JP6583837B2 - 金属箔と樹脂フィルムのラミネート用接着剤、積層体、電池外装用包装材並びに電池ケース及びその製造方法 - Google Patents
金属箔と樹脂フィルムのラミネート用接着剤、積層体、電池外装用包装材並びに電池ケース及びその製造方法 Download PDFInfo
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- JP6583837B2 JP6583837B2 JP2017565419A JP2017565419A JP6583837B2 JP 6583837 B2 JP6583837 B2 JP 6583837B2 JP 2017565419 A JP2017565419 A JP 2017565419A JP 2017565419 A JP2017565419 A JP 2017565419A JP 6583837 B2 JP6583837 B2 JP 6583837B2
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- adhesive
- resin film
- metal foil
- laminating
- metal
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Description
〔1〕カルボキシル基を有するポリオレフィン樹脂(A)と、多官能イソシアネート化合物(B)、並びに7族及び12族の少なくとも1種の金属の化合物である金属化合物(C)を有する、金属箔と樹脂フィルムのラミネート用接着剤。
〔2〕前記カルボキシル基を有するポリオレフィン樹脂(A)が、単量体単位としてプロピレン又はプロピレンとエチレン、及びエチレン性不飽和カルボン酸又はその酸無水物を含む変性ポリオレフィン樹脂を含む、上記〔1〕に記載の金属箔と樹脂フィルムのラミネート用接着剤。
〔3〕前記カルボキシル基を有するポリオレフィン樹脂(A)が、130℃で測定したMFRが5g/10分〜42g/10分であるカルボキシル基を有するポリオレフィン樹脂を含む、上記〔1〕又は〔2〕に記載の金属箔と樹脂フィルムのラミネート用接着剤。
〔4〕前記多官能イソシアネート化合物(B)が、ポリイソシアネートの多量体を含む、上記〔1〕〜〔3〕のいずれかに記載の金属箔と樹脂フィルムのラミネート用接着剤。
〔5〕前記ポリイソシアネートの多量体が、ポリイソシアネートのイソシアヌレート体を含む、上記〔1〕〜〔4〕のいずれかに記載の金属箔と樹脂フィルムのラミネート用接着剤。
〔6〕前記カルボキシル基を有するポリオレフィン樹脂(A)に含まれるカルボキシル基数に対する、多官能イソシアネート化合物(B)に含まれるイソシアナト基数の比率が、0.5〜13である、上記〔1〕〜〔5〕のいずれかに記載の金属箔と樹脂フィルムのラミネート用接着剤。
〔7〕前記金属化合物(C)が、7族及び12族の少なくとも1種の金属のカルボン酸塩を少なくとも1種以上含む、上記〔1〕〜〔6〕のいずれかに記載の金属箔と樹脂フィルムのラミネート用接着剤。
〔8〕前記金属化合物(C)が亜鉛又はマンガンのカルボン酸塩を含む、上記〔1〕〜〔7〕のいずれかに記載の金属箔と樹脂フィルムのラミネート用接着剤。
〔9〕溶剤(D)を更に含む、上記〔1〕〜〔8〕のいずれかに記載の金属箔と樹脂フィルムのラミネート用接着剤。
〔10〕金属箔と樹脂フィルムが、上記〔1〕〜〔9〕のいずれかに記載の金属箔と樹脂フィルムのラミネート用接着剤から得られる接着剤層を介して積層された、積層体。
〔11〕前記金属箔がアルミニウム箔であり、前記樹脂フィルムが熱融着性樹脂フィルムを含有する、上記〔10〕に記載の積層体。
〔12〕前記金属箔の厚さが10〜100μmであり、前記樹脂フィルムの厚さが9〜100μmである、上記〔10〕又は〔11〕に記載の積層体。
〔13〕上記〔10〕〜〔12〕のいずれかに記載の積層体を用いて得られる、電池外装用包装材。
〔14〕上記〔13〕に記載の電池外装用包装材を用いて得られる、電池ケース。
〔15〕上記〔13〕に記載の電池外装用包装材を深絞り成形又は張り出し成形する、電池ケースの製造方法。
本実施の形態に係る金属箔と樹脂フィルムのラミネート用接着剤は、カルボキシル基を有するポリオレフィン樹脂(A)と、多官能イソシアネート化合物(B)、並びに7族及び12族の少なくとも1種の金属の化合物である金属化合物(C)を有する。
本実施の形態に係る金属箔と樹脂フィルムのラミネート用接着剤において、前記カルボキシル基を有するポリオレフィン樹脂(A)は主剤に当たり、多官能イソシアネート化合物(B)は硬化剤に当たり、金属化合物(C)は反応促進剤に当たる。
ここで、本明細書における「〜」は、「〜」という記載の前の値以上、「〜」という記載の後の値以下を意味する。
本実施の形態に用いられるカルボキシル基を有するポリオレフィン樹脂(以下、「(A)成分」又は「(A)」ということがある)は、分子構造中にカルボキシル基を含有するものであれば特に制限されない。なお、ここでいうカルボキシル基とは、カルボン酸由来の構成単位に加え、カルボン酸無水物由来の構成単位も含むものとする。そのような樹脂としては、例えば、カルボキシル基を有する単量体をポリオレフィンにグラフト重合したもの、カルボキシル基を有する単量体をオレフィンと共重合したもの、またそれらを組み合わせて共重合したもの等が挙げられる。
本実施の形態に用いる多官能イソシアネート化合物(B)(以下、「(B)成分」又は「(B)」ともいう)としては、イソシアナト基を2つ以上含有するポリイソシアネート、もしくはその多量体であれば特に制限はない。本実施の形態における多官能イソシアネート化合物(B)は、本実施の形態の金属箔と樹脂フィルムのラミネート用接着剤に硬化剤として配合するものである。
本実施の形態における周期律表の7族及び12族の少なくとも1種の金属の化合物である金属化合物(C)(以下、「7族及び/又は12族の金属化合物(C)」又は「金属化合物(C)」又は「(C)成分」又は「(C)」ともいう)は、本実施の形態の金属箔と樹脂フィルムのラミネート用接着剤中のカルボキシル基を有するポリオレフィン樹脂(A)及び多官能イソシアネート化合物(B)の反応を促進するための反応促進剤として配合するものである。
7族及び12族の少なくとも1種の金属の化合物である金属化合物(C)として、例えば、金属ヘキサン酸塩、金属オクチル酸塩(2−エチルヘキサン酸塩)、金属ネオデカン酸塩、金属ステアリン酸塩、金属オレイン酸塩等の金属カルボン酸塩、金属アセチルアセトナート等が挙げられる。中でも長期電解液浸漬後の接着強度の観点から、金属化合物(C)が、7族及び12族の少なくとも1種の金属のカルボン酸塩を少なくとも1種以上含むことが好ましく、亜鉛及びマンガンから選ばれる金属のカルボン酸塩を少なくとも1種以上含むことがより好ましく、亜鉛のカルボン酸塩を含むことが更に好ましい。
具体的には、7族及び12族の少なくとも1種の金属の化合物である金属化合物(C)は、ネオデカン酸亜鉛(C20H38O4Zn)、2−エチルヘキサン酸亜鉛(オクチル酸亜鉛、ヘキソエート亜鉛、C16H30O4Zn)、ステアリン酸亜鉛(C36H70O4Zn)、亜鉛アセチルアセトナート(C10H14O4Zn)、2−エチルヘキサン酸マンガン(オクチル酸マンガン、ヘキソエートマンガン、C16H30O4Mn)が好ましく、ネオデカン酸亜鉛(C20H38O4Zn)、2−エチルヘキサン酸亜鉛(オクチル酸亜鉛、ヘキソエート亜鉛、C16H30O4Zn)がより好ましい。
カルボキシル基を有するポリオレフィン樹脂(A)100質量部に対する、7族及び12族の少なくとも1種の金属の化合物である金属化合物(C)の比率は特に制限されないが、カルボキシル基を有するポリオレフィン樹脂(A)100質量部に対して、金属化合物(C)の含有量は金属の質量で換算して0.0001質量部〜5質量部が好ましく、0.0005質量部〜5質量部がより好ましく、0.001質量部〜5質量部が更に好ましい。0.0001質量部以上であれば、本発明の金属箔と樹脂フィルムのラミネート用接着剤から得られる接着剤層の接着力が長期間電解液に浸漬後においても十分に高くなり、5質量部以下であれば常態の接着強度が高くなる。なお、7族及び/又は12族の金属化合物(C)は、カルボキシル基を有するポリオレフィン樹脂(A)の製造時に添加しても、接着剤の調製時に添加してもよい。
<溶剤(D)>
溶剤(D)は、カルボキシル基を有するポリオレフィン樹脂(A)、多官能イソシアネート化合物(B)及び7族及び12族の少なくとも1種の金属の化合物である金属化合物(C)を溶解又は分散可能なものであれば特に制限されない。例えば、トルエン、キシレン等の芳香族系有機溶剤、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の脂環式系有機溶剤、n−ヘキサン、n−ヘプタン等の脂肪族系有機溶剤、酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル系有機溶剤、アセトン、メチルエチルケトン、メチルブチルケトン等のケトン系有機溶剤等が挙げられる。これらは、単独又は2種以上混合して使用することができる。
これらの中では、特にカルボキシル基を有するポリオレフィン樹脂(A)の溶解性の見地から、酢酸エチル、酢酸プロピル、酢酸ブチル、トルエン、メチルシクロヘキサン、メチルエチルケトンが好ましく、酢酸エチル、トルエン、メチルシクロヘキサンがより好ましい。
本実施の形態に係る金属箔と樹脂フィルムのラミネート用接着剤中における、溶剤(D)の含有量は、30〜95質量%が好ましく、40〜90質量%であることがより好ましく、50〜80質量%であることが更に好ましい。30質量%以上であれば、本実施の形態の金属箔と樹脂フィルムのラミネート用接着剤の塗布時の操作性が良好となり、95質量%以下であれば、本実施の形態の金属箔と樹脂フィルムのラミネート用接着剤を塗布・硬化して得られる積層体の厚み制御性が良好となる。
本実施の形態の金属箔と樹脂フィルムのラミネート用接着剤は、必要に応じて、粘着付与剤、可塑剤等の添加剤を含有していてもよい。
本実施の形態の積層体は、金属箔と樹脂フィルムが本実施の形態の金属箔と樹脂フィルムのラミネート用接着剤(以下、単に「本実施の形態のラミネート用接着剤」ということがある。)から得られる接着剤層を介して積層されたものである。
また本実施の形態の積層体中に、金属箔と樹脂フィルムを本実施の形態のラミネート用接着剤から得られる接着剤層を介して接合した層が含まれれば、他に金属箔同士及び/又は樹脂フィルム同士が本実施の形態のラミネート用接着剤から得られる接着剤層を介して接合した層を含んでもよい。この接合方法は、ヒートラミネーション方式やドライラミネーション方式等の公知の方法を用いることができる。本実施の形態において、ヒートラミネーション方式とは、溶剤(D)を含まない本実施の形態のラミネート用接着剤を、接着剤層に接する層表面にて加熱溶融、又は接着剤層に接する層と共に加熱押し出しすることにより、積層体の層間に介在させ、接着剤層を形成する方式である。また、本実施の形態において、ドライラミネーション方式とは、溶剤(D)を含む本実施の形態のラミネート用接着剤を接着剤層に接する層表面に塗布、乾燥せしめた後に他方の層と重ね合せて圧着することにより、積層体の層間に介在させ、接着剤層を形成する方式である。
本実施の形態の電池外装用包装材は、本実施の形態の積層体を用いて得られる。
本実施の形態の電池外装用包装材は、本実施の形態の積層体の、金属箔の外側に樹脂フィルム特に耐熱性樹脂フィルムからなる外層を設けたものであることが好ましい。また、必要に応じて、機械的強度や耐電解液性等の特性を高めるために、第1中間樹脂層又は/及び第2中間樹脂層等を付加した構成にすることができる。好ましい形態としては、具体的に次のような構成にすることができる。なお、接着剤層は「本実施の形態のラミネート用接着剤から得られる接着剤層」を意味し、金属箔層をアルミニウム箔層として例示している。
(1)外層/アルミニウム箔層/接着剤層/樹脂フィルム層
(2)外層/第1中間樹脂層/アルミニウム箔層/接着剤層/樹脂フィルム層
(3)外層/アルミニウム箔層/第2中間樹脂層/接着剤層/樹脂フィルム層
(4)外層/第1中間樹脂層/アルミニウム箔層/第2中間樹脂層/接着剤層/樹脂フィルム層
(5)コート層/外層/アルミニウム箔層/接着剤層/樹脂フィルム層
(6)コート層/外層/第1中間樹脂層/アルミニウム箔層/接着剤層/樹脂フィルム層
(7)コート層/外層/アルミニウム箔層/第2中間樹脂層/接着剤層/樹脂フィルム層
(8)コート層/外層/第1中間樹脂層/アルミニウム箔層/第2中間樹脂層/接着剤層/樹脂フィルム層
上記において、第1中間樹脂層としては、ポリアミド樹脂、ポリエステル樹脂又はポリエチレン樹脂等が電池外装用包装材の機械的強度を向上させる目的で使用される。第2中間樹脂層としては、第1中間樹脂層と同様にポリアミド樹脂、ポリエステル樹脂又はポリエチレン樹脂やポリプロピレン等の熱接着性押出し樹脂が、主として耐電解液性を向上させる目的で使用される。樹脂フィルム層は、単層の樹脂フィルム、複層の樹脂フィルム(2層の共押出し又は3層の共押出し等により製造する)が使用できる。また、第2中間樹脂層も単層の樹脂フィルムや複層の共押出し樹脂フィルムが使用できる。第1中間樹脂層及び第2中間樹脂層の厚さは、特に限定されないが、これらを設ける場合は、通常0.1〜30μm程度である。
外層に使用する樹脂フィルムは、耐熱性、成形性、絶縁性等に優れたものであり、ポリアミド(ナイロン)樹脂又はポリエステル樹脂の延伸フィルムが一般的に使用される。この外層フィルムの厚さは、9〜50μm程度であり、9μm未満では包装材の成形を行うときに延伸フィルムの伸びが不足し、アルミニウム箔にネッキングが生じ、成形不良が起こり易い。一方、50μmを超える厚さの場合は、特段、成形性の効果が向上する訳でもなく、逆に体積エネルギー密度を低下させるとともにコストアップにつながるだけである。外層フィルムの厚さは10〜40μm程度であることがより好ましく、20〜30μmであることが更に好ましい。
金属箔は、水蒸気等に対するバリア性の役割を担うもので、材質としては純アルミニウム系又はアルミニウム−鉄系合金のO材(軟質材)が一般的に使用され、かつ好ましい。アルミニウム箔の厚さとしては、加工性の確保及び酸素や水分の包装内への浸入を防止するバリア性確保のために、10〜100μm程度が好ましい。アルミニウム箔の厚さが10μm未満の場合は、成形時においてアルミニウム箔の破断が生じたり、ピンホールが発生したりして酸素や水分の浸入のおそれがある。一方、アルミニウム箔の厚さが100μmを超えた場合は、成形時の破断の改善効果やピンホール発生防止効果が特段向上するわけでなく、単に包装材の総厚さが厚く、質量が増加し、体積エネルギー密度が低下する。アルミニウム箔は、一般的に30〜50μm程度の厚さのものが使用され、40〜50μmの厚さのものを使用することが好ましい。なお、アルミニウム箔には、樹脂フィルムとの接着性向上や耐食性向上のため、シランカップリング剤やチタンカップリング剤等のアンダーコート処理、クロメート処理等の化成処理をしておくことが好ましい。
樹脂フィルムとしては、ポリプロピレン、ポリエチレン、マレイン酸変性ポリプロピレン、エチレン−アクリレート共重合体又はアイオノマー樹脂等の熱融着性樹脂フィルムが好ましい。これらの樹脂は、ヒートシール性を有し、腐食性の強いリチウム二次電池の電解液等に対する耐薬品性を向上させる役割を担うものである。これらのフィルム厚さは、9〜100μmが好ましく、より好ましくは20〜80μmであり、40〜80μmであるのが更に好ましい。樹脂フィルムの厚さが9μm以上であれば、十分なヒートシール強度が得られ、電解液等に対する耐食性が良好となる。樹脂フィルムの厚さが100μm以下であれば、電池外装用包装材の強度が十分でありかつ、成形性が良好となる。
本実施の形態の電池外装用包装材は、外層の上にコート層を設けてもよい。コート層の形成法としては、ガスバリア性のポリマーをコートする方法、アルミニウム金属や酸化ケイ素、酸化アルミニウム等の無機酸化物を蒸着し、金属及び無機物の薄膜をコートする方法等がある。コート層を設けることにより、水蒸気及びその他のガスバリア性がより優れた積層体が得られる。
本実施の形態の電池ケースは、本実施の形態の電池外装用包装材を用いて得られる。例えば、電池外装用包装材を成形することによって得られる。
本実施の形態の電池外装用包装材は、耐電解液性や耐熱性、水蒸気及びその他のガスバリア性に優れており、二次電池、特にリチウムイオン電池用の電池ケースとして好適に用いられる。また、本実施の形態の電池外装用包装材は成形性が非常に良好であるため、公知の方法に従って成形することにより、本実施の形態の電池ケースを簡便に得ることができる。成形の方法は特に限定されないが、深絞り成形又は張り出し成形によって成形すると、複雑な形状や寸法精度が高い電池ケースを作製することができる。
<カルボキシル基を有するポリオレフィン樹脂(A)の酸価測定>
カルボキシル基を有するポリオレフィン樹脂(A)の酸価は、JIS 0070に基づいて測定した。
カルボキシル基を有するポリオレフィン樹脂(A)のMFRは、JIS K 7210に記載の方法にて、温度130℃、荷重2160gの条件で測定した。
<接着剤のNCO/COOH比の算出>
実施例1〜11及び比較例1〜3の金属箔と樹脂フィルムのラミネート用接着剤の製造に使用した多官能イソシアネート(B)に含まれるイソシアナト基数を、JIS K 6806に基づいて測定した。また、上記により測定したカルボキシル基を有するポリオレフィン樹脂(A)の酸価より、ポリオレフィン樹脂(A)に含まれるカルボキシル基のカルボキシル基数を算出した。そして、これらのイソシアナト基数及びカルボキシル基数を用いて、カルボキシル基に対するイソシアナト基数の比率を算出してNCO/COOH比とした。
接着剤を30℃で12時間、24時間、48時間保存した後、未延伸ポリプロピレンフィルム上に塗工し、塗工性の良否を以下の基準で判定した。
◎・・・48時間後、塗工できた。
○・・・24時間後、塗工できたが、48時間後、増粘もしくはゲル化して塗工できなかった。
△・・・12時間後、塗工できたが、24時間後、増粘もしくはゲル化して塗工できなかった。
×・・・12時間後、増粘もしくはゲル化して塗工できなかった。
<剥離強度>
(1)常態T字剥離強度
上記試験片及びオートグラフAG−X(株式会社島津製作所製)を用いて、23℃×50%RH雰囲気下に剥離速度100mm/minで剥離させ、アルミニウム箔層と未延伸ポリプロピレンフィルム層間の90°剥離強度を測定した。
(2)電解液溶媒浸漬後のT字剥離強度
上記試験片を電解液溶媒(プロピレンカーボネート/ジエチルカーボネート、質量比50/50)に浸漬し、85℃雰囲気下に1日放置した後に取り出し、その試験片を用いて上記(1)と同様にしてアルミニウム箔層と未延伸ポリプロピレンフィルム層間の90°剥離強度を測定した。
(合成例1)
メタロセン触媒を重合触媒として用いて製造した、プロピレン−エチレンランダム共重合体(プロピレン−エチレンモル比97:3、MFR10g/10分)100質量部、無水マレイン酸2質量部、メタクリル酸ラウリル1質量部及びジ−t−ブチルパーオキサイド1.5質量部を、シリンダー部の最高温度を170℃に設定した二軸押出機を用いて混練して反応させた。その後、押出機内にて減圧脱気を行い、残留する未反応物を除去してカルボキシル基を有するポリオレフィン樹脂(a1)を得た。
表1に示す通りのMFRの異なるプロピレン−エチレンランダム共重合体、プロピレン重合体、又はプロピレン−エチレン−ブテンランダム共重合体を用いた他は、合成例1と同様の方法にてカルボキシル基を有するポリオレフィン樹脂(a2)〜(a7)を得た。
(実施例1)
(A)成分としてカルボキシル基を有するポリオレフィン樹脂(a1)15gを、溶剤(D)としてトルエン/酢酸エチル(質量比9/1)の混合溶媒85.0g中に分散させた。次いで、(B)成分としてデュラネートTKA−100(旭化成ケミカルズ株式会社製、ヘキサメチレンジイソシアネートのイソシアヌレート体、イソシアネート基含量21.7%)を1.74g、(C)成分として「BiCAT Z」(Shepherd Chemical社製、ネオデカン酸亜鉛)を0.50g加えて金属箔と樹脂フィルムのラミネート用接着剤を調製した。
表2〜3に示す配合としたこと以外は実施例1と同様にして、実施例2〜11及び比較例1〜3の金属箔と樹脂フィルムのラミネート用接着剤を調製した。
外層:PET/延伸ポリアミド積層フィルム(厚さ27μm)
外層用接着剤:ウレタン系ドライラミネート用接着剤(東洋モートン株式会社製:AD502/CAT10、塗布量3g/m2(塗布時))
アルミニウム箔層:アルミニウム−鉄系合金のアルミニウム箔(AA規格8079−O材、厚さ40μm)
内層用接着剤:金属箔と樹脂フィルムのラミネート用接着剤(塗布量:乾燥後の厚さが2μm)
内層:未延伸ポリプロピレンフィルム(厚さ80μm)
接着後養生条件、期間:40℃、5%RH、24時間
実施例1〜11及び比較例1〜3の金属箔と樹脂フィルムのラミネート用接着剤の製造に用いたポリオレフィン樹脂の評価結果を表1に示す。また、実施例1〜11の金属箔と樹脂フィルムのラミネート用接着剤の評価結果を表2に示し、比較例1〜3の金属箔と樹脂フィルムのラミネート用接着剤の評価結果を表4に示す。さらに、実施例1〜11の金属箔と樹脂フィルムのラミネート用接着剤を用いて作製した電池ケース用包装材料の評価結果を表2に示し、比較例1〜3の金属箔と樹脂フィルムのラミネート用接着剤を用いて作製した電池ケース用包装材料の評価結果を表3に示す。
・ヘキソエート亜鉛:東栄化工株式会社製、2−エチルヘキサン酸亜鉛(65質量部)及びミネラルスピリット(35質量部)の混合物
・エフコ・ケム ZNS−P:株式会社ADEKA製、ステアリン酸亜鉛
・亜鉛アセチルアセトナート:東京化成工業株式会社製の試薬
・ヘキソエートマンガン:東栄化工株式会社製、オクチル酸マンガン(42質量部)及びミネラルスピリット(58質量部)の混合物
・KS−1260:堺化学工業株式会社製、ブチルスズジラウレート
・チタニウムアセチルアセトナート:東京化成工業株式会社製の試薬
・BiCAT8210:Shepherd Chemical社製、トリス(2−エチルヘキサン酸)ビスマス(ビスマストリス(2−エチルヘキサノエート))(89質量部)及び2−エチルヘキサン酸(11質量部)の混合物
表2の結果から、本発明の金属箔と樹脂フィルムのラミネート用接着剤(実施例1〜11)は、常態T字剥離強度、電解液溶媒浸漬後のT字剥離強度共に優れていることがわかった。
これに対して、表3に示すとおり、(C)成分を含まない金属箔と樹脂フィルムのラミネート用接着剤を用いる場合(比較例1〜3)は、常態T字剥離強度、電解液溶媒浸漬後のT字剥離強度共に不十分であることがわかった。
Claims (15)
- カルボキシル基を有するポリオレフィン樹脂(A)と、多官能イソシアネート化合物(B)、並びに7族及び12族の少なくとも1種の金属のカルボン酸塩、及び7族及び12族の少なくとも1種の金属のアセチルアセトナート、から選ばれる少なくとも1種の化合物である金属化合物(C)を有する、金属箔と樹脂フィルムのラミネート用接着剤。
- 前記カルボキシル基を有するポリオレフィン樹脂(A)が、単量体単位としてプロピレン又はプロピレンとエチレン、及びエチレン性不飽和カルボン酸又はその酸無水物を含む変性ポリオレフィン樹脂を含む、請求項1に記載の金属箔と樹脂フィルムのラミネート用接着剤。
- 前記カルボキシル基を有するポリオレフィン樹脂(A)が、130℃で測定したMFRが5g/10分〜42g/10分であるカルボキシル基を有するポリオレフィン樹脂を含む、請求項1又は2に記載の金属箔と樹脂フィルムのラミネート用接着剤。
- 前記多官能イソシアネート化合物(B)が、ポリイソシアネートの多量体を含む、請求項1〜3のいずれかに記載の金属箔と樹脂フィルムのラミネート用接着剤。
- 前記ポリイソシアネートの多量体が、ポリイソシアネートのイソシアヌレート体を含む、請求項4に記載の金属箔と樹脂フィルムのラミネート用接着剤。
- 前記カルボキシル基を有するポリオレフィン樹脂(A)に含まれるカルボキシル基数に対する、多官能イソシアネート化合物(B)に含まれるイソシアナト基数の比率が、0.5〜13である、請求項1〜5のいずれかに記載の金属箔と樹脂フィルムのラミネート用接着剤。
- 前記金属化合物(C)が、7族及び12族の少なくとも1種の金属のカルボン酸塩を少なくとも1種以上含む、請求項1〜6のいずれかに記載の金属箔と樹脂フィルムのラミネート用接着剤。
- 前記金属化合物(C)が亜鉛又はマンガンのカルボン酸塩を含む、請求項1〜7のいずれかに記載の金属箔と樹脂フィルムのラミネート用接着剤。
- 溶剤(D)を更に含む、請求項1〜8のいずれかに記載の金属箔と樹脂フィルムのラミネート用接着剤。
- 金属箔と樹脂フィルムが、請求項1〜9のいずれかに記載の金属箔と樹脂フィルムのラミネート用接着剤から得られる接着剤層を介して積層された、積層体。
- 前記金属箔がアルミニウム箔であり、前記樹脂フィルムが熱融着性樹脂フィルムを含有する、請求項10に記載の積層体。
- 前記金属箔の厚さが10〜100μmであり、前記樹脂フィルムの厚さが9〜100μmである、請求項10又は11に記載の積層体。
- 請求項10〜12のいずれかに記載の積層体を用いて得られる、電池外装用包装材。
- 請求項13に記載の電池外装用包装材を用いて得られる、電池ケース。
- 請求項13に記載の電池外装用包装材を深絞り成形又は張り出し成形する、電池ケースの製造方法。
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