating preferably has a foam content of 10% to 80%.
  • The coating preferably has air cells with an average diameter of 5 to 100 μm.
  • The foam content of the coating means a percentage of change in specific gravity of the material before and after foaming, and is determined by measuring, by the water displacement method, the percentage of change between the characteristic specific gravity of a material constituting a foam and the apparent specific gravity of the foam. The average diameter of air cells can be calculated from a microscope photograph of the cross-section of the foam.
  • The coating can be foamed by a conventionally known method. Examples of the method include (1) a method in which pellets of the TFE/HFP copolymer of the present invention containing a foam nucleating agent are prepared, and then extrusion coated while gas is continually introduced to the pellets, and (2) a method in which gas is generated by decomposing a chemical foaming agent, which has been mixed with the molten TFE/HFP copolymer of the present invention, through extrusion coating to provide air cells.
  • In the method (1), the foam nucleating agent may be a well-known one such as boron nitride (BN). Examples of the gas include chlorodifluoromethane, nitrogen, carbon dioxide, and a mixture of these.
  • Examples of the chemical foaming agent in the method (2) include azodicarbonamide and 4,4′-oxybis-benzenesulfonyl hydrazide. The conditions in each method, such as the amount of the foam nucleating agent added and the amount of the gas introduced in the method (1) and the amount of the chemical foaming agent added in the method (2), can be appropriately adjusted according to the kinds of the resin and the core wire to be used or a desired thickness of the coating.
  • The electric wire of the present invention may include a layer formed from a material other than the coating on the periphery of the coating or may include a layer formed from a material other than the coating between the core wire and the coating.
  • The layer may be any resin layer formed from a polyolefin resin such as a TFE/PAVE copolymer, a TFE/ethylene copolymer, a vinylidene fluoride polymer, or polyethylene (PE), or a resin such as polyvinyl chloride (PVC). Preferred among these are PE and PVC in view of cost effectiveness.
  • Each of the layer and the coating may have any thickness, and the thickness of the layer is preferably 1 mil to 20 mil and the thickness of the coating is preferably 1 mil to 20 mil.
  • When the electric wire of the present invention is a foamed electric wire, it may have a double-layered (skin-foam) structure including a core wire, the coating, and a non-foamed layer disposed between the core wire and the coating, a double-layered (foam-skin) structure including a non-foamed layer that coats the outer layer of the coating, or a triple-layered (skin-foam-skin) structure including a non-foamed layer that coats the outer layer of the skin-foam structure.
  • The non-foamed layer of the foamed electric wire may be any resin layer formed of a polyolefin resin such as a TFE/HFP copolymer, a TFE/PAVE copolymer, a TFE/ethylene copolymer, a vinylidene fluoride polymer, or polyethylene (PE), or a resin such as PVC.
  • The electric wire of the invention is suitable as an insulated wire for communication. Examples of the insulated wire for communication include cables for connecting a computer with a peripheral device such as data transmission cables (e.g. LAN cables). The insulated wire is also suitable for plenum cables to be installed in a space in the ceiling cavity (plenum area) of a building.
  • The electric wire of the present invention is also suitable for high-frequency coaxial cables, flat cables, and heat-proof cables. In particular, the electric wire is suitable for high-frequency coaxial cables.
  • The outer layer of a coaxial cable is not limited, and may be a conductive layer made of an outer conductor such as a metal mesh, or may be a resin layer (sheath layer) made of a TFE unit-containing fluorine-containing copolymer such as a TFE/HFP copolymer or a TFE/PAVE copolymer, PVC, PE, or any other resin.
  • The coaxial cable may be a cable that includes an outer conductive layer made of a metal on the periphery of the coated electric wire of the present invention, and the resin layer (sheath layer) on the periphery of the outer conductive layer.
  • A method for producing the electric wire of the present invention is described below.
  • The electric wire of the present invention can be prepared by a production method including the step of forming a coating by coating a core wire with the TFE/HFP copolymer of the present invention.
  • The core wire may be coated with the TFE/HFP copolymer of the present invention by a conventionally known coating method using an extruder.
  • The coating may be formed by applying a composition containing the TFE/HFP copolymer of the present invention, the filler described above, a thermoplastic resin other than the TFE/HFP copolymer of the present invention, other components such as additives, a foam nucleating agent, and a chemical foaming agent.
  • The composition can be prepared by mixing the TFE/HFP copolymer of the present invention, the filler described above, a thermoplastic resin other than the TFE/HFP copolymer of the present invention, other components such as additives, and a foam nucleating agent.
  • The composition can also be prepared by mixing a non-fluorinated TFE/HFP copolymer, the filler described above, a thermoplastic resin other than the TFE/HFP copolymer of the present invention, other components such as additives, a foam nucleating agent, and a chemical foaming agent, and then fluorinating the non-fluorinated TFE/HFP copolymer.
  • The mixing may be performed by a method using a Henschel mixer, a ribbon mixer, a V-blender, or a ball mill, for example. The mixing may also be performed, for example, by melt-kneading.
  • The composition may be prepared by kneading the above mixture obtained by mixing. The kneading can provide pellets. The kneading can be performed by a method using a conventionally known melt-kneader such as a single screw extruder or a twin screw extruder.
  • The fluorination may be performed on the composition (e.g. pellets) after kneading. For example, the fluorination may be performed by bringing the pellets prepared through the kneading into contact with the fluorine-containing compound.
  • When the coating is not a foamed one, the formation of a lump can be further prevented. Therefore, the coating speed in the formation of the coating is preferably 500 to 2500 ft/min, more preferably 1000 to 1600 ft/min.
  • The electric wire of the present invention is also preferably a foamed electric wire.
  • When the coating is a foamed one, that is, when the electric wire of the present invention is a foamed electric wire, the electric wire of the present invention can be prepared by a conventional method except that the TFE/HFP copolymer of the present invention is used. For example, the electric wire can be produced by extrusion foaming. Preferred molding conditions can be appropriately selected according to the formulation of the composition to be used and the size of the core wire.
  • The core wire is coated with the TFE/HFP copolymer of the present invention, for example, by a method in which the TFE/HFP copolymer of the present invention is fed into a screw extruder designed for foaming operations, and a continuous gas injection method is performed using a gas soluble in the molten TFE/HFP copolymer of the present invention (molten resin). The gas may be the same as that used in the method for producing a foam.
  • Preferably, the resulting coating includes a melt-solidified matter of the TFE/HFP copolymer of the present invention and air cells, and the air cells are uniformly distributed in the melt-solidified matter. The air cells may have any average cell size. For example, the average cell size is preferably 60 μm or smaller, more preferably 45 μm or smaller, still more preferably 35 μm or smaller, much more preferably 30 μm or smaller, particularly preferably 25 μm or smaller, more particularly preferably 23 μm or smaller. The average cell size is also preferably 0.1 μm or greater, more preferably 1 μm or greater.
  • The average cell size is determined as follows: an image of the cross section of the coating is taken by a scanning electron microscope (SEM), the image is processed to determine the diameter of each air cell, and the average cell size of the air cells is calculated.
  • The coating preferably has a foam content of 10% or higher. It is more preferably 20% or higher, still more preferably 30% or higher, much more preferably 35% or higher. The upper limit thereof may be, but not limited to, for example, 80%. The upper limit of the foam content may be 60%.
  • The foam content is determined by [{(specific gravity of TFE/HFP copolymer)−(specific gravity of foamed body)}/(specific gravity of TFE/HFP copolymer)]×100. The foam content can appropriately be adjusted to suit the use of the electric wire by, for example, controlling the amount of gas introduced into the extruder or selecting the type of gas to be dissolved.
  • EXAMPLE
  • The present invention will be described based on examples below.
  • The properties herein were measured by the following methods.
  • (Formulation)
  • The mass ratio of the polymerized units in the TFE/HFP copolymer was determined by measuring the proportions of the polymerized units using an NMR analyzer (e.g. AC300 available from Bruker Biospin Co., Ltd., high temperature probe) or an infrared spectrometer (model 1760 available from PerkinElmer, Inc.).
  • (Melting Point)
  • The melting point of the TFE/HFP copolymer was a temperature corresponding to the peak obtained by measurement using a differential scanning calorimeter (RDC220 available from Seiko Instruments Inc.) at a temperature rise rate of 10° C./min.
  • (MFR)
  • The MFR of the TFE/HFP copolymer was measured in conformity with ASTM D 1238 using a KAYENESS melt indexer (Series 4000 available from YASUDA SEIKI SEISAKUSHO, LTD.) with a die having a diameter of 2.1 mm and a length of 8 mm at a temperature of 372° C. and a load of 5 kg.
  • (Swell)
  • Using a KAYNESS melt indexer (Model 4002), about 2 g of a resin was placed in a 0.376-inch cylinder maintained at 372° C.±0.5° C., and the cylinder was allowed to stand for 5 minutes to cause the temperature to reach equilibrium. Thereafter, the resin was extruded through an orifice for die swell measurement having a diameter of 1 mm (margin of error: +0.002 mm or less) under a load of 5000 g with a piston. The extruded strand was allowed to cool to room temperature, and the diameter thereof was measured.
  • Here, the length of the strand was 30±5 mm, and the diameter was measured at a portion 5±1 mm from the tip portion extruded first of the strand. The average of the diameters of three strands obtained in the same period was determined, and the die swell was calculated using the following formula:

  • Die swell (%)=[(SD−OD)/OD]×100
  • SD: the diameter of strand (average of the diameters of three strands)
  • OD: the diameter of the orifice (1 mm).
  • (The Number of —CF2H Groups)
  • The number of —CF2H groups was determined from the integration value of the peak derived from the —CF2H groups obtained by 19F-NMR measurement at a temperature of “melting point of polymer+20° C.” using a nuclear magnetic resonance apparatus AC300 (available from Bruker-Biospin Co., Ltd).
  • (The Number of Unstable End Groups)
  • The number of the unstable end groups was determined as follows: a film with a thickness of 0.25 to 0.30 mm was prepared by cold-pressing the resulting pellets; the film was subjected to infrared absorption spectroscopy; the resulting infrared absorption spectrum was compared to the infrared absorption spectrum of a known film to identify the type of the end group; and the number of the unstable end groups was determined from the differential spectrum using the following formula:

  • Number of end groups(per 1×106 carbon atoms)=(1×K)/t
  • l: absorbance
  • K: correction factor
  • t: film thickness (mm).
  • Table 1 shows the correction factors and absorption frequencies of the target end groups.
  • TABLE 1
    End group Absorption frequency (cm−1) Correction factor
    COF group 1884 405
    COOH group 1813 (1795-1792) 455
    COOCH3 group 1795 355
    CONH2 group 3438 480
    CH2OH group 3648 2325
  • The correction factor was determined from the infrared absorption spectrum of a model compound so that the number of the end groups per 1×106 carbon atoms is calculated.
  • (Heating Weight Loss)
  • Using an electric furnace equipped with a turntable, a sample (TFE/HFP copolymer in the form of pellets) was placed on an aluminum cup which was already baked at 372° C. for 1 hour (the weight was expressed as A), and accurately weighed to 20±0.1 g using a precision scale (which measured in 0.1 mg increments). The entire weight was expressed as B.
  • Two samples were prepared for one measurement.
  • The two samples were quickly placed on the turntable of the electric furnace heated to 372° C. This turntable turned at 6 rpm.
  • The samples were taken out from the furnace 30 minutes after the temperature in the furnace had reached 372° C. again, and quickly put into a desiccator. The samples were allowed to cool for one hour or more, and then each sample was accurately weighed with the precision scale. The measured weight was defined as C.
  • The heating weight loss of each sample heated at 372° C. for 30 minutes was calculated from the equation below, and the average of the heating weight losses (% by weight) of the two samples was determined.

  • Heating weight loss (% by weight)=[(B−C)/(B−A)]×100
  • (Lump Size)
  • The size (height) of lumps with a size of 20 mil or larger was measured using a lump detector KW32TRIO (available from Zumbach). The average of the sizes of lumps in Table 2 was the arithmetic average of the sizes of lumps formed during two-hour molding.
  • (Lump Frequency)
  • The frequency of lumps (number of formed lumps) with a size of 20 mil or larger was determined with a lump detector KW32TRIO (available from Zumbach).
  • Example 1 (Polymerization)
  • An autoclave (1000 L) equipped with a stiffer was charged with 265 kg of deionized water, and sufficiently purged with nitrogen under vacuum. Thereafter, the air was removed to create a vacuum in the autoclave, and the autoclave was charged with 274 kg of HFP, 31 kg of TFE, and 3.0 kg of PPVE under vacuum, and heated to 32° C. Next, 1.7 kg of a 8% solution of di(w-hydroperfluorohexanoyl)peroxide (hereinafter, abbreviated to “DHP”) in perfluorohexane was put into the autoclave to initiate polymerization. The internal pressure of the autoclave at the start of the polymerization was set at 1.04 MPa, and this pressure was maintained by successively adding TFE. After 2 hours and 4 hours from the start of the polymerization, 1.7 kg of a 8% solution of DHP in perfluorohexane was added and the internal pressure was reduced by 0.01 MP. Further, after 6 hours, 8 hours, and 10 hours from the start of the polymerization, 1.3 kg of a 8% solution of DHP in perfluorohexane was added and the internal pressure was reduced by 0.01 MP. Thereafter, 1.7 kg of a 8% solution of DHP in perfluorohexane was added and the internal pressure was reduced by 0.01 MP every 2 hours. Here, 0.7 kg of PPVE was added when the total amount of TFE successively added reached 53 kg, 106 kg, and 159 kg.
  • Further, when the total amount of TFE successively added reached 40 kg, 4.0 kg of methanol was fed into the autoclave.
  • The polymerization was terminated when the total amount of TFE successively added reached 233 kg. After the termination of the polymerization, unreacted TFE and HFP were discharged to give wet powder. The wet powder was combined with pure water, and washed by stirring. Thereafter, the wet powder was dried at 150° C. for 10 hours to give 273 kg of dry powder.
  • (Pelletization)
  • Subsequently, the resulting dry powder was pelletized using a twin screw extruder at 370° C. and a screw speed of 300 rpm, and the pellets were subjected to deaeration at 200° C. for 8 hours.
  • (Fluorination)
  • The resulting pellets were placed in a vacuum vibration reactor, and heated to 200° C. After vacuuming, F2 gas diluted to 20% with N2 gas was introduced so that the pressure was increased to atmospheric pressure. After 3 hours from the introduction of the F2 gas, vacuuming was performed and then F2 gas was again introduced. The introduction of F2 gas and the vacuuming were repeated 6 times in total. Finally, the inside of the reactor was purged with N2 gas to terminate the reaction. The resulting pellets had a MFR of 37.4 g/10 min, a swell of −0.1%, no CF2H groups and no unstable end groups, a heating weight loss of 0.05% by weight, and a melting point of 256.5° C.
  • The formulation of the TFE/HFP/PPVE copolymer was evaluated to give a weight ratio of TFE/HFP/PPVE of 87.5/11.5/1.0.
  • Example 2 (Polymerization)
  • Dry powder was prepared by performing polymerization in the same manner as in Example 1 except that the amount of methanol was changed to 4.1 kg.
  • (Pelletization)
  • The resulting dry powder was pelletized in the same manner as in Example 1 except that the screw speed was changed to 297 rpm. The pellets treated with F2 gas had a MFR of 36.3 g/10 min. The swell, the sum of the numbers of CF2H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • The formulation of the TFE/HFP/PPVE copolymer was evaluated to give a weight ratio of TFE/HFP/PPVE of 87.5/11.5/1.0.
  • Example 3 (Polymerization)
  • Dry powder was prepared by performing polymerization in the same manner as in Example 1 except that the amount of methanol was changed to 3.2 kg.
  • (Pelletization)
  • The resulting dry powder was pelletized in the same manner as in Example 1 except that the screw speed was changed to 315 rpm. The pellets treated with F2 gas had a MFR of 35.1 g/10 min. The swell, the sum of the numbers of CF2H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • The formulation of the TFE/HFP/PPVE copolymer was evaluated to give a weight ratio of TFE/HFP/PPVE of 87.5/11.5/1.0.
  • Example 4 (Polymerization)
  • Dry powder was prepared by performing polymerization in the same manner as in Example 1 except that the amount of methanol was changed to 4.2 kg.
  • (Pelletization)
  • The resulting dry powder was pelletized in the same manner as in Example 1 except that the screw speed was changed to 320 rpm. The pellets treated with F2 gas had a MFR of 44.1 g/10 min. The swell, the sum of the numbers of CF2H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • The formulation of the TFE/HFP/PPVE copolymer was evaluated to give a weight ratio of TFE/HFP/PPVE of 87.5/11.5/1.0.
  • Comparative Example 1 (Polymerization)
  • Dry powder was prepared by performing polymerization in the same manner as in Example 1 except that the amount of methanol was changed to 4.9 kg.
  • (Pelletization)
  • The resulting dry powder was pelletized in the same manner as in Example 1 except that the screw speed was changed to 275 rpm. The pellets treated with F2 gas had a MFR of 37.0 g/10 min. The swell, the sum of the numbers of CF2H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • The formulation of the TFE/HFP/PPVE copolymer was evaluated to give a weight ratio of TFE/HFP/PPVE of 87.5/11.5/1.0.
  • Comparative Example 2 (Polymerization)
  • Dry powder was prepared by performing polymerization in the same manner as in Example 1 except that the amount of methanol was changed to 1.6 kg.
  • (Pelletization)
  • The resulting dry powder was pelletized in the same manner as in Example 1 except that the screw speed was changed to 360 rpm. The resulting pellets prepared using an extruder had a MFR of 34.9 g/10 min, and the pellets treated with F2 gas had a MFR of 35.8 g/10 min. The swell, the sum of the numbers of CF2H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • The formulation of the TFE/HFP/PPVE copolymer was evaluated to give a weight ratio of TFE/HFP/PPVE of 87.5/11.5/1.0.
  • Comparative Example 3 (Pelletization)
  • The dry powder prepared in Comparative Example 1 was pelletized in the same manner as in Example 1 except that the screw speed was changed to 325 rpm. The pellets treated with F2 gas had a MFR of 52.2 g/10 min. The swell, the sum of the numbers of CF2H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • Comparative Example 4 (Polymerization)
  • Dry powder was prepared by performing polymerization in the same manner as in Example 1 except that the amount of methanol was changed to 3.1 kg.
  • (Pelletization)
  • The resulting dry powder was pelletized in the same manner as in Example 1 except that the screw speed was changed to 295 rpm. The resulting pellets prepared using an extruder had a MFR of 29.0 g/10 min, and the pellets treated with F2 gas had a MFR of 30.5 g/10 min. The swell, the sum of the numbers of CF2H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • The formulation of the TFE/HFP/PPVE copolymer was evaluated to give a weight ratio of TFE/HFP/PPVE of 87.5/11.5/1.0.
  • Comparative Example 5 (Pelletization)
  • The dry powder prepared in Example 4 was pelletized in the same manner as in Example 4 except that no F2 gas treatment was performed. The resulting pellets prepared using an extruder had a MFR of 42.0 g/10 min. The swell, the sum of the numbers of CF2H groups and unstable end groups, the heating weight loss, and the melting point are as shown in Table 2.
  • (Production of Electric Wire)
  • Electric wires were produced using the pellets prepared in Examples 1 to 4 and Comparative Examples 1 to 5, and evaluated for lump size and lump frequency. In Comparative Example 3, an electric wire could not be continuously formed due to surging. Accordingly, a lump could not be evaluated.
  • Specifically, a single-screw extruder (available from Davis-Standard) having a cylinder with a cylinder diameter of 2 inches and an L/D ratio of 30 was provided with a crosshead (available from Unitek). The crosshead was equipped with a die having an inner diameter of 0.280 inches and a chip having an outer diameter of 0.160 inches. An electric wire was produced so as to have a final outer diameter of 0.0337 inches using a core wire (AWG 24) with an outer diameter of 0.0201 inches under the conditions of a time of 2 hours, a speed of 1600 ft/min, and a temperature shown in Table 3. Thereafter, the lump size and the number of lumps were evaluated.
  • TABLE 2
    Example and Comparative Example Nos.
    Compar- Compar- Compar- Compar- Compar-
    ative ative ative ative ative
    Example 1 Example 2 Example 3 Example 4 Example 1 Example 2 Example 3 Example 4 Example 5
    Screw speed (rpm) 300 297 315 320 275 360 325 2
    Figure US20200332037A1-20201022-P00899
    5
    320
    MFR (g/10 min) of pallets 37.4 3
    Figure US20200332037A1-20201022-P00899
    .
    Figure US20200332037A1-20201022-P00899
    35.1 44.1 37.0 3
    Figure US20200332037A1-20201022-P00899
    .
    Figure US20200332037A1-20201022-P00899
    52.2 30.5 42.0
    used for production of
    electric wire
    Swell (%) −0.1 3.9 −3.4 −1.0 13.
    Figure US20200332037A1-20201022-P00899
    Figure US20200332037A1-20201022-P00899
    .5
    −3.3 1.1 −0.8
    Sum of the numbers of CF
    Figure US20200332037A1-20201022-P00899
    H
    0 0 0 0 0 0 0 0 565
    groups and unstable end groups
    Heating weight loss (% by 0.05 0.05 0.04 005 0.0
    Figure US20200332037A1-20201022-P00899
    0.0
    Figure US20200332037A1-20201022-P00899
    0.04 0.04 0.0
    Figure US20200332037A1-20201022-P00899
    weight)
    Melting point (° C.) 25
    Figure US20200332037A1-20201022-P00899
    .5
    25
    Figure US20200332037A1-20201022-P00899
    .7
    255.0 25
    Figure US20200332037A1-20201022-P00899
    .5
    255.2 25a.5 25
    Figure US20200332037A1-20201022-P00899
    .0
    255.2 25
    Figure US20200332037A1-20201022-P00899
    .5
    Formulation (the third PPVE PPVE PPVE PPVE PPVE PPVE PPVE PPVE PPVE
    component)
    Evaluation of electric wire
    Number of lumps formed in 2 hr
    20 mil or larger-30 mil or 1 2 0 2 2 1 N/A 1 3
    smaller
    Larger than 30 mil-40 mil or 3 2
    Figure US20200332037A1-20201022-P00899
    4 4 2 N/A 1 2
    smaller
    Larger than 40 mil-50 mil or 1 2 1 0 4 3 N/A 4
    Figure US20200332037A1-20201022-P00899
    smaller
    Largar than 50 mil-60 mil or 1 1 0 0 4 3 N/A 10
    Figure US20200332037A1-20201022-P00899
    smaller
    Larger than 60 mil-70 mil or 0 0 0 1 2 3 N/A 8 2
    smaller
    Larger than 70 mil 0 0 0 0 0 1 N/A 2 0
    Average size of lumps formed 38.3 37.
    Figure US20200332037A1-20201022-P00899
    37.0 3
    Figure US20200332037A1-20201022-P00899
    .4
    45 51.2 N/A 5
    Figure US20200332037A1-20201022-P00899
    .2
    4
    Figure US20200332037A1-20201022-P00899
    .1
    in 2 hr (mil)
    Number of lumps formed in 2 hr 6 7 5 7 1
    Figure US20200332037A1-20201022-P00899
    13 N/A 26 19
    Figure US20200332037A1-20201022-P00899
    indicates data missing or illegible when filed
  • TABLE 3
    Zone-1 Zone-2 Zone-3 Zone-4 Zone-5 Clump Adaptor Crosshead Die
    Condition (° C.) 580 650 680 700 720 730 730 730 750
  • INDUSTRIAL APPLICABILITY
  • The TFE/HFP copolymer of the present invention is suitable for a material for forming a coating of an electric wire.

Claims (17)

What is claimed is:
1. An insulated communication wire comprising a conductive metal core wire and an insulative coating.
2. The insulated communication wire as claimed in claim 1, for connecting a computer with a peripheral device.
3. The insulated communication wire as claimed in claim 1, which is a data transmission cable or LAN cable.
4. The insulated communication wire as claimed in claim 1, wherein the conductive metal of the conductive metal core wire comprises copper or aluminum.
5. The insulated communication wire as claimed in claim 1, wherein the core wire is selected from the group consisting of an AWG-46 solid copper wire, an AWG-26 solid copper wire, and AWG-24 solid copper wire and an AWG-22 solid copper wire.
6. The insulated communication wire as claimed in claim 1, wherein the core wire of the conductive metal core wire has a diameter of 0.02 mm to 3 mm.
7. The insulated communication wire as claimed in claim 1, wherein the insulative coating has a thickness of 1 mil to 20 mil.
8. The insulated communication wire as claimed in claim 1, comprising a foamed layer disposed between the core wire and the insulative coating.
9. The insulated communication wire as claimed in claim 1, wherein the insulative coating is arranged on the periphery of the core wire.
10. The insulated communication wire as claimed in claim 1, wherein the insulative coating comprises a tetrafluoroethylene/hexafluoropropylene copolymer having a melt flow rate measured at 372° C. of 35.0 to 45.0 g/10 minutes and a die swell of −8.0% to 5.0%, and
the sum of the numbers of —CF2H groups and unstable end groups being 120 or less per 1×106 carbon atoms,
wherein die swell is measured by extruding the copolymer maintained at 372° C.±0.5° C. through an orifice having a diameter of 1 mm under a load of 5000 g with a piston to obtain an extruded strand, allowing the extruded strand to cool to room temperature, measuring the diameter of the cooled strand at a portion 5+1 mm from a first extruded tip portion of the strand, obtaining an average of the diameters of three strands obtained in the same period, and calculating the die swell according to the following formula:

die swell (%)=[(SD−OD)/OD]×100
where SD: the diameter of strand (average of the diameters of three strands) and OD: the diameter of the orifice (1 mm).
11. The insulated communication wire as claimed in claim 10, wherein the sum of the numbers of —CF2H groups and unstable end groups is 50 or less per 1×106 carbon atoms.
12. The insulated communication wire as claimed in claim 10, wherein the die swell is −6.0% to 4.9%.
13. The insulated communication wire as claimed in claim 10, wherein the sum of the numbers of —CF2H groups and unstable end groups is 20 or less per 1×106 carbon atoms.
14. The insulated communication wire as claimed in claim 10, wherein the tetrafluoroethylene/hexafluoropropylene copolymer has a heating weight loss of 0.1% by weight or less after heating at 372° C. for 30 minutes.
15. The insulated communication wire as claimed in claim 10, wherein the tetrafluoroethylene/hexafluoropropylene copolymer has a melting point of 245° C. to 280° C., and
wherein the melting point is determined as being a temperature corresponding to a peak obtained by measurement using a differential scanning calorimeter at a temperature rise rate of 10° C./min.
16. The insulated communication wire as claimed in claim 10, wherein the tetrafluoroethylene/hexafluoropropylene copolymer comprises a polymerized unit derived from tetrafluoroethylene, a polymerized unit derived from hexafluoropropylene, and a polymerized unit derived from a perfluoro(alkyl vinyl ether).
17. The insulated communication wire as claimed in claim 10, wherein the perfluoro(alkyl vinyl ether) is perfluoro(propyl vinyl ether).
US16/921,727 2014-02-05 2020-07-06 Insulated communication wire Abandoned US20200332037A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/921,727 US20200332037A1 (en) 2014-02-05 2020-07-06 Insulated communication wire

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US201461935949P 2014-02-05 2014-02-05
PCT/JP2015/052661 WO2015119053A1 (en) 2014-02-05 2015-01-30 Tetrafluoroethylene/hexafluoropropylene copolymer, and electric wire
US201615116406A 2016-08-03 2016-08-03
US16/274,119 US20190177453A1 (en) 2014-02-05 2019-02-12 Tetrafluoroethylene/hexafluoropropylene copolymer, and electric wire
US16/921,727 US20200332037A1 (en) 2014-02-05 2020-07-06 Insulated communication wire

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US16/274,119 Continuation US20190177453A1 (en) 2014-02-05 2019-02-12 Tetrafluoroethylene/hexafluoropropylene copolymer, and electric wire

Publications (1)

Publication Number Publication Date
US20200332037A1 true US20200332037A1 (en) 2020-10-22

Family

ID=53777860

Family Applications (3)

Application Number Title Priority Date Filing Date
US15/116,406 Active 2037-06-11 US11021556B2 (en) 2014-02-05 2015-01-30 Tetrafluoroethylene/hexafluoropropylene copolymer, and electric wire
US16/274,119 Abandoned US20190177453A1 (en) 2014-02-05 2019-02-12 Tetrafluoroethylene/hexafluoropropylene copolymer, and electric wire
US16/921,727 Abandoned US20200332037A1 (en) 2014-02-05 2020-07-06 Insulated communication wire

Family Applications Before (2)

Application Number Title Priority Date Filing Date
US15/116,406 Active 2037-06-11 US11021556B2 (en) 2014-02-05 2015-01-30 Tetrafluoroethylene/hexafluoropropylene copolymer, and electric wire
US16/274,119 Abandoned US20190177453A1 (en) 2014-02-05 2019-02-12 Tetrafluoroethylene/hexafluoropropylene copolymer, and electric wire

Country Status (5)

Country Link
US (3) US11021556B2 (en)
EP (1) EP3091042B1 (en)
JP (1) JP6134818B2 (en)
CN (1) CN105980426B (en)
WO (1) WO2015119053A1 (en)

Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015068082A1 (en) * 2013-11-08 2015-05-14 Bombardier Inc. Health monitoring of composite structures
CN108473688B (en) * 2016-08-04 2021-09-14 大金工业株式会社 Process for producing low-molecular-weight polytetrafluoroethylene, and powder
CN113563613A (en) 2016-08-04 2021-10-29 大金工业株式会社 Process for producing low molecular weight polytetrafluoroethylene
US20190365604A1 (en) * 2017-01-18 2019-12-05 Daikin Industries, Ltd. Container for administration, storage, delivery or transportation of protein having low protein adsorbability or protein-containing composition, and apparatus for producing protein or protein composition
CN109422843A (en) * 2017-08-25 2019-03-05 中昊晨光化工研究院有限公司 A kind of preparation method of the modified exhaustive fluorinated ethylene propylene of ether
JP2019051652A (en) 2017-09-15 2019-04-04 ダイキン工業株式会社 Method for manufacturing electric wire
EP4130146A4 (en) * 2020-03-25 2024-04-10 Daikin Ind Ltd Electrical wire for in-vehicle network cable, and in-vehicle network cable
CN116390957A (en) * 2020-09-30 2023-07-04 大金工业株式会社 Copolymer, injection-molded body, compressed member, and covered wire
EP4299619A1 (en) * 2021-02-26 2024-01-03 Daikin Industries, Ltd. Fluorine-containing copolymer
WO2022181835A1 (en) * 2021-02-26 2022-09-01 ダイキン工業株式会社 Fluorine-containing copolymer
WO2022181230A1 (en) * 2021-02-26 2022-09-01 ダイキン工業株式会社 Copolymer, molded body, injection molded body, and coated electrical wire
JP7121326B1 (en) * 2021-02-26 2022-08-18 ダイキン工業株式会社 fluorine-containing copolymer
CN116888170A (en) * 2021-02-26 2023-10-13 大金工业株式会社 Fluorine-containing copolymer
WO2022181836A1 (en) * 2021-02-26 2022-09-01 ダイキン工業株式会社 Fluorine-containing copolymer
JP7185169B2 (en) * 2021-02-26 2022-12-07 ダイキン工業株式会社 Copolymers, moldings, injection moldings and coated wires
WO2022181235A1 (en) * 2021-02-26 2022-09-01 ダイキン工業株式会社 Copolymer, molded body, injection molded body, and coated electrical wire
WO2022181842A1 (en) 2021-02-26 2022-09-01 ダイキン工業株式会社 Fluorine-containing copolymer
JP7177374B2 (en) * 2021-02-26 2022-11-24 ダイキン工業株式会社 Copolymers, moldings, injection moldings and coated wires
JP7177376B2 (en) * 2021-02-26 2022-11-24 ダイキン工業株式会社 Copolymers, moldings, injection moldings and coated wires
JP7364974B1 (en) 2022-03-30 2023-10-19 ダイキン工業株式会社 Fluorine-containing copolymer
WO2023190961A1 (en) * 2022-03-30 2023-10-05 ダイキン工業株式会社 Fluorine-containing copolymer
WO2023190900A1 (en) * 2022-03-30 2023-10-05 ダイキン工業株式会社 Fluorine-containing copolymer
WO2023190901A1 (en) * 2022-03-30 2023-10-05 ダイキン工業株式会社 Fluorine-containing copolymer
JP7364978B1 (en) 2022-03-30 2023-10-19 ダイキン工業株式会社 Fluorine-containing copolymer
WO2023190959A1 (en) * 2022-03-30 2023-10-05 ダイキン工業株式会社 Fluorine-containing copolymer
WO2023190919A1 (en) * 2022-03-30 2023-10-05 ダイキン工業株式会社 Fluorine-containing copolymer
JP7401832B2 (en) 2022-03-30 2023-12-20 ダイキン工業株式会社 Fluorine-containing copolymer
JP7401837B2 (en) 2022-03-30 2023-12-20 ダイキン工業株式会社 Fluorine-containing copolymer
JP7364986B1 (en) 2022-03-30 2023-10-19 ダイキン工業株式会社 Copolymers, molded bodies and injection molded bodies
JP7401836B2 (en) 2022-03-30 2023-12-20 ダイキン工業株式会社 Fluorine-containing copolymer
WO2023190954A1 (en) * 2022-03-30 2023-10-05 ダイキン工業株式会社 Fluorine-containing copolymer
WO2023190899A1 (en) * 2022-03-30 2023-10-05 ダイキン工業株式会社 Fluorine-containing copolymer
WO2023190957A1 (en) * 2022-03-30 2023-10-05 ダイキン工業株式会社 Fluorine-containing copolymer
WO2023190949A1 (en) * 2022-03-30 2023-10-05 ダイキン工業株式会社 Fluorine-containing copolymer
WO2023190962A1 (en) * 2022-03-30 2023-10-05 ダイキン工業株式会社 Fluorine-containing copolymer
JP7401834B2 (en) 2022-03-30 2023-12-20 ダイキン工業株式会社 Fluorine-containing copolymer
WO2023190918A1 (en) * 2022-03-30 2023-10-05 ダイキン工業株式会社 Fluorine-containing copolymer
JP7397384B2 (en) 2022-03-30 2023-12-13 ダイキン工業株式会社 Fluorine-containing copolymer
WO2024014518A1 (en) * 2022-07-15 2024-01-18 ダイキン工業株式会社 Fluorine-containing copolymer

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001089531A (en) * 1999-07-19 2001-04-03 Tokuyama Corp Fluorine-containing copolymer

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001036504A1 (en) 1999-11-16 2001-05-25 Daikin Industries, Ltd. Fluorocopolymer
US6743508B2 (en) 2002-01-17 2004-06-01 Daikin America, Inc. Fep pellet
CN101163739B (en) * 2005-05-18 2010-12-29 大金工业株式会社 Fluororesin composition and electric wire
JPWO2008047906A1 (en) * 2006-10-20 2010-02-25 ダイキン工業株式会社 Fluorine-containing copolymer, electric wire and method for producing the same
WO2009044753A1 (en) * 2007-10-03 2009-04-09 Daikin Industries, Ltd. Fluororesin composition and covered electric wire
CN103554326B (en) * 2008-02-15 2016-06-15 大金美国股份有限公司 Tetrafluoroethylene/hexafluoropropylene copolymer and its production method and electric wire
WO2010051350A1 (en) * 2008-10-31 2010-05-06 Daikin America, Inc. Foam electric wire
US8178592B2 (en) * 2009-05-15 2012-05-15 E.I. Du Pont De Nemours And Company Foamable fluoropolymer composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001089531A (en) * 1999-07-19 2001-04-03 Tokuyama Corp Fluorine-containing copolymer

Also Published As

Publication number Publication date
US20190177453A1 (en) 2019-06-13
WO2015119053A1 (en) 2015-08-13
US11021556B2 (en) 2021-06-01
EP3091042A1 (en) 2016-11-09
US20170008986A1 (en) 2017-01-12
JP6134818B2 (en) 2017-05-24
CN105980426B (en) 2018-01-02
EP3091042B1 (en) 2021-10-20
CN105980426A (en) 2016-09-28
EP3091042A4 (en) 2017-05-31
JPWO2015119053A1 (en) 2017-03-23

Similar Documents

Publication Publication Date Title
US11021556B2 (en) Tetrafluoroethylene/hexafluoropropylene copolymer, and electric wire
JP5844764B2 (en) Method for producing tetrafluoroethylene / hexafluoropropylene copolymer
JP5526506B2 (en) Coated wire and coaxial cable
US7723615B2 (en) Fluororesin composition and electric wire
JP5298853B2 (en) Fluorine-containing copolymer and molded product
EP2185648B1 (en) Fluororesin composition and covered electric wire
US20160005506A1 (en) Composition, and method for producing foam molded material and electric wire
JP2014224229A (en) Composition, and method for producing foam molded material and electric wire
US7105619B2 (en) Fluorine-containing copolymer
JPWO2019208401A1 (en) Twisted wire and its manufacturing method

Legal Events

Date Code Title Description
AS Assignment

Owner name: DAIKIN INDUSTRIES, LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ISAKA, TADAHARU;FUKAGAWA, RYOUICHI;SHIMONO, TAKESHI;AND OTHERS;SIGNING DATES FROM 20150218 TO 20150226;REEL/FRAME:053129/0191

Owner name: DAIKIN AMERICA, INC., NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ISAKA, TADAHARU;FUKAGAWA, RYOUICHI;SHIMONO, TAKESHI;AND OTHERS;SIGNING DATES FROM 20150218 TO 20150226;REEL/FRAME:053129/0191

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION