JP2015218276A - 樹脂フィルム、積層体及びその製造方法並びに燃料電池の製造方法 - Google Patents
樹脂フィルム、積層体及びその製造方法並びに燃料電池の製造方法 Download PDFInfo
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- JP2015218276A JP2015218276A JP2014103604A JP2014103604A JP2015218276A JP 2015218276 A JP2015218276 A JP 2015218276A JP 2014103604 A JP2014103604 A JP 2014103604A JP 2014103604 A JP2014103604 A JP 2014103604A JP 2015218276 A JP2015218276 A JP 2015218276A
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- resin
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- cyclic olefin
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Abstract
Description
本発明の樹脂フィルムは、環状オレフィン系樹脂(A)と塩素含有樹脂(B)とを含む樹脂組成物で形成されている。
環状オレフィン系樹脂(A)は、少なくとも繰り返し単位として環状オレフィン単位(A1)を含んでいればよい。環状オレフィン系樹脂(A)は、側鎖に長鎖アルキル基を有さないオレフィン系樹脂であり、特に、側鎖に炭素数3〜10のアルキル基を有するオレフィン単位(すなわち、C3−10アルキル基を有する鎖状オレフィン単位及び/又はC3−10アルキル基を有する環状オレフィン単位)を含まない環状オレフィン系樹脂であってもよい。
塩素含有樹脂(B)は、塩素化ポリエチレン、塩素化ポリプロピレンなどの塩素化された樹脂であってもよいが、通常、塩素含有モノマーを重合成分とする重合体である。本発明では、環状オレフィン系樹脂(A)に塩素含有樹脂(B)を配合すると、イオン交換樹脂を含む層に対する適度な密着性(離型性)を維持しつつ、易接着層などの接着層を介在させることなく、ポリエチレンテレフタレート(PET)フィルムなどの汎用の基材にフィルムに密着できる。
本発明の樹脂フィルムは、離型性及び耐熱性に優れるため、単独(単層)で離型フィルムとして使用してもよいが、燃料電池の生産性を向上でき、薄肉で厚みの均一なフィルムを形成し易い点から、基材層(基材フィルム)の少なくとも一方の面に、前記樹脂フィルムを離型層として積層するのが好ましい。
基材層は、燃料電池の製造工程において、離型フィルムの寸法安定性を向上でき、特に、ロール・ツー・ロール方式において張力が負荷されても、伸びを抑制でき、さらに乾燥工程や加熱圧着処理などによって高温に晒されても、高い寸法安定性を維持し、電解質膜や電極膜との剥離を抑制できる点から、耐熱性及び寸法安定性の高い材質で形成されているのが好ましく、具体的には、150℃における弾性率が100〜1000MPaの合成樹脂で形成されていてもよい。前記弾性率は、例えば、120〜1000MPa、好ましくは150〜1000MPa、さらに好ましくは200〜1000MPa程度であってもよい。弾性率が小さすぎると、寸法安定性が低下し、ロール・ツー・ロール方式での製造において電解質膜や電極膜との剥離が発生し、燃料電池の生産性が低下する。
本発明の積層フィルム(積層体)は、固体高分子型燃料電池を製造するための離型フィルムであってもよく、この離型フィルムとして利用される場合、前記積層フィルム(離型フィルム)の離型層の上に、イオン交換樹脂を含む層(電解質膜、電極膜、膜電極接合体)を密着させる。そのため、本発明の積層フィルムは、離型層(樹脂フィルム単独で形成された離型層又は積層フィルムの離型層)の上にイオン交換樹脂を含む層が積層された積層体であってもよい。
本発明の樹脂フィルムは、薄肉で、表面平滑なフィルムを形成し易い点から、基材の上に樹脂組成物を含む溶液をコーティングする方法により製造でき、具体的には、積層フィルムの場合、基材層の上に環状オレフィン系樹脂及び塩素含有樹脂を含む溶液をコーティング(又は流延)した後、乾燥する方法により製造できる。なお、樹脂フィルムを単層で製造する場合は、剥離可能な基材の上にコーティングしてもよい。
イオン交換樹脂溶液:側鎖にスルホン酸基を有するパーフルオロポリマーの溶液、デュポン社製「ナフィオン(登録商標)DE2021CS」、固形分20重量%
PETフィルム:ユニチカ(株)製「ポリエステルフィルム エンブレット S50」、厚み50μm、易接着層なし
OPPフィルム:豊科フイルム(株)製「P3018」、厚み30μm、易接着層なし
TACフィルム:富士フイルム(株)製「Z−TAC」、厚み60μm、易接着層なし
Nb/Et:2−ノルボルネン・エチレン共重合体、Topas Advanced Polymers GmbH社製「TOPAS(登録商標)6017S−04」、ガラス転移温度178℃
PVDC:塩化ビニリデン系共重合体、旭化成ケミカルズ(株)製「PVDCレジン R204」
実施例及び比較例で得られた離型フィルムを20℃、50RH%で1時間以上静置後、離型層の上にセロハンテープ(ニチバン(株)製「CT405AP−15」)を強く圧着させ、テープの端を45°の角度で一気に引き剥がし、テープを剥がした面積に対して塗膜が残存した面積を求めて評価した。
実施例及び比較例で得られた離型フィルム、イオン交換樹脂溶液(デュポン社製「ナフィオン(登録商標)DE2021CS」、イオン交換樹脂の水−アルコール分散液、固形分濃度20重量%)を用意し、ドクターブレードを用いて、前記離型フィルムの離型層の上に前記イオン交換樹脂溶液をキャストし、その塗膜を100℃のオーブン内で乾燥させて、電解質膜であるイオン交換樹脂層(厚み20μm)を含む積層体を形成した。
×…イオン交換樹脂層が剥がれない。
Nb/Etを、固形分濃度が5重量%となるように、トルエンに添加し、加温して溶解し、塗工液を調製した。得られた塗工液をメイヤーバーコーティング法によりPETフィルムの片面にコーティングし、100℃の温度で1分間乾燥して離型層(乾燥厚み0.3μm)を形成し、離型フィルムを得た。
PETフィルムの代わりにOPPフィルムを用いる以外は比較例1と同様にして離型フィルムを得た。
PETフィルムの代わりにTACフィルムを用いる以外は比較例1と同様にして離型フィルムを得た。
Nb/Et100重量部及びPVDC1重量部を、固形分濃度が5重量%となるように、トルエン及びテトラヒドロフランの混合溶媒(トルエン/テトラヒドロフラン=70/30(重量比))に添加し、加温して溶解し、塗工液を調製した。得られた塗工液を用いて比較例1と同様にして離型フィルムを得た。
PVDCの割合を1.2重量部に変更する以外は実施例1と同様にして離型フィルムを得た。
PVDCの割合を2重量部に変更する以外は実施例1と同様にして離型フィルムを得た。
固形分濃度を0.5重量%に変更し、乾燥後の離型層の厚み0.01μmとした以外は実施例3と同様にして離型フィルムを得た。
PVDCの割合を60重量部に変更する以外は実施例1と同様にして離型フィルムを得た。
Claims (17)
- 環状オレフィン系樹脂(A)と塩素含有樹脂(B)とを含む樹脂組成物で形成された樹脂フィルム。
- 塩素含有樹脂(B)が塩化ビニリデン系重合体である請求項1記載の樹脂フィルム。
- 環状オレフィン系樹脂(A)が、環状オレフィン系共重合体である請求項1又は2記載の樹脂フィルム。
- 環状オレフィン系樹脂(A)が、繰り返し単位として環状オレフィン単位(A1)及び鎖状オレフィン単位(A2)を含む請求項1〜3のいずれかに記載の樹脂フィルム。
- 環状オレフィン系樹脂(A)がノルボルネン類とα−鎖状C2−4オレフィンとの共重合体である請求項1〜4のいずれかに記載の樹脂フィルム。
- 環状オレフィン単位(A1)と鎖状オレフィン単位(A2)との割合(モル比)が、前者/後者=50/50〜90/10である請求項4又は5記載の樹脂フィルム。
- 環状オレフィン系樹脂(A)が、側鎖に炭素数3〜10のアルキル基を有するオレフィン単位を含まない環状オレフィン系樹脂である請求項1〜6のいずれかに記載の樹脂フィルム。
- 塩素含有樹脂(B)の割合が、環状オレフィン系樹脂(A)100重量部に対して、0.5〜60重量部である請求項1〜7のいずれかに記載の樹脂フィルム。
- 固体高分子型燃料電池の膜電極接合体を製造するための離型フィルムである請求項1〜8のいずれかに記載の樹脂フィルム。
- 基材層の少なくとも一方の面に、請求項1〜9のいずれかに記載のフィルムで形成された離型層が積層されている積層フィルム。
- 基材層が、ポリオレフィン、ポリビニルアルコール系重合体、ポリエステル、ポリアミド、ポリイミド及びセルロース誘導体からなる群より選択された少なくとも1種で形成されている請求項10記載の積層フィルム。
- 基材層が、ポリエステルで形成され、かつ易接着層を有していてない請求項11記載の積層フィルム。
- 離型層がコーティングで形成された平均厚み0.01〜20μmの層である請求項10〜12のいずれかに記載の積層フィルム。
- 離型層の上にイオン交換樹脂を含む層が積層された請求項10〜13のいずれかに記載の積層フィルム。
- イオン交換樹脂が側鎖にスルホン酸基を有するフッ素樹脂であり、かつイオン交換樹脂を含む層が、電解質膜及び/又は電極膜である請求項14記載の積層フィルム。
- 基材層の上に樹脂組成物を含む溶液をコーティングして離型層を形成する積層工程を含む請求項10〜15のいずかに記載の積層フィルムの製造方法。
- 請求項14又は15記載の積層フィルムからイオン交換樹脂を含む層を剥離する剥離工程を含む固体高分子型燃料電池の膜電極接合体の製造方法。
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