TWI659850B - 多層耐熱隔板材料及其製造方法 - Google Patents
多層耐熱隔板材料及其製造方法 Download PDFInfo
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- TWI659850B TWI659850B TW105102589A TW105102589A TWI659850B TW I659850 B TWI659850 B TW I659850B TW 105102589 A TW105102589 A TW 105102589A TW 105102589 A TW105102589 A TW 105102589A TW I659850 B TWI659850 B TW I659850B
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- resistant
- heat
- film
- separator material
- inorganic heat
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 229920000098 polyolefin Polymers 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 17
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
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- 150000001993 dienes Chemical class 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 230000010220 ion permeability Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
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- 150000004692 metal hydroxides Chemical class 0.000 description 1
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- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
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Classifications
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Abstract
本發明的目的在於提供一種翹曲或卷邊產生受到抑制的多層耐熱隔板材料。本發明的多層耐熱隔板材料是於含有聚烯烴製微多孔膜的基材膜的至少單面積層無機耐熱層而成,其卷邊高度低於10 mm,所述聚烯烴製微多孔膜於100℃下以10 N/mm2
拉伸時的伸長率為2%以下。在所述多層耐熱隔板材料的製造中,於80℃~120℃的溫度下、且4 N/mm2
~10 N/mm2
的拉伸力下將無機耐熱層乾燥、固化。
Description
本發明是有關於一種多層耐熱隔板材料及其製造方法。
聚烯烴製的微多孔膜可用於分離膜、電池隔板、電容器等。其中,電池隔板用途隨著近年的鋰離子電池的大力開發而受到關注。電池隔板是作為電解質的隔壁而發揮功能的構件,同時,其離子透過性是與電池的充放電能力有直接關係的功能。
近年來,謀求適於車輛或可攜式終端的鋰離子電池或鎳氫電池等小型且能量密度高、高輸出、耐久性或安全性高的電池。於此種電池中,介隔電解質層而含有聚烯烴製微多孔膜的電池隔板與片材狀電極是以積層或纏繞於電池本體內部的狀態配置於本體內部。
若電池內部的溫度高至聚烯烴的熔融溫度以上,則構成隔板的聚烯烴熔融而阻塞隔板的孔,電極間的離子移動停止而喪失電池功能。該停機動作是防止電池起火或冒煙的重要功能,是與離子傳導性並列的隔板的重要功能。然而,報告有該停機功能不足,電池內部溫度超過150℃而起火的事故例。
因此,最近為了進一步提高電池的耐熱性,而開發有隔
板被覆有無機粒子層的多層耐熱隔板材料。多層耐熱隔板材料是藉由在聚烯烴製微多孔膜等基材膜塗佈含有無機粒子與黏合劑的耐熱層材料並加以乾燥而製造。
然而,積層不同種材料獲得的隔板材料所特有的問題被指出。此種多層隔板材料存在日常因基材膜與耐熱材料層的收縮率的差而導致產生「翹曲」或「卷邊」之類的應變的問題。
專利文獻1、專利文獻2記載有防止積層以無機物質為主成分的耐熱層與含有樹脂的基材的情形時的卷邊的方法。專利文獻1記載有藉由調節基材膜與耐熱層的厚度來防止卷邊。專利文獻2記載有藉由於多層耐熱隔板材料的特定部位設置低空位區域來防止卷邊。然而,由於專利文獻1、專利文獻2所記載的多層隔板材料的基材實質上為聚乙烯製微多孔膜,因此可應用專利文獻1、專利文獻2所記載的卷邊防止方法的多層隔板材料受到限制。
如專利文獻3所記載般,本發明的申請人已成功地於聚烯烴製微多孔膜商品塗佈含有無機填料的塗敷液,形成耐熱層而製造多層耐熱隔板材料。然而,在專利文獻3所記載的多層耐熱隔板材料中,並未對卷邊防止進行研究。
[專利文獻1]國際公開第2012/176669號說明書
[專利文獻2]國際公開第2013/031012號說明書
[專利文獻3]國際公開第2014/030507號說明書
如上所述,尚未對抑制於聚烯烴製基材膜設置有耐熱層的多層耐熱隔板材料的卷邊的產生的方法進行充分研究。因此,本發明的發明者對使用聚烯烴製基材膜確實地抑制翹曲或卷邊產生的多層耐熱隔板材料進行了銳意研究。
其結果,發現藉由選擇特定的聚烯烴製微多孔膜作為基材,且於特定的條件下形成耐熱層,而顯著地抑制多層耐熱隔板材料的翹曲或卷邊。
即,本發明為以下者。
(發明1)一種多層耐熱隔板材料,其是於含有聚烯烴製微多孔膜的基材膜的至少單面積層無機耐熱層而成,所述聚烯烴製微多孔膜於100℃下以10N/mm2拉伸時的伸長率為2%以下,所述基材膜的厚度為10μm~30μm,所述無機耐熱層的1層的厚度為1μm~5μm,且藉由以下的方法(a)測定的卷邊高度低於10mm。
卷邊高度的測定方法(a):將自多層耐熱隔板材料切下的長度方向30cm×寬度方向20cm的長方形樣品於25℃環境下靜置24小時後,以收縮的表面側成為上表面的方式置於水平台上,測定樣品的四角距台的高度(mm),以4個高度(mm)的平均值(mm)作為卷邊高度(mm)而算出。
(發明2)如發明1的多層耐熱隔板材料,其中聚烯烴製微多孔膜是藉由包括冷延伸步驟與熱延伸步驟的乾式法將聚烯烴微多孔化而得的聚烯烴製微多孔膜。
(發明3)如發明1或發明2的多層耐熱隔板材料,其中聚烯烴製微多孔膜是熔流速率(melt mass-flow rate,MFR)(JIS K 6758,230℃,荷重21.18N)為0.1g/10分鐘~1.0g/10分鐘、熔點為150℃~170℃的可含有選自乙烯及碳數4~8的α-烯烴中的至少一種的丙烯聚合物。
(發明4)如發明1至發明3中任一項的多層耐熱隔板材料,其中無機耐熱層含有氧化鋁與黏合劑。
(發明5)一種多層耐熱隔板材料的製造方法,其包括以下步驟。
(步驟1)製造於100℃下以10N/mm2拉伸時的伸長率為2%以下、厚度為10μm~30μm的聚烯烴製微多孔膜的步驟。
(步驟2)於含有步驟1中獲得的聚烯烴製微多孔膜的基材膜的至少單面塗敷含有無機耐熱粒子與黏合劑的無機耐熱層劑的步驟。
(步驟3)於80℃~120℃的溫度下、且4N/mm2~10N/mm2的拉伸力下乾燥步驟2中獲得的膜而乾燥無機耐熱層劑的步驟。
(發明6)如發明5的多層耐熱隔板材料的製造方法,其中於步驟1中,藉由包括冷延伸步驟與熱延伸步驟的乾式法將聚烯烴微多孔膜化。
(發明7)如發明5或發明6的多層耐熱隔板材料的製造方法,其中於步驟1中,藉由包括冷延伸步驟與熱延伸步驟的乾式法將MFR(JIS K 6758,230℃,荷重21.18N)為0.1g/10分鐘~1.0g/10分鐘、熔點為150℃~170℃的可任意含有選自乙烯及碳數4~8的α-烯烴中的至少一種的丙烯聚合物微多孔膜化。
(發明8)如發明5至發明7中任一項的多層耐熱隔板材料的製造方法,其中於步驟2中使用含有氧化鋁與黏合劑的無機耐熱層劑。
本發明的多層耐熱隔板的卷邊被抑制為實用上無問題的範圍。於將結束所述步驟3後的多層耐熱隔板材料於25℃下在平台上保管24小時的情形時,即便所述隔板材料的端部因產生卷邊而自台的表面隆起,在長度方向30cm×寬度方向20cm的長方形樣品中,亦可將隆起量(自台表面至端部為止的高度)抑制為10mm以下。此種卷邊產生受到抑制的多層耐熱隔板材料在加工成電池隔板材料時實質上並無問題,不會妨礙電池性能。
[多層耐熱隔板材料]
本發明的多層耐熱隔板材料是於含有聚烯烴製微多孔膜的基材膜的至少單面積層無機耐熱層而成,所述聚烯烴製微多孔膜於
100℃下以10N/mm2拉伸時的伸長率為2%以下,所述基材膜的厚度為10μm~30μm,所述無機耐熱層的1層的厚度為1μm~5μm,且藉由以下的方法(a)測定的卷邊高度低於10mm。
卷邊高度的測定方法(a):將自多層耐熱隔板材料切下的長度方向30cm×寬度方向20cm的長方形樣品於25℃環境下靜置24小時後,以收縮的表面側成為上表面的方式置於水平台上,測定樣品的四角距台的高度(mm),以4個高度(mm)的平均值(mm)作為卷邊高度(mm)而算出。
[基材膜]
本發明所使用的基材膜是聚烯烴製微多孔膜。聚烯烴是將以烯烴類作為主體的單體聚合而得的聚合物。作為烯烴類,具代表性者為碳數2~10的直鏈狀烯烴類。可將該些與2-甲基丙烯、3-甲基-1-丁烯、4-甲基-1-戊烯等碳數4~8的支鏈狀烯烴類、苯乙烯類、二烯類併用。具代表性的聚烯烴是被稱為聚乙烯、聚丙烯的聚合物。聚乙烯是乙烯均聚物或將乙烯與含有選自碳數3~8的α-烯烴中的至少一種的共聚物共聚合而得的聚合物。聚丙烯是丙烯均聚物、或將丙烯與含有選自乙烯及碳數4~8的α-烯烴中的至少一種的共聚物共聚合而得的聚合物。
作為本發明所使用的基材膜的原料,較佳為高結晶性且高熔點的聚丙烯。尤佳的聚丙烯是熔流速率(MFR(melt mass-flow rate),於依照JIS K 6758(230℃,21.18N)的條件下測定)為0.1g/10分鐘~1.0g/10分鐘、熔點為150℃~170℃的可含有選自
乙烯及碳數4~8的α-烯烴中的至少一種的丙烯的聚合物。所述共聚物的含量只要基材膜滿足規定的伸長率條件,則可為任意範圍。
本發明所使用的基材膜滿足特定的伸長率條件。即,含有基材膜的試片於100℃下使用拉伸試驗機以10N/mm2拉伸時的伸長率處於2%以下的範圍。伸長率(%)是藉由以下的式求出。
伸長率(%)=[(拉伸後的試片的長度(mm))-(初期的試片的長度(mm))]/(初期的試片的長度(mm))×100
可於本發明的微多孔膜的原料中調配結晶成核劑或填充劑等添加劑。添加劑的種類或量只要滿足所述伸長率的條件,且為不損及隔板材料的基材所需的多孔性的範圍,則並無限制。
[基材膜的製造]
本發明所使用的基材膜只要為滿足上述的伸長率條件的聚烯烴製微多孔膜,則可為任意者。作為此種基材膜,較佳為因不使用有機溶媒而於成本方面有利的藉由所謂的乾式法所製造的聚烯烴製微多孔膜。作為此種聚烯烴製微多孔膜,尤佳為藉由包括以下的製膜步驟、熱處理步驟、冷延伸步驟、熱延伸步驟、鬆弛步驟的乾式法所製造的空位率為45%以上的微多孔膜。
(製膜步驟)
製膜步驟是將原料擠出成形而製造原片膜的步驟。將原料聚烯烴供於擠出機,於原料聚烯烴的熔點以上的溫度下將其熔融混煉,自安裝於擠出機前端的模頭將含有原料的聚烯烴的膜擠出。所使用的擠出機並無限定。作為擠出機,例如可使用單軸擠出機、
雙軸擠出機、串列型擠出機的任一種。所使用的模頭只要為用於膜成形者,則可使用任一種。作為模頭,例如可使用各種T型模頭。原片膜的厚度或形狀並無特別限定。較佳為模唇間隙與原片膜厚度的比(牽伸比)為100以上,進而較佳為150以上。較佳為原片膜的厚度為10μm~200μm,進而較佳為15μm~100μm。
(熱處理步驟)
熱處理步驟是對結束製膜步驟後的原片膜進行熱處理的步驟。於較原料聚烯烴的熔點低5℃~65℃、較佳為10℃~25℃的溫度下對原片膜施加長度方向的一定的張力。較佳的張力為原片膜的長度成為超過1.0倍且為1.1倍以下的大小。
(冷延伸步驟)
冷延伸步驟是於相對較低的溫度下將結束熱處理步驟後的原片膜延伸的步驟。延伸溫度為-5℃~45℃,較佳為5℃~30℃。延伸倍率在長度方向上為1.0~1.1,較佳為1.00~1.08,進而較佳為1.02以上且小於1.05。但延伸倍率大於1.0倍。延伸手段並無限制。可使用輥延伸法、拉幅機延伸法等公知的手段。延伸的階段數可任意設定。可為1段延伸,亦可經由多個輥進行2段以上的延伸。在冷延伸步驟中,構成原片膜的聚丙烯系聚合物的分子進行配向。其結果,可獲得具有分子鏈密集的片層部、及片層間的分子鏈稀疏的區域(裂紋)的延伸膜。
(熱延伸步驟)
熱延伸步驟是於相對較高的溫度下將結束冷延伸步驟後的延
伸膜延伸的步驟。延伸溫度為較聚丙烯系聚合物的熔點低5℃~65℃的溫度,較佳為較原料聚烯烴的熔點低10℃~45℃的溫度。延伸倍率在長度方向上為1.5倍~4.5倍,較佳為2.0倍~4.0倍。延伸手段並無限制。可使用輥延伸法、拉幅機延伸法等公知的手段。延伸的階段數可任意設定。可為1段延伸,亦可經由多個輥進行2段以上的延伸。在熱延伸步驟中,冷延伸步驟所產生的裂紋被延展而產生空位。
(鬆弛步驟)
鬆弛步驟是為了防止結束熱延伸步驟後的延伸膜的收縮而使膜鬆弛的步驟。鬆弛溫度為較熱延伸的溫度略高的溫度,通常為高0℃~20℃的溫度。鬆弛的程度可以結束鬆弛步驟後的延伸膜的長度最終成為0.7倍~1.0倍的方式進行調整。由此完成本發明所使用的基材膜。最終的基材膜的厚度為15μm~30μm,較佳為15μm~25μm。
[基材膜的伸長率]
本發明所使用的基材膜滿足特定的伸長率條件。即,將含有基材膜的試片於100℃下使用拉伸試驗機以10N/mm2拉伸時的伸長率處於2%以下的範圍。伸長率(%)是藉由以下的式求出。
伸長率(%)=[(拉伸後的試片的長度(mm))-(初期的試片的長度(mm))]/(初期的試片的長度(mm))×100
[無機耐熱層]
於所述基材膜的至少單面形成無機耐熱層。無機耐熱層是藉
由將含有無機耐熱粒子、黏合劑、溶媒的無機耐熱層劑塗佈於基材膜並將塗敷液乾燥、固化而形成。
作為無機耐熱粒子,使用一次粒子徑為5nm~100nm、熔點為200℃以上、絕緣性高、電化學穩定的無機物。例如可使用:氧化鋁、二氧化矽、二氧化鈦、氧化鋯、氧化鎂、鈦酸鋇等金屬氧化物類;氫氧化鋁、氫氧化鎂等金屬氫氧化物類;勃姆石、滑石、高嶺土、沸石、磷灰石、禾樂石(halloysite)、葉蠟石、蒙脫石、絹雲母、雲母、鎂鋁蛇紋石(amesite)、膨潤石、矽酸鈣、矽酸鎂等黏土系礦物類。亦可使用含有多種無機耐熱粒子的混合物。較佳的無機耐熱粒子為氧化鋁、二氧化矽、二氧化鈦、勃姆石。
黏合劑是作為基材與無機耐熱粒子的結著劑而發揮功能。作為黏合劑,可使用聚烯烴、含氟樹脂、橡膠或彈性體、纖維素類、水溶性樹脂等各種樹脂。較佳的黏合劑為聚四氟乙烯類(Polytetrafluoroethylene,PTFE)、聚氟乙烯類(聚偏二氟乙烯(polyvinylidenefluoride,PVDF))。
無機耐熱粒子與黏合劑的量比例(無機耐熱粒子:黏合劑,重量比)通常處於40:60~98:2的範圍,較佳為處於50:50~95:5的範圍,更佳為處於60:40~90:10的範圍。
通常於無機耐熱層劑中添加溶媒。作為溶媒,可使用水或丙酮、N-甲基吡咯啶酮、二甲基乙醯胺、二甲基甲醯胺、二甲基亞碸等極性有機溶媒。
除了無機耐熱粒子與黏合劑以外,亦可視需要於所述無機耐熱層劑中調配分散劑、抗菌劑、殺菌劑等添加劑。
將如上所述的無機耐熱粒子、黏合劑、溶劑、添加劑等原料混合、攪拌而製備無機耐熱層劑。只要無機耐熱粒子均勻地分散於無機耐熱層劑中,則混合、攪拌的手段並無限制。通常使用均質器或珠磨機、及噴射磨機。
[多層耐熱隔板材料的製造方法]
本發明的多層耐熱隔板材料的製造方法包括以下步驟1~步驟3。
(步驟1)
步驟1為製造於100℃下以10N/mm2拉伸時的伸長率為2%以下、厚度為10μm~30μm的聚烯烴製微多孔膜的步驟。聚烯烴製微多孔膜的原料及其製造方法如上所述。
(步驟2)
步驟2為於含有步驟1中獲得的聚烯烴製微多孔膜的基材膜的至少單面塗敷含有無機耐熱粒子與黏合劑的無機耐熱層劑的步驟。塗敷手段並無限定。例如,只要為將液狀物塗佈為平面膜狀的手段,則可使用凹版印刷塗佈機、微型凹版印刷塗佈機、模塗機、刮刀式塗佈機等的任一種。在步驟2中,以設置於基材膜的其中一面的無機耐熱層劑的厚度成為1μm~5μm、較佳為1.5μm~4.0μm的方式塗敷無機耐熱層劑。
(步驟3)
步驟3為於80℃~120℃的溫度下、且4N/mm2~10N/mm2的拉伸力下乾燥步驟2中獲得的膜而乾燥無機耐熱層劑的步驟。伴隨著乾燥,無機耐熱層劑固化而形成無機耐熱層。結束步驟3後,形成1層的厚度為1μm~5μm、較佳為1.5μm~4μm的無機耐熱層。由此完成本發明的多層耐熱隔板材料。
(步驟4)
步驟4是所完成的多層耐熱隔板材料的捲繞步驟。通常在步驟3後進行。將步驟3中獲得的本發明的多層耐熱隔板材料捲繞於輥上,包裝並於出貨前保管。通常將數十米至數百米長度的膜捲繞於1根輥芯上。
[實施例]
(基材膜A的製造)
作為原料,使用依照JIS K 6758(230℃,21.18N)所測定的熔流速率(MFR)為0.5g/10分鐘、熔點為165℃的丙烯聚合物。
(1)將在單軸擠出機中熔融混煉的原料以牽伸比206自T模頭擠出,製造厚度17μm的原片膜。
(2)繼而,於150℃下對原片膜進行熱處理。
(3)於30℃下將原片膜沿長度方向冷延伸為1.03倍。
(4)將延伸加熱器溫度維持為230℃,將步驟3獲得的延伸膜沿長度方向熱延伸為2.8倍。
(5)以所得的延伸膜的長度成為0.88倍的方式使其鬆弛。由此獲得空位率超過45%的微多孔膜。將所得的微多孔膜作為基
材膜A而用於下文所述的實施例、比較例。
(基材膜A的伸長率)
自所得的微多孔膜切下5片(膜長度(MD)方向120mm)×(膜寬度(TD)方向10mm)的帶狀試片。在100℃恆溫槽中,使用島津製作所製造的拉伸試驗機(自動立體測圖儀AGS-X),對1片試片施加拉伸力。拉伸條件設為初期夾頭間距離:50mm、拉伸速度:50mm/分、拉伸方向:試片MD方向、殼大拉伸力:10N/mm2(每膜截面面積的拉伸力)。使用拉伸力達到10N/mm2的時點時的試片的MD方向的長度(MD-max)(mm)與拉伸前的試片的MD方向的長度(120mm),藉由以下的式算出試片的伸長率(%)。
伸長率(%)=((MD-max)-120)÷120×100
藉由與以上相同的順序求出5片試片的伸長率(%)。將5片試片的伸長率(%)的平均值作為基材膜A的伸長率(%)而算出。基材膜A的伸長率為1.7%。
(基材膜B的製造)
作為原料,使用依照JIS K 6758(230℃,21.18N)測定的熔流速率(MFR)為1.5g/10分鐘、熔點為158℃的丙烯聚合物。
(1)將在單軸擠出機中熔融混煉的原料以牽伸比205自T模頭擠出,製造厚度22μm的原片膜。
(2)繼而,於150℃下對原片膜進行熱處理。
(3)於30℃下,將原片膜沿長度方向冷延伸為1.07倍。
(4)將延伸加熱器溫度維持為175℃,將所得的延伸膜沿長度方向熱延伸為3.2倍。
(5)以所得的延伸膜的長度成為0.88倍的方式使其鬆弛。由此獲得空位率超過45%的微多孔膜。將所得的微多孔膜作為比較用基材膜B而用於下文所述的比較例。
(基材膜B的伸長率)
按照與基材膜A相同的順序求出基材膜B的伸長率,結果為2.4%。
(無機耐熱層劑C的製造)
使用Al2O3(日本艾羅西爾(AEROSIL)股份有限公司製造的AEROXIDE AluC)作為無機耐熱粒子,使用聚偏二氟乙烯(阿科瑪(Arkema)股份有限公司製造的Kyner HSV 500)作為黏合劑。首先,在作為溶媒的N-甲基吡咯啶酮(NMP)中添加無機耐熱粒子(重量濃度9%)與黏合劑(重量濃度3%),使用分散器以轉數500rpm攪拌1小時。進而,使用高壓處理裝置(吉田機械興業股份有限公司製造的Nanovater),以200MPa的處理壓將所得的漿料處理1次並加以混合,而獲得無機耐熱粒子與黏合劑均勻分散的無機耐熱層劑C。
(實施例1)
(步驟1)如上述般製造基材膜A。
(步驟2)藉由凹版印刷塗佈機於基材膜A的單面塗敷無機耐熱層劑C。所塗敷的無機耐熱層劑的厚度為4μm。
(步驟3)對塗敷有無機耐熱層劑的基材膜施加張力4.4N/mm2,搬送至溫度95℃的乾燥爐中,將無機耐熱層劑乾燥、固化。由此獲得本發明的方法的多層耐熱隔板材料。藉由以下方法評價該多層耐熱隔板材料的卷邊產生。
將步驟1~步驟3的條件、卷邊產生的評價結果示於表1。
(卷邊產生的評價方法)
自多層耐熱隔板材料切下(長度(MD)方向30cm)×(寬度(TD)方向20cm)的長方形試片。將試片於25℃環境下靜置24小時。其後,目視判定試片的哪個面收縮而產生卷邊。以收縮的面成為上表面的方式將試片置於水平台上,使樣品的四角與台分離。即,設為橫向觀察時試片於台上以谷型卷邊的狀態。測定四角各自距台的高度(mm)。高度(mm)取將小數點以下四捨五入而得的整數值(例如,於一角距台的高度為0.1mm的情形時,取0mm作為高度的值)。最後,以4個高度(mm)的平均值(mm)作為卷邊高度(mm)而算出。於卷邊高度為10mm以上的情形時判定為不合格品。
(實施例2~實施例9)
變更實施例1的步驟1~步驟3的條件而製造本發明的多層耐熱隔板材料。將各自的步驟1~步驟3的條件、卷邊產生的評價結果示於表1。
(比較例1~比較例9)
變更實施例1的步驟1~步驟3的條件而製造比較用的多層耐熱隔板材料。將各自的步驟1~步驟3的條件、卷邊產生的評價結果示於表1。
於在步驟1中使用基材膜A、且在步驟2中於80℃~120℃的溫度下、4N/mm2~10N/mm2的拉伸力下進行乾燥的實施例1~實施例9中,實質上並無卷邊產生,或即便產生卷邊亦抑制為實用上無問題的低於10mm。相對於此,於在步驟1中使用基材膜B、或步驟2的乾燥條件不符合規定的比較例1~比較例9中,產生10mm以上的卷邊高度,實用上存在問題。
[產業上之可利用性]
藉由本發明,可防止多層耐熱隔板材料產生卷邊。本發
明的卷邊產生受到抑制的多層耐熱隔板材料在電池組裝步驟或電池性能方面有利。本發明的多層耐熱隔板材料可作為優異的電池隔板材料而受到期待。
Claims (5)
- 一種多層耐熱隔板材料,其是於含有聚烯烴製微多孔膜的基材膜的至少單面積層無機耐熱層而成,所述聚烯烴製微多孔膜於100℃下以10N/mm2拉伸時的伸長率為2%以下,聚烯烴製微多孔膜是熔流速率(JIS K 6758,230℃,荷重21.18N)為0.1g/10分鐘~1.0g/10分鐘、熔點為150℃~170℃的可含有選自乙烯及碳數4~8的α-烯烴中的至少一種的丙烯聚合物,所述基材膜的厚度為10μm~30μm,所述無機耐熱層含有無機耐熱粒子與黏合劑,所述無機耐熱粒子為氧化鋁,且所述無機耐熱粒子的一次粒子徑為5nm~100nm,熔點為200℃以上;所述無機耐熱層的1層的厚度為1μm~5μm,且藉由以下的方法(a)測定的卷邊高度低於10mm;卷邊高度的測定方法(a):將自多層耐熱隔板材料切下的長度方向30cm×寬度方向20cm的長方形樣品於25℃環境下靜置24小時後,以收縮的表面側成為上表面的方式置於水平台上,測定樣品的四角距台的高度(mm),以4個高度(mm)的平均值(mm)作為卷邊高度(mm)而算出。
- 如申請專利範圍第1項所述的多層耐熱隔板材料,其中聚烯烴製微多孔膜是藉由包括冷延伸步驟與熱延伸步驟的乾式法將聚烯烴微多孔化而得的聚烯烴製微多孔膜。
- 一種多層耐熱隔板材料的製造方法,其包括以下步驟:(步驟1)製造於100℃下以10N/mm2拉伸時的伸長率為2%以下、厚度為10μm~30μm的聚烯烴製微多孔膜的步驟,所述聚烯烴製微多孔膜是熔流速率(JIS K 6758,230℃,荷重21.18N)為0.1g/10分鐘~1.0g/10分鐘、熔點為150℃~170℃的可含有選自乙烯及碳數4~8的α-烯烴中的至少一種的丙烯聚合物;(步驟2)於含有步驟1中獲得的聚烯烴製微多孔膜的基材膜的至少單面塗敷含有無機耐熱粒子與黏合劑的無機耐熱層劑的步驟,所述無機耐熱粒子為氧化鋁,且所述無機耐熱粒子的一次粒子徑為5nm~100nm,熔點為200℃以上;(步驟3)於80℃~120℃的溫度下、且4N/mm2~10N/mm2的拉伸力下乾燥步驟2中獲得的膜而乾燥無機耐熱層劑的步驟。
- 如申請專利範圍第3項所述的多層耐熱隔板材料的製造方法,其中於步驟1中,藉由包括冷延伸步驟與熱延伸步驟的乾式法將聚烯烴微多孔膜化。
- 如申請專利範圍第4項所述的多層耐熱隔板材料的製造方法,其中於步驟1中,藉由包括冷延伸步驟與熱延伸步驟的乾式法將熔流速率(JIS K 6758,230℃,荷重21.18N)為0.1g/10分鐘~1.0g/10分鐘、熔點為150℃~170℃的可任意含有選自乙烯及碳數4~8的α-烯烴中的至少一種的丙烯聚合物微多孔膜化。
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- 2016-01-22 CN CN201680007664.8A patent/CN107210413A/zh active Pending
- 2016-01-22 US US15/546,663 patent/US20180205056A1/en not_active Abandoned
- 2016-01-22 KR KR1020177023511A patent/KR20170107523A/ko unknown
- 2016-01-22 WO PCT/JP2016/051786 patent/WO2016121630A1/ja active Application Filing
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Publication number | Publication date |
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TW201634256A (zh) | 2016-10-01 |
JP2016143469A (ja) | 2016-08-08 |
JP6435886B2 (ja) | 2018-12-12 |
EP3252850A1 (en) | 2017-12-06 |
KR20170107523A (ko) | 2017-09-25 |
EP3252850B1 (en) | 2020-07-01 |
WO2016121630A1 (ja) | 2016-08-04 |
US20180205056A1 (en) | 2018-07-19 |
CN107210413A (zh) | 2017-09-26 |
EP3252850A4 (en) | 2018-10-17 |
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