JP6828680B2 - 電池用包装材料、その製造方法及び電池 - Google Patents
電池用包装材料、その製造方法及び電池 Download PDFInfo
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- JP6828680B2 JP6828680B2 JP2017509933A JP2017509933A JP6828680B2 JP 6828680 B2 JP6828680 B2 JP 6828680B2 JP 2017509933 A JP2017509933 A JP 2017509933A JP 2017509933 A JP2017509933 A JP 2017509933A JP 6828680 B2 JP6828680 B2 JP 6828680B2
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Description
項1. 少なくとも、基材層、接着層、金属層、及び熱融着性樹脂層をこの順に備える積層体からなり、
前記基材層の一方向及び当該一方向と同一平面で直交する他方向における引張弾性率が、共に400N/15mm以上1000N/15mm以下の範囲にあり、
前記基材層の当該一方向及び他方向における引張弾性率の差の絶対値が、150N/15mm以下である、電池用包装材料。
項2. 前記金属層は、一方向の引張試験を行った時の耐力Aと、当該一方向と同一平面で直交する他方向の引張試験を行った時の耐力Bとが、共に20N/15mm以上70N/15mmの範囲にあり、かつ、前記耐力Aと前記耐力Bの差の絶対値が2N/15mm以下である、項1に記載の電池用包装材料。
項3. 前記積層体の厚みが、100μm以下である、項1または2に記載の電池用包装材料。
項4. 前記基材層の厚みが、10μm以上35μm以下の範囲にある、項1〜3のいずれかに記載の電池用包装材料。
項5. 前記金属層の厚みが、10μm以上35μm以下の範囲にある、項1〜4のいずれかに記載の電池用包装材料。
項6. 前記基材層が、ポリエステル樹脂及びポリアミドの少なくとも一方を含んでいる、項1〜5のいずれかに記載の電池用包装材料。
項7. 前記金属層の少なくとも一方の面に化成処理が施されている、項1〜6のいずれかに記載の電池用包装材料。
項8. 二次電池用の包装材料である、項1〜7のいずれかに記載の電池用包装材料。
項9. 少なくとも正極、負極、及び電解質を備えた電池素子が、項1〜8のいずれかに記載の電池用包装材料により形成された包装体中に収容されている、電池。
項10. 少なくとも、基材層、接着層、金属層、及び熱融着性樹脂層とがこの順となるように積層して積層体を得る工程を備えており、
前記基材層として、以下の物性を備えるものを用いる、電池用包装材料の製造方法。
前記基材層の当該一方向及び他方向における引張弾性率が、共に400N/15mm以上1000N/15mm以下の範囲にある。
前記基材層の一方向及び当該一方向と同一平面で直交する他方向における引張弾性率の差の絶対値が、150N/15mm以下である。
電池用包装材料は、図1に示すように、少なくとも、基材層1、接着層2、金属層3、及び熱融着性樹脂層4をこの順に備える積層体からなる。本発明の電池用包装材料において、基材層1が最外層になり、熱融着性樹脂層4は最内層になる。即ち、電池の組み立て時に、電池素子の周縁に位置する熱融着性樹脂層4同士が熱溶着して電池素子を密封することにより、電池素子が封止される。
[基材層1]
本発明の電池用包装材料において、基材層1は最外層を形成する層である。本発明においては、基材層1の一方向(基材層の厚みとは垂直方向)及び当該一方向と同一平面で直交する他方向における引張弾性率が、共に400N/15mm以上1000N/15mm以下の範囲にある。さらに、基材層1の一方向及び当該他方向における引張弾性率の差の絶対値が、150N/15mm以下である。本発明の電池用包装材料においては、少なくとも、基材層1、接着層2、金属層3、及び熱融着性樹脂層4をこの順に備える積層体において、基材層1がこのような特定の引張弾性率を備えていることにより、電池用包装材料の成形時にピンホールやクラックが生じ難く、優れた成形性を備えており、さらに、成形後のカールが効果的に抑制される。
本発明の電池用包装材料において、接着層2は、基材層1と金属層3を強固に接着させるために、これらの間に設けられる層である。
電池用包装材料において、金属層3は、電池用包装材料の強度向上の他、電池内部に水蒸気、酸素、光などが侵入することを防止するためのバリア層として機能する層である。金属層3を構成する金属としては、具体的には、アルミニウム、ステンレス、チタンなどが挙げられ、好ましくはアルミニウムが挙げられる。金属層3は、金属箔や金属蒸着などにより形成することができ、金属箔により形成することが好ましく、アルミニウム箔により形成することがさらに好ましい。電池用包装材料の製造時に、金属層3にしわやピンホールが発生することを防止する観点からは、例えば、焼きなまし処理済みのアルミニウム(JIS H4160 A8021H−O、JIS H4160 A8079H−O、JIS H4000:2014 A8021P−O、JIS H4000:2014 A8079P−O)など軟質アルミニウム箔により形成することがより好ましい。
本発明の電池用包装材料において、熱融着性樹脂層4は、最内層に該当し、電池の組み立て時に熱融着性樹脂層同士が熱溶着して電池素子を密封する層である。
本発明の電池用包装材料において、接着層5は、金属層3と熱融着性樹脂層4を強固に接着させために、これらの間に必要に応じて設けられる層である。
本発明の電池用包装材料においては、意匠性、耐電解液性、耐擦過性、成形性の向上などを目的として、必要に応じて、基材層1の上(基材層1の金属層3とは反対側)に、必要に応じて、表面被覆層(図示しない)を設けてもよい。表面被覆層は、電池を組み立てた時に、最外層に位置する層である。
本発明の電池用包装材料の製造方法については、所定の組成の各層を積層させた積層体が得られる限り、特に制限されず、少なくとも、基材層、接着層、金属層、及び熱融着性樹脂層とがこの順となるように積層して積層体を得る工程を備えており、基材層1として、以下の物性を備えるものを用いる製造方法を採用することができる。
前記基材層の一方向及び当該一方向と同一平面で直交する他方向における引張弾性率が、共に400N/15mm以上1000N/15mm以下の範囲にある。
前記基材層の当該一方向及び他方向における引張弾性率の差の絶対値が、150N/15mm以下である。
すなわち、基材層1として、「2.電池用包装材料を形成する各層」の欄で説明した基材層1を用いて、各層を積層することにより、本発明の電池用包装材料を製造することができる。
本発明の電池用包装材料は、正極、負極、電解質等の電池素子を密封して収容するための包装材料として使用される。すなわち、本発明の電池は、少なくとも正極、負極、及び電解質を備えた電池素子が、本発明の電池用包装材料により形成された包装袋中に収容されている。
<電池用包装材料の製造>
基材層の上に、両面に化成処理を施したアルミニウム箔(厚さ30μm)からなる金属層をドライラミネーション法により積層させた。具体的には、アルミニウム箔の一方面に、2液型ウレタン接着剤(ポリオール化合物と芳香族イソシアネート系化合物)を塗布し、金属層上に接着層(厚さ3μm)を形成した。次いで、金属層上の接着層と基材層をドライラミネーション法で積層した後、40℃で24時間のエージング処理を実施することにより、基材層/接着層/金属層の積層体を作成した。なお、金属層として使用したアルミニウム箔の化成処理は、フェノール樹脂、フッ化クロム化合物、及びリン酸からなる処理液をクロムの塗布量が10mg/m2(乾燥質量)となるように、ロールコート法によりアルミニウム箔の両面に塗布し、皮膜温度が180℃以上となる条件で20秒間焼付けすることにより行った。次に積層体の金属層の上に、カルボン酸変性ポリプロピレン(金属層側に配置)20μmとランダムポリプロピレン(最内層)20μmを共押し出しすることにより、金属層上に接着層/熱接着性樹脂層を積層させた。各実施例及び比較例で使用した各層の具体的な材料は以下及び表1の通りである。
基材層1として使用した2軸延伸ナイロン1〜6、ポリエチレンテレフタレート/ナイロン2層フィルム1,2、ポリプロピレンフィルム1,2、未延伸ナイロン1,2、ポリエチレンテレフタレート1,2の詳細を、それぞれ以下に示す。なお、表1に示す引張弾性率は、それぞれ、JIS K7161−1994の規定に準拠した方法で測定した値である。
ナイロン6を主成分とする原料からなる未延伸原反フィルムをチューブラー法による同時二軸延伸した後、210℃で熱処理することにより製造したものである。延伸倍率(MD・TD)はそれぞれ、ナイロン1(Ny1)が3.0倍、3.2倍、ナイロン6(Ny6)が2.9倍、3.1倍の条件で製造したものである。
ナイロン6を主成分とする原料からなる未延伸原反フィルムをテンター法による逐次二軸延伸した後、210℃で熱処理することにより製造したものである。延伸倍率(MD・TD)は、それぞれ、ナイロン2(Ny2)が、3.0倍、3.3倍、ナイロン3(Ny3)が二段延伸1.6倍+2.1倍、4.0倍、ナイロン4(Ny4)が2.7倍、3.5倍、ナイロン5(Ny5)が3.0倍、3.3倍の条件で製造したものである。
ナイロン6を主成分とする原料をTダイよりシート状に溶融押出した後、エアーナイフキャスト法により回転ドラムに密着させて急冷することにより製造したものである。未延伸ナイロン1(CN1)は、押出し温度270℃、ドラム温度50℃、未延伸ナイロン2(CN2)は、押出し温度260℃、ドラム温度25℃にて製造した。
ポリエチレンテレフタレートを主成分とする原料からなる未延伸原反フィルムをテンター法による逐次二軸延伸した後、200℃で熱処理することにより製造したものである。延伸倍率(MD・TD)は、それぞれ、ポリエチレンテレフタレート1(PET1)が4.7倍、5.5倍、ポリエチレンテレフタレート2(PET2)が5.3倍、6.4倍の条件で製造したものである。
以下に示す樹脂を主成分とするA層/B層/C層からなる未延伸原反フィルムをテンター法による逐次二軸延伸した後、210℃で熱処理することにより製造したものである。A層/B層/C層の層比、延伸倍率(MD・TD)はそれぞれ、ポリエチレン/ナイロン2層フィルム1(PET/Ny1)が5/1/19、3.2倍、3.4倍、ポリエチレン/ナイロン2層フィルム2(PET/Ny2)が4/1/10、3.0倍、4.0倍の条件で製造したものである。
なお、ポリエチレンテレフタレートフィルム側が最表面(金属層とは反対側)になるようにした。
・A層:ポリエチレンテレフタレートを主成分とする原料
・B層:無水マレイン酸変性ポリオレフィンを主成分とする原料
・C層:ナイロン6を主成分とする原料
ランダムポリプロピレンを主成分とする原料からなる未延伸原反フィルムをテンター法による逐次二軸延伸した後、160℃で熱処理することにより製造したものである。延伸倍率(MD・TD)はそれぞれ、ポリプロピレンフィルム1(PP1)が11.0倍、6.0倍、ポリプロピレンフィルム2(PP2)が8.0倍、7.0倍の条件で製造したものである。
軟質アルミニウム(JIS H4160 A8021H−O)厚さ30μmを使用した。焼きなまし条件を変更することにより、耐力の異なる5種類のアルミニウム箔(ALM1〜5)を得た。なお、アルミニウム箔の耐力は、JIS Z2241に規定された引張試験(全伸び法)により測定した値である。
基材層1と金属層3とを接着する接着層2として、ガラス転移点−5℃以上5℃、重量平均分子量10×103以上40×103以下、水酸基等量0.7個/mol以上1.9個/mol以下のポリオール化合物とトルエンジイソシアネート(TDI)のトリメチロールプロパン(TMP)アダクト体を主成分とする芳香族イソシアネートを1:3の比率で混合したウレタン樹脂系接着剤を用いた。
熱融着性樹脂層4と金属層3との接着する接着層5として、ビガット軟化点105℃、融点146℃のランダムタイプポリプロピレンベース不飽和カルボン酸変性ポリプロピレンを使用した。
エルカ酸アミド700ppmを添加した融点142℃、メルトインデックス10g/minのエチレンコンテント7%ランダムポリプロピレンを使用した。
上記で得られた各電池用包装材料を80mm×120mmの長方形に断裁してサンプルを作製した。このサンプルを30mm×50mmの口径を有する成形金型(雌型)と、これに対応した成形金型(雄型)を用いて、押さえ圧0.4MPaで0.5mmの成形深さから0.5mm単位で成形深さを変えて、それぞれ10個のサンプルについて冷間成形を行った。冷間成形後のサンプルについて、シワやアルミニウム箔にピンホール、クラックが10個のサンプル全てにおいて発生しない最も深い成形深さを、そのサンプルの限界成形深さとした。この限界成形深さから、以下の基準により電池包装材料の成形性を評価した。結果を表1に示す。
Aは限界成形深さ6.5mm超え
Bは限界成形深さ5.5mm以上6.5mm以下
Cは限界成形深さ4.0mm以上5.5mm未満
Dは限界成形深さ3.5mm以下
上記で得られた各電池用包装材料を裁断して、150mm×100mmの短冊片を作製し、これを試験サンプルとした。30mm×50mmの矩形状の雄型とこの雄型とのクリアランスが0.5mmの雌型からなるストレート金型を用い、雄型側に熱融着性樹脂層4側が位置するように雌型上に上記試験サンプルを載置し、成形深さ6mmとなるように当該試験サンプルを0.1MPaの押え圧(面圧)で押えて、冷間成形(引き込み1段成形)した。成形を行った位置の詳細は、図3に示される通りである。図4に示されるように、矩形状の成形部Mと電池用包装材料10の端部Pとの最短距離d=25mmとなる位置で成形した。次に、成形後の電池用包装材料10を、図に示すようにして水平面20におき、水平面20から端部Pまでの垂直方向yの距離の最大値tをカールしている部分の最大高さとした。成形後のカールの評価基準は、以下の通りである。結果を表に示す。Aはt=0mm以上、10mm未満であり、カールが小さく、生産性をほとんど低下させない
Bはt=10mm以上、20mm未満であり、カールがやや大きいが、生産性の低下は小さい
Cはt=20mm以上、30mm未満であり、カールが大きく、生産性の低下が大きい
Dはt=30mm以上であり、カールが非常に大きく、生産性の低下が非常に大きい
Ny:ナイロン
PET:ポリエチレンテレフタレート
PET/Ny:ポリエチレンテレフタレート/ナイロン2層フィルム、
PP:ポリプロピレン
CN:未延伸ナイロン
一方、これらの要件のいずれか1つでも満たさない比較例1〜22においては、実施例1〜8に比して成形性が劣っており、成形後のカールが生じるものもあった。
2 接着層
3 金属層
4 熱融着性樹脂層
5 接着層
10 電池用包装材料
M 成形部
P 端部
Claims (12)
- 少なくとも、基材層、接着層、金属層、及び熱融着性樹脂層をこの順に備える積層体からなり、
前記基材層の一方向及び当該一方向と同一平面で直交する他方向における引張弾性率が、共に400N/15mm以上1000N/15mm以下の範囲にあり、
前記基材層の当該一方向及び他方向における引張弾性率の差の絶対値が、150N/15mm以下であり、
前記金属層は、一方向の引張試験を行った時の耐力Aと、当該一方向と同一平面で直交する他方向の引張試験を行った時の耐力Bとが、共に20N/15mm以上70N/15mm以下の範囲にあり、かつ、前記耐力Aと前記耐力Bの差の絶対値が2N/15mm以下である、電池用包装材料。 - 少なくとも、基材層、接着層、金属層、及び熱融着性樹脂層をこの順に備える積層体からなり、
前記基材層の一方向及び当該一方向と同一平面で直交する他方向における引張弾性率が、共に400N/15mm以上1000N/15mm以下の範囲にあり、
前記基材層の当該一方向及び他方向における引張弾性率の差の絶対値が、150N/15mm以下であり、
前記積層体の厚みが、100μm以下である、電池用包装材料。 - 前記金属層は、一方向の引張試験を行った時の耐力Aと、当該一方向と同一平面で直交する他方向の引張試験を行った時の耐力Bとが、共に20N/15mm以上70N/15mm以下の範囲にあり、かつ、前記耐力Aと前記耐力Bの差の絶対値が2N/15mm以下である、請求項2に記載の電池用包装材料。
- 前記積層体の厚みが、100μm以下である、請求項1に記載の電池用包装材料。
- 前記基材層の厚みが、10μm以上35μm以下の範囲にある、請求項1〜4のいずれかに記載の電池用包装材料。
- 前記金属層の厚みが、10μm以上35μm以下の範囲にある、請求項1〜5のいずれかに記載の電池用包装材料。
- 前記基材層が、ポリエステル樹脂及びポリアミド樹脂の少なくとも一方を含んでいる、請求項1〜6のいずれかに記載の電池用包装材料。
- 前記金属層の少なくとも一方の面に耐酸性皮膜層を備えている、請求項1〜7のいずれかに記載の電池用包装材料。
- 二次電池用の包装材料である、請求項1〜8のいずれかに記載の電池用包装材料。
- 少なくとも正極、負極、及び電解質を備えた電池素子が、請求項1〜9のいずれかに記載の電池用包装材料により形成された包装体中に収容されている、電池。
- 少なくとも、基材層、接着層、金属層、及び熱融着性樹脂層をこの順に備える積層体からなる電池用包装材料の製造方法であって、
前記基材層の一方向及び当該一方向と同一平面で直交する他方向における引張弾性率が、共に400N/15mm以上1000N/15mm以下の範囲にあり、
前記基材層の当該一方向及び他方向における引張弾性率の差の絶対値が、150N/15mm以下であり、
前記金属層は、一方向の引張試験を行った時の耐力Aと、当該一方向と同一平面で直交する他方向の引張試験を行った時の耐力Bとが、共に20N/15mm以上70N/15mm以下の範囲にあり、かつ、前記耐力Aと前記耐力Bの差の絶対値が2N/15mm以下である、電池用包装材料の製造方法。 - 少なくとも、基材層、接着層、金属層、及び熱融着性樹脂層をこの順に備える積層体からなる電池用包装材料の製造方法であって、
前記基材層の一方向及び当該一方向と同一平面で直交する他方向における引張弾性率が、共に400N/15mm以上1000N/15mm以下の範囲にあり、
前記基材層の当該一方向及び他方向における引張弾性率の差の絶対値が、150N/15mm以下であり、
前記積層体の厚みが、100μm以下である、電池用包装材料の製造方法。
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JP4899317B2 (ja) * | 2005-02-21 | 2012-03-21 | 大日本印刷株式会社 | 電池用包装材 |
JP4380728B2 (ja) * | 2007-05-16 | 2009-12-09 | ソニー株式会社 | 積層型包装材料、電池用外装部材および電池 |
CN103518272B (zh) * | 2011-05-11 | 2017-02-15 | 凸版印刷株式会社 | 锂离子电池用外包装材料、锂离子电池及锂离子电池的制造方法 |
JP6102083B2 (ja) | 2012-05-10 | 2017-03-29 | 凸版印刷株式会社 | リチウムイオン電池用外装材の基材層、リチウムイオン電池用外装材の基材層を用いたリチウムイオン電池の製造方法、及びリチウムイオン電池用外装材 |
US9865847B2 (en) | 2012-05-10 | 2018-01-09 | Toppan Printing Co., Ltd. | Outer package material for lithium-ion battery and method for producing lithium-ion battery using the outer package material |
KR101494589B1 (ko) | 2012-06-04 | 2015-02-17 | 다이니폰 인사츠 가부시키가이샤 | 전지용 포장 재료 |
CN107845743A (zh) * | 2012-09-28 | 2018-03-27 | 大日本印刷株式会社 | 电池用包装材料 |
JP5954084B2 (ja) * | 2012-09-28 | 2016-07-20 | 東レ株式会社 | 積層体 |
JP2015107583A (ja) | 2013-12-04 | 2015-06-11 | 出光ユニテック株式会社 | 多層フィルム、包装材および電池 |
KR20170046725A (ko) | 2014-08-28 | 2017-05-02 | 다이니폰 인사츠 가부시키가이샤 | 전지용 포장 재료 |
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CN107408645A (zh) | 2017-11-28 |
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