TWI819380B - 絕緣電線及樹脂組成物 - Google Patents
絕緣電線及樹脂組成物 Download PDFInfo
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- TWI819380B TWI819380B TW110136048A TW110136048A TWI819380B TW I819380 B TWI819380 B TW I819380B TW 110136048 A TW110136048 A TW 110136048A TW 110136048 A TW110136048 A TW 110136048A TW I819380 B TWI819380 B TW I819380B
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- TW
- Taiwan
- Prior art keywords
- insulating layer
- mentioned
- resin
- aromatic polyetherketone
- insulated wire
- Prior art date
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Classifications
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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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
- H01B3/427—Polyethers
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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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- 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
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Abstract
本發明提供一種具有較薄之絕緣層且拉伸伸長率優異之絕緣電線。本發明之絕緣電線具有導體(A)及形成於上述導體(A)之外周的絕緣層(B),且特徵在於:上述絕緣層(B)含有芳香族聚醚酮樹脂(I)及含氟共聚物(II),且於60 sec
-1、390℃之熔融黏度為0.40~0.75 kPa·s,上述芳香族聚醚酮樹脂(I)於60 sec
-1、390℃之熔融黏度為0.30 kPa·s以下,上述絕緣層(B)之厚度為30~300 μm。
Description
本發明係關於一種絕緣電線及樹脂組成物。
汽車或機器人所使用之電線需要優異之絕緣性。又,近年來,高電壓、大電流化正在加速發展,為了防止絕緣層之劣化,需要具有介電常數低之絕緣層的電線。進而,搭載於汽車等之電線需要高耐熱性。
於此種背景下,為了提高電線之特性,而進行了各種研究,例如,如下所述,提出了使用2種以上之樹脂形成絕緣層之電線。
於專利文獻1中記載了一種絕緣電線,其具有導體(A)及形成於上述導體(A)之外周的絕緣層(B),且特徵在於:絕緣層(B)由含有芳香族聚醚酮樹脂(I)及氟樹脂(II)之樹脂組成物形成,氟樹脂(II)係四氟乙烯與下述通式(1)所表示之全氟乙烯性不飽和化合物之共聚物:
CF
2=CF-Rf
1(1)
(式中,Rf
1表示-CF
3或-ORf
2;Rf
2表示碳數1~5之全氟烷基),芳香族聚醚酮樹脂(I)與氟樹脂(II)之熔融黏度比(I)/(II)為0.3~5.0。
先前技術文獻
專利文獻
專利文獻1:國際公開第2013/088968號
[發明所欲解決之課題]
本發明提供一種具有較薄之絕緣層且拉伸伸長率優異之絕緣電線。又,提供一種加工特性及拉伸伸長率優異之樹脂組成物。
[解決課題之技術手段]
本發明係關於一種絕緣電線(以下記載為「本發明之絕緣電線」),其具有導體(A)及形成於上述導體(A)之外周的絕緣層(B),且特徵在於:上述絕緣層(B)含有芳香族聚醚酮樹脂(I)及含氟共聚物(II),且於60 sec
-1、390℃之熔融黏度為0.40~0.75 kPa·s,上述芳香族聚醚酮樹脂(I)於60 sec
-1、390℃之熔融黏度為0.30 kPa·s以下,上述絕緣層(B)之厚度為30~300 μm。
上述絕緣層(B)較佳為上述含氟共聚物(II)之平均分散粒徑r1、與按照ASTM D1238在380℃、5000 g負載及5分鐘預熱而測定熔體流動速率後之上述含氟共聚物(II)之平均分散粒徑r2的比r2/r1為1.60以下。
本發明之絕緣電線較佳為拉伸伸長率為100%以上。
上述芳香族聚醚酮樹脂(I)較佳為熔點為300~380℃。
上述芳香族聚醚酮樹脂(I)較佳為玻璃轉移溫度為130~220℃。
上述含氟共聚物(II)較佳為熔點為200~323℃。
上述含氟共聚物(II)較佳為四氟乙烯與由下述通式(1)所表示之全氟乙烯性不飽和化合物之共聚物,
CF
2=CF-Rf
1(1)
(式中,Rf
1表示-CF
3或-ORf
2;Rf
2表示碳數1~5之全氟烷基)。
上述絕緣層(B)較佳為上述芳香族聚醚酮樹脂(I)與上述含氟共聚物(II)之質量比(I):(II)為99:1~30:70。
上述芳香族聚醚酮樹脂(I)較佳為聚醚酮酮。
本發明亦係關於一種樹脂組成物(以下記載為「本發明之樹脂組成物」),其含有芳香族聚醚酮樹脂(I)及含氟共聚物(II),且於60 sec
-1、390℃之熔融黏度為0.40~0.75 kPa·s,上述芳香族聚醚酮樹脂(I)於60 sec
-1、390℃之熔融黏度為0.30 kPa·s以下。
[發明之效果]
本發明之絕緣電線因具有上述構成而拉伸伸長率較高,且具有較薄之絕緣層。又,本發明之樹脂組成物因具有上述構成而加工特性及拉伸伸長率優異。
具有由芳香族聚醚酮樹脂所構成之絕緣層之絕緣電線之強度及耐熱性優異,但柔軟性較差,因而可撓性較低。又,介電常數亦無法滿足高電壓化、高電流化之要求。另一方面,具有由氟樹脂所構成之絕緣層之絕緣電線之柔軟性及低介電性優異,但存在強度較低,耐磨性較差之問題。
本發明人等為了解決上述問題而進行了各種研究。本發明人等發現,由含有芳香族聚醚酮樹脂(I)及含氟共聚物(II)之樹脂組成物形成之絕緣電線的強度、耐熱性及低介電性優異。進而,令人驚訝地發現,於絕緣層及芳香族聚醚酮樹脂(I)之熔融黏度處於特定範圍內之情形時,能夠獲得具有源於可撓性之高拉伸伸長率及較薄之絕緣層的絕緣電線,以至完成了本發明之絕緣電線。
本發明之絕緣電線具有導體(A)及形成於上述導體(A)之外周的絕緣層(B),上述絕緣層(B)含有芳香族聚醚酮樹脂(I)及含氟共聚物(II),且於60 sec
-1、390℃之熔融黏度為0.40~0.75 kPa·s,上述芳香族聚醚酮樹脂(I)於60 sec
-1、390℃之熔融黏度為0.30 kPa·s以下,上述絕緣層(B)之厚度為30~300 μm(較佳為30~160 μm)。
藉由使絕緣層(B)及芳香族聚醚酮樹脂(I)具有上述構成,能夠形成成形性優異之絕緣層(B),進而,上述絕緣電線能夠具有較薄之絕緣層(B),因此能夠提高拉伸伸長率。
上述絕緣層(B)含有芳香族聚醚酮樹脂(I)及含氟共聚物(II),且於60 sec
-1、390℃之熔融黏度為0.40~0.75 kPa·s。就能夠使絕緣層(B)變得更薄,能夠使拉伸伸長率變得更高之方面而言,上述絕緣層(B)之熔融黏度較佳為0.50 kPa·s以上,更佳為0.55 kPa·s以上,進而較佳為0.60 kPa·s以上。當上述絕緣層(B)之熔融黏度過低時,存在使絕緣層(B)變薄時產生針孔等成形不良的隱憂。又,較佳為0.70 kPa·s以下。當上述絕緣層(B)之熔融黏度過大時,存在無法使絕緣層(B)成形得較薄的隱憂。絕緣層(B)之熔融黏度係依據ASTM D3835-02而測定。
上述芳香族聚醚酮樹脂(I)於60 sec
-1、390℃之熔融黏度為0.30 kPa·s以下。藉由使熔融黏度處於上述範圍內,加工特性提昇,進而,能夠獲得拉伸伸長率較高之絕緣層(B)。熔融黏度之較佳上限為0.26 kPa·s,更佳為0.20 kPa·s。熔融黏度之較佳下限並無特別限定,為0.10 kPa·s,當低於該下限時,存在損害成形性的隱憂。當芳香族聚醚酮樹脂(I)之熔融黏度過高時,無法將絕緣層(B)之熔融黏度維持於所需範圍內,存在無法形成較薄之絕緣層(B)的隱憂。芳香族聚醚酮樹脂(I)之熔融黏度係依據ASTM D3835-02而測定。
本發明之絕緣電線藉由使絕緣層(B)之熔融黏度及樹脂(I)之熔融黏度為上述特定範圍之組合,而使得成形性提昇,能夠使被覆層之厚度變薄,拉伸伸長率提昇。
於本發明之絕緣電線中,上述絕緣層(B)較佳為含氟共聚物(II)之平均分散粒徑r1、與按照ASTM D1238在380℃、5000 g負載及5分鐘預熱而測定熔體流動速率後之含氟共聚物(II)之平均分散粒徑r2的比r2/r1為1.60以下。就能夠使絕緣層(B)變得更薄,能夠進一步提昇拉伸伸長率之方面而言,比r2/r1更佳為1.50以下,進而較佳為1.47以下。比r2/r1之下限並無特別限定,可為0.80,亦可為0.90、1.00、1.10、1.20。
又,本發明之一樣態中,含氟共聚物(II)之r1、r2滿足r2≧r1之關係。
於上述絕緣層(B)中,藉由使用上述芳香族聚醚酮樹脂(I),能夠製成薄壁加工性提昇,拉伸伸長率較高之絕緣層(B)。
上述芳香族聚醚酮樹脂(I)無特別限制,只要包含由伸芳基、醚基[-O-]及羰基[-C(=O)-]所構成之重複單元即可,例如包含下述式(a1)~(a5)中任一者所表示之重複單元。
[-Ar-O-Ar-C(=O)-] (a1)
[-Ar-O-Ar-C(=O)-Ar-C(=O)-] (a2)
[-Ar-O-Ar-O-Ar-C(=O)-] (a3)
[-Ar-O-Ar-C(=O)-Ar-O-Ar-C(=O)-Ar-C(=O)-] (a4)
[-Ar-O-Ar-O-Ar-C(=O)-Ar-C(=O)-] (a5)
(式中,Ar表示可具有取代基之二價芳香族烴環基)
作為Ar所表示之二價芳香族烴環基,例如可例示:伸苯基(鄰、間或對伸苯基等)、伸萘基等碳數為6~10之伸芳基;伸聯苯基(2,2’-伸聯苯基、3,3’-伸聯苯基、4,4’-伸聯苯基等)等伸聯芳基(各伸芳基之碳數為6~10);鄰、間或對伸聯三苯基等伸聯三芳基(各伸芳基之碳數為6~10)等。該等芳香族烴環基可具有取代基,例如鹵素原子、烷基(甲基等直鏈狀或支鏈狀之碳數1~4之烷基等)、鹵烷基、羥基、烷氧基(甲氧基等直鏈狀或支鏈狀之碳數1~4之烷氧基等)、巰基、烷硫基、羧基、磺基、胺基、N-取代胺基、氰基等。再者,於重複單元(a1)~(a5)中,各Ar之種類可彼此相同亦可不同。較佳之Ar為伸苯基(例如對伸苯基)、伸聯苯基(例如4,4’-伸聯苯基)。
作為具有重複單元(a1)之樹脂,可例示聚醚酮(例如Victrex公司製造之「PEEK-HT」)等。作為具有重複單元(a2)之樹脂,可例示聚醚酮酮(例如Arkema+Oxford Performance Material公司製造之「PEKK」)等。作為具有重複單元(a3)之樹脂,可例示聚醚醚酮(例如Victrex公司製造之「VICTREX PEEK」、Evonik公司製造之「Vestakeep(註冊商標)」、Daicel-Evonik公司製造之「Vestakeep-J」、Solvay Speciality Polymers公司製造之「KetaSpire(註冊商標)」)、聚醚-二苯基-醚-苯基-酮-苯基(例如Solvay Speciality Polymers公司製造之「Kadel(註冊商標)」)等。作為具有重複單元(a4)之樹脂,可例示聚醚酮醚酮酮(例如Victrex公司製造之「VICTREX ST」)等。作為具有重複單元(a5)之樹脂,可例示聚醚醚酮酮等。於由伸芳基、醚基及羰基所構成之重複單元中,醚鏈段(E)與酮鏈段(K)之比例例如為E/K=0.5~3,較佳為0.5~2.0左右。醚鏈段對分子鏈賦予柔軟性,酮鏈段對分子鏈賦予剛直性,因此存在下述傾向:醚鏈段越多則結晶化速度越快,最終可達成之結晶度亦越高,酮鏈段越多則玻璃轉移溫度及熔點越高。該等芳香族聚醚酮樹脂(I)可單獨使用或組合兩種以上而使用。
於該等芳香族聚醚酮樹脂(I)中,較佳為具有重複單元(a1)~(a4)中任一者之芳香族聚醚酮樹脂。例如,作為上述芳香族聚醚酮樹脂(I),較佳為選自由聚醚酮、聚醚醚酮、聚醚酮酮及聚醚酮醚酮酮所組成之群中至少1種樹脂。進而,更佳為選自由聚醚酮、聚醚醚酮及聚醚酮酮所組成之群中至少1種樹脂。尤其就薄壁加工性提昇,拉伸伸長率變高之方面而言,較佳為聚醚酮酮。
上述芳香族聚醚酮樹脂(I)較佳為熔點為300℃以上。更佳為320℃以上。藉由使其熔點處於上述範圍內,能夠提高所獲得之成形品之耐熱性。又,熔點較佳為380℃以下,於混練具有該值以上之熔點之芳香族聚醚酮樹脂的情形時,存在混練時含氟共聚物之熱劣化劇烈而無法維持物性的隱憂。上述熔點係使用示差掃描熱測定(DSC)裝置以10℃/min之速度升溫時之熔解熱曲線中之極大值所對應的溫度。
上述芳香族聚醚酮樹脂(I)於380℃、5000 g負載之條件下所測得之熔體流動速率(MFR)較佳為1~150 g/10 min,更佳為5~130 g/10 min,進而較佳為10~100 g/10 min。藉由MFR為上述範圍,能夠獲得薄壁加工性提昇且拉伸伸長率較高之絕緣層(B)。上述芳香族聚醚酮樹脂(I)之MFR係依據ASTM D1238,使用熔融指數測定儀而測定。
上述芳香族聚醚酮樹脂(I)較佳為玻璃轉移溫度為130℃以上。更佳為135℃以上,進而較佳為140℃以上。藉由為上述範圍之玻璃轉移溫度,能夠獲得耐熱性優異之絕緣電線。玻璃轉移溫度之上限並無特別限制,就成形性之觀點而言,較佳為220℃以下,更佳為180℃以下。
上述玻璃轉移溫度係依據JIS K7121,使用示差掃描熱測定(DSC)裝置,於由20℃/min之升溫速度構成之測定條件下進行測定。
於上述絕緣層(B)中,上述含氟共聚物(II)例如係具有基於至少1種含氟乙烯性單體之聚合單元的聚合物。含氟共聚物(II)較佳為熔融加工性之氟樹脂。含氟共聚物(II)可使用1種,亦可使用2種以上。
作為上述含氟共聚物(II),例如可例舉:四氟乙烯(TFE)/六氟丙烯(HFP)共聚物、TFE/HFP/全氟(烷基乙烯基醚)(PAVE)共聚物、TFE/PAVE共聚物[PFA]、乙烯(Et)/TFE共聚物、Et/TFE/HFP共聚物、三氟氯乙烯(CTFE)/TFE共聚物、CTFE/TFE/PAVE共聚物、Et/CTFE共聚物、TFE/偏二氟乙烯(VdF)共聚物、VdF/HFP/TFE共聚物、VdF/HFP共聚物。
作為上述PAVE,較佳為具有碳數1~6之烷基者,可例舉:全氟(甲基乙烯基醚)、全氟(乙基乙烯基醚)、全氟(丙基乙烯基醚)、全氟(丁基乙烯基醚)等。
作為上述含氟共聚物(II),更佳為四氟乙烯(TFE)與下述通式(1)所表示之全氟乙烯性不飽和化合物之共聚物,
CF
2=CF-Rf
1(1)
(式中,Rf
1表示-CF
3或-ORf
2;Rf
2表示碳數1~5之全氟烷基)。於上述Rf
1為-ORf
2之情形時,上述Rf
2較佳為碳數為1~3之全氟烷基。藉由使用上述含氟共聚物(II),能夠獲得薄壁加工性提昇且拉伸伸長率較高之絕緣層(B)。
作為通式(1)所表示之全氟乙烯性不飽和化合物,就能夠獲得薄壁加工性提昇且拉伸伸長率較高之絕緣層(B)之方面而言,較佳為選自由六氟丙烯(HFP)、全氟(甲基乙烯基醚)(PMVE)、全氟(乙基乙烯基醚)(PEVE)及全氟(丙基乙烯基醚)(PPVE)所組成之群中至少1種,更佳為選自由六氟丙烯及全氟(丙基乙烯基醚)所組成之群中至少1種。
作為上述含氟共聚物(II),較佳為選自由TFE與HFP之共聚物、TFE、HFP及PPVE之共聚物、以及TFE與PPVE之共聚物所組成之群中至少1種,更佳為選自由TFE與HFP之共聚物、以及TFE、HFP及PPVE之共聚物所組成之群中至少1種。
上述含氟共聚物(II)較佳為由相對於所有聚合單元為98~75質量%之基於TFE之聚合單元(TFE單元)、及2~25質量%之基於上述通式(1)所表示之全氟乙烯性不飽和化合物之聚合單元所構成。構成上述含氟共聚物(II)之TFE之含量之下限更佳為77質量%,進而較佳為80質量%,特佳為83質量%,尤佳為85質量%。構成上述含氟共聚物(II)之TFE之含量之上限更佳為97質量%,進而較佳為95質量%,尤佳為92質量%。
又,構成含氟共聚物(II)之通式(1)所表示之全氟乙烯性不飽和化合物之含量之下限更佳為3質量%,進而較佳為5質量%。構成含氟共聚物(II)之通式(1)所表示之全氟乙烯性不飽和化合物之含量之上限更佳為23質量%,進而較佳為20質量%,特佳為17質量%,尤佳為15質量%。
含氟共聚物(II)較佳為僅由TFE及通式(1)所表示之全氟乙烯性化合物所構成之共聚物。
上述含氟共聚物(II)較佳為於60 sec
-1、390℃之熔融黏度為0.2~4.0 kPa·s。藉由熔融黏度為上述範圍,能夠獲得薄壁加工性提昇且拉伸伸長率較高之絕緣層(B)。
熔融黏度之更佳之下限為0.25 kPa·s,進而較佳為0.3 kPa·s,特佳為0.35 kPa·s,最佳為0.4 kPa·s。熔融黏度之更佳之上限為3.7 kPa·s,進而較佳為3.6 kPa·s,特佳為3.5 kPa·s。
上述含氟共聚物(II)之熔融黏度係依據ASTM D3835-02而測定。
上述含氟共聚物(II)在380℃、5000 g負載之條件下所測得之熔體流動速率(MFR)較佳為0.1~100 g/10 min,更佳為0.5~80 g/10 min,進而較佳為0.5~70 g/10 min,特佳為10~60 g/10 min。藉由MFR為上述範圍,能夠獲得薄壁加工性提昇且拉伸伸長率較高之絕緣層(B)。上述含氟共聚物(II)之MFR係依據ASTM D1238,使用熔融指數測定儀而測定。
上述含氟共聚物(II)之熔點並無特別限定,在成形過程中,較佳為含氟共聚物(II)於成形時所使用之芳香族聚醚酮樹脂(I)熔融之溫度時已經熔融,故較佳為上述芳香族聚醚酮樹脂(I)之熔點以下之溫度。例如,含氟共聚物(II)之熔點較佳為200~323℃,更佳為220~320℃,進而較佳為240~315℃。含氟共聚物(II)之熔點係使用示差掃描熱測定(DSC)裝置以10℃/min之速度升溫時之熔解熱曲線中之極大值所對應的溫度。
上述含氟共聚物(II)可為藉由公知之方法經氟氣處理者,亦可為經氨處理者。
於上述絕緣層(B)中,就容易抑制含氟共聚物相之凝聚、合體,將其分散粒徑之變化率控制在所欲範圍內之觀點而言,可使用含有反應性官能基之含氟共聚物。反應性官能基並無特別限定,具體而言,可例示:乙烯基、環氧基、羧基、酸酐基、酯基、醛基、羰二氧基、鹵甲醯基(haloformyl)、烷氧羰基、胺基、羥基、苯乙烯基、甲基丙烯酸基、丙烯酸基、脲基、巰基、硫基、異氰酸基、水解性矽基等,其中較佳為選自由環氧基、羧基、酸酐基、胺基及羥基所組成之群中至少1種,進而較佳為選自由羧基及酸酐基所組成之群中至少1種。亦可包含2種以上之該等反應性官能基。又,反應性官能基可導入至含氟共聚物之主鏈末端或側鏈中之一者。
含有上述反應性官能基之含氟共聚物之官能基量並無特別限定,從使反應充分進行之觀點及流動性惡化之觀點考慮,較佳為0.01莫耳%~15莫耳%之範圍。
上述絕緣層(B)較佳為含氟共聚物(II)以5.0 μm以下之平均分散粒徑形成分散相。藉由平均分散粒徑為上述範圍,能夠獲得薄壁加工性提昇且拉伸伸長率更高之絕緣層(B)。就能夠獲得具有更高特性之絕緣層(B),並且成形性更加優異之方面而言,上述平均分散粒徑較佳為4.0 μm以下,更佳為3.0 μm以下,進而較佳為2.5 μm以下,特佳為2.0 μm以下,最佳為1.5 μm以下。平均分散粒徑之下限並無特別限定,可為0.01 μm。
於上述絕緣層(B)中,上述含氟共聚物(II)之平均分散粒徑係按照以下順序確定。關於上述平均分散粒徑,藉由將上述絕緣層(B)於長度方向垂直地切削,而得到試驗片,利用共焦雷射顯微鏡觀察其剖面。使用影像解析軟體(Image J)來解析所獲得之顯微鏡影像。選擇分散相,求出圓等效直徑。算出20個分散相之圓等效直徑,將其平均值作為平均分散粒徑。
於上述絕緣層(B)中,芳香族聚醚酮樹脂(I)與含氟共聚物(II)之質量比(I):(II)並無特別限定,例如,較佳為99:1~30:70。又,更佳為95:5~35:65,進而較佳為95:5~40:60。
上述絕緣層(B)之相對介電常數較佳為2.80以下。更佳為2.70以下,進而較佳為2.60以下。藉由使相對介電常數小於上述範圍,能夠較佳地用作纏繞電線之被覆材料、可撓性印刷基板電路用膜。上述絕緣層(B)需要具有較高之絕緣性,因此相對介電常數越低越好,較佳為2.10以上。當使含氟共聚物之組成比變大至相對介電常數未達2.10之程度時,機械物性之下降變得顯著,存在難以獲得所需機械物性的隱憂。上述相對介電常數係藉由空腔共振擾動法所測得之值。
上述絕緣層(B)亦可視需要包含芳香族聚醚酮樹脂(I)及含氟共聚物(II)以外之成分。上述芳香族聚醚酮樹脂(I)及含氟共聚物(II)以外之成分並無特別限定,可使用:鈦酸鉀等之晶鬚、玻璃纖維、石棉纖維、碳纖維、陶瓷纖維、鈦酸鉀纖維、芳綸纖維、其他高強度纖維等纖維狀補強材料;滑石、雲母、黏土、碳粉末、石墨、人造石墨、天然石墨、玻璃珠等無機填充材;著色劑;阻燃劑等通常所使用之無機或有機填充材;聚矽氧油、二硫化鉬等潤滑劑;顏料;碳黑等導電劑;橡膠等耐衝擊性提昇劑;硬脂酸鎂等潤滑劑;苯并三唑化合物等紫外線吸收劑;氮化硼等發泡劑;其他添加劑等。
該等添加劑於不損害本案之效果之範圍內可加入至原料之芳香族聚醚酮樹脂(I)中,亦可加入至原料之含氟共聚物(II)中。又,於不損害本案之效果之範圍內,在將芳香族聚醚酮樹脂(I)與含氟共聚物(II)混練時,亦可藉由側進料方式等添加至熔融狀態之原料中。
(III)纖維狀填充劑
上述絕緣層(B)較佳為進而包含纖維狀填充劑(III)。上述絕緣層(B)中所使用之纖維狀填充材例如可例示:玻璃纖維、碳纖維、碳磨碎纖維、金屬纖維、石棉纖維、岩絨、陶瓷纖維、礦渣纖維、鈦酸鉀晶鬚、硼晶鬚、硼酸鋁晶鬚、碳酸鈣晶鬚、氧化鈦晶鬚、矽灰石、硬矽鈣石、坡縷石(厄帖浦石)及海泡石等纖維狀無機填充材;芳綸纖維、聚醯亞胺纖維及聚苯并噻唑纖維等耐熱有機纖維所代表之纖維狀耐熱有機填充材;以及該等填充劑經例如金屬或金屬氧化物等異種材料表面被覆而成之纖維狀填充材等。作為經異種材料表面被覆而成之填充材,例如可例示金屬塗層玻璃纖維及金屬塗層碳纖維等。作為異種材料之表面被覆方法,並無特別限定,例如可例舉公知之各種鍍覆法(例如電鍍、無電解鍍覆、熔融鍍覆等)、真空蒸鍍法、離子鍍覆法、CVD法(例如熱CVD、MOCVD、電漿CVD等)、PVD法及濺鍍法等。於該等纖維狀填充材中,較佳為選自由玻璃纖維、碳纖維、碳磨碎纖維及芳綸纖維所組成之群中至少1種,更佳為選自由玻璃纖維及碳纖維所組成之群中至少1種。
上述纖維狀填充材之纖維直徑較佳為處於0.1~20 μm之範圍內。纖維直徑之上限更佳為18 μm,進而較佳為15 μm。另一方面,纖維直徑之下限更佳為1 μm,進而較佳為6 μm。此處所謂纖維直徑,係指數量平均纖維直徑。再者,該數量平均纖維直徑係利用掃描電子顯微鏡觀察將成形品溶解於溶劑中或者以鹼性化合物分解樹脂後所採取之殘渣、以及於坩堝中進行焚化後所採取之焚化殘渣,根據觀察到的影像而算出之值。
於上述絕緣層(B)中所使用之纖維狀填充材為玻璃纖維之情形時,玻璃纖維之玻璃組成係採用A玻璃、C玻璃及E玻璃等所代表之各種玻璃組成,並無特別限定。該玻璃填充材亦可視需要含有TiO
2、SO
3及P
2O
5等成分。其中,更佳為E玻璃(無鹼玻璃)。就提昇機械強度之方面而言,該玻璃纖維較佳為經周知之表面處理劑,例如矽烷偶合劑、鈦酸酯偶合劑或鋁酸酯偶合劑等表面處理者。又,較佳為經烯烴系樹脂、苯乙烯系樹脂、丙烯酸系樹脂、聚酯系樹脂、環氧系樹脂及胺酯(urethane)系樹脂等集束處理者,就機械強度之方面而言,特佳為經環氧系樹脂、胺酯系樹脂集束處理者。經集束處理之玻璃纖維之集束劑附著量於玻璃纖維100質量%中較佳為0.1~3質量%,更佳為0.2~1質量%。上述絕緣層(B)中所使用之纖維狀填充材亦可使用扁平剖面玻璃纖維。該扁平剖面玻璃纖維係下述之玻璃纖維,即,纖維剖面之長徑之平均值較佳為10~50 μm,更佳為15~40 μm,進而較佳為20~35 μm,且長徑與短徑之比(長徑/短徑)之平均值較佳為1.5~8,更佳為2~6,進而較佳為2.5~5的玻璃纖維。於使用長徑與短徑之比之平均值為該範圍內之扁平剖面玻璃纖維的情形時,與使用該值未達1.5之非圓形剖面纖維之情形相比,各向異性得到大幅改良。又,作為扁平剖面形狀,除扁平狀以外,還可例舉:橢圓狀、繭狀及三葉狀、或者與之類似的形狀之非圓形剖面形狀。其中,就機械強度、低各向異性之改良之方面而言,較佳為扁平形狀。又,扁平剖面玻璃纖維之平均纖維長度與平均纖維直徑之比(長寬比)較佳為2~120,更佳為2.5~70,進而較佳為3~50。當纖維長度與平均纖維直徑之比未達2時,存在機械強度之提昇效果變小之情形,當纖維長度與平均纖維直徑之比超過120時,存在各向異性變大,此外,絕緣層(B)之外觀亦變差之情形。該扁平剖面玻璃纖維之平均纖維直徑係指,將扁平剖面形狀換算為相同面積之真圓形時之數量平均纖維直徑。又,平均纖維長度係指上述絕緣層(B)中之數量平均纖維長度。再者,該數量平均纖維長度係利用光學顯微鏡觀察絕緣層(B)之高溫焚化、利用溶劑之溶解、以及利用化學品之分解等處理中所採取的填充材之殘渣,根據觀察到的影像,藉由影像解析裝置而算出之值。又,於算出該值時,為採用下述方法獲得之值,以纖維直徑為標準時長度為該標準以下者不計數。
關於上述纖維狀填充劑(III)之質量比,相對於上述絕緣層(B),較佳為0~50質量%,更佳為5~40質量%,進而較佳為10~30質量%。
(其他添加劑)
關於上述絕緣層(B),為了改良其設計性等,使用添加劑較為有利。以下,對該等添加劑進行具體說明。
(IV)染顏料
上述絕緣層(B)可進而含有各種染顏料而提供表現出多樣之設計性之成形品。作為上述絕緣層(B)中所使用之染顏料,可例舉:苝系染料、香豆素系染料、硫靛藍系染料、蒽醌系染料、9-氧硫𠮿系染料、普魯士藍等亞鐵氰化物、芘酮系染料、喹啉系染料、喹吖啶酮系染料、二 系染料、異吲哚啉酮系染料及酞青系染料等。進而,上述絕緣層(B)中亦可摻合金屬顏料而獲得更加良好之金屬色彩。作為金屬顏料,鋁粉較為合適。又,可藉由摻合螢光增白劑或除其以外之發光之螢光染料,而賦予充分利用發光顏色之更好之設計效果。
(V)具有熱射線吸收能之化合物
上述絕緣層(B)可含有具有熱射線吸收能之化合物。作為該化合物,可較佳地例示:酞青系近紅外線吸收劑;ATO、ITO、氧化銥及氧化釕、氧化亞銨、氧化鈦等金屬氧化物系近紅外線吸收劑;硼化鑭、硼化鈰及硼化鎢等金屬硼化物系或氧化鎢系近紅外線吸收劑等近紅外吸收能優異之各種金屬化合物;以及碳填料。作為該酞青系近紅外線吸收劑,例如市售三井化學(股)製造之MIR-362,可容易地獲得。作為碳填料,可例示:碳黑、石墨(天然及人工石墨皆包括在內)及富勒烯等,較佳為碳黑及石墨。其等可單獨使用或併用2種以上。酞青系近紅外線吸收劑之含量相對於上述絕緣層(B)100質量份,較佳為0.0005~0.2質量份,更佳為0.0008~0.1質量份,進而較佳為0.001~0.07質量份。金屬氧化物系近紅外線吸收劑、金屬硼化物系近紅外線吸收劑及碳填料之含量於上述絕緣層(B)中較佳為處於0.1~200 ppm(質量比例)之範圍內,更佳為處於0.5~100 ppm之範圍內。
(VI)光高反射用白色顏料
可於上述絕緣層(B)中摻合光高反射用白色顏料而賦予其光反射效果。作為該白色顏料,特佳為二氧化鈦(尤其是經聚矽氧等有機表面處理劑處理之二氧化鈦)顏料。該光高反射用白色顏料之含量相對於樹脂組成物100質量份,較佳為3~30質量份,更佳為8~25質量份。再者,光高反射用白色顏料可併用2種以上。
(VII)紫外線吸收劑
可於上述絕緣層(B)中摻合紫外線吸收劑而賦予其耐候性。作為該紫外線吸收劑,具體而言,於二苯甲酮系中例如可例示:2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-辛氧基二苯甲酮、2-羥基-4-苄氧基二苯甲酮、2-羥基-4-甲氧基-5-磺醯基二苯甲酮、2,2’-二羥基-4-甲氧基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基-5-磺醯鈉二苯甲酮、雙(5-苯甲醯基-4-羥基-2-甲氧基苯基)甲烷、2-羥基-4-正十二烷氧基二苯甲酮及2-羥基-4-甲氧基-2’-羧基二苯甲酮等。作為紫外線吸收劑,具體而言,於苯并三唑系中例如可例示:2-(2-羥基-5-甲基苯基)苯并三唑、2-(2-羥基-5-第三辛基苯基)苯并三唑、2-(2-羥基-3,5-二異丙苯基苯基)苯基苯并三唑、2-(2-羥基-3-第三丁基-5-甲基苯基)-5-氯苯并三唑、2,2’-亞甲基雙[4-(1,1,3,3-四甲基丁基)-6-(2H-苯并三唑-2-基)苯酚]、2-(2-羥基-3,5-二第三丁基苯基)苯并三唑、2-(2-羥基-3,5-二第三丁基苯基)-5-氯苯并三唑、2-(2-羥基-3,5-二第三戊基苯基)苯并三唑、2-(2-羥基-5-第三辛基苯基)苯并三唑、2-(2-羥基-5-第三丁基苯基)苯并三唑、2-(2-羥基-4-辛氧基苯基)苯并三唑、2,2’-亞甲基雙(4-異丙苯基-6-苯并三唑苯基)、2,2’-對伸苯基雙(1,3-苯并 -4-酮)、及2-[2-羥基-3-(3,4,5,6-四氫鄰苯二甲醯亞胺甲基)-5-甲基苯基]苯并三唑、以及2-(2’-羥基-5-甲基丙烯醯氧基乙基苯基)-2H-苯并三唑與可跟該單體共聚之乙烯系單體的共聚物、或2-(2’-羥基-5-丙烯醯氧基乙基苯基)-2H-苯并三唑與可跟該單體共聚之乙烯系單體的共聚物等具有2-羥基苯基-2H-苯并三唑骨架之聚合物等。關於紫外線吸收劑,具體而言,於羥基苯基三系中例如可例示:2-(4,6-二苯基-1,3,5-三-2-基)-5-己氧基苯酚、2-(4,6-二苯基-1,3,5-三-2-基)-5-甲氧基苯酚、2-(4,6-二苯基-1,3,5-三-2-基)-5-乙氧基苯酚、2-(4,6-二苯基-1,3,5-三-2-基)-5-丙氧基苯酚、及2-(4,6-二苯基-1,3,5-三-2-基)-5-丁氧基苯酚等。進而可例示:2-(4,6-雙(2,4-二甲基苯基)-1,3,5-三-2-基)-5-己氧基苯酚等上述示例化合物之苯基變為2,4-二甲基苯基之化合物。關於紫外線吸收劑,具體而言,於環狀亞胺酯系中例如可例示:2,2’-對伸苯基雙(3,1-苯并 -4-酮)、2,2’-間伸苯基雙(3,1-苯并 -4-酮)、及2,2’-p,p’-二伸苯基雙(3,1-苯并 -4-酮)等。又,作為紫外線吸收劑,具體而言,於氰基丙烯酸酯系中例如可例示:1,3-雙-[(2’-氰基-3’,3’-二苯基丙烯醯基)氧基]-2,2-雙[(2-氰基-3,3-二苯基丙烯醯基)氧基]甲基)丙烷、及1,3-雙-[(2-氰基-3,3-二苯基丙烯醯基)氧基]苯等。進而,上述紫外線吸收劑具有可進行自由基聚合之單體化合物之結構,因此,可為使該紫外線吸收性單體及/或光穩定性單體與(甲基)丙烯酸烷基酯等單體共聚而成的聚合物型紫外線吸收劑。作為上述紫外線吸收性單體,可較佳地例示(甲基)丙烯酸酯之酯取代基中含有苯并三唑骨架、二苯甲酮骨架、三骨架、環狀亞胺酯骨架、及氰基丙烯酸酯骨架之化合物。上述之中,就紫外線吸收能之方面而言,較佳為苯并三唑系及羥基苯基三系,就耐熱性及色相之方面而言,較佳為環狀亞胺酯系及氰基丙烯酸酯系。具體而言,例如可例舉:Chemipro Kasei(股)製造之「ChemiSorb 79」、巴斯夫日本(股)製造之「TINUVIN 234」等。上述紫外線吸收劑可單獨使用或以2種以上混合物之形式使用。
關於紫外線吸收劑之含量,相對於上述絕緣層(B)100質量份,較佳為0.01~3質量份,更佳為0.01~1質量份,進而較佳為0.05~1質量份,特佳為0.05~0.5質量份。
(VIII)抗靜電劑
上述絕緣層(B)有時需要具有抗靜電性能,於此情形時,較佳為包含抗靜電劑。作為該抗靜電劑,例如可例舉:(1)十二烷基苯磺酸鏻鹽所代表之芳基磺酸鏻鹽及烷磺酸鏻鹽等有機磺酸鏻鹽、以及四氟硼酸鏻鹽之類的硼酸鏻鹽。該鏻鹽之含量相對於上述絕緣層(B)100質量份為5質量份以下較為合適,較佳為0.05~5質量份,更佳為1~3.5質量份,進而較佳為1.5~3質量份之範圍。作為抗靜電劑,例如可例舉:(2)有機磺酸鋰、有機磺酸鈉、有機磺酸鉀、有機磺酸銫、有機磺酸銣、有機磺酸鈣、有機磺酸鎂及有機磺酸鋇等有機磺酸鹼(土類)金屬鹽。如上所述,該金屬鹽亦可用作阻燃劑。更具體而言,該金屬鹽例如可例示十二烷基苯磺酸之金屬鹽或全氟烷磺酸之金屬鹽等。有機磺酸鹼(土類)金屬鹽之含量相對於上述絕緣層(B)100質量份為0.5質量份以下較為合適,較佳為0.001~0.3質量份,更佳為0.005~0.2質量份。特佳為鉀、銫及銣等之鹼金屬鹽。
作為抗靜電劑,例如可例舉:(3)烷磺酸銨鹽及芳基磺酸銨鹽等有機磺酸銨鹽。該銨鹽之含量相對於上述絕緣層(B)100質量份為0.05質量份以下較為合適。作為抗靜電劑,例如可例舉:(4)聚醚酯醯胺之類的含有聚(氧伸烷基)二醇成分作為其構成成分之聚合物。該聚合物之含量相對於上述絕緣層(B)100質量份為5質量份以下較為合適。
(IX)填充材
可於上述絕緣層(B)中摻合公知之各種填充材作為除纖維狀填充劑以外之補強填料。作為該填充材,可例舉各種板狀填充材及粒狀填充材。此處,板狀填充材係其形狀為板狀(包括表面具有凹凸者或板具有彎曲者)之填充材。粒狀填充材係包括不定形狀之除其等以外之形狀之填充材。
作為板狀填充材,可較佳地例示:玻璃薄片、滑石、雲母、高嶺土、金屬薄片、碳薄片及石墨、以及該等填充劑經例如金屬或金屬氧化物等異種材料表面被覆而成之板狀填充材等。其粒徑較佳為處於0.1~300 μm之範圍內。當該粒徑處於大致10 μm以下之範圍時,係利用液相沈積法之一的X射線穿透法測得之粒徑分佈之中值粒徑(D50)之值,當處於10~50 μm之範圍內時,係利用雷射繞射散射法測得之粒徑分佈之中值粒徑(D50)之值,當處於50~300 μm之範圍時,係利用振動式篩分法所得之值。該粒徑係在樹脂組成物中之粒徑。板狀填充材可藉由各種矽烷系、鈦酸酯系、鋁酸酯系及鋯酸酯系等之偶合劑進行表面處理,又,亦可藉由烯烴系樹脂、苯乙烯系樹脂、丙烯酸系樹脂、聚酯系樹脂、環氧系樹脂及胺酯系樹脂等各種樹脂或高級脂肪酸酯等進行集束處理,或者為經壓縮處理之造粒物。
(X)其他樹脂或彈性體
於不損害本發明之效果之範圍,亦可於上述絕緣層(B)中以較少比例使用其他樹脂或彈性體來代替樹脂成分之一部分。其他樹脂或彈性體之摻合量相對於上述絕緣層(B)100質量份,較佳為20質量份以下,更佳為10質量份以下,進而較佳為5質量份以下,最佳為3質量份以下。作為該其他樹脂,例如可例舉:聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯等聚酯樹脂;聚醯胺樹脂、聚醯亞胺樹脂、聚醚醯亞胺樹脂、聚胺酯樹脂、聚矽氧樹脂、聚苯醚樹脂、聚苯硫醚樹脂、聚碸樹脂、聚甲基丙烯酸酯樹脂、酚樹脂、環氧樹脂等樹脂。又,作為彈性體,例如可例舉:異丁烯/異戊二烯橡膠、苯乙烯/丁二烯橡膠、乙烯/丙烯橡膠、丙烯酸系彈性體、聚酯系彈性體、聚醯胺系彈性體、作為核殼型彈性體之MBS(甲基丙烯酸甲酯/苯乙烯/丁二烯)橡膠、MB(甲基丙烯酸甲酯/丁二烯)橡膠、MAS(甲基丙烯酸甲酯/丙烯腈/苯乙烯)橡膠、氟橡膠、含氟彈性體等。
(XI)其他添加劑
可於上述絕緣層(B)中摻合其他流動改質劑、抗菌劑、液態石蠟之類的分散劑、光觸媒系防污劑及光致變色劑等。
上述絕緣層(B)較佳為芳香族聚醚酮樹脂(I)及含氟共聚物(II)之合計為100質量%~50質量%。當該合計未達50質量%時,存在失去所需拉伸伸長率的隱憂。
上述絕緣層(B)之厚度為30~300 μm。就設置電線之裝置之小型化之觀點而言,較佳為厚度較薄,詳細而言,較佳為250 μm以下,更佳為150 μm以下,進而較佳為100 μm以下。就確保絕緣性之觀點而言,絕緣層(B)之厚度較佳為35 μm以上,更佳為40 μm以上。當使絕緣層(B)過薄時,存在失去絕緣性並且產生針孔等成形不良的隱憂。本發明之絕緣電線即便於絕緣層(B)之厚度較薄之情形時亦能夠提高拉伸伸長率。
上述絕緣層(B)形成於上述導體(A)之外周。本發明之絕緣電線可為導體(A)與絕緣層(B)直接相接者,亦可為導體(A)與絕緣層(B)之間包含1層以上之其他樹脂層的多層電線。又,本發明之絕緣電線還可為於絕緣層(B)之外周進而包含1層以上之其他樹脂層的多層電線。
上述其他樹脂層較佳為由下述樹脂所構成的層,該樹脂係選自由芳香族聚醚酮樹脂、氟樹脂、聚醯胺醯亞胺、聚醚醯亞胺、聚醚碸、聚苯硫醚、聚伸苯基碸、聚芳酯、液晶聚合物、聚醯胺、聚縮醛、聚碳酸酯、聚酯、聚苯乙烯、聚苯醚、聚氯乙烯、聚乙烯、聚丙烯、聚苯乙烯、ABS(丙烯腈/丁二烯/苯乙烯)樹脂、AS(丙烯腈/苯乙烯)樹脂、丙烯酸樹脂、酚樹脂、環氧樹脂、不飽和聚酯、矽樹脂、聚胺酯、尿素樹脂及三聚氰胺樹脂等所組成之群中至少1種。
上述多層電線可藉由以先前公知之串聯擠出法或使用多層模具之成型法,將構成各層之樹脂或樹脂組成物擠出成形為導體而簡便地製造。
作為上述導體(A)之形成材料,無特別限制,只要為導電性良好之材料即可,例如可例舉:銅、銅合金、銅包覆鋁、鋁、銀、金、鍍鋅鐵、碳等。上述導體(A)之形狀無特別限定,可為圓形,亦可為扁平形。上述導體(A)亦可為對銅施以鍍鎳或鍍銀而成者。
本發明之絕緣電線中所使用之絕緣層(B)亦可含有發泡絕緣層。發泡絕緣層之厚度並無特別限制。又,發泡絕緣層可由1層構成,亦可由2層以上之多層所構成。
本發明之絕緣電線較佳為拉伸伸長率為100%以上。拉伸伸長率更佳為150%以上,進而較佳為170%以上。拉伸伸長率越高越好,上限值並無限定,可為300%。
本發明之絕緣電線例如可較佳地用於航空航太用電線、地下輸電電纜、海底電力電纜、高壓電纜、超導電纜、纏繞電線、汽車用電線、線束/電力組件、機器人/FA用電線、OA機器用電線、資訊裝置用電線(光纜、LAN纜線、HDMI(註冊商標)纜線、閃電數據線(lightning cable)、音訊纜線等)、通信基站用內部配線、大電流內部配線(變流器、電力調整器、蓄電池系統等)、電子機器內部配線、小型電子機器/移動(mobile)配線、可動部配線、電氣設備內部配線、測定機器類內部配線、電力電纜(建設用、風力/太陽能發電用等)、控制/儀器裝配配線用纜線等。又,亦可較佳地用作線圈繞組(電磁線),若使用本發明之絕緣電線,則不容易於捲線加工中產生損傷。上述繞組適用於馬達、旋轉電機、壓縮機、變壓器(transformer)等,其所具有之特性亦足以承受在要求高電壓、高電流及高熱導率且需要進行高密度捲線加工之小型化/高輸出化馬達中之使用。又,亦適宜作為配電、輸電或通信用電線。
本發明之絕緣電線例如可藉由包括下述步驟之製造方法來製造:含芳香族聚醚酮樹脂(I)及含氟共聚物(II)之樹脂組成物之製備步驟;以及使上述樹脂組成物成形,於導體(A)之外周形成絕緣層(B)的成形步驟。
作為製造上述樹脂組成物之方法,例如可例舉如下方法等:將芳香族聚醚酮樹脂(I)及含氟共聚物(II)以適當之比例投入混合機中,視需要添加上述其他成分,於芳香族聚醚酮樹脂(I)及含氟共聚物(II)之熔點以上之溫度下進行熔融混練,藉此進行製造。
上述其他成分可預先添加至芳香族聚醚酮樹脂(I)及含氟共聚物(II)中並加以混合,亦可於摻合芳香族聚醚酮樹脂(I)及含氟共聚物(II)時添加。
製備上述樹脂組成物之步驟較佳為對上述芳香族聚醚酮樹脂(I)及含氟共聚物(II)施加較高之剪切力,同時進行熔融混練之步驟。具體而言,較佳為以600秒
-1(/sec)以上之剪切速度進行熔融混練。
上述剪切速度更佳為700秒
-1(/sec)以上,進而較佳為750秒
-1(/sec)以上,特佳為800秒
-1(/sec)以上。藉此,能夠使含氟共聚物(II)以次微米級分散於芳香族聚醚酮樹脂(I)中,進而能夠於成形時抑制含氟共聚物(II)凝聚之行為。結果所得到之樹脂組成物之流動性更優異,又,能夠提供薄壁加工性提昇且拉伸伸長率較高之絕緣層(B)。
再者,上述剪切速度(γ)係例如使用下述式而求出之值。
γ=πDr/C
D:螺桿外徑(mm)
r:螺桿轉速(rpm)
C:葉尖間隙(mm)
上述熔融混練較佳為在對上述芳香族聚醚酮樹脂及上述含氟共聚物施加較高之剪切力的同時實施。上述熔融混練中所使用之裝置並無特別限定,可藉由準備特殊螺桿及高轉速、窄間隙等能夠進一步有效地加以剪切之混練條件來實施,亦可利用先前使用之雙軸擠出機、單軸擠出機、多軸擠出機、串聯擠出機或批次式混練機即輥軋機、混練機(Laboplastomill)、班布里混合機、加壓捏合機、混合研磨機加以實施。藉此,能夠使上述含氟共聚物以次微米級分散於上述芳香族聚醚酮樹脂中,進而能夠於成形時抑制含氟共聚物凝聚之行為。其結果為,所得到之絕緣層(B)之表面不會剝離,又,能夠提供薄壁加工性提昇且拉伸伸長率較高之絕緣層(B)。作為能夠施加高剪切力之裝置,較佳為使用雙軸擠出機或混練部中具有內部回路型螺桿之高剪切加工機(回流式高剪切加工機)來實施。
內部回路型螺桿係從前端部向後端側形成有沿著螺桿中心軸之回路孔的螺桿。於混練部中具有內部回路型螺桿之高剪切加工機中,形成下述循環:注入至混練部中之熔融樹脂隨著內部回路型螺桿之旋轉而被輸送至前端側,從前端部之流入口流入至回路孔,向後方流動,從流出口流出,再次隨著內部回路型螺桿之旋轉被輸送至前端側。藉由該循環,熔融樹脂被高度分散、混合,能夠使分散相之尺寸變小。作為上述高剪切加工機,可例示日本特開2005-313608號公報、日本特開2011-046103號公報等中所記載之裝置。
於使用雙軸擠出機作為混練機之情形時,較佳為使用具有L/D較大之螺桿構成之雙軸擠出機。雙軸擠出機之螺桿構成較佳為L/D=30以上,更佳為L/D=35以上,進而較佳為L/D=40以上。再者,L/D係螺桿之有效長度(L)/螺桿直徑(D)。就提高混練性、生產性之觀點而言,最佳為利用雙軸擠出機進行熔融混練。
上述熔融混練之時間較佳為1~600秒,更佳為5~300秒。當熔融混練時間長於上述時間時,樹脂之劣化較為顯著,存在無法表現出所需性能的隱憂。又,當熔融混練時間短於上述時間時,分散性變差,存在無法獲得所需性能的隱憂。
上述熔融混練之溫度需要為上述芳香族聚醚酮樹脂之熔點以上且上述含氟共聚物(II)之熔點以上,較佳為240~450℃,更佳為260~400℃。
形成上述絕緣層(B)之方法並無特別限定,可設為各種條件並能以先前公知的方式進行。又,可使絕緣層(B)直接形成於導體(A)之上,或者亦可介隔其他層,例如其他樹脂層形成於導體(A)之上。
絕緣層(B)可藉由下述方法等形成:將上述樹脂組成物熔融擠出至導體(A)之表面或預先形成有其他樹脂層之導體(A)之該樹脂層之表面而形成的方法;或者,預先將樹脂組成物熔融擠出而製造膜,將該膜切割成特定大小之長條後,將該膜捲繞於導體(A)之表面或預先形成有其他樹脂層之導體(A)之該樹脂層之表面的方法。
於藉由熔融擠出來形成絕緣層(B)之情形時,形成之溫度通常較佳為所使用之上述芳香族聚醚酮樹脂(I)之熔點以上之溫度。又,成形溫度較佳為未達下述之溫度,即,上述含氟共聚物(II)之分解溫度及上述芳香族聚醚酮樹脂(I)之分解溫度中較低者之溫度。作為此種成形溫度,例如可為250~400℃。作為成形溫度,較佳為320~400℃。
本發明之絕緣電線可於形成絕緣層(B)之後進行加熱。上述加熱可於氟樹脂之熔點附近之溫度進行加熱。
本發明之樹脂組成物包含芳香族聚醚酮樹脂(I)及含氟共聚物(II),且於60 sec
-1、390℃之熔融黏度為0.40~0.75 kPa·s,上述芳香族聚醚酮樹脂(I)於60 sec
-1、390℃之熔融黏度為0.30 kPa·s以下。
藉由使芳香族聚醚酮樹脂(I)具有上述構成,能夠形成加工特性及拉伸伸長率優異之層。
本發明之樹脂組成物可較佳地用作絕緣電線中之絕緣層。本發明之絕緣電線中之絕緣層(B)、以及絕緣層(B)中所含有之芳香族聚醚酮樹脂(I)及含氟共聚物(II)之較佳形態亦可全部應用於本發明之樹脂組成物。
[實施例]
其次,舉出實施例對本發明進行說明,但本發明並非僅限定於該實施例。
<熔體流動速率(MFR)>
(1)含氟共聚物之MFR係依據ASTM D1238,於380℃、5000 g負載之條件下使用熔融指數測定儀進行測定。
(2)芳香族聚醚酮樹脂之MFR係依據ASTM D1238,於380℃、5000 g負載之條件下使用熔融指數測定儀進行測定。
<熔融黏度>
芳香族聚醚酮樹脂及絕緣層之熔融黏度係於60 sec
-1、390℃,依據ASTM D3835進行測定。
<熔點>
含氟共聚物之熔點係求出使用示差掃描熱測定(DSC)裝置以10℃/min之速度升溫時之熔解熱曲線中之極大值所對應的溫度作為其熔點。
芳香族聚醚酮樹脂之熔點係求出使用示差掃描熱測定(DSC)裝置以10℃/min之速度升溫時之熔解熱曲線中之極大值所對應的溫度作為其熔點。
<玻璃轉移溫度(Tg)>
藉由示差掃描熱測定(DSC)裝置進行測定。
<成形性>
於藉由熔融擠出以80 μm之厚度形成絕緣層(B)時,使用Zumbach製造之火花檢測器施加2 kV之電壓,於試製電線時檢查有無火花檢測器錯誤。每10000 m錯誤發生頻度為3次以上者記為×(不合格),未達3次者記為○(合格)。
<射出成形品之製作>
於120℃對實施例、比較例中所製造之樹脂組成物進行8小時乾燥後,利用小型射出成形機進行射出成形,藉此得到依據JIS K7161-2之試驗片。
<相對介電常數>
使用OMax製造之水刀從上述射出成型品切出試驗片(1.5×1.5×8.0 cm)。利用空腔共振擾動法(關東電子應用開發(股)製造之介電常數測定裝置、安捷倫科技(股)製造之網路分析儀)針對切出之試驗片測定於6 GHz之相對介電常數。
<拉伸伸長率>
拉伸伸長率係使用島津製作所公司製造之Autograph AGS-100NX進行測定。將電線切成10 cm,抽出導體,採取管狀絕緣層,作為試樣。使用上述拉伸試驗機,以50 mm/s之拉伸速度進行拉伸試驗。將夾頭間距離設為27 mm,將標線間距離設為25 mm,於n=5之試驗中求出斷裂時之標線間之伸長率平均值。
<耐裂痕試驗>
將電線切成15 cm,以不超過1次/秒之速度捲繞於直徑與絕緣電線相同之捲繞棒10次。捲繞後,以不超過1次/秒之速度回捲。於回捲操作之後,確認有無絕緣層之剝離或開裂等異常。每一實施例中進行5根之試驗,產生了異常之根數為2根以上者記為×(不合格),未達2根者記為○(合格)。
<平均分散粒徑>
藉由沿長度方向垂直地切削所形成之絕緣層,而得到測定樣品,使用共焦雷射顯微鏡確認其剖面。使用影像解析軟體(Image J)來解析所得到之顯微鏡影像。選擇分散相,求出圓等效直徑。算出20個分散相之圓等效直徑,將其平均值作為平均分散粒徑。
<平均分散粒徑比>
使用實施例中所得到之混練物(樹脂組成物),測定按照ASTM D1238在380℃、5000 g負載及5分鐘預熱而測定熔體流動速率後之含氟共聚物(II)之平均分散粒徑r2,求出其與測定前之平均分散粒徑r1之比r2/r1。
於實施例及比較例中,使用下述材料。
芳香族聚醚酮樹脂(1):聚醚酮酮(熔融黏度:0.20 kPa·s;熔點:332℃;Tg:162℃)
芳香族聚醚酮樹脂(2):聚醚醚酮(熔融黏度:0.26 kPa·s;熔點:343℃;Tg:149℃)
芳香族聚醚酮樹脂(3):聚醚醚酮(熔融黏度:0.19 kPa·s;熔點:343℃;Tg:147℃)
芳香族聚醚酮樹脂(4):聚醚酮酮(熔融黏度:0.37 kPa·s;熔點:356℃;Tg:160℃)
芳香族聚醚酮樹脂(5):聚醚醚酮(熔融黏度:0.17 kPa·s;熔點:343℃;Tg:150℃)
芳香族聚醚酮樹脂(6):聚醚醚酮(熔融黏度:1.14 kPa·s;熔點:334℃;Tg:143℃)
含氟共聚物(1):TFE/HFP/PPVE共聚物。MFR:29.8 g/10 min。熔點:255℃。
含氟共聚物(2):TFE/HFP/PPVE共聚物。MFR:12.3 g/10 min。熔點:250~260℃。
含氟共聚物(3):TFE/HFP共聚物。MFR:6 g/10 min。熔點:270℃。
實施例1~7及比較例1~4
將芳香族聚醚酮樹脂(1)~(6)中任一者與含氟共聚物(1)~(3)中任一者以表1所示之比例(質量%)乾摻,於120℃乾燥8小時,針對由此獲得者,於以下所示之規定條件下使用回流式高剪切加工機(NIIGATA MACHINE TECHNO股份有限公司製造)進行熔融混練,而得到樹脂組成物。再者,使用回路孔之直徑為ϕ2.5 mm者。
螺桿之L/D:1.8
混練溫度:370℃
混練時之剪切速度:870秒
-1混練時間:10秒
絕緣層之擠出中所使用之單軸擠出機係設為料缸直徑30 mm、L/D=22、模具內徑16 mm、葉尖外徑10.5 mm。以370~395℃之料缸溫度、12 rpm之螺桿轉速,使上述單軸擠出機運轉,從料斗供給藉由上述步驟所得之樹脂組成物。由流出之熔融樹脂組成物,於導體(A)(直徑0.5 mm、截面面積0.20 mm
2、軟銅線之實心線)上形成厚度為40 μm、100 μm、150 μm或300 μm之絕緣層(B),而得到絕緣電線。此時之線速度係設為18 m/min。
對所得到之絕緣電線進行各種評價。將結果示於表1。
[表1]
實施例1 | 實施例2 | 實施例3 | 實施例4 | 實施例5 | 實施例6 | 實施例7 | 比較例1 | 比較例2 | 比較例3 | 比較例4 | |
芳香族聚醚酮樹脂(1) (質量份) | 80 | 60 | 60 | 60 | 50 | ||||||
芳香族聚醚酮樹脂(2) (質量份) | 40 | ||||||||||
芳香族聚醚酮樹脂(3) (質量份) | 50 | ||||||||||
芳香族聚醚酮樹脂(4) (質量份) | 80 | ||||||||||
芳香族聚醚酮樹脂(5) (質量份) | 60 | 80 | |||||||||
芳香族聚醚酮樹脂(6) (質量份) | 50 | ||||||||||
含氟共聚物(1)(質量份) | 20 | 40 | 40 | 40 | 50 | 20 | 50 | ||||
含氟共聚物(2)(質量份) | 60 | 50 | |||||||||
含氟共聚物(3)(質量份) | 40 | 20 | |||||||||
芳香族聚醚酮樹脂之熔融黏度(kPa·s) | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.26 | 0.19 | 0.37 | 1.14 | 0.17 | 0.17 |
絕緣層之熔融黏度(kPa·s) | 0.69 | 0.7 | 0.7 | 0.7 | 0.62 | 0.57 | 0.52 | 0.46 | 0.65 | 0.95 | 0.8 |
絕緣層之厚度(μm) | 100 | 40 | 150 | 300 | 150 | 100 | 100 | 100 | 100 | 100 | 100 |
平均分散粒徑比(r2/r1) | 1.24 | 1.28 | 1.3 | 1.47 | 1.54 | 1.56 | 1.49 | 1.61 | - ※ | 1.46 | 1.36 |
成形性(火花檢測器(2 kV、膜厚80 μm)) | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | × | × | × |
相對介電常數 | 2.7 | 2.5 | 2.5 | 2.5 | 2.4 | 2.5 | 2.6 | 2.7 | 2.5 | 2.5 | 2.7 |
拉伸伸長率(%) | 212 | 228 | 194 | 152 | 172 | 156 | 167 | 86 | 13 | 56 | 92 |
耐裂痕試驗 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | × | ○ | ○ |
※因相轉移而無法測定 |
無。
無。
無。
Claims (10)
- 一種絕緣電線,其具有導體(A)及形成於上述導體(A)之外周的絕緣層(B),且特徵在於:上述絕緣層(B)含有芳香族聚醚酮樹脂(I)及含氟共聚物(II),且於60sec-1、390℃之熔融黏度為0.40~0.75kPa.s,上述芳香族聚醚酮樹脂(I)於60sec-1、390℃之熔融黏度為0.30kPa.s以下,上述絕緣層(B)之厚度為30~300μm。
- 如請求項1之絕緣電線,其中,上述絕緣層(B)之上述含氟共聚物(II)之平均分散粒徑r1、與按照ASTM D1238在380℃、5000g負載及5分鐘預熱而測定熔體流動速率後之上述含氟共聚物(II)之平均分散粒徑r2的比r2/r1為1.60以下。
- 如請求項1或2之絕緣電線,其拉伸伸長率為100%以上。
- 如請求項1或2之絕緣電線,其中,上述芳香族聚醚酮樹脂(I)之熔點為300~380℃。
- 如請求項1或2之絕緣電線,其中,上述芳香族聚醚酮樹脂(I)之玻璃轉移溫度為130~220℃。
- 如請求項1或2之絕緣電線,其中,上述含氟共聚物(II)之熔點為200~323℃。
- 如請求項1或2之絕緣電線,其中,上述含氟共聚物(II)係四氟乙烯與由下述通式(1)所表示之全氟乙烯性不飽和化合物之共聚物,CF2=CF-Rf1 (1)(式中,Rf1表示-CF3或-ORf2;Rf2表示碳數1~5之全氟烷基)。
- 如請求項1或2之絕緣電線,其中,上述絕緣層(B)之上述芳香族聚醚酮樹脂(I)與上述含氟共聚物(II)之質量比(I):(II)為99:1~30: 70。
- 如請求項1或2之絕緣電線,其中,上述芳香族聚醚酮樹脂(I)為聚醚酮酮。
- 一種樹脂組成物,其含有芳香族聚醚酮樹脂(I)及含氟共聚物(II),且於60sec-1、390℃之熔融黏度為0.40~0.75kPa.s,上述芳香族聚醚酮樹脂(I)於60sec-1、390℃之熔融黏度為0.30kPa.s以下。
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