WO2017126499A1 - フッ素樹脂のペレット、電線及びその製造方法 - Google Patents
フッ素樹脂のペレット、電線及びその製造方法 Download PDFInfo
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- WO2017126499A1 WO2017126499A1 PCT/JP2017/001404 JP2017001404W WO2017126499A1 WO 2017126499 A1 WO2017126499 A1 WO 2017126499A1 JP 2017001404 W JP2017001404 W JP 2017001404W WO 2017126499 A1 WO2017126499 A1 WO 2017126499A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/16—Auxiliary treatment of granules
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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
- C08F214/28—Hexyfluoropropene
- C08F214/282—Hexyfluoropropene with fluorinated vinyl ethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/06—Making preforms by moulding the material
- B29B11/10—Extrusion moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/06—Rod-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
- B29C48/154—Coating solid articles, i.e. non-hollow articles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/06—Insulating conductors or cables
- H01B13/14—Insulating conductors or cables by extrusion
- H01B13/147—Feeding of the insulating material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/06—Insulating conductors or cables
- H01B13/14—Insulating conductors or cables by extrusion
- H01B13/148—Selection of the insulating material therefor
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- 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
- H01B3/42—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 polyesters; polyethers; polyacetals
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- 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
- H01B3/443—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 from vinylhalogenides or other halogenoethylenic compounds
- H01B3/445—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 from vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/16—Auxiliary treatment of granules
- B29B2009/161—Absorbing, i.e. introducing a gas, a liquid or a solid material into the granules
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
- B29C48/34—Cross-head annular extrusion nozzles, i.e. for simultaneously receiving moulding material and the preform to be coated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
- B29L2031/3406—Components, e.g. resistors
Definitions
- the present invention relates to a fluororesin pellet. Moreover, this invention relates to the manufacturing method of the electric wire obtained from the said pellet and the said pellet using the said pellet.
- fluororesin pellets are often used as raw materials for producing fluororesin molded products.
- Patent Document 1 for the purpose of providing a method for manufacturing a thin-diameter thin insulated wire that enables insulation extrusion coating with an ultra-low attachment amount, the size of the pellet is 1.5 mm or less, and the screw of the extruder is used. It is described that the outer diameter is 20 mm or less.
- Patent Document 2 discloses a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) as a resin material for rotational molding that has no risk of metal contamination and that is satisfactory in terms of quality and performance of the rotational molded product.
- PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
- Patent Document 3 describes that the average particle diameter of the fluororesin pellets is 1.0 to 5.0 mm in consideration of handling properties when producing a fluororesin molded body using the fluororesin pellets. Yes.
- the wire has been made thinner, and the wire coating material has been required to have a fine wire formability and a thin wall formability.
- the influence of minute fluctuations in the wire diameter generated during forming on the final physical properties of the wire cannot be ignored, and more stable forming than before is required.
- a material having higher wire diameter stability and capacitance stability than the conventional materials is required.
- pellets of fluororesin are supplied from the hopper into the cylinder of the extruder, melted in the cylinder, and the molten fluororesin is fed onto the core wire fed from the back of the die. And extrude through a die to form a coating layer.
- the conventional pellets have room for improvement in the fluidity in the hopper. Further, it has been found that when a coating layer is formed on a core wire fed out at high speed using conventional pellets, the resulting coating layer has insufficient wire diameter stability and capacitance stability.
- the present invention has a high fluidity in an hopper of an extruder, and a novel coating layer having high wire diameter stability and capacitance stability can be formed even when subjected to high-speed wire coating molding. It is an object to provide pellets.
- the present inventors have found that the shape of the pellet greatly affects the wire diameter stability and capacitance stability of the coating layer of the electric wire, and complete the present invention. It came to. It has also been found that the pellet fluidity in the hopper of the extruder is improved by the shape of the pellet that realizes high wire diameter stability and capacitance stability.
- the present invention is a fluororesin pellet
- the outer shape of the pellet placed on the horizontal plane observed from the normal direction to the horizontal plane is a substantially circular shape or a substantially elliptical shape
- the major axis D 1 is 3.1 mm.
- the short diameter D 2 is 3.1 mm or less
- the pellet is a major diameter D 1 is 1.6mm or more, and a minor diameter D 2 is 1.6mm or more.
- the pellet preferably has a standard deviation of height L of 0.3 mm or less.
- the pellets preferably include 100 or less abnormal pellets per 100 g of the pellets.
- the pellet includes a pellet having bubbles within 10% by mass or less per 100 g of the pellet.
- the time for discharging 300 g of the pellet is 9.2 seconds or less.
- the pellet is preferably substantially spheroid, substantially cylindrical, or substantially elliptical.
- the fluororesin preferably has a total number of —COOH, —COOCH 3 , —CH 2 OH, —COF, —CONH 2 , and —CF 2 H of 120 or less per 1 ⁇ 10 6 carbon atoms. .
- This invention is also an electric wire provided with the core wire and the coating layer provided around the said core wire and obtained from the above-mentioned pellet.
- the present invention uses an extruder comprising a cylinder, a screw accommodated in the cylinder, a die attached to the tip of the cylinder, and a hopper for supplying pellets to the cylinder,
- a manufacturing method for manufacturing an electric wire comprising a coating layer, the step of producing the pellet, the step of feeding the pellet into the hopper, the step of supplying the pellet from the hopper to the cylinder, and in the cylinder
- It is also a method for producing an electric wire comprising: a step of melting the pellet to produce a molten fluororesin; and a step of extruding the molten fluororesin from the die to form the coating layer on the core wire.
- the pellet of this invention Since the pellet of this invention has the said structure, it is excellent in the fluidity
- the electric wire of the present invention has the above configuration, it is excellent in wire diameter stability and capacitance stability.
- the manufacturing method of the electric wire of the present invention has the above-described configuration, it is possible to manufacture an electric wire with high productivity and excellent wire diameter stability and capacitance stability.
- the outer shape of the pellet placed on the horizontal plane observed from the normal direction to the horizontal plane is a substantially circular shape or a substantially elliptical shape
- the major axis D 1 is 3.1 mm or less
- the minor axis D 2 is 3.1 mm or less
- FIG. 1 The schematic diagram at the time of observing the said pellet set
- 4 and 6 are photographs of the pellets of the present invention placed on a horizontal plane, taken from the direction normal to the horizontal plane.
- examples of the pellet include a pellet 11 having a substantially circular outer shape and a pellet 12 having a substantially elliptical outer shape.
- the major axis D 1 and the minor axis D 2 are as shown in FIG. 1.
- the major axis D 1 and the minor axis D 2 are the same length.
- the terms major axis and minor axis are used even when the lengths are the same.
- the major axis D 1 and the minor axis D 2 can be obtained from an average value obtained by arbitrarily extracting 20 g of pellets, placing them on a horizontal plane, measuring the major axis and the minor axis one by one.
- the measurement is performed after placing the pellet in a method that does not roll or fall even on a hard and smooth horizontal surface. For example, when the shape of the whole pellet is substantially cylindrical, the movement may stop if the side surface is placed on a horizontal plane, but if the vibration is applied, it may roll or fall. Such a placement is not appropriate, and the measurement is performed after the pellets are placed in a stable state.
- the pellet when the shape is substantially cylindrical, the pellet is put into a stainless steel bat, etc., the bat is subjected to strong vibration, the bottom surface of all the pellets is grounded, and after measuring a stable state, measurement is performed. be able to.
- Such a method of placing the pellet is also applied to the measurement of the height L described later.
- the pellet diameter D 1 is 3.1mm or less, and a short diameter D 2 is not more than 3.1mm.
- FIG. 2 and FIG. 3 are schematic views when the pellet placed on a horizontal plane is observed from the horizontal direction.
- 5 and 7 are photographs of the pellets of the present invention placed on a horizontal plane taken from the horizontal direction.
- the outer diameter shape when observed from the horizontal direction of the pellet is not particularly limited, and may be substantially elliptical as shown in FIG. 2, or may be substantially rectangular or trapezoidal as shown in FIG. May be. However, as will be described later, since the pellet satisfies the formula (1), the length (width) in the horizontal direction is always larger than the height.
- the height L is the length from the horizontal plane to the highest portion.
- the height L can be obtained by arbitrarily extracting 20 g of pellets, placing them on a horizontal surface, measuring the height L one by one, and obtaining the average value thereof. it can.
- a suitable numerical range of the height L is naturally determined from the following formula (1).
- the pellet preferably has a standard deviation of height L of 0.3 mm or less.
- the standard deviation is more preferably 0.2 mm or less.
- the standard deviation can be calculated from the result of arbitrarily extracting 20 g of pellets, placing them on a horizontal plane, and measuring the height L one by one.
- the above pellets are flat enough to satisfy the formula (1), and thus have excellent fluidity, high productivity, and a wire for forming a coating layer with excellent wire diameter stability and capacitance stability. It is suitable as a coating material.
- the upper limit of (D 1 + D 2 ) / 2L is preferably 2.4, and the lower limit is preferably 2.0.
- the pellet may have a substantially spheroidal shape, a substantially cylindrical shape, or a substantially elliptical column shape as a whole. It is preferable that 97 g or more of the pellets have these shapes out of 100 g of arbitrarily extracted pellets.
- the pellet is preferably discharged for 9.2 seconds or less, more preferably 8.9 seconds or less, in the pellet fluidity test. If the fluidity is high enough to discharge 300 g of pellets within 9.2 seconds, preferably within 8.9 seconds, a coating layer with higher wire diameter stability and capacitance stability can be produced with higher productivity. it can. Details of the pellet fluidity test are described in detail in the Examples section.
- the pellets of the present invention are fluororesin pellets.
- the fluororesin may have an end group such as —CF 3 , —CF 2 H, etc. at least in one of the polymer main chain and the polymer side chain, and is not particularly limited.
- the fluororesin is preferably fluorinated.
- a fluororesin that has not been subjected to fluorination treatment includes end groups that are unstable in terms of thermal and electrical properties, such as —COOH, —COOCH 3 , —CH 2 OH, —COF, —CONH 2 (hereinafter referred to as such end groups). May also be referred to as “unstable end groups”. Such unstable terminal groups can be reduced by the fluorination treatment. When the fluororesin is fluorinated, the pellets have a higher fluidity.
- the fluororesin preferably contains little or no unstable terminal groups, and the total number of unstable terminal groups is preferably 120 or less per 1 ⁇ 10 6 carbon atoms.
- the fluororesin is also the total number of the five unstable terminal groups and the —CF 2 H terminal group, ie, —COOH, —COOCH 3 , —CH 2 OH, —COF, —CONH 2 , and , —CF 2 H is more preferably 120 or less per 1 ⁇ 10 6 carbon atoms.
- the total number is within the above range, very good fluidity can be obtained.
- it exceeds 120 pieces there exists a possibility that a molding defect may arise.
- the number of unstable terminal groups is more preferably 50 or less, still more preferably 20 or less, and most preferably 10 or less.
- the number of unstable terminal groups is a value obtained from infrared absorption spectrum measurement.
- the unstable terminal group and —CF 2 H terminal group do not exist, and all may be —CF 3 terminal groups.
- the fluorination treatment can be performed by bringing a fluorine resin that has not been fluorinated into contact with a fluorine-containing compound.
- the fluorine radical source which generate
- 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.
- 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 fluororesin preferably has a melt flow rate (MFR) of 0.1 to 100 g / 10 min. More preferably, it is 20 to 100 g / 10 minutes, still more preferably 20 to 60 g / 10 minutes, and particularly preferably 35 to 45 g / 10 minutes.
- MFR melt flow rate
- the MFR is a value measured according to ASTM D-1238 or JIS K 7210 using a die having a diameter of 2.1 mm and a length of 8 mm at a load of 5 kg and 372 ° C.
- the fluororesin preferably has a melting point of 140 to 320 ° C, more preferably 160 ° C or higher, and further preferably 200 ° C or higher.
- 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].
- fluororesin a melt processable fluororesin is preferable. Moreover, as said fluororesin, a perfluoro resin is preferable.
- fluororesin examples include tetrafluoroethylene (TFE) / hexafluoropropylene (HFP) copolymer, TFE / perfluoro (alkyl vinyl ether) (PAVE) copolymer, polychlorotrifluoroethylene [PCTFE], and TFE. / CTFE / PAVE copolymer.
- PAVE perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], and the like. Of these, PPVE is preferable. These can use 1 type (s) or 2 or more types.
- the fluororesin may have a polymer unit based on another monomer in an amount that does not impair the essential properties of each fluororesin.
- said other monomer it can select suitably from TFE, HFP, perfluoro (alkyl vinyl ether), perfluoro (alkyl allyl ether) etc., for example.
- the perfluoroalkyl group constituting the other monomer is preferably one having 1 to 10 carbon atoms.
- the fluororesin is preferably at least one selected from the group consisting of a TFE / HFP copolymer and a TFE / PAVE copolymer, and more preferably a TFE / HFP copolymer because of having excellent heat resistance. .
- Two or more of the above fluororesins may be used in combination.
- it since it has the more excellent electrical property, it is also preferable that it is a perfluoro resin.
- fluororesin examples include a copolymer comprising 93 to 80% by mass of TFE units and 7 to 20% by mass of HFP units, 92 to 75% by mass of TFE units, 7 to 20% by mass of HFP units, and 0%.
- a copolymer consisting of 1 to 5% by mass of PAVE units is particularly preferred.
- the fluororesin can be synthesized by polymerizing the monomer component using usual polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, gas phase polymerization and the like. In the above polymerization reaction, a chain transfer agent such as methanol may be used.
- the fluororesin may be produced by polymerization and isolation without using a metal ion-containing reagent.
- the fluororesin preferably contains an alkali metal of less than 50 ppm. Preferably less than about 25 ppm, more preferably less than about 10 ppm, and most preferably less than about 5 ppm.
- the fluororesin obtained by the production method comprising polymerizing and isolating without using an alkali metal has an alkali metal content within the above range.
- the content of the alkali metal is measured by an ashing method.
- the above ashing method is obtained by adding 2 g of 0.2 mass% aqueous potassium sulfate solution and about 2 g of methanol to 2 g of sample and heating the resin at 580 ° C. for 30 minutes to burn off the resin.
- the residue was washed twice with 20 ml of 0.1N hydrochloric acid (10 ml ⁇ 2 times), and the 0.1N hydrochloric acid used for the washing was measured by an atomic absorption spectrometer (HITACHI Z-8100 type polarized Zeeman atomic absorption spectrophotometer). ), And the potassium element content was changed from the 0.2 mass% potassium sulfate aqueous solution to the 0.2 mass% sodium sulfate aqueous solution in the above conditions. is there.
- the pellets may contain known additives such as fillers and stabilizers.
- 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, and sericite. Diatomaceous earth, silicon nitride, fine silica, alumina, zirconia, quartz powder, kaolin, bentonite, titanium oxide and the like.
- the shape of the filler is not particularly limited, and examples thereof include a fiber shape, a needle shape, a powder shape, a granular shape, and a bead shape.
- the pellet may contain boron nitride, polyatomic anion-containing inorganic salt, sulfonic acid and its salt, and the like.
- the pellet containing these can be used suitably when forming the coating layer containing the bubble mentioned later.
- the sulfonic acid and its salt include F (CF 2 ) n CH 2 CH 2 SO 3 M, F (CF 2 ) n SO 3 M (wherein n is an integer of 2 to 12, M is H, NH 4 or Alkaline earth metal).
- the polyatomic anion-containing inorganic salt include those disclosed in US Pat. No. 4,764,538, and calcium tetraborate is preferred.
- the pellets may also contain fillers such as glass fibers, glass powders, asbestos fibers, reinforcing agents, stabilizers, lubricants, pigments, other additives, and the like.
- the pellet of the present invention can be produced by a production method including a step of melt-molding a fluororesin obtained by a known polymerization method.
- molding method A conventionally well-known method can be used.
- mold into a pellet form etc. are mentioned.
- the extrusion temperature at the time of melt extrusion needs to be changed depending on the melt viscosity of the fluororesin and the production method, and is preferably the melting point of the fluororesin + 20 ° C.
- the fluororesin cutting method is not particularly limited, and conventionally known methods such as a strand cut method, a hot cut method, an underwater cut method, and a sheet cut method can be employed.
- the obtained pellets may be treated by contacting with hot water of 30 to 200 ° C., water vapor of 100 to 200 ° C., or hot air of 40 to 200 ° C.
- the manufacturing method may further include a step of subjecting the fluororesin to the fluorination treatment.
- the fluorination treatment may be performed, for example, by bringing the pellets obtained by the melt molding into contact with the fluorine-containing compound, or before the melt molding, the fluororesin and the fluorine-containing compound. May be performed by bringing the fluororesin and the fluorine-containing compound into contact with each other a plurality of times before and after the melt molding. Therefore, the shape of the fluororesin that is brought into contact with the fluorine-containing compound is not limited, and may be powder, flakes, pellets, or the like. However, since the unstable end group may be generated by the melt molding, the fluorination treatment is performed in consideration of production efficiency and fluidity, the pellet obtained by the melt molding, the fluorine-containing compound, It is preferable to carry out by contacting.
- the characteristic shape of the present invention can be obtained by adjusting the feed rate of the raw material to the extruder, the rotational speed of the screw, the number of holes in the die, the hole diameter, the rotational speed of the cutter, and the like.
- the major axis and minor axis of the pellet can be adjusted by changing the hole diameter as long as the raw material supply rate and the number of holes in the die are the same.
- the height (thickness) of the pellet can be adjusted by the number of rotations of the cutter as long as the raw material supply speed and the number of holes in the die are the same.
- the said pellet may contain the pellet which has an abnormal shape, it is preferable that the number shall be 100 or less per 100g of pellets.
- FIG. 8 to 11 show photographs of pellets having an abnormal shape.
- the pellets shown in FIG. 8 and FIG. 9 have beards extending from the pellet body, so the overall shape is abnormal.
- the beard is dropped from the pellet body and becomes pellet waste, which may hinder the formation of a coating layer having high wire diameter stability and capacitance stability.
- the pellet shown in FIG. 10 has an abnormal overall shape because two or more fluororesin blocks having the size of a normal pellet are connected directly or via the beard.
- the pellet having such a shape prevents a smooth movement of the pellet from the hopper into the cylinder, or the whiskers fall off during the movement, thereby forming a coating layer having high wire diameter stability and capacitance stability. May interfere.
- the pellet shown in FIG. 11 has beards, burrs, protrusions, and the like, and has a jagged outer extension, so that the overall shape is abnormal.
- the pellet having such a shape is a coating that prevents smooth movement of the pellet from the hopper into the cylinder, or the whiskers and the burrs fall off during the movement, and has high wire diameter stability and capacitance stability. There is a risk of preventing the formation of the layer.
- the number of pellets having an abnormal shape can be measured by arbitrarily extracting 100 g of pellets and visually counting the number of pellets having an abnormal shape.
- the said pellet may contain the pellet which has a bubble inside a pellet, it is preferable that the number shall be 10 mass% or less per 100g of pellets. Such a pellet is not preferable because it may hinder the formation of a coating layer having high wire diameter stability and capacitance stability.
- the number of pellets having bubbles inside can be measured by arbitrarily extracting 100 g of pellets and visually counting the number of pellets having bubbles inside.
- the above-mentioned abnormally shaped pellets can be reduced by, for example, stably supplying fluororesin powder to the extruder when the pellet is produced using an extruder.
- An electric wire comprising a core wire and a coating layer provided around the core wire and obtained from the above pellets is also one aspect of the present invention.
- the core wire for example, a metal conductor material such as copper or aluminum can be used.
- the core wire preferably has a diameter of 0.02 to 3 mm.
- the diameter of the core wire is more preferably 0.04 mm or more, further preferably 0.05 mm or more, and particularly preferably 0.1 mm or more.
- the diameter of the core wire is more preferably 2 mm or less.
- the wire preferably has a coating layer thickness of 0.1 to 3.0 mm. The thickness of the coating layer is also preferably 2.0 mm or less.
- the core wire include, for example, AWG (American Wire Gauge) -46 (solid copper wire having a diameter of 40 micrometers), AWG-26 (solid copper wire having a diameter of 404 micrometers), and AWG-24 (diameter 510). Micrometer solid copper wire), AWG-22 (635 micrometer solid copper wire), or the like may be used.
- AWG American Wire Gauge
- AWG-46 solid copper wire having a diameter of 40 micrometers
- AWG-26 solid copper wire having a diameter of 404 micrometers
- AWG-24 diameter 510
- Micrometer solid copper wire AWG-22 (635 micrometer solid copper wire), or the like may be used.
- the coating layer may contain bubbles, and it is preferable that the bubbles are uniformly distributed in the coating layer.
- the average bubble diameter of the bubbles is not limited, for example, it is preferably 60 ⁇ m or less, more preferably 45 ⁇ m or less, further preferably 35 ⁇ m or less, and further preferably 30 ⁇ m or less. More preferably, it is 25 ⁇ m or less, particularly preferably 23 ⁇ m or less. Moreover, it is preferable that an average bubble diameter is 0.1 micrometer or more, and it is more preferable that it is 1 micrometer or more.
- the said average bubble diameter can be calculated
- the covering layer may have a foaming rate of 20% or more. More preferably, it is 30% or more, still more preferably 33% or more, and still more preferably 35% or more. Although an upper limit is not specifically limited, For example, it is 80%. The upper limit of the foaming rate may be 60%.
- the foaming ratio is a value determined as ((specific gravity of fluororesin ⁇ specific gravity of coating layer) / specific gravity of fluororesin) ⁇ 100.
- the foaming rate can be appropriately adjusted depending on the application, for example, by adjusting the amount of gas inserted into the extruder, which will be described later, or by selecting the type of gas to be dissolved.
- the electric wire may include another layer between the core wire and the coating layer, and may further include another layer (outer layer) around the coating layer.
- the electric wire has a two-layer structure (skin-foam) in which a non-foamed layer is inserted between the core wire and the coating layer, or two layers in which the outer layer is coated with a non-foamed layer.
- the structure (foam-skin) may be a three-layer structure (skin-foam-skin) in which the outer layer of the skin-foam is coated with a non-foamed layer.
- the non-foamed layer of the wire is not particularly limited, and is a polyolefin resin such as TFE / HFP copolymer, TFE / PAVE copolymer, TFE / ethylene copolymer, vinylidene fluoride polymer, polyethylene [PE], etc. Or a resin layer made of a resin such as polyvinyl chloride [PVC].
- a polyolefin resin such as TFE / HFP copolymer, TFE / PAVE copolymer, TFE / ethylene copolymer, vinylidene fluoride polymer, polyethylene [PE], etc.
- a resin layer made of a resin such as polyvinyl chloride [PVC].
- the electric wire can be used as a cable for connecting a computer and its peripheral devices, for example, a LAN cable.
- the wire is, for example, using an extruder comprising a cylinder, a screw housed in the cylinder, a die attached to the tip of the cylinder, and a hopper for supplying pellets to the cylinder,
- a manufacturing method for manufacturing an electric wire comprising a core wire and a covering layer, Producing the above-mentioned pellets, Introducing the pellets into the hopper; Supplying the pellets from the hopper to the cylinder; A step of melting the pellet in the cylinder to produce a molten fluororesin; and
- the molten fluororesin can be produced by a method for producing an electric wire, which includes a step of extruding the molten fluororesin from the die and forming the coating layer on the core wire.
- the coating layer containing the bubbles can also be formed by introducing a gas into the molten fluororesin in the cylinder.
- a gas such as chlorodifluoromethane, nitrogen, carbon dioxide, or a mixture of the gases can be used, and the gas may be introduced into the molten fluororesin in the extruder as a pressurized gas, You may generate
- Example 1 As a raw material, a dispersion obtained by emulsion polymerization using ammonium persulfate as a polymerization initiator was used.
- This fluororesin was coagulated with nitric acid, dehydrated by pressing, and dried at 170 ° C. for 4 hours.
- the white powder of the fluororesin was melted and pelletized with a twin screw extruder (manufactured by Nippon Steel Works).
- the raw material was supplied at a rate of 15 kg / hour, the screw rotation speed was 200 rpm, the polymer temperature coming out of the die was adjusted to 375 ° C., and the rotation speed of the cutter having two blades was 2270 rpm to obtain polymer pellets.
- polymer pellets were obtained by contact with 20% by volume fluorine gas diluted with nitrogen gas at a temperature of 180 ° C. for 24 hours.
- Measurement of the number of unstable terminal groups was rolled with a hydraulic press to produce a film having a thickness of about 0.3 mm, and the film was analyzed by FT-IR Spectrometer 1760X (manufactured by Perkin-Elmer).
- Pellet fluidity measurement Apparent density measuring device (standard JIS K6891 or 6892) hopper was used. 300 g of the obtained pellets were put into a hopper. The lid of the outlet was pulled out, and the time until all the pellets flowed was measured. The measurement was performed 4 times and the average value was calculated.
- PCI abnormal pellet shape number
- pellet foam weight ratio 100 g of the obtained pellets were weighed, the pellets in which bubbles were observed were taken out, the weight was measured, and the weight ratio of the pellets with bubbles was measured.
- Temperature conditions are cylinder part C1 (270 ° C), cylinder part C2 (325 ° C), cylinder part C3 (365 ° C), neck part (375 ° C), head part (385 ° C), die part (390 ° C), core wire Preheating was set at 200 ° C.
- An electric wire was manufactured with a melt melt cone length of 20 mm at the time of molding, and the wire diameter stability and capacitance stability of the electric wire were evaluated.
- the evaluation method of wire diameter stability and capacitance stability is as follows.
- (Wire diameter stability) Using an outer diameter measuring device (LS-9006M, manufactured by Keyence Corporation), the outer diameter (OD) was measured at an electric wire take-up speed of 200 m / min and 500 m, and calculated as a process capability index (Cp).
- Cp is NR-500, NR-HA08 (manufactured by Keyence Corporation), and the upper limit (USL) is 0.005 mm higher than the above-mentioned covered wire diameter 0.312 mm, and the lower limit (LSL) is 0.005 mm from the above-mentioned covered wire diameter. It was set to 005 mm lower and analyzed from the obtained outer diameter data.
- Capacitance stability It measured for 3 hours using the capacitance measuring device CAPAC HS (made by ZUMBACH), and computed as process capability index [Cp]. Cp was analyzed from the obtained outer diameter data with the upper limit (USL) set to +1.0 (pF / m) and the lower limit (LSL) set to -1.0 (pF / m).
- Examples 2-5 Example 1 except that the die diameter (die size), the number of die holes, the supply speed, the screw rotation speed, the die exit polymer temperature, and the cutter blade rotation speed during pelletization are changed as shown in Table 1. The pellets were obtained and the wire coating molding was evaluated.
- Example 6 Except for changing the amount of ammonium persulfate during emulsion polymerization, the same operation as in Example 1 was performed to obtain pellets, which were subjected to wire coating molding evaluation.
- Example 7 Except changing the amount of ammonium persulfate during emulsion polymerization, the same operation as in Example 1 was performed to obtain pellets.
- the same wire coating molding evaluation as in Example 1 was performed except that the extrusion setting temperature of the wire coating molding was changed to the following. Cylinder part C1 (280 degreeC), cylinder part C2 (335 degreeC), cylinder part C3 (375 degreeC), neck part (385 degreeC), head part (395 degreeC), die part (400 degreeC).
- Example 8 Pellets were obtained in the same manner as in Example 1 except that a fluororesin having a composition containing tetrafluoroethylene [TFE] units and hexafluoropropylene [HFP] units and having a melting point of 256 ° C. was used.
- the same wire coating molding evaluation as in Example 1 was performed except that the extrusion setting temperature of the wire coating molding was changed to the following. Cylinder part C1 (290 ° C), cylinder part C2 (345 ° C), cylinder part C3 (385 ° C), neck part (395 ° C), head part 405 ° C), die part (410 ° C).
- Example 9 Except changing the amount of ammonium persulfate during emulsion polymerization, the same operation as in Example 8 was performed to obtain pellets.
- the same wire coating molding evaluation as in Example 1 was performed except that the extrusion setting temperature of the wire coating molding was changed to the following. Cylinder part C1 (280 degreeC), cylinder part C2 (335 degreeC), cylinder part C3 (375 degreeC), neck part (385 degreeC), head part (395 degreeC), die part (400 degreeC).
- the same wire coating molding evaluation as in Example 1 was performed except that the extrusion setting temperature of the wire coating molding was changed to the following. Cylinder part C1 (280 degreeC), cylinder part C2 (335 degreeC), cylinder part C3 (375 degreeC), neck part (385 degreeC), head part (395 degreeC), die part (400 degreeC).
- Example 1 except that the die diameter (die size), die hole number, feed speed, screw rotation speed, die exit polymer temperature, and cutter blade rotation speed during pelletization are changed as shown in Table 2. Then, pellets were obtained, and the same electric wire coating molding evaluation as in Example 1 was performed.
- Comparative Example 6 The amount of ammonium persulfate at the time of emulsion polymerization was changed, and pellets were obtained under the pelletizing conditions shown in Table 2. The same electric wire coating molding evaluation as in Example 7 was performed.
- Comparative Example 7 Except changing the cutter blade rotational speed at the time of pelletization as shown in Table 2, the same operation as Example 8 was performed, the pellet was obtained, and electric wire covering forming evaluation was performed.
- Comparative Example 8 Except changing the aperture of the die
- Comparative Example 9 Except changing the cutter blade rotation speed at the time of pelletization as shown in Table 2, the same operation as Example 10 was performed, the pellet was obtained, and electric wire covering forming evaluation was performed.
- Example 11 Except that the fluorination treatment was not performed, the same operation as in Example 1 was performed to obtain pellets, which were subjected to wire coating molding evaluation. The results are shown in Table 3.
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Abstract
Description
D1=0.3~1.5、
D2= 0.3~1.5、
L=0.3~2.0、
2L/(D1+D2)=0.5~5の関係を全て満足する円柱ないし楕円柱状の形状のミニペレットが記載されている。
上記測定は、固く滑らかな水平面上でも、転がったり、倒れたりしない方法で上記ペレットを置いてから行う。例えば、ペレット全体の形状が略円柱状である場合、その側面を水平面に接地させるように置くと動きが止まることがあるが、弱い振動を与えると転がるか、倒れる。このような置き方は適切でなく、上記ペレットを安定した状態になるように置いてから、上記測定を実施する。例えば、形状が略円柱状である場合、上記ペレットをステンレス製のバット等に投入し、上記バットに強い振動を与え、全てのペレットの底面を接地させ、安定した状態を実現した後、測定することができる。
このようなペレットの置き方は、後述する高さLの測定にも適用される。
上記フッ素樹脂は、また、上記5種の不安定末端基と-CF2H末端基とを合計した数、すなわち、-COOH、-COOCH3、-CH2OH、-COF、-CONH2、及び、-CF2Hの合計数が、炭素数1×106個あたり120個以下であることがより好ましい。上記合計数が上記範囲内にあると、非常に優れた流動性が得られる。また、120個を超えると、成形不良が生じるおそれがある。上記不安定末端基は、50個以下であることがより好ましく、20個以下であることが更に好ましく、10個以下であることが最も好ましい。本明細書において、上記不安定末端基数は赤外吸収スペクトル測定から得られた値である。上記不安定末端基および-CF2H末端基が存在せず全て-CF3末端基であってもよい。
上記フッ素含有化合物としては特に限定されないが、フッ素化処理条件下にてフッ素ラジカルを発生するフッ素ラジカル源が挙げられる。上記フッ素ラジカル源としては、F2ガス、CoF3、AgF2、UF6、OF2、N2F2、CF3OF、フッ化ハロゲン(例えばIF5、ClF3)等が挙げられる。
上記F2ガス等のフッ素ラジカル源は、100%濃度のものであってもよいが、安全性の面から不活性ガスと混合し5~50質量%に希釈して使用することが好ましく、15~30質量%に希釈して使用することがより好ましい。上記不活性ガスとしては、窒素ガス、ヘリウムガス、アルゴンガス等が挙げられるが、経済的な面より窒素ガスが好ましい。
上記フッ素化処理の条件は、特に限定されず、溶融させた状態のフッ素樹脂とフッ素含有化合物とを接触させてもよいが、通常、フッ素樹脂の融点以下、好ましくは20~220℃、より好ましくは100~200℃の温度下で行うことができる。上記フッ素化処理は、一般に1~30時間、好ましくは5~25時間行う。
上記フッ素化処理は、フッ素化処理されていないフッ素樹脂をフッ素ガス(F2ガス)と接触させるものが好ましい。
上記MFRは、ASTM D-1238又はJIS K 7210に準拠して、直径2.1mmで長さが8mmのダイにて、荷重5kg、372℃で測定した値である。
スルホン酸及びその塩としては、F(CF2)nCH2CH2SO3M、F(CF2)nSO3M(式中、nは2~12の整数、MはH、NH4又はアルカリ土類金属)等が挙げられる。
上記多原子アニオン含有無機塩としては、米国特許第4,764,538号明細書に開示されているものが挙げられ、四ホウ酸カルシウムが好ましい。
上記ペレットは、また、ガラス繊維、ガラス粉末、アスベスト繊維等の充填剤や、補強剤、安定剤、潤滑剤、顔料、その他の添加剤等を含んでもよい。
上記電線は、上記被覆層の厚みが0.1~3.0mmであるものが好ましい。被覆層の厚みは、2.0mm以下であることも好ましい。
芯線の具体例としては、例えば、AWG(アメリカンワイヤゲージ)-46(直径40マイクロメートルの中実銅製ワイヤー)、AWG-26(直径404マイクロメートルの中実銅製ワイヤー)、AWG-24(直径510マイクロメートルの中実銅製ワイヤー)、AWG-22(直径635マイクロメートルの中実銅製ワイヤー)等を用いてもよい。
上記発泡率は、((フッ素樹脂の比重-被覆層の比重)/フッ素樹脂の比重)×100として求めた値である。上記発泡率は、例えば後述する押出機中のガスの挿入量の調節等により、あるいは、溶解するガスの種類を選択することにより、用途に応じて適宜調整することができる。
上記被覆層が気泡を含有する場合、上記電線は、上記芯線と上記被覆層の間に非発泡層を挿入した2層構造(スキン-フォーム)や、上記外層に非発泡層を被覆した2層構造(フォーム-スキン)、更にはスキン-フォームの上記外層に非発泡層を被覆した3層構造(スキン-フォーム-スキン)であってもよい。
上記電線の非発泡層は特に限定されず、TFE/HFP系共重合体、TFE/PAVE共重合体、TFE/エチレン系共重合体、フッ化ビニリデン系重合体、ポリエチレン〔PE〕等のポリオレフィン樹脂、ポリ塩化ビニル〔PVC〕等の樹脂からなる樹脂層であってよい。
上述のペレットを作製する工程、
上記ペレットを上記ホッパーに投入する工程、
上記ホッパーから上記シリンダーに上記ペレットを供給する工程、
上記シリンダー内で上記ペレットを溶融させて溶融フッ素樹脂を作製する工程、及び、
上記溶融フッ素樹脂を上記ダイから押し出して上記芯線上に上記被覆層を形成する工程
を含むことを特徴とする電線の製造方法により製造することができる。
原料としては重合開始剤として過硫酸アンモニウムを用いて乳化重合して得られたディスパージョンを用いた。フッ素樹脂の組成はテトラフルオロエチレン[TFE]単位、ヘキサフロプロピレン[HFP]単位、パーフルオロ(プロピルビニルエーテル)[CF2=CFOC3F7(PPVE)]単位を含み、融点は260℃であった。このフッ素樹脂を硝酸により凝析、圧搾により脱水し、170℃にて4時間乾燥した。
本押出機は、軸径32mm、L/D=52.5、原料投入側より供給部、可塑化部、ベント部、定量部各部位から構成されており、ダイは、口径2.5mm、4穴を用いた。15kg/時間の速度で原料を供給し、スクリュー回転数200rpmとし、ダイから出る重合体温度を375℃に調整し、2枚刃を有するカッターの回転数は2270rpmで重合体ペレットを得た。
更に、窒素ガスで希釈した20容量%フッ素ガスと180℃の温度下で24時間接触させて重合体ペレットを得た。
ASTM D 1238-98又はJIS K 7210に準拠したメルトインデックステスターを用いて、直径が2.1mmで長さが8mmのダイで、約6gの試料を372℃の温度下に荷重5kg(ピストンと重りの合計)にて測定した。
示差走査熱量計RDC220(Seiko Instruments社製)を用い、ASTM D-4591に準拠して、昇温速度10℃/分にて熱測定を行い、得られた吸熱曲線のピークから融点を求めた。
ペレットを油圧プレスにて圧延して厚さ0.3mm程度のフィルムを作製し、そのフィルムをFT-IR Spectrometer 1760X(Perkin-Elmer社製)により分析した。
炭素数1×106個あたりの不安定末端基の個数 =(I×K)/t
(I;吸光度、K;補正係数、t;フィルム厚さ(単位:mm))
各不安定末端基の補正係数(K)は、以下の通りである。
-COF(1884cm-1)・・・405
-COOH(1813cm-1、1775cm-1)・・・455
-COOCH3(1795cm-1)・・・355
-CONH2(3438cm-1)・・・480
-CH2OH(3648cm-1)・・・2325
核磁気共鳴装置AC300(Bruker-Biospin社製)を用い、測定温度を(フッ素樹脂の融点+20)℃として19F-NMR測定を行い、-CF2H基が存在することに由来するピークの積分値と他のピークの積分値から求めた。上記不安定末端基数と-CF2H末端基数とを合計した数を「不安定末端基数」として表1~3に示す。
得られたペレット20g秤量し、水平面に対するペレットの長径および短径、水平面から最も高い部位までの高さをノギスにて測定した。測定した各ペレットの平均値を算出した。
見かけ密度測定装置(規格 JIS K6891又は6892)のホッパーを使用した。得られたペレット300gをホッパー内に投入した。抜き出し口のふたを引き抜き、ペレット全てが流れ終わるまでの時間を測定した。測定は4回実施し、平均値を算出した。
得られたペレット100g秤量し、以下に示すペレットの数を数えた。
1.ヒゲ状部位を有するペレット(図8及び図9)
2.二つ以上がひっついた状態のペレット(図10)
3.異形ペレット(図11)
得られたペレット100g秤量し、ペレット内に気泡が見られたペレットを取り出し、重量を測定し、気泡があるペレットの重量割合を測定した。
電線の線径安定性およびキャパシタンス安定性を評価した。
具体的には、三葉製作所社製、シリンダー径20mm、L/D=24の単軸押出成形機、クロスヘッドには内径3.8mmのダイと外径2.3mmのチップを装着した。外径0.192mmの芯線(直径0.064mmの錫メッキ銅線を7本より合わせたもの)を用い、電線仕上がり外径を0.312mmとした。温度条件はシリンダー部C1(270℃)、シリンダー部C2(325℃)、シリンダー部C3(365℃)、ネック部(375℃)、ヘッド部(385℃)、ダイ部(390℃)に、芯線予備加熱を200℃に設定した。成形時の溶融メルトコーン長を20mmとして、電線を製造して、電線の線径安定性およびキャパシタンス安定性を評価した。
(線径安定性)
外径測定器(LS-9006M、キーエンス社製)を用いて外径(OD)を電線引取速度200m/分、500m測定し、工程能力指数(Cp)として算出した。なお、Cpは、NR-500、NR-HA08(キーエンス社製)にて、上限(USL)を上記被覆電線径0.312mmより0.005mm高く、下限(LSL)を上記被覆電線径より0.005mm低く設定して、得られた外径データから解析した。
(キャパシタンス安定性)
キャパシタンス測定器CAPAC HS(ZUMBACH社製)を用いて3時間測定し、工程能力指数〔Cp〕として算出した。なお、Cpは、上限(USL)を+1.0(pF/m)、下限(LSL)を-1.0(pF/m)に設定して、得られた外径データから解析した。
ペレット化時のダイの口径(ダイサイズ)、ダイの穴数、供給速度、スクリュー回転数、ダイ出口重合体温度、カッター刃回転速度を表1に示すように変更する以外は実施例1と同様の操作を行い、ペレットを得て、電線被覆成形評価を行った。
乳化重合時の過硫酸アンモニウムの量を変更する以外は実施例1と同様の操作を行い、ペレットを得て、電線被覆成形評価を行った。
乳化重合時の過硫酸アンモニウムの量を変更する以外は実施例1と同様の操作を行い、ペレットを得た。電線被覆成形の押出設定温度を以下に変更する以外は実施例1と同様な電線被覆成形評価を行った。シリンダー部C1(280℃)、シリンダー部C2(335℃)、シリンダー部C3(375℃)、ネック部(385℃)、ヘッド部(395℃)、ダイ部(400℃)。
フッ素樹脂として、組成がテトラフルオロエチレン[TFE]単位、ヘキサフロプロピレン[HFP]単位を含み融点256℃のものを用いる以外は実施例1と同様の操作を行い、ペレットを得た。電線被覆成形の押出設定温度を以下に変更する以外は実施例1と同様な電線被覆成形評価を行った。シリンダー部C1(290℃)、シリンダー部C2(345℃)、シリンダー部C3(385℃)、ネック部(395℃)、ヘッド部405℃)、ダイ部(410℃)。
乳化重合時の過硫酸アンモニウムの量を変更する以外は実施例8と同様の操作を行い、ペレットを得た。電線被覆成形の押出設定温度を以下に変更する以外は実施例1と同様な電線被覆成形評価を行った。シリンダー部C1(280℃)、シリンダー部C2(335℃)、シリンダー部C3(375℃)、ネック部(385℃)、ヘッド部(395℃)、ダイ部(400℃)。
フッ素樹脂として、組成がテトラフルオロエチレン[TFE]単位、パーフルオロ(プロピルビニルエーテル)[CF2=CFOC3F7]単位を含み融点300℃のものを用いて、表1に示すペレット化条件で、ペレットを得た。電線被覆成形の押出設定温度を以下に変更する以外は実施例1と同様な電線被覆成形評価を行った。シリンダー部C1(280℃)、シリンダー部C2(335℃)、シリンダー部C3(375℃)、ネック部(385℃)、ヘッド部(395℃)、ダイ部(400℃)。
ペレット化時のダイの口径(ダイサイズ)、ダイの穴数、供給速度、スクリュー回転数、ダイ出口重合体温度、カッター刃回転速度を表2に示すように変更する以外は実施例1と同様の操作を行い、ペレットを得て、実施例1と同様な電線被覆成形評価を行った。
乳化重合時の過硫酸アンモニウムの量を変更し、表2に示すペレット化条件で、ペレットを得た。実施例7と同様な電線被覆成形評価を行った。
ペレット化時のカッター刃回転速度を表2に示すように変更する以外は実施例8と同様の操作を行い、ペレットを得て、電線被覆成形評価を行った。
ペレット化時のダイの口径、カッター刃回転速度を表2に示すように変更する以外は実施例9と同様の操作を行い、ペレットを得て、電線被覆成形評価を行った。
ペレット化時のカッター刃回転速度を表2に示すように変更する以外は実施例10と同様の操作を行い、ペレットを得て、電線被覆成形評価を行った。
フッ素化処理を実施しないこと以外は実施例1と同様の操作を行い、ペレットを得て、電線被覆成形評価を行った。結果を表3に示す。
Claims (10)
- フッ素樹脂のペレットであって、
水平面に置いた前記ペレットについて、
水平面に対する法線方向から観察した外形形状が、略円形状又は略楕円形状であって、長径D1が3.1mm以下、かつ、短径D2が3.1mm以下であり、
長径D1、短径D2及び水平面から最も高い部位までの高さLが式(1):(D1+D2)/2L=1.8~2.6を満足する
ことを特徴とするペレット。 - 長径D1が1.6mm以上であり、短径D2が1.6mm以上である請求項1記載のペレット。
- 高さLの標準偏差が0.3mm以下である請求項1又は2記載のペレット。
- ペレット100g当たり100個以下の、異常な形状を有するペレットを含む請求項1、2又は3記載のペレット。
- ペレット100g当たり10質量%以下の、内部に気泡を有するペレットを含む請求項1、2、3又は4記載のペレット。
- ペレット流動性試験において、300gのペレットが排出される時間が9.2秒以下である請求項1、2、3、4又は5記載のペレット。
- 略回転楕円体状、略円柱状又は略楕円柱状である請求項1、2、3、4、5又は6記載のペレット。
- 前記フッ素樹脂は、-COOH、-COOCH3、-CH2OH、-COF、-CONH2、及び、-CF2Hの合計数が炭素数1×106個あたり120個以下である請求項1、2、3、4、5、6又は7記載のペレット。
- 芯線と、
前記芯線の周囲に設けられており、請求項1、2、3、4、5、6、7又は8記載のペレットから得られる被覆層と、
を備えることを特徴とする電線。 - シリンダーと、前記シリンダー内に収容されたスクリューと、前記シリンダーの先端に取り付けられたダイと、前記シリンダーにペレットを供給するためのホッパーとを備える押出機を使用して、芯線と被覆層とを備える電線を製造する製造方法であって、
請求項1、2、3、4、5、6、7又は8記載のペレットを作製する工程、
前記ペレットを前記ホッパーに投入する工程、
前記ホッパーから前記シリンダーに前記ペレットを供給する工程、
前記シリンダー内で前記ペレットを溶融させて溶融フッ素樹脂を作製する工程、及び、
前記溶融フッ素樹脂を前記ダイから押し出して前記芯線上に前記被覆層を形成する工程
を含むことを特徴とする電線の製造方法。
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