TW201641555A - 複合膜之製造方法 - Google Patents
複合膜之製造方法 Download PDFInfo
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- TW201641555A TW201641555A TW104144092A TW104144092A TW201641555A TW 201641555 A TW201641555 A TW 201641555A TW 104144092 A TW104144092 A TW 104144092A TW 104144092 A TW104144092 A TW 104144092A TW 201641555 A TW201641555 A TW 201641555A
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- resin
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- 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
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- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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Abstract
本發明提供一種複合膜之製造方法,本發明之實施形態係具有下述步驟:以滿足下述式之溫度T熱處理含熱可塑性樹脂之多孔質基材的步驟,Tg+60℃≦溫度T≦Tm
(Tg表示熱可塑性樹脂的玻璃轉移溫度〔℃〕,Tm表示熱可塑性樹脂的熔點〔℃〕);將前述多孔質基材之機械方向的張力應力調整在多孔質基材之伸度成為2%以下的範圍,在熱處理後的前述多孔質基材之單面或雙面塗佈至少含樹脂及溶劑的塗佈液,形成塗佈層的步驟;使前述塗佈層凝固,得到在前述多孔質基材之單面或雙面具有至少含樹脂的多孔質層之複合膜的步驟。
Description
本發明係有關複合膜之製造方法。
以往作為電池隔膜、氣體濾片、液體濾片等,已知在多孔質基材的表面具有多孔質層之複合膜。作為複合膜之製造方法提出在基材膜之單面或雙面塗佈含有機高分子化合物的塗佈液形成塗佈層,然後,浸漬於凝固液使塗佈層凝固,經過水洗與乾燥製作多孔質層時,將各步驟間以10m/分鐘以上之速度連續地搬運的技術(例如參照特許第5134526號公報)。特許第5134526號公報中記載藉由濕式凝固法形成多孔質層的方法,已知濕式凝固法係作為能將含樹脂之多孔質層良好地進行多孔化的製法。
然而,例如二次電池用隔膜之製造過程中,
在基材塗佈所期望之液時,基材之一部分產生鬆弛時,或有在基材本身存在表面凹凸或厚度不均之情形。如此在基材之不均勻係不僅引起塗佈層的膜厚之不均勻,視情形甚至會發生無法塗佈之未塗佈區域、或塗佈不均之顯著區域等塗佈不良之情形。另外,塗佈不良亦成為造成塗佈後之基材的搬運不良(例如蜿蜒)之一個原因。
再者,將塗佈後基材預先捲繞至選定之芯而得到輥時,在輥的最表面形成顯著凹凸,在輥的端部產生變形或不勻等要因。進一步,二次加工後之製品亦同樣地產生外觀不良。
搬運時加強賦予基材之張力時,外觀上會減少基材的鬆弛,基材本身的表面凹凸或厚度偏差。然而,因為對基材施予必要以上之張力應力,會超出彈性界限而塗佈後應變殘存,而對製品形狀造成影響,或者時間流逝及周圍環境影響會有形狀變化之情形。
因而,期望藉由塗佈等成膜時,不以必要以上之應力拉伸基材之狀態,直接進行塗佈等確保能安定地成膜之技術。
本發明係鑑於上述者,目的在於提供對多孔質基材不賦予多孔質基材之伸度超過2%的張力應力,且能安定地形成平滑性良好的多孔質層之複合膜的製造方法,並以達成此目的作為課題。
為了解決課題之具體手段包含下述形態。
<1>一種複合膜之製造方法,其係具有熱處理步驟與塗佈步驟與凝固步驟,熱處理步驟係以滿足下述式之溫度T熱處理含熱可塑性樹脂之多孔質基材,塗佈步驟係將前述多孔質基材之機械方向的張力應力調整在多孔質基材之伸度成為2%以下的範圍,在熱處理後的前述多孔質基材之單面或雙面塗佈至少含樹脂及溶劑的塗佈液,形成塗佈層,凝固步驟係使前述塗佈層凝固,得到在前述多孔質基材之單面或雙面具有至少含樹脂之多孔質層的複合膜。
Tg+60℃≦溫度T≦Tm
Tg:多孔質基材所包含之熱可塑性樹脂的玻璃轉移溫度[℃]
Tm:多孔質基材所包含之熱可塑性樹脂的熔點[℃]
<2>如前述<1>的複合膜之製造方法,其中,前述多孔質基材厚度的平均值在施予前述熱處理前為5μm~50μm。
<3>如前述<1>或前述<2>的複合膜之製造方法,其中,前述多孔質基材厚度的標準偏差在施予前述熱處理前為0.40μm~30μm。
<4>如前述<1>~前述<3>中任一項的複合膜之製造方法,其中,前述多孔質基材的玻璃轉移溫度在施予前述熱處理前為30℃以下。
<5>如前述<1>~前述<4>中任一項的複合膜之
製造方法,其中,得到複合膜之前述凝固步驟係藉由塗佈層與凝固液接觸使樹脂凝固,而得到在多孔質基材之單面或雙面具有至少含樹脂之多孔質層的複合膜(步驟)。
<6>如前述<1>~前述<5>中任一項的複合膜之製造方法,其中,前述塗佈液係進一步含填料,在前述凝固步驟使塗佈層凝固所得到之多孔質層亦進一步含填料。
根據本發明,能提供對多孔質基材不賦予多孔質基材之伸度超過2%的張力應力,且能安定地形成平滑性良好的多孔質層之複合膜的製造方法。
[圖1]圖1係表示本發明之製造方法的一實施形態概念圖。
[圖2]圖2係表示本發明之製造方法的其他一實施形態概念圖。
[圖3]圖3係為了說明多孔質基材的鬆弛等狀態概念圖。
[圖4]圖4係圖3的A-A’線剖面圖。
本說明書中數值範圍中的「~」之標記係表
示分別作為最小值及最大值所包含的「~」前後所記載之數值範圍。
本說明書中「步驟」之詞彙係不僅獨立的步驟,即使與其他步驟不能明確地區別,若能達成其步驟所期望的作用,則包含在本術語。
另外,「機械方向」意味製造成長尺狀之多孔質基材及複合膜的縱向方向,「寬方向」意味多孔質基材及複合膜中正交機械方向的方向。以下將「機械方向」亦稱為「MD」,將「寬方向」亦稱為「TD」。
以下,針對本發明的複合膜之製造方法詳細說明。
本發明的複合膜之製造方法至少具有熱處理步驟與塗佈步驟與凝固步驟,熱處理步驟係以滿足下述所示式之溫度T熱處理含熱可塑性樹脂之多孔質基材(以下熱處理步驟),塗佈步驟係將多孔質基材之機械方向的張力應力調整在多孔質基材之伸度成為2%以下的範圍,在熱處理後的多孔質基材之單面或雙面塗佈至少含樹脂及溶劑的塗佈液,形成塗佈層(以下塗佈步驟),凝固步驟係使前述塗佈層凝固,得到在前述多孔質基材之單面或雙面具有至少含樹脂之多孔質層的複合膜(以下凝固步驟)。
Tg+60℃≦溫度T≦Tm
式中,Tg表示多孔質基材所包含之熱可塑性樹脂的玻璃轉移溫度[℃],Tm表示多孔質基材所包含之熱可塑
性樹脂的熔點[℃]。
本發明的複合膜之製造方法係至少具有熱處理步驟、塗佈步驟及凝固步驟即可,凝固步驟係塗佈層與凝固液接觸使塗佈層所包含之樹脂凝固而得到多孔質層的濕式法,與去除塗佈層所包含之溶劑後使塗佈層所包含之樹脂凝固而得到多孔質層的乾式法之任一者均可。較佳為藉由濕式法的態樣。
本發明的複合膜之製造方法係具有去除複合膜中之水分的步驟(以下乾燥步驟)較佳,視需要進一步具有製備塗佈液的步驟(以下塗佈液製備步驟),亦能具有在凝固步驟後進行水洗複合膜的步驟(以下水洗步驟)等其他處理(步驟)。
圖1~圖2表示本發明的複合膜之製造方法中濕式法或乾式法的各形態例。針對各形態之各處理(步驟)的詳細內容後述。
圖1表示本發明的複合膜之製造方法的一實施形態。圖1所示實施形態具有塗佈液製備步驟、熱處理步驟、塗佈步驟、凝固步驟、水洗步驟、及乾燥步驟,以濕式法進行凝固步驟。圖1中在圖內左側放置供給複合膜製造之多孔質基材的輥,在圖內右側放置捲取了所製造複合膜的輥。本實施形態係依序連續地進行熱處理步驟、塗佈步驟、凝固步驟、水洗步驟,及乾燥步驟。並且,本實施形態係配合塗佈步驟的實施時期進行塗佈液製備步驟。
圖2表示本發明之製造方法的其他一實施形
態。圖2所示之實施形態具有塗佈液製備步驟、熱處理步驟、塗佈步驟,及凝固步驟,以乾式法進行凝固步驟的凝固。圖2中在圖式左側放置供給複合膜製造之多孔質基材的輥、在圖式右側放置捲取所製造複合膜的輥。本實施形態係依序連續地進行熱處理步驟、塗佈步驟,及凝固步驟。並且,本實施形態係配合塗佈步驟的實施時期進行塗佈液製備步驟。
本發明中預先對多孔質基材施予熱處理的熱處理步驟設置在塗佈步驟前,對多孔質基材不施予如應變殘存之張力應力而能進行塗佈。亦即,以往在多孔質基材上一旦形成塗佈層時,被塗物之多孔質基材之鬆弛,或者在於多孔質基材表面的凹凸形狀或多孔質基材的厚度偏差對塗佈層造成壞影響,故採用對多孔質基材賦予張力而形成均勻性良好塗佈層之方法。多孔質基材之鬆弛意指拉伸搬運輥間時在多孔質基材之寬方向端部所展現褶皺狀鬆弛,例如,如圖3所示之在從寬方向端部至內部方向的任意寬度(圖3中鬆弛寬度P)所產生之褶皺狀變形或如圖4所示之寬方向端部係重力方向垂下(圖4中垂下寬度Q)不能維持所期望平面狀態而產生之變形。
然而,對多孔質基材施加必要以上的張力時基材超出彈性界限,有塗佈後依所殘存的應變而製品變形之情形,或者時間流逝或周圍環境的影響而變形之情形。
本發明中藉由預先熱處理塗佈前的多孔質基材,減少多孔質基材的鬆弛、多孔質基材的表面凹凸或厚度不均,
同時減少基材的扭曲殘存(緩解壓力效果)。藉此,提升被塗物之多孔質基材的平滑性,終究能安定地製造具有均勻性高之塗佈層的複合膜。
以下,針對本發明之實施形態的複合膜製造方法之各步驟詳述。
熱處理步驟中作為後述塗佈步驟的前處理步驟,以滿足下述所示式之溫度T熱處理含熱可塑性樹脂之多孔質基材。藉由熱處理多孔質基材能得到緩和安定地進行塗佈時所需求之多孔質基材的性狀(例如多孔質基材的鬆弛、多孔質基材的表面凹凸或厚度不均)之效果。
Tg+60℃≦溫度T≦Tm
式中,Tg表示多孔質基材所包含之熱可塑性樹脂的玻璃轉移溫度[℃],Tm表示多孔質基材所包含之熱可塑性樹脂的熔點[℃]。
熱處理步驟係如圖1~圖2所示,塗佈步驟前設置即可,亦能設置在塗佈於從輥所取出多孔質基材前的搬運路。
熱處理係只要是在熱處理花費需要時間對多孔質基材能賦予需要溫度的方法,就沒有特別限制,能適宜選擇。
作為熱處理之具體手法沒有特別限制,能列舉例如放置在所設定需要溫度的烘箱或恆溫室保管多孔質基材,供
給塗佈之所保管多孔質基材的方法、對多孔質基材吹熱風的方法、藉由紅外線加熱器之輻射熱加熱多孔質基材的方法,藉由發熱燈(例如發熱電球)或雷射光源之曝露於光照射下的方法、熱輥或熱板與多孔質基材接觸而賦予熱的方法,照射微波的方法等。
藉由在塗佈步驟前的搬運路設置加熱手段能進行熱處理。此時,能對特定搬運速度搬運的多孔質基材之一面及另一面的任一面施予熱處理,亦能從一面及另一面的雙面施予熱處理。如圖1~圖2所示,例如藉由從搬運至搬運路之多孔質基材的雙面施予熱處理,對多孔質基材整面能賦予均勻良好的熱。
前述式中的溫度T係多孔質基材表面的溫度。溫度T係使熱電偶接觸多孔質基材表面而計測的方法,或藉由利用紅外線之紅外線溫度測定機器等非接觸地計測的方法等求出。
熱可塑性樹脂之玻璃轉移溫度(Tg)係使用差示掃描熱儀器(DSC;TA Instruments公司製Q-200)以下述條件所測定之值。Tg設為DSC曲線之溫度的開始下降點與結束下降點之中間溫度(小數點以下四捨五入)。
<條件>
測定室:氮環境
昇溫速度:5℃/min
開始測定溫度:-50℃
結束測定溫度:200℃
樣品量:5mg
另外,熔點(Tm)亦與上述同樣地使用示差掃描熱儀器(DSC),以同條件所測定之值。
溫度T成為「Tg+60℃」以上之方式施予熱處理。溫度T未達「Tg+60℃」時,藉由賦予熱多孔質基材的性狀(例如多孔質基材的鬆弛、多孔質基材的表面凹凸或厚度不均)之減少效果不足。並且,熱處理時的溫度T係抑制在熱可塑性樹脂之熔點Tm以下。熱處理時的溫度T超過熔點Tm時,多孔質基材軟化難以維持形狀,相反損及多孔質基材的均勻性時,其結果變成容易降低塗佈品質。
熱處理時的溫度T係與上述同樣地理由,在於滿足下述式(1)或式(2)的溫度範圍較佳。
Tg+60℃≦溫度T≦Tm-20℃‧‧‧(1)
Tg+80℃≦溫度T≦Tm-40℃‧‧‧(2)
作為熱處理的時間就沒有特別限制,使塗佈性更提升之觀點而言,視熱處理的溫度能適宜選擇。熱處理的時間係例如0.01秒~30秒較佳,0.1秒~5秒更佳。
熱處理時的多孔質基材之機械方向(MD)的張力應力係多孔質基材之伸度成為2%以下的範圍之方式做調整較佳。亦即,較佳為將對熱處理時的多孔質基材所賦予張力應力抑制在對MD能延伸2%之多孔質基材的範圍。本發明的製造方法中如後述藉由將MD的張力應力抑
制在多孔質基材之伸度成為2%以下的範圍,能製得不殘留複合膜所施予之應變。作為MD的張力應力具體地0.1N/cm以上3N/cm以下較佳,0.5N/cm以上2N/cm以下更佳。
藉由在溫度20℃的環境下使用拉伸試驗機對多孔質基材以100mm/分鐘之引張速度進行拉伸試驗計測多孔質基材的張力應力。
並且,作為熱處理的事先步驟,為了在熱處理步驟連續地拉出長尺狀多孔質基材,亦能藉由接著劑、雙面膠帶、熱熔接等邊連接多孔質基材彼此邊拉出多個或更多個長尺狀多孔質基材。此時,在所連接之多孔質基材表面有藉由連接所產生的表面附著物之情形。因此,視需要亦使用藉由弱黏著性輥、抽吸輥、空氣噴霧之去除附著物裝置。此外,依多孔質基材的材質而會帶靜電,亦有周圍的懸浮物附著之情形,故使用去除靜裝置。進一步,作為更提升熱處理之效果的方法,使用擴張輥、螺旋狀輥,具備為了拉伸多孔質基材的皺(波紋)之設備較佳。
塗佈步驟係將多孔質基材之機械方向的張力應力調整在多孔質基材之伸度成為2%以下的範圍,在熱處理後的多孔質基材之單面或雙面塗佈至少含樹脂及溶劑(較佳為填料)的塗佈液,形成塗佈層。藉由經過前述熱處理步驟塗佈液的塗佈減少鬆弛、表面凹凸、厚度不勻,同時對降
低了扭曲殘存的多孔質基材,形成均勻性高之塗佈層。
對多孔質基材之塗佈液的塗佈時,能適用馬亞棒塗佈、模嘴塗佈、逆轉輥塗佈、凹版塗佈等以往的塗佈手段。在多孔質基材的雙面形成多孔質層時,就生產性之觀點而言,對基材同時在雙面塗佈塗佈液較佳。
將多孔質基材張力在MD進行塗佈。此時,多孔質基材的伸度成為2%以下(未張力之長度的102%以下)的範圍之方式對多孔質基材之機械方向調整張力應力。亦即,能在減弱多孔質基材之機械方向的張力應力之狀態進行塗佈。換言之,為了消除起因在多孔質基材的鬆弛、多孔質基材的表面凹凸或厚度不勻等性狀而容易產生之塗佈層的不均,不需要如以往在機械方向以能消除上述性狀的應力張力多孔質基材,並且,塗佈之間維持其應力。
使用A&D Company製拉伸試驗機(TENSILON RTC-1225A)測定多孔質基材之伸度。
塗佈量能設為雙面的合計例如10ml/m2~60ml/m2。
塗佈步驟時之多孔質基材的搬運速度係藉由設置前述熱處理步驟,因易確保生產效率及塗佈安定性,而能於10m/分鐘以上100m/分鐘以下的範圍適當地進行。
本發明的複合膜之製造方法中能使用所保管的塗佈液
或上市的市售塗佈液等既製塗佈液,亦能使用配合塗佈所製備的塗佈液。後者時作為既述之用以在塗佈步驟進行塗佈的塗佈液,能設置製備至少含樹脂及溶劑的塗佈液之塗佈液製備步驟。塗佈液能使用含填料、樹脂及溶劑的塗佈液、含樹脂及溶劑的塗佈液,或含樹脂及溶劑的水系乳膠。
塗佈液係例如將樹脂溶解在溶劑而製備,或將樹脂溶解在溶劑,進一步分散填料而製備。
另外,用於塗佈液的製備之樹脂及填料,亦即針對多孔質層所含有的樹脂及填料的詳細內容,在後述的「多孔質層」之事項進行說明。
作為用於塗佈液的製備之溶解樹脂的溶劑(以下,亦稱為「良溶劑」。),能適宜使用N-甲基吡咯烷酮、二甲基乙醯胺、二甲基甲醯胺、二甲基甲醯胺等極性醯胺溶劑。
形成具有良好多孔構造的多孔質層之觀點而言,除添加良溶劑以外亦混合能引起相分離之相分離劑較佳。作為相分離劑能列舉水、甲醇、乙醇、丙醇、丁醇、丁二醇、乙二醇、丙二醇、三丙二醇等。相分離劑係在對塗佈能確保適當黏度之範圍與良溶劑混合較佳。
作為用於塗佈液的製備之溶劑係形成良好多孔構造之觀點而言,將良溶劑含60質量%以上,將相分離劑含10質量%~40質量%的混合溶劑較佳。
塗佈液係形成良好多孔構造之觀點而言,包
含3質量%~10質量%之濃度的樹脂,包含10質量%~90質量%之濃度的填料較佳。
在塗佈液製備步驟中製備之塗佈液的25℃時之黏度係0.1Pa‧s~5.0Pa‧s的範圍較佳。塗佈液之黏度係0.1Pa‧s以上時,能得到對多孔質基材的塗佈適性,同時更展現藉由塗佈時之本發明的複合膜之製造方法的效果。另外,塗佈液之黏度係5.0Pa‧s以下時,能更安定地供給塗佈液。
塗佈液之黏度(25℃)係1.0Pa‧s以上較佳,更佳為2.0Pa‧s以上。另外,塗佈液之黏度(25℃)係4.0Pa‧s以下較佳,更佳為3.0Pa‧s以下。
黏度係依溶劑、樹脂及填料的組成比能控制。
另外,黏度係將塗佈液調溫在25℃之狀態下使用旋轉型黏度計(EKO CORPORATION製B型黏度計)所測定之數值。
凝固步驟中藉由將在塗佈步驟所形成之塗佈層凝固,能得到在多孔質基材之單面或雙面具有至少含樹脂之多孔質層的複合膜。
凝固步驟係塗佈層與凝固液接觸使塗佈層所包含之樹脂凝固而得到多孔質層的濕式法,或去除包含在塗佈層的溶劑使塗佈層所包含之樹脂凝固而得到多孔質層的乾式法之任一者即可。雖然乾式法係以不需要濕式法之
對凝固液需要接觸及水洗的觀點步驟上優勢,但是與濕式法比較多孔質層容易變密。因而,本發明中得到良好多孔構造之觀點而言依濕式法之態樣較佳。
濕式法係將具有塗佈層的多孔質基材浸漬於凝固液之態樣較佳,具體而言,使具有凝固液的槽(凝固槽)流通較佳。
用於濕式法的凝固液係一般由用於塗佈液的製備之良溶劑及相分離劑與水所製備。良溶劑與相分離劑之混合比係生產上依用於塗佈液的製備混合溶劑之混合比較佳。水的濃度係就多孔構造形成性及生產性之觀點而言,相對於凝固液的總量,40質量%~80質量%的範圍適當。作為凝固液的溫度,係例如設為20℃~50℃。
沒有特別限制乾式法中從複合膜去除溶劑之方法,能列舉例如使複合膜與發熱構件接觸的方法、將複合膜搬送至已調整溫度及濕度之反應室內的方法等。對複合膜賦予熱時,熱的溫度為例如50℃~80℃。
本發明的複合膜之製造方法係作為凝固步驟採用濕式法時,在凝固步驟後具有水洗複合膜的水洗步驟較佳。水洗步驟中去除包含在複合膜之溶劑(用於塗佈液之溶劑及用於凝固液之溶劑)。
水洗步驟亦藉由將複合膜搬送至水浴中而進行即可。水洗用水的溫度為例如0℃~70℃。
本發明的複合膜之製造方法係在前述水洗步驟後具有從複合膜去除水的乾燥步驟較佳。沒有特別限制乾燥方法,列舉例如使複合膜與發熱構件接觸的方法、將複合膜搬送至已調整溫度及濕度之反應室內的方法等。
對複合膜賦予熱時,作為熱的溫度例如50℃~80℃。
其次,針對構成複合膜之多孔質基材及多孔質層詳細說明。
多孔質基材意味在內部具有空孔或空隙之基材。作為如此基材能列舉微多孔膜、由不織布、紙等纖維狀物構成的多孔性薄片、在該等微多孔膜或多孔性薄片積層1層以上之其他多孔性層的複合多孔質薄片等。
本發明中就複合膜之薄膜化及強度之觀點而言微多孔膜較佳。微多孔膜意指在內部具有多數之微細孔,且該等微細孔為連結之構造,意味從一面至另一面能流通氣體或液體的膜。
構成多孔質基材之材料係具有電氣絕緣性的材料較佳,有機材料及無機材料之任一者均可。
構成多孔質基材之材料係對多孔質基材賦予關閉功能之觀點而言,熱可塑性樹脂較佳。關閉功能意指
將複合膜適用於電池隔膜時,提升電池溫度之際藉由溶解構成材料閉塞多孔質基材的孔而遮斷離子移動,防止電池的熱失控之功能。
作為熱可塑性樹脂熔點未達200℃之熱可塑性樹脂適當,特別是聚烯烴較佳。
作為多孔質基材含聚烯烴之微多孔膜(以下,亦稱為聚烯烴微多孔膜。)較佳。作為聚烯烴微多孔膜列舉例如適用於以往的電池隔膜之聚烯烴微多孔膜,從此之中選出具有良好力學特性及物質透過性者即可。
聚烯烴微多孔膜係展現關閉功能之觀點而言,含聚乙烯及丙烯的一者或兩者較佳。該等之中聚烯烴微多孔膜係從上述同樣之觀點而言含聚乙烯較佳,進而,聚乙烯的含量為95質量%以上之聚乙烯微多孔膜較佳。
聚烯烴微多孔膜係從暴露於高溫時具有不容易破膜程度的耐熱性之觀點而言,為含聚乙烯及聚丙烯之聚烯烴微多孔膜較佳。作為如此聚烯烴微多孔膜能列舉一層中混在聚乙烯及聚丙烯之微多孔膜。如此微多孔膜中兼顧關閉功能及耐熱性之觀點而言,含95質量%以上的聚乙烯與5質量%以下的聚丙烯之聚烯烴微多孔膜較佳。並且,兼顧關閉功能及耐熱性之觀點而言、聚烯烴微多孔膜具有2層以上的積層構造,且具有至少1層含聚乙烯,至少1層含聚丙烯之積層構造的聚烯烴微多孔膜較佳。
聚烯烴微多孔膜所包含之聚烯烴係重量平均分子量為10萬~500萬適當。重量平均分子量為10萬以
上時,能確保良好力學特性。另外,重量平均分子量為500萬以下時,關閉特性良好而容易成膜。
例如以下述方法能製造聚烯烴微多孔膜。亦即,第1個方法係從T-嘴押出已熔化聚烯烴樹脂使薄片化,結晶化處理此後進行延伸,再進行熱處理而製得微多孔膜之方法。另外,第2個方法係將流動石蠟等可塑劑與已熔化聚烯烴樹脂同時從T-嘴押出,冷卻此使薄片化,進行延伸後,抽出可塑劑再進行熱處理而製得微多孔膜之方法。
作為由纖維狀物構成的多孔性薄片,列舉聚乙烯對苯二甲酸乙二酯等聚酯、聚乙烯、聚丙烯等聚烯烴、芳香族聚醯胺、聚醯亞胺、聚醚碸、聚碸、聚醚酮、聚醚醯亞胺等耐熱性樹脂、纖維素等由纖維狀物構成的不織布或紙等多孔性薄片。
耐熱性樹脂意指熔點為200℃以上的樹脂,或不具有熔點之分解溫度為200℃以上的樹脂。
作為複合多孔質薄片,採用在微多孔膜或由纖維狀物構成的多孔性薄片積層功能層的構成。作為如此複合多孔質薄片係依功能層進而能功能附加之關點而言較佳。功能層就例如賦予耐熱性之觀點而言,採用由耐熱性樹脂構成的多孔性之層或由耐熱性樹脂及無機填料構成的多孔性之層。作為耐熱性樹脂,列舉由芳香族聚醯胺、聚醯亞胺、聚醚碸、聚碸、聚醚酮及聚醚醯亞胺之中選出1種或2種以上的耐熱性樹脂。作為無機填料能適當使用
氧化鋁等金屬氧化物、氫氧化鎂等金屬氫氧化物等。作為複合化之手法,列舉在微多孔膜或多孔性薄片塗佈功能層之方法,以接著劑接合微多孔膜或多孔性薄片與功能層之方法、熱壓接微多孔膜或多孔性薄片與功能層之方法等。
熱可塑性樹脂之玻璃轉移溫度(亦即施予熱處理前之玻璃轉移溫度)係30℃以下的範圍佳,0℃以下的範圍較佳,-10℃以下的範圍更佳。藉由玻璃轉移溫度設為30℃以下,能容易進行熱處理。並且,玻璃轉移溫度係生產性之觀點而言,-50℃以上的範圍較佳,-30℃以上的範圍更佳。
對本發明的製造方法之多孔質基材的適合性之觀點而言,寬長為0.1m~3.0m的長尺物較佳。
作為多孔質基材之厚度係機械強度之觀點而言,平均值(亦即施予熱處理前之厚度的平均值)係5μm~50μm的範圍佳,5μm~30μm的範圍較佳,5μm~20μm的範圍更佳。
多孔質基材之厚度係使用接觸式厚度計(Mitutoyo Corporation製LITEMATIC),測定10cm×30cm內之任意20點,作為所測定之數值的平均值求出。並且,測定端子係使用直徑5mm之圓柱狀者,測定中調整為能施予7g的負載。
另外,多孔質基材之厚度的標準偏差(亦即施予熱處理前之厚度的標準偏差)係0.35μm~30μm的範圍佳,0.40μm~30μm的範圍較佳,0.45μm~20μm的範圍
更佳,0.45μm~5μm的範圍更佳,0.45μm~1μm的範圍更佳。如此厚度不均勻係即使使用比較大的多孔質基材,根據本發明之製造方法,能兼顧塗佈品質的提升及內部應力的降低。
厚度的標準偏差係由如上述所測定之厚度算出。
多孔質基材的光澤值(JIS P8117(2009))係機械強度及物質透過性之觀點而言,50秒/100cc~800秒/100cc較佳。
多孔質基材的空孔率係機械強度、操作性,及物質透過性之觀點而言,20%~60%較佳。
多孔質基材的平均孔徑係物質透過性之觀點而言,20nm~100nm較佳。此處,平均孔徑係依ASTM E1294-89使用棕櫚馬球儀器所測定之數值。
多孔質層係在內部具有多數之微細孔,且該等微細孔為連結之構造,從一面至另一面能流通氣體或液體的層。
多孔質層係將複合膜適用於電池隔膜時,與電極能接著之接著性多孔質層較佳。能僅在多孔質基材的單面具有接著性多孔質層,進而在多孔質基材的雙面具有多孔質基材之情形較佳。
藉由塗佈含填料、樹脂及溶劑的塗佈液、含樹脂及溶劑的塗佈液、或含樹脂及溶劑的水系乳膠形成多孔質層。因此,多孔質層含有樹脂及填料或樹脂。
以下,針對多孔質層,及用於形成多孔質層之塗佈液所含有的樹脂等成分進行說明。
沒有限制多孔質層所包含之樹脂的種類。作為多孔質層所包含之樹脂,具有連結填料的功能者(所謂黏結劑樹脂)較佳。多孔質層所包含之樹脂係將複合膜作為電池隔膜利用時,對電解液安定,電化學性安定,具有連結無機粒子的功能,與電極能接著者較佳。多孔質層所包含之樹脂係以濕式法製造複合膜時,就製造適合性之觀點而言,疏水性樹脂較佳。
多孔質層能包含1種亦能包含2種以上樹脂。
作為樹脂例如聚偏氟化乙烯、聚偏氟化乙烯共聚物、苯乙烯-丁二烯共聚物、丙烯腈或甲基丙烯腈等乙烯基腈類的單獨聚合物或共聚物、聚乙烯氧化物或聚丙烯氧化物等聚醚類較佳。該等之中聚偏氟化乙烯及聚偏氟化乙烯共聚物(綜合該等亦稱為聚偏氟化乙烯系樹脂。)特佳。
作為聚偏氟化乙烯系樹脂,列舉偏氟化乙烯的單獨聚合物(亦即聚偏氟化乙烯)、偏氟化乙烯與其他能共聚的單體之共聚物(亦即聚偏氟化乙烯共聚物),及該等之混合物等。
作為與偏氟化乙烯能共聚的單體,列舉例如四氟乙烯、六氟丙烯、三氟乙烯、三氯乙烯、氟乙烯等,能使用
1種類或2種類以上。
聚偏氟化乙烯系樹脂係藉由乳化聚合或懸濁聚合所得到。
多孔質層所包含的樹脂就耐熱性之觀點而言,耐熱性樹脂(熔點為200℃以上的樹脂,或不具有熔點之分解溫度為200℃以上的樹脂)較佳。
作為耐熱性樹脂,列舉例如聚醯胺(尼龍)、全芳香族聚醯胺(芳綸)、聚醯亞胺、聚醯胺醯亞胺、聚碸、聚酮、聚醚酮、聚醚碸、聚醚醯亞胺、纖維素、及該等混合物。該等之中形成多孔構造的容易度、與無機粒子之結著性、耐氧化性等之觀點而言,全芳香族聚醯胺較佳。全芳香族聚醯胺的該等之中容易成形之觀點而言,甲型全芳香族聚醯胺較佳,特別是聚甲基亞苯間苯二甲醯胺適當。
並且、本發明之實施形態的複合膜之製造方法中作為樹脂,能適宜使用上述者以外的粒子狀樹脂或水溶性樹脂。作為粒子狀樹脂,列舉聚偏氟化乙烯系樹脂或氟化橡膠、苯乙烯-丁二烯橡膠等含樹脂的樹脂粒子。水等分散媒中分散樹脂粒子製備塗佈液而能使用樹脂粒子。作為水溶性樹脂,能列舉例如纖維素系樹脂及聚乙烯醇等。此時,作為溶劑能使用水。上述粒子狀樹脂及水溶性樹脂係以乾式法實施凝固步驟時適當。
沒有限制多孔質層所包含之填料的種類,無機填料及
有機填料之任一者即可。填料係一次粒子之體積平均粒徑為0.01μm~10μm的粒子較佳。藉由填料之體積平均粒徑為上述範圍內,製造時提高平滑性並提高生產性,且能取得如滿足與電極之接著性及電解液之保持性的特性之平衡。填料的體積平均粒徑係0.1μm~10μm較佳,0.1μm~3.0μm更佳。
填料的體積平均粒徑係使用雷射繞射式粒度分布測定裝置所測定之數值。
作為填料多孔化及耐熱性之觀點而言,無機粒子較佳。多孔質層所包含之無機粒子係對電解液安定,且電化學性安定者較佳。多孔質層係能含1種亦能含2種以上的無機粒子。
作為無機粒子能列舉例如氫氧化鋁、氫氧化鎂、氫氧化鈣、氫氧化鉻、氫氧化鋯、氫氧化鈰、氫氧化鎳、氫氧化硼等金屬氫氧化物、矽石、氧化鋁、鋯、氧化鎂等金屬氧化物、碳酸鈣、碳酸鎂等碳酸鹽、硫酸鋇、硫酸鈣等硫酸鹽、矽酸鈣、滑石等黏土礦物等。該等之中就賦予難燃性或除電效果之觀點而言,金屬氫氧化物及金屬氧化物較佳。無機粒子亦能藉由矽烷偶合劑等進行表面修飾者。
無機粒子的粒子形狀係任意,球形、橢圓形、板狀、棒狀、不定形之任一者即可。無機粒子係一次粒子之體積平均粒徑就多孔質層的成形性、複合膜的物質透過性、及複合膜的平滑性之觀點而言,為0.01μm~
10μm較佳,為0.1μm~10μm更佳,為0.1μm~3.0μm特佳。
多孔質層含有無機粒子時,無機粒子佔樹脂與無機粒子之合計量的比例係例如30體積%~90體積%。
多孔質層係作為填料亦能含有有機填料。作為有機填料,列舉例如交聯聚(甲基)丙烯酸、交聯聚(甲基)丙烯酸酯、交聯聚矽氧烷、交聯聚苯乙烯、交聯聚二乙烯基苯、苯乙烯-二乙烯基苯共聚物交聯物、聚醯亞胺、三聚氰胺樹脂、酚醛樹脂、苯代三聚氰胺-甲醛縮合物等由交聯高分子構成的粒子、聚碸、聚丙烯腈、芳綸、聚縮醛、熱可塑性聚醯亞胺等由耐熱性樹脂構成的粒子等。
多孔質層的厚度係機械強度之觀點而言,多孔質基材的單面時0.5μm~5μm較佳。
多孔質層的空孔率係機械強度、操作性、及物質透過性之觀點而言30%~80%較佳。
多孔質層的孔徑係物質透過性之觀點而言,20nm~100nm較佳。此處,平均孔徑係依ASTM E1294-89使用棕櫚馬球儀器所測定之數值。
本發明的複合膜之製造方法中製作在含熱可塑性樹脂之多孔質基材上具有多孔質層的複合膜。
複合膜的厚度係例如5μm~100μm,電池隔膜用途中例如能設為5μm~50μm。
複合膜的光澤值(JIS P8117(2009))係就機械強度及物質透過性之觀點而言,50秒/100cc~800秒/100cc較佳。
複合膜的空孔率係機械強度、操作性、及物質透過性之觀點而言,30%~60%較佳。
作為複合膜的用途,列舉例如、電池隔膜、電容器用薄片、氣體濾片、液體濾片等。該等之中作為特別適當用途,本發明之複合膜係用於非水系二次電池用隔膜。
以下,藉由實施例更具體地說明本發明之一實施形態。惟,只要本發明之一實施形態的複合膜之製造方法不超出其主旨,沒有限定於以下的實施例。
針對在下述表示的實施例及比較例所製作之隔膜及鋰離子二次電池,進行以下的測定、評估。下述表1表示測定及評估的結果。
使用接觸式之厚度計(Mitutoyo Corporation製LITEMATIC)對多孔質基材測定10cm×30cm內之任意20點,從測定值算出厚度的平均值及標準偏差。並且,測定端子係使用直徑5mm之圓柱狀者,測定中調整為能施予7g的負載。
使用旋轉型黏度計(EKO CORPORATION製B型黏度計)測定塗佈液之25℃的黏度(Pa‧s)。
作為多孔質基材之撓曲,以下述方法測定由寬度方向兩端的鬆弛寬度,與在寬方向端部從膜表面至重力方向端部為止所垂下之高度差(垂下寬度)。
如圖3所示,在搬運路間距2m所固定配置之2個支撐輥間對聚乙烯微多孔膜賦予一定張力(各自之實施例或比較例的塗佈時之基材伸度)並拉伸狀態下拉伸,測定鬆弛區域之從寬方向端部的距離(鬆弛寬度P)。
如圖3~圖4所示,在搬運路間距2m所固定配置之
2個支持輥間對聚乙烯微多孔膜賦予一定張力(各自之實施例或比較例的塗佈時之基材伸度)而拉伸狀態下拉伸,算出從特定之高度至膜面(沒有鬆弛區域)為止的距離與從特定之高度垂下至重力方向之端部為止的距離之差(垂下寬度Q)。
使用差示掃描熱儀器(DSC;Q-200、TA INSTRUMENTS CORPORATION製)以下述條件測定多孔質基材所包含之熱可塑性樹脂的玻璃轉移溫度(Tg)。將DSC曲線之溫度的下降起始點與下降結束點之中間溫度小數點以下四捨五入求出Tg。
<條件>
‧測定室:氮環境
‧昇溫速度:5℃/min
‧開始測定溫度:-50℃
‧結束測定溫度:200℃
‧樣品量:5mg
使用差示掃描熱儀器(DSC;Q-200、TA INSTRUMENTS CORPORATION製)以上述相同條件測定多孔質基材所包含之熱可塑性樹脂的熔點(Tm)。
藉由將聚甲基亞苯間苯二甲醯胺溶解於二甲基乙醯胺與三丙二醇之混合溶劑,所獲得之溶液中使氫氧化鋁(無機填料、一次粒子的體積平均粒徑:0.8μm)分散,製備塗佈液。
塗佈液之組成係以質量比氫氧化鋁:聚甲基亞苯間苯二甲醯胺:二甲基乙醯胺:三丙二醇=16:4:40:40。
作為多孔質基材使用聚乙烯(熱可塑性樹脂、玻璃轉移溫度(Tg):-20℃、熔點(Tm):135℃)進行成膜,而準備了厚度16μm(平均值)、寬長450mm的長尺狀聚乙烯微多孔膜(光澤值:200秒/100ml、空孔率:50%)。
如圖3~圖4所示,從捲出輥重複地搬送至搬運路之聚乙烯微多孔膜係從寬方向兩端的鬆弛寬度P為分別95mm,寬方向端部中從膜面垂下至重力方向之端部為止的高度之差(垂下寬度Q)為17mm。並且,以上述方法測定鬆弛寬度及垂下寬度。
使此聚乙烯微多孔膜與60℃的熱板接觸1.2秒鐘施予熱處理。
邊慢慢地賦予張力邊將施予熱處理後之聚乙烯微多孔膜搬送至塗佈裝置的配置位置,對聚乙烯微多孔膜所施予張力達到9N(牛頓)時解除寬方向端部之鬆弛。此時之聚乙烯微多孔膜的伸度為0.1%。
對聚乙烯微多孔膜施予伸度0.1%的張力應力(=9N)之拉伸狀態下,藉由模塗佈機在聚乙烯微多孔膜之一面塗佈上述塗佈液,形成厚度3μm的塗佈層。塗佈步驟之聚乙烯微多孔膜的搬運速度為10m/分鐘。
將形成塗佈層之聚乙烯微多孔膜搬到凝固槽,浸漬於凝固槽中所放置之凝固液(水:二甲基乙醯胺:三丙二醇=43:40:17[質量比]、液溫30℃)使塗佈層凝固,獲得複合膜。
其次,將複合膜搬到水槽後放置於水槽,藉由調溫於水溫30℃之水浴中進行水洗。然後,使水洗後的複合膜流通乾燥裝置內並使乾燥。
連續地實施上述各步驟,製作聚乙烯微多孔膜之一面具有多孔質層的複合膜。
針對所獲得之複合膜進行下述評估。下述表1表示評
估結果。
針對多孔質基材上所塗佈之塗佈層,將寬方向之厚度測定12點求出平均值,同時以目視確認塗佈層的表面狀態,依下述評估基準進行評估。
A:在多孔質基材的整面形成塗佈層,對平均值之膜厚差係未達0.2μm。
B:在多孔質基材的整面形成塗佈層,對平均值之膜厚差係0.2μm~1μm。
C:多孔質基材之一部分有未塗佈的區域,對平均值之膜厚差亦超出1μm。
針對所獲得之複合膜,將切成一定尺寸的塗佈層經過一定時間後,藉由算出MD方向及TD方向的尺寸變化率求出內部應力,依下述評估基準進行評估。
A:內部應力未達0.1%,在複合膜未觀察到波狀變形。
B:內部應力係0.2%以上未達0.4%,在複合膜觀察
到波狀變形。
C:內部應力係0.4%以上,在複合膜顯著觀察到波狀變形。
將實施例1中多孔質基材的性狀、熱處理步驟的條件、同時塗佈時的張力應力及基材伸度變更為如表1所示以外,與實施例1同樣地連續實施各步驟,製作聚乙烯微多孔膜的一面具有多孔質層之複合膜。另外,實施例9中使用了使用聚丙烯(熱可塑性樹脂)進行成膜後之厚度18μm(平均值)、寬長450mm的長尺狀聚丙烯微多孔膜(光澤值:200秒/100ml、空孔率:50%)。
並且,與實施例1同樣地進行評估。表1表示評估結果。
塗佈液製備步驟中作為聚合物取代聚甲基亞苯間苯二甲醯胺使用聚偏氟化乙烯(PVDF)以外,與實施例1同樣地連續實施各步驟,製作聚乙烯微多孔膜之一面具有多孔質層的複合膜。並且,與實施例1同樣地進行評估。表1表示評估結果。
將實施例1中熱處理步驟的條件及塗佈時的基材伸度
變更為如表1所示以外,與實施例1同樣地連續實施各步驟,製作聚乙烯微多孔膜之一面具有多孔質層之複合膜。並且,與實施例1同樣地進行評估。表1表示評估結果。
如表1所示,藉由對多孔質基材之塗佈液的塗佈前預先在多孔質基材施予特定之熱處理,能安定地形成高均勻性的塗佈層,所獲得之複合膜亦能抑制在低內部應力。作為多孔質基材使用聚乙烯及聚丙烯之任一者時均顯示良好結果。
相對於此,未進行特定之熱處理的比較例1~4係所形成之塗佈層不均勻,多孔質基材之一部分亦有產生塗佈不良的情形。並且,塗佈時對多孔質基材賦予強應力之比較例3時,所獲得之複合膜的內部應力高,不能維持所期望的形狀。此點係如比較例6所示,即使施予熱處理複合膜的內部應力亦高,不能維持所期望的形狀。
另外,以多孔質基材之熔點超過熱處理之溫度進行熱處理的比較例5係觀察到基材本身的溶融,難以搬運及塗佈。
藉由參照全體將日本出願2015-073079之揭示併入本說明書。
本說明書所記載之全部文獻、專利申請,及技術規格係藉由參照所編入之個別文獻、專利申請、及技術規格的情形為藉由參照與具體且個別記載時相同程度併入本說明書中。
Claims (6)
- 一種複合膜之製造方法,其係具有下述步驟:以滿足下述式之溫度T熱處理含熱可塑性樹脂之多孔質基材的步驟,Tg+60℃≦溫度T≦Tm(Tg表示多孔質基材所包含之熱可塑性樹脂的玻璃轉移溫度[℃],Tm表示多孔質基材所包含之熱可塑性樹脂的熔點[℃]);將前述多孔質基材之機械方向的張力應力調整在多孔質基材之伸度成為2%以下的範圍,在熱處理後的前述多孔質基材之單面或雙面塗佈至少含樹脂及溶劑的塗佈液,形成塗佈層的步驟;使前述塗佈層凝固,得到在前述多孔質基材之單面或雙面具有至少含樹脂的多孔質層之複合膜的步驟。
- 如申請專利範圍第1項的複合膜之製造方法,其中,前述多孔質基材厚度的平均值在施予前述熱處理前為5μm~50μm。
- 如申請專利範圍第1或2項的複合膜之製造方法,其中,前述多孔質基材厚度的標準偏差在施予前述熱處理前為0.40μm~30μm。
- 如申請專利範圍第1或2項的複合膜之製造方法,其中,前述多孔質基材的玻璃轉移溫度在施予前述熱處理前為30℃以下。
- 如申請專利範圍第1或2項的複合膜之製造方法, 其中,得到前述複合膜之步驟係塗佈層與凝固液接觸使樹脂凝固,而得到在多孔質基材之單面或雙面具有至少含樹脂之多孔質層的複合膜之步驟。
- 如申請專利範圍第1或2項的複合膜之製造方法,其中,前述塗佈液係進一步含填料,使前述塗佈層凝固所得到之多孔質層亦進一步含填料。
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US20120085281A1 (en) * | 2010-10-07 | 2012-04-12 | Sandvik Thermal Process, Inc. | Apparatus with multiple heating systems for in-line thermal treatment of substrates |
TWI491096B (zh) * | 2010-12-06 | 2015-07-01 | Ind Tech Res Inst | 多層電池隔離膜及其製造方法 |
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