TWI357920B - A foamed resin composition, a foam using the same - Google Patents

A foamed resin composition, a foam using the same Download PDF

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TWI357920B
TWI357920B TW094102123A TW94102123A TWI357920B TW I357920 B TWI357920 B TW I357920B TW 094102123 A TW094102123 A TW 094102123A TW 94102123 A TW94102123 A TW 94102123A TW I357920 B TWI357920 B TW I357920B
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foaming
foam
whiskers
composition
electrically insulating
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TW200535194A (en
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Takayoshi Ohno
Shinya Yamada
Masato Yotsuya
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Junkosha Inc
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/48Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances fibrous materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066Use of inorganic compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0085Use of fibrous compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions 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
    • C08L27/02Compositions 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
    • C08L27/12Compositions 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • H01B3/445Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00Characterised 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
    • C08J2327/02Characterised 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
    • C08J2327/12Characterised 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Organic Insulating Materials (AREA)
  • Communication Cables (AREA)

Description

1.357920 九、發明說明: I:發明戶斤屬之技術領域3 本發明係有關於一種含有氟樹脂之組成物發泡後的發 泡體,該發泡體可用來作為以同軸絕緣電纜之導體的絕緣 5 層為主之絕緣體層及緩衝體層。以同軸絕緣電纜為例,以 含有氟樹脂之發泡體作為設於中心導體周圍之絕緣層時, 相較於未形成發泡體層之情況,可得較小的介電常數,因 此可高速傳送訊號,並可獲得具低電氣訊號衰減之優良特 性的電瘦。 10 【先前技都T】 發泡體層的形成是將氟樹脂等之組合物熔融後,於其 成形之際同時使其發泡而成,而含有氟樹脂之組成物於發 泡時,乃是使用氮等氣體作為發泡劑,且以氮化硼作為發 泡成核劑。發泡體層之介電常數由於會受到發泡體層之氣 15 孔率所左右,因此增大氣孔率時可獲得小介電常數之發泡 體層。 作為發泡成核劑使用之氮化硼,由於不具吸濕性且不 會對電特性產生不良的影響,因此於形成同軸絕緣電纜之 絕緣用發泡體層時,作為發泡成核劑是相當適當的成份, 20 但是由於其形成的氣泡很大,特別是針對中心導體的線徑 小且絕緣層厚度薄之同軸絕緣電纜而言,無法滿足形成微 小氣泡之要求,因此必須尋求可形成更微小氣泡之發泡組 成物及發泡體。 【發明内容】 5 ⑧ 1.357920 對於含有氟樹脂之發泡體,本發明的目的在於提供可 以大氣孔率形成微細氣泡之發泡用組成物、發泡體及同軸 絕緣電纜。 對於發泡性組合物,本發明的目的可藉由含有氟樹脂 5 及電絕緣性晶鬚之發泡性組合物予以達成。 上述的發泡性組合物中,電絕緣性晶鬚係選自於硼酸 I呂、棚酸錄、鈦酸斜及氮化碎之至少一種。 此外,對於合成樹脂發泡體,發泡體係將具有氟樹脂 及電絕緣性晶鬚之組成物混合發泡劑後使其發泡而成者。 10 再者,同軸絕緣電纜係具有於中心導體周圍設置絕緣 體層者,且該絕緣體層由含有氟樹脂及電絕緣性晶鬚之組 成物發泡而成之發泡體構成。 本發明之發泡性組成物係以晶鬚作為發泡成核劑,使 含有氟樹脂之發泡性組成物發泡者,且發泡後所形成之發 15 泡體具有微小的氣泡,即使於發泡體層厚度小的情況下, 因為可獲得機械及電氣性能安定之發泡體層,所以可提供 有用的發泡體作為需要高信賴性之同軸絕緣電纜用絕緣 層。 第1圖是說明本發明之實施例的顯微鏡照片; 20 第2圖是說明本發明之比較例的顯微鏡照片;及 第3圖是說明本發明之比較例的顯微鏡照片。 L實施方式3 以下,針對本發明之實施態樣進行說明。 本發明發現藉由使用電絕緣性晶鬚,相較於使用氮化 6 ⑧ 1357920 硼粒子作為發泡成核劑的情況,可獲得具有微細獨立氣泡 的發泡體。 亦即,到目前為止作為發泡成核劑使用的氮化硼,都 是使用粒子狀、鱗片狀的粒子,但是本發明意外發現到藉 5 由使用鬚狀且具絕緣性的晶鬚,可使發泡率增大並形成微 細的氣泡。 本發明中作為發泡成核劑使用的晶鬚,可使用不影響 電特性且具絕緣性之陶瓷系晶鬚。 具體而言,可舉例如:選自於硼酸鋁晶鬚、硼酸鎂晶 10 鬚、欽酸斜晶鬚、氮化碎晶鬚之晶鬚’且可混合使用一種 或多種前述晶鬚。例如,以棚酸銘晶鬚而言,可舉四國化 成製的ALBOREX Y(纖維平均直徑0.5〜1/zm,纖維平均長 度10〜30/zm)為例,而鈦酸鉀晶鬚可舉大塚化學製的 TISMO D (纖維平均直徑0.2〜0.5gm,纖維平均長度10~20 15 # m)為例。 此外,發泡組成物中之絕緣性晶鬚,以發泡組成物中 質量百分比0.1至5為佳,且以質量百分比0.1至1更佳。 絕緣性晶鬚的量較質量百分比0.1少時,由於發泡率會 降低,因此不佳,而較質量百分比5多時,由於氣泡會變大 20 且會降低電特性之故,因此亦不佳。 又,本發明中所用之電絕緣性晶鬚在縱橫比為10~100 左右,且直徑以在0.1//m〜1/zm之間為佳,而比此更大的 晶鬚便無法形成細微的氣泡。 另一方面,本發明之發泡用組成物及用於發泡體之氟 ⑧ 1357920 樹脂,可舉例如:四氟乙烯-六氟丙烯共聚合體、四氟乙烯 -全氟丙基乙烯醚共聚合體等之四氟乙烯-烷基乙烯醚共聚 合體、乙烯-四氟乙烯-全氟丁基乙烯共聚合體、乙烯-三氟 氯乙烯共聚合體、聚氟亞乙烯等熱可塑性的氟樹脂。 5 再者,本發明中發泡體之發泡,亦可於熔融的組成物 中注入氮等氣體作為發泡劑,或是藉由加熱進行熱分解, 並將產生氣體之發泡性物質等混合於發泡樹脂組成物的方 式來處理。 以下透過實施例及比較例來對本發明進行說明。 10 實施例1 將含有質量百分比99.5之四氟乙烯-氟合院基乙稀共 聚合體(三井.都朋氟化學(DUPONT-MITSUI Fluorochemicals)製FEP5100J)、質量百分比〇.5之蝴酸鋁晶 鬚(四國化成製,ALBOREX Y)的組成物置於押出機中, 15 在380GC的鑄模溫度下押出成形,且注入〇.52MPa的氮氣, 藉由在可於押出機之端部上移動且直徑〇.511mm的鍍銀軟 銅線上發泡成形’形成外徑為1.44mm的發泡體層,並於同 袖絕緣電纜之中心導體的周圍形成發泡體層的被覆體。然 後對獲得的發泡體層測定其電容量,且利用下式丨計算介電 20常數ε,最後基於求得的介電常數求取氣孔率v (% )。 式1 ε = (Cxlog (D/d)) /24.16 此處,C :每lm的電容量(pF) D :外徑(mm) d :導體的直徑(mm) ⑧ 8 1357920
式2 V= ( 1 — log ε/log £ f) xlOO 此處,ef:構成發泡體層之組成物於發泡前的介電常 數,每單位長的電容量:75.2pF/m,介電常數ε為1.400, 而氣孔率為54.6% 。 5 此外,所獲得之中心導體的被覆體由垂直其軸的面上 切斷,在顯微鏡下觀察此斷面,其顯微鏡照片如第1圖所示。 任意抽取5 0個氣泡之平均直徑為2 4.2 // m。 比較例1 使用於實施例1中之發泡用組成物,除了將其改為混合 10 有作為發泡劑之氮化硼粒子的氟樹脂組成物(DUPONT製 FR5030)外,在其他相同的條件下製作具有發泡體層之中 心導體的被覆體,然後同實施例1測定其電容量。電容量經 測定為77 pF/m,因而求得介電常數ε為1.434,而氣孔率為 51.4% 。 15 此外,所得之中心導體的被覆體沿垂直其軸之面切 斷,利用顯微鏡觀察之,其顯微鏡照片如第2圖所示。 任意抽取50個氣泡之平均直徑為41.7 μ m。 比較例2 除了將用於實施例1中之硼酸鋁晶鬚改為硼酸鋁粒子 20 (四國化成製阿魯玻萊特(了少示,彳卜)03T粒子平均 直徑3//m)以外,在其他相同條件之下製作具發泡體層之 中心導體的被覆體,如同實施例1測定其電容量。電容量測 得為78.5 pF/m,因而求得介電常數ε為1.462,而氣孔率為 48.8%。 ⑧ 1357920 此外,所得之中心導體的被覆體沿垂直其軸之面切 斷,利用顯微鏡觀察之,其顯微鏡照片如第3圖所示。 如上述之實施例、比較例所示,本發明中以晶鬚作為 發泡成核劑所形成的發泡體層,其介電常數低,且相較於 5 使用氮化硼等粒子的情況可形成小氣孔孔徑的發泡體。 產業上利用的可能性 本發明之:發泡性組成物係含有具氟樹脂且以晶鬚作為 發泡成核劑之發泡性組成物,且其發泡後的發泡體具有微 細氣泡,即使於發泡體層為薄厚度的情形下,因為可得機 10 械及電氣性能安定的發泡體層,因此適於作為需要高信賴 度且線徑小之同軸絕緣電纜的絕緣層。
L圖式簡單說明I 第1圖是說明本發明之實施例的顯微鏡照片; 第2圖是說明本發明之比較例的顯微鏡照片;及 15 第3圖是說明本發明之比較例的顯微鏡照片。 【主要元件符號說明】 無 ⑧

Claims (1)

1357920 ιΛ月々修正替換頁 第94102丨23號專利申請』申請專利範修正日⑽年” 十、申請專利範圍: Μ曰 1. 一種發泡性組成物,係含有氟樹脂及電絕緣性晶鬚者, 其中前述電絕緣性晶鬚之直徑為0丨以爪〜丨以坩, 、· 及在月IJ 述發泡性組成物中前述電絕緣性晶鬚之含量為〇 1 5 質量%。 _ 2·如申叫專利範圍第1項之發泡性組成物,其中該電絕緣
性晶鬚係選自於硼酸鋁、硼酸鎂、鈦酸鉀及氣化矽之至 少一種。 3· 一種發泡體,係合成樹脂發泡體,其特徵在於:該發泡 體係使如申請專利範圍第1項之具氟樹脂及電絕緣性晶 鬚之組成物與發泡劑混合後使其發泡而成者。
4· 一種同軸絕緣電纜,其在中心導體周圍具有絕緣體層, 而該絕緣體層係由使發泡性組成物發泡而成之發泡體 所構成者’且該發泡性組成物含有氟樹脂及電絕緣性晶 鬚’其中前述電絕緣性晶鬚之直徑為0.1 e m〜1 " m,且 在前述發泡性組成物中前述電絕緣性晶鬚之含量為0.1 至1質量%。 11
TW094102123A 2004-01-26 2005-01-25 A foamed resin composition, a foam using the same TWI357920B (en)

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JP2004016697A JP4540038B2 (ja) 2004-01-26 2004-01-26 発泡樹脂組成物、それを用いた発泡体および同軸絶縁ケーブル

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US (1) US7491887B2 (zh)
JP (1) JP4540038B2 (zh)
KR (1) KR100789760B1 (zh)
CN (1) CN1910224B (zh)
DE (1) DE112005000157B4 (zh)
TW (1) TWI357920B (zh)
WO (1) WO2005070999A1 (zh)

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DE112005000157T5 (de) 2008-07-17
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KR20070004583A (ko) 2007-01-09
US20080087454A1 (en) 2008-04-17
CN1910224B (zh) 2010-05-12
JP4540038B2 (ja) 2010-09-08
KR100789760B1 (ko) 2008-01-03
CN1910224A (zh) 2007-02-07
TW200535194A (en) 2005-11-01
DE112005000157B4 (de) 2014-08-14

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