JP7033414B2 - 成形用包装材、蓄電デバイス用外装ケース及び蓄電デバイス - Google Patents
成形用包装材、蓄電デバイス用外装ケース及び蓄電デバイス Download PDFInfo
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- JP7033414B2 JP7033414B2 JP2017176419A JP2017176419A JP7033414B2 JP 7033414 B2 JP7033414 B2 JP 7033414B2 JP 2017176419 A JP2017176419 A JP 2017176419A JP 2017176419 A JP2017176419 A JP 2017176419A JP 7033414 B2 JP7033414 B2 JP 7033414B2
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Description
前記ポリブチレンテレフタレート層と前記金属箔層とが外側接着剤層を介して接着されており、
前記外側接着剤層は、ポリエステルポリオールと、多官能イソシアネート化合物と、多価アルコールと、を含むウレタン接着剤の硬化膜で形成され、
前記ポリエステルポリオールは、ジカルボン酸成分を含み、
前記ジカルボン酸成分は、芳香族ジカルボン酸を含有し、前記ジカルボン酸成分中の前記芳香族ジカルボン酸の含有率が40モル%~80モル%であり、
前記ウレタン接着剤の硬化膜のヤング率が70MPa~400MPaであり、
前記ポリブチレンテレフタレート層の引張強度が、MD方向で100MPa~300MPaであり、TD方向で100MPa~300MPaであることを特徴とする成形用包装材。
前項5に記載の蓄電デバイス用外装ケースを少なくとも含む外装部材とを備え、
前記蓄電デバイス本体部が、前記外装部材で外装されていることを特徴とする蓄電デバイス。
前記積層物を37℃~55℃の温度で加熱エージング処理を行うことによって前記硬化型内側接着剤および前記硬化型外側接着剤を硬化させるエージング処理工程と、を含み、
前記ポリエステルポリオールは、ジカルボン酸成分を含み、
前記ジカルボン酸成分は、芳香族ジカルボン酸を含有し、前記ジカルボン酸成分中の前記芳香族ジカルボン酸の含有率が40モル%~80モル%であることを特徴とする成形用包装材の製造方法。
1)リン酸と、
クロム酸と、
フッ化物の金属塩及びフッ化物の非金属塩からなる群より選ばれる少なくとも1種の化合物と、を含む混合物の水溶液
2)リン酸と、
アクリル系樹脂、キトサン誘導体樹脂及びフェノール系樹脂からなる群より選ばれる少なくとも1種の樹脂と、
クロム酸及びクロム(III)塩からなる群より選ばれる少なくとも1種の化合物と、を含む混合物の水溶液
3)リン酸と、
アクリル系樹脂、キトサン誘導体樹脂及びフェノール系樹脂からなる群より選ばれる少なくとも1種の樹脂と、
クロム酸及びクロム(III)塩からなる群より選ばれる少なくとも1種の化合物と、
フッ化物の金属塩及びフッ化物の非金属塩からなる群より選ばれる少なくとも1種の化合物と、を含む混合物の水溶液
上記1)~3)のうちのいずれかの水溶液を塗工した後、乾燥することにより、化成処理を施す。
厚さ35μmのアルミニウム箔(JIS H4160に規定されるA8079のアルミニウム箔)4の両面に、リン酸、ポリアクリル酸(アクリル系樹脂)、クロム(III)塩化合物、水、アルコールからなる化成処理液を塗布した後、180℃で乾燥を行って、化成皮膜を形成した。この化成皮膜のクロム付着量は片面当たり10mg/m2であった。
ジカルボン酸成分として、アジピン酸(脂肪族ジカルボン酸)55モル部およびイソフタル酸(芳香族ジカルボン酸)45モル部からなるジカルボン酸成分を用いて得られた数平均分子量12000のポリエステルポリオール100質量部を使用した以外は、実施例1と同様にして、図1に示す構成の成形用包装材1を得た。
ジカルボン酸成分として、アジピン酸(脂肪族ジカルボン酸)25モル部およびイソフタル酸(芳香族ジカルボン酸)75モル部からなるジカルボン酸成分を用いて得られた数平均分子量24000のポリエステルポリオール100質量部を使用した以外は、実施例1と同様にして、図1に示す構成の成形用包装材1を得た。
数平均分子量が9000のポリエステルポリオール100質量部を使用した以外は、実施例2と同様にして、図1に示す構成の成形用包装材1を得た。
数平均分子量が29000のポリエステルポリオール100質量部を使用した以外は、実施例3と同様にして、図1に示す構成の成形用包装材1を得た。
ジカルボン酸成分として、アジピン酸(脂肪族ジカルボン酸)50モル部およびイソフタル酸(芳香族ジカルボン酸)50モル部からなるジカルボン酸成分を用いて得られた数平均分子量5000のポリエステルポリオール100質量部を使用した以外は、実施例1と同様にして、図1に示す構成の成形用包装材1を得た。
ジカルボン酸成分として、アジピン酸(脂肪族ジカルボン酸)45モル部およびイソフタル酸(芳香族ジカルボン酸)55モル部からなるジカルボン酸成分を用いて得られた数平均分子量8000のポリエステルポリオール100質量部を使用した以外は、実施例1と同様にして、図1に示す構成の成形用包装材1を得た。
ジカルボン酸成分として、アジピン酸(脂肪族ジカルボン酸)30モル部およびイソフタル酸(芳香族ジカルボン酸)70モル部からなるジカルボン酸成分を用いて得られた数平均分子量28000のポリエステルポリオール100質量部を使用した以外は、実施例1と同様にして、図1に示す構成の成形用包装材1を得た。
ジカルボン酸成分として、アジピン酸(脂肪族ジカルボン酸)25モル部およびイソフ
タル酸(芳香族ジカルボン酸)75モル部からなるジカルボン酸成分を用いて得られた数
平均分子量32000のポリエステルポリオール100質量部を使用した以外は、実施例
1と同様にして、図1に示す構成の成形用包装材1を得た。
当量比[NCO]/[OH]を5に変更した以外は、実施例1と同様にして、図1に示す構成の成形用包装材1を得た。
当量比[NCO]/[OH]を20に変更した以外は、実施例1と同様にして、図1に示す構成の成形用包装材1を得た。
トリメチロールプロパン(TMP)10質量部に代えて、エチレングリコール(EG)10質量部を使用した以外は、実施例1と同様にして、図1に示す構成の成形用包装材1を得た。
トリメチロールプロパン(TMP)10質量部に代えて、グリセリン10質量部を使用した以外は、実施例1と同様にして、図1に示す構成の成形用包装材1を得た。
トリレンジイソシアネート(TDI)25質量部に代えて、ジフェニルメタンジイソシアネート(MDI)25質量部を使用した以外は、実施例1と同様にして、図1に示す構成の成形用包装材1を得た。
MD方向の引張強度が190MPa、TD方向の引張強度が180MPaである2軸延伸ポリブチレンテレフタレートフィルムに代えて、MD方向の引張強度が250MPa、TD方向の引張強度が290MPaである2軸延伸ナイロンフィルムを用いた以外は、実施例1と同様にして、成形用包装材を得た。
MD方向の引張強度が190MPa、TD方向の引張強度が180MPaである2軸延伸ポリブチレンテレフタレートフィルムに代えて、MD方向の引張強度が240MPa、TD方向の引張強度が240MPaである2軸延伸ポリエチレンテレフタレートフィルムを用いた以外は、実施例1と同様にして、成形用包装材を得た。
ジカルボン酸成分として、アジピン酸(脂肪族ジカルボン酸)70モル部およびイソフタル酸(芳香族ジカルボン酸)30モル部からなるジカルボン酸成分を用いて得られた数平均分子量9000のポリエステルポリオール100質量部を使用した以外は、実施例1と同様にして、成形用包装材を得た。
ジカルボン酸成分として、アジピン酸(脂肪族ジカルボン酸)10モル部およびイソフタル酸(芳香族ジカルボン酸)90モル部からなるジカルボン酸成分を用いて得られた数平均分子量28000のポリエステルポリオール100質量部を使用した以外は、実施例1と同様にして、成形用包装材を得た。
ジカルボン酸成分として、アジピン酸(脂肪族ジカルボン酸)50モル部およびイソフタル酸(芳香族ジカルボン酸)50モル部からなるジカルボン酸成分を用いて得られた数平均分子量10000のポリエステルポリオール100質量部を使用した以外は、実施例1と同様にして、成形用包装材を得た。
ジカルボン酸成分として、アジピン酸(脂肪族ジカルボン酸)30モル部およびイソフタル酸(芳香族ジカルボン酸)70モル部からなるジカルボン酸成分を用いて得られた数平均分子量20000のポリエステルポリオール100質量部を使用した以外は、実施例1と同様にして、成形用包装材を得た。
外側接着剤として、酸変性ポリオレフィン樹脂を含有する熱硬化型オレフィン外側接着剤を使用した以外は、実施例1と同様にして、成形用包装材を得た。
外側接着剤として、メタアクリレート系樹脂を含有する熱硬化型アクリル外側接着剤を使用した以外は、実施例1と同様にして、成形用包装材を得た。
外側接着剤として、ビスフェノールA型エポキシ系樹脂を含有する熱硬化型エポキシ外側接着剤を使用した以外は、実施例1と同様にして、成形用包装材を得た。
MD方向の引張強度が190MPa、TD方向の引張強度が180MPaである2軸延伸ポリブチレンテレフタレートフィルムに代えて、MD方向の引張強度が70MPa、TD方向の引張強度が70MPaである2軸延伸ポリブチレンテレフタレートフィルムを用いた以外は、実施例1と同様にして、成形用包装材を得た。
MD方向の引張強度が190MPa、TD方向の引張強度が180MPaである2軸延伸ポリブチレンテレフタレートフィルムに代えて、MD方向の引張強度が340MPa、TD方向の引張強度が340MPaである2軸延伸ポリブチレンテレフタレートフィルムを用いた以外は、実施例1と同様にして、成形用包装材を得た。
実施例、比較例で使用した各外側接着剤を熱硬化させた硬化膜のヤング率(MPa)をJIS K7127-1999に準拠して測定した。具体的には、各外側接着剤をガラス板の上に50μmの厚さで塗布した後、40℃で11日間加熱エージング処理を行って、外側接着剤を熱硬化させて厚さ46μmの硬化物を得た。前記硬化物をガラス板から剥がした後、幅15mm×長さ100mmの大きさに切り出して試験片を作製し、島津製作所製ストログラフ(AGS-5kNX)を使用して引張速度200mm/分で前記試験片の引張試験を行ってヤング率(MPa)を測定した。
実施例、比較例で使用したポリブチレンテレフタレート樹脂(外側層形成用)を押出成形により厚さ25μmのフィルムを得た後、このポリブチレンテレフタレートフィルムをTD方向、MD方向のそれぞれの方向に沿って長さ150mm×幅10mmの大きさに切り出した各試験片について、JIS K7127-1999に準拠してチャック間隔100mm、試験速度200mm/分で引張試験を行って引張強度(MPa)を求めた。
株式会社アマダ製の深絞り成形具を用いて成形用包装材に対して縦55mm×横35mm×各深さの略直方体形状(1つの面が開放された略直方体形状)に深絞り成形を行い、即ち成形深さを変えて深絞り成形を行い、得られた成形体におけるコーナー部におけるピンホール及び割れの有無を調べ、このようなピンホール及び割れが発生しない「最大成形深さ(mm)」を調べ、下記判定基準に基づいて評価した。なお、ピンホールや割れの有無は、暗室にて光透過法で調べた。
(判定基準)
「○」…ピンホール及び割れが発生しない最大成形深さが5mm以上である
「△」…ピンホール及び割れが発生しない最大成形深さが3.5mm以上5mm未満である
「×」…ピンホール及び割れが発生しない最大成形深さが3.5mm未満である。
成形深さの深い成形として、上記深絞り成形具を用いて成形用包装材に対して縦55mm×横35mm×5mmの略直方体形状(1つの面が開放された略直方体形状)に深絞り成形を行った。この時、耐熱性樹脂層2が成形体の外側になるように成形を行った。各実施例、各比較例毎にそれぞれ2個の成形体を作製し、2個の成形体10のフランジ部(封止用周縁部;図2参照)29同士を接触させて重ね合わせて170℃×6秒間ヒートシールを行った後、目視観察によりヒートシール部39におけるデラミネーション(剥離)発生の有無および外観の浮きの有無を調べ、下記判定基準に基づいて評価した。
(判定基準)
「○」…デラミネーション(剥離)が認められず、且つ外観の浮きも認められなかった(合格)
「△」…僅かなデラミネーション(剥離)が稀に発生することがあるが、実質的にはデラミネーション(剥離)が無く、且つ外観の浮きもなかった(合格)
「×」…デラミネーション(剥離)が発生しており、外観の浮きもあった(不合格)。
成形用包装材を幅15mm×長さ100mmの短冊形にカットして試験片とした。この試験片を2枚作成し、これら2枚の試験片を内側層(熱融着性樹脂層)3同士が接触するように重ね合わせてその全面(全領域)にヒートシールを行って熱封止部(ヒートシール)を形成した。前記ヒートシールは、テスター産業株式会社製のヒートシール装置(TP-701-A)を用いて、シール圧0.2MPa(ゲージ表示圧)、225℃、2秒間の片面加熱により行った。ヒートシール後の熱封止部の表面を観察し、下記判定基準に基づいて評価した。
(判定基準)
「○」…変化なし(合格)
「△」…微細なしわが発生する程度である(合格)
「×」…表面が白化または溶融部分が発生した(不合格)。
2…ポリブチレンテレフタレート層(外側層)
3…熱融着性樹脂層(内側層)
4…金属箔層
5…外側接着剤層
6…内側接着剤層
10…外装ケース
15…外装部材
30…蓄電デバイス
31…蓄電デバイス本体部
Claims (6)
- 外側層としてのポリブチレンテレフタレート層と、内側層としての熱融着性樹脂層と、これら両層間に配置された金属箔層と、を含む成形用包装材において、
前記ポリブチレンテレフタレート層と前記金属箔層とが外側接着剤層を介して接着されており、
前記外側接着剤層は、ポリエステルポリオールと、多官能イソシアネート化合物と、多価アルコールと、を含むウレタン接着剤の硬化膜で形成され、
前記ポリエステルポリオールは、ジカルボン酸成分を含み、
前記ジカルボン酸成分は、芳香族ジカルボン酸を含有し、前記ジカルボン酸成分中の前記芳香族ジカルボン酸の含有率が40モル%~80モル%であり、
前記ウレタン接着剤の硬化膜のヤング率が140MPa~300MPaであり、
前記ポリブチレンテレフタレート層の引張強度が、MD方向で100MPa~200MPaであり、TD方向で100MPa~200MPaであり、
前記ポリエステルポリオールの数平均分子量が8000~30000の範囲であることを特徴とする成形用包装材。 - 前記外側接着剤層は、ウレタン結合、エステル結合、ウレア結合、アロファネート結合ビュレット結合およびアミド結合からなる群より選ばれる少なくとも1種の結合を含む請求項1に記載の成形用包装材。
- 前記ウレタン接着剤において、前記ポリエステルポリオールの水酸基のモル数に対する前記多官能イソシアネート化合物のイソシアネート基のモル数の比率(当量比)が2~25である請求項1または2に記載の成形用包装材。
- 請求項1~3のいずれか1項に記載の成形用包装材の成形体からなる蓄電デバイス用外装ケース。
- 蓄電デバイス本体部と、
請求項4に記載の蓄電デバイス用外装ケースを少なくとも含む外装部材とを備え、
前記蓄電デバイス本体部が、前記外装部材で外装されていることを特徴とする蓄電デバイス。 - 外側層としてのポリブチレンテレフタレート層と、内側層としての熱融着性樹脂層と、これら両層間に配置された金属箔層と、を含む積層物であって、前記ポリブチレンテレフタレート層は、引張強度が、MD方向で100MPa~200MPaであり、TD方向で100MPa~200MPaであるポリブチレンテレフタレートフィルムからなり、前記熱融着性樹脂層と前記金属箔層とが、硬化型内側接着剤を介して接着され、前記ポリブチレンテレフタレート層と前記金属箔層とが、ポリエステルポリオールと、多官能イソシアネート化合物と、多価アルコールと、を含む硬化型外側接着剤を介して接着された積層物を準備する工程と、
前記積層物を37℃~55℃の温度で加熱エージング処理を行うことによって前記硬化型内側接着剤および前記硬化型外側接着剤を硬化させるエージング処理工程と、を含み、
前記ポリエステルポリオールは、ジカルボン酸成分を含み、
前記ジカルボン酸成分は、芳香族ジカルボン酸を含有し、前記ジカルボン酸成分中の前記芳香族ジカルボン酸の含有率が40モル%~80モル%であり、
前記ポリエステルポリオールの数平均分子量が8000~30000の範囲であり、
前記硬化型外側接着剤の硬化膜のヤング率が140MPa~300MPaであることを特徴とする成形用包装材の製造方法。
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US11446902B2 (en) | 2022-09-20 |
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