WO2019187725A1 - Matériau de résine fluorée, matériau de résine fluorée pour transmission haute fréquence, et fil électrique recouvert pour transmission haute fréquence - Google Patents

Matériau de résine fluorée, matériau de résine fluorée pour transmission haute fréquence, et fil électrique recouvert pour transmission haute fréquence Download PDF

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WO2019187725A1
WO2019187725A1 PCT/JP2019/005096 JP2019005096W WO2019187725A1 WO 2019187725 A1 WO2019187725 A1 WO 2019187725A1 JP 2019005096 W JP2019005096 W JP 2019005096W WO 2019187725 A1 WO2019187725 A1 WO 2019187725A1
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Prior art keywords
fluororesin
fluororesin material
tfe
copolymer
less
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PCT/JP2019/005096
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English (en)
Japanese (ja)
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今村　均
昌宏 近藤
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ダイキン工業株式会社
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Priority to EP19777108.2A priority Critical patent/EP3778723A4/fr
Priority to CN201980020656.0A priority patent/CN111886284B/zh
Priority to US17/041,298 priority patent/US11926753B2/en
Priority claimed from JP2019023272A external-priority patent/JP6708275B2/ja
Publication of WO2019187725A1 publication Critical patent/WO2019187725A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—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
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C08F8/22—Halogenation by reaction with free halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B11/00—Communication cables or conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators 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
    • H01B3/44—Insulators 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

Definitions

  • This disclosure relates to a fluororesin material, a fluororesin material for high-frequency transmission, and a coated electric wire for high-frequency transmission.
  • microwaves of 3 to 30 GHz are used for high-frequency wireless LANs, satellite communications, mobile phone base stations, and the like.
  • Patent Document 1 proposes a tetrafluoroethylene-based resin molding material with excellent high-frequency electrical characteristics that gives a molded product having a relative dielectric constant of 12 or less at 12 GHz and a dielectric loss tangent of 1.90 ⁇ 10 ⁇ 4 or less. Has been.
  • Patent Document 1 since the tetrafluoroethylene-based resin molding material proposed in Patent Document 1 is non-melt-processable, it is melt-processed using conventional processing equipment such as an extruder and an injection-molding machine. Can't get.
  • an object of the present disclosure is to provide a fluororesin material that can be manufactured by melt processing and has excellent high-frequency electrical characteristics.
  • a fluororesin material containing a melt processable fluororesin, having a relative dielectric constant at 12 GHz of 2.1 or less and a dielectric loss tangent of 0.00030 or less.
  • the number of functional groups per 10 6 main chain carbon atoms of the fluororesin is preferably 6 or less.
  • the fluororesin is at least one selected from the group consisting of a tetrafluoroethylene / (per) fluoro (alkyl vinyl ether) copolymer and a tetrafluoroethylene / hexafluoropropylene copolymer.
  • a seed copolymer is preferred.
  • a fluororesin material for high frequency transmission containing the above fluororesin material is also provided.
  • a high-frequency transmission coated electric wire provided with the above-described fluororesin material as the insulating coating layer, wherein the insulating coating layer is a solid insulating coating layer.
  • the fluororesin material of the present disclosure contains a melt processable fluororesin.
  • melt processability means that the polymer can be melted and processed using conventional processing equipment such as an extruder and an injection molding machine. Therefore, the melt processable fluororesin usually has a melt flow rate of 0.01 to 500 g / 10 min as measured by the measurement method described later.
  • a melt-processable tetrafluoroethylene / hexafluoropropylene copolymer, a tetrafluoroethylene / (per) fluoro (alkyl vinyl ether) copolymer, and the like are hexafluoropropylene and ( Since per) fluoro (alkyl vinyl ether) is copolymerized, the dipole moment is increased, and a corresponding decrease in electrical characteristics appears remarkably in the microwave region having a high frequency.
  • the relative dielectric constant at 12 GHz of the fluororesin material of the present disclosure is 2.1 or less, and the dielectric loss tangent is 0.00030 or less.
  • the relative dielectric constant of the fluororesin material of the present disclosure is 2.1 or less, preferably 2.10 or less, more preferably 2.08 or less, and the lower limit is not particularly limited, but preferably 1.80. That's it.
  • the dielectric loss tangent of the fluororesin material of the present disclosure is 0.00030 or less, preferably 0.00020 or less, and the lower limit is not particularly limited, but is preferably 0.00001 or more.
  • the relative dielectric constant and dielectric loss tangent are values obtained by measuring changes in resonance frequency and electric field strength at a temperature of 20 to 25 ° C. using a network analyzer HP8510C (manufactured by Hewlett Packard) and a cavity resonator. .
  • the number of functional groups per 10 6 main chain carbon atoms of the fluororesin material contained in the fluororesin material of the present disclosure is preferably 6 or less, and more preferably, because excellent radio frequency electrical characteristics can be obtained. It is 4 or less, more preferably 2 or less, and particularly preferably 0.
  • the number of functional groups of the fluororesin is the number of functional groups of the fluororesin after irradiation when the fluororesin material is produced by irradiating the fluororesin before irradiation with radiation. Moreover, it is preferable that the number of functional groups of the fluororesin before irradiation is also in the above range.
  • the number of functional groups generated by irradiation is further improved by adjusting it within the above-mentioned range of functional groups. High frequency electrical characteristics can be obtained.
  • the number of functional groups of the fluororesin before irradiation is within the above range, it is presumed that when the fluororesin is irradiated with radiation, the reaction of cross-linking of the functional groups is suppressed and high-frequency electrical characteristics are improved.
  • the number of functional groups is within the above range, there is an advantage that molding defects such as foaming hardly occur when the fluororesin is molded.
  • Infrared spectroscopic analysis can be used for identification of the types of functional groups and measurement of the number of functional groups.
  • Table 1 shows the absorption frequency, molar extinction coefficient, and correction coefficient for the functional groups in the present disclosure.
  • the molar extinction coefficient is determined from FT-IR measurement data of a low molecular weight model compound.
  • the absorption frequencies of —CH 2 CF 2 H, —CH 2 COF, —CH 2 COOH, —CH 2 COOCH 3 , —CH 2 CONH 2 are shown in the table, respectively, —CF 2 H, —COF, —
  • the absorption frequency of COOH free, —COOH bonded, —COOCH 3 , and —CONH 2 is lower by several tens of Kaiser (cm ⁇ 1 ).
  • the number of functional groups of —COF is the number of functional groups determined from the absorption peak at an absorption frequency of 1883 cm ⁇ 1 due to —CF 2 COF and the absorption peak at an absorption frequency of 1840 cm ⁇ 1 due to —CH 2 COF. It is the total with the obtained number of functional groups.
  • the functional group is a functional group present at the main chain end or side chain end of the fluororesin, and a functional group present in the main chain or side chain.
  • the number of functional groups may be the total number of —CF ⁇ CF 2 , —CF 2 H, —COF, —COOH, —COOCH 3 , —CONH 2 and CH 2 OH.
  • the functional group is introduced into the fluororesin by, for example, a chain transfer agent or a polymerization initiator used when producing the fluororesin.
  • a chain transfer agent or a polymerization initiator used when producing the fluororesin.
  • alcohol is used as a chain transfer agent or a peroxide having a structure of —CH 2 OH is used as a polymerization initiator
  • —CH 2 OH is introduced at the end of the main chain of the fluororesin.
  • the said functional group is introduce
  • the fluororesin having the number of functional groups within the above range can be obtained by subjecting the fluororesin having such a functional group to fluorination treatment. That is, it is preferable that the fluororesin contained in the fluororesin material of the present disclosure is fluorinated.
  • the fluororesin contained in the fluororesin material of the present disclosure preferably has a —CF 3 terminal group.
  • the fluorination treatment can be performed by bringing a fluorine resin not subjected to fluorination treatment and a fluorine-containing compound into contact with each other.
  • produces a fluorine radical under fluorination process conditions is mentioned.
  • the fluorine radical source include F 2 gas, CoF 3 , AgF 2 , UF 6 , OF 2 , N 2 F 2 , CF 3 OF, and halogen fluoride (eg, IF 5 , ClF 3 ).
  • the fluorine radical source such as F 2 gas may have a concentration of 100%, but is preferably mixed with an inert gas and diluted to 5 to 50% by mass from the viewpoint of safety. It is more preferable to use it diluted to ⁇ 30% by mass.
  • the inert gas include nitrogen gas, helium gas, and argon gas. Nitrogen gas is preferable from the economical viewpoint.
  • the conditions for the fluorination treatment are not particularly limited, and the molten fluororesin and the fluorine-containing compound may be brought into contact with each other, but usually below the melting point of the fluororesin, preferably 20 to 220 ° C., more preferably Can be carried out at a temperature of 100 to 200 ° C.
  • the fluorination treatment is generally performed for 1 to 30 hours, preferably 5 to 25 hours.
  • the fluorination treatment is preferably performed by bringing a fluororesin that has not been fluorinated into contact with fluorine gas (F 2 gas).
  • the above-mentioned fluororesin preferably has a melting point of 190 to 322 ° C.
  • fusing point More preferably, it is 200 degreeC or more, More preferably, it is 220 degreeC or more, Especially preferably, it is 280 degreeC or more, More preferably, it is 315 degreeC or less.
  • the melting point is a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimeter [DSC].
  • the fluororesin is not particularly limited as long as it is a melt processable fluororesin, but tetrafluoroethylene units (TFE units) and (per) fluoro (alkyl vinyl ether) units are obtained because further excellent high-frequency electrical characteristics can be obtained.
  • TFE units tetrafluoroethylene units
  • alkyl vinyl ether alkyl vinyl ether
  • Copolymer hereinafter referred to as TFE / PAVE copolymer (or PFA)
  • TFE unit and hexafluoropropylene unit HFP unit
  • the fluororesin is a copolymer containing PAVE units because a fluororesin material having excellent high-frequency electrical characteristics and a relatively high breaking strength can be obtained.
  • the (per) fluoro (alkyl vinyl ether) may be a fluoroalkyl vinyl ether or a perfluoro (alkyl vinyl ether).
  • perfluoro (alkyl vinyl ether) is an alkyl vinyl ether containing no C—H bond.
  • CF 2 CFO (CF 2 CFY 1 O) p — (CF 2 CF 2 CF 2 O) q —R f (1)
  • Y 1 represents F or CF 3
  • R f represents a perfluoroalkyl group having 1 to 5 carbon atoms
  • p represents an integer of 0 to 5
  • q represents an integer of 0 to 5
  • CFX CXOCF 2 OR 1 (2)
  • X is the same or different and represents H, F or CF 3
  • R 1 represents at least one atom selected from the group consisting of H, Cl, Br and I, which is linear or branched.
  • the monomer represented by General formula (1) is preferable, From the group which consists of perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), and perfluoro (propyl vinyl ether) (PPVE). At least one selected is more preferable, and PPVE is more preferable.
  • the content of PAVE units in the TFE / PAVE copolymer is preferably 1.0 to 10% by mass, more preferably 2.0% by mass or more, and still more preferably based on all monomer units. Is 3.5% by mass or more, particularly preferably 4.0% by mass or more, most preferably 5.0% by mass or more, more preferably 8.0% by mass or less, and still more preferably 7% by mass. It is 0.0 mass% or less, Especially preferably, it is 6.5 mass% or less, Most preferably, it is 6.0 mass% or less.
  • the amount of the PAVE unit is measured by 19 F-NMR method.
  • the TFE / PAVE copolymer may be a copolymer composed only of TFE units and PAVE units.
  • the melting point of the TFE / PAVE copolymer is preferably 280 to 322 ° C., more preferably 290 ° C. or more, and more preferably 315 ° C. or less.
  • the glass transition temperature (Tg) of the TFE / PAVE copolymer is preferably 70 to 110 ° C, more preferably 80 ° C or higher, and more preferably 100 ° C or lower.
  • the glass transition temperature is a value obtained by measurement by dynamic viscoelasticity measurement.
  • the TFE / PAVE copolymer is produced by a conventionally known method such as emulsion polymerization or suspension polymerization by appropriately mixing monomers as constituent units and additives such as a polymerization initiator. Can do.
  • the TFE / HFP copolymer contains TFE units and HFP units.
  • the content of TFE units in the TFE / HFP copolymer is preferably 70% by mass or more, more preferably 85% by mass or more, and preferably 99.8% by mass with respect to all monomer units. % Or less, more preferably 99% by mass or less, and still more preferably 98% by mass or less.
  • the TFE / HFP copolymer preferably has a mass ratio (TFE / HFP) of TFE units to HFP units of 70 to 99/1 to 30 (mass%).
  • the mass ratio (TFE / HFP) is more preferably 85 to 95/5 to 15 (mass%).
  • the TFE / HFP copolymer can further contain (per) fluoro (alkyl vinyl ether) (PAVE) units.
  • PAVE fluoro (alkyl vinyl ether)
  • Examples of the PAVE unit contained in the TFE / HFP copolymer include the same PAVE units as those described above. Since the TFE / PAVE copolymer described above does not contain HFP units, it differs from the TFE / HFP / PAVE copolymer in that respect.
  • the mass ratio (TFE / HFP) / PAVE) is preferably 70 to 99.8 / 0.1 to 25 / 0.1 to 25 (mass%).
  • the mass ratio (TFE / HFP / PAVE) is more preferably 75 to 98 / 1.0 to 15 / 1.0 to 10 (mass%).
  • the TFE / HFP / PAVE copolymer preferably contains 1% by mass or more of HFP units and PAVE units in total.
  • the HFP unit is preferably 25% by mass or less based on the total monomer units.
  • the content of the HFP unit is more preferably 20% by mass or less, still more preferably 18% by mass or less, and particularly preferably 15% by mass or less. Further, the content of the HFP unit is preferably 0.1% by mass or more, more preferably 1% by mass or more, and particularly preferably 2% by mass or more.
  • the content of the HFP unit can be measured by 19 F-NMR method.
  • the content of the PAVE unit is more preferably 20% by mass or less, and further preferably 10% by mass or less. Especially preferably, it is 3 mass% or less. Further, the content of the PAVE unit is preferably 0.1% by mass or more, and more preferably 1% by mass or more.
  • the content of the PAVE unit can be measured by 19 F-NMR method.
  • the TFE / HFP copolymer may further contain other ethylenic monomer ( ⁇ ) units.
  • the other ethylenic monomer ( ⁇ ) unit is not particularly limited as long as it is a monomer unit copolymerizable with TFE, HFP and PAVE.
  • the content of other ethylenic monomer ( ⁇ ) units is preferably 0 to 25% by mass, more preferably 0.1 to 25% by mass.
  • the mass ratio (TFE / HFP / PAVE / other ethylenic monomer ( ⁇ )) is: It is preferably 70 to 98 / 0.1 to 25 / 0.1 to 25 / 0.1 to 25 (mass%).
  • the TFE / HFP / PAVE / other ethylenic monomer ( ⁇ ) copolymer preferably contains 1% by mass or more of monomer units other than TFE units in total.
  • the melting point of the TFE / HFP copolymer is preferably 200 to 322 ° C., more preferably more than 200 ° C., further preferably 220 ° C. or more, more preferably 300 ° C. or less, and further preferably It is 280 degrees C or less.
  • the glass transition temperature (Tg) of the TFE / HFP copolymer is preferably 60 to 110 ° C., more preferably 65 ° C. or more, and more preferably 100 ° C. or less.
  • the glass transition temperature is a value obtained by measurement by dynamic viscoelasticity measurement.
  • the TFE / HFP copolymer is prepared by a conventionally known method such as emulsion polymerization, solution polymerization, suspension polymerization, or the like by appropriately mixing monomers as constituent units and additives such as a polymerization initiator. Can be manufactured.
  • the fluororesin is preferably the TFE / PAVE copolymer and the TFE / HFP copolymer. That is, the TFE / PAVE copolymer and the TFE / HFP copolymer can be mixed and used.
  • the mass ratio ((A) / (B)) between the TFE / PAVE copolymer and the TFE / HFP copolymer is preferably 1/9 to 7/3, more preferably 5/5 to 2 / 8.
  • the above mixture is a mixture of two or more of the above fluororesins and melt-mixed (melt-kneaded), mixed with a resin dispersion after emulsion polymerization, and coagulated with an acid such as nitric acid to recover the resin, etc. It may be prepared by a known method.
  • the melt flow rate (MFR) of the fluororesin at 372 ° C. is preferably 0.1 to 100 g / 10 minutes, more preferably 0.5 g / 10 minutes or more, more preferably 80 g / 10 minutes or less. Yes, more preferably 40 g / 10 min or less.
  • MFR melt flow rate
  • ASTM D1238 the MFR uses a melt indexer (manufactured by Yasuda Seiki Seisakusho Co., Ltd.), and the mass of the polymer flowing out per 10 minutes from a nozzle having an inner diameter of 2 mm and a length of 8 mm under a load of 372 ° C. and 5 kg (g / 10) Min)).
  • the breaking strength of the fluororesin material of the present disclosure is preferably 13 MPa or more, more preferably 15 MPa or more, and the upper limit is not particularly limited, but may be 30 MPa or less, or 25 MPa or less.
  • the fluororesin material of the present disclosure can be manufactured by melt processing and at the same time has such a high breaking strength. When the breaking strength of the fluororesin material of the present disclosure is within the above range, the breaking strength of the fluororesin material of the present disclosure can be applied to applications that require high mechanical strength.
  • the fluororesin material of the present disclosure may contain other components as necessary.
  • Other components include additives such as crosslinking agents, antistatic agents, heat stabilizers, foaming agents, foaming nucleating agents, antioxidants, surfactants, photopolymerization initiators, antiwear agents, surface modifiers, etc. Can be mentioned.
  • the fluororesin material of the present disclosure can be manufactured, for example, by a manufacturing method including a step of irradiating 20 to 100 kGy of radiation at 80 to 240 ° C. with respect to an unirradiated fluororesin.
  • the irradiation temperature of the radiation is 80 to 240 ° C., preferably 100 ° C. or more, more preferably 140 ° C. or more, and preferably 220 ° C. from the viewpoint of achieving both excellent high-frequency electrical characteristics and high breaking strength. It is below, More preferably, it is 200 degrees C or less, More preferably, it is 180 degrees C or less.
  • the irradiation temperature is preferably within the above numerical range and lower than the melting point of the fluororesin before irradiation with radiation.
  • the adjustment of the irradiation temperature is not particularly limited, and can be performed by a known method. Specifically, a method of holding the above-mentioned fluororesin in a heating furnace maintained at a predetermined temperature, placing on a hot plate, energizing a heater built in the hot plate, or hot plate by an external heating means The method of heating is mentioned.
  • the radiation dose is 20 to 100 kGy, preferably 95 kGy or less, more preferably 80 kGy or less, preferably 30 kGy or more, from the viewpoint of achieving both excellent high-frequency electrical characteristics and high breaking strength. More preferably, it is 40 kGy or more.
  • Examples of radiation include electron beams, ultraviolet rays, gamma rays, X-rays, neutron rays, high energy ions, and the like.
  • an electron beam is preferable because it has excellent transmission power, a high dose rate, and is suitable for industrial production.
  • the method of irradiating radiation is not particularly limited, and examples thereof include a method performed using a conventionally known radiation irradiating apparatus.
  • the irradiation environment is not particularly limited, but the oxygen concentration is preferably 1000 ppm or less, more preferably in the absence of oxygen, and in an inert gas atmosphere such as nitrogen, helium or argon More preferably, it is in the middle.
  • the above-described method for producing a fluororesin material preferably further includes a step of molding a non-irradiated fluororesin or a step of molding a fluororesin after irradiation.
  • the molding since the molding is easy, it is preferable to mold the fluororesin before irradiating with radiation. That is, it is more preferable that the above method for producing a fluororesin material further includes a step of molding a fluororesin that has not been irradiated with radiation.
  • the above fluororesin material manufacturing method includes these steps, whereby a fluororesin material having a desired shape can be manufactured.
  • a method for molding the fluororesin a method can be used in which the fluororesin is heated to a melting point or higher and melted.
  • the method for molding the fluororesin is not particularly limited, and examples thereof include known methods such as extrusion molding, injection molding, transfer molding, inflation molding, and compression molding. What is necessary is just to select these shaping
  • molding methods suitably according to the shape of the fluororesin material obtained.
  • the shape of the fluororesin material of the present disclosure is not particularly limited, and examples thereof include pellets, films, sheets, plates, rods, blocks, cylinders, containers, electric wires, and tubes. Also, coating layers for cooking utensils such as rice cookers, hot plates and frying pans, and topcoat layers for fixing rollers for image forming devices such as electrophotographic or electrostatic recording copying machines and laser printers are formed.
  • a fluororesin coating film may be used.
  • the fluororesin coating film can be formed by applying a fluororesin paint to a substrate.
  • the fluororesin material of the present disclosure has a low relative dielectric constant and dielectric loss tangent, it can be particularly suitably used as a fluororesin material for high-frequency transmission.
  • the dielectric loss ⁇ of the high frequency signal can be calculated by the following equation.
  • k is a constant
  • ⁇ r is a relative dielectric constant
  • tan ⁇ is a dielectric loss tangent
  • f is a signal frequency
  • A is a dielectric loss contribution.
  • the product for high-frequency signal transmission is not particularly limited as long as it is a product used for high-frequency signal transmission.
  • Examples include bases for high-frequency vacuum tubes, molded articles such as antenna covers, and (3) covered electric wires such as coaxial cables and LAN cables.
  • the fluororesin material of the present disclosure can be suitably used as an insulator because it has a low relative dielectric constant and dielectric loss tangent.
  • the above (1) molded board is preferably a printed wiring board in that good electrical characteristics can be obtained.
  • said printed wiring board for example, the printed wiring board of electronic circuits, such as a mobile telephone, various computers, and communication apparatuses, is mentioned.
  • an antenna cover is preferable at a point with low dielectric loss.
  • a high-frequency transmission coated electric wire provided with the fluororesin material of the present disclosure is preferable as an insulating coating layer in that good electrical characteristics can be obtained.
  • the high frequency transmission covered electric wire may be a high frequency transmission cable, and a coaxial cable is preferable as the high frequency transmission cable.
  • the coaxial cable generally has a structure in which an inner conductor, an insulating coating layer, an outer conductor layer, and a protective coating layer are sequentially laminated from the core portion to the outer peripheral portion.
  • each layer in the above structure is not particularly limited, but usually the inner conductor has a diameter of about 0.1 to 3 mm, the insulating coating layer has a thickness of about 0.3 to 3 mm, and the outer conductor layer has a thickness of about
  • the protective coating layer has a thickness of about 0.5 to 2 mm.
  • the above-mentioned insulating coating layer may be a foamed insulating coating layer.
  • the coated electric wire for high-frequency transmission has the low relative dielectric constant and dielectric loss tangent of the fluororesin material of the present disclosure, and a low transmission loss can be obtained without foaming.
  • the insulating coating layer formed from the material may be a solid insulating coating layer.
  • the term “solid” means that the inside is filled with a fluororesin material and there is substantially no void.
  • a void formed unintentionally due to a molding defect or the like may be included.
  • many voids exist in the foamed insulation coating layer.
  • the fluororesin material of the present disclosure may be a solid fluororesin material.
  • the above-mentioned (3) covered electric wire includes, for example, a step of coating a non-radiated fluororesin on the inner conductor by extrusion molding to form a covering layer on the inner conductor, and the irradiation on the covering layer. It can be manufactured by a manufacturing method including a step of obtaining a covered electric wire including the fluororesin material as an insulating coating layer by irradiating radiation under conditions to form the fluororesin material.
  • the product for high-frequency signal transmission can be suitably used for devices using microwaves, particularly 3 to 30 MHz microwaves such as satellite communication devices and mobile phone base stations.
  • MFR mass (g / 10 minutes) of the polymer flowing out per 10 minutes from a nozzle having an inner diameter of 2 mm and a length of 8 mm under a load of 372 ° C. and 5 kg. Asked. (Melting point) It calculated
  • N I ⁇ K / t (A) I: Absorbance K: Correction coefficient t: Film thickness (mm)
  • Table 2 shows the absorption frequency, molar extinction coefficient, and correction coefficient for the functional groups in the present disclosure.
  • the molar extinction coefficient is determined from FT-IR measurement data of a low molecular weight model compound.
  • the dielectric loss tangent and relative dielectric constant of the test pieces (extrusion molding) obtained in the examples or comparative examples were measured by the cavity resonator method. Using a network analyzer (HP8510C, manufactured by Hewlett-Packard Company), changes in resonance frequency and Q value (electric field strength) were measured at a temperature of 20 to 25 ° C., and a dielectric loss tangent (tan ⁇ ) and a relative dielectric constant ( ⁇ r at 12 GHz). ) was measured. Further, the dielectric loss contribution A was determined from the following equation from the dielectric loss tangent and relative dielectric constant.
  • Comparative Example 2 The pellet used in Comparative Example 1 was put in a container, and fluorine gas diluted to 20 mass% with nitrogen gas was passed at 200 ° C. at normal pressure for 10 hours to perform fluorine gas treatment. When the number of functional groups was measured using pellets obtained by the fluorine gas treatment, no functional groups were detected. Further, a test piece (extrusion molding) and a test piece (compression molding) were obtained and evaluated in the same manner as in Comparative Example 1 except that pellets obtained by the fluorine gas treatment were used. The results are shown in Table 3.
  • Example 1 The test piece (extrusion molding) and the test piece (compression molding) obtained in Comparative Example 2 are accommodated in an electron beam irradiation container of an electron beam irradiation apparatus (manufactured by NHV Corporation), and then nitrogen gas is added to the container. Was put in a nitrogen atmosphere. After confirming that the temperature in the container was stable at the irradiation temperature described in Table 3, each test piece was listed in Table 3 under the conditions of an electron beam acceleration voltage of 3000 kV and an irradiation dose intensity of 20 kGy / 5 min. Irradiation dose of electron beam was applied. Evaluation was performed in the same manner as in Comparative Example 1 except that a test piece irradiated with an electron beam was used. The results are shown in Table 3.
  • Example 2-5 A test piece was obtained in the same manner as in Example 1 except that the electron beam was irradiated under the conditions described in Table 3. Evaluation was performed in the same manner as in Comparative Example 1 using the obtained test piece. The results are shown in Table 3.
  • Comparative Example 3 A test piece was obtained in the same manner as in Comparative Example 1 except that pellets of TFE / PPVE / HFP copolymer were used. Evaluation was performed in the same manner as in Comparative Example 1 using the obtained test piece. The results are shown in Table 3.
  • Comparative Example 4 Fluorine gas treatment was performed in the same manner as in Comparative Example 2 except that the pellets used in Comparative Example 3 were used. When the number of functional groups was measured using pellets obtained by the fluorine gas treatment, no functional groups were detected. Further, a test piece (extrusion molding) and a test piece (compression molding) were obtained and evaluated in the same manner as in Comparative Example 1 except that pellets obtained by the fluorine gas treatment were used. The results are shown in Table 3.
  • Example 6-7 A test piece was obtained in the same manner as in Example 1 except that the pellet obtained in Comparative Example 4 was used and irradiated with an electron beam under the conditions described in Table 3. Evaluation was performed in the same manner as in Comparative Example 1 using the obtained test piece. The results are shown in Table 3.
  • Comparative Example 5 A test piece was obtained in the same manner as in Comparative Example 1 except that pellets of TFE / HFP copolymer were used. Evaluation was performed in the same manner as in Comparative Example 1 using the obtained test piece. The results are shown in Table 3.
  • Comparative Example 6 A fluorine gas treatment was performed in the same manner as in Comparative Example 2 except that the pellets used in Comparative Example 5 were used. When the number of functional groups was measured using pellets obtained by the fluorine gas treatment, no functional groups were detected. Further, a test piece (extrusion molding) and a test piece (compression molding) were obtained and evaluated in the same manner as in Comparative Example 1 except that pellets obtained by the fluorine gas treatment were used. The results are shown in Table 3.
  • Example 8 A test piece was obtained in the same manner as in Example 1 except that the pellet obtained in Comparative Example 6 was used and irradiated with an electron beam under the conditions described in Table 3. Evaluation was performed in the same manner as in Comparative Example 1 using the obtained test piece. The results are shown in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne un matériau de résine fluorée qui contient une résine fluorée pouvant être traitée par fusion, qui présente une constante diélectrique relative inférieure ou égale à 2,1 à 12 GHz, et qui a une tangente de perte diélectrique inférieure ou égale à 0,00030.
PCT/JP2019/005096 2018-03-26 2019-02-13 Matériau de résine fluorée, matériau de résine fluorée pour transmission haute fréquence, et fil électrique recouvert pour transmission haute fréquence WO2019187725A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP19777108.2A EP3778723A4 (fr) 2018-03-26 2019-02-13 Matériau de résine fluorée, matériau de résine fluorée pour transmission haute fréquence, et fil électrique recouvert pour transmission haute fréquence
CN201980020656.0A CN111886284B (zh) 2018-03-26 2019-02-13 氟树脂材料、高频传输用氟树脂材料及高频传输用包覆电线
US17/041,298 US11926753B2 (en) 2018-03-26 2019-02-13 Fluororesin material, fluororesin material for high frequency transmission, and covered electric wire for high-frequency transmission

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JP2018057719 2018-03-26
JP2018-057719 2018-03-26
JP2019023272A JP6708275B2 (ja) 2018-03-26 2019-02-13 フッ素樹脂材料、高周波伝送用フッ素樹脂材料および高周波伝送用被覆電線
JP2019-023272 2019-02-13

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WO2022172903A1 (fr) * 2021-02-12 2022-08-18 ダイキン工業株式会社 Matériau de résine fluorée modifié, matériau destiné à une carte de circuits imprimés, stratifié destiné à une carte de circuits imprimés, carte de circuits imprimés et procédé de fabrication de matériau de résine fluorée modifié
WO2022181721A1 (fr) * 2021-02-26 2022-09-01 ダイキン工業株式会社 Corps moulé par injection, tuyau revêtu et soupape revêtue

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JPS4931785A (fr) * 1972-07-25 1974-03-22
JPS63146908A (ja) * 1986-07-18 1988-06-18 Yoneo Tabata 放射線による低分子量ポリテトラフルオロエチレン微粉末の製造方法
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WO2022172903A1 (fr) * 2021-02-12 2022-08-18 ダイキン工業株式会社 Matériau de résine fluorée modifié, matériau destiné à une carte de circuits imprimés, stratifié destiné à une carte de circuits imprimés, carte de circuits imprimés et procédé de fabrication de matériau de résine fluorée modifié
JP2022123855A (ja) * 2021-02-12 2022-08-24 ダイキン工業株式会社 改質フッ素樹脂材料、回路基板用材料、回路基板用積層体、回路基板、及び、改質フッ素樹脂材料の製造方法
JP7269518B2 (ja) 2021-02-12 2023-05-09 ダイキン工業株式会社 改質フッ素樹脂材料、回路基板用材料、回路基板用積層体、回路基板、及び、改質フッ素樹脂材料の製造方法
WO2022181721A1 (fr) * 2021-02-26 2022-09-01 ダイキン工業株式会社 Corps moulé par injection, tuyau revêtu et soupape revêtue
JP2022132165A (ja) * 2021-02-26 2022-09-07 ダイキン工業株式会社 射出成形体、ライニング管およびライニングバルブ
JP7280538B2 (ja) 2021-02-26 2023-05-24 ダイキン工業株式会社 射出成形体、ライニング管およびライニングバルブ

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