JP2021516176A - 微多孔膜、バッテリーセパレータ、及びこれらの製造方法、デバイス及び多層微多孔膜 - Google Patents
微多孔膜、バッテリーセパレータ、及びこれらの製造方法、デバイス及び多層微多孔膜 Download PDFInfo
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- JP2021516176A JP2021516176A JP2020545681A JP2020545681A JP2021516176A JP 2021516176 A JP2021516176 A JP 2021516176A JP 2020545681 A JP2020545681 A JP 2020545681A JP 2020545681 A JP2020545681 A JP 2020545681A JP 2021516176 A JP2021516176 A JP 2021516176A
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
したがって、各個別の顧客ニーズを満足し、及び/又はウェットプロセス膜との競合力があるか若しくはよりコスト的(環境的及び金銭的)に優れた改良された特性を有する新規ドライプロセス膜に対するニーズがある。更に、被覆する必要なく、被覆膜の強度を有する非被覆ドライプロセス膜を製造することが切望されている。
本明細書に記載されている方法は、以下の工程:(1)第一樹脂混合物を押出することによって第一非多孔性前駆体を製造し、次いで、縦方向(MD)に第一非多孔性前駆体膜を延伸して延伸第一非多孔性前駆体膜を製造する工程;(2)別に、第二非多孔性前駆体膜を製造し、次いで、縦方向(MD)に非多孔性前駆体膜を延伸して第二延伸非多孔性前駆体膜を製造する工程;次いで(3)延伸第一非多孔性前駆体と延伸第二非多孔性前駆体を積層する工程を含む、から成る、又はから本質的に成り得る。工程(2)を、工程(1)前、後、又は同時に行ってよい。好ましい実施形態では、延伸第一非多孔性前駆体を、第一非多孔性前駆体膜の後あるいは同時に、MD及びTD延伸によって製造する。例えば、第一非多孔性前駆体を、MD延伸してからTD延伸してもよく、MD及びTD延伸を同時に行ってもよい。別の好ましい実施形態では、延伸第一非多孔性前駆体膜を、工程(1)において上記のようにMD及びTD延伸し、次いで、該第一非多孔性前駆体膜を圧延することによって製造してよい。それから、MD及びTD延伸並びに圧延された第一非多孔性前駆体を、MD延伸第二非多孔性前駆体に積層してよい。更なる実施形態では、圧延工程(4)を、積層工程後に行ってよい。他の好ましい実施形態では、工程(1)において製造されたMD延伸第一非多孔性前駆体膜、工程(2)において製造されたMD延伸第二非多孔性前駆体膜、工程(1)において製造されたMD及びTD延伸第一非多孔性前駆体膜、又は工程(1)において製造されたMD及びTD延伸並びに圧延された第一非多孔性前駆体膜のいずれか又は両方に、処理工程(5)を行ってよい。処理工程(5)を、工程(1)及び/又は(2)後だが、積層工程(3)前に行う。例えば、いくつかの実施形態では、工程(1)後だが、第二延伸非多孔性前駆体膜を工程(2)において製造する前に、処理工程を延伸第一非多孔性前駆体膜に行ってよい。いくつかの実施形態では、処理工程を行って、MD延伸第一非多孔性前駆体膜、MD及びTD延伸非多孔性前駆体膜、又はMD及びTD延伸並びに圧延された非多孔性前駆体膜並びに延伸第二非多孔性前駆体膜間の接着性を改良する。
延伸(MD又はMD及びTD)又は延伸(MD又はMD及びTD)及び圧延第一非多孔性前駆体膜の製造工程は、そのように限定されない。工程は、第一樹脂混合物を押出して非多孔性前駆体膜を製造し、次いで、該非多孔性前駆体膜を延伸(MD又はMD及びTD)するか又は該非多孔性前駆体膜を延伸(MD又はMD及びTD)及び圧延することを含む、から成る、又はから本質的に成り得る。
延伸第二非多孔性前駆体膜の製造工程はそのように限定されない。工程は、第二樹脂混合物を押出して非多孔性前駆体膜を製造し、次いで、該非多孔性第二前駆体膜をMD延伸して、とりわけ、細孔を形成することを含む、から成る、又はから本質的に成り得る。
積層工程はそのように限定されず、本明細書に言及された目的に反しないいずれもの方法で行うことができる。積層工程は、延伸(MD又はMD及びTD)又は延伸(MD又はMD及びTD)及び圧延第一非多孔性前駆体膜と延伸第二非多孔性前駆体膜との積層を含む、から成る、又はから本質的に成る。いくつかの実施形態では、少なくとも1つの他の薄膜を、積層工程においてこれらの2つの薄膜と積層する。例えば、第三MD延伸非多孔性前駆体膜を工程(1)又は(2)と同様に製造してよく、第三MD及びTD延伸非多孔性前駆体膜を工程(1)と同様に製造してよく、又は工程(2)において製造されたものと同様に第三MD及びTD延伸並びに圧延された非多孔性前駆体膜を製造してよく、この第三膜をいずれの順序でも第一及び第二膜と積層してよい。いくつかの実施形態では、第一膜は、ポリプロピレン又は別の高融点樹脂を含む、から成る、又はから本質的に成り得、第二膜は、ポリエチレンを含む、から成る、又はから本質的に成り得、第三膜は、ポリプロピレン又は別の高融点樹脂を含む、から成る、又はから本質的に成り得る。かかる実施形態では、薄膜を、以下の順:第一、第二、第三(PP−PE−PP)で積層してよい。いくつかの他の実施形態では、第一膜は、ポリプロピレン又は別の高融点樹脂を含む、から成る、又はから本質的に成り得、第二膜は、ポリエチレンを含む、から成る、又はから本質的に成り得、第三膜は、ポリエチレンを含む、から成る、又はから本質的に成り得、MD延伸のみ行う。かかる実施形態では、薄膜を、以下の順:第二、第一、第三(PE−PP−PE)で積層してよい。
積層後の圧延工程はそのように限定されず、本明細書に言及された目的に反しないいずれもの方法で行うことができる。いくつかの好ましい実施形態では、積層工程(3)後に工程(1)の一部として圧延を行う。他の好ましい実施形態では、積層工程(3)後に圧延工程(4)の一部として圧延のみを行う。工程(4)における圧延条件は、上記工程(2)に記載されている通りである。
処理工程はそのように限定されず、本明細書に言及された目的に反しないいずれもの方法で行うことができる。処理工程の1つの目的は、積層工程において積層された薄膜の接着性を改良することである。これらの薄膜の少なくとも1つ(又はこれらの薄膜の全て)に対して、これらを製造した後に処理工程を行ってよい。例えば、延伸後の延伸(MD又はMD及びTD)第一非多孔性前駆体膜又は延伸及び圧延後の延伸(MD又はMD及びTD)及び圧延第一非多孔性前駆体膜に対して処理工程を行ってよい。
本明細書に開示されている多層微多孔膜はそのように限定されず、本明細書中上記方法のいずれかによって製造されたいずれかの膜であり得る。他の実施形態では、多層微多孔膜は、以下の特性:a)50〜400、100〜400、150〜400、100〜300、又は好ましくは100〜200のJISガーレー;b)150gf〜600gf、300gf〜600gf、320gf〜600gf、より好ましくは380gf〜600gf、最も好ましくは400gf〜600gf以上の突刺強度;c)500kg/cm2超、600kg/cm2超、700kg/cm2超、好ましくは1,000kg/cm2超のMD強さ;d)300kg/cm2超、350kg/cm2超、好ましくは500kg/cm2超、最も好ましくは600kg/cm2超のTD強さ;e)好ましくは30%以上、40%以上、50%以上、又はより好ましくは100%超のMD伸び;f)好ましくは30以上、又は40%、又は50%、又は60%又はより好ましくは70%以上のTD伸び;g)25%未満、より好ましくは20%未満、さらにより好ましくは15%未満;最も好ましくは10%以下である、105℃、120℃、130℃、又は140℃の少なくとも1つにおけるMD収縮率;h)15%未満、好ましくは10%未満、最も好ましくは5%未満である、105℃、120℃、130℃、又は140℃の少なくとも1つにおけるTD収縮率;j)良好な均一性、及び結果として、より高い最小絶縁破壊値;k)25ミクロン以下、好ましくは20ミクロン以下、最も好ましくは15ミクロン以下の厚さ;並びに減少された含水率の少なくとも1つを有するものである。膜は、前述の特性の2つ以上、3つ以上、4つ以上、5つ以上、6つ以上、7つ以上、8つ以上、9つ以上、10以上、11以上、又は12全てを有してよい。
別の態様では、本明細書に開示されている少なくとも1つの多層微多孔膜を備える、から成る、又はから本質的に成るバッテリーセパレータを記載する。いくつかの特に好ましい実施形態では、膜の特性は、例えば、収縮率を改良するためにコーティングを必要としないので、微多孔膜は、コーティング、特にセラミックコーティングを必要としない。セパレータをコーティングしないことは、セパレータの全体的コストを低くする。本明細書中いくつかの実施形態では、より低コストで優れたセパレータを製造し得、含水率を低減する。しかしながら、いくつかの実施形態では、コーティング、例えば、セラミックコーティングを、セパレータの特性をなお更に改良するために付加してよい。
直接これらと接して提供される、上記本明細書に記載されているいずれかのバッテリーセパレータ並びに1つ以上の電極、例えば、アノード、カソード、又はアノード及びカソードを備えるコンポジット又はデバイス。電極の種類はそのように限定されない。例えば、電極は、リチウムイオン二次電池における使用に適するものであり得る。
厚さ(μm)
Emveco Microgage210−Aマイクロメータ厚さ試験機及び試験手順ASTM D374を使用してミクロメートル、μmで厚さを測定する。
ガーレーは、日本工業規格(JISガーレー)と本明細書において定義され、OHKEN透気度試験機を使用して本明細書において測定する。JISガーレーは、100ccの空気が4.9インチの水の定圧において1平方インチの薄膜を通過するのに要する時間(単位:秒)と定義される。
2枚の紙の間に試験サンプルを入れ、一緒にクリップで留めて紙の間にサンプルを保持し、乾燥機内に吊すことによって収縮率を測定する。105℃、1時間の試験では、サンプルを105℃、1時間乾燥器内に入れる。乾燥器内において指定加熱時間後、各サンプルを取り出し、両面粘着テープを使用して平らなカウンター面に貼り付けて正確な長さ及び幅測定をするためにサンプルを平坦化し平滑化する。縦方向(MD)及び横方向(TD)の両方で収縮率を測定し、MD収縮率%及びTD収縮率%として表す。
縦方向(MD)引張強さを、Instron Model4201を使用して、ASTM−882手順に従って測定する。
MD破断点伸び%は、サンプルを破断するのに要する最大引張強さにおいて測定される試験サンプルの縦方向に沿った試験サンプルの伸びのパーセンテージである。
横方向(TD)引張強さを、Instron Model4201を使用して、ASTM−882手順に従って測定する。
TD破断点伸び%は、サンプルを破断するのに要する最大引張強さにおいて測定される試験サンプルの横方向に沿った試験サンプルの伸びのパーセンテージである。
Instron Model4442を使用して、ASTM D3763に基づいて突刺強度を測定する。微多孔膜の幅方向に測定を行い、突刺強度は試験サンプルを穿刺するのに必要な力と定義される。
サンプルの絶縁破壊が観察されるまで、電圧をセパレータ膜に印加する。強いセパレータは、高DBを示す。
サンプルを加熱し、シャットダウン開始温度を100W×cm2の抵抗読みにおいて記録し、単位℃で報告する。
カールフィッシャー滴定法によって含水率を測定する。
Claims (64)
- 多層微多孔膜の製造方法であって、前記方法は
第一樹脂混合物を押出して、第一非多孔性前駆体膜を製造して、次いで、少なくとも縦方向(MD)に前記第一非多孔性前駆体膜を延伸して細孔を形成することと、
別に、第二樹脂混合物を押出して、第二非多孔性前駆体膜を製造して、次いで、少なくとも縦方向(MD)に前記第二非多孔性前駆体膜を延伸して細孔を形成することと、
前記MD延伸第一前駆体と前記MD延伸第二前駆体とを積層することと
を含む、方法。 - 前記第一樹脂混合物は、ポリプロピレン樹脂及び140℃以上且つ330℃以下の融点を有する樹脂の少なくとも1つを含む、請求項1に記載の方法。
- 前記第二樹脂混合物は、ポリエチレン樹脂及び140℃以下、好ましくは135℃以下の融点を有する樹脂の少なくとも1つを含む、請求項2に記載の方法。
- 前記第一非多孔性前駆体膜及び前記第二非多孔性前駆体膜の少なくとも1つは、前記第一又は第二樹脂混合物と共に少なくとも1つの他の樹脂混合物を共押出することによって製造された共押出膜であり、前記他の樹脂混合物は前記第一又は第二樹脂混合物と同じであってもよく、異なっていてもよい、請求項1に記載の方法。
- 前記第一非多孔性前駆体を、積層前に、前記MDおよび横方向(TD)に順次又は同時に延伸する、請求項1に記載の方法。
- 前記第一非多孔性前駆体を、積層前に、MDおよびTDに順次又は同時に延伸する、請求項2に記載の方法。
- 前記MD延伸第一非多孔性前駆体を、積層前に圧延する、請求項1に記載の方法。
- 前記MD延伸第一非多孔性前駆体を、積層前に圧延する、請求項2に記載の方法。
- 前記MD及びTD延伸第一非多孔性前駆体を、積層前に圧延する、請求項5に記載の方法。
- 前記MD及びTD延伸第一非多孔性前駆体を、積層前に圧延する、請求項6に記載の方法。
- 前記MD延伸第一非多孔性前駆体と前記MD延伸第二非多孔性前駆体とを積層した後、積層物を圧延する、請求項1に記載の方法。
- 前記MD延伸第一非多孔性前駆体と前記MD延伸第二非多孔性前駆体とを積層した後、この積層物を圧延する、請求項2に記載の方法。
- 前記MD及びTD延伸第一非多孔性前駆体と前記MD延伸第二非多孔性前駆体とを積層した後、この積層物を圧延する、請求項5に記載の方法。
- 前記MD及びTD延伸第一非多孔性前駆体と前記MD延伸第二非多孔性前駆体とを積層した後、この積層物を圧延する、請求項6に記載の方法。
- 前記MD延伸第一非多孔性前駆体及び前記MD延伸第二非多孔性前駆体の少なくとも1つを、積層前に処理して接着性を向上する、請求項1に記載の方法。
- 前記MD延伸第一非多孔性前駆体及び前記MD延伸第二非多孔性前駆体の少なくとも1つを、積層前に処理して接着性を向上する、請求項2に記載の方法。
- 前記MD延伸第一非多孔性前駆体及び前記MD延伸第二非多孔性前駆体の少なくとも1つを、積層前に処理して接着性を向上する、請求項3に記載の方法。
- 前記MD及びTD延伸第一非多孔性前駆体並びに前記MD延伸第二非多孔性前駆体の少なくとも1つを、延伸後だが積層前に処理して接着性を向上する、請求項5に記載の方法。
- 前記MD及びTD延伸第一非多孔性前駆体並びに前記MD延伸第二非多孔性前駆体の少なくとも1つを、延伸後だが積層前に処理して接着性を向上する、請求項6に記載の方法。
- 前記MD及びTD延伸並びに圧延第一非多孔性前駆体並びに前記MD延伸第二非多孔性前駆体の少なくとも1つを、延伸及び圧延後だが積層前に処理して接着性を向上する、請求項9に記載の方法。
- 前記MD及びTD延伸並びに圧延第一非多孔性前駆体並びに前記MD延伸第二非多孔性前駆体の少なくとも1つを、延伸及び圧延後だが積層前に処理して接着性を向上する、請求項10に記載の方法。
- 前記MD延伸第一非多孔性前駆体及び前記MD延伸第二非多孔性前駆体の少なくとも1つを、延伸後だが積層前に処理して接着性を向上する、請求項11に記載の方法。
- 前記MD延伸第一非多孔性前駆体及び前記MD延伸第二非多孔性前駆体の少なくとも1つを、延伸後だが積層前に処理して接着性を向上する、請求項12に記載の方法。
- 前記MD及びTD延伸第一非多孔性前駆体並びに前記MD延伸第二非多孔性前駆体の少なくとも1つを、延伸後だが積層前に処理して接着性を向上する、請求項13に記載の方法。
- 前記MD及びTD延伸第一非多孔性前駆体並びに前記MD延伸第二非多孔性前駆体の少なくとも1つを、延伸後だが積層前に処理して接着性を向上する、請求項14に記載の方法。
- 前記前駆体に対する処理は、予備加熱、コロナ処理、プラズマ処理、粗面化、UV照射、エキシマ照射、又は接着剤塗布から成る群から選択される少なくとも1つである、請求項15〜25のいずれか一項に記載の方法。
- 前記多層微多孔膜は:
ポリプロピレン樹脂及び140℃以上且つ330℃以下の融点を有する樹脂の少なくとも1つを含む、前記第一MD延伸非多孔性前駆体膜と;
ポリエチレン樹脂を含む、前記第二MD延伸非多孔性前駆体膜と;
ポリプロピレン樹脂及び140℃以上且つ330℃以下の融点を有する樹脂の少なくとも1つを含む第三膜であって、この順、すなわち、第一前駆体−第二前駆体−第三膜の順で、前記膜を積層する、第三膜と
を備える、請求項1に記載の方法。 - ポリプロピレン樹脂及び140℃以上且つ330℃以下の融点を有する樹脂の少なくとも1つを含む樹脂混合物を押出して、第三非多孔性前駆体を製造し、次いで、前記縦方向(MD)に前記第三非多孔性前駆体を延伸して細孔を形成することによって前記第三膜を製造する、請求項27に記載の方法。
- 前記多層微多孔膜は:
ポリプロピレン樹脂及び140℃以上且つ330℃以下の融点を有する樹脂の少なくとも1つを含む、前記第一MD延伸非多孔性前駆体膜と;
ポリエチレン樹脂を含む、前記第二MD延伸非多孔性前駆体膜と;
ポリエチレンを含む第三膜であって、以下の順:第二前駆体、第一前駆体、第三前駆体の順で、前記膜を積層する、第三膜と
を備える、請求項1に記載の方法。 - ポリエチレン樹脂を含む樹脂混合物を押出して第三非多孔性前駆体を製造し、次いで、前記縦方向(MD)に前記第三非多孔性前駆体を延伸して細孔を形成することによって前記第三膜を製造する、請求項29に記載の方法。
- 前記多層微多孔膜は、二層微多孔膜である、請求項1に記載の方法。
- 前記多層微多孔膜は、三層微多孔膜である、請求項1に記載の方法。
- 前記多層微多孔膜は、四層以上を備える微多孔膜である、請求項1に記載の方法。
- 前記第一非多孔性前駆体を、積層前に、MDおよびTDに順次又は同時に延伸する、請求項3に記載の方法。
- 前記MD及びTD延伸第一非多孔性前駆体並びに前記MD延伸第二非多孔性前駆体の少なくとも1つを、延伸後だが積層前に処理して接着性を向上する、請求項34に記載の方法。
- 前記MD及びTD延伸第一非多孔性前駆体を、積層前に圧延する、請求項34に記載の方法。
- 前記MD延伸第一非多孔性前駆体及び前記MD延伸第二非多孔性前駆体の少なくとも1つを、延伸後だが積層前に処理して接着性を向上する、請求項36に記載の方法。
- 前記MD及びTD延伸第一非多孔性前駆体と前記MD延伸第二非多孔性前駆体とを積層した後、この積層物を圧延する、請求項34に記載の方法。
- 前記MD及びTD延伸第一非多孔性前駆体並びに前記MD延伸第二非多孔性前駆体の少なくとも1つを、延伸後だが積層前に処理して接着性を向上する、請求項38に記載の方法。
- 前記MD延伸第一非多孔性前駆体を、積層前に圧延する、請求項3に記載の方法。
- 前記MD延伸第一非多孔性前駆体及び前記MD延伸第二非多孔性前駆体の少なくとも1つを、積層前に圧延する、請求項3に記載の方法。
- 前記MD延伸第一非多孔性前駆体及び前記MD延伸第二非多孔性前駆体の両方を、積層前に圧延する、請求項41に記載の方法。
- 前記MD延伸非多孔性及び前記MD前駆体延伸第二非多孔性前駆体の少なくとも1つを、延伸後、圧延前又は圧延後、及び積層前に処理して接着性を向上する、請求項41又は42に記載の方法。
- 請求項1〜43のいずれか一項に記載の方法によって製造された多層微多孔膜。
- 以下の特性又は特徴
a)50〜400、100〜400、150〜400、100〜300、又は好ましくは100〜200のJISガーレー;
b)150gf〜600gf、300gf〜600gf、320gf〜600gf、より好ましくは380gf〜600gf、最も好ましくは400gf〜600gf以上の突刺強度、
c)500kg/cm2超、600kg/cm2超、700kg/cm2超、好ましくは1,000kg/cm2超のMD強さ、
d)300kg/cm2超、350kg/cm2超、好ましくは500kg/cm2超、最も好ましくは600kg/cm2超のTD強さ、
e)好ましくは30%以上、40%以上、50%以上、又はより好ましくは100%超のMD伸び、
f)好ましくは30%以上、又は40%、又は50%、又は60%又はより好ましくは70%以上のTD伸び、
g)25%未満、より好ましくは20%未満、さらにより好ましくは15%未満;最も好ましくは10%以下である、105℃、120℃、130℃、又は140℃の少なくとも1つにおけるMD収縮率、
h)15%未満、好ましくは10%未満、最も好ましくは5%未満である、105℃、120℃、130℃、又は140℃の少なくとも1つにおけるTD収縮率、
i)少ない割れ、
j)良好な均一性、及び結果として、より高い最小絶縁破壊値、
k)25ミクロン以下、好ましくは20ミクロン以下、最も好ましくは15ミクロン以下の厚さ、
l)1000ppm未満、900ppm未満、800ppm未満、700ppm未満、600ppm未満、400ppm未満、300ppm未満、最も好ましくは200ppm未満である含水率、
m)300kg/cm2超、350kg/cm2超、好ましくは500kg/cm2超、最も好ましくは600kg/cm2超のTD強さを有する多層微多孔膜及び15%未満、好ましくは10%未満、最も好ましくは5%未満である、105℃、120℃、130℃、又は140℃の少なくとも1つにおけるTD収縮率を有する層の少なくとも1つの層、並びに
n)160℃未満、好ましくは150℃未満、又はより好ましくは140℃未満、最も好ましくは135℃未満のシャットダウン温度を有する多層微多孔膜の少なくとも1つの層、
の少なくとも1つを有する、請求項44に記載の多層微多孔膜。 - 前記以下の特性のうち少なくとも2つ、3つ、4つ、5つ、6つ、7つ、8つ、9つ、10、11、12、13又は14を有する、請求項45に記載の多層微多孔膜。
- 請求項44〜46のいずれか一項に記載の多層微多孔膜の少なくとも1つを備えるバッテリーセパレータ。
- 前記多層微多孔膜の少なくとも1つを、その片面又は両面に被覆する、請求項47に記載のバッテリーセパレータ。
- 前記多層微多孔膜の少なくとも1つを、対向する2つの面に被覆する、請求項48に記載のバッテリーセパレータ。
- 前記多層微多孔膜の少なくとも1つを、その片面だけに被覆する、請求項48に記載のバッテリーセパレータ。
- 前記多層微多孔膜の少なくとも1つを、セラミックコーティングで被覆しない、請求項47に記載のバッテリーセパレータ。
- 請求項47〜51のいずれか一項に記載のバッテリーセパレータを備える二次リチウムイオン電池又はセル。
- 二次リチウムイオン電池用電極と直接接触している、請求項47〜51のいずれか一項に記載のバッテリーセパレータを備えるコンポジット。
- 請求項47〜51のいずれか一項に記載のバッテリーセパレータを備える乗り物又はデバイス。
- 請求項52〜53のいずれか一項に記載のコンポジット、バッテリー又はセルを備える乗り物又はデバイス。
- 請求項53に記載のコンポジットを備える乗り物又はデバイス。
- 前記多層微多孔膜は、ドライプロセス二層微多孔膜である、請求項1に記載の方法。
- 前記多層微多孔膜は、ドライプロセス三層微多孔膜である、請求項1に記載の方法。
- 前記多層微多孔膜は、ドライプロセス四層以上を備える微多孔膜である、請求項1に記載の方法。
- 請求項47〜51のいずれか一項に記載のドライプロセスバッテリーセパレータを備える乗り物又はデバイス。
- 請求項1〜43のいずれか一項に記載の方法によって製造されたドライプロセス多層微多孔膜。
- 請求項1〜43のいずれか一項に記載のドライプロセス方法によって製造された多層微多孔膜。
- 前記膜を、圧延してから被覆(又は処理)をするか、又は被覆してから圧延するか、又は圧延し、被覆してから再度圧延する、請求項1〜43のいずれか一項に記載の方法によって製造される多層微多孔膜。
- 前記膜を、圧延してから被覆(又は処理)をするか、又は被覆(又は処理)してから圧延する、請求項1〜43のいずれか一項に記載の方法によって製造される多層微多孔膜。
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