TWI534195B - A composition, a foamed molded article, and a method for manufacturing the electric wire - Google Patents
A composition, a foamed molded article, and a method for manufacturing the electric wire Download PDFInfo
- Publication number
- TWI534195B TWI534195B TW103102472A TW103102472A TWI534195B TW I534195 B TWI534195 B TW I534195B TW 103102472 A TW103102472 A TW 103102472A TW 103102472 A TW103102472 A TW 103102472A TW I534195 B TWI534195 B TW I534195B
- Authority
- TW
- Taiwan
- Prior art keywords
- composition
- salt
- fluororesin
- compound
- boron nitride
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/20—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wires
-
- 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
-
- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/402—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders the screws having intermeshing parts
-
- 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
- B29C48/92—Measuring, controlling or regulating
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0033—Use of organic additives containing sulfur
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D127/00—Coating 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
- C09D127/02—Coating 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
- C09D127/12—Coating 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
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
-
- 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
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/926—Flow or feed rate
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
-
- 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
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
-
- 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
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/03—Extrusion of the foamable blend
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
-
- 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
- C08J2207/00—Foams characterised by their intended use
- C08J2207/06—Electrical wire insulation
-
- 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
- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- 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
- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/20—Homopolymers or copolymers of hexafluoropropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Emergency Medicine (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Processes Specially Adapted For Manufacturing Cables (AREA)
Description
本發明係關於組成物、及發泡成形體及電線的製造方法。
作為電線之包覆材,欲提高電特性而被期望介電率降低,為使低介電率化有效地是將包覆材作成發泡體。以樹脂作為材料之發泡體通常係藉由使氣體存在於熔融樹脂中予以成形之發泡成形而得。
發泡體中之氣泡為了使所得發泡體之形狀或特性均一,較好係微細且均一分布。為了使氣泡細小化或均一分布,而有使發泡核劑存在於樹脂中以在發泡成形時成為產生氣泡之起點的方法。
作為添加於氟樹脂等樹脂中之發泡核劑係使用例如磺酸鹽。製於調配磺酸鹽獲得發泡體之方法揭示如下。
專利文獻1中記載含核形成上有效量之選自由磺酸及膦酸及該等之鹽所成之類群之至少一種熱安定化合物作為成核劑之擠出用發泡性熱可塑性樹脂組成物。
專利文獻2中記載在氮化硼核生成劑及(a)至少一種含多原子陰離子之無機鹽、或(b)至少一種磺酸或膦酸或該酸之鹽、或(c)(a)與(b)之組合之存在下的可熔融-加工之氟聚合物樹脂之發泡方法:。
專利文獻3中記載一種組成物,其係含熱可塑性樹脂以及本質上之核生成有效量之由(a)至少一種磺酸或膦酸或該等之鹽及(b)至少一種含多原子陰離子之無機鹽所成之核生成劑系的可發泡之熱可塑性樹脂組成物,且該組成物不含氮化硼。
專利文獻4、5及6中記載含有部分結晶性熔融加工性全氟聚合物與發泡核劑之發泡性組成物,且記載該發泡核劑係具有選自由磺酸及膦酸及該等之鹽所成之群的成核有效量之至少1種熱安定性化合物者。
專利文獻7中記載含可熔融成形之四氟乙烯/六氟丙烯共聚物、四氟乙烯/全氟(烷基乙烯基醚)共聚物、發泡核劑之成形用組成物,至於發泡核劑係使用氮化硼、四硼酸鈣、及F(CF2)nCH2CH2SO3Ba(n=6、8、10或12)之混合物。
專利文獻8、專利文獻9及專利文獻10中揭示使具有8.6m2/g之表面積的氮化硼與磺酸及膦酸以及該等酸之鹽併用。
專利文獻11中係在可熔融加工之氟聚合物樹脂之擠出發泡方法中,作為核生成劑係使用氮化硼、四硼酸鈣、F(CF2)nCH2CH2SO3Ba(式中,n為6、8、10、視情
況為12,主要為8)等。
專利文獻1:日本特公平6-89166號公報
專利文獻2:日本特開平10-45931號公報
專利文獻3:日本特開平10-36545號公報
專利文獻4:日本特表2010-513675號公報
專利文獻5:日本特表2010-513676號公報
專利文獻6:日本特表2010-513677號公報
專利文獻7:美國專利公報2010/0288533號
專利文獻8:日本特開昭59-11340號公報
專利文獻9:日本特開平1-172431號公報
專利文獻10:日本特開平10-195216號公報
專利文獻11:日本特表2000-511124號公報
然而,使用過去所用之氟烷基的長鏈磺酸或其鹽作為發泡核劑時,無法製造能因應於如PFOS(全氟辛烷磺酸鹽)問題而已知之環境問題、且進而平均泡徑小、且發泡率大、火花之發生少的發泡成形體及發泡電線。
鑑於上述現狀,本發明之目的係提供一種可
製造平均泡徑小、且發泡率大、火花之發生少的發泡成形體及發泡電線之組成物。
本發明人等為獲得可製造平均泡徑小、且發泡率大,火花之發生少的發泡成形體及發泡電線之包覆材而進行各種探討,發現藉由使用含特定之磺酸或其鹽之組成物作為發泡核劑,可製造平均泡徑小、且發泡率大、火花之發生少的發泡成形體及發泡電線。
亦即,本發明係一種組成物,其特徵為含有氟樹脂(A)與下述式(1)或下述式(2)所示之磺酸、或者此等鹽化合物(B),式(1):F(CF2)nSO3H (1)
(式中,n為4或5)
式(2):F(CF2)nCH2CH2SO3H (2)
(式中,n為4或5)。
化合物(B)較好為以式(1)或(2)表示之磺酸,或該鹼金屬鹽或鹼土類金屬鹽。
化合物(B)較好為式(1)或(2)所示磺酸的鋇鹽、鉀鹽、鈉鹽或銣鹽。
化合物(B)較好為上述式(1)所示磺酸或者其鹽。
氟樹脂(A)較好為四氟乙烯/六氟丙烯系共聚物、四氟乙烯/全氟(烷基乙烯基醚)共聚物或四氟乙烯/乙烯系共聚物。
氟樹脂(A)較好係經氟化處理所成的氟樹脂。
本發明之組成物較好進一步含有氮化硼。
氮化硼之平均粒子徑較好為8.0μm以上。
氮化硼之(D84-D16)/D50所示粒度分布(式中,D84、D50及D16係表示體積粒度分布之累積曲線成為84%之點的粒徑(μm)、成為50%之點的粒徑(μm)、成為16%之點的粒徑(μm),粒度分布之累積係自小粒徑側進行)較好為1.2以下。
氮化硼較好係經粉碎者。
本發明另亦係一種發泡成形體,其係由上述組成物所得。
本發明另亦係一種電線,其係具備芯線,與由包覆上述芯線的上述組成物所得之包覆材。
本發明另亦提供一種發泡成形體之製造方法,其特徵為含有將上述組成物進行發泡成形之步驟。
本發明另亦提供一種電線之製造方法,其特徵為含有將上述組成物包覆芯線而得電線之步驟。
本發明之組成物藉由具有上述構成,可製造
平均泡徑小、且發泡率大、火花之發生少的發泡成形體及發泡電線。
圖1係實施例2所得之電線剖面照片。
本發明之組成物係含有氟樹脂(A)與特定之磺酸或其鹽之化合物(B)者。
以下詳細說明本發明。
氟樹脂(A)若為可熔融加工者,則未特別限制,列舉為例如四氟乙烯(TFE)/六氟丙烯(HFP)系共聚物、TFE/全氟(烷基乙烯基醚)(PAVE)共聚物、TFE/乙烯系共聚物[ETFE]、氯三氟乙烯(CTFE)/乙烯共聚物[ECTFE]、聚偏氟化乙烯[PVdF]、聚氯三氟乙烯[PCTFE]、TFE/偏氟化乙烯(VdF)共聚物[VT]、聚氟化乙烯[PVF]、TFE/VdF/CTFE共聚物[VTC]、TFE/乙烯/HFP共聚物、TFE/HFP/VdF共聚物等。
作為上述PAVE列舉為例如全氟(甲基乙烯基醚)[PMVE]、全氟(乙基乙烯基醚)[PEVE]、全氟(丙基乙烯基醚)[PPVE]等。其中,以PPVE較佳。該等可使用1種或2種以上。
氟樹脂亦可係在不損及氟樹脂本質性質之範
圍的量下,具有基於其他單體之聚合單位者。上述其他單體可由例如TFE、HFP、乙烯、丙烯、全氟(烷基乙烯基醚)、全氟烷基乙烯、氫氟烯烴、氟烷基乙烯、全氟(烷基烯丙基醚)等中適當選擇。構成上述其他單體之全氟烷基較好為碳數1~10者。
基於具有優異之耐熱性,氟樹脂較好為TFE/HFP系共聚物、TFE/PAVE共聚物或TFE/乙烯系共聚物,更好為TFE/HFP系共聚物或TFE/PAVE共聚物。上述氟樹脂亦可併用2種以上。且,基於具有更優異之電特性而言亦較佳為全氟樹脂。
TFE/HFP系共聚物係TFE/HFP以質量比計較好為80~97/3~20,更好為84~92/8~16。
TFE/HFP系共聚物可為由TFE與HFP所成之2元共聚物,再者亦可為由TFE及HFP與可共聚合之輔單體所成之3元共聚物(例如,TFE/HFP/PAVE共聚物)。
TFE/HFP系共聚物亦較好含有基於PAVE之聚合單位的TFE/HFP/PAVE共聚物。
TFE/HFP/PAVE共聚物係TFE/HFP/PAVE以質量比計較好為70~97/3~20/0.1~10,更好為81~92/5~16/0.3~5。
TFE/PAVE共聚物係TFE/PAVE以質量比計較好為90~99/1~10,更好為92~97/3~8。
TFE/乙烯系共聚物係TFE/乙烯以莫耳比計較好為20~80/20~80,更好為40~65/35~60。且,TFE/乙烯系共聚物亦可含有其他單體成分。
亦即,TFE/乙烯系共聚物可為由TFE與乙烯所成之2元共聚物,進而亦可為由TFE及乙烯與可共聚合之輔單體所成之3元共聚物(例如,TFE/乙烯/HFP共聚物)。
TFE/乙烯系共聚物亦較好係含有基於HFP之聚合單位的TFE/乙烯/HFP共聚物。TFE/乙烯/HFP共聚物係TFE/乙烯/HFP以莫耳比計較好為40~65/30~60/0.5~20,更好為40~65/30~60/0.5~10。
氟樹脂之熔融流動速率(MFR)較好為0.1~100g/10分鐘,更好為4~70g/10分鐘,又更好為19~60g/10分鐘,基於可抑制火花之發生,使發泡率變大而言,更好為34~50g/10分鐘,最好為34~42g/10分鐘。
上述MFR係基於ASTM D-1238,以直徑2.1mm、長度8mm之模嘴,以荷重5kg、372℃下測定之值。
氟樹脂可藉由使用通常之聚合方法例如乳化聚合、懸浮聚合、溶液聚合、塊狀聚合、氣相聚合等各種方法使單體成分聚合而合成。上述聚合反應中,亦可使用甲醇等鏈轉移劑。亦可不使用含金屬離子之試藥,藉由聚合且單離而製造氟樹脂。
氟樹脂宜為聚合物主鏈及聚合物側鏈之至少一者之部位具有-CF3、-CF2H等末端基者,雖為無特別限制,但較好為經氟化處理之氟樹脂。未經氟化處理之氟樹脂有時具有-COOH、-CH2OH、-COF、-CONH2等之熱及電特性不安定之末端基(以下亦稱該末端基為「不安定末端基」)。該不安定末端基可藉由上述氟化處理而減低。氟
樹脂較好含較少或不含上述不安定末端基,更好上述4種不安定末端基與-CF2H末端基之合計數係每1×106個碳數為50個以下。超過50個時,有產生成形不良之虞。上述不安定末端基更好為20個以下,又更好為10個以下。本說明書中,上述不安定末端基係由紅外線吸收光譜測定所得之值。亦可不存在上述不安定末端基及-CF2H末端基而全部為-CF3末端基。
上述氟化處理可藉由使未經氟化處理之氟樹脂與含氟化合物接觸而進行。
上述含氟化合物並未特別限制,但列舉為在氟化處理條件下產生氟自由基之氟自由基源。上述氟自由基源列舉為F2氣體、CoF3、AgF2、UF6、OF2、N2F2、CF3OF及氟化丙烷(例如,IF5、ClF3)等。
上述F2氣體等之氟自由基源亦可為100%濃度者,但基於安全性方面而言較好與惰性氣體混合稀釋成5~50質量%,較好為15~30質量%後使用。上述惰性氣體列舉為氮氣、氦氣、氬氣等,但就經濟面而言以氮氣較佳。
上述氟化處理條件並未特別限制,可使經熔融狀態之氟樹脂與含氟化合物接觸,但通常可在氟樹脂之熔點以下,較好為20~220℃,更好為100~200℃之溫度下進行。上述氟化處理一般係進行1~30小時,較好為5~20小時。
上述氟化處理較好係使未經氟化處理之氟樹脂與氟氣體(F2氣體)接觸者。
化合物(B)係下述式(1)或下述式(2)所
示之磺酸、或者此等之鹽,式(1):F(CF2)nSO3H (1)
(式中,n為4或5)
式(2):F(CF2)nCH2CH2SO3H (2)
(式中,n為4或5)。
化合物(B)由於n為4或5,故可製造平均泡徑小、且發泡率大、火花發生少的發泡成形體及發泡電線。且,藉由使用上述化合物(B),可因應於如PFOS(全氟辛烷磺酸鹽)問題之環境問題。
式(1)或(2)所示之磺酸或其鹽中,n為3以下時包覆成形之情況下,所形成之包覆材中之氣泡之平均泡徑變大。n為6以上時,火花之發生容易變多。
基於平均泡徑小與易發生火花之均衡之觀點而言,化合物(B)較好上述n為4。
基於由本發明之組成物所得之包覆材之平均泡徑及發泡率之均衡而言,化合物(B)較好為以式(1)或(2)表示之磺酸、或其鹼金屬鹽或鹼土類金屬鹽。基於耐熱性優異而言更好為鹼金屬鹽或鹼土類金屬鹽。
基於由本發明之組成物所得之包覆材的平均泡徑及發泡率之均衡而言,更好為以式(1)或(2)表示之磺酸之鋇鹽、鉀鹽、鈉鹽或銣鹽。基於即使上述化合物(B)之含量亦可製造平均泡徑小、且發泡率大、火花發生少之包
覆材而言,最好為鈉鹽或銣鹽。
本發明之組成物中化合物(B)之含量相對於氟樹脂(A)較好為2000ppm以下,更好為1500ppm以下。更好為1000ppm以下,又更好為500ppm以下,最好為250ppm以下。本發明之組成物中化合物(B)含量相對於氟樹脂(A)較好為0.01ppm以上。更好為0.1ppm以上。
化合物(B)之含量過少時,所得包覆材中不易獲得微細氣泡,過多時會有產生較多火花之虞。
化合物(B)為鋇鹽時,本發明之組成物中化合物(B)含量相對於氟樹脂(A)較好為1500ppm以下。更好為1000ppm以下,又更好為500ppm以下。
化合物(B)為鋇鹽時,本發明之組成物中化合物(B)含量相對於氟樹脂(A)較好為0.01ppm以上。更好為0.1ppm以上,又更好為1ppm以上,再更好為4ppm以上,最好為10ppm以上。
化合物(B)之含量過少時不易獲得微細之氣泡,過多時有產生較多火花之虞。
化合物(B)為鉀鹽時,本發明之組成物中化合物(B)含量相對於氟樹脂(A)較好為2000ppm以下。更好為1500ppm以下,又更好為1000ppm以下,最好為500ppm以下。
化合物(B)為鉀鹽時,本發明之組成物中化合物(B)含量相對於氟樹脂(A)較好為0.01ppm以上。更
好為0.1ppm以上,又更好為1ppm以上,再更好為4ppm以上,最好為10ppm以上。
化合物(B)之含量過少時不易獲得微細之氣泡,過多時有產生較多火花之虞。
化合物(B)較好為鈉鹽。化合物(B)為鈉鹽時,本發明之組成物中化合物(B)含量相對於氟樹脂(A)較好為250ppm以下。更好為100ppm以下。
化合物(B)為鈉鹽時,本發明之組成物中化合物(B)含量相對於氟樹脂(A)較好為0.01ppm以上。更好為0.1ppm以上,又更好為1ppm以上,再更好為4ppm以上,最好為10ppm以上。
化合物(B)之含量過少時不易獲得微細之氣泡,過多時有產生較多火花之虞。
基於可極容易地控制發泡率,化合物(B)較好為銣鹽。化合物(B)為銣鹽時,本發明之組成物中化合物(B)含量相對於氟樹脂(A)較好為500ppm以下。更好為250ppm以下。化合物(B)為銣鹽時,本發明之組成物中化合物(B)含量相對於氟樹脂(A)較好為0.01ppm以上。更好為0.1ppm以上,又更好為1ppm以上,再更好為4ppm以上,最好為10ppm以上。
化合物(B)之含量過少時不易獲得微細之氣泡,過多時有產生較多火花之虞。
一般,相較於C-H鍵,C-F鍵之鍵能較大,為化學堅固之構造,故化合物(B)更好為不含C-H鍵之
式(1)表示之磺酸或其鹽。
本發明之組成物更好含氮化硼。藉由含氮化硼,能獲得平均泡徑更小、具有微細均一氣泡之包覆材。
氮化硼之平均粒子徑較好為8.0μm以上。過去,有氮化硼之平均粒子徑較小之傾向,並未具體檢討使用平均粒子徑較大之氮化硼。
本發明之組成物藉由含有具有上述特定範圍之平均粒子徑的氮化硼,可形成具備平均泡徑更小、發泡率大的包覆材之發泡電線。
氮化硼之平均粒子徑更好為9.0μm以上,又更好為10.0μm以上,再更好為10.5μm以上,最好為11.0μm以上,又最好為12.0μm以上,再最好為13.0μm以上。
此外,氮化硼之平均粒子徑過大時會有平均泡徑變大之虞,或有發生較多火花之虞。氮化硼之平均粒子徑較好為25μm以下,更好為20μm以下。
藉由使氮化硼之平均粒子徑為上述範圍,可形成具有微細且均一氣泡之包覆材。
氮化硼之平均粒子徑係使用雷射繞射.散亂式粒度分布分析裝置求出之值。使用濕式法時,雖只要適當選擇介質即可,但只要使用例如甲醇等即可。
氮化硼之以(D84-D16)/D50表示之粒度分布較好為1.2以下。
D84、D50及D16係表示以氮化硼之粉體集團之總體
積作為100%求出累積曲線時,其累積曲線成為84%之點的粒徑(μm)、成為50%之點的粒徑(μm)、成為16%之點的粒徑(μm)。又,粒度分布之累積係自小粒徑側進行。上述粉體集團之總體積係將氮化硼之粉體分散於甲醇等介質中調製樣品,使用雷射繞射.散亂式粒度分布分析裝置(例如,日機裝(股)製之Microtrack MT3300)而得。
藉由使氮化硼之粒度分布為上述範圍,可形成具有微細且均一氣泡之包覆材,並且可進一步抑制火花之發生。
上述粒度分布更好為1.1以下,又更好為1.0以下。粒度分布之下限並無特別限制,但例如可為0.1。
上述粒度分布(體積粒度分布)之累積曲線係使用雷射繞射.散亂式粒度分布分析裝置(例如,日機裝(股)製之Microtrack MT3300)獲得者。使用濕式法時,只要適當選擇介質即可,但若使用例如甲醇等即可。
氮化硼較好為經粉碎者。氮化硼為經粉碎者時,可進一步抑制火花之發生。
上述粉碎可藉由可將氮化硼之平均粒子徑或粒度分布落入上述範圍內之方法及條件進行。例如,適當選擇粉碎機之種類、條件而進行。上述粉碎機可使用例如噴射式研磨機、錘式研磨機、球磨機、針軸研磨機等。
氮化硼亦可藉分級而調整成上述範圍之平均粒子徑或粒度分布。
本發明之組成物中氮化硼之含量並無特別限
制,但例如較好為0.1~10質量%,更好為0.1~2.0質量%,又更好為0.1~1.5質量%,再更好為0.1~1.0質量%。氮化硼含量過少時,會有所得發泡電線之包覆材中不易獲得微細氣泡之虞,過多時,會有製造成本變高之虞。
本發明之組成物在不損及本發明效果之範圍內,亦可進一步含有含多原子陰離子之無機鹽。
上述含多原子陰離子之無機鹽列舉為美國專利第4,764,538號說明書中揭示者。
本發明之組成物在不損及本發明效果之範圍內,亦可進一步含有磺酸、膦酸或該等之鹽(上述化合物(B)除外)。
本發明之組成物中除了氟樹脂及化合物(B)以外,在不損及本發明效果之範圍內亦可含過去習知之填充材。
上述填充材列舉為例如石墨、碳纖維、焦炭、二氧化矽、氧化鋅、氧化鎂、氧化錫、氧化銻、碳酸鈣、碳酸鎂、玻璃、滑石、雲母(mica)、雲母、氮化鋁、磷酸鈣、絹雲母(sericite)、矽藻土、氮化矽、微細二氧化矽、氧化鋁、氧化鋯、石英粉、高嶺土、膨潤土、氧化鈦等。上述填充材之形狀並無特別限制,列舉為纖維狀、針狀、粉末狀、粒狀、珠粒狀等。又,上述填充材係與氮化硼不同者。
本發明之組成物亦可為進一步含有上述氟樹脂以外之熱可塑性樹脂者。上述氟樹脂以外之熱可塑性樹
脂列舉為例如聚乙烯樹脂、聚丙烯樹脂、氯乙烯樹脂、聚苯乙烯樹脂等廣用樹脂;尼龍、聚碳酸酯、聚醚醚酮樹脂、聚苯硫醚樹脂等之工程塑膠。
本發明之組成物亦可進一步含有添加劑等其他成分。其他成分列舉為例如玻璃纖維、玻璃粉末、石綿(asbest)纖維等填充材,或補強劑、安定劑、潤滑劑、顏料、其他添加劑等。
本發明之組成物亦可藉由例如包含混合氟樹脂與化合物(B)、及視需要添加之氮化硼、填充劑、添加劑等獲得混合物之混合步驟的製造方法(以下稱為「組成物之製造方法」)而得。
上述混合方法可使用例如過去習知之方法等,但較好為不易使上述化合物(B)凝聚之混合方法。
上述混合方法亦列舉為例如亨歇爾混練機、螺帶式混練機(ribbon mixer)、V型摻合機、球磨機等之方法等。此外,亦舉例有例如藉由熔融混練而混合之方法。
本發明之組成物為含氮化硼者時,上述組成物之製造方法,在上述混合步驟前,亦可包含將氮化硼粉碎及/或分級之步驟。例如,藉由上述粉碎及/或分級,可獲得平均粒子徑為8.0μm以上之氮化硼,或上述粒度分布為1.2以下之氮化硼。就可抑制火花發生而言,上述步驟更好為使氮化硼粉碎者。
本發明之組成物之製造方法亦可包含使由上述混合步驟所得之混合物混練之混練步驟者。藉由上述混
練,可獲得顆粒。上述混練可藉由使用例如單軸螺旋擠出機、2軸螺旋擠出機等過去習知之熔融混練機之方法進行。
上述組成物之製造方法亦可包含使氟樹脂進行氟化處理之步驟。氟化處理可使用上述方法。氟化處理可藉由例如使由上述混練所得之顆粒與上述含氟化合物接觸而進行。
本發明之組成物中可含有之已說明之氟樹脂以外的熱可塑性樹脂;氮化硼;含多原子陰離子之無機鹽;填充材;其他添加劑等各成分可依據其性質等,於上述組成物之製造方法之各步驟中適當添加。此外,亦可進一步添加氟樹脂、氮化硼。
本發明之組成物可較好地使用作為發泡性組成物。且,上述組成物可較好地使用作為發泡成形體用組成物。再者,上述組成物可較好地使用作為用以形成電線包覆材之電線包覆用組成物。
本發明之發泡成形體之製造方法包含使上述組成物發泡成形之步驟者。
使上述組成物發泡成形之方法並無特別限制,可使用例如過去習知之方法,列舉為例如於經熔融之上述氟樹脂(熔融樹脂)中使用氣體,將本發明之樹脂組成物投入於設計成發泡操作用之螺旋擠出機中,使用連續氣體射出法之方法等。
上述氣體可使用例如氯二氟甲烷、氮氣、二
氧化碳等氣體或上述氣體之混合物,亦可作為加壓氣體導入於擠出機內之熔融樹脂中,亦可藉由將化學發泡劑混合於熔融樹脂中而產生。上述氣體係溶解於上述擠出機內之熔融樹脂中。
溶解於上述熔融樹脂中之氣體藉由熔融物之壓力在離開擠出模嘴時突然減低,而使溶解於熔融樹脂中之氣體可自熔融物釋出。自擠出機擠出之擠出物接著以例如導入於水中等之方法冷卻而固化。
上述發泡成形體由於係使上述組成物發泡成形而得者,故係介電率低、呈現安定的電容(capacitance)、且輕量、可獲得作為後述之包覆材之線徑、厚度等之大小穩定之形狀。
發泡成形體中之氣泡總容積可藉由例如調節上述擠出機中之氣體插入量等,或者藉由選擇溶解之氣體種類,依據用途適當調整。
上述發泡成形體可為自上述擠出機擠出時依據用途所成形之成形體之形態。上述成形方法只要是加熱熔融成形即無特別限制,列舉為例如擠出發泡成形、射出發泡成形、模具發泡成形等。
上述發泡成形體之形狀並無特別限制,可為例如發泡電線等之包覆材;線材等之纖絲狀;薄片狀;薄膜狀;棒狀;管狀等各種形狀。上述發泡成形體可使用作為例如電絕緣材;隔熱材;隔音材;漂浮材等輕量構造材;避震等緩衝材等。且,上述發泡成形體可特別較好地
使用作為發泡電線之包覆材。
所得發泡成形體係含有本發明之組成物之熔融固化體及氣泡者,上述氣泡較好係均一分布於熔融固化體中者。上述氣泡之平均泡徑並無限制,但較好為例如60μm以下。又,平均泡徑較好為0.1μm以上。
上述發泡成形體之發泡率並無特別限制但較好為20%以上。發泡率之上限並無特別限制,例如為80%。
本發明之電線的製造方法係包含將上述組成物包覆於芯線上而得電線之步驟者。藉由使用上述組成物,可形成具備具有微細、均一氣泡之包覆材的發泡電線。獲得上述電線之步驟較好係使上述組成物發泡成形者。
藉上述電線的製造方法所得之電線係由自上述組成物所形成之包覆材與芯線而成者。將上述組成物包覆於芯線上所得之電線亦為本發明之一。
上述包覆材由於係將上述組成物包覆於芯線上所得者,故具有微細且均一氣泡。且,介電率低、呈現安定的電容、輕量、且可獲得線徑、厚度等之大小穩定之形狀。
上述電線除了將上述組成物包覆於芯線上以外,可以與過去相同之方法作成,例如可使用擠出發泡成形而製造。較佳之擠出成形條件可依據所使用之組成物組成或芯線之尺寸適當選擇。
將上述組成物包覆於芯線上之方法列舉為例
如使用於熔融氟樹脂(熔融樹脂)中為可溶性之氣體,將本發明之組成物投入於設計供發泡操作用之螺旋擠出機,使用連續氣體射出法之方法等。上述氣體可使用與發泡成形體之製造方法中所用之氣體相同者。
所得包覆材係含有本發明之組成物的熔融固化體及氣泡者,較好係上述氣泡均一分布於熔融固化體中者。
上述氣泡之平均泡徑並無限制,但例如較好為60μm以下,更好為45μm以下,又更好為35μm以下,再更好為30μm以下,最好為25μm以下,又最好為23μm以下。此外,平均泡徑較好為0.1μm以上,更好為1μm以上。
該包覆材之構造係如上述,係起因於本發明之組成物中之氮化硼具有上述特定之平均粒子徑而得者。
上述平均泡徑係利用掃描型電子顯微鏡(SEM)拍攝包覆材剖面之影像,藉影像處理算出各泡之直徑,且予以平均而求出之值。
上述包覆材之發泡率較好為20%以上。更好為30%以上,又更好為33%以上,再更好為35%以上。上限並無特別限制,例如為80%。發泡率之上限亦可為60%。
上述發泡率為((氟樹脂之比重-發泡體之比重)/氟樹脂之比重)×100求出之值。上述發泡率可藉由例如調節上述擠出機中之氣體插入量等,或者藉由選擇溶解之
氣體種類,依據用途適當調整。
上述包覆材較好每3500m之火花數未達5個。更好未達3個,又更好為1個以下。上述火花數係利用Beta LaserMike Sparktester HFS1220,在1500V之電壓下測定所得之值。
芯線之材料可使用例如銅、鋁等金屬導體材料。芯線較好為直徑0.02~3mm者。芯線之直徑較好為0.04mm以上,更好為0.05mm以上,最好為0.1mm以上。芯線直徑更好為2mm以下。
上述電線較好為上述包覆材厚度為0.1~3.0mm者。包覆材之厚度亦較好為2.0mm以下。
芯線之具體例亦可使用例如AWG(美國金屬線規格)-46(直徑40微米之中心實心銅製金屬線)、AWG-26(直徑404微米之中心實心銅製金屬線)、AWG-24(直徑510微米之中心實心銅製金屬線)、AWG-22(直徑635微米之中心實心銅製金屬線)等。
上述發泡電線係由芯線及包覆芯線之包覆材所成者。上述發泡電線可使用作為連接電腦及其周邊設備之纜線類,例如LAN用纜線等。
上述電線亦可為在芯線與包覆材間插入非發泡層之2層構造(皮層-發泡體),或於外層包覆非發泡層之2層構造(發泡體-皮層),以及於皮層-發泡體之外層包覆非發泡層之3層構造(皮層-發泡體-皮層)。
上述電線之非發泡層並無特別限制,亦可為由
TFE/HFP系共聚物、TFE/PAVE共聚物、TFE/乙烯系共聚物、偏氟化乙烯系聚合物、聚乙烯[PE]等聚烯烴樹脂、聚氯乙烯[PVC]等樹脂所成之樹脂層。
以下列舉實施例說明本發明,但本發明並非僅限於該實施例。
本說明書中之各種特性係藉以下方法測定。
將氮化硼之粉體約30mg投入於甲醇約20ml中後,以超音波洗淨機(電力100W)分散2分鐘,使用日機裝(股)製之Microtrack MT3300,以濕式法(透過,粒子折射率1.63)進行測定。平均粒子徑及粒度分布分別測定2次且予以平均。
粒度分布係將氮化硼之粉體集團之總體積作為100%求出累積曲線,由其累積曲線算出D84、D50及D16,且以(D84-D16)/D50表示之值作為粒度分布之指標。D84、D50及D16表示累積曲線成為84%之點的粒子徑(μm)、成為50%之點的粒子徑(μm)、成為16%之點的粒子徑(μm)。又,粒度分布之累積係由小粒徑側進行。
本粒度分布之測定方法中,D50係作為累積平均徑(中心徑:Median徑)一般被利用作為評價粒度分布之
參數之一者。
氟樹脂之熔點係使用RDC220(Seiko電子公司製),以升溫速度10℃/分鐘測定時之波峰所對應之溫度作為熔點。
氟樹脂之MFR係依據ASTM D-1238,使用KAYENESS熔融指數測定機(melt indexer)4000系列(安田精機公司製),以直徑2.1mm、長度8mm之模嘴,以372℃、5kg荷重測定時之值。
拍攝電線剖面之SEM影像,以影像處理算出各泡之直徑,且予以平均求出平均泡徑。
使用CAPAC 300 19C(Zumbach公司製)測定電容。
使用Beta LaserMike Sparktester HFS1220,以1500V之電壓測定每3500m之火花數。
以((氟樹脂之比重-發泡體之比重)/氟樹脂之比重)×100求出。
準備平均粒子徑為13.5μm、8μm、2μm之未粉碎之氮化硼(以下亦稱為「BN」)。
且,使用噴射式研磨機粉碎平均粒子徑為19μm或22μm之未粉碎BN,獲得平均粒子徑8μm、13μm之粉碎BN。
測定該等未粉碎BN及粉碎BN之粒度分布。各實施例及比較例中使用之BN之粒度分布示於表1~6。
該等未粉碎BN或粉碎BN與經氟化處理之下述FEP顆粒係以成為FEP顆粒及BN之合計量之5重量%之方式進行摻合,以與國際公開第03/000792號相同之方法製備顆粒。
且,以使添加劑之含量成為FEP顆粒及添加劑之合計量之1重量%之方式調配下述表1~6所示之添加劑與氟化處理之FEP顆粒,以與國際公開第03/000792號相同之方法製備顆粒。
以使下述表1~6所示之添加劑成為目的重量之方式,藉熔融混練混合該等顆粒與經氟化處理之下述FEP顆粒,製作顆粒(組成物)。
以與日本特表2011-514407號公報之實施例2所記載
之方法相同之方法所得之FEP顆粒(A):TFE/HFP/PAVE共聚物,TFE/HFP/PAVE=87.5/11.5/1.0(重量比),熔點:255℃,熔融流動速率(MFR):23g/10分鐘,不安定末端基與-CF2H末端基合計之數為0個。
以與日本特表2011-514407號公報之實施例8所記載之方法相同之方法所得之FEP顆粒(B):TFE/HFP/PAVE共聚物,TFE/HFP/PAVE=87.7/11.3/1.0(重量比),熔點:255℃,熔融流動速率(MFR):36g/10分鐘,不安定末端基與-CF2H末端基合計之數為0個。
以與日本特表2010-539252號公報之實施例1所記載之方法相同之方法所得之FEP顆粒(C):TFE/HFP/PAVE共聚物,TFE/HFP/PAVE=87.8/11.2/1.0(重量比),熔點:255℃,熔融流動速率(MFR):35g/10分鐘,不安定末端基與-CF2H末端基合計之數為0個。
除了將分子量調節用之甲醇投入量變更為125LBS以外,餘以與日本特表2011-514407號公報之實施例8所記載之方法相同之方法所得之FEP顆粒(D):TFE/HFP/PAVE共聚物,TFE/HFP/PAVE=87.7/11.3/1.0(重量比),熔點:255℃、熔融流動速率(MFR):41g/10分鐘,不安定末端基與-CF2H末端基合計之數為0個。
又,表1~6中之添加劑係如下述。
C4Ba鹽:(C4F9SO3)2Ba
C4K鹽:C4F9SO3K
C4Na鹽:C4F9SO3Na
C4Rb鹽:C4F9SO3Rb
C1Na鹽:CF3SO3Na
C3Li鹽:C3F7SO3Li
C8Ba鹽:{F(CF2)6CH2CH2SO3}2Ba
於設定為表8所示之擠出機溫度之於熔融混練部中導入有氮氣作為發泡劑之發泡成形用擠出機中,供給以上述方法所得之顆粒(組成物)並進行擠出發泡成形,且藉由包覆於銅線上獲得具有包覆材之電線。實施例2所得之電線之剖面照片示於圖1。
針對所得電線評價各特性之結果示於表1~6。
又,上述發泡成形用擠出機係由聖製作所公司製之擠出機及系統、Micodia公司製之氣體噴射噴嘴、以及Unitec公司製之十字頭(cross head)構成。且,擠出機之構成及條件係如下述表7所示,螺桿上具備使導入之氮均一分散之混練區。
本發明之組成物尤其可較好地作為用於形成發泡電線之包覆材的材料。
Claims (14)
- 一種組成物,其特徵為含有可熔融加工的氟樹脂(A)與下述式(1)或下述式(2)所示磺酸,或者此等鹽化合物(B),式(1):F(CF2)nSO3H (1)(式中,n為4或5)式(2):F(CF2)nCH2CH2SO3H (2)(式中,n為4或5)。
- 如請求項1之組成物,其中化合物(B)為式(1)或(2)所示磺酸,或者該鹼金屬鹽或鹼土類金屬鹽。
- 如請求項1之組成物,其中化合物(B)為式(1)或(2)所示磺酸的鋇鹽、鉀鹽、鈉鹽或銣鹽。
- 如請求項1之組成物,其中化合物(B)為前述式(1)所示磺酸或者其鹽。
- 如請求項1、2、3或4之組成物,其中氟樹脂(A)為四氟乙烯/六氟丙烯系共聚物、四氟乙烯/全氟(烷基乙烯基醚)共聚物或四氟乙烯/乙烯系共聚物。
- 如請求項5之組成物,其中氟樹脂(A)係經氟化處理所成的氟樹脂。
- 如請求項6之組成物,其中進一步含有氮化硼。
- 如請求項7之組成物,其中氮化硼之平均粒子徑 為8.0μm以上。
- 如請求項8之組成物,其中氮化硼之(D84-D16)/D50所示粒度分布為1.2以下。
- 如請求項9之組成物,其中氮化硼係經粉碎者。
- 一種發泡成形體,其特徵為由如請求項10之組成物所得者。
- 一種電線,其特徵為具備芯線、與由包覆前述芯線的如請求項1、2、3、4、5、6、7、8、9或10之組成物所得之包覆材。
- 一種發泡成形體之製造方法,其特徵為含有將如請求項1、2、3、4、5、6、7、8、9或10之組成物進行發泡成形之步驟。
- 一種電線之製造方法,其特徵為含有將如請求項1、2、3、4、5、6、7、8、9或10之組成物包覆芯線而得電線之步驟。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013011484 | 2013-01-24 | ||
JP2013088771 | 2013-04-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201434920A TW201434920A (zh) | 2014-09-16 |
TWI534195B true TWI534195B (zh) | 2016-05-21 |
Family
ID=51227416
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW103102472A TWI534195B (zh) | 2013-01-24 | 2014-01-23 | A composition, a foamed molded article, and a method for manufacturing the electric wire |
Country Status (7)
Country | Link |
---|---|
US (1) | US10557006B2 (zh) |
EP (1) | EP2949700B1 (zh) |
JP (1) | JP5757348B2 (zh) |
KR (1) | KR101728259B1 (zh) |
CN (2) | CN104955892B (zh) |
TW (1) | TWI534195B (zh) |
WO (1) | WO2014115624A1 (zh) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10304585B2 (en) | 2013-01-24 | 2019-05-28 | Daikin Industries, Ltd. | Composition, and method for producing foam molded material and electric wire |
EP2949700B1 (en) | 2013-01-24 | 2018-04-18 | Daikin Industries, Ltd. | Composition, and method for producing foam molded material and electric wire |
US10730980B2 (en) | 2015-02-12 | 2020-08-04 | 3M Innovative Properties Company | Tetrafluoroethylene/hexafluoropropylene copolymers including perfluoroalkoxyalkyl pendant groups |
WO2016130911A1 (en) | 2015-02-12 | 2016-08-18 | 3M Innovative Properties Company | Tetrafluoroethylene/hexafluoropropylene copolymers including perfluoroalkoxyalkyl pendant groups and methods of making and using the same |
WO2016130894A1 (en) * | 2015-02-12 | 2016-08-18 | 3M Innovative Properties Company | Tetrafluoroethylene copolymers having sulfonyl groups |
CN105206321A (zh) * | 2015-09-28 | 2015-12-30 | 张翔 | 一种风力发电用电缆 |
US20200262952A1 (en) * | 2016-01-18 | 2020-08-20 | Daikin Industries, Ltd. | Fluoroplastic pellets, electric wire, and method for producing same |
EP3475382A1 (en) * | 2016-06-27 | 2019-05-01 | United Technologies Corporation | Electrocaloric heat transfer system |
US11300330B2 (en) | 2016-06-27 | 2022-04-12 | Carrier Corporation | Electrocaloric heat transfer system |
US11739206B2 (en) * | 2018-08-28 | 2023-08-29 | Daikin Industries, Ltd. | Resin composition and molded article |
TWI824275B (zh) | 2020-08-03 | 2023-12-01 | 日商大金工業股份有限公司 | 發泡成形用組成物、發泡成形體、電線、發泡成形體之製造方法、及電線之製造方法 |
Family Cites Families (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL258835A (zh) | 1959-12-18 | |||
JPS5911340A (ja) | 1982-07-12 | 1984-01-20 | Sumitomo Electric Ind Ltd | ふつ素樹脂発泡体の製造方法 |
US4716073A (en) | 1986-06-02 | 1987-12-29 | E. I. Du Pont De Nemours And Company | Thin wall high performance insulation on wire |
US4711811A (en) | 1986-10-22 | 1987-12-08 | E. I. Du Pont De Nemours And Company | Thin wall cover on foamed insulation on wire |
US4764538A (en) | 1987-12-16 | 1988-08-16 | E. I. Du Pont De Nemours And Company | Foam nucleation system for fluoropolymers |
US4877815A (en) | 1989-02-17 | 1989-10-31 | E. I. Du Pont De Nemours And Company | Nucleating agents for thermoplastic resins |
US5032621A (en) | 1989-02-17 | 1991-07-16 | E. I. Du Pont De Nemours And Company | Nucleating agents for thermoplastic resins |
CA2010297C (en) | 1989-02-17 | 2001-05-29 | Marlin D. Buckmaster | Nucleating agents for thermoplastic resins |
US5180754A (en) * | 1990-06-14 | 1993-01-19 | Mitsubishi Cable Industries, Ltd. | Polymer composition for foam molding |
JPH0689166A (ja) | 1992-09-08 | 1994-03-29 | Kobe Nippon Denki Software Kk | 部品処理記述展開方式 |
IT1271409B (it) | 1993-09-13 | 1997-05-28 | Dow Corning | Composizioni utilizzabili come grassi a base di oli di polimeri fluorurati e nitruro di boro esagonale |
JP3508116B2 (ja) | 1994-06-30 | 2004-03-22 | ダイキン工業株式会社 | 樹脂発泡体用組成物及び樹脂発泡体、並びにこれらの製造方法 |
US5712318A (en) * | 1996-04-10 | 1998-01-27 | E. I. Du Pont De Nemours And Company | Two-part nucleating agent system |
US5610203A (en) * | 1996-04-10 | 1997-03-11 | E. I. Du Pont De Nemours And Company | Foamable fluoropolymer composition |
US5688457A (en) * | 1996-04-10 | 1997-11-18 | E. I. Du Pont De Nemours And Company | High speed extrusion |
US5821273A (en) | 1996-05-22 | 1998-10-13 | E. I. Du Pont De Nemours And Company | Extrusion foaming of fluoropolymers |
US5726214A (en) | 1996-12-26 | 1998-03-10 | E. I. Du Pont De Nemours And Company | Self-foaming fluoropolymer composition |
JP2000344927A (ja) | 1999-06-03 | 2000-12-12 | Reiko Udagawa | 高発泡絶縁電線 |
US6395795B1 (en) | 2000-09-29 | 2002-05-28 | Ausimont Usa, Inc. | Titanium dioxide nucleating agent systems for foamable polymer compositions |
US7241826B2 (en) | 2001-06-26 | 2007-07-10 | Daikin Industries, Ltd. | Resin composition, process for production thereof, and foam-insulated electric wire |
JP2004155946A (ja) | 2002-11-07 | 2004-06-03 | Mitsubishi Rayon Co Ltd | 熱可塑性樹脂用改質剤及びこれを用いた熱可塑性樹脂組成物ならびに製品 |
US7126056B2 (en) | 2003-05-14 | 2006-10-24 | E. I. Du Pont De Nemours And Company | High melt flow fluoropolymer |
US7122609B2 (en) | 2003-05-14 | 2006-10-17 | E. I. Du Pont De Nemours And Company | High melt flow fluoropolymer |
WO2006123694A1 (ja) | 2005-05-18 | 2006-11-23 | Daikin Industries, Ltd. | フッ素樹脂組成物及び電線 |
US20080153936A1 (en) * | 2006-12-21 | 2008-06-26 | E. I. Du Pont De Nemours And Company | Foamed Fluoropolymer Article |
US20080149899A1 (en) | 2006-12-21 | 2008-06-26 | E. I. Du Pont De Nemours And Company | Foamable Fluoropolymer Composition |
US20080161435A1 (en) | 2006-12-21 | 2008-07-03 | E. I. Du Pont De Nemours And Company | Extrusion of a Foamable Fluoropolymer |
ES2628059T3 (es) | 2007-10-03 | 2017-08-01 | Daikin Industries, Ltd. | Composición de fluororesina y cable eléctrico recubierto |
WO2009102660A1 (en) | 2008-02-15 | 2009-08-20 | Daikin America, Inc. | Tetrafluoroethylene/hexafluoropropylene copolymer and the production method thereof, and electrical wire |
US8178592B2 (en) * | 2009-05-15 | 2012-05-15 | E.I. Du Pont De Nemours And Company | Foamable fluoropolymer composition |
US8985818B2 (en) | 2009-11-26 | 2015-03-24 | Nitto Denko Corporation | LED mounting substrate |
US10304585B2 (en) | 2013-01-24 | 2019-05-28 | Daikin Industries, Ltd. | Composition, and method for producing foam molded material and electric wire |
EP2949700B1 (en) | 2013-01-24 | 2018-04-18 | Daikin Industries, Ltd. | Composition, and method for producing foam molded material and electric wire |
-
2014
- 2014-01-15 EP EP14743297.5A patent/EP2949700B1/en active Active
- 2014-01-15 WO PCT/JP2014/050580 patent/WO2014115624A1/ja active Application Filing
- 2014-01-15 US US14/761,138 patent/US10557006B2/en active Active
- 2014-01-15 JP JP2014005064A patent/JP5757348B2/ja active Active
- 2014-01-15 CN CN201480005648.6A patent/CN104955892B/zh active Active
- 2014-01-15 KR KR1020157018520A patent/KR101728259B1/ko active IP Right Grant
- 2014-01-15 CN CN201710755375.2A patent/CN107603089B/zh active Active
- 2014-01-23 TW TW103102472A patent/TWI534195B/zh active
Also Published As
Publication number | Publication date |
---|---|
CN104955892B (zh) | 2019-03-12 |
CN107603089A (zh) | 2018-01-19 |
CN104955892A (zh) | 2015-09-30 |
WO2014115624A1 (ja) | 2014-07-31 |
EP2949700A4 (en) | 2016-07-27 |
JP5757348B2 (ja) | 2015-07-29 |
EP2949700A1 (en) | 2015-12-02 |
KR20150094735A (ko) | 2015-08-19 |
US10557006B2 (en) | 2020-02-11 |
TW201434920A (zh) | 2014-09-16 |
JP2014224229A (ja) | 2014-12-04 |
KR101728259B1 (ko) | 2017-04-18 |
US20150353700A1 (en) | 2015-12-10 |
CN107603089B (zh) | 2021-04-20 |
EP2949700B1 (en) | 2018-04-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI534195B (zh) | A composition, a foamed molded article, and a method for manufacturing the electric wire | |
TWI523905B (zh) | 組成物、發泡成形體及電線的製造方法 | |
ES2628059T3 (es) | Composición de fluororesina y cable eléctrico recubierto | |
JP5206002B2 (ja) | 樹脂組成物及びその製造方法並びに発泡電線 | |
EP3378617B1 (en) | Pellets comprising a fluororesin, their use and method for producing an electric wire therewith | |
JP7307387B2 (ja) | 組成物、回路基板、及び、組成物の製造方法 | |
CN118076693A (zh) | 组合物、电路基板和组合物的制造方法 |